SOFC Anode: Hydrogen Oxidation at Porous Nickel and Nickel/yttria-Stabilised Zirconia Cermet Electrodes

SOFC Anode
Hydrogen oxidation at porous nickel and nickel/yttriastabilised zirconia cermet electrodes
Baukje de Boer
Boer, Baukje de
SOFC Anodes : Hydrogen oxidation at porous nickel and nickel/yttria-stabilised zirconia cermet electrodes Thesis Enschede. With ref. With summary in Dutch. ISBN 90-36511909
Copyright 1998 by B. de Boer, the Netherlands.
SOFC ANODE
HYDROGEN OXIDATION AT POROUS NICKEL AND NICKEL/YTTRIA-STABILISED ZIRCONIA CERMET ELECTRODES
PROEFSCHRIFT
ter verkrijging van de graad van doctor aan de Universiteit Twente, op gezag van de rector magnificus, prof. dr. F.A. van Vught, volgens besluit van het College voor Promoties in het openbaar te verdedigen op vrijdag 9 oktober 1998 te 16.45 uur.
door
Baukje de Boer geboren op 8 oktober 1968 te Appelscha
Dit proefschrift is goedgekeurd door de promotor prof. dr. ir. H. Verweij en de assistent promotor dr. H.J.M. Bouwmeester
I have yet to see any problem, however complicated, which, when you looked at it in the right way, did not become still more complicated
P. Anderson, 1926 (New scientist, 25 September 1969, p 639)
The investigations described in this thesis were supported financially by the Netherlands Energy Research Foundation, ECN.
Summary In the ongoing search for alternative and environmental friendly power generation facilities, the fuel cell is a good candidate. There are several types of fuel cells with large differences in application, size, cost and operating range. The Solid Oxide Fuel Cell (SOFC) is a high temperature fuel cell, interesting for decentralised generation of heat and power. Nickel/yttria-stabilised zirconia cermet is the state-of-the-art material for use as anode in SOFCs. This thesis describes a number of experimental studies on the anode of the SOFC. The emphasis is on two important aspects of this type of electrode, the kinetics of the hydrogen oxidation reaction and the effect of the microstructure on the electrochemical performance of the electrode. Insight in these two aspects will lead to a better understanding and further improvements of the anode. A general introduction in fuel cells is given in Chapter 1, followed by a brief review on SOFC materials and SOFC anode kinetics as reported in literature. This last part gives a review of different mechanisms proposed in literature from which it is evident that the exact nature of the reaction kinetics has still not been well established. In Chapter 2 the experimental set-up and the design for the electrochemical cell is described. Let it be a warning to every researcher who needs to do concessions when an experimental set-up is built to study only part of the system. Porous nickel electrodes are the subject of Chapter 3 and 4. The choice to study this type of electrodes is initiated because of their less complicated microstructure compared with the Ni/YSZ cermet electrodes. The lithograpically prepared nickel pattern electrodes (Chapter 3) have a well defined microstructure in terms of electrolyte area covered with nickel and the Triple Phase Boundary (TPB) line between electrolyte, electrode and gas phase. Line patterns with variation in nickel line width from 10 to 75 m resulted after electrochemical measurements in TPB lengths in the range 1.6 to 11.3 mcm-2. For electrochemical characterisation of the electrodes impedance and I- type of measurements are performed. Impedance measurements performed under standard conditions resulted in spectra, which when analysed with an equivalent circuit, are built up out of three semicircles, one of these dominating the overall behaviour. A relation between the TPB length and the overall electrode performance seems apparent, but experimental data show large scatter. The porous nickel electrodes described in Chapter 4 can be regarded as a nickel layer perforated with small holes. Although quantification of the microstructure of this type of electrode is less straightforward compared with that of the lithographic electrodes, reasonable results are obtained with image analysis. TPB lengths of this type of electrode are in the range 45 to 61 mcm-2. Again a relation is obtained between the TPB length and the electrode conductivity. At equilibrium the impedance diagram consists of one dominant arc at the high frequency side of the spectra and a significantly smaller arc at the low frequency side. Results of impedance and I- measurements as a function of pH2 and pH2O are discussed in view of a tentative multi-step mechanism formulated for the electrode reaction. The results indicate that a simple description in terms of a Butler-Volmer formalism, based on a single rate determining step, is excluded. It is suggested that a strong variation in the fractional coverage of adsorbed intermediates with overpotential on ei-
ther nickel or yttria-stabilised zirconia surfaces must be taken into consideration to account for the experimental data. To study the effect of YSZ in cermet electrodes the surface of a porous nickel electrode was modified with fine YSZ (Chapter 5). The surface modification leads to a significant improvement in the electrochemical activity compared with that of bare porous nickel electrodes, e.g. the total electrode resistance decreases with more than 50%. This effect is ascribed to an increase in the number of reaction sites. The polarisation and impedance behaviour at different H2 and H2O partial pressures for the modified nickel electrodes is found to be very similar to that observed for bare nickel electrodes. In Chapter 6, the study on the nickel/yttria-stabilised zirconia cermet electrodes starts with analysis of the microstructure. By using different ratios of fine to coarse YSZ powder during the preparation of the electrodes seven different microstructures were obtained. The microstructures was quantified by image analysis in terms of porosity, nickel particle size and surface coverage of the interface between the electrode and the electrolyte. The relation between the electrochemical performance of the electrode and the surface coverage indicates that, for coarse cermet structures, the electrode reaction is confined to the immediate interface between the cermet electrode and the electrolyte. For fine cermet structures on the other hand, the electrode reaction zone extends into the bulk of the cermet. To obtain more insight in the spatial extension of the TPB perimeter in a direction perpendicular to the electrolyte / porous electrode interface a ladder network (continuous transmission line) model is involved in analysis of impedance data as discussed in Chapter 7. For this network an analytical expression is derived for the impedance. The variables in the model are the impedances associated with the transport of ionic and electronic charge carriers through both constituent phases of ceramic and metal, and that of the charge transfer reaction at the TPB points. The results show that the replacement of coarse YSZ particles by a corresponding fraction of fine YSZ particles in electrode preparation reduces the total polarisation losses, but does not change the requirements regarding the thickness of the electrodes in order to optimise their performance. In Chapter 8 the kinetics of the hydrogen oxidation reaction at the cermet electrodes is studied by impedance measurements as a function of pH2 and pH2O partial pressures, anodic polarisation and temperature. The impedance spectra show a complex behaviour at the low frequency side, which is not completely understood. This part consists of a small semicircle with a large capacitance value at the low frequency side and an inductive loop in the mid-frequency region. The appearance of an inductive loop can be associated with concentration relaxation of adsorbed intermediates. The high frequency arc can be related with the TPB length and is therefore ascribed to charge transfer. In the last chapter an evaluation of the results in this thesis work is given. As four different types of electrodes, with their own specific microstructure are studied under the similar experimental conditions, a perfect opportunity is created to obtain insight in the relation between the microstructure and the electrochemical performance of the electrodes. The electrodes cover a large range in the triple phase boundary length. For the nickel electrodes a linear relationship exists between the TPB length, which is related with the active area for the electrode reaction, and the total electrode conductivity. Based upon this linear rela-
tionship it is concluded that for the cermet electrodes part of the bulk is active in the electrode reaction, consistent with the results from transmission line modelling of the impedance behaviour of the cermet. A transmission line model indicates that for all cermet electrodes the bulk will be active. For increasing fractions of fine to coarse YSZ in the cermet electrodes the TPB length per unit volume of the electrode increases, leading to a decrease in the electrode resistance. This result emphasises the importance of a fine and highly percolative structure for the cermet electrode The combined results of reaction kinetic studies at the different types of electrode support the conclusion that under the conditions covered by these experiments the electrode processes are governed by charge transfer.
Samenvatting In de voortdurende zoektocht naar alternatieve en milieuvriendelijke mogelijkheden voor de opwekking van electriciteit, wordt de brandstofcel gezien als een goede kandidaat. Er zijn verscheidende type brandstofcellen die zich onderscheiden op het gebied van toepassing, grootte, kosten en werkgebied. De vaste oxide brandstofcel (SOFC) is een brandstofcel met een hoge werktemperatuur, deze cel is vooral interessant voor het gedecentraliseerd opwekken van warmte en electriciteit. Nikkel/yttria-gestabiliseerd zirconia cermet is op dit moment het state-of-the-art materiaal voor de anode van de SOFC. Het accent van dit werk ligt bij twee belangrijke aspecten van dit type electrode, de kinetiek van de waterstof oxidatie reactie en het effect van de microstructuur op het electrochemisch gedrag van de electrode. Inzicht in deze aspecten zal leiden tot een beter begrip en tot betere prestaties van de anode. Een algemene introductie in brandstofcellen wordt gegeven in Hoofdstuk 1. Dit wordt vervolgd met een kort overzicht van de SOFC materialen en de SOFC anode kinetiek zoals gegeven in de literatuur. Uit de verschillende reactie mechanismen zoals deze zijn voorgesteld kan geconcludeerd worden dat de eigenlijke aard van de anode reactie nog niet is vastgesteld. In Hoofdstuk 2 wordt de experimentele opstelling en het ontwerp van de electrochemische cel beschreven. Laat het een waarschuwing zijn voor alle onderzoekers die concessies moeten doen op het moment dat een meetopstelling wordt gebouwd waarin slechts een deel van het uiteindelijke systeem wordt bestudeerd. Poreuze nikkel electroden zijn het onderwerp van Hoofdstuk 3 en 4. De keuze om aan dit type electroden te meten wordt ingegeven door de eenvoudige microstructuur van nikkel electroden in vergelijking met die van de Ni/YSZ cermet electroden. De nikkel patroon electroden die gemaakt zijn met lithografische technieken (Hoofdstuk 3) bezitten een goed gedefinieerde microstructuur in termen van het met nikkel bedekte electrolyt oppervlak en de drie-fase-grens (TPB) tussen het electrolyt, de electrode en de gas fase. Lijn patronen waarbij de nikkel lijn breedte wordt gevarieerd tussen 10 en 75 m resulteert, na electrochemische metingen, in een TPB lengte tussen de 1.6 en 11.3 mcm-2. Voor de electrochemische karakterisering van de electroden wordt gebruik gemaakt van impedantie en I- metingen. Impedantie spectra die volgen uit impedantie metingen onder standaard condities worden geanalyseerd met een equivalent circuit. Deze fit bestaat uit drie halve bogen, waarvan n boog het totale gedrag domineert. Een relatie werd gevonden tussen de TPB lengte en het totale electrode gedrag, waarbij vermeld dient te worden dat er in de electrochemische data van de patroon electroden een behoorlijke spreiding zit. De poreuze nikkel electroden zoals beschreven in Hoofdstuk 4 kunnen worden beschouwd als nikkel lagen met vele kleine gaatjes. De quantificering van dit type microstructuren is minder eenvoudig dan die van patroon electroden. Met behulp van beeldanalyse technieken kunnen redelijke resultaten worden verkregen. Voor dit type electrode ligt de TPB lengte tussen de 45 en 61 mcm-2. Ook hier werd een relatie gevonden tussen de TPB lengte en het totale electrode gedrag. In evenwicht bestaat het impedantie diagram uit n dominante boog aan de hoog frequente zijde en een significant kleinere boog aan de laag frequente zijde. Resultaten van impedantie en I- metingen als functie van de pH2 en pH2O worden
besproken in het licht van meer-stappen mechanisme voor de electrode reactie. De resultaten geven aan dat een eenvoudige beschrijving in termen van een Butler-Volmer mechanisme, gebaseerd op n snelheidsbepalende stap, is uitgesloten. Er wordt gesuggereerd dat er een sterke variatie bestaat in de fractionele bezetting van geadsorbeerde deeltjes op nikkel ofwel YSZ, als functie van de overpotentiaal . Om het effect van YSZ in cermet electroden te bestuderen wordt het oppervlak van een poreuze nikkel electrode gemodificeerd met fijn YSZ (Hoofdstuk 5). De oppervlakte modificatie leidt tot een significante verbetering van de electrochemische activiteit. In vergelijking met een niet gemodificeerde poreuze nikkel electrode, neemt de totale electrode weerstand af met meer dan 50%. Dit effect wordt toegeschreven aan een toenemend aantal actieve plaatsen. Het polarisatie en impedantie gedrag voor de gemodificeerde nikkel electrode als functie van de H2 en H2O druk vertoont overeenkomst met de nikkel electroden. In Hoofdstuk 6 start het onderzoek aan de nikkel/yttria-gestabiliseerd zirconia cermet electroden met een analyse van de microstructuur. Door gebruik te maken van verschillende verhoudingen in de fracties fijn en grof YSZ poeder was het mogelijk om zeven verschillende microstructuren te verkrijgen. De microstructuren werden gequantificeerd in termen van porositeit, nikkel deeltjes grootte en oppervlakte bedekking van het grensvlak tussen de electrode en het electrolyt. De relatie tussen het electrochemische gedrag van de electrode en de bedekkingsgraad, indiceert dat voor grove cermet structuren de electrode reactie wordt beperkt tot het directe grensvlak tussen de cermet electrode en het electrolyt. Aan de andere kant breidt voor fijne cermet structuren de actieve laag zich uit in the bulk van de cermet. Om meer inzicht te krijgen in de ruimtelijke uitbreiding van de TPB grens in een richting loodrecht op die van de poreuze electrode / het electrolyt wordt, in Hoofdstuk 7, een ladder model (transmissie lijn model) betrokken bij de analyse van de impedantie data. Voor dit netwerk is een analytische oplossing afgeleid voor de impedantie. De variabelen in dit model zijn geassocieerd met het transport van ionische lading dragers in het YSZ, met electronische lading dragers door het nikkel en de lading overdracht reactie of de TPB punten. Het resultaat toont aan dat, wanneer grove YSZ deeltjes in het cermet vervangen worden door een corresponderende fractie fijne YSZ deeltjes, dit leidt tot een verlaging van de polarisatie weerstand. De vereisten voor een optimale prestatie met betrekking tot de dikte van de electroden verandert niet. In Hoofdstuk 8 worden de resultaten gegeven van een studie naar de kinetiek van de waterstof oxidatie reactie aan de cermet electroden. Deze is uitgevoerd met behulp van impedantie metingen als functie van de partile pH2 en pH2O druk, de anodische polarisatie en de temperatuur. De impedantie vertoont een complex gedrag aan de laag frequente zijde, welke niet geheel begrepen wordt. Dit deel bestaat voor de laag frequenties uit een kleine halve cirkel met een hoge capaciteit waarde en voor het mid-frequentie gebied uit een inductieve boog. De verschijning van de inductieve boog kan geassocieerd worden met concentratie relaxatie van geadsorbeerde tussen producten. De hoog frequente boog kan gerelateerd worden aan de TPB lengte en wordt daarom toegeschreven aan lading overdracht.
In het laatste hoofdstuk wordt een evaluatie gegeven van de resultaten zoals beschreven in dit proefschrift. Doordat vier verschillende types electroden zijn bestudeerd, die elk met hun eigen specifieke microstructurele eigenschappen onder dezelfde experimentele condities zijn bestudeerd, is een perfecte mogelijkheid gecreerd om het inzicht te vergroten in de relatie tussen de microstructuur en het electrochemische gedrag van de electroden. De electroden beslaan een groot bereik in TPB lengte. Voor de nikkel electroden is een lineaire relatie gevonden tussen de TPB lengte, gerelateerd aan het actieve gebied voor de electrode reactie, en de totale electrode geleidbaarheid. Gebaseerd op deze lineaire relatie kan geconcludeerd worden dat voor cermet electroden de bulk van de electrode actief moet worden. Dit resultaat is overeenstemming met resultaten verkregen uit transmissie lijn modellering, welke indiceert dat voor alle cermet electroden de bulk actief zal zijn. Voor toenemende fracties fijn YSZ in de cermet electroden neemt de TPB lengte per volume eenheid van de electrode toe, dit leidt tot een afname van de electrode weerstand. Dit resultaat benadrukt het belang van een fijne en hoog percolatieve structuur voor cermet electroden. De gecombineerde resultaten van de studie naar de reactie kinetiek aan verschillende type electroden onderschrijft de conclusie dat onder de toegepaste experimentele condities het electrode proces wordt gedomineerd door lading overdracht.
Table of contents 1 Introduction 1 1.1 The Fuel Cell 1 1.1.1 Definition of a fuel cell 1 1.1.2 Historical background 2 1.1.3 Types of fuel cells 2 1.1.4 Advantages and drawbacks of fuel cells 4 1.2 Solid Oxide Fuel Cell 5 1.2.1 Thermodynamic principles 5 1.2.2 Fuel Cell efficiency 6 1.2.3 SOFC materials 9 1.2.4 SOFC anode kinetics 11 1.3 Scope of this thesis 20 2 Experimental considerations 25 2.1 Introduction 25 2.2 The experimental set-up 25 2.2.1 The electrochemical cell 25 2.2.2 Sample holder 26 2.2.3 Gas conditioning and controlling system 27 2.2.4 Furnace and controller 27 2.2.5 Measurement Equipment 27 2.3 Sample choice in view of geometric requirements for the electrode configuration 28 2.3.1 Experimental 30 2.3.2 Results 31 2.3.3 Discussion 31 2.3.4 Comparison of results of different type of electrolytes for porous nickel and cermet type of electrodes. 34 2.3.5 Conclusions 35 3 Hydrogen oxidation at nickel pattern electrodes on yttria-stabilised zirconia 37 3.1 Introduction 37 3.2 Experimental 38 3.2.1 Sample preparation 38 3.2.2 Characterisation of the electrode microstructure 38 3.2.3 Electrochemical characterisation 39 3.3 Results 40 3.3.1 Microstructure 40 3.3.2 Electrochemical performance 43 3.4 Discussion 50 3.4.1 Relationship of electrode performance with microstructure 50 3.4.2 Electrochemical measurements 51 3.4.3 Comparison with data from Mizusaki et al. 52 3.5 Conclusions 53 4 Hydrogen oxidation at porous nickel electrodes on yttria-stabilised zirconia 55 4.1 Introduction 55 4.2 Theory 56 4.2.1 Reaction scheme 56 4.2.2 Langmuir adsorption 57 4.2.3 I - relationship 58 4.3 Experimental 60 4.3.1 Sample preparation 60 4.3.2 Characterisation of the electrode microstructure 61 4.3.3 Electrochemical characterisation 61
4.4 Results 62 4.4.1 Microstructure 62 4.4.2 Electrochemical performance 64 4.5 Discussion 70 4.5.1 Reaction mechanism 70 4.5.2 Relationship of the microstructure with electrode conductivity 75 4.5.3 Comparison with literature 75 4.6 Concluding remarks 78 5 Hydrogen oxidation at porous nickel electrodes on yttria-stabilised zirconia: Effect of surface modification with fine YSZ. 81 5.1 Introduction 81 5.1.1 Fabrication of electrolyte and electrodes 82 5.1.2 Electrochemical characterisation 83 5.2 Results 84 5.2.1 Microstructure 84 5.2.2 Electrochemical performance 85 5.3 Discussion 91 5.3.1 Microstructure 91 5.3.2 Polarisation and impedance characteristics 95 5.4 Conclusions 96 6 Cermet electrodes, relation between microstructure and performance 99 6.1 Introduction 99 6.2 Experimental 100 6.2.1 Sample preparation 100 6.2.2 Electrochemical characterisation 101 6.2.3 Microstructural characterisation 102 6.3 Results and Discussion 102 6.3.1 Microstructure 102 6.3.2 Electrochemical performance 106 6.3.3 Relation between microstructure and electrochemical performance 110 6.4 Conclusions 112 7 Impedance of porous cermet electrodes 115 7.1 Introduction 115 7.2 Theory 116 7.3 Discussion of the model 118 7.4 Experimental 120 7.5 Results and discussion 121 7.5.1 Impedance analysis using 'Equivalent Circuit' 121 7.5.2 Impedance analysis using the ladder network model 123 7.6 Conclusions 125 8 Investigation into the kinetics of hydrogen oxidation on the Ni/YSZ cermet electrode 129 8.1 Introduction 129 8.2 Experimental 130 8.2.1 Sample preparation 130 8.2.2 Electrochemical characterisation 130 8.3 Results 131 8.3.1 Impedance measurements 131 8.3.2 I- measurements 141 8.4 Discussion 141 8.4.1 Processes observed on the cermet electrode 141 8.4.2 Comparison with porous nickel electrodes 145 8.4.3 Comparison with literature 146 8.4.4 Overall comparison 148 8.5 Conclusions 149 9 Evaluation 151
9.1 Introduction 9.2 Relationship of the microstructure with electrode resistance 9.3 Hydrogen oxidation reaction at the anode Dankwoord Levensloop
151 151 155 159 161
1 Introduction
Abstract A general introduction is given on fuel cells. The history, different types, advantages and drawbacks of fuel cells are discussed. The second part of this introductory chapter is concerned with the Solid Oxide Fuel Cell (SOFC), its principles, materials employed and electrode kinetics. Particular attention is drawn to the presently available knowledge on kinetics of the anodic reaction. At the end of the chapter the scope of this thesis is presented. 1.1 The Fuel Cell
1.1.1 Definition of a fuel cell Fuel cells are electrochemical devices that directly convert chemical energy, from a reaction between a fuel and an oxidant, into electrical energy. The basic elements of a typical fuel cell, as depicted in Figure 1.1, consist of an electrolyte phase in intimate contact with a porous anode (negative electrode) and a porous cathode (positive electrode). The fuel and oxidant gases flow along the surface of the anode and cathode, respectively, and react electrochemically in the three-phase-boundary region established at the gas / electrolyte / electrode interface. A fuel cell can theoretically produce electrical energy for as long as fuel and oxidant are fed to the porous electrodes, but the degradation or malfunction of some of its components often limits the practical life span of al fuel cell. Different fuels can be used, such as hydrogen, ethanol, methanol, or gaseous fossil fuels like natural gas. Solid or liquid fossil fuels need to be gasified first before they can be used
Figure 1.1: Schematic representation of a fuel cell.
1 Introduction
as a fuel. Oxygen or air can be used as oxidant. 1.1.2 Historical background The fuel cell concept dates from the beginning of the 19th century and is ascribed to Sir Humprey Davy 0. The possibility of making it a reality was demonstrated by Sir William Grove, who operated a successful hydrogen-oxygen cell in 1839, generally stated as the start of fuel cell history. Grove built a cell in which the reaction of hydrogen and oxygen produced water, and generated an electric current. He stated: A shock was given which could be felt by five persons joining hands, and which when taken by a single person was painful 0. The history of the solid oxide electrolytes can be considered to commence at the end of the 19th century, when Nernst produces his glower 0. Nernst discovered that the very high electrical resistance of pure solid oxides could be greatly reduced by addition of certain other oxides. The most promising of these mixtures consisted mainly of zirconia (ZrO2) with small amounts of added yttria (Y2O3). This is still the most widely used electrolyte material in the Solid Oxide Fuel Cells (SOFC). The first working SOFC was demonstrated by Baur and Preis (1937), using stabilised zirconia as electrolyte and coke and magnetite as a fuel and oxidant, respectively 0. At a current density of approximately 0.3mA/cm2 the cell voltage was 0.65V. Although the operation of the first SOFC was demonstrated, the current output of this cell was too low for practical purposes. A first period of intense activity in SOFC research began in the early 1960s, with intensive research programs driven by new energy needs mainly for military, space and transport applications 000. At that time basic research dealt with the improvement of electrolyte conductivity and the first steps in SOFC technology. A second period of high activity began in the mid-1980s and goes on today, focussing on electrode materials and technology. Efforts thus far have resulted in almost commercial units which are part of our power generation facilities. Leading companies in SOFC commercialisation are Siemens and Sulzer (Europe) 0, Westinghouse Electrical Cooperation (USA) 0 and Fuji Electric Corporate Research and Development, Ltd and Tokyo Electric Power Co. (Japan) 0. In the Netherlands the first 100 kWe SOFC field unit (Westinghouse SOFC technology) was put into operation at the end of 1997 as a demonstration project where 6 Danish Production Companies names ELSAM and a Consortium of 5 Dutch Energy Distribution Companies, EnergieNed and the Dutch Subsidiser NOVEM co-operate 0. 1.1.3 Types of fuel cells The various types of fuel cells are usually classified by the applied electrolyte (Table 1.1). The following types are known the polymer electrolyte fuel cell (PEFC); alkaline fuel cell (AFC); the phosforic acid fuel cell (PAFC); the molten carbonate fuel cell (MCFC); the solid oxide fuel cell (SOFC).
PEM Anode Pt black or Pt/C Cathode Pt black or Pt/C Electrolyte (mol%) Nafionc
AFCa 80% Pt 20% Pd
AFCb Ni
PAFC Pt/C
MCFC Ni-10% Cr
SOFC Ni YSZ cermet
90% Au 10% Pt
Li-doped NiO
Pt/C
Li-doped NiO
Sr-doped LaMnO3
35-45% KOH
85% KOH
100% H3PO4
62 Li2CO3-38 K2CO3 0.1-1 650 H2 +CO3= H2O + CO2 + 2e-
Yttria-Stabilized ZrO2 (YSZ) 0.1 1000 H2 +2O= H2O + 2eO2 + 4e- 2O=
Abs pressure (Mpa) Temperature (C) Anode reaction
0.1-0.5 80 H2 2H+ + 2e-
0.4 80-90 H2 +2OH- 2H2O + 2e-
~0.4 260 H2 +2OH- 2H2O + 2eO2 + 2H2O + 4e- 4OH-
0.1-1 200 H2 2H+ + 2e-
Cathode reaction
O2 + 4H+ + 4e- 2H2O
O2 + 2H2O + 4e- 4OH-
O2 + 4H+ + 4e- 2H2O
O2 + 2CO2 + 4e- 2CO3=
Table 1.1: Typical components, operating conditions and electrochemical reactions in Fuel Cells. a Space shuttle Orbiter, b Apollo Program, c Fluorinated sulfonic acid, registered trademark of E.I. du Pont de Nemours & Company, Inc. 0.
1.1 The Fuel Cell
1 Introduction
Large differences exist in application, design, size, cost and operating range for the different type of fuel cells. The fuel cells above are listed in order of increasing operating temperature, ranging from ~80C for PEFC to 1000C for SOFC. The low temperature fuel cells (PEFC, AFC, PAFC) utilise aqueous electrolytes in which H+ or OH- ions are the dominant ionic current carriers. At higher temperatures, CO32- ions in the molten salt electrolyte of the MCFCs and O2ions in the solid electrolyte of the SOFC are the ionic current carriers. The operating temperature has consequences for design, the efficiency of the fuel cell, the choice of other materials needed in and around the fuel cell and the kind of fuel that may be used. For low temperature fuel cells (PEFC, AFC and PAFC) the operating temperature is too low to enable direct oxidation of hydrocarbon fuels like natural gas, therefore fuels like hydrogen and methanol are used. Low temperature fuel cells are generally seen as interesting for small scale applications, for example mobile applications like cars (PEFC0), notebooks, phones etc. For high temperature fuel cells (MCFC and SOFC) it is possible to use natural gas which can be reformed internally into hydrogen and carbon monoxide (depending on operating temperature a catalyst will be necessary). The high temperature fuel cells, but also PAFC, are interesting for the decentralised generation of heat and power. 00000 1.1.4 Advantages and drawbacks of fuel cells The advantages and drawbacks of fuel cell systems are determined by their type and application. As it can be useful to compare a SOFC or MCFC system with traditional generators, a small fuel cell developed for applications as notebooks or mobile phones should be compared with traditional batteries. The advantages and drawbacks given here are mostly based on SOFC systems, but in general part of it will be valid for other types of fuel cells. The main advantages: (1) High energy conversion efficiency. Because of the direct conversion of free enthalpy into electrical energy the usual losses from fuel to electrical energy, due to the conversion of fuel to heat, heat to mechanical energy and mechanical energy to electrical energy, is avoided. The efficiency is further improved when the by-product heat is fully utilised. (2) Environmental compatibility. Fuel cells are capable of using practical fuels as an energy source with minor environmental impacts (less CO2 and NOx produced per kWatt power). (3) Modularity. Fuel cells have the characteristics of modularity, i.e. cells can be made in modular sizes. The size of a fuel cell can be easily increased or decreased and its electric efficiency is relatively independent of size. (4) Siting flexibility. Because fuel cells can be made in a variety of sizes they can be placed at different locations with minimum siting restrictions. Fuel cell operation is quiet because a fuel cell has no moving parts. Consequently fuel cells can be easily located near points of use such as urban residential areas. 0
1.2 Solid Oxide Fuel Cell
Unfortunately, there are some drawbacks which have caused a slow introduction of solid oxide fuel cells on the energy market 0: (1) Material problems in relation with costs: For SOFC there are roughly two design types, tubular 0 and flat plate 0. For the tubular cell material problems are less, but fabrication costs are high. For the flat plate design fabrication costs are less, but more material problems arise. (2) Economics. Introduction on the energy market would presently involve a high capital cost-to-performance ratio. 1.2 Solid Oxide Fuel Cell
1.2.1 Thermodynamic principles The principle of an SOFC is illustrated in Figure 1.2, two electrodes (the anode and cathode) being separated by a solid electrolyte. Oxidant is reduced at the cathode and fuel is oxidised at the anode. If hydrogen and oxygen are used as fuel and oxidant, respectively, in an SOFC with an oxygen ion conducting electrolyte the reactions in the fuel cell involve the oxidation and reduction of oxygen at the electrodes. At the cathode the reduction of oxygen is given as
O2 c + 4e = 2Oe2 (1.1)
where the subscripts c and e refer to states at the cathode and in the electrolyte, respectively. At the anode the reverse reaction of (1.1) takes place:
2Oe2 = O2 a + 4e (1.2)
where the subscript a refers to states at the anode. Consequently, the overall cell reaction (which determines the cell voltage) can be represented by the following equation
O2 c = O2 a (1.3)
The SOFC is therefore considered to be an oxygen concentration cell, and the electromotive force (emf) or reversible (thermodynamic) voltage, Er, is given by the Nernst equation:
Er = pO2 c RT ln 4F pO2 a (1.4)
Figure 1.2: A Solid Oxide Fuel Cell.
1 Introduction
T (K) 1000 1250 G0 (kJ) -192.5 -178.2 H0 (kJ) -247.3 -249.8 E0 (V) 0.997 0.924 T 0.78 0.71
Table 1.2: Thermodynamic data and efficiency (T) for the hydrogen oxidation reaction 0.
where R is the gas constant, T the temperature, F the Faraday constant and pO2 the partial pressure of oxygen at the electrode. For a certain oxygen partial pressure at the cathode, pO2 c, the magnitude of Er depends on the anode oxygen partial pressure, pO2 a, and thus on the type and composition of the fuel fed to the anode. For example, when H2 is fed to the anode, the following cell reaction takes place:
H2 a +
1 2 Ki H2O a O2 c
(1.1)
Where Ki is the equilibrium constant of (1.1). The equilibrium oxygen partial pressure at the anode is given by
pO2 a =

pH 2 Oa (1.2) pH 2 a K i pH 2 a RT RT ln pO2 c + ln 4F 2 F pH 2Oa
Substituting the equation for the anode oxygen partial pressure (1.2) into (1.4) yields
Er = E 0 + (1.3)
where E0 is the reversible voltage at the standard state and is given as

E0 = RT ln Ki 4F (1.4)
At the standard state, Er equals E0, and the following equation is established for any fuel G 0 H 0 TS 0 (1.5) E0 = = zF zF where G0 is the standard Gibbs free energy change of the combustion reaction of the fuel, H0 the standard enthalpy change, S0 the standard entropy change and z the number of electrons involved in the reaction to convert a single fuel molecule. The maximum energy obtained in this case is given by -G0 and the ideal thermodynamic efficiency, T, represented by G0/H0. Table 1.2 gives G0, H0, E0 and T for the combustion of H2 as fuel. 0 1.2.2 Fuel Cell efficiency The overall efficiency of an SOFC, FC, is the product of the electrochemical efficiency, E, and the heating efficiency, H. The electrochemical efficiency is, in turn, the product of the thermodynamic efficiency, T, the voltage efficiency, V, and the Faradaic or current efficiency, J, of the fuel cell. Thus, (1.6) FC = E H = T V J H
1.1.1.1 Heating efficiency The heating efficiency must be considered in cases where the fuel contains inert gases, impurities and other combustibles in addition to the electrochemically active species. The heating value efficiency, H, is defined as: H 0 (1.7) H = Hcom where H0 represents the amount of enthalpy of fuel species available in the fuel cell to generate electricity and Hcom represents the amount of enthalpy included in all combustible species in the fuel gases fed to the fuel cell. 1.1.1.2 Thermodynamic efficiency In an SOFC the free enthalpy change of the cell reaction, G, may be totally converted to electrical energy. Thus a fuel cell has an intrinsic (maximum) thermodynamic efficiency given by G T S (1.8) T = = 1 H H 1.1.1.3 Voltage efficiency In an operating SOFC the cell voltage is always less than the reversible voltage. As the current is drawn from the fuel cell, the cell voltage is reduced due to various losses. The reduction in the cell voltage under current load depends on current density and several factors such as temperature, pressure, gas flow rate, gas combustion and cell material. The voltage efficiency, V, is defined as the ratio of the operating cell voltage under load, E, to the equilibrium cell voltage, Er, and is given as E (1.9) V = Er The difference between the operating cell voltage and the expected reversible voltage is termed polarisation or overpotential and is presented as . The total polarisation of a cell is the sum of four types of polarisation: charge transfer or activation polarisation, A, diffusion or concentration polarisation, D, reaction polarisation, R, and resistance or ohmic polarisation, : (1.10) = A + D + R + Polarisation cannot be eliminated but can be minimised by material choice and cell design. Temperature, pressure, electrolyte composition and electrode material naturally influence cell polarisation. Charge transfer or activation polarisation 1.1.1.3.1 (Electro) chemical reactions involve an energy barrier that must be overcome by reacting species. This energy barrier, called the activation energy, results in activation or charge transfer polarisation, A. Activation polarisation is related to current density, i, by the following equation:
i = i0 exp
a A F RT
i0 exp
c A F RT
(1.11)
1 Introduction
Where is the symmetry coefficient and i0 is the exchange current density. The symmetry coefficient is considered as the fraction of the change in polarisation which leads to a change in the reaction rate constant. The exchange current density is related to the balanced forward and reverse electrode reaction rates at equilibrium. A high exchange current density means a high electrochemical reaction rate and, in that case, a good fuel cell performance is expected. The exchange current density can be determined experimentally by extrapolating plots of log i versus to =0. For large values of (either negative or positive) one of the bracketed terms in (1.11) becomes negligible. After rearranging one obtains
A = a b log i
(1.12)
which is usually referred to as the Tafel equation. Parameters a and b are constants which are related to the applied electrode material, type of electrode reaction and temperature. Diffusion or concentration polarisation 1.1.1.3.2 Diffusion or concentration polarisation, D, becomes eminent when the electrode reaction is hindered by mass transport effects, i.e., when the supply of reactant and/or the removal of reaction products by diffusion to or from the electrode is slower than that corresponding to the charging/discharging current i. When the electrode process is governed completely by diffusion, the limiting current, iL, is reached. The limiting current can be calculated from the diffusion coefficient of the reacting species, D, their concentration, cM, and the thickness of the diffusion layer, , by applying Fick's law as
iL = zFDc M (1.13)
For an electrode process free of activation polarisation, the diffusion or concentration polarisation can be expressed as
D =
RT i ln 1 zF iL (1.14)
In general, mass transport is a function of temperature, pressure and concentration of the species involved. In SOFCs the reactants must diffuse through the porous anode and cathode, emphasising the importance of the microstructure and design of electrodes. Reaction polarisation 1.1.1.3.3 The reaction polarisation, R, appears when the rate of the electrode process is influenced by a chemical reaction. A possible reaction includes the incorporation of oxygen in the oxide sublattice at the cathode. 1.1.1.4 Resistance or ohmic polarisation The ohmic polarisation is caused by the resistance of the conducting ions (through the electrolyte), electrons (through the electrodes and current collectors) and contact resistances between cell components. The ohmic polarisation, , is given as
= iRi
(1.15)
where Ri represents the total ohmic cell resistance, including both ionic and electronic resistances.
component Anode
composition Ni/YSZ cermet
specific conductivity at 1000C (S/m) 400 - 1000
conductivity depending on Ni/YSZ particle size ratio Ni content
Cathode
SrxLa1-xMnO3- Y2O3-ZrO2
6 - 60
Porosity Sr content
Electrolyte
10 - 15
Density Yttria content
Interconnect
LaCrO3
Table 1.3: State of the art materials used in SOFC and relevant properties 00.
1.1.1.5 Current efficiency The efficiency of a SOFC drops if all of the reactants are not converted to reaction products. For 100% conversion of a fuel, the amount of current density, iF, produced is given as (Faraday's law)
iF = zF df dt (1.16)
where df/dt is the molar flow rate of the fuel. For the amount of fuel actually consumed, the current density produced is given by
i = zF
df dt consumed
(1.17)
The current efficiency, J, is the ratio of the actual current produced to the current available from complete electrochemical conversion of the fuel
J =
i iF (1.18)
In the case of fuel cells, the current efficiency is commonly expressed as fuel utilisation. 0 1.2.3 SOFC materials The basic components of a ceramic fuel cell stack are the electrolyte, the anode, the cathode and the interconnect. Each component serves several functions in the fuel cell and has to meet certain requirements. These requirements include: proper stability (chemical, phase, morphological and dimensional) in oxidising and/or reducing environments, chemical compatibility with other components and a proper conductivity. The electrolyte and interconnect must be dense in order to separate the oxidant and fuel gases, whereas both anode and cathode must be porous to allow gas transport to the reaction sites. An overview of the state of the art materials is given in Table 1.3. Extended reviews are provided in the literature 000. A short discussion about the electrolyte and cathode follows, more attention is given to the anode. 1.1.1.6 The electrolyte Yttria-stabilized zirconia ((Y2O3)0.08-(ZrO2)0.92 abbreviated as YSZ) is the most common electrolyte in SOFCs because the material possesses an adequate level of oxygen-ion con-
1 Introduction
ductivity and exhibits desirable stability in oxidising and reducing atmospheres. ZrO2 in its pure form does not serve as a good electrolyte because its ionic conductivity is too low. Therefore it is doped with Y2O3, which means a direct substitution of a trivalent cation of appropriate size, e.g. Y3+, for the host lattice cation Zr4+. The substitution not only creates a large concentration of oxygen vacancies but also stabilises the cubic fluorite structure 00. 1.1.1.7 The cathode The perovskite materials SrxLa1-xMnO3- (SLM) with x between 0.15 and 0.50 is considered as the standard SOFC cathode material. SLM is mainly an electronic conductor and the oxygen reduction reaction is assumed to take place at the interface between cathode material, electrolyte and the oxygen gas phase 0. Only at high overpotentials does SLM show appreciable ionic conductivity 0. 1.1.1.8 The anode The nickel/yttria-stabilised zirconia (Ni/YSZ) cermet (ceramic-metal mixture) is at this moment the state of the art material for the anode. Nickel is used because it is one of the metals that is able to withstand the operating conditions of a SOFC: reducing conditions and a temperature of 1000C. Other possible materials are cobalt and noble metals, but taking into account volatility, chemical stability, catalytic activity and cost, nickel appears to be the best candidate. Nickel plays the role of the electronic conducting phase and needs to transport the electrons from the reaction site to the current collector. YSZ is added to support the nickel-metal particles, to inhibit coarsening of the metallic particles and to provide a thermal expansion coefficient acceptably close to those of the other cell components. The functional properties of the YSZ in the anode are a matter of discussion, it is suggested that it may play an active role by forming conductive paths for oxygen transport, thereby enlarging the active area available for the electrode reaction. The third important phase in the cermet structures is the porous phase. This phase is important for easy gas phase diffusion to (hydrogen) and from (water) the active sites. 00000. The most important requirements for the anode are: Long term stability. Sinter activity during operation has to be virtually absent, meaning maintaining good electronic and ionic conductive phases as well as porosity. Low polarisation resistance of the electrode. Physical and chemical stability under a reducing atmosphere at high temperature. Matching of the thermal expansion coefficient to the electrolyte to prevent the electrode from flaking of the electrolyte. High catalytic activity to promote reaction of the fuel with oxide ions. 00000 The above requirements cannot be satisfied only by choosing the appropriate composition. The nature of the starting powder and the applied manufacturing technique has a strong effect on the electrochemical properties of the electrode in the final assembly. For instance, parameters like the particle morphology of the powder and the porosity of the sintered electrode will influence the electrical conductivity of the electrode structure. These two parameters also influence the total amount of electrode particles which occupy the electrolyte interface. Other parameters such as the sintering temperature and the sintering time 10
of the electrode will have an effect on the adherence of the electrode structure to the electrolyte and possible formation of deleterious reaction products between the electrode and the electrolyte. Hence, the manufacturing procedure is very important 0. Other materials that have been studied as anode are: Nickel without the addition of YSZ, especially for research purposes in order to perform experiments with simple geometrical structures 000. Ruthenium/stabilised ZrO2 cermet. This material shows a lower polarisation then that of Ni/YSZ cermet. Ruthenium has the advantage of a better resistance to sintering and also a higher reforming activity compared with nickel 00. Disadvantages are cost and evaporation of ruthenium oxide. (Ni-Mg)O-YSZ. The use of this material improves the overvoltage characteristics of the anode compared to Ni-YSZ cermet anodes which is attributed to a finer porous structure that induces a greater specific surface area 0. To decrease the anodic overpotential, it was suggested to insert a mixed conductor between YSZ and the metallic conductors. A significant decrease of polarisation was found when ceria-based solid solutions like (CeO2)0.6(LaO1.5)0.4 were used 0. This effect was attributed to mixed conduction resulting from the partial reduction of Ce4+ to Ce3+ in the reducing operating conditons. A decrease in anodic polarization was also found for other oxide components such as praseodymium oxide (PrOx), ceria (CeOx) and samaria-doped ceria (SDC) 0. Other studies indicated a significant decrease of the ohmic drop when YSZ was used with a thin modified layer of mixed conductors 0. A comparative study of ceria and titania doped YSZ has shown that additions in the order of 10 mol% titania increased the electronic conductivity of the solid solution 00. This suggests that such solids solutions may be good candidates as anode cermet components for SOFC. 1.2.4 SOFC anode kinetics Even though studies on SOFC electrodes started back in 1960 and a lot of work has been published ever since, the exact nature of the reaction kinetics is still not established. In this section, an impression is given of what is known about the reaction kinetics on nickel metal and Ni/YSZ cermet electrodes. 1.1.1.9 Nickel electrodes Studies on nickel metal electrodes have been initiated because of their less complicated microstructure compared with that of Ni/YSZ cermet electrodes. Using these electrodes it should be possible to avoid structural limitations and measure purely chemical parameters and relate them with the microstructure. Attempts to relate the polarisation resistance to the length of the Triple Phase Boundary (TPB) have been done for simple geometries using nickel wires and porous nickel layers 00, nickel stripes 000000 and a nickel ball 00. A survey of the results from measurements on various nickel electrodes is given in Table 1.4.
11
12
1 Introduction
Authors
Type of electrode
TPB Length (mcm )

