Alkaline Fuel Cell

Introduction

 The alkaline fuel cell (AFC), also known as the Bacon fuel cell after its British
inventor, Francis Thomas Bacon, is one of the most developed fuel cell
technologies. Alkaline fuel cells consume hydrogen and pure oxygen, to
produce potable water, heat, and electricity. They are among the most efficient
fuel cells, having the potential to reach 70%.
 Alkaline fuel cells (AFCs) were one of the first fuel cell technologies to be
developed and were originally used by NASA in the space programme to
produce both electricity and water abroad spacecraft. AFCs continued to be
used on NASA space shuttles throughout the programme, alongside a limited
number of commercial applications.
 AFCs use an alkaline electrolyte such as potassium hydroxide in water and are
generally fuelled with pure hydrogen. The first AFCs operated at between
1000C and 2500C but typical operating temperatures are now around 70 0C. As a
result of the low operating temperature, it is not necessary to employ a
platinum catalyst in the system and instead, a variety of non-precious metals
can be used as catalysts to speed up the reaction occurring at the anode and
cathode. Nickel is the most commonly used catalyst in AFC units.
Working

 Alkaline-based fuel cells are no different from acidic proton exchange

membrane fuel cells (PEMFCs). The general workings of an alkaline-based
fuel cell, utilising either a liquid or a polymer electrolyte is exhibited in Fig. 9

Figure 9. The essentials of alkaline-based fuel cells, where

layer 1 and 5 represent the anode/cathode gas diffusion
layer (GDL), layer 2 and 4 the anode/cathode catalyst layer
(CL) and layer 3 the liquid/polymer electrolyte.

Chemical reaction

 Humidified hydrogen gas is supplied to the anode, which reacts with the
hydroxide ions in the electrolyte to produce water and electrons after
penetrating the GDL and reaching the catalyst layer (CL), as displayed in Eq.
(1)
  A humidified oxygen source, typically purified air/oxygen is supplied to the
cathode together with water. Oxygen gas, solvated in water, is reduced at the
cathode CL to form hydroxide ions, which diffuse through the electrolyte to
participate in the hydrogen oxidation reaction (HOR) that takes place on the
anode. The ideal oxygen reduction reaction (ORR) also labelled the direct 4-
electron pathway is displayed in Eq. (2).

 Additional highly relevant details to this reaction are further elaborated under
the sub-section Oxygen Reduction Reaction. The red-ox reactions in Eqs. (1)
and (2) are combined to form the overall mechanism given in Eq. (3)

 Equivalently with every other reaction, there are various inefficiencies and
losses which lower the achievable potentials in Eqs. (1)-(3). These losses are
generally defined as overpotentials and are categorised as charge transfer,
ohmic or mass-transport overpotential. These overpotentials variably affect a
cell at specific current densities. Charge transfer overpotential is mostly linked
with activation losses and is most visible at low current densities. Ohmic
overpotential originates in the electrical resistance of the cell components,
determines the slope of the current-voltage graph and is most visible at
intermediate current densities. At high current densities the fuel cell will be
limited by the speed at which reactants can reach the electrode, inducing mass
transportation losses.

Components

Electrodes

 The AFC electrodes can be hydrophobic or hydrophilic. The hydrophobic

electrodes are carbon-based with PTFE, while the hydrophilic electrodes are
usually made of metallic materials such as nickel and nickel-based alloys. The
 electrodes usually have several layers with different porosities for the liquid
electrolyte, fuel, and oxidant. AFCs can use both precious and nonprecious
metal catalysts. The precious metal catalysts used are platinum or platinum
alloys that are deposited on carbon supports or manufactured on nickel-based
metallic electrodes. The catalyst loading is typically 0.25 mg Pt/cm2 and up.
The most commonly used nonprecious metal catalysts are Raney nickel for the
anodes at a loading of 120 mg Ni/cm2, and silver-based powders for the
cathodes with a loading between 1.5 to 2 mg Ag/cm2.

