anne de guibert boston december 3, 2010 critical materials and alternative for storage batteries
TRANSCRIPT
Anne de Guibert Boston December 3, 2010
Critical materials and alternative for storage
batteries
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