Composition based on poly(vinylidene fluoride)

Abstract

The present invention relates to a composition comprising a fluoropolymer P1 and a polymer additive P2 comprising at least one functional group containing a phosphorus atom.

Description

Title of the invention: Composition based on polyvinylidene fluoride) Technical field

[0001] The present invention relates generally to the field of electrical energy storage in rechargeable secondary batteries of the Li-ion type. More specifically, the present invention relates to a composition comprising a fluorinated polymer and an additive. The composition can be used as a binder for the electrode. Technological background of the invention

[0002] In recent years, there have been remarkable developments in electronic technology, and the functionality of miniature mobile devices has become increasingly advanced, which has created a demand for smaller and lighter power supplies (to have a higher energy density) for use in such devices. As high energy density batteries, non-aqueous electrolyte secondary batteries such as lithium-ion secondary batteries are widely used.

[0003] An electrode for lithium-ion secondary batteries can be obtained, for example, by the following means: First, a formulation is obtained by mixing powdery electrode materials such as an electrode active material and a conductive agent, which can be added if necessary, with a binder and dissolving or dispersing the mixed material in a suitable solvent. Subsequently, an electrode for lithium-ion secondary batteries can be obtained by covering a current collector with the obtained electrode mixture slurry, evaporating the solvent.

[0004] The active materials used in electrodes are generally nickel-based and more specifically contain predominantly nickel. However, when the ratio of nickel in the active material of the electrode increases, the electrode mixture slurry becomes prone to gelation. For example, document EP3795430 is known, which describes an electrode composition comprising a vinylidene fluoride-based polymer comprising a polar group and at least 10% of an acrylic polymer. However, it has been observed that the electrode composition is much too viscous (above 40,000 cP initially) to be implemented on an industrial scale. Also known from document EP2147029 is a copolymer between vinylidene fluoride and acrylic acid which has a strong tendency to sediment over time.

[0005] Generally speaking, an electrode composition must be industrially processable, stable (not sediment) and not gel over time. There is therefore There is still a need for electrode compositions exhibiting a good compromise between the different properties. The present invention aims to resolve all or part of the drawbacks of current electrode compositions by providing a particular polymer composition. Summary of the invention

[0006] According to a first aspect, the present invention relates to a composition comprising a fluorinated polymer carrying polar groups PI and a polymer additive P2 comprising repeating units derived from a monomer M 2 of formula (I), (II), (III), (IV), (V), (VI), (VII) or a mixture thereof

[0007] R1R2C=C(R3)((X2)PC(O)R4) (I)

[0008] R5R6C=C(R7)(OC(O)R8) (II)

[0009] R9R10C=CRnC(O)OC(O)CR12=CR13R14 (III)

[0010] R30R31C=CR32(CN) (VI)

[0011] R33R34C=CR35(C(O)NR36R37) (VII)

[0012] in which

[0013] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C5 alkyl;

[0014] R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR25 with R25 selected from the group consisting of H and C1-C18 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0015] R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2H functional groups;

[0016] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027] p' is 0 or 1; R5, R6 and R7 are independently selected from the group consisting of H and C1-C5 alkyl; R8 is C1-C5 alkyl; R9 R10 R11 R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R30 R31 R32 33 34 35 , R , R , R are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3; R36 and R37 are, independently of each other, selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38; R38 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more functional groups CO2H; characterized in that said polymer additive P2 also comprises at least one functional group containing a phosphorus atom. The applicant surprisingly found that the specific composition according to the present invention exhibited a very good compromise between the various properties required for its use in applications such as electrode compositions. The composition exhibits an ideal viscosity for industrial processing, does not sediment over time and does not gel over time. According to a preferred embodiment, the phosphorus content in said polymer additive P2 is between 0.01 and 15 mol% per mol of polymer additive P2. According to a preferred embodiment, the functional group containing a phosphorus atom is selected from the group consisting of -P(O)(O X+)-, -P(O)(O X+)2 and -P(O)(O X+)H with X selected from the group consisting of H, Na, Li and K. According to a preferred embodiment, the mass ratio between said fluorinated polymer PI and said polymer additive P2 is greater than or equal to 1, advantageously greater than or equal to 5, preferably greater than or equal to 10, more preferably greater than or equal to 15, in particular greater than or equal to 20. According to a preferred embodiment, the mass ratio between said fluorinated polymer PI and said polymer additive P2 is less than or equal to 1000, preferably less than or equal to 400. According to a preferred embodiment, said polymer PI comprises repeating units derived from a monomer Mla selected from the group consisting of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers 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 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 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.

[0028] According to a preferred embodiment, said fluoropolymer PI comprises repeating units derived from the monomer Mla and repeating units derived from a monomer Mlc and optionally repeating units derived from a monomer Mlb; said monomer Mla being vinylidene fluoride; said monomer Mlb selected from the group consisting of vinyl fluoride; trifluoroethylene (VF3); 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 product of formula CF2=CFOCF2CF(CF3)OCF2CF 2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF 2 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; perfluorobutyl ethylene (PFBE); trifluoropropene, tetrafluoropropene, hexafluoroisobutyl ene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof; said monomer Mlc being selected from the group consisting of formula RaRbC=C(Rc)((X3)p -C(O)Rd) in which the substituents Ra, Rb and Rc are independently of each other selected from the group consisting of H, CO2H and Ci-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 CrCi8 alkyl optionally substituted by one or more groups -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 ring chain; Rd” being selected from the group consisting of C1-C6 alkyl or C6-C12 aryl optionally substituted by one or more groups -OH, -CO2 H, -SO3H, -PO3H; p” is 0 or 1; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with w2 being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5;R ,R ,R ,R are independently of each other, independently for each unit w2, selected from the group consisting of H and C1-C5 alkyl.

[0029] According to a preferred embodiment, said monomer Mlc is present in said polymer PI in a molar content of 0.01% to 5%.

[0030] According to a preferred embodiment, said monomer Mlb is present in said polymer PI in a molar content of 1% to 25%.

[0031] According to a preferred embodiment, said polymer additive P2 has a molar mass by weight of between 500 g / mol and 50000 g / mol, preferably between 500 g / mol and 25000 g / mol.

[0032] According to a preferred embodiment, said polymer additive P2 comprises repeating units derived from a monomer M2 of formula (I), (III) or (IV) which

[0033] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0034] R4 is -OR25 with R25 selected from the group consisting of H and C1-C15 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0035] R25' is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2H functional groups;

[0036] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0037] p' is 0 or 1;

[0038] R9, R10, R11, R12, R13, R14, R15, R16 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0039] According to a preferred embodiment, said polymer additive P2 comprises repeating units derived from a monomer M2 of formula (I), (III) or (IV) in which R1, R2 and R3 are independently of one another selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0040] R4 is -OR25 with R25 selected from the group consisting of H and C1-C10 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0041] R25 is selected from the group consisting of C1-C5 alkyl and C6 substituted aryl by one or more CO2H functional groups;

[0042] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C5 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0043] p' is 0 or 1;

[0044] R9, R10, R11, R12, R13, R14, R15, R16 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0045] According to a preferred embodiment, said composition has a sedimentation factor S of between 0.8 and 1.1; calculated according to the protocol detailed in the present application.

