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Technological development and prospect of alkaline fuel cells

Meng Ni a, Michael K.H. Leung b, Dennis Y.C. Leung c

a
Department of Mechanical Engineering, University of Hong Kong, Pokfulam Road, Hong Kong,
nmlemon@hkusua.hku.hk
b
Department of Mechanical Engineering, University of Hong Kong, Pokfulam Road, Hong Kong,
mkhleung@hku.hk
c
Department of Mechanical Engineering, University of Hong Kong, Pokfulam Road, Hong Kong,
ycleung@hku.hk

ABSTRACT:

This paper reviewed the technological development of alkaline fuel cell (AFC). Although the technology was
popular in 1970s and 1980s, there has been a decline in AFC research over the past decade, mainly due to
the poisoning of CO2. Continuous efforts have demonstrated that CO2 concentration could be reduced to an
acceptable level by a number of viable methods such as absorption, adsorption, electrochemical process,
electrolyte circulation, use of liquid hydrogen, and use of solid anionic exchange membranes. Literature
survey showed that AFC lifetime could achieve up to 5000 hours. In addition, the use of ammonia as a fuel
for AFC was identified as a promising technology. Comparison between AFC and proton exchange
membrane fuel cell (PEMFC) was presented to evaluate the AFC technology and its economics. The
present review and assessment showed the promise of AFC for the coming hydrogen economy and
sustainable development.

KEYWORDS: Alkaline fuel cell; Proton exchange membrane fuel cell; Hydrogen economy

1. Introduction

Alkaline fuel cell (AFC) was the first fuel cell technology applied to practical power generators. They
were introduced in 1960s, with great success in the Apollo missions [1]. Today, they are still serving as
power suppliers for space shuttles and drinking water supplier for astronauts. However, due to CO2
poisoning, AFC was considered not suitable for terrestrial transportation applications, as the ambient CO2
concentration far exceeds the acceptable level for an AFC. As a result, in early 1990s, R&D works on AFC
in many companies and institutions were drastically reduced, or even terminated [2]. For comparison, proton
exchange membrane fuel cells (PEMFC) emerged as a potential technology for transportation application
and attracted increasingly more attention. Since several methods have been developed to successfully
resolve the AFC CO2 poisoning problem in recent years, AFC re-emerged as a possible low temperature,
moderate power generator for terrestrial applications. It is well known that oxygen reduction reaction kinetics
is much faster in alkaline environment than in acidic environment; therefore, cheap nickel and silver, instead
of expensiive platinum, can be used as catalyst materials in AFC [3]. In addition, KOH solution is used as
electrolyte and thus expensive polymer membrane is omitted. The low cost of catalyst and electrolyte
materials result in a higher cost-effectiveness for AFC in comparison with other low temperature fuel cells,
i.e. PEMFC. In addition to economic competitiveness, AFC also has several other advantages. In an AFC,
the need for reactant gas humidification is eliminated, which is important and require additional equipments
for PEMFCs. Besides, the use of liquid electrolyte simplifies the cell cooling system, while for PEMFC, water
and thermal management is still a challenge [4]. Therefore, it’s necessary to re-evaluate the potential of
AFC technology for terrestrial applications. In this paper, the technological development of AFC was
reviewed. Challenges and possible solutions for AFC were discussed. Comparison between AFC and
PEMFC was also presented for a better understanding. The paper is structured as follows. In section 2, the
working principles of AFC are briefly described. Carbon dioxide poisoning and lifetime issues are
summarized in sections 3 and 4, respectively. Potential of using ammonia as a fuel was evaluated in section
5. In section 6, the comparison between AFC and PEMFC and the potential of AFC for terrestrial
applications are presented.

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2. Working principles

The working principles of AFC are illustrated in Fig. 1. Potassium hydroxide solution is normally
used as the electrolyte, with typical concentration of about 30%. Hydrogen is fed to the anode, where
hydrogen molecules are oxidized and combined with OH- to form water. Electrons are extracted to the
external load to provide power and then flow to the cathode, where oxygen reduction takes place. The OH-
ions produced at the cathode diffuse through the electrolyte to complete a cycle. The overall reaction is
given by
2H 2 + O 2 → 2H 2 O (1)

e- DC
e-

H2 O2

4OH-

Electrolyte
KOH solution
H2O

Anode Cathode
- -
H2 + 4OH 4H2O + 4e O2 + 2H2O + 4e- 4OH-
Figure 1. Operation mechanism of alkaline fuel cell

