Sofc - Future Source of Susta...

SOFC - FUTURE SOURCE OF SUSTA...
SOFC - FUTURE SOURCE OF SUSTAINABLE POWER
Dr J D Bapat *
Abstract
The state-of-the-art on the solid oxide fuel cell (SOFC) is presented, covering the basic principles underlying its working, thermodynamic and
chemical aspects, utilization of fuels and available options, cell design configurations, power generation and the materials used for electrolyte and
electrodes. The major advantages of SOFC are multi-fuel capacity, non-requirement of expensive catalysts, high quality exhaust heat useful for
cogeneration and wide applications. The major disadvantages are high temperature operation, limited unit cell size due brittle ceramic components
and high capital cost-to-output ratio. The conduction of oxygen ions through the electrolyte takes place due to the oxygen vacancies in the crystal
structure generated due to the defect reactions. The maximum thermodynamic or the open circuit potential of the SOFC is given by the Nernst
equation. The actual potential is less than that predicted on thermodynamic considerations, on account of the irreversible losses occurring due to the
resistance to the transport of gaseous species through the porous electrodes (concentration overpotential), activation energy barriers for the
electrochemical reaction (activation overpotential), resistance to the transport of ions or electrons through the electrolyte or electrodes (ohmic
overpotential), leakage electronic current through the electrolyte (leakge overpotential) and the interfacial resistances at the material boundaries
(interface overpotential). All the overpotentials are the functions of current density. The mathematical correlations commonly used to estimate these
overpotentials are given. The trends reveal that increasing working temperature results in extended operating current range and reduced irreversible
losses, but reduced open circuit potential also. The cathode contributes most to the cell irreversible losses. The four factors, commonly used to
evaluate the performance of fuel cells, namely fuel utilisation factor, air ratio, power output and fuel efficiency are defined. The two ways to utilise
fuel have been discussed, namely the reforming and the direct oxidation of hydrocarbons. The direct oxidation yields maximum open circuit
potential but the process is still under development. The internal steam reforming of fuels is preferred over external reforming, on account of
significant reduction in losses and capital, operating costs. However there are drawbacks, namely possibility of carbon deposition at the anode
deteriorating the cell operating performance and life and rapid endothermic cooling leading to large temperature gradients across the cell and the
interconnect. The carbon deposition can be prevented by maintaining the steam-to-fuel ratio above the limiting value calculated on the basis of
thermodynamic equilibrium considerations. However such steam-dilution of fuel leads to the reduction in its chemical potential. The problem of
large temperature gradients is tackled, to some extent, by partial pre-reforming of fuels or by reducing the anode’s catalytic activity towards
reforming reaction. The oxidative reforming, in which a mixture of hydrocarbon fuel and stoichiometrically deficient quantity of oxygen is fed to
the anode, is being studied for use in small size SOFC. The Nernst potential reduces with fuel utilisation. It is possible to improve the cell
efficiency maintaining the fuel utilisation at low levels and increasing the fuel recycle ratio. However this measure increases the cost and
complexity of the fuel cell system. The alternative simpler approach is the multistage oxidation of fuel, in which partially utilised fuel from one
stack is fed to the next stack. The direct oxidation of hydrocarbons at high temperature, on the conventional Ni-based anodes suffers from the
drawback of carbon formation. Alternate anode materials are being tried to tackle this phenomenon. The fuels which could be used in SOFC,
besides hydrocarbons, are natural gas and other hydrocarbons, methanol, ethanol and biogas. The selection of the most appropriate fuel for SOFC
for the given application is a multi-criteria task involving both qualitative and quantitative parameters. Based on the overall considerations, various
fuel options could be arranged in the following order of preference: methane >ethanol>biogas>gasoline. The two principal design configurations of
SOFC are planar and tubular designs. The operation at elevated pressure yields higher cell power output. In a megawatt capacity plant, such SOFC
can successfully replace the combustor in a gas/steam turbine power generation system and achieve fuel efficiency up to 70%. The individual SOFC
are arranged in stack. The interconnect connects the cathode of one cell to the anode of the other, while protecting it from the reducing atmosphere.
A power generation unit may consist of groups of fuel cell stacks of a particular size and output, held in containment vessels. The tubular SOFC is
more useful for stationary power generation, whereas the planar design for auxiliary power units, due to relatively higher power density. The
requirements for the selection of materials are given. The cathode is porous and possesses high electronic and small ionic conductivity and also
catalytic activity towards oxygen molecule dissociation and reduction. The ABO 3 oxide system of perovskite structure satisfies most of the
requirements. The commonly used SOFC cathode material is a mixture of strontium substituted lanthanum manganite (LSM) and the yttria
substituted zirconia (YSZ). The anode materials are also porous and require high stability in reducing atmosphere. The transition metals best fit the
requirement, as they have high catalytic activity towards hydrocarbon reforming or oxidation. The Ni-YSZ cermets are commonly used as anodes.
The Cu-ceria anodes have been reported to effectively tackle the problem of carbon deposition. The YSZ is commonly used electrolyte material at
present. The advantages in reducing the operating temperature of SOFC are stated. The mixed oxide electrolytes made from ceria doped with yttria,
gadolinia and samaria show high oxygen ion conductivity at low temperatures, but suffers from the drawback of Ce 4+ reduction to Ce 3+ at low
oxygen partial pressures, obtaining at the anode. Promising results have also been obtained on ceria based multi-phase (heterogeneous) materials.
The doped lanthanum gallate is another promising electrolyte material under investigation. At operating temperatures below 700 0 C, it is possible to
use stainless steel, which is comparatively inexpensive and readily available material, as the interconnect. The SOFC is the means of pollution free,
sustainable power generation of the future but its success will depend upon the effective dealing of certain aspects like reducing capital cost-to-
https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

output ratio, developing low cost large volume production techniques, developing materials and techniques for low temperature, multi-fuel
operation.
Key words: fuel cells, power generation, electrolytes, electrodes, hydrocarbon reforming
* Paper presented at the 3 rd National Symposium on Forefronts of Engineering, Theme: Power for Sustainable Development, AISSMS College of
Engineering, 25-26 September 2008, Pune, India
1/ Introduction:
The rapid growth of industrialisation and urbanisation in the twentieth century have set apace the demand for electric power in the industrial as well
as domestic sectors. The sustainable development requires that the power generation should be done making minimum use of the non-renewable
natural resources and the environmental pollution, in all forms, should be minimised. The generation of power using fossil fuels, namely coal and
diesel and that using nuclear fission, entails huge environmental pollution besides depletion of natural resources. The combustion of fossil fuels also
results in emission of carbondioxide, which is a green house gas. The International Energy Agency estimated that in the year 1996, there were
634x106 vehicles on road which collectively emitted some 3.7x109 tons of carbondioxide [1}; the figure must have gone up by at least 20 % by
now. The generation of thermal power requires the conversion of thermal energy, produced from combustion of fuel, to work. The Carnot efficiency
defines the absolute limit of efficiency of any heat engine operating on thermodynamic principles. However, it is an unachievable value. The Carnot
efficiency relates to a heat engine that operates both internally and externally reversibly, and while the former is theoretically possible, the latter
cannot be achieved, if the engine produces power output. In practice, the achievable efficiency of a heat engine is just 35 to 45 %, in most cases.
Whilst the alternative, renewable, energy sources such as solar panels and wind farms are useful as they are pollution free, there are limitations on
their applicability, such as storage of solar power, portability, sustained availability of wind, and so on. Under this situation, the fuel cells appear to
be a promising means of power generation, for the future.
A fuel cell is an electrochemical device that converts the free energy of an electrochemical reaction directly into electrical energy (and heat). The
free energy is provided by the electrochemical oxidation of fuel, such as hydrogen, a mixture of hydrogen and carbon monoxide or a hydrocarbons
like methane, methanol, butane or even gasoline and diesel. The fuel cell harvests the electrochemical energy by controlling the path and the means
by which such a reaction occurs. The device is simple and contains no moving parts and only four basic functional units, namely cathode,
electrolyte, anode and the interconnecting device. In some aspects, fuel cell is similar to an electrolytic cell. Like an electrolytic cell, fuel cell has
positive and negative electrodes separated by electrolyte. However unlike the former, the reactants are not stored in the cell but continuously fed to
the cell and the products of the reaction are continuously removed. Thus fuel cell operation is a steady flow process and continues as long as the
steady supply of reactants is assured. The fuel cells convert the energy in the fuel directly into electricity and are not subject to the second law of
thermodynamics, in the same way as the heat engines are. They operate at higher efficiency at low loads than the high loads, which makes them
more suitable for vehicular application, in comparison with the internal combustion engines [2].
The name of the fuel cell generally refers to the type of electrolyte used in the cell. The prominent fuel cell technologies are alkaline fuel cell
(AFC), phosphoric acid fuel cell (PAFC), proton exchange membrane fuel cell (PEMFC), molten carbonate fuel cell (MCFC), and solid oxide fuel
cell (SOFC). The Table-1 draws a brief comparison between these technologies [3,4]. The present paper reviews the latest developments in the
SOFC technology.
2/ Working of SOFC:
The SOFC is constructed with two porous electrodes which sandwich an electrolyte. Air (oxidant) flows along the cathode, which is therefore called
air electrode. The gaseous fuel flows along the anode, which is therefore called the fuel electrode. The oxygen diffuses through the porous cathode
and comes in contact with the cathode-electrolyte interface. The oxygen molecule catalytically acquires four electrons from the cathode and gets
reduced into two oxygen ions (O= ). These ions are transported to the anode-electrolyte interface, through the ion-conducting electrolyte. The fuel
diffuses through the porous anode. Both, the fuel and the oxygen ions meet at anode-electrolyte interface. They react catalytically at the gas-anode-
electrolyte three phase boundaries (TPB) giving off water, carbon dioxide, heat and most importantly electrons. The products, i.e. water and carbon
dioxide, are then transported back to the fuel channel through the porous anode. The electrons transport back to the cathode through the external
circuit and the process continues. The SOFC has the following advantages
a/ High efficiency (> 60%) and low performance degradation (< 0.1%/1000 h) achievable.
b/ Multi fuel capacity: methane, propane, methanol, gasoline, diesel can be used
c/ Environment friendly: No or negligible NOx , SOx , VOC, particulates
d/ Modular construction, noiseless operation
e/ Multiple applications: stationary, transportation and military

f/ Moderate power density (w/m 2 )

g/ Reasonable tolerance to gas phase poisons, S or CO
h/ Expensive catalysts like platinum or ruthenium are not needed
i/ High quality exhaust heat (800-900 0 C) useful for cogeneration
j/ Combined cycle operation possible
The device also has the following drawbacks:

a/ High electrolyte resistivity and electrode polarisation
b/ Formation of low conducting phases due to solid state reactions at cathode/electrolyte interface
c/ Brittle ceramic components, which limit the maximum cell size to 0.2 m 2 , in comparison to PAFC and MCFC having a standard cell size o
around 0.5 m 2 . The smaller size of SOFC puts a limit on the scale-up of SOFC based power plants to megawatt capacity.
d/ High capital cost-to-output ratio.
e/ Higher Temperature of Operation
3/ Thermodynamic and electrochemical aspects:

The study of thermodynamic and electrochemical aspects reveals useful information such as the open circuit potential, thermodynamic efficiency,
irreversible losses in the fuel cell and various performance related factors.
3.1/ Open circuit potential of a reversible cell:

As explained earlier, fuel cell is an electrochemical device in which the energy released during the reaction, appears at least in part, directly as the
electrical energy. The reactants are not stored but fed to it continuously and the products of reaction are also continuously withdrawn. Thus, it
operates as a continuous flow system, so long as the reactants are supplied, producing a steady electric current.
The fuel electrode (anode) is fed with fuel such as hydrogen, methane, propane, methanol, ethanol, etc., The air electrode ( cathode) is continuously
fed with the oxidant i.e. air. The solid electrolyte, through which the oxygen ions migrate from cathode to anode, has high oxygen ion conductivity
due to high concentration of oxygen vacancies. The oxygen vacancies are produced by doping a semiconductor like zirconia (ZrO2 ) by soluble,
aliovalent, rare earth oxide impurity like yttria (Y2 O 3 ). The electrolyte is known as yttria stabilised zirconia (YSZ). The oxygen vacancies are
generated through the following defect reaction, written in the Kröger-Vink notations
-- --- (1)
As per the Eqn. (1), one oxygen vacancy is created for every mole of dopant Y 2 O 3 . The cathode operates in an oxidising environment at about
1000 0 C and participates in the following reduction process.
½ O 2 (g) + 2e - → O = --- ----- (2)
The fuel (hydrogen, for example) is transported through porous anode to the anode/ electrolyte interface, where it gets oxidised at the TPB
O = + H 2 (g) → H 2 O (g) + 2e - --- ----- (3)
The electrons generated flow back to cathode through the external circuit. The overall oxidation reaction can be written as follows.
H 2 (g) + ½ O 2 (g) → H 2 O (g) --- ---- (4)
The decrease in free energy in a chemical reaction [like reaction (4)] at constant pressure and temperature, known as the Gibbs free energy
(ΔG P,T ), represents the maximum electrical work (WE) that can be obtained from a fuel cell.
-ΔG P,T = W E -- -- -- (5)
If the electromotive force (emf) or the open circuit potential of a reversible cell is E volts and the process involves passage of N Faradays of
electricity
-ΔG P,T = NFE -- -- -- (6)
or
E = -ΔG P,T / NF -- -- -- (7)
The value of N in an electrochemical oxidation reaction is equal to four times the number of oxygen molecules required to oxidize one molecule of
fuel.
Considering fuel cell as a steady flow process, operating reversibly and isothermally, the First Law of Thermodynamics takes the form
ΔH = TΔS + W E -- -- (8)

or
W E = ΔH - TΔS = -ΔG P,T = NFE -- -- (9)
3.2/ Thermodynamic efficiency:

The thermodynamic or the maximum efficiency obtainable in a fuel cell is defined as
η th = (thermodynamically feasible maximum energy generation) / (total input energy) -- (10)

= -ΔG P,T / ΔH = NFE / ΔH -- -- (11)
3.3/ Nernst potential:

The Eqn. (7) gives the open circuit potential of a reversible cell. Consider the following chemical reaction taking place in a reversible cell
aA + bB + -- -- -- = lL + mM + -- --- -- (12)
If the reactants and the products are considered at their standard state , then the open circuit potential (E 0 ) is given by
E0 = - ΔG 0 / NF -- -- -- (13)
Where ΔG 0 is the free energy change at standard state. Similarly the free energy change for the chemical reaction is given by
--- -- (14)
Based on Eqn.(7) and (13), the open circuit potential of the reversible cell may be derived from Eqn. (14) as
… … (15)
Where ‘a’ are the activities of the reactants and the products. In practice, the activity, as an approximation, can be expressed in terms of the
concentration or the partial pressure of the constituent in gas phase reactions. Thus the open circuit potential for the oxidation reaction (4) may be
written as
-- -- (16)
The Eqn. (16) is the famous Nernst equation and the open circuit potential is also called the Nernst potential.
3.4/ Cell operating potential:

The actual potential in an electrochemical cell is less than that predicted on thermodynamic considerations, on account of the following irreversible
losses or the so called overpotentials.
a) Concentration overpotential: This loss is due to the resistance to the transport of gas phase species through the porous electrodes i.e. the
anode (E c-an ) and the cathode (E c-ct). The loss becomes important when the fuel utilisation and the current density in the cell are high [5].
b) Activation overpotential: This loss is due to the activation energy barrier for the electrochemical reaction at the electrode-electrolyte
interface, on the anode (E v-an ) and the cathode (E v-ct) side. The modeling of activation overpotential requires an understanding of the elementary
thermal and electrochemical reaction mechanisms and the microstructure of the electrode. The value of the activation overpotential is usually small
at high temperatures, as obtained in the SOFC [6]. The loss becomes important when the electrochemical reaction is controlled by slow electrode
kinetics. In case of SOFCs using composite electrodes with mixed ionic and electronic conduction, such as Ni -YSZ for anode and lanthanum-
strontium-manganite or LSM-YSZ for cathode, the electrochemical reaction zone can be extended from the electrode-electrolyte interface into the
electrode resulting in the reduction in the activation overpotential. The micro structural properties of composite electrode, such as grain size and the
volume fraction of components will affect the exchange current density.
c) Ohmic overpotential: This loss (E o ) is due to the resistance to the transport of oxygen ions through the electrolyte or the electronic flow
through the electrode. The electronic conductivity of electrodes is high in SOFC, due to high metal loading. Thus the ohmic overpotential in SOFC
is typically due to the ion transfer resistance through the electrolyte. The loss can be reduced by decreasing the electrolyte thickness and enhancing
its ionic conductivity.

d) Leakage overpotential: This loss (E l ) is due to the leakage electronic current through the electrolyte
e) Interface overpotential: This loss (E n ) is due to the contact resistance at the material boundaries, created due the discontinuities.
The cell operating potential (E cell )may be expressed taking into account these irreversible losses
Ecell = E - Ec-an - Ec-ct - Ev-an - Ev-ct - Eo - El – En -- -- (17)
The overpotentials mentioned in Eqn. (17) can be evaluated using correlations reported in the literature [7, 8, 9]. The correlations commonly used
to estimate these overpotentials are given Table – 2. All the overpotentials are functions of current density. The trends given by these correlations
reveal that increasing working temperature of fuel cell brings about the advantage of increased limiting current density, resulting in the extended
operating range and reduced irreversible losses. The overall result is improved efficiency and power density of the fuel cell. However the drawback
is reduced open circuit voltage (E) or Nernst potential, associated with the increased cell temperature [8] (Eqn. (9)) . The cell potential at any point
in space in the cell (E cell-L) is determined by the local current density (iL) and the internal local area specific resistance (RL), which includes the
overpotentials around the operating point
Ecell-L = EL - iL. RL -- -- (18)
All the three terms on the right hand side of the Eqn. (18) vary spatially in the cell. Assuming uniformity in the cell thickness, the variation in the
current density is caused by the variation in the local Nernst potential caused by the reactants (fuel) depletion and the change in the material
resistivity caused by the local temperature variations in the cell. Thus the actual cell potential can be obtained by integrating the local cell potential
over the active cell area
-- -- (19)
3.5/ Performance indicators:

The four factors, defined as follows, are commonly used to evaluate the performance of the fuel cells.
a) Fuel utilization factor (u): It refers to the fraction of total electrical energy available in the inlet fuel that is actually used to produce
electricity in the fuel cell.
----- --- (20)

b) Air ratio (‫)ג‬: The air ratio indicates the excess air supplied to the fuel cell, in relation to that required stoichiometrically
----- --- (21)

c) Power output (P SOFC ):
P SOFC = (average current density)x(active anode surface area for electrochemical reactions)x
(output potential)
----- --- (22)
d) Fuel efficiency ( f ): The fuel efficiency represents the fraction of total thermal energy in the inlet fuel stream, that is converted into
electrical energy

----- --- (23)
The net chemical energy consumed in the fuel cell is converted either to the electrical energy (power) or to the heat on account of the entropy
change during the electrochemical reaction and the irreversible losses due to the overpotentials.
4/ Fuels – utilisation and options:

4.1/ Fuels utilisation:
In the fuel cell, gaseous fuel is fed at the anode and the oxidant at the cathode. There are two ways to utilize the fuel, namely (a) reforming
hydrocarbon fuels by steam and (b) direct oxidation of hydrocarbons. However the technology of direct oxidation is under development and in most
cases, fuels are steam reformed outside or inside (internal reforming) the fuel cell. The process suffers from the drawback of the loss of chemical
potential on account of the conversion of hydrocarbons to lower hydrocarbons, H 2 , CO, CO 2 [11]. The Nernst potential is highest for the direct
oxidation of hydrocarbons. It is also a function of fuel utilisation. The fuel fed at the anode inlet gets gradually converted to the oxidation products.
Thus the concentration or the partial pressure of the fuel (reactants) gets reduced as it flows towards the exit and consequently the Nernst potential is
also reduced as can be seen in Eqns. 14 to 16. The authors, Zhu and Kee [7], calculated the Nernst potentials presuming that the oxidiser is pure air
i.e. no depletion of oxygen in air. The two methods of fuel utilisation are briefly discussed, highlighting the current trends, in Sections 4.1.1 and
4.1.2
4.1.1/ Internal steam reforming:
The reforming process converts the hydrocarbon fuel into a mixture of lower hydrocarbons, hydrogen, carbonmonoxide and carbondioxide. The
overall reaction of steam reforming may be represented as:
----- --- (24)
Where ‘m’ is the steam reforming factor or steam-to-fuel molar ratio. The internal steam reforming requires anode material that has good catalytic
reforming properties as well as those required for the oxidation of fuel in the fuel cell. At the SOFC temperature, the anode material is also active
towards shift reaction and the reaction, given as follows, is generally in equilibrium.
CO + H 2 O H 2 + CO 2 --- --- (25)

