Fluoropolymer Hybrid Composites

Abstract

The present invention relates to a method for producing a polymer electrolyte based on a fluoropolymer hybrid organic / inorganic composite material, to the polymer electrolyte obtained therefrom, and to the use of said polymer electrolyte and membranes obtained therefrom in various applications, in particular in electrochemical and photoelectrochemical applications.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to European Patent Application No. 18306704.0, filed December 17, 2018, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a method for producing a polymer electrolyte based on a fluoropolymer hybrid organic / inorganic composite material, to the polymer electrolyte obtained therefrom, and to the use of said polymer electrolyte and membranes obtained therefrom in various applications, in particular in electrochemical and photoelectrochemical applications. [Background technology]

[0003] Organic-inorganic polymer hybrids, in which inorganic solids are dispersed in organic polymers at the nano- or molecular level, have attracted considerable scientific, technological and industrial interest due to their unique properties.

[0004] To create organic-inorganic polymer hybrid composites, the sol-gel method using metal alkoxides is the most useful and important approach.

[0005] By appropriately controlling the reaction conditions for the hydrolysis and polycondensation of metal alkoxides, especially alkoxysilanes (e.g., tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS)), in the presence of preformed organic polymers, it is possible to obtain hybrids with improved properties compared to the parent compounds. The polymer can improve the toughness and processability of otherwise brittle inorganic materials, while the inorganic network can improve the scratch resistance, mechanical properties, and surface properties of the hybrids.

[0006] Hybrids made by sol-gel techniques starting from fluoropolymers, in particular vinylidene fluoride polymers, are known in the art.

[0007] For example, WO 2011 / 121078 describes a method for producing a fluoropolymer hybrid organic-inorganic composite material, in which at least a portion of the hydroxyl groups of the fluoropolymer are reacted in solution or in the melt with a compound of formula X 4-m AY m (X is a hydrocarbon group, Y is a hydrolyzable group, A is a metal selected from Si, Ti, and Zr, and m is an integer of 1 to 4) is reacted with at least a portion of the hydrolyzable group of a metal compound. This patent document also states that a film made of the hybrid organic / inorganic composite material is then swollen with an electrolyte solution containing a solvent (a mixture of ethylene carbonate and propylene carbonate) and an electrolyte (LiPF6). Nevertheless, once the film is cast, it is not an easy task to swell it again with the electrolyte solution, and as a result, the final amount of electrolyte solution actually permeating the separator is relatively low, and as a result, the ionic conductivity is also relatively low.

[0008] In the face of the above drawbacks, WO 2013 / 160240 discloses the preparation of a fluoropolymer hybrid organic / inorganic composite in the presence of a liquid medium to provide a free-standing fluoropolymer film that stably contains and retains the liquid medium and has outstanding ionic conductivity. When the hybrid organic / inorganic composite is for use as a polymer electrolyte separator in electrochemical and photoelectrochemical devices, it comprises a fluoropolymer, a polymer of formula X 4-m AY m The resulting liquid mixture can be then processed into a film by casting.

[0009] Unfortunately, the preparation of films by casting techniques requires the use of organic solvents such as NMP, DMA and the like, which is undesirable in industrial production processes.

[0010] WO 2014 / 067816 discloses a method for preparing a fluoropolymer hybrid organic / inorganic composite by a process comprising forming an aqueous solution of a pregelled metal compound and reacting it with a functional fluoropolymer. The composite is typically obtained in the form of pellets that can be processed into a film by extrusion or compression techniques.

[0011] One drawback of the fluoropolymer films obtained according to this method is that the distribution of atoms in the film is not homogeneous.

[0012] Applicants have now surprisingly found that it is possible to prepare polymer electrolytes based on hybrid organic / inorganic composite materials that exhibit outstanding ionic conductivity, and that said polymer electrolytes can also be suitably processed into films with improved atomic homogeneity by a method that does not involve solvent casting, with the additional advantage of avoiding the use of said solvents and their subsequent recovery and disposal. Summary of the Invention

[0013] Accordingly, there is provided a method for preparing a polymer electrolyte based on a fluoropolymer hybrid organic / inorganic composite material, said method comprising the steps of: (i) Formula: X 4-m AY m (wherein m is an integer of 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, Y is a hydrolyzable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, and X is a hydrocarbon group optionally containing one or more functional groups). a metal compound [compound (M)] having the formula: - an electrolyte solution [solution (ES)] comprising at least one metal salt [metal salt (S)] and a liquid medium [medium (L)]; - at least one acid catalyst; and optionally, an aqueous medium [medium (A)] in the presence of a pregelled metal compound [compound (P-GM)] obtained by partial hydrolysis and / or polycondensation (The pregelling metal compound [compound (P-GM)] contains one or more inorganic domains consisting of ≡AOA≡ bonds and one or more residual hydrolyzable groups Y.) providing a composition comprising: (ii) reacting at least a portion of the hydroxyl groups of a functional fluoropolymer [polymer (F)] containing at least one hydroxyl group in the molten state with at least a portion of the hydrolyzable groups Y of said compound (P-GM) to obtain a polymer electrolyte comprising a fluoropolymer hybrid organic / inorganic composite material incorporating an electrolyte solution (ES); is an object of the present invention.

[0014] In a second object, the present invention provides a composition comprising a pregelling metal compound [compound (P-GM)], said composition being obtained according to step (i) of the method as defined above.

[0015] In a third object, the present invention relates to a method for producing a membrane for an electrochemical device, comprising processing the polymer electrolyte obtained by the method of the present invention by compression molding or extrusion techniques.

[0016] A further object of the present invention is therefore a polyelectrolyte obtainable by a process as defined above.

[0017] The polymer electrolyte membranes of the present invention are endowed with high conductivity and homogeneity of atomic distribution throughout their structure, despite being obtained by a process that does not involve casting a solution of polymer in a solvent, thus avoiding significant variations in surface composition and creating predictable and efficient ion transport pathways. DETAILED DESCRIPTION OF THE INVENTION

[0018] By the term "pregelling metal compound (P-GM)" is intended herein to mean a metal compound (M) that can gel to provide a polymer electrolyte when reacted with a functional fluoropolymer containing at least one hydroxyl group, which has been subjected to partial hydrolysis and / or polycondensation in the presence of an electrolyte solution and an acid catalyst.

[0019] formula 4-m AY m The metal compound [compound (M)] may contain one or more functional groups on either group X or group Y, preferably on at least one group X.

