Table of Contents

1.0 INTRODUCTION AND OBJECTIVE .............................................................................. 4

2.0 TECHNICAL APPROACH................................................................................................ 5

2.1 Ruthenium Catalyst......................................................................................................... 6

2.2 Vulcan Carbon ................................................................................................................ 6

2.3 VGCF (Vapor Grown Carbon Fiber).............................................................................. 6

3.0 WORK COMPLETED ....................................................................................................... 7

3.1 Cathode Formulation and Construction .......................................................................... 7

3.2 Cathode Characterization................................................................................................ 8

3.3 Cathode Testing .............................................................................................................. 8

4.0 RESULTS ......................................................................................................................... 10

4.1 Polarization Tests.......................................................................................................... 12

4.2 Cell Discharge Testing.................................................................................................. 14

5.0 CONCLUSIONS............................................................................................................... 15

6.0 APPENDIX....................................................................................................................... 16

3
1.0 INTRODUCTION AND OBJECTIVE

The dismounted marine currently uses portable power systems mainly for radio communications,
however the future will require a wide range of portable power systems for an "electronics rich"
environment. The marine is already burdened with traditional equipment and the addition of new
equipment will likely add to this load. This places a premium on reducing the weight of the
power sources to maintain the mobility and effectiveness during combat. This need for
lightweight power sources is the catalyst for developing higher energy density (Wh/kg) power
sources.

Current power source requirements are met with the LiSO2 (BA-5590) primary batteries and any
possible substitute power sources shall be compared to this baseline. A power source that offers
promise in this application is the Aluminum-air system (for the chemistry see the Appendix).
This system actually has a higher energy density than the LiSO2 system and could be
significantly higher, if a larger portion of its theoretical energy density could be realized. The
system displays a significant difference between the practical and theoretical energy densities
(Table I). Part of the inefficiency is due to the difference in the theoretical Al-air voltage (2.7V)
and the practical operating Al-air voltage (1.35V). The goal of this program was to improve the
practical energy density of the Al-air system. The focus of this Phase I program was to identify
and evaluate alternative cathode materials to reduce this difference between the practical and
theoretical energy density of the aluminum anode. Several new air cathodes were developed
using different catalysts and carbons. These new cathodes were characterized and then
discharged in actual aluminum air cells. One new air cathode formulation performed better than
our existing cathode. The new Vulcan cathode performed better than the existing Mn cathode at
the current densities of 5 and 10 mA/cm2 with an improvement as high as 21%.

4
 Table I: Gravimetric Energy Density of Various Battery Systems1

Electrochemical Theoretical Practical Theoretical Practical Energy

System Equivalent of Metal Cell Voltage Operating Energy Density of Density of Cells
(Ah/g) (V) Voltage (V) Metal (Wh/kg) (Wh/kg)
690 (Dry Cell)
Al-air 2.98 2.7 1.35 8,100
320 (Wet cell)
Zn-air 0.82 1.6 1.2 1,300 340 (Button cell)
LiSO2 3.86 3.1 2.8 13,000 260 (Cylindrical)
LiMnO2 3.86 3.5 2.7 13,000 230 (Cylindrical)

2.0 TECHNICAL APPROACH

The goal of the Phase I program was to improve the energy density of the aluminum air system
by changing the air cathode chemistry. During the Phase I study, the cathode formulation was
modified by investigating new catalysts and carbons. A critical component of the aluminum-air
battery is the air cathode, which serves as the oxygen-reducing electrode during battery
discharge. The main factors affecting performance of this electrode are as follows:

Type of catalyst for oxygen reduction reaction (to increase voltage)

Type of carbon for oxygen reduction capacity (to increase capacity)

The type of catalyst used in the air cathode, and method of application onto the carbon, affects
the operating voltage of the cell. Effective catalysts will increase the voltage of the cell. The
catalyst also reduces the amount of energy needed to reduce molecular oxygen, and fully reduces
oxygen to a two minus oxidation state producing more electrons for the cell. More electrons
correspond to more energy available for the cell to produce. The carbon type is another important
factor in the air cathode. Carbon affects the reduction rate of oxygen and the capacity of the cell.
Carbons come in many types, forms, shapes, and surface areas. The carbons directly affect the
porosity of the air cathode structure with our cathode fabrication technique. The main
modifications we investigated were: the new ruthenium catalyst, a Vulcan carbon, and a carbon
called VGCF. The three main modifications and the reasoning behind each will be discussed
below.

