A solid oxide fuel cell (or SOFC) is an electrochemical conversion device that produces electricity directly from oxidizing a fuel. Fuel cells are characterized by their electrolyte material; the SOFC has a solid oxide or ceramic electrolyte.
Advantages of this class of fuel cells include high efficiency,
long-term stability, fuel flexibility, low emissions, and relatively low
cost. The largest disadvantage is the high operating temperature which results in longer start-up times and mechanical and chemical compatibility issues.
Introduction
Solid oxide fuel cells are a class of fuel cells characterized by the use of a solid oxide material as the electrolyte.
SOFCs use a solid oxide electrolyte to conduct negative oxygen ions
from the cathode to the anode. The electrochemical oxidation of the
oxygen ions with hydrogen or carbon monoxide thus occurs on the anode
side. More recently, proton-conducting SOFCs (PC-SOFC) are being
developed which transport protons instead of oxygen ions through the
electrolyte with the advantage of being able to be run at lower
temperatures than traditional SOFCs.
They operate at very high temperatures, typically between 500 and
1,000 °C. At these temperatures, SOFCs do not require expensive platinum catalyst material, as is currently necessary for lower temperature fuel cells such as PEMFCs, and are not vulnerable to carbon monoxide catalyst poisoning. However, vulnerability to sulfur poisoning has been widely observed and the sulfur must be removed before entering the cell through the use of adsorbent beds or other means.
Solid oxide fuel cells have a wide variety of applications, from
use as auxiliary power units in vehicles to stationary power generation
with outputs from 100 W to 2 MW. In 2009, Australian company, Ceramic Fuel Cells successfully achieved an efficiency of an SOFC device up to the previously theoretical mark of 60%. The higher operating temperature make SOFCs suitable candidates for application with heat engine energy recovery devices or combined heat and power, which further increases overall fuel efficiency.
Because of these high temperatures, light hydrocarbon fuels, such
as methane, propane, and butane can be internally reformed within the
anode. SOFCs can also be fueled by externally reforming
heavier hydrocarbons, such as gasoline, diesel, jet fuel (JP-8) or
biofuels. Such reformates are mixtures of hydrogen, carbon monoxide,
carbon dioxide, steam and methane, formed by reacting the hydrocarbon
fuels with air or steam in a device upstream of the SOFC anode. SOFC
power systems can increase efficiency by using the heat given off by the
exothermic electrochemical oxidation within the fuel cell for
endothermic steam reforming process. Additionally, solid fuels such as coal and biomass may be gasified to form syngas which is suitable for fueling SOFCs in integrated gasification fuel cell power cycles.
Thermal expansion
demands a uniform and well-regulated heating process at startup. SOFC
stacks with planar geometry require on the order of an hour to be heated
to light-off temperature. Micro-tubular fuel cell design geometries promise much faster start up times, typically in the order of minutes.
Unlike most other types of fuel cells, SOFCs can have multiple geometries. The planar fuel cell design
geometry is the typical sandwich type geometry employed by most types
of fuel cells, where the electrolyte is sandwiched in between the
electrodes. SOFCs can also be made in tubular geometries where either
air or fuel is passed through the inside of the tube and the other gas
is passed along the outside of the tube. The tubular design is
advantageous because it is much easier to seal air from the fuel. The
performance of the planar design is currently better than the
performance of the tubular design, however, because the planar design
has a lower resistance comparatively. Other geometries of SOFCs include modified planar fuel cell designs
(MPC or MPSOFC), where a wave-like structure replaces the traditional
flat configuration of the planar cell. Such designs are highly promising
because they share the advantages of both planar cells (low resistance)
and tubular cells.
Operation
A solid oxide fuel cell is made up of four layers, three of which are ceramics
(hence the name). A single cell consisting of these four layers stacked
together is typically only a few millimeters thick. Hundreds of these
cells are then connected in series to form what most people refer to as
an "SOFC stack". The ceramics used in SOFCs do not become electrically
and ionically
active until they reach very high temperature and as a consequence, the
stacks have to run at temperatures ranging from 500 to 1,000 °C.
