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Cells and Stacks

SD Fraser, V Hacker, and K Kordesch, Graz University of Technology, Graz, Austria

& 2009 Elsevier B.V. All rights reserved.

AFC Design Principles alkaline environment. Thus, comparably cheap metal

catalysts (e.g., nickel, silver, gold) can be used with the
Fuel cells use a continuous stream of gaseous and/or cathode. However, this is not possible with acidic fuel
liquid fuels and oxidizers to electrochemically generate cells designed for low-temperature operation, which
an electrical output power. The overall electrochemical strongly depend on platinum and platinum-based
reaction converting fuel and oxidizer into the reaction catalysts.
product is the same for alkaline and acidic fuel cells. The One of the major problems associated with AFCs is
presence of an alkaline environment, however, has a the carbon dioxide sensitivity of the alkaline electrolytes.
significant influence on the electrochemical conversion The resulting reactions form carbonates, which block the
process governing fuel cell operation. Significant differ- electrolyte and gas pores and eventually mechanically
ences exist between alkaline and acidic fuel cells with separate the active layers from the fuel cell electrodes.
respect to fundamental electrode reactions as well as These reactions can be written as follows:
basic cell and stack design features. An overview of al-
kaline fuel cell fundamentals is provided in the following. CO2 2OH -CO3 2 H2 O

Electrode Reactions CO2 OH -HCO3 

CO2 2KOH-K2 CO3 H2 O
The electrochemical half-cell reactions governing alka-
line fuel cell (AFC) operation can be written as follows:
Thus, AFCs have often been used only when a carbon
dioxide-free supply of oxidizer was available. Air contains
Anode reaction : 2H2 4OH - 4H2 O 4e
some 0.03% carbon dioxide; therefore, carbonates may be
Cathode reaction : O2 4e 2H2 O-4OH formed during air-breathing fuel cell operation, which
Overall reaction : 2H2 O2 -2H2 O
may lead to serious cell degradation effects. Removal of
the carbon dioxide content of the air can be done by
Hydroxyl ions are thus converted into water at the using an absorbing tower containing soda lime. With
anode by consuming hydrogen fuel. Two electrons are carbon dioxide removal, terrestrial air-breathing AFC
released per molecule of hydrogen in this half-cell re- operation is thus made possible without serious degrad-
action. The hydroxyl ions are generated at the cathode, ation effects limiting the long-term stability of the cells.
consuming oxygen, water, and four electrons per mol- The degree of carbon dioxide tolerance does, however,
ecule of oxygen. strongly depend on the electrode and cell design and will
Two transport processes occur between the electrodes therefore be specifically addressed later in the section
of an AFC: hydroxyl ions migrate from the cathode to the entitled AFC Single-Cell Designs. Recent investigations
anode, whereas liquid water is transported in the opposite indicate that AFC electrodes can be built to show no
direction. The overall reaction produces 1 mol of water effect caused by carbon dioxide, and that only the elec-
for each mole of hydrogen consumed in the electro- trolyte is influenced by the presence of carbon dioxide.
chemical reaction. Thus, significant quantities of water
are produced within an AFC, particularly if the cell is Requirements with Respect to Alkaline Fuel Cell
operated at high current densities. and Stack Design
Electrons that are generated at the anode flow through
The design of an AFC cell or stack basically has to
the external circuit and are consumed in the cathode
comply with the following:
half-cell reaction. The cathode is the positive terminal
because, by convention, electrons always flow toward
the cathode. The anode is therefore the negative
provide a sufficient and uniform supply of hydrogen
the whole electrode area;
terminal where electrons are generated. Technically, the
positive current flows in the direction opposite to that of
the wholea sufficient
provide and uniform supply of oxygen over
electrode area;
the electrons, i.e., from the positive to the negative
provide a way of conducting the electrons to an ex-
electrical circuit;
One of the main advantages of AFC technology are
the facile kinetics of the oxygen reduction reaction in an
cathode toa way
provide of transporting the anions from the
the anode; and