[0020] If compound (M) contains at least one functional group, it is referred to as a functionalized compound (M); if neither the X nor the Y group contains a functional group, compound (M) is referred to as a non-functionalized compound (M).

[0021] The functional compound (M) can advantageously provide the fluoropolymer hybrid organic / inorganic composite with functional groups, thus further modifying the chemistry and properties of the hybrid composite over the original polymer (F) and the original inorganic phase.

[0022] Non-limiting examples of functional groups include epoxy groups, carboxylic acid groups (in their acid, ester, amide, anhydride, salt or halide form), sulfonic acid groups (in their acid, ester, salt or halide form), hydroxyl groups, phosphate groups (in their acid, ester, salt or halide form), thiol groups, amine groups, quaternary ammonium groups, ethylenically unsaturated groups (such as vinyl groups), cyano groups, urea groups, organosilane groups, aromatic groups.

[0023] For the purpose of obtaining a polymer electrolyte based on a fluoropolymer hybrid organic / inorganic composite material having functional groups, it is advantageous to select a compound of formula X such that each A atom, after complete hydrolysis and / or polycondensation in step (i) of the method, is nevertheless bound to a group containing a functional group. 4-m AY mIt is generally preferred that any of the groups X in compound (M) contains one or more functional groups, and that m is an integer from 1 to 3.

[0024] Preferably, X in compound (M) is a C1-C aryl group optionally containing one or more functional groups. 18 More preferably, X in compound (M) is a C1-C hydrocarbon group, optionally containing one or more functional groups. 12 It is a hydrocarbon group.

[0025] For the purpose of producing polymer electrolytes based on fluoropolymer hybrid organic / inorganic composites capable of exhibiting functional behavior in terms of hydrophobicity or ion conductivity, the functional groups of compound (M) are preferably selected from among carboxylic acid groups (in their acid, anhydride, salt or halide form), sulfonic acid groups (in their acid, salt or halide form), phosphoric acid groups (in their acid, salt or halide form), amine groups and quaternary ammonium groups; carboxylic acid groups (in their acid, anhydride, salt or halide form) and sulfonic acid groups (in their acid, salt or halide form) will be most preferred.

[0026] The choice of hydrolyzable group Y of compound (M) is not particularly limited, provided that it allows the formation of an -OA≡ bond under appropriate conditions; said hydrolyzable group can be, inter alia, a halogen (especially a chlorine atom), a hydrocarboxy group, an acryloxy group or a hydroxyl group.

[0027] Examples of functional compounds (M) are, inter alia, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrismethoxyethoxysilane of formula CH2=CHSi(OC2H4OCH3)3, vinyltrismethoxyethoxysilane of formula: TIFF0007779735000001.tif26170 2-(3,4-epoxycyclohexylethyltrimethoxysilane), formula: TIFF0007779735000002.tif26170 Glycidoxypropylmethyldiethoxysilane, formula: TIFF0007779735000003.tif26170 Glycidoxypropyltrimethoxysilane, formula: Methacryloxypropyltrimethoxysilane of TIFF0007779735000004.tif20170, formula: TIFF0007779735000005.tif22170 aminoethylaminepropylmethyldimethoxysilane, formula: H2NC2H4NHC3H6Si(OCH3)3 aminoethylaminepropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-chloroisobutyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, n-(3-acryloxy2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, 3-(n-allylamino)propyltrimethoxysilane, 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane, carboxyethylsilanetriol, and sodium salts thereof of the formula: TIFF0007779735000006.tif22170 triethoxysilylpropylmaleamic acid, 3-(trihydroxysilyl)-1-propane-sulfonic acid of formula HOSO2-CH2CH2CH2-Si(OH)3, N-(trimethoxysilylpropyl)ethylene-diaminetriacetic acid, and its sodium salt, of formula: TIFF0007779735000007.tif33170 3-(triethoxysilyl)propylsuccinic anhydride, acetamidopropyltrimethoxysilane, of formula H3C-C(O)NH-CH2CH2CH2-Si(OCH3)3, of formula Ti(A) X (OR) Y where A is an amine-substituted alkoxy group, such as OCH2CH2NH2, R is an alkyl group, and x and y are integers such that x+y=4.

[0028] Examples of non-functional compounds (M) are, inter alia, triethoxysilane, trimethoxysilane, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, tetra Ethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, and tetra-n-stearyl zirconate.

[0029] By the term "metal salt (S)" it is intended herein to mean a metal salt containing a conductive ion.

[0030] A variety of metal salts can be used as the metal salt (S). Metal salts that are stable and soluble in the selected liquid medium (L) are generally used.

[0031] Non-limiting examples of suitable metal salts (S) include, among others, MeI, Me(PF6), n , Me(BF4) n , Me(ClO4) n , Me(bis(oxalato)borate) n ("Me(BOB) n ”), MeCF3SO3, Me[N(CF3SO2)2] n , Me[N(C2F5SO2)2] n , R F Me[N(CF3SO2)(R F SO2)] n , Me(AsF6) n , Me[C(CF3SO2)3] n, Me2S n wherein Me is a metal, preferably a transition metal, alkali metal or alkaline earth metal, more preferably Li, Na, K or Cs, and n is the valence of the metal, typically n is 1 or 2.

[0032] Preferred metal salts (S) are the following: LiI, LiPF, LiBF, LiClO, lithium bis(oxalato)borate ("LiBOB"), LiCF, SO, LiN(CFSO) ("LiTFSI"), LiN(CSO), R F M[N(CF3SO2)(R F SO2)] n , LiAsF6, LiC(CF3SO2)3, Li2S n and combinations thereof.

[0033] The medium (L) in the electrolyte solution (ES) typically comprises at least one ionic liquid (IL), preferably consisting of an ionic liquid. For the purposes of the present invention, the term "ionic liquid" is intended to mean a compound formed by the combination of positively charged cations and negatively charged anions in the liquid state at atmospheric pressure and at temperatures below 100°C.

[0034] Ionic liquids (ILs) are typically protic ionic liquids (ILs) p ) and aprotic ionic liquids (IL a ) is selected.

[0035] The term "protic ionic liquid (IL)" p )" to make the cation more than one H + It is intended herein to mean an ionic liquid that contains hydrogen ions.

[0036] One or more Hs +Non-limiting examples of cations containing hydrogen ions include, among others, imidazolium, pyridinium, pyrrolidinium, or piperidinium rings, where the positively charged nitrogen atom is H + It is bonded to a hydrogen ion.

