Lithium-ion battery with easy recycling

Abstract

The present invention relates to a secondary lithium-ion battery comprising a cathode, an anode and a separator disposed between said cathode and said anode; said cathode comprising a current collector C' and a layer C comprising a first active material, a conductive agent and a first binder; said anode comprising a current collector A' and a layer A comprising a second active material and a second binder; said separator comprising either a porous polymeric support S and a coating SC disposed on said porous support S or a solid electrolyte comprising a coating SC characterized in that said first binder L1, said second binder L2 and said coating SC each comprise at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent S1 having a donor number greater than 4 kcal / mol.

Description

Title of the invention: Lithium-ion battery with easy recycling Technical field of the invention

[0001] The present invention relates generally to the field of electrical energy storage in rechargeable Li-ion secondary batteries. More specifically, the invention relates to an easily recyclable battery. Technological background of the invention

[0002] An elementary cell of a Li-ion storage battery or lithium battery comprises an anode, and a cathode generally composed of a metal oxide type lithium insertion compound, such as LiMn2O4, LiCoO2 or LiNiO2, between which is inserted an electrolyte which conducts lithium ions.

[0003] Rechargeable or secondary cells are more advantageous than primary (non-rechargeable) cells because the associated chemical reactions that take place at the positive and negative electrodes of the battery are reversible. The electrodes of secondary cells can be regenerated several times by applying an electrical charge. Many advanced electrode systems have been developed to store an electrical charge. In parallel, considerable effort has been devoted to the development of electrolytes capable of improving the capabilities of electrochemical cells.

[0004] For their part, the electrodes generally include at least one current collector on which is deposited, in the form of a film, a composite material consisting of a material called active material because it has electrochemical activity with respect to lithium, a polymer which acts as a binder, plus one or more electronically conductive additives which are generally carbon black or acetylene black, and possibly a surfactant.

[0005] Binders are classified among the components called inactive components since they do not directly contribute to the cell's capacity. However, their key role in electrode processing and their considerable influence on the electrochemical performance of electrodes have been extensively described. The main relevant physical and chemical properties of binders are thermal stability, chemical and electrochemical stability, tensile strength (strong adhesion and cohesion), and flexibility. The primary objective of using a binder is to form stable networks of the solid components of the electrodes, i.e., the active materials and the conductive agents (cohesion). In addition, the binder must ensure close contact between the composite electrode and the current collector (adhesion).

[0006] The binders used today are generally poly(vinylidene fluoride) at the cathode, carboxymethyl cellulose (CMC) and synthetic elastomers obtained by copolymerization of butadiene and styrene (SBR).

[0007] Given the very different chemical and physical properties of the binders mentioned above, their recovery from end-of-life batteries is complex, and currently, their recycling is not implemented. Indeed, the usual methods for recycling secondary Li-ion batteries are pyrometallurgy and hydrometallurgy. Pyrometallurgy involves heating the battery modules to very high temperatures (approximately 700°C) to incinerate the plastic materials and electrolytes and recover the metals they contain. Hydrometallurgy allows the dissolution of metals by liquid / liquid extraction in an acidic medium at a high temperature (approximately 80°C). In both cases, the polymer materials are not recovered but destroyed during these steps.The present invention aims to overcome at least some of these drawbacks by providing an eco-designed battery that allows for the recovery of all or part of the polymer materials present in the battery. Summary of the invention

[0008] According to a first aspect, the present invention relates to a secondary lithium-ion battery comprising a cathode, an anode and a separator disposed between said cathode and said anode; said cathode comprising a current collector C' and a layer C comprising a first active material, a conductive agent and a first binder L1; said anode comprising a current collector A' and a layer A comprising a second active material and a second binder L2; said separator comprising either a porous polymeric support S and a coating SC disposed on said porous support S or a solid electrolyte comprising a coating SC characterized in that said first binder L1, said second binder L2 and said coating SC each comprise at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol.

[0009] The present invention makes it possible, through the specific choice of polymer P for the cathode, the anode, and the separator coating, to provide a battery in which the binders are similar or compatible for their extraction at the end of the battery's life. By having binders of similar or compatible compositions, solvent treatment makes it possible to extract them from the other battery components and thus recover their value. Furthermore, the use of similar or compatible binders does not alter the electrochemical properties of the battery.

[0010] According to a preferred embodiment, said polymer P is selected from the group consisting of a fluorinated polymer PI or a hydrophilic polymer P2 or a mixture of the two.

[0011] According to a preferred embodiment, said fluorinated polymer PI comprises monomeric units derived from a fluorinated monomer Ml selected from the group consisting of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (TrFE); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); the monomer of formula CF2=CFOCF2CF(CF3 )OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO 3H; the monomer of formula CF2=CFOCF2CF2SO2F; the monomer of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the monomer of formula R1CH2OCF=CF2 in which R1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; the monomer of formula R2OCF=CH2 in which R2 is F(CF2)p and p is 1, 2, 3 or 4;trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof. ;

[0012] According to a preferred embodiment, said hydrophilic polymer P2 comprises monomeric units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI) or (VII) or a mixture thereof:

[0013] R'R2C=C(R3)C(O)R4 (I)

[0014] R17R18C=C(R19)(OC(O)R20) (II)

[0015] R17R18C=CR19C(O)OC(O)CR21=CR22R23 (III)

[0016] R17R18C=CR19(CN) (IV) O Kl, / / J> KO

[0017] R17R18C=CR19(C(O)NR5R6) (VII)

[0018] in which the substituents R1, R2 and R3 are, independently of each other, selected from the group consisting of H, CO2H, and C1-C5 alkyl; R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R21, R22 and R23 are, independently of each other and independently for each formula, selected from the group consisting of H and C1-C5 alkyl; R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR24 with R24 selected from the group consisting of H and CrCi8 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 and a five- or six-membered heterocycle comprising at least one nitrogen atom in its cyclic chain;R20 is selected from the group consisting of -OR25 with R25 selected from the group consisting of H and CrCi8 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31; R5 and R6 are, independently of each other, selected from the group consisting of H and Ci-Cio alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 groups; R31 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups.

[0019] According to a preferred embodiment, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a fluorinated polymer PI comprising at least 70% by mol of monomeric units derived from a monomer M1 as defined in this application.

[0020] According to a preferred embodiment, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a hydrophilic polymer P2 comprising at least 70% by mol of monomeric units derived from a monomer M2 as defined in this application.

[0021] According to a preferred embodiment, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a mixture comprising at least 70 mole percent of a fluorinated polymer PI as defined in this application and a hydrophilic polymer P2 as defined in this application.

[0022] According to a preferred embodiment, said battery also comprises a liquid electrolytic composition comprising a lithium salt selected from the group consisting of LiCF3SO3, LiPF6, LiClO4, LiBF4, LiB(C2O4)2, LiN(SO2F)2, LiN(SO2CF3)2, LiN(SO2C2F3)2, LiN(SO2C2F5)2, LiN(SO2F)(SO2CF3), LiN(SO2F)(SO2 C2F5), LiN(SO2CF3)(SO2C2F5), LiAsF6, LiBF2C2O4, LiNO3, LiPF3(CF2CF3)3, LiBETI, LiTDI, or a mixture thereof.

[0023] According to another embodiment, said solid electrolyte also comprises an inorganic material containing a sulfur atom selected from the group consisting of: - metallic polysulfide MxSy with x is an integer from 1 to 3 and y is an integer from 1 to 10 and M is a metallic element selected from the group consisting of an alkali metal, an alkaline earth metal such as Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof; preferably the metal M is selected from the group consisting of Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, and Al; in particular the metallic polysulfide is selected from the group consisting of Li2S6, Li2S7, Li2S8, Li2S9, Li2SiO, Na2S6, Na2S7, Na2S8, Na2S9, Na2S10, K2S6, K2S7, K2S8, K2S9, or K2S10; - lithium tin sulfide phosphorus ("Isps") such as LiiOSnP2Si2; - Lithium sulfide phosphorus (“Ips”) of formula (Li2S)x(P2S5)y, wherein x+ y=l and 0 < x < 1, Li7P3Sn, Li7PS6, Li4P2S6, Li9>6P3Si2 and Li3PS4; - Doped Lps such as Li2CuPS4, Lii+2xZni_xPS4, in which 0 < x < 1, Li3 33Mg 0.33P2S6, and Li4 3xScxP2S6, in which 0 < x < 1; - Lithium sulfide phosphorus oxygen ("LPSO") of formula LixPySzO, in which 0.33 < x < 0.67, 0.07 < y < 0.2, 0.4 < z < 0.55, 0 < w < 0.15; - Lithium sulfide phosphorus ("Ixps") with x Si, Ge, Sn, As, Al, such as Lii0 GeP2Si2 or Lii0SiP2Si2; - Lithium sulfide phosphorus oxygen ("LXPSO") with x Si, Ge, Sn, As, Al; - Lithium sulfide silica (“LSS”) such as Li2SiS3, Li2S-P2S5-SiS2, Li2S-P2S5-SiS 2-LiCl, Li2S-SiS2-P2S5, Li2S-SiS2-P2S5-LiI, Li2S-SiS2-LiI, Li2S-SiS2, Li9 54Si174P i.44Si 17Clo.3, and Li2S-SiS2-Al2S3; - Lithium boron sulfide such as Li3BS3 or L2S-B2S3-Li; - Lithium tin sulfide and lithium arsenite such as LiO₂₈SnO₂₈S₂, Li₄SnS₄, Li₃₈Sn o,833Aso i66S4, Li3AsS4-Li4SnS4, Li3AsS4; And Li4PS4Cl, Li15P3S16Cl3, Li7P2S8Cl, and Li7P2S8I; - Materials of formula Li6PS5Y in which Y is Cl, Br or I such that; Li6 x PS5 XYUx, in which 0 < x < 0.5; preferably Li6PS5Cl; Li2S-GeS2-ZnS, Li3SbS4, Na3PS4, Na10SnP12S12, and NanSn2PS12; - and mixtures thereof.