3. Effect of CO2 on electrode and electrolyte

3.1. CO2 poisoning

Like other fuel cells, alkaline fuel cells have limitations in the amount of impurities in their feed gas
stream. It is a common opinion that carbon dioxide contained in the oxidant gas stream can restrain
operation of alkaline fuel cells. This is regarded as the most serious problem for alkaline fuel cell
commercialization for terrestrial applications, as ambient air (with considerable amount of CO2) is used in
practical applications. The poisoning reaction is supposed to be [5-7]

CO2 + 2KOH → K2CO3 + H2O (2)

This reaction indicates that the CO2 in the feed stream can reduce the available OH- ions and thus reduce
the ionic conductivity of the electrolyte. This can result in an increase in electrolyte ohmic polarization. In
addition, reduction in OH- concentration reduces the electrolyte pH value and thus the electrochemical
reaction kinetics become low, which in turn increase the activation polarization. The effect of CO2 poisoning
on AFC electrolyte has been experimentally demonstrated [7]. The composition change of the electrolyte as
well as the low electrochemical reaction kinetics have been observed [7].
It was postulated that the carbonate (K2CO3) produced could precipitate and block the pores in the
electrodes [2]. This could impede gas transportation in the porous structure, which is important for
electrochemical reaction of the feed gas stream. Besides, the crystallized carbonate might destroy the layers
of the electrodes mechanically.
Al-Saleh et al. [8] studied the CO2 effect on AFC electrodes and found that degradation of Ag/PTFE
(polytetraflourethylene) electrode did not occurred at 72oC. At a temperature of 25oC, however, performance
degradation on Ag/PTFE electrode was observed in one experiment and K2CO3 precipitation was detected
by X-ray diffraction (XRD). However, when K2CO3 was mixed with KOH electrolyte, no precipitation of K2CO3
was observed in their XRD experiments for both Ni/PTFE and Ag/PTFE electrode. This study indicated that
the CO2 poisoning effect on AFC electrode was insignificant, if any.
Gulzow [2] developed gas-diffusion electrodes with a cold-rolling machine at German Aerospace
Research Establishment (DLR). With 5% CO2 in the H2 fuel stream, CO2 absorption by electrode and
dissolution into electrolyte were detected. However, no carbonate salt precipitation in the fine electrode pore
structure was observed. In 2004, Gulzow and Schulze [5] reported the long-term influence of CO2 containing
reaction gases on electrodes manufactured by the rolling process. It was found that the CO2 neither
mitigated the degradation process nor induced a new detrimental degradation process. Through the X-ray-

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induced photoelectron spectroscopy (XPS) analysis after operation of the silver anodes for more than 2600
hrs, no noticeable amount of carbonate salt precipitation was detected. As expected, the carbonate
concentration in electrolyte increased with operation time. As a result, the operation of AFC was terminated
after 3600 hrs due to the CO2 poisoning effect on electrolyte.

3.2. Strategies for controlling CO2 poisoning

From the above literature survey, it can be seen that CO2 imposes negligible effect on the AFC
electrode performance during normal operation, but its adverse effect on AFC electrolyte is significant. The
allowable concentration of CO2 for alkaline fuel cell is generally taken as 50ppm [9]. In order to minimize the
CO2 poisoning effect, a number of methods have been proposed, as described in the subsequent sections.

3.2.1. Soda lime absorption

It is well known that carbon dioxide removal can be successfully accomplished by absorption using
soda lime, lithium hydroxide or magnesium oxide in a canister [10-12]. Among all these materials, soda lime
is the cheapest and commonly used material for CO2 absorption. It was estimated that 1 kg of soda lime
could clean 1000 m3 air, which was sufficient to generate 135-250 kWh under normal alkaline fuel cell
operating conditions (20-30% oxygen utilization) [10,13,14].

3.2.2. Regenerative adsorbers using molecular sieves

Molecular sieve adsorption is also an effective process for CO2 removal [15]. The adsorption and
regeneration can be achieved by temperature swing, pressure swing, purge gas or any combination of the
three methods [16]. Normally several beds are used to increase adsorption capacity. Desorption can be
achieved by heating the beds to 250-350oC, followed by cooling down for cyclic operation. For effective CO2
removal, large bed and low gas velocity are required [13,14].