1
Data from Handbook of Batteries and Fuel Cells 3rd Edition (David Linden), except for the Al-air system which is
based on previous Alupower Al-air cell.

5
2.1 Ruthenium Catalyst
Catalysts used in the existing cathodes include: platinum, silver, manganese and cobalt.
Ruthenium is known for its catalytic ability and has received much attention in the fuel cell
industry. Because cathodes for metal air cells are essentially the same for fuel cells, since they
both reduce oxygen, ruthenium was selected to be investigated. Ruthenium metal (5 wt. % on
carbon, from Aldrich) was used as a catalyst. Using the metal on the carbon saved time and
money because the reactive site of the molecular oxygen is on the surface of the carbons. The
carbon had a surface area of about 900 m2/g, and the type was listed as proprietary by the
manufacturer. The ruthenium catalyst should increase the voltage of the cell.

2.2 Vulcan Carbon

Vulcan XC-72R is carbon black with a surface area of 254 m2/g (Cabot Corp.). It was chosen
because it is a different form of carbon that is highly conductive. Vulcan XC-72R is an
amorphous carbon that is more conductive than typical carbon blacks. It also has good
processing characteristics. This form also has a lower surface area than the typical carbon used.
Yardney uses Black Pearls, which has approximately 1500 m2/g. The Vulcan carbon should
result in a cell with increased voltage, since it is highly conductive, and has the possibility of
increasing capacity.

2.3 VGCF (Vapor Grown Carbon Fiber)

The vapor grown carbon fibers are nanoscale tubes (nanotubes) from Mitsubishi. This carbon is
widely used as an additive in lithium ion batteries to increase conductivity. These highly
conductive nanotubes were added to the air cathode structure in an attempt to decrease the
resistance of the cathode. These carbon nanotubes will mix with the carbon and provide an
electrical path from the catalyzed carbon particles, where the oxygen reduction takes place, to the
metal current collector. VGCF should increase the conductivity, thus increasing the voltage at
high rates of discharge. There is a chance of capacity gain also.

Another cathode was made with no catalysts present to verify that metal catalysts improve the
performance of the cathodes. All modifications mentioned above involved a change in only one
parameter to test its effect on our existing cathodes structures. This way the change in the
cathodes performance can be attributed to the new modification.

6
3.0 WORK COMPLETED

3.1 Cathode Formulation and Construction

Air cathodes were made using different catalysts and carbons (see Table II) following the
procedure in the proposal. The low-cost air cathode patented by Alupower consists of two active
carbon/catalyst layers sandwiching a nickel current collector with a hydrophobic Teflon film on
the airside of the cathode (Figure 1). The parameters tested were particular types of catalysts and
carbons. The cathodes contained metals such as: manganese, silver, cobalt, platinum, and
ruthenium. The carbons used were Black Pearls 2000, proprietary carbons, Vulcan XC-72R, and
Vapor Grown Carbon Fibers (VGCF). There were nine different types of cathodes, and each
batch was large enough in area to produce several electrodes for testing.

Table II Cathode types with designated catalysts and carbons. The * represents new cathode
formulations tested. BP2000 is Black Pearls 2000, Vulcan is Vulcan XC-72R, and not
designated means the supplier of catalyzed carbon has proprietary carbon, VGCF is vapor
grown carbon fibers (nanoscale).

