Methods for preparing functionalized lithium salts

Abstract

The present invention relates to at least one -S(O) 2 A lithium salt B containing a -F group is reacted with a compound represented by the formula (I) RO-SiR 1 R 2 R 3 to form at least one group -S(O) 2 The present invention relates to a method for preparing a lithium salt A comprising step a) forming a product mixture comprising a lithium salt A containing -OR, wherein the catalyst D is a compound having a pKa greater than 11 measured at 25° C. The present invention also relates to a lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd).

Description

[Technical field]

[0001] The present invention relates to a method for preparing a lithium salt, and in particular to a method for preparing a lithium salt having a functional group. [Background technology]

[0002] Lithium-ion batteries are used as an energy source in many devices such as mobile phones, computers and electric vehicles. Most current batteries contain a liquid solution of electrolyte consisting of lithium salts in a solvent, which is generally highly flammable (e.g. carbonate-type solvents). Other emerging technologies use electrolytes in the form of gels, which limit the flammable liquid content but are not without risk. The most promising technologies are based on all-solid-state batteries, which contain no flammable compounds and offer high energy density.

[0003] Many lithium salts are available for this type of battery application. In particular, lithium perchlorate, lithium hexafluorophosphate, bis(trifluoromethanesulfonyl)imide and lithium bis(fluorosulfonyl)imide can be mentioned. The lithium sulfonyl imide salts are the most promising in terms of stability and conductivity. New lithium salts suitable for new battery technologies have been evaluated. In this respect, the use of polymeric materials containing lithium sulfonyl imide salts has been considered. For example, WO2016 / 012670 describes the preparation of conductive polymers of the polyaryletherketone or polyethersulfone type containing lithium salts of grafted bis(sulfonyl)imides. The synthesis of this type of polymer is complex and requires multiple reaction steps, sometimes under more severe operating conditions.

[0004] Therefore, there is a need to prepare new lithium bis(sulfonyl)imide salts in good yields by a simple procedure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 012670 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention is directed to at least partially overcoming the shortcomings of the prior art. [Means for solving the problem]

[0007] According to a first aspect, the present invention provides a method for preparing a lithium salt A, comprising reacting a lithium salt B comprising at least one -S(O)2-F group with a compound of formula (I) RO-SiR 1 R 2 R 3 to form a product mixture comprising said lithium salt A comprising at least one group -S(O)2-OR, said catalyst D being a compound having a pKa greater than 11 measured at 25°C.

[0008] The present invention allows the preparation of functionalized lithium salts in a mild operating reaction with good yields and thus avoiding side reactions.In particular, this method avoids the use of nucleophilic compounds such as alkoxides or amines, which lead to the dissociation of the sulfonyl imide structure.This method allows the fluorine atom carried by the sulfur atom of lithium salt B to be replaced with the functional group -OR group derived from compound C.The lithium salt A thus formed contains a functional group -OR group bonded to the sulfur atom.

[0009] According to a preferred embodiment, the substituent R of said compound C comprises at least one carbon-carbon double bond. The presence of a carbon-carbon double bond is advantageous for the preparation of polymers containing lithium salts.

[0010] According to a preferred embodiment, the lithium salt B is of formula LiN(S(O)2-F)(S(O)2R') and the lithium salt A is of formula (IV) LiN(S(O)2-OR)(S(O)2R'), where R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy.

[0011] According to a preferred embodiment, the lithium salt B comprises two -S(O)2-F groups, forming a lithium salt A comprising two groups -S(O)2-OR, which thus comprises two groups -OR, each containing at least one carbon-carbon double bond, and which can facilitate the formation of a polymer comprising the lithium salt.

[0012] According to a preferred embodiment, the lithium salt B is Li-N(S(O)2-F)2 and the lithium salt A is Li-N(S(O)2-OR)2 of formula (III).

[0013] According to a preferred embodiment, said compound C is a RO-SiR of formula (I) 1 R 2 R 3 (wherein the group R 1 , R 2 and R 3 are each independently H and C1 to C 10 alkyl).

[0014] According to a preferred embodiment, said compound C is a RO-SiR of formula (I) 1 R 2 R 3 where the group R is of the formula R 4 -X-(Y) n - where R 4 is a group containing at least one carbon-carbon double bond, and X is selected from the group consisting of O, S and N(R 5 )(R5 is H or C1-C 10 and Y is a heteroatom selected from the group consisting of C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-, and (R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F or CH3, m is an integer from 1 to 50, and if X is O then z=0), and n is an integer from 1 to 50.

[0015] According to a preferred embodiment, the group R 4 is of formula (Ia), (Ib), (Ic) or (Id).

[0016] [ka] During the ceremony, A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 10 Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups.10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 12 aryl; W is selected from O and S; R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ether, C1-C4 ester, C1-C4 thioether, and C1-C4 thioester.

[0017] According to a preferred embodiment, said catalyst D is selected from the group consisting of N,N-diisopropylethylamine, 1,8-diazabicyclo(5.4.0)undec-7-ene, 6-(dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, polystyrene-bound 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, polystyrene-bound 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,4-diazabicyclo[2.2.2]octane, quinuclidine, 1,5-diazabicyclo(4.3.0)non-5-ene, 2,6-di-tert-butylpyridine, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3] undecane, cyclodiphosphazane, lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium.

[0018] According to a preferred embodiment, the method also comprises a step b) of purifying said lithium salt A, which step b) comprises extracting said lithium salt A with a non-polar organic solvent.

[0019] According to a preferred embodiment, step a) is carried out at a temperature between 10°C and 50°C.

[0020] According to a second aspect, the present invention provides a lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd)

[0021] [ka] TIFF2025513355000003.tif211161TIFF2025513355000004.tif248161In the formula, the substituents A, B, V and W are as defined above in accordance with the present invention, the substituents X, Y are as defined above in accordance with the present invention, n is as defined above in accordance with the present invention, and R' is as defined above in accordance with the present invention.

[0022] According to a preferred embodiment, the lithium salt is A and B are the same and are selected from the group consisting of H, F, Cl, Br and I; V is H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 10 Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 12aryl, where R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ether, C1-C4 ester, C1-C4 thioether and C1-C4 thioester, and preferably V is selected from the group consisting of H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl, C6R 10 6(R 10 are independently selected from H, F, and C1-C5 alkyl; W is O, X is O, Y is a group selected from the group consisting of CH2CH2, CH2CF2, CF2CF2, CH2CHF, CF2CH2 and CHFCH2, and n is an integer from 1 to 25; or Y is the group -[(C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-(R 8 and R 9 is independently selected from H, F or CH3 for each carbon atom and for each unit Y, and m is an integer from 1 to 25; and n is 1; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy. of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd).

[0023] According to a preferred embodiment, the lithium salt is represented by the formula: A and B are H, V is CH3, W is O, X is O, Y is a group selected from the group consisting of CH2CH2, CH2CF2, CF2CF2, CH2CHF, CF2CH2 and CHFCH2, and n is an integer from 1 to 10; or Y is the group -[(C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-(R 8 and R 9 is independently selected from H, F or CH3 for each carbon atom and for each unit Y, and m is an integer from 1 to 25; and n is 1; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy. of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd).

[0024] According to a preferred embodiment, the lithium salt is a compound in which A and B are H, V is CH3, W is O, X is O, Y is a group selected from the group consisting of CH2CH2, CH2CF2, CF2CF2, CH2CHF, CF2CH2 and CHFCH2, and n is an integer from 1 to 10; or Y is a group -[(C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9)]-(R 8 and R 9 is of formula (IIIa), where for each carbon atom and for each unit Y, is independently selected from H, F or CH3, and m is an integer from 1 to 25, and n is 1.