2
Temp (C) pH2
Gas phase conditions (10 Pa)

5
Impedance (nr arcs)
Electrode resistance ()
Gas phase dependence of electrode conductivity (1/R)
Current expression
pH2O 0.027 0.053 0.048-0.2 0.055 0.0063 1 65ka pH2O

1/2
Guindet et al. 0
Ni ball
9.4 mm ----
960 975
0.2-0.58 0.75 0.7 0.037-0.9
2 1
850 1970 1.697 pH2O1/2 0.016 pH2-1/2+0.396 pH21/2
i = i0 exp (2F/RT)
MohamediNi ball Boulenouard et al. 0
i = i0 exp (aF/RT) with (a=1.4-1.7)
Norby et al. 0
Ni wire
3.3-15.7 mm 121 m
900
0.0012
---(at low pH2) ---pH2O

1/2
Norby et al.0
Porous Ni layer
900
0.0012
0.0063
1.6b (at low pH2)
Mizusaki et al. 0000 Yamamura et al. 00
Ni stripe
0-6
500-850
0.1 0.01
0.017 0.004-0.16
1c
10.5kc pH2O (at high pH2)

0 1
(3 parallel reactions) i1 = k1 pH2 exp (2FE/RT) - k1 pH2O pH2O (at low pH2 & <750C) i2 = k2 (pH2)1/2 k2 (pH2O)1/2 exp (-FE/RT)
0.01-0.19
0.009
pH20 (700-800C pH2-1/2 (850C) pH20

2
i3 = k3 pH2 k3 pH2O exp (-2FE/RT)
Nakagawa et al. 0
Porous Ni layer
----
1000
0.98
0.02
2.1 (cm )
---1/2
pH2O
Table 1.4:
Results from electrochemical measurements on different type of nickel electrodes obtained by various researchers. afor electrode with TPB length of 3.3 mm; bresistance corresponding to first arc in impedance spectra, representing the charge transfer resistance; c value given at 700C for an electrode with TPB length of 3.26 m/cm2.
Guindet et al. 0 studied H2 oxidation on a nickel ball pressed onto an YSZ disc at 960C. They paid special interest to polarisation curves, having selected points on the curve characterised by impedance spectroscopy. A maximum current density was found for an anodic polarisation close to 850 mV versus air. Since this value is close to that of the Ni-NiO system, the formation of nickel oxide is suggested. For lower anodic potentials between 1000 and 850 mV versus air, hydrogen oxidation takes place on the nickel and the log i versus curve follows Tafel behaviour (see Table 1.4). At anodic potentials between -850 and 650 mV versus air NiO is formed. Hydrogen oxidation still takes place on nickel, but now also on passivating NiO. The electrode resistance increases and a large capacitive effect is seen in the impedance plot. For anodic potentials smaller than 650 mV versus air, hydrogen oxidation takes place only on NiO and an inductive loop appears at the low frequency side of the impedance diagram. In later work Guindet and co-workers 0 also studied the influence of H2 and H2O partial pressures. The interfacial conductivity showed a minimum in pH2. For low pH2 values the conductivity was found to be proportional to pH2-1/2 and for high pH2 to pH21/2. At fixed pH2, a pH2O1/2 dependence was found. Anodic polarisation curves, measured as a function of pH2O, were analysed with Butler-Volmer type of equations, resulting in an apparent anodic transfer coefficients, a, varying between 1.4 and 1.7. Based on analysis of the polarisation curves, the authors concluded that charge transfer is not the rate determining step in the anodic reaction. Norby et al. 0 paid special attention to the relation between the TPB and the electrode performance. As electrodes these authors used a nickel wire wrapped around an alumina rod and an electroplated nickel layer (2m thick) with circular holes made by microlithography. For the nickel wire electrodes an impedance diagram with one semicircle was recorded. The resistance associated with this semicircle was attributed to charge transfer and the Constant Phase Element (CPE) was attributed to the double layer capacitance. For the porous nickel layer two semicircles were found in the impedance diagram. The semicircle appearing at the low frequency side dominated the spectrum and was ascribed to a reaction resistance and associated surface coverage of adsorbed intermediates. This resistance decreased with increasing pH2O, while increasing with pH2. The charge transfer resistance varied approximately with pH2O-1/2 at low pH2 values. At moderate pH2 values, the charge transfer resistance exhibited a inverse linear relationship with the TPB length. The general conclusion drawn by Norby et al. is that for electrodes with a small TPB length and a large nickel and YSZ area available per unit TPB length, the rate is limited by charge transfer, due to the restricted TPB length. On the other hand, the reaction resistance dominates for the electrode with a large TPB length and a smaller accessible area of nickel and YSZ per unit TPB length. The authors suggested that for the latter electrode and probably for most of the Ni-YSZ cermet electrodes, the rates are limited by a too small or inactive surface rather than by a small TPB length. Mizusaki et al. 0000 and Yamamura et al. 00 studied nickel pattern electrodes. With photolithography, 16 pattern electrodes were prepared, different in the width and distance be-
13
1 Introduction
tween the stripes (5-10-25-50m for nickel and/or YSZ). In 00, they present a linear relation between the electrode conductivity and the TPB length. Impedance spectra consisted of one semicircle. The associated resistance was found to be essentially independent of pH2 and, at high vapour pressure, proportional to pH2O-1, but becoming asymptotically constant with decreasing pH2O. Based on these results and the polarisation curves measured as a function of pH2 and pH2O, the following model was proposed 0. The major adsorbed species on the nickel surface are assumed to be Oads, OHads, Hads and H2Oads. The coverages of these species are taken to be low and, therefore, the portion of vacant adsorption sites, v close to 1. Between YSZ and nickel, Oad adatoms exchange reversibly. The following equilibria are expected to hold near the TPB (1.20) H 2Oad + se H ad + OH ad (1.21) OH ad + se H ad + Oad
Oad Oad ,YSZ + se (1.22)
x O
Oad , YSZ + 2e O
H 2O g + se H2Oad where se denotes a vacant site on the nickel surface. The reaction, 2 H ad H 2 g + 2se
(1.23) (1.24) (1.25)
is assumed to be slow and does not reach equilibrium near the TPB. Under virtual equilibrium condition for reactions (1.20) - (1.24), three possible rate determining reaction steps are considered: (i) direct attack of H2(g) on Oad: 2 FE (1.26) H 2 g + Oad H2Oad : i1 = k1 pH2 exp k1' pH2O RT which process predominates under anodic polarisation. (ii) surface diffusion of Had on the nickel surface towards reaction sites near the TPB

TPB Had Had
' i2 = k 2 pH21/ 2 k 2 pH2 O1/ 2 exp
FE
RT
(1.27)
where the constants k2 and k2 comprise, among other factors, the ratio of a diffusion coefficient over an effective distance in accordance with Ficks first law of diffusion. This process would dominate under small cathodic polarisation. (iii) dissociative adsorption of H2(g) near the TPB 2 FE ' (1.28) H 2 g + 2Vad 2 Had : i3 = k3 pH 2 k3 pH 2O exp RT which process predominates under large cathodic polarisation. All three rate-determining processes proceed in parallel. The magnitude of the rate constants and the oxygen activity at the nickel/YSZ interface determine which process dominates.

A kind of intermediate electrode between nickel electrodes and cermet electrodes was studied by Nakagawa et al. 0. The investigated electrodes consisted of a sputtered nickel layer having a thickness between 0.8 and 12.9 m, coated with a plasma-sprayed porous
14
YSZ layer (0-207m). The effect of the porous ceramic top layer appeared in the impedance diagram at equilibrium, but not under polarisation in dc experiments. For a 2 m thick nickel layer without a porous YSZ top layer, one depressed arc was found in the impedance diagram. Upon coating with YSZ a second arc appeared. The associated resistance was found to be proportional to the thickness of the applied porous YSZ layer and attributed to the diffusion of H2O inside the porous YSZ layer. Because no effect was observed on the electrode performance in the applied range of the nickel layer thickness, the effective reaction zone for the rate determining process on nickel was estimated to be less than 1m from the electrode/electrolyte interface. The results led the authors to the overall conclusion that under polarisation an activation process and not a diffusion process is important for the anodic reaction. Table 1.4 summarises results on nickel electrodes obtained by different authors. Overall it can be stated that comparison between the results is difficult mainly because different type of electrodes are used by different authors, measurements being performed at different temperatures and under different ambient conditions. One of the reasons to use nickel electrodes in many investigations is to search for the expected inverse relationship between the specific resistance and the TPB length. Results are compared in Table 1.5, where the specific resistances observed in different studies are normalised for the TPB length of the electrode used in the investigation. Huge differences can be seen in the normalised values. No corrections were made for differences in the gas phase conditions employed by the various authors. It should however be mentioned that such a correction cannot account for the observed scatter, so other factors need to be considered. 1.1.1.10Cermet electrodes The most widely studied anode for oxidation of hydrogen in SOFCs is the Ni/YSZ cermet anode. Use of the cermet structure is a basic requirement to increase adhesion between anode and electrolyte and stability of the electrode, compared to nickel. Another reason to use a cermet structure is the possibility of increasing the number of reaction sites per nominal electrode area. The complex microstructure of Ni/YSZ cermet anodes, the problem of establishing a quantitative description of such structures and the complex impedance spectra obtained have resulted in a significant number of studies on this system. A survey of measurement results is given in Table 1.6 (impedance) and Table 1.7 (polarisation). Below some possible reaction mechanisms are given as described by various authors. In 1993, Mogensen and Lindegaard 0 proposed a mechanism for the oxidation of hydrogen on a Ni/YSZ cermet electrode. This model is probably most often referred to in literature. It is based on impedance data where the polarisation resistance consisted of two separate contributions, only one of these being strongly dependent on both the H2 partial pressure and the ratio pH2/pH2O. The high frequency semicircle is assumed to arise partly from the transfer of ions across the TPB line and partly from the resistance inside the electrode particles. The associated CPE is probably connected with the accumulation of charge 15
16
Authors Type of electrode TPB Length (mcm )
2
1 Introduction
Temp (C)
Gas phase conditions (105 Pa) pH2 pH2O 0.053
Impedance (nr arcs)
R ()
Eact (kJmol )
-1
R () (900)
RlTPB () (900) 48
Mohamedi-Boulenouar et al. 0 Norby et al. 0 Norby et al.0
Ni ball
9.4mm
975
0.75
1970
154.4
5102
Ni wire
3.3mm
900 900
0.0012 0.0012
0.0063 0.0063
1 2
65k 1.6*
65k 1.6
214 194
Porous Ni 121 m layer Ni stripe 3.26
Mizusaki et al. 0
700
0.1
0.017
10.5k
68.1
2500
2950
Table 1.5:
Comparison of resistance as function of TPB length for different nickel electrodes. * Only the first arc = Rct, Rr unknown.
Vol% nickel in Cernet Authors Mogensen et al. NiO 55w/o 0 YSZ 45w/o Primdahl et al. 0 40
Temp (C) 1000
Impedance R (cm2) 0.2() 0.2() 0.1 0.07 0.31 0.24 0.04 0.05 1.81 (total)
Gas phase condition (105Pa) pH2 0.97 pH2O 0.03
PH2 order dependence Range (105Pa) 0.97-0.015 (pO2:4.5*10 ) 0.05-0.95

* * -18
PH2O order dependence Range (105Pa) 0.03-0.0022 (pH2: 1) 0.25-0.03 (pH2: 0.5) 0.025-0.25 (pH2: 1) 0.002-0.04 (pH2: 0.5)
arc 1 2
order 0 1-2
order 0 1 0 1 1
1000
1 2 3
0.97
0.03
0-0* 0.2-1 0.1-1
(pH2O: 0.01 or 0.03) ( pH2 >0.5) 0.1-1 (pH2O: 0.02)

*
Aaberg et al. 0
40
1000
1 2 3
0.5
0.02
Tjelle et al. 0
40
1000
1 2 3
0.3
0.03
0.1 0.1 -
0.1-97 (pH2O: 0.03)
Lee et al. 0
45
1000
1 2
3.4a1 13.5
a1
0.97
0.03
45
1000
1 2
0.044a2 0.018 0.3b1 2.6

b2 a2
0.97
0.03
Kawada et al. 0
40
1000
1 1 3
0.97
0.03
10.5(tot)b3
Table 1.6:
Result from impedance analyses for cermet electrodes obtained by various researchers a1&2Effect of the particle size: (a1) YSZ: 0.21m; NiO: 12.5m; (a2) YSZ:3.1m; NiO: 3.1m; b1&2&3Effect of the sinter temperature of the electrode (arc means here the number of arcs in the impedance spectra) (b1) sinter T=1500C; (b2) sinter T=1400C; (b3) sinter T=1200C.
17
18
Authors Vol% nickel Temp in cermet (C) Gas phase conditions (10 Pa) pH2 Kawada et al. 0 40 1000 0.97 pH2O 0.03 i = i0(exp (2F/RT) - exp (-F/RT)) Electrode characteristics depend on sinter temp. (only valid for well prepared electrodes) i = i0(exp (F/RT) exp (-F/RT)) 725-825C: = 0.7 (independent of temp.) 890C: =0.25 950C: =0.47 Aaberg et al. 00 (a) 33 (b) 50 1000 0.3 0.02 ia = i0 exp (F/RT) (a) =2 (b) =1
5
1 Introduction
Current expression
Validity of given current expression
Divisek et al. 0
----
725-950
0.48
0.05
value of depends on microstructure
Table 1.7:
Result from polarisation measurements for cermet electrodes obtained by various researchers.
at the interface between the Ni and YSZ particles. It does not behave as an ideal capacitance (CPE with n=0.67), which is attributed to a variation in grain size and orientation, causing a distribution in relaxation times. The semicircle at low frequencies is attributed to a reaction resistance associated with the formation of water (equation (1.32)), which is assumed to occur at the YSZ surface. The CPE associated with the low frequency semicircle would be related to the degree in coverage of protons and H2O on the Ni surface. Based on the above interpretations the following mechanism was proposed: (1.29) H 2 2 Had , Ni
+ 2 Had , Ni Had , Ni + e + Diffusion of H ad , Ni to the Ni YSZ boundary + 2 2 Had , Ni + OYSZ OH YSZ
(1.30)
2 (1.32) 2 OHYSZ H 2O + OYSZ Recently this mechanism was reformulated 0, allowing incorporation of protons in the bulk of the Ni and YSZ as well as on the surface: + 2e H2 g 2 H Ni H Ni H i,YSZ x 2 H i + OO H 2Oad ,YSZ + VO
(1.31)
(1.33) (1.34)
H 2Oad ,YSZ H 2O g
(1.35) (1.36)
Reactions (1.34) and (1.35) are assumed to be rate-limiting. This mechanism accounts for two arcs in the impedance plot. Recent studies on Ni/YSZ cermet electrodes by Mogensen and Primdahl 0 indicate that most structures are well described by three, more or less overlapping arcs, implying that at least three (physical or chemical) processes contribute to the limitation of the reaction rate. The high frequency arc is sensitive to the cermet structure (particle size) and relatively insensitive to atmospheric composition and overvoltage. The related CPE is interpreted as a double layer capacitance at the Ni/YSZ interface. The medium- and low frequency arc are sensitive to atmospheric composition and overvoltage. The capacitance associated with the low frequency arc behaves ideal, is in the order 0.5-2.5 F/cm2 and is very dependent on pH2O. This magnitude of the capacitance suggests changes in the bulk composition of the gas phase above the electrode, rather than surface adsorption of charged species. A more or less similar reaction scheme has been suggested by Aaberg et al. 00.
H2 g 2 Hads , Ni Hads, Ni
Hads ,YSZ
(1.37) +e
(1.38) (1.39)
2 Hads ,YSZ + OO H2 O + VO
Aaberg et al. assumed, in agreement with earlier findings by Skaarup et al. 0, that adsorption and mobility of hydrogen on nickel is fast. Consequently, it is reasonable to assume that hydrogen adatoms are abundantly present at the Ni/YSZ boundary even when the electrode is moderately polarised to anodic potentials. The electrochemical transfer of protons from the metal to the electrolyte is assumed to be the potential dependent step, which is assumed to be close to equilibrium. The rate determining step will be the combi19
1 Introduction
nation of protons and oxide ions on the electrolyte surface. This is probably a multi step process. With the above assumptions and the assumption that (1.38) is not far from equilibrium, Aaberg et al. arrived at the following equation for the anodic current:
' ia = 2 Fk 3 pH2 exp (2 FE / RT )
(1.40)
k3 is the rate constant. This is identical to the relation Mizusaki et al. 0 found for the anodic current under anodic polarisation. Experimentally the transfer coefficient was found to vary between 1 and 2, depending on the microstructure. An alternative route for (1.38) could be
Hads / abs , Ni Hi + e (1.41)
and illustrates protons being absorbed in the electrolyte. If (1.39) is slow the interstitial protons will accumulate in the electrolyte. Reaction (1.41) than acts merely as a large capacitance, but does not contribute much to the overall rate unless sub-surface diffusion of protons extends towards the reaction zone. Its involvement may account for the large capacitance experimentally found at low frequencies, provided that the diffusion coefficient for protons in zirconia is high. The solubility of hydrogen in zirconia, as reported earlier by Wagner 0, is proposed to contribute to an extension of the reaction zone. Whether the protons are transferred across the TPB in an adsorbed state only, or additionally, across the metal zirconia interface as hydrogen dissolved in the metal, is not clear. Impedance analysis is a widely used tool for kinetic studies on electrodes. Very frequently and as described above, the impedance data is fitted to a number of RQ-arcs, to which no physical meaning can be ascribed in a simple manner. Especially for cermet electrodes, containing both electronic and ionic conducting phases, the use of a chain ladder network is of interest. With this type of network (also known as transmission line model) bulk activity of the cermet is visualised. 000000 1.3 Scope of this thesis
A number of studies on different types of nickel anode for SOFC are described in this thesis. Emphasis is put on the relation between the microstructure and the electrode performance. A broad range of microstructures is covered by starting with pattern electrodes and porous nickel structures, finally arriving at the complex microstructures of Ni/YSZ cermet structures. Attention is paid to the kinetics of the hydrogen oxidation reaction. The experimental set-up is described in Chapter 2, where the design of the electrochemical cell is also discussed. Nickel electrodes are the subject of Chapters 3 and 4. These types of electrode are not directly interesting as an anode for real SOFC applications, but are very interesting for research purposes because of their uncomplicated geometry. This makes them indispensable for studies on the relation between microstructure and electrochemical performance. Lithographically prepared nickel pattern electrodes are the subject of Chapter 3. This type of electrode results in relatively small nickel perimeters. Results from impedance and polarisation types of measurements are discussed. In Chapter 4 results on porous nickel electrodes are described. These electrodes have a nickel perimeter about 5 times longer than the lithographically prepared electrodes. Besides impedance and polarisation measure20
1.3 Scope of this thesis
ments under different conditions a model is proposed for the hydrogen oxidation reaction at the nickel anode. A kind of intermediate electrode between the nickel and cermet electrode is discussed in Chapter 5. By modifying a porous nickel electrode with fine YSZ particles the effect of the YSZ in a cermet is studied. The real state-of-the-art SOFC anodes are treated in the Chapters 6-8. The influence of the microstructure on the electrode performance is described in Chapter 6. The microstructure is affected by changing the particle size of the YSZ fraction in the preparation of the Ni/YSZ cermet electrode. Coarse and fine YSZ powder were mixed in different ratios resulting in seven different microstructures. Impedance measurements were performed to study the electrode performance. In Chapter 7 impedance data are analysed with a network model. Chapter 8 describes impedance and polarisation measurements obtained under different conditions aiming at kinetic parameters of the hydrogen oxidation reaction at the cermet electrode. A brief evaluation of the results obtained in this thesis is given in Chapter 9. References
H. Davy, Nicholsons J. Nat. Phil., 144, 1802. W.R. Grove, Phil. Mag., 14, 127, 1839. W. Nernst, ber die elektrolytische Leitung fester Krper bei sehr hohen Temperaturen, Z. Elektrochem., 6, 41, 1899. E. Baur and H.Z. Preis, ber Brennstoff-ketten mit FestLeitern, Z. Electrochem., 43, 727-32, 1937. E. M. Cohn, NASAs Fuel Cell Program, Fuel Cell Systems, Advances in Chemistry series 47, Ed. by G.J. Young, H.R. Linden, pp 1-8, Am. Chem. Soc. 1965. B.S. Baker, L.G. Marianowski, J. Meek and H.R. Linden, High Temperature Natural Gas for Fuel Cells, Fuel Cell Systems, Advances in Chemistry series 47, Ed. by G.J. Young, H.R. Linden, pp 247-62, Am. Chem. Soc. 1965. W.T. Reid, Fuel Cells for Practical Energy Conversion Systems, From Electrocatalysis to Fuel Cells, Ed. by G. Sandstede, University of Washington Press, ISBN 0-295-95178-8, 1972. P. Zegers, Status of Solid Oxide Fuel Cell Development in Europe, Proc. of the 3th Int. Symp. On SOFC-III, pp 16-20, Honolulu, Hawaii, 1993. M.C. Williams, Status of Solid Oxide Fuel Cell Development in Japan, Proc. of the 4th Int. Symp. On SOFC-IV, pp 3-9, Yokohama, Japan, 1995. M. Nishikawa, Status of Solid Oxide Fuel Cell Development in the United States, Proc. of the 4th Int. Symp. On SOFCIV, pp 10-19, Yokohama, Japan, 1995. J. Kuipers, Status of the Westinghouse, EDB and ELSAM 100kWe SOFC Field Unit, European Fuel Cell News, pp 19, 5, 1, 1998. E. Barendrecht, H. Barten, L de Vaal, Brandstofcel nadert prcommercile fase, Chemisch Magazine, 10, 424-427, 1994. U. Bnger, Fuel Cells and Hydrogen in the City of Tomorrow, European Fuel Cell News, pp 11-13, 5, 1, 1998. T. Bozzoni, PAFC in the City of Tomorrow, European Fuel Cell News, pp 14-15, 5, 1, 1998. P.J. Kortbeek, R.G. Ottervanger, MCFCs in the City of Tomorrow, European Fuel Cell News, pp 15-16, 5, 1, 1998. H.E. Vollmar, W. Drenckhahn, Stationary PEMFCs and SOFCs in the City of Tomorrow, European Fuel Cell News, pp 17-18, 5, 1, 1998. K. Kinoshita, Electrochemical oxygen technology pp 163-259, ISBN 0-471-57043-5, John Wiley & Sons, Inc. New York, 1992. S.C. Singhal, Tubular Solid Oxide Fuel Cells, in Proc. Of the third Int. Symp. on Solid Oxide Fuel Cells, pp 665-77, Hawaii, 1993. A. Hammou, J. Guindet, Solid Oxide Fuel Cells, Chapter 12 in The CRC Handbook of Solid State Electrochemistry, pp 409-45, CRC Press, 1997. N.Q. Minh, Science and technology of Ceramic Fuel Cells, ISBN 0-444-89568, Elsevier, Tokyo, 1995. E. Siebert, A. Hammouche, M. Kleitz, Impedance Spectroscopy Analysis of La1-xSrxMnO3/Yttria-Stabilized Zirconia Electrode Kinetics, Electrochemica Acta, 40, 1741-53, 1995. F. van Heuveln, 'Characterisation of porous cathodes for application in Solid Oxide Fuel Cells', thesis, University of Twente, 1997. A. Hammou, J. Guindet, 'Solid Oxide Fuel Cells', Ch 12 of 'The CRC Handbook of Solid-State Electrochemistry', pp 409-445, CRC Press, Inc., 1997. N.Q. Minh, 'Ceramic Fuel Cells', J. Am. Ceram. Soc., 76 [3] 563-88, 1993. T. Shirakawa, S. Matsuda, and A. Fukushima, 'Characterisation of NiO/YSZ electrodes by Temperature Programmed Reduction', pp.464-72 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993.
21
1 Introduction
F.H. van Heuveln, F.P.F. van Berkel, and J.P.P. Huijsmans, 'Electrochemical characterisation of porous electrodes and applications in SOFC'; pp. 53-68 in: Ris High Temp. Electrochemical Behaviour of Fast Ion and Mixed Conductors, 14th Ris Inter. Symp. On Material Science, 1993. F.P.F. van Berkel, F.H. van Heuveln and J.P.P. Huijsmans, Status of SOFC Components Development at ECN, pp. 53341 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. K.C. Chou, S. Yuan, and U. Pal, 'Deposition, electrical property and direct porosity measurement of Ni-ZrO2 cermet electrodes'; pp 744-751 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. M. Mogensen and T. Lindegaard, 'The kinetics of hydrogen oxidation on a Ni/YSZ SOFC electrode at 1000C'; pp. 48493 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. J. Divisek, A. Kornyshev, W. Lehnert, U. Stimming, I.C. Vinke and K. Wioppermann, Advanced characterisation techniques for Nickel-YSZ Cermet Electrodes used in Solid Oxide Fuel Cells, Electrochemical Proceedings Volume 97-18, 606-16, 1997. A. Ioselevich, A.A. Kornyshev and W. Lehnert, Degradation of SOFC Anodes due to Sintering of Metal Particles: Correlated Percolation Model, J. Electroch. Soc., 144, 3010-19, 1997. T. Kawada, N. Sakai, J. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Structure and Polarisation Characteristics of Solid Oxide Fuel Cell Anodes, SSI, 40/41, 402-06, 1990. T. Norby, O.J. Velle, H. Leth-Olsen and R. Tunold, 'Reaction resistance in relation to three phase boundary length of Ni/YSZ electrodes', pp.473-78 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993 J. Mizusaki, H. Tagawa, T. Saito, K. Kamitani, T. Yamamura, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu and S. Nakagawa, 'Preparation of Nickel pattern electrodes on YSZ and their electrochemical properties in H2-H2O atmospheres'; pp. 533-41 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. J. Guindet, C. Roux, and A. Hammou, 'Hydrogen oxidation at the Ni/Zirconia electrode', pp.553-58 in: Proc. of the 2nd Int. Symp. on Solid Oxide Fuel Cells, Athens, Greece, July 2-5, 1991. M. Suzuki, H. Sasaki, S. Otoshi, and M. Ippommatsu, Development of Ru/Y2O3 SOFC anode', pp.585-91 in: Proc. of the 2nd Int. Symp. on Solid Oxide Fuel Cells, Athens, Greece, July 2-5, 1991. M. Suzuki, H. Sasaki, S. Otoshi, A. Kajimura and M. Ippommatsu, 'High power density solid oxide electrolyte fuel cells using Ru/Y2O3 stabilised zirconia cermet anodes, Solid State Ionics, 62, 125-30, 1993. K. Okumura, Y.Yamamoto, T. Fukui, S. Hanyu, Y. Kubo, Y. Esaki, M. Hattori, A. Kusunoki and S. Takeuchi, 'Microstructure and overvoltage characteristics of the anode for Solid Oxide Fuel Cells', pp. 444-53 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. C.S. Tedmon, H.S. Spacil and S.P. Mittof, General Electric, Rep. 69-C-056, 1969. K. Eguchi, T. Setoguchi, K. Okamoto and H. Arai, 'An investigation on anode materials and anodic reaction for Solid Oxide Fuel Cell', pp. 494-503 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. H. Miyamoto, M. Sumi, K. Mori, I. Koshiro, F. Nanjo and M. Funatsu, Improvement of Anode Performance by YSZ Surface Modification, in Proc. Of the Third Int. Symp of SOFC, pp 504-12, The Electrochemical Society, Pennington, NJ, 1993. R.M.C. Marques, J.R. Frade, F.M.B. Marques, Ceramic materials for SOFC anode cermetsin Proc. Of the Third Int. Symp of SOFC, pp 513-22, The Electrochemical Society, Pennington, NJ, 1993. M.T. Colomer, J.R. Jurado, R.M.C. Marques, F.M.B. Marques, Evaluation of Titania Doped YSZ for SOFC Anodes, in Proc. Of the Third Int. Symp of SOFC, pp 523-32, The Electrochemical Society, Pennington, NJ, 1993. M. Mogensen, S. Sunde and S. Primdahl, SOFC Anode Kinetics, pp 77-100 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. T. Kawada, N. Sakai, H. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Characteristics of slurry-coated nickel zirconia cermet anodes for solid oxide fuel cells, J. Electrochem. Soc. 137, 10 , 3042-47, 1990. J. Divisek, L.G.J. de Haart, P. Holtappels, U. Stimming and I.C. Vinke, Elelctrode kinetics of hydrogen oxidation on Nickel/YSZ cermet anodes, pp 235-40 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. J. Mizusaki, T. Yamamura, H. Yoshitake, H. Tagawa, K. Hirano, S. Ehara, T. Takagi, M. Hishinuma, H. Sasaki, T. Sogi, Y. Nakamura, and K. Hishimoto, Kinetic studies on Ni/YSZ anode reaction of SOFC in H2-H2O atmospheres by the use of Nickel pattern electrodes, pp 363-68 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. J. Mizusaki, H. Tagawa, T. Saito, K. Kamitain, T. Yamamura, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu, S. Nakagawa, K. Hashimoto, Preparation of Nickel Pattern Electrodes on YSZ and Their Electrochemical Properties in H2-H2O Atmospheres, J. Electrochem. Soc., 141, 2129-34, 1994. J. Mizusaki, H. Tagawa, T. Saito, T. Yamamura, K. Kamitani, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu, S. Nakagawa, K. Hashimoto, 'Kinetic studies of the reaction at the nickel pattern electrode on YSZ in H2-H2O atmospheres', Solid State Ionics, 70/71, 52-58, 1994. P.A. Osborg, T. Norby, Characterisation of a H2+H2O/Ni/YSZ point electrode system by impedance spectroscopy, pp47-50, in 7th SOFC Workshop, theory and measurement of microscale processes in Solid Oxide Fuel Cells, Wadahl, Norway, 18-20 Jan., 1995. T. Yamamura, H. Tagawa, T. Saito, J. Mizusaki, K. Kamitani, K. Hirano, S. Ehara, T. Takagi, Y. Hishinuma, H. Sasaki, T. Sogi, Y. Nakamura, K. Hashimoto, Reaction Kinetics at the Nickel Pattern Electrode on YSZ and its dependence on Temperature, Proc. of the 4th Int. Symp. On SOFC-IV, pp 741-49, Yokohama, Japan, 1995. T. Yamamura, H. Yoshitaka, H. Tagawa, N. Mori, K. Hirano, J. Mizusaki, S. Ehara, T. Takagi, M. Hishinuma, H. Sasaki, Y. Nakamura, K. Hashimoto, Experimental Evidence for Three Phase Boundary as Active Site on Nickel/YSZ System, pp 617-25 in: Proc. Of 2nd European SOFC Forum, Oslo, Norway, 1996.
22
1.3 Scope of this thesis
F.Z. Mohamedi-Boulenouar, J. Guindet and A. Hammou, Influence of Water Vapour on Electrochemical Oxidation of Hydrogen at the Ni/Zirconia Interface, pp 441-50 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. N. Nakagawa, H. Sakurai, K. Kondo and K. Kato, 'Study on the extension of reaction zone from Ni/YSZ interface by using fixed film electrodes', pp 721-30 in Proc. of the 4th Int. Symp. On SOFC-IV, pp 741-49, Yokohama, Japan, 1995. S. Primdahl and M. Mogensen, Oxidation of Hydrogen on Ni/Yttria-Stabilized Zirconia Cermet Anodes, J. Electrochem. Soc., 144, 3409-19, 1997. R.J Aaberg, R. Tunold, S. Tjelle, R. degrd, Oxidation of CO and H2 on Ni/YSZ cermet electrodes, pp 511-16 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. R.J Aaberg, R. Tunold, S. Tjelle, R. degrd, A Possible Reaction Mechanism for the Oxidation of H2 on Ni/YSZ cermet Electrodes, pp 557- 64 in: The Electrochemical Society, Aachen, 1997. S. Skaarup, B. Zachau-Christiansen and T. Jacobsen, Surface Species and Surface Mobility on Ni/YSZ Anodes, pp 42330 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. C. Wagner, Ber. Bunsenges. Physic Chem., 72, 778-81, 1968. S. Tjelle, R. Tunold and R. degrd, Oxidation of H2 and CO on Ni/YSZ cermet, pp 67-72 in: Proc. Of the 7th SOFC workshop, Advanced Fuel Cells Programme Annex II Modelling and Evaluation of Advanced SOFC, Wadahl, Norway, 1995. C-H Lee, C-H Lee, H-Y Lee and S.M Oh, Microstructure and anodic properties of Ni/YSZ cermets in Solid Oxide Fuel Cells, Solid State Ionics 98, 39-48, 1997. Ch. Bleise, J. Divisek, B. de Haart, P. Holtappels, B. Steffen and U. Stimming, Kinetic Modelling of the Anodic Reaction Considering the Porous Structure, pp 31-39 in: Proc. Of the 7th SOFC workshop, Advanced Fuel Cells Programme Annex II Modelling and Evaluation of Advanced SOFC, Wadahl, Norway, 1995. A. Hahn, H. Landes, Investigations into the kinetics of SOFC cathodes pp 595-605 in Proc. Of the 5th Int. Symp. On SOFC, Ed. U. Stimming, S.C. Singhal, H. Tagawa, and W. Lehnert, The Electrochemical Society, Aachen, 1997. F. Richter, Impedance Measurements under High Current for Development and Quality Control of Solid Oxide Fuel Cells (SOFCs), pp 3-7, Electrochemical Applications 1/97, Zahner-elektrik GmbH & Co, 1997. G. Paasch, P.H. Nguyen, Impedance of Inhomogeneous Porous Electrodes, a novel Transfer Matrix Calculation Method, pp 7-9, Electrochemical Applications 1/97, Zahner-elektrik GmbH & Co, 1997. M.H.R. Lankhorst, F.H. van Heuveln and F.P.F. van Berkel, Analytical Expressions for the Impedance of Networks, ECN-internal report, 1997.
23
2 Experimental considerations
2.1
Introduction
In this thesis interest is focused on the electrochemical performance of nickel and nickel / yttria-stabilised zirconia cermet anodes in the hydrogen oxidation reaction. The present chapter describes: the experimental set-up, the design considerations regarding the electrochemical cell. 2.2 The experimental set-up
The experimental set-up is schematically represented in Figure 2.1 and is suitable for: impedance and polarisation measurements, electrochemical measurements as a function of gas condition (pH2, pH2O), polarisation and temperature. Essential parts are described in more detail in the following sections. 2.2.1 The electrochemical cell One of the important requirements for the electrochemical cell is the possibility to perform halfcell measurements. Half-cell measurements allow the study of one electrode, in this case the anode. The consequence of half-cell measurements is the need for an additional electrode, the reference electrode. The commonly used terminology of electrodes is working, counter and reference electrode. The working electrode is the electrode whose performance or characteristics are under study. The counter electrode is
Figure 2.1: Overview of the experimental set-up.
25
the other current carrying electrode positioned on the opposite site of the electrolyte. The reference electrode is used for controlling and measuring the potential of Figure 2.2: Schematic side view of the three-electrode electrothe working electrode and chemical cell. does not carry any appreciable current. A schematic representation of the electrochemical cell used throughout this thesis is given in Figure 2.2. A detailed discussion of the requirements for the electrode configuration is given in section 2.3. 2.2.2 Sample holder The ceramic sample holder is schematically shown in Figure 2.3.a. The holder has an open structure to allow gas flow to and from the electrode. A Pt/Pt-10%Rh thermocouple is placed near the electrode for temperature measurement. Pt grids are used as current collector. An additional wire is led to the working electrode to monitor the potential of this electrode. A weight of about 325 g is placed on the test cell to ensure good electrical contact between electrode and current collector. The ceramic sample holder is placed in a quartz tube through which gas of desired composition can flow (Figure 2.3.b). Such a measurement set-up, where the cell is surrounded by a single gas environment, is usually referred to as an undivided cell, whereas a cell im-
(a)
(b)
Figure 2.3: Experimental set-up: (a) ceramic sample holder; (b) quartz tube with sampleholder.
26
2.2 The experimental set-up
Figure 2.4: Experimental set-up: gas conditioning and controlling system.
posed between two different gas atmospheres is referred to as a divided cell. The undivided set-up is seen as less complicated, since it circumvents the problems of high temperature sealing to separate fuel and air gases. 2.2.3 Gas conditioning and controlling system A schematic representation of the gas conditioning and controlling system is given in Figure 2.4. Desired gas mixtures are obtained by mixing hydrogen, helium and nitrogen. Brooks 5800 Mass Flow Controllers (maximum flow rate 200 ml/min) control all gas flows. Passing the gas mixture through two water bubblers controls the water concentration. The temperature of the water in these bubblers is controlled with an electric heating and cooling device containing a mixture of ethylene-glycol and water. The water bubbler second in line is used as a cold trap, fixing the water vapour pressure in the gas to that in thermal equilibrium with the water in the bubbler. The temperature of the first water bubbler is set at 5C above the second one. To avoid water condensation in the tubes, heating cables are used to control the tube temperature. 2.2.4 Furnace and controller The quartz tube is placed in a furnace. Several precautions are taken to reduce background noise introduced by the furnace. First, the quartz tube is covered by a metallic shield connected to earth. Second, a special winding technique is used for the heating elements. Besides bifilar winding of the heating element, two separate windings are used which are connected parallel and crossed to the power supply. The power is supplied through a transformer with a midsection tap connected to common ground. This creates a virtual earth in the middle of the furnace (see Figure 2.5). The temperature of the furnace is controlled with an Eurotherm 91E. In this study a temperature range of 600 to 850C is used for electrochemical measurements. This is slightly below the actual working temperature of an SOFC (1000C) and based on the expected stability problems of nickel electrodes at these high temperatures. 2.2.5 Measurement Equipment Two types of measurements are considered, polarisation (dc) and impedance (ac) measurements.
27
Figure 2.5: Experimental set-up: schematic drawing of the heating cables in the furnace with the connection to the power supply.
For polarisation measurements a Solartron Electrochemical Interface (model 1287) is used. The actual measurements are controlled with a computer program (using Test Point [1]). This program enables measurement of the current through the cell as function of the voltage drop between working and reference electrode, in a certain overpotential range, with a certain time and a certain voltage interval. For impedance measurements a Solartron Frequency Response Analyser 1255 is used in combination with a Solartron Electrochemical Interface 1287. The Frequency Response Analyser generates an ac signal in the frequency range of 1 MHz to 10 mHz, the Electrochemical Interface controls the amplitude of the ac signal placed between working and reference electrode (10 mV). Measurements are performed using Zplot 0, a commercially available computer program for impedance measurements. 2.3 Sample choice in view of geometric requirements for the electrode configuration
To study the performance of an SOFC, anodic and cathodic overvoltages have to be measured independently. A reference electrode is commonly used for this purpose. However, the positioning of the electrodes is a point of controversy among investigators 000 and a variety of electrode configurations have been proposed in literature. An survey is given in 0. For a good comparison with real SOFC conditions thin electrolytes are favourable. For these electrolytes, with a thickness of 100 150 m, the reference electrode has to be placed next to the working or counter electrode. The separation or gap between the reference and the adjacent current carrying electrode should be large compared with the thickness of the electrolyte. Ideally, no different lines of equipotential should enter the reference electrode, because in the case that a potential difference occurs along the reference electrode an electrochemical driven reaction over the reference electrode will appear. If the reference electrode is placed further from the working electrode, the potential difference will normally decrease, in that respect it should be placed as far away from the current carrying electrodes as possible. A few examples of electrode geometries with current lines and the expected equipotential line measured by the reference electrode are given in Figure 2.6. 28
2.3 Sample choice in view of geometric requirements for the electrode configuration
Figure 2.6: Examples of electrode configurations on thin electrolytes. Expected current lines through the cell and assumed equipotential line as measured by the reference electrode are indicated schematicly.
Electrode geometry requirements have been given extensive attention recently. Besides experimental results 00 numerical calculations are also reported 000. Potential and current density distributions in different cell geometries were calculated numerically leading to the conclusion that non-uniform current densities at the working electrode could very easily lead to erroneous results. This situation occurs when the electrodes are slightly displaced on a scale of the order of the electrolyte thickness, leading to either under- or overestimation of the polarisation resistance of the electrode, depending on the direction of displacement. In those cases the reference electrode equipotential lines intersect the electrolyte/electrode interface which means that part of the polarisation resistance of the working electrode is excluded from the measurement or part of the polarisation resistance of the counter electrode is included, depending on the direction of the electrode displacement. More details on the numerical calculations can be found in the above mentioned literature. Our first choice of electrochemical cell is given in Figure 2.7, where L is 130 m and d = 2.5 mm. With these parameters the separation between working and reference electrode is almost 20 times the electrolyte thickness. The requirement that the reference electrode should be placed as far away as possible from the working electrode seems to be Figure 2.7: First used electrochemical cell design fulfilled. Hence, it was not expected that for anodic studies, L = 130 m and d misalignment of working and counter = 2.5 mm. 29
electrode could lead so easily to unacceptable errors. Yet, the results of the numerical calculations together with relative high polarisation resistances obtained with thin electrolytes were the motive for the experiments on different electrode configurations as presented here. 2.3.1 Experimental Electrode configurations with different alignment of the working and counter Figure 2.8: Different cell geometries used for validation of nuelectrode (see Figure 2.8) merical calculations. were prepared on thin electrolytes. As thin electrolytes, tape-casted 8 mol% yttria stabilised zirconia plates with a thickness of 130 m and a surface area of 5.1 cm2 were used. All three electrodes were painted on the electrolyte plates with Pt paste (Demetron), to prepare electrodes with comparable polarisation values and behaviour. The exact alignment of working and counter electrode, representing one of the electrode configurations, is questionable with simply painting the electrodes by hand. As a symmetric cell an YSZ rod of 16.0 mm diameter and 4.0 mm thickness was used, where a small groove was made at half thickness to guide the reference Pt electrode wire (0.2 mm) (Figure 2.2). The groove was painted with Pt paste to ensure good contact between electrolyte and reference electrode. These electrodes were also painted with Pt paste. The whole assembly was annealed at 1000C for one hour in air. Figure 2.9: Schematic representation of the The experimental set-up as described in 2.2 was used, with an additional lead to the
different measurement configurations to measure the whole cell, as well as working and counter electrode separately.
30
counter electrode to monitor the potential of this electrode. Impedance measurements were performed on the working electrode, but also on the counter electrode and the whole cell (see Figure 2.9). This type of experiment should provide information about the equipotential line that is probed by the reference electrode. All measurements were performed in air at 850C. For comparison additional experiments on nickel and cermet electrodes on thin asymmetric as well as thick symmetric cells are presented. These measurements are performed in a hydrogen atmosphere with 2.3% water at 850C and are part of the hydrogen oxidation study on nickel and cermet electrodes as described in this thesis. 2.3.2 Results Impedance spectra obtained for the working and counter electrode and the whole cell, for the different electrode geometries are given in Figure 2.10 to Figure 2.13. A survey of the high and low frequency intercepts of the impedance arc is given in Table 2.1. Let us consider the results for electrode configuration 1 as given in Figure 2.10. In principle, there exists a large misalignment between working and counter electrode for this configuration. Calculations predict a large error for the measured polarisation resistance of the working electrode. As seen in Figure 2.10 a polarisation resistance of 23.7 is found for the working electrode. For the whole cell a value of 57 is found. The difference between these two values should be equal to the polarisation resistance of the counter electrode. Hence a value of 33.3 is expected, but a value of only 0.8 is measured. If the working electrode is measured again, after measuring the counter electrode, this value is reduced to 3.4 . These results suggest that it is not possible to measure an accurate value for the counter electrode and that measuring of this counter electrode has a large effect on the whole cell. For electrode configuration 2 and 3 the same kind of behaviour is observed. For these configurations it did not seem possible to measure the working electrode. The results of the impedance measurements performed on the symmetric cell show that independent measurement of the performance of the working and counter electrode is possible with a reference electrode (Figure 2.13). 2.3.3 Discussion Results as presented in section 2.3.2 indicate that problems do arise for thin electrolytes with misaligned electrodes if the polarisation resistance of the working as well as the counter electrode have to be measured. The smallest electrode can be encountered as the problem electrode, meaning that impedance measurements on this electrode cannot be performed without affecting the performance of the whole cell. Measurement results as given in section 2.3.2 can be explained by assuming that the equipotential line measured by the reference electrode changes with frequency (the measured resistance changes with frequency and therefore also the current distribution) and intersects the electrolyte/electrode interface (as predicted by calculations 0). If for electrode configuration 1, at a certain frequency, the equipotential line measured by the reference electrode does intercept the electrode/electrolyte interface of the counter electrode the potential of the reference electrode
31
30 25
Work electrode 1 Counter electrode Whole cell Work electrode 2
1.0 Work electrode 1 Counter electrode Whole cell Work electrode 2
20
15 10
0.5
Im ag
Imag
0.0 0.0
0 10 20 30 40 50 60
0.5
1.0
1.5
2.0
Real
-5 -10
Real
-0.5
(a) (b) Figure 2.10: Impedance spectra for the working and counter electrode and the whole cell obtained for cell configuration 1, (a) and (b) represent the same data on a different scale. The order of measurements affects the obtained results. Data measured at 850C in air.
10 Work electrode Whole cell 1 Counter electrode Whole cell 2
1.0 Work electrode Whole cell 1 Counter electrode Whole cell 2 0.5
Imag
Imag
0.0 0.0 0.5 1.0 1.5 2.0
Real
0 0 -2 2 4 6 8 10 12 14 16
-0.5
Real
(a) (b) Figure 2.11: Impedance spectra for the working and counter and the whole cell obtained for cell configuration 2, (a) and (b) represent the same data on a different scale. The order of measurements affects the obtained results. Data measured at 850C in air.
15 Whole cell 1 Counter electrode Work electrode Whole cell 2
0.125
10
0.000 0.00
0.25
0.50
Imag
Imag
Real
-0.125 0 0 5 10 15 20 25 Whole cell 1 Counter electrode Work electrode Whole cell 2 -0.250
Real
-5
(a) (b) Figure 2.12: Impedance spectra for the working and counter and the whole cell obtained for cell configuration 3, (a) and (b) represent the same data on a different scale. The order of measurements affects the obtained results. Data measured at 850C in air.
32
6 Work electrode Counter electrode Whole cell Sum work & counter
Imag
0 2 4 6 8 10 12
Real
-2
-4
Figure 2.13: Impedance spectra for the working and counter and the whole cell obtained for a symmetric cell configuration. Data measured at 850C in air. The summed spectrum of working and counter electrode is also given.
120 100 80 60
Whole cell 1 Work electrode Counter electrode Whole cell 2 Sum work & counter
Imag
40 20 0 0 -20 -40 -60 50 100 150 200
Real
Figure 2.14: Impedance spectra for the working, counter and whole cell obtained for cell configuration 1, measured without potentiostat. Data measured at 850C in air. The summed spectrum of working and counter electrode is also given.
Electrode conf. 1 Intercept hf () WE-RE:1 WE-CE RE-CE WE-RE:2 (WE-CE) (WE-RE) 0.09 0.13 0.031 0.087 lf () 23.7 57.0 0.76 3.4 33.3
Electrode conf. 2 Intercept hf () 0.081 0.16 0.080 0.082 lf () 0.88 12.0 11.7 0.86 11.1
Electrode conf. 3a Intercept hf () 0.044 0.14 0.14 0.14