Reduction of oxygen into oxygen ions occurs at the cathode. These ions
can then diffuse through the solid oxide electrolyte to the anode where
they can electrochemically oxidize the fuel. In this reaction, a water
byproduct is given off as well as two electrons. These electrons then
flow through an external circuit where they can do work. The cycle then
repeats as those electrons enter the cathode material again.
Balance of plant
Most of the downtime of a SOFC stems from the mechanical balance of plant, the air preheater, prereformer, afterburner, water heat exchanger, anode tail gas oxidizer, and electrical balance of plant, power electronics, hydrogen sulfide sensor and fans. Internal reforming leads to a large decrease in the balance of plant costs in designing a full system.
Anode
The ceramic anode
layer must be very porous to allow the fuel to flow towards the
electrolyte. Consequently, granular matter is often selected for anode
fabrication procedures. Like the cathode, it must conduct electrons, with ionic conductivity a definite asset. The most common material used is a cermet made up of nickel
mixed with the ceramic material that is used for the electrolyte in
that particular cell, typically YSZ (yttria stabilized zirconia) nanomaterial-based catalysts,
this YSZ part helps stop the grain growth of nickel. Larger grains of
nickel would reduce the contact area that ions can be conducted through,
which would lower the cells efficiency. The anode is commonly the
thickest and strongest layer in each individual cell, because it has the
smallest polarization losses, and is often the layer that provides the
mechanical support. Electrochemically speaking, the anode’s job is to use the oxygen ions that diffuse through the electrolyte to oxidize the hydrogen fuel.
The oxidation reaction
between the oxygen ions and the hydrogen produces heat as well as water
and electricity.
If the fuel is a light hydrocarbon, for example, methane, another
function of the anode is to act as a catalyst for steam reforming the
fuel into hydrogen. This provides another operational benefit to the
fuel cell stack because the reforming reaction is endothermic, which
cools the stack internally. Perovskite materials (mixed ionic/electronic
conducting ceramics) have been shown to produce a power density of 0.6
W/cm2 at 0.7 V at 800 °C which is possible because they have the ability
to overcome a larger activation energy.
Electrolyte
The
electrolyte is a dense layer of ceramic that conducts oxygen ions. Its
electronic conductivity must be kept as low as possible to prevent
losses from leakage currents. The high operating temperatures of SOFCs
allow the kinetics of oxygen ion transport to be sufficient for good
performance. However, as the operating temperature approaches the lower
limit for SOFCs at around 600 °C, the
electrolyte begins to have large ionic transport resistances and affect
the performance. Popular electrolyte materials include yttria-stabilized zirconia (YSZ) (often the 8% form 8YSZ), scandia stabilized zirconia (ScSZ) (usually 9 mol%Sc2O3 – 9ScSZ) and gadolinium doped ceria (GDC). The electrolyte material has crucial influence on the cell performances. Detrimental reactions between YSZ electrolytes and modern cathodes such as lanthanum strontium cobalt ferrite (LSCF) have been found, and can be prevented by thin (<100 a="" class="mw-redirect" href="https://en.wikipedia.org/wiki/Ceria" nbsp="" nm="" title="Ceria">ceria100>
diffusion barriers.
If the conductivity for oxygen ions in SOFC can remain high even
at lower temperatures (current target in research ~500 °C), material
choices for SOFC will broaden and many existing problems can potentially
be solved. Certain processing techniques such as thin film deposition can help solve this problem with existing materials by:
- reducing the traveling distance of oxygen ions and electrolyte resistance as resistance is proportional to conductor length;
- producing grain structures that are less resistive such as columnar grain structure;
- controlling the microstructural nano-crystalline fine grains to achieve "fine-tuning" of electrical properties;
- building composite possessing large interfacial areas as interfaces have been shown to have extraordinary electrical properties.
