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ENVIRONMENTALLY FRIENDLY MANUFACTURING OF
LI-ION HIGH-CAPACITY / HIGH-VOLTAGE
ELECTRODES VIA AQUEOUS PROCESSING
Idoia UrdampilletaHead of Materials for Energy Unit
Specialists in adding value
Health
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Cleaning & preparationProtection
Functionalization
Tribology
Aesthetics
IK4-CIDETEC Technological offer
31/01/2017 2
EnergyStorage
Advanced materials
Cell manufacturing
Modules & packs
Modeling & simulation
Battery testing
Specialists in adding value
IK4-CIDETEC Technological offer
31/01/2017 3
EnergyStorage
Advanced materials
Cell manufacturing
Modules & packs
Modeling & simulation
Battery testing
SECTORS:
Energy Storage
Electromobility SmartGrids
Cell manufacturers
Materials industry
Oír Philosophy - Experts in the whole value chain
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… Bridging the gap between R&D and Industry
High
Low
Manufacturing-innovation process
Basic Oriented
Research
GAP Private sector
Basic
manufacturing
research
Proof of
conceptProduction
in laboratory
Capacity to
produce
Capability in
production
environment
Demostration of
production rates
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> Good quality electrodes =
Why is electrode processing so important for Li-ion
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I. Introduction
Good performance
Good durability
Cost efficiency
Environmentally friendliness
Easy manufacturing
Smooth surface
No cracks, wrinkles, hard spots
Good adhesion
> leading to:
+ the basis for further technological progress: post-Li ion, etc
> Straightforward Benefits =
Aqueous processing for Li-ion - Why
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II. Our Proposal
Good performance
Good durability
Cost efficiency
Environmentally friendliness
> Objective - demonstrate:
No NMP
No VoC’s
Specially at the Cathode side
> Our Challenge – demonstrate water processability of Next-Gen HV Cathode Materials
III. How
IK4-CIDETEC Electrode and Cell Manufacturing Plant Facility
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CALENDERINGELECTRODE COATING
Battery Manufacturing Pilot Plant Facility - outline
ELECTRODE CUTTING LAMINATION & STACKING
Our Final product
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UP TO 40AH LI ION CELLS – VARIOUS CHEMISTRIES AVAILABLE
PLUS HAND-ASSEMBLED, LAB-TEST 1AH CELLS
(PICTURES NOT IN THE SAME SCALE)
> Challenges
Starting point: development of a G/LFP full size pouch cell
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IV. Our Strategy
A. Kvasha et al., Electrochimica Acta 215, 238-246, 2016
Develop basic background of knowledge
To cut our teeth in front of the machine !! ☺
Develop a dynamic data base of materials / qualities / suppliers
• Importance of mixing intensity on stability of C/LiFePO4 in contact with water• Residual water and drying step adjustment for capacity retention:
< 450ppm H2O in cathode
> Most promising materials identified, already in the pipeline
> Cooperative Environment & Support from EU FP7 + H2020
Next (& current) steps: advanced, HV, HE materials
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IV. Our Strategy
Target materials Supporting EU Consortia
NMCGREENLION*MAT4BAT
Li-Rich NMCMARS-EV*MAT4BAT
LMFP SPICY
LMNOeCAIMAN (organic processing)MARS-EV* (Aqueous processing)
* PROJECT COORDINATOR IK4-CIDETEC
➢ CMC/SBR and acrylate-based systems:
✓ NMC111 pH>10: slurry agglomeration, Mnleaching and Al corrosion pH adjustment by mild acid treatment
LiNixMnyCozO2 - NMC (111) & waterborne binders
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V. Selected Results
➢WB-PVDF (Solvay) system:
✓ slurry pH 8, no adjustment required
A. Kvasha et al., ECS Transactions 73(1), 325-330, 2016
Patent DE-10-2013-111-826.7, G.-T. Kim, N. Loeffler, I. Doberdo, N. Laszczynski, D. Bresser, S. PasseriniGreenLion White Paper, Ch.III @ www.greenlionproject.eu
NMC/C45/CMC/Binder(+H3PO4) = 89/7/2/2
➢ LR-NMC/VOx coated particles allowing electrode preparation using waterborne binders with delayed capacity decay
➢ Ongoing work on CMC/Acrylate systems for thicker and flexible electrodes (>2mAh/cm2 loading)
Li-rich NMC electrodes avoiding metal-leaching
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V. Selected Results
N. Laszczynski et al. ChemElectroChem 2(11) 1768–1773 (2015).
DOI: 10.1002/celc.201500219
High Voltage Phosphates: LiMn1-xFexPO4 (LMFP)
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V. Selected Results
➢ CMC/SBR systems: stable for up to 4.5V operation
➢Modified acrylate-based latex binders for high Mn content phosphates
1C/1C Loading 7-8 mg/cm2
Long term cyclabilityLiMn1-xFexPO4 - Li4Ti5O12
5C/10C, DOD 100%, 25oC
2,5
3
3,5
4
4,5
0 50 100 150
Vo
ltag
e[V
vs
Li/L
i+]
Specific capacity / mAh.g-1 LMFP
C/10 C/10 C/3C/2 1C 2C3C 10C 20C
5V-SPINEL LiMn1.5Ni0.5O4 (LMNO) slurry processing
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V. Selected Results
➢ Organic solvent systems (PVDF/NMP):
✓ PVDF copolymer blend (Arkema)
✓ Slurry mixing adjustment to achieve
homogeneous coating
➢ Aqueous system (CMC/Acrylate latex):
✓ Challenge: particle agglomeration different CMC and mixing conditions
✓ slurry pH 8-9 Ok
for processing
✓LNMO reaction in
water minimal (<2·10-4 % Ni in H2O)
0
20
40
60
80
100
120
140
160
Sp
eci
fic
cap
aci
ty (
mA
h/g
LN
MO
)
D/5 1D 2D 5D 8D 10D 1C 3C
Densification
improved electrical contact
Good adhesion: 35-45 N/m (90º peel)2,5
3
3,5
4
4,5
5
5,5
0 50 100
E /
V v
s Li
/Li+
Specific capacity (mAh/g LNMO)
C/5 Charge C/2 Charge
1C Charge C/5
C/2 1C
AQ comparable to ORG (only 8% less capacity at C/5)
> Aqueous processing of Li-ion electrodes has demonstrated good performance, durability, environmental and cost benefits
> We have demonstrated this with key advanced cathode materials – such as Li-Rich NMC, LMFP, LNMO
> Mastering Li-ion electrode processing is a necessary step before approaching Next Gen battery technologies [LiS, solid electrolyte, etc] with stringent requirements
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VI. Conclusions
> Next Steps
Full size [30-40Ah] cells for near-product validation
High carbon, composite based cathodic electrodes for LiS
High polymer content based cathodes for S.E. Li cells
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Acknowledgements
> IK4-CIDETEC is member of:
> IK4-CIDETEC is partner of:
