10.

Medium temperature fuel cells (200 - 650 C)

Medium temperature fuel cells

Advantages of operating at elevated temperature Enhanced cathode kinetics. Heat recovery. Simpler operation. Enhanced CO tolerance. Matching with hydrogen supply system. This will facilitate integration with the fuel cell stack and hence smaller, lighter, more efficient and simpler systems.

10.1

The phosphoric acid fuel cell (PAFC)

The PAFC (1)

Phosphoric acid, at temperatures > 150 C, has a high conductivity, high solubility for oxygen and low chemisorption on Pt (the latter two characteristics facilitating the oxygen reduction reaction), and is the only inorganic acid that is stable and with a low volatility at these temperatures.

The PAFC (2) Was the only commercially available fuel cell (> 200 fuel cell systems have been installed all over the world) Runs on H2, methane, natural gas, sulfur free petrol + air/O2 Generate electricity at > 40% efficiency (ca. 85% if the steam produced is used for cogeneration; cff ca. 35% for the utility power grid in the USA) Graphite felt+low Pt loading, concentrated phosphoric acid (polyphosphoric acid) electrolyte absorbed in SiC Operating temperatures 150 - 220 C High O2 solubility CO tolerant ca. 1 2 % due to higher operating T

PAFCs had outputs up to 200 kW (11 MW units had also been tested).
Combined Heat and Power operation.

The PAFC (3)

PAFCs are CHP units.

Typically, the hydrogen fuel is produced by reformation of natural gas. The performance of PAFCs has improved significantly over the last 30 or so years, with power densities of ca. 320 mW cm-2 obtainable at a cell voltage of 0.75 V, electrical efficiency (of the fuel cell stack only) of ca. 40% and overall CHP system efficiencies of 85%.

The PAFC (4)

100% phosphoric acid electrolyte immobilised in a ca. 0.2 mm-thick, PTFE-bonded, particulate silicon carbide matrix. Pure phosphoric acid freezes at 42 C, and so the PAFC stack must be maintained above this temperature if potentially destructive freeze/thaw stress is to be avoided. Conductivity of the acid falls below 150 C and its volatility is too high & it tends to decompose at temperatures above 220 C, hence the operating temperature is ca. 200 C.

The electrodes of the PAFC comprise small (ca. 2 nm) Pt particles deposited on porous carbon, at the same loadings as in the PEMFC, and supported on porous carbon paper or graphite felt GDLs.

The PAFC (5)

PAFC stacks externally manifolded, utilise boiling water as the coolant for 100 kW systems, and air for lower power systems, typically with every 5th cell cooled, and an operating temperature up to 220 C.
PAFC employ multicomponent bipolar plates.

Multicomponent bipolar plate: a = anode, e = electrolyte and c = cathode

The PAFC (6)

Applications Stationary supply Large vehicles

400kW Stationary Fuel Cell

The PAFC (7)

PAFC Problems 2000 per kW; fuel cost 0.50 per kWh with reformer H2S in reformate poisons anode catalyst Need desulfurizer, water separator, heat exchanger and reformer- complex (especially wrt heat management) & heavy system hence mainly stationary applications, although also buses.

Oxidation of carbon support, agglomeration of Pt particles, flooding of electrodes and loss of acid- eg. reliability, lifetime and maintenance costs
Corrosive electrolyte Low power density

10.2

The molten carbonate fuel cell

The MCFC (1) Genesis in work of Broers and Ketaar in 1950s: materials largely unchanged since mid-1970s.

Operational T = 650 C Anode Reaction: CO32- + H2 H2O + CO2 + 2eElectrolyte: molten lithium carbonate + potassium carbonate Moving ions Cathode Reaction: CO2+ O2 + 2eCO32-

CO2 would cancel in overall cell reaction, concealing its role, so:

H2 + O2 + CO2(Cathode) H2O + CO2(Anode)

The MCFC (2)

Electrolyte: molten mixture of Li2CO3+K2CO3 or Li2CO3+Na2CO3, ca. 60 wt.%, in ceramic matrix 40 wt.% LiAlO2, the latter being in the form of fibres 1 mm in diameter (formed by tape casting). Anode Ni/Cr/Al alloy, cathode NiO; both porous. Relative pore sizes of the anode, cathode and LiAlO2 matrix are employed to create 3-phase region.