[0037] The term "aprotic ionic liquid (IL)" a )" to make the cation H + It is intended herein to mean an ionic liquid that does not contain hydrogen ions.

[0038] The liquid medium typically consists essentially of at least one ionic liquid (IL) and, optionally, at least one additive (A), wherein said ionic liquid (IL) is a protic ionic liquid (IL p ), aprotic ionic liquids (IL a ) and mixtures thereof.

[0039] Ionic liquids (ILs) are typically chosen from those containing as cations a sulfonium ion or an imidazolium, pyridinium, pyrrolidium or piperidium ring, said rings optionally substituted on the nitrogen atom by one or more alkyl groups, especially having 1 to 8 carbon atoms, and substituted on the carbon atoms by one or more alkyl groups, especially having 1 to 30 carbon atoms.

[0040] Within the meaning of the present invention, the term "alkyl group" means a saturated hydrocarbon chain or group having one or more double bonds and containing 1 to 30 carbon atoms, advantageously 1 to 18 carbon atoms, and even more advantageously 1 to 8 carbon atoms. Examples that may be mentioned include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, 2,2-dimethylpropyl, hexyl, 2,3-dimethyl-2-butyl, heptyl, 2,2-dimethyl-3-pentyl, 2-methyl-2-hexyl, octyl, 4-methyl-3-heptyl, nonyl, decyl, undecyl and dodecyl groups.

[0041] In an advantageous embodiment of the invention, the cation of the ionic liquid (IL) is: - a pyrrolidinium ring of formula (III) herein: TIFF0007779735000008.tif39170 (wherein R1 and R2 each independently represent an alkyl group having 1 to 8 carbon atoms, and R3, R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms), and - a piperidinium ring of formula (IV) herein: TIFF0007779735000009.tif46170 (wherein R1 and R2 each independently represent an alkyl group having 1 to 8 carbon atoms, and R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, and even more preferably 1 to 8 carbon atoms). is selected from.

[0042] In a particularly advantageous embodiment of the invention, the cation of the ionic liquid (IL) is: Selected from TIFF0007779735000010.tif81170.

[0043] The ionic liquid (IL) is advantageously chosen from those containing as anion one selected from halide anions, perfluorinated anions and borates.

[0044] The halide anion is in particular chosen from the following anions: chloride, bromide, fluoride or iodide.

[0045] In a particularly advantageous embodiment of the invention, the anion of the ionic liquid (IL) is: bis(trifluoromethylsulfonyl)imides of the formula (SOCF)N-, hexafluorophosphate of the formula PF6-, tetrafluoroborates of the formula BF4-, and - Formula: TIFF0007779735000011.tif39170 oxaloborates.

[0046] The medium (L) in the electrolyte solution (ES) may further comprise one or more additives.

[0047] When one or more additives are present in the liquid medium, non-limiting examples of suitable additives include, among others, those that are soluble in the liquid medium.

[0048] In a preferred embodiment, the electrolyte solution (ES) consists of LiTFSI and at least one ionic liquid (IL).

[0049] The concentration of LiTFSI in the medium (L) in the electrolyte solution (ES) is advantageously at least 0.01M, preferably at least 0.025M, more preferably at least 0.05M.

[0050] The concentration of LiTFSI in the medium (L) in the electrolyte solution (ES) is advantageously at most 3M, preferably at most 2M, more preferably at most 1M.

[0051] The choice of acid catalyst is not particularly limited, and is typically selected from the group consisting of organic acids and inorganic acids.

[0052] The acid catalyst is preferably selected from the group consisting of organic acids.

[0053] Very good results have been obtained with citric acid and with formic acid.

[0054] Those skilled in the art will recognize that the amount of acid catalyst used in step (i) will depend strongly on the identity of the acid catalyst itself.

[0055] The amount of acid catalyst used in step (i) of the process of the invention may therefore advantageously be of at least 0.1% by weight, based on the total weight of metal compounds (M).

[0056] The amount of acid catalyst used in step (i) of the process of the invention is advantageously at most 40% by weight, preferably at most 30% by weight, based on the total weight of metal compounds (M).

[0057] In step (i) of the process of the present invention, the metal compound (M) may optionally be partially hydrolyzed and / or polycondensed in the presence of an aqueous medium [medium (A)].

[0058] By the term "aqueous medium" it is intended herein to mean a liquid medium comprising water in the liquid state at 20°C under atmospheric pressure.

[0059] The aqueous medium (A) more preferably consists of water and one or more alcohols. The alcohol contained in the medium (A) is preferably ethanol.

[0060] The amount of metal compound (M) used in step (i) of the process of the invention is such that the reaction mixture of step (i) comprises advantageously at least 20% by weight, preferably at least 25% by weight, more preferably at least 30% by weight of said metal compound (M), based on the total weight of metal compound (M) and electrolyte solution (ES) in said mixture.

[0061] In one embodiment of the present invention, step (i) of the process is carried out in the presence of an aqueous medium [medium (A)] comprising, preferably consisting of, water and one or more alcohols.

[0062] The amount of medium (A) in the composition provided in step (i) of the method of the present invention is not particularly critical.

[0063] In a preferred embodiment, the amount of water in medium (A) is such that it represents 8 to 10% by weight of the composition provided in step (i) of the process, while the amount of one or more alcohols in medium (A) is such that it represents 6 to 7% by weight of the composition provided in step (i) of the process.

[0064] In step (i) of the process of the present invention, the hydrolysis and / or polycondensation of the metal compound (M) as defined above is usually carried out at room temperature or by heating at a temperature below 100° C. Temperatures between 20° C. and 90° C., preferably between 20° C. and 70° C., will be preferred.

[0065] It is understood that in this step (i) of the process of the present invention, the hydrolyzable groups Y of the metal compound (M) as defined above partially hydrolyze and / or polycondense in the presence of an aqueous medium to produce a pregelled metal compound [compound (P-GM)] comprising an inorganic domain consisting of an ≡AOA≡ bond and one or more residual hydrolyzable groups Y.

[0066] In step (i) of the method of the present invention, the composition comprising compound (P-GM) comprises the following components as defined above, preferably in the order shown herein below: - Electrolyte solution [solution (ES)], - Metal compound [compound (M)], at least one acid catalyst, and optionally, an aqueous medium [medium (A)] to a reaction vessel.

[0067] As will be appreciated by those skilled in the art, the hydrolysis and / or polycondensation reactions usually produce low molecular weight by-products which may be, inter alia, water or alcohols, depending on the identity of the metal compound (M) as defined above.

