PVDF阿克玛

Confidential Kynar for Lithium BatteriesKynar for Lithium Batteries Mike Burchill Confidential Details of Kynar for Li ion BatteriesDetails of Kynar for Li ion Batteries • Atofina begins selling Kynar for Li ion batteries in China in 1996 Sales offices – Shanghai, Guongzhou, Beijing and Hong Kong • Warehouse for Kynar Products – Hong Kong, Shanghai • Technical services for Li ion battery – Kyoto, Japan – King of Prussia, USA – Cerdato, France • Reorganized in 2004 to Arkema Inc Confidential Key Attributes of Battery BinderKey Attributes of Battery Binder Processing aspectsChemical nature of binder Good adhesion to metallic collectors Good cohesion btw active material particles Good solubility in industrial solvents Good homogeneity of slurries at RT No peel-off Electrochemical properties Good initial capacity Good cycling behavior GOOD ELECTRODE No cracking Confidential Attributes of PVDF BinderAttributes of PVDF Binder In a Li-ion battery, PVDF provides : Electrochemical stability (0 to 5 V vs. Li0/Li+) Oxidation resistance Chemical resistance Good wettability / swelling in electrolyte Availability in large cost-effective quantities PVDF is a binder of choice Confidential Commercial KYNAR GradesCommercial KYNAR Grades 460500155-160------ ADS9038HFP/TFE SL12027TFE 2500115-12019HFP 2750130-13515HFP 28202800140-14510HFP 2840153-1557HFP 2850155-1605HFP 3120163-16610HFP 720 710 500+740760165-170------ 6000 9000 40001000169-171------ 5-010-515-1020-1525-2030-2535-30 M.P. (C)Wt% Comon. Co- monomer Melt Viscosity (kPs) Confidential Kynar for Lithium BatteriesKynar for Lithium Batteries • Liquid Cells – KYNAR 761 – KYNAR 761A – KYNAR 301F • Polymer Cells – KYNAR POWER FLEX – KYNAR FLEX 2801 • Developmental grade – ADX-161 – RC-10186 Confidential Kynar HomopolymerKynar Homopolymer • Semi-crystalline polymer • Melting point Tm ~ 170°C • Wide processing window as Td ~ 340°C • Kynar® for AtofinaC C H H F F C C H H F F C C H H F F C C H H F F C C H H F F PVDF – [CH2-CF2]n – Confidential Kynar Flex and Power Flex Kynar Flex and Power Flex CopolymersCopolymers • Co-polymerization with : – HFP ( -[CF(CF3)-CF2]- ) • Amount and distribution can be tailored. • Kynar Flex® and Kynar Power Flex®-LBG C C H H F F C C H H F F C C F F F CF3 C C H H F F C C H H F F PVDF-HFP – [CH2-CF2]n – [CF(CF3)-CF2)]m – Confidential Key Physical Properties of PVDF Key Physical Properties of PVDF Binders for Li BatteriesBinders for Li Batteries ***Li ion Liquid battery **Li ion polymer battery 7 360 4.9 61 172 250000 625000 Kynar 761A 60 NA 33 143 155000 470000 Kynar Flex 2801 Kynar Power Flex Competitive 2Kynar 761 2277Swelling: max DMC uptake (wt%) 350360T (°C) for 5% mass loss in O2 NA3.74.9Inverse Units (mol%) 446361DH (J/g) 154174172Tm (°C) 175000160,000 150,000Mn 450000360,000 370,000Mw Confidential General Factors which Control General Factors which Control AdhesionAdhesion • Formulation • Molecular Weight of the Binder • Processing Conditions • Functionality of the Binder Confidential Anode Preparation ProcedureAnode Preparation Procedure • A KYNAR:NMP (n-methyl pyrrolidinone, high purity Burdick and Jackson brand) solution with a concentration of 1:10 (wt) is prepared at 60°C for about 2 hours or until dissolved. • Carbon (MCMB 10-28) is added to the solution in