[0046] According to another aspect, the present invention provides a binder for a Li-ion battery comprising said composition according to the present invention.

[0047] According to another aspect, the present invention provides an electrode composition comprising an active material and said binder according to the present invention.

[0048] According to another aspect, the present invention provides an electrode for a lithium-ion battery comprising a metal collector of which at least one face is covered with said electrode composition according to the present invention.

[0049] According to another aspect, the present invention provides a Li-ion secondary battery comprising an anode, a cathode and a separator, wherein the anode or the cathode is an electrode according to the present invention. Detailed Description of the Present Invention

[0050] According to a first aspect of the present invention, a composition is provided. Said composition may be in powder form or in the form of a latex or a solution in the presence of an organic solvent. Preferably, said composition is in powder form.

[0051] Said composition comprises a fluoropolymer PI and a polymer additive P2 which are detailed below. According to a particular embodiment, said composition consists of a fluoropolymer PI and a polymer additive P2 which are detailed below. Said polymer PI carries polar groups.

[0052] In said composition, the mass ratio between said fluoropolymer PI and said polymer additive P2 is greater than or equal to 1, advantageously greater than or equal to 5, preferably greater than or equal to 10, more preferably greater than or equal to 15. Advantageously, the mass ratio between said fluoropolymer PI and said polymer additive P2 is greater than or equal to 20, advantageously greater than or equal to 21, preferably greater than or equal to 22, more preferably greater than or equal to 23, in particular greater than or equal to 24, more particularly greater than or equal to 25, preferably greater than or equal to 26. The mass ratio refers to the ratio of the mass contents in the composition of the two compounds considered.Preferably, the mass ratio between said fluorinated polymer PI and said polymer additive P2 is greater than or equal to 27, advantageously greater than or equal to 28, preferably greater than or equal to 29, more preferably greater than or equal to 30, in particular greater than or equal to 31, more particularly greater than or equal to 32, preferably greater than or equal to 33, advantageously greater than or equal to 34, preferably greater than or equal to 35, more preferably greater than or equal to 36, particularly preferably greater than or equal to 37, more particularly preferably greater than or equal to 38.

[0053] The content of polymer additive P2 in said composition influences the viscosity in the electrode composition with which it is prepared. Thus, it has been found that when the ratio between the fluoropolymer PI and the polymer additive P2 is less than 19, the viscosity of the electrode composition is too high to be processable on an industrial scale.

[0054] Advantageously, in said composition, the mass ratio between said fluorinated polymer PI and said polymer additive P2 is less than or equal to 1000, preferably less than or equal to 900, more preferably less than or equal to 800, in particular less than or equal to 700, more particularly less than or equal to 600, preferably less than or equal to 500, advantageously less than or equal to 400.

[0055] According to a particular embodiment, in said composition, the mass ratio between said fluoropolymer PI and said polymer additive P2 is less than or equal to 375, preferably less than or equal to 350, more preferably less than or equal to 325, in particular less than or equal to 300, more particularly less than or equal to 275, preferably less than or equal to 250, advantageously less than or equal to 225, preferably less than or equal to 200. It has been found that when the mass ratio between the fluoropolymer PI and the polymer additive P2 is too high, the electrode composition prepared with said composition sediments over time. Thus, in order to improve the stability of the electrode composition over time and thus avoid sedimentation thereof, it is preferable to have a mass ratio P1 / P2 as expressed above.

[0056] According to a particular embodiment, when said composition is in powder form, it comprises at least 95% by weight of said fluoropolymer PI based on the total weight of the composition, advantageously at least 96% by weight, preferably at least 97% by weight, more preferably at least 98% by weight, in particular at least 98.5% by weight of said fluoropolymer PI based on the total weight of the composition.

[0057] According to a particular embodiment, when said composition is in powder form, it comprises less than 5% by weight, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1.5% by weight, of said polymer additive P2 based on the total weight of the composition.

[0058] According to a particular embodiment, when said composition is in powder form, it consists of from 0.01% to 5%, advantageously from 0.05% to 4%, preferably from 0.1% to 3%, more preferably from 0.5% to 2.5%, in particular from 0.5 to 2.0%, more particularly from 0.75 to 1.5% by weight of said polymer additive P2 based on the total weight of said composition; the remainder being said fluoropolymer PI.

[0059] Said composition may be prepared by mixing the constituents, for example in powder form, in the required proportions. Alternatively, the constituents may be mixed in the form of an aqueous solution or an organic solution (i.e. in the presence of an organic solvent, in the required proportions and then the solution may be dried to obtain a powder or used as such. Said organic solvent is not specifically limited and is chosen so as to solubilize said fluoropolymer PI and said polymer additive P2. Said organic solvent may be de manière non limitative n-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), triethylphosphite (TEP), acétone, cyclopentanone, tetrahydrofurane, 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 ; et les mélanges de ceux-ci.

[0060] According to a preferred embodiment, the ratio between the viscosity V2 and the viscosity VI is between 0.25 and 5.0; the viscosity V2 corresponds to the viscosity obtained from the composition according to the present invention and the viscosity VI corresponds to the viscosity obtained from the fluoropolymer PI. Advantageously, said ratio V2 / V1 is between 0.5 and 4.5, preferably between 0.75 and 4.0, more preferably between 0.75 and 3.5, in particular between 0.75 and 3.0, more particularly between 0.75 and 2.5. Said viscosities VI and V2 are measured according to the protocol described below in the examples. When the ratio V2 / V1 is in the range mentioned above, the electrode composition comprising the composition according to the invention has very good rheological behavior to facilitate the process stability thereof during the preparation of an electrode.

[0061] According to a preferred embodiment, the sedimentation factor S of said composition according to the invention is between 0.8 and 1.1, advantageously between 0.82 and 1.05, preferably between 0.84 and 1.05, more preferably between 0.86 and 1, in particular between 0.88 and 1, more particularly between 0.90 and 1. The sedimentation factor S corresponds to the ratio between the solid content of a composition at t = 0 and the solid content of a composition at t = 120h. The sedimentation factor is calculated according to the protocol detailed below in the examples. Said composition according to the present invention makes it possible to avoid sedimentation of the electrode composition comprising it. To ensure good implementation of an electrode, it is preferable for the sedimentation factor S to remain within the range mentioned above.More particularly, thanks to the composition according to the present invention, the sedimentation factor S is between 0.95 and 1, advantageously between 0.96 and 1, preferably between 0.97 and 1, more preferably between 0.98 and 1. The stability over time, that is to say the absence of sedimentation, makes it possible to guarantee homogeneity of the electrode composition during the preparation of an electrode, which improves the quality and performance thereof. The composition according to the present invention makes it possible to achieve this objective.

