Composition based on poly(vinylidene fluoride)

Abstract

The present invention relates to a composition comprising a fluorinated polymer 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 Li-ion secondary batteries. 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, creating 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 secondary lithium-ion batteries can be obtained, for example, by the following means: First, a formulation is obtained by mixing powdered electrode materials, such as an active electrode material and a conductive agent, which may be added if necessary, with a binder and dissolving or dispersing the mixed material in a suitable solvent. Subsequently, an electrode for secondary lithium-ion batteries can be obtained by coating a current collector with the resulting electrode mixture slurry and evaporating the solvent.

[0004] The active materials used in electrodes are generally nickel-based and, more specifically, predominantly contain nickel. However, when the nickel content in the electrode's active material increases, the electrode mixture slurry becomes prone to gelation. For example, EP3795430 describes an electrode composition comprising a vinylidene fluoride-based polymer with a polar group and at least 10% of an acrylic polymer. However, it has been observed that this electrode composition is far too viscous (initially exceeding 40,000 cP) for industrial-scale implementation. EP2147029 also describes a copolymer between vinylidene fluoride and acrylic acid that exhibits a strong tendency to sediment over time.

[0005] Generally speaking, an electrode composition must be processable from an industrial standpoint, stable (not to settle) and not to gel over time. Therefore There is always a need for electrode compositions that offer a good compromise between different properties. The present invention aims to resolve all or part of the drawbacks of current electrode compositions by providing a specific polymer composition. Summary of the invention

[0006] According to a first aspect, the present invention relates to a composition comprising a fluorinated polymer bearing polar PI groups and a polymer additive P2 comprising repeating units derived from a monomer M2 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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C5;

[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 Ci-Ci8 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 cyclic chain;

[0015] R25 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 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 an alkyl Ci-Cio hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) 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 alkyl Ci-C5;

[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 Ci-C5 alkyl; R8 is Ci-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 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 -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38 group(s); R38 is selected from the group consisting of C1-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups; characterized in that said polymer additive P2 also comprises at least one functional group containing a phosphorus atom. The applicant was surprised to find that the specific composition according to the present invention offered a very good compromise between the various properties required for its use in applications such as electrode compositions. The composition has 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 PI polymer comprises repeating units 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-l-propene or a mixture thereof.

[0028] According to a preferred embodiment, said PI fluorinated polymer comprises repeating units from monomer Mla and repeating units from monomer Mlc and optionally repeating units from 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, hexafluoroisobutylene, 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 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 -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-C12 aryl optionally substituted by 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 Ci-Cio alkyl hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) group(s); with w2 being an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, in particular beyond 5; R, R, R, R are independently of each other, independently for each w2 unit, selected from the group consisting of H and Ci-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 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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C3;

[0034] 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 cyclic chain;

[0035] R25' is selected from the group consisting of C1-C5 alkyl and C6-Ci2 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 bearing one or more -OH, -CO2H or ester(s) 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 C1-C5 alkyl;

[0037] p' is 0 or 1;

[0038] R9, R10, R11, R12, R13, R14, R15, R16 are independent of each other selected from the group consisting of H and Ci-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 from a monomer M2 of formula (I), (III) or (IV) in which R1, R2 and R3 are independently selected from each other from the group consisting of H, CO2H and Ci-C3 alkyl;

[0040] 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 cyclic chain;

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

[0042] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a Ci-C5 alkyl hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) group(s); with wl being an integer 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 Ci-C5 alkyl;

[0043] p' is 0 or 1;

[0044] R9, R10, R11, R12, R13, R14, R15, R16 are independent of each other selected from the group consisting of H and Ci-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 between 0.8 and 1.1; calculated according to the protocol detailed in this application.

[0046] According to another aspect, the present invention provides a binder for 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 a lithium-ion battery electrode comprising a metallic collector of which at least one face is coated with said electrode composition according to the present invention.

[0049] According to another aspect, the present invention provides a secondary Li-ion battery comprising an anode, a cathode, and a separator, wherein the anode or 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. This composition may be in powder form or in the form of a latex or a solution in the presence of an organic solvent. Preferably, this composition is in powder form.