a
Symmetric conf. Intercept hf () 3.2 5.5 2.1 lf () 7.8 11.6 3.9
lf () 0.11 21.7 20.0 3.7

a
1.7
3.8
Table 2.1: Results of impedance measurements on different electrode configurations. The high and low frequency intercept for the impedance arc are given. a where first the whole cell is measured, followed by counter and work electrode, WE-RE:2 is in this case WE-CE:2.
33
can get (almost) equal to the potential of the counter electrode. If in that case an impedance measurement with potentiostatic control is performed between these two electrodes, the potentiostat will increase the current through the cell until the adjusted potential difference between the electrodes is obtained. This is not possible if the equipotential line of the reference electrode equals the potential of the counter electrode. The large current, which is forced through the cell due to these experiments, seems to have a large effect on the whole cell, resulting in a large decrease and instability of the measured polarisation resistances. The explanation as given here for electrode configuration 1 also holds for electrode configuration 2 and 3. For configuration 2 the misalignment already seems large enough to make the equipotential line of the reference electrode equal to the working electrode, indicating that misalignments in the order of 5 times the electrolyte thickness are already disastrous. It is clear that the misalignment of configuration 3 will be too large. The explanation given here can be confirmed by a measurement without potentiostatic control. Without potentiostatic control the current through the cell will not reach extreme values. For electrode configuration 1, results for the different electrodes measured without potentiostat are given in Figure 2.14. There are still some problems encountered for high frequency values, but without potentiostat reasonable polarisation values can be obtained for the counter electrode. But this does not mean that the polarisation value measured at the working electrode is not influenced. It is still very well possible that part of the polarisation of the counter electrode is added to the polarisation value measured by the working electrode. Unfortunately the reproducibility of the Pt electrodes as prepared here is to small for measuring the effects of misalignment in the electrodes. Measurements on a symmetric cell confirmed that for this type of electrodes no problems arise. 2.3.4 Comparison of results of different type of electrolytes for porous nickel and cermet type of electrodes. Comparison of electrochemical results on SOFC anodes on thin electrolyte plates and 4 mm thick electrolyte rods will provide additional information on the effect of the electrode configuration. This especially could be interesting for the ratio of the polarisation resistances between working and counter electrode, Rw/Rc. Van Heuveln 0 stated that for accurate measurements of the polarisation resistance of the working electrode this ratio should be larger then 10. Based on the experimental results as obtained here, Pt electrodes are assumed to have polarisation values in the order of 10 25 . This means that problems can be expected because we do not expect polarisation resistance values of 100 250 for cermet electrodes. Results for porous nickel electrodes and cermet electrodes for thin and thick electrolytes are given in Figure 2.15 and Figure 2.16, respectively. These graphs strongly suggest that part of the polarisation resistance of the counter electrode is added to the measured polarisation resistance of the working electrode. For the porous nickel as well as the cermet electrode the small semicircle appearing on the high frequency side is of the same order of magnitude (if the different electrode areas are considered) as the polarisation resistance measured on thick electrolyte rods. In that case, the large semicircle on the low frequency
34
15
10
8
10
Imag
4
5
Imag
0 0 5 10 15 20 25 30
0 0 -2 2 4 6 8 10 12 14 16 18
Real
-5
Real
-4
(a) (b) Figure 2.15: Impedance spectra obtained for porous nickel electrodes on (a) thin electrolyte plates and (b) 4 mm thick electrolyte rods. Measurements were performed under H2 atmosphere with 2.3% H2O at 850C.
6 5 15 4 10 3 Cermet on thin electrolyte 20 Work electrode Counter electrode Whole cell Sum work & counter
Imag
Imag
2 1
0 0 0 -1 -2 2 4 6 8 10 12 -5 0 10 20 30 40
Real
Real
-10
(a) (b) Figure 2.16: Impedance spectra obtained for nickel/YSZ cermet electrodes on (a) thin electrolyte plates and (b) 4 mm thick electrolyte rods. Measurements were performed under H2 atmosphere with 2.3% H2O at 850C.
side is caused by misalignment of the working and counter electrode. This causes errors in the order of 100% for the nickel electrode and 400% for the cermet electrode. 2.3.5 Conclusions Validation of the numerical calculations on the used electrode configuration for a thin electrode is not straightforward. Besides the electrode geometry the measurement method influences the results. Strong evidence is found for the idea that the equipotential line of the reference electrode probes part of the counter or working electrode depending on the alignment of these electrodes. It is possible that the actual alignment and the ratio between the polarisation resistances of the working and counter electrodes influence the size of the actual error in the polarisation. However, considering preparation techniques of the electrodes and expected uncertainty in polarisation resistances of, for example Pt paint electrodes, the asymmetric electrode configuration on a thin electrolyte is in our opinion not suitable for kinetic studies on electrode reactions. For the symmetric cell design (Figure 2.2) the numerical calculations did not predict errors in measured polarisation resistances of the electrodes, which was confirmed by our experiments. Therefore it was decided to perform all electrochemical measurements on these thick electrolytes in a symmet-
35
ric electrode configuration, realising that thick electrolytes have disadvantages like a large uncompensated resistance between working and counter electrode. References
[1] Test Point, Capital Equipment Corp. Zplot W, Data acquisition of impedance, gain phase and group delay measurements, Scribner Associates and Solartron Instruments Ltd. M. Nagata, Y. Itoh and H. Iwahara, Dependence of Observed Overvoltages on the Positioning of the Reference Electrode on the Electrolyte, Solid State Ionics, 67, 215-24, 1994. F.H. van Heuveln, F.P.F. van Berkel, and J.P.P. Huijsmans, Electrochemical Characterisation of Porous Electrodes and Applications in SOFC, Proc of the 14th Ris Int. Symp. on materials science, High Temp. electrochemical behaviour of fast ion and mixed conductors, pp 75-84, 1993. G. Hsieh, T.O. Mason, E.J. Garboczi, L.R. Pederson, Experimental limitations in impedance spectroscopy: Part III. Effect of the reference electrode geometry/position, Solid State Ionics, 96, 153-72, 1997. J. Winkler, P.V. Hendriksen, N. Bonanos, and M. Mogensen, Geometric requirements of Solid Electrolyte Cells with a Reference Electrode, J. Electrochem. Soc. 145, 1184-94, 1998. G. Reinhardt and W. Gpel, Electrode reactions at Solid Electrolytes: Finite Difference Calculations to describe Geometric and Electrical Properties of Planar Devices, Proc. of the Third Int. Symp. on: Ionic and Mixed Conducting Ceramics, Proc. Vol. 97-24, pp 610-30, 1997. F.H. van Heuveln, Characterisation of porous cathodes for application in solid oxide fuel cells, thesis, University of Twente, 1997.
36
3 Hydrogen oxidation at nickel pattern electrodes on yttria-stabilised zirconia
Abstract Nickel pattern electrodes were prepared by lithographic techniques. Different patterns were prepared by varying the width of and the distance between adjacent nickel stripes. Impedance and polarisation measurements were used for characterisation. Despite some grain growth during these experiments, the patterned layers remained dense and showed good adherence to the zirconia electrolyte. With changes in the microstructure comes variation of the total electrode resistance, which suggests that the performance of the pattern electrodes scales with the available length of the nickel perimeter. Current passage seems to cause positive effects on the performance. 3.1 Introduction
Ni/YSZ cermet is the state of the art material for the anode of the Solid Oxide Fuel Cell (SOFC) [1]0. The cermet consists of an electronic conducting phase (nickel), an ionic conducting phase (YSZ) and sufficient porosity to enable mass transport via the gas phase to (and from) the active areas when used as an anode. The microstructure is complex and has a large influence on the electrochemical performance 00000. It is therefore an important topic for research aiming at a further improvement of the performance of the Ni/YSZ anode. Such considerations may however underestimate the role which might be played by the reaction mechanism in determining the overall performance. The microstructure of the cermet electrodes is hard to quantify in measurable parameters. The cermet structure therefore does not seem to be the most obvious choice for studying the anodic reaction mechanism. The less complicated geometries of nickel electrodes, e.g. nickel point 000, lithographically prepared porous nickel layers 0 and pattern electrodes 00000 offer better starting points for research, but comparison of these results is not straightforward because of the different measurement conditions employed in the different studies cited. The present work can be regarded as the first of a series of studies on hydrogen oxidation at different types of nickel and Ni/YSZ cermet electrodes, covering a large variety of electrode microstructures. By using the same measurement conditions for these electrodes a better understanding of the anodic reaction mechanism and associated relation with the microstructure is aimed at. In this study nickel pattern electrodes are prepared with litho37
graphic techniques. Impedance and polarisation measurements are performed to characterise the electrodes. A discussion on the hydrogen oxidation reaction that will occur at the anode is presented in Chapter 4 of this thesis. 3.2 Experimental
3.2.1 Sample preparation Yttria-stabilised zirconia (Tosoh-Zirconia TZ-8Y) rods of 25 mm diameter were obtained by uniaxial pressing at 1.5 bar for 1 min, followed by isostatic pressing at 4000 bar for 5 min. These rods were sintered at 1400C for 5 h in air. Electrolyte discs of 16.0 mm diameter and 4.0 mm thickness were cut from the sintered rods. A small groove around the disc was made at half thickness for positioning of the reference electrode. Prior to use both sides of the disc were mechanically polished with 320 MESH SiC and 3 m diamond MM and diamond paste (1 m). After polishing the samples were ultrasonically cleaned with ethanol. An Archimedes method was used to determine the density of the discs. Only disks with a density larger than 5.89 gcm-3, i.e. 99% of the theoretical density of YSZ, were used for experiments. 1.1.1.11Electrode preparation Photolithography was used for preparation of the pattern electrodes. A compact nickel layer of 1.3 m thickness was prepared on the electrolyte disc with E-beam evaporation. On top of this layer a 1.5 m thick standard photoresist layer (AZ1813) was spincoated. Using an appropriate mask a photoresist pattern was created on the nickel layer. The undesired nickel was removed by wet chemical etching with Alu-ets (80:16:14 phoshoric, acetic and nitric acid). The width of the nickel and YSZ stripes was in the range of 10 to 75 m. To prevent parts of the electrode to be disconnected from the current collector, additional nickel lines with a width of 50 m were deposited perpendicular to the lines belonging to the pattern, as shown schematically in Figure 3.1. Ten pattern electrodes were prepared with different nickel and YSZ line-widths. Each pattern covered a total electrode area with a diameter of 14 mm. For electrochemical experiments, counter and reference electrodes were painted on the electrolyte disc with Pt paste (Demetron). The whole assembly was annealed at 1000C for 1 h in reducing atmosphere (10% H2 - 90% N2). The cell geometry is shown schematically in Figure 3.2. 3.2.2 Characterisation of the electrode microstructure Before and after the electrochemical experiments SEM (Scanning Electron Micros38
Figure 3.2: Schematic side view of the three-electrode Figure 3.1: Schematic representation electrochemical cell. of the pattern electrode.
3.2 Experimental
copy) micrographs of the nickel pattern electrodes were taken at different positions on the surface. These were used to measure the width of both the nickel and YSZ stripes. To account for grain growth at the edge of the nickel stripes and for measuring the grain size of the nickel particles, the SEM pictures were edited to black and white representations and transferred into an image analysis system. The results enabled calculation of the total perimeter of the nickel structure, the surface coverage of nickel, the nickel grain size and the grain boundary length. 3.2.3 Electrochemical characterisation Electrochemical experiments were performed in a single-gas environment at atmospheric pressure. At standard conditions a gas flow of 100 mlmin-1 H2 (STP) with 2.3% H2O at 850C was used. All gas flows were controlled by Brooks 5800E Mass Flow Controllers. Passing the gas mixture through a water bubbler system in a temperature bath controlled the water vapour pressure. Impedance measurements were performed over frequencies ranging from 1 MHz to 0.01 Hz using a Solartron Frequency Response Analyser 1255 in combination with a Solartron Electrochemical Interface 1287. An excitation voltage of 10 mV (rms) was used to ensure that measurements were performed in the linear regime. The impedance data was analysed using the computer program Equivalent Circuit 0. The dc polarisation of the nickel pattern electrodes was studied using a Solartron Electrochemical Interface 1287 for potentiostatic control. Overpotentials were corrected for the uncompensated resistance of the electrolyte, the value of which was evaluated from data of impedance spectroscopy. After heating the electrode to 850C in a hydrogen atmosphere with 2.3% water vapour the following experiments were conducted. Impedance measurements under standard conditions until reproducibility of the data was obtained. I- measurements under standard conditions. Prior to measurement the work electrode was anodically biased at 500 mV for 30 min. After this the I- curve was recorded by decreasing the potential stepwise in cathodic direction. Impedance measurements under standard conditions. Next a number of electrodes were subjected to one or more of the following experiments: Impedance measurements as a function of pH2 and pH2O. These were performed in the pH2 range of 9.98104 4.95103 Pa with pH2O fixed at 2.33103 Pa and a total gas flow of 100 mlmin-1. By increasing the total flow rate to 150 and 200 mlmin-1 the pH2 range was extended in the low pH2 range to 6.67103 2.56103 Pa. In the pH2O-range, measurements were performed from 6.03102 3.08104 Pa fixing pH2 8.11104 Pa. Helium was used as the balancing gas. Impedance measurements under standard conditions, the electrode being anodically polarised at 50, 100, 150, 200, 250, 300, 400 and 500 mV relative to the reference electrode. Potential values given here are not corrected for the ohmic IR drop of the electrolyte.
39
(a) (b) Figure 3.3: SEM micrographs of nickel pattern electrodes (a) after wet chemical etching and (b) after completing the electrochemical experiments on the electrode.
Impedance measurements as a function of temperature. These were performed at standard conditions by decreasing the temperature from 850 to 600C. Between these experiments impedance spectroscopy was applied under standard conditions to check the change in performance of the nickel pattern electrodes with time. 3.3 Results
3.3.1 Microstructure Examples of SEM pictures of nickel pattern electrodes, after wet-chemical etching of the nickel layer (before anneal at 1000C; see experimental section) and after cell evaluation, are given in Figure 3.3. Figure 3.5 shows a typical height pattern of the nickel stripes obtained after carrying out the etching procedure. As seen from Figure 3.3.a, etching leads to irregularly shaped edges of the nickel layer. Figure 3.3.b shows that annealing at 1000C smoothens out its boundary with the stabilised zirconia, but it also causes grain growth of nickel. Additional annealing experiments demonstrated that this grain growth starts at temperatures between 500 - 700C.
40
3.3 Results
Grain growth clearly affects the perimeter of the nickel stripes. SEM pictures with a different magnification were used to quantify the microstructure of the nickel electrodes. Using a relatively small magnification (<500x) both nickel and YSZ line width was measured. This data was used to calculate the surface coverage of the nickel pattern. Figure 3.5: Typical height pattern of the nickel stripes as observed after the lithographic process. SEM pictures with a larger magnification (>750x) were transformed into black and white images to measure the effect of grain growth on the nickel perimeter. Data based on mask-dimensions together with experimental data from image analysis, before (after the anneal at 1000C; see experimental section) and after cell evaluation, are listed in Table 3.1 and Table 3.2. These results indicate that there is some difference between the expected and the measured line width for the nickel and YSZ stripes. This may be caused by under-etching, meaning that etching does not only occur in a direction perpendicular to the electrode surface, but also parallel to it (i.e. under the photoresist mask). Another reason is sintering of nickel during annealing at 1000C for 1 h, prior to experiments and in the course of these experiments. For most of the electrodes it is observed that the nickel stripe width decreases and, as a consequence, the YSZ stripe width increases during cell evaluation. Compared with the structure before sintering, grain growth increases the nickel perimeter observable to SEM with values between 10-23%. The difference in nickel perimeter before and after cell evaluation is, however, small and within experimental error. Even though the width of the nickel stripes during the experiments decreases due to sintering, this no longer influences the apparent nickel perimeter. Table 3.3 shows results of image analysis on the 25 grain size and the grain boundary length of nickel. The nickel grain Before cell evaluation After cell evaluation 20 size has increased for all samples during cell evaluation. On average 15 this increase is from 8.5 m2 to 2 12.5 m . The grain boundary length has decreased. The scatter 10 in the average grain size, especially that measured before cell 5 evaluation, indicates that it is not homogeneous all over the surface. 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42more A graphic representation of the 2 nickel particle size (m ) particle size distribution measured before and after cell evaluation is Figure 3.4: Nickel grain size before and after cell evaluation for all nickel pattern electrodes. Data is given in Figure 3.4.
% nickel particles
obtained from image analysis.
41
Maska Line width Sample Litho-a Litho-b Litho-c Litho-d Litho-e Litho-f Ni (m) 25 10 20 75 15 50 YSZ (m) 25 10 20 75 15 50 Ni perimeter (m/cm2) 3.9 9.6 4.9 1.4 6.4 2.0
Image Small Magnificationb Line width Ni (m) 22.8 9.0 16.3 73.7 9.4 48.8 YSZ (m) 26.2 10.6 23.5 75.7 20.9 49.5 Nickel coverage (%) 46.5 45.9 41.0 49.4 31.0 49.7
Image Large Magnificationc Nickel perimeter straight (m/cm2) 4.1 9.7 4.9 1.4 6.6 2.1 effect grains (m/cm2) 4.9 10.7 5.4 1.6 7.8 2.5
Table 3.1: Results from image analysis on the nickel pattern electrodes before the electrochemical experiments. aLine width and nickel perimeter as expected based on the used mask; bQuantitative values based on SEM image with relative small magnification, nickel coverage calculated from the measured line width and the used pattern; cQuantitative values based on SEM images with relative large magnification where the nickel perimeter is based on image analysis of SEM micrographs. The difference between straight and effect grains indicates the effect of grain growth on the actual nickel perimeter compared with original nickel pattern (average values are given from data of three SEM pictures).
Maska Line width Sample Litho-a Litho-b Litho-c Litho-d Litho-e Litho-f Ni (m) 25 10 20 75 15 50 YSZ (m) 25 10 20 75 15 50 Ni perimeter (m/cm2) 3.9 9.6 4.9 1.4 6.4 2.0
Image Small Magnificationb Line width Ni (m) 22.8 7.1 13.2 73.0 7.0 48.7
d
Image Small Magnificationc Nickel perimeter straight (m/cm2) 3.8 9.7 5.1 1.3 6.1 2.0
d
Nickel coverage (%) 45.1 36.4 39.5 48.4 23.0 48.9

d
YSZ (m) 27.8 12.4 26.3 77.8 23.5 50.9

d
effect grains (m/cm2) 4.5 11.3 5.7d 1.6 7.2 2.3
Table 3.2: Results from image analysis on the nickel pattern electrodes after the electrochemical experiments. aLine width and nickel perimeter as expected based on the used mask; bQuantitative values based on SEM image with relative small magnification, nickel coverage calculated from the measured line width and the used pattern; cQuantitative values based on SEM images with relative large magnification where the nickel perimeter is based on image analysis of SEM micrographs. The difference between straight and effect grains indicates the effect of grain growth on the actual nickel perimeter compared with the original nickel pattern (average values are given from data of three SEM pictures). d Part of the electrode came of the electrolyte, values are based on the edge of the sample.
42
3.3 Results
Before experiments Sample Average grain size (m2) Litho-a Litho-b Litho-c Litho-d Litho-e Litho-f all 7.5 6.7 10.0 10.1 5.8 11.2 8.5 Number of measured particles 156 70 80 192 116 69 683 Grain boundary length (m/cm2) 91.5 89.2 73.9 79.0 95.9 69.1 Average grain size (m2) 10.8 11.5 13.2 12.7 10.9 15.0 12.5
After experiments Number of measured particles 78 48 42 84 80 75 407 Grain boundary length (m/cm2) 73.2 75.0 63.7 66.0 76.7 59.8
Table 3.3: Results from image analysis on nickel pattern electrodes before and after electrochemical measurements. Grain size and grain boundary length are given for the surface covered with nickel.
3.3.2 Electrochemical performance 1.1.1.12Impedance Spectroscopy 1.1.1.12.1 Impedance measurements under standard conditions Typical impedance spectra for the pattern electrodes measured under standard conditions at zero bias are given in Figure 3.6. Fitting the data indicated that the quality of the high frequency data was poor, which was confirmed by performing a linear Kronig-Kramers Transform test on the data 0. Only data in the range of 10kHz to 10mHz appeared to be useful. Experimental data in this range could be fitted to the circuit LwRe(R1Q1)(R2Q2)(R3Q3), where L represents an inductance, R a resistance and Q a constant phase element (CPE). The impedance of a CPE is given by ZCPE = 1/Q(i)n, where i is the imaginary unit and the angular frequency. Fitting parameters thus obtained are
100
Litho-a Litho-d Litho-e
50
Imag
0 0 50 100 150 200 250
Real
-50
Figure 3.6: Impedance spectra for different nickel pattern electrodes measured under standard conditions at zero bias.
43

Litho-a L Re R1 Q1 n1 R2 Q2 n2 R3 Q3 n3 Rtot ps
2
Litho-b 3.21E-06
Litho-c 2.28-06 1.73 9.79 4.89E-04 1 71.0 2.95E-04 0.9 20.0 1.15E-02 0.65 100.9 2.34E-05
Litho-d 4.05E-07 1.57 22.3 4.75E-04 1 149 4.86E-04 0.9 64.3 8.53E-03 0.65 235.7 4.14E-05
Litho-e 1.00E-08 1.70 3.15 3.30E-04 1 93.5 1.26E-04 0.9 37.1 8.10E-03 0.65 133.7 6.33E-05
Litho-f 1.00E-08 1.66 30.9 8.61E-04 1 286 6.25E-04 0.9 76.1 2.55E-02 0.65 393.2 2.17E-04
1.76 10.7 5.11E-04 1 71.8 2.95E-04 0.9 23.7 1.01E-02 0.65 106.2 5.40E-05
1.49 19.1 3.56E-04 1 78.4 3.51E-04 0.9 19.1 2.49E-02 0.65 116.7 2.11E-04
Table 3.4: Parameters obtained from fitting the impedance data of different nickel pattern electrodes to the circuit LRe(R1Q1)(R2Q2)(R3Q3). Inductance L in H, resistances R in ; constant phase element (Qn) in secn-1, where n is their exponent value. The ps2 values indicate reliability of the fitting procedure 0. Data of the last impedance measurement of the stabilisation curve after I- measurement is used for analyses.
listed in Table 3.4. Lw is associated with the inductance of the wiring and instruments. The apparent value is probably affected by the poor quality of the experimental data in the high frequency range as mentioned above. Re is the uncompensated electrolyte resistance, for which a value of 1.4 was calculated, assuming a specific conductivity for YSZ of 0.1 1 cm-1 0. As can be seen in Table 3.4, the measured value for each electrode is slightly higher than the calculated value. The reason for this difference is not clear. A small scatter may be introduced by the inaccuracy in determining the exact position of the wire reference electrode, which is wrapped around the electrolyte disc. The remainder of the equivalent circuit describes the electrode response. To enable a more meaningful comparison of data obtained for the different electrodes, the values of the frequency powers n1, n2 and n3 were fixed to 1, 0.9 and 0.65, respectively. The electrode response is dominated by arc (R2Q2), contributing more than 60-70% to the total electrode resistance. Q1 and Q2 are of the same order of magnitude, Q3 is substantially higher (see Table 3.4). Impedance measurements as function of pH2 and pH2O 1.1.1.12.2 For the electrode Litho-c impedance spectra were recorded as function of pH2 and pH2O. Conductivity data are graphically represented in Figure 3.7 and Figure 3.8. These were calculated from i = 1/(ARi), where A equals the area of the work electrode (1.54 cm2) and Ri is the value of the resistance obtained from the fitting procedure with the aid of the same circuit as mentioned above. The order of i with respect to pH2 and pH2O is indicated in the figures, it should be noted that these values do not represent reaction orders. Note that the order for 2 depends on both the applied pH2 and pH2O ranges. The electrolyte conductivity should be invariant with pH2 and pH2O, as observed. Q-values obtained from the
44
3.3 Results
fitting procedure are plotted as function of pH2 and pH2O in Figure 3.9 and Figure 3.10, respectively.
45
1 e 1 0 -0.001 2 3 tot
log i ( cm )
-1 -2
-1 -0.44
-0.54 -0.42 -0.016
-2
-0.25
-3 3.0 3.5 4.0 4.5 5.0 5.5 6.0
log pH2 (Pa)
Figure 3.7: pH2 dependence of the conductivities obtained from analysis of impedance data at zero bias for Litho-c measured at pH2O = 2.3103 Pa and T = 850C.
e 1 0 2 3 tot -0.006 0.49 0.61
log i ( cm )
-1 -2
-1 0.091 0.067 -2 0.35
-3 2.0 2.5 3.0 3.5 4.0 4.5 5.0
log pH2O (Pa)
Figure 3.8: pH2O dependence of the conductivities obtained from analysis of impedance data at zero bias for Litho-c measured at pH2 = 8.1104 Pa and T = 850C.
46
3.3 Results
0 Q1 Q2 Q3
-1
n -1 log Q (sec )
-2
-3
-4 3.0 3.5 4.0 4.5 5.0 5.5
log pH2 (Pa)
Figure 3.9: pH2 dependence of the Q values of the CPE elements obtained from analysis of impedance data at zero bias, where n values were fixed to n1 = 1, n2 = 0.9, n3 = 0.65. Data is given for Litho-c measured at pH2O = 2.3103 Pa and T = 850C.
-1 Q1 Q2 Q3
n -1 log Q (sec )
-2
-3
-4 2.0 2.5 3.0 3.5 4.0 4.5 5.0
log pH2O (Pa)
Figure 3.10: pH2O dependence of the Q values of the CPE elements obtained from analysis of impedance data at zero bias, where n values were fixed to n1 = 1, n2 = 0.9, n3 = 0.65. Data is given for Litho-c measured at pH2 = 8.1104 Pa and T = 850C.
47
60 50
20
15
40 30
10
Imag
20 10 0 0 -10 -20 20 40 60 80 100 120
Imag
5 0 0 5 10 15 20 25 30
Real
-5
Real
= 0 mV
3
= 93 mV
0.6
0.4
Imag
0.2 Im ag
0 1 2 3 4 5 6
0.0 1.50
1.75
2.00 Real
2.25
2.50
Real
-1
-0.2
= 194 mV = 250 mV Figure 3.11: Survey of impedance spectra measured at different overvoltages, measured under standard conditions.
1.1.1.12.3 Impedance measurements under bias Typical impedance data recorded under anodic polarisation is given in Figure 3.11 from which can be noted that the shape of the spectrum is greatly influenced by the magnitude of the applied bias. In some regions an inductive loop is apparent at low frequencies, while it is not in others. In principle, the appearance of an inductive loop in the spectra can be accounted for by assigning negative values to the appropriate R and Q in the equivalent circuit. Since the spectra recorded over the applied bias range could not be fitted with one unique circuit at each bias value, these fit results are not presented here. Note from Figure 3.11 that the dc resistance decreases with increasing potential value. Such behaviour is consistent with an activated electrode process. 1.1.1.12.4 Impedance measurements as function of temperature The Arrhenius plots of the electrolyte and total electrode conductivity are given in Figure 3.12. The activation energies are 81 kJmol-1 and 155 kJmol-1, respectively. 1.1.1.13I- measurements under standard conditions Tafel plots for the nickel pattern electrodes measured under standard conditions are given in Figure 3.13. A knee in the curve occurs at 200 mV, a phenomenon which splits the cathodic branch in two regions with different Tafel slopes. The apparent transfer coefficient c decreases from roughly a value of 1.5 at low overpotentials to 0.5 at high overpotentials, as indicated in the figure. Opposite behaviour is found for the anodic branch where evaluation yields a transfer coefficient a changing from about 1.5 to 2.5 at increasingly
48
3.3 Results
Electrolyte Electrode
-2
-1 ln 1/Ri ( )
-4
81 kJ/mol
-6
-8
-10
155 kJ/mol
-12 0.8 0.9 1.0 1.1 1.2 1.3 1.4
1000/T (1/K)
Figure 3.12: Temperature dependence of electrolyte and total electrode conductivity for electrode Litho-f measured under pH2 = 9.98104 Pa and pH2O = 2.3103 Pa.
log I (mA cm )
-2
0.5 1.5 1.5
2.5
-1
-2
-3
Litho-b Litho-c Litho-d Litho-e Litho-f
-4 -600
-400
-200
200
400
(mV)
Figure 3.13: Tafel plots for the different electrodes showing anodic and cathodic branches. Data measured under standard conditions.
49

200 180 160 140 120 180 160 140 120
Impedance pH2 Impedance pH2O I- Impedance anodic polarised
Rtot ()
Rtot ()
100 80 60
100 80 60 40 20 0 0 20 40 60 80 100 120 140 160 180 200
I- measurements
40 20 0 0 20 40 60 80 100 120 140 160 180 200 220
Time (h)
Time (h)
(a) (b) Figure 3.14: Total electrode resistance as function of time. Data obtained from analysis of impedance data for sample (a) Litho-e and (b) Litho-c measured under standard conditions.
high overpotential. Determination of the -values is ambiguous, as linear regions of the Tafel slopes are difficult to identify. Therefore, care must be taken in using these values in interpretating the reaction mechanism. 1.1.1.14Electrode stability The total electrode resistance as a function of time for electrode Litho-e is given in Figure 3.14.a. Data was obtained from impedance measurements under standard conditions, but this was interrupted for the time needed to acquire data from I- measurements as indicated in the figure. About 100 h are needed to attain a steady performance. The I- measurements also have a large influence on the apparent resistance value. After these measurements a certain time is again required before a steady resistance is established. Figure 3.14.b shows data obtained for electrode Litho-c, which has been subjected to different types of electrochemical measurements. The general behaviour is similar to that observed in Figure 3.14.a, in a sense that each type of measurement affects the momentary value of the electrode resistance. This is most pronounced if the electrode is anodically polarised for longer times (about 4 h) as with the impedance measurements under anodic bias. Within approximately 40 h of measurement this change in performance appeared to be irreversible. Similar observations were made for other pattern electrodes. 3.4 Discussion
3.4.1 Relationship of electrode performance with microstructure Despite the grain growth that happens during the course of the electrochemical experiments, the patterned nickel layers remained dense and showed good adherence to the YSZ electrolyte. Figure 3.15 shows the total electrode conductivity calculated from data of impedance measurements under standard conditions as a function of the nickel perimeter obtained from image analysis. The conductivity value was taken from the first impedance measurement and after the I- measurements and subsequent stabilisation. The general trend is an increase of the electrode conductivity with an increasing perimeter length of the nickel pattern, which agrees with data on nickel pattern electrodes obtained by Mizusaki et 50
3.4 Discussion
0.014 0.012 0.010 First experiment Last experiment
tot ( -1 cm-2)
0.008 0.006 0.004 0.002 0.000 0 2 4 6 8 10 12

