136 SOLID OXIDE FUEL CELLS

Eng. Rawan Alhaddad

 Solid oxide fuel cells (SOFCs) have an electrolyte that is a solid, non-porous
metal oxide, usually Y2O3-stablilized ZrO2.

 The cell operates at 600-1000 oC where ionic conduction by oxygen ions

takes place. Typically, the anode is a Ni-ZrO2 cermet and the cathode is Sr-
doped LaMnO3.

 There is no liquid electrolyte with its attendant material corrosion or

electrolyte management problems. The high temperature of the SOFC,
however, places stringent requirements on its materials.

 The development of suitable low cost materials and the low-cost fabrication of
ceramic structures are presently the key technical challenges facing SOFCs.

 Solid oxide fuel cells (SOFC) allow conversion of a wide range of fuels,
including various hydrocarbon fuels. The relatively high operating temperature
allows for highly efficient conversion to power, internal reforming, and high
quality by-product heat for cogeneration or for use in a bottoming cycle.
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 The operating temperature of the SOFC is currently

between 600 and 1000∘C. The high operating
temperature provides both challenges and advantages.
 The challenges include stack hardware, sealing, and cell
interconnect issues. High temperature makes the materials
requirements, mechanical issues, reliability concerns, and
thermal expansion matching tasks more difficult.
 Advantages include fuel flexibility, high efficiency, and the
ability to employ cogeneration schemes using the high-
quality waste heat that is generated. The electrical
efficiency of the SOFC is about 50–60%; in combined
heat and power applications, efficiencies could reach
90%.
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 More recently, (planar) SOFC systems with high power densities

operating at lower temperatures (700 to 850 °C instead of 900 to
1000 °C as was previously the norm) have been developed.

 An intermediate-temperature (400–700∘C) SOFC design could remove

most of the disadvantages associated with high-temperature operation
while maintaining the most significant SOFC benefits.

 Such SOFCs could employ much cheaper sealing technologies and

robust, inexpensive metal (rather than ceramic) stack components. At
the same time, these SOFCs could still provide reasonably high
efficiency and fuel flexibility.

 However, there are still many fundamental problems that need to be

solved before the routine operation of lower temperature SOFCs can
be achieved.

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 SOFC Advantages
 Fuel flexibility
 Nonprecious metal catalyst
 High-quality waste heat for cogeneration applications
 Solid electrolyte
 Relatively high power density

 SOFC Disadvantages
 Significant high-temperature materials issues
 Sealing issues
 Relatively expensive components/fabrication

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 The cell is constructed with two porous electrodes that sandwich an electrolyte.
 Air flows along the cathode. When an oxygen molecule contacts the cathode/electrolyte
interface, it acquires electrons from the cathode. The oxygen ions diffuse into the
electrolyte material and migrate to the other side of the cell where they contact the anode.
 The oxygen ions encounter the fuel at the anode/electrolyte interface and react
catalytically, giving off water, carbon dioxide, heat, and electrons. The electrons transport
through the external circuit, providing electrical energy.
 Since water is formed at the anode side where hydrogen is supplied as the reactant, the
issue of mass transfer loss as a result of water flooding at the anode is relatively low and
less critical in SOFC due the higher diffusivity of hydrogen in water. A major
characteristic of SOFC is that the oxygen reduction kinetics in the cathode side is
relatively fast and results in a lower activation voltage loss, and hence does not require
any noble metals as catalyst.

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 Configurations Eng. Rawan Alhaddad

SOFCs are available in two basic geometrical designs:

(i) circular and tubular design and (ii) planar design.

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 Planar Design
 This is the most popular design, which includes integrated planar and sequential
cells. Planar SOFC systems have been receiving attention largely because of
ease of manufacturing and high performance compared to tubular SOFCs.

 The advantages of a planar design are the simplicity in manufacturing of the

stacked cell components leading to a highly compact structure with higher
power densities. However, a planar design requires sealing to avoid crossover
of reactant gases and has increased risk of cell fractures, particularly during
thermal cycling.