Cathode Type Catalyst Carbon

1 Mn BP2000
2 Ag BP2000
3 Co and Mn BP2000
4 Co BP2000
5 Pt Not designated
6* Ru Not designated
7* Mn Vulcan
8* No catalyst BP2000
9* Mn BP2000 + VGCF

7
 Air Side

er

Fi FE
er
h
y

y
es
La

La

PT
lm
M
C-

C-
Ni
0.6 mm

Electrolyte Side
Figure 1 Diagram of the layered carbon electrode used as an air cathode in aluminum air cells.
The PTFE is a Teflon membrane to repel water from the atmosphere. The C is the carbon layer
that contains the metal catalysts. The nickel mesh is the current collector.
3.2 Cathode Characterization
The structure, elemental composition, and catalyst distribution of the cathodes was studied by
Scanning Electron Microscopy (SEM). This provided detailed images of the cathodes to
investigate porosity and coating. Elemental analysis was useful for determining the efficiency of
mixing, coating, and distribution of the catalysts.

3.3 Cathode Testing

The cathodes performance was tested by two methods: polarization with a three-electrode
measurement, and by discharging in a SOFAL cell which are detailed below.

The polarization test set up consists of a test cell with removable electrodes (Figure 2). An anode
and the air cathode to be tested are fitted into the sides of the test cell. These electrodes are
discharged at different rates to observe the polarization. Polarization is essentially the electrical
energy expended to drive the reaction forward. Lower polarization corresponds to less wasted
energy, which means more of the potential energy in the aluminum anode is being utilized.
Polarization tests were done both in 9% NaCl (aq) and 6.5 M KOH (aq) electrolytes. The NaCl
(aq) electrolyte was used to test the new cathodes since the existing cathodes were tested in that
electrolyte previously. 6.5 molar KOH (aq) is the optimal concentration for performance as it
allows for the precipitation of the aluminum from the electrolyte.

New cathodes were also tested as components in actual SOFAL cells (Figure 3). SOFAL stands
for Special Operations Forces Aluminum-Air Battery. These are aluminum air primary battery
hybrid systems manufactured here (Figure 4). Each unit contains 16 cells for the aluminum

8
battery and these were the cells we tested the new cathodes in. In the SOFAL cell, each cell
contains two air cathodes around a patented aluminum alloy anode consisting of 99.995%
Aluminum and a smaller percentage of magnesium and tin (see Figure 3). The anodes
dimensions were is 3.5 x 2 which corresponds to 7 in2 (45 cm2). The cathodes are about 2.5 x
4 in dimension which has an area of 10 in2 (65 cm2). The electrolyte was 6.5 M KOH (aq)
solution with an additive of sodium stannate. This additive reduces the corrosion of the
aluminum alloy and evolution of hydrogen gas. These cells fit into the SOFAL unit but were not
tested in the full battery design. SOFAL cells were discharged on a computer controlled battery
cycling system at 2.0 amps, 22mA/cm2, 22oC and with a pressure about 1 atmosphere in air.

Al Anode Air Cathode (+)

(-)

Air (O2)
Electrolyte
Figure 2 Diagram of the test cell used to measure polarization. The reference electrode would be
located in the electrolyte.

Air
Cathode

Figure 3 Picture of the actual SOFAL cells used to test the new air cathodes.

9
Figure 4 View of the SOFAL aluminum air battery unit. This unit is an aluminum air battery
produced by the company. The SOFAL cells are stacked together inside the unit. The cells are
about four inches across.
4.0 RESULTS

Several new cathodes were constructed with different catalysts and carbons (Table II). These
cathodes were then analyzed by SEM for structural and elemental characteristics. Images were
taken to view overall construction and pores. The cathode must contain pores to allow both the
oxygen gas and electrolyte to come in contact with the catalysts and carbon. Due to the catalysts
role and the cost of precious metal catalysts it is important to evenly distribute the catalysts in the
air cathode and prevent clumping. Distributing the catalysts increases the reactivity of the
cathode, and decreases material cost. Elemental analysis was done to view the elements present
and the distribution of the metal catalysts. The image below (Figure 5) is representative of the
cathodes constructed. The images of the cathodes were similar and a representative sample from
the Mn catalyzed air cathode (number 1 in Table II) is used to illustrate the porosity and
distribution of catalysts in both Figure 5 and Figure 6.

10
 Carbon Fiber

Pores

Carbon/binder/catalyst mix
100 m

Figure 5 Scanning electron microscope (SEM) image of the Mn catalyst air cathode showing
porosity and an open nature.

