Electrode formulation for a Li-ion battery and solvent-free method for electrode manufacturing
The present invention relates generally to the field of electrical energy storage in rechargeable secondary batteries of Li-ion type. More specifically, the invention relates to an electrode formulation for a Li-ion battery, comprising a binder based on a mixture of fluoropolymers. The invention also relates to a process for preparing electrodes using said formulation, by a technique of solvent-free deposition on a metal substrate. The invention relates finally to an electrode obtained by this process and also to Li-ion secondary batteries comprising at least one such electrode.
1 . A Li-ion battery electrode comprising an active filler for anode or cathode, an electronically conductive filler and a fluoropolymer binder, characterized in that said binder consists of the mixture of: a fluoropolymer A, the melt viscosity of which is greater than or equal to 1000 Pa·s at 232° C. and at a shear of 100 s −1 , and of a fluoropolymer B having a melt viscosity of at least 250 Pa·s lower, at 232° C. and at a shear of 100 s −1 , than that of fluoropolymer A, wherein the fluoropolymer A consists of one or more copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), the HFP content of each copolymer being greater than or equal to 3% by weight.
2 . The electrode of claim 1 , wherein said fluoropolymer B contains at least one repeating unit derived from a fluoromonomer chosen from the group consisting of: vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers; perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); a product of formula CF 2 —CFOCF 2 CF(CF 3 )OCF 2 CF 2 X wherein X is SO 2 F, CO 2 H, CH 2 OH, CH 2 OCN or CH 2 OPO 3 H; CF 2 ═CFOCF 2 CF 2 SO 2 F; a product of formula F(CF 2 )nCH 2 OCF—CF 2 wherein n is 1, 2, 3, 4 or 5; a product of formula R 1 CH 2 OCF═CF 2 wherein R 1 is hydrogen; a product of formula R 2 OCF═CH 2 wherein R 2 is F(CF 2 ) p and p is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene; and 2-trifluoromethyl-3,3,3-trifluoro-1-propene.
3 . The electrode of claim 1 ,
fluoropolymer B comprises a VDF homopolymer and/or at least one VDF-HFP copolymer.
4 . The electrode of claim 1 , wherein said fluoropolymer A has a viscosity of greater than or equal to 1500 Pa·s at 232° C. and at a shear of 100 s −1 .
5 . The electrode of claim 1 , wherein the fluoropolymer A consists of a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) having an HFP content of greater than or equal to 3% by weight.
6 . The electrode of claim 1 , wherein the fluoropolymer A consists of a mixture of two or more copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), the HFP content of each copolymer being greater than or equal to 3% by weight.
7 . The electrode of claim 1 , wherein said fluoropolymer B has a viscosity at least 500 Pa·s lower, at 232° C., at a shear of 100 s −1 , than that of the fluoropolymer A.
8 . The electrode of claim 1 , wherein the fluoropolymer B is a homopolymer of vinylidene fluoride or a mixture of homopolymers of vinylidene fluoride.
9 . The electrode of claim 1 , wherein the fluoropolymer B consists of a VDF-HFP copolymer having an HFP content of between 3% and 55% by weight.
10 . The electrode of claim 1 , wherein the fluoropolymer B consists of a mixture of two or more VDF-HFP copolymers.
11 . The electrode of claim 1 , wherein said mixture comprises:
i. a weight content of fluoropolymer A of greater than or equal to 1% and less than or equal to 20%, and
ii. a weight content of fluoropolymer B of less than or equal to 99% and greater than 80%.
12 . The electrode of claim 1 , wherein said active filler is selected from the group consisting of lithium metal, graphite, silicon/carbon composites, silicon, graphene, fluorographites of the formula CFx where x is between 0 and 1 and lithium titanates.
13 . The electrode of claim 1 , wherein said active filler is selected from the group consisting of LiMO 2 , of LiMPO 4 , Li 2 MPO 3 F, Li 2 MSiO 4 where M is Co, Ni, Mn, Fe or a combination of these, LiMn 2 O 4 and S 8 .
14 . The electrode of claim 1 , having the following composition by weight:
50% to 99.9% of active filler,
0.05% to 25% of electronically conductive filler,
0.05% to 25% of fluoropolymer binder,
0 to 5% of at least one additive chosen from the list: plasticizer, ionic liquid, dispersant for the fillers, flow agent for the formulation, fibrillating agent,
the sum of all these percentages being 100%.
15 . A process for manufacturing the Li-ion battery electrode of claim 1 , said process comprising the following steps:
mixing the active filler, the fluoropolymer binder and the electronically conductive filler by means of a process which makes it possible to obtain an electrode formulation that can be applied to a metal substrate by a solvent-free process;
depositing said electrode formulation on the metal substrate by a solvent-free process so as to obtain a Li-ion battery electrode, and
consolidating said electrode by a heat treatment and/or thermomechanical treatment.
16 . The process of claim 15 , wherein the mixing step is carried out in two steps:
mixing the electronically conductive filler and the fluoropolymer binder using a solvent-free process or by co-spraying, to obtain an intimate mixture, then
mixing the active filler with said intimate mixture using a solvent-free process or by co-spraying, to obtain an electrode formulation.
17 . The process of claim 15 , wherein said mixing step is carried out by a process selected from the group of: agitation, air-jet mixing, milling of the mixture, high-shear mixing, mixing with a V-mixer, mixing with a screw mixer, double-cone mixing, drum mixing, conical mixing, double Z-arm mixing, mixing in a fluidized bed, in a planetary mixer, extrusion, calendering, and mechanofusion.
18 . The process of claim 15 , wherein said solvent-free process is carried out by depositing the electrode formulation on the metal substrate by a process chosen from the following processes: pneumatic spraying, electrostatic spraying, dipping in a fluidized powder bed, dusting, electrostatic transfer, deposition with rotary brushes, deposition with rotary metering rolls, and calendering.
19 . The process of claim 15 , wherein said solvent-free process is carried out in two steps: a first step which comprises producing a self-supporting film from the electrode formulation which has been premixed using a thermomechanical process, and a second step wherein the self-supporting film is assembled with the metal substrate by a process allying temperature and pressure.
20 . The process of claim 15 , wherein the consolidation of said electrode is carried out by at least one heat treatment selected from the group of passing through an oven, under an infrared lamp and through a calender with heated rolls.
21 . A secondary Li-ion battery comprising an anode, a cathode and a separator, wherein at least one of the anode or cathode is the electrode according to claim 1 .