Cathode
The cathode, or air electrode, is a thin porous layer on the electrolyte where oxygen reduction takes place. The overall reaction is written in Kröger-Vink Notation as follows:
Cathode materials must be, at a minimum, electronically conductive. Currently, lanthanum strontium manganite
(LSM) is the cathode material of choice for commercial use because of
its compatibility with doped zirconia electrolytes. Mechanically, it has
a similar coefficient of thermal expansion to YSZ and thus limits
stress buildup because of CTE mismatch. Also, LSM has low levels of
chemical reactivity with YSZ which extends the lifetime of the
materials. Unfortunately, LSM is a poor ionic conductor, and so the
electrochemically active reaction is limited to the triple phase boundary
(TPB) where the electrolyte, air and electrode meet. LSM works well as a
cathode at high temperatures, but its performance quickly falls as the
operating temperature is lowered below 800 °C. In order to increase the
reaction zone beyond the TPB, a potential cathode material must be able
to conduct both electrons and oxygen ions. Composite cathodes consisting
of LSM YSZ have been used to increase this triple phase boundary
length. Mixed ionic/electronic conducting (MIEC) ceramics, such as
perovskite LSCF,
are also being researched for use in intermediate temperature SOFCs as
they are more active and can make up for the increase in the activation
energy of the reaction.
Interconnect
The
interconnect can be either a metallic or ceramic layer that sits
between each individual cell. Its purpose is to connect each cell in
series, so that the electricity each cell generates can be combined.
Because the interconnect is exposed to both the oxidizing and reducing
side of the cell at high temperatures, it must be extremely stable. For
this reason, ceramics have been more successful in the long term than
metals as interconnect materials. However, these ceramic interconnect
materials are very expensive as compared to metals. Nickel- and
steel-based alloys are becoming more promising as lower temperature
(600–800 °C) SOFCs are developed. The material of choice for an
interconnect in contact with Y8SZ is a metallic 95Cr-5Fe alloy.
Ceramic-metal composites called 'cermet' are also under consideration,
as they have demonstrated thermal stability at high temperatures and
excellent electrical conductivity.
Polarizations
Polarizations,
or overpotentials, are losses in voltage due to imperfections in
materials, microstructure, and design of the fuel cell. Polarizations
result from ohmic resistance of oxygen ions conducting through the
electrolyte (iRΩ), electrochemical activation barriers at the anode and
cathode, and finally concentration polarizations due to inability of
gases to diffuse at high rates through the porous anode and cathode
(shown as ηA for the anode and ηC for cathode). The cell voltage can be calculated using the following equation:
where:
- = Nernst potential of the reactants
- = Thévenin equivalent resistance value of the electrically conducting portions of the cell
- = polarization losses in the cathode
- = polarization losses in the anode
In SOFCs, it is often important to focus on the ohmic and
concentration polarizations since high operating temperatures experience
little activation polarization. However, as the lower limit of SOFC
operating temperature is approached (~600 °C), these polarizations do
become important.
Above mentioned equation is used for determining the SOFC voltage
(in fact for fuel cell voltage in general). This approach results in
good agreement with particular experimental data (for which
adequate factors were obtained) and poor agreement for other than
original experimental working parameters. Moreover, most of the
equations used require the addition of numerous factors which are
difficult or impossible to determine. It makes very difficult any
optimizing process of the SOFC working parameters as well as design
architecture configuration selection. Because of those circumstances a
few other equations were proposed:
where:
- = cell voltage
- = maximum voltage given by the Nernst equation
- = maximum current density (for given fuel flow)
- = fuel utilization factor
- = ionic specific resistance of the electrolyte
- = electric specific resistance of the electrolyte.
This method was validated and found to be suitable for optimization
and sensitivity studies in plant-level modelling of various systems with
solid oxide fuel cells.
With this mathematical description it is possible to account for
different properties of the SOFC. There are many parameters which impact
cell working conditions, e.g. electrolyte material, electrolyte
thickness, cell temperature, inlet and outlet gas compositions at anode
and cathode, and electrode porosity, just to name some. The flow in
these systems is often calculated using the Navier-stokes equation.