[0024] According to a preferred embodiment, said solvent SI is selected from the group consisting of dimethyl sulfoxide, ethanol, methanol, water, acetone, N-Methyl-2-pyrrolidone, pyridine, triethylamine, methyl isobutyl ketone (MIBK), cyclopentanone, isobutyl isobutyrate (IBIB), ethyl acetate, propylene glycol monomethyl ether acétate, l,3,2-dioxathiolan-2-oxide, 1,2-dimethoxyethane, l,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, l,3-dimethyl-2-imidazolidinone, l,3-dioxolan-2-one, 1,3-dioxolane, 2,2,2-trifluoro-N,N-dimethylacetamide, 2,2,4,4-tetramethyl-3-pentanone, 2,2,4-trimethylpentan-3-one, 2,2,5,5-tetramethylhexan-3-one, 2,2,6,6-tetramethyl-4-heptanone, 2,2-dimethylpentan-3-one, 2,3-butanedione, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 2-butanone, 2-methylpentan-3-one, 2-methylpropanenitrile, 2-methyltetrahydrofuran, 2-pentanone, 2-phenylacetonitrile, 3,3-dimethyl-2-butanone, 3-methyl-2-butanone, 3-pentanone, 4-methyl-2-oxo-l,3-dioxolane, 4-methyl-2-pentanone, acétonitrile, acétophénone, benzaldéhyde, benzonitrile, benzophénone, bis(2-chloroethyl) éther, butanenitrile, butyl acétate, chloroacetonitrile, cyclohexanone, cyclopentanone, dibenzyl ether, dibutyl ether, diethyl carbonate, diethyl éther, diisopropyl éther, dimethyl carbonate, dipropyl carbonate, dimethylcyanamide, dioxane,diphenylphosphinic chloride, dipropyl ether, ethyl 2,2-dimethylpropanoate, ethyl 2-methylpropanoate, ethyl acetate, ethyl benzoate, ethyl butanoate, ethyl chloroacetate, ethyl chloroformate, ethyl formate, ethyl propanoate, formamide, isopropyl 2,2-dimethylpropanoate, isopropyl acetate, isopropyl pivalate, methyl 2,2-dimethylpropanoate, methyl acetate, methyl benzoate, methyl propanoate, methyl propyl ether, N,N-dimethylbenzylamine, N,N-dimethylcarbamoyl chloride, N,N-dimethylformamide, N,N-dimethyltrifluoroacetamide, N,N-dimethylurethane, N-methyl-2-pyrrolidone, oxane, oxolan-2-one, phenylphosphonic dichloride, phenylphosphonic difluoride phosphorus oxychloride, propanenitrile, propyl acetate, sulfolane, tetrahydrofuran, tributyl phosphate, triethyl phosphate, trimethyl phosphate, tripyrrolidinophosphine oxide, l-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide,butyl-methylpyrrolidinium bis-(trifluoromethylsulfonyl)imide, butyl-methylpiperidinium bis-(trifluoromethylsulfonyl)imide, ethyl-dimethyl-propylammonium bis-(trifluoromethylsulfonyl)imide, triethylsulfonium bis-(trifluoromethylsulfonyl)imide, mesitylène, phénol, biacetyl, methyl propanoate, benzonitrile, ethyl chloroacetate, propanenitrile, butanenitrile, propanol, hexanol, o-chloroaniline, di-n-propyl ether, dibenzyl ether, diethyl ether, glycerol, butanol, propanol, 1,2-ethandiol, 1,3-dioxolane, 2-methyl-2-propanol, tetrahydropyran, 2-phenyl éthanol, benzyl alcohol, pentanol, N-methyl formamide, N,N-dimethylaniline, N,N-dimethylacetamide, isopentanol, octanol, quinoline, decanol, dibutyl sulfoxide, N,N-diethylacetamide, isopropanol, aniline et N-methyl aniline. ,

[0025] According to a preferred embodiment, said first active material is selected from the group consisting of LiCoO2, Li(Ni,Co,Al)O2, Li(i+x)NiaMnbCoc (x represents a real number of 0 or more, a = 0.9, 0.8, 0.6, 0.5, or 1 / 3, b = 0.05, 0.1, 0.2, 0.3, or 1 / 3, c = 0.05, 0.1, 0.2, or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3 03, Li3Fe2(PO4)3, Li3V2(PO4)3, a Li Mn spinel substituted by a different element having a composition represented by Lii+xMn2_x_yMyO4, M representing at least one metal chosen from Al, Mg, Co, Fe, Ni, and Zn, x and y independently representing a real number between 0 and 2, lithium titanate LixTiOy - x and y independently representing a real number between 0 and 2, and a metal and lithium phosphate having a composition represented by LiMPO4, M representing Fe, Mn, Co, or Ni.

[0026] According to a preferred embodiment, said second active material is selected from the group consisting of a lithium alloy, lithium metal, a metal oxide, a carbon material such as graphite or hard carbon, silicon, silicone, a silicon alloy and Li4TiO12.

[0027] According to a preferred embodiment, said cathode comprises a current collector coated with a layer Cl, disposed between the current collector C' and said layer C, and comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and carbon particles; and / or said anode comprises a current collector A' coated with a layer Al, disposed between the current collector and said layer A, and comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and carbon particles.

[0028] According to a preferred embodiment, said cathode comprises a current collector C' whose edges are coated with a layer C2 comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and optionally inorganic particles; and / or said anode comprises a current collector A' whose edges are coated with a layer A2 comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and optionally inorganic particles.

[0029] According to another aspect, the present invention relates to a method for recycling a secondary lithium-ion battery according to the present invention, characterized in that it comprises the steps of: a. Crushing or mechanical separation of said battery to recover a material comprising said first binder L1, said second binder L2 and said coating SC; b. Dissolving said material in an SI solvent having a donor number greater than 4 kcal / mol or in an alkaline solution to obtain a solution including said first binder L1, said second binder L2 and said coating SC; c. Recovery of at least one of said first binder L1, second binder L2 and coating SC by precipitation of the latter or these from said solution obtained in step b). Detailed description of the invention

[0030] According to a first aspect, the present invention provides a secondary lithium-ion battery. A lithium-ion battery includes, in particular, a cathode, an anode, and a separator disposed between the cathode and the anode.

[0031] Said cathode comprises a current collector C' and at least one layer C comprising a first active material, a conductive agent, and a first binder L1. Said first active material, said conductive agent, and said first binder L1 form the electrode composition used to prepare said cathode. The current collector C' may be coated with a layer Cl disposed between the current collector and said layer C of electrode composition. This layer Cl improves adhesion between the current collector and the electrode composition. Said cathode may also comprise a coating, called an edge coating, disposed on the edges of the current collector. Thus, the edges of said current collector of the cathode are coated with a layer C2.

[0032] The anode comprises a current collector A' and at least one layer A comprising a second active material and a second binder L2. The second active material and the second binder L2 form the electrode composition used for preparing the anode. The current collector A' may be coated with a layer A1 disposed between the current collector and the electrode composition layer A. This layer A1 improves adhesion between the current collector and the electrode composition. The anode may also comprise a coating, called an edge coating, disposed on the edges of the current collector. Thus, the edges of the anode's current collector are coated with a layer A2.

[0033] Said separator comprises either a porous polymeric support S and a coating SC disposed thereon or a solid electrolyte comprising a coating SC. As mentioned below, said separator may also comprise inorganic particles. Polymer P

[0034] In said secondary battery, said polymer P may be a fluorinated polymer PI, a hydrophilic polymer P2 or a mixture of these.

[0035] PI Polymer

[0036] According to a preferred embodiment, said fluorinated polymer PI comprises in its chain at least one fluorinated monomer Ml selected from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group, at least one fluorine atom, a fluoroalkyl group or a fluoroalkoxy group.

[0037] Preferably, said fluorinated polymer PI comprises monomeric units derived from a monomer Ml selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether and perfluoro(propyl vinyl) ether; perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole); the product of formula CF2=CFOCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2 =CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R1CH2OCF=CF2 in which R1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; the product of formula R2OCF=CH2 in which R2 is F(CF2)p and p is 1, 2, 3 or 4; perfluorobutylethylene (PFBE);Trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, and 2-trifluoromethyl-3,3,3-trifluoro-1-propene, or a mixture thereof. Examples of trifluoropropene include 3,3,3-trifluoropropene. Examples of tetrafluoropropene include 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. Examples of pentafluoropropene include 1,1,3,3,3-pentafluoropropene and 1,2,3,3,3-pentafluoropropene. Chlorofluoroethylene can refer to either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. Chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.

[0038] In particular, said fluorinated polymer PI comprises at least monomeric units derived from a monomer Ml being vinylidene fluoride. The fluorinated polymer PI may be a homopolymer or a copolymer of vinylidene fluoride.

[0039] According to a particular embodiment, the PI fluorinated polymer is a vinylidene fluoride homopolymer.

[0040] According to another particular embodiment, the fluorinated polymer PI is a polymer comprising monomeric units derived from a monomer Ml being vinylidene fluoride and monomeric units derived from a fluorinated monomer Ml’ copolymerizable with vinylidene fluoride, or monomeric units derived from a non-fluorinated monomer Ml” or a mixture of the two.

[0041] According to one embodiment, said fluorinated polymer PI comprises monomeric units derived from a monomer Ml being vinylidene fluoride and monomeric units derived from a fluorinated monomer Ml' selected from the group consisting of vinyl fluoride; trifluoroethylene, chlorotrifluoroethylene; 1,2-difluoroethylene; tetrafluoroethylene; hexafluoropropylene; perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether and perfluoro(propyl vinyl) ether; perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole); the product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2 =CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R1CH2OCF=CF2 in which R1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; the product of formula R2 OCF=CH2 in which R2 is F(CF2)p and p is 1, 2, 3 or 4;perfluorobutylethylene (PFBE); trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, and 2-trifluoromethyl-3,3,3-trifluoro-1-propene, or a mixture thereof. Preferably, the fluorinated polymer PI comprises monomeric units derived from a monomer Ml being vinylidene fluoride and monomeric units derived from a fluorinated monomer Ml' selected from the group consisting of vinyl fluoride; trifluoroethylene; chlorotrifluoroethylene; 1,2-difluoroethylene; tetrafluoroethylene; hexafluoropropylene; perfluoro(alkyl vinyl)ethers such as perfluoro(methyl vinyl)ether, perfluoro(ethyl vinyl)ether, or perfluoro(propyl vinyl)ether; perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole); the product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF 2CF2SO2F;the product of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R'CH2OCF=CF2 in which R' is hydrogen or F(CF2 )z and z is 1, 2, 3 or 4; the product of formula R”OCF=CH2 in which R” is F(CF2 )z and z is 1, 2, 3 or 4; trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene or 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof. In particular, the fluorinated polymer PI comprises monomeric units derived from a monomer Ml being vinylidene fluoride and monomeric units derived from a fluorinated monomer Ml' selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene and hexafluoropropylene or a mixture thereof.

[0042] According to another embodiment, said fluorinated polymer PI comprises monomeric units derived from a monomer Ml being vinylidene fluoride and monomeric units derived from a non-fluorinated monomer Ml” of formula RaRb C=C(Rc)C(O)Rd in which the substituents Ra, Rb and Rc are independently selected from the group consisting of H and C1-C5 alkyl; Rd is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 or -ORd’ with Rd’ selected from the group consisting of H and Ci-Ci8 alkyl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd” or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its cyclic chain; Rd” being selected from the group consisting of Ci-C6 alkyl or C6-Ci2 aryl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H group(s). Said heterocycle may be saturated or unsaturated or aromatic.The heterocycle may be monocyclic or bicyclic. It may be a pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, oxindole, isatin, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, or 4-imidazolidinone ring. The heterocycle may be substituted by one or more C1-C5 alkyl groups. As mentioned above, the alkyl CrCi8 group is optionally substituted by the heterocycle. The heterocycle may be linked to the alkyl chain by the nitrogen atom or any other atom forming the heterocycle. Preferably the heterocycle is 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, 4-imidazolidinone.The monomer Ml” may be of the formula RaRbC=C(Rc)C(O)Rd in which the substituents Ra, Rb and Rc are independently selected from the group consisting of H and Ci-C5 alkyl; Rd is selected from the group consisting of -NHC(CH3)2CH2 C(O)CH3 or -ORd' with Rd' selected from the group consisting of H and Ci-Ci8 alkyl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd” or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its cyclic chain; Rd” being selected from the group consisting of Ci-C6 alkyl or C6-Ci2 aryl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H. Preferably, the heterocycle is as defined above, in particular the heterocycle is 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone.Preferably, the substituent Rd' is selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-dodecyl, amyl, isoamyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, ethyl. replaced by a ureido group. In particular, said monomer M1” has the formula RaRbC=C(Rc)C(O)Rd in which the substituents Ra and Rb are H; Rc is H or CH3; R is -ORd' with Rd' selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, hydroethyl, hydroxypropyl, hydroxybutyl, 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. More particularly, said monomer M1” may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-dodecyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate,Hydroxybutyl acrylate, methyl acrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-dodecyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, ureido methacrylate, monomers with the formula CH2=CH(CO2CH2CH2CO2H), CH2=CH(CO2CH2CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH2CH2CH2-OC(O)-CH2CH2CO2H), ch2 =CH(CO2CH(CH3)CH2-OC(O)-CH2CH2CO2H),CH2=CH(CO2CH2CH2-OC(O)-C6H4CO2H), CH2=CH(CO2CH2CH2CH2CH(CO2H)CH2CH2CO2H); and mixtures thereof. Among these, said monomer M1” with an alkyl group having from 1 to 8 carbon atoms is preferred,and an alkyl group having 1 to 5 carbon atoms is more preferable. Said fluorinated polymer PI may comprise one or more monomeric units derived from said monomer M1” as defined herein.