Fuel Cells Alkaline Fuel Cells | Cells and Stacks 345

provide a way of removing the reaction product water
the cell.
(3) cells with alkaline anion exchange membranes
All these requirements have to be met in a light and Each of these fundamental approaches will be briefly
compact fuel cell design that is cheap enough for mass discussed in the following.
production, rugged enough for real-world applications,
and durable enough to provide a shelf life and oper-
Cell Designs with Immobilized Liquid
ational life demanded by the potential customers.
Most of these issues can only be met by developing
cell and stack designs that can be easily produced using Cells using immobilized liquid electrolyte basically
established mass production technologies. Only a pru- consist of a spacer or matrix material soaked with liquid
dent cell and stack design will be able to turn the in- electrolyte sandwiched between two gas diffusion elec-
trinsic advantages of AFC technology into a commercial trodes (Figure 1). The gas diffusion electrodes are nor-
success. Many challenges are yet to be faced, although mally designed for monopolar operation, with a metal
many have already been solved in previous approaches to mesh providing sufficient electrical conductivity within
cell and stack designs. the gas diffusion electrodes.
This article will first provides an overview of funda- The cell design with immobilized liquid electrolyte is
mental AFC single-cell designs, and then moves on to very simple and does not require any moving parts other
discussing fuel cell stack designs. Three examples of AFC than optional blowers for the anode and cathode gas
stacks taken from different stages in the technological de- channels. The simplicity of this design , however, comes
velopment of AFCs will then be discussed in order to with some challenges with respect to the durability and
provide the reader with an overview of the historical and the robustness required in regular commercial appli-
recent possibilities and limitations in AFC stack technology. cations. Because the liquid electrolyte can neither be
removed nor be completely replaced once it has been
inserted into the electrolyte chamber, any impurities or
Alkaline Fuel Cell Single-Cell Designs
carbonates formed within the electrolyte will inevitably
accumulate within the electrolyte chamber. This can
Three major approaches to AFC single-cell design can
drastically reduce the cell performance and may even
be distinguished:
lead to complete failure of the cell. Alkaline fuel cells
(1) cells with immobilized liquid electrolytes, with immobilized electrolytes are therefore primarily
(2) cells with circulating liquid electrolytes, and used when highly pure anode and cathode input gases are

Electric load

H2 O2 (air)

Cathode porous gas

diffusion electrode
Anode porous gas
diffusion electrode
H2O Metal mesh
current collector

Heat Heat

Immobilized liquid

Figure 1 Alkaline fuel cell (AFC) single-cell with immobilized liquid electrolyte.
346 Fuel Cells Alkaline Fuel Cells | Cells and Stacks

available. An accumulation of impurities and/or car- anode and cathode gas streams. This requires that the
bonates within the liquid electrolyte can thus be limiting, anode and cathode gas streams be supplied with high
but the advantages of a simple cell design may outweigh stoichiometries. The evaporation of water into the elec-
the limitations with respect to electrolyte replacement. trode gas streams is also desired with respect to internal
Another problem that has to be addressed with an cell cooling, as the phase change of water can be effect-
immobilized liquid electrolyte cell design is thermal ively used for cell cooling purposes. Dead-end operation
management. If a circulating liquid electrolyte design is of cells with immobilized electrolytes is normally not a
applied, the liquid electrolyte is also used for cell heating feasible option, as product water removal would only be
and cooling purposes. This can be easily done by limited to the purging intervals of the electrode gas
pumping the electrolyte through an external heat ex- streams.
changer before feeding it back into the electrolyte
chamber. If the electrolyte is immobilized, however, dif-
Cells Designs with Circulating Liquid
ferent methods of heating and cooling the cells have to be
considered. Moreover, an introduction of active tem-
perature control systems increases the complexity of the Fuel cells with a circulating liquid electrolyte design
fuel cell system. (Figure 2) are designed similarly to the immobilized cell
Product water removal is also an important issue with design, but the liquid electrolyte can be continuously or
immobilized liquid electrolyte cells: as the electrolyte intermittently replaced during operation or even com-
cannot be pumped out of the cell, the reaction product pletely drained when the cell is deactivated.
water cannot be removed by feeding the electrolyte As mentioned earlier, the main advantages of the
through external regenerators or vaporization units. circulating electrolyte design are as follow. First, the
Therefore, the water has to be removed by evaporating it electrolyte itself can be used as a cleaning medium, re-
through the porous gas diffusion electrodes into the moving impurities and carbonates out of the cell. The