-2
14
16
18
20
Nickel perimeter (m cm )
Figure 3.15: Total electrode conductivity as a function of the measured nickel perimeter. Data were taken from analysis of impedance data measured under standard condition, where the last impedance measurement are taken (for Litho-c the last impedance measurement before additional measurements). The nickel perimeter is obtained from image analysis of the electrode microstructure before and after cell evaluation. Line is given as a guide to the eye.
al. 0. There is, however, significant scatter present in Figure 3.15, which may be due to the fact that the edges of the nickel layer at the boundary with YSZ are not well defined. The shape of the edges changes during the time span of the experiments due to grain-growth. An other reason that could cause scatter is inhomogeneous current collection over the electrode area. From the data as given in Figure 3.15, it is not possible to distinguish if the nickel grain boundary length affects the overall electrode process. The observations mentioned above would suggest that the rate determining process takes place at or in the near proximity of the three-phase-boundary line between nickel, zirconia and the gas phase as has been suggested by others 00. On the other hand, such considerations cannot explain the increase in conductivity observed after anodically biasing the electrode (see section 1.1.1.14). As noted before, image analysis of SEM pictures of the electrode morphology before and after cell evaluation did not reveal a change in the nickel perimeter length. This observation evokes the question whether there are other factors involved in establishing the electrode performance. A possible explanation could be that some electrochemical damage occurs during current passage which, from the present view on the mechanistic basis of the electrode reaction, would lead to an effective broadening of the reaction zone. Clearly more studies are needed to evaluate this effect. 3.4.2 Electrochemical measurements Impedance data from this study indicate that there are several contributions to the overall electrochemical performance of the pattern electrodes. The most important contribution comes from the arc designated as (R2Q2). The associated conductivity is a function of pH2 and pH2O as indicated in Figure 3.7 and Figure 3.8, respectively. As long as the comparison is restricted to similar ranges in pH2 and pH2O, the observed orders are consistent with 51
those observed for the contribution that dominates the impedance of porous nickel electrodes 0. Of special note is that the latter electrodes have a significantly larger length for the perimeter of nickel, up to ~60 m.cm-2. Since the power frequency n2 is close to unity, Q2 acts as an almost ideal capacitance. In principle, its presence can be interpreted in different ways but is not clearly understood. If its contribution originates solely from the Mott-Schottky barrier formed between the nickel layer and zirconia, one would expect a linear relationship between Q2 and the total surface coverage of nickel. On the other hand if its contribution would originate from some charged intermediate adsorbed in the vicinity of the three-phase-boundary, one might expect that the magnitude of Q2 changes linearly with the length of the nickel perimeter. Neither are shown here as large scatter dominated the plots, preventing any conclusion to be drawn. Finally, referring to Figure 3.13, it is stressed that the change in the Tafel slopes at anodic overpotentials beyond approximately 200 mV may originate from the beneficial effect associated with current passage, as was discussed in the previous section. Evidence for this must await further research. 3.4.3 Comparison with data from Mizusaki et al. Results on nickel pattern electrodes similar to those in the present study have been reported by Mizusaki et al. 0000. The major contribution by these authors lies in the analysis of I-E measurements as a function of H2 and H2O partial pressures. A single semi-circle is stated to describe the impedance. A total electrode resistance of 4 kcm2 at 700C, pH2 = 1.65103 Pa and pH2O = 1.0104 Pa is measured for an electrode with a nickel perimeter length of 3.3 m.cm-2. For the sake of comparison, data from this study for an electrode with a perimeter length of 2.9 m.cm-2 is shown in Figure 3.16. This spectrum was recorded at conditions close to those mentioned above (700C, pH2 = 9.98104 Pa and pH2O = 2.3 103 Pa). The fitting procedure indicated that only two arcs could properly describe the data, even 4000 though the spectrum suggests the intuitive appearance of a single 3000 arc. The total electrode resistance is 9.4 kcm2, 2000 a value which is in fair agreement with that ob1000 tained by Mizusaki et al. when differences in the 0 0 1000 2000 3000 4000 5000 6000 experimental conditions Real in both studies are taken -1000 into account. (A value of Figure 3.16: Impedance spectra obtained for nickel pattern elec4.7 kcm2 is calculated trode Litho-f with a nickel perimeter of 2.9 m/cm2, based upon the pH2O measured at 700C under pH2 = 9.98104 Pa and pH2O dependence of the total = 2.3103 Pa. 52
Imag
3.5 Conclusions
electrode resistance as measured for electrode Litho-c at 850C.) Comparing the results of the I- measurements is not straightforward. These were done as a function of the electrode potential E relative to Pt/air in the study by Mizusaki et al. In the present study these were made as a function of the overpotential , i.e. the reference electrode being in equilibrium with the atmosphere imposed to the anode. 3.5 Conclusions
We have shown that, in principle, several mechanistic processes determine the electrochemical performance of nickel pattern electrodes. However, in the range of H2 and H2O partial pressures covered by the experiments one of these is found to be dominant. Variation of the total electrode resistance with microstructure suggests that the performance scales with the available length of the nickel perimeter. Positive effects on the performance may be induced by current passage. Acknowledgement M.W. den Otter and F.J.G. Roesthuis are thanked for preparation of the lithographic samples. References
S.C. Singhal, Status of Solid Oxide Fuel Cell Technology, Proceedings of the 17th Ris International Symposium on Materials Science, High temperature Electrochemistry: Ceramics and Metals, 123-38, 1996. N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. T. Kawada, N. Sakai, J. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Structure and Polarisation Characteristics of Solid Oxide Fuel Cell Anodes, SSI, 40/41, 402-06, 1990. F.P.F. van Berkel, F.H. van Heuveln and J.P.P. Huijsmans, Characterisation of Solid Oxide Fuel Cell Electrodes by Impedance Spectroscopy and I-V Characteristics, Solid State Ionics, 72, 240-47, 1994. S. Primdahl and M. Mogensen, Oxidation of Hydrogen on Ni/Yttria-Stabilized Zirconia Cermet Anodes, J. Electrochem. Soc., 144, 3409-19, 1997. R.J Aaberg, R. Tunold, S. Tjelle, R. degrd, Oxidation of CO and H2 on Ni/YSZ cermet electrodes, pp 511-16 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. C-H Lee, C-H Lee, H-Y Lee and S.M Oh, Microstructure and anodic properties of Ni/YSZ cermets in Solid Oxide Fuel Cells, SSI 98, 39-48, 1997. J. Guindet, C. Roux, and A. Hammou, 'Hydrogen oxidation at the Ni/Zirconia electrode', pp.553-58 in: Proc. of the 2nd Int. Symp. on Solid Oxide Fuel Cells, Athens, Greece, July 2-5, 1991. F.Z. Mohamedi-Boulenouar, J. Guindet and A. Hammou, Influence of Water Vapour on Electrochemical Oxidation of Hydrogen at the Ni/Zirconia Interface, pp 441-50 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. P.A. Osborg, T. Norby, Characterisation of a H2+H2O/Ni/YSZ point electrode system by impedance spectroscopy, pp47-50, in 7th SOFC Workshop, theory and measurement of microscale processes in Solid Oxide Fuel Cells, Wadahl, Norway, 18-20 Jan., 1995. T. Norby, O.J. Velle, H. Leth-Olsen and R. Tunold, 'Reaction resistance in relation to three phase boundary length of Ni/YSZ electrodes', pp.473-78 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. J. Mizusaki, H. Tagawa, T. Saito, K. Kamitani, T. Yamamura, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu and S. Nakagawa, 'Preparation of Nickel pattern electrodes on YSZ and their electrochemical properties in H2-H2O atmospheres'; pp. 533-41 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. J. Mizusaki, H. Tagawa, T. Saito, K. Kamitain, T. Yamamura, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu, S. Nakagawa, K. Hashimoto, Preparation of Nickel Pattern Electrodes on YSZ and Their Electrochemical Properties in H2-H2O Atmospheres, J. Electrochem. Soc., 141, 2129-34, 1994. J. Mizusaki, H. Tagawa, T. Saito, T. Yamamura, K. Kamitani, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu, S. Nakagawa, K. Hashimoto, 'Kinetic studies of the reaction at the nickel pattern electrode on YSZ in H2-H2O atmospheres', Solid State Ionics, 70/71, 52-58, 1994. T. Yamamura, H. Tagawa, T. Saito, J. Mizusaki, K. Kamitani, K. Hirano, S. Ehara, T. Takagi, Y. Hishinuma, H. Sasaki, T. Sogi, Y. Nakamura, K. Hashimoto, Reaction Kinetics at the Nickel Pattern Electrode on YSZ and its dependence on Temperature, Proc. of the 4th Int. Symp. On SOFC-IV, pp 741-49, Yokohama, Japan, 1995. J. Mizusaki, T. Yamamura, H. Yoshitake, H. Tagawa, K. Hirano, S. Ehara, T. Takagi, M. Hishinuma, H. Sasaki, T. Sogi, Y. Nakamura, and K. Hishimoto, Kinetic studies on Ni/YSZ anode reaction of SOFC in H2-H2O atmospheres by
53

the use of Nickel pattern electrodes, pp 363-68 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. B.A. Boukamp, A Nonlinear least squares fit procedure for analysis of immittance data of electrochemical systems, Solid State Ionics, 20, 31-44, 1986. B.A. Boukamp, A linear Kronig-Kramers Transform Test for Immitance Data Validation, J. Electrochem. Soc., 142, 1885-94, 1995. F.P.F. van Berkel, J.P. de Jong, De Relatie tussen de Morfologie en de Electrochemische Eigenschappen van Ni/YSZ Anodematerialen, ECN Internal Report, 2918-GR14,1993. Chapter 4 of this thesis.
54
4 Hydrogen oxidation at porous nickel electrodes on yttria-stabilised zirconia
Abstract The hydrogen oxidation reaction at porous nickel electrodes on yttria-stabilised zirconia is studied using impedance and polarisation measurements as a function of temperature, overpotential, H2 and H2O partial pressures. The microstructure of the nickel electrodes is varied by using a different layer thickness, annealing time and temperature in subsequent E-beam assisted evaporation steps. Image analysis is used to characterise the microstructure. At equilibrium, the impedance diagram is characterised by a single arc even though the fitting procedure indicates that it is overlapping a second, significantly smaller arc. The associated resistance of the dominant arc becomes smaller with increasing anodic polarisation. This observation is consistent with data from steady-state polarisation measurements. The activation energy of the conductivity associated with the dominant arc is 152 kJ mol-1. The electrochemical performance of the prepared nickel electrodes relates to the exposed length of the triple phase boundary. The associated pH2 and pH2O dependencies are different under equilibrium (from impedance), anodic and cathodic polarisation. The observations are discussed in view of a tentative multi-step mechanism formulated for the electrode reaction. The results from this study invalidate a simple description in terms of a Butler-Volmer formalism, based on a single rate determining step. It is expected that a strong variation in the fractional coverage of adsorbed intermediates on either nickel or zirconia surfaces has to be considered. 4.1 Introduction
The porous cermet electrode made of nickel and yttria-stabilised zirconia (Ni/YSZ) is commonly used as anode for SOFC applications [1][2]. Despite numerous studies on the kinetics of oxygen reduction taking place at the SOFC cathode [3][4][5], the fuel oxidation reaction has received much less attention. The kinetics of hydrogen oxidation have been studied to some extent, but still there is no consensus about major details in the reaction mechanism. It is generally accepted that nickel is highly active for H2 oxidation. However, the microstructure of the cermet has a major impact on the electrode performance 55
0[7][8][9][10][11]. Its contribution obscures the interpretation of experimental data and, hence, a correct diagnosis of pathways in the reaction mechanism. The cermet structure is basically required to obtain adhesion and stability when using nickel as the active anode [12]. It may contribute electrochemically by the increased number of active sites in the electrode compared with that of a planar electrode design. The active sites are assumed to be located in the close vicinity of the triple phase boundary, the area where gas phase, electrode and electrolyte meet. However, due to the complicated microstructure of the cermet structure the number of these active sites, which may vary across the volume of the cermet, is very difficult to assess. Furthermore, percolativity of the cermet structure is required to enable gas phase, electronic and ionic transport. As a consequence electrocatalytic effects may be mixed with transport effects. For all these reasons the elucidation of the hydrogen oxidation kinetics on the Ni/YSZ cermet is quite cumbersome. So far only a few studies have been initiated on nickel point [13]00, lithographic porous layer 0 and pattern electrodes [17][18]0[20]0, having less complicated geometries than the cermet electrode. However, mechanisms and essential pathways for the hydrogen oxidation reaction as quoted by the different authors differ considerably. For the results of these studies to be unambiguous, the experiments should have been carried out under standardised conditions. The conditions often vary strongly from experiment to experiment so that comparison of the results obtained is hardly meaningful. In the present study, we concentrate on hydrogen oxidation on porous nickel electrodes. The electrode kinetics are investigated using combined application of impedance and steady-state polarisation measurements under different gas phase conditions. The parameters describing the microstructure of the porous electrode, as obtained from image analysis, are compared with its electrochemical performance. The results are discussed following a classical formulation of the electrode kinetics based on a tentative multi-step mechanism for the hydrogen oxidation reaction. Results are compared with data reported in literature. 4.2 Theory
4.2.1 Reaction scheme The overall hydrogen oxidation reaction,

H2 +
1 2
O2 H 2 O
(4.1)
can be seen to exist of several sequential reaction steps, each of which may be rate determining. To enable discussion of the experimental data from this study, the following scheme for the electrode reaction is postulated: step 1 H 2 + 2 selectrode 2 H ads (4.2)
step 2 step 3 step 4 step 5
x OH O + e + selectrode H ads + OO OH O
+ selectrolyte
OH ads
OH ads
VO
(4.3) (4.4) (4.5) (4.6)
H ads +
H 2 Oads + e + selectrode
H2 Oads H 2 Ogas + selectrolyte
where selectrode and selectrolyte denote vacant sites on the nickel electrode surface and the solid electrolyte surface, respectively. Step 1 describes the dissociative adsorption of hydrogen 56
4.2 Theory
gas molecules on the nickel surface. Charge transfer occurs at the triple phase boundary in both steps 2 and 4, whereas step 3 represents the exchange between protonated ions on the oxygen sublattice and hydroxide ions on the oxide surface. In step 4, these hydroxide ions are again protonated to form adsorbed water molecules. The latter are desorbed from the oxide surface in step 5. The inclusion of step 3, involving the interstitial protons as a mediator in the reaction scheme, was first proposed by Mogensen et al. [22]. This would account for the important role the triple phase boundary perimeter plays in the hydrogen oxidation kinetics on Ni/YSZ anodes observed by many investigators in the field 0[18]. However, there is no direct evidence from experiment for the involvement of the interstitial protons in the reaction kinetics. A plausible mechanism may therefore also be one in which steps 2 and 3 are replaced by x + selectrolyte VO + OH ads + e + selectrode step 2a H ads + OO (4.7) In what follows, the above-described mechanism is used to derive the i- relationship. Basic assumptions made in the derivation are 1) microscopic reversibility, i.e. the sequence of reaction steps for forward and backward reactions are the same, 2) the rate constants are independent of the fractional coverages of surface intermediates on either nickel or stabilised zirconia, 3) adsorption of gases and/or intermediate species can be described by the Langmuir-type isotherm. Hydrogen atoms are adsorbed only on the nickel surface, H2O and OH- adsorb simultaneously and competitively on the electrolyte surface, 4) no steps are bounded by a limited diffusion or migration of species, 5) virtual equilibrium for all steps except the rate limiting step. The rate equations corresponding to steps 1-5 are
step 1 step 2 step 3 step 4 step 5 r1 r2 r3 r4 r5 = = k1 1 H pH 2
2
k 1 H 2
O
k2 H exp 2 fE k2 aOH 1 H exp 2 fE

O
(4.8) (4.9) (4.10) (4.11) (4.12)
= k3 aOH 1 OH H 2O
k3 OH = = k4 H OH exp 4 fE k 4 H2 O 1 H exp 4 fE k5 H 2O k5 pH 2 O 1 OH H2O
where f = F/RT, E the electrode potential, i the symmetry coefficient, is are the fractional coverage of surface species i, and ki and k-i are the specific rate constants for the forward and backward reaction, respectively. The activities of VO and Oox in the electrolyte are taken to be constant. 4.2.2 Langmuir adsorption Assuming that for the dissociative equilibrium of H2 on the nickel surface the Langmuir adsorption isotherm is applicable, the equilibrium constant can be written as
Kads
H
k = 1 = 2 k1 pH 2 (1 eq H)
eq 2
(4.13)
57
provided that k1 and k-1 are independent of the surface coverage of Had adatoms and that only these are adsorbed on the surface. The surface coverage by Had adatoms under (virtual) equilibrium can be written as
eq H =
K ads
pH 2
2 1
1 + Kads pH 2
eq
(4.14)
2
and that of the empty sites

1 H
=
1 1 + Kads pH 2
1 2
(4.15)
Two limiting cases can be considered: At high temperature and/or low hydrogen partial pressure where K ads pH2 2 << 1 , one obtains
eq H pH 2 eq H 1
1 2 1
and
1 H
1
eq
1
(4.16)
At low temperature and/or high hydrogen partial pressure, K ads pH2 2 >> 1 , one obtains
and
1 H

eq
pH 2
12
(4.17)
This treatment may be extended to cover the adsorption of two different species on a surface, for example that of H2O and OH- on the electrolyte surface. 4.2.3 I - relationship To illustrate the procedure to derive the i- relationship the fourth step of the reaction scheme (reaction (1.1)) is taken as rate-determining. Hence all other steps are in virtual equilibrium. Substituting the relevant mass action equations in the corresponding rate expression, we obtain
i = nF k1 k2 k3 ) k4 1 H 1 OH H2 O
pH 2 exp( 3 2 fE k 1 k 2 k 3 k ) nF k4 5 1 H 1 OH H2 O
pH 2 O exp( 1 2 fE k5
(4.18)
with i = nFr and where the symmetry coefficient is taken to be 1/2. The total number of electrons n involved in the reaction is 2. At equilibrium, the net rate is zero, icathodic = ianodic, which yields
i0 = nF k1 k2 k3 eq eq 3 k4 1 eq H
1 OH H 2O
pH 2 exp( 2 fEeq ) k 1 k 2 k 3 k eq eq 1 = nF k4 5 1 eq H
1 OH H 2O
pH 2 O exp( 2 fEeq ) k5 = constant + 1 pH 2 O ln 2f pH 2
(4.19)
where io is the exchange current density. The equilibrium cell voltage is given by
Eeq
(4.20)
The constant collects all forward and backward rate constants. Substitution of Eqs. (1.1) and (1.2) into (1.4), in the absence of contributions to the overpotential due to concentration polarisation, leads to
i = i0 e
3 2
f
e
12 f
(4.21)
58
4.2 Theory
where the overpotential is defined as: = E - Eeq. Hence values of 3/2 and 1/2 are expected for the apparent anodic and cathodic transfer coefficients. Limiting cases are considered for the surface coverages of adsorbed intermediates to derive the dependence of i0 on H2 and H2O partial pressures. To simplify the derivations, the coverage of OH- is assumed to be small under any condition. The limiting cases are: 1. Low surface coverage of adsorbed hydrogen atoms on the nickel, hence 1 H 1 , and low surface coverage of H2O on the electrolyte, hence 1 OH H2 O
1 . Back substitution of Eq. (1.11) into Eq. (4.19) gives (4.22) 2. Low surface coverage of adsorbed hydrogen atoms on the nickel, hence 1 H 1 ,
4
i0 pH2
pH 2 O
and high surface coverage of H2O on the electrolyte

1 OH
OH
<< H2 O
, hence
H2O
pH 2 O 1 . These assumptions lead to
1 4
i0 pH 2
pH 2 O
3. High surface coverage on the nickel, hence 1 H pH 2

i0 pH 2 4 pH 2 O
1 3
12
(4.23) , and low surface coverage
of H2O on the electrolyte, hence 1 OH H2 O

1 . This gives
4
4. High surface coverage on the nickel, hence 1 H pH 2

i0 pH 2
1
12
(4.24) , and high surface cover-
age of H2O on the electrolyte, hence, 1 OH H2O

pH 2 O 1 . This gives (4.25) Looking at the reaction scheme, different rate-determining steps can be proposed. This leads to transfer coefficients and gas phase pressure dependencies of i0 summarised in Table 4.1. The values given in Table 4.1 can be used to compare with experimental results and should give insight in the rate determining step.
4 4
pH 2 O
step a 1 2 3 4 5 0
transfer coefficients c 2 3/2 1 1/2 0 pH2 1 1/4 0 1/4 0 LL pH2O 0 1/4 1/2 3/4 1
gas phase pressure dependence of i0 LH pH2 1 1/4 0 1/4 0 pH2O 0 1/4 -1/2 -1/4 0 pH2 0 -1/4 0 -1/4 0 HL pH2O 0 1/4 1/2 3/4 1 pH2 0 -1/4 0 -1/4 0 HH pH2O 0 1/4 -1/2 -1/4 0
1/2 1 3/2 2
Table 4.1: Anodic and cathodic transfer coefficients and gas phase partial pressure dependencies of the exchange current density io assuming quasi equilibrium for all steps except the rate limiting step. Steps 1-5 refer to sequential steps of the reaction mechanism outlined in the text. Only limiting cases are considered for the surface coverage of adsorbed gases. Notations LL, LH, HL and HH refer to the assumption made in the derivation of either a high or low value for H and H2O . The value of OH is assumed to be small under all conditions.
59

Sample Step 1 Ni-1 Ni-2 Ni-3 Ni-4 350 150 150 150 Step 2 150 150 150 150 Thickness (nm) Step 3 150 150 150 150 Step 4 500 400 500 500 300 Step 5 total 1150 1150 950 950 Annealing conditions 2 h - 1000C 2 h - 1000C 2 h - 1100C 4 h - 1150C
Table 4.2: Thickness of the deposited layer after sequential E-beam evaporation steps during the preparation of the porous nickel electrodes. Intermediate annealing was performed in a 10% H2 - 90% N2 gas mixture at a total flow rate of 100 mlmin-1.
4.3
Experimental
4.3.1 Sample preparation Yttria-stabilised zirconia rods of 25 mm diameter were obtained by uniaxial pressing of Tosoh-Zirconia TZ-8Y powder at 1.5 bar for 1 min, followed by isostatic pressing at 4000 bar for 5 min. These rods were sintered at 1400 C for 5 hours in air. Electrolyte discs of 16.0 mm diameter and 4.0 mm thickness were cut from the sintered rods. A small groove was made around the disc at half thickness for positioning of the reference electrode. Prior to use both sides of the disc were mechanically polished with 320 MESH SiC and 3 m diamond MM and diamond paste (1 m). After polishing the discs were ultrasonically cleaned with ethanol. An Archimedes method was used for determination of their density. Only samples having a density larger than 5.89 gcm-3, corresponding with 99% of the theoretical density, were used for experiments. Porous nickel electrodes (16 mm diameter) were prepared by means of an E-beam evaporation process. To obtain electrodes with different microstructures the following process parameters were varied: the thickness of the evaporated nickel layer, annealing time and temperature between subsequent evaporation steps, the total number of evaporation steps. Process parameters used for the preparation of the different nickel electrodes are listed in Table 4.2. For electrochemical experiments, the counter and reference electrodes were painted on the electrolyte disc with Pt paste (Demetron). The whole assembly was annealed at 1000C for 1 hour under reducing conditions (10%H2 90%N2). The cell geometry is shown sche-
Figure 4.1: Schematic side view of the three-electrode electrochemical cell.
60
4.3 Experimental
matically in Figure 4.1. 4.3.2 Characterisation of the electrode microstructure Before and after the electrochemical experiments SEM (Scanning Electron Microscopy) micrographs of the porous nickel electrodes were made at five different positions on the surface. The pictures obtained were edited to black and white representations, which were transferred into an image analysis system. The results enabled calculation of the total length of the nickel perimeter and the surface coverage by nickel. 4.3.3 Electrochemical characterisation Electrochemical experiments were performed in a single-gas environment at atmospheric pressure. At standard conditions a gas flow of 100mlmin-1 H2 with 2.3% H2O at 850C was used. Brooks 5800E Mass Flow Controllers controlled all gas flows. Passing the gas mixture through two water bubblers controlled the water concentration. The water temperature in these bubblers was controlled with an electric heating/cooling device containing a mixture of ethylene-glycol and water. The second water bubbler was used as a cold trap, fixing the water concentration in the gas to the aqueous vapour pressure over water at the temperature maintained in this bubbler. For all electrochemical measurements helium was used as inert gas. Impedance measurements were performed in the frequency range of 1 MHz to 0.01 Hz using a Solartron Frequency Response Analyser 1255 in combination with a Solartron Electrochemical Interface 1287. An excitation voltage of 10 mV (rms) was used to ensure that measurements were performed in the linear regime. The impedance data was analysed using the computer program Equivalent Circuit [23]. The dc polarisation behaviour of the porous nickel electrodes was studied using a Solartron Electrochemical Interface 1287 for potentiostatic control. The current through the electrochemical cell was measured after reaching steady-state. Overpotentials were corrected for the uncompensated resistance of the electrolyte, the value of which was evaluated from data obtained from impedance spectroscopy. After heating the nickel electrode to 850C in the standard gas mixture, impedance diagrams were recorded. When stable performance was attained, the following series of experiments were conducted. Impedance measurements as a function of pH2 and pH2O. These were performed in the pH2 range from 9.98104 to 4.95103 Pa with pH2O fixed at 2.33103 Pa, and in the pH2O-range from 1.22103 to 2.00104 Pa fixing pH2 at 8.11104 Pa. I- measurements under standard conditions. Prior to measurement the work electrode was anodically biased at 500 mV. Subsequently the I- curve was recorded by decreasing the potential stepwise in the cathodic direction. I- measurements as a function of pH2 and pH2O. These were performed under both cathodic and anodic polarisation. The applied pH2 and pH2O ranges correspond to those listed above. Impedance measurements under standard conditions, the electrode being anodically polarised at 50, 150, 200, 250, 300, 400 and 500 mV relative to the reference elec-
61
(a) (b) Figure 4.2: SEM micrograph a) Ni-1 and b) Ni-3, taken after completing the electrochemical experiments on both electrodes.
trode. Potential values given in this list are not corrected for the ohmic IR drop of the electrolyte. Impedance measurements as a function of temperature. These were performed at standard conditions, decreasing the temperature from 850 to 600C. Between these experiments impedance diagrams were recorded under standard conditions to monitor the performance of the nickel electrode as a function of time. 4.4 Results
4.4.1 Microstructure Examples of SEM pictures, of nickel electrodes having different microstructures, are given in Figure 4.2. Each SEM picture covers an area of 2.5103 m2, which is equivalent to 0.0012% of the total electrode surface area. The results obtained from image analysis before and after electrochemical experiments are given in Table 4.3. For determination of the nickel perimeter only the continuos nickel network is taken into account. The small nickel droplets that are not connected with the network are not expected to be active in the electrode reaction and are therefore not included in the nickel perimeter. Figure 4.3 shows the relationship between the computed nickel perimeter and the nickel coverage. In general, the experiments seem to influence the microstructure in such a way that the nickel perimeter decreases when the nickel coverage increases. No clear relationship is found between the nickel coverage and the nickel perimeter. The effect of the different preparation steps on the electrode microstructure is not clear either.
62
4.4 Results
Nickel perimeter (m/cm2) Before measurements Sample Ni-1 Ni-2 Ni-3 Ni-4 average 59 79 62 56 stdev 2 3 3 4 After measurements average 45 61 52 56 stdev 2 5 6 5
Surface coverage Ni (%) Before measurements Sample Ni-1 Ni-2 Ni-3 Ni-4 average 69 61 68 59 stdev 2 3 2 3 Aftere measurements average 72 65 69 60 stdev 2 2 3 2
Table 4.3: Results from image analysis on the porous nickel electrodes before and after the electrochemical experiments. Average values are given from data taken at five different positions at the surface.
80
70
Ni-1 Ni-3
Ni-1
Ni-3
% Ni coverage
Ni-2 60 Ni-4
Ni-2
50 Before experiments After experiments 40 30 40 50 60 70

