Journal of Power Sources 187 (2009) 39–48

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Journal of Power Sources

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Review of gas diffusion cathodes for alkaline fuel cells

F. Bidault a , D.J.L. Brett b , P.H. Middleton c , N.P. Brandon a,∗
a
Department of Earth Science and Engineering, Imperial College London, UK
b
The Centre for CO2 Technology, University College London, UK
c
Faculty of Engineering and Science, University of Agder, Grimstad, Norway

a r t i c l e i n f o a b s t r a c t

Article history: This paper gives a technical background to alkaline fuel cells (AFCs), introducing the advantages and
Received 7 August 2008 drawbacks of the technology. AFCs offer the potential for low cost, mass producible fuel cells, without the
Received in revised form dependency on platinum based catalysts and (currently) expensive membrane electrolytes. The AFC uses
26 September 2008
relatively low cost electrolytes based on aqueous bases such as potassium hydroxide. The inherent CO2
Accepted 18 October 2008
sensitivity of the electrolyte can be addressed by filtering out the CO2 from the air intake using a simple
Available online 5 November 2008
scrubber and periodically replacing the liquid electrolyte.
A review of the state-of-the-art in gas diffusion cathode development is given. The overall cell perfor-
Keywords:
Alkaline fuel cell
mance and stability is dominated by the behaviour of the cathode, leading to a focus of research effort
Gas diffusion cathode on cathode development. The performance and durability of the gas diffusion electrode is very much
Electrode design dependent on the way in which the layer structures are fabricated from carbon and polytetrafluoroethy-
lene (PTFE). The choice and treatment of the carbon support is of prime importance for the final catalytic
activity. Noble metal and non-noble metal catalysts have been investigated and show good performance,
however, more work is still needed on cathode durability to ensure the long term success of the alkaline
fuel cell.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction Historically, four different types of AFC cells have been devel-
oped and a description of each has been given by Gulzow [10]. These
Alkaline fuel cells (AFCs) were the first practical working fuel cell can be summarised as follows: (i) cells with free liquid electrolyte,
following the pioneering work of Bacon [1]. AFCs can realise a high (ii) cells with liquid electrolyte in the pore-system, (iii) matrix cells
overall electrical efficiency greater than most other fuel cell types where the electrolyte is fixed in the electrode matrix, and (iv) falling
[2]. Recently, a system consisted of a 6 kW stack connected to the film cells. The one common aspect of these cells is that they all
grid showed an efficiency between 50 and 60% (LHV) [3]. The AFC use porous electrode architectures which are similar to the elec-
was developed and studied extensively throughout the 1960s to trode used in metal air batteries [12]. More recently, the alkaline
the 1980s [4], prior to the emergence of the proton exchange mem- anion-exchange membrane (AAEM) has attracted increasing atten-
brane fuel cell (PEMFC), which has subsequently attracted most of tion [13–15]. The feasibility of an AAEM direct methanol fuel cell
the attention from developers. However, primarily because the pre- has been discussed, taking into account the thermodynamic dis-
dicted cost reduction in PEMFCs remains problematic, a resurgence advantage induced by the pH difference across the membrane, and
of interest in AFCs has occurred in recent years [5–9]. The uti- kinetic advantages; it was concluded that the technology was worth
lization of non-noble metal catalysts and liquid electrolyte makes further study [16]. The development of AAEM fuel cells have several
the AFC a potentially low cost technology compared to PEMFCs, important advantages over conventional AFCs: (i) since there is no
which employ platinum catalysts and specially engineered elec- mobile cation there is no precipitated carbonate, (ii) no electrolyte
trolyte materials. Cost analyses have shown that ambient air AFC weeping, (iii) reduced methanol crossover, (iv) potentially simpli-
systems, for mobile and low power applications, are less expen- fied water management, due to the fact that the water is produced
sive than ambient air PEMFC systems, and that AFCs still have at the anode and consumed at the cathode, (v) a larger repertoire of
the potential of major improvements with modest investment effective catalyst materials, and (vi) potentially reduced corrosion
[10,11]. [17]. However, while the AAEM fuel cell holds great promise, devel-
opments still need to be made to achieve suitably conducting and
stable membranes.The anode electrode for AFCs has been less stud-
∗ Corresponding author. Tel.: +44 20 7594 5704; fax: +44 20 7594 7444. ied than the cathode, where catalyst containing platinum-group
E-mail address: [email protected] (N.P. Brandon). metals such as Pt/Pd has shown good performance and stability

0378-7753/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jpowsour.2008.10.106
40 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48