The MCFC (3)

Electrolyte management of this nature is critical in, and unique, to the MCFC.

The MCFC (4)

Unusually for a fuel cell, the cathode must be supplied with CO2 as well as air, and this is usually achieved by mixing the anode exhaust, after combustion of any unspent H2, with air and feeding to the cathode inlet. If the partial pressures of CO2 in the anode and cathode compartments are equal, then this has no effect upon the cell voltage; however, the cell voltage is altered if the pressures are different, due to the participation of CO2 in both electrode reactions. This effect is given by the Nernst Equation for the MCFC: E = E0 +(RT/2F)loge(PCO2(Cathode)PH2PO21/2/PH2OPCO2(Anode)) H2 + O2 H2O H2 + O2 + CO2(Cathode) H2O + CO2(Anode)

The MCFC (5)

Thin stainless steel bipolar plates, with both internal and external manifolding being employed. Efficiencies ca. 60%, BUT at lower current densities (150 mA cm-2 at ca. 0.8V) achievable with other fuel cells.

The MCFC (6) The increased temperature of operation reduces the maximum cell voltage for thermodynamic reasons from 1.23 V to 1.02 V, which contributes to the relatively poor performance of MCFCs at higher current densities. However, it does have a number of advantages: Noble metal catalysts no longer necessary. At the anode CO can be employed as a fuel: CO + CO32or: CO + H2O CO2 + H2 (water-gas shift reaction) 2CO2 + 2e-

followed by oxidation of the H2. Reaction is catalysed by Ni alloy anode catalyst.

The MCFC (7)

Indirect Internal Reforming (IIR). A wider range of feedstocks is accessible.

The MCFC (8)

Majority of voltage loss is due to resistance of electrolyte (thickness d): DV = 0.533d Thus, the cell voltage of a MCFC with a 0.02 mm thickness of electrolyte would be 96 mV higher than that having a 0.2 mm thickness. MCFC thickest electrolyte HERE.

The MCFC (9)

Problems: Cost.

Durability.
System complexity.

11.

High temperature fuel cells: the SOFC (1000 C)

SOFC (1)

Genesis of SOFCs in discovery of solid oxide electrolytes by Nernst in 1899. Haber filed the first patent on a fuel cell with a solid electrolyte in 1905. The SOFC is a completely solid state device utilising an ion conducting ceramic as the electrolyte & mixed metal oxide-based anodes and cathodes with an operating temperature of typically 1000 C. The high temperature means that the theoretical open circuit voltage is only 0.92 V but kinetic losses are no longer a problem, and the most significant loss in SOFCs is due to Ohmic losses in the electrodes, electrolyte and interconnects between the cells.

SOFC (2) Pioneered by Westinghouse Power Corp (now Siemens Westinghouse Power Corp).

Tubular design still the most commonly employed.

At the anode: H2 + O2- H2O + 2e-

CO + O2- CO2 + 2eAt the cathode: O2 + 4e- 2O2Overall: H2 + CO + 2O2- H2O + CO2

CO now a fuel rather than a poison

Moving ion

SOFC (3) The specific advantages of the SOFC, largely due to the high operational temperature, are: It is simpler in concept than any of the other fuel cells. CO is a fuel rather than a poison. The SOFC is the most sulfur-tolerant of the fuel cells, although sulfur is usually removed from the fuel stream prior to reformation. Precious metal catalysts not required.

Internal reforming is possible.

A wide range of fuels can be employed. Reduced Ohmic losses (due to enhanced conductivities) through electrode and electrolyte materials.

SOFC (4)

Overall system efficiencies (with CHP or cogeneration) of 85% have been quoted, lifetimes of 20,000 hours without performance loss (target 40,000 hours) and power densities up to 2 W cm-2 reported; to what extent the former is a fact or aspiration is unclear. NOTE: In order to drive a gas turbine, the fuel cell must be pressurised, and this has only recently been demonstrated over a prolonged period using a SOFC.