[0025] According to another aspect, the present invention provides a polymer comprising monomer units derived from at least one lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd) according to the present invention.

[0026] According to a preferred embodiment, the polymer also has the formula R 1 R 2 C=C(R 3 )C(O)R monomer units obtained from the monomer M1, 1 , R 2 and R 3 are each independently selected from the group consisting of H and C1-C5 alkyl, R is -NHC(CH3)2CH2C(O)CH3 or -OR' (R' is a C1-C alkyl group optionally substituted with H and one or more -OH groups or a 5- or 10-membered heterocycle containing at least one nitrogen atom in its cyclic chain); 18 Also included are those selected from the group consisting of alkyl.

[0027] According to a preferred embodiment, the polymer is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), monomers of formula CF2=CFOCF2CF(CF3)OCF2CF2X (X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H), monomers of formula CF2=CFOCF2CF2SO2F, monomers of formula F(CF2) nMonomers of CH2OCF=CF2 (n is 1, 2, 3, 4 or 5), formula R 1 CH2OCF=CF2(R 1 is hydrogen or F(CF2) m and m is 1, 2, 3 or 4, 2 OCF=CH2(R 2 is F(CF2) p and p is 1, 2, 3, 4), and a monomer M2 selected from the group consisting of perfluorobutylethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, or 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

[0028] According to a preferred embodiment, the present invention provides a binder for an electrode or a coating for a separator comprising said polymer according to the invention.

[0029] According to a preferred embodiment, the present invention provides an electrode or separator comprising said polymer according to the invention.

[0030] According to a preferred embodiment, the present invention provides a battery, preferably a lithium-ion battery, comprising said electrode or said separator according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] According to a first aspect of the present invention, there is provided a method for preparing a lithium salt A, said method comprising reacting a lithium salt B containing at least one -S(O)2-F group with a compound of formula (I)RO-SiR 1 R 2 R 3The lithium salt A is formed by an exchange reaction between a fluorine atom carried by the group -S(O)2 of the lithium salt B and a group -OR carried by a silicon atom of the compound C. The lithium salt A thus formed contains at least one group -S(O)2-OR. The method according to the invention also comprises the step of producing a co-product F-SiR 1 R 2 R 3 This method avoids the formation of HF (a fluorine atom bonded to a Si atom) during the reaction, which would require its neutralization with an excess of base or an additional purification step. The invention allows the preparation of functionalized lithium salts in good yields under mild operating conditions, thus avoiding side reactions.

[0032] <Compound B> As mentioned above, the lithium salt B comprises at least one -S(O)2-F group. According to a preferred embodiment, the lithium salt B is of formula LiN(S(O)2-F)(S(O)2R'), where R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C44 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy. Thus, preferably, the process comprises reacting LiN(S(O)2-F)(S(O)2R'), preferably in the presence of a catalyst D as defined in the present patent application, with a compound of formula (I)RO-SiR as defined in the present patent application. 1 R 2 R 3 with compound C of formula (I).

[0033] Preferably, the lithium salt B contains two -S(O)2-F groups.

[0034] In particular, said lithium salt B is Li-N(S(O)2-F)2, i.e. lithium bis(sulfonyl)imide, also called LiFSI. Thus, preferably, the process comprises converting Li-N(S(O)2-F)2, preferably in the presence of a catalyst D as defined in the present application, into a compound of formula (I) RO-SiR2R2R2R2R2R2R2R2R1 as defined in the present application. 1 R 2 R 3 with compound C of formula (I).

[0035] <Compound C> According to a preferred embodiment, said compound C has the formula (I) RO-SiR 1 R 2 R 3 It is of the following.

[0036] According to a preferred embodiment, said compound C has the formula (I) RO-SiR 1 R 2 R 3 (group R 1 , R 2 and R 3 are, independently of each other, H, C1 to C 20 Alkyl, C3-C 20 Cycloalkyl and C6-C 20 aryl). Preferably, the group R 1 , R 2 and R 3 are, independently of each other, H, C1 to C 15 Alkyl, C3-C 15 Cycloalkyl and C6-C 15 More preferentially, the group R 1 , R 2 and R 3 are, independently of each other, H, C1 to C 10 Alkyl, C3-C 10 Cycloalkyl and C6-C 12 In particular, the group R 1 , R 2 and R 3 are each independently H and C1 to C 10 More specifically, the group R1 , R 2 and R 3 are independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl and pentyl. 1 , R 2 and R 3 are independently selected from the group consisting of H, methyl, ethyl, propyl and tert-butyl. In a preferentially preferred manner, the group R 1 and R 2 are identical and are selected from the group consisting of H, methyl and ethyl; 3 is selected from the group consisting of H, methyl, ethyl, propyl and tert-butyl. In a particularly preferred manner, the group R 1 , R 2 and R 3 are the same and are selected from the group consisting of H, methyl and ethyl.

[0037] According to a preferred embodiment, the substituent R of said compound C comprises at least one carbon-carbon double bond. As mentioned above, the presence of a carbon-carbon double bond is advantageous for the preparation of polymers containing lithium salts.

[0038] Preferably, the group R of compound C has the formula R 4 -X-(Y) n - provided that: R 4 is a group containing at least one carbon-carbon double bond, X is O, S and N(R 5 )(R 5 is H or C1-C 10 alkyl), preferably R 5 is H, CH3 or C2H5, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6)(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]- (R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10; When X is O, then z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10).

[0039] According to a preferred embodiment, in said compound C, the group R 4 is of formula (Ia), (Ib), (Ic) or (Id).

[0040] [ka] During the ceremony, A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 20 Alkyl, C2-C optionally substituted with one or more substituents R 20 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 20 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 20Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 20 aryl; W is selected from O and S, preferably O; R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ether, C1-C4 ester, C1-C4 thioether and C1-C4 thioester, preferably F, C1-C4 ether, C1-C4 ester, C1-C4 thioether and C1-C4 thioester.

[0041] Preferably, in said compound C, the group R 4 A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R″; 15 Alkyl, C2-C optionally substituted with one or more substituents R 15 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 15 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 15 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 15 aryl; W is selected from O and S, preferably O; R″ is of the above formula (Ia), (Ib), (Ic) or (Id) selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters.

[0042] More preferentially, in said compound C, the group R 4 A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 10Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 10 aryl; W is selected from O and S, preferably O; R″ is of the above formula (Ia), (Ib), (Ic) or (Id) selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters.

[0043] In particular, in said compound C, the group R 4 A, B and V are each independently H, F, Cl, Br, I, C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C4-C 10 Cycloalkenyl, C6-C 10 Aryl, C1-C 10 Perfluoroalkyl, C2-C 10 Perfluoroalkenyl, C3-C 10 Perfluorocycloalkyl, C4-C 10 Perfluorocycloalkenyl and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O, of formula (Ia), (Ib), (Ic) or (Id) above.

[0044] More particularly, in said compound C, the group R 4A, B and V are each independently H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and C6R 10 5; R 10 is independently selected from H, F, and C1-C5 alkyl; W is selected from O and S, preferably O, of formula (Ia), (Ib), (Ic) or (Id) above.

[0045] Preferably, in said compound C, the group R 4 A and B are each independently selected from the group consisting of H, F, Cl, I, Br, CH3, C2H5, CF3, C2F5 and phenyl; V is selected from the group consisting of H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O, of formula (Ia), (Ib), (Ic) or (Id) above.

