FMC LithiumTechnology Seminar - Battery Japan

Stabilized Lithium Metal Powder (SLMP )

March 2nd, 2011

Our Global Locations: Argentina, China, India, Japan, United Kingdom, United States, and Taiwan.

FMC Lithium Summary

Salar del Hombre Muerto, Argentina

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Business Confidential

BrineExpansion

Existing Salar ponds

Salar del Hombre Muerto , ArgentinaLocated in the high Andes at about 4000 m or 14,000 feet above sea level30% expansion over current capacity

Creating new ponds

Addressing New Product Requirements

Grades of :Li Carbonate

Industrial GradeTechnical GradeMicronized Technical GradeBattery GradeMicronized Battery Grade

Li HydroxideTechnical GradePurifiedBattery Quality Grade

Li metal

Stabilized Lithium Metal Powder (SLMP®)

4

5

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Cathode Active23%

Anode Active

6%Electrolyte

6%

Separator8%

Ancillaries22%

Production Cost35%

Cell Cost Components (%)

Li7% Ni

6%

Co25%

Mn2%

Process43%

Margin17%

Cathode Break-down (%)

Lithium is ~1.5% of cell costLess than 1% of final battery cost

Source: Deutsche Bank

Large format battery (i.e. automotive):Cells (150 Cells) $7,395Mechanical parts, packaging, labor $4,005Margin $3,600Total Packed Cost (25 kWh) $15,000*Assuming NCM cathode

Li-ion battery will not work without Li, but Li is not the cost driver. Li is only a small part of the battery cost.

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Lower Cost, Higher Energy, and Better Safety

New electrode materials are necessary to increase energy density of Li-ion batteriesLi-ion technology has been expanding into large format batteries Automotive use demands lower cost and improved safety

Need more choices for active and inactive materials!Need to break the current limitation that all lithium has to come from the cathode of the Li-ion cell.

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Lectro® Max 100 Series, Stabilized Lithium Metal Powder

Normal lithium powderCan only be handled in an argon filled glove boxNot commercially available as powder

Stabilized Lithium Metal Powder (SLMP )Safe to handle in a dry roomCan be transported by air or seaMetallic Li content is at least 98%

FMC has been producing lithium powder for its own use at the level of hundreds of tons/year for over 30 years

SEM Image of SLMP

Optical Microscope Image of SLMP sprayed on the electrode

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Dry Room Stability

0

20

40

60

80

100

120

0

20

40

60

80

100

120

0 100 200 300 400

SLM

P Ca

paci

ty, %

Li, %

Hours of Exposure

SLMP-powder SLMP-derived thin foil

SLMP-derived thin foilSLMP coated onto Cu foil and pressed at 12,000 lbs per 1.2 cm2

Electrodes exposed to a Dry Room environment with Dew Point of ~ -50oC for predetermined time periodActive Li was measured by the specific capacity from those electrodes using half cells. The cells were charged at 0.1mA to 3.0 V. The average loading per cell was about 1mg.

SLMP PowderDew Point -30oC or betterMaterial spread in thin layer in Petri dishesMaterial is not disturbed during exposureMaterial is thoroughly mixed prior to analytical analyses

Ultra thin Li foils generated with SLMP stability same as foils, and electrochemical activity same as foils

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Benefits of SLMPOpening up choices for active materials

Anode choice no longer limited to graphite.Allows the use of new materials with both large reversible and irreversible capacities, such as Si composites and Sn intermetallics.

Cathode choice no longer limited to lithium providing materials.Much wider selections of non lithium providing materials offering more possibilities: more overcharge tolerant, lower cost, and larger capacities.