[0068] The composition thus obtained containing the pregelled metal compound [compound (P-GM)] therefore typically further contains, as low molecular weight by-products, one or more alcohols which are generally produced by hydrolysis and / or polycondensation of the metal compound (M) as defined above.

[0069] The electrolyte solution (ES) is typically prepared by dissolving a metal salt (S) in a liquid medium (L) to provide an electrolyte solution, wherein the concentration of the salt is advantageously at least 0.01 M, preferably at least 0.025 M, more preferably at least 0.05 M, and at most 1 M, preferably 0.75 M, more preferably 0.5 M.

[0070] In a second object, the present invention provides a composition comprising a pregelling metal compound [compound (P-GM)], said composition being obtained according to step (i) of the method as defined above.

[0071] In step (ii) of the process of the present invention, the compound (P-GM) is reacted in the molten state with the functional fluoropolymer [polymer (F)].

[0072] By the term "functional fluoropolymer comprising at least one hydroxyl group [polymer (F)]" it is intended herein to mean a fluoropolymer comprising repeating units derived from at least one fluorinated monomer and at least one comonomer comprising at least one hydroxyl group [comonomer (MA)].

[0073] The term "at least one comonomer (MA)" is understood to mean that the polymer (F) may comprise repeat units derived from one or more comonomers (MA) as defined above. In the remainder of the text, the expressions "comonomers (MA)" are understood for the purposes of the present invention both in the plural and in the singular, i.e., they refer to both one or more comonomers as defined above.

[0074] The comonomer (MA) may be selected from the group consisting of fluorinated monomers containing at least one hydroxyl group and hydrogen-containing monomers containing at least one hydroxyl group.

[0075] The term "at least one fluorinated monomer" is understood to mean that the polymer (F) may comprise repeat units derived from one or more fluorinated monomers. In the remainder of the text, the expressions "fluorinated monomers" are understood for the purposes of the present invention both in the plural and in the singular, i.e., they refer to both one or more fluorinated monomers as defined above.

[0076] By the term "fluorinated monomer" it is intended herein to mean an ethylenically unsaturated monomer containing at least one fluorine atom.

[0077] By the term "hydrogen-containing monomer" it is intended herein to mean an ethylenically unsaturated monomer which contains at least one hydrogen atom and which does not contain any fluorine atoms.

[0078] The polymer (F) preferably comprises at least 0.01 mol %, more preferably at least 0.05 mol %, even more preferably at least 0.1 mol % of repeat units derived from at least one comonomer (MA) as defined above.

[0079] The polymer (F) preferably comprises at most 20 mol %, more preferably at most 15 mol %, even more preferably at most 10 mol %, and most preferably at most 3 mol % of repeat units derived from at least one comonomer (MA) as defined above.

[0080] The average molar percentage of comonomer (MA) repeat units in polymer (F) can be determined by any suitable method, notably NMR.

[0081] The comonomer (MA) is typically selected from the group consisting of hydrogen-containing monomers containing at least one hydroxyl group.

[0082] The comonomer (MA) is preferably a (meth)acrylic monomer of formula (I) or a vinyl ether monomer of formula (II) TIFF0007779735000012.tif56170 (wherein R1, R2 and R3, which are equal to or different from each other, are independently a hydrogen atom or a C1-C3 hydrocarbon group; R OH is a C1-C5 hydrocarbon moiety containing a hydrogen atom or at least one hydroxyl group) is selected from the group consisting of:

[0083] The comonomer (MA) is even more preferably of formula (IA): TIFF0007779735000013.tif36170 (wherein R'1, R'2 and R'3 are hydrogen atoms, and R' OH is a C1-C5 hydrocarbon moiety containing at least one hydroxyl group) Follow.

[0084] Non-limiting examples of suitable comonomers (MA) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethylhexyl (meth)acrylate, among others.

[0085] The comonomer (MA) is more preferably: - expression Hydroxyethyl acrylate (HEA) from TIFF0007779735000014.tif27170; - Formula: TIFF0007779735000015.tif36170 either 2-hydroxypropyl acrylate (HPA), and mixtures thereof is selected among.

[0086] The comonomer (MA) is even more preferably HPA and / or HEA.

[0087] The polymer (F) may be amorphous or semi-crystalline.

[0088] The term "amorphous" is intended herein to mean a polymer (F) having a heat of fusion of less than 5 J / g, preferably less than 3 J / g, more preferably less than 2 J / g, as measured according to ASTM D-3418-08.

[0089] The term "semi-crystalline" is intended herein to mean a polymer (F) having a heat of fusion, measured according to ASTM D3418-08, of 10 to 90 J / g, preferably of 30 to 60 J / g, more preferably of 35 to 55 J / g.

[0090] The polymer (F) is preferably semi-crystalline.

[0091] The polymer (F) has in particular an intrinsic viscosity, measured in N,N-dimethylformamide at 25° C., comprised between 0.03 and 0.20 l / g, preferably between 0.03 and 0.15 l / g and more preferably between 0.08 and 0.12 l / g.

[0092] Non-limiting examples of suitable fluorinated monomers include, among others: - C3-C8 perfluoroolefins, such as tetrafluoroethylene and hexafluoropropene; - C2-C8 hydrogen-containing fluoroolefins such as vinylidene fluoride, vinyl fluoride, 1,2-difluoroethylene and trifluoroethylene; - Formula CH2=CH-R f0 (In the formula, R f0 is a C1-C6 perfluoroalkyl); - chloro- and / or bromo- and / or iodo-C2-C6 fluoroolefins, such as chlorotrifluoroethylene; - Formula CF2=CFOR f1 (In the formula, R f1 is C1-C6 fluoro- or perfluoroalkyl, for example, CF3, C2F5, C3F7), (per)fluoroalkyl vinyl ethers according to CF2=CFOX0(per)fluoro-oxyalkyl vinyl ether (wherein X0 is C1-C 12 Alkyl or C1-C 12 C1-C with one or more ether groups, such as oxyalkyl or perfluoro-2-propoxy-propyl 12 (per)fluorooxyalkyl); - Formula CF2=CFOCF2OR f2 (In the formula, R f2 is a C1-C6 fluoro- or perfluoroalkyl, for example a C1-C6 (per)fluorooxyalkyl having one or more ether groups, such as CF3, C2F5, C3F7 or -C2F5-O-CF3), (per)fluoroalkyl vinyl ethers according to Formula CF2 = CFOY0 (wherein Y0 is C1 to C 12 Alkyl or (per)fluoroalkyl, or C1-C 12 oxyalkyl, or (per)fluorooxyalkyl having one or more ether groups, and Y0 contains a carboxylic or sulfonic acid group in its acid, acid halide or salt form); functional (per)fluoro-oxyalkyl vinyl ethers according to - Fluorodioxoles, especially perfluorodioxoles Examples include:

[0093] Non-limiting examples of suitable hydrogen-containing monomers include, among others, non-fluorinated monomers such as ethylene, propylene, vinyl monomers such as vinyl acetate, acrylic monomers such as methyl methacrylate, butyl acrylate, and styrenic monomers such as styrene and p-methylstyrene.