In most terrestrial applications, the KOH electrolyte is circulated

through the stack, which has some advantages over the alternative
immobilized systems which have been favoured in space applica-
tions such as Apollo and the Space shuttle. The use of a circulating
electrolyte allows thermal and water management to be easily
controlled. Moreover, impurities (e.g. carbon from electrodes or car-
bonates) can be easily removed, making the circulating electrolyte
systems less sensitive to CO2 poisoning than the immobilized elec-
trolyte systems. The OH− concentration gradient is also greatly
decreased and the build up of gas bubbles in the gap between
the electrodes minimized [28]. However, electrolyte leakage and
parasitic losses are challenging problems and need to be carefully
considered by developers. The main advantage of the immobilized
systems is the simplicity of construction and the ready removal
of product water from the hydrogen side of the system. However,
Fig. 1. Diagram showing the fundamentals of an alkaline fuel cell. such systems are very prone to degradation of the electrolyte due to
impurities, and require very pure hydrogen and oxygen to function
reliably. Because of this, they are ideally suited for space applica-
[18,19]. Nickel has also been studied as a potential low cost catalyst tions where tanked hydrogen and oxygen are used for propulsion.
for AFCs anodes [20,21]. Raney nickel, which offers the advantage As a consequence of the CO2 sensitivity, AFCs have tended to
of high surface area, has been shown to be one of the most active be demonstrated in special applications where pure hydrogen and
catalysts for the hydrogen oxidation reaction in alkaline media, but pure oxygen are provided, such as space. In such systems the KOH
has reported to suffer from deactivation [22–24] which could be electrolyte has been immobilized in a matrix constructed from thin
improved by the addition of copper [25] or treatment with H2 O2 asbestos sheets. Asbestos is the preferred material in this applica-
[26]. tion due to its exceptional stability and absorption properties. The
The power output and lifetime of alkaline fuel cells are directly use of a porous matrix, soaked with KOH, which allows the elimi-
linked to the behaviour of the cathode, where most of the polar- nation of moving parts, was developed by NASA. Bacon’s invention
ization losses occur, because the oxygen reduction reaction (ORR) of the double-layer sintered electrode made from nickel powder
is a slow reaction compared with hydrogen oxidation reaction at was the starting point of this technology, which led to its use as
the anode. As a consequence, cathode development requires spe- the electrical power source in the Apollo missions to the moon
cial attention to find the best catalyst and electrode structure to and later in the shuttle Orbiter. The Orbiter fuel cell system, which
combine performance and stability. After a brief technology back- operated at 4 atmospheres and 95 ◦ C, was manufactured by United
ground, this review focuses on the state-of-the-art gas diffusion Technologies Corp, (UTC) Fuel Cells. The system has given impres-
cathode materials and designs used with circulating electrolyte sive performance up to 470 mA cm−2 at 0.88 V. However, in order
AFCs. to achieve this performance, the electrodes required a high noble
metal loading of 10 mg cm−2 at the anode (80% Pt–20% Pd), and
20 mg cm−2 at the cathode (90% Au–10% Pt) [29].
2. AFC technical review
Alkaline fuel cells were the first fuel cell technology to be put into
mobile applications through its demonstration as the power source
In an alkaline fuel cell (Fig. 1), hydroxyl ions are produced at the
for a farm tractor in the late 1950s by Allis Chalmers. Union Carbide
cathode and migrate to the anode side where they react with hydro-
Corp. (UCC) developed circulating electrolyte systems leading to
gen. Some of the water formed at the anode diffuses to the cathode
the demonstration of Kordesch’s Austin A 40 fuel cell car for several
and reacts with oxygen to form hydroxyl ions in a continuous pro-
years on public roads in the early 1970s [4,30].
cess. The overall reaction produces water and heat as by-products
In more recent years, AFC companies such as Zetek [31,32]
and generates four electrons per mole of oxygen, which travel via
focused on the design of circulating electrolyte low temperature
an external circuit producing the electrical current.
unpressurised systems for backup power, stationary and mobile
The use of a non-noble metal catalyst is possible because the
applications. The aim was to achieve a low cost mass production
oxygen reduction reaction in alkaline media is more facile than in
fuel cell. Injection-moulded plastic frames (usually polypropylene),
acid media. As a consequence, higher voltages at a given current
which house the electrodes, were used to build the stack. Each
density can be obtained, leading to a higher electrical efficiency
frame was friction welded to the next to ensure that the stack was
[4].
leak-free. Low cost electrode production was ensured by the use
The main disadvantage of AFCs is that carbon dioxide can react
of standard industrial processes such as rolling (calendaring) and
with the electrolyte to form carbonate Eq. (1), decreasing the elec-
pressing.
trolyte conductivity, oxygen solubility and electrode activity. The
The electrolyte of choice for terrestrial applications running on
formation of precipitated carbonate Eq. (2) can also lead to the
air and industrial grade hydrogen is 30–40% KOH, circulated though
blockage of the electrolyte pathways and electrode pores.
the stack with a pump. This has the advantage of allowing easy
replacement when CO2 absorption has reached an unacceptably
CO2 + 2OH− → CO3 2− + H2 O (1)
high level. Moreover, circulating electrolytes provides a very effec-
CO3 2− + 2K+ → K2 CO3 (2) tive way of cooling the stack and heat recovery via a heat exchanger.
The system is designed to be as simple as possible as outlined in
Potassium hydroxide solution (KOH) is almost exclusively used (Fig. 2).
as the electrolyte because it has a higher ionic conductivity than The electrolyte circulation loop consists of a KOH tank, a KOH
sodium hydroxide solution, and potassium carbonate has a higher pump and a heat exchanger. During start up the KOH is heated to the
solubility product that sodium hydroxide, which renders the former desired operating temperature, typically 70 ◦ C. During operation
less likely to precipitate [27]. the heat exchanger is used to remove excess heat. This can be recov-
 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48 41

Fig. 4. Evolution in AFC system performance: H2 /air performance is shown as solid

lines and H2 /O2 performance is shown as dashed lines [29].
Fig. 2. Schematic of a circulating electrolyte alkaline system.

