An electrochemical device comprising a separator containing PVDF and an electrolyte composition having high viscosity or high polarity

Abstract

The present invention relates to an electrochemical device including a separator and an electrolyte composition, wherein the separator includes a monomer unit of vinylidene fluoride and a monomer unit of a formula R 1 R 2 C=C(R 3 )C(O)R (wherein substituents R 1 , R 2 and R 3 are independently selected from the group consisting of H and C 1 ~C 5 alkyl, and R is selected from the group consisting of -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR’ (R’ is selected from the group consisting of H and C 1 ~C 18 alkyl which may be substituted with one or more -OH groups, or a 5-membered or 6-membered heterocyclic ring containing at least one nitrogen atom in its cyclic chain)), and includes at least one coating containing a polymer resin, and the electrolyte composition includes a solvent and a lithium salt, and the electrolyte composition has a viscosity exceeding 2 cP as measured by shear at 20 °C and 20 s -1 , or the solvent has a dipole moment exceeding 2 debyes at 25 °C.

Description

Technical Field

[0001] The present invention generally relates to the field of storage of electrical energy in Li-ion type rechargeable batteries. More specifically, the present invention relates to an electrochemical device comprising a separator specifically adapted to a high-viscosity or high-polarity electrolyte.

Background Art

[0002] The market for separators for electrochemical devices is dominated by the use of polyolefins (e.g., Celgard® or Hipore®) manufactured by extrusion and / or stretching using dry or wet processes. Separators must simultaneously have a thin thickness, sufficient mechanical strength and heat resistance, good electrochemical resistance to the voltages to which they are exposed, an optimal affinity for the electrolyte, and more generally, enable excellent ionic conductivity. Among the most advantageous alternatives to polyolefins, polymers that exhibit better affinity for standard electrolytes, such as poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), and poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)), have been proposed to reduce the internal resistance of the system. Another option is to deposit a coating on one or both sides of a polyolefin separator. In the presence of the electrolyte used in the electrochemical device, the separator must have good wettability to enable good efficiency of the device. However, polyolefin-based separators, such as polypropylene or polyethylene, have low wettability in the presence of high-viscosity electrolytes or high-polarity electrolytes. Therefore, electrochemical devices are disadvantaged by a long induction period to achieve their initial performance (adverse effects on cell construction and its productivity), and then more generally exhibit poor performance with respect to both charging and discharging.

[0003] Poly(vinylidene fluoride) (PVDF) and its derivatives exhibit advantages as polyolefin separator coatings with respect to their electrochemical stability and their high dielectric constant that promotes the dissociation of ions and thus conductivity. The crystallinity of the P(VDF-co-HFP) copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) is lower than that of PVDF. For this reason, an advantage of these P(VDF-co-HFP) copolymers is that they promote conductivity.

[0004] Document EP 2,528,141 describes a separator for secondary batteries that includes a porous substrate, an adhesive layer, and a polar electrolyte. It has been found that the wettability of this separator in the presence of a polar electrolyte is not sufficient.

[0005] Therefore, there is still a need to develop a novel coating for separators that is easy to implement, exhibits good wettability with respect to high-viscosity electrolytes or high-polarity electrolytes, and shows a good compromise among dry adhesiveness, adhesiveness in the wet state, ion conductivity, and thermal stability.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] Therefore, an object of the present invention is to overcome at least one of the drawbacks of the prior art, that is, to propose a polymer coating for a separator that can promote wettability with respect to a high-viscosity electrolyte or a high-polarity electrolyte.

Means for Solving the Problems

[0008] The present invention provides an electrochemical device comprising a separator and an electrolyte composition, characterized by the following: i) The separator comprises at least one coating containing a polymer resin including monomer units of vinylidene fluoride and a monomer unit of a compound represented by the formula R 1 R 2 C=C(R 3 )C(O)R (wherein the substituents R 1 , R 2 and R 3 are independently selected from the group consisting of H and C 1 -C 5 alkyl, and R is selected from the group consisting of -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR' (wherein R' is selected from the group consisting of H and C 1 -C 18 alkyl which may be substituted with one or more -OH groups, or a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain). ii) The electrolyte composition comprises a solvent and a lithium salt, and the electrolyte composition has a viscosity exceeding 2 cP as measured by shear at 20 °C and 20 s -1 , or the solvent has a dipole moment exceeding 2 Debye at 25 °C. The present invention provides an electrochemical device characterized by the above.