Catalyst particles

Figure 6 SEM image of the Mn catalyst air cathode (same as Figure 5) showing the Mn catalyst
well distributed over the cathode structure.

Figure 5 show the fibrous non-woven carbon mat with the carbon/binder/catalyst mixture (white
and gray portions) bound to the mat with many large and small pores (black portions) through
out the air cathode to allow passage of electrolyte and oxygen. Figure 6 is the elemental analyses
showing the distribution of the Mn catalyst of the same exact portion seen in Figure 5 with the
white dots representing the Mn particles. Note how the particles are small and widely distributed

11
in the air cathode. Overall, these pictures represent very good air cathode construction with open
pores and a highly distributed catalyst.

4.1 Polarization Tests

Polarization tests were done on the new cathodes in two types of electrolytes; 9% NaCl (aq) and
6.5 M KOH (aq). The NaCl (aq) electrolyte was used to test the new cathodes since the existing
cathodes were tested in that electrolyte previously. The 6.5 molar KOH (aq) is the optimal
concentration for performance for basic electrolytes (high pH values). Low voltage values close
to zero (on the y-axis) correspond to low polarization. Lowering the polarization essentially
increases the energy obtained from the aluminum anode. The first graph (Figure 7) is the
polarization in the NaCl (aq) electrolyte. This is a comparison of the new cathodes (ruthenium,
Vulcan, and VGCF) with the existing cathode catalyzed by Mn (respectively cathodes numbered
6,7,9, and 1 in Table II). These tests were run in air at 22oC and no heating of the cell or
electrolyte was done. The conditions were 9%NaCl (aq) electrolyte with no additives, a nickel
anode, and a standard calomel reference electrode (CRE). The Vulcan cathode (#7 in Table II)
performed significantly better than all of the new cathodes and the existing cathode (Mn, #1).
This can be due to Vulcans highly conductive nature. At the lower current densities, the new
Vulcan cathodes improved over 10% over the existing Mn cathode (Table III). At the higher
densities of 30 mA/cm2 they were equal.

0.1

0
0 5 10 15 20 25 30
-0.1
Potential (V) vs CRE

Vulcan (7)
-0.2

-0.3
Mn (1)

-0.4
Ruthenium (6)

-0.5

VGCF (9)
-0.6
Current density (mA/cm2)

Figure 7 Polarization graph of the new air cathodes compared to the existing Mn catalyzed
cathode in NaCl (aq) electrolyte. The labels and numbers of each curve refer to specific cathode
formulations in Table II.

12
 Table III Improvement of polarization with the new Vulcan cathode with the NaCl (aq).

Current Densities
2
5 mA/cm 10 mA/cm2 18 mA/cm2
Existing Cathode (Mn) Potential -.24 V -.30 V -.36 V
New Cathode (Vulcan) Potential -.21 V -.27 V -.35 V
% Improvement 13 10 3

The second graph (Figure 8) is the polarization in the KOH (aq) electrolyte. This is a comparison
of the new cathodes (Ruthenium, Vulcan, no catalyst, and VGCF) with the existing cathode
catalyzed by Mn (respectively cathodes numbered 6, 7, 8, 9, and 1 in Table II). These tests were
run at 22oC and no heating of the cell or electrolyte was done. The atmosphere was air. The
conditions were 6.5 M KOH (aq) electrolyte with no additives, a nickel anode, and a standard
calomel reference electrode (CRE). The new Vulcan cathode performed better than all of the
other new cathodes formulations in the range of current densities tested. The new Vulcan
cathode performed better than the existing Mn cathode at the current densities of 5 and 10
mA/cm2, but at 18 mA/cm2 the situation was reverse (Table IV). This can be due to the porosity
of the Vulcan cathode not being optimized for higher rates (which can be done in the Phase II).

0.2

0.15

0.1
Mn (1)
0.05
Potential (V) vs CRE

0
0 5 10 15 20 25
-0.05 Vulcan (7)
VGCF (9)
-0.1

-0.15
Ruthenium (6)
-0.2

-0.25
No catalyst
-0.3
Current density (mA/cm2)

Figure 8 Polarization graph of the new air cathodes compared to the existing Mn catalyzed
cathode in KOH (aq) electrolyte. The labels and numbers refer to specific cathode formulations
in Table II.

