Lithium Metal Air

Battery Technology
Owen Crowther, Darshana Bansal,
Arthur Driedger III, Benjamin Meyer,
Michael Morgan, and Mark Salomon
MaxPower, Inc.
Harleysville, PA 19438
owen.crowther@maxpowerinc.com

Mary Hendrickson
US Army CERDEC
Army Power Division
Fort Monmouth, NJ 07703

MaxPower Inc .
Special Purpose Batteries
1
 Primary Li-Air Technology
MaxPower is currently developing a
primary Li-Air battery system for:
• Portable Electronic Devices
• Charger Applications
Current research areas:
• Cathode Structures
• Protected Cathode Membrane
• Protected Anode Membrane
• Electrolyte Solutions
• Prototype Single Cell Development

2
 Primary Li-Air Technology
MaxPower is currently developing a
primary Li-Air battery system for:
• Portable Electronic Devices
• Charger Applications
Current research areas:
• Cathode Structures
• Protected Cathode Membrane
• Protected Anode Membrane
• Electrolyte Solutions
• Prototype Single Cell Development

2
 Why Li-Air
Specific Specific
Metal-Air and Li-Ion Systems OCV
Energy Capacity

V Wh kg-1 mAh g-1

2Li + 0.5O2 ↔ Li2O
2.913 11,248 3,862
(aprotic organic)
Li + 0.5O2 ↔ ½Li2O2
2.959 11,425 3,862
(aprotic organic)
2Li + 0.5O2 + H2O ↔ 2LiOH
3.446 5,789 1,681
(aqueous)
2Li + 0.5O2 + H2SO4 ↔ Li2SO4 +
H2O 4.274 1,091 255
(aqueous)
2Li + 0.5O2 + HCl ↔ 2LiCl + H2O
4.274 3,142 366
(aqueous)
Zn + 0.5O2 ↔ ZnO
1.65 1,353 820
(aqueous)
6C + LiCoO2 ↔ xLiC6 + Li1-xCoO2
~4.2 420 139
(aprotic organic)

3
Cell Designs

H2O

O2
O2

HH22OO

4
 Presentation Topics
• Cathode Development
• Catalyst
• Electrolyte Additive
• Discharge in Air
• Cell Scale Up

5
 Generation 1 Cathode
Surface Particle Pore
commercially available E4A
Carbon Area Size Volume
Black Pearls 2000 m2g-1 nm cm3 g-1
Vulcan XC72 Super P 62 40 ~3.8
Super P
4 Vulcan XC-72 235 30 0.59
KJB EC300G
1480
KJB EC600G Black Pearls 2000 12 2.35
3
800
Ketjen Black 300 J 40 ~3.3
E/V

2 1415
Ketjen Black 600 J 40 5

0.2 mA cm-2 Darco G60 853 180 0.95

1 O2 900-
Calgon PWA 440 0.90
2 1000
10 cm 20% PTFE
0 Shawinigan black 70 NA ~4.6
0 500 1000 1500 2000 2500
-1
q / mAh g C

• KJB EC600G demonstrates highest capacity

• Largest pore volume for discharge products
6
 Generation 1 Performance
4000
-2
0.2 mA cm O2
3 O2
3000 1.5 V cutoff

q / mAh g-1 C
10 cm2
2
E/V

2000

1 1000
MaxPower
ECS Trans. 3 (2008) 87
0 0
0 1000 2000 3000 4000 0.0 0.5 1.0 1.5 2.0
q / mAh g-1 C i / mA cm-2

• 80% KJB EC600G 20% PTFE

• Can fabricate cathode pads > 300 cm2
• Compares favorably to literature
• Relatively high capacities at high rates
• Reproducible 7
 Generation 2 Cathode
• 95 – 97.5 % Carbon
7500
80% KJB
• Teflon based binder
• Fabricate large pads
q / mAh g-1 cathode

