1.

5 FUEL CELL TYPES

There are five major types of fuel cells, differentiated from one another by their electrolyte:
1. Phosphoric acid fuel cell (PAFC)
2. Polymer electrolyte membrane fuel cell (PEMFC)
3. Alkaline fuel cell (AFC)
4. Molten carbonate fuel cell (MCFC)
5. Solid-oxide fuel cell (SOFC)

While all five fuel cell types are based on the same underlying electrochemical principles, they all
operate at different temperature regimens, incorporate different materials, and often differ in their
fuel tolerance and performance characteristics, as shown in Table 1.1. Most of the examples in this
book focus on PEMFCs or SOFCs. We will briefly contrast these two fuel cell types.

• PEMFCs employ a thin polymer membrane as an electrolyte (the membrane looks and feels a lot
like plastic wrap). The most common PEMFC electrolyte is a membrane material called
NafionTM. Protons are the ionic charge carrier in a PEMFC membrane. As we have already seen,
the electrochemical half reactions in an H2–O2 PEMFC are

H
2 → 2H+ + 2e-
12
O2 + 2H+ + 2e- → H2O

PEMFCs are attractive for many applications because they operate at low temperature and have
high power density.
• SOFCs employ a thin ceramic membrane as an electrolyte. Oxygen ions (O2–) are the ionic
charge carrier in an SOFC membrane. The most common SOFC electrolyte is an oxide material
called yttria-stabilized zirconia (YSZ). In an H2–O2 SOFC, the electrochemical half reactions are

H
2 + O2- → H2O + 2e-
12
O2 + 2e- → O2-

To function properly, SOFCs must operate at high temperatures (>600∘C). They are attractive for
stationary applications because they are highly efficient and fuel flexible.

Note how changing the mobile charge carrier dramatically changes the fuel cell reaction
chemistry. In a PEMFC, the half reactions are mediated by the movement of protons (H+),
and water is produced at the cathode. In a SOFC, the half reactions are mediated by the
motion of oxygen ions (O2–), and water is produced at the anode. Note in Table 1.1 how
other fuel cell types use OH– or CO32– as ionic charge carriers. These fuel cell types will
also exhibit different reaction chemistries, leading to unique advantages and disadvantages.
Part I of this book introduces the basic underlying principles that govern all fuel cell
devices. What you learn here will be equally applicable to a PEMFC, a SOFC, or any other
fuel cell for that matter. Part II discusses the materials and technology-specific aspects of the
five major fuel cell types, while also delving into fuel cell system issues such as stacking,
fuel processing, control, and environmental impact.

hal 273

8.2 PHOSPHORIC ACID FUEL CELL

In the PAFC, liquid H3PO4 electrolyte (either pure or highly concentrated) is contained in a thin
SiC matrix between two porous graphite electrodes coated with a platinum catalyst. Hydrogen is
used as the fuel and air or oxygen may be used as the oxidant. The anode and cathode reactions
are

Anode: H2 → 2H+ + 2e-

Cathode: 1
2O2 + 2H+ + 2e- → H2O (8.1)

A schematic of a PAFC is provided in Figure 8.1. Figure 8.2 gives a photograph of a 200-kW
stationary power commercial PAFC system. Pure phosphoric acid solidifies at 42∘C. Therefore,
PAFCs must be operated above this temperature. Because freeze–thaw cycles can cause serious
stress issues, commissioned PAFCs are usually maintained at operating temperature. Optimal
performance occurs at temperatures of 180–210∘C. Above 210∘C, H3PO4 undergoes an
unfavorable phase transition, which renders it unsuitable as an electrolyte. The SiC matrix provides
mechanical strength to the electrolyte, keeps the two electrodes separated, and minimizes reactant
gas crossover. During operation, H3PO4 must be continually replenished because it gradually
evaporates to the environment (especially during higher-temperature operation). Electrical
efficiencies of PAFC units are ≈ 40% with combined heat and power units achieving ≈ 70%.
Because PAFCs employ platinum catalysts, they are susceptible to carbon monoxide and sulfur
poisoning at the anode. This is not an issue when running on pure hydrogen but can be important
when running on reformed or impure feedstocks. Susceptibility depends on temperature; because
the PAFC operates at higher temperatures than the PEMFC, it exhibits somewhat greater tolerance.
Carbon monoxide tolerance at the anode can be as high as 0.5–1.5%, depending on the exact
conditions. Sulfur tolerance in the anode, where it is typically present as H2S, is around 50 ppm
(parts per million).