 Planar designs require high‐temperature gas‐tight seals between the

components in the SOFC stack. Sealing therefore remains one of the most
significant technical barriers to the commercialization of planar SOFCs. Also of
concern are the thermal stresses at the interfaces between the different cell
and stack materials that can cause mechanical degradation.

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 Tubular design
 The tubular configuration of the SOFC is the most advanced of the major
geometries being researched right now. Its unique configuration eliminates the
need to design gas seals.

 These cells do come at a cost unassociated with the other types of cells, and that
is the increased Ohmic loss. Since the tubular design forces the electrons to
travel along a much longer path than most other fuel cells, the losses due to
interconnect resistance are significant.

 The tubular design has suffered from the major problems such as low‐power
density and punitive fabrication costs. The low‐power density resulted from
both the long path for the electrical power through each cell and the large voids
within the stack structure (i.e., between the tubes). The unfavorable costs arise
from the preparation of the electrolyte and electrode via electrostatic vapour
deposition, which is a batch process conducted in a vacuum chamber.

 One significant advantage of the tubular design of SOFC is that

high‐temperature gas‐tight seals are eliminated. 145
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 Cell Components Eng. Rawan Alhaddad
 Electrolyte
 Currently, yttrium stabilized zirconia (YSZ) is the most commonly used electrolyte for SOFC.
 YSZ provides high conductivity at temperatures above 700 °C, while exhibiting negligible
electronic conductivity at these temperatures (above 1500 °C it becomes an electronic
conductor).
 In a fuel cell operating with a current density of 250 mA/cm2 at 1000 °C and an
electrolyte of 200 μm thickness, the resistance loss in the electrolyte would be 50 mV.
However, for mechanical reasons it is desirable to operate the SOFC at lower temperatures.
 To operate at 800 °C, the electrolyte thickness would have to be reduced by about an
order of magnitude to maintain a similar ohmic loss in the electrolyte.
 However, the state-of-the-art ceramic electrolyte material used in SOFC is the YSZ because
YSZ has the highest oxide ion conductivity, lowest electronic conductivity, and lowest gas
permeability to prevent gas crossover losses.
 The base material in the YSZ is the zirconia (ZrO2), which is doped with yttria (Y2O) as the
dopant element to create oxygen vacancy sites and stabilize the structures of zirconia
over the low to high temperature range during heating and cooling.
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 Anode
 The most common anode material is nickel-yttria stabilized zirconia (Ni-YSZ) Cermet or
a mixture of nickel and YSZ. While nickel serves for the required catalytic activity and
electron conductivity, YSZ lowers the effective coefficient of expansion to march with
adjacent YSZ electrolyte. However, use of YSZ extends the active zone for the anode
reaction. Depending on the design, Ni to YSZ volume ratio varies in the range from 30%
to 50% in the composite mixture.

 Nickel serves as the electrocatalyst for anode reaction and as the electronic conductor
for the electrons produced at the anode.

 The typical thickness of anode varies in the range of 40–100 μm. In recent times, a
thicker anode in the range of 350–750 μm is used to develop the so-called anode-
supported SOFCs that allow for a thinner electrolyte layer.

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 Cathode

 Most cathode materials used in SOFC today are lanthanum manganite

(LaMnO3). During early development, platinum and other noble metals, and
even magnetite, were used as cathode materials for SOFC. They are no longer
pursued actively because of chemical and physical instability, incompatibility
with most electrolytes, and, in the case of platinum, cost.

 While the thickness of a typical cathode electrode in an SOFC is around 50 μm,

research is also in progress to develop a cathode-supported SOFC cell that
supports a thinner electrolyte deposited over a cathode electrode of thickness
on the order of 350−1500 μm.

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 Interconnect
 The identification and fabrication of interconnect materials are a challenge in the
development of SOFCs. The primary function of interconnect is to carry the electrical
current from the electrochemical cell to the external circuit. Interconnect can be either
a metallic or a ceramic material that connects two individual cells.
 Interconnect must be extremely stable because it is exposed to oxidation and reduction
on either side of the material.
 A generally used interconnect is La(ca)CrO3.
 The main disadvantage of this material is it degrades during long-term operation.

