Anne de Guibert Boston December 3, 2010 Critical materials and alternative for storage batteries

Bruxelles 30 November Agenda 1.Table of Storage Batteries 2.Critical materials 3.Lead-acid 4.Nickel metal hydride batteries 5.Li-ion batteries 6.Other systems

3 Bruxelles 30 November 2010 Comparison of battery systems : power vs energy , , Specific energy, Wh/kg at cell level Lead acid Lead acid spirally wound Ni-Cd Ni-MH LiM-Polymer Specific power, W/kg at cell level Super capacitors Li-ion High Energy Li-Ion Very High Power Li-Ion High Power Na / NiCl2 Na/S

4 Bruxelles 30 November 2010 Rare/Strategic elements for batteries

5 Bruxelles 30 November 2010 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

6 Bruxelles 30 November 2010 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

7 Bruxelles 30 November 2010 NEGATIVE Electrolyte Séparator POSITIVE Ion lithium Ion nickel Carbon Oxygen Séparator LiMM’O 2 Carbon Lithium-ion system Lithium ions present in positive and electrolyte salt

8 Bruxelles 30 November 2010 Lithium situation Lithium production 2008: tons Lithium stocks in salars 11 millions tons Producers : 3 big companies + state Chinese companies Source : Usine Nouvelle

9 Bruxelles 30 November 2010 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 : tons en million electric cars :  tons of equivalent metallic lithium contained storage systems of 1 MWh contained  tons Conclusion : realistic vs reserve, higher than yearly production of tons No recycling presently (insufficient volume of material to recycle)

10 Bruxelles 30 November 2010 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 Li2CO

11 Bruxelles 30 November 2010 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

12 Bruxelles 30 November 2010 Li-ion : stress on cobalt Annual cobalt production : tons  batteries are consumer n°1 High price ; volatile for geopolitical reasons (Congo, Chinese competition for African resources) LiCoO 2 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

13 Bruxelles 30 November 2010 Positive active material : reduction to cobalt exposure Chemistry Energy(materials only) Calendar lifeSafety Battery management Cost Li(NiCoAl)O Wh/kg 10 years at 40 o C 50% SOC Cathode reactivityVoltage vs. SOCReference Li(NiMnCo)O Wh/kg Lower than NCA Opportunity to improve Cathode reacticityVoltage control vs. SOCClose to reference LiMn 2 O Wh/kg Lower than NCA Mn dissolution Cathode reactivityVoltage control vs. SOC Lower cathode material cost Balance of system same LiFePO Wh/kg Lower than NCA To be demonstrated Limited by electrolyte reactivity Specific strategy Lower cathode material cost Systems cost same Originallylly LiCoO 2 :

14 Bruxelles 30 November 2010 Other future systems High temperature batteries (Nas, NaNiCl 2 ) 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