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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.
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