[0046] In a preferentially preferred manner, the group R 4 teeth, A and B are the same and are selected from the group consisting of H, F, Cl, I and Br; or A is H and B is selected from the group consisting of F, Cl, Br, I, CH3, C2H5, CF3, C2F5, and phenyl; V is H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and (R 10 is independently selected from H, F, and C1-C5 alkyl 10 5, W is selected from O and S, preferably O, of formula (Ia), (Ib), (Ic) or (Id) above.

[0047] Thus, according to the invention, said compound C may be of formula (Ia), (Ib), (Ic) or (Id).

[0048] [ka] (In the formula, substituents A, B, V, W, X, Y, R 1 , R 2 and R 3 is as defined above in this patent application according to any of the described embodiments.

[0049] According to a preferred embodiment, said compound C may be of formula (Ia), (Ib), (Ic) or (Id).

[0050] [ka] During the ceremony, R 1 , R 2 and R 3 are, independently of each other, H, C1 to C 20 Alkyl, C3-C 20 Cycloalkyl and C6-C 20 aryl, advantageously R 1 , R 2 and R 3 are, independently of each other, H, C1 to C 15 Alkyl, C3-C 15 Cycloalkyl and C6-C 15 aryl, preferably R 1 , R 2 and R 3 are, independently of each other, H, C1 to C 10 Alkyl, C3-C 10 Cycloalkyl and C6-C 12 aryl, more preferentially selected from the group consisting of R 1 , R 2 and R 3 are each independently H and C1 to C 10 alkyl, in particular R 1 , R 2 and R 3are each independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl and pentyl, more specifically R 1 , R 2 and R 3 are each independently selected from the group consisting of H, methyl, ethyl, propyl and tert-butyl; X is O, S and N(R 5 ), where R 5 is H or C1-C 10 is alkyl, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R20 Alkyl, C2-C optionally substituted with one or more substituents R 20 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 20 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 20 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 20 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, advantageously A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 15 Alkyl, C2-C optionally substituted with one or more substituents R 15 alkenyl, optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 15 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 15 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 15 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 10 Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups;10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 10 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, and more preferentially A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C4-C 10 Cycloalkenyl, C6-C 10 Aryl, C1-C 10 Perfluoroalkyl, C2-C 10 Perfluoroalkenyl, C3-C 10 Perfluorocycloalkyl, C4-C 10 Perfluorocycloalkenyl and C6-C 10 perfluoroaryl, in particular A, B and V are independently selected from the group consisting of H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O.

[0051] According to a particular embodiment, said compound C may be of formula (Ia), (Ib), (Ic) or (Id).

[0052] [ka] During the ceremony, R 1 and R 2are the same and are selected from the group consisting of H, methyl and ethyl; R 3 is selected from the group consisting of H, methyl, ethyl, propyl and tert-butyl, preferably R 1 , R 2 and R 3 are the same and are selected from the group consisting of H, methyl and ethyl; X is O, S and N(R 5 ), where R 5 is H or C1-C 10 alkyl, preferably R 5 is H, CH3 or C2H5, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A and B are independently selected from the group consisting of H, F, Cl, I, Br, CH3, C2H5, CF3, C2F5 and phenyl, preferably A and B are the same and are selected from the group consisting of H, F, Cl, I and Br, or A is H and B is selected from the group consisting of F, Cl, Br, I, CH3, C2H5, CF3, C2F5 and phenyl, V is H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl, and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O.

[0053] <Compound A> As described above, the lithium salt A is a compound represented by the formula (I) RO-SiR 1 R 2 R 3 is formed by an exchange reaction between the group -OR derived from the compound C and

[0054] According to a preferred embodiment, the lithium salt A comprises at least one group -S(O)2-OR. Preferably, when the lithium salt B comprises two -S(O)2-F groups, the lithium salt A comprises two groups -S(O)2-OR. Thus, the lithium salt A has two groups -OR, each containing at least one carbon-carbon double bond, which can facilitate the formation of a polymer containing the lithium salt.

[0055] According to a particular embodiment, the lithium salt A has the formula R 4 -X-(Y) n -(In the formula, R 4 is a group containing at least one carbon-carbon double bond, and X is selected from the group consisting of O, S and N(R 5 ), where R 5 is H or C1-C 10 alkyl, preferably R5 is H, CH3 or C2H5), Y is -C(R6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is of formula (III) Li-N(S(O)2-OR)2 with R of: (III) Li-N(S(O)2-OR)2, where for each carbon atom and for each unit Y, is independently selected from H, F or CH3, m is an integer from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, and if X is O, z=0 and n is an integer from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10).

[0056] When the lithium salt A is of formula (III) Li-N(S(O)2-OR)2, the substituents R are selected independently of each other for each of the functional groups S(O)2-OR.

[0057] Thus, according to a preferred embodiment, said lithium salt A is of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi) or (IIIj).

[0058] [ka] TIFF2025513355000010.tif176160In the formula, X is O, S and N(R 5 ), where R 5 is H or C1-C 10 is alkyl, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 20 Alkyl, C2-C optionally substituted with one or more substituents R 20 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 20Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 20 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 20 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, advantageously A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 15 Alkyl, C2-C optionally substituted with one or more substituents R 15 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 15 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 15 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 15 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 10 Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups10 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, and more preferentially A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C4-C 10 Cycloalkenyl, C6-C 10 Aryl, C1-C 10 Perfluoroalkyl, C2-C 10 Perfluoroalkenyl, C3-C 10 Perfluorocycloalkyl, C4-C 10 Perfluorocycloalkenyl and C6-C 10 perfluoroaryl, in particular A, B and V are independently selected from the group consisting of H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O.

[0059] Preferably, the lithium salt A is of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi) or (IIIj), in which X is O, S and N(R 5 ), where R 5 is H or C1-C 10 alkyl, preferably R 5 is H, CH3 or C2H5, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A and B are independently selected from the group consisting of H, F, Cl, I, Br, CH3, C2H5, CF3, C2F5 and phenyl, preferably A and B are the same and selected from the group consisting of H, F, Cl, I and Br, or A is H and B is selected from the group consisting of F, Cl, Br, I, CH3, C2H5, CF3, C2F5 and phenyl, V is H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl, and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O.

[0060] In particular, said lithium salt A is of formula (IIIa), (IIIb), (IIIc) or (IIId) as defined above.

[0061] Alternatively, when the lithium salt B is of formula LiN(S(O)2-F)(S(O)2R'), the lithium salt A is of formula (IV)LiN(S(O)2-OR)(S(O)2R'). The lithium salt A is of formula (IV)LiN(S(O)2-OR)(S(O)2R'), where R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, and R is as defined above in this patent application.

[0062] Thus, said lithium salt A is of formula (IV) LiN(S(O)2-OR)(S(O)2R'), where R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy; R is the formula R 4 -X-(Y) n - in which R 4 is a group containing at least one carbon-carbon double bond, and X is selected from the group consisting of O, S and N(R 5 ), where R 5 is H or C1-C 10 alkyl, preferably R 5 is H, CH3 or C2H5, and Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8)(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F or CH3, m is an integer from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, and when X is O, z=0 and n is an integer from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10.

[0063] Thus, said lithium salt A is of formula (IVa), (IVb), (IVc) or (IVd).

[0064] [ka] During the ceremony, X is O, S and N(R 5 ), where R 5 is H or C1-C 10 is alkyl, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 20 Alkyl, C2-C optionally substituted with one or more substituents R 20 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 20 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 20 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 20 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, advantageously A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 15 Alkyl C2-C optionally substituted with one or more substituents R 15 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 15 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 15Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 15 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 10 Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 10 aryl, R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, and more preferentially A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C4-C 10 Cycloalkenyl, C6-C 10 Aryl, C1-C 10 Perfluoroalkyl, C1-C 10 Perfluoroalkenyl, C3-C 10 Perfluorocycloalkyl, C4-C 10 Perfluorocycloalkenyl and C6-C 10perfluoroaryl, in particular A, B and V are independently selected from the group consisting of H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy.

[0065] Preferably, the lithium salt A is of formula (IVa), (IVb), (IVc) or (IVd), in which X is O, S and N(R 5 ), where R 5 is H or C1-C 10 alkyl, preferably R 5 is H, CH3 or C2H5, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A and B are independently selected from the group consisting of H, F, Cl, I, Br, CH3, C2H5, CF3, C2F5 and phenyl, preferably A and B are the same and selected from the group consisting of H, F, Cl, I and Br, or A is H and B is selected from the group consisting of F, Cl, Br, I, CH3, C2H5, CF3, C2F5 and phenyl, V is H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl, and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy.

[0066] <Catalyst D> The process for preparing the lithium salt is carried out in the presence of a catalyst D. Advantageously, the catalyst D is a non-nucleophilic compound. The use of a non-nucleophilic compound helps to avoid decomposition of the lithium salt B.

[0067] According to a preferred embodiment, said catalyst D is a compound having a pKa greater than 11, measured in water at 25° C. According to a particular embodiment, said catalyst D has a pKa greater than 11.5, advantageously greater than 12.0, preferably greater than 12.5, in particular greater than 13.0.

[0068] Preferably, the molar ratio of catalyst to lithium salt B is greater than or equal to 0.1, preferably greater than or equal to 0.2. Preferably, the molar ratio of catalyst to lithium salt B is less than or equal to 2.5, preferably less than or equal to 2.

[0069] According to a preferred embodiment, said catalyst D is selected from the group consisting of N,N-diisopropylethylamine, 1,8-diazabicyclo(5.4.0)undec-7-ene, 6-(dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, polystyrene-bound 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, polystyrene-bound 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,4-diazabicyclo[2.2.2]octane, quinuclidine, 1,5-diazabicyclo(4.3.0)non-5-ene, 2,6-di-tert-butylpyridine, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3] undecane, cyclodiphosphazane, lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium.

[0070] In particular, said catalyst D is selected from the group consisting of 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-tert-butyl-1,1,3,3-tetramethylguanidine, polystyrene-bound 1,5,7-triazabicyclo[4.4.0]dec-5-ene and polystyrene-bound 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0071] <Implementation of the method according to the present invention> The process can be carried out under mild operating conditions. Step a) of the process is preferably carried out in a reactor made of materials such as Inconel®, Hastelloy® or Monel®.

[0072] According to a preferred embodiment, the process is carried out at a temperature comprised between 10°C and 70°C, advantageously between 10°C and 50°C, preferably between 10°C and 30°C.

[0073] Although pressure is not a critical parameter in the implementation of the process, said process can be carried out at a pressure between 0.5 and 3 bara, preferably at atmospheric pressure.

[0074] The process may be carried out under an atmosphere which may or may not be inert.

[0075] Preferably, in step a), the lithium salt B is contacted with the catalyst D, followed by the addition of the compound C. This allows for improved conversion of the reaction between the lithium salt and compound C.

[0076] The reaction between the lithium salt and compound C is preferably carried out in stoichiometry or with a slight excess or deficiency of compound C. Thus, for example, if the lithium salt B contains two S(O)2-F groups, then two equivalents of compound C are added relative to the moles of lithium salt B.

[0077] The process can be carried out without a solvent, but the process can also be carried out in the presence of a solvent, which, if used, can be, for example, acetonitrile, benzonitrile, dimethylsulfoxide, dimethylformamide, 1,4-dioxane, nitromethane, dimethylcarbonate, diethylcarbonate, propylcarbonate, ethylene carbonate, N-methyl-2-pyrrolidone or a mixture thereof.

[0078] In addition to lithium salt A, the product mixture may contain unreacted lithium salt B, or unreacted compound C, or a mixture of the two.

[0079] The product mixture is also represented by R 1 , R 2 and R 3 F-SiR with 1 R 2 R 3 R 1 , R 2 and R 3 If is CH3, the F-Si(CH3)3 formed in step a) is easily removed given its boiling point (Bp=16° C.).

[0080] If the lithium salt B has two S(O)2-F groups, the product mixture may also include compounds in which only one of the fluorine atoms is replaced. For example, if the lithium salt B is LiN(S(O)2-F)2, the product mixture may include LiN(S(O)2F)(S(O)2-OR).

[0081] The lithium salt B may optionally contain impurities related to the method of its preparation, such as LiCl, LiF or FSO3Li, with a mass content of less than 1000 ppm, advantageously less than 500 ppm, preferably less than 100 ppm, relative to the total weight of the lithium salt. In particular, FSO3Li, if present, represents a mass content of less than 5 ppm relative to the total weight of the lithium salt B. Other impurities may also be present in the lithium salt B, as described in WO2018 / 104674. These impurities may optionally be present in the lithium A salt in contents up to those stated for the lithium salt B.

[0082] According to a preferred embodiment, the method also comprises a step b) of purifying the mixture of products obtained in step a) in order to isolate the lithium A salt. If step a) is carried out in the presence of a solvent, the solvent is preferably distilled off before carrying out step b). Step b) in particular comprises a step of extracting the lithium A salt with a non-polar organic solvent, which may be, for example, a C5-C 10 Alkyl, C5-C 10 Cycloalkyl, C6-C 10 Aryl, C1-C3 haloalkyl, diethyl ether, 1,4-dioxane, tetrahydrofuran or a mixture thereof. Preferably, the non-polar organic solvent is n-hexane, pentane, heptane, cyclohexane, cyclopentane, benzene, toluene, xylene, cumene, CCl4, CHCl3, diethyl ether, 1,4-dioxane, tetrahydrofuran or a mixture thereof.

[0083] The process according to the invention gives the lithium salt A in very high purity. The mixture comprising the lithium salt and the non-polar solvent obtained in step b) is distilled to remove the non-polar solvent and recover the lithium salt A. The implementation of step b) results in a composition comprising at least 95% by weight, preferably at least 98% by weight, in particular at least 99% by weight, more particularly at least 99.5% by weight of lithium salt A relative to the total weight of the composition.

[0084] The composition comprises compound C, compound B and compound R as defined in this patent application. 1 , R 2 and R 3 F-SiR with 1 R 2 R 3 When the lithium salt B is LiN(S(O)2-F)2, the composition may contain less than 1% by weight, preferably less than 0.5% by weight, of an additional compound selected from the group consisting of: 1 , R 2 and R 3 F-SiR with 1 R 2 R 3 and LiN(S(O)2F)(S(O)2-OR) in an amount of less than 1% by weight, preferably less than 0.5% by weight.

[0085] <Lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc), or (IVd)> According to a second aspect of the present invention, there is provided a lithium salt, according to a preferred embodiment, said lithium salt being of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd).

