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Applied Energy 74 (2003) 113–124

www.elsevier.com/locate/apenergy

Aluminum–hydrogen peroxide fuel-cell studies


David J. Brodrecht, John J. Rusek*
Swift Enterprises Ltd., 1291 Cumberland Avenue, Suite B102, West Lafayette, Indiana 47906, USA

Abstract
Swift has developed an Al–H2O2 semi fuel-cell (SFC) that uses a novel approach to increase
the maximum power output of the cell. Pure, high surface area aluminum flakes, courtesy of
Transmet Corporation of Columbus, Ohio, are compressed to form the anode of the fuel cell.
Using compressed flakes creates a greater surface area than is available with planar electrodes.
The cathode is a gold-plated mesh, which allows the potassium hydroxide electrolyte and
H2O2 oxidizer to flow through. A nylon mesh is situated between the cathode and anode in
order to prevent short circuiting within the cell. This paper reports upon the viability of using
these compressed aluminum flakes with hydrogen peroxide in a fuel-cell system. Tests are
conducted to determine the maximum power available, the duration of the cell’s effectiveness,
and the efficiencies associated to corrosion of aluminum and decomposition of hydrogen
peroxide. The above figures-of-merit are used to determine the optimum porosity of the alu-
minum anode. This porosity is also bounded by its ability to keep the electrical connection
without breaking apart in the solution. Also discussed is the optimization of the potassium-
hydroxide electrolyte and the hydrogen-peroxide concentrations.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Fuel cell; Aluminumm; Hydrogen peroxide; Power density; Portable power

1. Introduction

The aluminum–hydrogen peroxide semi-fuel cell (SFC) has been under study by
Swift as well as Purdue University and the US Navy, for a variety of uses in volume
limited applications. Work at Purdue University was focused upon the use of com-
mon aluminum alloys [1], while Swift is currently looking at the use pure aluminum
flakes. The most predominant application to date has been in unmanned underwater
vehicles (UUVs). UUVs require high energy and power densities, and do not have the
benefit of using oxygen from air as an oxidizer. Aluminum provides an abundance of

* Corresponding author. Fax: +1-765-464-1877.


E-mail address: john.rusek@swiftenterprises.net (J.J. Rusek).

0306-2619/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0306-2619(02)00137-X
114 D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124

electrochemically available energy. Hydrogen peroxide is an ideal, high energy den-


sity, oxidizing agent and is easier to store on board a UUV than compressed oxygen.

1.1. Aluminum–hydrogen peroxide reactions

Initial work on aluminium–hydrogen peroxide fuel cells was conducted by Zar-


omb beginning in the late 1960s [2]. Since then, work has been accomplished upon
these fuel cells [3–9] and other metal hydrogen-peroxide fuel-cells [10,11].
The reaction mechanisms for aluminum and hydrogen peroxide in a semi-fuel cell
have been elucidated in a couple of these papers [3,9]. Specifically, there are the
desired electrochemically coupled oxidation and reduction reactions, and three detri-
mental chemical reactions. These undesirable reactions include an aluminum corro-
sion reaction, hydrogen-peroxide decomposition, and a direct aluminium–hydrogen
peroxide reaction.
The electrochemical reaction has two parts: a reaction that occurs at the cathode,
and a reaction that occurs at the anode. The reactions are as follows:
Anode reaction:
2AlðsÞ þ 8OH ðaqÞ ! 2AlO
2 ðaqÞ þ 4H2 OðlÞ þ 6e