[0043] According to another embodiment, said fluorinated polymer PI comprises monomeric units derived from a monomer Ml being vinylidene fluoride, monomeric units derived from a fluorinated monomer Ml', monomeric units derived from a non-fluorinated monomer Ml" of formula RaRbC=C(Rb)C(O)Rd; said monomers Ml' and Ml" being as defined above.

[0044] In said fluorinated polymer PI, the molar content of monomeric units Ml is at least 50%, advantageously at least 60%, preferably at least 70%, more preferably at least 80%. Preferably, when the fluorinated monomer Ml is vinylidene fluoride, the molar content of vinylidene fluoride monomeric units in said fluorinated polymer PI is at least 50%, advantageously at least 60%, preferably at least 70%, more preferably at least 80%, in particular at least 90%. Preferably, When the PI polymer comprises monomeric Ml units, the molar content of these units in the PI polymer is less than 40%, preferably less than 30%, and in particular is between 1 and 20%. Preferably, when the PI polymer comprises monomeric Ml units, the molar content of these units in the PI polymer is less than 20%, preferably less than 10%, and in particular is between 0.1 and 5%.

[0045] According to a particular embodiment, the fluorinated PI polymer can be functionalized in whole or in part, which allows it to improve adhesion to metal. Thus, said fluorinated PI polymer can comprise monomeric units bearing at least one of the functions selected from the group consisting of carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups such as glycidyl, amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolic, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic; preferably at least one carboxylic acid or hydroxyl function.

[0046] The function is introduced by a chemical reaction which may be grafting, or a copolymerization of the fluorinated monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the fluorinated monomer, according to techniques well known to those skilled in the art.

[0047] According to one embodiment, the functional group carries a carboxylic acid function which is a (meth)acrylic acid type group selected from acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate and acryloyloxy propylsuccinate.

[0048] According to one embodiment, the units bearing the carboxylic acid function further comprise a heteroatom selected from oxygen, sulfur, nitrogen and phosphorus.

[0049] According to one embodiment, the functionality is introduced via the transfer agent used in the synthesis process. The transfer agent is a polymer with a molecular mass less than or equal to 20,000 g / mol and bearing functional groups selected from the following groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolic, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, and phosphonic. An example of such a transfer agent is acrylic acid oligomers. According to a preferred embodiment, the transfer agent is an acrylic acid oligomer with a molecular mass less than or equal to 20,000 g / mol. Alternatively, the functional group may be introduced by an oligomeric compound or a polymer comprising said functional group and mixed with the fluorinated polymer PI. The oligomeric or polymeric compound may be impregnated in, mixed with, or intimately blended with the fluorinated polymer PI. In this case, the functional group may be derived from a (meth)acrylic acid compound selected from acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethylhexyl (meth)acrylate, and acryloyloxy propylsuccinate. For example, the functional group may be an oligomer or a polymer comprising monomeric units from a monomer selected from the group consisting of acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate and acryloyloxy propylsuccinate.According to one embodiment, the oligomer or polymer has a weight-average molecular weight less than or equal to 100,000 g / mol, advantageously less than 80,000 g / mol, preferably less than 60,000 g / mol, more preferably less than 40,000 g / mol, and in particular less than 20,000 g / mol. The weight-average molecular weight is determined by GPC using a Waters 2695e instrument coupled with a Wyatt NEON refractometer equipped with two PL Gel mixed C columns and a guard column (7.8 mm ID x 30 cm, 5 µm) under the following conditions: Temperature: 35°C; flow rate: 1.0 mL / min; injection volume: 100 pL. Samples are prepared at a concentration of 1 mg / ml in THF. Twelve samples of poly(methylmethacrylate) with a molecular mass ranging from 535 to 2,210,000 g / mol are used as calibration standards. This oligomer or polymer is preferably added during the production process of the fluorinated polymer PI.The functional group content of PVDF is at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

[0050] Said PI fluorinated polymer preferably has a high molecular weight. By high molecular weight, as used here, is meant a PI fluorinated polymer having a melt viscosity greater than 100 Pa.s, preferably greater than 500 Pa.s, more preferably greater than 1000 Pa.s, according to the ASTM D-3835 method measured at 232°C and 100 sec-1.

[0051] The fluorinated PI polymer used in the invention can be obtained by known polymerization methods such as emulsion or suspension polymerization. According to a preferred embodiment, the fluorinated PI polymer is prepared by an emulsion polymerization process in the presence of a non-fluorinated surfactant. Thus, the fluorinated PI polymer may comprise between 10 ppm and 2 wt% of a non-fluorinated surfactant comprising polyethylene glycol or polypropylene glycol units. Preferably, said non-fluorinated surfactant has an HLB value of 1 to 20, in particular an HLB value of 1 to 5 or 10 to 15. In particular, said non-fluorinated surfactant comprises at least one polyethylene glycol segment and at least one polypropylene glycol segment, and has an HLB value of 1 to 5 and a weight-average molecular weight of 5000 to 10000 g.mol-1. Alternatively, said surfactant comprises at least one polyethylene glycol segment and at least one polypropylene glycol segment, and has an HLB value of 10 to 15 and a weight-average molecular weight of 500 to 2500 g.mol-1.

[0052] Said fluorinated polymer PI may be in the form of a latex generally having a solids content of 10 to 60% by weight, preferably 10 to 50%, and having a weight-average particle size of less than 1 micrometer, preferably less than 1000 nm, preferably less than 800 nm, and more preferably less than 600 nm. The weight-average particle size is generally at least 20 nm, preferably at least 50 nm, and advantageously the average size is in the range of 100 to 400 nm.

[0053] According to a preferred embodiment, said fluorinated PI polymer is prepared by a suspension polymerization process. In this case, said fluorinated PI polymer may be in the form of a latex generally having a solids content of 10 to 60% by weight, preferably 10 to 50%, and having a weight-average particle size greater than 2 µm, preferably greater than 10 µm, preferably greater than 20 µm, and more preferably a weight-average particle size of 20 to 100 µm. The particle sizes are measured by laser granulometry.

[0054] Said fluorinated polymer PI can be in powder form. This is obtained from latex which is subjected, for example, to a drying step and optionally to granulation.

[0055] According to certain embodiments, the vinylidene fluoride contained in said PI fluorinated polymer is bio-based. The term "bio-based" means "derived from biomass." This improves the polymer's environmental footprint. Bio-based VDF can be characterized by a renewable carbon content, i.e., carbon of natural origin from a biomaterial or biomass, of at least 1 atomic percent as determined by the 14C content according to standard NF EN 16640. The term "renewable carbon" indicates that the carbon is of natural origin and comes from a biomaterial (or biomass), as described below.According to some embodiments, the bio-carbon content of VDF may be greater than 5%, preferably greater than 10%, preferably greater than 25%, preferably greater than or equal to 33%, preferably greater than 50%, preferably greater than or equal to 66%, preferably greater than 75%, preferably greater than 90%, preferably . greater than 95%, preferably greater than 98%, preferably greater than 99%, advantageously equal to 100%.

[0056] Polymer P2

[0057] According to the present invention, said hydrophilic polymer P2 comprises monomeric units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI) or (VII) or a mixture thereof:

[0058] R1R2C=C(R3)C(O)R4 (I)

[0059] R17R18C=C(R19)(OC(O)R20) (II)

[0060] R17R18C=CR19C(O)OC(O)CR2=CR2 2R2 3 (III)

[0061] R17R18C=CR19(CN) (IV)

[0062] R17R18C=CR19(C(O)NR5R6) (VII)

[0063] in which the substituents R1, R2 and R3 are, independently of each other, selected from the group consisting of H, CO2H, and Ci-C5 alkyl;

[0064] R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R21, R22 and R23 are, independently of each other and independently for each formula, selected from the group consisting of H and Ci-C5 alkyl;

[0065] R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR24 with R24 selected from the group consisting of H and CrCi8 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 and a five- or six-membered heterocycle comprising at least one nitrogen atom in its cyclic chain;

[0066] R20 is selected from the group consisting of -OR25 with R25 selected from the group consisting of H and Ci-Ci8 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31;

[0067] R5 and R6 are, independently of each other, selected from the group consisting of H and Ci-Cio alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 group(s);

[0068] R31 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups.

[0069] Preferably, said polymer P 2 comprises monomeric units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI) or (VII) or a mixture thereof

[0070] in which the substituents R1, R2 and R3 are, independently of each other, selected from the group consisting of H, CO2H, and Ci-C5 alkyl;

[0071] R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R21, R22 and R23 are, independently of each other and independently for each formula, selected from the group consisting of H and Ci-C3 alkyl;

[0072] R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR24 with R24 selected from the group consisting of H and CrCi 0 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 and a five- or six-membered heterocycle comprising at least one nitrogen atom in its cyclic chain;

[0073] R20 is selected from the group consisting of -OR25 with R25 selected from the group consisting of H and Ci-Ci 0 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31;

[0074] R5 and R6 are, independently of each other, selected from the group consisting of H and Ci-C5 alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 group(s);

[0075] R31 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups.

[0076] In particular, said polymer P2 comprises monomeric units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI) or (VII) or a mixture thereof

[0077] in which the substituents R1, R2 and R3 are, independently of each other, selected from the group consisting of H, CO2H, and CrC3 alkyl;

[0078] R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R21, R22 and R23 are, independently of each other and independently for each formula, selected from the group consisting of H and Ci-C3 alkyl;

[0079] R4 is selected from the group consisting of -OR24 with R24 selected from the group consisting of H and CrCi 0 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31;

[0080] R20 is selected from the group consisting of -OR25 with R25 selected from the group consisting of H and Ci-Ci 0 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31;

[0081] R5 and R6 are, independently of each other, selected from the group consisting of H and Ci-C5 alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 group(s);

[0082] R31 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups.

[0083] More particularly, said polymer P2 comprises monomeric units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI) or (VII) or a mixture thereof

[0084] in which the substituents R1, R2 and R3 are, independently of each other, selected from the group consisting of H, CO2H, and CrC3 alkyl;

[0085] R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R21, R22 and R23 are, independently of each other and independently for each formula, selected from the group consisting of H and Ci-C3 alkyl;

[0086] R4 is selected from the group consisting of -OR24 with R24 selected from the group consisting of H and Ci-C5 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31;

[0087] R20 is selected from the group consisting of -OR25 with R25 selected from the group consisting of H and Ci-C5 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31;

[0088] R5 and R6 are, independently of each other, selected from the group consisting of H and Ci-C5 alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 group(s);

[0089] R31 is selected from the group consisting of CrC3 alkyl and C6-aryl substituted by one or more functional CO2H groups.

[0090] Preferably, said monomer M 2 can be selected from the group consisting of acrylic acid, 2-carboxyethyl acrylate, methacrylic acid, maleic acid, maleic anhydride, methacrylic anhydride, tetrahydrophthalic anhydride, fumaric acid, crotonic acid, itaconic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-dodecyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-dodecyl methacrylate, methacrylate amyl, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, monomers of formula CH2=CH(CO2CH2CH2CO2H),CH2=CH(CO2CH2CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH2CH2CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH(CH3)CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH2CH2-OC(O)-C6H4CO2H), CH2=CH(CO2CH2CH2CH(CO2H)CH2CH2CO2H), ureido methacrylate, acrylonitrile, N-methylol acrylamide, acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, ethylene glycol methacrylate phosphate and mixtures thereof.

[0091] Said polymer P2 may also comprise monomeric units derived from styrene, isoprene, 1,3-butadiene, divinylbenzene. Said polymer P2 may be in the form of a solution, an emulsion, or a dispersion.