13
Table IV Polarization comparison of the existing Mn cathode with the new Vulcan cathode with
the KOH (aq) electrolyte.
Current Densities
5 mA/cm2 10 mA/cm2 18 mA/cm2
Existing Cathode (Mn) Potential -.096V -.120 V -.142 V
New Cathode (Vulcan) Potential -.076 V -.117 V -.165 V
% Improvement 21 2 -16

4.2 Cell Discharge Testing

Three new cathodes were tested by incorporating them into SOFAL cells and discharging. They
were the Ruthenium, Vulcan, and VGCF cathodes (respectively cathodes numbered 6, 7, and 9 in
Table II). The cells were discharged at a constant current of at 2.0 amps, a current density of
22mA/cm2, at 22oC in air at about 1 atm. of pressure (Figure 9). Better results would be obtained
if the atmosphere was pure oxygen, and especially if it was pressurized. With oxygen gas at
about 20% in the atmosphere, the cells rate of discharge would increase 5 times in pure oxygen
presuming the same chemistry. If the pure oxygen was pressurized the cells performance would
increase further and now the system would become more of a fuel cell. In the graphs the peaks
around 20 hours are due to addition of more electrolyte that is according to the test procedure to
maintain an adequate level of electrolyte. It is important to note that these cells did not leak
electrolyte nor weep electrolyte. Some electrolyte was lost due the rate of evaporation. Each air
cathode was run in duplicate and displayed very similar graphs showing the reproducibility of
the cells. The air cathodes with VGCF additive had a higher voltage than those without. The
main purpose of the VGCF additive was to increase the voltage of the cell. This was expected
since the VGCF carbon was added with the intention to increase conductivity. This carbon
additive only replaced 10% (weight) of the Black Pearls 2000. Higher amounts should further
increase the conductivity and voltage. During the Phase I only one concentration was
investigated to test feasibility. The VGCF air cathodes displayed the greatest energy produced, in
terms of watt-hours, since it had the highest voltage. The Vulcan carbons (Vu) had the shortest
discharge times around 32 hours. Surprisingly the Vulcan carbon air cathodes, which performed
so well during the polarization tests, were not the top performers in the cell discharge testing.
This is probably due the long discharge time of the SOFAL cell compared to the short discharge
times of the polarization tests. The structure of the air cathode due to the morphology of the
carbon is also a factor in the long-term discharge. The Vulcan carbons are more round in nature
14
while the VGCF nanotubes are very long. The nanotubes should provide longer conductive paths
for the electrons through the air cathode structure providing a structure with better endurance.
The graph of the Ruthenium catalyzed cathode (Ru) was about the average of the other two in
terms of voltage, but did have a 10% longer discharge. The ruthenium catalyst did not perform
better than the lower cost manganese (Mn) catalysts used in both the VGCF and Vulcan air
cathodes. Since the current was 2 amps the capacity is twice the discharge hours. The Vulcan,
VGCF, and Ruthenium cathodes produced 65, 71, and 75 amp hours respectively, until the 1.2
cutoff voltage.

1.5
Potential (Voltage)

VGCF
1.4
1.3
Ru
1.2 Vu
1.1
1
0:00:00 12:00:00 24:00:00 36:00:00 48:00:00
Time (hours:minutes:seconds)
Figure 9 Discharge graph of three new cathodes in SOFAL cells.

5.0 CONCLUSIONS

The Phase I work demonstrated the feasibility of improving the air cathodes to use more
available energy in the aluminum anode. The air cathodes chemistry was improved by using two
different carbons: Vulcan and VGCF nanotubes. The Vulcan carbons decreased polarization and
increased the efficiency of the system. The VGCF nanotubes increased the conductivity and
voltage. In this study the chemistry was investigated and the air cathode structure was not
optimized. The structure will be optimized in Phase II. The next generation air cathode will
combine the strengths of all three carbons investigated in the Phase I. The Black Pearls 2000 will
be used for its capacity, the Vulcan will decrease polarization, and the VGCF nanotubes will
increase the voltage. All three carbons combined in one cathode will install the strength of each

15
carbon to produce a superior cathode. This combined with the manganese (Mn) catalyst that
performed well and has a low cost, should provide an energy efficient air cathode capable of
harnessing more potential energy of the aluminum anode than current air cathodes.