[0094] Polymer (F) preferably comprises more than 25 mol %, preferably more than 30 mol %, more preferably more than 40 mol % of repeat units derived from at least one fluorinated monomer.

[0095] Polymer (F) preferably comprises more than 1 mol %, preferably more than 5 mol %, more preferably more than 10 mol % of repeat units derived from at least one hydrogen-containing monomer different from comonomer (MA).

[0096] The fluorinated monomer may further contain one or more other halogen atoms (Cl, Br, I). If the fluorinated monomer does not contain a hydrogen atom, it is called a per(halo)fluoromonomer. If the fluorinated monomer contains at least one hydrogen atom, it is called a hydrogen-containing fluorinated monomer.

[0097] When the fluorinated monomer is a hydrogen-containing fluorinated monomer, such as vinylidene fluoride, trifluoroethylene, vinyl fluoride, etc., the hydrogen-containing fluoropolymer of the present invention can be a polymer comprising repeating units derived from said hydrogen-containing fluorinated monomer alone, in addition to repeating units derived from at least one comonomer (MA) as defined above, or it can be a copolymer comprising repeating units derived from at least one comonomer (MA) as defined above, said hydrogen-containing fluorinated monomer, and at least one other monomer.

[0098] When the fluorinated monomer is a per(halo)fluoromonomer, such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, etc., the hydrogen-containing fluoropolymer of the present invention is a polymer comprising repeating units derived from at least one comonomer (MA) as defined above, repeating units derived from said per(halo)fluoromonomer, and repeating units derived from at least one other hydrogen-containing monomer different from said comonomer (MA), such as ethylene, propylene, vinyl ether, acrylic monomer, etc.

[0099] Preferred polymers (F) are those in which the fluorinated monomer is selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), hexafluoropropene (HFP) and chlorotrifluoroethylene (CTFE).

[0100] The polymer (F) is preferably: (a) at least 60 mol%, preferably at least 75 mol%, more preferably at least 85 mol% vinylidene fluoride (VDF); (b) optionally, 0.1 mol % to 15 mol %, preferably 0.1 mol % to 12 mol %, more preferably 0.1 mol % to 10 mol % of a fluorinated comonomer selected from chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), perfluoromethyl vinyl ether (PMVE), and mixtures thereof; (c) 0.05 mol % to 10 mol %, preferably 0.1 mol % to 7.5 mol %, more preferably 0.2 mol % to 3.0 mol % of a comonomer (MA) having formula (I) as defined above; Includes.

[0101] In step (ii) of the method of the present invention, the functional fluoropolymer [polymer (F)] and the mixture containing the pregelling metal compound [compound (P-GM)] are reacted in the molten state, typically at a temperature of 100°C to 300°C, preferably 150°C to 250°C, depending on the melting point of polymer (F).

[0102] It is understood that in this step (ii) of the method of the present invention, at least a portion of the hydroxyl groups of the functionalized fluoropolymer [polymer (F)] and at least a portion of the residual hydrolyzable groups Y of the pregelled metal compound [compound (P-GM)] react to produce a fluoropolymer hybrid composite consisting of organic domains consisting of chains of polymer (F) and inorganic domains consisting of ≡AOA≡ bonds, thus providing a polymer electrolyte comprising a fluoropolymer hybrid organic / inorganic composite already comprising the electrolyte solution (ES).

[0103] The fluoropolymer hybrid organic / inorganic composite material contained in the polyelectrolyte obtained from the process of the invention advantageously contains 0.01 to 60% by weight, preferably 0.1 to 40% by weight, of inorganic domains consisting of ≡AOA≡ bonds.

[0104] In step (ii) of the method of the present invention, the polymer (F) and the composition comprising the pregelling metal compound [compound (P-GM)] are reacted in the molten state, typically using melt processing techniques.

[0105] The preferred melt processing technique used in step (ii) of the present process is extrusion, generally at temperatures comprised between 100°C and 300°C, preferably between 150°C and 250°C.

[0106] The reaction in step (ii) of the process of the present invention is typically carried out in a twin-screw extruder, with excess heat of reaction generally being dissipated through the barrel wall.

[0107] The polymer (F) is preferably fed to the twin-screw extruder in an amount of 15% by weight to 99.99% by weight, preferably 20% by weight to 50% by weight, based on the total weight of the polymer (F) and the composition containing the pregelling metal compound [compound (P-GM)].

[0108] The polymer electrolytes obtained by the methods of the present invention can be conveniently processed into membranes, typically by extrusion or by compression molding.

[0109] For the purposes of the present invention, the term "membrane" is intended to mean a discrete, generally thin, interface that restricts the permeation of chemical species in contact with it. This interface may be homogeneous, i.e., completely uniform in structure (dense membrane), or it may be chemically or physically heterogeneous, for example, containing voids, pores, or holes of finite dimensions (porous membrane).

[0110] In a third object, the present invention relates to a method for producing a membrane for an electrochemical device, comprising processing the polymer electrolyte obtained by the method of the present invention by traditional compression molding or extrusion techniques.

[0111] In one preferred embodiment of the present invention, step (ii) of the process is carried out in an extruder and the polyelectrolyte obtained at the end of the reaction in the molten state is directly processed into a membrane by film extrusion using an extruder equipped with a flat die.

[0112] A further object of the present invention is therefore a polymer electrolyte membrane obtainable by a method as defined above.

[0113] The membrane of the present invention typically has a thickness comprised between 5 μm and 500 μm, preferably between 10 μm and 250 μm, more preferably between 15 μm and 50 μm.

[0114] The polymer electrolyte membranes of the present invention can be advantageously used as polymer electrolyte separators in electrochemical and photoelectrochemical devices.

[0115] Non-limiting examples of suitable electrochemical devices include, inter alia, secondary batteries, particularly lithium-ion batteries and lithium-sulfur batteries, and capacitors, particularly lithium-ion capacitors.