[0062] Fluorinated polymer PI

[0063] According to a preferred embodiment, said fluorinated polymer PI comprises in its chain at least one fluorinated monomer Mla chosen 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. As mentioned above, said fluoropolymer PI carries polar groups. These polar groups may be present in said fluoropolymer PI via a monomer carrying said polar groups. Alternatively, said polar groups may be grafted onto a fluoropolymer to give said fluoropolymer PI according to known techniques. Preferably, the polar groups are introduced into said fluoropolymer PI via a monomer carrying said polar groups, for example via the Mlc monomers as described below in the present application.

[0064] Preferably, said fluoropolymer PI comprises repeating units derived from a monomer Mla selected from the group consisting of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers 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 product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2 H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF2 SO2F; 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. Trifluoropropenes include 3,3,3-trifluoropropene. Tetrafluoropropenes include 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene. Pentafluoropropenes include 1,1,3,3,3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene. Chlorofluoroethylene may 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. ;

[0065] In particular, said fluoropolymer PI comprises at least repeating units derived from a monomer Mla being vinylidene fluoride. The fluoropolymer PI is preferably a copolymer of vinylidene fluoride.

[0066] According to another particular embodiment, the fluoropolymer PI is a polymer comprising repeating units derived from a monomer Mla being vinylidene fluoride and repeating units derived from a monomer Ml c and optionally repeating units derived from a fluoromonomer Mlb. In said fluoropolymer PI, the mass content of the repeating units Mla is at least 50%, preferably at least 60%, more preferably greater than 70% and advantageously greater than 80%.

[0067] According to another embodiment, said fluorinated polymer PI comprises repeating units derived from a monomer Mla being vinylidene fluoride and repeating units derived from a monomer Ml c.

[0068] In this case, said monomer Mlc may be of formula RaRbC=C(Rc)((X3)p C(O)R d) in which the substituents Ra, Rb and Rc are independently of each other selected from the group consisting of H, CO2H and Ci-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 CrCi8 alkyl optionally substituted by one or more groups -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 ring chain; Rd” being selected from the group consisting of C1-C6 alkyl or C6-C12 aryl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H group(s); p” is 0 or 1; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s);with w2 being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5;R26, R27, R28, R29 are independently of each other, independently for each w2 unit, selected from the group consisting of H and C1-C5 alkyl. Said heterocycle may be saturated or unsaturated or aromatic. Said heterocycle may be monocyclic or bicyclic. Said heterocycle may be a pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, oxindole, isatin, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ring. Said heterocycle may be substituted by one or more C1-C5 alkyl groups. As mentioned above, the CrCi8 alkyl is optionally substituted by said heterocycle. The latter 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. ;

[0069] Advantageously, said monomer M le may be of formula RaRbC=C(Rc)((X3 )P”C(O)Rd) in which the substituents Ra, Rb and Rc are independently of one another selected from the group consisting of H, CO2H and C1-C5 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and C1-C18 alkyl optionally substituted by one or more groups -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 ring chain; Rd” being selected from the group consisting of C1-C6 alkyl or C6-C12 aryl optionally substituted by one or more groups -OH, -CO2H, -SO3H, -PO3H; p” is 0 or 1; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and a Ci-Cio alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s);with w2 being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each unit w2, selected from the group consisting of H and C1-C5 alkyl.;

[0070] Preferably, said monomer M le may be of formula R'RbC=C(RLX(X3)p C(O)Rd) in which the substituents Ra, Rb and Rc are independently of each other selected from the group consisting of H, CO2H and C1-C5 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and C1-C1 5 alkyl optionally substituted by one or more groups -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd”; Rd” being selected from the group consisting of C1-C5 alkyl or C6-C1 0 aryl optionally substituted by one or more groups -OH, -CO2H, -SO3H, -PO3H; p” is 0 or 1; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with w2 being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5;R26, R27, R28, R29 are independently of each other, independently for each w2 unit, selected from the group consisting of H and C1-C5 alkyl. ;

[0071] More preferably, said monomer M le may be of formula RaRbC=C(Rc)((X3)p-C(O)Rd) in which the substituents Ra, Rb and Rc are independently of one another selected from the group consisting of H, CO2H and C1-C3 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd”; Rd” being selected from the group consisting of C1-C5 alkyl or C6 aryl optionally substituted with one or more -OH, -CO2H, -SO3H, -PO3H groups; p” is 0 or 1; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and a C1-C5 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester groups; with w2 being an integer beyond5;R ,R ,R ,R are independently of each other, independently for each unit w2, selected from the group consisting of H and C1-C3 alkyl.

[0072] In particular, said monomer M le may be of formula RaRbC=C(Rc)(C(O)Rd ) in which the substituents Ra, Rb and Rc are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd”; Rd” being selected from the group consisting of C1-C5 alkyl or C6 aryl optionally substituted by one or more groups -OH, -CO2H, -SO3H, -PO3H.

[0073] Said monomer Mlc may also be of formula ReRfC=C(Rs)(OC(O)Rh); R'Rj C=CRkC(O)OC(O)CR=CRmRn; R°RpC=CRq(CN); RrRsC=CRt(C(O)NRuRv);

[0074] in which

[0075] Rh is CrC5 alkyl;

[0076] Re, Rf, Rg, Rh, R\ Rj, Rk, R1, R” Rn, R°, RP, R\ Rr, Rs, R', Ru, Rv are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0077] Said Mlc monomer may also be of formula

[0078] in which R““, Rab, Rac, Rad, Rae, Raf, Rag, Rah, R”, Raj, R1*, Ral are independently of each other selected from the group consisting of H and Cr C5 alkyl, preferably selected from the group consisting of H and CH3.

[0079] According to a particularly preferred embodiment, said monomer M le 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, maleic anhydride, vinyl acetate, acrylamide, acrylonitrile, methacrylic anhydride of formula CH2=C(CH3)C(O)OC(O)C(CH 3)=CH2, the monomers of formula CH2=CH(CO2CH2CH2CO2H), CH2=CH(CO2CH 2CH2-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 M le with an alkyl group having from 1 to 8 carbon atoms is preferred, and an alkyl group having from 1 to 5 carbon atoms is more preferable. Said fluoropolymer PI may comprise one or more repeating units derived from said monomer M le as defined herein. Preferably, when containing, said polymer PI comprises from 0.01% to 10%, preferably from 0.05% to 5%, in particular from 0.1% to 5% by weight of repeating units derived from said monomer M le based on the total weight of said polymer PI. ;

[0080] Preferably, when the fluorinated monomer Mla is vinylidene fluoride, the mass content of vinylidene fluoride repeating units in said fluorinated polymer PI is at least 50%, preferably at least 60%, more preferably at least 70%, in particular at least 80%, more particularly at least 90%, preferably at least 95%.

[0081] In particular, said fluoropolymer PI comprises at least 50%, preferably at least 60%, more preferably at least 70%, in particular at least 80%, more particularly at least 90%, preferably at least 95% by weight of repeating units derived from a monomer Mla being vinylidene fluoride and from 0.01% to 5% by weight of repeating units derived from a monomer Mlc as defined above, based on the total weight of said polymer PI;in particular said monomer M le is selected from the group consisting of 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, maleic anhydride, vinyl acetate, acrylamide, acrylonitrile, methacrylic anhydride of formula CH2=C(CH 3)C(O)OC(O)C(CH3)=CH2, 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(CO2CH 2CH2-OC(O)-C6H4CO2H), CH2=CH(CO2CH2CH2CH2CH(CO2H)CH2CH2CO2H); and mixtures thereof.