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

[0052] In said composition, 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. Advantageously, the mass ratio between said fluorinated polymer 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 preferred greater than or equal to 34, preferentially preferred greater than or equal to 35, more preferentially preferred greater than or equal to 36, particularly preferred greater than or equal to 37, more particularly preferred greater than or equal to 38.

[0053] The content of polymer additive P2 in said composition influences the viscosity of the electrode composition with which it is prepared. Thus, it has been found that when the ratio between the fluorinated polymer 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 fluorinated polymer 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 observed that when the mass ratio between the fluorinated polymer 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 thereby avoid sedimentation, 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 fluorinated polymer PI on the basis of 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 fluorinated polymer PI on the basis of 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 on the basis of the total weight of the composition.

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

[0059] Said composition can be prepared by mixing the constituents, for example in powder form, in the required proportions. Alternatively, the constituents can 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 the solution can then be dried to obtain a powder or used as is. Said organic solvent is not specifically limited and is chosen so as to solubilize said fluorinated polymer PI and said polymer additive P2. Said organic solvent can 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 viscosity V2 and viscosity VI is between 0.25 and 5.0; viscosity V2 corresponds to the viscosity obtained from the composition according to the present invention, and viscosity VI corresponds to the viscosity obtained from the fluoropolymer PI. Advantageously, said V2 / V1 ratio 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, and 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 V2 / V1 ratio is within the range mentioned above, the electrode composition comprising the composition according to the invention exhibits very good rheological behavior to facilitate its processability during electrode preparation.

[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, and more particularly between 0.90 and 1. The sedimentation factor S corresponds to the ratio between the solids content of a composition at t = 0 and the solids 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 prevents sedimentation of the electrode composition comprising it. To ensure proper implementation of an electrode, it is preferable that the sedimentation factor S remain within the range mentioned above.More specifically, 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, and more preferably between 0.98 and 1. Stability over time, i.e., the absence of sedimentation, ensures homogeneity of the electrode composition during electrode preparation, thereby improving its quality and performance. The composition according to the present invention achieves 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 selected from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group is at least one fluorine atom, a fluoroalkyl group, or a fluoroalkoxy group. As mentioned above, said PI fluorinated polymer bears polar groups. These polar groups may be present in said PI fluorinated polymer via a monomer bearing said polar groups. Alternatively, said polar groups may be grafted onto a fluorinated polymer to give said PI fluorinated polymer by known techniques. Preferably, the polar groups are introduced into said PI fluorinated polymer via a monomer bearing said polar groups, for example, via Mlc monomers as described below in this application.

[0064] Preferably, said fluorinated polymer PI comprises repeating units 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. 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.

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

[0066] According to another particular embodiment, the fluorinated polymer 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 fluorinated monomer Mlb. In said fluorinated polymer PI, the mass percentage 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 from a monomer Mla being vinylidene fluoride and repeating units 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 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 -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd” group(s) 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); 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 bearing one or more -OH, -CO2H or ester(s) 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, and R29 are independently selected from the group consisting of H and Ci-C5 alkyl groups, independently for each ω2 unit. This heterocycle may be saturated, unsaturated, or aromatic. It 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. This heterocycle may be substituted with one or more Ci-C5 alkyl groups. As mentioned above, the alkyl CrCi8 group is optionally substituted with this heterocycle. The latter can 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 may be of the formula RaRbC=C(Rc)((X3)P”C(O)Rd) in which the substituents Ra, Rb and Rc are independently 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 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 ; p” is 0 or 1 ; X3 is selected from the group consisting of -[-C(O)OC(R26 )(R27 )C(R28 )(R29 )-]w 2- and an alkyl Ci-Cio hydrocarbon group optionally bearing 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 Ci-C5 alkyl.

[0070] Preferably, said monomer M may be of formula R'RbC=C(RLX(X3)p C(O)Rd) in which the substituents Ra, Rb and Rc are independently selected from the group consisting of H, CO2H and Ci-C5 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and Ci-Ci 5 alkyl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd” group(s); Rd” being selected from the group consisting of Ci-C5 alkyl or C6-Ci 0 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 bearing 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 may be of the formula RaRbC=C(Rc)((X3)p-C(O)Rd) wherein the substituents Ra, Rb, and Rc are independently selected from the group consisting of H, CO2H, and Ci-C3 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and C1-C10 alkyl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd” group(s); Rd” being selected from the group consisting of C1-C5 alkyl or C6 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 Ci-C5 alkyl hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) group(s); with w2 being an integer beyond 5; R, R, R, R are independently of each other, independently for each w2 unit, selected from the group consisting of H and Ci-C3 alkyl.