Use of SLMP in battery material synthesisSi and Sn Composite anode materials

Bottom line: increase in energy density, improvements in safety and calendar life, cost reductions

Using Lithium from SLMP will cost less than using Lithium from LiCoO2 cathode and you can pocket other advantages too

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(G raphite+SL MP )/MnO2

A non-lithium providing cathode is now possible lower cost and safer

0 5 10 15 20 25 30

Cycle Number

0

100

200

300

Spec

ific

Capa

city

, (di

scha

rge

mAh

/g)

Constant Current 0.1mA, Charge 4.3V, Disharge 1.5V0.5

1

1.5

2

2.5

3

3.5

4

0 2 4 6 8 10 12 14 16

vs.Li-1st disvs.Li2nd disvs.Li 3rd disvs.LiMCMB-1st disvs.LiMCMB 2nd disvs.LiMCMB 3rd dis

Cel

l Vol

tage

Discharge Time (h)

BiF3 Nanocomposite

LiPF6 EC:DMC

24oC 15 mA /g

"Li2.45

BiF3"

BiF3

(G raphite+SL MP )/ BiF3 Nanocomposite

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High capacity anode is now possible

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Cell examples

First Cycle Efficiency Improvement in LiCoO2/Graphite System Using SLMP (Data courtesy of MaxPower Corporation)

Capacity0.0% 20.0% 40.0% 60.0% 80.0% 100.0%

Volta

ge (V

)

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

Baseline First Cycle DischargeGraphite/LiCoO2 Cell

First Cycle DischargeSLMP+Graphite/LiCoO2 Cell

Improvement

A L i-ion cell: G raphite+SL MP //LiCoO2

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Cycle number (n)0 10 20 30 40 50 60

Capa

city

(mAh

)

0

10

20

30

40

50

60

Baseline cell: chargeBaseline cell: dischargeSLMP incorporated: chargeSLMP incorporated: discharge

Capacity (%) Based on First Charge0 20 40 60 80 100

Volta

ge (V

)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

Baseline First Cycle DischargeGraphite/LiMn2O4Cell

First Cycle DischargeSLMP+Graphite/LiMn2O4Cell

Improvement

First Cycle Efficiency Improvement in LiMn2O4/Graphite System Using SLMP, and it cycles better too!

A L i-ion cell: (G raphite+SL MP)/ L iMn2O4

Cell examples

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First Cycle Efficiency Improvement in LiMn2O4/Hard Carbon System Using SLMP, more benefits for automotive systems!

A L i-ion cell: (Hard Carbon+SL MP)/L iMn2O4

Cell examples

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0 10 20 30 40 50 60 70 80

Volta

ge, V

Capacity, mAh

ImprovementBaseline First Cycle Discharge Hard Carbon/ LiMn2O4 Cell

First Cycle Discharge Hard Carbon+ SLMP/ LiMn2O4 Cell

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SLMP Introduction into the CellTwo general methods to apply SLMPSlurry application

Include SLMP in the slurry mix when the anode sheet is being cast no additional step but the slurry solvent needs to be compatible with lithium.

Surface applicationCoat SLMP suspension on the surface of a pre-fabricated anode sheet no need to change the existing anode fabrication process

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Industrially Scalable Processes

Set-up designed for D-cell production with SLMPTM Technology incorporatedunder US Army contract W15P7T-06-C-P242.

Slurry basedMicro Gravure coating method

Video clip

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SLMP can be transferred to electrode surface through a carrier filmSolvent Free!

Lithium Metal Carrier Film Technology (LMCF)

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Video clip

AdvantagesNo solvent involved at cell assembly placeJust attach, press and peel

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LMCF Applied to MCMB prefabricated anode sheet

LMCF applied to Hard Carbon prefabricated anode sheet

First Cycle Efficiency Improvement Using LMCF Technology

Cathode composition: LiMn2O4 (90%), Super P carbon black (5%), Kynar 761 PVdF (5%). We used Novolyte 1M LiPF6 /EC+DEC (1:1) electrolyte.

The cell test protocol : constant current charge at 0.5 mA/cm2 to 4.3 V followed by 4 hours constant voltage charge at 4.3 V and constant current discharge at 0.5

mA/cm2 to 3.0 V.

Anode formulation: 90% MCMB 25-28, 5% PVdF, 5% Conductive Carbon (Super P)

Anode formulation: 90% Carbotron PS(F), 7% PVdF, 3% Conductive Carbon (Super P)

0 10 20 30 40 50 60 70 80 90 100

Capacity (mAh)

0

1

2

3

4

5

Volta

ge (V

)

First cycle DischargeGraphite + SLMP/LiMn2O4 Cell

Baseline First Cycle DischargeGraphite/LiMn2O4 Cell

Improvement

0 10 20 30 40 50 60 70

Capacity (mAh)

0

1

2

3

4

5

Volta

ge (V

)

First cycle DischargeHard Carbon + SLMP / LiMn2O4 Cell

Baseline First Cycle DischargeHard Carbon / LiMn2O4 Cell

Improvement

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SLMP Lithiation vs. Electrochemical Lithiation

Figure. The capacity-voltage profiles of the 1st cycle for the baseline, SLMP lithiated, and electrochemically lithiated cells.

