VOLTAMMETRIC STUDIES OF YBaCo2O5 IN ALKALINE AQUEOUS SOLUTION

Mircea Dan, Narcis D !ean

,

An"rea Ke##en$er%er, Nico#ae Vas&i#csin

University Politehnica of Timisoara, Faculty of Industrial Chemistry and Environmental Engineering, P-ta Victoriei , !""""# Timisoara, $omania A$s!rac! The paper presents the electrochemical investigation of mixed oxide YBaCo2O5 in alkaline aqueous solution during oxygen insertion/release !lectrochemical "ehaviour of YBaCo 2O5 has "een studied "y cyclic voltammetry and electrochemical impedance spectroscopy The compound structure and morphology #as investigated "y $%&ay diffraction and scanning electron microscopy coupled #ith energy dispersive $%ray analysis The mixed oxide porosity #as determined using B!T technique and the results are in accordance #ith thermogravimetric studies carried out in oxygen flo#' emphasi(ing the oxygen intake / release property of YBaCo2O5' Ke()or"s* mixed oxides' YBaCo2O5' electrochemical "ehaviour of YBaCo 2O5' cyclic voltammetry' B!T technique In!ro" c!ion )ctual challenge for solid oxide fuel cells *+O,C- technology is represented "y the development of ne# electrode materials #ith high conductivity .ue to the ma/or voltage losses on the cathodic side of the +O,C' experimental studies are carried out in accordance #ith that 012 3n practice' the catalytic activity for oxygen reduction reaction is heavily affected "y the temperature reduction Considering this it is vital to develop a ne# class of high performance cathodes #ith important catalytic activity and also #ith lo# overpotential 01' 22 ) suita"le candidate is represented "y a ne# class of perovskite 4 like compounds' 5BaCo 2O567 *5 8Y' 9d' :r- This ne# class of compounds has an 112 phases 012 and from structural point of vie# they present a layered structure 01' ;2 Bo"rovskii et al demonstrate in 2<<= that the compound structure is derived from orthorhom"ic structure of 112 perovskite' #here on lattice c axis are stacked sand#iches of CoO 24BaO4CoO245Ox' #here the CoO2 layers are

dissevered "y the 5Ox layer 0;2 #hich induces some remarka"le properties 012 )ctually' the 5Ox layer is acting like a carrier for charge donors 0;' >2' and is expected that the oxygen transport via perovskite layer is easy 01' >2 Bo"orvskii et al demonstrate that the system charge can "e easy controlled only "y changing oxygen concentration into the intermediate oxide layers 0;2 Oxygen content in YBaCo2O5 can "e easily modified "y temperature' surrounding oxygen partial pressure' and also "y oxygen intake/release mechanism into the perovskite net#ork #hich translates in variation of compound physical and chemical properties This causes variations among the most important oxygen transport properties like oxygen nonstoichiometry' oxygen ion permea"ility and diffusion' #hich must "e regarded as a highly important issue #hen studying perovskite%like oxides 052 )ny#ay' in the ma/ority of practical studies until no#' the oxygen transport properties of YBaCo2O5 #ere investigated "y direct oxygen permeation measurement through a mem"rane' electrical conductivity measurement' coulometric relaxation method' isotopic exchange analysis' revealing the perovkite structure 01' 5' ?2 The aim of this paper is to study and elucidate the electrochemical "ehaviour of YBaCo2O5 perovskite in aqueous alkaline solution 9iven the possi"ility of electrochemical intercalation of oxygen atoms in co"altites' the alkaline medium #as chosen 0@%=2 &egarding the electrochemical studies presented in this paper' it is relevant to mention that in each unit cell there are t#o different Co cations' Co*33- and Co*333-' #ith an atomic ratio of 1A1 as #ell as that the electrochemical "ehavior of Y% 112 is determined "y the mixed ionic and electronic conductivity 05' ?' 1<%122 .ue to the presence of Co26 #hich oxidi(es to Co;6 during the electrochemical process of adsorption' the structure is allo#ing the intake of B O' as oxygen adsorption takes place "y permitting the oxygen diffusion into the oxides net#ork and "onding an oxygen atom to t#o co"alt atoms from neigh"oring unit cells Cntil no# the oxidation capacity of Y%112 compound and also the reversi"ility of the oxidation process have "een studied using only thermogravimetric measurements carried out under oxygen flo# Thus' oxidation capacities of the compound up to YBaCo2O567' #here 7 8 1 < #ere o"tained 05' ?' 1<%122