In comparison to the external reforming the internal reforming is preferred for the following reasons [12]:
(a) The catalytic steam reforming of hydrocarbons is carried out between 750-900 0 C. The high operating temperature of SOFC allows for the
internal reforming of gaseous fuels
(b) The heat released from the fuel oxidation provides endothermic heat required for the reforming process.
(c) A part of the steam required for the reforming reaction can be obtained from the steam generated by fuel cell reaction. This is more so with
anode off-gas recycle
(d) The reforming reaction can proceed beyond the thermodynamic equilibrium, as the products hydrogen, carbonmonoxide, are continuously
removed from the reaction site by the fuel cell reactions
(e) The excess air load required for cooling at the anode is reduced due to endothermic nature of the reforming reaction. In a typical case of
methane reforming, the cooling load is reduced by 40-50 %.
(f) Significant reduction in capital and operating costs in comparison to external reforming
(g) Capacity to offer faster response to load variations
The internal steam reforming on the Ni-YSZ based anodes has the following limitations
(a) There is a risk of carbon formation on the anode, according to the Boudouard reaction
----- --- (26)
The carbon formation deteriorates the cell operating performance and life, hence it should be prevented. The criterion for carbon formation in the
reforming reaction is given by the Eqn. 27, based on the equilibrium concsiderations [12].
-- --- (27)

The Eqn. (27), giving the limiting carbon activity, states that the carbon formation is thermodynamically favored when ac ≥ 1. The limiting steam-
to-fuel ratios, corresponding to the limiting carbon activity, above which carbon formation is thermodynamically impossible, for gasoline, ethanol,
methane and methanol fuels, have been calculated by Douvertzides et.al. [13]. Higher steam-to-fuel ratios lower the electrical efficiency of the fuel
cell due to steam dilution of the fuel. Hence there is a search for advanced catalysts, which will allow internal reforming at low steam-to-fuel
ratios.
(b) Excessively large temperature gradients can develop across the cell and the interconnect, due to endothermic cooling. The reforming is usually
complete within a small distance on the anode leading to strong cooling effect and large temperature gradients.
There are two common approaches to tackle the problem, mentioned as follows:
i. Partial pre-reforming of fuels: With increased levels of pre-reforming, some of the advantages of full internal reforming of fuel are
sacrificed.
ii. Reduction of reforming rate on the anode: This is achieved by partial poisoning of active sites. Ahmed and Foger [12] report that both the
number and the nature of active sites are changed by the incorporation of a basic compound in Ni/YSZ anode formation and as a result,
much lower reforming rates are obtained. Similar results have also been reported by Finnerty et.al. and Marina et.al, using Mo and Ce
dopants [14]
Both the techniques mentioned as above need to be optimised. Hiei et.al. [15] report about the oxidative reforming of methane, in which a mixture
of methane and stoichiometrically deficient quantity of oxygen is fed to anode. The methane gets partially oxidized in the first step
CH 4 + ½ O 2 ⇄ CO + 2H2 (exothermic) - -- (28)
Subsequently complete oxidation of methane takes place, leading to generation of electric power
CO + ½O 2 ⇄ CO 2 (exothermic) -- --- (29)

H 2 + ½O 2 ⇄ H 2 O (exothermic) -- --- (30)
This is followed by the reforming of CH 4 with CO 2 and H 2 O producing gaseous mixture of CO and H 2 (synthesis gas) which can be used for the
synthesis of methanol
CH 4 + H 2 O ⇄ CO + 3H2 (endothermic) -- -- (31)

CH 4 + CO 2 ⇄ 2CO + 2H2 (endothermic) -- -- (32)
The reaction heat is smoothly removed and consequently thermal stresses are reduced. The feeding of oxygen (air) for the purpose of oxidative
reforming is easier in comparison to that of steam required for steam reforming. The authors claim that high electric power and the synthesis gas
consisting of CO and H 2 in the molar ratio of 2:1 was obtained using La0.9Sr 0.1Ga 0.8Mg 0.2O 3 , Ni, and La0.6Sr 0.4CoO 3 as the electrolyte, the
anode and the cathode respectively. However, oxidiser (oxygen) in fuel channel does not take part in the current generation; only fuel oxidation
with oxidiser from the cathode can produce power. Thus any oxidiser in fuel channel must reduce the cell potential because of its diluting effect.
The small size SOFCs (typically of 2.5 mm outside diameter, 50 mm length and 150 μm thickness) are currently being studied for applications such
as portable power units, domestic heat and power generators and automotive power units. Using butane as fuel Sammes et.al. [14] observed that
steam reforming is inadequate for the operation of small size SOFC system, irrespective of the presence of dopants on the anode, instead the
oxidative reforming using butane, air mixture proved promising.
It can be seen in Eqn. (14) to (16), the Nernst potential reduces with fuel utilisation. Thus it is possible to improve the cell efficiency by keeping the
conversion at low level (thereby ensuring practically uniform potential from inlet to exit ) and operating the cell with a high fuel recycle ratio,
combined with the removal of reaction products ( H 2 O and CO 2 ) external to the cell. Thus the fuel recycling my increase the total system
efficiency of a single-stage system but with considerable cost in the capital and complexity. The alternative and simpler approach is the multistage
oxidation of fuel. The Eqn. (11) assumes cent percent fuel utilisation and it also does not account for the variation in ΔG with fuel utilisation.
Rewriting the Eqn. (11), accounting for the variation of ΔG with fuel utilisation
-- -- (33)
The integral in Eqn. (33) may be viewed as the summation over infinite number of reversible cells fed in series. Elangovan et.al. [16] examined the
multistage oxidation concept on a configuration consisting of multiple stacks with sequential fuel flow. In that system, the fuel exhaust from one
stack, containing partially utilised fuel, was fed to the next stack. The planar SOFC design and the co-flow arrangement of fuel and air streams was

considered. The analysis and the experimental verification of the multistage oxidation concept showed that the stack efficiency increases due to
smaller variation in the Nernst potential across the cell area. The system reliability is increased due to reduced temperature gradients. The higher
power density was also observed. The multistage system eliminates the complexity of the fuel recycling system.
4.1.2 / Direct oxidation of hydrocarbons:

In fuel cells, the direct oxidation may be defined as the oxidation of hydrocarbons (to H 2 O, CO 2 ) at the anode in the absence of oxygen supplied in
the fuel stream. Theoretically, direct oxidation of any hydrocarbon fuel is possible in fuel cell, as the species that migrate through the electrolyte are
oxygen anions. The elimination of reforming step will reduce the complexity of the fuel cell system. However, there is a thermodynamic driving
force towards carbon formation, with dry hydrocarbons at high temperatures.
CH 4 C + 2H2 --- -- (34)
The direct oxidation of methane and the other hydrocarbons is reported in the literature. Using conventional Ni-based anodes, Murray et.al. [17]
reported excellent power densities and stable operation for dry CH 4 fuel between 500-700 0 C, because carbon formation is not thermodynamically
favored at these temperatures. The use of conducting oxides as anodes, like ceria and bismuth oxide, has been reported to solve the problem, as they
do not catalyse C-C bond formation in the same manner as the nickel does [18]. However the power densities achieved were too low for practical
use. One limitation of the direct oxidation is that the free radical chemistry can lead to the carbon formation in the anode compartment even in the
absence of catalyst. Gorte [19] observed this phenomenon while using butane as fuel at 1070 K, when tars were formed on the sides of alumina tube.
The typical electrochemical reaction for direct oxidation, in case of methane and n-butane could be written as follows
CH 4 + 4O= CO 2 + 2H2 O + 8e - -- -- (35)

C4 H 10 + 13O = 4CO 2 + 5H2 O + 26e- -- -- (36)
Abudula et.al.[20] studied the direct oxidation of methane at low concentrations (4-9 %) at 1000 0 C, considering Ni/YSZ cermet anode as a
completely mixed reactor. The threshold current, I tsh, below which the carbon deposition is favored, is given by the following Equation.
--- -- (37)
The value of threshold current as obtained by the experiments conducted by the authors and as given by the Eqn. (37), will be more when, (a) the
anode thickness increases, as the area of tpb also increases in proportion, (b) the diameter of NiO particles decreases, (c) the methane concentration
increases, (d) the temperature increases. Thus to keep the rate of carbon formation or the threshold current at the minimum, there is a need to
optimize the thickness of anode, YSZ electrolyte (to minimise ohmic overpotential), anode structure (NiO particle size) and the operating
temperature of SOFC.
4.2 / Fuel options:

The research conducted in the area so far indicates that, besides hydrogen, the natural gas (methane) and other hydrocarbons (butane, gasoline, etc),
methanol, ethanol, biogas can be used as fuels in the fuel cells. The direct oxidation is welcome but the process is under development; hence in
most cases, steam reforming of fuels is carried out. The steam reforming produces H 2 and CO. It is hydrogen which primarily contributes towards
the power generation, whereas CO is consumed in the shift reaction producing additional hydrogen.
The methane and the other hydrocarbons are mineral fuels. Their deposits are limited and their oxidation contributes to the generation of greenhouse
gas (CO 2 ), hence they do not provide a long term solution to the energy problem. The utilization of other renewable, environment friendly fuels,
such as methanol, ethanol or biogas is drawing considerable attention of the researchers. The ethanol is considered a very promising and reliable
fuel option because it can be alternatively produced biochemically from the biomass.
The Eqn. (24) gives the overall reaction of steam reforming of a fuel represented by Cx H y O z. Douvertzides et.al. [13] analyzed the performance of
methane, methanol, ethanol and gasoline fuels for the generation of electric power in SOFC, in terms of the electromotive force (emf) and the
systems efficiency. The limiting reforming factor, ‘m’ (steam-to-fuel ratio), varies as per the boundary of carbonisation for different fuels and the
temperatures. The authors have made the following observations, based on their analysis.
1. Higher the carbon content of the fuel higher is the reforming factor (m), at a given temperature.
2. The limiting value of m, as given by the boundary of carbonization, decreases as the temperature increases.
3. The behavior of methane and ethanol is similar for T >1100 K; for example, under that condition they have an identical value of steam-to-
fuel ratio as well as the maximum average emf generated.
4. As the temperature increases, the equilibrium concentration of H 2 and CO produced after steam reforming of hydrocarbons, also increases.