PAFC Advantages
• Mature technology
• Excellent reliability/long-term performance
• Electrolyte is relatively low cost
PAFC Disadvantages
• Expensive platinum catalyst
• Susceptible to CO and S poisoning
• Electrolyte is a corrosive liquid that must be replenished during operation

8.3 POLYMER ELECTROLYTE MEMBRANE FUEL CELL

The PEMFC is constructed from a proton-conducting polymer electrolyte membrane, usually a

perfluorinated sulfonic acid polymer. Because the polymer membrane is a proton conductor, the
anode and cathode reactions in the PEMFC (like the PAFC) are

Anode: H2 → 2H+ + 2e-

Cathode: 1
2O2 + 2H+ + 2e- → H2O (8.2)
A schematic diagram of a PEMFC is provided in Figure 8.3. Figure 8.4 gives a photograph of the
system layout of a Hyundai ix35 fuel cell vehicle powered by PEMFCs. The polymer membrane
employed in PEMFCs is thin (20–200 μm), flexible, and transparent. It is coated on either side
with a thin layer of platinum-based catalyst and porous carbon electrode support material. This
electrode–catalyst–membrane–catalyst–electrode sandwich structure is referred to as a membrane
electrode assembly (MEA). The entire MEA is less than 1 mm thick. Because the polymer
membrane must be hydrated with liquid water to maintain adequate conductivity (see Chapter 4),
the operating temperature of the PEMFC is limited to 90∘C or lower. Because of the low operating
temperature, platinum-based materials are the only practical catalysts currently available. While
H2 is the fuel of choice, for low-power (< 1-kW) portable applications, liquid fuels such as
methanol and formic acid are also being considered. One such liquid fuel solution, the direct
methanol fuel cell (DMFC), is a PEMFC that directly oxidizes methanol (CH3OH) to provide
electricity. The DMFC is under extensive investigation at this time (2016). Some researchers
assign these alternative-fuel PEMFCs their own fuel cell class. Later in this chapter, Section 8.7.1
provides additional information on the DMFC. The PEMFC currently exhibits the highest power
density of all the fuel cell types (500–2500 mW/cm2). It also provides the best fast-start and on
off cycling characteristics. For these reasons, it is well suited for portable power and transport
applications. Fuel cell development at most of the major car companies is almost exclusively
focused on the PEMFC.

PEMFC Advantages
• Highest power density of all the fuel cell classes
• Good start–stop capabilities
• Low-temperature operation makes it suitable for portable applications
PEMFC Disadvantages
• Uses expensive platinum catalyst
• Polymer membrane and ancillary components are expensive
• Active water management is often required
• Very poor CO and S tolerance
8.4 ALKALINE FUEL CELL
The AFC employs an aqueous potassium hydroxide electrolyte. In contrast to acidic fuel cells
where H+ is transmitted from the anode to the cathode, in an alkaline fuel cell OH– is conducted
from the cathode to the anode. The anode and cathode reactions are therefore

Anode: H2 + 2OH- → 2H2O + 2e-

Cathode: 1
2O2 + 2e- + H2O → 2OH-

Thus, water is consumed at the cathode of an AFC while it is produced (twice as fast) at the anode.
If the excess water is not removed from the system, it can dilute the KOH electrolyte, leading to
performance degradation. A schematic diagram of an AFC is provided in Figure 8.5. Figure 8.6
gives a photograph of an AFC fuel cell unit that was used on the NASA Apollo missions.

For reasons that are still poorly understood, the cathode activation overvoltage in an AFC is
significantly less than in an acidic fuel cell of similar temperature. Also, many more metal-based
catalysts are stable in an alkaline environment. Thus, under some conditions, nickel (rather than
platinum) catalysts can be used as the cathode catalyst. Because the ORR kinetics proceed much
more rapidly in an alkaline medium than in an acidic medium, AFCs can achieve operating
voltages as high as 0.875 V. Remember that a high operating voltage leads to high efficiency—an
important point if fuel is at a premium. Depending on the concentration of KOH in the electrolyte,
the AFC can operate at temperatures between 60 and 250∘C. Alkaline fuel cells require pure
hydrogen and pure oxygen as fuel and oxidant because they cannot tolerate even atmospheric
levels of carbon dioxide.

The presence of CO2 in an AFC degrades the KOH electrolyte as follows:

2OH- + CO2 → CO32- + H2O (8.4)

Over time, the concentration of OH– in the electrolyte declines. Additionally, K2CO3 can begin
to precipitate out of the electrolyte (due to its lower solubility), leading to significant problems.
These issues can be partially mitigated by the use of CO2 scrubbers and the continual resupply of
fresh KOH electrolyte. However, both solutions entail significant additional cost and equipment.
Due to these limitations, the AFC is not economically viable for most terrestrial power
applications. However, the AFC demonstrates impressively high efficiencies and power densities,
leading to an established application in the aerospace industry. Alkaline fuel cells were employed
on the Apollo missions as well as on the Space Shuttle orbiters. Recently, a number of solid
polymer based alkaline electrolyte membrane materials have been developed that partially mitigate
the CO2 instability issue associated with AFC operation. Thus, a number of research initiatives
are now reexamining the AFC for portable terrestrial applications.