[0072] In particular, said monomer M may be of formula RaRbC=C(Rc)(C(O)Rd ) in which the substituents Ra, Rb and Rc are independently selected from the group consisting of H, CO2H and Ci-C3 alkyl; Rd is -ORd' with Rd' selected from the group consisting of H and C1-C1 0 alkyl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)Rd”, -C(O)O-Rd” group(s); Rd” being selected from the group consisting of C1-C5 alkyl or C6 aryl optionally substituted by one or more -OH, -CO2H, -SO3H, -PO3H group(s).

[0073] Said monomer Mlc can also be of the 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 selected from the group consisting of H and C1-C5 alkyl, preferably selected from the group consisting of H and CH3.

[0077] Said monomer Mlc may also be of formula

[0078] wherein 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 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 (formula C6H2O2) 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 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 fluorinated polymer PI may comprise one or more repeating units derived from said monomer M as defined herein. Preferably, when it contains them, 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 on the basis of the total weight of said polymer PI.

[0080] Preferably, when the fluorinated monomer Mla is vinylidene fluoride, the mass percentage in repeating units of vinylidene fluoride 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 fluorinated polymer 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 from a monomer Mla being vinylidene fluoride and from 0.01% to 5% by weight of repeating units from a monomer Mlc as defined above, on the basis of the total weight of said polymer PI;in particular said monomer M 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 with the formula CH2=C(CH3)C(O)OC(O)C(CH3)=CH2, 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(CO2CH 2CH2-OC(O)-C6H4CO2H), CH2=CH(CO2CH2CH2CH2CH(CO2H)CH2CH2CO2H); and mixtures of these.

[0082] Optionally, said fluorinated polymer PI also comprises repeating units derived from a fluorinated monomer Mlb. Said fluorinated monomer Mlb is different from 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, hexafluoroisobutylene, 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 from a monomer M1 being vinylidene fluoride and repeating units from a fluorinated monomer M1 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(l,3-dioxole); perfluoro(2,2-dimethyl-l,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=CFOCF2CF2SO2F; 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 repeating units from a monomer Mla being vinylidene fluoride and repeating units 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 fluorinated polymer PI comprises from 1% to 40%, preferably from 1% to 30%, in particular from 2% to 20% by weight of repeating units from said monomer Mlb on the basis of the total weight of said polymer.

[0083] According to another embodiment, said fluorinated polymer PI comprises repeating units from a monomer Mla being vinylidene fluoride, repeating units from a fluorinated monomer Mlb, repeating units 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 PI fluorinated polymer is prepared by a suspension or emulsion polymerization process forming a latex which can optionally be dried to obtain a PI fluorinated polymer 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 diffraction. A Malvern INSITEC System particle size analyzer is used for the measurement. This measurement is performed using a dry method by laser diffraction on a powder with a focal length of 100 mm.

[0086] 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 ecological 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 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 includes 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 can 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 can 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 can be located at the end of chains or along the chain of said polymer P2.

[0092] The applicant has found, surprisingly, that the presence of at least one functional group containing a phosphorus atom in the polymer additive P2 improves the viscosity of an electrode composition while preventing its sedimentation. The viscosity improvement is characterized by a lower viscosity, thus 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, CO2H and Ci-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 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 cyclic chain; R25 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups; X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29 )-]wr and an alkyl Ci-Ci0 hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) 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 alkyl Ci-C5; p' is 0 or 1; R5, R6 and R7 are independently 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 , R , R , R are independently 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 selected from the group consisting of H and Ci-Cio 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 C1-C5 alkyl and C6-Ci2 aryl substituted by 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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C5;

[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 Ci-Ci 5 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 cyclic chain;

[0118] R25 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 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 an alkyl hydrocarbon group Ci-Ci0 optionally bearing 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 unit wl, selected from the group consisting of H and Ci-C5 alkyl;

[0120] p' is 0 or 1;

[0121] R5, R6 and R7 are independently selected from each other from the group consisting of H and Ci-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 selected from the group consisting of H and Ci-C3 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 Ci-C5 alkyl optionally substituted by one or more -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38 group(s); 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 P2 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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C5;

[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 Ci-Ci8 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 cyclic chain;

[0134] R25' is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 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 an alkyl hydrocarbon group Ci-Ci0 optionally bearing 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 unit wl, selected from the group consisting of H and Ci-C5 alkyl;

[0136] p' is 0 or 1;

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

[0138]

[0139] R8 is Ci-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 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 -OH, -CO2H, SO3H, -OPO32, -C(O)OR38, -OC(O)R38 group(s); R38 is selected from the group consisting of C1-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups.

