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Beyond Lithium ion – future research trends and strategies

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1 Beyond Lithium ion – future research trends and strategies
powered by Lithium Beyond Lithium ion – future research trends and strategies Dr. Christoph Hartnig Business Development Lithium © 2008 CHEMETALL GMBH - This document and all information contained herein is the proprietary information of CHEMETALL GMBH. No intellectual property rights are granted by the delivery of this document or the disclosure of its content. This document shall not be reproduced or disclosed to a third party without the express written consent of CHEMETALL GMBH. This document and its content shall not be used for any purpose other than that for which it is supplied.

2 Forward Looking Statements
This presentation may contain certain "forward-looking statements" within the meaning of the Private Securities Litigation Reform Act of 1995 concerning the business, operations and financial condition of Rockwood Holdings, Inc. and its subsidiaries (“Rockwood”). Although Rockwood believes the expectations reflected in such forward-looking statements are based upon reasonable assumptions, there can be no assurance that its expectations will be realized. "Forward-looking statements" consist of all non-historical information, including the statements referring to the prospects and future performance of Rockwood. Actual results could differ materially from those projected in Rockwood’s forward-looking statements due to numerous known and unknown risks and uncertainties, including, among other things, the "Risk Factors" described in Rockwood’s 2008 Form 10-K with the Securities and Exchange Commission. Rockwood does not undertake any obligation to publicly update any forward-looking statement to reflect events or circumstances after the date on which any such statement is made or to reflect the occurrence of unanticipated events.

3 Lithium – de la nube al cristal
Salar de Atacama

4 Sociedad Chilena de Litio (SCL)
Chemetall’s daughter company in Chile History SCL was established in August 13, 1980 First brine production in 1984 Lithium Carbonate plant (Li2CO3 TG) since 1984 Potassium Chloride plant (KCl) since 1988, at El Salar Lithium Chloride plant (LiCl) since 1997 High Purity Lithium Carbonate (Li2CO3 HP) since 2004 Other products Magnesium chloride (MgCl2.6H2O) Sodium Chloride (NaCl) Potash (KCl) Chemetall has invested about 10 Mio USD/year during the last 5 years Chemetall employs about 200 people in Chile, of which about 70 people live in Peine area

5 Chemetall‘s strategic position in Lithium
world’s largest producer of lithium salts and Lithium based organic specialties more than 50% market share for Lithium Products; for Li2CO3 market share is approx. 30% long history and experience in Lithium production since 1925 complete backward integration long-term technology leader leading-edge producer of lithium compounds used in Li-ion batteries production and R&D facilities in North and South America, Europe and Asia-Pacific significant additional investments to strengthen our global market presence: R&D facility at the Salar de Atacama and La Negra

6 Lithium – more than e-mobility
Key Products Key Applications Cement Aluminum Lithium carbonate Li-ion batteries Glass ceramics Lithium hydroxide Li-ion batteries Grease CO2 Absorption Mining Lithium metal Li primary batteries Pharmaceuticals Al - alloys Butyl- lithium Elastomers Pharmaceuticals Agrochemicals Lithium specialties Electronic materials Pharmaceuticals Agrochemicals

7 consumption of Lithium by end-use (2009)
[total: mt LCE]

8 hot topic: e-mobility CO2 emissions ambitious targets worldwide:
main driver: transportation ambitious targets worldwide: Japan: reduction of CO2 emission by 25% compared to 1990 Germany: 43 gCO2/km in average by 2050 (>70% ZEVs) USA: 165 gCO2/km by 2016 new generation of vehicles: 1 Mio e-cars in Germany by 2020 China: ~ 120 mio electrified vehicles (e-bikes, pedelecs, scooter,..) within the next years

9 electric cars – first generation
Lohner Porsche (1899)  410 kg lead acid batteries driving range: 50 km (not too much of improvement so far)

10 the horsepower race Toyota SUV today = Ferrari in 1984
attractive driving performance requires high energy batteries [taken from: D. Sperling, U. California, 2009]

11 batteries – energy densities
energy density – what do we need? key issues: safety, cyclability, charging behavior type of battery energy density [Wh/kg] comment lead acid 30-40 high weight, low density NiCd 40-70 environment!, high self-discharge NiMH 60-80 currently used in hybrid vehicles Li-ion fast charge/discharge beyond lithium ion >450 safety, price, stability, R&D level

12 Li-ion batteries battery weight for 100 km driving distance (1 kWh  5 km) Gen III Gen IV

13 energy densities – future generations
effective range [km] >500 - ca Wh/kg Li-sulfur Li-air 500 300 Wh/kg Alloy anode high voltage cathode 200 Wh/kg risk 130 Wh/kg LiB LiB optimized 100 50 time today 2012 near future future

14 and now to the chemistry

15 Li-ion batteries charge transport achieved by Li+ ions, intercalation compounds on the anode and cathode [source: Axeon – Battery guide]

16 new battery technologies
severely enhanced power densities obeying safety issues high stability (number of cycles) durability (calendar life) target: >300 Wh/kg on cell level >200 Wh/kg on system level most promising candidates high voltage cathodes Li / air Li / sulfur Gen III Gen IV

17 Gen III – improved materials

18 future trends of existing materials
Layered Spinel Olivine commercialized Ni0.8Co0.15Al0.05O2 (NCA) Ni1/3Mn1/3Co1/3O2 (NMC) LiCoO2 (LCO) LiMn2O4 (LMO) LiFePO4 (LFP) next gen NMC-Al doped high energy NMC LiMn1.5Ni0.5O4 LiMn1.5(Fe,Cr,Co)0.5O4 LiCoPO4, LiMnPO4 LiFeSiO4