[0092] According to a particular embodiment, said polymer P may optionally comprise, in addition to polymer PI, P2 and a mixture thereof, cellulose and a cellulose derivative. Cellulose or a cellulose derivative is understood to mean at least one of the following: cellulose, cellulose ester, cellulose ether, cellulose nitrate, carboxyalkylcellulose and cellulose salt; preferably cellulose, cellulose acetate, methylcellulose, ethylcellulose, hydroxylpropylcellulose (HPC), hydroxyethylcellulose (HEC), cellulose nitrate, carboxymethylcellulose (CMC), carboxyethylcellulose, carboxypropylcellulose, carboxyisopropylcellulose, sodium cellulose, sodium cellulose nitrate and sodium carboxyalkylcellulose. In some embodiments, said polymer P may optionally comprise carboxymethylcellulose (CMC).

[0093] As mentioned above, the present invention makes it possible, through a specific choice of polymers, to obtain a battery whose constituents have similar properties, thus facilitating their recycling. Thus, said polymer P, as described above, is used in several battery elements. Preferably, said polymer P is used as the first binder L1 to the cathode, and the second binder L2. at the anode and SC coating in the separator. By using said polymer P in these various components, it can be easily recovered at the end of the battery's life, regardless of the recycling process applied to the battery. More specifically, as will be explained below, said polymer P can be recovered via a solvent extraction step.

[0094] Thus, said polymer P has a solubility greater than 0.01 g / ml at room temperature in said solvent SI. Advantageously, said polymer P has a solubility greater than 0.02 g / ml, greater than 0.03 g / ml, greater than 0.04 g / ml, greater than 0.05 g / ml, greater than 0.06 g / ml, greater than 0.07 g / ml, greater than 0.08 g / ml, greater than 0.09 g / ml, greater than 0.10 g / ml, at room temperature in said solvent SI. The solubility of polymer P in said solvent SI can be increased beyond 0.1 g / ml by heating. Solvent SI

[0095] The term solvent includes mixtures of several solvents having a donor number as specified in this application. Preferably, said solvent has a donor number greater than or equal to 4 kcal / mol. The donor number of a solvent represents the value -AH, AH being the enthalpy of the interaction between the solvent and antimony pentachloride (according to the method described in Journal of Solution Chemistry, vol. 13, no. 9, 1984).

[0096] Said solvent SI allows the solubilization of said polymer P. Thus, said solvent SI has a donor number greater than 4 kcal / mol. Preferably, said organic solvent has a donor number greater than 5 kcal / mol. According to a preferred embodiment, said solvent SI has a donor number greater than 6 kcal / mol, advantageously greater than 7 kcal / mol, preferably greater than 8 kcal / mol, more preferably greater than 9 kcal / mol, in particular greater than 10 kcal / mol, more particularly greater than 11 kcal / mol, preferably greater than 12 kcal / mol, advantageously greater than 13 kcal / mol, preferably greater than 14 kcal / mol, particularly greater than 15 kcal / mol.

[0097] According to a preferred embodiment, said solvent SI has a donor number of less than 50 kcal / mol, advantageously less than 49 kcal / mol, preferably less than 48 kcal / mol, more preferably less than 47 kcal / mol, in particular less than 46 kcal / mol, more particularly less than 45 kcal / mol, preferably less than 44 kcal / mol, advantageously preferred less than 43 kcal / mol, preferably preferred less than 42 kcal / mol, more preferably preferred less than 41 kcal / mol, particularly preferred less than 40 kcal / mol.

[0098] Thus, according to a preferred embodiment, said solvent SI has a donor number greater than 4 kcal / mol, advantageously greater than 5 kcal / mol, preferably greater than 6 kcal / mol, more preferably greater than 7 kcal / mol, in particular greater than 8 kcal / mol, more particularly greater than 9 kcal / mol, preferably greater than 10 kcal / mol; and less than 50 kcal / mol, advantageously less than 49 kcal / mol, preferably less than 48 kcal / mol, more preferably less than 47 kcal / mol, in particular less than 46 kcal / mol, more particularly less than 45 kcal / mol, preferably less than 44 kcal / mol, advantageously less than 43 kcal / mol, preferably less than 42 kcal / mol, more preferably less than 41 kcal / mol, particularly less than 40 kcal / mol. According to a particular embodiment, said solvent SI has a donor number between 4 and 50 kcal / mol, advantageously between 5 and 45 kcal / mol, preferably between 10 and 40 kcal / mol.

[0099] Said solvent SI may include, in particular, esters, carbonates, nitriles or dinitriles, ethers or diethers, amines, ketones or phosphines, provided that it has a donor number as specified in this application. Said solvent SI may be water.

[0100] According to a particular embodiment, said solvent SI is selected from the group consisting of dimethyl sulfoxide, ethanol, methanol, water, acetone, N-Methyl-2-pyrrolidone, pyridine, triethylamine, methyl isobutyl ketone, cyclopentanone, isobutyl isobutyrate (IBIB), ethyl acetate, propylene glycol monomethyl ether acetate, 1,3,2-dioxathiol-2-oxide, 1,2-dimethoxyethane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolan-2-one, 1,3-dioxolane, 2,2,2-trifluoro-N,N-dimethylacetamide, 2,2,4,4-tetramethyl-3-pentanone, 2,2,4-trimethylpentan-3-one, 2,2,5,5-tetramethylhexan-3-one, 2,2,6,6-tetramethyl-4-heptanone, 2,2-dimethylpentan-3-one, 2,3-butanedione, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 2-butanone, 2-methylpentan-3-one, 2-methylpropanenitrile, 2-methyltetrahydrofuran, 2-pentanone, 2-phenylacetonitrile, 3,3-dimethyl-2-butanone, 3-methyl-2-butanone, 3-pentanone, 4-methyl-2-oxo-l,3-dioxolane, 4-methyl-2-pentanone,acetonitrile, acetophenone, benzaldehyde, benzonitrile, benzophenone, bis(2-chloroethyl) ether, butanenitrile, butyl acetate, chloroacetonitrile, cyclohexanone, cyclopentanone, dibenzyl ether, dibutyl ether, diethyl carbonate, diethyl ether, diisopropyl ether, dimethyl carbonate, dipropyl carbonate, dimethylcyanamide, dioxane, diphenylphosphinic chloride, dipropyl ether, ethyl 2,2-dimethylpropanoate, ethyl 2-methylpropanoate, ethyl acetate, ethyl benzoate, ethyl butanoate, ethyl chloroacetate, ethyl chloroformate, ethyl formate, ethyl propanoate, formamide, isopropyl 2,2-dimethylpropanoate, isopropyl acetate, isopropyl pivalate, methyl 2,2-dimethylpropanoate, methyl acetate, methyl benzoate, methyl propanoate, methyl propyl ether, N,N-dimethylbenzylamine, N,N-dimethylcarbamoyl chloride, , N,N-dimethylformamide, N,N-dimethyltrifluoroacetamide, N,N-dimethylurethane, N-methyl-2-pyrrolidone, oxane, oxolan-2-one, phenylphosphonic dichloride, phenylphosphonic difluoride, phosphorus oxychloride, propanenitrile, propyle acétate, sulfolane, tétrahydrofurane, tributyle phosphate, triéthyle phosphate, trimethyle phosphate, tripyrrolidinophosphine oxide, l-butyl-3-methylimidazolium tetrafluoroborate, 1 -butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide, butyl-methylpyrrolidinium bis-(trifluoromethylsulfonyl)imide, butyl-methylpiperidinium bis-(trifluoromethylsulfonyl)imide, ethyl-dimethyl-propylammonium bis-(trifluoromethylsulfonyl)imide, triethylsulfonium bis-(trifluoromethylsulfonyl)imide, mesitylène, phénol, biacetyl, methyl propanoate, benzonitrile, ethyl chloroacetate, propanenitrile, butanenitrile, propanol, hexanol, o-chloroaniline, di-n-propyl ether, dibenzyl ether, diethyl ether, glycerol, butanol, propanol, 1,2-ethandiol, 1,3-dioxolane, 2-methyl-2-propanol,tetrahydropyran, 2-phenyl ethanol, benzyl alcohol, pentanol, N-methyl formamide, N,N-dimethylaniline, N,N-dimethylacetamide, isopentanol, octanol, quinoline, decanol, dibutyl sulfoxide, N,N-diethylacetamide, isopropanol, aniline and N-methyl aniline. ,

[0101] When the solvent SI is water, it may be in the form of an alkaline solution comprising sodium hydroxide or potassium hydroxide at a concentration of 1% to 70%, preferably 5% to 50% by weight of sodium hydroxide or potassium hydroxide on the basis of the total weight of said alkaline solution.

[0102] According to a preferred embodiment, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a fluorinated polymer PI comprising at least 70% by mol of monomeric units derived from a monomer M1 as defined in this application.Advantageously, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a fluorinated polymer PI comprising at least 72% by mol, preferably at least 74% by mol, more preferably at least 76% by mol, in particular at least 78% by mol, more particularly at least 80% by mol, preferably at least 82% by mol, advantageously preferably at least 84% by mol, preferably preferably at least 86% by mol, particularly preferably at least 88% by mol, more particularly preferably at least 90% by mol of monomeric units derived from a monomer M1 as defined in this application.

[0103] According to another preferred embodiment, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a fluorinated polymer P2 comprising at least 70 mol% of monomeric units derived from a monomer M2 as defined in this application. Advantageously, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a fluorinated polymer P 2 comprising at least 72% by mol, preferably at least 74% by mol, more preferably at least 76% by mol, in particular at least 78% by mol, more particularly at least 80% by mol, preferably at least 82% by mol, advantageously preferred at least 84% by mol, preferably preferred at least 86% by mol, particularly preferred at least 88% by mol, more particularly preferred at least 90% by mol of monomeric units derived from a monomer M 2 as defined in this application.

[0104] According to another preferred embodiment, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a mixture comprising at least 70 mole percent of a fluorinated polymer PI as defined in this application and a hydrophilic polymer P2 as defined in this application.Advantageously, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a mixture comprising at least 72% by mol, preferably at least 74% by mol, more preferably at least 76% by mol, in particular at least 78% by mol, more particularly at least 80% by mol, preferably at least 82% by mol, advantageously preferred at least 84% by mol, preferably preferred at least 86% by mol, particularly preferred at least 88% by mol, more particularly preferred at least 90% by mol of a fluorinated polymer PI as defined in this application and of a hydrophilic polymer P2 as defined in this application.

[0105] As mentioned above, said secondary battery comprises a cathode including a current collector C' and a layer C comprising a first active material, a conductive agent, and a first binder L1. The conductive agents in the electrode are composed of one or more materials that can improve conductivity. Some examples include carbon blacks such as acetylene black and Ketjen black; carbon fibers, such as a carbon nanotube, a carbon nanofiber, or a carbon fiber grown by vapor phase; and metal powders such as SUS powder and aluminum powder. The active materials in the electrode compositions are materials that are capable of storing and releasing lithium ions.Thus, the first active material is preferably selected from the group consisting of LiCoO2, Li(Ni, Co, Al)O2, Li(i+x)NiaMnbCoc (x represents a real number of 0 or more, a = 0.9, 0.8, 0.6, 0.5, or 1 / 3, b = 0.05, 0.1, 0.2, 0.3, or 1 / 3, c = 0.05, 0.1, 0.2, or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3O3, Li3Fe2(PO4)3, Li3V2(PO4)3, a Li Mn spinel substituted by a different element having a composition represented by . Li₂ + xMn₂ x yMyO₄, where M represents at least one metal chosen from Al, Mg, Co, Fe, Ni, and Zn, and x and y independently represent real numbers between 0 and 2; lithium titanate LₓTiO₄, where x and y independently represent real numbers between 0 and 2; and a lithium metal phosphate having a composition represented by LiMPO₄, where M represents Fe, Mn, Co, or Ni. The shape of the active positive electrode material is not particularly limited but is preferably particulate. Furthermore, the surface of each of the materials described above can be coated. The coating material is not particularly limited as long as it has lithium ion conductivity and contains a material capable of being maintained as a coating layer on the surface of the active material. Examples of coating materials include LiNbO₃, Li₄Ti₅O₂, and Li₃PO₄.