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

[0142] 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 cyclic chain;

[0143] R25 is selected from the group consisting of C1-C5 alkyl and C6-Ci2 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 bearing one or more -OH, -CO2H or ester(s) 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 C1-C5 alkyl;

[0145] p' is 0 or 1;

[0146] R9, R10, R11, R12, R13, R14, R15, R16 are independent 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 selected from the group consisting of H, CO2H and Ci-C3 alkyl;

[0148] 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 cyclic chain;

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

[0150] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a Ci-C5 alkyl hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) group(s); with wl being an integer 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 Ci-C5 alkyl;

[0151] p' is 0 or 1;

[0152] R9, R10, R11, R12, R13, R14, R15, R16 are independent of each other selected from the group consisting of H and Ci-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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C3;

[0155] R4 is -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, -OPO32, -C(O)OR25, -OC(O)R25;

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

[0157] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wr and a Ci-C5 alkyl hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) group(s); with wl being an integer 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 Ci-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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C3;

[0162] R4 is -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, -OPO32, -C(O)OR25, -OC(O)R25;

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

[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 the 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 the formulas (I) to (VII) above. By copolymer is meant repeating units derived from at least two monomers M2 according to any one of the 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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C5;

[0173] R4 is -OR25 with R25 selected from the group consisting of H and CrCi8 alkyl substituted by 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-Ci2 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 an alkyl CrCio hydrocarbon group optionally bearing one or more -OH, -CO2H or ester(s) 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 alkyl Ci-C5;

[0176] p' is 0 or 1;

[0177] R9, R10, R11, R12, R13 and R14 are selected independently of each other from the group consisting of H and Ci-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 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 Ci-Cio 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 Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups; 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 selected from each other from the group consisting of H and Ci-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 Ci-Ci8 alkyl and a five- or six-membered heterocycle comprising at least one nitrogen atom in its cyclic chain;

[0184] X2 is selected from the group consisting of -[-C(O)OC(R26)(R27)C(R28)(R29)-]wi - and an alkyl Ci-Cio hydrocarbon group optionally bearing 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 unit wl', selected from the group consisting of H and alkyl Ci-C5;

[0185] p” is 0 or 1;

[0186] R5, R6 and R7 are independently selected from each other from the group consisting of H and Ci-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 selected from each other 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 by 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 bearing one or more -OH, -CO2H or ester(s) 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 C1-C5 alkyl;

[0196] p' is 0 or 1;

[0197] R9, R10, R11, R12, R13 and R14 are selected independently of 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 of each other 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 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 hydrocarbon group Ci-Cio alkyl optionally bearing 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 unit wl', selected from the group consisting of H and Ci-C5 alkyl;

[0205] p” is 0 or 1;

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

[0207] R8 is CrC5 alkyl.

[0208] In particular, said polymer additive P2 may be a copolymer comprising: - repeating units 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 selected from each other from the group consisting of H, CO2H and alkyl Ci-C3;

[0213] R4 is -OR25 with R25 selected from the group consisting of H and Ci-C5 alkyl substituted by 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 Ci-C3 alkyl and C6 aryl substituted by one or more functional groups CO2H;

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

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

[0221] Some copolymers are illustrated in the examples without limitation.

[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 test portion of the polymer solution corresponding to 90 mg of dry matter is introduced into a 10 mL bottle. Mobile phase, supplemented with 0.04% dimethylformamide (DMF), is added up 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 wt%. The CES system consists of a Waters 510 isocratic pump with a flow rate set at 0.8 mL / min, a Waters 717+ autosampler, and a furnace containing a 6 cm long, 40 mm internal diameter Waters Guard Column Ultrahydrogel pre-column, followed by a 30 cm long, 7.8 mm internal diameter Waters Ultrahydrogel linear column. Detection is performed using a Waters 410 RI differential refractometer. The furnace is heated to 60°C and the refractometer to 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 1106 g / mol and polymolecularity indices 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] Usage

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

[0225] The composition described in this application can be used in numerous applications. Thus, the composition can be used as a binder for electrodes (cathode or anode).