[0116] The present invention further relates to a metal-ion secondary battery comprising the polymer electrolyte membrane of the present invention as defined above as a polymer electrolyte separator.

[0117] Metal-ion secondary batteries are generally formed by assembling a negative electrode (cathode) and a positive electrode (anode) with the polymer electrolyte membrane of the present invention as defined above.

[0118] The metal ion secondary battery is preferably an alkaline or alkaline earth secondary battery, more preferably a lithium ion secondary battery.

[0119] Non-limiting examples of suitable photoelectrochemical devices include dye-sensitized solar cells, photochromic devices, and electrochromic devices, among others.

[0120] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that the term may be unclear, the statements of this application shall control.

[0121] The present invention will now be described with reference to the following examples, the purpose of which is merely illustrative and not limiting.

[0122] raw materials Polymer FA: VDF / HEA copolymer containing 0.7 mol % hydroxyethyl acrylate (HEA). Polymer FB: VDF / HEA (0.4 mol%) / HFP (2.5 mol%) copolymer with an intrinsic viscosity of 0.11 l / g in DMF at 25°C. Tetraethyl orthosilicate (TEOS) >99% purity, commercially available as a liquid from Aldrich Chemistry. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic liquid (IL): Formula: TIFF0007779735000016.tif36170 N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr13TFSI). Citric acid: commercially available as crystals from Sigma Aldrich, 99% purity. ES: 0.5M LiTFSI in Pyr13TFSI.

[0123] Measurement of ionic conductivity (σ) The polymer electrolyte membrane is placed in a ½ inch stainless steel Swagelok cell prototype. The resistance of the polymer electrolyte membrane is measured at 25° C. and the ionic conductivity (σ) is calculated using the following equation: TIFF0007779735000017.tif16170 (where d is the film thickness and R b is the bulk resistance and S is the area of ​​the stainless steel electrode) was obtained using

[0124] Measurement of intrinsic viscosity of polymer (F) (DMF at 25°C) The intrinsic viscosity [η] (dl / g) was measured using an Ubbelhode viscometer by dissolving the polymer (F) in dimethylformamide at a concentration of about 0.2 g / dl at 25°C, based on the dropwise addition time, according to the following equation: TIFF0007779735000018.tif16170 (where c is the polymer concentration in g / dl; ηr is the relative viscosity, i.e., the ratio between the dropping time of the sample solution and the dropping time of the solvent; η sp is the specific viscosity, i.e., η r -1; Γ is an empirical factor, which is equal to 3 for polymer (F). was determined using

[0125] Measurement of SiO2 content in fluoropolymer hybrid organic / inorganic composites The amount of SiO2 in the fluoropolymer hybrid organic / inorganic composites was measured by energy dispersive spectroscopy (EDS) analysis of silicon (Si) and fluorine (F) elements on micrographs obtained from scanning electron microscopy (SEM). The SiO2 content was determined by using the following equation (1): SiO2[%]=[[SiO2] / ([SiO2]+[F])]×100 (1). where [SiO2] and [F] in equation (1) are respectively expressed by the following equations (2) and (3): [SiO2]=([Si EDS ]×60) / 28) (2) [F]=([F EDS ]×64) / 38) (3) (In the formula: -Si EDS and F EDS are the wt% of Si and F obtained by EDS, - 60 is the molecular weight of SiO2, - 28 is the atomic weight of Si, - 64 is the molecular weight of CH2=CF2, - 38 is the atomic weight of two F atoms) Calculate using:

[0126] Measurement of film morphology by SEM-EDS The morphology of the membrane specimens was investigated using a LEO-1450VP Scanning Electron Microscope (beam voltage: 20 kV; working distance: 15 mm). Cross sections of membrane specimens obtained by brittle fracture in liquid nitrogen were attached to stubs with conductive adhesive tape and sputtered with gold. Elemental analysis (EDS) was performed using an X-ray probe (INCA Energy Oxford, Cu-Kα X-ray source, k = 1.540562 Å). EDS analysis was performed on approximately 20 × 20 μm sections. 2 The area was measured at a magnification of 2500x.

[0127] Preparation of polymer FA An 80-liter reactor equipped with an impeller operating at 300 rpm was sequentially charged with 48,204 g of demineralized water and 20.2 g of METHOCEL® K100 GR suspending agent. The reactor was vented and pressurized to 1 bar with nitrogen, and then 10.8 g of hydroxyethyl acrylate (HEA) monomer and 127.7 g of diethyl carbonate (DEC) were charged, followed by 204 g of a 75 wt. % solution of t-amyl perpivalate initiator in isododecane and 25,187 g of vinylidene fluoride (VDF) monomer. The reactor was then gradually heated to 52°C up to a final pressure of 110 bar. The temperature was maintained constant at 52°C throughout the entire run. The pressure was kept constant at 110 bar throughout the entire run by feeding a 19.9 g / L aqueous solution of HEA monomer up to a total of 16.5 kg, then the pressure started to decrease. The polymerization experiment was stopped by degassing the suspension until atmospheric pressure was reached. The polymer so obtained was then recovered, washed with demineralized water and oven-dried at 65°C. Approximately 75% conversion of the comonomer was obtained.

[0128] Preparation of polymer FB An 80-liter reactor equipped with an impeller operating at 250 rpm was sequentially charged with 50.2 kg of demineralized water and a pair of suspending agents: 3.80 g of METHOCEL® K100GR and 15.21 g of Alkox® E45. The reactor was purged with several vacuum (30 mmHg) and nitrogen purges at 20°C. Next, 187.3 g of a 75 wt. % solution of t-amyl perpivalate initiator in isododecane was added. The stirring speed was increased to 300 rpm. Finally, 16.3 g of hydroxyethyl acrylate (HEA) and 2555 g of hexafluoropropylene (HFP) monomer were introduced into the reactor, followed by 22.8 kg of vinylidene fluoride (VDF). The reactor was gradually heated to a set-point temperature of 55°C, and the pressure was fixed at 120 bar. During the polymerization, the pressure was kept constant at 120 bar by feeding 16.96 kg of an aqueous solution containing 188 g of HEA. After this feeding, no further aqueous solution was introduced and the pressure began to drop. The polymerization was then stopped by degassing the reactor until atmospheric pressure was reached. Approximately 81% conversion of the comonomer was obtained. The polymer thus obtained was then recovered, washed with demineralized water and oven-dried at 65°C.