[0082] Optionally, said fluorinated polymer PI also comprises repeating units derived from a fluorinated monomer Mlb. Said fluorinated monomer Mlb is different from the monomer Mla. Preferably, said fluorinated monomer Mlb is selected from the group consisting of vinyl fluoride; trifluoroethylene (VF3); 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 product of formula CF2=CFOCF2CF(CF3)OCF2CF 2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF 2 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; perfluorobutyl ethylene (PFBE); trifluoropropene, tetrafluoropropene, hexafluoroisobutyl ene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene or a mixture thereof. Preferably, the fluoropolymer PI comprises repeating units derived from a monomer Mla being vinylidene fluoride and repeating units derived from a fluorinated monomer Mlb 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 SO2;F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF 2SO2F; 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-1-propene or a mixture thereof. In particular, the fluoropolymer PI comprises repeating units derived from a monomer Mla being vinylidene fluoride and repeating units derived from a fluorinated monomer Mlb selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene and hexafluoropropylene or a mixture thereof.Preferably, when it contains it, said fluoropolymer PI comprises from 1% to 40%, preferably from 1% to 30%, in particular from 2% to 20% by weight of repeating units derived from said monomer Mlb based on the total weight of said polymer.

[0083] According to another embodiment, said fluorinated polymer PI comprises repeating units derived from a monomer Mla being vinylidene fluoride, repeating units derived from a fluorinated monomer Mlb, repeating units derived from a monomer Ml c; said monomers Mlb and Ml c being as defined above in the proportions as defined above.

[0084] According to a preferred embodiment, said fluoropolymer PI is prepared by a suspension or emulsion polymerization process forming a latex which can optionally be dried to result in a fluoropolymer PI in powder form.

[0085] According to one embodiment, the average particle size of said PI polymer is between 10 and 1000 nm. According to another embodiment, the average particle size is between 1 pm and 200 pm, preferably between 1 pm and 100 pm. The average particle size is determined by laser granulometry. A particle size analyzer of the Malvern INSITEC System type is used for the measurement. This is carried out in a dry process by laser diffraction on a powder with a focal length of 100 mm.

[0086] According to certain embodiments, the vinylidene fluoride contained in said fluoropolymer PI is biosourced. The term “biosourced” means “derived from biomass”. This makes it possible to improve the ecological footprint of the polymer. The biosourced VDF can be characterized by a renewable carbon content, i.e. carbon of natural origin and originating from a biomaterial or biomass, of at least 1 atomic % 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 indicated below. According to certain embodiments, the bio-carbon content of the 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%.

[0087] Polymer additive P2

[0088] As mentioned above, said composition comprises a polymer additive P2.

[0089] Said polymer additive P2 comprises at least one functional group containing a phosphorus atom.

[0090] Preferably, the phosphorus content in said polymer additive P2 is between 0.01 and 15 mol% per mol of polymer additive P2. Thus, the phosphorus content may be between 0.05 mol% and 14 mol%, advantageously between 0.1 mol% and 13 mol%, preferably between 0.25 mol% and 12 mol%, more preferably between 0.5 mol% and 11 mol%, in particular between 0.75 mol% and 10 mol%, more particularly between 1 mol% and 10 mol% per mol of polymer additive P2.

[0091] Said functional group containing a phosphorus atom may be selected from the group consisting of -P(O)(O X+)-, -P(O)(OX+)2 and -P(O)(O X+)H with X selected from the group consisting of H, Na, Li and K. Said functional group containing a phosphorus atom may be located at the end of chains or along the chain of said polymer P2.

[0092] The applicant surprisingly found that the presence of at least one functional group containing a phosphorus atom in the polymer additive P2 improved the viscosity of an electrode composition while preventing sedimentation thereof. The improvement in viscosity is characterized by a lower viscosity facilitating the processability of an electrode composition compared to a polymer additive not containing a functional group with a phosphorus atom.

[0093] The polymer additive P2 also comprises repeating units derived from a monomer M2 of formula (I), (II), (III), (IV), (V), (VI), (VII) or a mixture thereof

[0094] R1R2C=C(R3)((X2)PC(O)R4) (I)

[0095] R5R6C=C(R7)(OC(O)R8) (II)

[0096] R9R10C=CRnC(O)OC(O)CR12=CR13R14 (III)

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] R30R31C=CR32(CN) (VI) R33R34C=CR35(C(O)NR36R37) (VII) in which R1, R2 and R3 are independently selected from the group consisting of H, C02H and C1-C5 alkyl; R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR25 with R25 selected from the group consisting of H and CrCi8 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain; R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted with one or more CO2H functional groups; X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl; p' is 0 or 1; R5, R6 and R7 are independently selected from the group consisting of H and C1-C5 alkyl; R8 is CrC5 alkyl; R9 R10 R11 R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R30 R31 R32 , R , R , R are independently of each other selected from the group consisting of H and C 1-C 5 alkyl, preferably selected from the group consisting of H and CH3; R36 and R37 are, independently of each other, selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38; R38 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted with one or more CO2H functional groups.

[0109] Advantageously, the polymer additive P2 comprises repeating units derived from a monomer M2 of formula (I), (II), (III), (IV), (V) or a mixture thereof

[0110] R1R2C=C(R3)((X2)PC(O)R4) (I) [YES] R5R6C=C(R7)(OC(O)R8) (II)

[0112] R9R10C=CR11C(O)OC(O)CR12=CR13R14 (III)

[0113] R30R31C=CR32(CN) (VI)

[0114] R33R34C=CR35(C(O)NR36R37) (VII)

[0115] in which

[0116] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C5 alkyl;

[0117] R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR25 with R25 selected from the group consisting of H and C1-C15 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0118] R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2H functional groups;

[0119] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 10, 26 27 28 29 in particular beyond5;R ,R ,R ,R are independently of each other, independently for each wl unit, selected from the group consisting of H and Ci-C5 alkyl;

[0120] p' is 0 or 1;

[0121] R5, R6 and R7 are independently of each other selected from the group consisting of H and C1-C3 alkyl;

[0122] R8 is CrC3 alkyl;

[0123]

[0124]

[0125] r9 r10 R11 r12 r13 r14 r15 r16 r17 r18 r19 r20 r21 r22 r23 r24 r30 r31 r32 , R , R , R are independently of each other selected from the group consisting of H and C 1-C 3 alkyl, preferably selected from the group consisting of H and CH 3 ; R36 and R37 are, independently of each other, selected from the group consisting of H and C1-C5 alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38 groups; R38 is selected from the group consisting of CrC3 alkyl and C6 aryl substituted by one or more CO2H functional groups. Preferably, said polymer additive P 2 comprising repeating units derived from a monomer M2 of formula (I), (II), (III) (IV), (V), (VI), (VII) or a mixture thereof

[0126] R1R2C=C(R3)((X2)PC(O)R4) (I)

[0127] R5R6C=C(R7)(OC(O)R8) (II)

[0128] R9R10C=CR11C(O)OC(O)CR12=CR13R14 (III)

[0129] R30R31C=CR32(CN) (VI)

[0130] R33R34C=CR35(C(O)NR36R37) (VII)

[0131] in which

[0132] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C5 alkyl;

[0133] R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR25 with R25 selected from the group consisting of H and C1-C18 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, -SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0134] R25' is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2H functional groups;

[0135] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0136] p' is 0 or 1;

[0137] R5, R6 and R7 are independently of each other selected from the group consisting of H and C1-C5 alkyl;

[0138] R8 is CrC5 alkyl;

[0139] R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R30, R31, R32 33 34 35 , R , R , R are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3;

[0140] R36 and R37 are, independently of each other, selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38; R38 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more functional groups CO2H.