Ohmic polarization
Ohmic
losses in an SOFC result from ionic conductivity through the
electrolyte. This is inherently a materials property of the crystal
structure and atoms involved. However, to maximize the ionic
conductivity, several methods can be done. Firstly, operating at higher
temperatures can significantly decrease these ohmic losses.
Substitutional doping methods to further refine the crystal structure
and control defect concentrations can also play a significant role in
increasing the conductivity. Another way to decrease ohmic resistance is
to decrease the thickness of the electrolyte layer.
Ionic conductivity
An ionic specific resistance of the electrolyte as a function of temperature can be described by the following relationship:
where: – electrolyte thickness, and – ionic conductivity.
The ionic conductivity of the solid oxide is defined as follows:
where: and – factors depended on electrolyte materials, – electrolyte temperature, and – ideal gas constant.
Concentration polarization
The
concentration polarization is the result of practical limitations on
mass transport within the cell and represents the voltage loss due to
spatial variations in reactant concentration at the chemically active
sites. This situation can be caused when the reactants are consumed by
the electrochemical reaction faster than they can diffuse into the
porous electrode, and can also be caused by variation in bulk flow
composition. The latter is due to the fact that the consumption of
reacting species in the reactant flows causes a drop in reactant
concentration as it travels along the cell, which causes a drop in the
local potential near the tail end of the cell.
The concentration polarization occurs in both the anode and
cathode. The anode can be particularly problematic, as the oxidation of
the hydrogen produces steam, which further dilutes the fuel stream as it
travels along the length of the cell. This polarization can be
mitigated by reducing the reactant utilization fraction or increasing
the electrode porosity, but these approaches each have significant
design trade-offs.
Activation polarization
The
activation polarization is the result of the kinetics involved with the
electrochemical reactions. Each reaction has a certain activation
barrier that must be overcome in order to proceed and this barrier leads
to the polarization. The activation barrier is the result of many
complex electrochemical reaction steps where typically the rate limiting
step is responsible for the polarization. The polarization equation
shown below is found by solving the Butler–Volmer equation
in the high current density regime (where the cell typically operates),
and can be used to estimate the activation polarization:
where:
- = gas constant
- = operating temperature
- = electron transfer coefficient
- = electrons associated with the electrochemical reaction
- = Faraday's constant
- = operating current
- = exchange current density
The polarization can be modified by microstructural optimization. The
Triple Phase Boundary (TPB) length, which is the length where porous,
ionic and electronically conducting pathways all meet, directly relates
to the electrochemically active length in the cell. The larger the
length, the more reactions can occur and thus the less the activation
polarization. Optimization of TPB length can be done by processing
conditions to affect microstructure or by materials selection to use a
mixed ionic/electronic conductor to further increase TPB length.
Target
DOE target requirements are 40,000 hours of service for stationary fuel cell applications and greater than 5,000 hours for transportation systems (fuel cell vehicles) at a factory cost of $40/kW for a 10 kW coal-based system
without additional requirements. Lifetime effects (phase stability,
thermal expansion compatibility, element migration, conductivity and
aging) must be addressed. The Solid State Energy Conversion Alliance 2008 (interim) target for overall degradation per 1,000 hours is 4.0%.
Research
Research
is going now in the direction of lower-temperature SOFCs (600 °C). Low
temperature systems can reduce costs by reducing insulation, materials,
start-up and degradation-related costs. With higher operating
temperatures, the temperature gradient increases the severity of thermal
stresses, which affects materials cost and life of the system.
An intermediate temperature system (650-800 °C) would enable the use of
cheaper metallic materials with better mechanical properties and thermal conductivity.
New developments in nano-scale electrolyte structures have been shown
to bring down operating temperatures to around 350 °C, which would
enable the use of even cheaper steel and elastomeric/polymeric components.