2
80
90
nickel perimeter (m/cm )
Figure 4.3: Relationship between the nickel perimeter and the percentage of nickel coverage for different electrodes. Results are given from image analysis before and after electrochemical experiments.
63
4.4.2 Electrochemical performance 1.1.1.15Impedance Spectroscopy Impedance measurements under standard conditions 1.1.1.15.1 Impedance spectra for the porous nickel electrodes measured under standard conditions at zero bias are given in Figure 4.4. Even though these spectra suggest the appearance of a single semicircle, the fitting procedure pointed to a more complex circuit represented by LwRe(R1Q1)(R2Q2). The circuit description code has been adopted from [23]. In this notation L represents an inductance, R a resistance and Q a constant phase element (CPE). The impedance of a CPE is given by ZCPE = 1/Q(i)n, where is the angular frequency and i = -1. The CPE includes two constants, Q and n. If n = -1 the CPE behaves as an inductance with L = Q-1, if n = 0 as a resistance R = Q-1 and if n = 1 as a capacitance with C = Q. Intermediate values of n indicate the degree of non ideal behaviour compared with the idealised capacitor, resistor or inductor with the notion that if n = 1/2 the CPE acts as a Warburg diffusion impedance [24]. Parameters obtained from fitting are listed in Table 4.4, an indication of the quality of the obtained fit is given by the pseudo 2 [23]. Lw is associated with the inductance of the wiring and instruments, and Re represents the uncompensated electrolyte resistance. A value of 1.42 was calculated for Re, assuming a specific conductivity for YSZ of 0.1 1 cm-1 [25]. Table 4.4 shows that the measured values are in good agreement with this calculated value. The small scatter is introduced by the inaccuracy in determining the exact position of the wire reference electrode, which is wrapped around the electrolyte disc. The series combination of (RQ)'s describes the electrode response. The indexing of both arcs is baded on their increasing time constant, RQ, using the magnitude of Q as an ideal capacitance. To enable a more meaningful comparison of data the values of the frequency powers n1 and n2 were fixed to 0.93 and 0.5, respectively. Within the frequency range of 10 mHz to 50 kHz this procedure yielded errors less than 1.5% in both the real and imaginary parts. Similar errors were obtained in data analysis of the impedance diagrams from
10 Ni-1 Ni-2 Ni-3 Ni-4
Imag
0 0 -2 2 4 6 8 10 12 14 16 18
Real
Figure 4.4: Impedance spectra for the different nickel electrodes from this study measured under standard conditions at zero bias.
64
4.4 Results
Ni-1 Lw Re R1 Q1 n1 R2 Q2 n2 Rtot ps
2
Ni-2 5.0E-08 1.59 8.30 1.55E-03 0.93 0.59 2.61E-01 0.5 8.9 3.44E-5
Ni-3 1.9E-07 1.33 12.5 1.86E-03 0.93 1.1 2.62E-01 0.5 13.6 1.59E-5
Ni-4 6.5E-08 1.48 10.5 2.82E-03 0.93 2.5 7.17E-02 0.5 13.0 2.80E-4
2.3E-07 1.32 13.8 1.65E-03 0.93 0.99 6.70E-01 0.5 14.8 2.15E-5
Table 4.4: Parameters obtained from fitting the impedance data of different porous nickel electrodes to the circuit LwRe(R1Q1)(R2Q2). Resistance R in ; inductance L in H; constant phase elements Q in secn-1. The ps2 values indicate the reliability of the fitting procedure [23].
measurements described below. Only in the case of sample Ni-4, listed in Table 4.4, the error was about 3%. 1.1.1.15.2 Impedance measurements as function of pH2 and pH2O Impedance data were obtained as a function of pH2 and pH2O. These were fitted to the equivalent circuit mentioned above. Conductivity data calculated from i = 1/(ARi), where A is the geometric area of the work electrode and Ri the parameter obtained from fitting, are given in Figure 4.5 and Figure 4.6. It should be noted that these gasphase dependencies do not represent the reaction orders. The former shows that 1 is independent of pH2, while 2 shows a pH2-0.8 dependence. From Figure 4.6 it is seen that 1 varies with pH2O0.4 and 2 with pH2O1.1. In both cases the total electrode conductivity, total = 1+2, is dominated by the value of 1. The conductivity of the electrolyte is found to be independent of pH2 and pH2O, as was expected. The CPE parameters Qi and ni are of a similar magnitude as those listed in Table 4.4. A survey of the pH2 and pH2O dependence of the total electrode conductivity for all nickel electrodes from this study is given in Table 4.5. Impedance measurements under bias 1.1.1.15.3 Typical impedance data obtained under anodic polarisaOrder dep of tot tion are given in Figure 4.7. Polarisation values indiSample pH2 pH2O cated in this figure have been corrected for the ohmic drop of the electrolyte. At high overpotential Ni-1 -0.06 0.43 ( > 100mV), the small semicircle on the low frequency Ni-2 0.02 0.40 side disappears and an inductive loop appears. For very Ni-3 -0.12 0.46 high overpotentials another semicircle appears on the Ni-4 -0.07 0.48 low frequency side. Parameters obtained from the fitting Table 4.5: Order of gas phase procedure are listed in Table 4.6. Where pressure dependence of the total electrode conductivity. Results LwRe(R1Q1)(R2Q2)(R3Q3)(R4Q4) was used to take all apfrom impedance measurements pearing semicircles into account.
at zero bias on different porous nickel electrodes.
65
1 -0.8 e 1 2 tot -0.01
log ( cm )
-1 -2
-1 -0.03
-2 3.5 4.0 4.5 5.0 5.5
log (pH2) (Pa)
Figure 4.5: pH2 dependence of the conductivities obtained from analysis of impedance data at zero bias for sample Ni-1 measured at pH2O = 2.3105 Pa and T = 850C.
e 1 2 tot 1.1
log ( cm )
-2
0 0.002
-1
-1
0.4
-2
log pH2O (Pa)
Figure 4.6: pH2O dependence of the conductivities obtained from analysis of impedance data at zero bias for sample Ni-1 measured at pH2 = 8.1104 Pa and T = 850C.
66
4.4 Results
6
2
Imag
Imag
2
0 0 1 2 3 4 5 6 7 8
0 0 2 4 6 8 10 12 14
-1
Real
Real
-2
-2
= 0 mV
0.75
0.4
= 83 mV
0.3
0.50
0.25
0.2
Imag
1.0 -0.25
1.5
2.0
2.5
3.0
Imag
0.00
0.1
Real
0.0 1.0 -0.1 1.5 2.0
Real
-0.50
-0.2
-0.75
-0.3
-1.00
= 190 mV = 245 mV Figure 4.7: Impedance spectra for Ni-1 electrode measured at standard conditions at different values for the anodic polarisation.
Anodic polarisation 0 L Re R1 Q1 n1 R2 Q2 n2 R3 Q3 n3 R4 Q4 n4 Rtot ps2 12.62 1.32E-5 10.81 2.47E-5 7.10 8.24E-5 3.97 8.06E-5 2.56 2.60E-5 1.55 3.58E-5 1.03 3.12E-5 0.57 5.07E-5 2.54E-7 1.29 11.7 1.74E-3 0.93 0.92 0.404 0.50 43 2.22E-7 1.32 10.2 1.51E-3 0.93 0.61 0.639 0.5 -0.24 -0.337 1.0 -0.23 -9.11 0.94 -0.17 -6.31 0.56 -0.48 -0.103 0.60 -0.42 -0.139 0.58 -0.30 -0.300 0.59 -0.40 -0.339 0.50 0.077 140 1.00 0.42 5.57E-5 83 1.97E-7 1.33 7.34 1.41E-3 0.93 118 2.29E-7 1.29 4.20 1.66E-3 0.90 146 2.40E-7 1.28 2.73 2.16E-3 0.86 170 2.69E-7 1.25 2.03 4.01E-3 0.77 190 2.55E-7 1.24 1.45 5.20E-3 0.74 221 2.25E-7 1.21 0.87 7.08E-3 0.70 245 1.97E-7 1.22 0.74 4.77E-3 0.71
Table 4.6: Parameters obtained from fitting the impedance data for sample Ni-1 obtained at different values for the anodic polarisation to the circuit LRe(R1Q1)(R2Q2)(R3Q3)(R4Q4). Resistance R in ; inductance L in H, constant phase elements (Qn) in secn-1. The ps2 values indicate reliability of the fitting procedure [23].
67
The inductive loop could 25 be accounted for by asR R signing negative values to 20 R parameters R3 and Q3. R R 15 Contrary to the impedance diagrams of the different 10 electrodes under equilibrium ( = 0 mV) it was 5 not possible to fix the values of n over the entire 0 0 50 100 150 200 250 300 range in overpotential. (mV) -5 Figure 4.8 shows that the magnitude of R1 decreases Figure 4.8: Resistance values as a function of anodic overpotensignificantly under anodic tial. Data derived from analysis of impedance spectra polarisation. R2 shows a for sample Ni-1 measured at standard conditions. small decrease and vanishes above = 50 mV. The value of R3 is relatively small, showing no clear dependence of overpotential. Impedance measurements as function of temperature 1.1.1.15.4 The Arrhenius plots of the electrolyte and total electrode conductivity total are given in Figure 4.9. The activation energies are 82 kJmol-1 and 152 kJmol-1, respectively.
e 1 2 3 4
1.1.1.16I- measurements 1.1.1.16.1 I- measurements under standard conditions Tafel representations of the I- measurements, performed under standard conditions for the different nickel electrodes, are given in Figure 4.10. The use of Tafelplots is justified by the observed impedance spectra, which are domi2 nated by one process. The Electrolyte Tafel slopes, in both ano0 Electrode dic and cathodic directions, slightly diverge with -2 increasing overpotential. 82 kJ/mol -4 Because of the thick electrolyte disc used in the -6 experiments, a large IRe correction had to be made. -8 152 kJ/mol The slope of the log i versus at a given value of -10 0.8 1.0 1.2 1.4 was calculated from the 1000/T (1/K) first
ln i ()
Figure 4.9: Temperature dependence of electrolyte and total electrode conductivity for electrode Ni-1 measured at standard conditions.
68
R ( cm )
-1 -2
4.4 Results
log (i) (mA cm )
-2
3/2 1/2
-1 Ni-1 Ni-2 Ni-3 Ni-4
-2
-3 -500
-400
-300
-200
-100
100
200
300
(mV)
Figure 4.10: Tafel plots for the different electrodes showing anodic and cathodic branches. Data measured at standard conditions.
2.0
1.5
1.0
0.5
0.0 -400
-300
-200
-100
100
200
300
(mV)
Figure 4.11: Apparent transfer coefficient as a function of overpotential calculated from the first derivative of the curve shown in Figure 1.10.
Sample
From impedance measurements a
From i- measurements a 1.4 1.7 1.4 1.9 c 0.8 0.7 0.5 0.5
Ni-1 Ni-2 Ni-3 Ni-4
1.4 1.7 1.4 1.9
Table 4.7: Estimated values for the apparant charge transfer coefficients from impedance (under anodic polarisation) and i - measurements for the different nickel porous electrodes.
69
derivative of a polynomial fit to the experimental data. The values normalised to (F/2.3RT) are plotted as a function of the overpotential in Figure 4.11, where no constant Tafel slopes are observed in both directions. Instead the slope at a given decreases with increasing overpotential. The values obtained from extrapolation to high overpotential are listed in Table 4.7, which are taken to represent the apparent transfer coefficients a and c. I- measurements as function of pH2 and pH2O 1.1.1.16.2 The pH2 and pH2O dependencies of the current were measured under both cathodic and anodic polarisation. The anodic current as a function of log (pH2), at overpotentials 150, 200 and 250 mV, is given in Figure 4.12. At the lowest of these values, = 150 mV, the current is proportional to pH20.25. At higher overpotentials this apparent proportionality breaks down in the applied pH2 range. That is, the functional dependence fitting the data at high pH2 values is pH2-0.39, while at low pH2 the current turns out to be independent of pH2. The cathodic current at different overpotentials as a function of log (pH2) is given in Figure 4.13. In every case a linear behaviour is found, corresponding to a pH20.18 dependence at = 100 mV which increases up to pH20.27 at = 400 mV. A similar procedure was used to extract information about the pH2O dependence of the current under both anodic and cathodic polarisation. Corresponding results are given in Figure 4.14 and Figure 4.15. Results from both type of experiments are compiled in Table 4.8. 1.1.1.17Electrode stability Impedance measurements under standard conditions were conducted after every ac or dc type of experiment in order to monitor the performance of the electrode as a function of time. A typical example of the total electrode resistance as a function of time is given in Figure 4.16. It is seen that the resistance increases with time during the first 30 hours, after which it tends to stabilise. Each type of measurement seems to have some impact on the apparent electrode resistance, albeit that the time required before reaching a stable performance is longest at the start of a series of experiments. 4.5 Discussion
4.5.1 Reaction mechanism 1.1.1.18Impedance measurements The results from impedance measurements indicate that, under most of the conditions covered by our experiments, the electrode process is mainly governed by the rate of a single process. Even though the equivalent circuit used in the fitting procedure suggests that the overall electrode reaction is composed of two serial steps, it is the high-frequency semicircle that dominates the complex impedance. The electrode resistance R1 associated with this semicircle, and therefore the significance of this process to the overall electrode response, decreases under anodic polarisation. As can be deduced from Figure 4.8, R1 decreases almost exponentially with overpotential , which is in accord with a Tafel behaviour for the
70
4.5 Discussion
2.2
Anodic
2.0 -0.03
log (i) (mA cm )
-2
1.8
-0.15 -0.39
1.6 -0.35 1.4 = 150 mV = 200 mV = 250 mV
1.2
-0.25
1.0 3 4 5 6
log pH2 ( Pa)
Figure 4.12: pH2 dependence of current i at selected values for the anodic overpotential . Data for sample Ni-1 measured at pH2O = 2.3105 Pa and T = 850C.
3 = -200 mV = -300 mV = -400 mV
Cathodic
log (i) (mA cm )
-2
2 0.27 0.19 1 0.18
0 3 4 5 6
log pH2 ( Pa)
Figure 4.13: pH2 dependence of current i at selected values for the cathodic overpotential . Data for sample Ni-1 measured at pH2O = 2.3105 Pa and T = 850C.
71
3 = 150 mV = 200 mV = 250 mV
0.27 0.38
log (i) (mA cm )
-2
2 0.74 0.69 1 0.66
0.43
Anodic
0 2 3 4 5
log pH2O ( Pa)
Figure 4.14: pH2O dependence of current i at selected values for the anodic overpotential . Data for sample Ni-1 measured at pH2 = 8.1104 Pa and T = 850C.
3 = -200 mV = -300 mV = -400 mV 2 0.16 0.26 1 0.20
log (i) (mA cm )
-2
Cathodic
0 2 3 4 5
log pH2O ( Pa)
Figure 4.15: pH2O dependence of current i at selected values for the cathodic overpotential . Data for sample Ni-1 measured at pH2 = 8.1104 and T = 850C.
72
4.5 Discussion
anodic Low pH2 low high pH2O low high -0.25 -0.25 0.66 0.43 high -0.03 -0.39 0.74 0.27
cathodic low 0.18 0.18 0.20 0.20 high 0.27 0.27 0.16 0.16
Table 4.8: Observed order of the pH2 and pH2O dependence of the current under both anodic and cathodic polarisation. Note that the order is different in distinct regimes of the H2 and H2O partial pressures and overpotential .
15
10
Impedance pH2 & pH2O
I- (pH2)
Impedance (anodic pol.) I- (pH2O)
Relectrode ()
I- standard
0 0 20 40 60 80 100 120 140 160 180
time (hours)
Figure 4.16: Total electrode resistance as a function of time. Data obtained from analysis of impedance data for sample Ni-2 measured at standard conditions.
anodic reaction. The transfer coefficient a derived from it is given in Table 4.7. As seen from this table, the values for the different samples derived this way show good agreement with those estimated from the slopes of the corresponding log i versus plots. The impedance diagrams recorded under anodic polarisation ( > 100 mV) are composed of a capacitive loop (R1Q1) followed by a small inductive loop at low frequencies (R3Q3) (Figure 4.7). Similar diagrams have been observed in studies of the passivation behaviour of certain metals [26][27]. The occurrence of the inductive loop may be explained by the presence of intermediate adsorbed species bounded by two consecutive reaction steps. Depending on the potential dependence of the reaction rates, the associated capacitance can be positive or negative, leading in the latter case to an inductive loop. A similar procedure was also exploited by Van Hassel et al. [28][29] in explaining the occurrence of an inductive loop under cathodic polarisation of the Au, O2 (g)/stabilised zirconia interface.
73
The conductivity 1 = 1/R1 is found to vary with pH2O0.5, while no dependence is found on pH2 (see Figure 4.5). This is further discussed below. The parameter 2 = 1/R2, corresponding to the low frequency arc in the impedance diagram appears to be proportional to pH2O1.1. Since the order is close to unity, a possible explanation is the limited rate of desorption/adsorption or diffusion of water from and to the anode surface. At first glance it is conceivable from the observed gas phase pressure dependence of 1 that the resistive process is due to a limited diffusion or reaction involving either protonated oxygens OH inside the zirconia matrix or hydroxyl ions OH-1 at the zirconia surface. If the coverage of adsorbed species on the zirconia surface is considered to be small, their concentrations vary with H2 and H2O partial pressure in agreement with the observed pressure dependencies of 1 (Table 4.1). The observed value for n1 is close to unity, implying that the corresponding CPE element acts almost as a pure capacitance. This points to a slow reaction step which governs the overall electrode reaction, rather than a process limited by diffusion. Considering the five different steps in the postulated reaction scheme, these results may point to step 3 as the rate-determining step (Table 4.1). Even though the impedance data show that one process is dominant within the range of experimental conditions, it is however impossible to deduce conclusive information about the reaction mechanism solely from these data. 1.1.1.19Current-overpotential measurements Analysis of the slopes in the Tafel plots yields approximate values of 3/2 and 1/2 for the apparent anodic and cathodic transfer coefficients (see Table 4.7). As noted before, the observed values for the anodic transfer coefficient are in a good agreement with corresponding values deduced from data of impedance measurements under anodic polarisation. With the symmetry coefficient = 1/2 the above values for the transfer coefficients can only be accounted for if it is assumed that the charge transfer occurs in two subsequent steps. If the electrode kinetics were governed by a chemical reaction one would expect integer values for the apparent anodic and cathodic transfer coefficients a and c (note that we deliberately use the symbol instead of , which we use for elementary reactions). Within experimental error the constraint a + c = 2 is obeyed, suggesting that the stoichiometric number for the rate determining step is unity. If in the proposed mechanism step 4 is taken to be rate determining, then this would be in agreement with the observed transfer coefficients for both the cathodic and anodic reaction (Table 4.1). As outlined in the theoretical section, such a situation leads to distinct gas phase pressure dependencies for the exchange current density i0. None of the limiting cases that is considered in Table 4.1 fits the pressure dependencies observed from impedance data, and thus other factors need to be considered. Possibly a variation in the surface coverages H , OH and H2O needs to be taken into account to explain the discrepancies with experiment. In view of the inaccuracy in the determination of the transfer coefficients, we do not want to exclude either the possibility of step 3 as rate limiting step or that of a chemical reaction involving hydroxyl ions OH- at the zirconia surface.
74
4.5 Discussion
Due to the difficulties in obtaining accurate values for the Tafel slopes the gas phase pressure dependencies of the current i() were measured at various values for the overpotential in both cathodic and anodic directions. Whenever the overall electrode kinetics follow a Butler-Volmer type of relation the pressure dependencies of i() are expected to be similar to those of the exchange current density io. A survey of the experimental results is given in Table 4.8. When this data is compared with the gas phase pressure dependencies from impedance data (at zero overpotential), given in Table 4.5, it is clear that the order dependencies change with the applied overpotential and partial pressures pH2 and pH2O. Moreover, the orders are different for the cathodic and anodic directions. One might think that the rate limiting steps for the cathodic and anodic reactions are different, but this would violate the principle of microscopic reversibility. According to this principle the forward and backward reactions at or near equilibrium must be the same. From the results we are inclined to believe that the overall electrode kinetics are strongly influenced by the impact of the overpotential on the surface coverages H , OH and H2O . In this respect it may be noted that the impedance data under anodic polarisation gives no direct evidence of a sudden change in mechanism under the conditions covered by experiment. However, impedance spectroscopy is essentially unable to resolve two consecutive processes that have nearly equal characteristic times. Accordingly the concentration of one or more of the surface intermediates bounded by these processes, will strongly vary in the course of a potential variation whenever their rates are a function of the applied overpotential . Quantitative modelling of the experimental data from this study allowing for potential variations in the concentration of surface intermediates must await further study. 4.5.2 Relationship of the microstructure with electrode conductivity Image analysis of the nickel electrodes, before and after the electrochemical measurements, indicates that significant changes in the microstructure have occurred during the measurements (see Figure 4.3). Figure 4.16 shows that the total electrode resistance increases sharply during the first 30 hours of measurement, after which it tends to become constant with time. It seems obvious to attribute the change in the magnitude of the resistance to the change in microstructure. Figure 4.17 shows, for all electrodes in this study, the total electrode conductivity derived from the first impedance measurement, plotted against the nickel perimeter derived from image analysis of their initial microstructure together with that derived from the last impedance measurement against the nickel perimeter of the final microstructure. While the former data are scattered, significantly less spread is found in the latter case where the data points are more confined to the expected linear line. The conductivity increases with the increasing nickel perimeter, indicating that the accessibility of the TPB area is an important parameter for the performance of the porous nickel electrode. This observation agrees with earlier reported results in literature for nickel pattern electrodes 0[18]. 4.5.3 Comparison with literature The results presented in this study can be compared with data from measurements on similar nickel electrodes by Norby et al. 0. These authors noted two semi-circles in the im75
0.20 First experiment Last experiment 0.15
tot (1cm-2)
0.10
0.05
0.00 30 40 50 60 70
2
80
90
Nickel perimeter (m/cm )
Figure 4.17: Total electrode resistance as a function of the nickel perimeter. Data were taken from analysis of impedance data measured at standard conditions. The nickel perimeter resulted from image analysis of the electrode microstructure. The resistance derived from the first impedance measurement is plotted against the nickel perimeter before, and that of the last impedance measurements against the nickel perimeter obtained after finishing the series of electrochemical experiments indicated.
pedance diagrams, which could be fitted to the equivalent circuit LR0(RctQdl)(RrQr). Measurements were carried out at different conditions (pH2 = 120 Pa, pH2O = 630 Pa, 900C), this complicates direct comparison of their results with those obtained from the present study. The resistance associated with the high frequency semicircle Rct varied approximately with pH2O-0.5 and was found to be linearly related with the TPB length. These observations fully match the results from the present study. For an electrode specimen having a total TPB length of 120 m Norby et al. measured a value of 1.6 for Rct. For sample Ni2 with a TBP length of 121 m we measured under conditions closest to those employed by Norby et al. a value of 4.4 for R1. This value was measured at pH2 = 8104 Pa, pH2O = 2104 Pa and 850C. The similarity is excellent when the difference in temperature applied in both studies is taken into account. Using the activation energy of 160 kJ.mol-1 from this study, a value of 2.1 at 900C is calculated. Norby et al. attributed the high-frequency semicircle to the charge transfer resistance shunted by the double layer capacitance. The low frequency semicircle was ascribed to a reaction resistance Rr and associated surface coverage of adsorbed species Qr. Due to the different experimental conditions in the study by Norby et al., it is not entirely clear whether this semicircle ought to be compared with the small semicircle at the low frequency side found in the present work. Mizusaki and co-workers [17][18][20]0 have done a series of studies on nickel pattern electrodes on yttria-stabilized single crystals. This approach enables a good control of the value of the total TPB length per cm2, a value which is about a factor 10 smaller than the value estimated for the porous nickel electrodes in this study. The impedance spectrum of 76
4.5 Discussion
the nickel pattern electrode is governed by a single semicircle, which resembles, except for the small low frequency arc, the spectra found for the porous nickel electrodes. The total electrode resistance is in the range 1.0104 - 1.3104 .m (1.0 - 1.25 m TPB length, 700C, pH2 = 1.0104 Pa, pH2O = 1.65103 Pa) to be compared with 1.3104 - 1.9104 m (90 121 m TPB length, 700C, pH2 = 1.0105 Pa, pH2O = 2.3103 Pa) for the porous nickel electrodes in this study. The above ranges take into account the difference in the TPB length of both type of nickel electrodes. Several studies carried out by different authors have stressed the importance of the TPB length in the overall kinetics of the hydrogen oxidation reaction on Ni/YSZ electrodes 0[18]. The electrode resistance is expected to vary inversely proportional to the TPB. This behavior holds over a wide range in TPB length, as described elsewhere in this thesis where the results from different type of electrodes used are compared (Chapter 9). Expressions for the current i, for H2 to H2O oxidation on nickel pattern electrodes have been, presented by Mizusaki et al. 0. As these expressions were derived from experiments in which not the overpotential but rather the potential E was fixed (relative to Pt/air), comparison of the results obtained with those from the present study is not straightforward. The following rate expression was obtained by Mizusaki et al. from current measurements under anodic and cathodic polarization,
i = k f pH2 e 2 fE kb pH 2O1/ 2 e fE (4.26)
The observed transfer coefficients a = 2 and c = 1 differ from the values a = 3/2 and c = 1/2 found in this study. Equation (4.26) clearly contradicts the concept of a single ratedetermining step as the reaction orders for both anodic and cathodic reaction are different. Hence this equation cannot be valid at conditions near to equilibrium ( 0), where the principle of microscopic reversibility must apply. Since, by definition, = E - Eeq, one gets upon substitution, i = k f pH2 e
2 fEeq
2 f E Eeq
kb pH 2O1/ 2e
' kb pH 2 1/ 2
fEeq
f E Eeq
= k 'f pH2O e2 f
e f
(4.27)
where additional use is made of the exponential form of the Nernst equation (Eq. (4.20)). The meaning of the forward and backward rate constants kf and kb have slightly altered from that given in Eq. (4.26), as indicated by the prime notation. The values for the pH2 and pH2O dependencies indicated in Eq. (4.27) may be compared with those given in Table 4.8. The obvious reason for the moderate agreement obtained is the difference in the experimental approaches in both studies as outlined above. Another difficulty lies in identifying linear Tafel regions in log (i) versus plots for both the cathodic and anodic reactions, which affects the pH2 and pH2O dependencies obtained in Eq. (4.27). The important feature observed in both studies is the changing gas phase pressure dependencies with applied (over-) potential. Mizusaki and co-workers [20] proposed another rate expression for the cathodic current under high polarisation values. All these results seem to support the conclusion drawn in the previous section that the electrode kinetics cannot be interpreted in terms of a single rate-determining step.
77
4.6
Concluding remarks
The assumptions generally made in treating multi-step electrode kinetics are that one step is rate determining and that the steps before and afterward are in virtual equilibrium. The results from this study put evidence forward that such a simple description does not hold for the hydrogen oxidation reaction at porous nickel electrodes on stabilised zirconia. The observed H2 and H2O pressure dependency on the properties of these electrodes, varying with the applied overpotential, suggest that concomitant changes in the fractional coverage of adsorbed intermediates occur either on nickel or zirconia. Whenever limited by two consecutive processes, whose rates are activation controlled, also the intermediate concentration will vary in the course of potential variations. Hence the surface coverage of the intermediate may strongly depart from the coverage under virtual equilibrium conditions, which is one of the tacit assumptions in classical analysis of the electrode kinetics. Within the experimental range 45 - 61 m/cm2 the electrochemical performance of the porous nickel electrode relates with the exposed length of the nickel perimeter (expected to be related with TPB). Similar observations have been made by others 0[18] and these suggest that the rate determining reaction step(s) take(s) place at or in the near vicinity of this boundary line. The data from impedance measurements shows that the significance of this step to the overall electrode performance decreases under anodic polarisation. In cermet structures of Ni/YSZ its contribution to the overall kinetics therefore may become mixed with contributions of another kind. Acknowledgement Ms. M. Gonzalez is thanked for performing part of the measurements. References
S.C. Singhal, Status of Solid Oxide Fuel Cell Technology, Proceedings of the 17th Ris International Symposium on Materials Science, High temperature Electrochemistry: Ceramics and Metals, 123-38, 1996. [2] C. Bagger, N. Christiansen, P.V. Hendriksen, E.J. Jensen, S.S. Larsen, M. Mogensen, Techno- Economic Problems of SOFC Commercialization, Proceedings of the 17th Ris International Symposium on Materials Science, High temperature Electrochemistry: Ceramics and Metals, 167-74, 1996. [3] T. Jacobsen, B. Zachau-Christiansen, L. Bay and S. Skaarup, SOFC Cathode Mechanisms, Proceedings of the 17th Ris International Symposium on Materials Science, High temperature Electrochemistry: Ceramics and Metals, 2940, 1996. [4] F.H. van Heuveln, H.J.M. Bouwmeester, and F.P.F. van Berkel, Electrode Properties of Sr-Doped LaMnO3 on Yttria-Stabilized Zirconia, I. Three Phase Boundary Area, J. Electrochem. Soc., 144, 126-33, 1997. [5] F.H. van Heuveln, H.J.M. Bouwmeester, Electrode Properties of Sr-Doped LaMnO3 on Yttria-Stabilized Zirconia, I. Electrode kinetics, J. Electrochem. Soc., 144, 134-40, 1997. [6] S. Primdahl and M. Mogensen, Oxidation of Hydrogen on Ni/Yttria-Stabilized Zirconia Cermet Anodes, J. Electrochem. Soc., 144, 3409-19, 1997. [7] T. Kawada, N. Sakai, H. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Characteristics of slurry-coated nickel zirconia cermet anodes for solid oxide fuel cells, J. Electrochem. Soc. 137, 10 , 3042-47, 1990. [8] F.P.F. van Berkel, F.H. van Heuveln and J.P.P. Huijsmans, Characterisation of Solid Oxide Fuel Cell Electrodes by Impedance Spectroscopy and I-V Characteristics, SSI, 72, 240-47, 1994. [9] J. Divisek, A. Kornyshev, W. Lehnert, U. Stimming, I.C. Vinke and K. Wioppermann, Advanced characterisation techniques for Nickel-YSZ Cermet Electrodes used in Solid Oxide Fuel Cells, Electrochemical Proceedings Volume 97-18, 606-16, 1997. [10] A. Ioselevich, A.A. Kornyshev and W. Lehnert, Degradation of SOFC Anodes due to Sintering of Metal Particles: Correlated Percolation Model, J. Electroch. Soc., 144, 3010-19, 1997. [11] H. Itoh, T. Yamamoto, M. Mori, T. Horita, N. Sakai, H. Yokokawa and M. Dokiya, Configurational and Electrical Behavior of Ni-YSZ Cermet with Novel Microstructure for Solid Oxide Fuel Cell Anodes, J. Electrochem. Soc. 144, 641-46, 1997. [12] N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. [1]
78
4.6 Concluding remarks
[13] J. Guindet, C. Roux, and A. Hammou, 'Hydrogen oxidation at the Ni/Zirconia electrode', pp.553-58 in: Proc. of the 2nd Int. Symp. on Solid Oxide Fuel Cells, Athens, Greece, July 2-5, 1991. [14] F.Z. Mohamedi-Boulenouar, J. Guindet and A. Hammou, Influence of Water Vapour on Electrochemical Oxidation of Hydrogen at the Ni/Zirconia Interface, pp 441-50 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. [15] P.A. Osborg, T. Norby, Characterisation of a H2+H2O/Ni/YSZ point electrode system by impedance spectroscopy, pp47-50, in 7th SOFC Workshop, theory and measurement of microscale processes in Solid Oxide Fuel Cells, Wadahl, Norway, 18-20 Jan., 1995. [16] T. Norby, O.J. Velle, H. Leth-Olsen and R. Tunold, 'Reaction resistance in relation to three phase boundary length of Ni/YSZ electrodes', pp.473-78 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. [17] J. Mizusaki, H. Tagawa, T. Saito, K. Kamitani, T. Yamamura, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu and S. Nakagawa, 'Preparation of Nickel pattern electrodes on YSZ and their electrochemical properties in H2-H2O atmospheres'; pp. 533-41 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. [18] J. Mizusaki, H. Tagawa, T. Saito, K. Kamitain, T. Yamamura, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu, S. Nakagawa, K. Hashimoto, Preparation of Nickel Pattern Electrodes on YSZ and Their Electrochemical Properties in H2-H2O Atmospheres, J. Electrochem. Soc., 141, 2129-34, 1994. [19] J. Mizusaki, H. Tagawa, T. Saito, T. Yamamura, K. Kamitani, K. Hirano, S. Ehara, T. Takagi, T. Hikita, M. Ippommatsu, S. Nakagawa, K. Hashimoto, 'Kinetic studies of the reaction at the nickel pattern electrode on YSZ in H2-H2O atmospheres', Solid State Ionics, 70/71, 52-58, 1994. [20] J. Mizusaki, T. Yamamura, H. Yoshitake, H. Tagawa, K. Hirano, S. Ehara, T. Takagi, M. Hishinuma, H. Sasaki, T. Sogi, Y. Nakamura, and K. Hishimoto, Kinetic studies on Ni/YSZ anode reaction of SOFC in H2-H2O atmospheres by the use of Nickel pattern electrodes, pp 363-68 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. [21] T. Yamamura, H. Tagawa, T. Saito, J. Mizusaki, K. Kamitani, K. Hirano, S. Ehara, T. Takagi, Y. Hishinuma, H. Sasaki, T. Sogi, Y. Nakamura, K. Hashimoto, Reaction Kinetics at the Nickel Pattern Electrode on YSZ and its dependence on Temperature, Proc. of the 4th Int. Symp. On SOFC-IV, pp 741-49, Yokohama, Japan, 1995. [22] M. Mogensen, S. Sunde and S. Primdahl, SOFC Anode Kinetics, pp 77-100 in: Proc. of the 17th Ris Int. Symp. on Material Science: High Temp. Electrochemistry: Ceramics and Metals, Roskilde, Denmark, 1996. [23] B.A. Boukamp, A Nonlinear least squares Fit Procedure for Analysis of Immittance data of Electrochemical Systems, Solid State Ionics, 20, 31-44, 1986. [24] J.R. MacDonald, Impedance Spectroscopy, John Wiley and sons, 1987. [25] F.P.F. van Berkel, J.P. de Jong, De Relatie tussen de Morfologie en de Electrochemische Eigenschappen van Ni/YSZ Anodematerialen, ECN Internal Report, 2918-GR14,1993. [26] I. Epelboin, M. Keddam, and J.C. Lestrade, Faradaic Impedances and Intermediates in Electrochemical Reactions, Faradaic Impedances and Intermediates in Electrochemical Reactions, Disc. Faraday Soc. 56, 264-275, 1973. [27] I. Epelboin, C. Gabrielli, M. Keddam and H. Takenouti, The Study of the Passivation Process by the Electrode Impedance Analysis, Chapter 3 of Comprehensive Treatise of Electrochem., Ed. J. OM Bockris, B.E. Conway, E. Yeager and R.E. White, 151-94, New York/London, Plenium 1981. [28] B.A. van Hassel, B.A. Boukamp, A.J. Burggraaf, Electrode Polarisation at the Au, O2(g) /Yttria Stabilized Zirconia Interface, I Theoretical Considerations of Reaction Model, Solid State Ionics, 48, 139-54, 1991. [29] B.A. van Hassel, B.A. Boukamp, A.J. Burggraaf, Electrode Polarisation at the Au, O2(g) /Yttria Stabilized Zirconia Interface, II Electrochemical measurements and Analysis, Solid State Ionics, 48, 155-71, 1991.
79
5 Hydrogen oxidation at porous nickel electrodes on yttria-stabilised zirconia: Effect of surface modification with fine YSZ.
Abstract Investigations have been performed in order to elucidate the role of zirconia in the nickelzirconia cermet used as anode in solid oxide fuel cells. Instead of the cermet electrode, the hydrogen oxidation reaction has been studied at porous nickel electrodes whose surfaces have been modified by dispersion with fine particles of yttria-stabilised zirconia. The surface modification leads to a significant improvement in the electrochemical activity compared with the bare porous nickel electrodes. The results are explained in terms of an increased number of reaction sites. The very similar polarisation and impedance behaviour at different H2 and H2O partial pressures, compared with that observed for the bare nickel electrodes, gives strong credence for this hypothesis. 5.1 Introduction
In Solid Oxide Fuel Cells (SOFC), the porous cermet made of nickel and yttria-stabilised zirconia (Ni/YSZ) is generally used as anode material [1]0. The major purpose of the porous structure is the customary one: creating a large internal surface to keep local current densities and overpotentials low while achieving a large external current density. At present however, there is no consensus about the detailed kinetics of, e.g., the hydrogen oxidation reaction on Ni/YSZ cermet electrodes. The precise function and relative importance of the cermet components are unclear. From one point of view the presence of YSZ acts as a support for the nickel particles, preventing them from sintering together, as well as providing a better thermal match with the electrolyte 0. Along this view the important steps in the electrode reaction would take place on the nickel surface, at or in the near vicinity of the triple-phase-boundary line (TPB) between electrode, electrolyte and gas phase. An alternative view is to assign a definite active role in the electrochemistry to the YSZ component 000000. In a previous study we have investigated porous nickel electrodes by steady-state polarisation measurements and complex impedance spectroscopy. Electrodes with a variable microstructure were obtained by using a different layer thickness, annealing time and tem-
81
Sample 1 Ni-1m Ni-2m Ni-3m 350 150 150 Layer thickness (nm) of evaporation step 2 150 150 150 3 150 150 150 4 500 500 500 300 300 5 Total thickness (nm) 1150 1250 1250 Annealing step 2h - 1100C 2h 1100C 4h - 1150C
Table 5.1: Thickness of the deposited layers of the sequential E-beam evaporation steps during the preparation of the porous nickel electrodes. Intermediate annealing was performed in a 10% H2 - 90% N2 gas mixture at a total flow rate of 100 mlmin-1.
perature in subsequent E-beam assisted evaporation steps. The electrochemical performance in H2 oxidation could be related to the nickel perimeter of the electrodes. The results furthermore emphasise that the kinetics for this reaction cannot be described in terms of a single rate-determining step, without considering a strong variation in the fractional coverage of intermediates on either nickel or YSZ surfaces. In this study we wish to clarify the role of the YSZ component in the cermet electrode. To this end the performance of porous nickel electrode whose surface was modified by dispersion with fine YSZ particles are investigated. Such an electrode bears some resemblance to the cermet electrode, which has a considerably more complex microstructure. 5.1.1 Fabrication of electrolyte and electrodes The method of preparation of the samples and the construction of the electrochemical cell have been described extensively elsewhere 0. The sintered yttria-stabilised zirconia (prepared from Tosoh-Zirconia TZ-8Y) discs had a diameter of 16.0 mm and thickness of 4.0 mm. A small groove was made around the disc at half thickness for positioning of the reference electrode. Porous nickel electrodes were prepared by means of an E-beam evaporation process. Processing steps varied include: the total number of evaporation steps, the applied layer thickness in each step and the firing conditions between sequential steps. This resulted in a very open and porous electrode structure. The total electrode area was 2 cm2. The thickness of the formed nickel layers was estimated to be slightly above 2 m. Process steps used for the different electrodes are listed in Table 5.1. Figure 5.1 shows a schematic diagram of the electrochemical cell. Pt paste (Demetron) was applied onto the electrolyte disc for counter and reference electrodes. Prior to surface modification the cell assembly was annealed at 1000C for 1 h under reducing conditions (10% H2 90% N2). The surface of the nickel electrodes was modified with fine YSZ powder. Zirconium-(IV)nitrate (Zr(NO3)45H2O) and yttrium-(III)-nitrate (Y(NO3)35H2O) dissolved in ethanol was used as a precursor solution. The Y:Zr ratio was set equivalent to that in Figure 5.1: Schematic side view of the three-electrode electro8mol% YSZ. A small chemical cell. 82
5.1 Introduction
droplet of this solution was placed on the electrode. The solution-treated discs were dried and heated at 200C for 2 h in air. The coating method is only used for the purpose of demonstration, no attempt was undertaken to fully develop the method. Scanning electron microscopy (SEM) analysis confirmed that no homogeneous dispersion of YSZ particles on the surface of the electrodes was obtained. SEM micrographs of the nickel electrodes were taken, before and after cell evaluation, at five different positions on the surface. The pictures obtained were transferred to an image analysis system for determining the total coverage and the extent of open porosity of the formed nickel network. 5.1.2 Electrochemical characterisation Electrochemical experiments were performed in a single-gas environment at atmospheric pressure. At standard conditions a gas flow of 100 mlmin-1 H2 (STP) with 2.3% H2O at 850C was used. Brooks 5800E Mass Flow Controllers controlled all gas flows. Passing the gas mixture through a water bubbler system in a temperature bath controlled the water vapour pressure. For electrochemical measurements helium was used as inert gas. The details of the impedance and polarisation measurements have been described before 0. In summary, polarisation measurements were carried out using a Solartron electrochemical interface (model 1287) for potentiostatic control. Impedance data was measured over the frequency range 1 MHz to 0.01 Hz using a Solartron frequency response analyser (model 1255) in combination with the Solartron electrochemical interface. Data analysis was performed using the software package Equivalent circuit 0. Overpotentials were corrected for the uncompensated resistance of the electrolyte, the value of which was evaluated from the high frequency intercept on the real impedance axis. After heating the electrode to 850C under standard conditions, the following experiments were conducted in the sequence as indicated: Impedance measurements under standard conditions until reproducibility of the data was obtained Impedance measurements in the pH2-range 9.98104 to 4.95103 Pa with pH2O fixed at 2.33103 Pa and in the pH2O-range of 1.22103 to 2.00104 Pa with pH2 fixed at 8.11104 Pa. I- measurements under standard conditions. The work electrode was anodically biased at 500 mV for 30 min. Hereafter, the I- curve was recorded by decreasing the potential stepwise in the cathodic direction. I- measurements as a function of pH2 and pH2O. The applied pH2 and pH2O ranges correspond to those listed above. Impedance measurements under anodic bias. These were performed at 50, 100, 150, 200, 250, 300, 400 and 500 mV relative to the reference electrode. Standard conditions are used for H2 and H2O partial pressure. Impedance measurements as a function of temperature. These were performed at standard conditions in the range of 850 to 600C. Between these experiments impedance spectroscopy was applied under standard conditions to check the electrode performance.
83
(a)
(b)
(c) (d) Figure 5.2: SEM micrographs of (a) & (b) a bare and (c) & (d) modified porous nickel electrode, taken after completing the electrochemical measurements.
5.2
Results
Below are the experimental observations made on the modified nickel electrodes discussed. Data obtained for the bare nickel electrodes has been presented and discussed elsewhere in this thesis 0. 5.2.1 Microstructure Figure 5.2 shows the microstructure of both bare and modified nickel electrodes after cell evaluation. From these it can be seen that the nickel forms a continuous network with considerable open porosity. To obtain a variable microstructure the electrodes were fired after successive E-beam evaporation steps at 1100-1150C (for 2-4h in 10%H2 90%N2), temperatures much higher those that during the measurements. Five SEM pictures at different positions on the surface were used for image analysis. These images covered together 0.006% of the electrode area. From these the surface coverage and the total perimeter of the nickel particles contributing to the network were estimated. Results from SEM pictures taken before and after cell evaluation are listed in Table 5.2. Although the total perimeter of the nickel network in Table 5.2 is expected to be related to the TPB length, it is not immediately clear from the SEM analysis whether there are differ-
84
5.2 Results
Perimeter of nickel network (m/cm2) Before measurements Sample Ni-1m Ni-2m Ni-3m average 45 59 59 deviation 2 3 5 After measurements average 53 54 59 stdev 3 4 6
Surface coverage Ni (%) Before measurements Sample Ni-1m Ni-2m Ni-3m average 60 76 69 deviation 2 3 3 Aftere measurements average 55 73 65 stdev 2 4 2
Table 5.2: Results from image analysis on the nickel structure of modified porous nickel electrodes before and after electrochemical experiments. Average values are given from data taken at five different positions at the surface.
ences between both types of electrodes on a smaller microscopic level. Figure 5.2 shows that, in the case of the modified electrode, small YSZ particles are apparent on the nickel surface as residues of the solution-treatment. Sometimes these residues appeared in the form of flakes (not shown). Also some roughening effect of the electrolyte surface is apparent, which could be caused by a thin layer of small YSZ particles. To which extent the presence of small YSZ particles contributes to the TPB length effective for the modified electrode cannot be judged from the SEM observations. 5.2.2 Electrochemical performance 1.1.1.20Impedance Spectroscopy 1.1.1.20.1 Impedance measurements under standard conditions The bare and modified nickel electrodes give similar spectra. Impedance representations (measured at zero bias) of the different modified nickel electrodes are given in Figure 5.3. In general, data could be fitted to the equivalent circuit LwRe(R1Q1)(R2Q2), where L is an inductance, R a resistance and Q designates the impedance of a constant phase element (CPE). The latter is given by ZCPE=1/Q(i)n, where i is the imaginary unit, the angular frequency and n the frequency power. For the electrode Ni-3m the arc (R2Q2) could not be taken into account accurately. Parameters obtained from fitting are listed in Table 5.3. The inductance Lw is ascribed to leads and instruments. Re is the uncompensated electrolyte resistance. The values for Re, given in Table 5.3, may be compared with 1.4 calculated assuming a specific conductivity for YSZ of 0.1 -1cm-1 0. The series combination of (RQ)s describe the electrode response. To enable a more meaningful comparison of data the frequency powers n1 and n2 were fixed during fitting to values 0.93 en 0.5, respectively (for Ni-3m, n1 = 0.84). The reliability of the fitting procedure is indicated by ps2 in Table 5.3 0. The (R1Q1) arc is found to be dominant and makes up a contribution
85
3 Ni-1m Ni-2m Ni-3m 2
Imag
0 1 2 3 4 5 6 7
Real
-1
Figure 5.3: Impedance spectra for the different modified porous nickel electrodes from this study measured under standard conditions at zero bias.
Ni-1m L Re R1 Q1 n1 R2 Q2 n2 Rtot ps
2
Ni-2m 1.14E-07 1.33 4.76 1.92E-03 0.93 0.33 2.59E-01 0.5 5.09 3.49E-06
Ni-3m 1.52E-07 1.31 4.40 3.40E-03 0.84
1.23E-08 1.50 4.98 1.57E-03 0.93 0.28 9.68E-02 0.5 5.26 1.24E-05
4.40 1.96E-05
Table 5.3: Parameters obtained from fitting the impedance data of different modified porous nickel electrodes to the circuit LRe(R1Q1)(R2Q2), where Rtot equals R1+R2. Resistance in , inductance in H, capacitance in Farad, Constant Phase Element (Qn) in secn-1. The ps2 values indicate reliability of the fitting procedure 0.
86
5.2 Results
Sample
Order dependence of tot pH2 pH2O 0.53 0.49 0.39
Ni-1m Ni-2m Ni-3m
0.10 -0.15 -0.03
Table 5.4: Order of gas phase pressure dependence on the total electrode conductivity. Results from impedance measurements at zero bias on different modified porous nickel electrodes where pH2 dependent data is measured at pH2O = 2.3105Pa and pH2O dependent data at pH2 = 8.1104Pa and T = 850C.
of, on average, 90% of the total electrode resistance. At the low frequency side it overlaps the much smaller contribution of (R2Q2). Impedance measurements as function of pH2 and pH2O 1.1.1.20.2 Conductivity data calculated from i = 1/(ARi), where A equals the total electrode area and Ri the resistance obtained from fitting, as a function of pH2 and pH2O for sample Ni2m are given in Figure 5.4 and Figure 5.5, respectively. It should be noted that the obtained order is not equal to the reaction order. As for the measurements under standard conditions, the (R1Q1) arc governs the impedance in the applied range of partial pressures. The associated conductivity resembles the total electrode conductivity. Both are weakly dependent on pH2, whereas the order is close to 1/2 upon variation with pH2O. Noteworthy is the high value of the order found for 2 upon variation of pH2O (see Table 5.4). It should be mentioned that the error made in estimating this value is large due to the minor contribution of (R2Q2) to the total impedance. The electrolyte conductivity should be invariant with pH2 and pH2O (as observed). Not shown are fit parameters obtained for the CPE elements. These vary slightly with pH2 and pH2O, but they were found to be of similar magnitude as those listed in Table 5.3. Data for the total electrode conductivity of all modified nickel electrodes from this study is summarised in Table 5.4. Impedance measurements under anodic bias 1.1.1.20.3 Typical data at selected overpotentials is given in Figure 5.6. With overpotential the (R2Q2) arc disappears and an inductive loop appears at the low frequency side (R3Q3). In the fitting procedure this could be accounted for by assigning negative values to R3 and Q3. Contrary to the impedance data measured under equilibrium conditions (=0), it was not possible to fix the frequency powers n1 and n2 over the entire range in overpotential. Figure 5.7 shows that the magnitude of R1 decreases under anodic polarisation, which is in accord with Tafel behaviour for the anodic reaction. The transfer coefficient derived from this curve and for corresponding curves for other investigated electrodes are listed in Table 5.5. The magnitude of R3 seems to decrease with increasing overpotential. Impedance measurements as function of temperature 1.1.1.20.4 Activation energies estimated from the Arrhenius plots of the electrolyte and of the total electrode conductivity are 82 kJmol-1 and 134 kJmol-1, respectively (Figure 5.8).
87
-0.17
log ( cm )
-2
0 0.003
-1
-1 e 1 2 tot -2 3.5 4.0 4.5 5.0
-0.15
5.5
log pH2 (Pa)
Figure 5.4: pH2 dependence of the conductivities obtained from analysis of impedance data for sample Ni-2m measured at zero bias and pH2O = 2.3105 Pa and T = 850C.
2 e 1 1
-1 -2 log ( cm )
2 tot
1.4 -0.008
-1 0.49
-2 2.5 3.0 3.5 4.0 4.5 5.0
log pH2O (Pa)
Figure 5.5: pH2O dependence of the conductivities obtained from analysis of impedance data for sample Ni-2m measured at zero bias and pH2 = 8.1104 Pa and T = 850C
88
5.2 Results
1.25
1.00 2 0.75
Imag
0.50 1
Imag
0.25
0 1 2 3 4 5 6 7
0.00 1.5 -0.25 2.0 2.5 3.0 3.5
Real
-1
Real
-0.50
= 0 mV
0.50 0.3
= 58 mV
0.2
0.25 0.1
Imag
Imag
0.0 1.4 0.00 1.4 1.6 1.8 2.0 2.2 2.4 -0.1 1.5 1.6 1.7 1.8 1.9 2.0 2.1
Real
Real
-0.25
-0.2
= 127 mV = 176 mV Figure 5.6: Impedance spectra for Ni-1m electrode measured under standard conditions with different values for the anodic polarisation.
Re R1 R2 R3
R ()
0 0 -1 20 40 60 80 100 120 140 160 180 200
(mV)
Figure 5.7: Resistance values as a function of anodic overpotential. Data derived from analysis of impedance spectra for sample Ni-1m measured under standard conditions.
89
2 Electrolyte Electrode
ln 1/R ( )
-1
-2 82 kJ/mol -4
-6
134 kJ/mol
-8 0.8 1.0 1.2 1.4
1000/T (1/K)
Figure 5.8: Temperature dependence of electrolyte and total electrode conductivity for electrode Ni-2m measured under standard conditions.
2 1 1.5 1
log i (mA cm-2)
1 0.5
-1
Ni-1m Ni-2m Ni-3m
-2 -400
-300
-200
-100
100
200
300
(mV)
Figure 5.9: Tafel plots for the different electrodes showing anodic and cathodic branches. Data measured under standard conditions.
90
5.3 Discussion
Sample
From impedance measurements a
From i- measurements a 1.2 1.3 1.2 c 0.80 0.66 0.73
Ni-1m Ni-2m Ni-3m
1.3 1.3 1.2
Table 5.5: Estimated values for the apparent charge transfer coefficients from impedance (under anodic polarisation) and i- measurements for the different modified porous nickel electrodes.
1.1.1.21I- measurements 1.1.1.21.1 I- measurements under standard conditions Cathodic and anodic transfer coefficients estimated from the Tafel plots, shown in Figure 5.9, are given in Table 5.5. As noted from this figure the Tafel plots do not really exhibit a linear region. The transfer coefficients listed in Table 5.5 were calculated from the first derivative of a polynomial, fitting the experimental data in both directions, at the highest range of the overpotential covered by experiments. I- measurements as function of pH2 and pH2O 1.1.1.21.2 Gas partial pressure dependencies of the current are derived at certain overpotentials. Typical experimental data are shown in Figure 5.10 - Figure 5.13. It should be noted that the gas phase dependence may be different in cathodic and anodic directions. Similar observations were made with other modified electrodes. 1.1.1.22Electrode stability Figure 5.14 shows the overall electrode resistance as a function of time. The data obtained from impedance spectra recorded at standard conditions at the beginning and end of the indicated experiments show ageing of the electrode. The increase in the magnitude of the resistance, being most pronounced in the initial period, extends up to the time of the last registration. Similar results were obtained for other modified electrodes. 5.3 Discussion
5.3.1 Microstructure In contrast with the standard porous nickel electrodes 0, small deviations are found in the results from SEM analysis before and after cell evaluation. Figure 5.15 shows the overall electrode conductivity for the modified nickel electrodes. Data derived from the first and the very last impedance measurement are plotted against the perimeter of the nickel network determined before and after cell evaluation. Where previously a large scatter was found in the data before cell evaluation, this is not the case in Figure 5.15. The results indicate that increase in magnitude of the electrode resistance, which occurs in the course of the electrochemical experiments, is not related to changes in the microstructure observable with SEM. The more stable microstructure of the nickel network, compared with that in the
91
2.4
Anodic
2.2 -0.01
log i (mA cm )
2.0 -0.06 1.8
-2
1.6 -0.08 1.4 = 100 mV = 150 mV = 200 mV 3 4 5 6
1.2
log pH2 (Pa)
Figure 5.10: pH2 dependence of current i at selected values for the anodic overpotential . Data for sample Ni-1m measured at pH2O = 2.3105 Pa and T = 850C. indicates the slope of the trend lines given in the figure.
2.2
Cathodic
2.0 0.24
log i (mA cm )
1.8
0.27
-2
1.6
0.35
1.4 = -200 mV = -250 mV = -300 mV
1.2
1.0 3 4 5 6
log pH2 (Pa)
Figure 5.11: pH2 dependence of current i at selected values for the cathodic overpotential . Data for sample Ni-1m measured at pH2O = 2.3105 Pa and T = 850C. indicates the slope of the trend lines given in the figure.
92
5.3 Discussion
2.50
2.25
= 125 mV = 150 mV = 175 mV
0.30 0.30
log i (mA cm )
-2
2.00
0.31
1.75
1.50
Anodic
1.25 2 3 4 5
log pH2O (Pa)
Figure 5.12: pH2O dependence of current i at selected values for the anodic overpotential . Data for sample Ni-1m measured at pH2 = 8.1104 Pa and T = 850C. indicates the slope of the trend lines given in the figure.
2.25 = -200 mV = -250 mV = -300 mV 0.22
2.00
0.22
log i (mA cm )
-2
1.75 0.16
1.50
Cathodic
1.25 2 3 4 5
log pH2O (Pa)
Figure 5.13: pH2O dependence of current i at selected values for the cathodic overpotential . Data for sample Ni-1m measured at pH2 = 8.1104 Pa and T = 850C. indicates the slope of the trend lines given in the figure.
93
I- pH2O Impedance (pH2) I-
Rtot ()
Impedance (pH2O)
2 break down meas. prog
I- (pH2)
Impedance (anodic pol.)
50
100
150
200
250
300
time (hours)
Figure 5.14: Total electrode resistance as function of time. Data are obtained from analysis of impedance data for sample Ni-2m measured under standard conditions.
0.6 First experiment Last experiment
0.5
0.4
tot (-1 cm-2)
0.3
0.2
0.1
0.0 30 40 50 60 70
2
80
90
Figure 5.15: Total electrode conductivity as function of the total perimeter of the nickel network for the different modified porous nickel electrodes. Conductivity data were taken from analysis of impedance data measured under standard conditions. The total perimeter of the nickel network resulted from image analysis of the electrode microstructure. The conductivity derived from the first impedance measurement is plotted against the nickel perimeter before, and that of the last impedance measurements against the nickel perimeter obtained cell evaluation.
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5.3 Discussion
0.4 unmodified nickel modified nickel 0.3
tot (-1 cm-2)
0.2
0.1
0.0 30 40 50 60
2
70
80
Figure 5.16: Total electrode conductivity as function of the total perimeter of the nickel network for bare and modified porous nickel electrodes. Conductivity data were taken from analysis of the last impedance data measured under standard conditions. The total perimeter of the nickel network resulted from image analysis of the electrode microstructure after cell evaluation.
previous work, is ascribed to the higher annealling temperatures between successive Ebeam evaporation steps employed in the present study (see experimental section). It can however not be excluded that sintering of the nickel network is constrained by the presence of fine YSZ particles. 5.3.2 Polarisation and impedance characteristics The electrochemical behaviour of the studied modified electrodes bears a strong resemblance to the behaviour of the bare nickel electrodes. The latter have been discussed in detail in the previous chapter. The main differences in the experimental observations from both studies can be summarised as follows The overall electrode conductivity total has increased considerably compared with that of the unmodified nickel electrode. Figure 5.16 shows the total of both types of electrode plotted as a function of the perimeter of the nickel network. In both cases the conductivity increases with the perimeter exhibited by the electrode. At similar nickel perimeter length, however, the conductivity of the modified nickel electrode is about twice that exhibited by the bare nickel electrode. Possibly the surface modification treatment affects the TPB length or area which is active in the electrode reaction, on a scale that it is unfortunately not visible with SEM. The data from impedance measurements of both types of electrodes can be analysed in a similar manner (with the exception of electrode, Ni-3m). Besides the same equivalent circuit, the parameters for the CPE elements obtained from the fitting procedure are of
95
the same order of magnitude. Only, as noted above, the resistance values have changed. Within experimental error the ratio R1/R2 for both types of electrodes does not change. The latter might indicate that the electrode modification affects both processes to a similar extent. The activation energy of the overall electrode process is found to be slightly lower than that on the bare nickel electrode, 134 and 154 kJmol-1. The transfer coefficient a derived from impedance data under different anodic bias values shows good correspondence with the s determined from the slope of log(i) versus plots. Overall the values, obtained for both cathodic and anodic transfer coefficients, tend to be slightly lower than those observed for the bare nickel electrodes (cf. Table 5.5 with Table 4.7). As for the bare nickel electrodes, the H2 and H2O partial pressure dependencies of the electrode performance are different under equilibrium (from impedance data), anodic and cathodic polarisation. Observed dependencies at similar values for the overpotential may however slightly differ for both types of electrodes. Conclusions
5.4
Porous nickel electrodes on yttria-stabilised zirconia have been modified by dispersion with fine particles of the YSZ phase. The marked similarity in the performance of bare and modified nickel electrodes in hydrogen oxidation strongly suggests that essential steps in the electrode mechanism on both types of electrodes are similar. Hence, views on the mechanism presented in the previous chapter essentially remain unaltered. The significant reduction in overall electrode resistance of the modified electrodes, compared with that of the bare nickel electrode, can be attributed to an increased number of active sites. Such behaviour is reminiscent of the increase in the number of active sites encountered in cermet structures of nickel and YSZ. Acknowledgement Ms. M. Gonzalez is thanked for her assistance in performing part of the measurements. References
S.C. Singhal, Status of Solid Oxide Fuel Cell Technology, Proceedings of the 17th Ris International Symposium on Materials Science, High temperature Electrochemistry: Ceramics and Metals, 123-38, 1996. N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. M. Mogensen and T. Lindegaard, The kinetic of hydrogen oxidation on a Ni-YSZ SOFC electrode at 1000C, Proc of Solid Oxide Fuel Cells 1993 (SOFC-III), pp 484-93, 1993. M. Mogensen, Electrode kinetics of SOFC anodes s and cathode, Proc of the 14th Ris Int. Symp. on materials science, High Temp. electrochemical behaviour of fast ion and mixed conductors, pp 117-35, 1993 M. Mogensen and S. Skaarup, Kinetic and geometric aspects of solid oxide fuel cell electrodes, Solid State Ionics, 8688, pp1151, 1996. H. Itoh, T. Yamamoto, M. Mori, T. Horita, N. Sakai, H. Yokokawa and M. Dokiya, Configurational and Electrical Behavior of Ni-YSZ Cermet with Novel Microstructure for Solid Oxide Fuel Cell Anodes, J. Electrochem. Soc. 144, 641-46, 1997. J. Divisek, A. Kornyshev, W. Lehnert, U. Stimming, I.C. Vinke and K. Wioppermann, Advanced characterisation techniques for Nickel-YSZ Cermet Electrodes used in Solid Oxide Fuel Cells, Electrochemical Proceedings Volume 97-18, 606-16, 1997. A. Ioselevich, A.A. Kornyshev and W. Lehnert, Degradation of SOFC Anodes due to Sintering of Metal Particles: Correlated Percolation Model, J. Electroch. Soc., 144, 3010-19, 1997. Chapter 4 of this thesis
96
5.4 Conclusions
N. Nakagawa, H. Sakurai, K. Kondo and K. Kato, Study on the extension of reaction zone from Ni/YSZ interface by using fixed film electrodes, pp 721-30 in: Proc. of 4th Int. Symp. on SOFC, Japan, 1995. B.A. Boukamp, A nonlinear least squares fit procedure for analysis of Immitance data of Electrochemical Systems, Solid State Ionics, 20, 31-44, 1986. F.P.F. van Berkel, J.P. de Jong, De Relatie tussen de Morfologie en de Electrochemische Eigenschappen van Ni/YSZ Anodematerialen, ECN Internal Report, 2918-GR14,1993.
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6 Cermet electrodes, relation between microstructure and performance
Abstract The microstructure of screen-printed Nickel/Yttria Stabilised Zirconia (Ni/YSZ) cermet electrodes was varied by using in their preparation different ratios of fine and coarse YSZ powder. The nickel volume fraction was fixed at 55% of total solids. The porosity, the nickel particle size and associated coverage on the electrolyte were determined by image analysis techniques. The electrochemical performance of the electrode measured by impedance spectroscopy could be related to the length of the Triple Phase Boundary. Two situations can be considered, for coarse cermet structures the electrode reaction is confined to the immediate interface between cermet electrode and electrolyte. For fine cermet structures the electrode reaction zone extends into the bulk of the cermet. 6.1 Introduction
In Solid Oxide Fuel Cells (SOFC) porous Ni/YSZ cermet is generally used for the anode [1]. For this type of electrode the microstructure is an important parameter for its performance 000. Open porosity is required for the electrode to supply fuel and for the removal of reaction products. The Ni particles, forming a percolative network, are responsible for transporting electrons from the place where the electrode reaction takes place to the external circuit. Besides having a high catalytic activity, the application of Ni instead of Pt or Pd is attractive from an economic point of view. The addition of YSZ is necessary to support the nickel particles, to inhibit coarsening by sintering into larger particles at the usual operating temperatures of an SOFC, and to give the cermet a thermal expansion coefficient acceptably close to that of other cell components 0. As such, the presence of YSZ in the anode is considered to be inactive for the electrode reaction. Others have suggested that YSZ plays an active role in the electrode reaction by forming conductive paths for oxygen transport, thereby enlarging the active area available for the electrode reaction 000. There is, at present, no consensus about the role of YSZ in cermet electrodes. This study concentrates mainly on the relationship between electrode performance and microstructure. The microstructure has been varied using different ratios of fine and coarse YSZ powder. Particular attention is paid to characterisation of the microstructure in terms of porosity, particle sizes and surface coverage of the electrode on the electrolyte. The 99
electrochemical performance has been analysed using impedance spectroscopy. In the following chapters of this thesis more attention will be paid to the electrode kinetics. 6.2 Experimental
6.2.1 Sample preparation Yttria stabilised zirconia (Tosoh-Zirconia TZ-8Y) disks of 25 mm diameter were obtained by uniaxial pressing at 1.5 bar for 1 min, followed by isostatic pressing at 4000 bar for 5 min. The disks were sintered at 1400C for 5 hours in air. Electrolyte disks of 16.0 mm diameter and 4.0 mm thickness were cut from the sintered disks. A small groove was made at half thickness for positioning of the reference electrode. Prior to use the electrolytes were mechanically polished with 320 MESH SiC, 3 m diamond MM and diamond paste (1 m). After polishing, the samples were ultrasonically cleaned with ethanol. An Archimedes method was used for determination of the density. Only samples with a density larger than 5.89 gcm-3, which corresponds with 99% of the theoretical density, were used for experiments. For electrochemical experiments, counter and reference electrodes were painted on the electrolyte disk with Pt paste (Demetron). The whole assembly was annealed at 1000C for 1 hour in air. The cell geometry is shown schematically in Figure 6.1. For the preparation of the anode materials, NiO and 8 mol% YSZ (Tosoh-Zirconia TZ-8Y) were used as starting materials. The NiO powders were milled, with a median particle size of the NiO powder after milling of 2 m. The YSZ powder consists of spray-dried spheres with an average diameter of 45 m, which are composed of crystallites with a size of about 0.02 m. To obtain a systematic variation of the microstructure of the anode, different ratios of fine and coarse YSZ-particles were used. The particles have a median particle size of 0.2 m for the fine and of 10 m for the coarse particles. The coarse YSZ particles were prepared by calcining the as-received Tosoh powder followed by milling. For the fine YSZ particles as-received Tosoh powder was used. These powders were mixed into screen-print pastes in which the weight ratio of fine and coarse zirconia was varied, resulting in 0, 5, 10, 15, 20, 50 and 100 weight% of the total zirconia content of the anode, and with the NiO content kept at a value of 70 weight%, which results in an Ni content of 55 vol% of total solids after reduction. These different anode pastes were screen-printed on the thick electrolyte pellet, using a DEK 247 screen printing machine. The deposited anodes were sintered at 1300 oC for 5 hours in air. 1.1.1.23NiO/YSZ cermet reduction
Figure 6.1: Schematic side view of the three-electrode electrochemical cell.
100
6.2 Experimental
Gas composition N2 (ml/min) Step 0 Step 1 Step 2 Step 3 Step 4 100 99 97 80 0 H2 (ml/min) 0 1 3 20 100 H2O (%) 2.3 2.3 2.3 2.3 2.3
Time (min) 500 50 50 50 Till end meas.
Table 6.1: Gas composition used for the reduction steps.
For the reduction of the NiO/YSZ cermet anodes a procedures is used where reduction takes place at operating temperature. The sample was heated to 850C at a rate of 2Cmin1 in an N2 atmosphere (100 mlmin-1), after which reduction was carried out in a step-wise fashion. Each step consisted of a change in gas condition as indicated in Table 6.1. The reduction process was followed by performing impedance measurements between the reduction steps. 6.2.2 Electrochemical characterisation Electrochemical experiments were performed in a single-gas environment at atmospheric pressure. At standard conditions a gas flow was used of 100 mlmin-1 H2 (STP) with 2.3% H2O at 850C. All gas flows were controlled by Brooks 5800E Mass Flow Controllers. The water concentration was controlled by passing the gas mixture through two water bubblers. The temperature of the water in the bubblers was controlled with an electric heating and cooling device containing a mixture of ethylene-glycol and water. The second water bubbler was used as a kind of cold trap, fixing the water concentration in the gas flow to the aqueous vapour pressure over water at the temperature of the second water bubbler. Impedance measurements were performed over the frequency range from 1 MHz to 0.01 Hz using a Solartron Frequency Response Analyser 1255 in combination with a Solartron Electrochemical Interface 1287. An excitation voltage of 10 mV (rms) was used to ensure that measurements were performed in the linear regime. The impedance data was analysed using the computer program Equivalent Circuit 0. Steady-state polarisation of the cermet was studied using a Solartron Electrochemical Interface 1287 for potentiostatic control. The potential between the reference and work electrode was varied stepwise and the steady-state current through the electrochemical cell was measured. Overpotential data were corrected for the uncompensated resistance of the electrolyte, the value of which was evaluated from impedance spectroscopy data. After reduction of the electrode, stability was checked with impedance measurements. When steady performance was attained, the effect of a load on the cell was investigated by biasing 750mV between reference and work electrode for 30 min. Followed by an IV measurement in anodic direction. Immediately hereafter the impedance was measured. The lateral conductivity of the cermet electrode was measured as a function of temperature by means of a four-probe method 0. The frequency was 130 Hz and the oscillation current 200 A. With the used set-up it was only possible to do accurate measurements for conductivity values higher than 10 Scm-1. Measurements were performed in reducing atmos101
pheres using a gasmixture of 5 vol% H2 / 95 vol% N2. The maximum temperature of the measurements was 950oC. 6.2.3 Microstructural characterisation After completing the electrochemical experiments Scanning Electron Microscopy (SEM) micrographs were taken from the cermet structures. Representative pictures were used for image analysis to quantify the microstructure of the cermet electrodes (7 SEM micrographs for every type of electrode). Porosity was calculated from values of the layer thickness, mass and theoretical densities of both Ni and YSZ. The Ni particle size was estimated by using a lineal intercept technique 0. Intercepts were taken from a raster of lines covering more than 400 particles. SEM pictures of the fracture surface were used to obtain an estimate of the surface coverage of the cermet structure on the electrolyte and the particle size at the interface. 6.3 Results and Discussion
6.3.1 Microstructure Examples of SEM pictures of electrode specimens containing different ratios of fine/coarse YSZ powder are given in Figure 6.2. Results obtained from image analysis are given in Table 6.2 and Figure 6.3, Figure 6.4 and Figure 6.5. The presence of the coarse fraction relative to that of fine YSZ ensures a comparatively high porosity of the cermets. This can be seen in the data presented in Table 6.2 and Figure 6.3, where the porosity decreases from 63% to 50% upon full replacement of coarse with fine YSZ. The addition of fine YSZ to the cermet also influences the sintering behaviour of nickel particles. Their growth is constrained by the presence of fine YSZ. Figure 6.4 shows that the average sintered Ni particle size decreases substantially with increasing weight percentage of fine YSZ, from a value of 2.2 m to 1.0 m for 0 w/0 and 100 w/0 fine YSZ, respectively. The associated coverage on the electrolyte surface increases from 17 to 53%. The most significant change takes place at small fractions of fine YSZ (Table 6.2 and Figure 6.5). It should be noted, however, that the degree of surface coverage includes both Ni and YSZ particles. Another important aspect emerging from image analysis is the contact diameter of the particles at the interface This value is hardly influenced by the w/0 of fine YSZ in the cermet and takes a constant value of about 1.1 m. This suggests that sintering of the Ni particles occurs to some extent in the bulk of the cermet, but is constrained at the immediate interface with the electrolyte.
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6.3 Results and Discussion
(a)
(b)
(c)
(d)
(e)
(f)
Figure 6.2: Micrographs of Ni/YSZ cermet electrodes prepared with different fractions of fine/coarse YSZ powder, (a) 0 w/0; (b) 10 w/0; (c) 15 w/0; (d) 20 w/0; (e) 50 w/0 and (f) 100 w/0 fine YSZ.
103
Microstructural parameters Fraction fine YSZ (w/0) 0 5 10 15 20 50 100 Porosity (%) 63 62 60 64 64 57 50 Ni particle size (m) 2.2 2.2 2.1 1.7 1.6 1.3 1.0 Surface coverage (%) 17 26 30 36 45 52 53 Interface particle size (m) 1.2 1.1 1.0 1.1 1.1 1.0 1.1
Table 6.2: Results of image analysis on cermets prepared with different fractions fine/coarse YSZ. For surface coverage and the interface particle size Ni as YSZ are taken in account.
70
60
50
Porosity (%)
40
30
20
10
0 0 20 40 60 80 100
w/0 fine YSZ
Figure 6.3: Porosity as a function of the weight percentage fine YSZ in different cermets.
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2.5
2.0
Ni particle size (m)
1.5
1.0
0.5
0.0 0 20 40 60 80 100
w/0 fine YSZ
Figure 6.4: Average Ni particle size as a function of the weight percentage fine YSZ in different cermets.
60
50
Interface coverage (%)
40
30
20
10
0 0 20 40 60 80 100
w/0 fine YSZ
Figure 6.5: Surface coverage electrode/electrolyte interface as a function of the weight percentage fine YSZ in different cermets.
105
6.3.2 Electrochemical performance 1.1.1.24Impedance Spectroscopy Impedance diagrams for different cermet structures are given in Figure 6.6. The equivalent circuit that was found to match most closely the observed impedance diagrams can be represented by LwRe(R1Q1)(R2Q2)(R3Q3), where the circuit description code is taken from ref. 0. In this notation, L represents an inductance, R a resistance and Q a constant phase element (CPE). The impedance of a CPE is ZCPE = 1/Q(i)n, where is the angular frequency and i = -1. The CPE includes two constants, Q and n. If n = -1 the CPE behaves as an inductance with L=Q-1, if n = 0 as a resistance with R=Q-1, if n = as a Warburg diffusion impedance and if n = 1 as a capacitance with C=Q. Intermediate values of n indicate the degree of non-ideal behaviour compared to the idealised capacitor, resistor, inductor or diffusion process 0. The values of the elements for the equivalent circuit obtained from fitting are listed in Table 6.3. Lw is associated with the inductance of the wiring and instruments, and Re represents the uncompensated electrolyte resistance. A value of 1.42 was calculated for Re, using a specific conductivity for YSZ of 0.1 -1cm-1 at 850C. The measured values are in close agreement with this calculated value (Table 6.3). The three parallel combinations of a resistance and a CPE in series describe the electrode response. The high frequency semicircle (R1Q1) can be attributed to charge transfer (R1) and the double layer capacitance represented by a CPE (Q1). R1 decreases with increasing w/0 YSZ (see also Figure 6.7). The addition of a small fraction of fine YSZ already induces a pronounced decrease in the value of R1. The CPE values related with the double layer are in the range of 10-3 10-4 -1secn, values that are common for a double layer (00). No clear relation is found between Q1 and the fraction of fine YSZ in the cermet (see Figure 6.8). The n1-value of about 0.8 indicates that there is a slight departure from ideal capacitive behaviour. The combination (R2Q2) with negative values for R2 and Q2 is necessary to fit the inductive loop appearing in the mid-frequency range. This inductive loop appears only in data for cermet microstructures in which part of the coarse YSZ has been replaced by a corresponding fraction of fine YSZ powder. As seen from Figure 6.6, the inductive loop becomes smaller for samples containing less fine YSZ. The appearance of the inductive loops is not completely understood. Possible explanations could be the presence of intermediate adsorbates during the reaction sequence (000). The electrode kinetics is subject of Chapter 8 of this thesis. The low-frequency semicircle is relatively small. The corresponding Q-values are in the range of 0.1-1 -1secn. The appearance of semicircles at the low frequency side with these relative high capacitive values are in literature ascribed to changes in the chemical composition of the bulk phase above the electrode 00. 1.1.1.25Conductivity experiments Figure 6.10 shows the electrical DC lateral resistance of the cermets with different ratios fine/coarse YSZ. The resistance initially increases with the increasing fraction of fine YSZ,
106
0.8
0.6
0.4
Imag
Imag
0 1 2 3 4 5
0.2
0.0 1.5 -0.2 2.0 2.5 3.0
Real
Real
-1
-0.4
(a)
0.75
(b)
0.3
0.50
0.2
0.25
0.1
Imag
0.00 1.0 -0.25 1.5 2.0 2.5 3.0
Imag
0.0 1.4 -0.1 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
Real
Real
-0.50
-0.2
-0.75
-0.3
(c)
0.20 0.15
(d)
0.10
0.05
0.10 0.05
Imag
0.00 1.4 -0.05 -0.10 1.5 1.6 1.7 1.8 1.9 2.0
Imag
0.00 1.40
1.45
1.50
1.55
1.60
1.65
1.70
1.75
Real
-0.05
Real
-0.10
-0.15 -0.20
-0.15
(e) (f) Figure 6.6: Impedance diagrams for different cermet microstructures: (a) 0 w/0; (b) 10 w/0; (c) 15 w/0; (d) 20 w/0; (e) 50 w/0 and (f) 100 w/0 fine YSZ.
107
cermet microstructures (w/0 fine YSZ) 0 w/0 L Re R1 Q1 n1 R2 Q2 n2 R3 Q3 n3 Rtot ps2 1.03E-07 1.46 2.43 2.23E-04 0.86 0.36 1.06E-03 0.73 0.16 0.399 0.73 2.95 4.03E-06 5 w/0 1.38E-07 1.55 1.86 2.57E-04 0.78 -0.18 -2.46E-03 1.00 9.6E-02 7.65E-01 0.63 1.78 3.09E-06 10 w/0 1.31E-08 1.57 1.33 2.57E-04 0.80 -5.6E-02 -2.82E-03 1.18 6.0E-02 7.73E-01 0.94 1.33 1.66E-05 15 w/0 1.37E-07 1.48 1.18 2.57E-04 0.80 -9.6E-02 -4.26E-03 0.99 6.2E-02 7.75E-01 0.88 1.15 2.07E-06 20 w/0 9.59E-08 1.45 6.8E-01 6.84E-04 0.75 -1.3E-01 -1.02E-02 0.93 8.2E-02 6.27E-01 0.82 0.63 1.64E-06 50 w/0 8.78E-08 1.45 4.6E-01 4.79E-04 0.78 -4.9E-02 -1.57E-02 1.00 5.7E-02 8.39E-01 0.88 0.47 1.17E-06 100 w/0 1.11e-7 1.42 2.6E-01 5.55E-03 0.60 -6.7E-02 -8.41E-03 1.00 6.1E-02 8.84E-01 0.84 0.25 1.39E-06
Table 6.3: Fit result obtained by the Equivalent Circuit program for different cermet microstructures for circuit LRe(R1Q1)(R2Q2)(R3Q3). Resistance in ; inductance in H; capacitance in Farad; Constant Phase Element (Qn) in secn-1, where n is their exponent value ps2 values indicate the quality of the fitting procedure 0.
3 Re R1 R2 2 R3
R()
0 0 20 40 60 80 100
w/0 fine YSZ

