Aluminum / Air
Cells
Although, to our way of thinking, the metal/air batteries
are strictly primary, cells have been designed to have the metal replaceable.
These are called mechanically rechargeable batteries. Aluminum/air is an
example of such a cell. Aluminum is attractive for such cells because it is
highly reactive, the aluminum oxide protective layer is dissolved by hydroxide
electrolytes, and it has a nice, high voltage. The overall chemical reaction
is:
Location |
Half Cell reactions |
Voltage |
Anode |
Al + 4 OH->
Al(OH)4- + 3e |
-2.35 |
Cathode |
3/4 O2 + 3/2 H2O + 3e>
3OH- |
0.40 |
Overall |
Al + 3/2 HO + 3/4 O2 >
Al(OH)3 |
2.75 V |
As I mentioned above, alkali (chiefly potassium hydroxide)
electrolytes are used, but so also are neutral salt solutions. The alkali cell
has some problem with the air electrode, because the hydroxide ion makes a gel
in the porous electrode, polarizing it. The typical aluminum hydroxide gel is a
problem on either electrode because it sucks up a lot of water. Using a
concentrated caustic solution prevents this, but is very reactive with the
aluminum electrode, producing hydrogen gas. Another way to prevent the gel
formation is to seed the electrolyte with aluminum trihydroxide crystals. These
act to convert the aluminum hydroxide to aluminum trihydroxide as the crystals
grow. To prevent hydrogen gas evolution tin and zinc have been used as
corrosion inhibitors. A number of additives are used to control the reactions.
A disadvantage of the alkaline electrolyte is that it reacts with atmospheric
carbon dioxide.
Aluminum / air cells have also been made for marine
applications. These are "rechargeable" by replacing the seawater electrolyte
until the aluminum is exhausted, then replacing the aluminum. Some cells that
are open to seawater have also been researched. Since salt water solutions tend
to passivate the aluminum, pumping the electrolyte back and forth along the
cell surface has been successful. For those cells that don't need to use ocean
water, an electrolyte of KCL and KF solutions is used.
Air electrodes of Teflon-bonded carbon are used without a
catalyst. |