A 20,000 h life time of accumulated module operation has been

achieved by Siemens using a Ni-anode and Ag-cathode [33] and
ered for space heating applications. An air blower forces air into a
15,000 h with a shorter stack than usually used in the space-shuttle
CO2 scrubber (usually containing soda lime), from where the air is
by UTC [2]; however, this performance data was obtained with pure
directed to the air-intake. McLean estimates the cost of the scrub-
oxygen and hydrogen. When air is supplied to the system, even with
bing using soda lime between 0.2 and 2.6 Dollar cents/kWh [10].
scrubbing a large part of the CO2 , lifetime is much less. A stack made
The outlet air is directly exhausted to the atmosphere whereas the
by Zevco has been reported to have delivered power for 5000 h
hydrogen is re-circulated or dead ended for maximum efficiency.
using low platinum loading and a circulating electrolyte system
The hydrogen circulation is achieved by means of a jet pump which
[32]. Insufficient studies have been done to date and the durability
facilitates the evacuation of the excess water that is collected in a
of AFC systems remains a key issue, especially when using non-
water trap. The start-up/shut-down procedure is quick and easily
noble metal catalysts and air.
performed by means of a nitrogen purge [32–34].
Both monopolar [31,32] and bipolar stack designs [6,34] have
been demonstrated. The monopolar stack design (Fig. 3) presents 3. AFC gas diffusion cathode
several advantages: (i) low cost due to the avoidance of expensive
bipolar plates, (ii) stack thickness decreases as there is only one gas 3.1. Electrode design
chamber between two electrode, (iii) no mechanical pressure is
required because cells are usually glued or welded, (iv) modularity In general, AFC electrodes consist of several PTFE-bonded
of the power delivered by changing the external current connectors carbon-black layers, which fulfil different functions. The three-layer
and (v) the disconnection of a bad cell facilitates maintenance of the electrode structure shown schematically in Fig. 5, consists of a back-
stack [28]. However, the monopolar design is limited to a current ing material (BM), a gas diffusion layer (GDL) and an active layer
density of up to 100 mA cm−2 due to the losses associated with (AL). This design is preferentially used over single layer electrodes
current collection on the side of each electrode. By contrast, the [35]. More complex electrode designs with more than three layers
bipolar design demonstrates a uniform current density over all of have been reported, for example, two different GDLs on top of each
the electrode surface and higher terminal voltage with less power other and an AL, however such geometries are rare [28].
limitation, and is therefore the preferred geometry for high power The BM should have a high permeability to gases, high structural
applications [34]. strength, good corrosion resistance and high electronic conductiv-
Typical AFC performance obtained at different temperature and ity. In a monopolar design, the BM serves as the current collector,
pressure are given in Fig. 4. so metal screens, meshes or foams, usually made of nickel, are gen-
erally used. In bipolar designs, the BM is in direct contact with the
bipolar plate. This means the BM can also be made of carbon cloth
or porous carbon paper in a similar way to the design of PEM fuel
cells [34].

Fig. 3. Picture of a monopolar Zetek stack (University of Agder). Fig. 5. Design of a double layer electrode for a bipolar stack design.
42 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48

