Successful water processing of cathode materials...

© copyright 2014 IK4·CIDETEC

Successful water processing

of cathode materials

for lithium-ion batteries

3th of June, 2015

MAT4BAT Summer School

June 2nd to 4th, 2015

EIGSI La Rochelle

Andriy Kvasha

[email protected]


RTD Foundation created in 1997

Member of IK4 Technological Alliance

125 People, with 50% Ph.D and 90% Degree

10 M€ Income in 2014

Board of Management:

Organization

Who we are


Energy Batteries

Battery R&D at IK4-CIDETEC

Main target:

• Lithium Ion Battery technology development

• Industrial transference

• Focus on: Electromobility + Stationary Energy Storage

3


Energy Batteries


Main target:




Scope:

Commercial materials validation

Electrode formulation & optimization

Cell development

Modules & packs development

Validation & comprehensive testing

Modeling

Ante and post mortem analysis

4


Energy Batteries


Main target:




Scope:

Commercial materials validation

Electrode formulation & optimization

Cell development

Modules & packs development

Validation & comprehensive testing

Modeling

Ante and post mortem analysis

Longer term approach:

New concepts for next generation batteries:

Advanced Li-ion

Post Li-ion: Li-S, Li-air, Na-ion

Zn based batteries

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Reference EU Projects: Lithium ion batteries

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Project CIDETEC role

GREENLION Advanced

Manufacturing Processes for Low Cost GREENer

Li-ION Batteries

Coordinator; support industrial partners on electrode coating scale-up cell design and testing; module design and assembly

MARS-EV Materials for Ageing Resistant Li-ion High

Energy Storage for the Electric Vehicle

Coordinator; water-based electrode formulation, scale-up and evaluation of new active materials; prototype cell testing; ageing assessment/modelling

MAT4BAT Advanced materials

for batteries

Consortium member; Water-based electrode formulation, formulation scale-up, cell development, cell testing & ageing assessment


Aqueous processing &

Lithium ion battery technology

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8

COST

ENERGY DENSITY

DURABILITY

SAFETY

ENVIROMENTAL FRIENDLINESS

Lithium ion batteries. COST.


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COST

ENERGY DENSITY

DURABILITY

SAFETY



Now: $500 / kWh


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COST

ENERGY DENSITY

DURABILITY

SAFETY



Now: $500 / kWh

Holy grail EV: $100 / kWh


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Lithium ion batteries. Aqueous processing.


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Lithium ion batteries. Aqueous processing.

D.L. Wood III et al. / Journal of Power Sources 275 (2015) 234-242

…It is shown that aqueous electrode processing can cut

the electrode processing cost and energy consumption by an

order of magnitude due to higher dispersion solids loading,

lower drying temperature, lower air flow rate, and shorter

drying time due to the lower boiling point, higher vapor

pressure, and lower heat of vaporization of water…


Lithium ion batteries & aqueous processing

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Carbon coated LiFePO4 likes to react with water!



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Nevertheless, LiFePO4 can effectively work even in aqueous lithium ion batteries!



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Nevertheless, LiFePO4 can effectively work even in aqueous lithium ion batteries!

J.-Y. Luo et al. / Nature Chemistry, 2010 DOI: 10.1038/NCHEM.763

The LiFePO4 contains 15 wt. % of coating carbon and shows excellent stability.


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Electrodes LIB: Aqueous vs. Organic processing

Electrode Pros Cons Status

Negative (carbon based)

• Greener • Cheaper • Energy saving • Decreasing

binder content

• Hydrophobicity of carbon materials (graphite, MCMB, carbon black etc.)

• Processing issues (agglomeration etc.) • Water uptake

Mature Mass production


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Electrodes LIB: Aqueous vs. Organic processing

Electrode Pros Cons Status

Negative (carbon based)


binder content

• Hydrophobicity of carbon materials (graphite, MCMB, carbon black etc.)