E+,eri-en!a# .ar! 2

The mixed oxide YBaCo2O5 #as o"tained using solid state reaction "y mixing the precursors Y2O; *)ldrich == ==D-' BaCO; *)ldrich == ===D- and CoO>/; *Eormapur == =D- according to the stoichiometric cations ratio )fter decar"onisation at =<<FC the po#der #as pressed into pellets #ith geometrical active surface area of 1 cm2 and later fired in air for >G h at 11<<FC and then removed rapidly from furnace and set to am"ient temperature 01' 5' ?' 112 +urface morphology of YBaCo 2O5 samples has "een characteri(ed "y scanning electron microscopy *+!5- using a ,!3 3E+:!CT + :)Ealytical microscope coupled #ith energy dispersive $%ray detector The structure of o"tained YBaCo 2O5 compound *,ig 1- #as checked "y $%&ay po#der diffraction *:hilips $%pert :ro)ll electrochemical studies #ere carried out using an )utola" :9+T)T ;<2E The electrochemical cell #as equipped #ith t#o graphite counter electrodes positioned symmetrically against the #orking electrode *YBaCo 2O5 pellets- and a )g/)gCl reference electrode )ll potentials in this #ork are given versus the reference electrode Cyclic voltammograms *CH- have "een recorded at several scan rates in 1 mol I%1 JOK electrolyte solution !lectrochemical impedance spectoscopy *!3+- measurements #ere carried out using an )utola" ;<2E in the frequency range from < <<1 K( to 1<< kK( and an )C voltage amplitude of 1< mH !ach spectrum consisted of ?< points collected #ith a logarithmic distri"ution of 1< points per decade !lectrochemical impedance data #ere fitted to the electrical equivalent circuit "y a complex nonlinear least squares *CEI+- Ieven"erg%5arquardt procedure using LHie# +cri"ner )ssociated 3nc soft#are The surface area #as determined according to the Brunauer/!mmet/Teller *B!T- method using an )+): 2<2< 5 *5icromeritics 3nstrument Corporation C+)3n )"stract scrie despre Mthermogravimetric studiesN in !xperimental nu apare nimic Res #!s an" "isc ssion Physical characterisation The structure of mixed oxide is presented in fig 1 and it #as investigated "y $% ray po#der diffraction $%ray diffraction spectra for o"tained YBaCo 2O5 mixed oxide #ere recorded for the 2O range "et#een 2<F and G<F and are presented in fig 2 :eaks from recorded diffraction pattern #ere identified and from that #e can conclude that the o"tained compound is YBaCo 2O5 mixed oxide +imultaneously the

elemental composition of mixed oxide #as confirmed "y energy dispersive $%&ay analysis *!.$- as it can "e o"served in ,ig ;

Counts );

><<<

2<<<

< ;< >< 5< ?< @<

:osition 0F2Theta2 *Copper *Cu--

,ig 1 Crystal structure of the YBaCo 2O5

,ig 2 $&. pattern of YBaCo2O5

,ig ; YBaCo2O5 !.$ spectrum The compound porosity #as determined "y the B!T technique and the results are presented in ta"le 1 Ta"le 1 B!T surface area' pore diameter' and pore volume of the YBaCo 2O5 sample B!T +urface )rea BQK .esorption average pore diameter *>H/)BQK .esorption cumulative volume of pores "et#een < 22 mP/g 1< 25 nm < <<<?=? cmR/g 4