[0129] Example 1: Preparation of polymer electrolyte using polymer FA Step (i): Preparation of pregelled metal compounds The following ingredients were added sequentially to a 50 ml beaker equipped with a magnetic stirrer operating at moderate speed: - ES: 13.68g - TEOS: 6.62g - Water: 2.30g (molar ratio TEOS:H2O = 1:4) - Ethanol: 1.66g (weight ratio TEOS:EtOH = 4:1) - Citric acid: 0.089 g (1% by weight of TEOS + H2O).

[0130] The theoretical amount of SiO2 produced in each batch was 1.89 g (17.91% of the starting TEOS, water, ethanol components); the pregelled metal compound composition was maintained under vigorous stirring throughout the process.

[0131] Step (ii) Preparation of polymer electrolytes containing fluoropolymer hybrid organic / inorganic composites: The solution obtained in step (i) and polymer FA (8.4 g) were introduced into the feed hopper of a mini-extruder and melt-blended using a co-rotating twin-screw micro-extruder, DSM Xplore 15 ml Microcompounder. The micro-extruder is formed by a separable, fluid-tight mixing section containing two detachable, conical mixing screws. The residence time was fixed at 2 min. The screw speeds were fixed at 50 rpm for feeding and 100 rpm for mixing, respectively. The heating temperature was set at 180 °C. At the end of the 2 min of mixing, the material was extruded through a nozzle.

[0132] The amounts of the components of the polyelectrolyte thus obtained were as follows: - SiO2: 8% by weight; - polymer FA: 35% by weight; - ES: 57% by weight.

[0133] Example 2 - Comparison -: Preparation of fluoropolymer hybrid organic / inorganic composite using polymer FA A fluoropolymer hybrid organic / inorganic composite was prepared according to the method disclosed in WO 2014 / 067816, in which polymer FA was extruded and reacted with a metal compound in the absence of an electrolyte solution, resulting in a 75 / 25 wt.% polymer FA / SiO2 composite. The composite was obtained in the form of pellets. 10.08 g of the pellets were charged into the feed hopper of a mini-extruder along with 13.92 g of ES and maintained at 180°C. After 2 minutes, the product was discharged. The product resulting from the extrusion had some transparent and some opaque portions. The extrudate did not exhibit significant melt consistency.

[0134] Example 3: Preparation of polymer electrolyte using polymer FB Step (i): Preparation of pregelled metal compounds Step (i) was carried out as described in Example 1 above.

[0135] Step (ii) Preparation of polymer electrolytes containing fluoropolymer hybrid organic / inorganic composites: Step (ii) was carried out in a twin-screw co-rotating intermeshing extruder (Leistritz 18 ZSE 18 HP with a screw diameter D of 18 mm and a screw length (40 D) of 720 mm). The extruder was equipped with a main feeder, a secondary feeder and a degassing unit. The barrel consisted of eight temperature control zones and one cooling zone (at the main feeder), which made it possible to set the desired temperature profile. The molten polymer emerged from a die consisting of a flat profile 3 mm thick and 15 mm long. The extrudate was cooled in air.

[0136] The polymer FB was fed into the extruder through the main hopper. At the same time, the pregel obtained in step (i) was fed into the extruder through a second hopper located in block zone 3 (270-360 mm). The screw profile for this step consisted of a region of conveying elements with a regular decrease in pitch (zones 0-1), followed by a kneading block (zone 2) consisting of three kneading elements and one counterflow element, followed by a long conveying zone (zones 3-4); after this series of elements, five kneading blocks (zones 5-6) were added.

[0137] Finally, five conveying elements and a degassing unit were located before the die exit (zones 6-8). The temperature profile used is reported here below in Table 1. The extruder rotation speed was 350 rpm.

[0138] TIFF0007779735000019.tif42170

[0139] The material appears to be continuous and self-supporting, with melt strength that allows it to be pulled.

[0140] Example 4: Preparation of polymer electrolyte using polymer FB Step (i): Preparation of pregelled metal compounds The following ingredients were added sequentially to a 50 ml beaker equipped with a magnetic stirrer operating at moderate speed: - ES: 13.68g - TEOS: 6.62g - Formic acid: 1.83 g (27% by weight of TEOS).

[0141] The pregelled metal compound composition was maintained under vigorous stirring throughout the process.

[0142] Step (ii) Preparation of polymer electrolytes containing fluoropolymer hybrid organic / inorganic composites: Step (ii) was carried out as in step (ii) of Example 3.

[0143] The amounts of the components of the polyelectrolyte thus obtained were as follows: - SiO2: 8% by weight; - polymer FB: 35% by weight; - ES: 57% by weight.

[0144] Example 5 - Membrane preparation The extrudates obtained from the methods as detailed under Examples 1, 2, 3 and 4 were processed by compression molding in a hot compression molding press at a heating temperature of 150°C and a pressure of 10 MPa for 3 minutes to obtain a 60 x 60 x 0.2 mm 3 The film specimen was then held at 120°C for 120 minutes as part of the post-processing step.

[0145] Example 6 - Elemental analysis of the sample obtained in Example 5 Table 2 reports the elemental analysis of the sample obtained in Example 5.

[0146] TIFF0007779735000020.tif77170

[0147] The polyelectrolytes of the present invention provide fairly uniform films, with the atoms in the film being well distributed throughout the film, whereas the sample obtained using the extrudate of Comparative Example 2 shows areas where some of the elements are not uniformly present.

[0148] Example 7 - Ionic conductivity of the sample obtained in Example 5 In Table 3 the ionic conductivities of the samples obtained in Example 5 are reported.

[0149] TIFF0007779735000021.tif80170

[0150] The polymer electrolytes according to the present invention exhibit ionic conductivity that makes them suitable for use in battery applications, such as in separators in Li-ion batteries.

[0151] Example 8: Fabrication of polymer electrolyte membranes using polymer FB by film extrusion Step (i): Preparation of pregelled metal compounds Step (i) was carried out as described in Example 1 above.

[0152] Step (ii) Preparation of polymer electrolytes containing fluoropolymer hybrid organic / inorganic composites: Step (ii) was carried out as in Example 3, but at the end of the reaction, the molten polymer emerged from a die consisting of a flat profile 1 mm thick and 40 mm long. The extrudate film was stretched between two cylinders 100 mm in diameter and 100 mm wide with a gap of 100-500 μm. The extrudate was cooled in air.

[0153] Example 9: Preparation of polymer electrolyte membrane using polymer FB by film extrusion Step (i): Preparation of pregelled metal compounds Step (i) was carried out as described in Example 4 above.