Lowering operating temperatures has the added benefit of
increased efficiency. Theoretical fuel cell efficiency increases with
decreasing temperature. For example, the efficiency of a SOFC using CO
as fuel increases from 63% to 81% when decreasing the system temperature
from 900 °C to 350 °C.
Research is also under way to improve the fuel flexibility of
SOFCs. While stable operation has been achieved on a variety of
hydrocarbon fuels, these cells typically rely on external fuel
processing. In the case of natural gas, the fuel is either externally or internally reformed and the sulfur
compounds are removed. These processes add to the cost and complexity
of SOFC systems. Work is under way at a number of institutions to
improve the stability of anode materials for hydrocarbon oxidation and,
therefore, relax the requirements for fuel processing and decrease SOFC
balance of plant costs.
Research is also going on in reducing start-up time to be able to implement SOFCs in mobile applications. This can be partially achieved by lowering operating temperatures, which is the case for proton exchange membrane fuel cells (PEMFCs). Due to their fuel flexibility, they may run on partially reformed diesel, and this makes SOFCs interesting as auxiliary power units (APU) in refrigerated trucks.
Specifically, Delphi Automotive Systems are developing an SOFC that will power auxiliary units in automobiles and tractor-trailers, while BMW
has recently stopped a similar project. A high-temperature SOFC will
generate all of the needed electricity to allow the engine to be smaller
and more efficient. The SOFC would run on the same gasoline
or diesel as the engine and would keep the air conditioning unit and
other necessary electrical systems running while the engine shuts off
when not needed (e.g., at a stop light or truck stop).
Rolls-Royce is developing solid-oxide fuel cells produced by screen printing
onto inexpensive ceramic materials. Rolls-Royce Fuel Cell Systems Ltd
is developing an SOFC gas turbine hybrid system fueled by natural gas
for power generation applications in the order of a megawatt (e.g. Futuregen).
3D printing is being explored as a possible manufacturing
technique that could be used to make SOFC manufacturing easier by the
Shah Lab at Northwestern University. This manufacturing technique would
allow SOFC cell structure to be more flexible, which could lead to more
efficient designs. This process could work in the production of any part
of the cell. The 3D printing process works by combining about 80%
ceramic particles with 20% binders and solvents, and then converting
that slurry into an ink that can be fed into a 3D printer. Some of the
solvent is very volatile, so the ceramic ink solidifies almost
immediately. Not all of the solvent evaporates, so the ink maintains
some flexibility before it is fired at high temperature to densify it.
This flexibility allows the cells to be fired in a circular shape that
would increase the surface area over which electrochemical reactions can
occur, which increases the efficiency of the cell. Also, the 3D
printing technique allows the cell layers to be printed on top of each
other instead of having to go through separate manufacturing and
stacking steps. The thickness is easy to control, and layers can be made
in the exact size and shape that is needed, so waste is minimized.
Ceres Power
Ltd. has developed a low cost and low temperature (500–600 degrees)
SOFC stack using cerium gadolinium oxide (CGO) in place of current
industry standard ceramic, yttria stabilized zirconia (YSZ), which allows the use of stainless steel to support the ceramic.
Solid Cell Inc. has developed a unique, low-cost cell
architecture that combines properties of planar and tubular designs,
along with a Cr-free cermet interconnect.
The high temperature electrochemistry center (HITEC) at the
University of Florida, Gainesville is focused on studying ionic
transport, electrocatalytic phenomena and microstructural
characterization of ion conducting materials.
SiEnergy Systems, a Harvard spin-off company, has demonstrated
the first macro-scale thin-film solid-oxide fuel cell that can operate
at 500 degrees.
SOEC
A solid oxide electrolyser cell (SOEC) is a solid oxide fuel cell set in regenerative mode for the electrolysis of water with a solid oxide, or ceramic, electrolyte to produce oxygen and hydrogen gas.
SOECs can also be used to do electrolysis of CO2 to produce CO and oxygen or even co-electrolysis of water and CO2 to produce syngas and oxygen.