Electric load

KOH Electrolyte inlet duct

H2 O2 (air)

Cathode porous gas

diffusion electrode
Anode porous gas
diffusion electrode
H2O Metal mesh
current collector

Flow of liquid

Electrolyte outlet duct


Figure 2 Alkaline fuel cell (AFC) single cell with circulating electrolyte.
Fuel Cells Alkaline Fuel Cells | Cells and Stacks 347

electrolyte can even be completely replaced from time to membranes allow higher operating temperatures than do
time, similar to an oil change in an internal combustion PFSA membranes; this considerably improves the kinetics of
motor. the oxygen reduction reaction and therefore enables a re-
Second, the electrolyte can also be pumped through an duction in the noble metal loading of the fuel cell electrode
external heat exchanger and thus be used to either heat or catalyst layers. Polybenzimidazole membranes can also be
cool the cell during operation. This simplifies the stack doped with alkaline salts and thus find use in membrane-
design considerably, as no additional cooling elements based AFCs. The first investigations made with AAEM-
have to be included in the fuel cell stack assembly. based AFCs in laboratory-scale single-cell assemblies have
Finally, the reaction product water can also be washed proven promising, although the area-specific current and
out of the cell with the continuous flow of liquid elec- power density achieved were still considerably lower than
trolyte. This water can be subsequently removed from the those obtained with state-of-the-art PEMFCs.
electrolyte in an external water removal unit (e.g., water The advantages of having a membrane instead of an
vaporizing units) to avoid a dilution and hence also a loss immobilized or circulating liquid electrolyte are that the
in conductivity of the electrolyte. membranes are normally more reliable against reactant gas
leaks. Moreover, membranes can be applied in much
thinner layers than liquid electrolytes, whereas the liquid
Cell Designs with Alkaline Anion Exchange
electrolyte channels have to have a certain thickness to
ensure that the whole electrode area is covered with the
The third and last basic design approach is the AAEM electrolyte. The use of thin membranes also enables the
design (Figure 3). This approach is essentially equivalent design of very compact fuel cell stacks. Finally, membranes
to the design developed for modern proton-exchange provide a safe operation independent of the cell orien-
membrane fuel cell (PEMFC) systems. The liquid elec- tation and independent of acceleration forces that might
trolyte used with the immobilized or circulating liquid be present if the stack is, for example, operated in vehicles.
electrolyte designs is thus replaced by a solid AAEM. However, limitations regarding thermal management and
Several membranes have been considered and investi- removal of impurities from the electrolyte are similar to
gated with respect to their application as an AAEM in AFCs. those in the immobilized liquid electrolyte approach.
Acid-doped polybenzimidazole (PBI) membranes are con- To date, AAEM-based AFCs have been primarily
sidered as alternatives to perfluorosulfonic acid (PFSA) developed and tested on a laboratory scale. The devel-
polymer membranes in PEMFCs. Polybenzimidazole opment of large (kilowatt-scale) stacks or the use of

Electric load

H2 O2 (air)

Cathode porous gas

diffusion electrode
Anode porous gas
diffusion electrode

H2O Cathode gas channel/

bipolar plate
Anode gas channel/
bipolar plate
Heat Heat

Alkaline anion exchange


Single Cell i 1 Single Cell i Single Cell i + 1

Figure 3 Alkaline fuel cell (AFC) single cell with alkaline anion exchange membrane (AAEM) and bipolar design.
348 Fuel Cells Alkaline Fuel Cells | Cells and Stacks