-1
Figure 6.7: R values as a function of weight percentage fine YSZ. Data from Table 6.3.
108
1e+2 Q2 |Q3| 1e+1 Q4
1e+0
n -1 Q (sec )
0 1e-1
20
40
60
80
100
w/0 fine YSZ
1e-2
1e-3
1e-4
Figure 6.8: Q values as a function of weight percentage fine YSZ. Data from Table 6.3.
1.4
1.2
1.0
0.8
n
0.6 0.4 n1 0.2 n2 n3 0.0 0 20 40 60 80 100
w/0 fine YSZ
Figure 6.9: n values as a function of weight percentage fine YSZ. Data from Table 1.3.
109
7e-3 0 w/0 fine YSZ 10 w/0 fine YSZ 20 w/0 fine YSZ 50 w/0 fine YSZ 100 w/0 fine YSZ
6e-3
5e-3
R ( cm )
2
4e-3
3e-3
2e-3
1e-3
0 0 200 400 600 800 1000

0
Temp ( C)
Figure 6.10:
Lateral electrical conductivity experiments
with a maximum at 50 w/o fine YSZ. With 100 w/0 fine YSZ the resistance is somewhat lower, but still evidently higher than the resistance obtained for 20 w/0 fine YSZ. The fine YSZ prevents Ni from sintering. A larger fraction fine YSZ causes a smaller Ni particle size, resulting in a finer Ni network and a larger value for the resistance, which can be explained by partial blocking of the Ni network. 6.3.3 Relation between microstructure and electrochemical performance The results from this study clearly demonstrate that a change in microstructure can be established by varying the fraction of fine YSZ powder relative to that of coarse grained powder in the preparation of the Ni/YSZ electrode. The electrochemical performance is significantly altered with the presence of fine YSZ powder in the cermet structure. The functional dependence of the Ni particle size (Figure 6.4) on the fraction of fine YSZ powder in the cermet shows a strong resemblance with that of the electrode resistance (Figure 6.7). Both the Ni particle size and the electrode resistance decrease with increasing fraction of fine YSZ. Figure 6.11 shows the relation between the total electrode resistance and the Ni particle size. For particle sizes in the range of 1 to 1.5 m the change of the electrode resistance is small, but above 2 m the electrode resistance increases sharply with only a small increase in the Ni particle size. This suggests that a finer nickel network creates more active sites in the electrode, thereby decreasing the total electrode resistance. It should be noted however, that the Ni particle size is a bulk property of the cermet and it remains questionable whether the whole bulk of the cermet participates in the electrode reaction.
110
3.5
3.0
2.5
Rdc ()
2.0
1.5
1.0
0.5
0.0 0.5 1.0 1.5 2.0 2.5
Ni particle size (m)
Figure 6.11: Total electrode resistance as a function of the Ni particle size for cermet microstructures with different fractions fine YSZ. (Line is guide to the eye)
3.5 Ni Ni & YSZ
3.0
2.5
Rdc ()
2.0
1.5
1.0
0.5
0.0 0 50 100 150

2
200
250
300
TPB length (m/cm )
Figure 6.12: Total electrode resistance as a function of the TPB length based on the Ni/YSZ-surface and Ni-surface coverage at the interface for cermet microstructures with different fractions fine YSZ.
111
Figure 6.12 shows that the total electrode resistance decreases with increasing surface coverage. The surface coverage relates to the length of the Triple Phase Boundary at the interface. It was observed that with the application of the present screen printing technique, the coarse YSZ particles get positioned within the bulk but not at the interface between electrode and electrolyte. With this observation we can calculate the degree of Ni coverage at the interface from the relative fractions of fine YSZ and Ni in the cermet. With the additional observation of an almost constant particle size at the interface, the Triple Phase Boundary length at the interface, can be calculated and will be linearly related with the Ni coverage. Figure 6.12 shows that an inverse linear relationship between electrode resistance and TPB length is indeed seen at relatively small fractions of fine YSZ, but not at higher values. A possible explanation for the observed behaviour is that with low fractions of fine YSZ the electrode reaction is confined to the immediate vicinity of the interface, but at high fractions extends into the bulk of the cermet structure. 6.4 Conclusions
The results from SEM imaging show that the particle size of YSZ imposes a large influence on the microstructure of Ni/YSZ electrodes. While the presence of a coarse YSZ powder ensures a relatively high porosity of the cermet structure, fine YSZ powder prevents Ni from sintering into larger agglomerates. Similar results were also found by other investigators 000. The presence of fine YSZ therefore leads to a finer Ni network and guarantees a high degree of surface coverage for Ni particles at the interface between the cermet electrode and the electrolyte. Varying the relative amounts of coarse and fine YSZ in the preparation of the cermet electrodes resulted in a significantly improved electrode performance with higher fractions of fine YSZ. At low fractions of fine YSZ, where percolativity is predicted to be poor, the results from impedance spectroscopy suggest that the electrode reaction is confined to the immediate interface between cermet electrode and electrolyte. The observed inverse linear relationship in this region between the electrode resistance and the calculated TPB length suggests that the electrode reaction concentrates at the triple phase perimeter, which is distributed over the electrolyte surface. Only at high fractions of fine YSZ does the electrode reaction zone extend into the bulk of the cermet. The extent of the inward expansion of the active electrode area could not be calculated from the present data and awaits further studies. Acknowledgement The Netherlands Energy Research Foundation (ECN) is thanked for the preparation of the cermet electrodes. References
S.C. Singhal, Status of Solid Oxide Fuel Cell Technology, Proc. of the 17th Ris Int. Sym. on Materials Science, High Temperature Electrochemistry: Ceramics and Metals, 123-38, 1996. H. Itoh, T. Yamamoto, M. Mori, T. Horita, N. Sakai, H. Yokokawa and M. Dokiya, Configurational and Electrical Behavior of Ni-YSZ Cermet with Novel Microstructure for Solid Oxide Fuel Cell Anodes, J. Electrochem. Soc. 144, 641-46, 1997. F.P.F. van Berkel, F.H. van Heuveln and J.P.P. Huijsmans, Characterisation of Solid Oxide Fuel Cell Electrodes by Impedance Spectroscopy and I-V Characteristics, Solid State Ionics, 72, 240-47, 1994. D.W. Dees, T.D. Claar, T.E. Easler, D.C. Fee and F.C. Mrazek, Conductivity of Porous Ni/ZrO2-Y2O3 Cermets, J. Electrochem. Soc., 134, 2141-46, 1987.
112
6.4 Conclusions
N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. J. Divisek, A. Kornyshev, W. Lehnert, U. Stimming, I.C. Vinke and K. Wippermann, Advanced characterisation techniques for Nickel-YSZ Cermet Electrodes used in Solid Oxide Fuel Cells, Electrochemical Proceedings Volume 97-18, 606-16, 1997. A. Ioselevich, A.A. Kornyshev and W. Lehnert, Degradation of SOFC Anodes due to Sintering of Metal Particles: Correlated Percolation Model, J. Electroch. Soc., 144, 3010-19, 1997. T. Kawada, N. Sakai, J. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Structure and Polarisation Characteristics of Solid Oxide Fuel Cell Anodes, SSI, 40/41, 402-06, 1990. B.A. Boukamp, A Nonlinear least squares fit procedure for analysis of immittance data of electrochemical systems, Solid State Ionics, 20, 31-44, 1986. L Plomp, a. Booy, J.A.M. van Roosmalen, and E.H.P. Cordfunke, A Four Probe Apparatus for the High Resolution Conductivity Measurements of Ceramic Oxides at high Temperatures, Rev. Sci. Instrum., 61, 1949-53, 1990. M.I. Mendelson, Average Grain Size in Polycrystalline Ceramics, J. Am. Ceram. Soc., 52, 443-46 (1996). J.R. MacDonald, Impedance Spectroscopy, John Wiley and Sons, New York, 1987. T. Kenjo and K. Wada, Geometrical effects on pseudocapacitance in Pt/YSZ high temperature air cathodes, Solid State Ionics, 67, 249-55, 1994. R.D. Armstrong and B.R. Horrocks, The Double Layer Structure at the Metal-Solid Electrolyte Interface, Solid State Ionics, 94, 181-87, 1997. F.J.F. Miranda, O.E. Barcia, O.R. Mattos, and R. Wiart, Electrodeposition of Zn-Ni Alloys in Sulfate Electrolytes: I. Experimental Approach, J. Electrochem. Soc., 144, 3441-48 (1997). F.J.F. Miranda, O.E. Barcia, O.R. Mattos, and R. Wiart, Electrodeposition of Zn-Ni Alloys in Sulfate Electrolytes: II. Reaction Modeling, J. Electrochem. Soc., 144, 3449-57 (1997). Y.C. Hsiao, J.R. Selman, The degradation of SOFC electrodes, Solid State Ionics, 98, 33-38 (1997) S. Primdahl and M. Mogensen, Gas conversion impedance: SOFC Anodes in H2/H2O Atmospheres, pp 530-29 in Electrochemical proc. Vol 97-18 Aachen, 1997 J. Geyer, H. Kohlmller, H. Landes, R. Stbner, Investigations into the kinetics of the Ni-YSZ Cermet anode of a Solid Oxide Fuel Cell, Electrochemical Proceedings Volume 97-18, 1997.
113
7 Impedance of porous cermet electrodes
Abstract An analytical expression is derived for the impedance of a porous cermet electrode. The model that accounts for the spatial extension of the triple phase boundary (TPB) length between gas, electrolyte and metal phases in a direction perpendicular to the electrolyte / porous electrode interface is that of a ladder network (continuous transmission line). The variables in this model are the impedances associated with the transport of ionic and electronic charge carriers through both constituent phases of metal and ceramic, and that of the charge transfer reaction at the TPB points. The expression obtained enables calculation of the optimum thickness for the porous composite electrode. The model is used for analysis of the impedance of nickel/yttria-stabilised-zirconia electrodes in the hydrogen oxidation reaction. 7.1 Introduction
It is generally known that nickel has a high activity in hydrogen oxidation. To obtain adhesion with the electrolyte (usually YSZ) and stability under conditions encountered in solid oxide fuel cells (SOFCs) (i.e. high temperature and reducing conditions), these usually employ Ni-YSZ composites as anode [1]00. Another benefit of the application of porous electrodes is a high specific surface area and thus reduced polarisation losses in the fuel cell. In the Ni-YSZ composite anode, which consists of nickel particles, electrolyte particles and pores, the actual electrochemical activity is present at the three-phase-boundary. Each of the three components must be continuous, i.e. the composite must provide conductive pathways for electronic and (oxygen) ionic transport, and for the diffusive transport of fuel and reaction products. As a consequence of this spatial expansion from the electrode / electrolyte interface into the bulk of the electrode, the electrochemical activity may vary in distance from the electrode / electrolyte surface. The optimal composite structure is determined in a competitive interplay of the fundamental properties exhibited by each of the components. Several studies have been initiated to explore the effect of microstructure on the electrochemical performance of Ni/YSZ cermet anodes 0000. The latter is frequently characterised by impedance measurements. A major problem in this respect concerns the origin and physical interpretation of empirical equivalent circuits used to fit the experimental data.
115
These often include time constants of parallel RC and RQ circuits (where Q denotes a constant phase element), which can be studied experimentally by varying measurement conditions as, for example, the composition of the gas phase. The limited success of these studies in realisation of better anode structures is, at least partially, due to the fact that the equivalent circuits used in evaluation often lack a thorough physical interpretation. An attempt to take the actual microstructure of a cermet into account in impedance analyses with equivalent circuits, is the transmission line model. In such a model it is assumed that the lines describe the percolative nickel and YSZ paths in the cermet and the connecting paths represent the active sites, where the actual reaction takes place 0000. In this paper, a continuous transmission line model is used for the impedance of a porous cermet electrode. This model is used in analysis of impedance data for the hydrogen oxidation reaction on Ni/YSZ anodes. 7.2 Theory
Our analysis is based on a transmission model for the porous electrode as depicted in Figure 7.1. The porous electrode is considered as a slab of thickness d. It is in contact with an equipotential electrolyte surface at x = d on one side and with a current collector at x = - d at the other side. The distributed impedance elements Z1, Z2 and ZCT are considered to be position independent, i.e. the structure of the electrode is taken to be uniform. Each element may be composed of an arbitrary number of resistances, capacitances or inductances. The current passing through Z2 visualises the transport of electrons from the active
DimenMeaning sions Z1 Ohm/cm Ionic impedance Z2 Ohm/cm Electronic impedance Zct Ohm cm Charge transfer impedance x Cm Position coordinate d cm Thickness of the electrode layer I, I1, I2 A.s Fourier transform of current V, V1, V.s Fourier transform of voltage V2 Figure 7.1: Transmission line model for the Faradaic impedance of a porous composite electrode. Each impedance element may involve a number of other elements
116
7.2 Theory
sites in the interior of the electrode to the current collector, while the current through Z1 is associated with the transport of oxygen ions from the electrolyte to the active sites. The path with Zct reflects the electrochemical exchange of charge at the three-phase-boundary contact points. It is further assumed that the porous electrode is homogeneous in its area of contact with both the electrolyte membrane and the current collector, limitations regarding the conductivity occur only in the thickness direction of the electrode, mass transport of fuel and reaction products proceeds via the pores without any diffusion limitation. With these definitions and assumptions, the model can be represented by the following coupled differential equations
dV1 ( x ) = Z1 I1 ( x ) dx dV2 ( x ) = Z2 I 2 ( x ) dx dI1 ( x ) dI ( x ) V ( x ) V2 ( x ) = 2 = 1 dx dx Zct (7.1) (7.2) (7.3)
with the boundary conditions

I = I1 ( x ) + I 2 ( x ) 1 1 I = I1 ( x = d ) = I 2 ( x = d ) 2 2 1 1 V = V2 ( x = d ) V1 ( x = d ) 2 2 (7.4) (7.5) (7.6)
Symbols and parameters are defined in Figure 7.1. Solutions to the differential equations read
I1 ( x ) =
Z1 I Z1 + Z2 Z1 I Z1 + Z 2
cosh kx +I 1 cosh kd 2 cosh kx I 1 cosh kd 2
1 sinh k ( x + d ) 2 sinh kd 1 sinh k ( x + d ) 2 sinh kd
(7.7)
I 2 ( x) =
Z1 I Z1 + Z 2
Z1 + I Z1 + Z 2
(7.8)
1 cosh k ( x + d ) I sinh kx Z1 I 2 +C V1 ( x ) = sinh kd k cosh 1 kd k 2 1 cosh k ( x + d ) Z 22 I sinh kx Z1 Z2 Z1 I 2 +C + V2 ( x ) = Ix sinh k kd Z1 + Z2 Z1 + Z 2 k cosh 1 kd 2

ZZ Z Z 1 2 Ix 1 2 Z1 + Z 2 Z1 + Z 2
(7.9)
(7.10)
where C is an arbitrary constant and the parameter k is defined by

k = Z1 + Z2 Z ct (7.11)
On combining (1.1), (1.1), (1.2), (1.4) and (1.11) we obtain
117
7 Impedance of porous cermet electrodes 1 coth kd + 2 Zp k k sinh kd
Z = Z p d + (Zs 2 Z p )
(7.12)
where Z1 Z2 Z1 +Z2 Zs = Z1 + Z2 Zp = 7.3 Discussion of the model

(7.13) (7.14)
To consider some important implications of (1.1) a network as given in Figure 7.2 is considered. R1, R2, Rct and Cct make up the contributions to the overall impedance of the ladder network:.
Z1 = R1 Z 2 = R2 Z ct = Rct 1 + jRct Cct (7.15) (7.16) (7.17)
The latter expression is for the impedance of a parallel RC circuit. In Figure 7.3 some complex plane plots for this network are given. It is clear that the impedance plot can vary from a depressed circular arc, passing or non-passing through the origin, to a typical response characteristic for the presence of distributed elements. Following are a number of interesting simplifications of eq. (4.19) (for the network made up by R1, R2, Rct and Cct). Case 1: R2/R1 <<1 (negligible electronic resistance) The situation where R2/R1 refers to the case of a negligible resistance for the electronic charge carriers. Eq. (4.26) can be simplified to
Z = R1 coth ( kd ) k (7.18)
Meaning R1 Ionic resistance R2 Electronic resistance Rct Charge transfer resistance Cct Charge transfer capacitance Figure 7.2: Transmission line model for the Faradaic impedance of a porous composite electrode. The network consists of 4 elements. The dimensions and the possible physical meaning of the elements is shown as well.
Dimensions Ohm/cm Ohm/cm Ohm cm F/cm
118
7.3 Discussion of the model
Figure 7.3: Some impedance plots for the network shown in Figure 7.3. The values of the parameters used are indicated in the figure.
where k = R1 / Zct . Case 2: kd>>1 (non-percolative electrodes of high frequency limit) When either the electronic or the ionic conductive phase in the electrode is nonpercolative, kd>>1 may be valid. That is, when, (R1 +R2) d2 >> Rct. If kd>>1, Eq (4.20) tends to the form
Z = R p d + ( Rs 2 R p ) Z ct / Rs (7.19)
(Note that both cosh and sinh contain the term exp(kd).) But even when both phases are percolative the condition kd>>1 is still valid at high frequencies, i.e. >> Rs Cct d 2
. If in addition, >> Rct Cct
1 1
Eq.(4.26) leads to a linear
behaviour in the complex plane with an angle of 45 to the real axis, being characteristic for the semi-infinite length Warburg impedance. When k goes to infinity Eq. (1.11) yields Z = Rp d from which equation the high frequency axis cut-off can be determined. Case 3: kd<<1 (dominating charge transfer process) When the charge transfer resistance is large compared to the resistance associated with the transport of ions and electrons (Rct>>Rs d2), Eq. (1.41) reduces for relatively low frequencies to
Z = Zct d (7.20)
which leads to a single semicircle in the impedance plot. Case 4: 0 (steady state) In the steady state regime all impedance elements in Eq (4.27) may be replaced by their real part components, yielding
R = Z 0 = R p d + ( Rs 2 R p ) coth kd 1 + 2 Rp k k sinh kd (7.21)
where
119
Figure 7.4: Plot of the optimal electrode thickness versus R1 and Rct at given R2. k = Rs Rct (7.22)
The optimal electrode thickness dopt can be obtained from (1.38) by setting the partial derivative of R with respect to d to zero. The following expression is obtained:
d opt = Rct / Rs ln 1 + Rs / R p +
1 +
Rs / R p 1