[0086] [ka] TIFF2025513355000013.tif231161TIFF2025513355000014.tif222161TIFF2025513355000015.tif42161In the formula, X is O, S and N(R 5 ), where R 5 is H or C1-C 10is alkyl, Y is -C(R 6 )(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A, B and V are each independently H, F, Cl, Br, I, C1-C optionally substituted with one or more substituents R 20 Alkyl, C2-C optionally substituted with one or more substituents R 20 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 20 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 20 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 20aryl, the substituent R″ being selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, advantageously A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, optionally substituted with one or more substituents R″; 15 Alkyl, C2-C optionally substituted with one or more substituents R 15 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 15 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 15 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 15 A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, and preferably A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I ... 10 Alkyl, C2-C optionally substituted with one or more substituents R 10 alkenyl, C3-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups; 10 Cycloalkyl, C4-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups. 10 Cycloalkenyl, C6-C optionally substituted with one or more substituents R" or one or more C1-C5 alkyl groups 10aryl, the substituent R″ is selected from the group consisting of F, Cl, I, Br, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, preferably F, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, and more preferentially A, B and V are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C4 ethers, C1-C4 esters, C1-C4 thioethers and C1-C4 thioesters, 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C4-C 10 Cycloalkenyl, C6-C 10 Aryl, C1-C 10 Perfluoroalkyl, C2-C 10 Perfluoroalkenyl, C3-C 10 Perfluorocycloalkyl, C4-C 10 Perfluorocycloalkenyl and C6-C 10 A, B and VV are each independently selected from the group consisting of H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy.

[0087] Preferably, the lithium salt is X is O, S and N(R 5 ), where R 5 is H or C1-C 10 alkyl, preferably R 5 is H, CH3 or C2H5, Y is -C(R 6)(R 7 )-, -C(R 6 )(R 7 )C(R 6 )(R 7 )SC(R 6 )(R 7 )- and -[(O) z (C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-; R 6 and R 7 is independently selected from H or F for each carbon atom and for each unit Y; R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F, or CH3; m is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, When X is O, z=0; n is an integer ranging from 1 to 50, advantageously from 1 to 40, preferably from 1 to 30, more preferentially from 1 to 20 and in particular from 1 to 10, A and B are each independently selected from the group consisting of H, F, Cl, I, Br, CH3, C2H5, CF3, C2F5 and phenyl, preferably A and B are the same and are selected from the group consisting of H, F, Cl, I and Br, or A is H and B is selected from the group consisting of F, Cl, Br, I, CH3, C2H5, CF3, C2F5 and phenyl, V is H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl, and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is selected from O and S, preferably O; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy. of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd).

[0088] In particular, the lithium salt is A and B are each independently selected from the group consisting of H, F, Cl, I, Br, CH3, C2H5, CF3, C2F5 and phenyl, preferably A and B are the same and are selected from the group consisting of H, F, Cl, I and Br, or A is H and B is selected from the group consisting of F, Cl, Br, I, CH3, C2H5, CF3, C2F5 and phenyl, V is H, F, Cl, Br, I, C1-C5 alkyl, C1-C5 perfluoroalkyl, and C6R 10 5; R 10 is independently selected from H, F and C1-C5 alkyl; W is O, X is O, Y is a group selected from the group consisting of CH2CH2, CH2CF2, CF2CF2, CH2CHF, CF2CH2 and CHFCH2, and n is an integer from 1 to 25; or Y is a group -[(C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-R 8 and R 9 is independently selected from H, F or CH3 for each carbon atom and for each Y unit, and m is an integer from 1 to 25; and n is 1; R' is a substituent selected from the group consisting of F, C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy, preferably C1-C4 alkyl, C1-C4 perfluoroalkyl, C1-C4 alkoxy and C1-C4 perfluoroalkoxy. of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd).

[0089] According to a preferred embodiment, the lithium salt is A and B are H; V is CH3 or H; W is O, X is O, Y is a group selected from the group consisting of CH2CH2, CH2CF2, CF2CF2, CH2CHF, CF2CH2 and CHFCH2, and n is an integer from 1 to 10; or Y is a group -[(C(R 8 )(R 9 )-C(R 8 )(R 9 )O) m -C(R 8 )(R 9 )C(R 8 )(R 9 )]-R 8 and R 9 is independently selected for each carbon atom and for each unit Y from H, F or CH3, and m is an integer from 1 to 25), and n is of formula (IIIa)

[0090] According to another aspect of the present invention, a polymer is provided, said polymer comprising monomer units derived from at least one of the lithium salts according to the present invention, i.e. according to any one of formulae (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc) or (IVd). The polymer may comprise monomer units derived from one of the lithium salts according to the present invention, or monomer units derived from several of these salts. The lithium salts can be polymerized via their vinyl functional groups.

[0091] According to a preferred embodiment, the polymer also has the formula R 1 R 2 C=C(R 3 )C(O)R monomer units obtained from the monomer M1, 1 , R 2 and R 3 are each independently selected from the group consisting of H and C1-C5 alkyl, R is -NHC(CH3)2CH2C(O)CH3 or -OR' (R' is a C1-C alkyl group optionally substituted with H and one or more -OH groups or a 5- or 10-membered heterocycle containing at least one nitrogen atom in its cyclic chain); 18 The heterocycle may be saturated, unsaturated, or aromatic. The heterocycle may be monocyclic or bicyclic. The heterocycle may be a pyrrole ring, a pyrrolidine ring, a pyridine ring, a piperidine ring, a pyrimidine ring, a pyrazine ring, a 1,4-dihydropyridine ring, an indole ring, an oxindole ring, an isatin ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, an imidazoline ring, a pyrazolidine ring, a 2-pyrrolidone ring, a δ-lactam ring, a succinimide ring, a 2-imidazolidinone ring, or a 4-imidazolidinone ring. The heterocycle may be substituted with one or more C1-C5 alkyl groups. As described above, the C1-C5 alkyl groups may be substituted with one or more C1-C5 alkyl groups. 18The alkyl may be substituted with said heterocycle. The heterocycle may be attached to said chain via a nitrogen atom or any other atom that forms the heterocycle. Preferably, the heterocycle is 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidinone or 4-imidazolidinone.

[0092] Preferably, the monomer M1 has the formula R 1 R 2 C=C(R 3 )C(O)R, where R 1 , R 2 and R 3 are each independently selected from the group consisting of H and C1-C5 alkyl, R is -OR', R' is H and C1-C5 alkyl optionally substituted with one or more -OH groups; 18 According to a preferred embodiment, the substituent R' is selected from the group consisting of ureido, hydroxyethyl, hydroxypropyl or hydroxybutyl substituted H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-dodecyl, amyl, isoamyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxybutyl, hydroxypropyl and ethyl.

[0093] In particular, the monomer M1 has a substituent R 1 and R 2 is H and R 3 is H or CH3, R is -OR', and R' is selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, hydroxypropyl, hydroxybutyl, 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidinone, and 4-imidazolidinone. 1 R 2 C=C(R 3 )C(O)R.

[0094] Thus, the monomer M1 may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-dodecyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl 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 and mixtures thereof. Among these, alkyl acrylates having an alkyl group with 1 to 8 carbon atoms are preferred, and alkyl acrylates having an alkyl group with 1 to 5 carbon atoms are more preferred. These compounds can be used alone or in combination of two or more.