1 @<<< nm and ;<< <<<< nm diameter The results indicate a large specific surface area' #ith pores and channels that favour adsorption and desorption of oxygen during electrochemical polari(ation Compared #ith a dense "ulk sample' this porous structure sho#s fast oxygen adsorption and desorption rates

a-

"-

,ig G +!5 images of YBaCo2O5 electrodeSs surface "efore electrochemical oxidation/reduction at ;<<<x *a- and 12<<<x *"- magnification )n important factor influencing the oxidation process kinetics is the surface morphology #hich has "een analy(ed using scanning electron microscopy +!5 images o"tained for YBaCo2O5 pellet electrode involved in this #ork are presented in ,ig G )naly(ing the +!5 image a porous structure due to acicular crystallites agglomeration can "e o"served Iarge pores amount leads to a higher specific surface #ith channels that favours oxygen adsorption / desorption process Electrochemical characterisation :reliminary attempts have sho#n that it is possi"le to separate the peaks associated #ith the electrochemical processes occurring at the interface YBaCo 2O5 4 JOK 1 mol I%1 only if the potential scan rate is around 1 mH s %1 The cyclic voltammograms recorded for YBaCo 2O5 electrode are depicted in ,ig >

< <<; < <<2 < <<1 30)2 < <<< %< <<1 5 %< <<2 %< <<; %< <<> %1 2 0 %1 < %< G %< ? %< > %< 2 << ! 0H2 vs )g/)gCl <2 <> 3 2 1

<?

,ig > Cyclic voltammograms on YBaCo 2O5 #orking electrode in 1 mol I%1 JOK solution at 1 mH s%1 scan rate )naly(ing the voltammograms sho#n in figure >' it can "e o"served the appearance on the for#ard scan of an anodic peak *2- assigned to Co *33- oxidation *Co33 T Co333 6 eU- )t higher potentials the current increase *;- #as associated #ith oxygen evolution reaction On the "ack#ard scan' a limiting cathodic current #ith lo# intensity #as o"served *peak >-' #hich #as correlated #ith reduction of remanent oxygen on the electrode surface and also from the space "et#een YBaCo 2O5 crystallites Vhen the potential "ecomes more negative' a cathodic peak *5- associated #ith Co *333reduction process *Co333 6 e% T Co33- #as recorded )t more negative potential' the current increase *?- is associated #ith the hydrogen evolution reaction Continuing the scan in the anodic direction from hydrogen evolution reaction (one until the open circuit potential *OC:-' a ne# anodic peak *1- associated #ith oxidation of adsor"ed hydrogen #as o"served at approximately %< @5 H versus +C!

< <15 < <1< < <<5 < <<< %< <<5 %< <1< %< <15

30)2

%1 5

%1 <

%< 5 << ! 0H2 vs )g/)gCl

<5

1<

,ig 5 Cyclic voltammograms on YBaCo 2O5 #orking electrode in 1 mol I%1 JOK solution at 1< mH s%1 scan rate 3ncreasing the potential scan rate from 1mH s %1 to 1< mH s%1' some changes in the anodic part of the cyclic voltammograms #ere o"served )naly(ing the CH presented in ,ig 5' it can "e noticed that the anodic peak *2- presented in ,ig > #as replaced #ith a net plateau associated #ith oxidation of Co *33- ions The plateau current density is almost dou"le compared #ith the height of peak *2- from ,ig >

< <G < <? < <> < <2 30)2 < << %< <2 %< <> %2 < %1 5 %1 < %< 5 << <5 1< 15 2< ! 0H2 vs )g/)gCl

,ig ? Cyclic voltammograms on YBaCo 2O5 #orking electrode in 1 mol I%1 JOK solution at 5< mH s%1 scan rate

Vhen the CHs #ere recorded at much higher scan rate' for example at 5< mH s%1 *,ig ?-' the anodic part of the CH changes drastically' in this case the oxidation peak 2 and also the limiting current #ere not o"served This can "e explained if #e consider that the oxidation of YBaCo 2O5 electrode occurs only at the electrode/electrolyte interface Based on that #e can conclude that the electrochemical oxidation of Co*33ions to Co*333- ions actually consists in the insertion of oxygen ions into the YBaCo 2O5 crystalline net#ork 3n consequence' during the electrochemical oxidation process' the crystalline net#ork "ecomes more compact and in this #ay further oxygen diffusion into the net#ork is restricted +imultaneously' the electrochemical "ehavior of the YBaCo 2O5 electrode #as studied using chronoamperometric techniques 3n this case the #orking potential #as set at %< 25 H versus )g/)gCl reference electrodeW this value #as chosen in accordance #ith the oxidation potential for the YBaCo 2O5 electrode o"tained from the recorded CHs The chronoamperometry data are presented in ,ig @

< 2G

< 2?