[0226] The composition according to the present invention can be used as a binder for an electrode. Thus, the present invention provides an electrode composition comprising the 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% active material, preferably 50% to 99%

[0229] b. 0% to 25% of conducting 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 an auxiliary flow agent;

[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 improve conductivity. Some examples include carbon blacks such as acetylene black, Ketjen black; carbon fibers, such as a carbon nanotube, a carbon nanofiber, a carbon fiber by vapor phase growth; 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 active material of the negative electrode 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 chosen from the group consisting of LiCoO2, Li(Ni, Co, Al)O2, Li(i+x)NiaMnbCoc (x represents a 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 L1 + xMn2 - x - yMyO4, where M represents 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 L1xTiO4 - x and y independently representing a real number 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 material for the positive electrode 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, Li4Ti50i2, and Li3PO4.

[0237] Said electrode composition can be deposited on at least one face of a current collector to form said electrode. 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.

[0238] Said process for preparing the dry-coated electrode comprises the following steps:

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

[0240] - deposition of said electrode composition on said current collector for to manufacture an electrode, and

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

[0242] The dry-coated electrode is thus prepared according to a "solvent-free" process, meaning that it does not require a residual solvent evaporation step after the deposition step because all the constituents are mixed in a dry, powdered state, 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 with heated rollers or a plate press that can also be heated.

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

[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 onto the metallic substrate, by a pneumatic spraying process, by electrostatic spraying, by dipping in a fluidized powder bed, by sprinkling, by electrostatic screen printing, by deposition with rotary brushes, by deposition with rotary adding rollers, by calendering.

[0245] According to one embodiment, the consolidation of the electrode after a deposition process on the metallic substrate by solvent-free spraying (pneumatic spraying, electrostatic spraying, fluidized bed immersion, sputtering, electrostatic screen printing, deposition with rotary brushes, deposition with rotary addition rollers) is carried out by a calendering process. This process consists of applying pressure to the electrode using two rollers, which may be heated. The consolidation step is optional. Its implementation depends on the technique used to deposit the constituents onto the electrode. Thus, when the deposition step has been carried out by calendering, this consolidation step is optional because calendering allows for the simultaneous deposition and consolidation of the electrode.

[0246] According to one embodiment, after the powder mixing step, the electrode is manufactured by a solvent-free, two-step process. The first step consists of manufacturing a self-supporting film from the premixed formulation using a thermomechanical process such as extrusion, calendering, or thermocompression. In a second step, the self-supporting film is laminated onto the metallic 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 that allows the film formation and coating transfer to the current collector to be performed in a single step, i.e., without a separate step for manufacturing a self-supporting film. To achieve 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 usually heated and have differential rotation speeds to shear the powder. The coating formed and remaining adhered to the fastest roller is then directly laminated onto the current collector with a third roller. The electrode thus obtained can be subsequently passed through another 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, 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.

[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 multilayer structure extruded in the form of a film, sheet, or tube. Said composition can also be used as a coating on a metal. Examples

[0250] The following materials are used for the examples below:

[0251] Solvent: NMP Sigma Aldrich anhydrous 99.5% (<50 ppm H2O); conducting agent: Imerys C65 Carbon Black; active ingredient: NMC 811; fluorinated polymer PI: PVDF-AA comprising 1.1% by weight of acrylic acid in the PVDF chain; polymer additive P2a: poly(acrylic acid) with a weight molar mass (Mw) of approximately 3000 to 4000 g / mol not containing functional groups containing a phosphorus atom; polymer additive P2b: poly(acrylic acid) with a weight molar mass (Mw) of approximately 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 hot (320 K) ³¹P and ¹H NMR. The NMR spectra were acquired on a Bruker AV III HD 500 spectrometer equipped with a 5 mm BBI probe. The polymer additive P2 was dissolved in DMSO-d6. The signals between 20 and 22 ppm in ³¹P NMR, between 24 and 31 ppm in ³¹P NMR, and between 28 and 48 ppm in ³¹P NMR, and the signal at 6.9 ppm in ¹H NMR are characteristic of the functional groups containing a phosphorus atom present in said polymer additive P2. ¹H NMR analysis allows the quantity of monomer M2 in said polymer additive P2 to be determined. The signals to be integrated in ¹H NMR depend on the monomer M2 used. For example, in example B3 below, the characteristic signals of acrylic acid are located at 1 ppm and 2.7 ppm.