[0141] More preferably, said polymer additive P2 is of formula (I), (III), or (IV) in which R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0142] R4 is -OR25 with R25 selected from the group consisting of H and C1-C15 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0143] R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2H functional groups;

[0144] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0145] p' is 0 or 1;

[0146] R9, R10, R11, R12, R13, R14, R15, R16 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0147] In particular, said polymer additive P2 is of formula (I), (III) or (IV) in which R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0148] R4 is -OR25 with R25 selected from the group consisting of H and C1-C10 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0149] R25 is selected from the group consisting of C1-C5 alkyl and C6 substituted aryl by one or more CO2H functional groups;

[0150] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C5 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0151] p' is 0 or 1;

[0152] R9, R10, R11, R12, R13, R14, R15, R16 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0153] More particularly, the polymer additive P2 comprises repeating units derived from a monomer M2 of formula (I), (III) or (IV) in which

[0154] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0155] R4 is -OR25 with R25 selected from the group consisting of H and C1-C10 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25;

[0156] R25 is selected from the group consisting of C1-C5 alkyl and C6 substituted aryl by one or more CO2H functional groups;

[0157] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C5 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0158] p' is 0 or 1;

[0159] R9, R10, R13, R14, R15, R16 are H; R11 and R12 are CH3.

[0160] Preferably, the polymer additive P2 comprises repeating units derived from a monomer M2 of formula (I) R'R2C=C(R3)(C(O)R4) (I), (III) as defined above or (IV) as defined above in which

[0161] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0162] R4 is -OR25 with R25 selected from the group consisting of H and C1-C5 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25;

[0163] R25' is selected from the group consisting of CrC3 alkyl and C6 substituted aryl by one or more CO2H functional groups;

[0164] R9, R10, R13, R14, R15, R16 are H; R11 and R12 are CH3.

[0165] According to one embodiment, said polymer additive P2 is a homopolymer of said monomer M2 according to any one of formulas (I) to (VII) above. According to another embodiment, said polymer additive P2 is a copolymer of several monomers M2 according to any one of formulas (I) to (VII) above. By copolymer is meant repeating units derived from at least two monomers M2 according to any one of formulas (I) to (VII) above.

[0166] Thus, according to a particular embodiment, said polymer additive P2 may be a copolymer comprising: - repeating units derived from a monomer M2a of formula (I), (III), (IV), (V), (VI) or (VII)

[0167] R1R2C=C(R3)((X2)PC(O)R4) (I)

[0168] R9R10C=CRnC(O)OC(O)CR12=CR13R14 (III)

[0169] R30R31C=CR32(CN) (VI)

[0170] R33R34C=CR35(C(O)NR36R37) (VII)

[0171] in which

[0172] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C5 alkyl;

[0173] R4 is -OR25 with R25 selected from the group consisting of H and CrCi8 alkyl substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25;

[0174] R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more CO2H functional groups;

[0175] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a CrCio alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and Ci-C5 alkyl;

[0176] p' is 0 or 1;

[0177] R9, R10, R11, R12, R13 and R14 are independently selected from each other from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0178] R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R30, R31, R32, R33, R34 and R35 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3; R36 and R37 are, independently of each other, selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38; R38 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more functional groups CO2H; and - repeating units derived from a monomer M2b of formula (I'), (II) or (III); or a mixture thereof

[0179] R1 R2 C=C(R3 ')((X2 ')p • -C(O)R4 ') (I')

[0180] R5R6C=C(R7)(OC(O)R8) (II)

[0181] in which

[0182] R1;R2 and R3 are independently of each other selected from the group consisting of H and C1-C5 alkyl;

[0183] R4 is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 and -OR25 with R25 selected from the group consisting of C1-C18 alkyl and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain;

[0184] X2 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 ) (R29 )-]wi - and a C1-C10 alkyl hydrocarbon group optionally carrying one or more group(s) or ester(s); with wl' being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl' unit, selected from the group consisting of H and C1-C5 alkyl;

[0185] p” is 0 or 1;

[0186] R5, R6 and R7 are independently of each other selected from the group consisting of H and C1-C5 alkyl;

[0187] R8 is CrC5 alkyl.

[0188] Preferably, said polymer additive P2 may be a copolymer comprising: - repeating units derived from a monomer M2a of formula (I), (III), (IV), (V)

[0189] R1R2C=C(R3)((X2)PC(O)R4) (I)

[0190] R9R10C=CRnC(O)OC(O)CR12=CR13R14 (III)

[0191] in which

[0192] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C5 alkyl;

[0193] R4 is -OR25 with R25 selected from the group consisting of H and C1-C10 alkyl substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25;

[0194] R25 is selected from the group consisting of CrC3 alkyl and C6-Ci 0 aryl substituted by one or more CO2H functional groups;

[0195] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and C1-C5 alkyl;

[0196] p' is 0 or 1;

[0197] R9, R10, R11, R12, R13 and R14 are independently selected from each other from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0198] R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 are independently one of others selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3; and - repeating units derived from a monomer M2b of formula (!), (II) or (III); or a mixture thereof

[0199] R1 R2 C=C(R3 ')((X2 ')p • -C(O)R4 ') (I')

[0200] R5R6C=C(R7)(OC(O)R8) (II)

[0201] in which

[0202] R1, R2 and R3 are independently of each other selected from the group consisting of H and CrC3 alkyl;

[0203] R4' is -OR25 with R25 selected from the group consisting of Ci-Ci 0 alkyl;

[0204] X2 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 ) (R29 )-]wi - and a C1-C10 alkyl hydrocarbon group optionally carrying one or more group(s) or ester(s); with wl' being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl' unit, selected from the group consisting of H and C1-C5 alkyl;

[0205] p” is 0 or 1;

[0206] R5, R6 and R7 are independently of each other selected from the group consisting of H and C1-C5 alkyl;

[0207] R8 is CrC5 alkyl.