[0095] According to a preferred embodiment, the polymer may also be a monomer of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), monomers of formula CF2=CFOCF2CF(CF3)OCF2CF2X (X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H), monomers of formula CF2=CFOCF2CF2SO2F, monomers of formula F(CF2) n Monomers of CH2OCF=CF2 (n is 1, 2, 3, 4 or 5), formula R 1 CH2OCF=CF2(R 1 is hydrogen or F(CF2) m and m is 1, 2, 3 or 4,2 OCF=CH2(R 2 is F(CF2) p and p is 1, 2, 3 or 4), and a monomer M2 selected from the group consisting of perfluorobutylethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene or 2-trifluoromethyl-3,3,3-trifluoro-1-propene. Preferably, the monomer M2 is selected from the group consisting of vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), monomers of formula CF2=CFOCF2CF(CF3)OCF2CF2X, where X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H, monomers of formula CF2=CFOCF2CF2SO2F, monomers of formula F(CF2) n Monomers of formula R 1 CH2OCF=CF2(in the formula, R 1 is hydrogen or F(CF2) m and m is 1, 2, 3 or 4, 2 OCF=CH2(wherein, R 2 is F(CF2) p where p is 1, 2, 3 or 4), tetrafluoropropene or chlorotrifluoropropene. In particular, the monomer M2 is selected from the group consisting of vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, tetrafluoropropene and chlorotrifluoropropene.

[0096] The polymers also include those made of fumaric acid, crotonic acid, itaconic acid; vinyl ester compounds such as vinyl acetate and vinyl neodecanoate; amide compounds such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N,N-dialkylacrylamide, N,N-dialkylmethacrylamide, and diacetoneacrylamide; N-dialkylaminoethyl acrylate, glycidyl acrylate, n-dodecyl acrylate, and the like. The monomer unit may be derived from a monomer M3 selected from the group consisting of decyl acrylate, fluoroalkyl acrylate, dialkylaminoethyl methacrylate, fluoroalkyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, maleic anhydride, alkenyl glycidyl ether compounds such as allyl glycidyl ether, conjugated dienes such as 1,3-butadiene and isoprene, divinyl hydrocarbon compounds such as divinylbenzene, and alkenyl cyanides such as acrylonitrile and methacrylonitrile. These compounds may be used alone or as a mixture of two or more. Among these, preferred compounds are 1,3-butadiene and acrylonitrile.

[0097] The polymers described in this patent application can be used in many applications: Thus, they can be used as binders for electrodes (cathode or anode) or as coatings for separators.

[0098] Thus, according to another aspect, the present invention provides an electrode composition comprising said polymer according to the present invention, an active material, and optionally a conductive agent.

[0099] In a preferred embodiment, the electrode composition has the following mass composition: a. 50% to 99.9%, preferably 50% to 99%, of an active material; b. 25% to 0%, preferably 25% to 0.5%, of a conductive agent; c. 25% to 0.05%, preferably 25% to 0.5%, of the binder according to the present invention; d. 0-5% of at least one additive selected from the group consisting of plasticizers, ionic liquids, dispersants for conductive agents, and flow aids; All these percentages add up to 100%.

[0100] The conductive agent in the electrode is composed of one or more materials that can improve electrical conductivity. Some examples include carbon black, such as acetylene black or ketjen black; carbon nanotubes, carbon nanofibers, carbon fibers such as vapor-grown carbon fibers; or metal powders such as SUS powder and aluminum powder.

[0101] The active material in the electrode composition is a material capable of storing and releasing lithium ions.

[0102] In a preferred embodiment, the electrode is a negative electrode. In particular, in the case of a negative electrode, the active material is a lithium alloy, lithium metal, a metal oxide, a carbon material such as graphite or hard carbon, silicon, silicone, silicon and Li4TiO 12 The shape of the negative electrode active material is not particularly limited, but it is preferably in the form of particles.

[0103] In another preferred embodiment, the electrode is a positive electrode. Preferably, in the case of a positive electrode, the active material is LiCoO2, Li(Ni,Co,Al)O2, Li (1+x) Ni a Mn b Co c (x represents a real number equal to or greater than 0, a=0.8, 0.6, 0.5, or 1 / 3, b=0.1, 0.2, 0.3, or 1 / 3, and c=0.1, 0.2, or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3O3, Li3Fe2(PO4)3, Li3V2(PO4)3, Li 1+x Mn 2-x-y M yLiMn spinel substituted with different elements having a composition represented by O4 (M represents at least one metal selected from Al, Mg, Co, Fe, Ni and Zn, and x and y independently represent real numbers between 0 and 2), lithium titanate Li x TiO y (x and y are independently a real number between 0 and 2), and lithium metal phosphate having a composition represented by LiMPO4 (M represents Fe, Mn, Co, or Ni). The shape of the positive electrode active material is not particularly limited, but it is preferably particulate. The surface of each of the above materials may be coated. The coating material is not particularly limited as long as it is conductive to lithium ions and contains a material that can be held in the form of a coating layer on the surface of the active material. Examples of the coating material include LiNbO3, Li4Ti5O 12 , Li3PO4, etc.

[0104] To form the electrode, the electrode composition can be deposited on at least one side of a current collector. The deposition can be done in the presence of an organic solvent, water, a mixture of the two, or via a solvent-free method. The organic solvent can be selected from the group consisting of N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), triethylphosphite (TEP), acetone, cyclopentanone, tetrahydrofuran, methyl ethyl ketone (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.

[0105] According to another aspect of the present invention, there is provided a Li-ion battery. Preferably, the Li-ion battery comprises a positive electrode, a negative electrode and a separator, and at least one electrode is an electrode according to the present invention.

[0106] According to another aspect of the invention, the polymer according to the invention may be used as a coating in a separator placed between two electrodes. The separator according to the invention comprises a coating comprising, preferably consisting of, a polymer according to the invention, optionally placed on one or both sides of a porous support. In this case, the coating is used to coat the support of the separator in the form of a single layer or multiple layers on at least one side. The choice of the support to be coated with the coating of the invention is not particularly limited, as long as it is a porous substrate having pores. If it comprises several layers, the coating according to the invention is placed on the outer surface of the support, i.e. the surface that is first in contact with the electrolyte composition used in the battery. Advantageously, the application of the coating to the support is carried out by an aqueous or solvent route. The porous substrate may be in the form of a membrane or a fibrous fabric. When the porous substrate is fibrous, it may also be a nonwoven web forming a porous web, for example a web obtained by direct spinning or meltblowing (spunbond or meltblown type) or electrospinning. Examples of porous substrates useful as supports in the present invention include, but are not limited to, the following: polyolefins, polyethylene terephthalate, polybutylene terephthalate, polyesters, polyacetals, polyamides, polycarbonates, polyimides, polyether ether ketones, polyether sulfones, poly(phenylene oxides), poly(phenylene sulfides), polyethylene naphthalates, or mixtures thereof. However, other engineering plastics that are heat resistant may be used without particular limitation. Nonwoven materials made from natural or synthetic materials may also be used as substrates for the separator. The porous substrate generally has a thickness of 1-50 μm and typically consists of a membrane or cast nonwoven fabric obtained by extrusion and stretching (wet or dry method). The porous substrate preferably has a porosity between 5% and 95%. The average size (diameter) of the pores is preferably between 0.001 and 50 μm, more preferably between 0.01 and 10 μm. The substrate may also be aluminum or aluminum coated with a polymer layer.

[0107] In addition to the composition, the separator coating may contain inorganic particles that serve to form micropores (gaps between inorganic particles) in the coating. The addition of inorganic particles can also contribute to heat resistance or improve wettability. According to one embodiment, the coating contains 50% to 99% by weight of inorganic particles based on the weight of the coating. These inorganic particles must be electrochemically stable (not subject to oxidation and / or reduction within the range of voltages used). In addition, the powdered inorganic material preferably has high ionic conductivity. Low density materials are preferred over high density materials, as they can reduce the weight of the battery produced. A dielectric constant of 5 or more is preferred. According to one embodiment, the inorganic particles are selected from the group consisting of BaTiO3, Pb(Zr,Ti)O3, Pb 1-x La x Zr y O3(0 <x<1、0<y<1)、PBMg3Nb 2 / 3 )3, PbTiO3, hafnia (HfO(HfO2)), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, Y2O3, boehmite (γ-AlO(OH)), Al2O3, TiO2, SiC, ZrO2, borosilicate, BaSO4, nanoclay or mixtures thereof. The coating for the separator may optionally contain 0% to 15% by weight, preferably 0.1% to 10% by weight, based on the polymer, of an additive selected from thickeners, pH adjusters, anti-settling agents, surfactants, wetting agents, fillers, defoamers and fugitive or non-fugitive adhesion promoters. The fillers in the additives referred to here are different from the inorganic particles described above.

