The Growth of the Lithium-ion Battery Market
Jonathan Lee, Byron Capital Markets
December 2011
Graphite Demand Distribution
December 2011
30%
14%
7% 14%
14%
21%
Refractories
Expanded Graphite &Carbon Products
Crucibles and Lubricants
Gaskets and Packing
Pencils
Other Iron and Steel
Source: Roskill (2009)
Two-Dimensional Growth
Nickel-metal hydride battery was the pre-cursor
Uses a metal hydride as anode (typically rare earth – lanthanum)
Or Cadmium in nickel-cadmium batteries
Graphite used as the anode in the lithium-ion market
Growth in graphite with switch to lithium-ion market from NiMH
We previously looked at the growth of batteries and electric vehicles
Growth area for graphite - synthetic and natural
December 2011
More than Lithium
According to Argonne National Laboratory Study (2009)
Estimated Graphite:Lithium (kg/kg) ratio
NCA (lithium nickel/cobalt/aluminum): 8
LFP (lithium iron phosphate): 13
LMO (lithium manganese oxide): 15
In LTO (lithium-titanate); anode:lithium (kg/kg) ratio: 8
No graphite used in this type of Li-ion battery
December 2011
Future Graphite Demand
December 2011
(1,000,000)
(500,000)
-
500,000
1,000,000
1,500,000
2,000,000
2,500,000
20
10
20
11
20
12
20
13
20
14
20
15
20
16
20
17
20
18
20
19
20
20
Surplus/Deficit
Total Graphite Demand
Total New GraphiteDemand
Possible Substitutions for graphite
Synthetic Graphite
Li4Ti5O12 – Lithium titanate
Tin based anodes: Cu6Sn5 (Copper-Tin), FeSn5 (Iron-Tin), Carbon-Tin
Al-based anodes
Silicon based anodes
December 2011
Anode Types and Capacity
December 2011
Metal Li Si Al Sn Al Graphite
Lithiated Compound Li Li22Si5 Al4Li9 Li22Sn5 AlLi LiC6
Theoretical Capacity (mAh/g) >3,800 >3,000 2,234 994 993 372
Volume Change (%) Dendritic
Growth 323 - 300 97 9
Source: Kamali and Fray
Anode Costs
Just for the raw material costs:
Lithium Titanate - $23k/tonne
Copper-Tin: $16k/tonne
Iron-Tin: $19k/tonne
Co3O4-Al: $23k/tonne
Does not include costs for producing anode
Titanium and Tin expensive metals – Key drivers in costs
Natural graphite anodes – we estimate $10k/tonne cost
December 2011
Synthetic Graphite
Low capacity – theoretical capacity of 372 mAh/g
Good power
Less energy density
Better control of properties during manufacturing
Expensive – Petroleum coke graphitised at 2,800 C
December 2011
Lithium Titanate
Long cycle life
High rate capability
Capacity of only 175 mAh/g
Lower voltage and energy density (See right)
Faster charging time – 10 minutes compared
to 8 hours
Recharge rates of 98%
December 2011
Source: Jim McDowall
Tin Based Anodes
High capacity (990mAh/g)
Constructed under heat and argon atmosphere for 12 hours – Makes even more expensive
Limited cycle life - Deconstruction of CuSn after lithiation. Volumetric changes as well
Found that volume change could be reduced by using nano-sized tin particles (Kamali and
Fray, 2010)
Graphite-tin were more complicated to produce using carbon nanotubes or tin-filled carbon
nanofibres
May have difficulties in commercial applications
Would still use graphite in production anyhow
December 2011
Aluminum based anodes
Co3O4-Al
High theoretical capacity (over 900mAh/g)
However, low capacity retention due to
volume change
Work performed at University of
Electronic Science and Technology of
China (2011)
Changed particle sizes to increase
capacity retention
Range of only 60-70%
Retention after first charge – Very Low
December 2011
Source: Lei, Ma, Sun
Silicon Based anodes
Much higher capacity (3,000 mAh/g vs. 350 mAh/g)
Silicon is a crystalline structure – inflexible
Expansion occurs when absorbing lithium – causes stress on crystalline structure
PNNL recently had success with Si-based electrodes
Porous Si was used to allow expansion, still a crystalline structure
Carbon coated and KB carbon added
Over 3,000 mAh/g in initial capacity
1,600 mAh/g after 30 cycles – Most losses during
December 2011
Conclusion
Natural Graphite demand will continue to grow two fold:
Conversion to lithium-ion batteries from NiMH
Growth sector of lithium-ion batteries in vehicles
Alternative anode materials far more expensive and less developed
Especially for automotive, very long lead time to get materials and parts approved before
into mass production
Titanium, cobalt, and tin make other anodes expensive
Volumetric changes in batteries make other anodes unworkable, to date
Early stage in Silicon based anodes
Synthetic graphite has a tremendous energy input with graphite having a high melting
point
Growth of EV’s will coincide with rising energy prices
December 2011