[0254] Preparation of compositions

[0255] The fluorinated polymer PI was mixed with said polymer additive P2 in dry form (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 PI / P2 ratio* 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 1.5 g of conducting agent. The quantity of solution was chosen so as to take 1.5 g of composition B (i.e., the quantity of solution taken is sufficient to prepare a composition C comprising 1.5 g of (PI and P2)). The mixture was stirred four times with a Thinky ARE-250 mixer at 2000 rpm. 97 g of active material were added to this mixture, and the resulting mixture was stirred three times at 2000 rpm for one minute. NMP was added in three stages (7 g, 7 g, then 6.5 g), followed by mixing for one minute. at 2000 rpm after each addition. The solids content of the electrode compositions is 73%.

[0261] Rheological analysis of electrode compositions

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

[0263] Table 2 below details the viscosities at 25°C and a shear rate of 10 s⁻¹ for the different prepared electrode compositions. 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 viscosity of 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 performed at 140°C. Two electrode composition samples were each placed in a 1 cm internal diameter, 5 cm high HDPE tubular container. A thermobalance was performed at t = 0 on the first sample, taking 1 ml of the electrode composition. The second sample was left to stand for 120 h. After this stand time, 1 ml of the electrode composition taken from near the surface was analyzed by thermobalance to determine the solids content. The sedimentation factor S is calculated by dividing the solids content measured at t = 120 h by the solids content measured at t = 0. For composition C2, the sample was pre-adjusted to an electrode composition viscosity of approximately 5700 cP.To this end, a quantity of NMP was added to decrease the viscosity to the aforementioned value while maintaining a solids content of approximately 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 thus surprisingly discovered a composition that allows for the preparation of electrode compositions that are stable over time and have a viscosity suitable for electrode manufacturing.

Claims

1. Demands Composition comprising a fluorinated polymer bearing polar PI groups and a polymer additive P2 comprising repeating units from a monomer M2 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 Ci-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 Ci-Ci8 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 cyclic chain; R25 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by 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 an alkyl hydrocarbon group Ci-Cio optionally bearing 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 independent 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, R35 are 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 Ci-Cio alkyl optionally substituted by one or more -OH, -CO2H, SO3 H, -OPO32, -C(O)OR38, -OC(O)R38 group(s); R38 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups; 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 PI polymer 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=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 PI fluorinated polymer comprises repeating units from monomer Mla and repeating units from monomer Mlc and optionally repeating units from 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 the formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of the formula CF2 =CFOCF2CF2SO2F; the product of the 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-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 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 C1-C18 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 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-C10 alkyl hydrocarbon group optionally bearing 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 in 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 from a monomer M2 of formula (I), (III) or (IV) in which R1, R2 and R3 are independently selected from the group consisting of H, CO2H and Ci-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 cyclic chain; R25 is selected from the group consisting of Ci-C5 alkyl and C6-Ci2 aryl substituted by one or more CO2H functional groups;X2 is selected from the group consisting of -[-C(O)OC(R26) (R27)C(R28)(R29)-]wi- and an alkyl Ci-Cio hydrocarbon group optionally bearing one or more -OH, -CO2 H or ester(s) 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 selected from the group consisting of H and Ci-C5 alkyl, preferably selected from the group consisting of H and CH3.

12. A composition according to any one of the preceding claims, characterized in that said polymer additive P2 comprises repeating units derived from a monomer M2 of formula (I), (III), or (IV), wherein R1, R2, and R3 are independently 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 cyclic chain; R25 is selected from the group consisting of C1-C5 alkyl and C6 aryl substituted by 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 bearing 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 unit wl, 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 between 0.8 and 1.1; calculated from solids content measurements carried out by thermobalance at 140°C.

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

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

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

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