< 2>

3 0m)2

< 22

< 2<

< 1G

< 1? < 1<< 2<< ;<< ><< 5<< ?<<

timp 0s2

.e schim"at figura in engle(a ,ig @ Chronoamperometry of the YBaCo2O5 pellets electrode at !8%< 25 H vs )g/)gCl for ?<<s in 1 mol I%1 JOK solution ,rom the graph presented in ,ig @ #e can conclude that #hen the electrode potential #as kept at %< 25 H versus )g/)gCl' the current density is decreasing in time due to the electrode oxidation at this potential )t higher oxidation time' the current density "ecomes <' due to the mass or superficial oxidation of the YBaCo 2O5

electrode' #hen the electrode surface #as coated #ith a layer of YBaCo 2O567 oxide *78 max <'5Based on to the data presented a"ove' an electrochemical mechanism for glo"al oxidation process of YBaCo 2O5 mixed oxide has "een proposed 3n accordance #ith this mechanism an oxygen activity gradient "et#een superficial layer and "ulk of mixed oxide occurs at anodic polari(ation of electrode This leads to oxygen diffusion into the YBaCo 2O5 crystal simultaneously #ith oxidation of Co*33ions on the superficial layer Oxidation of Co*33- ions onto the electrode surface and oxygen diffusion from electrode surface is equivalent #ith apparition of a superficial charge' compensated "y the diffusion of hydroxyl ions from "ulk of solution to the electrode surface :resence of ad/acent hydroxyl ions onto the electrode surface leads to formation of oxygen ions "y #ater elimination This ne# oxygen ion #ill diffuse into the electrode "ulk !3+ data demonstrate that the rate of oxygen diffusion into the perovskite structure is much lo#er than the rate of charge transfer reaction and the diffusion of hydroxyl ions to the interface 0@2 )t lo#er current densities' electrochemical mechanism for perovskite glo"al oxidation takes place in t#o different stages 3n first one' superficial Co*33- ions are oxidi(ed at Co*333- ions in accordance #ith follo#ing reactionA

)s an effect' an excess of positive superficial charges appears at interface 3nterfacial charge is compensated "y near hydroxyl ions #hich interact #ith interfacial Co ;6 ionsA

)t lo#er current densities' adsor"ed hydroxyl concentration at interface is really small' so that the collision "et#een t#o different adsor"ed hydroxyl ions is not pro"a"le' even if the adsor"ed KO% ions are migrating over anode surface 5ore feasi"le are the collisions "et#een adsor"ed KO % ions and the KO% ions #hich are diffusing from "ulk of solution to the electrode surfaceA

Vhen the current density is increasing' concentration of adsor"ed KO % ions is rising proportionally #ith current density' so the O 2% formation can also occur "y collision "et#een t#o different adsor"ed KO% ionsA

3n accordance #ith proposed mechanism' oxidation of Co ions onto the electrode surface at anodic polarisation near OC: is controlled "y charge transfer reaction )t more positive potential' Co oxidation and oxygen ions "ulk diffusion is controlled "y the electrolyte diffusion ,ig = sho#s the !3+ spectra recorded for YBaCo 2O5 electrode recorded during oxidation / reduction process The main features of the complex plane impedance plots are the presence of a slightly curved line in the high frequency region' follo#ed "y diagonal line #ith a slope of >5F and a large semicircle in the lo# frequency region' #hich dominates the entire !3+ spectra The Bode plots o"tained during oxidation at < 125 H and reduction at %< 25 H have a slope of < 5 and a phase angle value of >5F in the frequency range from 1< to < 1 K( #hich points to a diffusion controlled process