AAEM-based AFCs in demonstration applications is not causes an additional voltage drop and thus decreases the
known to the authors. output power and efficiency of the cell assembly. Carbon
electrodes are good electrical conductors, but most
monopolar cells have metal meshes installed into their gas
Alkaline Fuel Cell Stack Designs diffusion electrodes to increase the in-plane conductivity
and thus reduce the planar voltage drop.
The voltage of an operational single fuel cell is normally
lesser than 1 V. This voltage is too small for its direct
use in most applications. A number of single cells there- Bipolar Stacks
fore have to be connected electrically in series to produce A completely different approach to interconnecting the
usable output voltages. Thus, the resulting stack voltage is individual cells is the bipolar stack design, shown in
derived by multiplying the single-cell voltage with the Figure 5. In this approach, the electrons generated or
number of cells installed in the stack, and the single-cell consumed within the active layers of the electrodes do
current is the same as the stack current. not have to flow to one or more current collection points
There are essentially two different ways of integrating located at the edge(s) of the electrode, but they can
many single cells into a fuel cell stack: the monopolar and directly flow through so-called bipolar plates located
the bipolar approach. Both approaches are briefly dis- between the anode and the cathode of two adjacent cells.
cussed in the following, highlighting their relevance with The electrons therefore do not have to flow within the
respect to AFC technology. plane of the electrodes, but rather perpendicular to the
electrodes; hence, the voltage drop is significantly smaller
than with a monopolar design, and the introduction of a
Monopolar Stacks
metal mesh into the porous gas diffusion electrode is not
In a monopolar stack design, the anode of one cell is required. Gas channels machined into the bipolar plates
connected to the cathode of the next cell, using a highly are also used to supply and distribute fresh fuel and
conductive separate link (e.g., a wire or a metal mesh oxidizer over the cell area. Separate cooling channels can
attached to one or more edges of the electrodes) to also be machined into the bipolar plates if the cell is, for
connect the cells. A simplified schematic of this mono- example, to be cooled by a water cooling cycle.
polar design is shown in Figure 4. Bipolar stack designs are the state-of-the-art approach
The major limitation faced with monopolar cell designs used with the majority of PEMFCs. The reason why the
is that the electrons generated and consumed over the bipolar plate design is also so beneficial for PEMFCs is
whole geometrical surface area of the electrode have to that the individual membraneelectrode assemblies
flow through the electrode to get to a current collection (MEAs) being very thin and flexible are mechanically
point that is usually located at one or more edges of the supported by the bipolar plates; the stack can thus be
electrode. This nonuniform current distribution inevitably made very compact and robust.

H2 O2 H2 O2 H2 O2

Figure 4 Monopolar stack design.

Fuel Cells Alkaline Fuel Cells | Cells and Stacks 349


Membraneelectrode assembly (MEA)

Bipolar plate

H2 O2 H2 O2 H2 O2 H2 O2

Figure 5 Bipolar stack design.