The Phase II ideas and work include combining the new carbons together in one cathode,
optimizing the structure, and further improving the conductivity of the cathode. The next area of
improvement for the air cathodes appears to be conductivity. The best catalyst and the carbon
types have been identified in these Phase I tests. The Vulcan and VGCF carbons and Mn metal
catalyst appear to reduce oxygen at the required rates but the means of conducting the electrons
to the tab of the cell needs further improvement. Modification of the current collector, binder, or
Teflon layer will improve the performance of the cathode and thus the aluminum air system.
These components can be investigated next to increase the useable energy form the aluminum air
system. Improving the conductivity, using a blend of three carbons, and using the low cost Mn
catalyst will provide an aluminum air battery capable of providing portable power for military
equipment.

6.0 APPENDIX

The chemical reaction that occurs in an Al-air cell, using alkaline electrolyte, proceeds according
to the following reaction:

4 Al + 3 O 2 + 6 H 2 O + 4 OH 4 Al(OH) 4
During discharge, the dissolved aluminate ion produced in this reaction precipitates out as
crystalline hydrargillite (aluminum hydroxide):

Al(OH) 4 4 Al(OH)3 + OH
In addition to producing energy in this reaction, a parasitic corrosion occurs at the anode that
contributes to the dissolution of aluminum, generating minute quantities of hydrogen gas and
heat.

2Al + 6H 2 O + 2OH 3 H 2 + 2 Al(OH) 4

This corrosion of the anode, in an alkaline electrolyte, is one of the factors that reduce the
coulombic efficiency and the energy density of the Al-air cell.

16
Development of Aluminum
Air Batteries (alkaline) :
The challenges
We are going to review:

Aluminum production The Bayer Process

The attractiveness of aluminum as an anode

Aluminum Air Battery the general system

Aluminum Air Battery

The Aluminum Anode

The Air cathode

The electrolyte

Battery management
Aluminum production The Bayer Process
Aluminum is the most abundant metal in the Earth's crust .
Still, its price is , relatively, not so cheap. Why?

The main source for aluminum is Bauxite

Bauxite is an aluminum ore that consists primarily of aluminum oxide and aluminum
hydroxide minerals, mixed with two iron oxides, the clay mineral kaolinite and small amounts
of anatase
Aluminum is produced via Bayer process: Digestion , Crystallization, Calcination
1.Digestion in NaOH at elevated temperature and pressure

2. Crystallization of Al(OH)3 particles at lower temperature

and preesure with the aid of seeds

3. Calcination (>4000C) to obtain Al2O3

Aluminum production The Bayer Process

The alumina particles are dissolved in a molten salt- cryolite at 10000C.

The Aluminum is than electrochemically reduced over an iron electrode.

The price for 1Kg pure Aluminum is in the range of 2$

Why Aluminum is attractive as an anode material?
Aluminum posses an impressive specific gravimetric capacity and more
impressive volumetric capacity
Element Capacity (Ah/g)
Lithium 3.86
Aluminum 2.98
Magnesium 2.20
Zinc 0.82

Specific gravimetric capacity

Element Capacity (Ah/ml)

Aluminum 8.04
Zinc 5.85
Magnesium 3.83
Lithium 2.06

Specific volumetric capacity

 Aluminum Air Battery the general system
The battery components / structure

The reaction over the Anode The reaction over the Cathode
Al + 3OH-Al(OH)3+ 3e E=2.31 V (vs. NHE) O2 + 2H2O + 4e 4OH E=+0.40 V (vs. NHE)
Al(OH)3+KOH Al(OH)4-

Overall reaction - 4Al + 3O2 + 6H2O 4Al(OH)3 E= 2.71 V

The practical potential obtained for a cell is around 1.2V

Aluminum Air battery is a primary battery, where the anode is mechanically

recharged (via Bayer process)
The potential performance of Aluminum Air Battery

Aluminum Air battery vs. metal air batteries theoretical performance

In theory Aluminum posses energy density as high as ~8kWh/Kg (!)
.
In practice, Aluminum prides ~1.3 kWh/Kg

Al in electric vehicle?
In a rough estimation of 10kWh/100km, 10Kg of aluminum may be
equivalent to ~ 130km when considering aluminum as a fuel.