[0106] As mentioned above, said secondary battery comprises an anode including a current collector A' and a layer A comprising a second active material and a second binder L2. Said second active material is preferably selected from the group consisting of a lithium alloy, lithium metal, a metal oxide, a carbon material such as graphite or hard carbon, silicon, silicone, a silicon alloy, and Li4Ti50i2. The shape of the negative electrode active material is not particularly limited but is preferably particulate.

[0107] In a preferred embodiment, the composition of said layers A and C has the following mass composition:

[0108] a. 50% to 99.95% of said first active substance or said second active substance, advantageously 80% to 99.95%; alternatively 50% to 99%, in particular 80% to 99%

[0109] b. 25% to 0% of conducting agent, advantageously 10% to 0%; alternatively 25% to 0.5%, preferably 10% to 0.5%

[0110] c. 25% to 0.05% of said first binder L1 or of said second binder L2, advantageously 10% to 0.05%; alternatively 25% to 0.5%, in particular 10% to 0.5%

[0111] d. 0% to 5% of at least one additive chosen from the group consisting of a plasticizer, an ionic liquid, a dispersing agent for conductive additive, and a flow-aiding auxiliary agent; the sum of all these percentages being 100%.

[0112] Said layer A and said layer C can be deposited on at least one face of said current collector A' and C' to form said anode or said cathode respectively. This deposition can be carried out in the presence of an organic solvent, water, a mixture of the two, or by a solvent-free process, i.e., by a dry coated electrode production process. Said organic solvent can be selected from the group consisting of n-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), triethylphosphite (TEP), acetone, cyclopentanone, tetrahydrofuran, methyl ethylketone (MEK), methyl isobutyl ketone (MiBK), ethyl acetate (EA), butyl acetate (BA), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), gamma-butyrolactone and N-butylpyrrolidone; and mixtures thereof.

[0113] The battery also includes a separator disposed between the cathode and the anode. According to a first embodiment, the separator comprises a porous polymeric support S and a coating SC disposed on the porous support S. The coating may be disposed on one or both faces of the porous polymeric support S. There is no particular limitation in the choice of the support to be coated with the coating of the invention, as long as it is a polymeric support having pores. Examples of porous polymeric supports S useful in the invention as a support include, but are not limited to: polyolefins, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, poly(phenylene oxide), poly(phenylene sulfide), polyethylene naphthalene, or mixtures thereof.The separator may contain inorganic particles that serve to form micropores in the coating (the spaces between the inorganic particles). The addition of inorganic particles may also contribute to heat resistance or improve wettability. In one embodiment, the coating comprises from 50 to 99 percent by weight of inorganic particles, relative to the weight of the coating. These inorganic particles must be electrochemically stable (not subject to oxidation and / or reduction within the voltage range used). Furthermore, the powdered inorganic materials preferably have high ionic conductivity. Low-density materials are preferred to higher-density materials because the weight of the resulting battery can be reduced. The dielectric constant is preferably equal to or greater than 5.According to one embodiment, said inorganic particles are chosen from the group consisting of: BaTiO3, Pb(Zr,Ti)O3, Pbi xLaxZryO3 (0 <x<l, 0<y< 1), PbMg3Nb 2 / 3, PbTiO3, hafnie (HfO ou HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, Y2O3, bohémite (y-AlO(OH)), A12O3, TiO2, SiC, ZrO2, silicate de bore, BaSO4, nano-argiles, ou leurs mélanges. Le revêtement pour séparateur peut éventuellement comprendre de 0 à 15 % en poids sur la base du polymère, et de préférence 0,1 à 10 % en poids d'additifs, choisis parmi les dispersants, les épaississants, les agents d'ajustement du pH, les agents anti-sédimentation, les tensioactifs, les agents mouillants, les charges, les agents anti-mousse et les promoteurs d'adhésion fugitive ou non. Les charges mentionnées ici dans les additifs sont différentes des particules inorganiques . mentioned above. Said SC coating comprises a P polymer as described above.

[0114] Said secondary battery may also include an electrolyte.

[0115] The electrolyte may be liquid in the form of an electrolytic composition comprising a lithium salt selected from the group consisting of LiCF3SO3, LiPF6, LiC1O4, LiBF4, LiB(C2O4)2, LiN(SO2F)2, LiN(SO2CF3)2, LiN(SO2C2F3)2, LiN(SO2C2F5)2, LiN(SO2F)(SO2CF3), LiN(SO2F)(SO2C2F5), LiN(SO2CF3)(SO2C2F5), LiAsF6, LiBF2C2O4, LiNO3, LiPF3(CF2CF3)3, LiBETI, LiTDI, or a mixture thereof. Said electrolytic composition also comprises a solvent S2. Said solvent S2 is preferably selected from the group consisting of propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, gamma-butyrolactone, 3-fluoro-gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, epsilon-caprolactone, gamma-caprolactone, butyrolactam, valerolactam, N-methylbutyrolactam, N-methylvalerolactam, fluoroethylene carbonate, fluoropropylene carbonate, monofluoromethyl methyl carbonate, 2,2-methyl,2-Trifluoroethyl carbonate, trifluoroethyl ethyl carbonate, bis(2,2,2-trifluoroethyl carbonate), propyl 2,2,2-trifluoroethyl carbonate, methylnonafluorobutyl ether, hexafluoroisopropyl methyl ether, bis(2,2,2-trifluoroethyl)ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, methyl isopropyl carbonate, ethyl isopropyl carbonate, propyl ethyl carbonate, methyl propyl carbonate, 1-fluoropropyl methyl carbonate, 2-fluoropropyl methyl carbonate, 1,1,1-trifluoropropyl methyl carbonate, 1,1,1,2,2-pentafluoropropyl methyl carbonate, 1,1,2,2-tetrafluoropropyl methyl carbonate, 1,1,1-trifluoroethyl methyl carbonate, 1,1-difluoroethyl methyl carbonate, 1-fluoroethyl methyl carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl fluoromethyl carbonate, 1-fluoroethyl ethyl carbonate, 1,1-difluoroethyl ethyl carbonate, 1,1,1-trifluoroethyl ethyl carbonate, vinyl ethylene carbonate, vinylene carbonate, ethyl ethanoate,1-Ethyl 1-fluoroethanoate, 1,1-ethyl difluoroethanoate, 1-fluoroethyl ethanoate, methyl ethanoate, 1-methoxyisopropyl ethanoate, 1-fluoroethyl propanoate, 2-ethyl fluoropropanoate, methyl butanoate, ethyl butanoate, methyl methoxyethanoate, N-methyl-2-oxazolidinone, ethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dioxane, 1,3-dioxolane, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate, methyl phenyl carbonate, ethylene 2,3-Dimethylcarbonate, vinylene carbonate, ethylene 2-vinyl carbonate, , methyl benzoate, ethyl benzoate, 5-valerolactone, trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, triethyl phosphate, acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methylglutaronitrile, valeronitrile, butyronitrile, isobutyronitrile, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, N-methylpyrrolidone, N-vinylpyrrolidone, dimethylsulfone, ethylmethylsulfone, diethylsulfone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dimethyl sulfoxide, methyl ethyl Sulfoxide, diethyl sulfoxide, benzonitrile, tolunitrile, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(l,H)-pyrimidinone, 3-methyl-2-oxazolidinone, nitromethane, nitroethane, nitropropane, nitrobutane. These solvents can be used individually or in combination.Alternatively, said solvent S2 may be an ionic liquid. Preferably, the ionic liquid has the formula (Cation)FSI or (cation)TFSI where FSI is bis(fluorosulfonyl)imide and TFSI is bis(trifluoromethanesulfonyl)imide. De préférence, le cation est de type ammonium, imidazolium, pyrrolidinium, piperidinium, phosphonium, sulfonium, oxonium. De façon non limitative, on peut citer (l-Ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), (l-Butyl-3-methylimidazolium bis(fluorosulfonyl)imide), ( 1 -Butyl-1 -methylpyrrolidinium bis(fluorosulfonyl)imide), (l-Propyl-3-methylpyrrolidinium bis(fluorosulfonyl)imide), ( 1 -butyl-1 -methylpiperidinium bis(fluorosulfonyl)imide), ( 1 -méthyl-1 -propylpiperidinium bis(fluorosulfonyl)imide), (Methyl(tri-n-butyl)phosphonium bis(fluorosulfonyl)imide), (Methyl(tri-n-ethyl)phosphoium bis(fluorosulfoyl )imide), ( 1 -Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imid e), (l-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide), ( 1 -Butyl-1 -methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), ( 1 -Propyl-3-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), (1-butyl-1 -methylpiperidinium bis(trifluoromethanesulfonyl)imide),(1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide), (Methyl(tri-n-butyl)phosphonium bis(trifluoromethanesulfonyl)imide), (Methyl(tri-n-ethyl)phosphoium bis(trifluoromethanesulfonyl)imide). ,

[0116] According to another embodiment, said separator may be a solid electrolyte comprising a coating SC. Said coating SC comprises a polymer P as described above. In this case, said solid electrolyte also comprises an inorganic material containing a sulfur atom selected from the group consisting of: - metallic polysulfide MxSyavec where x is an integer from 1 to 3 and y is an integer from 1 to 10 and M is a metallic element selected from the group consisting of an alkali metal, an alkaline earth metal such as Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof; preferably the metal M is selected from the group consisting of Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, and Al; in particular the metal polysulfide is selected from the group consisting of Li2S6, Li2S7, Li2S8, Li2S9, Li2SiO, Na2S6, Na2S7, Na2S8, Na2S9, Na2S10, K2S6, K2S7, K2S8, K2S9, or K2S10; - lithium tin sulfide phosphorus ("Isps") such as LiiOSnP2Si2; - Lithium sulfide phosphorus (“Ips”) of formula (Li2S)x(P2S5)y, wherein x+ y=l and 0 < x < 1, Li7P3Sn, Li7PS6, Li4P2S6, Li9>6P3Si2 and Li3PS4; - Doped Lps such as Li2CuPS4, Lii+2xZni_xPS4, in which 0 < x < 1, Li3 33Mg 0.33P2S6, and Li4 3xScxP2S6, in which 0 < x < 1; - Lithium sulfide phosphorus oxygen ("LPSO") of formula LixPySzO, in which 0.33 < x < 0.67, 0.07 < y < 0.2, 0.4 < z < 0.55, 0 < w < 0.15; - Lithium sulfide phosphorus ("Ixps") with x Si, Ge, Sn, As, Al, such as Lii0 GeP2Si2 or Lii0SiP2Si2; - Lithium sulfide phosphorus oxygen ("LXPSO") with x Si, Ge, Sn, As, Al; - Lithium sulfide silica (“LSS”) such as Li2SiS3, Li2S-P2S5-SiS2, Li2S-P2S5-SiS 2-LiCl, Li2S-SiS2-P2S5, Li2S-SiS2-P2S5-LiI, Li2S-SiS2-LiI, Li2S-SiS2, Li9 54Sii.74P i.44Sn 7Clo3, and Li2S-SiS2-Al2S3; - Lithium boron sulfide such as Li3BS3 or L2S-B2S3-Li; - Lithium tin sulfide and lithium arsenite such as LiO₂₈SnO₂₈S₂, Li₄SnS₄, Li₃₈Sn 0.833^89.i6gS4, Li3AsS4-Li4SnS4, Li3AsS4; And LqPS^l Li15P3Si6Cl3, Li7P2S8Cl, and Li7P2S8I; - Materials of formula Li6PS5Y in which Y is Cl, Br or I such that; Li6.x PS5 XYi+x, in which 0 < x < 0.5; preferably Li6PS5Cl; - Li2S-GeS2-ZnS, Li3SbS4, Na3PS4, Nai0SnPi2Si2, and NanSn2PSi2; and mixtures thereof.