Alkaline fuel cells (AFCs) are primarily made with that has been used with the National Aeronautics and
monopolar cells. This is particularly true for cells with Space Administration (NASA) Apollo missions to the
liquid electrolytes, and a contact between anode and Moon. The third and last stack is a recent semi-
cathode which would short-circuit the cell has to be commercial AFC stack developed by the ZeTek
avoided at all times. This can be achieved by introducing Corporation.
an electrically isolating spacer or matrix materials that
prevent direct contact between the anode and the cath- Karl Kordeschs Austin A40 Alkaline Fuel Cell
ode at the cost of preventing the use of a very thin System
electrolyte channel design and including the mass of an
inert spacer material. Most AFCs with liquid electrolytes In 1970, Karl Kordesch privately built a fuel cell/battery
are therefore based on monopolar designs. A bipolar hybrid vehicle based on the Austin A40 and used it for his
approach for circulating liquid electrolyte AFCs has been personal transportation on public roads for 3 years. The
developed and tested at Graz University of Technology, AFC stacks were built from electrodes donated by Union
although AFCs with AAEMs are attractive candidates for Carbide Corporation and had previously also been used
PEMFC-like bipolar stack designs. with the fuel cell system developed for the General
Once thin and sufficiently conductive AAEMs can be Motors (GM) Electrovan.
produced and reproducibly built into MEAs, bipolar The fuel cell (FC) stacks were installed in the rear
stack designs would indeed be a very attractive option for compartment of Karl Kordeschs Austin. The fuel cell
AFCs, too. Many of the findings about flow field design, balance of plant components required, for example, for
bipolar plate materials, and the reduction of the contact automatic start-up and shutdown of the FC system were
resistance between electrodes and bipolar plates could also installed into the rear compartment as shown in
thus also be applied with AFC technology. Figure 6. A lead battery was installed into the engine
compartment next to the electric motor.
These FC stacks can be seen in Figure 6. Each stack
Overview of Historical Alkaline Fuel Cell has a voltage of 30 V and an electric output power of
Stacks 2 kW. The transparent plastic container located on top of
the stacks contains soda lime. Fresh soda lime is red and
Three different AFC stacks are presented in the fol- turns blue when used for carbon dioxide scrubbing due to
lowing. The first AFC stack discussed is the one installed an optical indicator. The soda lime container is therefore
into Karl Kordeschs Austin A40, the first privately built subdivided into six compartments in order to enable a
fuel cell/battery hybrid vehicle driven on public roads. simple visual identification of the soda lime condition by
The second stack discussed is the Apollo AFC system tracing the blue region of used soda lime, located near
350 Fuel Cells Alkaline Fuel Cells | Cells and Stacks

Figure 6 Six-kilowatt alkaline fuel cell (AFC) stacks in the rear

of Karl Kordeschs car. Courtesy of Prof. Kordesch.

the air inlet duct, toward the fuel cell supply line. The
two manometers located on the left- and right-hand side
of the soda lime container are used for pressure and flow
indication. The picture was taken from the passenger
cabin looking toward the opened trunk lid. The fuel cell
system was therefore easily accessible from the passenger
cabin as well as through the trunk. Seven 12 V leadacid
batteries, located in the engine compartment of the ve-
hicle, were electrically connected in series and operated
in parallel to the hydrogen/air AFC.
When the propulsion system was operated with low
electrical output power levels, the voltage of the AFC
stacks exceeded the voltage of the leadacid batteries.
The batteries were thus automatically recharged by the
AFC. A diode was installed to prevent the batteries from
electrolyzing water in the AFC when the AFC voltage
was lower than the battery voltage (e.g., because no
reactants were supplied to the AFC). The AFC could
thus be shut down completely and the electrolyte could
even be completely drained from the system and the
vehicle could still be moved by the battery power.

The Apollo Alkaline Fuel Cell System

The first manned capsules of the NASA were only de-
veloped for short excursions into space (on the Mercury Figure 7 Apollo alkaline fuel cell (AFC) stack. Reproduced
from Richard BF (1969) Apollo fuel cell power system.
program). The capsules were therefore powered by bat- Proceedings of the 23rd Annual Power Sources Conference,
teries. The second manned spaceflight program (Gemini pp. 1113.
program) was already aiming at developing techniques
for advanced space travel in preparation of landing the patents and subsequently won the NASA contract to
first American on the Moon. National Aeronautics and power the Apollo spacecraft with AFCs.
Space Administration therefore decided to replace the Pratt & Whitney Aircraft developed the PC3A-2 AFC
battery pack with a fuel cell system. At first, an acidic system for the NASA Apollo program. A photograph of
PEMFC system was chosen for the Gemini spacecraft. the PC3A-2 is shown in Figure 7.
Due to continuing problems in the development of The AFC was based on sintered nickel electrodes with
durable PEMFC systems for space applications, NASA platinum metal catalysts and very high noble metal
decided to switch to AFC technology. In the early 1960s, loadings of up to 40 mg cm2. The electrodes were
Pratt & Whitney Aircraft licensed the Bacon AFC 2.5 mm thick and circular with a diameter of 200 mm.
Fuel Cells Alkaline Fuel Cells | Cells and Stacks 351