5. The optimum T and m for the operation of SOFC correspond to their values at the carbonization boundary, as these conditions of reforming
yield the maximum possible fuel-to-oxidant ratio.
6. The maximum average emf obtainable, for the four fuels studied, decreased with the temperature and so did the overall efficiency of the fuel
cell. However the worst absolute value of efficiency for any fuel and temperature is still above 80 %
7. The actual fuel cell efficiency was correlated with the maximum (thermodynamic) efficiency as follows:
---- --- (38)
-- -- (39)
The expression in Eqn. (38) shows that the fuel cell efficiency is half of the maximum efficiency,
when it runs at full power (pr = 1), as the conditions are far from reversibility.
8. The selection of most appropriate fuel for SOFC is a multicriteria task involving both qualitative and quantitative parameters. Based on their
evaluation, the authors arranged the fuel options in the following sequence.
methane>ethanol>methanol>gasoline
The choice of the fuel and its processing also depends upon the type of application. Sammes et.al. [14] found that for small size SOFC , the so
called micro-SOFC working on butane fuel, the steam reforming is inadequate. Herle et.al. [21] observed that the use of biogas as the SOFC fuel
will encourage wide scale use of SOFC units in 5-500 kW range at farms, landfill sites, sewage treatment plants, organic solid waste digesters or
organic liquid effluent treatment sites. The use of fuels like methanol or ethanol will be more advantageous for the SOFC applications in the
electric motor vehicles.
5/ Cell design configurations and power generation:

The two principal design configurations of SOFC, namely the planar and the tubular designs, are discussed in this Section. The typical conceptual
arrangements, showing the basic building blocks, of the stationary and the auxiliary power units based on SOFC, is also presented. The details of
the design and the operation of SOFC based power plants have been kept out of the purview of this paper.
5.1/ Cell design configurations:
SOFC are designed in planar and tubular configurations of SOFC [22]. In the planar design, the cell components are configured in thin, flat plates.
The interconnection has ribs on both sides and serves as bipolar gas separator, connecting the anode and the cathode of the adjoining cells. In the
tubular design, the components are arranged in the form of a hollow tube, with the cell i.e. the electrolyte and the anode constructed in layers around
the tubular cathode. Air flows through the inside of the tube and the fuel flows around the exterior. The Table – 3 shows typical materials and
fabrication processes for SOFC [22, 23]
The Table – 4 compares the two configurations in terms of the achievable power density, requirement of the high temperature seals, the
manufacturing cost and the limitations. The tubular SOFCs have also been operated at high pressures up to 15 atm. The operation at elevated
pressures yields higher cell power at any current density due to increased Nernst potential and reduced cathode overpotential. The voltage output is
directly proportional to the partial pressure of oxygen at the cathode and that increases with the pressure. The SOFCs can be successfully used as a
replacement for combustors in gas turbine power generation systems, with pressurised operation. Such hybrid, pressurised SOFC- gas turbine
power systems, in multi-megawatt size, are expected to reach efficiency up to 70 % and thus result in reduced fuel consumption and capital cost per
unit power output [24]. The concept of mass customisation, initiated by the Solid State Energy Conversion Alliance (SECA) of the United States
Department of Energy, has enabled to bring in sizeable cost reductions in planar design SOFCs [25]. The concept involves the development of 3-10
kW size core planar SOFC modules which can be mass produced and the combined to obtain power for different applications in stationary,
transportation and military sectors. The anode supported planar SOFC design use electrolyte at a very low thickness of 5-20 μm, which decreases
its ohmic overpotential and makes it suitable for low temperature operation. It is possible to obtain very high power densities in such cells, as
required by the mass customisation concept.
5.2/ Power generation:

The individual SOFCs are arranged in stacks, for the purpose of power generation. The cells need to be connected together and a mechanism for the
collection of electrical current need to be provided. In a typical case, the tubular cells are arranged in rectangular arrays called bundles. The
interconnect connects the cathode of one cell to the anode of the other, while protecting it from the reducing atmosphere of the anode. The
individual cells in the bundle are connected in both series as well as parallel arrangements. These bundles or the modular groups of the individual
cells are used to construct a stack. The stacks have the necessary mechanical arrangements and electrical connections to support, separate, insulate
and service the bundles of individual cells. The Siemens Westinghouse fabricated a 100 kW power generation system, using this scheme. The

SOFC stack in the system consisted of 1152 cells, each of 2.2 cm diameter and 150 cm active cell length, arranged in 12 bundle-rows. Each row
comprised of four cell bundles and each bundle contained 24 cells (12x4x24 = 1152). The system was successfully operated for 2 years in the
Netherlands on desulphurised natural gas without any significant performance degradation [24]. The fuel cell power generating unit consists of a
number of stacks of a particular size and output. In a modular construction power plant, groups of stacks are held in containment vessels. The
output, size and the shape of the vessels must be such as to give maximum reliability and maintainability to the power station. Another advantage of
the containment vessel is that if the SOFCs are to operate at elevated pressure, the vessel can be pressurised, thereby reducing the mechanical and
thermal loading on the fuel cell components [3]. The APU is used in the transport and military applications. As mentioned in Table – 4, the tubular
SOFC is more useful for stationary power generation due to lower power densities, whereas the planar design finds greater application in APU due
to high power densities. The APU requires fast heat up and ability to be thermally cycled.
6/ Materials:
Among the key features of SOFC are the solid-state materials of construction and high temperature (800-1000 0 C) operation. The SOFC can be
fabricated in thin layers and configured in different shapes, as all components are in solid state. This feature permits compact, lightweight cell
designs and additional performance improvement. The high operating temperature makes it suitable for internal reforming or direct oxidation of
hydrocarbon fuels as well as for integration with gas/steam turbines to form highly efficient, hybrid power generation systems, as discussed earlier.
The materials for different cell components are selected based on the following criteria:
1. Suitable electronic and/or ionic conducting properties required to perform intended cell functions
2. Adequate chemical and structural stability at high temperatures during cell operation as well as during cell fabrication.
3. Minimal reactivity and inter-diffusion among the cell components.
4. Matching thermal expansion among different cell components
5. Ability to be formed into films with desired microstructure and good adherence to each other
In the past few years, significant developments have taken place in the area of materials science and technology for SOFC. These developments
include, (i) cathodes with improved microstructure to reduce the overpotential losses and high electronic conductivity, (ii) anodes for direct
oxidation of hydrocarbon fuels, (iii) electrolytes for operation at reduced temperature, (iv) interconnect or bipolar plate (in planar design) for high
temperature operation and (v) fabrication and processing techniques to make thin film components with required microstructure [10].
The SOFCs commonly operate at temperatures around 1000 0 C. These temperatures lead to materials constraints, high cost of manufacture and
problems of long term stability. Lowering the operating temperature makes the fabrication and operation of SOFC more cost effective. On the other
hand, decreasing fuel cell operating temperature limits the performance of the electrodes, affecting the cell power generation capacity. The cathode
polarization resistance rapidly increases with the reduction in operating temperature. The La0.9Sr 0.1MnO 3 cathode, for instance, exhibits an area
based polarisation resistance of less than 1.0 ohm.cm 2 at 1000 0 C which increases to above 2000 ohm.cm 2 at 500 0 C. [26]. The rate of internal
reforming has also been found low at reduced temperatures.
In the proceeding Sections, a brief review will be taken of the current developments in the materials for the SOFC components. The details of the
fabrication and processing have been kept out of the purview of this paper.
6.1/ Cathode materials:

The cathode must meet all the general requirements and in addition it must possess high electronic conductivity (> 100 ohm -1 .cm -1 ), small ionic
conductivity (0.1 ohm -1 .cm -1 ) and sufficient porosity to facilitate transport of molecular oxygen from the gas phase to the electrode-electrolyte
interface. It must also possess high catalytic activity towards oxygen molecule dissociation and oxygen reduction. In the tubular design, the cathode
contributes over 90 % of the cells weight and therefore provides structural support to the cell.
The ABO 3 oxide system of perovskite structure satisfies most of these requirements; where A is a rare earth element (mostly La in SOFC cathode)
and B is a transition metal (Fe, Ni, Co, Mn). The most commonly used cathode material is lanthanum manganite, LaMnO 3 , which is a p-type
perovskite. The alkaline earth cations (Sr2+, Ca 2+) partially substitute the rare earth element, to enhance its conductivity. Such cathode material is
referred to as La1-x Sr x MnO 3 or LSM and behaves as a mixed (electronic + ionic) conductor. It has been found that the conductivity is highest at x
= 0.5. In general, the SOFC cathodes use a mixture of LSM and YSZ . The ionic conducting YSZ is added to LSM to extend the triple phase
boundary, where oxygen reaction takes place.
The LSM has adequate functionality at intermediate (about 700 0 C) temperatures. Recently various approaches have been reported to engineer
cathode microstructure to improve performance at reduced temperatures. Some of the approaches reported by Minh [10] are (a) catalysed YSZ
electrolyte interface with a small amount of dopant such as Mn and Ce, (b) use of highly dispersed (nanometer size) noble metal particles on LSM
surface, (c) structured electrolyte surface covered with a thin microporous LSM film.
The fabrication of LSM depends upon the cell design. In the tubular SOFC, for instance, the cell is constructed extruding the cathode tube and
building the rest of the cell around it. In a typical planar SOFC, cathode is designed as a bottom supporting layer, fabricated by tape casting using
nanoscale particles, followed by sintering.
6.2/ Anode materials:

The anode (fuel electrode) must meet most of the requirements as that of the cathode, like high electrical conductivity, compatibility of thermal
expansion and porosity. In addition, anode materials require high stability in reducing atmosphere (CO, H 2 , CH 4 ) and the surroundings containing
trace levels of higher hydrocarbons, particulate matter and sulphur compounds. The transition metals are the best because of their high catalytic
activity.
The most commonly used anode for hydrogen oxidation is porous cermet structure consisting of Ni metal powder and YSZ particles. The YSZ
ceramic phase mainly has mechanical function, namely supporting the Ni particles, preventing them from sintering together and closing the pores,
giving electrode a thermal expansion coefficient close to that of YSZ electrolyte. The microstructure of cermets, i.e. particle size and distribution of
both the phases, optimum surface area, connectivity of Ni particles, porosity and the triple phase contact between gas, electrode and electrolyte, play
an important role in determining the performance and the long-term stability of anode in the fuel cell operating environment. The gas phase in
pores accounts for about 50% of the volume. Thus the Ni-YSZ structure has a large internal pore surface area. This makes it possible to maintain
large external current densities on the one hand, while keeping the internal (local) current densities and the resultant overpotentials low, on the other.
The slurry of Ni is applied over the cell and then YSZ is deposited by electrochemical vapor deposition. Alternatively, Ni-YSZ slurry is applied and
sintered. More recently, NiO-YSZ slurry has been used wherein NiO gets reduced to particulate Ni in the firing process. According to the recent
research finding, using freeze drying approach, it is possible to develop excellent porous structure [27].
As discussed earlier (Section-4 ), the hydrocarbon fuel systems depend upon reforming- external or internal. When fuel is reformed by steam, the
high equilibrium conversions require high temperatures, for example the equilibrium conversion of methane at methane/steam ratio of 1.0 at 1 atm.
pressure is 37 % at 600 0 C, 68 % at 700 0 C, 87 % at 800 0 C [28]. Even if the reformation reaction is carried out externally, the operating
temperature at the anode will have to be maintained at higher levels to prevent the methanation (Reaction-31 in the reverse direction) as the nickel
is also one among the best methanation catalysts [29].
The nickel and most other reforming metals are also excellent catalysts for C-C bond formation and therefore tend to catalyse the formation of
carbon deposits. When the internal reforming of fuel is carried out in SOFC, the problem of carbon deposition is encountered at the anode
(Reaction-26), especially when the reforming factor ‘m’ (steam/fuel ratio) is below the thermodynamic minimum, as indicated by the carbonisation
boundary. Therefore more steam is added to fuel only to keep ‘m’ above the carbonisation threshold.
The direct oxidation of methane and other hydrocarbons, without the addition of steam or oxygen, has been achieved by number of groups [19]. It is
seen that the C-C bond formation is not thermodynamically favored in case of dry methane, between 500-700 0 C, using conventional nickel based
anodes. However, this thermodynamic window of stability is different for different hydrocarbons and for some it does not exist. Some workers
successfully approached the problem of carbon formation by using conducting ceramic oxides as anodes, since they do not favor the formation of C-
C bond in the same way as the nickel based anodes do. Some of the ceramic oxides which have been tried are ceria and bismuth oxides,
La0.8Ca 0.2CrO 3 , Sm-doped ceria. However the power densities with this type of anodes are always low due to their limited electronic conductivity
in comparison to metals.
The nickel has good tolerance towards small levels of sulphur in the fuel, however degradation is observed when it was exposed to gaseous sulphur
compounds during the fuel cell operation [30].Therefore alternative anode materials are being investigated, which will prevent C-C bond formation,
offer higher microstructural stability and higher tolerance to impurities, such as sulphur in gas phase.
Park et.al. [31] report that that the problem of carbon deposition can be effectively tackled by replacing Ni-YSZ anode by Cu-Ceria anode. The
copper is an excellent electronic conductor but a poor catalyst for C-C bond formation, therefore carbon formation is avoided by the Cu-cermets.
The ceria has high activity towards hydrocarbon oxidation and high ionic conductivity. The tubular SOFC used in the experiment had 12.5 mm
diameter, cathode containing LSM and YSZ mixed in 1:1 proportion , 60 μm thick YSZ electrolyte and anode made from 40 % Cu, 20 % CeO2
(m/m) held in place by YSZ matrix formed from zircon fibres. The authors recommend the use of thin film electrolytes to obtain higher power
densities at low operating temperatures. Minh [10] reports that using the new anode material, direct oxidation of methane, ethane, butane, decane,
butene, toluene and synthetic diesel is possible, without carbon formation and peak power densities above 200 mW/cm2 have been achieved above
800 0 C. The stability of Cu to sintering after long time exposure to water vapor and CO 2 , needs to be further investigated.
6.3/ Electrolyte materials:

At present SOFCs mostly use yttria stabilised zirconia (YSZ) as electrolyte material. The conventional design SOFCs typically employ electrolytes
thicker than 50 μm and operate at temperatures of about 1000 0 C to minimise the electrolyte ohmic losses. The ionic conductivity of YSZ at 10
mole percent yttria is the maximum at 0.1 ohm -1 cm-1 , at 1000 0 C and the electronic transference number is low (<10-3 ). It has a stable cubic
structure at SOFC operating temperature and therefore shows relatively small decrease in ionic conductivity with time. The electrolytic domain
extends over several orders of magnitude of oxygen partial pressure (typically 1-10-20 atm), with a significant influence of temperature. The
activation energy for ionic conduction is also the least (~ 0.8 eV) near this composition. The thermal expansion coefficient (TEC) is about 10x10 -6 /
0 C; the materials for other cell components are chosen to have TEC near this value. In order to get the optimum performance, the YSZ electrolyte
must be free of porosity, so as not to allow gases to penetrate from one side of the electrolyte to the other and it should be uniformly thin to
minimise ohmic loss.

The high temperature operation of SOFC results in several materials related problems mentioned as follows [32]
1. Development of poor conducting phases due to interfacial diffusion. The lanthanum and strontium, for instance, from cathode, diffuse into
YSZ electrolyte forming poor conducting SrZrO 3 and La2 Zr 2 O 7 at the cathode side, especially when (La, Sr)CoO 3 cathode is employed.
2. Mechanical stresses due to differential thermal expansion of cell components, destroying good surface contact.
3. Corrosion of compnenets
4. High cost of materials that withstand high temperatures on long term.
Thus decreasing operating temperature of SOFC is important both from technical as well as commercial angles. The need is felt to develop oxide
ion electrolytes with high ionic conductivity at low temperatures; two promising cases are discussed below.
6.3.1/ Doped Ceria:

The pure ceria (CeO 2 ) has a cubic fluorite structure and negligible ionic conductivity However it shows high oxygen ion conductivity and low
activation energy for conduction, when doped with aliovalent cations such as yttrium (Y), gadolinium (Gd) or samarium (Sm) by forming oxide
based mixed electrolytes such as yttria doped ceria or YDC (CeO 2 -Y 2 O 3 ) [33], gadolinia doped ceria or GDC (CeO 2 -Gd2 O 3 ) [34], samaria doped
ceria or SDC (CeO 2 -Sm 2 O 3 ). It has been reported that ceria based, fluorite type, gadolinium doped solid solutions exhibit highest oxide ion
conductivity when the amount of Gadolinium oxide is 20 mol percent. The doped ceria however tends to undergo reduction (Ce4+ Ce 3+) at the
low oxygen partial pressures (fuel side) with consequent introduction of electronic defects (electronic conductivity). This reduction tendency
increases with temperature. Therefore, for efficient operation, doped CeO2 is used at 500 0 C or at lower temperatures. Another approach is to coat
it with more stable ionic conducting compound such as YSZ, on the fuel side [10].
Zhu et.al. report results on innovative nano- and hybrid-conducting ceria based composite materials [35]. These composite, multi-phase, materials
were prepared by (a) mixing cationic doped ceria with salts like chlorides, fluorides, hydroxides or carbonates, (b) mixing ceria with other rare-
earth oxide different from ceria, like lanthanum oxide (La 2 O 3 ). The conventional doped ceria (YDC, SDC, GDC, etc.) is a single phase material
(solid solution) with strict restrictions on dopant kinds and dopant levels. Whereas, ceria based composites are two or multi-phase (heterogeneous)
materials. The amount mixed is larger than the normal doping levels, as it is not controlled by the solubility of the compound mixed. It has been
found that the significant increase in the ionic conductivity and diffusivity is achieved due to the interfacial conducting path between the two phases.
The high defect concentration existing in the nano-structured host oxide phase can provide a large number of active sites for ion conduction as well
as that for gas-solid catalysis. The authors further report that the ceria composites exhibit dual conduction, oxygen ions from ceria and protons
from salt . The phenomenon was actually seen during the experiments, when water formation was observed on both sides of the electrode. This duel
conduction enhances the overall material conductivity and may also promote the electrode reaction and the kinetics at TPB, resulting in high current
outputs. The conductivity in the region of 0.01 to 1.0 ahm -1 .cm -1 was obtained between 300 to 700 0 C, using these materials. The cell could
function at temperatures as low as 200 0 C. The two-cell stack studied by the authors showed expected performance for several months. The new
findings will promote further research in the development of low temperature SOFC.
6.3.2/ Lanthanum gallate:

Recently a new family of perovskites (ABO3 structure), based on LaGaO 3 , have shown potential for the use as electrolyte in SOFC [36]. In these
materials, lanthanum can be partially replaced by Sr, Co or Ba or some other rare earth element such as Nd or Sm , at A-site. Whereas gallium at B-
site can be partially substituted by Mg, In, Al or Zn. It has been shown that for Sr substitution of at least 10-20 % at A-site and Mg substitution
between 10-20 % at B-site, the materials have relatively high ionic conductivity in both oxidising and reducing atmospheres, over wide range of
oxygen partial pressure and TEC comparable with the other fuel cell components. The conductivity of La0.9Sr 0.1Ga 0.8Mg 0.2O 2.85 (LSGM) is about
four times that of YSZ at 800 0 C, as an example. The conductivity of this composition can be further enhanced by doping the material with a small
amount of Co or Fe. The SOFC based on LaGaO 3 has been fabricated and tested using various cathode and anode materials. However the new
electrolyte is unstable in fuel (reducing) environment [30]. The depletion of Ga takes place under reducing atmospheres. The addition of Sr at A-
site accelerates the depletion further. Thangadurai and Weppner [32] report that the instability of LSGM structure, under reducing atmosphere, can
be effectively dealt by applying an interlayer of CeO2 doped with 40 mol percent La2 O 3 between anode and the LSGM based electrolyte. However
La diffusion at the cathode/electrolyte interface is still a potential problem, which needs further investigation. The pervoskites based on lanthanum
gallate are very sensitive to small change on stoichiometry and lead to formation of impurity phases like SrGaO 3 , La4 SrO7 , LaSrGaO4 ,
LaSrGa 3 O 7 . It is essential to control Sr/Mg ratio in order to obtain single phase materials.
At lower operating temperatures (700-800 0 C), it is possible to use very thin film electrolyte (up to 10 μm), to reduce its ohmic resistance and
increase ionic conductivity. However, the denseness of film need to be maintained, to avoid short-circuiting of gases. In general, the oxygen ion
conductivity increases in the following order YSZ < doped ceria < LSGM [30].
In SOFC, a solid oxide electrolyte is sandwiched between the electrodes. The interfacial resistances exist on account of the materials characteristics
as well as the discontinuities remaining during the fabrication processes. The research is being carried out to develop SOFC with only one material
with homogeneous composition, to effectively deal with the problem of interfacial resistances. Such a material becomes excess electron conducting

at the anode and hole conducting at the cathode, but remains predominantly ion conducting at the intermediate activities of the elctroactive
components. The solid oxides with perovskite ABO 3 structure are considered a promising material for the purpose, in view of its large flexibility
for different substitutions both at A and B sites [32,37]
6.4/ Interconnect materials:

In power generation, the cells need to be connected together and a mechanism for collection of electrons giving rise to electrical current need to be
provided; hence the requirement of interconnects. The interconnect connects the anode of one SOFC to the cathode of the other. Thus it will be
exposed simultaneously to the reducing environment at the anode and the oxidising environment at the cathode. The high operating temperature of
he cell combined with the severe environment means that the interconnect must satisfy the most stringent materials requirements of all the cell
components, given as follows [38].
1. High electronic conductivity (> 1.0 ohm -1 cm-1 ) with small variation within the oxygen partial pressure range form air to fuel gas
2. Chemical and phase stability in oxidising and reducing conditions and during fabrication
3. Matching TEC with cell components
4. Physical and electrochemical gas tightness
The interconnect material of choice for SOFC, using YSZ electrolyte and operating at 1000 0 C, is LaCrO 3 doped at A-site with rare earth element
(Ca, Mg, Sr etc.) to improve its conductivity. Ca-doped yttrium chromite (YCrO 3 ) is also being considered as it has better thermal expansion
compatibility, especially in reducing atmosphere. The interconnect is applied to the anode by plasma spraying and the entire cell is co-fired.
The thermal conductivity of the conventional interconnect materials is extremely low
(< 5 Wm -1 k -1 ), which imposes severe thermal gradients in the fuel cell stack. Moreover the materials expand differentially on heating in oxidising
or reducing environments, leading to stresses and warpage of interconnect bipolar plates (planar design) . The materials are brittle and the costs
associated with fabrication, forming and machining are relatively high [30].
The metals or alloys are preferred as interconnects due to their relatively low cost, easy machinability and high thermal as well as electrical
conductivity. However most metals have TEC much higher than other cell components and they also corrode rapidly at SOFC operating
temperature. Thus only high temperature oxidation resistant alloys with built-in protection mechanism are suitable. At operating temperature of
900-1000 0 C nickel base alloys like Inconel-600, below 800 0 C ferritic steels and below 700 0 C it becomes possible to use stainless steel, which is
comparatively inexpensive and readily available.
6.5/ Seal materials [30]:

The tubular SOFC does not require a seal. However seals are an integral part of planar design, as they are required to stop mixing of air and fuel.
The seals are exposed to oxidising and reducing environment. The seals must remain leak-proof and insulating over the lifetime of the stack (>
50,000 h). They must withstand thermal cycles and pressures above atmospheric. The commonly used materials are cement, glass or glass-ceramic
composites.
7/ Future of SOFC:
The SOFC is the means of pollution free and sustainable power generation of the future. However improvements in certain areas, briefed as follows,
need to take place before SOFC finds a wide application on commercial scale
1. Reducing capital cost-to-output ratio
2. Low cost, large volume production techniques
3. Broadening the application range in stationary, transportation and military sectors
4. Performance improvement in terms of electrolyte resistivity and electrode polarisation
5. Low temperature operation.
6. Stability of materials
7. Internal reforming and direct oxidation of fuels.
8. Capacity to handle multiple fuels.
9. Fast start-up.
10. Thin film and cost effective fabrication processes.
11. Brittleness of ceramic components.
8/ Conclusions:
The following broad conclusions can be drawn on the basis of foregoing discussion.
8.1/ The fuel cell is an electrochemical device that converts the free energy of an electrochemical reaction directly into electrical energy (and heat).
The free energy is provided by the electrochemical oxidation of fuels which may be hydrogen, carbon monoxide or hydrocarbons. The operation is
a steady flow process and continues as long as the continuous supply of fuel and the oxidant is assured. As the free energy of he chemical reaction is

directly converted to the electrical energy, the operation of fuel cell is not subject to the second law of thermodynamics. The name of fuel cell
generally refers to the type of electrolyte used in the cell.
8.2/ In SOFC, the solid oxide electrolyte is sandwiched between two porous electrodes. The oxygen, supplied at the cathode, gets reduced to oxygen
ions and diffuses through the electrolyte to the anode-electrolyte interface. The gaseous fuel, supplied at the anode, also diffuses to the anode-
electrolyte interface and catalytically reacts with oxygen ions, giving off water, carbon monoxide, heat and electrons. The gaseous products are
transported back to the fuel channel through the porous anode and the electrons flow back to the cathode through the external circuit.
8.3/ The SOFC has advantages like high efficiency with low performance degradation, multi-fuel capacity, multiple applications, moderate power
density, reasonable tolerance to gas phase poisons , high quality exhaust heat useful for cogeneration of power. It also as certain drawbacks like
high electrolyte resistivity an electrode polarisation, high temperature of operation, brittleness of ceramic components and high capital cost-to-
output ratio
8.4/ The thermodynamic maximum or the open circuit potential of the oxidation reaction occurring in the fuel cell is given by the Nernst Equation.
However the operating potential is less than the open circuit potential of the cell on account of the irreversible losses called overpotentials . These
losses are due to the resistance to the transport of gases through porous electrodes (concentration overpotential), activation energy barriers to the
electrochemical reactions that occur at the electrode-electrolyte interface (activation overpotential), resistance to the transfer of ions through the
electrolyte (ohmic overpotential), leakage electronic current through the electrolyte (leakage overpotential) and due to the contact resistance at the
materials boundaries (interface overpotential). Generally the cathode contributes maximum to the cell potential losses. The high working
temperature of SOFC (about 1000 0 C) reduces the open circuit potential but reduces the irreversible losses also. The cell operation at elevated
pressure yields increased Nernst potential and reduced cathode overpotential.
8.5/ The four factors commonly used to evaluate SOFC performance are , (i) fuel utilisation factor, (ii) air ratio, (iii) power output and (iv) fuel
efficiency.
8.6/ The two ways to utilise the hydrocarbon fuel in SOFC are the steam reforming (internal or external), and the direct oxidation. The reforming
process converts hydrocarbon fuels into a mixture of lower hydrocarbons, hydrogen, carbon monoxide and carbon dioxide. The chemical potential
of the fuel is partially lost in this process. The steam-to-fuel molar ratio is known as the steam reforming factor , ‘m’. In comparison to the
external, the internal steam reforming of fuel is considered more energy efficient and saves the capital as well as the operating costs. However it
suffers from the drawback of carbon formation on the Ni-YSZ based anodes, leading to the deterioration in the performance and the lifetime of the
anode material. However above a certain limiting value of ‘m’, the carbon formation is thermodynamically impossible. Therefore excess steam is
added to the fuel to maintain ‘m’ above that limiting value, which lowers the electrical efficiency on account of the fuel dilution. The reforming
factor at any given temperature increases with the carbon content of the fuel. The optimum temperature and ‘m’ for the SOFC operation correspond
to their values at the carbonisation boundary, referring to the limiting value of ‘m’. There is a search for the advanced catalysts which will allow
internal steam reforming of hydrocarbons at low ‘m’.
8.7/ The kinetic rate of endothermic steam reforming reaction on the Ni-YSZ anode-catalyst is usually high and, as a result, the reaction gets
completed over a short distance in the fuel channel. This leads to the excessively sharp temperature gradients, on account of the endothermic effect.
The problem can be tackled by (i) partial pre-reforming of fuels, (ii) reduction in the reforming rate by modifying the anode catalytic activity and
(iii) oxidative reforming. The oxidative reforming is preferred for the portable power units using SOFC.
8.8/ Thermodynamically it can be seen that the Nernst potential gets reduced with the fuel utilisation. One way to tackle the problem is to operate
the cell with high recycle ratio combined with external removal of reaction products, maintaining the conversion per cycle at low level. However
increasing the systems efficiency by this method entails considerable cost in the capital and the complexity. The alternative simpler approach is the
multi-stage oxidation of fuel. In this approach, the partially oxidised fuel from one fuel cell stack is fed to the next stack.
8.9/ The direct oxidation of fuel in the fuel cell may be described as the oxidation of hydrocarbons , to H 2 O and CO 2 , in the absence of steam or
oxygen supplied in the fuel stream. Thermodynamically, any fuel can be directly oxidised in the SOFC, as the species that migrate through the
electrolyte are oxygen ions. However , with dry hydrocarbons at high temperature, there is also a thermodynamic driving force towards the
formation of carbon, at the anode. In order to keep the carbon formation at the minimum, the thickness of anode (Ni-YSZ) and electrolyte (YSZ),
anode microstructure and the operating temperature of the cell need optimisation.
8.10/ The research conducted in the area shows that besides hydrogen, natural gas (methane), hydrocarbons (butane, gasoline, etc.), methanol,
ethanol, biogas can be used as fuels in the SOFC. Based on the overall considerations, the available fuel options could be arranged in the following
order of preference: methane> ethanol > biogas > methanol > gasoline > others. The ethanol and the biogas could be considered as the promising
fuels for the future, as they can be produced from the biomass.