ð1Þ
Cathode reaction:
3HO  
2 ðaqÞ þ 3H2 OðlÞ þ 6e ! 9OH ðaqÞ ð2Þ
Overall reaction:
2AlðsÞ þ 3HO 
2 ðaqÞ ! 2AlO2 ðaqÞ þ OH ðaqÞ þ H2 OðlÞ ð3Þ
The anode and cathode reactions are both considered half reactions. The asso-
ciated electromotive force is, for the anode reaction, 2.31 V, and for the cathode
reaction, 0.87 V. These voltages are with respect to a reference hydrogen electrode at
unit activities. This gives an overall voltage of 3.18 V.
Another aluminum corrosion reaction is detrimental to the efficiency of the fuel cell.
While it is an electrochemical reaction, it does not induce an electron flow. Aluminum
is effectively wasted and hydrogen gas is evolved. The reaction is as follows:
2AlðsÞ þ 2OH ðaqÞ þ 2H2 OðlÞ ¼ 2AlO
2 ðaqÞ þ 3H2 ðgÞ ð4Þ
The aluminum efficiency ("Al) is calculated as a ratio of aluminum involved in the
electrochemical reaction and the total amount of aluminum reacted. The majority of
the non-electrochemically reacted aluminum results from this reaction. The other
major problem from this reaction is the evolution of hydrogen-gas bubbles, which
can block a usable anode or cathode surface area. This is a major problem that will
be discussed later.
Another major contributor to reducing efficiency is the decomposition of hydro-
gen peroxide. H2O2 is a highly reactive substance that decomposes quite readily in
the presence of contaminants. This reaction evolves oxygen gas as seen below:
2H2 O2 ðlÞ ¼ O2 ðgÞ þ 2H2 OðlÞ ð5Þ
D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124 115

This reaction can be the most problematic when dealing with concentrations of
over 50% since the decomposition accelerates itself with the production of heat. The
efficiency associated with the loss of hydrogen peroxide is symbolized by "HP. In
order to alleviate this, H2O2 should be stored separately from the electrolyte. Once
again, decomposition within the cell causes gas bubbles, which can reduce the elec-
trode surface area.
Finally, there is the direct reaction of aluminum. This reaction appears to be the
same as the overall electrochemical reaction, but the mechanism is entirely different.
Contact between the aluminum and the peroxide ion is the cause of the chemical
reaction. Therefore, no current is being sent through the external circuit.
2AlðsÞ þ 3HO  
2 ðaqÞ ¼ 2AlO2 ðaqÞ þ OH ðaqÞ þ H2 OðlÞ ð6Þ

1.2. Flow system

There are two basic flow system set-ups for a metal hydrogen peroxide semi-fuel
cell. There can be a dual-channel flow system, and a single-channel flow system.
Both have advantages and disadvantages depending on the application and the type
of metal used. These are described in the following subsections. The dual-channel
semi-fuel cell has separate flow paths for the oxidizer and electrolyte. This is similar
to H2-O2 fuel-cells which have one stream for hydrogen, and one stream for oxygen.
The primary purpose for separating the hydrogen peroxide and electrolyte is because
H2O2 is known to poison the aluminum corrosion reaction [3]. One problem asso-
ciated with the dual flow system is the added complexity of having two flow systems.
This adds to the volume and weight of the entire cell. Also problematic is the added
cost of a porous membrane and cathode.
The single flow-channel fuel-cell was the one chosen for studies at Purdue and at
Swift. The primary reason for this was the relaxed requirement on the cathode and
to simplify the flow system. With a single-flow system, the cathode does not need to
be porous, as it would be in a dual-flow system. The cell configuration in a planar
format is shown in Fig. 1.
The fuel cell under study uses separate streams of hydrogen peroxide and recycled
electrolyte. These are mixed just prior to entering the cell. Another variation of the
flow system could involve a non-recycling electrolyte. However, this would not be an
efficient use of the electrolyte in a laboratory setting. This would be possible in deep-
sea applications, where sea water would act as the electrolyte.

2. Experimental

The first generation aluminum-hydrogen peroxide fuel-cell was designed by Swift


to utilize pucks of compressed aluminum flakes from Transmet Corporation. These
flakes are 99.93% pure aluminum, manufactured using Transmets rapid solidification
technology [12]. Table 1 shows the concentrations of various elements in the alumi-
num flakes. These values were found by Transmet using ICP mass spectrometry.
116 D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124

Fig. 1. Single flow-path fuel-cell configuration.