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Fi%' 4' !xperimental Eyquist *a- and Bode *"- plots for YBaCo 2O5 mixed oxide during oxidation / reduction %&en sym'ols are experimental points and continuous lines are simulated "y the CEI+ fitting according to the equivalent circuit The impedance data have "een modelled using a t#o time constant equivalent electric circuit *!!C- given in ,ig 1< The !!C consists of a serial connection of the ohmic resistance *$Ohm-' a 9erischer element *(e- and a parallel connection of a Var"urg element *)- and a resistance *$- in series #ith a capacitor * C- The ohmic resistance includes the uncompensated electrolyte resistance and a contri"ution from the resistance of YBaCo2O5 electrode

Fi%' 35' !quivalent electric circuit for modelling oxygen insertion / release into the YBaCo2O5 electrode The appearance of a 9erischer element has "een associated #ith systems involving a diffusion process coupled to a chemical reaction 01;2 3n its most simple form' the impedance of a 9erischer element is given "yA *9! 8 *< / *+ 6 /-1/2 *2-

#here Lo is the magnitude of the impedance at 8 1 rad s%1 and + is a rate constant of the chemical reaction The impedance of the Var"urg element in case of a finite length thickness of the diffusion layer , is given "yA *# 8 *$#*/ .-%- coth */ .- *;-

#here $# is the diffusion resistance' . is the diffusion time constant given "y . 8 ,2/-' #ith , 8 diffusion layer thickness and - 8 diffusion coefficient and is an exponent "et#een < and 1 This version of the Var"urg element terminates in a finite resistance )t lo# frequencies' the real part of the Var"urg impedance approaches $V' and the imaginary part goes to (ero The !!C parameters o"tained "y fitting the experimental impedance data are listed in Ta"le 2 together #ith their relative errors

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Ta"le 2 !xperimental values of !!C during oxidation / reduction of YBaCo 2O5 :arameter $Ohm 0X2 *< 0X cm2 s1/22 + 0s2 $V 0X cm22 . 0s2 $ 0X cm22 C 0, cm%22 2 E 8 < 125 H = 1 *1 ? D5 ?@ 1<%; *< = D< ;? *1< 2 D5;< *; 5 D< ;? *;5 ; D< >5 *; = D1< >2 *; @ D1 2< 1<%2 *5 ? D; ; 1<%> E 8 %< 25 H G = *2 < D2 =2 1<%; *1 ; D< ;2 *1G = DG@2 *> < D2? ;G *2= = D< ;? *; 2 D12 GG *5 2 D2 G; 1<%; *@ ? D5 < 1<%> E 8 %< @5 H G 1 *1 ? D= <2 1<%; *1 G D@ >< *? 2 D;=> *2 1 D>> 1= *= 5 D< 2G *1 < D2> 5? *2 > D> ?= 1<%; *; GD D> 2 1<%>

The 9erischer type impedance has "een reported for a num"er of mixed conductors that can "e used as anode or cathode materials in solid oxide fuel cells 01>%1@2 and it is generally ascri"ed to "ulk diffusion and surface reaction kinetics The closed values of the rate constant + and diffusion time constant . o"tained for the oxidation indicate that "oth chemical and diffusion step control the overall process .uring reduction' the diffusion of oxygen ions inside the solid host electrode is the rate determining step )lso' "ased of the diffusion time constant values it can "e estimated that oxygen insertion during oxidation takes place faster than oxygen release during reduction CONCLUSIONS &esults o"tained "y cyclic voltammetry in alkaline aqueous solution sho#ed that the YBaCo2O5 mixed oxide is sensitive to anodic or cathodic polari(ation Based on the experimental data #e can conclude that the electrochemical oxidation of Co*33ions consists in oxygen insertion in the mixed oxide structure Because of that' during oxidation the Y%112 crystalline net#ork "ecomes denser' so that oxygen diffusion rate is lo#ered The compaction of Y%112 during oxidation imposes a partial irreversi"le character of this process' and as a consequence the oxidation leads to disappearance of the oxidation plateau and also to the attenuation of the reduction peak 3mpedance measurements during YBaCo 2O5 oxidation indicate the presence of a chemical step tentatively assigned to the formation of O 2% ions from the reaction

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"et#een t#o hydroxyl groups and a diffusion process of oxygen ions from the surface to the "ulk of the mixed conductor

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