The GDL supplies the reactant gas to the AL and prevents the are the main characteristics of the carbon black structure. Stud-
liquid electrolyte from passing through the electrode. This effect is ies have been carried out in order to gain better control of the
often termed ‘weeping’. carbon structure during the fabrication process [45]. Oxygen and
Monopolar designs almost exclusively use a GDL made from hydrogen groups are introduced onto the carbon surface during
porous PTFE. The porosity is achieved by mixing the PTFE sus- the manufacturing process. The carbon-oxygen group is by far the
pension with sugar or ammonium carbonate. When sintered at most important and influences the physico-chemical properties of
elevated temperature, the ammonium carbonate filler decomposes, carbon blacks. Chemisorption of oxygen, and a build-up of carbon-
producing gas bubbles which create porosity in the PTFE film [36]. oxygen surface compounds, occurs at temperatures below 400 ◦ C,
Bipolar designs require a GDL that is electronically conducting. whereas decomposition of these compounds occurs above 400 ◦ C.
This precludes using pure PTFE and instead favours mixtures of Formation of these groups by oxidative treatment in gaseous and
PTFE with conducting carbon support [37]. The ratio of carbon/PTFE liquid phases has been comprehensively studied [44,46].
(25–60% PTFE) is a trade-off between the level of hydrophobic Despite the preference to use carbon black in gas diffusion elec-
behaviour of the PTFE and the conductivity of the carbon sup- trode (GDE) fabrication, alternative catalyst supports have been
port. Ideally the GDL should be completely water repellent and of tried. Hacker reported similar performance between silver and
metallic conductivity. platinum catalysts supported on carbon nanofibres showing the
The active layer (AL) contains the catalyst which is usually sup- capability of the fibres to provide the required porosity and pore
ported on carbon black and bonded together with PTFE. The carbon structure to obtain good performance [47]. Huang showed higher
black is chosen to have a high surface area to maximise the power performance using a binary catalyst support composed of carbon
density. The level of PTFE in the AL is less than in the GDL, typi- nanotubes (CNT) and active carbon black compared with a single-
cally the AL will contain between 2 and 25% PTFE, depending on support catalyst. The best performance was obtained when the
the level of hydrophobicity required. The basic function of the PTFE mass ratio was 50:50 [48]. Yang also showed good electrochemical
in the active layer is to bind the carbon black together, but still pro- performance with the same kind of binary support using MnO2 as
vide multiple three-phase contact points where gas, electrolyte and catalyst. A higher accessible surface area, an improved conductiv-
carbon supported catalyst meet [38]. Different structures depend- ity, and faster ORR kinetics explain the improvement [49]. Carbon
ing on the nature of the carbon support, carbon/PTFE ratio and nanotube/perovskite composite materials have also been tested by
electrode fabrication process can be obtained where electronic con- Weidenkaff with promising results [50].
ductivity, ionic transport and gas transport have to be provided [39].
3.3. Operational mechanism
3.2. Materials used in electrode fabrication
The electrochemical behaviour of the GDE can be controlled
AFC electrodes can be made of different materials with different by varying the structure of its component layers and in partic-
structures, but modern electrodes tend to use high surface area ular by varying the ratio of hydrophobic and hydrophilic pores
carbon supported catalysts and PTFE to obtain the necessary three within the carbon support. Two structures have been developed,
phases boundary (TPB). Electrode performance in AFCs depends on each playing a different role within the electrode. The primary
catalyst surface area rather than catalyst weight. As with all other ‘macro’ structure is formed at distances greater than 1 ␮m, and
fuel cells, the catalyst loading is a critical parameter in determining is created by the partial enclosure of the carbon particles by the
performance. The nature of the catalyst support is also of prime PTFE. It forms the skeleton structure which ensures electronic con-
importance to achieve high catalytic activity. ductivity throughout the electrode and also provides mechanical
PTFE is a hydrophobic polymer material which has become the support. Different macrostructures can be obtained by varying the
binding agent of choice since its commercial introduction in the carbon particle size and shape, the carbon/PTFE ratio, and the elec-
1950s by Dupont; although other materials are sometimes used trode fabrication process. The secondary ‘micro’ structure, created
(paraffin, polyethylene, polypropylene, wax etc.). It is available by the pore system inside of the carbon particles, depends on the
either as dry powder additives, or as a ready made aqueous sus- surface area and pore structure of the carbon used. This structure is
pension (containing proprietary dispersants). Both of these forms directly linked to the carbon manufacturing and activation process
have been used to make electrodes [39]. PTFE can be present in the which greatly influences the micro-porosity of the carbon parti-
form of spherical particles, fibrils or thin films on porous substrates cles [39]. Indeed, the carbon particles have been shown to consist
[40]. The PTFE penetrates deep into the sub-surface of the carbon of macropores which are hydrophobic, and micropores (<0.01␮m)
when the dispersion is mixed with the carbon black powder. How- which are hydrophilic. The hydrophilic and hydrophobic property
ever, generally it is necessary to melt the PTFE in order to provide of the carbon depends on the nature of the surface groups which
a thin film over the entire surface of the carbon black. This process can be selected by various thermal and chemical treatments. The
is usually called sintering and takes place at temperatures around hydrophobic macropores have been shown to play an essential role
320 ◦ C [41,42]. in gas mass-transport by acting as gas supplying channels. The ORR
The electrical, chemical and structural properties of carbon mechanism occurs in the hydrophilic micropores which are filled
make it an ideal material for use in AFC electrodes [43]. Carbon with electrolyte and on the boundary of micro and macropores
blacks, which are the most commonly used carbon support in AFC [51,52].
electrode fabrication, consist of carbon in the form of near spherical The TPB is formed in the outer regions of the carbon particle
particles obtained by the thermal decomposition of hydrocarbons. shell where it is covered by a film of liquid electrolyte at the inter-
High surface area is achieved in a separate step, by treatment with face between the carbon micro and macro structures. The carbon
steam at a temperature in the range of 800–1000 ◦ C. The inner core particles arrangement is described as a ‘tight bed of packed spheres’
of the carbon particle is less ordered than the outside, and as a con- where the large vacancies between the particles are filled with
sequence the action of the steam causes large numbers of pores to electrolyte ensuring the ionic transport and where the carbon pore
form which interconnect to create the characteristic high surface system and hydrophobic channels created by the PTFE ensure the
area. The particle, however, does not completely disintegrate, but gas transport as shown in Fig. 6 [39].
remains agglomerated to its neighbours. Specific surface areas of The thicknesses of the different layers have to be controlled to
over 1000 m2 g−1 can be obtained [44]. Porosity and surface area optimise electrode performance. The GDL thickness has to be as
 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48 43

Fig. 6. Schematic illustration of the carbon macro and micro structure within the
active layer.