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 Seal Materials
 The challenges of sealing the oxidant from fuel in planar SOFC stacks is
significant, hence a sub-section is devoted to potential seal materials
here. The function of SOFC seals includes:
 Prevent mixing of fuel and oxidant
 In some configurations, prevent mixing of reactants with the ambient environment
 In some configurations, provide mechanical bonding of components
 In some designs, provide electrical insulation between stack components

 Seal materials must be chemically and physically stable at operating

conditions. In some applications (e.g. in on-road vehicles), the seal must
also be able to withstand acceleration forces associated with
vibration and shock. Finally, seal materials must be low in cost and
amenable to low-cost stack manufacturing methods.

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 Performance Eng. Rawan Alhaddad

 The SOFC, like the MCFC, is a high temperature fuel

cell, but unlike the MCFC is not susceptible to a wide
variety of contaminates. This comes at a cost, it has a
lower open circuit voltage as compared to the MCFC.

 The overall losses of the SOFC are mainly those

associated with Ohmic losses.

 Since the cell operates at high temperatures is has

almost no activation losses, and the usefulness of the cell
in not in the range of mass transportation losses.

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1. Effect of pressure

 SOFCs, show enhanced performance

by increasing cell pressure.
 The effect of pressure on cell
performance at, 1000 Co:
 ∆VP = 59 log (P2/P1)
P1, P2: different cell pressures.

 Although higher pressure operation is beneficial for better SOFC performance,

the cost and effort involved in making stronger SOFC components (including
the connecting pipes) and gas-tight sealing as well as the operational cost
involved in the compression of the reactant gases are significant, minimizing the
benefit of higher pressure operation.

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2. Effect of temperature
 Figure shows the effect of temperature on cell performance.

 The ohmic polarization decreases as the operating temperature increases to 1050 Co

and correspondingly, the current density at a given cell voltage increases.
 From figure a larger decrease in cell voltage with decreasing temperature between
800 to 900 Co than that between 900 to 1000 Co at constant current density.
 Eng. Rawan Alhaddad

 Therefore, the voltage gain with respect to temperature is

a strong function of temperature and current density:
∆VT (mV) = 1.3 (T2 – T1) Co
 Eng. Rawan Alhaddad

3. Effect of reactant gas composition and utilization

 Oxidant: the performance of SOFCs, improves with pure O2 rather than air as
the oxidant.
 The difference in cell voltage with pure O2 and air increases as the current
density increases, which suggests that concentration polarization plays a role
during O2 reduction in air.
 The differences in voltage between air and oxygen increases with increasing
current density.

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 Fuel: the presence of hydrogen in the fuel produces two results:

1. The potential is higher
2. The oxygen/carbon (O/C) atom ratio corresponding to complete oxidation
extends to higher values.
 The addition of hydrogen to the fuel gas will yield a higher open circuit
potential in SOFCs.
 The cell voltage decreases with an increase in the fuel utilization at constant
current density.
 Eng. Rawan Alhaddad

4. Effect of impurities

 Hydrogen sulfide (H2S), hydrogen chloride (HCL) and ammonia (NH3)

are impurities found in the coal gas.

 Some of these substances may harm the performance of SOFCs.

 Silicon (Si) also can be found in coal gas as a contaminant.

It is accumulate on the fuel electrode in the form of silica (SiO2).

 However, some limited studies indicate that solid oxide fuel cell may be
able to tolerate NH3 upto 5000 ppm, HCl upto 1 ppm, and H2S upto
0.1 ppm; 1 ppm of H2S would cause an immediate drop in the cell
potential.

 The adverse effect ofH2S on the cell performance could be reversed

by providing clean fuel, free ofH2S, to the anode.
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5. Effect of current density

 The voltage level of a SOFC is reduced by ohmic, activation and concentration
losses which increase with increasing current density.
∆VJ (mV) = -0.73∆J (T = 1000 Co)
J: the current density (mA/cm2) at which the cell is operating.
 Eng. Rawan Alhaddad

6. Effect of cell life

 Experiments showed that:
 0.5% mV/1000 hours for 69000 hours
 0.2% mV/1000 hours for 44000 hours (25 kW)
 0.5% mV/1000 hours for 16000 hours (100 kW)

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