[0108] According to another aspect of the present invention, there is provided a Li-ion battery. Preferably, the Li-ion battery comprises a positive electrode, a negative electrode and the separator according to the present invention. EXAMPLES

[0109] [Example 1] In a 50 ml reactor, 1.06 g of LiFSI is dissolved in 20 ml of acetonitrile at room temperature (22° C.). 1.5 ml of 1,8-diazabicyclo(5.4.0)undec-7-ene (2 equivalents relative to LiFSI-pKa, pKa of 13.5 in water at 25° C.) is added to this solution, the resulting mixture is stirred for 5 minutes, followed by the addition of 2.54 ml of 2-(trimethylsiloxy)ethyl methacrylate (2 equivalents relative to LiFSI). The reaction mixture is stirred for 24 hours at room temperature under ambient atmosphere. The acetonitrile is evaporated using a rotary evaporator at 30° C. and 1 mbar. The residue is mixed with petroleum ether to produce two phases. The upper phase containing lithium salt A and petroleum ether is separated and the petroleum ether is evaporated using a rotary evaporator at 30° C. and 1 mbar. The recovered product is the lithium salt of formula (IIIa) where A and B=H, V=CH3, W=O, X=O and Y is CH2CH2, and n=1. The conversion of LiFSI is 100%. The purity of the lithium salt is greater than 99%.

[0110] [Example 2] Example 1 is reproduced with 0.17 ml of 1,8-diazabicyclo(5.4.0)undec-7-ene (0.2 equivalents relative to LiFSI). The recovered product is the lithium salt of formula (IIIa) where A and B=H, V=CH3, W=O, X=O and Y are CH2CH2, and n=1. The conversion of LiFSI is 100%. The purity of the lithium salt is greater than 99%.

[0111] [Example 3] Example 1 is reproduced using 0.17 ml of 1,8-diazabicyclo(5.4.0)undec-7-ene (0.2 equivalents relative to LiFSI) and 2 molar equivalents of p-(trimethylsilyloxy)styrene. The recovered product is the lithium salt of formula (IIId) where A and B=H, V=H, and X=O. The conversion of LiFSI is 79%. The purity of the lithium salt is greater than 99%.

[0112] [Example 4] Example 1 is reproduced using 0.17 ml of 1,8-diazabicyclo(5.4.0)undec-7-ene (0.2 equivalents relative to LiFSI), 1 molar equivalent of p-(trimethylsilyloxy)styrene and 1 molar equivalent of 2-(trimethoxysilyl)ethyl methacrylate. The recovered products are lithium salts of formula (IIIg) where A and B=H, V=H, X=O, and A and B=H, V=CH3, W=O, X=O and Y is CH2CH2 and n=1. The conversion of LiFSI is 83%.

[0113] [Comparative Example 1] Example 1 is reproduced using 2.16 ml of triethylamine (2 equivalents relative to LiFSI). Triethylamine has a pKa of less than 11. The recovered product is the lithium salt of formula (IIIa) where A and B=H, V=CH3, W=O, X=O and Y is CH2CH2, and n=1. The conversion of LiFSI is 8%.

[0114] [Example 5] To polymerize the monomer according to the invention, the following procedure is followed: 3 g of water are introduced into a reactor equipped with a mixing and heating device. The temperature is set to 95° C. Over a period of 2 hours, 3 g of a mixture of the compound of formula (IIIa) and methacrylic acid (10 / 90 molar percent) and 0.4 g of sodium persulfate are introduced into 7 g of water. The temperature is maintained for 2 hours. The reactor is cooled to room temperature.

Claims

1. A method for preparing lithium salt A, comprising at least one -S(O) ２ - A lithium salt B containing an F group is subjected to the reaction of formula (I) R-O-SiR in the presence of catalyst D. １ R ２ R ３ When compound C is brought into contact with at least one group -S(O) ２ A method comprising step a) forming a mixture of products containing the lithium salt A containing -OR, wherein the catalyst D is a compound having a pKa greater than 11 as measured at 25°C.

2. The method according to claim 1, characterized in that the substituent R of compound C contains at least one carbon-carbon double bond.

3. The lithium salt B is of the formula LiN(S(O) ２ -F)(S(O) ２ R'), and the lithium salt A is of the formula (IV) LiN(S(O) ２ -OR)(S(O) ２ R') (wherein R' is a substituent selected from the group consisting of F, C １ to C ４ alkyl, C １ to C ４ perfluoroalkyl, C １ to C ４ alkoxy and C １ to C ４ perfluoroalkoxy, preferably a substituent selected from the group consisting of C １ to C ４ alkyl, C １ to C ４ perfluoroalkyl, C １ to C ４ alkoxy and C １ to C ４ perfluoroalkoxy). The method according to claim 1, characterized in that.

4. Two groups - S(O) ２ -In order to form lithium salt A containing OR, lithium salt B contains two -S(O) ２ The method according to claim 1, characterized by containing an F group.

5. The lithium salt B is Li-N(S(O) ２ -F) ２ The lithium salt A is of formula (III) Li-N(S(O) ２ -OR) ２ The method according to claim 1, characterized in that...

6. The aforementioned compound C is of formula (I) R-O-SiR １ R ２ R ３ (Base R) １ , R ２ and R ３ H and C are independent of each other. １ ~C １０ The method according to claim 1, characterized by being selected from the group consisting of alkyl groups.

7. The aforementioned compound C is of formula (I) R-O-SiR １ R ２ R ３ (wherein the formula R is the base R) ４ -X-(Y) ｎ - It is a thing, however, R ４ is a group containing at least one carbon-carbon double bond, where X is O, S and N (R ５ ) (Caution ５ is H or C １ ~C １０ A heteroatom selected from the group consisting of alkyl groups, where Y is C(R ６ ) (Caution ７ )-, C(R ６ ) (Caution ７ ) C (R ６ ) (Caution ７ )SC(R ６ ) (Caution ７ ) - and - [(O) ｚ (C(R ８ ) (Caution ９ )-C(R ８ ) (Caution ９ )O) ｍ -C(R ８ ) (Caution ９ ) C (R ８ ) (Caution ９ ) ] - ( R ６ and R ７ For each carbon atom and for each unit Y, H or F is independently selected, and R ８ And R9 is H, F, or CH for each carbon atom and for each unit Y. ３ The method according to claim 1, characterized in that it is independently selected from, m is an integer from 1 to 50, z = 0 when X is O, and n is an integer from 1 to 50.