amounts as high as 10 times the amount of resin in the solution. Steel balls are added to the mixture which is then rolled for about 1 hour until completely dispersed. • A piece of Cu foil is wiped with toluene and the toluene is left to evaporate in the hood (room temperature). Confidential Anode Preparation (2)Anode Preparation (2) • The dispersion is coated on the Cu foil using a 8 mil gap blade (1mil=25.4 mm). • The coating is dried in a convection oven, at an oven set temperature of 145 to 165 °C for 30 min. • When the sample is pulled out of the oven, it is left at room temperature to cool down. • The thickness of the dry coating is about 100 mm. Confidential CathodeCathode Preparation ProcedurePreparation Procedure • Dissolve 3 g of PVDF in 62 g of NMP at 50°C / 2 h. • Mix 45.5 g of LiCoO2, 1.5 g of acetylene black and ensure slurry homogeneity. • Coat 200 µm of slurry on an Al foil. • Dry the coating 30 min in a convection oven at 120°C. • Cut a strip of 25 mm width (coating thickness = 120 µm) and fix it to a stainless plate with a double face tape. • Measure the peel strength between the Al foil and the coating by 180° peel test at 10 cm/min. Confidential Peeling TestPeeling Test Al or Cu Upper chuck Stainless plate Tape Coating (PVDF) Lower chuck (fixed) Confidential Peeling strength vs. Molecular Peeling strength vs. Molecular weightweight Drying T = 155°C 0 50 100 150 200 250 300 0 100 200 300 400 500 600 A verage m olecular w eight Mw (g / m ole) x 10 3 Pe el in g st re ng th (g / 25 m m ) Confidential Effect of Anode Formulation on Peel Effect of Anode Formulation on Peel StrengthStrength 0 20 40 60 80 100 120 140 160 180 1:9:9 1:10:10 1:9:15 1:9:20 Pe el S tr en gt h (g /2 5m m ) KYNAR 741EA:Carbon:NMP = 1:10:10 155 °C drying temperature Confidential Anode Peel StrengthAnode Peel Strength • Atofina products match the peel strength of competitive products 0 50 100 150 200 250 300 K741 K741EA K761EA Comp.1 Comp.2 Pe el St re ng th (g /2 5m m ) Resin:MCMB10-28:NMP = 1:10:10, 165 °C drying temperature Confidential Anode Peel Strength: Anode Peel Strength: Dependence on Processing TemperatureDependence on Processing Temperature 0 50 100 150 200 250 300 350 400 120 130 140 150 160 170 Temperature C Pe el S tr en gt h (g /2 5 m m ) Kynar 761 Kynar 761A Comp 2 Confidential Kynar 761AKynar 761A High Molecular Weight Homopolymer Confidential Key Physical Properties of PVDF Key Physical Properties of PVDF Binders for Li BatteriesBinders for Li Batteries ***Li ion Liquid battery **Li ion polymer battery 7 360 4.9 61 172 250000 625000 Kynar 761A 60 NA 33 143 155000 470000 Kynar Flex 2801 Kynar Power Flex Competitive 2Kynar 761 2277Swelling: max DMC uptake (wt%) 350360T (°C) for 5% mass loss in O2 NA3.74.9Inverse Units (mol%) 446361DH (J/g) 154174172Tm (°C) 175000160,000 150,000Mn 450000360,000 370,000Mw Confidential RheologicalRheological Properties of NMP Properties of NMP SolutionsSolutions 1.00E-01 1.00E+00 1.00E+00 1.00E+01 1.00E+02 1.00E+03 Shear Rate (sec-1) Vi sc os ity (P as ) Kynar 761A @ Kynar 761A @ 10% 10% w/volw/vol Kynar 761 @ Kynar 761 @ 10% 10% w/volw/vol Confidential Effect of Solution Concentration on Effect of Solution Concentration on Viscosity Viscosity 0 1000 2000 3000 4000 5000 6000 7000 8000 1 5 10 15 Concentration (wt%) Vi sc os ity (m Po is e) 30 °C 50 °C 70 °C 30 °C 50 °C 70 °C KYNAR Competitive 2 NMP solutions Confidential Comparison of Adhesion achieved Comparison of Adhesion achieved with Various Binderswith Various Binders 30.7Kynar 761 31.7Kynar 761A 31.9Comp. 2 Scotch TestPeeling Strength (N/inch) PVDF Type Confidential Advantages of KYNAR ResinsAdvantages of KYNAR Resins • Faster solubilization in NMP • Longer solution stability in NMP • Higher concentrations possible • Better thermal stability • Equivalent adhesion to competitive products Confidential Kynar Kynar PowerflexPowerflex--LBGLBG Confidential Kynar Powerflex-LBG® 4 key properties of Soluble in acetone while moderate swelling in carbonates No « extractibles » in the electrolyte Higher thermal resistance in electrolyte Extra-quality control Properties of Kynar Properties of Kynar PowerflexPowerflex--LBGLBG Confidential Advantages of KYNAR Advantages of KYNAR POWERFLEXPOWERFLEXTMTM --LBGLBG • Longer solution stability in acetone • Lower extractables in battery electrolyte • Improved conductivity • Lower polymer flow under compression at high temperature • Improved tensile strength • Increased heat deflection temperature • Lower solubility of binder and separator in electrolyte at high temperature Confidential Key Physical Properties of PVDF Key Physical Properties of PVDF Binders for Li BatteriesBinders for Li Batteries ***Li ion Liquid battery **Li ion polymer battery 7 360 4.9 61 172 625000 Kynar 761A 60 NA 33 143 155000 470000 Kynar Flex 2801 Kynar Power Flex Competitive 2Kynar 761 2277Swelling: max DMC uptake (wt%) 350360T (°C) for 5% mass loss in O2 NA3.74.9Inverse Units (mol%) 446361DH (J/g) 154174172Tm (°C) 175000160,000 150,000Mn 450000360,000 370,000Mw Confidential Thermal / Mechanical Polymer Thermal / Mechanical Polymer PropertiesProperties 1307039462KYNAR POWERFLEX 805026462KYNARFLEX 2801 Heat Distortion Temperature °C (0.45 MPa) Heat Distortion Temperature °C (1.80 MPa) Tensile (strength at yield) MPa TGA (5% Loss in N2) °C Polymer Confidential Maximum Solvent Uptake:Maximum Solvent Uptake: Pure SolventsPure Solvents Molded Polymer Plaques 36%22%16%3%KYNAR POWERFLEX Diss.60%45%21%KYNARFLEX 2801 60 °C30 °C60 °C30 °C DMCDMCDECDEC Confidential Maximum Solvent Uptake:Maximum Solvent Uptake: Solvent MixturesSolvent Mixtures Molded Polymer Plaques 54%27%31%7%KYNAR POWERFLEX Diss.35%Diss.41%KYNARFLEX 2801 60 °C30 °C60 °C30 °C EC/DMC (1/1) EC/DMC (1/1) EC/DEC (1/1) EC/DEC (1/1) Confidential Solution Stability of Separator Solution Stability of Separator Composition in AcetoneComposition in Acetone 0.1 1 10 100 0.001 0.01 0.1 1 10 100 1000 10000 after 1 hour after 1 day after 7 days Shear gradient (1/s) Vi sc os ity (P a. s) Initial solution: KYNAR POWERFLEX / DBP/ silica / acetone: 2 / 2 / 1 / 16 Silica: Cab-O-Sil TS-530 Solution stability: ~ 9 days Confidential Stability of KYNAR POWERFLEXStability of KYNAR POWERFLEXÔÔ-- LBG Solutions (Acetone/Silica/DBP)LBG Solutions (Acetone/Silica/DBP) K Y N A R P O W E R FLE X Ô -LB G (g) 1 .2 1 .2 1 .2 1 .2 1 .2 A cetone (g) 7 .2 8 10 .1 11 .1 12 S ilica (g) 0 .80 0 .80 0 .80 0 .80 0 .80 D B P (g) 1 .60 1 .60 1 .60 1 .60 1 .60 R atio K Y N A R P O W E R FLE X Ô - LB G :S ilica :D B P 6:4 :8 6 :4:8 6 :4:8 6 :4 :8 6 :4:8 P V D F/tota l (w t % ) 11 .1 10.3 8 .7 8 .2 7 .7 s tab ility 1 day th ick flu id flu id flu id flu id flu id s tab ility 2 days gel gel flu id flu id flu id s tab ility 5 days gel gel flu id flu id flu id Solutions prepared at 45 °C, cooled and held at room temperature under constant stirring Silica is Cab-O-Sil TS530 Confidential Mechanical Behavior of Impregnated Mechanical Behavior of Impregnated (EC/DMC) Separator films(EC/DMC) Separator films 1 E+07 1 E+08 1 E+09 20 30 40 50 60 70 80 90 100 El as tic M od ul us (P a) KYNAR POWERFLEX -LBG KYNAR FLEX 2801 Temperature (°C) Confidential Stability of Separator Films in Stability of Separator Films in Electrolyte Electrolyte • Powerflex resists in electrolyte up to 80°C. 50°C 60°C 70°C 80°C Kynarflex® 2801 Kynar Powerflex-LBG1 Kynar Powerflex-LBG2 Competitive product Shape after dipping 3 sec a « Bellcore »-type separator in EC/DMC/DEC 40/40/20 Confidential Thermal / Mechanical Polymer Thermal / Mechanical Polymer PropertiesProperties 160300300KYNAR POWERFLEX 00300KYNARFLEX 2801 after dipping in hot electrolyte3 after dipping in hot PC2 initial1Polymer Peel strength of Cu / anode / Cu sandwich (g / inch) 1 after lamination at 148°C 2 at 65°C after 2.3 hours 3 at 90°C after 2 hours Confidential Separator Film PropertiesSeparator Film Properties 4%2.4 mS/cm~50 %1KYNAR POWERFLEX 17%1.4 mS/cm~50 %32KYNARFLEX 2801 Compressive creep of separator film at 160 °C4 Conductivity of the separator film3 Porosity of a separator film2 % extractables1 Polymer 1 after 1 day at 40°C in DMC 2 film of ~ 70 µm dried at RT 3 1M LiClO4 PC solution 4 1mm thick separator film (3/2/4 PVdF/silica/DBP) sandwiched between two disks and heated at 10 °C/min Confidential Quality ControlQuality Control • Melting point – measures HFP level • Rotational viscometry – molecular weight – molecular number – polydispersity • Turbidity measurement – HFP level – product uniformity • Metal analysis Confidential Developmental ProgramsDevelopmental Programs Confidential ADXADX--160160 Functionalized homopolymer for improved anode/cathode adhesion Confidential Controlled functionalityControlled functionality Our approach : functionalize PVDF within the polymerization process A new binder : ADX-160 A high Mw PVDF homopolymer with ca. 0.1 % polar functions along the chain Confidential Peel Strength of Functionalized Peel Strength of Functionalized PolymerPolymer 4804.7Competitive 3 5325.2ADX-160 1061.0KYNAR 761A Peel Strength (g/25 mm) Peel Strength (N/25 mm) Confidential RCRC--1018610186 UH Mw Kynar homopolymer Confidential 10-1 100 101 102 10-1 100 101 Rate [s-1] Et a ( ) [P a- s] Kynar mkb 272 SOLEF 1015 kYNAR 461 kYNAR 50 LD kYNAR ADX-120kYNAR 741 A Kynar 761 A Kynar 761 kYNAR POWERFLEX LBG Kynar RC 10.185 Kynar RC 10.186 OVERLAY KYNAR 10% IN NMP AT 20 °C Confidential 10-2 10-1 100 101 102 103 10-1 100 101 Rate [s-1] h ( ) [P a- s] 70% - 30% RC10186 and ADX161-10% sol in NMP) RC10186-10% in NMP ADX161-10% in NMP 75% - 25% RC10186 and ADX161-10% sol in NM Soltuion viscosity of RC10186 and ADX161 and their blends in NMP (10% wt.) Confidential Effect of Adding Effect of Adding FunctioanlizedFunctioanlized Kynar to Kynar to UHMwUHMw KynarKynar 0 0.5 1 1.5 2 2.5 0 20 40 60 80 100 % of ADX-160 Pe el S tr en gt h (N /2 5 m m ) UHMw homopolymer control Confidential EndEnd