thin as possible to maximise oxygen accessibility, while the AL has

to be optimized to maximise the reaction area constituted by the
Fig. 8. Electrode fabrication: the rolling method.
TPB. Kiros obtained maximum limiting current densities with two
different catalysts, the AL thickness lying between 0.5 and 0.6 mm
[53]. Further single cell (anode/electrolyte/cathode) models have
shown that cathode reaction kinetics are particularly important
3.4. Electrode modelling in determining the overall cell performance, predicting that the
diffusion of dissolved oxygen contributes most to the polarization
Many publications have discussed the behaviour of porous elec- losses at low potentials (high current region), while the electronic
trodes in alkaline fuel cells. Whereas some authors have focused resistance contributes most at high cell potentials (low current
on specific issues such as current distribution [54], or the degree region). As a consequence, cell performance can be increased by
of catalyst utilization [55,56], the majority have tried to under- means of improved cathode fabrication methods, in which both
stand the overall mechanism of operation in the GDE related to the gas-liquid and liquid-solid interfacial surface areas are increased
structure; considering factors such as gas diffusion and electrolyte and the diffusion path of dissolved oxygen to catalytic sites is
penetration. Several models have been used such as the simple pore reduced [30,56,66–68].
model [57], the thin film model [58] or the dual scale of poros-
ity model [59]. In the former, a range of porosities is considered, 3.5. Electrode fabrication
where macropores are gas filled and micropores are electrolyte
filled [60,61]. Giner [62] listed the limitations of this ‘flooded porous Since different electrode structures lead to different cathode
electrode’ model introducing the concept of ‘flooded agglomerates’. performance, the electrode fabrication requires special attention
The operational mechanism of this structure, shown in Fig. 7, con- where the gas permeability of the GDL and the wettability of
sists of catalyst particles which form porous agglomerates ‘flooded’ the AL are the two main performance-limiting factors [69]. Struc-
with electrolyte under working condition. The agglomerates are tural parameters of the different layers can to be optimized by
kept together by the PTFE which creates hydrophobic gas channels. varying the carbon support used, the carbon/PTFE ratio and the
Reactant gases diffuse through the channels and dissolve in the fabrication conditions to obtain the best cathode performance
electrolyte contained in agglomerates to react on available catalyst [12,39,70–72]. The electrochemical performance of the electrodes
sites. It has been reported elsewhere that the concept of ‘flooded is also controlled by the initial porous structure and chemical sur-
agglomerates’ gives a satisfactory explanation for the behaviour of face properties of the active carbon, which in turn depend on the
PTFE-bonded gas diffusion electrodes, and is in good accordance process fabrication route. An activation step appears to improve the
with experimental findings [40,63–65]. electrochemical activity and stability of the carbon black by means
of thermal, physical and chemical treatments [73,74]. Increased
surface area, formation of a defined inter-pore structure and an
increased surface activity by the formation of catalytically active
groups on the surface occurs during such treatment. The activity of
carbon black is proportional to its surface area, the higher the bet-
ter [75]. High temperature treatment leads to a higher surface area
and as a consequence to a higher electrochemical activity. Carbon
pre-treatment needs to be specific to the type of carbon black. For
example, the surface area has been found to increase significantly
for Vulcan XC-72 in the presence of CO2 , whereas a N2 atmosphere
is required for Ketjenblack when heat-treated at 900 ◦ C [76].
Pressing, rolling, screen-printing and spraying methods are used
in the production of AFC electrodes [72,77]. The rolling method is
the most commonly applied. The process shown in Fig. 8 is generic
and variations include addition of filler materials such as sugar
or ammonium bicarbonate, along with various washing or dry-
ing steps. If PTFE powder is used and ground with the carbon,
Fig. 7. Schematic illustration of the ‘flooded agglomerate’ model. the method is referred to as the ‘dry-method’. If PTFE suspension
44 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48