SOFC (5)

Anode

Cathode

The most commonly employed electrolyte is Zirconia, ZrO2, stabilised by ca. 8 10% Yttria, Y2O3, YSZ. Anionic conduction of O2- species starts at temperatures above 800 C with a conductivity of 0.02 W-1 cm-1 at 800 C rising to 0.1 W-1 cm-1 at 1000 C. YSZ is relatively stable at high temperatures in both oxidising and reducing atmospheres and can be made very thin (25 50 mm) to minimise Ohmic loss.

SOFC (6) The use of relatively high surface area, supported Ni as the anode catalyst again offers the possibility of Direct Internal Reforming, and the incorporation of internal reforming in the SOFC is seen by many as essential for the commercial realisation of the technology due to the elimination of the complexity and cost of an external reformer. Problems: The endothermic reforming reaction. Coking via: CH4 C + 2H2 and Boudouard CO + H2 C + H2O. Oxidation of Ni to NiO: Ni 8.9 g cm-3 and NiO 6.96 g cm-3.
Ni

SOFC (7)

Anode

Catalysts limited to Ni, Co, Pt and Au.

Typically, NiO mixed with YSZ to form Cermet (CERamic+METal).

Direct Internal Reforming possible in theory.

SOFC (8)

Cathode must be: Active wrt oxygen reduction. Stable. Highly electronically conducting. Porous to O2. Unreactive wrt other components. La(1-x)SrxMnO3 (0.10 < x < 0.25) most commonly employed.

SOFC (9) The great advantage of the tubular design SOFC is that it does not utilise high temperature, gas-tight seals and this undoubtedly contributed to its appearance as the first development SOFC.

Air is admitted into the central void of the cell via a thin alumina tube mounted along its axis. In essence, the simplicity of the design in completely spatially separating the fuel and oxidant flow paths eliminates any sealing problems.

Diagram showing the absence of gas tight, high temperature seals in the tubular SOFC. T = tubular fuel cell; S = deliberately imperfect seals around tube; S = seal easy to maintain.

SOFC (10)

(b)

2 cm dia. YSZ 1-2 mm thick

(a)

(d)
(c)

(a) SOFC bundle of 24 tubular cells. (b) & (c) Schematic showing cross section of single tubular cell. (d) Cross section of stack consisting of Bundles.

SOFC (11)

In the common tubular SOFC design, interconnects:

Link the anode & cathode of adjacent cells. Must be stable at high temperatures in oxidising & reducing environments. Must not react with the electrode materials.

Must be impermeable to the fuel and air.

Must be a thermal match with YSZ electrolyte. Most SOFCs use Sr, Ca or Mg doped LaCrO3.

SOFC (12) (BIG) problems with tubular design: Cost per kWh not known. High Ohmic loss /low power densities. Coatings made via electrochemical vapour deposition. LaCrO3 (interconnects) difficult to process (expensive) due to chromia evaporation at high temperature leading to poor densification.

Hence planar designs Utilise significantly shorter conduction paths hence higher power densities. Interconnects bipolar plates providing both electronic connection and fuel/oxidant distribution. BUT sealing!

SOFC (13)

Planar solid oxide fuel cell (SOFC)

Air channel

bipolar plate
Cathode current collector cathode electrolyte anode porous metallic substrate Fe-26Cr-(Mo, Ti, Mn, Y2O3) alloy bipolar plate

Fuel channel

SOFC (14)

But- sealing is a MAJOR problem in planar SOFCs: Glass ceramics only sealing option: very brittle and prone to thermal stress failure. Glass seals are also prone to failure under the tension necessary to facilitate sealing. Difficult to manufacture thin enough. Difficult to manufacture large areas, severely restricted, eg. to ca. 10 cm x 10 cm.

SOFC (15)

Possible application of planar SOFC: 7-series BMW as battery replacement. Target power output = 135 kW.

SOFC (16)

High temperatures and brittle nature of components = long start-up & cooling times, hence primary application stationary power generation (steady state operation). Difficult to get operational data.

SOFC (17)

Siemens-Westinghouse design

SFC-200 system