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1 Main presentation title Presentation sub-title Developments in battery chemistries Dr. Marcel Meeus (Umicore):

2 Agenda 1. Umicore materials supplier to the battery industry 2. Generic insight battery technologies, opportunities and challenges 3. Further advances to increase performances and reduce cost 4. Pace of technology evolution 5. Glossary

3 Umicore is committed to all rechargeable battery systems ( and to Zn primary as well) Overpelt (Belgium) Hofors (Sweden) Battery recycling Pyrometallurgy Closed-loop Zn Powders for primary alkaline batteries Cheonan (Korea) Cathode material production Application Lab Research & Technology Powder Technology Olen (Belgium) Headquarters R&D Precursor production Resources efficient Total workforce: >500 people Jiangmen (China) JV (40%) Ni-hydroxide production Cost-efficient/high-volume 3 Shanghai (China) Zn Powders for primary alkaline batteries Jiangmen (China) JV (60%) Precursor production Cathode material production Fig. 1

4 Umicore today application know-how metals chemistry material material science solutions metallurgy material solutions recycling Fig. 2 4

5 Agenda 1. Umicore materials supplier to the battery industry 2. Generic insight battery technologies, opportunities and challenges 3. Further advances to increase performances and reduce cost 4. Pace of technology evolution 5. Glossary

6 Electrochemical cell basic components > > (separator) Fig. 3 The anode (Greek anodos, way up) is the electrode at which oxidation takes place and electrons are fed into the external circuit. The cathode (Greek cathodos, way down) is the electrode at which reduction takes place and into which electrons are fed from the external circuit. In a primary cell, the anode is also the negative electrode and the cathode, the positive electrode. In a secondary cell on charge, the negative electrode becomes the cathode and the positive electrode, the anode. The electrolyte serves as a medium for completing the electrical circuit via the transport of ions. The reactants comprising the electrodes may be gaseous, liquid or solid, massive or porous. The electrolyte may be liquid or solid. 6

7 Wide portfolio of battery chemistries (non-exhaustive list) Positive A snapshot out of > 50 primary and > 10 rechargeable systems O2 Pb02 Mn02 Negative H2 MH Zn Pb Cd Fe Li LiC6 Al Na Fuel cell KOH Zn/air KOH ZnCl2 H2S04 Pb/acid NiOOH KOH KOH KOH KOH KOH Organic Li/Air organic KOH HgO KOH AgO KOH KOH LiCoO2 LiNiO2 LiMn2O4 LiNiMnCoO2 LiFePO4 organic organic organic organic organic l,br,s aq. (CFx)n organic S Li/S High t Na/S Most important commercial cells 7

8 Trends NiMH (1.2V) Li-Ion (~3.6V) Advanced Li-Ion (3.6V and more) New Systems Fig. 4 Current Li-ion battery materials Fig. 5 Anode (= negative) graphite/carbon Separator Ion permeable inert membrane Cathode (= positive) Lithium cobaltite and new generation materials Electrolyte Liquid or gel Charge: Li-ions from cathode to anode Discharge: Li-ions from anode to cathode 8

9 Continuous improvement to Advanced Li-ion systems -> New cathode materials -> New anode materials LiCoO2 graphite (372 mah/g) 0.1V NMC (1/3Ni, 1/3Mn, 1/3 Co or high Mn formulations) or Li 4 Ti 5 O 12 Si,Sn/C composite materials NCA (Ni, Co, Al) commercial in development ( mah/g) ongoing or (1.5V) (0.1V) LMO (Mn spinel) or mixtures or 2008 LiFePO4 > 3000 mah 2800 mah -> 5V cathode materials in development -> In combination with new electrolytes (solid polymer or ionic liquids 5V) Gravimetric Energy Density (Wh/kg) Charging voltage: 4.10 to 4.20V 1994 ± 1200 mah Volumetric Energy Density (Wh/l) Fig. 6 9

10 Cathode material evolution Mixed compounds (eg NMC: Ni/Co/Mn) for example Cellcore MX introduced since 2005 NMC compounds reduce cobalt use; first enters low-mid end Other materials for future generations of Li-ion technology Some battery specifics ~ # cathodes (C anode) Cap. Cathode mah/g Cap. Batt. Safety Cyclability Cost LiCoO LiNiO LiNiMnCoO LiMn 2 O Fig. 7 LiFePO

11 New chemistries anodes and cathodes Various cathode and anode materials for LIB are studied to further improve capacities: Potential vs Li/Li + (V) V LiMn 2 O 4 LiCoO 2 LiNiO 2 MnO 2 Li 4 Ti 5 O 12 Other carbons Graphite Vanadium oxides (V 2 O 5, LiV 3 O 8 ) Intermetallics d = 4-8 Polyanionic compounds (Li 1-x VOPO 4, Li x FePO 4 ) Phosphides (d 8) 5.0V 4.9V 4.7V 4.2V 3D metal oxides Nitrides d = 2.1 LiCoPO 4 (160mAh/g) Doped LiMn 2 O 4 ( mah/g) LiMnPO 4 (170 mah/g) Si-C d = 2.3 Li metal Sn-C Sn Si Capacity (Ah/kg) Negative materials Positive materials Acc. To Prof. J. M. Tarascon (Amiens) cathodes anodes Fig. 8 11

12 New chemistries anodes and cathodes Cathodes -> more safety, higher potential, higher capacity NANOTECHNOLOGIES Anodes -> replacement of C by new materials with higher capacity (e.g. Sn and Si based intermetallics) Problem to be overcome is swelling of the new materials 12

13 New rechargeable energy storage systems in development: Focus >> 400 Wh/kg, >> 1000 Wh/l Zn-Air (1,6V, ± 500 Wh/kg, ± 1500 Wh/l practical values) Electrolyte Aqueous KOH Negative metal Zinc Positive reversible air electrode carbon with catalyst Power density is still uncertain. Carbon/carbon supercapacitors or a hybrid capacitor could be used for high pulse power. Electrical rechargeability still confronted with fundamental problems:shape change and dendrite formation. Solutions are still actively pursued 13 Ref. Powerair Corp. Fig. 9

14 New rechargeable energy storage systems in development: Focus >> 400 Wh/kg, >> 1000 Wh/l Li-Air (3,4V, ± 1300 Wh/kg) practical values Battery of the future?? Issues: Electrolyte choice/organic aqueous Reversibility, cyclability Safety Univ. St. Andrews (P. Bruce) Fig

15 Li-S (2.1V, 350 Wh/kg, 350 Wh/l) Liquid cathode, safety? Tolerant of overvoltages Important players: Sion Power Intelikraft Ltd. Poly Plus Battery Cy PolyPlus Battery Company Fig

16 Na-S (2V) Fig. 12 High temperature system more developed for electricity storage for grid support (NGK Insulators Japan) 16

17 Agenda 1. Umicore materials supplier to the battery industry 2. Generic insight battery technologies, opportunities and challenges 3. Further advances to increase performances and reduce cost 4. Pace of technology evolution 5. Glossary

18 Further advances to increase performance and reduce cost Fig

19 Focus Li-ion Present average cost at cell manufacture level in $/kwh: Consumer electronics : HEV : (pack price is ) Target HEV : 250 (e.g. USABC targets) How to achieve this? 1. Increase cell/module capacity: advanced Li-Ion, new systems (see previous chapter) 2. Reduce material cost: LiCoO 2 -> cheaper materials (see previous chapter) 3. Automation and mass production (HEV/EV) 19

20 Current cost structure in Li-ion battery industry Two different models: Japan/Korea (automated) vs China (more manual) For the Japan/Korea model: materials > 50% of the total battery cost The pressure will remain on finding new materials that reduce/eliminate cobalt use Fig. 14 Fig

21 Agenda 1. Umicore materials supplier to the battery industry 2. Generic insight battery technologies, opportunities and challenges 3. Further advances to increase performances and reduce cost 4. Pace of technology evolution 5. Glossary

22 Timeline for implementation of new technologies Now/done NiMH Li-Ion Advanced Li-Ion Ongoing fast substitution (fig. 16) ongoing for cathode materials (fig. 17) In roadmaps and announced for anode materials > 2020 New battery Systems Possible introduction depends on application: In HEV/EV not before 2020? In Consumer applications may be earlier especially for Zn Air (already exists in primary cells) and Li-Air RECYCLING (fig. 18) Fig 16, 17 & 18 see next pages 22

23 Rechargeable Battery Market value (in M$/yr) Fig

24 Potential evolution of share of cathode materials technology Fig

25 Critical step to Li-Ion and new battery systems further market development is to offer recycling capabilities Umicore patented and award-winning process VAL EAS Fig

26 Agenda 1. Umicore materials supplier to the battery industry 2. Generic insight battery technologies, opportunities and challenges 3. Further advances to increase performances and reduce cost 4. Pace of technology evolution 5. Glossary

27 Glossary Precursor Spinel Ionic Liquids LMO NCA Li-S Na-S HEV EV NiMH Feed material to produce the lithium metal oxide compound a crystallographic structure (AB204) a term generally used to refer to salts that form stable liquids Product designation for Li-ion battery cathode oxides containing Manganese (Lithium Manganese Oxide) Umicore product designation for Li-ion battery cathode oxides containing Nickel, Cobalt and Aluminium Lithium Sulphur rechargeable battery Sodium Sulphur rechargeable battery Hybrid Electrical Vehicles Electrical Vehicle Nickel Metal Hydride battery 27