(7.23)
At fixed values for R2 and Rct, dopt decreases with increasing R1, as illustrated in Figure 7.4. A large value of Rct leads to a large value for dopt, as expected. Increasing the layer thickness would reduce the potential losses in such a case. This holds up to the point where the total losses due to charge transfer across the three-phase-boundary contact points, are in balance with the total ohmic losses due to the transport of charge in both phases. In Figure 7.5 a clear minimum in the dc resistance is only observed when R1 and R2 are comparable in magnitude. When R2 << R1, no minimum is observed. Judging from Eq. (7.23), the parameter dopt in this case would become infinitely large. On the other hand Figure 7.5 shows that above a certain thickness the dc resistance decreases only marginally with increasing layer thickness. For this reason Hahn and Landes 0 defined the parameter d110, which corresponds with the electrode thickness at which the dc resistance is only 10% larger than that for an infinitely thick layer. Using Eq. (7.23) this condition may be written as
d 110 = ln(21) 2 Rct Rct . 152 R1 R1 (7.24)
7.4
Experimental
Zirconia cells were prepared from powder stabilised with 8 mol% yttria (Tosoh-Zirconia TZ-8Y) isostatically pressed into a thick rod. It was sintered to full density (> 99% theoretical density) at 1400C in air for 5 h. From the sintered rod discs were cut 16.0 mm in diameter and a thickness of 4.0 mm. Prior to use both surfaces were polished with 1 m
120
7.5 Results and discussion
Figure 7.5: Dc resistance versus electrode thickness. Calculations are based upon Eq. 7.23 using the parameters indicated in the figure.
diamond paste and ultrasonically cleaned with ethanol. A screen printing technique was used to form the Ni/YSZ working electrode at one of the polished surfaces. Different ratios of fine and coarse YSZ powder were used in the screen printing paste to obtain a systematic variation in the microstructure. The nickel content in the paste was fixed to a value of 55 vol% of the total solid mass obtained after reduction. The deposited anodes were sintered at 1300C for 5 h in air. Reduction of the NiO was carried out in-situ, prior to the electrochemical experiments at 850C, by stepwise changing the gas flow from nitrogen to a standard gas mixture as described below. Platinum paint (Demetron) was applied to the other side of the disc to form the counter electrode. A small groove around the disc was used for embedding of the platinum wire reference electrode. This groove was coated with platinum paint to improve the reference contact. Platinum wires ( = 0.2 mm) were used as current leads and potential probes. Before the cell was mounted in the apparatus for electrochemical measurements it was fired in air at 1000C for 1 h to anneal the Pt paint. Electrochemical experiments were done at 850C in hydrogen gas saturated with 2.3% H2O (100mlmin-1 (STP)), using the electrochemical cell in an undivided set-up. Impedance spectra were acquired over the range form 1 MHz to 10 mHz using a Solartron 1255 frequency response analyser with a Solartron 1287 electrochemical interface. This data was analysed using the 'Equivalent Circuit' program 0 and the transmission line model described in Section 7.2. The experimental set-up has been described in detail elsewhere 0. 7.5 Results and discussion
7.5.1 Impedance analysis using 'Equivalent Circuit' Typical impedance diagrams obtained for cermet electrodes with different microstructures are given in Figure 7.6. These could be fitted using the 'Equivalent Circuit' program 0 with the aid of the circuit LwRe(R1Q1)(R2Q2)(R3Q3), where L is an inductance, R a resistance and Q designates the impedance of a constant phase element (CPE). The latter is 121
0.8
0.6
0.4
Imag
Imag
0 1 2 3 4 5
0.2
0.0 1.5 -0.2 2.0 2.5 3.0
Real
Real
-1
-0.4
(a)
0.3 0.10 0.2
(b)
0.05
0.1
Imag
0.0 1.4 -0.1 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
Imag
0.00 1.40
1.45
1.50
1.55
1.60
1.65
1.70
1.75
Real
-0.05
Real
-0.10
-0.2
-0.3
-0.15
(c) (d) Figure 7.6: Impedance diagrams of Ni/YSZ cermet electrodes with a different microstructure: (a) 0 w/0; (b) 10 w/0; (c) 20 w/0 and (d) 100 w/0 fine YSZ.
cermet microstructures (w/0 fine YSZ) 0 w/0 Lw Re R1 Q1 n1 R2 Q2 n2 R3 Q3 n3 Rtot ps

2
5 w/0 1.46E-07 1.54 2.02 3.09E-04 0.78 -2.9E-01 -1.19E-03 1
10 w/0 1.73E-08 1.56 1.41 3.08E-04 0.78 -1.4E-01 -3.34E-03 1 6.7E-02 8.09E-01 0.85 1.34 8.79E-06
15 w/0 1.43E-07 1.47 1.22 2.99E-04 0.78 -1.2E-01 -2.93E-03 1 6.0E-02 9.42E-01 0.85 1.16 2.73E-06
20 w/0 8.52E-08 1.46 0.64 4.83E-04 0.78 -9.4E-02 -9.75E-03 1 7.8E-02 6.13E-01 0.85 0.62 2.96E-06
50 w/0 8.80E-08 1.45 0.46 4.82E-04 0.78 -5.0E-02 -1.58E-02 1 6.1E-02 9.15E-01 0.85 0.47 9.61E-07
100 w/0 8.75E-08 1.45 0.19 1.03E-03 0.78 -4.4E-02 -1.74E-02 1 6.7E-02 7.21E-01 0.85 0.21 5.41E-06
6.86E-08 1.49 2.84 3.58E-04 0.78
9.7E-02 1.52E+00 0.85 2.94 4.38E-05
5.8E-02 1.10E+00 0.85 1.79 7.09E-06
Table 7.1: Parameters obtained from fitting impedance spectra of Ni/YSZ cermet electrodes with different microstructure to the circuit LwR1(R2Q2)(R3Q3)(R4Q4). Units are, in parentheses, R (); L (H); C (F) and Qn (secn-1). ps2 values indicate reliability of the fitting procedure 0.
122
7.5 Results and discussion
given by ZCPE=1/Q(i)n, where i is the imaginary unit and the angular frequency. Parameters obtained from fitting are listed in Table 7.1. Lw is associated with the inductance of the wiring and instruments, whereas Re represents the uncompensated resistance of the electrolyte membrane. The three parallel RQ subcircuits describe the electrode response. The frequency powers n1, n2 and n3 of the CPE elements were fixed to enable comparison between the corresponding Q-values obtained for the different electrodes (see Table 7.1). For the cermet structure with zero w/0 of fine YSZ powder only two RQ subcircuits are needed to obtain a sufficiently low value for ps2, a parameter which is indicative for the reliability of the fit procedure 0. In Figure 7.6 an inductive loop is apparent in the mid-frequency range. In the fitting procedure this could be accounted for by assigning negative values to parameters R2 and Q2. The origin of the inductive loop might be explained in terms of the relaxation involving the surface coverage of an adsorbed intermediate species limited by two frequency-dependent rate processes. To derive the Faradaic impedance of heterogeneous reaction mechanisms due to adsorbed intermediates several methods have been developed 0. Analysis basically requires information about the potential dependence of the rate constants involved, the fractional coverage of the surface and of the free and blocked sites (in case there are two or more adsorbed intermediates) and the total amount of active sites available. Model calculations of these kind of processes have not been reported for the hydrogen oxidation reaction on Ni/YSZ composite electrodes, which is most certainly due to the complexity of its reaction mechanism. Even though impedance measurements are indispensable to obtain information about the time constants of the rate processes involved, they do not provide direct information about the nature of the adsorbed intermediates. Comparable inductive behaviour is reported for SOFC cathodes by Hsiao et al. 0. Resistance values as a function of the fraction of fine YSZ in the cermet structure are shown in Figure 7.7. As seen from this figure, the absolute value of R2 decreases with increasing fraction of fine YSZ, which observation emphasises on the importance of the microstructure in determining essential features in the impedance diagram. The resistance R1 associated with the high-frequency arc decreases significantly if only a small fraction of coarse YSZ is replaced by fine YSZ. As this arc is commonly interpreted as due to charge transfer 000, the increased number of three-phase-boundary contact points in the composite with increasing the volume fraction of fine YSZ can explain such behaviour. The resistance R3 associated with the low-frequency arc appears to be almost independent of the cermet microstructure. The Q values of the CPE elements of the three semicircles are represented in Figure 7.8. 7.5.2 Impedance analysis using the ladder network model In this section the impedance data is analysed using the ladder network model. To simplify matters, is assumed that Eqs. (7.15), (7.16) and (7.17) give the expressions for the elements of the network (see also Figure 7.2). Only the high frequency data of the spectra is considered. Therefore the experimental data was corrected by subtracting (R2Q2)(R3Q3) as obtained by fitting the experimental data with the program 'Equivalent Circuit'. To include properly the excluded (R2Q2)(R3Q3) of the spectrum in the network analysis, more should
123
4 Re R1 3 R2 R3 Rtot
R (cm )
2
0 0 20 40 60 80 100
w/0 fine YSZ in cermet

-1
Figure 7.7: Resistance values obtained from impedance data at zero bias for cermet structures with different fractions fine YSZ powder.
2 Q1 1 Q2 Q3
n n -1 log Q (sec )
0 0 -1 20 40 60 80 100
-2
-3
-4
Figure 7.8: Q values of the CPE elements obtained from impedance data at zero bias for cermet structures with different fractions fine YSZ powder, n values were fixed at (n1,n2,n3) = (0.78, 1, 0.85).
124
7.6 Conclusions
be known about the origin of these two arcs. If it is assumed that the appropriate elements can spread through the electrode, the network becomes much too complicated for a first assumption. In the analysis the network is taken to be terminated by Lw and Re to account for the inductance of the wires and instruments and the uncompensated resistance of the electrolyte. Parameters thus obtained from fitting are listed in Table 7.2. A typical fit spectrum is given in Figure 7.9. The fitted spectra appeared to be somewhat insensitive to the magnitude of R2. This is most certainly due to the fact that the matrix conductivity of the nickel network is much higher than that of the YSZ network. For this reason R2 for the different electrodes was fixed to a constant value of 0.9410-3 .cm-1. Hence the structural change in the composite electrodes, induced by the variation of the ratio of fine and coarse YSZ in their preparation, is reflected by corresponding changes in the values for R1, Rct and Cct. The gross behaviour found is that the resistance of the YSZ matrix (R1) and the charge transfer resistance (Rct) decrease with increasing weight fraction of fine YSZ, as shown in Figure 7.10. Such behaviour is expected when considering the microstructure of the electrodes. A finer YSZ network will lead to shorter pathways for oxygen ionic transport and, hence, to a higher value for the effective conductivity per unit length. A high ionic conductivity is beneficial in reducing ohmic potential losses over the ionic conducting phase. Image analysis of SEM micrographs of the electrodes revealed that the fine YSZ particles, present in the composite, prevent nickel particles from sintering together into larger agglomerates 0. The increased number of reaction sites enhances the electrode reaction kinetics per unit length of the electrode and, hence, contributes to a decrease in the effective value of the charge transfer resistance. Slow reaction rates force the reaction to be uniformly distributed over the depth of the electrode. Fast reactions, on the other hand, confine the reaction to proceed in a narrow region adjacent to the electrolyte / electrode interface. These competing effects of ohmic potential losses and reaction rates determine the resulting distribution, and also explain why the theoretical optimum electrode thickness for the different electrodes hardly varies within the experimental range of 0 to 100 w/0 fine YSZ. The behaviour of Cct with the weight fraction of fine YSZ, showing a minimum at 15 w/0, is less understood and must await a more rigorous treatment of the experiments of this study. 7.6 Conclusions
An analytical expression is derived to provide the basis for examining the Faradaic impedance of a porous composite electrode. The basic model adopted is a continuous transmission line, which accounts for the transport of ionic and electronic charge carriers to the distributed sites of the charge transfer process. The model is applied to impedance data of nickel/stabilised-zirconia electrode in the hydrogen oxidation reaction. The results show that the replacement of coarse YSZ particles by a corresponding weight fraction of fine YSZ in electrode preparation reduces total polarisation losses, but does not change requirements regarding the thickness of the electrodes in order to optimise their performance.
125
cermet microstructures (w/0 fine YSZ) 0 w/0 R1 (/cm) Rct (cm) Cct F/cm R2 (/cm) d (m) dopt (m) 25e03 3.3E-04 0.954 9.4E-04 26 10.6 5 w/0 20e3 2.0E-04 0.750 9.4E-04 26 9.3 10 w/0 14e3 1.4E-04 0.693 9.4E-04 24 9.0 15 w/0 13e3 1.2E-04 0.663 9.4E-04 24 8.6 20 w/0 5.8e3 7.3E-05 0.894 9.4E-04 26 9.5 50 w/0 4.3e3 5.1E-05 0.832 9.4E-04 25 9.1 100 w/0 1.1e3 3.6E-05 1.03 9.4E-04 21 13.7
Table 7.2: Parameters obtained from network model fitting of the impedance spectra of the Ni/YSZ cermet electrodes with different microstructure after subtraction processes that appear on the low frequency side of the spectra.
0.3
0.2
0.1
Imag
0.0 1.4 -0.1 1.5 1.6 1.7 1.8 1.9 2.0 2.1
Real
-0.2 Measured data network fit -0.3
Figure 7.9: Typical fit result obtained with chain ladder analyses for the cermet structure containing 20w/0 fine YSZ (the low frequency processes are subtracted from the data.).
3e+4 R1 Rct
3.5e-4
3e+4
3.0e-4
2.5e-4 2e+4
Rct (cm)
-1 R1 (cm )
2.0e-4 2e+4 1.5e-4 1e+4 1.0e-4 5e+3
5.0e-5
0 0 20 40 60 80 100 120
0.0
Figure 7.10: Resistance values as obtained with chain ladder analyses for the different cermet structures.
Acknowledgement
126
7.6 Conclusions
M.H.R. Lankhorst is thanked for useful discussions and for the mathematical analysis presented in this chapter. F.P.F. van Berkel is thanked for critical reading of the manuscript. References
S.C. Singhal, Status of Solid Oxide Fuel Cell Technology, Proc. of the 17th Ris Int. Sym. on Materials Science, High Temperature Electrochemistry: Ceramics and Metals, 123-38, 1996. N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. A. Hammou, J. Guindet, 'Solid Oxide Fuel Cells', Ch 12 of 'The CRC Handbook of Solid-State Electrochemistry', pp 409-445, CRC Press, Inc., 1997. H. Itoh, T. Yamamoto, M. Mori, T. Horita, N. Sakai, H. Yokokawa and M. Dokiya, Configurational and Electrical Behavior of Ni-YSZ Cermet with Novel Microstructure for Solid Oxide Fuel Cell Anodes, J. Electrochem. Soc. 144, 641-46, 1997. F.P.F. van Berkel, F.H. van Heuveln and J.P.P. Huijsmans, Characterisation of Solid Oxide Fuel Cell Electrodes by Impedance Spectroscopy and I-V Characteristics, Solid State Ionics, 72, 240-47, 1994. D.W. Dees, T.D. Claar, T.E. Easler, D.C. Fee and F.C. Mrazek, Conductivity of Porous Ni/ZrO2-Y2O3 Cermets, J. Electrochem. Soc., 134, 2141-46, 1987. S. Primdahl and M. Mogensen, Oxidation of Hydrogen on Ni/Yttria-Stabilized Zirconia Cermet Anodes, J. Electrochem. Soc., 144, 3409-19, 1997. T. Kawada, N. Sakai, J. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Structure and Polarisation Characteristics of Solid Oxide Fuel Cell Anodes, SSI, 40/41, 402-06, 1990. A. Hahn, H. Landes, Investigations into the kinetics of SOFC cathodes pp 595-605 in Proc. Of the 5th Int. Symp. On SOFC, Ed. U. Stimming, S.C. Singhal, H. Tagawa, and W. Lehnert, The Electrochemical Society, Aachen, 1997. F. Richter, Impedance Measurements under High Current for Development and Quality Control of Solid Oxide Fuel Cells (SOFCs), pp 3-7, Electrochemical Applications 1/97, Zahner-elektrik GmbH & Co, 1997. G. Paasch, P.H. Nguyen, Impedance of Inhomogeneous Porous Electrodes, a novel Transfer Matrix Calculation Method, pp 7-9, Electrochemical Applications 1/97, Zahner-elektrik GmbH & Co, 1997. B.A. Boukamp, A Nonlinear least squares fit procedure for analysis of immittance data of electrochemical systems, Solid State Ionics, 20, 31-44, 1986. Chapter 2 of this thesis. J.R. MacDonald, Impedance Spectroscopy, John Wiley and Sons, New York, 1987. Y.C. Hsiao, J.R. Selman, The degradation of SOFC Electrodes, Solid State Ionics 98 33-38, 1997. T. Norby, O.J. Velle, H. Leth-Olsen and R. Tunold, 'Reaction resistance in relation to three phase boundary length of Ni/YSZ electrodes', pp.473-78 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. M. Mogensen and T. Lindegaard, 'The kinetics of hydrogen oxidation on a Ni/YSZ SOFC electrode at 1000C'; pp. 48493 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. Chapter 6 of this thesis.
127
8 Investigation into the kinetics of hydrogen oxidation on the Ni/YSZ cermet electrode
Abstract The hydrogen oxidation reaction on screen-printed Nickel/Yttria Stabilised Zirconia (Ni/YSZ) cermets with different microstructure has been studied by impedance and I- measurements. For the impedance measurements conditions such as H2 and H2O partial pressure, anodic polarisation and temperature were varied. Impedance spectra as obtained under standard conditions indicate that at least three processes play a role in the electrode reaction. The process that dominates the electrode process for most cermets is located at the high frequency side of the impedance spectra and is because of its strong dependence on the vicinity of the TPB ascribed to a charge transfer process. The other two processes that are observed on the low frequency side of the spectra show a large dependence on gas phase conditions. In the mid-frequency range an inductive behaviour is found, which sometimes appears as an 'inductive loop' and is related with concentration relaxation of adsorbed intermediates. On the low frequency side of the spectra a small semicircle is observed, which is characterised by a high capacitive value. Under certain experimental conditions (low pH2 and high pH2O) additional arcs appear in the spectra, the origin of these arcs is not known at this moment. 8.1 Introduction
In Solid Oxide Fuel Cells (SOFC), the porous Ni/YSZ cermet is generally used for the anode [1]00. For this type of electrode the microstructure is an important parameter for its performance 000. Open porosity is required for the electrode for a unrestricted flow of the fuel and for the rapid removal of reaction products. The Ni particles, forming a percolative network, are responsible for transporting electrons from the reaction zone to the external circuit. The addition of YSZ is necessary to inhibit coarsening by sintering into larger particles at the usual operating temperatures of an SOFC, to give the cermet a thermal expansion coefficient acceptably close to that of other cell components 0, and to form a percolative network of YSZ particles to transport oxygen ions to the electrode 000. The above description stresses the importance of the cermet structure but does not indicate how the hydrogen oxidation reaction proceeds. Insight in the reaction is however important as it will contribute to further improvement of the anode. Impedance spectra obtained for 129
cermet electrodes often indicate that several processes play a role in the electrode performance, but tracing the origin of the observed processes is often found difficult 000. This study concentrates on the analysis of electrochemical measurements for different Ni/YSZ cermet structures. The electrochemical performance has been analysed using impedance spectroscopy and I- measurements. The characterisation of the microstructure is described in Chapter 6 and the electrochemical performance under standard conditions in Chapter 7. In this chapter impedance analysis as a function of pH2, pH2O, overvoltage and temperature is used for reaction kinetic studies on different cermet microstructures. 8.2 Experimental
8.2.1 Sample preparation The method of preparation of the samples and construction of the electrochemical cell has been described extensively elsewhere 0. The sintered yttria-stabilised zirconia (prepared from Tosoh-Zirconia TZ-8Y) discs had a diameter of 16.0 mm and a thickness of 4.0 mm. A small groove around the disc was made at half thickness for positioning of the reference electrode. Pt paste (Demetron) was applied onto the electrolyte discs for counter and reference electrodes. Ni/YSZ cermet electrodes were prepared with a screen printing technique (electrode diameter 14 mm). NiO and 8 mol% YSZ (Tosoh-Zirconia TZ-8Y) were used as starting materials. To obtain a systematic variation of the microstructure of the anode, different ratios of fine (0.2 m) and coarse(10 m) YSZ-particles have been used 0. The weight ratio of fine YSZ was set to 0, 5, 10, 15, 20, 50 and 100 weight% of the total zirconia content of the anode. The NiO content was kept at a value resulting in a Ni content of 55 vol% of total solids after reduction. The NiO/YSZ cermet anodes were reduced at operating temperature (850C) by stepwise increasing the hydrogen content in the gas flow. The cell geometry is shown schematically in Figure 8.1. 8.2.2 Electrochemical characterisation Electrochemical experiments were performed in a single-gas environment at atmospheric pressure. At standard conditions a gas flow of 100 mlmin-1 H2 (STP) with 2.3% H2O at 850C was used. For electrochemical measurements helium was used as an inert gas. The details of impedance and polarisation measurements have been described elsewhere 0. In summary, impedance measurements were performed over the frequency range from 1 MHz to 0.01 Hz using a Solartron frequency response analyser 1255 in combination with a Solartron electrochemical interface 1287. Data analysis was performed using the software package Equivcrt 0. Polarisation measureFigure 8.1: Schematic side view of the three-electrode electrochemical cell. ments were carried out 130
8.3 Results
using a Solartron electrochemical interface (model 1287) for potentiostatic control. Overpotential data were corrected for the uncompensated resistance of the electrolyte, the value of which was evaluated from impedance spectroscopy data. After heating the electrode to 850C under nitrogen atmosphere, the following experiments were conducted in the sequence as indicated: Reduction of the NiO in the electrode by stepwise changing to a standard measurement atmosphere: 97.7% H2 and 2.3% H2O. Impedance measurements were performed untill a steady performance was obtained. I- measurements under standard conditions. Prior to measurement the working electrode was anodically biased at 750 mV for 30 min. Hereafter, the I- curve was recorded by decreasing the potential stepwise to zero. Immediately hereafter the impedance was measured. Impedance measurements under anodic polarisation of the electrode at 100, 200, 300, 400, 500, 600, 700 and 750 mV relative to the reference electrode. Potential values given here are not corrected for the IR drop of the electrolyte. For three of the seven cermet structures (0, 20 and 100w/0 fine YSZ) the following additional experiments were conducted. Impedance measurements as function of pH2 and pH2O. These were performed in the pH2 range of 9.98104 to 4.95103 Pa, fixing pH2O at 2.33103 Pa and in the pH2O range from 1.22103 to 2.00104 Pa, fixing pH2 at 8.11104 Pa. Impedance measurements as function of temperature. These were performed at standard conditions by decreasing the temperature from 850 to 600C. Between the experiments impedance diagrams were recorded under standard conditions to monitor the performance of the cermet electrode as a function of time. 8.3 Results
8.3.1 Impedance measurements 1.1.1.26Impedance measurements under standard conditions A survey of the obtained impedance spectra as function of the fraction fine YSZ is given in Figure 8.2. The data was fitted with the equivalent circuit LwRe(R1Q1)(R2Q2)(R3Q3). Results of the fitting procedure as function of the microstructure are presented in Chapter 7 of this thesis 0. 1.1.1.27Impedance measurements as function of pH2 and pH2O To illustrate the effect of the gas phase on impedance data for the different cermet microstructures (0, 20 and 100 w/0 fine YSZ) typical spectra are given as function of pH2 and pH2O in Figure 8.3 to Figure 8.8. For the cermet structure with only coarse YSZ (Figure 8.3 and Figure 8.4) no changes are observed in the qualitative appearance of the
131
0.8
0.6
0.4
Imag
0 1 2 3 4 5
Imag
0.2
0.0 1.5 -0.2 2.0 2.5 3.0
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-1
-0.4
(a)
0.75 0.3
(b)
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0.00 1.0 -0.25 1.5 2.0 2.5 3.0
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1.55
1.60
1.65
1.70
1.75
Real
-0.05
Real
-0.10
-0.15
(e) (f) Figure 8.2: Impedance spectra for different cermet structures measured at zero bias under standard conditions: (a) 0 w/0; (b) 10 w/0; (c) 15 w/0; (d) 20 w/0; (e) 50 w/0 and (f) 100 w/0 fine YSZ.
132
8.3 Results
Imag
0 1 2 3 4 5
Real
pH2 = 1.0 10 Pa -1 pH2 = 5.0 10 Pa pH2 = 2.0 10 Pa
4 4 5
Figure 8.3: Typical impedance spectra as function of pH2 at zero bias for cermet microstructure containing 0w/0 fine YSZ powder measured at pH2O = 2.3 103Pa and T = 850C.
Imag
0 1 2 3 4 5 6 7
Real
-1 pH2O = 1.2 10 Pa pH2O = 4.2 10 Pa -2 pH2O = 2.0 10 Pa
4 3 3
Figure 8.4: Typical impedance spectra as function of pH2O at zero bias for cermet microstructure containing 0w/0 fine YSZ powder measured at pH2 = 8.1 104 Pa and T = 850C.
133
0.50
0.25
Imag
0.00 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
Real
-0.25 pH2 = 1.0 10 Pa pH2 = 3.0 10 Pa -0.50 pH2 = 5.0 10 Pa
3 4 5
Figure 8.5: Typical impedance spectra as function of pH2 at zero bias for cermet microstructure containing 20w/0 fine YSZ powder measured at pH2O = 2.3 103 Pa and T = 850C.
0.75
0.50
0.25
Imag
0.00 1.5 -0.25 2.0 2.5 3.0
Real
-0.50
pH2O = 1.2 10 Pa pH2O = 4.3 10 Pa

3 4
-0.75
pH2O = 2.0 10 Pa
134
8.3 Results
0.10
0.05
Imag
0.00 1.45
1.50
1.55
1.60
1.65
1.70
1.75
Real
-0.05 pH2 = 1.0 10 Pa pH2 = 3.0 10 Pa -0.10 pH2 = 5.0 10 Pa
3 4 5
Figure 8.7: Typical impedance spectra as function of pH2 at zero bias for cermet microstructure containing 100w/0 fine YSZ powder measured at pH2O = 2.3 103 Pa and T = 850C.
0.2
0.1
Imag
0.0 1.5 1.6 1.7 1.8 1.9 2.0
Real
-0.1
-0.2
pH2O = 1.2 10 Pa pH2O = 2.3 10 Pa pH2O = 2.0 10 Pa

4 3
135
impedance spectra with changes in pH2 and pH2O gas phase. For the other electrodes, where part of the coarse YSZ has been replaced by fine YSZ, significant changes occur at the low frequency side of the spectra. For low pH2 an additional arc appears between the high frequency arc and the inductive loop (Figure 8.5 and Figure 8.7). The same holds for high pH2O where additionally the small semicircle on the low frequency side disappears (Figure 8.6 and Figure 8.8). Note the increasing relative importance of the inductive loop in the total polarisation of the electrode with increasing weight fraction fine YSZ. The spectra indicate the need for a more complex circuit. The circuit is represented by LwRe(R1Q1)(R2Q2)(R3Q3)(R4Q4) where (R2Q2) represents the appearing semicircle in the mid-frequency range. For the pH2 and pH2O dependent data n-values of the CPE elements are fixed, (n1, n2, n3, n4) = (0.78, 1, 1, 0.85). The inductive loop could be accounted for by assigning negative values to parameters R3 and Q3. Typical results obtained for the cermet structure with 20w/0 fine YSZ are presented below. Conductivity data calculated from i = 1/(ARi), where A is the geometric area of the working electrode (1.54 cm2) and Ri the value of the resistance obtained from the fitting procedure, are given in Figure 8.9 and Figure 8.10 for pH2 and pH2O. It should be noted that the given orders are no reaction orders. The order with respect to pH2 and pH2O is indicated in the figures. Note that the order of 3, associated with the inductive loop, depends on both the pH2 and pH2O range. The conductivity of the electrolyte is found to be invariant with pH2 and pH2O, as expected. Q-values of the CPE elements as a function of pH2 and pH2O are presented in Figure 8.11 and Figure 8.12, respectively. A survey of the dependence of 1 and tot as a function of pH2 and pH2O is given in Table 8.1. The deviation between these values indicates that the high frequency part of the spectra does not dominate the total impedance spectra anymore. 1.1.1.28Impedance measurements under bias Impedance graphs at specific -values for the cermet containing 20w/0 fine YSZ powder are shown in Figure 8.13. The spectra are strongly influenced by anodic polarisation. For increasing anodic polarisation first the low frequency arc disappears, after which the inductive loop becomes smaller and a new arc appears between the high-frequency arc and the inductive loop. For high polarisation values a new low-frequency arc appears with a size almost equal to the high-frequency arc. It is clear that this data cannot be analysed with a simple equivalent circuit. With LwRe(R1Q1)(R2Q2)(R3Q3)(R4Q4)(R5Q5), where (R5Q5) represents the arc that appears at low frequency, reasonable fits could be obtained. The frequency powers of the constant phase elements n1, n2, n3, n4 and n5 where fixed to 0.78, 1, 1, 0.85 and 0.8. Conductivity values and the corresponding Q values are given in Figure 8.14 and Figure 8.15. 1.1.1.29Impedance measurements as function of temperature The Arrhenius plots of the electrolyte and total electrode conductivity are given in Figure 8.16 for the cermet electrode containing 20 w/0 fine YSZ powder. The activation energies are 78 kJmol-1 and 94 kJmol-1, respectively. For the cermet containing 0 and
136
8.3 Results
2 e 1 0.05 1 0.19 -0.62 0.05 2 3 4 tot
log ( cm )
-1 -2
-0.14
-0.26 0.004
-1 3.5 4.0 4.5 5.0 5.5
log pH2 (Pa)
Figure 8.9: pH2 dependence of the conductivities obtained from analysis of impedance data at zero bias for a cermet containing 20w/0 fine YSZ powder. The absolute value is taken for the conductivity calculation of negative R values of the fit.
2 1.5 1.8 0.32
log ( cm )
-2
1 0.11 e 1 2 3 4 tot -1 3 4 5 0.005 0.38
-1
log pH2O (Pa)
Figure 8.10: pH2O dependence of the conductivities obtained from analysis of impedance data at zero bias for a cermet containing 20w/0 fine YSZ powder. The absolute value is taken for the conductivity calculation of negative R values.
137
1 Q1 Q2 Q3 Q4
n n -1 log Q (sec )
-1
-2
-3
-4 3 4 5 6
log pH2 (Pa)
Figure 8.11: pH2 dependence of the Q values of the CPE elements as resulted from analysis of impedance data at zero bias for a cermet containing 20w/0 fine YSZ powder. The absolute value is taken for the negative Q values.
1 Q1 Q2 0 Q3 Q4
log Qn (secn-1)
-1
-2
-3
-4 3 4 5
log pH2O (Pa)
Figure 8.12: pH2O dependence of the Q values of the CPE elements as resulted from analysis of impedance data at zero bias for a cermet containing 20w/0 fine YSZ powder. The absolute value is taken for the negative Q values.
138
8.3 Results
Fraction fine YSZ (w/0) 0 20 100 1 -0.18 -0.26 -0.39
pH2 tot -0.16 -0.14 -0.22 1 0.38 0.38 0.32
pH2O tot 0.36 0.36 0.37
Table 8.1: Order of gas phase pressure dependence of the electrode conductivity of the high frequency semicircle and of the total electrode conductivity. Results from impedance measurements at zero bias on electrodes with different fractions fine and coarse YSZ powder.
0.3
0.15 0.10
0.2 0.05 0.1 0.00 1.4 1.5 1.6 1.7 1.8 1.9
Imag
Imag
0.0 1.4 -0.1 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
-0.05 -0.10 -0.15
Real
Real
-0.2
-0.20 -0.25
-0.3
= 0 mV
0.10 0.10
= 41 mV
0.05
0.05
0.00 0.00 1.4 1.5 1.6 1.7 1.8 -0.05 1.4 1.5 1.6 1.7 1.8
Real
Imag
-0.05
Real
Imag
-0.10
-0.10
-0.15
-0.15
-0.20
-0.20
-0.25
= 78 mV
= 107 mV
Figure 8.13: Impedance spectra for cermet with 20 w/0 fine YSZ measured at standard conditions under different values of anodic polarisation.
139
e 1 2 3 4 5
log ( cm )
-1 -2
20
40
60
80
100
120
(mV)
Figure 8.14: Anodic porlarisation dependences of resistances as resulted from analysis of impedance data for a cermet containing 20w/0 fine YSZ powder. The absolute value is taken for the negative R values of the fit.
log Q (sec )
n -1
-1
Q1 Q2 Q3 Q4 Q5
-2
-3
-4 0 20 40 60 80 100 120
(mV)
Figure 8.15: Anodic polarisation dependence of CPE parameter Q as resulted from analysis of impedance data for a cermet containing 20w/0 fine YSZ powder. The absolute value is taken for the negative Q values of the fit.
140
8.4 Discussion
1 94 kJ/mol 0 Electrode Electrolyte
ln 1/Ri ( )
-1
-1
78 kJ/mol
-2
-3
-4 0.8 0.9 1.0 1.1 1.2 1.3
1000/T (1/K)
Figure 8.16: Temperature dependence of electrolyte and electrode conductivity for cermet with 20w/0 fine YSZ.
100w/0 fine YSZ the activation energies of the total electrode conductivity are respectively 112 kJmol-1 and 107 kJmol-1. 8.3.2 I- measurements Anodic branches of the Tafel plots for all cermet structures are given in Figure 8.17. As indicated in this figure the observed Tafel slopes are in the range of 1.4(F/RT) and 2(F/RT). No clear relations are found between the microstructure and the observed Tafel slope. 8.4 Discussion
Impedance results obtained for different cermet structures show a large dependence on gas condition, anodic polarisation and temperature. Within the applied experimental range five different processes appear in the impedance spectra. To unravel the origin of the different processes the semicircles are discussed in detail and impedance spectra obtained for cermet electrodes are compared with those of porous nickel electrodes. Finally a comparison is made with results found in the literature for different Ni/YSZ cermet electrodes. 8.4.1 Processes observed on the cermet electrode As a starting point the dependencies of the R and Q values for the different semicircles on varying conditions are summarised in Table 8.2.
141
4 2.0
log i (mA cm-2)
2 1.5
Anodic
0 w/0 fine YSZ 5 w/0 fine YSZ 10 w/0 fine YSZ 15 w/0 fine YSZ 20 w/0 fine YSZ 50 w/0 fine YSZ 100 w/0 fine YSZ 0 20 40 60 80 100 120 140 160 180
-1
-2
(mV)
Figure 8.17: Tafel plot showing anodic branch, measured at standard conditions for cermet microstructures with different fractions fine YSZ.
1.1.1.30(R1Q1) This semicircle appears at high frequencies and is attributed to charge transfer at sites distributed over a certain dept of the electrode. As seen from Figure 8.2 and results presented in chapter 7 a sharp decrease of R1 occurs already if in the electrode preparation only a small fraction of coarse YSZ is replaced with fine YSZ. This is due to the increased number of reaction sites as the presence of fine YSZ particles prevents the nickel particles from sintering together into larger agglomerates 0. But, on the other hand, a finer YSZ network leads to shorter pathways for oxygen ionic transport and, hence to a increase in ionic conductivity per unit length of the electrode. Both effects are beneficial in reducing total potential losses. Yet they compete as regards the depth of penetration of the reaction into the bulk of the electrode. Transmission line analysis of the high frequency semicircle (measured under standard conditions) showed that the optimal electrode thickness does not vary too a large extent in the range of 0 100 w/0 fine YSZ 0. The constant phase element Q1 does not act as a pure capacitance, i.e. the value of its frequency power n1 departs from unity. This behaviour is caused by the distribution of active sites over some electrode depth. The fact that the high frequency semicircle could be fitted with n1 = 0.78 for all electrodes may be taken as an indication for a similar distribution of the reaction kinetics in the interior of the electrodes. Data measured as function of the gas phase partial pressure clarify that the microstructure has a significant influence on the observed reaction order of H2 and H2O partial pressures. Though a detailed mechanism for the hydrogen oxidation reaction on nickel/YSZ elec
142
R1 Microstructure strong R1 fine YSZ pH2 0: m=-0.18 20: m=-0.26 100: m=-0.39 n larger if fine YSZ pH2O 0: m=0.38 20: m=0.38 100: m=0.32 n independent of pH2O Anodic polarisation Q1 (n = 0.78) Microstructure low fine YSZ constant high fine YSZ Q1 pH2a constant R1
R2 Does not appear
R3 Only for fine YSZ fine YSZ R3
R4 Constant
R5
0: does not appear 20: pH2 R2 100: pH2 R2
0: does not appear 20: high pH2 constant low pH2 R3 100: goes through max
0: constant 20: no clear dependence 100: pH2 R4
0: does not appear 20: pH2O R2 100: pH2O R2 20&100 only for high pH2O R2 appears
0: does not appear 20: pH2O R3 100 pH2O reaches max
0: constant 20:pH2OR4 & disappear 100:pH2OR4&disappear
low R3 high R3 & disappear
R4 & disappear
high appears & R5 Q5 (n = 0.85)
Q2 (n = 1)
Q3 (n = 1) low fine YSZ Q3 high fine YSZ constant
Q4 (n = 0.85) fine YSZ Q3
pH2 appears and Q2 slight
pH2 Q3
pH2 Q4 slight (some scatter)
pH2Oa
pH2O Q1 slight
pH2O appears & constant
low pH2O constant high pH2O Q3 Q3
pH2O Q4 and disappear
Anodic polarisation
b
constants
Q4 & disappears
high Q5 slight
8.4 Discussion
Table 8.2: Summary of the observed results out of impedance analysis for the different cermet structures; aas found for 20 and 100w/0 fine YSZ, no dependences where found for 0w/0 fine YSZ. b as found for 20 w/0 fine YSZ.
143
trodes is lacking at this moment, this observation suggests that in the sequence of reaction steps the number of adsorption sites accessible to the gases and/or intermediates play an important role. The present coupling of the high-frequency semicircle with charge transfer kinetics has also been suggested by others 000. 1.1.1.31(R2Q2) This semicircle appears with increasing pH2O and decreasing pH2 and was only observed for cermet electrodes where part of the coarse YSZ was replaced by fine YSZ. The nature of this semicircle is not known at the moment. 1.1.1.32(R3Q3) This semicircle associated with the inductive loop is observed in the spectra for cermet structures where part of the coarse YSZ is replaced by fine YSZ. Its associated resistance R3 decreases with increasing weight fraction of fine YSZ. For moderate fractions fine YSZ the resistance decreases with pH2 and pH2O and R3 seems to have a maximum value for 100w/0 fine YSZ. If the electrode is anodically polarised R3 first increases, but at high overpotential values vanishes. Compared with the other semicircles Q3 shows the strongest dependence on microstructure, gas condition and overvoltage. In our earlier studies on porous nickel electrodes inductive loops were only observed in the low frequency range during anodic polarisation 0. Similar diagrams have been observed in studies of the passivation behaviour of certain metals [26][27] and for the Au/YSZ electrode in air by van Hassel et al. 00. For the Ni/YSZ cermet structures the inductive loop already appears at equilibrium. A first suggestion is that its appearance is related with the microstructure of the electrodes since inductive loops have not been observed for the porous nickel electrodes in equilibrium 0. Inductive effects in the spectra may occur whenever a stepwise electron transfer takes place towards adsorbed intermediates 000. The actual appearance depends on the value of the rate constants and hence on the potential dependence of the fractional coverages of the adsorbed intermediates. Another possible explanation given in literature for the appearance of inductive loops concerns the passivation behaviour of nickel upon formation of NiO. Studying a Ni ball electrode pressed on YSZ (Guindet et al. [13]) assumed formation of NiO at anodic potentials between 850 and -650 mV vs air. Inductive loops appeared in the impedance spectra for anodic potentials smaller than 650 mV vs. air. As in this study inductive loops already appear in spectra recorded under standard conditions their presence is not ascribed to the formation of NiO. No relation was found between the magnitude of R3 and the decrease in porosity of the cermet structure with increasing weight fractions of fine YSZ. At 20w/0 fine YSZ, R3 shows a change in order dependence for the applied pH2 and pH2O range. Q3 shows a large dependence on all varied conditions but the meaning of this is not clear at this moment. 1.1.1.33(R4Q4) The low frequency semicircle (R4Q4) is characterised by its relatively high Q value (depending on microstructure, values of 0.5 -1sec0.85 and higher are observed 0). R4 is ob144
8.4 Discussion
served to be constant with different microstructures. Estimation of capacitance values, as performed by Primdahl et al. 0, related to monocharged species adsorbed on either the YSZ and/or the Ni surface in the electrode gives values in the order of 50 mF/cm2. This makes Q4 too high to be ascribed to adsorbed monocharged species. Of particular note is the disappearance of (R4Q4) with increasing pH2O observed for cermet structures with some weight fraction of fine YSZ as well as with increasing anodic polarisation. The results given in Table 8.2 suggest a dependence on microstructure and gas partial pressure but the appearance of this semicircle is not understood at this moment. 1.1.1.34(R5Q5) This semicircle is found at low frequencies and only under high anodic polarisation values as can be seen in Figure 8.13. Figure 8.18 gives an survey of impedance spectra for different cermet structures obtained under high anodic polarisation. In all spectra shown the semicircle (R5Q5) has a similar appearance. Data analysis indicates that it is characterised by a high Q value (of the same order as Q4). Since it appears at high anodic polarisation (R5Q5) seems to be involved with water production at the anode, which could suggest that this semicircle represents a kind of gas phase capacitance 0. 8.4.2 Comparison with porous nickel electrodes Compared with impedance spectra for the cermet structures, relatively simple spectra were obtained showing two semicircles for porous nickel electrodes 0. The semicircle associated with charge transfer dominates the spectrum in the case of the porous nickel electrodes. The large decrease in the charge transfer resistance observed for cermet electrodes can be
0.20 0.15 0.10
0.15
0.10
0.05
0.05
Imag
0.00 1.35 -0.05 -0.10 -0.15
Imag
0.00 1.35 -0.05
1.40
1.45
1.50
1.55
1.60
1.65
1.70
1.75
1.40
1.45
1.50
1.55
1.60
1.65
1.70
1.75
Real
Real
-0.10
= 122 mV -0.20
-0.15 = 107 mV -0.20
0 w/0 fine YSZ