95% KJB
5000
• High Capacity
• Per gram of cathode
O2
1.5 V cutoff
10 cm2 • Not including grid
2500 • Extremely Large Spread
• Work is ongoing
0
0.0 0.5 1.0 1.5 2.0 2.5
i / mA cm-2

135 cm2 95% KJB EC600G

8
 MnO2 Catalyst
• Known to increase
capacity
[Angew. Chem. , Int. Ed. 147 (2008) 4521]
• Capacity increased by 1.6
on active materials basis
• Vdischarge = 2.44 V compared
to 2.07 V
• Reproducible > 500 mAh g-1
• Not Optimized

543 mAh g-1

at 1 mA cm-2
9
 MaxPower Electrolyte Additive
4 -2
4
0.2 mA cm 1 mA cm-2
O2 O2
3 3
E/V

E/V
2 2

1 standard electrolyte 1 standard electrolyte

standard electrolyte + additive standard electrolyte + additive
0 0
0 500 1000 1500 2000 0 100 200 300 400
-1 -1
q / mAh g cathode q / mAh g cathode
i q V avg

• Increase of 0.65 V for Cell Type

mA cm-2
mAh
cathode
g-1
V

large portion of baseline 0.2 1802.4 2.61

discharge at 0.2 mA cm-2

baseline +
0.2 1970.7 3.16
catalyst

• PATENT PENDING baseline +

catalyst
0.2 1785.5 3.16

baseline 1 248.4 2.43

baseline +
1 390.3 2.59
catalyst
10
 Cathode Membrane Technology
• Hydrophobic membrane that allows
O2 from air into cell and blocks H2O
• Stops evaporation of volatile
electrolyte solvents – DMC, DME, etc
• Various Materials
• Polysiloxanes – High O2 solubility and diffusivity
• Combined with alkyl methacrylates
• Similar to contact lense materials
• Perflourocarbons
• High O2 solubility but difficult to work with
• Perfluorinated polyethers – such as Krytox
• PATENT PENDING

11
Cathode Membrane Processing
Process
Development

Free Standing Supported

Films Films

Bellcore Tape Tape Pouring Spraying Smearing Spin

Cast Pouring Cast Coating

Hot- Plugged
Key: Pressing Pores
Processing Failure
Processing worked but no permeation testing
Processing worked and permeation testing
Smearing Spraying
Not tried yet

12
 Cell Discharge in Wet Air
• Silicone membrane
3
porex control • 19000 g O2∙mm∙m-2∙day-1
silicone 6-7 mil • 50 cm2 for 2A discharge
silicone 7 mil
• Increased capacity
2
• Lower Vdischarge
E/V

• Lithium is in much better

1
tested in air ~ 35% RH condition
-2
0.2 mA cm
0
0 500 1000 1500 2000
q / mAh g-1 C

13
 Coated Cathode

42.9% RH
3 -2
0.2 mA cm

E/V
1
porex control
3-3.5 mil silicone coated on cathode
0
0 100 200 300 400 500 600
q / mAh g-1 C

• Thinner membrane on cathode

• Increased capacity at same Vdischarge
14
 Scale Up
100 cm2 fixtured cell
in air from 10 cm2
pouch cell in O2

10 100 cm2

15
100 cm2 Test Fixture
• 100 cm2 cathodes
• Reproducibility
• Same cell volume
• No heat sealing
• Decreased
electrolyte
• Vacuum filling

16
 100 cm2 Cathode Discharge
4
0.2 mA cm-2
O2
3

E/V
2

2
1 10 cm pouch
100 cm2 fixture

0
0 500 1000 1500 2000 2500 3000
q / mAh g-1 C

• 1st Attempt to Scale to Larger Format

• 100 cm2 cathode retains 90% of small
format pouch capacity
• Voltage drop all iR 17
 Conclusions
As a program we are integrating
advances in technology into practical
hardware to develop a primary Li-air
battery with an energy density
greater than 700 Wh kg-1
We are currently researching:
• Component Technology
• Prototype Development
• We would like to acknowledge the
US Army for funding this research
and development under contract
W15P7T-09-C-S330 18