[0117] Said solid electrolyte is generally in the form of a film comprising said SC coating as described above, said inorganic material containing a sulfur atom, and optionally a lithium salt. Said lithium salt is as defined above. Said solid electrolyte may optionally contain a plasticizer preferably selected from the group consisting of an ionic liquid comprising an anion selected from the group consisting of tetrafluoroborate (BF4), bis(oxalato)borate BOB-, hexafluorophosphate (PF6), hexafluoroarsenate (AsF6), triflate or trifluoromethylsulfonate (CF3SO3), bis(fluorosulfonyl)imide (FSI), bis-(trifluoromethanesulfonyl)imide (TFSI), nitrate (NO3), 4,5-dicyano-2-(trifluoromethyl)imidazole (TDI), an acrylate or a methacrylate; and a cation selected from the group consisting of ammonium, sulfonium, pyridinium, pyrrolidinium, imidazolium, imidazolinium, phosphonium, guanidinium, piperidinium, thiazolium, triazolium, oxazolium, pyrazolium, and mixtures thereof.

[0118] Alternatively, said electrolyte may be in the form of a gelled membrane. Said gelled membrane comprising said SC coating as described above and an electrolytic composition comprising at least one solvent S3 and at least one lithium salt as defined above. Said film may be a mixture of two fluoropolymers as described in this application: for example, a fluoropolymer Pla comprising at least one vinylidene fluoride (VDF) and hexafluoropropylene (HFP) copolymer having an HFP content greater than or equal to 3% by weight, and a fluoropolymer Pib comprising a homopolymer of VDF and / or at least one VDF-HFP copolymer, said fluoropolymer Pib having an HFP content at least 3% lower by weight than the HFP content of the Pla polymer.For example, the fluoropolymer Pla comprises at least one VDF-HFP copolymer having an HFP content greater than or equal to 3% by weight, preferably greater than or equal to 8%, advantageously greater than or equal to 13% and less than or equal to 55%, preferably 50%. For example, the fluoropolymer Pib comprises at least one VDF-HFP copolymer having an HFP mass content at least 3% lower than the HFP mass content of the polymer Pla, or the fluoropolymer Pib is a vinylidene fluoride (VDF) homopolymer, or a mixture of vinylidene fluoride homopolymers, or the polymer Pib is a mixture of vinylidene fluoride homopolymer with one or more VDF-HFP copolymers. Preferably, when it contains it, the HFP content in this fluorinated polymer Pib is between 1% and 10% inclusive, in particular between 1% and 5% inclusive.

[0119] Said solvent S3 may be selected from the group consisting of cyclic and acyclic alkyl carbonates, ethers, glymes, formates, esters, and lactones. Examples of ethers include linear or cyclic ethers such as dimethoxyethane (DME), methyl ethers of oligoethylene glycols from 2 to 100 oxyethylene units, dioxolane, dioxane, dibutyl ether, tetrahydrofuran, and mixtures thereof. Examples of esters include phosphoric acid esters and sulfite esters. Examples include methyl formate, methyl acetate, methyl propionate, ethyl acetate, butyl acetate, or mixtures thereof. The glymes used have the general formula Ra-O-Rb-O-Rc where Ra and Rc are linear alkyls of 1 to 5 carbons and Rb is a linear or branched alkyl chain of 3 to 10 carbons.

[0120] Among the lactones, gamma-butyrolactone is a notable example. Among the nitriles, acetonitrile, pyruvonitrile, and propionitrile are examples. methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, malononitrile, and mixtures thereof.Examples of carbonates include cyclic carbonates such as ethylene carbonate (EC) (CAS: 96-49-1), propylene carbonate (PC) (CAS: 108-32-7), butylene carbonate (BC) (CAS: 4437-85-8), dimethyl carbonate (DMC) (CAS: 616-38-6), diethyl carbonate (DEC) (CAS: 105-58-8), methyl ethyl carbonate (EMC) (CAS: 623-53-0), diphenyl carbonate (CAS 102-09-0), methyl phenyl carbonate (CAS: 13509-27-8), dipropyl carbonate (DPC) (CAS: 623-96-1), and methyl propyl carbonate (MPC). (CAS: 1333-41-1), ethyl propyl carbonate (EPC), vinylene carbonate (VC) (CAS: 872-36-6), fluoroethylene carbonate (FEC) (CAS: 114435-02-8), trifluoropropylene carbonate (CAS: 167951-80-6), or mixtures thereof. The gelled membrane may further comprise inorganic fillers such as silicon oxides, titanium dioxide, aluminum oxides, and zirconia.The mass percentage of inorganic fillers is less than or equal to 25% relative to the weight of polymer P. Said gelled membrane may further comprise solid electrolytes such as lithium ionic superconductors [Lithium superionic conductor (LISICON)] and derivatives, thio-LISICON, Li4SiO4-Li3PO4 type structures, sodium ionic superconductors and derivatives [Sodium superionic conductor (NASICON)], Lii.3Alo.3Tii.7(PO4)3 (LATP) type structures, Li7La3Zr2O12 (LLZO) garnet structures and derivatives, Li3xLa2 / 3 □ 1 / 3 2xTiO3 (0. <x<0,16) (llto) et les sulfures amorphes, cristallins ou semi-cristallins. le taux massique des électrolytes solides est inférieur égal à 10% par rapport au poids du polymère p.

[0121] As mentioned above, said current collector C' of said cathode may be coated with a layer Cl disposed between the current collector and said layer C. This layer Cl improves the adhesion between the current collector and the electrode composition. Said layer Cl comprises said at least one polymer P as defined in this application, i.e., having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol. In addition, said layer Cl comprises carbon particles, preferably selected from the group consisting of carbon blacks such as acetylene black, Ketjen black; carbon fibers, such as a carbon nanotube, a carbon nanofiber, a carbon fiber grown by vapor phase.The mass ratio between the polymer P contained in the Cl layer and the carbon particles contained in the Cl layer is between 10 / 90 and 90 / 10, preferably between 25 / 75 and 75 / 25, in particular between 40 / 60 and 60 / 40.

[0122] Said current collector A' of said anode may be coated with a layer A1 disposed between the current collector and said layer A. This layer A1 improves the adhesion between the current collector and the electrode composition. Said layer A1 comprises said at least one polymer P as defined in this application, i.e., having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol. In addition, said layer A1 comprises carbon particles, preferably selected from the group consisting of carbon blacks such as acetylene black, Ketjen black; carbon fibers, such as a carbon nanotube, a carbon nanofiber, a carbon fiber grown by vapor phase.The mass ratio between the polymer P contained in layer A 1 and the carbon particles contained in layer a 1 is between 10 / 90 and 90 / 10, preferably between 25 / 75 and 75 / 25, in particular between 40 / 60 and 60 / 40.

[0123] The electrodes, cathode and / or anode, may also include a coating, called an edge coating, disposed on the edges of the current collector. Thus, the edges of said cathode current collector are coated with a C2 layer and the edges of said anode current collector are coated with an A2 layer. Said A2 layer and said C2 layer comprise said at least one polymer P as defined in this application, i.e., having a solubility greater than 0.01 g / ml at room temperature in an SI solvent having a donor number greater than 4 kcal / mol. Optionally, said A2 layer and said C2 layer comprise inorganic particles. For example, said inorganic particles may be bohemite (γ-AlO(OH)) or Al2O3 or mixtures thereof. Process

[0124] The present invention allows for the easy recycling of certain battery components. Given the specific choice of polymers and their miscibility, a single dissolution step allows for the extraction of most of the polymers contained in the battery.

[0125] Thus, according to another aspect of the present application, a recycling process is provided. Said recycling process for said secondary battery according to the present invention comprises the steps of: a. Mechanical crushing or separation of said battery according to the present invention to recover a material comprising said first binder L1, said second binder L2 and said coating SC; b. Dissolving said material in an SI solvent having a donor number greater than 4 kcal / mol or in an alkaline solution to obtain a solution including said first binder L1, said second binder L2 and said coating SC; c. Recovery of at least one of said first binder L1, second binder L2 and coating SC by precipitation of the latter or these from said solution obtained in step b).

[0126] Several types of recycling currently exist for Li-ion batteries, including pyrometallurgical and hydrometallurgical processes. Pyrometallurgy uses furnaces and reducers to produce metallic alloys of Co, Cu, Fe, and Ni. Its main advantages over hydrometallurgy are its ability to process different battery chemistries and cell types, to limit the need for pretreatment (mechanical or pre-discharge), and its process safety. The main disadvantages are high operating costs due to high energy input, reduced recycling efficiency because Al, Li, and Mn are lost in the final waste and recycled in the concrete industry, and also the emission of harmful gases. A crushing and separation step can also be carried out to separate metallic elements such as aluminum and copper.In the case of pyrolysis, step a) of the present process, i.e. the extraction of the material comprising said first binder L1, said second binder L2 and said coating SC, is carried out upstream of the heat treatment to avoid degradation of the polymer.

[0127] Hydrometallurgy involves the use of aqueous solutions to leach target metals from the cathode. The cells must first be opened and handled. Lithium-ion batteries under a gaseous atmosphere have proven to be the optimal cell treatment method. Numerous pilot-scale hydrometallurgical processes have been exploited, and recoveries of up to 75% of the active material have been reported. The complexity of the cell design involves an initial fragmentation step, followed by a series of leaching and mechanical separation steps using density, ferromagnetism, and hydrophobicity to separate the "black mass" (active material separated from the current collectors).Foam flotation can also be used to separate carbons from metal oxides; however, pre-sorting and labeling of batteries before recycling could reduce the need for these steps while increasing the quality of the recycled materials. A separation step for metals such as aluminum and copper can be carried out upstream of the leaching treatments. In a hydrometallurgical process, step a) of the present process, namely the extraction of the material comprising said first binder L1, said second binder L2, and said coating SC, is carried out before the separation steps or before the leaching steps.

[0128] Another recycling technique involves combining the two previous techniques to improve leaching yields. The cells are crushed. The aluminum, Copper and polymers can be separated. A pyrolysis step is then carried out at a lower temperature than the conventional pyrometallurgical process. This black mass is then leached in a conventional hydrometallurgical process. In this third case, step a) of the present process, i.e., the extraction of the material comprising said first binder L1, said second binder L2, and said coating SC, is carried out before the separation steps or before the pyrolysis steps. The relative advantages of the different recycling techniques were summarized by Lv et al. (W. Lv, Z. Wang, H. Cao, Y. Sun, Y. Zhang, and Z. Sun, A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries, ACS Sustainable Chem. Eng., 2018, 6, 1504–1521).

[0129] Said alkaline solution used in step b) may be a solution of sodium hydroxide or potassium hydroxide at a concentration of 1% to 70%, preferably 5% to 50% by weight of sodium hydroxide or potassium hydroxide on the basis of the total weight of said alkaline solution.