and water are mixed with the carbon black it is referred to as the facilitate the 4-electron transfer process at high pH is relatively
‘wet-method’ [71]. small compare to the potential required at low pH in the case of
The method of mixing the carbon black with the PTFE will Ag (111). At high pH, no specific chemical interaction between the
have a direct effect on the electrode activity and stability. Musilova catalyst and O2 or O2 − is required, whereas strong chemical inter-
showed that using an aqueous PTFE deposition process onto the action is necessary at low pH. Blizanac also explained how the low
carbon surface leads to a hydrophobic blend. However, if ethanol is activity of catalysts in acid media is exacerbated by the presence
used instead, the electrode is more hydrophilic [78]. Motoo and of spectator species adsorbed onto the electrode surface, which act
Watanabe showed that very fine networks of gas channels are to physically block the active sites and also lower the adsorption
needed in the AL to obtain high performance. Since diffusion of energy for intermediates, so retarding the reaction rate.
dissolved reactant gas is a limiting factor for high current genera-
tion, good dispersion of the carbon and PTFE particles is required 3.7. Cathode catalyst materials
to increase the number of gas dissolving sites and reduce the dif-
fusion path length of dissolved gas to the catalyst sites, resulting Due to the inherently faster kinetics for the ORR in alkaline
in a performance increase. To achieve this, new techniques of fab- media, a wide range of catalysts have been studied including noble
rication have been applied involving, for example, colloid mill and metals, non-noble metals, perovskites, spinels, etc. However, it is
ultrasonic agitation [79–81]. important to appreciate that the carbon support plays a role in the
kinetics as well as the catalyst supported on its surface, so that in
3.6. The oxygen reduction reaction (ORR) in alkaline media evaluating the performance, it is necessary to assess the loading
of the catalyst and the type of carbon used where its hydrophobic
Optimizing the cathode performance is essential because it gov- properties as well as its surface groupings greatly affect the final
erns the overall performance of the fuel cell. According to Bockris hydrophobic structure and the TPB length of the electrode. The per-
at high current density, 80% of the polarization may be due to the formance of the catalyst/support system is considered since carbon
oxygen reduction [2]. The ORR is a complex process involving four participates in the reaction by a 2-electron process. The catalytic
coupled proton and electron transfer steps. Several of the elemen- activity of the system is directly linked to the physical and chem-
tary steps involve reaction intermediates leading to a wide choice ical characteristics of the carbon support. The catalyst deposition
of reaction pathways. The exact sequence of the reactions is still not method is critical since a high catalytic activity relies on a very
known, and identification of all reaction steps and intermediates, fine and well dispersed catalyst particle. In the case of platinum,
and their kinetic parameters is required, which is clearly challeng- the particle size is generally in the nanometre range. The carbon
ing. Appleby has reviewed and discussed the issues relating to the impregnation of metal salt solution with further reduction of the
ORR in acid and alkaline solution [82]. In acid electrolyte, the ORR metal is commonly used, and well known for it simplicity and abil-
reaction is electrocatalytic, as pH values become alkaline, redox ity to produce metal nanoparticles with nearly mono-dispersed size
processes involving superoxide and peroxide ions start to play a distribution and easy scale-up.
role and dominate in strongly alkali media. The reaction in alkaline
electrolytes may stop with the formation of the relatively stable 3.7.1. Noble metal catalyst
HO2 − solvated ion, which is easily disproportionated or oxidized Platinum is the most commonly used and active catalyst for the
to dioxygen. Although there is no consensus on the exact reaction electro-reduction of oxygen and all of the platinum-group metals
sequence, two overall pathways take place in alkaline media [83]: reduce oxygen in alkaline media according to the direct 4-electron
process [87–95]. At a very low Pt/C ratio, the overall number of
(i) Direct 4-electron pathway electrons exchanged is approximately two due to the carbon con-
tribution, but increases as the Pt/C ratio increases, reaching four
O2 + 2H2 O + 4e− → 4OH− (3) electrons at 60% wt.Pt [96]. Pt-based alloys have been studied and
Peroxide pathway or ‘2 + 2-electron’ pathway: generally exhibit higher activity [97] and stability [98] than Pt-
alone. The enhanced electrocatalytic activity of Pt-alloy systems has
O2 + H2 O + 2e− → HO2 − + OH− (4) been explained by a number of phenomena, including: (i) reduc-
With tion in Pt–Pt bond distance, favouring the adsorption of oxygen; (ii)
the electron density in the Pt 5d orbital and (iii) the presence of sur-
HO2 − + H2 O + 2e− → 3OH− (5) face oxide layers [96,99–102]. Due to the high cost of Pt, techniques
have been developed to reduce loading [56,96,102–104]. For exam-
The peroxide produced may also undergo catalytic decomposi- ple, monolayer deposition of Pt on non-noble metal nanoparticles
tion with the formation of dioxygen and OH− , given by: showed improved catalytic properties with a very small amount
of Pt [104,105]. The carbon impregnation with hexachloroplatinic
2HO2 − → 2OH− + O2 (6)
acid solution (H2 PtCl6 .6H2 O) followed by metal reduction using
The kinetics of the ORR reaction is more facile in alkaline heat treatment or wet chemical methods, have been widely used
medium than in some acid medium such as H2 SO4 [84]. This is to produce a catalyst particle size lying between 12 and 34 nm
also illustrated by the comparison made by Blurton [85] for the [48,78,96,106,107]. A more complex colloidal precursor deposition
operating potentials of a fuel cell running on H2 /O2 at a controlled technique showed a PtRu particle diameter close to 2 nm [108,109].
current density of 100 mA cm−2 at 70 ◦ C with platinum electrodes. Silver has been studied as a potential replacement of Pt due to
These workers reported a potential of 0.67 V for 13.9 M H3 PO4 and its high activity for the ORR and its lower cost. Silver in alkaline
a potential of 0.89 V for 6.9 M KOH versus a hydrogen reference solutions is oxidized in two steps; first a layer of Ag2 O is formed
electrode. The higher voltage (performance) of the alkaline system which is partly oxidized in the second to AgO [110]. ORR occurs
was explained by the preferred formation of peroxide species in with the participation of 2 and 4-electron processes, depending on
the alkaline medium which desorbs more readily than in the acid the surface state and in particular on its oxidation state and elec-
counterpart. trode potential [47,111–119]. The size of the Ag particles affects the
Blizanac [86] used a thermodynamic analysis to explain the ori- different catalytic activity for these two processes. Four electrons
gin of the pH effect, showing that the overpotential required to are exchanged during ORR on nano-dispersed silver particles on
 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48 45

