technical marketing engineer solvay - elibama...oct 06, 2014 · milena stanga technical marketing...
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GREEN PVDF FOR GREEN BATTERIES
ELIBAMA STAKEHOLDERS CONFERENCE
Newcastle, Oct 14. 2014
Milena Stanga Technical Marketing Engineer
SOLVAY
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STATE OF THE ART
ELIBAMA STAKEHOLDERS CONFERENCE
Newcastle, Oct 14. 2014
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• PVDF powder in NMP solvent
• PVDF is a partially fluorinated semi-crystalline polymer
with excellent thermo-mechanical and chemical properties.
ELIBAMA STAKEHOLDERS CONFERENCE
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Advantages of PVDF
• Stable adhesion during time
• High cohesion
• Long cycle life
• Good chemical affinity with commercial
separator
• Better lamination process
• Good compatibility with artificial graphite
• Low resistivity for power application
Disadvantages of PVDF
• Use of NMP (Toxic & costly)
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A NEW WATER BASED
BINDER COMBINING
ADVANTAGES OF
PVDF AND WATER
ELIBAMA STAKEHOLDERS CONFERENCE
Newcastle, Oct 14. 2014
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• Solvay Specialty Polymers has taken advantages of its expertise in
fluorine chemistry and polymerization technologies for design a new
generation of fluoro-polymers for LIB Application
• Solvay introduces a novel fluorinated binder in aqueous dispersion
with proprietary chemical modification (not blending materials) for
improved adhesion and flexibility.
ELIBAMA STAKEHOLDERS CONFERENCE
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• Solef® PVDF water-based dispersions are stable and have
the special feature of nano-sized primary particles of
PVDF in the shape of spheres
• Latex viscosity: <5 cps [Brookfield, spindle#1, 60 rpm]
• Solid content of latex: 25-35% w
• pH: 3-5 (stable to pH adjustment up to 13)
• Stable to shear stress
ELIBAMA STAKEHOLDERS CONFERENCE
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• Solef® PVDF water-based ensures continuous film of
binder between active material particles, through
Thermal Process of Film Formation
ELIBAMA STAKEHOLDERS CONFERENCE
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• 1.Aqueous slurry
Dispersion of AM/binder
• 2. Particles packing
&deformation
aggregation of PVDF primary particles &
water evaporation
• 3.Coalescence
Melting into Mechanically
coherent dry film
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• Solef® PVDF water-based ensures continuous film of
binder between active material particles, through
Thermal Process of Film Formation
ELIBAMA STAKEHOLDERS CONFERENCE
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Graphite PVDF
particles
PVDF film
after film formation
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• The chemical modification in Solef® PVDF Latex ensures
higher and more stable adhesion in combination with
flexibility of the final electrode
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Solef® PVDF Water Based Binder SBR Water Based Binder
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• Applying the proper processing conditions, electrodes
made with Solef® PVDF Latex show same adhesion
level as standard PVDF polymer processed in NMP
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0
0,01
0,02
0,03
0,04
0,05
0,06
0,07
0,08
0,09
0,1
Solef® PVDF Latex PVDF in NMP
Pe
elin
g st
ren
ght
(N/c
m)
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• Taking advantage of Solef® PVDF Latex high adhesion
and lower volume at equal weight compared to SBR,
reduced amount of binder can be used increasing the
amount of active material (to exploit the theoretical
capacity and energy density of the battery).
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ELIBAMA STAKEHOLDERS CONFERENCE
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• Flexibility is a key property which determines final
performance of batteries. A good binder guarantees the
electrode to be bent in winding or z-fold configuration with
no cracks formation
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ELIBAMA STAKEHOLDERS CONFERENCE
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Lamination Polyolefin
Separator with Electrode
PVDF
latex Lamination
SBR latex NO
Lamination
• Good interphase between electrodes and separator is a key
factor to reduce internal resistance.
• Chemical affinity of PVDF with commercial polyolefin
separators allows to laminate (ensuring better interface)
them together.
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ELIBAMA STAKEHOLDERS CONFERENCE
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• Swelling behavior of the electrode is a key parameter
• The electrode from PVDF latex is perfectly stable to both
stressful treatments, showing very similar performance to
SBR electrode, although pure PVDF polymer film is
gellified at RT and is dissolved at 90°C
0
10
20
30
PVDF XPH859 (Binder 3% v/v) SBR std (Binder 3% v/v)
% U
pta
ke
Swelling @ Room Temperature <1h> <2h> <24h> < % uptake su materiale rimasto >
0
10
20
30
PVDF XPH859 (Binder 3% v/v) SBR std (Binder 3% v/v)
% U
pta
ke
Swelling @ 90°C
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• Test: Cycling at 1C at RT
• Testing system: Full cell (pouch cell 383562)
• Anode formulation: 94 % SCMG, 3 % Super P, 1.2 % Solef® Latex, 1.8
% CMC
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• Test: Cycling at 1C
• Testing system: Full cell (pouch cell 53437)
• Anode formulation: 89 % LTO, 5 % Super P, 5 % Solef® Latex, 1 %
CMC
Aqueous based
NMP based Aqueous based
NMP based
1C CCCV – 1D
Voltage cut-offs : [1.5V – 2.8V]
RT
1C CCCV – 1D
Voltage cut-offs : [1.5V – 2.8V]
55°C
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GREEN PVDF FOR
GREEN BATTERIES
ELIBAMA STAKEHOLDERS CONFERENCE
Newcastle, Oct 14. 2014
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• Towards a fully water-based production process for all
components of the battery:
• Preliminary validation of Solef® PVDF Latex as binder at
high voltage cathode
• NMC 532/carbon black/Solef XPH 859=90/5/5 wt%
• Confirms residual water from all-aqueous processing is not a
concern if routine secondary drying conditions are used.
• More effective and energy efficient to use dry-room air to remove
trace adsorbed water than vacuum pumping for long time periods.
ELIBAMA STAKEHOLDERS CONFERENCE
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• NMC 532/carbon black/Solef XPH 859=90/5/5 wt%
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ELIBAMA STAKEHOLDERS CONFERENCE
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The ELIBAMA project is granted by the European Commission under the
“Nanosciences, nanotechnologies, materials & new production technologies” (NMP) Theme
of the 7th Framework Programme for Research and Technological Development.