3.2.3. Electrochemical process

Interestingly, CO2 can be removed electrochemically by operating AFC at high current density for a
-
short time [14,17]. At high current density, a very low OH concentration at the anode side can be created.
-2
This effect causes CO3 to migrate to the anode, where the free carbonic acid is formed and then
decomposed into CO2 and H2 due to the electrolyzing at high current density. The reaction can be
expressed as,

H2CO3 → CO2 + H2 (3)

Then CO2 produced can be flushed out with H2 and vented from the system.

3.2.4. Electrolyte circulation

Replacing the liquid electrolyte every few hundred operation-hours is a practical and advantageous
method to mitigate the adverse effect of CO2, as the use of circulating KOH solution eases the thermal and
water management [6]. Kordesch et al. [18] applied AFC-lead acid battery hybrid system for electric vehicle
applications. Carbon dioxide was removed through circulating KOH solution combined with soda lime
absorbing. The lifetime of 4000 hrs, which was equivalent to 200,000 km of driving, could be achieved.

3.2.5. Use of liquid hydrogen

Liquid hydrogen can be used to condense CO2 out of the air. Ahuija [9,13,14] proposed this novel
and simple method to use liquid hydrogen as a fuel for alkaline fuel cell. In his design, hydrogen boil-off was
used to continuously sublime and remove CO2 from the air, prior to the purified air and hydrogen being
supplied to an alkaline fuel cell. Through both theoretical and experimental studies, it was found that a
regenerative process by refrigeration purification, using cooling from exergy recovery from liquid hydrogen,
could decrease CO2 concentration to below 10 ppm. Although no further study on this method has been
reported afterwards, it is a promising way for effective and practical CO2 removal, since liquid hydrogen is
also commonly used in both space and terrestrial applications.
In addition to the above-mentioned five methods for CO2 removal, recently, solid alkaline fuel cell
using anionic exchange membrane has been developed to cope with CO2 poisoning effect on liquid KOH
electrolyte [19-24]. Using a solid anion exchange membrane as electrolyte, CO2 dissolution into electrolyte
can be eliminated. This technology is rather new and further research is required to enhance its
performance. From the above literature survey, it can be seen that the CO2 problem can be successfully
resolved via a number of feasible methods, indicating the prospect of AFC for terrestrial applications.

4. Lifetime of alkaline fuel cells

Another major drawbacks confronting AFC is its lifetime. The main factors limiting AFC lifetime are
CO2 poisoning, corrosion, and electrode weeping [25-27]. Through the methods discussed in section 3, the

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CO2 problem can be resolved. For example, the AFC with circulating electrolyte could operate for 5000 hrs
[6]. The corrosion is easy to occur, as the hot KOH electrolyte is highly caustic. In order to prevent corrosion
of catalyst and metallic current collectors, graphite-coat or embedding the current collector into the diffusion
layer can be applied. During electrode preparation procedure, the electrode hydrophobicity may be
destroyed, leading to electrolyte penetration through the electrode. This process is called electrode
weeping, which prevents gas diffusion in the electrode layer. In order to inhibit this effect, optimized
electrode production is required [25-27]. With gas diffusion electrode prepared by rolling method, AFC could
operate for 3500 hrs even in an environment containing CO2 [5]. Due to the continuous efforts, AFC lifetime
of 5000 hrs is achievable for terrestrial applications. Recently reported AFC lifetime for different systems are
summarized in Table 1.

Table 1. Recent reported lifetime of AFC

AFC lifetime (hrs) Current density System information Reference

2
(mA/cm )

5000 100 Gas diffusion Ni-anode [2]

15000 50 Fuel cell for shuttle (NASA) [28]

5000 100 ZEVCO Alkaline Fuel Cell Module [29]

4000 100 AFC vehicle [18]

11000 100 Biomass-based fuel [30]

1200 100 Anode : Ni/PTFE [25]

3500 150 Ni, Cu/PTFE, Cu web [5]

5000 50 Anode : Ni/PTFE [27]

Cu web used for electric conduction

5000 100 Ag cathode [26]

5000 unknown Ammonia AFC [6]