Table 1
Composition of aluminum flakes

%Al %Cu %Fe %Mg %Mn %Si %Ti %Zn %Ga

99.915 0.001 0.032 0.000 0.004 0.030 0.001 0.013 0.004

The fuel-cell system was designed around the use of a compressed puck of alumi-
num flakes. These pucks were provided by Transmet in a range of porosities from
72% up to 94% aluminum. Dimensions for the pucks are as follows: 2.93 cm dia-
meter, and 1.29 cm width. The cell is designed to corrode around the outside of the
cylinder, so the initial effective planar surface area is 11.9 cm2. The volume within the
cell is 18.3 cm3 including the space occupied by the aluminum puck and the cathode.
Two gold-plated cathodes were prepared using both a coarse and fine mesh. The
initial electrode separation distance was 0.4 cm. Fig. 2 shows a picture of the set-up.
The flow system was designed to keep the hydrogen peroxide and electrolyte
separate until needed in the cell. Fig. 3 is a diagram of the basic flow-system. The
electrolyte is reused, while the oxidizer is slowly bled into the electrolyte recircula-
tion stream.
The hydrogen peroxide was kept separate from the electrolyte in order to prevent
it from decomposing too readily. This had been observed in previous experiments,
where the electrolyte and oxidizer had been mixed at the beginning of the run. A
peristaltic pump using two pump heads to synchronize the flow of the electrolyte
and H2O2 is utilized. Using a larger tube size allows a greater flow of electrolyte; the
ratio of the H2O2 tube’s area to the KOH tube’s section area was 0.0212:1. This
ratio is used to calculate the relative volumes and concentrations within the cell.
The concentration mapping was accomplished, using an analysis of variance
(ANOVA), to find the magnitude of effect by potassium hydroxide and hydrogen
D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124 117

Fig. 2. Fuel-cell test set-up with recycling electrolyte.

Fig. 3. Fuel-cell flow diagram.

peroxide. ANOVA is a good method for determining if there is an effect of changing


concentrations. However, it does not give exact correlations between the variables
and the calculated parameter. The analysis undertaken in this work used the
ANOVA2.m function in Matlab, which was derived from Hogg and Ledolter’s text
[13].
Potassium hydroxide and hydrogen peroxide were used in a two-factor ANOVA
analysis to find a way to maximize the power output. In total, four experiments were
conducted with combinations of 1 and 0.2 M KOH, with 10 and 1% hydrogen per-
oxide. These concentrations were diluted within the cell by varying the pumped
volume of each reactant. The concentration of KOH did not vary substantially,
whereas the effective hydrogen-peroxide concentration was 0.0212 times the stored
118 D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124

concentration. All the tests were performed upon the highest-density aluminum
puck with the fine mesh cathode. A total flow rate of 0.928 ml/s was used for the
majority of the time, with small exceptions when it was increased to see if there were
observable effects.
The experiments used in the ANOVA analysis were also used to determine the
effects of changing the load on the cell and to observe qualitatively the effects of
changing the total flow rate. The results are tabulated with the results from the
saltwater tests. Voltage versus time and current plots are constructed.
The purpose of the saltwater test was to see if an electrolyte with approximately
the same characteristics as seawater could be used as a substitute for alkaline elec-
trolytes. This would result in a savings on the weight of the cell, since the electrolyte
would not need to be stored onboard a fuel cell operating in seawater.
The set-up for this experiment was the same as the individual ANOVA experi-
ments. The resistance was varied to find the power versus load characteristics. Tests
were performed on the aluminum puck with the highest porosity. The sodium chlo-
ride electrolyte solution was spiked with 1 ml of 10 M KOH to introduce a small
number of hydroxide ions to the solution.