• Processing issues (agglomeration etc.) • Water uptake

Mature Mass production

Positive (Li-oxides,

phosphates)


binder content

• Hydrolysis and high alkalinity of slurry • Aluminum current collector corrosion • Hydrophobicity of conductive

additives (carbon black etc.) • Processing issues (agglomeration etc.) • High water uptake • Cycle life issues

Under development R&D Pilot scale Mass production


Aqueous processing of cathode

Case studies

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The cathode prepared using a commercial LiNixMnyCoO2 and waterborne binders.

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Charge – discharge profiles at 1C/2C (HCC) Capacity retention at 1C/1C (FCC)

Half coin cell: NMC cathode loading 12-13 mg/cm2, 25oC

Full coin cells: anode - C-NERGY ACTILION 1 (IMERYS Graphite & Carbon), DOD 100%, 3.0-4.2 V, 25oC

Water based PVdF binders for anode and cathode were provided by SOLVAY SPECIALTY POLYMERS

LiNixMnyCozO2


The cathode prepared using a commercial LiMn1-xFexPO4 and waterborne CMC/SBR binders.

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Charge – discharge profiles at 1C/1C (HCC) Discharge C-rate capability (HCC)

Test details: half coin cell, cathode loading 7-8 mg/cm2, 25oC

LiMn1-xFexPO4


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Test details: full coin cell, cathode loading 7-8 mg/cm2

Long term cyclability

LiMn1-xFexPO4 - Li4Ti5O12

Both electrodes prepared using a commercial materials and waterborne CMC/SBR binders.

2C/5C, DOD 100%, 45oC 5C/10C, DOD 100%, 25oC

LiMn1-xFexPO4- Li4Ti5O12


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LiFePO4

Mixing intensity has crucial impact on stability of C/LiFePO4 at contact with water.

Discharge C-rate capability (HCC)

ICE

97.2%

106.2%

Test details: half coin cell, cathode loading 9 mg/cm2, 2.00-3.65V, 25oC


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LiFePO4


Discharge profiles at C/5 and 10C (HCC) Discharge C-rate capability (HCC)

ICE

97.2%

106.2%



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LiFePO4


Discharge profiles at C/5 and 10C (HCC) Discharge C-rate capability (HCC)

ICE

97.2%

106.2%


High Initial Coulombic Efficiency (ICE) and plateau at 2.6V on discharge curves

suggest appearance of LixFeIIIPO4(OH)x phase* due to interaction of LFP with water.

* J. F. Martin et al. / J. Power Sources 196 (2011) 2155–2163


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LiFePO4- Graphite

Test details: full coin cell, cathode loading 10-11 mg/cm2, 2.00-3.65V

1C/1C, DOD 100%, 25oC

Electrode Water

residue*, ppm

LFP micro 460

LFP nano 920

LFP nano (enhanced)

650

* - Karl Fischer Oven Method,

furnace temperature 160oC

Specific surface → Water uptake → Cell capacity retention


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Pouch cell: LiFePO4 - C

Long term cyclability has been achieved for LFP-C pouch cells with

negative and positive electrodes prepared via aqueous processing

route.


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Pouch cell: LiFePO4 - C

Test details: pouch cell, cathode loading 11-12 mg/cm2, 2.00-3.65V, DOD 100%, 25oC

0.5 Ah pouch cell (1C/1C) 1 Ah pouch cell (1C/4C)

Long term cyclability has been achieved for LFP-C pouch cells with

negative and positive electrodes prepared via aqueous processing

route.


Aqueous processing of the cathodes is a viable approach for lithium ion battery

technology.

The approach is already stepped out of R&D and pilot scale level.

Conclusions and perspectives

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Aqueous processing of the cathodes is a viable approach for lithium ion battery

technology.

The approach is already stepped out of R&D and pilot scale level.

More development of cathode materials tailored for water processing is needed.

We believe that cathode aqueous processing will penetrate to the industry toward

manufacturing of low cost and greener batteries.

Conclusions and perspectives

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Acknowledgements

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MAT4BAT Project CEGASA group


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Successful water processing of cathode materials...

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