5. Using ammonia as a fuel

As a hydrogen carrier, ammonia has been considered as one of a promising alternative fuels for
AFC. The characteristics of ammonia and the possibility of applying ammonia to AFC were discussed
recently [6,31]. The advantages of using ammonia as a fuel are summarized as follows [6,11,31-34]: (1)
Non-flammable: the explosion range of ammonia in air is narrow (15-28vol%); (2) Liquid at low pressure:
ammonia can be liquefied easily at ambient temperatures and pressure of 8-9 bar, so high-pressure vessels
are not required; (3) Ammonia contains more hydrogen than liquid hydrogen at the same volume ; (4) Low
cost: ammonia is worldwide produced mainly as a chemical feedstock for fertilizers; (5) Available distribution
technology: ammonia is easily distributed as it is widely used; (6) Simple to be cracked: ammonia can be
easily cracked at 500oC, expressed as, 2NH3 → N2 + 3H2 ; (7) Easy to detect leakage: ammonia has strong
odor, which is an alarming signal for leakage.

6. Comparison between AFC and PEMFC

Since the critical problem of CO2 could be resolved, it is beneficial to compare AFC with PEMFC to
evaluate its prospect for terrestrial applications. From the technological aspects, both fuel cells are low-
temperature fuel cells and have the advantage of fast startup, compared with high-temperature fuel cells
such as solid oxide fuel cell (SOFC) and molten carbonate fuel cell (MCFC). Although the achievable power
density of PEMFC is higher than that of AFC, water and thermal management in PEMFC is normally difficult
and requires considerable subsidaries. For comparison, water and thermal management is easy via
electrolyte circulation. But care should be given to deal with caustic electrolyte. In addition, NH3 and CO
have no adverse effect on AFC performance and NH3 can even be used as a fuel. In contrast, the presence

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of NH3 and CO in the gas streams could significantly reduce the performance of PEMFC. In order to sustain
PEMFC operation, concentration of CO must be controlled under 10 ppm, which require extremly high purity
reactant gases. From the economic point of view, AFC is more cost competitive as low cost metallic catalyst
and electrolyte materials can be used. For large-scale mass production, the cost of AFC was estimated to
be about US$400-500/kW [2]. In a more ambitious study, the cost of AFC was estimated to be US$150/kW
[35]. For comparison, PEMFC is more costly because expensive Pt and PEM are used as catalyst and
electrolyte, respectively. The mass production cost of PEMFC was estimated to be US$1833/kW [36].
Technological and economic comparisons between AFC and PEMFC are summarized in Table 2. It can be
seen that despite its lower power density, AFC is economically attractive; therefore, more R&D should be put
into this technology for practical applications.

Table 2 Comparison between AFC and PEMFC [31,35-38]

Alkaline Fuel Cell PEM Fuel Cell

Operating temperature (oC) Up to 260 Up to 90

Current density (mA/cm2) 300-600 >600

Voltage per cell (V) 0.8-0.85 0.65-0.7

Power density (W/cm2) ~0.2 0.3-0.8

Lifetime (hrs) 5000 Estimated to be 5000 hours

Catalyst Ni, Ag, non- precious metals Only noble metals can be used

Electrolyte KOH solution, cheap Proton exchange membrane,

expensive

Cost per Kw US$ 400-600 US$ 1800-2000

Water and thermal management Easy via electrolyte circulation Difficult

Recoverability after misuse High Low

Maximum fuel impurities

CO Not critical <10ppm

CO2 <50ppm Not critical

NH3 Not critical Very critical

7. Conclusion

In this study, the technological development of AFC was reviewed. The challenges and viable
solutions for AFC were discussed. Comparison with PEMFC was made to evalute the prospect of AFC for
practical applications. It is found that the CO2 poisoning effect on AFC can be effectively resolved by a
number of viable methods. In addition, AFC lifetine of 5,000 hours can be achieved, making AFC
techniquely feasible for terrestrial applications. Using ammonia as a fuel makes AFC more advantageous.
Compared with PEMFC, AFC is easy to maintain, except that care should be given when dealling with
caustic electrolyte. Existance of a small amount of CO or NH3 in the gas stream can apparently reduce
PEMFC efficiency. For comparison, AFC is more tolerant with impurities in the gas streams. In terms of
economics, AFC is more competitive, due to low cost of catalyst and electrolyte materials. With continuous
R&D efforts for further performance enhancement, AFC will play an important role in the development of
hydrogen economy.

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