0.15
0.15
20 w/0 fine YSZ

0.10
0.10
0.05
0.05
Imag
Imag
0.00 1.35 -0.05
1.40
1.45
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1.75
0.00 1.35 -0.05
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1.50
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1.75
Real
Real
-0.10
-0.10
-0.15
-0.15
= 92 mV
-0.20
= 63 mV
-0.20
50 w/0 fine YSZ 100 w/0 fine YSZ Figure 8.18: Impedance spectra obtained under high anodic polarisation for different cermet structures. All spectra show the appearance of a relative dominant semicircle at the low frequency side.
145
attributed to a large internal surface with a large number of active sites for charge transfer. The decrease in n value from 0.93 to 0.78 is caused by an increase of the number of active sites in the electrode, something not possible for the almost two dimensional porous nickel electrodes (and therefore close to one). Whereas the cermet structure brings about a large change in R, this is not the case for the corresponding Q values. The low frequency semicircle of the nickel electrode shows resemblance with the low frequency semicircle observed for the cermet electrode. Both have a relatively large Q value, a resistance value relatively small compared with the high frequency semicircle, and a strong dependence on pH2O. The dependence on overpotential agrees with the appearance of a small semicircle on the low frequency side for high overpotential values (Figure 4.7). For nickel electrodes it seems to appear at a higher overpotential and it seems less dominant, but it is of comparable size. This support of the suggestion that this semicircle is related to the change in gas phase composition. Despite the higher overpotential the current will be of the same order, resulting in a comparable water production. If gas phase dependence is compared over the whole range of electrodes it is clear that the dependence of tot as function of pH2 and the pH2O shows large resemblance. Also comparison of I- data indicates no clear changes in electrode performance. Although determination of Tafel slopes is difficult for all type of electrodes, the appearance of the different Tafel plots show large resemblance. These results obtained for the different type of electrodes indicates that the hydrogen oxidation reaction mechanism for the different type of electrodes will be the same. The complex behaviour of cermet electrodes at the low frequency side will be related with microstructural changes. 8.4.3 Comparison with literature Impedance measurements reported in literature are mostly performed at a temperature of 1000C, in a divided set-up at an open circuit voltage against Pt in air of about 1070 mV and a gas mixture of hydrogen saturated at room temperature with water (3%). To make comparison possible our resistance values are scaled from 850C to 1000C using the measured activation energies (see Table 8.3). Special attention is given here to the appearance of the impedance spectra and the origin of the observed arcs. The microstructure of the cermet is thought to be important, but quantitative values of the cermet structure are hardly available in literature. Because the starting materials and preparation process determine the final microstructural properties, Table 8.4 connects the preparation process with obtained Fraction fine YSZ R1 Rtot impedance results. On basis of these observations (w/0) (cm2) (cm2) it can be concluded that the microstructure has a 0 0.91 0.89 large influence on the total polarisation resistance 20 0.40 0.41 of the electrode, values found are between 0.27 2 100 0.28 0.31 and 16.9 cm . The particle size distribution, Ni/YSZ content, sintering temperature and prepaTable 8.3: Resistance values for different cermet microstrucration method affects the final microstructure, but tures scaled to a temperaa clear relation does not exist.
ture of 1000C using activation energies.
146
Author
Ni/YSZ (vol %)
Particle size NiO(m) 12.5 YSZ(m) 0.21
Preparation method Painted Painted Painted Screen printing
Sintering condition 5h 1500C 5h 1400C 5h 1300C 1.5h 1400C 5h 1350C
Layer thickness (m) 100 100 100 30-40 arc 1 1 total 1 2 30-40 1 2
Impedance R (cm2) 0.3 2.6 10.5 3.4 13.5 0.044 0.018 0.031 0.018 0.22 0.098 0.074 0.20 4.0 (4.4)a 0.14 (0.15)a 0.99 (0.92)
a
Comment Rtot (cm2)
Kawada et al. 0
55/45w/0 55/45w/0 55/45w/0
Overlapping arcs, probably 3 First value given, not stable 16.9 First value, not stable 0.062 Anode type seen as standard Arc 1 is ascribed to microstructure 0.27 Fine powder type of anode 0.37
Lee et al. 0
45/55
45/55
3.1
3.1
Screen printing
Primdahl et al. 0
40/60
0.4&10 6:1
0.4
Spray painting
2h 1300C
40-50
1 2 3
50/50
Spray painting
2h 1300C
1 2 3
this chapter
55/45
0.2&10 0:100
Screen printing
5h 1300C
25-30
1 2
4.14
55/45
0.2&10 20:80
Screen printing
5h 1300C
25-30
1 2 3
-0.14 (-0.13)a 0.12 (0.11)a 0.30 (0.28)a -0.07 (-0.06)a 0.10 (0.10)a 0.33 8.4 Discussion 0.97
55/45
0.2&10 100:0
Screen printing
5h 1300C
25-30
1 2 3
147
Table 8.4:
Survey of results as obtained in literature for different cermet structures, showing their preparation route and electrode performance. Performance is measured at OCV at 1000C in 97% H2 and 3% H2O, except for a these measurements are performed in one gas atmosphere at 850C.
The total polarisation resistance may be based on one, two or three different contributions, where one can even have an 'inductive' behaviour. The relative importance of the observed arcs depends on microstructure. Kawada et al. 0 reported that a higher sinter temperature resulted in a lower total polarisation resistance of the electrode and impedance spectra dominated by one arc, where three arcs were observed for lower sinter temperatures. The particle size of the starting materials seems important. Lee et al. 0 showed that a too large NiO particle size compared with YSZ leads to high polarisation resistances. Better results were obtained for particles of the same size. Primdahl et al. 0 reported polarisation resistances for 8 different types of cermet electrodes (two are given in Table 8.4). They observed a tendency towards higher polarisation resistances when finer powders (both Ni and YSZ) or coarser YSZ was used. Three semicircles where observed and their contribution to the total polarisation resistance was found to be dependent on microstructure. In this study higher polarisation resistances are also observed for higher fractions of coarse YSZ, but here the polarisation resistance decreased towards finer YSZ particles. The number of different contributions to the total polarisation resistance is comparable to that found by Primdahl et al. although the individual contributions show large discrepancies. Comparison can only be made for the high frequency semicircle, which is in both cases ascribed to the microstructure. For our electrodes a relatively large part of the total polarisation is ascribed to microstructure, but our rest potential (related to (R2Q2)(R3Q3) is small compared to the one observed by Primdahl et al. This lead to the overall conclusion that something can still be gained by improving the cermet microstructure. 8.4.4 Overall comparison In this study 'inductive loops' are observed in impedance spectra for cermet electrodes at zero bias. This is generally not found for porous nickel electrodes, nor has it been reported for cermet electrodes in literature. This strongly indicates that the appearance of the inductive loop is related to the complex microstructure of porous cermet electrodes. Parameters that characterise the cermet structure are porosity, pore diameter, tortuousity, particle size and surface area of nickel as well as YSZ. Because the inductive loop is also affected by gas composition and anodic polarisation it should also be related to the hydrogen oxidation reaction that occuring at the anode. A possible reaction mechanism is proposed in chapter 4. The charge transfer step is already related to the high frequency semicircle. Gas phase diffusion of H2 to the active sites and H2O in the opposite direction are related to porosity and pore diameter. But the Faradaic impedance of such a process does not result in an inductive loop. In addition vacant sites on the nickel as well as on the YSZ surface together with adsorbed species as H on the nickel and H2O and OH- on the YSZ (based on the reaction mechanism proposed in chapter 4 0) are related with the microstructure. The surface area of nickel and YSZ determines the number of available sites. This returns us to the hypothesis of heterogeneous reaction mechanisms due to adsorbed intermediates 0. The Faradaic impedance that can be derived for such processes requires information about the potential dependence of the rate constants involved, the fractional coverage of the surface and of free and blocked sites (in case there are two or more ad-
148
8.5 Conclusions
sorbed intermediates), and the total number of active sites available. If one of these parameters is critical and if it is sensitive to small variations in potential it is believed that inductive loops can appear. Evidence for this model should be obtained by applying numerical calculation for this type of reaction mechanisms, with the amount of active sites and surface coverages as variables. From the experimental side it will be useful to obtain more quantitative information about the microstructure. 8.5 Conclusions
The observed behaviour for cermet electrodes with different microstructures is complex. For a cermet electrode with only coarse YSZ two semicircles could give an appropriate fit of the impedance spectra. Replacing part of the coarse YSZ by fine YSZ made three semicircles necessary. Changing the gas partial pressure or polarising the electrode made equivalent circuits with 5 semicircles necessary. Despite the increasing complexity of impedance behaviour, the total polarisation resistance decreases for finer cermet microstructures. This makes the microstructure an important research tool for further development of the anode performance. Despite an enormous amount of measurements the nature of the rate-limiting processes is not yet completely understood. The dominating part of the electrode response, appearing at the high frequencies, can be ascribed to charge transfer in the electrode. It is believed that the characteristic inductive loop as it appears for our type of cermet electrodes is related to a relaxation process involving the surface coverage of an adsorbed intermediate species bound by two frequency-dependent rate processes. Further research is necessary to obtain a more complete understanding of the electrode behaviour. Acknowledgement The Netherlands Energy Research Foundation (ECN) is thanked for the preparation of the cermet electrodes. References
S.C. Singhal, Status of Solid Oxide Fuel Cell Technology, Proc. of the 17th Ris Int. Sym. on Materials Science, High Temperature Electrochemistry: Ceramics and Metals, 123-38, 1996. N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. A. Hammou, J. Guindet, 'Solid Oxide Fuel Cells', Ch 12 of 'The CRC Handbook of Solid-State Electrochemistry', pp 409-445, CRC Press, Inc., 1997. H. Itoh, T. Yamamoto, M. Mori, T. Horita, N. Sakai, H. Yokokawa and M. Dokiya, Configurational and Electrical Behavior of Ni-YSZ Cermet with Novel Microstructure for Solid Oxide Fuel Cell Anodes, J. Electrochem. Soc. 144, 641-46, 1997. F.P.F. van Berkel, F.H. van Heuveln and J.P.P. Huijsmans, Characterisation of Solid Oxide Fuel Cell Electrodes by Impedance Spectroscopy and I-V Characteristics, Solid State Ionics, 72, 240-47, 1994. D.W. Dees, T.D. Claar, T.E. Easler, D.C. Fee and F.C. Mrazek, Conductivity of Porous Ni/ZrO2-Y2O3 Cermets, J. Electrochem. Soc., 134, 2141-46, 1987. N.Q. Minh, Ceramic Fuel Cells, J. Am. Ceram. Soc., 76, 563-88, 1993. Chapter 6 of this thesis. Chapter 7 of this thesis. T. Kawada, N. Sakai, J. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Structure and Polarisation Characteristics of Solid Oxide Fuel Cell Anodes, Solid State Ionics, 40/41, 402-06, 1990. B.A. Boukamp, A Nonlinear least squares fit procedure for analysis of immittance data of electrochemical systems, Solid State Ionics, 20, 31-44, 1986. F.P.F. van Berkel, J.P. de Jong, De Relatie tussen de Morfologie en de Electrochemische Eigenschappen van Ni/YSZ Anodematerialen, ECN Internal Report, 2918-GR14,1993.
149
S. Primdahl and M. Mogensen, Oxidation of Hydrogen on Ni/Yttria-Stabilized Zirconia Cermet Anodes, J. Electrochem. Soc., 144, 3409-19, 1997. S. Primdahl and M. Mogensen, Gas conversion impedance: SOFC anodes in H2/H2O atmospheres, pp 530-39 in Electrochemical Proceedings Volume 97-18, Aachen, 1997. Chapter 4 of this thesis. J.R. Macdonald, Impedance Spectroscopy, John Wiley & Sons, Inc. New York, 1978. T. Norby, O.J. Velle, H. Leth-Olsen and R. Tunold, 'Reaction resistance in relation to three phase boundary length of Ni/YSZ electrodes', pp.473-78 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. M. Mogensen and T. Lindegaard, 'The kinetics of hydrogen oxidation on a Ni/YSZ SOFC electrode at 1000C'; pp. 48493 in: Proc. Of the 3rd Int. Symp. On Solid Oxide Fuel Cells, Honolulu, Hawaii, 1993. B.A. van Hassel, B.A. Boukamp, and A.J. Burggraaf, Electrode polarisation at the Au, O2(g) /Yttria Stabilised Zirconia Interface I Theoretical Considerations of Reaction Model, Solid State Ionics, 48, 139-54, 1991. B.A. van Hassel, B.A. Boukamp, and A.J. Burggraaf, Electrode polarisation at the Au, O2(g) /Yttria Stabilised Zirconia Interface II Electrochemical measurements and Analysis, Solid State Ionics, 48, 155-71, 1991. I. Epelboin, M. Keddam, and J.C. Lestrade, Faradaic Impedances and Intermediates in Electrochemical Reactions, Faradaic Impedances and Intermediates in Electrochemical Reactions, Disc. Faraday Soc. 56, 264-275, 1973. I. Epelboin, C. Gabrielli, M. Keddam and H. Takenouti, The Study of the Passivation Process by the Electrode Impedance Analysis, Chapter 3 of Comprehensive Treatise of Electrochem., Ed. J. OM Bockris, B.E. Conway, E. Yeager and R.E. White, 151-94, New York/London, Plenium 1981. J. Guindet, C. Roux, and A. Hammou, 'Hydrogen oxidation at the Ni/Zirconia electrode', pp.553-58 in: Proc. of the 2nd Int. Symp. on Solid Oxide Fuel Cells, Athens, Greece, July 2-5, 1991. T. Kawada, N. Sakai, H. Yokokawa, M. Dokiya, M. Mori and T. Iwata, Characteristics of slurry-coated nickel zirconia cermet anodes for solid oxide fuel cells, J. Electrochem. Soc. 137, 10 , 3042-47, 1990. C-H Lee, C-H Lee, H-Y Lee and S.M Oh, Microstructure and anodic properties of Ni/YSZ cermets in Solid Oxide Fuel Cells, Solid State Ionics 98, 39-48, 1997.
150
9 Evaluation
Abstract To establish a high performance for a solid oxide fuel cell, the internal losses for the various elements should be as low as possible. For the anode this means that the electrode resistance should be minimised. A thorough understanding of the mechanism of the hydrogen oxidation reaction as well as insight in the most important features of the microstructure will assist further improvement of its performance. The four different types of electrodes studied in this thesis, i.e. from relatively simple pattern electrodes to very complex cermet structures, cover a broad range in microstructure types. The linear relationship between the Triple Phase Boundary (TPB) length and the electrode conductivity, as observed for the nickel type of electrodes, indicates that the electrode reaction occurs in the near vicinity of the TPB. From this linear relationship we conclude that in the cermets there is a significant contribution from accessible TPB area in the bulk of the electrode. The relative importance of this contribution increases with the fraction of fine with respect to coarse YSZ powder used in the preparation of the cermets. The obtained results support the conclusion that the dominant semicircle in impedance diagrams, recorded at equilibrium and under anodic polarisation, is due to charge transfer. Non-linear behaviour of the Tafelplots is attributed to changes in the fractional coverage of adsorbed intermediates. Recommendations are given for further research. 9.1 Introduction
In this chapter the main results of this thesis are briefly evaluated. The effect of the microstructure on the electrode performance is discussed. Some recommendations for further research are given. 9.2 Relationship of the microstructure with electrode resistance
It is generally accepted that the complex microstructure of the Ni/YSZ cermet electrode has a large influence on its electrochemical performance. The near vicinity of the triple phase boundary, where the electronic conducting nickel, ionic conducting YSZ and the gas phase come together, would be the place where the electrode reaction proceeds. One of the primary goals of the work presented in this thesis was to uncover this microstructure151
9 Evaluation
performance relationship for the Ni/YSZ electrode. To enable such a study quantitative data are needed for the electrochemical performance as well as for the microstructure. Different types of electrodes were therefore used, i.e. from relatively simple pattern electrodes to the complex cermet electrodes. Electrochemical characterisation was done using impedance and I- type of measurements. The total electrode conductivity derived from impedance data obtained at equilibrium was used as a characteristic parameter, noting that one semicircle was found to be dominant in the spectra of all electrodes studied. SEM pictures of the electrode were taken and analysed with image analysis techniques for characterisation of the microstructure (see Chapters 3 to 6). Quantification of the microstructure in measurable parameters, however, appeared to be difficult. For the purpose of discussion the electrodes are divided into two groups: the nickel electrodes, which for image analysis can be considered as possessing a two dimensional structure, and the cermet electrodes, which possess a three dimensional structure. Nickel type electrodes were characterised by measuring the nickel perimeter and the area of the electrolyte covered with nickel. Characterisation of the cermet electrodes resulted in values for the porosity, the nickel particle size and the surface coverage of the electrode / electrolyte interface. As mentioned above, changes in the characteristic TPB length are expected to have the most important effect on the electrochemical performance. For nickel type electrodes the length of the nickel perimeter shows the closest resemblance with the length of the TPB. For the cermet electrodes it is less obvious how to obtain a reliable value for the length of the TPB. In a first approximation it is assumed that the active TPB is located at the immediate interface between electrode and electrolyte. A value for the TPB length can thus be obtained from the associated surface coverage. When results obtained from image analysis of the electrodes are used as described above, the following points should be noted: The actual electrode area being studied with image analysis is very small (less than 0.01%). Therefore, if the image analyses results are taken as valid for the whole electrode area, for both nickel and cermet electrodes, the microstructure must be assumed to be homogeneous over the entire electrode area. By assuming a direct relation between the measured nickel perimeter and the length of the TPB a possible deviation on a scale not observable from SEM images is not accounted for. Furthermore, the diameter of the contact area of the nickel particles with the electrolyte may differ from the observed diameter of the nickel particles due to wetting. The assumption that the active TPB for the cermet electrodes is only located at the immediate interface between electrode and electrolyte does not account for an active role of the bulk of the electrode in the electrode reaction. By taking the TPB length as the descriptive parameter for the active area its width is assumed to be infinitely small. For reasons of current density it seems reasonable to assume that the active area related with the TPB has a certain width. It will depend on the actual value of the width whether or not the TPB length can be used as an appropriate parameter.
152
9.2 Relationship of the microstructure with electrode resistance
log i (cm )
-2
slope 1 -1
-2
Ni-litho Ni porous Ni mod Cermets
-3 0 1 2 3
-2
log TPB (m cm )
Figure 9.19: Total electrode conductivity for different type of anodes as function of the measured nickel perimeter.
The plot showing the total electrode conductivity as function of triple phase boundary length for the different types of electrodes is given in Figure 9.19. For the nickel type electrodes the total electrode conductivity is proportional to the available TPB length, indicating that the rate-determining step of the electrode reaction is confined to the near vicinity of the TPB. In Chapter 6, it was suggested that for coarse cermet structures the electrode reaction would be limited to the immediate interface between the electrode and the electrolyte. The results presented in Figure 9.19 suggest that this is not entirely true. Figure 9.19 gives strong evidence that even for the coarse cermet structure part of the bulk of the cermet electrode is active. The contribution of the bulk in the electrode process increases for finer cermet structures as can be concluded from the increase in the total electrode conductivity with the weight % of fine YSZ. This increase occurs in spite of the fact that the TPB length (calcultated from the surface coverage at the interface) varies only in a narrow range. Modification of the porous nickel electrode with fine YSZ particles leads to more active sites as well. It thus seems that there might also be some active role of YSZ in the electrode reaction, comparable to that of cermet structures. A question that emerges from these results is, if it would be possible to estimate the active thickness of the cermet electrodes. Using the linear relationship between the TPB length and the electrode conductivity, as observed for the nickel type electrodes, estimates can be obtained for the available TPB length of the cermet electrodes. Results are obtained in the range of 220 to 2600 mcm-2. Figure 9.20 shows the TPB length of the cermet electrodes, normalised to the TPB value from the surface coverage at the interface, as a function of the weight fraction fine YSZ in the cermet structure. This leads us to the conclusion that most of the active TPB sites are located in the bulk of the cermet, which increases with the
153
9 Evaluation
25 weight % fine YSZ. For calculation of the active thick20 ness of the electrode a value for the TPB length per unit of 15 thickness is necessary. In Chapter 7 a transmission 10 line model was used to model the spatial extension of the 5 TPB into the bulk of the cermet electrode. This model en0 0 20 40 60 80 100 ables calculation of the optiw/0 fine YSZ in cermet structure mal electrode thickness. If we interpret this value in terms of Figure 9.20: TPB lengths calculated for cermet electrodes following the linear relation between TPB length the active thickness of the and electrode conductivity obtained for nickelcermet electrodes, we may type electrodes, normalised to the TPB length calculate the TPB length per based on the surface coverage of the interface unit volume of electrode, as between electrode and electrolyte as function of the fraction fine YSZ in the cermet structures. shown in Figure 9.21. From this figure it is clear that the TPB length per unit volume is largest for the electrode prepared with most fine YSZ powder. The results as described above indicate the importance of the microstructure of the cermet structures. A change to finer cermet structures will lead to a larger amount of active sites per unit thickness of the electrode. Results obtained from network analysis indicate that the optimum electrode thickness hardly varies with the microstructure of the cermet. It emphasises the importance of fine and highly percolative cermet structures. Concluding remarks: 1.1.1.34.1 Image analysis is a useful tool for characterisation of the electrode microstructure. A linear relationship exists between the TPB length and the total electrode conductivity of the nickel elec200 trodes. 175 The linear relationship 150 between available TPB 125 length and electrode 100 conductivity, observed for the nickel electrodes, 75 suggests that there is a 50 spatial extension of the 25 active TPB area into the 0 bulk of the cermet elec0 20 40 60 80 100 trode. w/0 fine YSZ in cermet structure 1.1.1.34.2 RecommenFigure 9.21: TPB length (m(cm-2m-1) as function of w/0 dations:
-2 -1 TPB length (m/(cm m ))
TPB length (calc)/ TPB length (surface cov)
fine YSZ in the cermet structures.
154
9.3 Hydrogen oxidation reaction at the anode
The width of the active TPB seems to be an interesting subject for further study. The strategy that should be followed to gain more insight in this issue is difficult to indicate. Lithographically prepared electrodes seem a good starting point, because in this case the nickel perimeter and the TPB width will scale linearly. It is, however, questionable if lithographic samples can be made on the proper scale. There is an urgent need for a better quantification of the microstructure of cermet electrodes. Information about the TPB length per volume unit of the electrode is considered to be very useful in estimating the active thickness of the electrode. The results presented indicate that the electrode resistance decreases with decreasing particle size of the YSZ used for the preparation of the cermets. It is a challenge to further decrease this particle size to improve the performance, or to look for other morphologies. For other morphologies the use of micro emulsion systems could be studied. Transmission line modelling of impedance data yields useful parameters that are considered to be relevant for further optimisation of the microstructure of the cermets. It is therefore recommended to pay more attention to this approach. Hydrogen oxidation reaction at the anode
9.3
The hydrogen oxidation reaction at the anode is generally recognised to be composed of several sequential reaction steps. A better understanding of the reaction mechanism in terms of rate-determining steps enables further optimisation of the electrode performance. Therefore unravelling of the hydrogen oxidation reaction is of great importance. Information on the kinetics of the electrode reaction can be obtained from impedance and I- measurements, using gas phase conditions, temperature and overpotential as variables. For all different types of electrodes a similar experimental approach was used, as described extensively in the previous chapters. In Chapter 4 a model is proposed for the hydrogen oxidation reaction at the anode. Although impedance measurements at equilibrium indicated that the electrode reaction was governed by one dominating process, the assumption of one rate determining step with the other steps in virtual equilibrium did not hold. The H2 and H2O partial pressure dependency of the properties of the nickel electrodes varied with applied overpotential. These results suggest that changes in the fractional coverage of adsorbed intermediates occur either on nickel or YSZ, invalidating a classical analysis of the electrode kinetics. The appearance of inductive loops for cermet type of electrodes presents another indication that adsorbed intermediates might play an important role in the electrode reaction. Despite the fact that the proposed model can not easily be verified, it is useful to compare the electrochemical performance for the different type of electrodes. Table 9.5 gives an overview of the results obtained from impedance measurements under standard conditions and as function of gas phase condition and temperature. The impedance behaviour, in terms of the number of arcs, depends very much on the type of electrode. Porous nickel and modified nickel electrodes can be described with two arcs, where the high frequency arc is clearly dominating. The impedance spectra of the pattern electrodes are fitted with three arcs where the mid frequency arc dominates. The impedance spectra of the cermet 155
9 Evaluation
TPB length (mcm )
-2
Standard conditions nr Arcs 3 2 2 2 3 Rtot (cm )

2
Gas dependence pH2 -0.25 -0.12 - 0.02 -0.15 0.10 -0.16 -0.22 pH2O 0.35 0.40 0.48 0.39 0.53 0.36 0.37
Act E (kJmol-1) 155 152 134 112 107
Ni-litho Ni-porous Ni-porous/mod Cermet (coarse YSZ) Cermet (fine YSZ)
1.6 11.3 45 61 55 73 71 228

a b b
155 - 606 17.8 29.6 8.8 10.6 4.5 0.34
Table 9.5: Results of impedance measurements at zero bias for different types of anodes. a TPB length based only on the porous Ni structurre; bTPB length based on Ni/YSZ-surface coverage at the interface of electrode/electrolyte.
electrodes are most complex. Contrary to what is the case for the nickel electrodes an 'inductive loop' in the mid frequency range is necessary to fit the spectra. But again, the dominant semicircle is found at the high frequency side of the spectra. Using the conclusions of the previous section the dominant semicircle shows a most significant relation with the microstructure. The linear relationship that is found between the electrode conductivity and the available TPB length for nickel-type electrodes suggests that charge transfer is rate determining. The origin of other semicircles in the spectra is not yet completely understood. For a discussion see Chapter 8. The fact that the 'inductive loop' appears only for cermet electrodes suggests that its appearance is also related with the microstructure, most probably the available nickel of YSZ area per active site. In that case its presence may also be explained by concentration relaxation behaviour of adsorbed intermediates. The small semicircle at the low frequency side of the spectra is found for almost all electrodes and is characterised by a high capacitive value, which could suggest an effect of gas conversion above the electrode. The gas phase pressure dependence of the total electrode conductivity at zero bias shows a large similarity for the different type of anodes. tot varies between pH2O0.4 and pH2O0.5. The pH2 dependence of tot is less pronounced, with an order varying between 0.25 and 0. The fact that no clear changes in gas phase dependence are found for the different types of electrodes suggests that there are no significant differences in mechanism of the hydrogen oxidation, within the constrains of the experiment. This justifies the use of nickel electrodes for reaction kinetic studies. The activation energy of the electrode reaction decreases for electrodes with increasing TPB length. I- data for the different electrodes measured under standard conditions are shown in Figure 9.22. The Tafel slope contains information about the reaction mechanism. In general a linear behaviour would suggest that the rate of the electrode reaction is determined by one step in the electrode mechanism. Figure 9.22 indicates no marked changes in the slope for the different type of electrodes, examination of the curves show that these are not linear. For the anodic branch of the nickel pattern electrode an increasing slope is observed at high overpotentials, its origin is not clear. For the cermet structure with 100 w/0 fine YSZ the applied overpotential values may be too small to reach the linear region.
156
9.3 Hydrogen oxidation reaction at the anode
log I (mA/cm )
-1
-2
Ni litho Ni porous Ni modified Cermet coarse Cermet fine
-3 -100
100
200
300
(mV)
Figure 9.22:
Tafel plots as measured for different electrodes under standard conditions.
1.1.1.34.3 Concluding remarks: The hydrogen oxidation reaction cannot be described in terms of a multi-step electrode reaction where one step is rate-determining and the others are in virtual equilibrium. The dominant process of the electrode reaction relates with the available TPB length and is therefore ascribed to a charge transfer process. No evidence is found for a change in reaction mechanism with changes of the microstructure of the electrodes. 1.1.1.34.4 Recommendations: In classical analyses of the electrode reaction mechanism, quasi-equilibrium is assumed for all steps except the rate-determining one. With these methods ButlerVolmer type of equations are obtained. A simulation of the reaction mechanism, e.g. by methods developed by Epelboin [26][27] would be more appropriate, as these account for the potential dependence of the concentration of adsorbed intermediates. References
[30] I. Epelboin, M. Keddam, and J.C. Lestrade, Faradaic Impedances and Intermediates in Electrochemical Reactions, Faradaic Impedances and Intermediates in Electrochemical Reactions, Disc. Faraday Soc. 56, 264-275, 1973. [31] I. Epelboin, C. Gabrielli, M. Keddam and H. Takenouti, The Study of the Passivation Process by the Electrode Impedance Analysis, Chapter 3 of Comprehensive Treatise of Electrochem., Ed. J. OM Bockris, B.E. cathodic anodic Conway, E. Yeager and R.E. White, 151-94, New York/London, Plenium 1981. ((RT/F)) ((RT/F)) Ni-litho Ni-porous Ni-porous/mod Cermet 1.5 0.5 0.5 0.5 1.0 --1.5 2.5 1.5 1.0 1.5 1.5 2.0
Table 9.6: Tafel slopes in cathodic and anodic direction for different type of anodes.
157
Dankwoord
Het is gelukt! U bent bijna aan het einde gekomen van dit proefschrift en ook ik ben bijna beland aan het einde van mijn loopbaan als AIO. Op zon moment krijgt de mens van nature de drang om de achterliggende periode te overdenken. Ik zal u daar niet te veel mee lastig vallen. Echter wel met n punt, ik zou namelijk graag op deze plaats enige mensen willen bedanken die hebben bijgedragen aan de totstandkoming van dit proefschrift. Henk Verweij voor het bieden van de mogelijkheid om binnen zijn groep als AIO te werken. Ik heb er veel van geleerd. Henny Bouwmeester voor zijn enorme motivatie, het corrigeren van manuscripten en de vele discussies over anodes en hun werking. Ik heb bewondering voor het enthousiasme wat jij hebt voor de wetenschap en ben er van overtuigd dat het grote invloed heeft gehad op de totstandkoming van dit proefschrift. Mijn (ex-)kamergenoten, Renate, Martijn, Balu, Marcel, Arian, Nieck en Marjan voor de gezellige sfeer, de vele kamer etentjes en alle andere zaken die zich binnenskamers afspelen. Renate, jou wil ik in het bijzonder bedanken voor je vriendschap in zware tijden. Martijn voor alle wetenschappelijke discussies, waar je altijd tijd voor maakte, natuurlijk voor Hoofdstuk 7 en niet te vergeten de gezelligheid. Bernard voor de ondersteuning in de eerste jaren en het kritisch lezen van dit manuscript. Sylvie Briot voor al het werk aan de dunne electrolyt cellen, honderden metingen waar ik helaas weinig mee heb kunnen doen. Het schijnt te horen bij onderzoek, maar is niet leuk. Mercedes Gonzales voor je enorme inzet om in korte tijd zeer veel metingen uit te voeren en uit te werken en natuurlijk voor de gezellige gesprekken. Matthijs den Otter voor je onvermoeibare inzet om tot patroon electroden te komen. Het is gelukt! Wim Hoeyenbos voor het schrijven van de programmatuur voor de I- metingen. Andr, Bas, Caroline, Cis, Claudia, Eddy, Jos, Matthijs, Nicole, Ren, Sven, Zeger en alle andere vakgroep genoten die niet met name zijn genoemd voor de prettige werksfeer in het lab en gezellige vakgroep activiteiten.
159
9 Evaluation
De vakgroep technici voor alle ondersteuning in het lab en alle technici van externe werkplaatsen voor het maken dan wel repareren van meetcellen en apparatuur en preparatie van electrolyten en electroden. Frans van Berkel, voor je onvermoeibare inzet voor dit project, maar ook voor de vele discussies, de mogelijkheid om bij het ECN metingen uit te voeren en voor alle geprepareerde electroden en electrolyten. Gerard Schipper wil ik bedanken voor alle gemaakte cermet electroden. Nieck, Peter, Edgard en prof P.J. Gellings voor het nauwkeurig corrigeren van dit manuscript. Iedereen die ik vergeten ben. Mijn ouders, verdere familie en vrienden voor de steun die ik in de afgelopen jaren heb gekregen. En heit, nu is dan de tijd gekomen om cht aan het werk te gaan! Tot slot, Andr voor alles.
Baukje de Boer
160
Levensloop
De schrijver van dit proefschrift werd op 8 oktober 1968 geboren in Appelscha. In 1987 behaalde zij aan het Ichthus College te Drachten het VWO diploma. In datzelfde jaar begon zij aan de studie Technische Natuurkunde aan de Universiteit Twente. De doctoraal stage verrichte zij in 1991 bij het Department of Crystallography aan de University of Pittsburgh. Onder begeleiding van prof. dr. B.M. Craven voerde zij een onderzoek uit naar de verfijning van de kristal structuur van beryllium acetaat op basis van Rntgen en neutronen diffractie data. In augustus 1993 studeerde zij af bij de vakgroep Chemische Fysica van prof. dr. D. Feil. Het betrof een onderzoek waarbij door middel van Rntgen diffractie experimenten en quantum mechanische berekeningen werd gekeken naar het effect van een intern electrisch veld op de ladingsdichtheidsverdeling in een moleculair kristal. Vanaf oktober 1993 was zij als Assistent in Opleiding werkzaam bij de groep Anorganische Materiaalkunde binnen de faculteit Chemische Technologie aan de Universiteit Twente. Het in dit proefschrift beschreven onderzoek werd uitgevoerd onder begeleiding van prof. dr. ir. H. Verweij en dr. H.J.M. Bouwmeester.
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SOFC Anode: Hydrogen Oxidation at Porous Nickel and Nickel/yttria-Stabilised Zirconia Cermet Electrodes

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SOFC Anode: Hydrogen Oxidation at Porous Nickel and Nickel/yttria-Stabilised Zirconia Cermet Electrodes

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SOFC Anode

Hydrogen oxidation at porous nickel and nickel/yttriastabilised zirconia cermet electrodes

Copyright 1998 by B. de Boer, the Netherlands.

Baukje de Boer geboren op 8 oktober 1968 te Appelscha

151 151 155 159 161

Figure 1.1: Schematic representation of a fuel cell.

AFCa 80% Pt 20% Pd

SOFC Ni YSZ cermet

62 Li2CO3-38 K2CO3 0.1-1 650 H2 +CO3= H2O + CO2 + 2e-

Abs pressure (Mpa) Temperature (C) Anode reaction

0.1-0.5 80 H2 2H+ + 2e-

0.4 80-90 H2 +2OH- 2H2O + 2e-

~0.4 260 H2 +2OH- 2H2O + 2eO2 + 2H2O + 4e- 4OH-

0.1-1 200 H2 2H+ + 2e-

O2 + 4H+ + 4e- 2H2O

O2 + 2H2O + 4e- 4OH-

O2 + 4H+ + 4e- 2H2O

O2 + 2CO2 + 4e- 2CO3=

1.2 Solid Oxide Fuel Cell

Figure 1.2: A Solid Oxide Fuel Cell.

pH 2 Oa (1.2) pH 2 a K i   pH 2 a RT RT ln pO2 c + ln 4F 2 F pH 2Oa

where E0 is the reversible voltage at the standard state and is given as

1.2 Solid Oxide Fuel Cell

1.2 Solid Oxide Fuel Cell

composition Ni/YSZ cermet

specific conductivity at 1000C (S/m) 400 - 1000

conductivity depending on Ni/YSZ particle size ratio Ni content

Density Yttria content

1.2 Solid Oxide Fuel Cell

TPB Length (mcm )

Temp (C) pH2

Gas phase conditions (10 Pa)

Impedance (nr arcs)

Gas phase dependence of electrode conductivity (1/R)

pH2O 0.027 0.053 0.048-0.2 0.055 0.0063 1 65ka pH2O

0.2-0.58 0.75 0.7 0.037-0.9

850 1970 1.697 pH2O1/2 0.016 pH2-1/2+0.396 pH21/2

MohamediNi ball Boulenouard et al. 0

i = i0 exp (aF/RT) with (a=1.4-1.7)

---(at low pH2) ---pH2O

1.6b (at low pH2)

Mizusaki et al. 0000 Yamamura et al. 00

10.5kc pH2O (at high pH2)

pH20 (700-800C pH2-1/2 (850C) pH20

i3 = k3 pH2 k3 pH2O exp (-2FE/RT)

1.2 Solid Oxide Fuel Cell

(1.23) (1.24) (1.25)

TPB Had Had

' i2 = k 2 pH21/ 2 k 2 pH2 O1/ 2 exp

1.2 Solid Oxide Fuel Cell

Gas phase conditions (105 Pa) pH2 pH2O 0.053

Impedance (nr arcs)

Mohamedi-Boulenouar et al. 0 Norby et al. 0 Norby et al.0

Porous Ni 121 m layer Ni stripe 3.26

Temp (C) 1000

Gas phase condition (105Pa) pH2 0.97 pH2O 0.03

PH2 order dependence Range (105Pa) 0.97-0.015 (pO2:4.5*10 ) 0.05-0.95

0-0* 0.2-1 0.1-1

(pH2O: 0.01 or 0.03) ( pH2 >0.5) 0.1-1 (pH2O: 0.02)

0.1-97 (pH2O: 0.03)

0.044a2 0.018 0.3b1 2.6

1.2 Solid Oxide Fuel Cell

pH 2 Oa (1.2) pH 2 a K i pH 2 a RT RT ln pO2 c + ln 4F 2 F pH 2Oa

k2 H exp 2 fE k2 aOH 1 H exp 2 fE

3. High surface coverage on the nickel, hence 1 H pH 2

4. High surface coverage on the nickel, hence 1 H pH 2