[0009] The use of certain coatings based on fluoro-acrylic polymer resins enables the use of efficient and effective electrochemical devices when the electrolyte composition used has a high viscosity or high polarity. These properties are highly sought after, particularly with regard to wettability. In fact, the good wettability observed makes it possible to shorten the time required to achieve a uniform distribution of the viscous or highly polar electrolyte within the separator and thus within the lithium-ion battery. Also, by improving the wettability, the battery filling rate can be increased. When the separator is based on a polyolefin or fluoropolymer that does not contain an acrylate or acrylic component, this uniform distribution of the viscous or highly polar electrolyte composition is not observed or is difficult to achieve.

[0010] According to a preferred embodiment, the electrolyte composition has a viscosity of more than 5 cP, preferably more than 10 cP, particularly more than 15 cP, as measured at 20 °C and a shear of 20 s -1

[0011] According to a preferred embodiment, the electrolyte composition has a viscosity of less than 1000 cP as measured at 20 °C and a shear of 20 s -1

[0012] According to a preferred embodiment, the solvent has a dipole moment of more than 2.5 Debye, preferably more than 3.0 Debye, more preferably more than 3.5 Debye, particularly more than 4.0 Debye at 25 °C.

[0013] According to a preferred embodiment, the polymer resin is a copolymer comprising monomer units of vinylidene fluoride and monomer units of the formula R 1 R 2 C=C(R 3 )C(O)R, or the polymer resin is a fluoropolymer comprising monomer units of vinylidene fluoride and a polymer of the formula R 1 R 2 C=C(R 3 )C(O)R (wherein the substituents R 1 , R 2 and R​​3 are, independently of one another, H and C 1 ~C 5 selected from the group consisting of alkyl, and R is -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR'(wherein R' is H and C which may be substituted with one or more -OH groups 1 ~C 18 alkyl, or selected from the group consisting of a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain)), and is a mixture with an acrylic polymer containing monomer units selected from the group consisting of)).

[0014] According to a preferred embodiment, the polymer resin is a fluoropolymer containing monomer units of vinylidene fluoride, and a formula R 1 R 2 C=C(R 3 )C(O)R(wherein the substituents R 1 , R 2 and R 3 are, independently of one another, H and C 1 ~C 5 selected from the group consisting of alkyl, and R is -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR'(wherein R' is H and C which may be substituted with one or more -OH groups 1 ~C 18 alkyl, or selected from the group consisting of a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain)), and is a mixture with an acrylic polymer containing monomer units selected from the group consisting of)), and the fluoropolymer is selected from the group consisting of polyvinylidene fluoride homopolymer and a copolymer based on polyvinylidene fluoride and at least one comonomer compatible with vinylidene fluoride).

[0015] According to a preferred embodiment, the comonomer is selected from vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, perfluoroalkyl vinyl ether, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, chlorotrifluoropropene, and ethylene.

[0016] According to a preferred embodiment, the fluoropolymer is a polyvinylidene fluoride - hexafluoropropylene copolymer having a weight percentage of hexafluoropropylene monomer units of 2 wt% to 25 wt%, preferably 4 wt% to 15 wt%, based on the weight of the copolymer.

[0017] According to a preferred embodiment, the fluoropolymer comprises monomer units having at least one of the following functional groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, epoxy group, amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenol, ester, ether, siloxane, sulfonic acid, sulfuric acid, phosphoric acid, or phosphonic acid.

[0018] According to a preferred embodiment, the acrylic polymer contains monomers selected from the group consisting of 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, hydroxybutyl acrylate, hydroxypropyl methacrylate, methylacrylic acid, methyl methacrylate, ureidomethacrylate, and combinations thereof.