8. group R ４ The method according to claim 1, characterized in that the formula is (Ia), (Ib), (Ic), or (Id). 【Chemistry 1】 [In the formula, A, B, and V may be independently substituted with H, F, Cl, Br, I, or one or more substituents R''. １ ~C １０ C, which may be substituted with alkyl or one or more substituents R''. ２ ~C １０ Alkenyl, one or more substituents R'' or one or more C'' １ ~C ５ C may be substituted with an alkyl group. ３ ~C １０ Cycloalkyl, one or more substituents R'' or one or more C'' １ ~C ５ C may be substituted with an alkyl group. ４ ~C １０ Cycloalkenyl, one or more substituents R'' or one or more C'' １ ~C ５ C may be substituted with an alkyl group. ６ ~C １２ Selected from the group consisting of aryls, W is selected from O and S, "R” is F, Cl, I, Br, C １ ~C ４ ether, C １ ~C ４ ester, C １ ~C ４ thioether and C １ ~C ４ thioester, preferably selected from the group consisting of F, C １ ~C ４ ether, C １ ~C ４ ester, C １ ~C ４ thioether and C １ ~C ４ thioester. ]

9. The catalyst D is N,N-diisopropylethylamine, 1,8-diazabicyclo(5.4.0)undeca-7-ene, 6-(dibutylamino)-1,8-diazabicyclo[5.4.0]undeca-7-ene, polystyrene-bonded 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca 5-ene, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, polystyrene-bonded 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1,4-diazabicyclo[2.2.2]octane, quinuclidine, 1,5-diazabicyclo(4.3.0)nona-5-ene, 2,6-di-tert-butylpyridine, 2,8,9-trimethyl-2,5,8,9- Tetraaza-1-phosphabicyclo[3.3.3]undecane, cyclodiphosphazan, lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF ２ KHF ２ The method according to claim 1, characterized in that it is selected from the group consisting of N,N'-diisopropylimidazonium, bifluoride, and tetrabutylammonium.

10. The method according to claim 1, comprising step b) purifying the lithium salt A, wherein step b) includes extracting the lithium salt A with a nonpolar organic solvent.

11. The method according to claim 1, characterized in that step a) is performed at a temperature of 10°C to 50°C.

12. Lithium salts of formulas (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc), or (IVd). 【Chemistry 2】 【change】 【change】 【change】 [In the formula, substituents A, B, V, and W are as defined in claim 8, substituents X and Y are as defined in claim 7, n is as defined in claim 7, and R' is as defined in claim 3.]

13. A and B are the same, and selected from the group consisting of H, F, Cl, Br, and I. V may be substituted with H, F, Cl, Br, I, or one or more substituents R''. １ ~C １０ C, which may be substituted with alkyl or one or more substituents R''. ２ ~C １０ Alkenyl, one or more substituents R'' or one or more C'' １ ~C ５ C may be substituted with an alkyl group. ３ ~C １０ Cycloalkyl, one or more substituents R'' or one or more C'' １ ~C ５ C may be substituted with an alkyl group. ４ ~C １０ Cycloalkenyl, one or more substituents R'' or one or more C'' １ ~C ５ C may be substituted with an alkyl group. ６ ~C １２ Aryl (where R'' is F, Cl, I, Br, C) １ ~C ４ Ether, C １ ~C ４ Ester, C １ ~C ４ Thioether, C １ ~C ４ Selected from the group consisting of thioesters, preferably V is H, F, Cl, Br, I, C １ ~C ５ Alkyl, C １ ~C ５ Perfluoroalkyl, C ６ R １０ ６ (R １０ H, F, and C １ ~C ５ Selected from the group consisting of (independently selected from alkyl), W is O, X is O, Y is CH ２ CH ２ ,CH ２ CF ２ CF ２ CF ２ ,CH ２ CHF, CF ２ CH ２ and CHFCH ２ A base selected from the group consisting of, and n is an integer from 1 to 25, or Y is the base - [(C(R ８ ) (Caution ９ )-C(R ８ ) (Caution ９ )O) ｍ -C(R ８ ) (Caution ９ ) C (R ８ ) (Caution ９ ) ] - ( R ８ and R ９ For each carbon atom and for each unit Y, H, F, or CH ３ (Selected independently from, where m is an integer from 1 to 25), and n is 1. R' is F, C １ ~C ４ Alkyl, C １ ~C ４ Perfluoroalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ Perfluoroalkoxy, preferably C １ ~C ４ Alkyl, C １ ~C ４ Perfluoroalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ A lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc), or (IVd) according to claim 12, wherein the substituent is selected from the group consisting of perfluoroalkoxys.

14. A and B are H, and V is CH ３ And W is O, X is O, and Y is CH ２ CH ２ ,CH ２ CF ２ CF ２ CF ２ ,CH ２ CHF, CF ２ CH ２ and CHFCH ２ A base selected from the group consisting of, and n is an integer from 1 to 10, or Y is the base - [(C(R ８ ) (Caution ９ )-C(R ８ ) (Caution ９ )O) ｍ -C(R ８ ) (Caution ９ ) C (R ８ ) (Caution ９ ) ] - ( R ８ and R ９ For each carbon atom and for each unit Y, H, F, or CH ３ (Selected independently from, where m is an integer from 1 to 25), and n is 1. R' is F, C １ ~C ４ Alkyl, C １ ~C ４ Perfluoroalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ A lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc), or (IVd) according to claim 12, wherein the substituent is selected from the group consisting of perfluoroalkoxys.

15. A and B are H, and V is CH ３ And W is O, X is O, and Y is CH ２ CH ２ ,CH ２ CF ２ CF ２ CF ２ ,CH ２ CHF, CF ２ CH ２ and CHFCH ２ A base selected from the group consisting of, and n is an integer from 1 to 10, or Y is the base - [(C(R ８ ) (Caution ９ )-C(R ８ ) (Caution ９ )O) ｍ -C(R ８ ) (Caution ９ ) C (R ８ ) (Caution ９ ) ] - ( R ８ and R ９ For each carbon atom and for each unit Y, H, F, or CH ３ A lithium salt of formula (IIIa) according to claim 12, wherein m is independently selected from (where m is an integer from 1 to 25) and n is 1.

16. A polymer comprising monomer units derived from at least one lithium salt of formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IVa), (IVb), (IVc), or (IVd) as described in claim 12.

17. Formula R １ R ２ C = C(R ３ ) A monomer unit obtained from monomer M1 of C(O)R (wherein substituent R is present in the formula) １ , R ２ and R ３ H and C are independent of each other. １ ~C ５ Selected from the group consisting of alkyl groups, R is -NHC(CH ３ ) ２ CH ２ C(O)CH ３ or -OR'(R' may be substituted with H and one or more -OH groups or a 5-membered or 10-membered heterocycle containing at least one nitrogen atom in its cyclic chain) １ ~C １８ The polymer according to claim 16, characterized in that it also includes (selected from the group consisting of alkyl groups).

18. Vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ether, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), formula CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ X (X is SO ２ F, CO ２ H, CH ２ OH, CH ２ OCN or CH ２ OPO ３ A monomer of H, formula CF ２ = CFOCF ２ CF ２ SO ２ Monomer of F, formula F(CF) ２ ) ｎ CH ２ OCF = CF ２ A monomer of formula R (where n is 1, 2, 3, 4, or 5). １ CH ２ OCF = CF ２ (R １ is hydrogen or F(CF) ２ ) ｍ A monomer of formula R (where m is 1, 2, 3, or 4), where m is 1, 2, 3, or 4. ２ OCF=CH ２ (R ２ is F(CF ２ ) ｐ The polymer according to claim 16, characterized in that it contains monomer units derived from monomer M2 selected from the group consisting of monomers (where p is 1, 2, 3 or 4), perfluorobutylethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, or 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

19. A coating for an electrode binder or separator comprising the polymer according to any one of claims 16 to 18.

20. An electrode or separator comprising the polymer according to any one of claims 16 to 18.

21. A battery comprising the electrode or the separator according to claim 20, preferably a lithium-ion battery.

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