Theoretical specific energy for Metal Air batteries (normalized to the metal weight)
Aluminum Air Battery The Aluminum Anode

We will focus on the most two challenging issues regarding the

aluminum anode:

1. Over - potentials.

2. Minimum self discharge ( or corrosion) high columbic efficiency

 Aluminum Air Battery The Aluminum Anode
Aluminum Anode potential in alkaline solution

Thermodynamically, aluminum should exhibit a potential of ~ -2.35 V (vs. NHE

electrode) .

Practically aluminum anode operates at much lower potential because:

1. Aluminum is normally covered by an oxide film which causes a delay in reaching a
steady-state voltage due to internal resistance
Al(OH)3 passivation layer

- -
- -
Al Al Al
- 3OH- -
OH-
- -
- -
Al + 3(OH)- Al(OH)3 +3e- Al(OH)3+OH-Al(OH)4-
Sequence of passivation layer creation and exfoliation during discharging

2.Aluminum undergoes a parasitic corrosion reaction, resulting in less than 100%

utilization of the metal and the evolution of hydrogen.
2 Al + 2 KOH + 6 H2O = 2 K[Al(OH)4]- + 3 H2
Hydrogen evolution reaction by Al in KOH electrolyte
Aluminum Air Battery The Aluminum Anode

Anode corrosion
Aluminum is thermodynamically unstable in an alkaline electrolyte and reacts with
the electrolyte to generate hydrogen
2 Al + 2 KOH + 6 H2O = 2 K[Al(OH)4]- + 3 H2
Hydrogen evolution reaction by Al in KOH electrolyte

This parasitic corrosion reaction, or self-discharge, degrades the Columbic efficiency

of the anode and must be suppressed in order to minimize the capacity loss.

Operating the battery at high currents (>100mA) results with higher columbic
efficiencies (>85%).

The difference at corrosion rate as a function of current densities for typical aluminum anode
Aluminum Air Battery The Aluminum Anode

Anode corrosion

There are two ways to improve the anode behavior:

One is doping the aluminum with other elements in order to render it less corrodible in
the electrolyte- Elements which posses high overvoltage for hydrogen evolution are
Ga, In, Sn, Zn, Mg, Ca, Pb, Hg, Mn

The second and the cheaper one is to modify the electrolyte by adding inhibitors,
additive agents or complexing agents in order to make the electrolyte less corrosive, as
we will see on the next slide.
Aluminum Air Battery The Aluminum Anode

Anode corrosion

For example Stannate (Sn(OH)62-)

Additives which can be reduced and deposited by the aluminum anode (such as
Sn(OH)62-) are introduced to the electrolyte

Sn micro=particles
Al Al

Sn(OH)62-

Illustration of reduction of tin ions over the aluminum which results with
microparticles deposition of tin over the anode
 The Air cathode

(ORR reaction)

Gas diffusion electrodes (GDE) are electrodes with a conjunction of a solid, liquid
and gaseous interface, and an electrical conducting catalyst supporting.

H2O
O2

e-
The triple point
For most of the catalyst in alkaline media, the ORR is a complex process
involving four coupled proton and electron transfer steps
The Air cathode
Hydrophilic channels
Typical structure A triple point

Nickel mesh current collector

Hydrophobic channels KOH
O2
electroly
electrolyte

O2

Active layer Gas Diffusion layer

Cross section of the active layer
The GDL supplies the reactant gas to the AL and prevents the liquid electrolyte from
passing through the electrode. The GDL is usually made of porous PTFE.