[0019] In a preferred embodiment, the coating is BaTiO 3 , Pb(Zr,Ti)O 3, Pb 1-x La x Zr y O 3 (0 < x < 1, 0 < y < 1), PBMg 3 Nb 2 / 3 ) 3 , PbTiO 3 , hafnia (HfO(HfO 2 )), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, Y 2 O 3 , boehmite (y - AlO(OH)), Al 2 O 3 , TiO 2 , SiC, ZrO 2 , borosilicate, BaSO 4 , nanoclay, or a mixture thereof, selected from the group consisting of inorganic particles.

[0020] In a preferred embodiment, the device is selected from the group consisting of a lithium - ion battery, a capacitor, an electric double - layer capacitor, and a membrane electrode assembly (MEA) for a fuel cell, preferably a lithium - ion battery.

[0021] According to a preferred embodiment, the device is a lithium - ion secondary battery and also includes an anode and a cathode.

Mode for Carrying Out the Invention

[0022] The present invention relates to an electrochemical device. The electrochemical device particularly includes a separator and an electrolyte composition described in more detail below. In addition to these two components, the electrochemical device includes an anode and a cathode. The separator according to the present invention is disposed between the anode and the cathode of the electrochemical device. Preferably, the electrochemical device is selected from the group consisting of a lithium - ion battery, a capacitor, an electric double - layer capacitor, and a membrane electrode assembly (MEA) for a fuel cell. Preferably, the electrochemical device is a lithium - ion secondary battery.

[0023] <Separator> The present invention relates to an electrochemical device comprising a separator including at least one coating. The coating comprises monomer units of vinylidene fluoride and a formula R 1 R 2 C=C(R 3 )C(O)R (wherein the substituents R 1 , R 2 and R 3 are independently of each other selected from the group consisting of H and C 1 ~C 5 alkyl, and R is selected from the group consisting of -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR' (provided that R' is selected from the group consisting of H and C 1 ~C 18 alkyl which may be substituted with one or more -OH groups, or a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain)), and contains a polymer resin comprising monomer units thereof. Accordingly, the polymer resin contains a fluorine-containing moiety and an acrylic moiety. The resin may be in the form of a mixture of a fluoropolymer and an acrylic polymer, or may be in the form of a copolymer of fluorinated monomer units and acrylic monomer units.

[0024] Preferably, the polymer resin is present in a non-crosslinked form in the separator coating. The polymer resin may be linear or branched.

[0025] According to various embodiments, the coating comprises the following features which are combined where appropriate. The indicated contents are expressed by weight unless otherwise indicated. For all the ranges shown, the limit values are included unless otherwise indicated.

[0026] According to a preferred embodiment, the polymer resin comprises monomer units of vinylidene fluoride and a formula R 1 R 2 C=C(R 3)It is a copolymer containing a monomer unit of C(O)R. The copolymer will be described in more detail below.

[0027] According to another embodiment, the polymer resin is a fluoropolymer containing a monomer unit of vinylidene fluoride and a formula R 1 R 2 C=C(R 3 )C(O)R (wherein the substituents R 1 , R 2 and R 3 are independently of each other selected from the group consisting of H and C 1 ~C 5 alkyl, and R is -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR' (where R' is selected from the group consisting of H and C 1 ~C 18 alkyl which may be substituted with one or more -OH groups, or a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain)), and is a mixture with an acrylic polymer containing a monomer unit selected from the group consisting of). Hereinafter, the fluoropolymer and the acrylic polymer will be described.

[0028] i) Fluoropolymer The fluoropolymer is based on the vinylidene difluoride monomer and is generally referred to by the abbreviation PVDF.

[0029] According to one embodiment, the fluoropolymer is the homopolymer poly(vinylidene fluoride).