ITSOFC
SOFCs
that operate in an intermediate temperature (IT) range, meaning between
600 and 800 °C, are named ITSOFCs. Because of the high degradation rates
and materials costs incurred at temperatures in excess of 900 °C, it is
economically more favorable to operate SOFCs at lower temperatures. The
push for high-performance ITSOFCs is currently the topic of much
research and development. One area of focus is the cathode material. It
is thought that the oxygen reduction reaction is responsible for much of
the loss in performance so the catalytic activity of the cathode is
being studied and enhanced through various techniques, including
catalyst impregnation. The research on NdCrO3 proves it to be
a potential cathode material for the cathode of ITSOFC since it is
thermos chemically stable within the temperature range.
Another area of focus is the electrolyte materials. To make SOFC
competitive in the market, ITSOFC is always the focus of the research
and people try to lower the operational temperature by using the
alternative new materials. However, the efficiency and stability of the
materials limit their feasibility. One choice for the electrolyte new
materials is the ceria-salt ceramic composites (CSCs). The two-phase CSC
electrolytes GDC (gadolinium-doped ceria)- and SDC (samaria-doped
ceria)-MCO3 (M=Li, Na, K, single or mixture of carbonates) can reach the power density of 300-800 mW*cm−2.
LT-SOFC
Low-temperature
solid oxide fuel cells (LT-SOFCs), operating lower than 650 °C, are of
great interest for future research because the high operating
temperature is currently what restricts the development and deployment
of SOFCs. A low-temperature SOFC is more reliable due to smaller thermal
mismatch and easier sealing. Additionally, a lower temperature requires
less insulation and therefore has a lower cost. Cost is further lowered
due to wider material choices for interconnects and compressive
nonglass/ceramic seals. Perhaps most importantly, at a lower
temperature, SOFCs can be started more rapidly and with less energy,
which lends itself to uses in portable and transportable applications.
As temperature decreases, the maximum theoretical fuel cell
efficiency increases, in contrast to the Carnot cycle. For example, the
maximum theoretical efficiency of an SOFC using CO as a fuel increases
from 63% at 900 °C to 81% at 350 °C.
This is a materials issue, particularly for the electrolyte in
the SOFC. YSZ is the most commonly used electrolyte because of its
superior stability, despite not having the highest conductivity.
Currently, the thickness of YSZ electrolytes is a minimum of ~10 μm due
to deposition methods, and this requires a temperature above 700 °C.
Therefore, low-temperature SOFCs are only possible with higher
conductivity electrolytes. Various alternatives that could be successful
at low temperature include gallium-doped ceria (GDC) and
erbia-cation-stabilized bismuth (ERB). They have superior ionic
conductivity at lower temperatures, but this comes at the expense of
lower thermodynamic stability. CeO2 electrolytes become electronically
conductive and Bi2O3 electrolytes decompose to metallic Bi under the
reducing fuel environment.
To combat this, researchers created a functionally graded
ceria/bismuth-oxide bilayered electrolyte where the GDC layer on the
anode side protects the ESB layer from decomposing while the ESB on the
cathode side blocks the leakage current through the GDC layer. This
leads to near-theoretical open-circuit potential (OPC) with two highly
conductive electrolytes, that by themselves would not have been
sufficiently stable for the application. This bilayer proved to be
stable for 1400 hours of testing at 500 °C and showed no indication of
interfacial phase formation or thermal mismatch. While this makes
strides towards lowering the operating temperature of SOFCs, it also
opens doors for future research to try and understand this mechanism.
Researchers at the Georgia Institute of Technology dealt with the instability of BaCeO3 differently. They replaced a desired fraction of Ce in BaCeO3
with Zr to form a solid solution that exhibits proton conductivity, but
also chemical and thermal stability over the range of conditions
relevant to fuel cell operation. A new specific composition,
Ba(Zr0.1Ce0.7Y0.2)O3-δ (BZCY7) that displays the highest ionic
conductivity of all known electrolyte materials for SOFC applications.