The nominal operating temperature of the system was 7 kW, respectively. In 2000, ZeTek introduced a new taxi,
between 200 and 230 1C, applying highly concentrated the Millennium Taxi.
potassium hydroxide (85%) as liquid electrolyte. Fuel cells used in these demonstration applications
Thirty-one single cells were stacked together and were based on the ZeTek Mk2 module (Figure 8). The
connected electrically in series; three of these stacks were ZeTek Mk2 stacks had an electrical power output of
electrically connected in parallel. The nominal rating of 434 W. Each stack consisted of 24 individual cells, con-
one of these AFC stacks was 1.5 kW (an overload oper- nected in a combined series/parallel configuration, and
ation at 2.3 kW was possible); each stack had a mass of provided an output current of 108 A at 4 V. Current
109 kg. densities of up to 120 mA cm2 were measured at an
Ninety-two systems were delivered by Pratt & operating temperature of 70 1C. The normal operating
Whitney. Fifty-four of these systems had actually been point was 100 mA cm2 at an average cell voltage of
used. The operation history of the Pratt & Whitney 0.67 V.
systems includes nine flights to the Moon, three Skylab
missions, and the Apollo/Soyuz rendezvous mission.

The ZeTek Mk2 Alkaline Fuel Cell Stack AFCs have been investigated and developed extensively
since the 1950s. Many of the spectacular milestones in
ZeTek was the parent organization of three companies
fuel cell history were achieved with AFC technology.
involved in the development of products for transporta-
Despite the achievements in alkaline technology, AFCs
tion, marine, and stationary power generation appli-
were nevertheless been overtaken by other fuel cell
cations. ZeTek was developing and building AFC stacks
technologies in the mid-1980s and 1990s. PEMFC
that were used in a number of demonstration applications
technology has replaced AFCs in most applications, as
including a prototype taxi operated on the streets of
state-of-the-art PEMFCs are compact, light, and robust.
London, England. This taxi used a 5 kW AFC with cir- A wider market introduction of PEMFCs has not yet
culating liquid electrolyte. Following this first onboard been achieved, though. One of the reasons is that
power generation application, ZeTek introduced a series
PEMFCs are still far away from being competitive with
of commercial vehicles including airport tow tugs and
established energy conversion technologies on a com-
fuel cellpowered boats. Two delivery vans, one with a
mercial scale. The problems and delays in finding an-
maximum power of 63 kW and the other with 68 kW,
swers to the pressing questions in PEMFC development
were built. The fuel cell power of those vans was 5 and
have fueled a renewed interest in AFCs. AFCs can pro-
vide useful solutions to the cost problems in PEMFC
technology. For instance, the excellent oxygen reduction
kinetics in alkaline environments allow use of low-cost
noble metalfree electrodes. Such catalysts will most
likely not be available anytime soon for the acidic
PEMFCs. Carbonate formation in AFCs, often cited as
one of the major problems that would even prevent their
use in terrestrial applications, can be limited by applying
soda lime, circulating electrolytes, or advanced electrode
structures. Lastly, the availability of new and innovative
materials will also provide the possibility to investigate,
develop, and finally apply new and innovative approaches
in AFC cell and stack design.

Abbreviations and Acronyms
AAEM alkaline anion exchange membrane
AFC alkaline fuel cell
FC fuel cell
GM General Motors
Figure 8 Phantom view of the ZeTek Mk2 AFC stack. Courtesy
MEA membrane-electrode assembly
of Zetec Corp.
352 Fuel Cells Alkaline Fuel Cells | Cells and Stacks

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