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Beyond Lithium ion – future research trends and strategies

Dr. Christoph HartnigBusiness Development Lithium

powered by Lithium

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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.

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Lithium – de la nube al cristal

Salar de AtacamaSalar de Atacama

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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

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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

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Lithium – more than e-mobility

Key Products Key Applications

Lithium carbonate

Butyl-lithium

Lithium metal

Lithium hydroxide

Lithium specialties

Pharmaceuticals

Pharmaceuticals

Pharmaceuticals

Glass ceramics

Grease CO2 Absorption

Elastomers

Aluminum

Li primary batteries

Electronic materials

Cement

Al - alloys

Mining

Agrochemicals

Agrochemicals

Li-ion batteries

Li-ion batteries

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consumption of Lithium by end-use (2009)

[total: 100.000 mt LCE]

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hot topic: e-mobility

CO2 emissions

– 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

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electric cars – first generation

Lohner Porsche (1899) 410 kg lead acid batteries driving range: 50 km (not too much of improvement so far)

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the horsepower race

Toyota SUV today = Ferrari in 1984 attractive driving performance requires high energy batteries

[taken from: D. Sperling, U. California, 2009]

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batteries – energy densities

energy density – what do we need? key issues: safety, cyclability, charging behavior

type of batteryenergy 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 120-190 fast charge/discharge

beyond lithium ion

>450 safety, price, stability, R&D level

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167

105

40

571

286

Pb acid NiMH Li-ion/LFP Li-ion/NMC next gen

wei

gh

t [k

g]

Li-ion batteries

battery weight for 100 km driving distance (1 kWh 5 km)

Gen III Gen IV

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energy densities – future generations

time

today

130 Wh/kg130 Wh/kg

LiB

300 Wh/kg300 Wh/kg

Alloy anodehigh voltage

cathode

>500 -ca. 1500 Wh/kg

>500 -ca. 1500 Wh/kg

Li-sulfurLi-air

2012

150-170 Wh/kg150-170 Wh/kg

LiB optimized

50

100

500

200

effective range [km]

near future future

risk

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and now to the chemistry

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Li-ion batteries

charge transport achieved by Li+ ions, intercalation compounds on the anode and cathode

[source: Axeon – Battery guide]

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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

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Gen III – improved materials

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future trends of existing materials

LayeredLayered SpinelSpinel OlivineOlivine

commercialized

Ni0.8Co0.15Al0.05O2 (NCA)

Ni1/3Mn1/3Co1/3O2 (NMC)

LiCoO2 (LCO)LiMn2O4 (LMO) LiFePO4 (LFP)

next genNMC-Al doped

high energy NMC

LiMn1.5Ni0.5O4

LiMn1.5(Fe,Cr,Co)0.5O4

LiCoPO4, LiMnPO4

LiFeSiO4

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adaption of particle size

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]

nano-sizedhigh power density

micro-aggregateshigh energy density

example: Li-iron-phosphate (LFP)

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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]

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layered-layered oxides (HE-NMCs)

Li2MnO3Li(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]

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high-energy NMCs

[source: J. Lampert, BASF, IBA-2011, Cape Town]3.5 US$/kg

40 US$/kg

25 US$/kg

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high capacity anodes

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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.]

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Gen IV – beyond Li-ion

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Li/sulfur – principle

discharge / power supply: 2 Li + S Li2S– anodic reaction: Li Li+ + e–

– cathodic reaction: 2 Li+ + Sx + 2 e– Li2Sx

Limetal

Li+

separator sulfurelectrode

electrolyte

2 Li+ + S8

Li2S8

Li2S4

Li2S2

Li2Sanode cathode

charging (Li plating)

discharging (Li stripping)

Li0

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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

190 µm

0 sec 600 sec 900 sec

separator

interface

[source: A. West, Columbia University, 2008]

penetration of separator leads to internal shortings EOL

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Li/sulfur

[source: J. Affinito, Sion Power, ORNL, 2010]

upperplateau

lowerplateau

S8

S8 + 2 e– + 2 Li+ Li2S8

Li2S8 + 2 e– + 2 Li+ 2 Li2S4

Li2S4 + 4 e– + 4 Li+ 4 Li2S2

4 Li2S2 + 8 e– + 8 Li+ 4 Li2S2

theoretical performance !

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Li/sulfur

[source: J. Affinito, Sion Power, ORNL, 2010]

theoretical

losses due to cross over

reduced shuttle activity

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solubility of Li-sulfide compounds

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

Li2S8 Li2S6/Li2S4 Li2S2 Li2S

high good/moderate very low insoluble

solubility

upper plateau – fast kinetics lower plateau – slow kinetics

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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

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Li/air – principle

discharge / power supply: 2 Li + O2 Li2O2

– anodic reaction: Li Li+ + e–

– cathodic reaction: 2 Li+ + O2 + 2 e– Li2O2

Limetal

O2

O2

O2

O2

separator air electrode

air

charging (Li plating)

discharging (Li stripping)

Li+

Li0

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Li/air – challenges

at first glance, the stability looks ok for a lab cell (space for improvement)

[source: F. Mizuno, Toyota, ORNL, 2010]

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Li/air – challenges

[source: F. Mizuno, Toyota, ORNL, 2010]

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Li/air – challenges

[source: F. Mizuno, Toyota, ORNL, 2010]

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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]

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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

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R&D roadmap – market launch

2010 2015 2020 20302025

Li/S

Li/air

Li-ion III

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Chemetall – R&D network

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dedication – global R&D network

Strong R&D network to meet future market needs for LIB

AsiaAmericas

Europe

Other Research Institutes

Industry and Trade Associations

Equipment Suppliers

Chemical Industry

Automotive Industry

ITRI

DOE

German & US Governmental Offices

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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.