[0130] The implementation of said precipitation in step c) can be implemented by adding a counter-solvent chosen according to the component(s) to be recovered, i.e. the first binder L1, the second binder L2 or the coating SC. The counter-solvent is a liquid compound in which the solubility of said first binder L1, said second binder L2 or said coating SC is less than 0.0001 g / ml at room temperature.As a non-limiting example, the counter solvent can be 1,2-dichloroethane, 1,3,5-trimethylbenzene, 2,2,4,4-tetramethyl-3-pentanone, 2,2,4-trimethylpentan-3-one, 2,2,5,5-tetramethylhexan-3-one, 2,2,6,6-tetramethyl-4-heptanone, 2,2-dimethylpentan-3-one, 2,3-butanedione, 2-methyltetrahydrofuran, 3-pentanone, 4,4,5,5-tetrachloro-l,3-dioxolan-2-one, acetic anhydride, acetonitrile, acetophenone, acetyl chloride, benzene, benzonitrile, butyl acetate, chloroacetonitrile, cyclohexane, dichloromethane, dioxane, ethyl 2,2-Dimethylpropanoate, ethyl benzoate, ethyl chloroacetate, heptane, hexane, isopropyl 2,2-dimethylpropanoate, isopropyl pivalate, methyl 2,2-dimethylpropanoate, methyl benzoate, methyl propanoate, phenol, phosphorus oxychloride, selenium oxychloride, sulfolane, sulfuryl chloride, tetrachloromethane, thionyl chloride, toluene, or water. The choice of counter-solvent is adapted according to the polymer constituting said binders L1, L2 and said coating SC.

[0131] In the present application, the molar composition of the repeating units in the fluorinated polymers can be determined by various means such as infrared spectroscopy or Raman spectroscopy. Conventional methods of elemental analysis in carbon, fluorine, and chlorine, bromine, or iodine, such as X-ray fluorescence spectroscopy, allow for the unambiguous calculation of the mass composition of the polymers, from which the molar composition can be deduced. The following techniques can also be employed: Multinuclear NMR spectroscopy, specifically using proton (1H) and fluorine (19F) spectroscopy, is performed by analyzing a solution of the polymer in a suitable deuterated solvent. The NMR spectrum is recorded on a FT-NMR spectrometer equipped with a multinuclear probe. The specific signals given by the different monomers are then identified in the spectra acquired for each nucleus. Examples

[0132] Example 1

[0133] Preparation of the negative and positive electrode composition

[0134] In this example, the binding composition is an acrylic styrene copolymer emulsion having a dry extract of 39.0 - 41.0%.

[0135] The manufacture of a negative electrode composition is carried out according to the following steps: a solution of a 2% dry carboxymethylcellulose composition is prepared until completely dissolved. Then, C-NERGY™ SUPER C65 carbon black is added to this solution. The mixture is combined using a Thinky planetary mixer, adjusting the rotation speed to 2000 rpm. Next, the active material (GHDR-15-4 Natural Graphite, Imerys) and water are added alternately in several stages, mixing between each stage. A final addition of water allows for adjusting the dry extract and viscosity. Finally, the binder is added to the ink at a lower agitation speed (500 rpm) in a single step. The resulting electrode composition has a final dry extract of between 45 and 60%. The dry composition of the electrode composition is 94% by weight of active material, 3% by weight of binder, 2% by weight of carbon black and 1% by weight of carboxymethylcellulose.

[0136] The manufacture of a positive electrode composition is carried out according to the following steps: an emulsion of a styrene-acrylic copolymer having a dry extract of 39.0–41.0% is prepared. Then, Super P C65 carbon black (supplier Timcal) is added to this solution. The solution is mixed using a mechanical stirrer. Then, the active material NMC811 is added. N-methyl-2-pyrrolidone can then be added to adjust the final dry extract. The resulting ink contains, by weight, 97 parts of carbon-coated active materials, 1.5 parts of carbon black, and 1.5 parts of binders per 100 parts of the active materials / carbon black / binder mixture.

[0137] Measurement of the viscosity of the electrode composition applicable to a metallic support

[0138] The viscosity of the electrode compositions was measured at 23°C using a TA HR 10 rheometer. The ink was deposited between two parallel plates (40 mm diameter) with a gap of 500 pm. A solvent trap was installed to prevent solvent evaporation during the test. The viscosity values ​​were obtained at different shear rates ranging from 0.1s-1 to 100 s-1. The value of 10s-1 is mentioned in the table below.

[0139] Measurement of the delta of the electrode composition applicable to a metallic support

[0140] The dynamic viscosity of the electrode formulations was measured @ 23°C, at Using a TA HR 10 rheometer, the ink is deposited between two parallel plates (40 mm diameter) with a 500 µm gap. A solvent trap is installed to prevent solvent evaporation during the test. Dynamic viscosity values ​​are obtained at various stress levels ranging from 0.1% to 100% at an oscillation frequency of 1-100 Hz. The delta is then calculated using a formula known to those skilled in the art. The delta value at 0.1% is used for comparison between the different compositions.

[0141] The rheological properties of the different positive and negative electrode compositions are detailed in Table 1 below.

[0142] [Tables 1] Electrode composition Negative Positive Binder composition 3 1.5 Viscosity at t=0 (10 s1, cP) 3870 882 Dry extract (%) 52.10 73 Delta t=0 (°) 56 45

[0143] Application of electrode inks to the current collector

[0144] Negative electrode: A wet coating thickness of 240 µm is applied to a 10 µm thick copper strip using a pilot coating line with a roll-to-roll manufacturing structure. After drying, the negative electrode is calendered using a calenderer (40-ton pressure). Before battery assembly, the electrode is vacuum-dried using a Büchi dryer for a minimum of 12 hours.

[0145] Positive electrode: A wet coating thickness of 190 µm is applied to a 20 µm thick aluminum strip using a pilot coating line with a roll-to-roll manufacturing structure. After drying, the positive electrode is calendered using a calender (40-ton pressure). Before battery assembly, the electrode is vacuum-dried using a Büchi dryer for a minimum of 12 hours.

[0146] Example 2

[0147] The fabrication of an anode formulation was carried out by following these steps: a 9% by mass solution of poly(vinylidene fluoride) is prepared in N-methyl-2-pyrrolidone until completely dissolved. Then, to this, is added Super P C65 carbon black solution (supplier Timcal) is mixed using a mechanical stirrer. Then the active material (GHDR-15-4 natural graphite, Imerys) is added. N-methyl-2-pyrrolidone can then be added to adjust the final dry extract. The resulting ink contains, by weight, 94 parts carbon-coated active material, 2 parts carbon black, and 4 parts binder per 100 parts of the active material / carbon black / binder mixture.

[0148] The manufacture of a positive electrode composition is carried out according to the following steps: a 9% by mass solution of poly(vinylidene fluoride) is prepared in N-methyl-2-pyrrolidone until completely dissolved. Then, Super P C65 carbon black (supplier Timcal) is added to this solution. The solution is mixed using a mechanical stirrer. Then, the active material NMC811 is added. N-methyl-2-pyrrolidone can then be added to adjust the final dry extract. The resulting ink contains, by weight, 97 parts of carbon-coated active material, 1.5 parts of carbon black, and 1.5 parts of binders per 100 parts of the active material / carbon black / binder mixture.

[0149] [Tables2] Electrode composition Negative Positive Binder composition 4 1.5 Viscosity at t=0 (10 s1, cP) 2637 3250 Dry extract (%) 55.15 72.7 Delta t=0 (°) 83 75

[0150] Electrodes are prepared according to the protocol described in Example 1.

[0151] Examples

[0152] Example 2 has been reproduced except for the negative electrode composition, which is that of Example 1.

[0153] Example 4

[0154] A separator is produced as follows: An aqueous formulation is applied at room temperature (~22°C) using a manual applicator (Hohsen Corp. bar coater, wet deposit thickness ~23 mm, manual application speed approximately 100 mm / sec) onto a Celgard 2400 substrate (single-layer PP, 25 µm thick, 89 mm wide, approximately 30 cm long), and then dried on a plate at 65°C for 10 minutes. The dry deposit has a measured thickness of 5–6 mm depending on the sample (Mitsutoyo Digimatic Indicator IDH053D micrometer). The resulting separator has a width of 89 mm and a length of 30 cm. The aqueous formulation deposited on the substrate comprises a vinylidene fluoride-hexafluoropropylene copolymer latex.

[0155] Example 5

[0156] The binder recycling process consists of contacting the material to be recycled, comprising the positive and negative electrodes prepared in Example 2 and the separator of Example 4, with at least one polar solvent such as N-methylpyrrolidone. Contact is made at a temperature of 50°C. Extraction is carried out under atmospheric pressure. This extraction is performed in batches. The contact time is 6 hours. The ratio of material to be extracted to the weight of solvent used is 1. After filtration, the resulting solution is concentrated by evaporation under vacuum. Dichloromethane is added to the solution to precipitate the polymers described in the invention. These polymers are then recovered and dried by any method known to those skilled in the art. These polymers can then be reused in a battery application or in another field of application.

[0157] The same operation was repeated with the positive and negative electrodes of Example 1.

[0158] Example 6 (comparative)

[0159] The manufacture of a negative electrode composition is carried out according to the following steps: a solution of a 2% dry carboxymethylcellulose composition is prepared until completely dissolved. Then, C-NERGY™ SUPER C65 carbon black is added to this solution. The mixture is combined using a Thinky planetary mixer, adjusting the rotation speed to 2000 rpm. Next, the active material (GHDR-15-4 Natural Graphite, Imerys) and water are added alternately in several stages, mixing between each stage. A final addition of water allows for adjusting the dry extract and viscosity. Finally, the binder (a styrene-butadiene latex with a dry extract of 39.0 to 41.0% is used) is added to the ink at a lower agitation speed (500 rpm) in a single step. An electrode composition is obtained with a final dry extract of between 45 and 60%.The dry composition of the electrode composition is 94% by weight of active material, 3% by weight of binder, 2% by weight of carbon black and 1% by weight of carboxymethylcellulose.

[0160] The manufacture of a positive electrode composition is carried out according to the following steps: a 9% by mass solution of poly(vinylidene fluoride) is prepared in N-methyl-2-pyrrolidone until completely dissolved. Then, Super P C65 carbon black (supplier Timcal) is added to this solution. The solution is mixed using a mechanical stirrer. Then, the active material NMC811 is added. More N-methyl-2-pyrrolidone can then be added to adjust the final dry extract. The resulting ink contains, by weight, 97 parts of carbon-coated active material, 1.5 parts of carbon black, and 1.5 parts of binders per 100 parts of the active material / carbon black / binder mixture.

[0161] The rheological properties of the different positive and negative electrode compositions are detailed in Table 1 below.

[0162] [Tables3] Electrode composition Negative Positive Binder composition 3 1.5 Viscosity at t=0 (10 s1, cP) 4400 3250 Dry extract (%) 52 72.7 Delta t=0 (°) 49 75

[0163] The binders used in the preparation of the negative and positive electrodes, i.e. styrene-butadiene and PVDF in this example, are not soluble in the same solvent. Thus, the recycling process for these components was complicated and did not allow for the recovery of the polymers used at the anode, cathode, and separator.

Claims

Demands

1. Lithium-ion secondary battery comprising a cathode, an anode and a separator disposed between said cathode and said anode; said cathode comprising a current collector C' and a layer C comprising a first active material, a conductive agent and a first binder L1; said anode comprising a current collector A' and a layer A comprising a second active material and a second binder L2; said separator comprising either a porous polymeric support S and a coating SC disposed on said porous support S or a solid electrolyte comprising a coating SC characterized in that said first binder L1, said second binder L2 and said coating SC each comprise at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol.

2. Lithium-ion secondary battery according to the preceding claim characterized in that said polymer P is selected from the group consisting of a fluorinated polymer PI or a hydrophilic polymer P2 or a mixture of both.

3. Lithium-ion secondary battery according to the preceding claim characterized in that said fluorinated polymer PI comprises monomeric units derived from a fluorinated monomer Ml selected from the group consisting of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (TrFE); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); the monomer of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the monomer of formula CF2 =CFOCF2CF2SO2F; the monomer of formula F(CF2)nCH2OCF=CF 2 in which n is 1, 2, 3, 4 or 5; the monomer of formula R'CH 2OCF=CF2 in which R1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4;the monomer of formula R2OCF=CH2 in which R2 is F(CF2)P and p is 1, 2, 3 or 4; trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene; and 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof.