The active layer (AL) contains the catalyst which is usually supported on carbon black and
bonded together with PTFE.
Typically the AL will contain between 2 and 25% PTFE
The AL enables multiple three-phase contact points
The Air cathode

Typical ORR catalyst in alkaline environment

The common catalysts for ORR in alkaline media are platinum, silver, manganese
oxide, manganese cobalt oxide Recently, perovskite and spinel structures are
considered.
The Air cathode

2 Major issues concerning the air cathode in aluminum air battery

1. CO2 effect

2. Weeping and flooding effect

The Air cathode

CO2 effect

Among time, the alkaline electrolyte exposed to the ambient, may react with CO2
from the air to form potassium carbonate

2KOH+CO2 H2O + K2CO3

The formation of potassium carbonate is much more severe when tends to occur
within the air cathodes channels.

When the carbonate concentration reaches certain level it may precipitate within
the hydrophilic channels and block the access for oxygen

Scrubbers for CO2 capture mounted on metal batteries were suggested but the
significant increase at the weight and volume should be considered.
The Air cathode
Weeping / Flooding
As a consequence of a difference at a physical characteristic between
the electrolyte within the air cathode channels and the electrolyte in
the bulk (concentration difference), high pressure in the channels
could be developed as a drag of water

This may result with the so called weeping or flooding where

electrolyte penetrates to the hydrophobic zone.

Electrolyte in the hydrophobic zone impede oxygen accessibility to

the three phase point and cause to degradation in the battery
performance.
The Air cathode
The electrolyte

Potassium hydroxide solution (KOH) is almost exclusively used

as the electrolyte because:

1.it has a higher ionic conductivity than sodium hydroxide solution.

2. potassium carbonate has a higher solubility product that sodium

hydroxide, which renders the former less likely to precipitate

Specific conductivity vs. concentration of several electrolytes

The Air cathode
The electrolyte

Electrolyte degradation

The anode product, i.e. . Al(OH)3 proceed to react with the electrolyte to form aluminate
ion- (Al(OH)4-)
Al + 3OH-Al(OH)3+ 3e E=2.31 V (vs. NHE)
Al(OH)3+KOH Al(OH)4-

This causes to a decrease at the [OH]- at the expense of Al((OH)4-.

The decrease at the [OH]- concentration and electrolyte conductivity lead to

battery failure.

The electrolyte can absorb between 300-400 Ah/l till it should be replaced,
way far before the aluminum anode should be replaced.
The Air cathode
The electrolyte

Electrolyte degradation

Electrolyte regeneration
In fact , the reaction Al(OH)4- Al(OH)3 +OH- should occur spontaneously when the
aluminate concentration reaches a certain level

This reaction is very slow and cannot compete with the rate of which the aluminum
produces aluminate

This reaction can be hasten by using Al(OH)3 seeds.

The seeds should facilitate the nucleation process and hence, regenerate the electrolyte
either in the battery or outside the battery (like in the Bayer process).

Al(OH)4- OH-

Al(OH)3 seed Illustration of precipitation of aluminate with the aid of Al(OH) 3 seeds
The electrolyte
Electrolyte degradation

Introduction of seeds increases the weight and volume of the system.

The precipitants are in the form of a paste and not easy to be filtered out

Special micro-filtration apparatus should be assembled, else the precipitants

will adhere to the battery components.

However, the product, Al(OH)3 can proceed to aluminum production in the

Bayer process,
Battery

filtration Precipitation tank

Electrolyte tank

seeds
Schematic illustration of electrolyte regeneration with seeds
Battery management

The benefit of electrolyte circulation

circulation of the electrolyte enables the CO2 removal.

The anode reaction is exothermic. Heat management is mandatory and it

could be achieved by electrolyte circulation.

The circulation of electrolyte prevents the build up of H2 bubbles adjacent

the anode.
Battery management

Start-Stop

Start Stop of the battery is still one of its challenge as far as we are aim for
electric vehicle..

At zero current the corrosion is maximal and very dangerous.

Evacuating all the electrolyte from the battery during stopping is

unacceptable, since entrapped droplets of KOH continue to react with
aluminum anode leaving beyond ugly pits.
Questions?