8.11/ The two design configuration of SOFC are the planar and the tubular designs. Whereas, in the planar design, the cell components are
configured in thin flat plates, in tubular design, they are arranged in a hollow cylindrical shape. The SOFCs are suitable for stationary, large size,
hybrid (in combination with gas or steam turbine) power generation plants due to their operation at elevated temperature and pressure. Such power
plants can reach efficiency up to 70 %. The SOFC finds application in the transportation and the military sectors also.
8.12/ The individual cells are arranged in stacks for the purpose of power generation. In the stacks, the cells need to be connected together and a
mechanism for the collection of electrical current needs to be provided. The fuel cell power generating unit consists of number of such stacks of
particular size and output and the groups of stacks may be held in containment vessels.
8.13/ The SOFC components can be fabricated in thin layers and configured in different shapes, as they are all in the solid state. The selection of
materials for different cell components is based on certain criteria like, (i) electronic and ionic conduction properties, (ii) chemical and structural
stability at high temperatures, (iii) minimal reactivity and inter-diffusion among the cell components, (iv) matching thermal expansion, (v) ability to
be formed in the desired microstructure and good adherence to each other.
8.14/ The high temperature of operation of SOFC (around 1000 0 C) leads to materials constraints, high cost of manufacture and the problems of
long-term stability. Lowering the temperature makes SOFC fabrication and operation more cost effective; the limitations on the polarisation
resistance, internal reforming and the power generating capacity due to lower operating temperature, notwithstanding
8.15/ The material used for cathode must possess high electronic conductivity (> 100 ohm -1 cm-1 ), small ionic conductivity (~ 0.1 ohm -1 cm-1 ),
adequate porosity to transport molecular oxygen from the gas phase to the electrode-electrolyte interface and high catalytic activity towards oxygen
dissociation and reduction. The most commonly used cathode material for SOFC is strontium doped lanthanum manganite (LSM), suitably mixed
with YSZ
8.16/ The anode materials must satisfy all the requirements as that of the cathode materials. In addition, the anode requires high stability in
surroundings containing high concentration of reducing agents, trace levels of hydrocarbons, particulate matter and sulphur compounds. The Ni-
YSZ cermet is the commonly used anode. The macrostructure, particle size and surface area, connectivity of Ni particles, porosity and the three
phase boundary play an important role in determining the performance and the long-term stability of anode in the fuel cell operating environment.
The new anode material, Cu-ceria cermet , effectively solves the problem of carbon formation at the anode, during the direct oxidation of
hydrocarbons.
8.17/ The YSZ containing around 10 mole percent yttria is the most commonly used electrolyte material in the SOFC. The two new electrolyte
materials, which showed promising results at low temperature operation are (i) ceria based electrolytes, such as ceria doped with yttrium,
gadolinium or samarium; multiphase materials prepared from cationic doped ceria mixed with salts or mixing ceria with other rare earth oxide
different from ceria, like lanthanum oxide and (ii)lanthanum gallate. At lower operating temperature, the ohmic resistance of electrolytes can be
reduced by reducing its thickness. In general, ionic conductivity increases in the following order: YSZ < doped ceria < LSGM
8.18/ The interconnect needs to satisfy the most stringent requirements of all the SOFC components, as it is exposed to both oxidising as well as
reducing surroundings, simultaneously, at high temperature. The important requirements are, high electronic conductivity in the oxygen partial
pressure range obtained at anode and cathode sides, chemical and phase stability, matching TEC and gas tightness. The commonly used
interconnect materials are lanthanum or yttrium chromite, doped with Co, Mg, or Sr. The reduction in the operating temperature of SOFC (below
700 0 C) enables the use of comparatively inexpensive and readily available stainless steel as the interconnecting material.
8.19/ In order to eliminate the interfacial resistances and other related problems like formation of non-conducting compounds, attempts are being
made to develop SOFC with only one material with homogeneous composition, which will become excess electron conducting (anode), hole
conducting (cathode) and ion conducting (electrolyte), under the appropriate conditions of surroundings, temperature and pressure.
8.20/ The SOFC technology will have to overcome the challenges posed by the problems in the areas of operating parameters, materials and the
manufacturing processes and costs, before it is accepted as the alternate means of power generation, on the commercial scale.
Nomenclature:
Symbols:
a : activity of the reactants or products

ac : activity of carbon
A an , A ct : pre-exponential factor in the rate equation for reactions
at anode ad cathode, A.L -2
C : constant, ohm -1 .K.L
[CH 4 ] : concentration of methane, mol.mol-1 , dimensionless
ΔGP,T : Gibbs free energy, Joule, ML 2 T-2
ΔG(U) : Gibbs free energy at fuel utilisation U, Joule, ML 2 T-2
W E : electrical work, Joule, ML 2 T-2
D s : diffusion factor, C/s.cm 2 .atm
D g : free gas diffusivity, L2 T-1
E : open circuit potential of reversible cell, Volt
Ecell : cell operating potential, Volt
Ecell-L : cell potential at any point in space in the cell, Volt
EL : open circuit cell potential at any point in space in the cell, Volt
Ec-an, Ec-ct : concentration overpotentials at anode and cathode respectively, Volt
Ev-an , Ev-ct : activation overpotentials at anode and cathode respectively, Volt
Eo : ohmic oveptential, Volt
El : leakage overpotential, Volt
El-op : leakage overpotential at open circuit, Volt
En : interface overpotential, Volt
m : exponent
N : number of unit charges transferred in the reaction, dimensionless
F : Faraday constant, 96487 C/mol or 96487 J/V.mol
ΔH : enthalpy change in the process, Joule, ML 2 T-2
i : average current density, A/cm2
iL : local current density, A/cm2
imax : maximum current density, A/cm2
I : current, A
I tsh : threshold current, A
k t : tortuosity factor, dimensionless
K c : equilibrium constant for the Boudouard reaction
K b : rate constant for carbon formation, mol.T -1
m : fuel reforming factor or steam/fuel molar ratio, dimenionless
n i : number of moles of ith species produced in the reforming reaction
p : partial pressure of the gaseous constituents, atm, MLT -2
p r : power ratio, P SOFC / P th , dimensionless
P SOFC : actual power output of SOFC, W, ML 2 T-3
P th : maximum (thermodynamic) power output of SOFC, W, ML 2 T-3
R : universal gas constant, 8.314 J/mol.K or 82.06 cm3 .atm/gmol.K
Ran , Rct : activation resistance at anode and cathode, ohm.L 2
RL : local area specific resistance, ohm.L 2
Ro : ohmic resistance of electrolyte, Ohm
S tpb : area of three phase boundary per unit anode volume, L2 .L -3
T : temperature, K
Tf , Ta : temperature in fuel and air channel, K
u : fuel utilisation factor, dimensionless
U : fuel utilisation, mole/mole (dimensionless)
U an , U ct : activation energy for anode and cathode reaction, J/mol

U in : activation energy for ionic transport, J/mol

δ e : electrode thickness, L
δ el : electrolyte thickness, L
ε : void fraction, dimensionless
: air ratio
ηth : thermodynamic efficiency of a fuel cell, dimensionless
f : actual fuel efficiency of a fuel cell, dimensionless
-1 -1
in : ionic conductivity of electrolyte, Ohm .L
Superscripts:
0 : standard state
Subscripts:
a : air channel
f : fuel channel
in : ionic
P, T : pressure, temperature
E : electrical
e : electrode
el : electrolyte
th : thermodynamic
c : concentration
an, ct : anode, cathode
v : activation (overpotential)
o : ohmic (overpotential)
l : leakage (overpotential), local
n : interface (overpotential)
s : diffusing species
SOFC : solid oxide fuel cell
tsh threshold
tpb : three phase boundary
x, y, z : number of atoms in the molecular formula
References:
[1] Appleby A.J., “ The electrochemical engine for vehicles “ Scientific American, July 1999, pp 58-63. [2] Winterbone D.E., “ Engines versus
electrons: the future of power production”, Proc. Instn. Mech. Engrs., J. Power & Engineering, Part A, Vol 214, No. A-1, 2000, pp 1-11.
[3] Fry M.R., Watson H., Hatchman .J.C., “ Design of a prototype fuel cell / composite cycle power station “, Proc. Instn. Mech. Engrs., J. Power &
Engineering, Part A, Vol 211, No. A-2, 1997, pp 171-180.
[4] Acres G.J.K., “ Recent advances in fuel cell technology and its applications “ J. Power Sources, Vol. 100, 2001, pp 60-66
[5] Neophytides S.G., “ The reverse flow operation of a cross flow solid oxide fuel cell monolith ”, Chem.Eng.Sci., Vol. 54, 1999, pp 4603-13
[6] Minh N.Q., Takahashi T., “ Science and technology of ceramic fuel cells ”, Elsevier, Amsterdam, 1995
[7] Zhu H., Kee R.J., “ A general mathematical model for analyzing the performance of fuel cell membrane-electrode assemblies ”, J. Power
Sources, Vol. 117, 2003, pp 61-74
[8] Chan S.H., Ho H.K., Tian Y., “ Multi-level modeling of SOFC-gas turbine hybrid system ”, Int. J. Hydrogen Energy, Vol. 28, 2003, 889-900
[9] Aguiar P., Chadwick D., Kershenbaum L., “Modelling of an indirect internal reforming solid oxide fuel cell ”, Chem. Eng. Sci., Vol. 57, 2002,
pp 1665-77
[10] Minh N.Q., “ Recent developments in material science and technology for solid oxide fuel cells ”, Proc. Symp. High Temperature Materials,
Philadelphia, Ed. S.C.Singhal, Electrochemical Society, Vol. 2002-5, 13-15 May 2002, pp 54-59
[11] Gardner F.J., “ Thermodynamic processes in solid oxide and other fuel cells”, Proc. Inst. Mech. Engrs. Part A, J. Power & Energy, Vol. 211,
No. A-5, 1997, PP 367-80
[12] Ahmed K., Foger K., “ Kinetics of internal steam reforming of methane on Ni/YSZ based anodes for solid oxide fuel cells ”, Catalysis Today,
Vol. 63, 2000, pp 479-87
[13] Douvertzides S.L., Coutelieris F.A., Demin A.K., Tsiakaras P.E., “ Fuel options for solid oxide fuel cells: a thermodynamic analysis ”,