Electrolyte

 The two electrodes are separated by a porous matrix saturated with an aqueous
alkaline solution, such as potassium hydroxide (KOH). Aqueous alkaline
solutions do not reject carbon dioxide (CO2) so the fuel cell can become
"poisoned" through the conversion of KOH to potassium carbonate (K2CO3).
Because of this, alkaline fuel cells typically operate on pure oxygen, or at least
purified air and would incorporate a 'scrubber' into the design to clean out as
much of the carbon dioxide as is possible. Because the generation and storage
requirements of oxygen make pure-oxygen AFCs expensive, there are few
companies engaged in active development of the technology. There is,
however, some debate in the research community over whether the poisoning is
permanent or reversible. The main mechanisms of poisoning are blocking of
the pores in the cathode with K2CO3, which is not reversible, and reduction in
the ionic conductivity of the electrolyte, which may be reversible by returning
the KOH to its original concentration. An alternate method involves simply
replacing the KOH which returns the cell back to its original output.
 When carbon dioxide reacts with the electrolyte carbonates are formed. The
carbonates could precipitate on the pores of electrodes that eventually block
them. It has been found that AFCs operating at higher temperature do not show
 a reduction in performance, whereas at around room temperature, a significant
drop in performance has been shown. The carbonate poisoning at ambient
temperature is thought to be a result of the low solubility of K2CO3 around
room temperature, which leads to precipitation of K2CO3 that blocks the
electrode pores. Also, these precipitants gradually decrease the hydrophobicity
of the electrode backing layer leading to structural degradation and electrode
flooding.

 On the other hand, the charge-carrying hydroxide ions in the electrolyte can
react with carbon dioxide from organic fuel oxidation (i.e. methanol, formic
acid) or air to form carbonate species.

 Carbonate formation depletes hydroxide ions from the electrolyte, which

reduces electrolyte conductivity and consequently cell performance. As well as
these bulk effects, the effect on water management due to a change in vapor
pressure and/or a change in electrolyte volume can be detrimental as well.

Catalyst

 The catalyst layer can use either platinum or nonprecious metal catalysts such
as nickel and the electrolyte has historically consisted of liquid KOH or a KOH
filled matrix. A disadvantage of AFCs is that pure hydrogen and oxygen have
to be fed into the fuel cell because it cannot tolerate the small amount of carbon
dioxide from the atmosphere.
 Anode Catalysts: Pt, Pd, Raney Ni
 Cathode Catalysts: Pt, Pd, Ag, MnO2

Advantages

 Alkaline Fuel Cells (AFCs) are easy to handle, have very high electrical
efficiency and are very suitable for dynamic operating modes.
 They can be built into small compact systems as well as in large power plants.
  The AFC has the highest electrical efficiency (around 70%) of all fuel cells, but
it typically uses very pure gases.
 They can operate at atmospheric pressure and low temperature
 They have good response time and fast start time
 They have low weight and volume, etc.
 AFCs are the cheapest fuel cells to manufacture. This is because the catalyst
required on the electrodes can be selected from a number of materials that are
relatively inexpensive compared with the catalysts required for other types of
fuel cells


Disadvantages

 It is easily poisoned by carbon dioxide (CO2). In fact, even the small amount of
CO2 in the air can affect this cell’s operation, making it necessary to purify
both the hydrogen and oxygen used in the cell. This purification process is
costly. Susceptibility to poisoning also affects the cell’s lifetime (the amount of
time before it must be replaced), further adding to cost.
 The high cost of catalyst and electrode used in the alkaline fuel cells, rapid
degradation of electrodes due to a corrosive environment, intolerance of carbon
dioxide, degradation of catalysts, poor durability.
 They have short operating life since they use a liquid solution of potassium
hydroxide(KOH) as an electrolyte that is highly corrosive, thus eroding its
parts.
 It required oxygen must be provided after purification since they are very
intolerant of carbon dioxide.
 The electrolyte used in corrosive and it can attack the components with which
it is contact.
 They have high costs for commercialized applications.
 In principle, AFCs are cheaper than PEMFCs, but bigger and heavier and also
the presence of liquids within the cells limits their use in mobile APUs.
Applications

 Alkaline fuel cells (AFCs) are one of the most developed technologies and
have been used since the mid-1960s by NASA in the Apollo and space shuttle
programs. The fuel cell onboard these spacecrafts provide electrical power for
onboard systems, as well as drinking water.
 Alkaline Fuel Cells (AFCs) have the advantage of being less sensitive to
impurities of the fuel. Typical power densities are in the 150 mW cm−2 range.
Hydrogen and also methanol can be used as fuel. There are AFC realizations
without and with platinum as catalytic material, some with about 70 W for
portables (military) and some with a power level of about 6 kW for stationary,
residential use.
 The world's first fuel-cell ship, the Hydra, used an AFC system with 5 kW net
output.
 Another recent development is the solid-state alkaline fuel cell, utilizing a solid
anion exchange membrane instead of a liquid electrolyte. This resolves the
problem of poisoning and allows the development of alkaline fuel cells capable
of running on safer hydrogen-rich carriers such as liquid urea solutions or metal
amine complexes.