generated by the discharge of MnO2 rather than through a direct

2-electron reduction [133]. ␥-MnOOH exhibits higher activity than
␥-MnO2; this has been explained by the fact that amorphous man-
ganese oxide has more structural distortion and is more likely
to have active sites compared to crystalline manganese oxides
[126,134].
Pyrolysed macrocyles on carbon supports have been studied
in alkaline media showing high activity towards the ORR. Cobalt
phthalocyanine has been shown to reduce oxygen with simi-
lar kinetics to that of Pt [135]. Electrodes made of Cobalt/Iron
tetraphenylporphyrin (CoTPP, FeTPP) demonstrated good per-
formance, outperforming electrodes made of silver catalysts.
Structural changes and increased surface area is required to
enhance the catalytic activity, which is obtained by chemical and
heat treatment of the carbon and the porphyrins [37,71,136]. This
high catalytic activity was attributed to the combined effect of the
macrocycle black and Co; however, poor stability has been shown
where the loss of Co appeared to be important, leading to perfor-
Fig. 9. TEM photograph for reduced carbon-supported silver nanoparticles [110]. mance deterioration [137]. CoCO3 + TetraMethoxyPhenylPorphyrin
(TMPP) + carbon showed better performance than CoTMPP + carbon
carbon, with an optimum loading lying between 20 wt% [112] and confirming the fact that the structure of the metal macrocycle is not
30 wt% [114]. The effect of electrolyte concentration is positive for responsible for catalytic activity, but its origin is due to the simulta-
silver catalyst but not for Pt catalyst, which is slightly hindered due neous presence of the metal precursor, active carbon and a source
to greater absorbed species coverage. Silver becomes competitive of nitrogen, supposed already to be part of the catalytic process
to Pt due to favoured kinetics in high concentration alkaline media [138,139].
[47,111], but shows a strong propensity to dissolution at open circuit Perovskite-type oxides, which have an ABO3 -type crystal struc-
voltages following Eq. (7) [28]: ture, have shown a high cathode activity in alkaline media
proceeding by a 2-electron pathway where HO2 − is further reduced
4Ag + O2 + H2 O → 4Ag+ + 4OH− (7)
[140]. Good performance has been reported with different cat-
At an overpotential of 100–300 mV, this dissolution was found alyst composition such as La0.5 Sr0.5 CoO3 , La0.99 Sr0.01 NiO3 [141],
not to be significant [114]. The impregnation of AgNO3 is commonly La1−X Ax CoO3 (A = Ca, Sr) [142], Ca0.9 La0.1 MnO3 [143] and Pr0.6 Ca0.4
used, associated with different techniques of Ag reduction [47,120]. MnO3 , La0.6 Ca0.4 CoO3 [144]. The catalyst support choice seemed
Chatenet using impregnation of AgNO3 and electrochemical reduc- to be crucial to obtain stable performance. Graphite supports
tion in sulphuric acid to obtain silver particle sizes in the range appeared less stable [145] than high surface area carbon black [140].
5–10 nm (Fig. 9) [111]. A spinel is a ternary oxide with an AB2 O4 structure in which the
choice of the B cation is critical since it plays an important part in the
3.7.2. Non-noble metal catalyst activity of the catalyst [146,147]. Studies of MnCo2 O4 catalysts have
Whereas carbon supports show poor electrochemical activity in mainly indicated an ORR mechanism that involves a 2-electron pro-
acidic media [121], carbon blacks and graphite have been shown to cess with HO2 − formation [148,149]. The catalytic activity depends
catalyse the ORR in alkaline media with the formation of HO2 − in a greatly on the preparation route; the decomposition of Co and Mn
two electron process Eq. (2), where high surface area carbon blacks nitrates and subsequent heat treatment is most commonly used
such as Vulcan XC-72R (25 nm, 250 m2 g−1 ) showed an increased [150–152].
activity [74,75,121–123].
Recently, manganese oxides have attracted more attention as 3.8. Performance
potential catalysts for both fuel cells [124,125] and metal-air bat-
teries [126] because of their attractive cost and good catalytic A summary of the data in the literature describing cathode per-
activity toward O2 reduction. The investigation of different man- formance for different catalysts is given in Tables 1 and 2, which
ganese oxides dispersed on high surface area carbon black showed have been separated according to whether the measurements were
low activity for MnO/C and high activity for MnO2 /C and Mn3 O4 /C. made in oxygen or air. All the potentials are reported against an
The higher activity of MnO2 was explained by the occurrence of Hg/HgO reference electrode, the KOH concentration lying between
a mediation process involving the reduction of Mn(IV) to Mn(III), 5 and 8 M. The electrolyte temperature varied between 25 and 70 ◦ C
followed by the electron transfer from Mn(III) to oxygen. The reac- and is reported for each instance.
tion was sensitive to the manganese oxide/carbon ratio in which,
at lower ratios, the reaction proceeds by the 2-electron pathway, 3.9. Electrode durability
evolving to an indirect 4-electron pathway with disproportion-
ation of HO2 − into O2 and OH− at higher catalyst/carbon ratios Several degradation rates have been reported; Tomantschger
[126–129]. The catalytic activity for the disproportionation reaction reported performance degradation under working conditions of
has led to a new approach of dual system catalysis in which one 10–30 mV/1000 h over a period of 3500 h at 0.1 A cm−2 [141].
catalyst is used for the reduction of O2 through the two-electron Gouerec showed a degradation rate of 5–10 mV/1000 h over a
process producing HO2 − , which is subsequently decomposed by period of 2800 h at 0.1 A cm−2 [19]; Gulzow reported, over 3500 h at
MnO2 , leading to a four-electron process [130–132]. The MnO2 cat- 0.15 A cm−2 , a degradation rate of 17 mV/1000 h with silver based
alytic activity was found to vary following its crystalline structure in electrodes [139]. Several causes or effects have been proposed to
the sequence: ␤-MnO2 < ␭-MnO2 < ␥-MnO2 < ␣-MnO2 ≈ ␦-MnO2 , explain the degradation of AFC cathode performance with time;
in which higher activity seems to go with higher discharge ability, they are described in the following sections. The understanding of
proceeding through chemical oxidation of the surface Mn3+ ions these effects and their studies is very important in the develop-
46 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48

Table 1
Cathode performance using different catalysts with O2 .