A.I.Ch.E.J., Vol. 49, No. 1, Jan 2003, pp 248-257

[14] Sammes N.M., Boersma R.J., Tompsett G.A., “ Micro-SOFC system using butane fuel ”, Solid State Ionics, Vol. 135, No 1-4, 2000, pp 487-
491
[15] Hiei Y., Ishihara T., Takita Y., “ Partial oxidation of methane for internally reformed solid oxide fuel cell”, Solid State Ionics, Vol.86-88,
1996, pp 1267-72
[16] Elangovan S., Hartvigsen J., Khandkar A., “ Efficiency enhancement in fuel cells: multistage oxidation concept ”, J. Electrochem. Soc.,
Vol.144, No 10, October 1997, pp 3337-41
[17] Murray P., Tsai T., Barnett S.A., “ A direct methane fuel cell with a ceria based anode ”, Nature, Vol. 400, 1999, pp 649-651
[18] Steele B.C.H., Kelly I., Middleton P.H., Rudkin R., “ Oxidation of methane in solid-state electrochemical reactors”, Solid State Ionics, Vol.
28, 1988, pp 1547-52
[19] Gorte R.J., “ Anode development for direct oxidation of hydrocarbons”, Symp. High Temperature Materials, Ed, S.C. Singhal, Philadelphia,
Elctrochem. Soc. Proc., Vol. 2002-5,13-15 May 2002, pp60-71
[20] Abudula A., Ihara M., Komiyama H., Yamada K., “ Oxidation mechanism and effective anode thickness of SOFC for dry methane fuel ”,
Solid State Ionics, Vol. 86-88, 1996, pp 1203-1209
[21] Herle J.V., Marechal F., Leuenberger S., Favrat D., “ Enery balance model of a SOFC cogenerator operated with biogas ”, J. Power Sources,
Vol. 118, 2003, pp 375-383
[22] Singhal S.C. “ Status of solid oxide fuel cell technology ”, Proc. 17th Riso Int, Symp. Mat. Sci. High Temperature Electrochemistry: Ceramics
and Metals. Ed. F.W.Poulsen, N. Bonanos, S. Linderoth, M. Mogensen and B. Zachau-Christiansen, Riso National Laboratory, Roskilde, Denmark,
1996, pp 123-138.
[23] Singh Prabhakar, “ Solid oxide fuel cell (SOFC) power generation systems: technology status and commercialization challenges ”, Pacific
Northwest National Laboratory, United States Department of Energy, presented at Ohio Fuel Cell Coalition Meeting, Oct.3, 2002
[24] Singhal S.C., “ Solid oxide fuel cells for stationary, mobile and military applications ”, Solid State Ionics, Vol. 152-153, 2002, pp 405-410
[25] Surdoval W.A., Singhal S.C., Mc Vay G.L., Proc. 7 th Int. Symp. Solid Oxide Fuel Cells, Ed. Yokokawa N., Singhal S.C., PV 2001-16, The
Electrochemical Society, Pennington, NJ, 2001, p 53
[26] Doshi R., Richards V.L., Carter J.D., Wang X., Krumpelt M., “ Development of solid oxide fuel cells that operate at 500 0 C ”, J. Electrochem.
Soc., Vol. 146, No. 4, 1999, pp 1273-1278
[27] Moon J.W., Hwang M., Maeda K., “ Preparation of NiO-YSZ tubular support with radially aligned pore channels ”, Materials Letters, Vol. 57,
No. 8, Feb. 2003, pp 1428-1434
[28] Gorte R.J., Park S., Vohs J.M., Wang C., “ Anodes for direct oxidation of dry hydrocarbons in a solid oxide fuel cell ”, Adv. Materials, Vol.
12, No. 19, October 2, 2000, pp 1465-1469
[29] Groggins P.H., “ Unit processes in organic synthesis ”, Tata McGraw-Hill Publication Co. Ltd., New Delhi, 1996
[30] Badwal S.P.S., “ Stability of solid oxide fuel cell components ”, Solid State Ionics, Vol. 143, 2001, pp 39-46
[31] Park S., Vohs J.M., Gorte R.J., “ Direct oxidation of hydrocarbons in a solid-oxide fuel cell ”, Nature, Vol. 404, 16 March 2000, pp 265-266
[32] Thangadurai V., Weppner W., Solid oxide fuel cells: materials concept for singe element arrangements (SEAs)”, Proc. Symp. High
Temperature Materials, Ed. S.C.Singhal, Electrochemical Society. Vol. 2002-5, Philadelphia, USA, 13-15 May 2002, pp 106-115
[33] Tuller H.L., Nowick A.S., "Doped ceria as solid electrolyte", J. Electrochem. Soc. Vol.122,
1975, p. 255
[34] Kudo T., Obayashi H.,"Oxygen ion conduction of the fluorite type Ce (1-x)Ln(x) O(2-x/2) Ln(Lanthanide Element)”, J. Electrochem. Soc.
Vol.122, 1975, p. 142
[35] Zhu B., Yang X.T., Xu J., Zhu Z.G., Ji S.J., Sun M.T., Sun J. C., “ Innovative low temperature SOFCs and advanced materials ”, J. Power
Sources, Vol. 118, 2003, pp 47-53
[36] Ishihara T., Matsuda H., Takita Y., “ Effects of rare earth cations doped for La site on the oxide ion conductivity of LaGaO 3 -based perovskite
type oxide”, Solid State Ionics, Vol. 79, July 1995, pp 147-51
[37] Wappner W., “ Ceramics: towards the 21st century ”, Ed. Soga N., Kato A., The Ceramic Society of Japan, 1991, pp 19-23
[38] Hammou A., Guindet J., “ Solid oxide fuel cells ”, The CRC Handbook of Solid State Electrochemistry, Ed. Gillings P.J., Bouwmeester
H.J.M., CRC Press, NY 1997.
TABLE – 1
COMPARISON OF FUEL CELLS
Sl No Parameter AFC PAFC PEMFC MCFC SOFCa

1 Electrolyte KOH Phosphoric Sulphonic Li/K Doped semi-

acid acid polymer carbonate conductor
mixture
2 Operating 50-90 190-210 80-150 600-700 800-1000

temperature ( 0 C)
3 Fuel H2 H 2 , natural H 2 , natural H 2 , natural gas, CO, gasified

gas gas (CO<30 hydrocarbons
ppm)
4 Efficiency (%)
with
4.1 H2 80 55 60 55 55
4.2 Natural gas -- 40 35 50 50
4.3 Bottoming cycle -- -- -- 60-70 60-70
5 Pollution Very low Very low Very low Low Low
6 Noise ~ 60 db ~ 60 db ~ 60 db ~ 60-80 db ~ 60 db
7 Power density 750 1600 7000 1600 2500

w/m 2
8 Liquid Not Difficult to Difficult to Possible Possible

hydrocarbon fuel possible use use
9 Cell life (years) 1-2 5 3-5 3 5
10 Start-up time Fast Moderate Fast Moderate Slow
11 Internal Not Not Not possible possible

reforming possible possible possible
12 Combined cycle Not Not Not Possible Possible

operation possible possible possible
13 Applications Stationary Mobile units: Stationary Stationary &

power: 50- 2-10 kW, power: distributed
----- 200 kW, Stationary & 250 kW & 2 power: 1,
Large units: distributed MW 100, 220 kW
1,5,11 MW power up to
demonstrated 250 kW
a: SOFC tubular design

TABLE – 2
CORRELATIONS TO ESTIMATE OVERPOTENTIALS
IN SOFC USING HYDROGEN AS FUEL
Sl Overpotential Correlation Reference
No
1 Concentration [8]
overpotential
2 Activation Ev-an = Ran .i , Ev-ct = Rct .i [9]

overpotential
3 Ohmic [7]
overpotential
4 Leakage [7]
overpotential

TABLE – 3
TYPICAL MATERIALS AND FABRICATION PROCESSES FOR SOFC [Prabhakar Singh]
Sl SOFC Materials Thickness Fabrication Processes

No Component
1 Electrolyte Doped 5-40 μm a Electrochemical vapor

semiconductors, deposition, tape
YSZ, dense casting-sintering
2 Anode Ni-YSZ cermets, 25- 600 Slurry spray,

porous μm b electrochemical vapor
deposition, tape
casting-sintering
3 Cathode Doped 25- Extrusion or screen

lanthanum 2000 μm printing-sintering
perovskites like
Sr-doped
lanthanum
manganite
(LSM) or ferrite
(LSF), porous
4 Interconnects Doped chromites 30 – Plasma spraying

(LaCrO3 ), 130 μm
alloys, dense
5 Seals Insulating -- --
ceramics, dense
6 Manifolds Heat resistant -- Structural

alloys,
dense
a: for electrolyte supported planar design working at 1000 0 C = > 150 μm

b: upto 1500 μm, for anode/cathode supported planar designs working at 700-800 0 C

TABLE – 4
COMPARISON OF PLANAR AND TUBULAR DESIGNS OF SOFC
Sl Parameter Planar SOFC Tubular SOFC

No
1 Power density High (up to 2 w/cm2 ) due to Low (0.25-0.30 w/cm2 ) due
short current paths to long current paths
2 High temperature Required to isolate oxidant Seal-less stack design

seal from fuel possible
3 Manufacturing cost Low High
4 Limitations Difficulties in successful More suitable for stationary

development of high power generation due to low
temperature seals puts power density
limitations on the use for
stationary power generation


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SOFC - FUTURE SOURCE OF SUSTA...

SOFC - FUTURE SOURCE OF SUSTAINABLE POWER

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

f/ Moderate power density (w/m 2 )

The device also has the following drawbacks:

3/ Thermodynamic and electrochemical aspects:

3.1/ Open circuit potential of a reversible cell:

½ O 2 (g) + 2e - → O = --- ----- (2)

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

W E = ΔH - TΔS = -ΔG P,T = NFE -- -- (9)

3.2/ Thermodynamic efficiency:

η th = (thermodynamically feasible maximum energy generation) / (total input energy) -- (10)

3.3/ Nernst potential:

3.4/ Cell operating potential:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

Ecell = E - Ec-an - Ec-ct - Ev-an - Ev-ct - Eo - El – En -- -- (17)

Ecell-L = EL - iL. RL -- -- (18)

3.5/ Performance indicators:

----- --- (20)

----- --- (21)

----- --- (22)

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

----- --- (23)

4/ Fuels – utilisation and options:

----- --- (24)

CO + H 2 O H 2 + CO 2 --- --- (25)

----- --- (26)

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

CH 4 + ½ O 2 ⇄ CO + 2H2 (exothermic) - -- (28)

CO + ½O 2 ⇄ CO 2 (exothermic) -- --- (29)

CH 4 + H 2 O ⇄ CO + 3H2 (endothermic) -- -- (31)

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

4.1.2 / Direct oxidation of hydrocarbons:

CH 4 C + 2H2 --- -- (34)

CH 4 + 4O= CO 2 + 2H2 O + 8e - -- -- (35)

4.2 / Fuel options:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

---- --- (38)

5/ Cell design configurations and power generation:

5.2/ Power generation:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

6.1/ Cathode materials:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

6.3/ Electrolyte materials:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

6.3.1/ Doped Ceria:

6.3.2/ Lanthanum gallate:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

6.4/ Interconnect materials:

6.5/ Seal materials [30]:

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

U in : activation energy for ionic transport, J/mol

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

A.I.Ch.E.J., Vol. 49, No. 1, Jan 2003, pp 248-257

Sl No Parameter AFC PAFC PEMFC MCFC SOFCa

https://docs.google.com/View?docid=dfb2ks7_31ckwkpsqv&hl=en[5/21/2011 11:35:21 PM]

1 Electrolyte KOH Phosphoric Sulphonic Li/K Doped semi-

2 Operating 50-90 190-210 80-150 600-700 800-1000

3 Fuel H2 H 2 , natural H 2 , natural H 2 , natural gas, CO, gasified