[0208] In particular, said polymer additive P2 may be a copolymer comprising: - repeating units derived from a monomer M2a of formula (I), (III), (IV),

[0209] R'R2C=C(R3)(C(O)R4) (I)

[0210] R9R10C=CR11C(O)OC(O)CR12=CR13R14 (III) i [ V )

[0211] in which

[0212] R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl;

[0213] R4 is -OR25 with R25 selected from the group consisting of H and C1-C5 alkyl substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25;

[0214] R25' is selected from the group consisting of C1-C3 alkyl and C6 substituted aryl by one or more CO2H functional groups;

[0215] R9, R10, R11, R12, R13 and R14 are independently selected from each other from the group consisting of H and CrC3 alkyl, preferably selected from the group consisting of H and CH3;

[0216] R15, R16 are independently selected from the group consisting of H and CrC3 alkyl, preferably selected from the group consisting of H and CH3; and - repeating units derived from a monomer M2b of formula (!), (II) or (III); or a mixture thereof

[0217] R1 R2 C=C(R3)(C(O)R4) (I')

[0218] in which

[0219] R1, R2 and R3 are independently of each other selected from the group consisting of H and CrC3 alkyl;

[0220] R4' is -OR25 with R25 selected from the group consisting of C1-C5 alkyl.

[0221] Certain copolymers are illustrated in the examples in a non-limiting manner.

[0222] According to a preferred embodiment, said polymer additive P2 has a molar mass by weight of between 500 g / mol and 50000 g / mol, advantageously between 500 g / mol and 40000 g / mol, preferably between 500 g / mol and 30000 g / mol, more preferably between 500 g / mol and 25000 g / mol, in particular between 500 g / mol and 20000 g / mol, more particularly between 500 g / mol and 15000 g / mol, preferably between 500 g / mol and 10000 g / mol. The molecular or molar mass is determined by Size Exclusion Chromatography (SEC). A sample of the polymer solution corresponding to 90 mg of dry matter is introduced into a 10 mL flask. Mobile phase, containing 0.04% dimethylformamide (DMF), is added to a total mass of 10 g.The composition of this mobile phase is as follows: NaHCO3: 0.05 mol / L, NaNO3: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3 0.03% by mass. The CES chain is composed of a Waters 510 isocratic pump, whose flow rate is set at 0.8 mL / min, a Waters 717+ autosampler, an oven containing a Waters Guard Column Ultrahydrogel precolumn of 6 cm length and 40 mm inner diameter, followed by a Waters Ultrahydrogel linear column of 30 cm length and 7.8 mm inner diameter. Detection is ensured by means of a Waters RI 410 differential refractometer. The oven is brought to the temperature of 60°C and the refractometer is brought to the temperature of 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standards Service with peak molecular weights between 1000 g / mol and 1.106 g / mol and polydispersity indexes between 1.4 and 1.7.The calibration curve is . linear type and takes into account the correction obtained using the flow marker: dimethylformamide (DMF).

[0223] Use

[0224] Said composition according to the present invention can be prepared by mixing the different components thereof in the required proportions.

[0225] Said composition as described in the present application can be used in numerous applications. Thus, said composition can be used as a binder for an electrode (cathode or anode).

[0226] Said composition according to the present invention can be used as a binder for an electrode. Thus, the present invention provides an electrode composition comprising said composition according to the present invention, an active material and optionally a conductive agent.

[0227] In a preferred embodiment, the electrode composition has the following mass composition:

[0228] a. 50% to 99.95% of active material, preferably 50% to 99%,

[0229] b. 0% to 25% of conductive agent, preferably 0.5% to 25%,

[0230] c. 0.05% to 25% of said binder according to the invention, preferably 0.5% to 25%,

[0231] 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 aid;

[0232] the sum of all these percentages being 100%.

[0233] The conductive agents in the electrode are composed of one or more materials that can enhance conductivity. Some examples include carbon blacks such as acetylene black, Ketjen black; carbon fibers, such as carbon nanotube, carbon nanofiber, vapor-grown carbon fiber; metal powders such as SUS powder, and aluminum powder.

[0234] The active materials in the electrode compositions are materials that are capable of storing and releasing lithium ions.

[0235] In a preferred embodiment, said electrode is a negative electrode. In particular, for a negative electrode, said 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 Li4Ti50i2. The shape of the negative electrode active material is not particularly limited but is preferably particulate.

[0236] In another preferred embodiment, said electrode is a positive electrode. Preferably, for a positive electrode, said active material is selected from the group consisting of LiCoO2, Li(Ni, Co, AI)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 spinel Li Mn substituted by a different element having a composition represented by Lil+xMn2-x-yMyO4, 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 phosphate and of lithium having a composition represented by LiMPO4, M representing Fe, Mn, Co, or Ni. The shape of the positive electrode active material is not particularly limited but is preferably particulate. In addition, the surface of each of the materials described above may 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 the coating material include LiNbO3, Li4Ti50i2, and Li3PO4. .

[0237] Said electrode composition may be deposited on at least one face of a current collector to form said electrode. This deposition may be carried out in the presence of an organic solvent, water, a mixture of both or by a solvent-free process, i.e. by a dry coated electrode production process. Said organic solvent may be selected from the group consisting of n-methylpyrrolidone (NMP), dimethylsulfoxide (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.

[0238] Said method of preparing the dry coated electrode comprises the following steps:

[0239] - mixing the active material in powder form, said binder according to the present invention, and optionally the conductive agent in powder form, the additive in powder form or both to form said electrode composition according to the present invention;

[0240] - depositing said electrode composition on said current collector for make an electrode, and

[0241] - optionally consolidation of said electrode by a treatment thermomechanical.

[0242] Said dry coated electrode is thus prepared according to a “solvent-free” process, i.e. one which does not require a step of evaporation of residual solvent after the deposition step because all the constituents are mixed in the dry state, in powder form, and the deposition is also carried out without solvent. A thermomechanical treatment refers to the application of mechanical pressure to the electrode at a given temperature. Such a thermomechanical treatment can be carried out, for example, by a calendering machine comprising rollers which can be heated or a plate press which can also be heated.

[0243] As solvent-free mixing processes of the various constituents of the electrode composition before the deposition phase on the collector, the following may be mentioned, without being exhaustive: mixing by stirring, mixing by air jet, high shear mixing, mixing by V-mixer, mixing by screw mass mixer, mixing by double cone, mixing by drum, conical mixing, mixing by double Z-arm, mixing in a fluidized bed, mixing in a planetary mixer, mixing by mechanical fusion, mixing by extrusion, mixing by calendering, mixing by grinding.

[0244] According to one embodiment, after the powder mixing step, the electrode is manufactured by a solvent-free spraying process, by depositing the electrode composition on the metal substrate, by a pneumatic spraying process, by electrostatic spraying, by dipping in a fluidized powder bed, by spraying, by electrostatic screen printing, by deposition with rotating brushes, by deposition with rotating addition rollers, by calendering.

[0245] According to one embodiment, the consolidation of the electrode after a deposition process on the metal substrate by solvent-free spraying (pneumatic spraying process, by electrostatic spraying, by dipping in a fluidized powder bed, by sprinkling, by electrostatic screen printing, by deposition with rotating brushes, by deposition with rotating addition rollers) is carried out by a calendering process. This process consists of applying pressure to the electrode using two possibly heated rollers. The consolidation step is optional. Its implementation depends on the technique used to deposit the constituents on the electrode. Thus, when the deposition step has been implemented by calendering, this consolidation step is optional because the calendering allows the deposition and consolidation of the electrode simultaneously.

