Solvay s New Developments in Electrolyte Additives and Solef PVDF Binders

Transcription

1 Solvay s New Developments in Electrolyte Additives and Solef PVDF Binders Thomas Mathivet & Thierry Baert AABC Conference January 30 th February 2 nd 2017 Mainz, Germany

2 Agenda 1. Solvay in brief 2. Solvay Materials for Lithium ion batteries 3. SA 27 : New additive for Li-Ion electrolytes 4. Polymers for LIB combining high electrochemical stability and ultra-high adhesion 5. Solid Polymer Electrolytes 6. Conclusions 2

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4 Agenda 1. Solvay in brief 2. Solvay Materials for Lithium ion batteries 3. SA 27 : New additive for Li-Ion electrolytes 4. Polymers for LIB combining high electrochemical stability and ultra-high adhesion 5. Solid Polymer Electrolytes 6. Conclusions 4

5 5 Industry Battery Roadmap met by Solvay LIB materials

6 R&I Labs Investment dedicated to LIB Market Experiment Room Dry Room 6 We are able to support customers globally and locally Market needs quickly transferred to R&I and Innovative product and solution introduced to market Partnership with leading institutes: EWHA (Korea), DoE in USA, FP7 H2020 in Europe, and CEA in France.

7 Solvay in the Li-ion Battery Value Chain Electrolyte salts LiTFSI, LiTA Components Cell Manufacturing Secondary Battery Consumer Electronics Computer Communication Electrolyte additives F1EC / F2EC / TAB / SA derivatives Electrolyte Battery Cell Battery Pack Solvent Transportation PVDF based binder Cathode Cathode Cathode Active Material PVDF based binder Anode Active Material Anode Anode Energy & Construction PVDF based coating PE / PP Polyolefin Separator Specialty polymers 7 SOLVAY product Non SOLVAY Product

8 Agenda 1. Solvay in brief 2. Solvay Materials for Lithium ion batteries 3. SA 27 : New additive for Li-Ion electrolytes 4. Polymers for LIB combining high electrochemical stability and ultra-high adhesion 5. Solid Polymer Electrolytes 6. Conclusions 8

9 SA 27 is a new fluoro additive of Solvay for HV Li-ion Chemical property Chemical Name SA27 Molecular weight Melting point <-70 C Boiling point 167 C Viscosity(mpas) 2.5 Electrochemical property F1EC VC SA27 Oxidation Reduction SA27 is a liquid, low molecular weight fluorinated additive with a comparatively broad electrochemical stability window. 9

10 Performance in cycling of SA27 additive NMC622 Cell NMC622/Graphite Cell type : Pouch cell (stack type) Standard : 1M LiPF6 in EC/EMC(3/7 v/v) 1C-chg./2C-dischg V ; T=23 C No additive VC 1.5 / PS 0.5 VC 1.5 / PS 0.5 / SA VC 1.5 / PS 0.5 / SA VC 1.5 / PS 0.5 / SA VC= vinylene carbonate PS=1,3 propane sultone + 15% At 1% concentration, SA27 increases by 15% the cycling efficiency (at 80% initial capacity) SA27 enables to improve the battery lifetime Cycle number

11 SA27 in the high temperature (60, 80 C) storage test NMC622 Without SA 27 Cell NMC 622 / Graphite Cells after storage test at 60ºC for 4 weeks & 80ºC for 1week Standard : 1M LiPF6 in EC/EMC(3/7 v/v) Additive : VC 1,5% ; PS 0,5% VC= vinylene carbonate PS=1,3 propane sultone With 1,0% SA 27 Anode surface protection improvement (post mortem analysis) SA27 improves the stability of cells at high temperature Limited electrode degradation Safety improvement 11

12 SA 27 cycling performance with high nickel system LCO/NCA Cell : LCO/NCA, Graphite Cell type : Stacking pouch cell Standard electrolyte : Standard : 1.15M LiPF6 EC/EMC/DMC 2/4/4 Testing temperature : Room temperature 900 Capacity(mAh) % of initial capacity Cycles VC + SA27 ` ` ` ` SA % + VC 0.5% SA % + VC 1% SA027 1% + PS 1% VC 1% SA % STD VC= vinylene carbonate A synergy between SA 27 & VC enhances the cycling performance of the cell. 12

13 Recovery capacity(mah) SA27 performance with high nickel system LCO/NCA Swelling Recovered capacity Before storage After storage % % Storage test : 70 C, 1 week Cell: LCO/NCA, Graphite Cell typestacking pouch cell Standard electrolyte : 1.15M LiPF6 EC/EMC/DMC 2/4/4 VC= vinylene carbonate Swelling and recovered capacity are significantly improved in presence of SA27 13