19 adaption of particle size
example: Li-iron-phosphate (LFP) nano-sized high power density micro-aggregates high energy density influence of particle size on the performance of the electrode material  high surface for fast transport, large volume for high capacity [source: Th. Laars, Sued-Chemie, Battery Seminar, 2010]

20 state-of-the-art cathode materials
nickel-manganese-cobalt (NMC) NMC (1:1:1): 3.7 V Al-doping: Al0.1: 3.75 V Al0.13: 3.85 V [source: J. Dahn, Dalhousie University, 2009]

21 layered-layered oxides (HE-NMCs)
Li2MnO3Li(Nix Coy Mnz)O2: The Li2 MnO3 domains result in higher capacity when activated above 4.4V [source: J. Lampert, BASF, IBA-2011, Cape Town]

22 high-energy NMCs 40 US$/kg 25 US$/kg 3.5 US$/kg
[source: J. Lampert, BASF, IBA-2011, Cape Town]

23 high capacity anodes

24 carbon composites – tin/silicon
increased capacity (by a factor of up to 5) self assembly of tin-carbon and silicon-carbon composite anode materials leads to reduced volume expansion during charge and discharge [sources: J. Hassoun et al., J. Power Sources 196 (2011) 349; Georgia Institute of Technology, 2011; Biswal Lab, Rice Univ.]

25 Gen IV – beyond Li-ion

26 discharge / power supply: 2 Li + S  Li2S
Li/sulfur – principle charging (Li plating) discharging (Li stripping) 2 Li+ + S8 Li2S8 Li2S4 Li2S2 Li2S Li metal Li+ Li0 anode cathode sulfur electrode separator electrolyte discharge / power supply: 2 Li + S  Li2S anodic reaction: Li  Li+ + e– cathodic reaction: 2 Li+ + Sx + 2 e–  Li2Sx

27 most critical problem: dendrite formation
major challenge in Li-metal based batteries inhomogeneous Li-deposition during charging (Li-plating)  in-situ study on dendrite formation interface 900 sec separator 600 sec 190 µm 0 sec penetration of separator leads to internal shortings  EOL [source: A. West, Columbia University, 2008]

28 theoretical performance !
Li/sulfur S8 S8 + 2 e– + 2 Li+  Li2S8 Li2S8 + 2 e– + 2 Li+  2 Li2S4 upper plateau Li2S4 + 4 e– + 4 Li+  4 Li2S2 4 Li2S2 + 8 e– + 8 Li+  4 Li2S2 lower plateau theoretical performance ! [source: J. Affinito, Sion Power, ORNL, 2010]

29  losses due to cross over  reduced shuttle activity
Li/sulfur  theoretical  losses due to cross over  reduced shuttle activity [source: J. Affinito, Sion Power, ORNL, 2010]

30 solubility of Li-sulfide compounds
Li2S6/Li2S4 Li2S2 Li2S high good/moderate very low insoluble solubility upper plateau – fast kinetics lower plateau – slow kinetics high solubility plus fast kinetics of Li2S8 leads to a loss of ~400 mAh/g S S8, Li2S8, Li2S6, Li2S4, Li2S3 are (highly) soluble, Li2S2 and Li2S are very low or insoluble formation of Li2S on the anode side by reduction of polysulfides

31 Li/sulfur – conclusion
high theoretical capacity: 1672 Ah/kg (S) high solubility and shuttle behavior of polysulfides might lead to severe performance losses: Li2Sx shuttle from cathode to anode reduction and subsequent formation of Li2S on the anode performance loss up to 400 mAh/g (S) new separator materials and technologies to minimize polysulfide cross-over are needed

32 discharge / power supply: 2 Li + O2  Li2O2
Li/air – principle charging (Li plating) discharging (Li stripping) Li metal O2 Li+ Li0 O2 air O2 O2 separator air electrode discharge / power supply: 2 Li + O2  Li2O2 anodic reaction: Li  Li+ + e– cathodic reaction: 2 Li+ + O2 + 2 e–  Li2O2

33 Li/air – challenges at first glance, the stability looks ok for a lab cell (space for improvement) [source: F. Mizuno, Toyota, ORNL, 2010]

34 Li/air – challenges [source: F. Mizuno, Toyota, ORNL, 2010]

35 Li/air – challenges [source: F. Mizuno, Toyota, ORNL, 2010]

36 Li/air – challenges state-of-the-art power densities of Li/air cells need to be increased by approx 2 orders of magnitude  challenge for highly active bi-functional catalysts [source: Y. Shao-Horn, MIT, ORNL, 2010]

37 Li/air – conclusion maximum number of 100 cycles has been proven
Li2O2 is not the main discharge product; XO-(C=O)-OLi-type alkylcarbonates are formed, with CO2 formation during recharging the large voltage gap of 1.4 V during discharging and charging is caused by the side reaction leading to the formation of alkyl carbonates propylene carbonate is attacked by the O2 radical electrolyte solvents with high electrochemical stability against O2, such as ionic liquids, are required active bi-functional catalysts are key factor for application

38 R&D roadmap – market launch
2010 2015 2020 2025 2030 Li-ion III Li/S Li/air

39 Chemetall – R&D network

40 dedication – global R&D network
Asia Americas Europe Other Research Institutes Industry and Trade Associations Equipment Suppliers Chemical Industry Automotive Industry ITRI DOE German & US Governmental Offices Strong R&D network to meet future market needs for LIB

41 Chemetall as the leading producer of lithium compounds is committed to continuously expand its R&D activities and to maintain its position as reliable supplier to new markets and technologies.


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