Full automotive power

requires 100 kWh

Cost + Energy Densities +

Safety + Cycle Life +
…..are key to EVs
Lithium-air battery
Lithium-air battery

Mullen Technologies Inc.

Poly Plus Battery Company
Lithium Air Industries
Lithium-air battery

Cathode
Lithium-air battery

Theoretically, a Li-air
battery is empty
(discharged)
all pores of whenthe
positive electrode
(right-hand side) are
filled with lithium
peroxide,
here filling from
shown
top
to bottom.

Figure: Li-Air
Battery
 Why Lithium-air battery ?
 Extremely high specific capacity of Li anode material (3842 mAh g-1 for
lithium, vs. 815 mAh g-1 for Zinc)
 The couple voltage of Li-O2 in alkaline electrolytes is 2.91 V (compared to
1.65 for Zn-O2)
 The Li-air battery, when fully developed, could have practical
specific energies of 1000-3000 Wh kg-1
 Li-air cell IS electrically rechargeable, (far more so than the Zn-air battery.)
 Why Lithium-air battery?
Advantages Disadvantages
High energy density Dependent on environmental conditions:
Flat discharge voltage - Drying out limits shelf life once opened
to air
Long shelf life (dry storage)
- Electrolyte flooding limits power
output
Non toxic (on metal use basis) Limited power density
Low cost (on metal use basis) Limited operating temperature range

Currently, Li-air batteries are still in the opening development stage, and their actual
parameters fall far short of the theoretical values.

Li-air Li-ion
Specific Energy 362 Wh kg-1 (lab model!) 200 Wh kg-1
Specific Power ~ 0.46 mW g-1 42 mW g-1 (when
discharged at 0.2C)

Li-air cell capacity fades twice as fast after 50 cycles (compared to 25% capacity fade after
300 cycles for an ordinary Li-ion cell).
A Li-air cell creates voltage from the availability of oxygen molecules (O2) at the positive electrode.
O2 reacts with the positively charged lithium ions to form lithium peroxide (Li2O2) and generate
electric energy. Electrons are drawn out of the electrode and such a battery is empty (discharged) if
no more Li2O2 can be formed.
Li-air batteries with
lithium peroxide
(left, blocking the
carbon electrode)
and lithium
hydroxide (right,
with electrode
unblocked) as
discharge
products. Note
that the electrode
pore structure is
not drawn for
simplicity.

Li2O2 is a very bad electron conductor. If deposits of Li2O2 grow on the electrode surface that supplies the
electrons for the reaction, it dampens and eventually kills off the reaction, and therefore the battery’s power. This
problem can be overcome if the reaction product (lithium peroxide in this case) is stored close to the electrode
but does not coat it.
With this combination of chemicals, the reaction as the battery discharges does not form
the Li2O2 that would gunged up the electrode’s conducting surface (see image below, left
hand side). Instead it incorporates hydrogen stripped from the water (H2O) to form
lithium hydroxide (LiOH) crystals. These crystals fill the size of the pores in the fluffy
carbon electrode, but crucially they don’t coat and block the vital carbon surface that is
generating the supply of voltage (right hand side). So the presence of lithium iodide as
“facilitator” (though its exact role is not yet clear) and water as co-reactant in the process
boosts the Li-air battery’s capacity.

Difference
between
LIB and Li-
Air?!
 How Will Li-Air Change Things?
This process which ensures the electrode surface is kept clear is essential to boost battery
capacity. However, the drawback is that the same lack of electrical contact between the
electrode and the discharge product that boosts its capacity should in principle make it
difficult to recharge.

Recharging Li-air batteries. Left: lithium peroxide has to be removed from the carbon
surface. Right: cycle of iodide and triiodide, where triiodide chemically dissolves lithium
hydroxide, freeing the elements so they can be re-combined again to produce electricity.
 How Will Li-Air Change Things?
In fact this mechanism is even more effective than the recharge of Li2O2 attached to
the electrode surface. Since the electrons do not need to travel through a Li2O2
layer, less voltage is required to recharge a Li-air battery with the iodine additive
than without it. So less energy is needed to recharge the battery, which would
make an electric car running on such a Li-air battery more energy efficient. It is
noted that it is approaching an energy efficiency of around 90% – which brings this
new battery technology close to that of conventional Li-ion batteries.
Types of Li-Air Cell
Types of Li-Air Cell
 Secondary Li-Air Cells
How are Li-air cells rechargeable?

