anne de guibert boston december 3, 2010 critical materials and alternative for storage batteries
TRANSCRIPT
Bruxelles 30 November 2010
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Agenda
1. Table of Storage Batteries
2. Critical materials
3. Lead-acid
4. Nickel metal hydride batteries
5. Li-ion batteries
6. Other systems
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Comparison of battery systems : power vs energy
1
10
100
1,000
100,000
0 20 40 60 80 100 120 140 160 180 200
Specific energy, Wh/kg at cell level
Lead acid
Lead acidspirally wound
Ni-Cd Ni-MH
LiM-Polymer
Sp
ecif
ic p
ow
er,
W/k
g a
t ce
ll l
evel
Supercapacitors
Li-ionHigh
Energy
Li-IonVery High Power
Li-IonHigh Power
Na / NiCl2 Na/S
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Rare/Strategic elements for batteries
Electrochemical system
Rare materials employed
Recycling Substitution Applications
Rechargeable
Lead-acidSn
(Ag)Yes not Sn SLI, Industrial
NiMH
Rare Earths(La, Ce, Nd, Pr)
Y, YbCo
No direct reusefundamental constituant
HEV, ELU
Other alkalineY, YbCo
No direct reuselithium
batteries
Li-ionCoCuLi
Yes Co, CuNo Li
not for Lipresent everywhere
HT (NaS, NaNiCl2) none Nas for storage
Primary cells H.T Li cells Ga No No today oil drillingZinc cells none
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Lead-acid battery
Lead-acid batteries are used for SLI in conventional cars: they will remain used in micro-hybrid (stop-and-start) slightly
larger batteries
They also have many industrial applications: traction (forklifts, AGVs) standby (telecom networks, UPS, alarms, power plants,
submarines …)
Lead-acid batteries positive electrodes are grids made of lead alloys: the most common alloys use tin (0.5 to 1.2 %) ; some use a small
amount of silver
Replacement : tin decrease will reduce cycle life of automotive batteries silver suppression will reduce life (corrosion increase) – not dramatic no known solution
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Maintenance free High Energy density
more than 70 Wh/kg 140 Wh/dm3
Stable Power vs dod and life 2,000 cycles / 80% dod / RT 46,000 cycles / 20% dod/ 35°C
Operation over large temperature range
Pass the most severe ELU tests (4 years float at 55 °C) Operation over large T° field
More Pay load to the system (bus, heavy vehicles)
Low Life Cycle Cost
Allows best operation even with high
voltage systems
NiMH : a good, safe system for hybrid vehicles (Prius) or ELU
Cost and availability issues : NiMH negative electrode use rare earth materials (La, Ce, Nd, Pr) as negative
oxide materials Positive electrode material can use additives such as Y or Yb or Nb 95 % of rare earths presently come from China which reduces exportation
drastically Availability decrease & price increase will contribute to faster move to Li-ion
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NEGATIVEElectrolyteSéparatorPOSITIVE
Ion lithium
Ion nickel
Carbon
Oxygen
Séparator
LiMM’O2 Carbon
Lithium-ion system
Lithium ions present in positive and electrolyte salt
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Lithium situation
Lithium production 2008: 27400 tons
Lithium stocks in salars 11 millions tons
Producers : 3 big companies + state
Chinese companies
Source : Usine Nouvelle
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How much lithium needed for Li-ion : scenario 2020
Necessary : 165 grams of equivalent metallic lithium /battery kWh
3-4 kg for 1 electric car ; low price risk
Portable applications : 2 billions cells in 2008; 1800 tons of equivalent metallic lithium
contained 8-10 % yearly growth : 4 500 tons en 2020
10 million electric cars : 35 000 tons of equivalent metallic lithium contained
10 000 storage systems of 1 MWh contained 1 650 tons
Conclusion : realistic vs reserve, higher than yearly production of 27 000 tons
No recycling presently (insufficient volume of material to recycle)
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Room for speculation
Lithium carbonate price was multiplied by 3 in 4 years
Offer is presently in excess (no shortage), but there are only 3 suppliers
All resources presently in exploitation are salars in Chile & Argentina, plus Chinese resource internally. Bolivia not yet exploited.
SQM (Chile, N°1) controls the market
Price of Li2CO3 1990-2009
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Risks factors
Important risk factor if fast market increase : 5-10 years needed to open a new exploitation
Long term stabilization factor : recycling today, only metals are recycled (Co, Ni, Cu) contained lithium finishes in slag it could be recovered and recycled if the quantity is large enough
Other stabilization factor : ores which become exploitable if prices increase a lot. They have a better geographical repartition
Conclusion : risk factor manageable for Li-ion cost issue more difficult for primary lithium cells
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Li-ion : stress on cobalt
Annual cobalt production : 63000 tons batteries are consumer n°1
High price ; volatile for geopolitical reasons (Congo, Chinese competition for African resources)
LiCoO2 is the “historical material” of Li-ion positive electrodes
Cobalt (CoO, Co(OH)2) is also used in alkaline NiCd, NiMH and NiZn
For Li-ion, it exists technical solutions to decrease cobalt content, or to eliminate for less stringent applications
Co volatility 1989-2010
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Positive active material : reduction to cobalt exposure
Chemistry Energy(materials only) Calendar life Safety
Battery management
Cost
Li(NiCoAl)O2 529 Wh/kg10 years at 40oC
50% SOCCathode reactivity Voltage vs. SOC Reference
Li(NiMnCo)O2
476 Wh/kgLower than NCAOpportunity to
improveCathode reacticity
Voltage control vs. SOC
Close to reference
LiMn2O4 419 Wh/kgLower than NCAMn dissolution
Cathode reactivityVoltage control vs.
SOC
Lower cathode material cost
Balance of system same
LiFePO4 424 Wh/kgLower than NCA
To be demonstrated
Limited by electrolyte reactivity
Specific strategy
Lower cathode material costSystems cost
same
Originallylly LiCoO2 :
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Other future systems
High temperature batteries (Nas, NaNiCl2) do not contain large quantities of critical materials
Air batteries (Li-air) need catalyst in the reversible air electrode : could contain platinum or at least cobalt
Other sodium batteries could be an interesting research topic
Conclusion : no alternative for NiMH materials moderate lithium risk cobalt exposure risk decrease is going on in Li-ion batteries