3. Results and discussion

The most basic observation of the output data is the voltage versus time curve.
Within these graphs, the resistance is periodically changed to find differences in
voltage and current. Fig. 4 shows the typical results from the concentration tests.
Specifically this is the graph from the 1.0 M KOH with a 10% hydrogen-peroxide
test.
The first thing that one notices in this graph is the large amount of apparent noise.
It was observed that, each time a large bubble is released within the cell, the voltage
spikes up to a maximum. The subsequent decay in the voltage is then caused by the
accumulation of gas. The period, of bubble formation and release, changes depend-
ing upon the concentrations and other uncontrollable factors. Fig. 5 shows the
postulated location of the growth of the gas bubble.
This picture also explains how the majority of the aluminum eaten away is on the
bottom of the cell. Physical observations of the aluminum pucks show the top to be
less corroded than the bottom (as they are situated in the cell). The best observation
of this is with the 72% aluminum puck after the long duration tests.
Fig. 6 is a graph of the voltage versus current characteristics for the four concen-
tration tests. This graph is informative because it shows the ideal operating region
for the fuel cell.
The most effective operating area is the flat top of the curve before it drops off at
the higher current levels. It is noticed from these graphs that the higher electrolyte
concentration gives a higher maximum current before the voltage drop. This would
lead one to increase the KOH concentration further. However, tests previous to
these showed that, above 2 M KOH, a very large amount gas was produced in the
cell. This gas is most likely to originate from the aluminium-corrosion reaction,
D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124 119

Fig. 4. Voltage versus time graph for 1.0 M KOH with 10% hydrogen peroxide.

Fig. 5. Gas-bubble formation and trapping within the fuel cell.

which produces the hydrogen. While observing the increased bubbling in the cell, the
bulk electrolyte temperature was observed to increase by more than 10  C. The
amount of heat given off to raise 500 ml of electrolyte by this amount could be
enough to boil the liquid in the cell itself. That is another possible source of the gas
production.
To confirm that the concentrations of hydrogen peroxide and electrolyte have a
significant effect on the power, an ANOVA analysis was performed using data from
the four concentration experiments. The figure of merit being examined is the average
120 D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124

Fig. 6. Voltage versus current graph for the concentration tests.

power at a resistance of 20 ohm. The results from the Matlab analysis are seen in
Table 2.
The F value gives the magnitude of the effectiveness. Using an F distribution
chart, with an alpha value of 0.01, the F value for the error is 9.33 [13]. Comparing
the F values from the table shows that the KOH and hydrogen peroxide concentra-
tions have definite effects on the power output. The interaction of the two species
has an F value less than the error, so it does not have an appreciable effect.
Numerical integration of the voltage readings in the concentration tests gives the
values seen in Table 3. Included in this are the saltwater results, which will be dis-
cussed next.

Table 2
ANOVA results

Source SS d.f. MS F

KOH concentration 0.04734 1 0.04734 168.48


HP concentration 0.00892 1 0.00892 31.75
Interaction 0.00117 1 0.00117 4.15
Error 0.00337 12 0.00028
Total 0.608 15
D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124 121

Table 3
Results from numerical integration of the concentration and saltwater tests

Test Electrolyte Electrolyte Electrolyte H2O2 H2O2 H2O2 Max V Max I Max P Total E Charge
(M) (ml) (%) (ml) (mol) (V) (A) (W) (J) (C)

ANOVA1 KOH 0.2 500 1.0 100 0.056 1.55 0.464 0.297 152.9 220.0
ANOVA2 KOH 0.2 500 10.0 100 0.580 1.44 0.183 0.093 81.3 168.2
ANOVA3 KOH 1.0 500 1.0 100 0.056 1.55 0.615 0.378 509.2 664.6
ANOVA4 KOH 1.0 500 10.0 100 0.580 1.53 0.828 0.686 630.5 875.0
Saltwater NaCl 0.5 800 7.5 200 0.861 1.28 0.166 0.028 108.8 217.3