[0246] According to one embodiment, after the powder mixing step, the electrode is manufactured by a two-step solvent-free process. A first step consists of manufacturing a self-supporting film from the premixed formulation with a thermomechanical process such as extrusion, calendering or thermocompression. In a second step, the self-supporting film is laminated onto the metal substrate by a process combining temperature and pressure such as calendering or thermocompression.

[0247] According to one embodiment, after the powder mixing step, the electrode is manufactured by a solvent-free process using a calendering process which makes it possible to carry out the film-forming and transfer step of the coating onto the current collector in a single step, i.e. without going through a step of manufacturing a self-supporting film. To do this, the calender used has several rollers (at least three). The powder obtained after the mixing step is introduced between the first two rollers, which are most often heated and have differential rotation speeds to shear the powder. The coating formed and remaining stuck on the fastest roller is then directly laminated onto the current collector with a third roller. The electrode thus obtained can be subsequently passed through a calender to adjust its porosity or thickness if necessary.

[0248] According to another aspect of the present invention, a Li-ion battery is provided. Preferably, the Li-ion battery comprises a positive electrode, a negative electrode and a separator. At least one of the electrodes is an electrode according to the present invention. Preferably, said Li-ion battery also comprises a lithium salt selected from the group consisting of LiCF3SO3, LiPF6, LiC104, 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.

[0249] According to another aspect of the present invention, said composition can be used in the preparation of a conductive polymer, a solid electrolyte for fuel cells, a hydrophilic coating, a hydrophobic coating or a UV-absorbing coating. Said composition can be used as an adhesive for a multi-layer structure extruded in the form of a film, a sheet or a tube. Said composition can also be used as a coating on a metal. Examples

[0250] For the examples below the following materials are used:

[0251] Solvent: NMP Sigma Aldrich anhydrous 99.5% (<50ppm H2O); conductive agent: Carbon black Imerys C65; active material: NMC 811; fluoropolymer PI: PVDF-AA comprising 1.1% by weight of acrylic acid in the PVDF chain; polymer additive P2a: poly(acrylic) acid with a molar mass by weight (Mw) of the order of 3000 to 4000 g / mol not containing functional groups containing a phosphorus atom; polymer additive P2b: poly(acrylic) acid with a molar mass by weight (Mw) of the order of 3000 to 4000 g / mol containing 1.8 mol % of functional groups containing a phosphorus atom per mol of polymer additive P2b.

[0252] Determination of the quantity of functional groups containing a phosphorus atom

[0253] The molar content of functional groups containing a phosphorus atom is determined by 31P NMR and hot 'H NMR (320°K). The NMR spectra were carried out on a Bruker AV III HD 500 spectrometer equipped with a 5mm BBI probe. The polymer additive P2 was dissolved in DMSO-d6. The signals located between 20 and 22 ppm in 31P NMR, between 24 ppm and 31 ppm in 31P NMR and between 28 ppm and 48 ppm in 31P NMR and the signal at 6.9 ppm in 'H NMR are characteristic of the functional groups containing a phosphorus atom present in said polymer additive P2. The *H NMR analysis makes it possible to determine the quantity of monomer M2 in said polymer additive P2. The signals to be integrated in 1H NMR depend on the monomer M2 used. For example, for example B3 below, the characteristic signals of acrylic acid are located at 1 ppm and 2.7 ppm.

[0254] Preparation of the compositions

[0255] The fluoropolymer PI was mixed with said polymer additive P2 in a dry state (i.e. the two components are mixed in powder form) in the proportions detailed below in Table 1.

[0256] [Tables 1] Composition B Fluorinated polymer PI Polymer additive P2 Ratio PI / P2* B1 (comp.) PI 7g - 0g - B2 (comp.) PI 7g P2a 0.0355 g 197 B3 (Inv.) PI 7g P2b 0.0355 g 197

[0257] * Ratio between the mass content of PI and the mass content of P2 in said composition

[0258] To the compositions prepared above, N-methylpyrrolidone (NMP) was added to form a solution with a mass of 100 g.

[0259] Preparation of electrode compositions C

[0260] A quantity of the solutions prepared above was added to 1.5g of conductive agent. The quantity of the solution was chosen so as to take 1.5g of composition B (i.e. the quantity of solution taken makes it possible to prepare a composition C comprising 1.5g of (PI and P2)). The mixture was stirred 4 times with a Thinky ARE-250 mixer at 2000 rpm. 97g of active material was added to this mixture and the resulting mixture was stirred 3 times at 2000 rpm for 1 minute. NMP was added in three times (7g, 7g then 6.5g) followed by mixing for 1 minute. at 2000 rpm after each addition. The solid content of the electrode compositions is 73%.

[0261] Rheological analysis of electrode compositions

[0262] After their preparation, the electrode compositions are analyzed at 25°C using a TA HR 10 rheometer. The geometry used is a 40mm parallel plate with a gap of 500qm. The flow curves are generated by performing a shear rate sweep from 0.1 s-1 to 100 s-1. The shear rate 10s-1 is used to compare all compositions.

[0263] Table 2 below details the viscosities at 25°C and at a shear of 10s-1 for the different prepared electrode compositions. The viscosity is expressed in centipoise (cP).

[0264] [Tables2] Electrode composition C Composition B used Viscosity (c P) Viscosity ratio V2 / V1 Sedimentation factor S Cl (comp.) B1 (comp.) 5021 - 0.68 C2 (comp.) B2 (comp.) 7350 1.46 0.91 C3 (Inv.) B3 (Inv.) 5790 1.15 0.99

[0265] * The viscosity ratio V2 / V1 corresponds to the ratio between the viscosity of the electrode composition considered and the viscosity of the composition Cl.

[0266] Evaluation of the sedimentation factor S

[0267] The solids content of the electrode compositions was measured using a PCE-MA-100 thermobalance from PCE instruments. The analysis was carried out at 140°C. Two samples of electrode compositions were each introduced into a tubular HDPE pot with an internal diameter of 1 cm and a height of 5 cm. A thermobalance was carried out at t = 0 for the first sample by taking 1 ml of electrode composition. The second sample was left to stand for 120 h. After this standing time, 1 ml of electrode composition taken near the surface was analyzed by thermobalance to determine the solids content. The sedimentation factor S is calculated by the ratio between the solids content measured at t = 120 h and the solids content measured at t = 0. For composition C2, the sample is previously adjusted to a viscosity of the electrode composition of the order of 5700 cP.For this purpose, a quantity of NMP was added to reduce the viscosity to the above-mentioned value while maintaining a solids content of around 72%. The results are shown in Table 2 above.

[0268] As demonstrated by the results presented in Table 2 above, when the polymer additive contains at least one functional group containing a phosphorus atom, a decrease in the viscosity of the electrode composition is observed, without the need for dilution, while maintaining a very high sedimentation factor. No sedimentation was observed for composition C3 after 120 hours. The applicant has thus surprisingly found a composition allowing the preparation of electrode compositions that are stable over time and have a viscosity suitable for electrode manufacture.