14 Agenda 1. Solvay in brief 2. Solvay Materials for Lithium ion batteries 3. SA 27 : New additive for Li-Ion electrolytes 4. Polymers for LIB combining high electrochemical stability and ultra-high adhesion 5. Solid Polymer Electrolytes 6. Conclusions 14

15 Solef PVDF for Electrode Binder Combining electrochemical stability of up to 4,5V with developments towards much lower binder concentration From Standard PVDF to Solef 5130 and beyond Gen 1 Solef 6010, PVDF homopolymer Gen 2 Solef 6020, PVDF High MW Gen 3 Solef 5130 modified PVDF High Adhesion for Large format LIBs Beyond Solef 5120 Solef 5140 (Exp) modified PVDF Multiple Technologies Chemical Modification Molecular Weight Increasing From Gen 1 to Gen 4: the 3% binder reduction brings a value of 10 Eur/kWh with a cost of only 2 /kwh 15

16 Peeling Strength (N/m) Ultra-High Adhesion Solef PVDF Binder Grade: Solef 5140, a Step Further in Electrode Reliability TSC 65% TSC 70% Solef Solef 5130 Solef Solef Ultra Adhesion 5140 Formulation [ %wt ] PVDF Super C65 LCO ,5 2 97,5 Slurry TSC 70% Electrode porosity 30% Thickness µm Formulation [ %wt ] Solef 5130 Super C65 LCO Electrode porosity 30% Thickness µm Solef 5120 further addresses the improved dissolution and lower slurry viscosity 16

17 Transfer of, Proven Successful Technology to a New PVDF Latex Generation Solef PVDF XPH latexes (experimental) Solid latex content: 25% w ph: 3 (stable to ph adjustment to up to 13) Crystallinity Calendering T Flexibility Solef XPH 838 Latex High 130 C Standard Solef XPH 859 Latex None < 60 C Excellent Solef XPH 884 Latex Medium C Very good New Solef XPH Latex High 120 C Good 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 17

18 Melting Point/ C A Range of Solef PVDF Latex to Fit Adhesion and Coating Process Requirements Solef PVDF Latex for cost-efficient water-based processing Different grades designed for different processing temperatures Select the suitable grade, whether for ceramic binder or lamination promoter * * Not applicable 18

19 Adhesion N/m Adhesion N/m A Range of Solef PVDF Latex to Fit Adhesion and Coating Process Requirements Coatings with or without ceramic are proven to be feasible PVDF Coating Separator Formulation: 10% PVDF 90% Al 2 O 3 PVDF Binders Ceramic Separator 19

20 Agenda 1. Solvay in brief 2. Solvay Materials for Lithium ion batteries 3. SA 27 : New additive for Li-Ion electrolytes 4. Polymers for LIB combining high electrochemical stability and ultra-high adhesion 5. Solid Polymer Electrolytes 6. Conclusions 20

21 Solid Polymer Electrolyte: a New, Safer and Durable Solution LiTFSI Main salt or additive for electrolyte Solef PVDF Coating F1EC, F2EC, TAB Additives for electrolyte TOWARDS SOLID- STATE BATTERY: Separator substitution by gel/solid electrolyte ANODE POLYMER CATHODE ELECTROLYTE On-going Developments Solef PVDF Binder Key Features High ionic conductivity even at room T (1 ms/cm) Flexibility Solef PVDF Binder Safety > No liquid electrolyte leakage > No flammable ingredients Processability by conventional printing techniques High energy density architecture Use of metallic Li anode and high voltage cathodes Ionic conductivity at low temperature Electrodes/electrolyte interface management, new electrode structure design Scale-up of the process PEO+LiTFSi Electrolyte Liquid Electrolyte New Technology: PVDF-based+ mineral particles 1/T While requiring improvements to fulfill all the battery challenges 21

22 Agenda 1. Solvay in brief 2. Solvay Materials for Lithium ion batteries 3. SA 27 : New additive for Li-Ion electrolytes 4. Polymers for LIB combining high electrochemical stability and ultra-high adhesion 5. Solid Polymer Electrolytes 6. Conclusions 22

23 Conclusions The development of new materials for Li-ion battery by Solvay are oriented towards : Capacity and cyclability improvement New additives, solvents ans salts for Li ion electrolyte development Increased adhesion Solef PVDF binders. Waterborn Solef PVDF Latex for Separator coating. Safety enhancement and production costs Polymer electrolyte solution. We will be pleased to cover additional topics as materials as metal replacement, for lighter battery pack housing, or flexible binders for highly loaded electrodes, at our booth or at the poster session 23