It can be seen, in this table, that the maximum open-circuit voltage for each of the
concentration tests was around 1.5 V. The differences occur when looking at the
maximum current, and maximum power. As was shown in the ANOVA results, the
largest contributor to the power and hence the current is the electrolyte concen-
tration. The use of 1 M electrolyte has a significantly higher maximum power than
the 0.2 M electrolyte. This is also evident in the total energy consumed, and the total
charge transferred.
The saltwater tests were performed to determine the initial feasibility of using a
seawater electrolyte. The same graphs as were compiled in the concentration tests

Fig. 7. Voltage versus time graph for the saltwater test.


122 D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124

are presented here. Fig. 7 shows the voltage versus time characteristics with a vari-
able resistance.
The first thing one notices in this graph is that the bubble-induced oscillations are
much smaller than in the concentration tests. There are a number of possible causes
for this. One is the rate of bubble creation is lower in the saltwater test.
Fig. 8 shows the voltage versus current characteristics of the saltwater test. It is
observed here that the voltage drop occurs sooner than was seen with the KOH
electrolyte. This curve also shows more noise than those for the concentration tests.
One reason for this is simply the experimental error. The length of time that the
particular resistances were held constant was shorter than those during the concen-
tration tests. This causes the average values to be less accurate because not as many
points are sampled. In spite of this, it can still be seen that the curve indicates a
lower maximum power, and a voltage drop at a lower current.
Looking at Table 3, it can be seen that the maximum values from the saltwater
tests are all lower than those with the KOH electrolyte. While this is the case, it does
not entirely rule out the use of salt water and KOH mix for an electrolyte. One
possible design could see a concentrated KOH solution being stowed onboard, and
diluted with seawater to give an effective electrolyte.
A number of issues arose with the non-planar fuel-cell. These were mostly caused
by the design of the fuel cell, as opposed to the use of the aluminum flakes. The
largest effect was seen in the production and trapping of bubbles within the fuel cell.

Fig. 8. Voltage versus current graph for the saltwater test.


D.J. Brodrecht, J.J. Rusek / Applied Energy 74 (2003) 113–124 123

This was the cause of the majority of the oscillations within the cell and completely
overshadowed any other effects that may have introduced noise into the system.
One item of specific interest that was not noticeable was the pulsing of the peri-
staltic pump. This pump introduced an oscillating flow rate and pressure to the
system. While a small perturbation would be expected from this, it could not be
noticed due to the magnitude of the bubble formation.
In order to properly quantify the characteristics from the aluminum flakes, the
bubbles must be removed from the system. For this reason, a new design is pro-
posed, which makes use of aluminum flakes in a mat.
The other problem encountered in the non-planar cell was the aluminum oxide
build-up on the anode. This could be countered by not using a recycling electrolyte.
The aluminum oxide is only slightly soluble in water. This not only reduces the
effective surface area, but also makes calculating the left-over aluminum next to
impossible. It cannot be chemically removed because the acid would eat away the
aluminum as fast, if not faster, than the oxide.

4. Conclusions and recommendations

Ongoing work at Swift has found an excellent median between common alloys
and high-purity aluminum. Transmet’s aluminum flakes show promise to be able to
achieve a high power-density at a low cost. Further research must be done in order
to remove bubbles from the system, but once that is accomplished, the aluminum
flakes should prove to offer a higher current than planar aluminum anodes. The
following recommendations would help in bringing this about:

 Numerical flow-analysis can be done internal to the cell to find possible


concentration differences and to optimize the flow geometry. This would help
to keep the power versus time characteristics predictable.
 Studies into the stacking of these cells must be done. This would involve
finding geometries that are conducive to stacking, while not increasing the
overall volume of the cell. Minimizing the internal resistance would also be a
goal of this endeavor.
 The use of more efficient electrocatalysts would enhance the porosity tests.
The cathode must be able to handle the current density that the high surface
area anode is capable of supplying.

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