Claims

1. Claims Composition comprising a fluorinated polymer carrying polar groups PI and a polymer additive P2 comprising repeating units derived from a monomer M 2 of formula (I), (II), (III), (IV), (V), (VI), (VII) or a mixture thereof R1R2C=C(R3)((X2)PC(O)R4) (I) R5R6C=C(R7)(OC(O)R8) (II) R9R1 °C=CR11C(O)OC(O)CR12=CR13R14 (III) R30R31C=CR32(CN) (VI) r33r34C=CR35(C(O)NR36R37) (VII) in which R1, R2 and R3 are independently selected from the group consisting of H, CO2H and C1-C5 alkyl; R4 is selected from the group consisting of -NHC(CH3)2CH2 C(O)CH3 and -OR25 with R25 selected from the group consisting of H and C1-C18 alkyl optionally substituted with one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six membered heterocycle comprising at least one nitrogen atom in its ring chain; R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted with one or more CO2 H functional groups; X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2 H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each unit wl, selected from the group consisting of H and Cr C5 alkyl; p' is 0 or 1; R5, R6 and R7 are independently of each other selected from the group consisting of H and Ci-C5 alkyl; R8 is CrC5 alkyl; R9 R10 R11 R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 , R30, R31, R32, R33, R34, R35are independently of each other selected from the group consisting of H and Ci-C5 alkyl, preferably selected from the group consisting of H and CH3; R36 and R37 are, independently of each other, selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more groups -OH, -CO2H, SO3 H, -OPO32, -C(O)OR38, -OC(O)R38; R38 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted by one or more functional groups CO2H; characterized in that said polymer additive P2 also comprises at least one functional group containing a phosphorus atom.

2. Composition according to the preceding claim, characterized in that the phosphorus content in said polymer additive P2 is between 0.01 and 15 mol% per mol of polymer additive P2.

3. Composition according to any one of the preceding claims characterized in that the functional group containing a phosphorus atom is selected from the group consisting of -P(O)(OX+)-, -P(O)(O X+)2 and -P(O)(O X+)H with X selected from the group consisting of H, Na, Li and K.

4. Composition according to any one of the preceding claims, characterized in that the mass ratio between said fluorinated polymer PI and said polymer additive P2 is greater than or equal to 1, advantageously greater than or equal to 5, preferably greater than or equal to 10, more preferably greater than or equal to 15, in particular greater than or equal to 20.

5. Composition according to any one of the preceding claims, characterized in that the mass ratio between said fluorinated polymer PI and said polymer additive P2 is less than or equal to 1000, preferably less than or equal to 400.

6. Composition according to any one of the preceding claims characterized in that said polymer PI comprises repeating units derived from a monomer Mla selected from the group consisting of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers 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 product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2 H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2 =CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF 2 in which n is 1, 2, 3, 4 or 5; the product of formula R'CH2 OCF=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-l-propene or a mixture thereof.;

7. Composition according to any one of the preceding claims, characterized in that said fluoropolymer PI comprises repeating units derived from the monomer Mla and repeating units derived from a monomer Mlc and optionally repeating units derived from a monomer Mlb; said monomer Mla being vinylidene fluoride; said monomer Mlb selected from the group consisting of vinyl fluoride; trifluoroethylene (VF3); 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 product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2 H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2 =CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF

8.

9.

10. 2 in which n is 1, 2, 3, 4 or 5; the product of formula R'CH2 OCF=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; perfluorobutyl ethylene (PFBE); trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene or a mixture thereof; said monomer Mlc being selected from the group consisting of formula RaRbC=C(Rc)((X3)p -C(O)Rd) in which the substituents Ra, Rb and Rc are independently of each other selected from the group consisting of H, CO2H and Ci-C5 alkyl;Rd is selected from the group consisting of -NHC(CH3)2CH2C(O)CH 3 or -ORd' with Rd' selected from the group consisting of H and C1-C18 alkyl optionally substituted with one or more groups -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 ring chain; Rd” being selected from the group consisting of C1-C6 alkyl or C6-C12 aryl optionally substituted with one or more groups -OH, -CO2H, -SO3H, -PO3H; p” is 0 or 1; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with w2 being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5;R26, R27, R28, R29 are independently of each other, independently for each w2 unit, selected from the group consisting of H and C1-C5 alkyl.; Composition according to the preceding claim, characterized in that said monomer Mlc is present in said polymer PI in a molar content of 0.01% to 5%. Composition according to claim 7 characterized in that said monomer Ml b is present in said polymer PI in a molar content of 1% to 25%. Composition according to any one of the preceding claims, characterized in that said polymer additive P2 has a molar mass by weight between 500 g / mol and 50000 g / mol, preferably between 500 g / mol and 25000 g / mol.

11. Composition according to any one of the preceding claims characterized in that said polymer additive P2 comprises repeating units derived from a monomer M 2 of formula (I), (III) or (IV) in which R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and C1-C3 alkyl; R4 is -OR25 with R25 selected from the group consisting of H and C1-C15 alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five or six-membered heterocycle comprising at least one nitrogen atom in its ring chain; R25 is selected from the group consisting of C1-C5 alkyl and C6-C12 aryl substituted with one or more CO2 H functional groups;X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wi- and a C1-C10 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2 H or ester group(s); with wl being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and Cr C5 alkyl; p' is 0 or 1; R9, R10, R11, R12, R13, R14, R15, R16 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.;

12. Composition according to any one of the preceding claims characterized in that said polymer additive P2 comprises repeating units derived from a monomer M 2 of formula (I), (III) or (IV) in which R1, R2 and R3 are independently of each other selected from the group consisting of H, CO2H and CrC3 alkyl; R4 is -OR25 with R25 selected from the group consisting of H and Ci-Cio alkyl optionally substituted by one or more group(s) selected from the group consisting of -OH, -CO2H, SO3H, -OPO32, -C(O)OR25, -OC(O)R25, and a five- or six-membered heterocycle comprising at least one nitrogen atom in its ring chain; R25 is selected from the group consisting of C1-C5 alkyl and C6 aryl substituted with one or more CO2H functional groups; X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a C1-C5 alkyl hydrocarbon group optionally carrying one or more -OH, -CO2H or ester group(s); with wl being an integer from 1 to 5; R26, R27, R28, R29 are independently of each other, independently for each wl unit, selected from the group consisting of H and Cr C5 alkyl; p' is 0 or 1; R9, R10, R11, R12, R13, R14, R15, R16 are independently of each other selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

13. Composition according to any one of the preceding claims, characterized in that it has a sedimentation factor S of between 0.8 and 1.1; calculated from measurements of solid contents carried out by thermobalance at 140°C.

14. A binder for a Li-ion battery comprising said composition according to any one of the preceding claims.

15. An electrode composition comprising an active material and said binder according to the preceding claim.

16. Electrode for lithium-ion battery comprising a metal collector of which at least one face is covered with said electrode composition according to the preceding claim.

17. A Li-ion secondary battery comprising an anode, a cathode and a separator, wherein the anode or the cathode is an electrode according to the preceding claim.