Li(s) → Li+ + e- (anode reaction)

Li+ + ½O2 + e- → ½Li2O2 (cathode
reaction) Li+ + e- + ¼O2 → ½Li2O (cathode
reaction)
In 2006, Bruce et al. demonstrated that
Li2O2 is formed on charging and decomposes
according to the reaction below

Li2O2 → O2 + 2Li+ + 2e-

 Factors That Affect Performance
• Most metals are unstable in water and react with the electrolyte to corrode the metal,
resulting in self-discharge.
• Electrode polarization: sharp voltage drop-off with increasing current because of oxygen
diffusion limitations, making metal-air batteries more suited to low-power applications rather
than high-power.
• Electrode carbonation: Absorption of CO2 (since the cell is an open system), results in
crystallization of carbonate in the air electrode, clogging pores and decreasing performance.
• Water transpiration: Movement of water vapor either into or out of the cell.
– Excessive water loss can lead to drying of the cell and premature failure.
– Excessive gain of water can dilute the electrolyte.
 Air Electrode Requirements (Cathode)
• Cathode must be able to sustain an oxygen reduction reaction (and oxidation
if battery is rechargeable).
• Cathode must be highly porous.
• Catalysts are typically incorporated into the carbon layer.
 Electrocatalysts
Critical challenges that limit the practical use of this technology currently
include:
 Sluggish oxygen reduction reaction (ORR) kinetics (during discharging).
 Sluggish oxygen evolution reaction (OER) kinetics (during charging).
Currently, these reactions are too slow for practical applications in electric
vehicles. As a result, a lot of effort has been put into developing effective,
bifunctional, electrocatalysts for the ORR and OER

In a recently published paper (2010), Lu et al. have shown, Pt/Au nanoparticles applied to a
carbon cathode were shown to strongly enhance the kinetics of the ORR and OER, with Au
enhancing the ORR, and Pt enhancing the OER.
Li-air batteries built with this catalyst boasted the highest cell efficiency reported for a Li-
air cell with an efficiency of 77%.
 Air Cathode Challenges
• Cathode reaction delivers most of the energy, and because most of the cell voltage
drop occurs at the air cathode.
• It is thought that non-aqueous Li-air energy falls far short of the theoretical values
because the discharge terminated well before all of the pores in the air electrode are
filled with Lithium oxides.
• How can this be combated?
– Develop new cathode materials that can accommodate large amounts of oxides.
– Including additives that improve the solubility of the precipitates.
– Develop catalysts that alter the morphology of lithium-oxide deposits.
 Li-Metal Anode Challenges
• Lithium metal anodes are the anodes of choice for Li-air cells because of their
high energy density compared to Lithium intercalation anodes.
• Implementation of Li-metal anodes is associated with:
– Dendrite formation (which can lead to dangerous battery shorts)
– Electrolyte incompatibility (which results in resistive films forming on the
anode surface)
• How to combat this?
• Incorporating a solid polymer electrolyte,
– Inert to Lithium metal
– Conducts Li-ions
– Prevents dendrite formation
 Electrolyte Challenges

Aqueous Non-Aqueous
Major challenge is related to the Li-battery grade electrolytes are quite
prevention of water and volatile!
access to the Li-metal. oxygen Solutions?
Solutions? • Develo
• One such ping
potential hydrop
which
solutionwas
makes Li-metal stable in hobic
water
the LiSICON electrol
Durability and manufacturing the
porous glass ytes
filmconcept,
in large quantities may become with
an additional challenge. low
volatilit
y
• Developing compound electrolytes
(i.e, electrolytes with multiple
layers with different properties)
 Summary & Conclusions
Li-air
Not moisture-stable, increasing cost
and manufacturing complexity.
Lithium and non-aqueous electrolytes
are costly
Still in research phase
Reversible reactions (and improving!)
Highest operating potential

Important to continue development of Li-Air battery !!!

Summary & Conclusions
 Summary & Conclusions

Final Exam.: 100 marks

Report: 40 marks
Attendance: 10 marks
Total: 150 marks

Report: Prospect of Li-Air and Li-

ion batteries as Energy Storage
Systems.
Marks: 20
Due Date: End of semester (Before
Final Exam.)