Catalyst KOH Temperature (◦ C) KOH Concentration (M) Potential vs. Hg/HgO (V) Current Density (mA cm−2 ) Source

Pt/Pd/C 4wt.%Pt/6wt.%Pd 25 6 −0.1 900 [153]

−0.2 1600
−0.3 2100

Ag/C 47 mg cm−2 70 7 −0.1 250 [118]

−0.2 540

La0.5 Sr0.5 CoO3 /C 7%wt 25 6 −0.1 250 [141]

−0.2 700
−0.3 1600

CoTPP/C 1.76 mg cm−2 40 5 −0.06 150 [37]

−0.14 600
−0.18 950

La0.6 Ca0.4 CoO3 /C 9–13 mg cm−2 25 6 −0.1 150 [145]

−0.2 500
−0.3 1000

Table 2
Cathode performance using different catalysts with air.

Catalyst KOH Temperature (◦ C) KOH Concentration (M) Potential vs. Hg/HgO (V) Current density (mA cm−2 ) Source

Pt/CNT/C 100 ␮g cm−2 25 6 −0.2 125 [48]

−0.5 520

Pr0.8 Ca0.2 MnO3 /C 50 wt.% 60 8 −0.1 115 [144]

−0.15 260

CoTMPP/C Not known 25 5 −0.1 140 [71]

−0.2 350
−0.25 500

MnO2 /C 3.63 mg cm−2 25 8 −0.2 91 [154]

−0.5 440

LaMnO3 /C 6.9 mg cm−2 60 8 −0.08 300 [155]

−0.1 400

MnCo2 O4 /C 14 mg cm−2 60 6 −0.1 150 [152]

−0.2 300

ment of increased AFC lifetimes. However, few studies have been conductivity, which could be mitigated by exchanging the elec-
reported in the literature to date. trolyte every few hundreds hours (McLean estimates the KOH cost
at 0.25 dollar cents/kWh if the electrolyte is changed every 500 h
for a stack lifetime of 5000 h. Based on published evidence, the CO2
3.9.1. CO2 effect
effect seems to be electrode structure dependant, wherein the pore
Carbon dioxide is generally believed to be detrimental to the
structure of the electrode is crucial. Sato observed a different CO2
performance of the alkaline electrolyte due to the formation of
effect on the cathode stability depending on the carbon support
carbonate species which will eventually cause a decrease in ionic
used. It was found that CO2 had a strong effect on cathode stability
conductivity. Thus, air is generally scrubbed to reduce the CO2 con-
when electrodes were prepared from activated carbon. No CO2 dis-
tent to between 5 and 30 ppm, depending on the technology used,
solution or progressive wetting was observed with Asahi-90 black
before it enters the fuel cell [19]. However, residual CO2 reacts to
which was explained by the small particle size of this carbon and
form carbonate ions following Eq. (1), which increases the ionic
its compact electrode structure [158].
resistance of the KOH because the conductivity of CO3 2− is lower
than that of OH− . If carbonate formation occurs, it forms in the
pores of the electrode active layer. Subsequent mass transport will 3.9.2. Corrosion effect
take place causing the carbonate species to be transferred to the The degradation reported by Tomantschger [159] of the electro-
bulk liquid electrolyte. If the wash out process, which depends on chemical performance of the electrode with increasing operating
the porosity of the AL and the electrolyte viscosity, is fast enough, time was assigned to the corrosion of carbon, and PTFE degrada-
no CO2 effect is observed; otherwise potassium carbonate is pre- tion caused by the KOH electrolyte. The carbon is slowly oxidized
cipitated in the pores Eq. (2) blocking them, or causing destruction due to attack by the HO2 − radical formed as an intermediate
of the structure due to the expansion of the precipitate [156]. during oxygen reduction. Korovin [160] identified the discreet pro-
Authors are not unanimous on the effect of CO2 on cathode cesses of electrocatalyst deterioration as composed of corrosion,
degradation. Whereas Rolla [156] attributes CO2 to be the main fac- chemical dissolution, cathode hydrogenization and metal interca-
tor determining cathode ageing, Gulzow [157] has demonstrated lation. An increase in current density, temperature and ligand (OH− )
3500 h of operation with a cathode in the presence of CO2 con- concentration was found to accelerate corrosion. A multi-catalyst
centrations 150 times that in air, asserting that CO2 in air had system has been proposed to increase lifetime using the most stable
no influence on the cathode, but rather degradation in the fuel support in a compromised conditions (medium electrolyte concen-
cell performance was attributed solely to its impact on electrolyte tration, etc.). PTFE was shown to lose some hydrophobicity after
 F. Bidault et al. / Journal of Power Sources 187 (2009) 39–48 47

KOH exposure, which was attributed to surface chemical changes. range of options for the materials support and catalyst, as com-
It was shown that the contact angle reached a minimum; the higher pared to acidic media which offers more limited materials choice.
the KOH temperature and concentration, the shorter the time taken Alternatives to platinum have been investigated, showing good per-
to reach this minimum [161]. formance, comparable sometimes to platinum itself, but more work
is needed to meet the durability targets required for commercial
application.
3.9.3. Weeping and flooding effects
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