[0154] Step (ii) Preparation of polymer electrolytes containing fluoropolymer hybrid organic / inorganic composites: Step (ii) was carried out as described in Example 8.

[0155] Example 10 - Elemental analysis of samples obtained in Examples 8 and 9 Table 4 reports the elemental analysis of the samples obtained in Examples 8 and 9.

[0156] TIFF0007779735000022.tif90170

[0157] The polyelectrolytes of the present invention provide fairly uniform membranes: the atoms in the membrane are well distributed throughout the film.

[0158] Example 11 Ionic Conductivities of Samples Obtained in Examples 8 and 9 In Table 5 the ionic conductivities of the samples obtained in Examples 8 and 9 are reported.

[0159] TIFF0007779735000023.tif59170

[0160] Polymer electrolyte membranes according to the present invention exhibit ionic conductivity that makes them suitable for use in battery applications, such as in separators in Li-ion batteries.

Claims

1. 1. A method for producing a polymer electrolyte based on a fluoropolymer hybrid organic / inorganic composite material, the method comprising the steps of: (i) Formula: X ４－ｍ AY ｍ wherein m is 4, A is a metal selected from the group consisting of Si, Ti, and Zr, Y is a hydrolyzable group selected from the group consisting of an alkoxy group, an acyloxy group, and a hydroxyl group, and X is a hydrocarbon group, optionally containing one or more functional groups. In a reaction vessel, a metal compound having the formula [compound (M)] is added. an electrolyte solution [solution (ES)] comprising at least one metal salt [metal salt (S)] and a liquid medium [medium (L)]; at least one acid catalyst; and optionally an aqueous medium [medium (A)] to partially hydrolyze and / or polycondense in the presence of a pregelled metal compound [compound (P-GM)] (The pregelling metal compound [compound (P-GM)] comprises one or more inorganic domains consisting of ≡A-O-A≡ bonds and one or more residual hydrolyzable groups Y.) and then obtaining a composition comprising (ii) after obtaining a composition containing a pregelled metal compound [compound (P-GM)], reacting in a molten state in an apparatus separate from the reaction vessel at least a portion of the hydroxyl groups of a functional fluoropolymer [polymer (F)] containing at least one hydroxyl group with at least a portion of the hydrolyzable groups Y of the compound (P-GM) to obtain a polymer electrolyte containing a fluoropolymer hybrid organic / inorganic composite material incorporating the electrolyte solution (ES); A method comprising:

2. The compound (M) is selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, tetraethyl zirconate, and tetra-n-propyl 2. The method of claim 1, wherein the non-functional compound (M) is selected from the group consisting of zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, and tetra-n-stearyl zirconate.

3. The at least one metal salt (S) may be selected from the group consisting of MeI, Me(PF), ... ６ ) ｎ , Me(BF ４ ) ｎ , Me(ClO ４ ) ｎ , Me(bis(oxalato)borate) ｎ ("Me (BOB) ｎ "), MeCF ３ SO ３ , Me[N(CF ３ SO ２ ) ２ ] ｎ , Me[N(C ２ F ５ SO ２ ) ２ ] ｎ , R Ｆ is C ２ F ５ , C ４ F ９ or CF ３ OCF ２ CF ２ Me[N(CF ３ SO ２ ) (R Ｆ SO ２ )] ｎ , Me(AsF ６ ) ｎ , Me[C(CF ３ SO ２ ) ３ ] ｎ , Me ２ S ｎ 3. The method of claim 1 or 2, selected from the group consisting of:

4. The metal salt (S) is LiI, LiPF ６ , LiBF ４ , LiClO ４ , lithium bis(oxalato)borate (“LiBOB”), LiCF ３ SO ３ , LiN(CF ３ SO ２ ) ２ (“LiTFSI”), LiN(C ２ F ５ SO ２ ) ２ , R Ｆ is C ２ F ５ , C ４ F ９ , C.F. ３ OCF ２ CF ２ Me[N(CF ３ SO ２ ) (R Ｆ SO ２ )] ｎ , LiAsF ６ , LiC(CF ３ SO ２ ) ３ , Li ２ S ｎ and combinations thereof.

5. The medium (L) in the electrolyte solution (ES) comprises at least one ionic liquid (IL), and the anion of the ionic liquid (IL) is - Formula (SO ２ CF ３ ) ２ N － bis(trifluoromethylsulfonyl)imide, - Formula PF ６ － hexafluorophosphate, - Formula BF ４ － tetrafluoroborate, and - Formula:

5. The method of claim 1, wherein the oxaloborates are selected from the group consisting of:

6. The method according to any one of claims 1 to 5, wherein the electrolyte solution (ES) consists of at least one ionic liquid (IL) and LiTFSI.

7. The method according to any one of claims 1 to 6, wherein the acid catalyst is an organic acid.

8. The method according to any one of claims 1 to 7, wherein the medium (A) consists of water and ethanol.

9. Under step (ii), the polymer (F) comprises repeating units derived from at least one fluorinated monomer and a repeating unit of formula (I): (wherein R １ , R ２ , R ３ Each of the groups independently represents a hydrogen atom or C １ ~C ３ is a hydrocarbon group, R ＯＨ is a C containing at least one hydroxyl group １ ~C ５ hydrocarbon portion) and repeat units derived from at least one comonomer containing at least one hydroxyl group having the formula: [comonomer (MA)].

10. Under step (ii), the polymer (F) is (a) at least 60 mole % vinylidene fluoride (VDF); (b) optionally, 0.1 mol% to 15 mol% of a fluorinated comonomer selected from chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), perfluoromethyl vinyl ether (PMVE), and mixtures thereof; (c) 0.05 mol % to 10 mol % of a compound represented by formula (I) (wherein R １ , R ２ , R ３ Each of the groups independently represents a hydrogen atom or C １ ~C ３ is a hydrocarbon group, R ＯＨ is a C containing at least one hydroxyl group １ ~C ５ hydrocarbon portion) Comonomer (MA) and The method according to any one of claims 1 to 8, comprising:

11. A method for producing a polymer electrolyte membrane, comprising: Producing a polymer electrolyte by the method according to any one of claims 1 to 10; processing the polymer electrolyte into a film by compression molding or extrusion techniques to obtain a polymer electrolyte membrane; A method for producing a polymer electrolyte membrane comprising the steps of:

12. 1. A method for producing an electrochemical device including a polymer electrolyte membrane, comprising:

12. A process for producing a polymer electrolyte membrane by the method of claim 11. A manufacturing method comprising:

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