This electrolyte was fabricated by dry-pressing powders, which allowed
for the production of crack free films thinner than 15 μm. The
implementation of this simple and cost-effective fabrication method may
enable significant cost reductions in SOFC fabrication.
However, this electrolyte operates at higher temperatures than the
bilayered electrolyte model, closer to 600 °C rather than 500 °C.
Currently, given the state of the field for LT-SOFCs, progress in
the electrolyte would reap the most benefits, but research into
potential anode and cathode materials would also lead to useful results,
and has started to be discussed more frequently in literature.
SOFC-GT
An SOFC-GT system is one which comprises a solid oxide fuel cell combined with a gas turbine. Such systems have been evaluated by Siemens Westinghouse and Rolls-Royce as a means to achieve higher operating efficiencies by running the SOFC under pressure. SOFC-GT systems typically include anodic and/or cathodic atmosphere recirculation, thus increasing efficiency.
Theoretically, the combination of the SOFC and gas turbine can give result in high overall (electrical and thermal) efficiency. Further combination of the SOFC-GT in a combined cooling, heat and power (or trigeneration) configuration (via HVAC) also has the potential to yield even higher thermal efficiencies in some cases.
Another feature of the introduced hybrid system is on the gain of
100% CO2 capturing at comparable high energy efficiency. These features
like zero CO2 emission and high energy efficiency make the power plant
performance noteworthy.
DCFC
For the direct use of solid coal fuel without additional gasification and reforming processes, a direct carbon fuel cell (DCFC)
has been developed as a promising novel concept of a high-temperature
energy conversion system. The underlying progress in the development of a
coal-based DCFC has been categorized mainly according to the
electrolyte materials used, such as solid oxide, molten carbonate, and
molten hydroxide, as well as hybrid systems consisting of solid oxide
and molten carbonate binary electrolyte or of liquid anode (Fe, Ag, In,
Sn, Sb, Pb, Bi, and its alloying and its metal/metal oxide) solid oxide
electrolyte. People's research on DCFC with GDC-Li/Na2CO3 as the electrolyte, Sm0.5Sr0.5CoO3 as cathode shows good performance. The highest power density of 48 mW*cm−2 can be reached at 500 °C with O2 and CO2 as oxidant and the whole system is stable within the temperature range of 500 °C to 600 °C.
SOFC operated on landfill gas
Every household produces waste/garbage on a daily basis. In 2009,
Americans produced about 243 million tons of municipal solid waste,
which is 4.3 pounds of waste per person per day. All that waste is sent
to landfill sites. Landfill gas which is produced from the decomposition
of waste that gets accumulated at the landfills has the potential to be
a valuable source of energy since methane is a major constituent.
Currently, the majority of the landfills either burn away their gas in
flares or combust it in mechanical engines to produce electricity. The
issue with mechanical engines is that incomplete combustion of gasses
can lead to pollution of the atmosphere and is also highly inefficient.
The issue with using landfill gas to fuel an SOFC system is that
landfill gas contains hydrogen sulfide. Any landfill accepting
biological waste will contain about 50-60 ppm of hydrogen sulfide and
around 1-2 ppm mercaptans. However, construction materials containing
reducible sulfur species, principally sulfates found in gypsum-based
wallboard, can cause considerably higher levels of sulfides in the
hundreds of ppm. At operating temperatures of 750 ⁰C hydrogen sulfide
concentrations of around 0.05 ppm begin to affect the performance of the
SOFCs.
Ni + H2S → NiS + H2
The above reaction controls the effect of sulfur on the anode.
This can be prevented by having background hydrogen which is calculated below.
At 453 K the equilibrium constant is 7.39 x 10−5
ΔG calculated at 453 K was 35.833 kJ/mol
Using the standard heat of formation and entropy ΔG at room temperature (298 K) came out to be 45.904 kJ/mol
On extrapolation to 1023 K, ΔG is -1.229 kJ/mol
On substitution, Keq at 1023 K is 1.44 x 10−4. Hence theoretically we need 3.4% hydrogen to prevent the formation of NiS at 5 ppm H2S.