Figure. The capacity-voltage profiles of the 2nd cycle for the baseline, SLMP lithiated, and electrochemically lithiated cells

Procedure to construct an electrochemically lithiated cell: 1. Assemble baseline hard carbon / LiMn2O4 pouch cells with no SLMP added2. Charge cells to 30 mAh and disassemble to recover the partially charged hard carbon anode (assumption: 3000 mAh/g capacity

for SLMP)3. Assemble new pouch cell using partially lithiated anode and spinel cathode

Cycle cells using the following protocol: constant current charge at 0.25 mA/cm2 to 4.3 V, and then constant voltage charge at 4.3 V; the whole charge process proceeded for about 10 hours followed by a constant current discharge at 0.25 mA/cm2 to 3.0 V.

0 10 20 30 40 50 60 70

Capacity (mAh)

2.8

3.0

3.2

3.4

3.6

3.8

4.0

4.2

4.4

Volta

ge (V

) SLMP Lithiation ChargeSLMP Lithiation DischargeEC Lithiation ChargeEC Lithiation DischargeBaseline ChargeBaseline Discharge

0 10 20 30 40 50 60 70

Capacity (mAh)

2.8

3.0

3.2

3.4

3.6

3.8

4.0

4.2

4.4

Volta

ge (V

) Basel ine Charge Basel ine DischargeSLMP Lithiation ChargeSLMP Lithiation DischargeEC Lithiation ChargeEC Lithiation Discharge

Thin Li foil as applied onto the surface of pre-fabricated anode

After 7 days of storage at 25oC

After 9 days of storage at 25oC

Graphite anode22

Rolled Li thin foil (<30 micron): macro viewLithiation with thin Li foils a very slow process

Prior to electrolyte addition after electrolyte addition, time=1hr

time=1 day time=7 days23

Rolled Li thin foil (<30 micron): macro viewLithiation with thin Li foils a very slow process

LiC 6

Li0.

5C6

Li0.

25C 6

Optical observation of Li staging in graphite. The color bands indicate different Li concentration phases, as Li ions move from the foil attached into the graphite electrode

Li/Graphite Voltage curve courtesy of Tao Zheng, PhD Thesis Simon Fraser University 1996

The Li concentration inside of the graphite electrode near the foil remains high due to slow Li diffusion in graphite it takes a long time for Li concentration to equalize due to the distance Li has to travel.

SLMP provides a localized Li distribution much faster to reach equilibrium with SLMP treated electrode compared to foil treated one.

Unless you want to wait for days,use SLMP to lithiate your electrode

much faster diffusion

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SummaryFMC Lithium has an extensive play in the lithium-ion battery market, from providing basic lithium raw materials to developing new materials and technologies.

Out of box thinking is needed to meet the more challenging requirements of large format batteries.

SLMP enables more material choices to meet the increasing demands for more energy, lower cost and better safety for Li-ion batteries by providing an independent source of lithium for Li-ion batteries.

SLMP can be introduced into the cell through industrially scalable methods.

We welcome the Battery Community to visit CLEAR and apply SLMP onto your current and advanced electrode materials and get trained in safe Lithium handling

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CLEAR Lab Capabilities

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Center for Lithium Energy Advanced Research

Located at our Bessemer City, North Carolina plant

Equipped with a state-of-the-art R&D Dry Room for testing rechargeable lithium-ion battery components

Used for development and demonstration of SLMP®--stabilized lithium metal powder

Used by customers for evaluation of their proprietary material with SLMP

Core SLMP Technical Team: Brian Fitch, Scott Petit, Mike Barr, Marina Yakovleva, Chris Woltermann, Terry Arnold, Yangxing Li

Core SLMP Technical Team

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