AFC Advantages
• Improved cathode performance
• Potential for nonprecious metal catalysts
• Low materials costs, extremely low cost electrolyte

AFC Disadvantages
• Must use pure H2–O2
• KOH electrolyte may need occasional replenishment
• Must remove water from anode

8.5 MOLTEN CARBONATE FUEL CELL

The electrolyte in the MCFC is a molten mixture of alkali carbonates, Li2CO3 and K2CO3,
immobilized in a LiO–AlO2 matrix. The carbonate ion, CO32-, acts as the mobile charge carrier
in the MCFC. The anode and cathode reactions are, therefore,

Anode: H2 + CO32- → CO2 + H2O + 2e-

Cathode: 1
2O2 + CO2 + 2e- → CO2 3- (8.5)

In the MCFC, CO2 is produced at the anode and consumed at the cathode. Therefore, MCFC
systems must extract the CO2 from the anode and recirculate it to the cathode. (This situation
contrasts with the AFC, where CO2 must be excluded from the cathode.) The CO2 recycling
process is actually less complicated than one might suppose. Typically, the waste stream from the
anode is fed to a burner, where the excess fuel combusts. The resulting mixture of steam and CO2
is then mixed with fresh air and supplied to the cathode. The heat released at the combustor
preheats the reactant air, thus improving the efficiency and maintaining the operating temperature
of the MCFC. A schematic diagram of a MCFC is provided in Figure 8.7. Figure 8.8 gives a
photograph of a 2.5-MW pressurized MCFC system.

The electrodes in a typical MCFC are nickel based; the anode usually consists of a
nickel/chromium alloy while the cathode consists of a lithiated nickel oxide. At both electrodes,
the nickel provides catalytic activity and conductivity. At the anode, the chromium additions
maintain the high porosity and surface area of the electrode structure. At the cathode, the lithiated
nickel oxide minimizes nickel dissolution, which could otherwise adversely affect fuel cell
performance. The relatively high operating temperature (650∘C) of the MCFC provides fuel
flexibility. The MCFC can run on hydrogen, simple hydrocarbons (like methane), and simple
alcohols. Carbon monoxide tolerance is not an issue for MCFCs; rather than acting as a poison,
CO acts as a fuel! Due to stresses created by the freeze–thaw cycle of the electrolyte during startup/
shutdown cycles, the MCFC is best suited for stationary, continuous power applications. The
electrical efficiency of a typical MCFC unit is near 50%. In combined heat and power applications,
efficiencies could reach close to 90%.

MCFC Advantages
• Fuel flexibility
• Nonprecious metal catalyst
• High-quality waste heat for cogeneration applications
MCFC Disadvantages
• Must implement CO2 recycling
• Corrosive, molten electrolyte
• Degradation/lifetime issues
• Relatively expensive materials

8.6 SOLID-OXIDE FUEL CELL

The SOFC employs a solid ceramic electrolyte. The most popular SOFC electrolyte material is
yttria-stabilized zirconia (YSZ), which is an oxygen ion (oxygen vacancy) conductor. Since O2–
is the mobile conductor in this case, the anode and cathode reactions are
Anode: H2 + O2- → H2O + 2e-
Cathode: 1
2O2 + 2e- → O2- (8.6)

In an SOFC, water is produced at the anode, rather than at the cathode, as in a PEMFC. A schematic
of an SOFC is provided in Figure 8.9. Figure 8.10 is a photograph of an SOFC prototype.

The anode and cathode materials in an SOFC are different. The fuel electrode must be able to
withstand the highly reducing high-temperature environment of the anode, while the air electrode
must be able to withstand the highly oxidizing high-temperature environment of the cathode. The
most common material for the anode electrode in the SOFC is a nickel–YSZ cermet (a cermet is a
mixture of ceramic and metal). Nickel provides conductivity and catalytic activity. The YSZ adds
ion conductivity, thermal expansion compatibility, and mechanical stability and maintains the high
porosity and surface area of the anode structure. The cathode electrode is usually a mixed ion
conducting and electronically conducting (MIEC) ceramic material. Typical cathode materials
include strontium-doped lanthanum manganite (LSM), lanthanum–strontium ferrite (LSF),
lanthanum–strontium cobaltite (LSC), and lanthanum–strontium cobaltite ferrite (LSCF). These
materials show good oxidation resistance and high catalytic activity in the cathode environment.

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%. 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.
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