4. Lithium-ion secondary battery according to any one of the preceding claims 2 or 3 characterized in that said hydrophilic polymer P2 comprises monomeric units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI) or (VII) or a mixture thereof R'R2C=C(R3)C(O)R4 (I) R17R18C=C(R19)(OC(O)R20) (II) R17R18C=CR19C(O)OC(O)CR21=CR22R23 (III) R17R18C=CR19(CN) (IV) OJ , R"' ° Wj (VB R17R18C=CR19(C(O)NR5R6) (VII) wherein the substituents R1, R2 and R3 are, independently of each other, selected from the group consisting of H, CO2H, and Ci-C5 alkyl; R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R21, R22 and R23 are, independently of each other and independently for each formula, selected from the group consisting of H and Ci-C 5 alkyl;R4 is selected from the group consisting of -NHC(CH3)2CH2 C(O)CH3 and -OR24 with R24 selected from the group consisting of H and CrCi8 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2 H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 and a five- or six-membered heterocycle comprising at least one nitrogen atom in its cyclic chain; R is selected from the group consisting of -OR with R selected from the group consisting of H and Ci-Ci8 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -PO3 H, -C(O)OR31, -OC(O)R31; R5 and R6 are independently selected from the group consisting of H and C1-C1 alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -PO3H, -C(O)OR31, -OC(O)R31 groups; R31 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2 functional groups.

5. n. Secondary lithium-ion battery according to claim 1 characterized in that, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a fluorinated polymer PI comprising at least 70% by mol of monomeric units derived from a monomer M1 as defined in claim 3.

6. Lithium-ion secondary battery according to claim 1 characterized in that, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a hydrophilic polymer P2 comprising at least 70% by mol of monomeric units derived from a monomer M2 as defined in claim 4.

7. Lithium-ion secondary battery according to claim 1 characterized in that, in said first binder L1, said second binder L2 and said coating SC, said at least polymer P is a mixture comprising at least 70 mole percent of a fluorinated polymer PI as defined in claim 3 and a hydrophilic polymer P2 as defined in claim 4.

8. Lithium-ion secondary battery according to any one of the preceding claims characterized in that it also comprises an electrolytic composition comprising a lithium salt selected from the group consisting of LiCF3SO3, LiPF6, LiC104, LiBF4, LiB(C2O4)2, LiN(SO2F)2, LiN(SO2CF3)2, LiN(SO2 C2F3)2, LiN(SO2C2F5)2, LiN(SO2F)(SO2CF3), LiN(SO2F)(SO2C2F5), LiN(SO2CF3)(SO2C2F5), LiAsF6, LiBF2C2O4, LiNO3, LiPF3(CF2CF3)3, LiBETI, LiTDI, or a mixture thereof.

9. Lithium-ion secondary battery according to any one of the preceding claims 1 to 8, characterized in that said solid electrolyte also comprises an inorganic material containing a sulfur atom selected from the group consisting in: metal polysulfide MxSy with x is an integer from 1 to 3 and y is an integer from 1 to 10 and M is a metallic element selected from the group consisting of an alkali metal, an alkaline earth metal such as Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof; preferably the metal M is selected from the group consisting of Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, and Al; in particular the metal polysulfide is selected from the group consisting of Li2S6, Li2S7, Li2S8, Li2S9, Li2S10, Na2S6, Na2S7, Na2S8, Na2S9, Na2S10, K2S6, K2S7, K2S8, K2S9, or K2S10; lithium tin sulfide phosphorus ("Isps") such as LiI0SnP2Si2; Lithium sulfide phosphorus (“Ips”) of formula (Li2S)x(P2S5)y, wherein x+ y=l and 0 < x < 1, Li7P3Sn, Li7PS6, Li4P2S6, Li9>6P3Si2 and Li3PS4; Lps doped such as Li2CuPS4, Lii+2xZni xPS4, in which 0 < x < 1, Li3 33Mgo.33P2S6, and LU3xScxP2S6, in which 0 < x < 1; Lithium sulfide phosphorus oxygen ("LPSO") of formula LixPySzO, in which 0.33 < x < 0.67, 0.07 < y < 0.2, 0.4 < z < 0.55, 0 <w<0,15;Lithium sulfide phosphorus ("Ixps") with x Si, Ge, Sn, As, Al, such as Lii0GeP2Si2 or Lii0SiP2Si2; Lithium sulfide phosphorus oxygen ("LXPSO") with x Si, Ge, Sn, As, Al; Lithium sulfide silica (“LSS”) such as Li2SiS3, Li2S-P2S5-SiS2, Li2S-P2S5-SiS2-LiCl, Li2S-SiS2-P2S5, Li2S-SiS2-P2S5-Lil, Li2S-SiS2-LiI, Li2S-SiS2, Li9.54Sii.74Pi.44Sn.7Clo.3, and Li2 S-SiS2-Al2S3; Lithium boron sulfide such as Li3BS3 or L2S-B2S3-Li; Lithium tin sulfide and lithium arsenite such as LiOj8SnOj8S2, Li4SnS4, Li3j833SnOj833AsOji66S4, Li3AsS4-Li4SnS4, Li3AsS4; and Li4PS4Cl Li15P3Si6Cl3, Li7P2S8Cl, and Li7P2S8I;

10. - Materials of formula Li6PS5Y in which Y is Cl, Br or I such that; Li6 XPS5 XY[+x, in which 0 < x < 0.5; preferably Li6PS5Cl; Li2S-GeS2-ZnS, Li3SbS4, Na3PS4, Na10SnP12Si2, and Na„Sn 2PS12; - and mixtures thereof. secondary lithium-ion battery according to any one of the preceding claims characterized in that said solvent SI is selected from the group consisting of dimethyl sulfoxide, ethanol, methanol, water, acetone, N-methyl-2-pyrrolidone, pyridine, triethylamine, methyl isobutyl ketone (MIBK), cyclopentanone, isobutyl isobutyrate (IBIB), ethyl acetate, propylene glycol monomethyl ether acetate, 1,3,2-dioxathiol-2-oxide, 1,2-dimethoxyethane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolan-2-one, 1,3-dioxolane, 2,2,2-trifluoro-N,N-dimethylacetamide, 2,2,4,4-tetramethyl-3-pentanone, 2,2,4-trimethylpentan-3-one, 2,2,5,5-tetramethylhexan-3-one, 2,2,6,6-tetramethyl-4-heptanone, 2,2-dimethylpentan-3-one, 2,3-butanedione, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 2-butanone, 2-methylpentan-3-one, 2-methylpropanenitrile, 2-methyltetrahydrofuran, 2-pentanone, 2-phenylacetonitrile, 3,3-dimethyl-2-butanone, 3-methyl-2-butanone,3-pentanone, 4-methyl-2-oxo-l,3-dioxolane, 4-methyl-2-pentanone, acetonitrile, acetophenone, benzaldehyde, benzonitrile, benzophenone, bis(2-chloroethyl) ether, butanenitrile, butyl acetate, chloroacetonitrile, cyclohexanone, cyclopentanone, dibenzyl ether, dibutyl ether, diethyl carbonate, diethyl ether, diisopropyl ether, dimethyl carbonate, dipropyl carbonate, dimethylcyanamide, dioxane, diphenylphosphinic chloride, dipropyl ether, ethyl 2,2-dimethylpropanoate, ethyl 2-methylpropanoate, ethyl acetate, ethyl benzoate, ethyl butanoate, ethyl chloroacetate, ethyl chloroformate, ethyl formate, ethyl propanoate, formamide, isopropyl 2,2-dimethylpropanoate, isopropyl acetate, isopropyl pivalate, methyl 2,2-dimethylpropanoate, methyl acetate, methyl benzoate, methyl propanoate, methyl propyl ether, N,N-dimethylbenzylamine, N,N-dimethylcarbamoyl chloride, N,N-dimethylformamide, N,N-dimethyltrifluoroacetamide, N,N-, dimethylurethane, N-methyl-2-pyrrolidone, oxane, oxolan-2-one, phenylphosphonic dichloride, phenylphosphonic difluoride, phosphorus oxychloride, propanenitrile, propyle acétate, sulfolane, tétrahydrofurane, tributyle phosphate, triéthyle phosphate, trimethyle phosphate, tripyrrolidinophosphine oxide, l-butyl-3-methylimidazolium tetrafluoroborate, l-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide, butyl-methylpyrrolidinium bis-(trifluoromethylsulfonyl)imide, butyl-methylpiperidinium bis-(trifluoromethylsulfonyl)imide, ethyl-dimethyl-propylammonium bis-(trifluoromethylsulfonyl)imide, triethylsulfonium bis-(trifluoromethylsulfonyl)imide, mesitylène, phénol, biacetyl, methyl propanoate, benzonitrile, ethyl chloroacetate, propanenitrile, butanenitrile, propanol, hexanol, o-chloroaniline, di-n-propyl ether, dibenzyl ether, diethyl ether, glycerol, butanol, propanol, 1,2-ethandiol, 1,3-dioxolane, 2-methyl-2-propanol, tetrahydropyran, 2-phenyl éthanol, benzyl alcohol, pentanol,N-methyl formamide, N,N-dimethylaniline, N,N-dimethylacetamide, isopentanol, octanol, quinoline, decanol, dibutyl sulfoxide, N,N-diethylacetamide, isopropanol, aniline et N-methyl aniline.,

11. A lithium-ion secondary battery according to any one of the preceding claims, characterized in that said first active material is selected from the group consisting of LiCoO2, Li(Ni,Co,Al)O2, Li(i+x)NiaMnbCoc (x represents a real number of 0 or more, a = 0.9, 0.8, 0.6, 0.5, or 1 / 3, b = 0.05, 0.1, 0.2, 0.3, or 1 / 3, c = 0.05, 0.1, 0.2, or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3O3, Li3Fe2(PO4)3, Li3V2(PO4)3, a LiMn spinel substituted by a different element having a composition represented by Lii+xMn2xyMyO4, M representing at least one metal selected from Al, Mg, Co, Fe, Ni, and Zn, x and y independently representing a real number between 0 and 2, lithium titanate LixTiOy - x and y independently representing a real number between 0 and 2, and a metal and lithium phosphate having a composition represented by LiMPO4, M representing Fe, Mn, Co, or Ni.

12. A secondary lithium-ion battery according to any one of the preceding claims, characterized in that said second active material is selected from the group consisting of a lithium alloy, lithium metal, a metal oxide, a material carbon such as graphite or hard carbon, silicon, silicone, a silicon alloy and Li4Ti50i2.

13. Lithium-ion secondary battery according to any one of the preceding claims characterized in that: - said cathode comprises a current collector coated with a layer Cl, disposed between the current collector C' and said layer C, and comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and carbon particles; and / or - said anode comprises a current collector A' coated with a layer Al, disposed between the current collector and said layer A, and comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and carbon particles.

14. Lithium-ion secondary battery according to any one of the preceding claims characterized in that: - said cathode comprises a current collector C' whose edges are coated with a layer C2 comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and optionally inorganic particles; and / or - said anode comprises a current collector A' whose edges are coated with a layer A2 comprising said at least one polymer P having a solubility greater than 0.01 g / ml at room temperature in a solvent SI having a donor number greater than 4 kcal / mol and optionally inorganic particles.

15. A method for recycling a secondary lithium-ion battery according to any one of the preceding claims, characterized in that it comprises the steps of: a. Crushing or mechanical separation of said battery to recover a material comprising said first binder L1, said second binder L2 and said coating SC; b. Dissolution of said material in a solvent SI having a donor number greater than 4 kcal / mol or in an alkaline solution to obtain a solution comprising said first binder L1, said second binder L2 and said coating SC; c. Recovery of at least one of said first binder L1, second binder L2 and coating SC by precipitation of the latter or these from said solution obtained in step b).