[0030] According to another embodiment, the fluoropolymer is a copolymer of vinylidene difluoride and at least one comonomer compatible with vinylidene difluoride. The comonomer compatible with vinylidene difluoride may or may not be halogenated (fluorinated, chlorinated or brominated). Examples of suitable fluorinated comonomers are vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropene, especially 3,3,3-trifluoropropene, tetrafluoropropene, especially 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, especially 1,1,3,3,3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkyl vinyl ether, especially of the general formula Rf-O-CF=CF 2 (wherein Rf is an alkyl group, preferably a C 1 ~C 4 alkyl group (preferred examples are perfluoropropyl vinyl ether and perfluoromethyl vinyl ether)).

[0031] The fluorinated comonomer can contain a chlorine atom or a bromine atom. This can be selected in particular from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene can represent either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. Chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.

[0032] The VDF copolymer can also contain non-halogenated monomers, such as ethylene, and / or acrylic or methacrylic comonomers.

[0033] The fluoropolymer preferably contains at least 50 mol% of vinylidene difluoride.

[0034] According to one embodiment, the fluoropolymer is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), and the weight percentage of hexafluoropropylene monomer units is 2% to 30% by weight, preferably 2% to 25% by weight, preferably 2% to 20% by weight, preferably 4% to 15% by weight based on the weight of the copolymer.

[0035] According to one embodiment, the fluoropolymer is a copolymer of vinylidene fluoride and tetrafluoroethylene (TFE).

[0036] According to one embodiment, the fluoropolymer is a copolymer of vinylidene fluoride and chlorotrifluoroethylene (CTFE).

[0037] According to one embodiment, the fluoropolymer is a VDF-TFE-HFP terpolymer. According to one embodiment, the fluoropolymer is a VDF-TrFE-TFE terpolymer (TrFE is trifluoroethylene). In these terpolymers, the content of VDF is at least 10% by weight, and the comonomers are present in various ratios.

[0038] According to one embodiment, the fluoropolymer contains monomer units having at least one of the following functional groups: carboxylic acid, carboxylic anhydride, carboxylic ester, epoxy group (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenol, ester, ether, siloxane, sulfonic acid, sulfuric acid, phosphoric acid or phosphonic acid. The functional group can be introduced by a chemical reaction such as grafting or copolymerization of a fluorinated monomer and a monomer having a vinyl functional group that can copolymerize with at least one of the functional groups and the fluorinated monomer according to techniques well known to those skilled in the art.

[0039] According to one embodiment, the functional group has a carboxylic acid functional group which is a (meth)acrylic acid type group selected from acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxyethylhexyl (meth)acrylate.

[0040] According to one embodiment, the unit having a carboxylic acid functional group further contains a heteroatom selected from oxygen, sulfur, nitrogen, and phosphorus.

[0041] According to one embodiment, the functional group is introduced via a transfer agent used in the synthesis process. The transfer agent has a molar mass of 20,000 g / mol or less and is a polymer having a functional group selected from the following groups, namely, carboxylic acid, carboxylic anhydride, carboxylic ester, epoxy (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenol, ester, ether, siloxane, sulfonic acid, sulfuric acid, phosphoric acid, or phosphonic acid. An example of this type of transfer agent is an acrylic acid oligomer.

[0042] The content rate of the functional group of the fluoropolymer is at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

[0043] More specifically, the transfer agent having a functional group is incorporated into the chain end of the fluoropolymer. Therefore, the fluoropolymer can contain a terminal group composed of the transfer agent. In particular, the transfer agent is a polymer having a molar mass of 20,000 g / mol or less and a functional group selected from the group consisting of carboxylic acid or carboxylic ester.

[0044] The fluoropolymer preferably has a high molecular weight. The term "high molecular weight" used herein is according to the ASTM D-3835 method, at 232 °C and 100 s -1It is understood to mean a fluoropolymer having a melt viscosity, measured at, exceeding 100 Pa·s, preferably exceeding 500 Pa·s, more preferably exceeding 1000 Pa·s.

[0045] According to one embodiment, a fluoropolymer having functional groups can be crosslinked by self-condensation of its functional groups or by reaction with a catalyst and / or a crosslinking agent such as a melamine resin, an epoxy resin, etc., as well as low molecular weight known crosslinking agents such as diisocyanate or higher polyisocyanates, polyaziridine, polycarbodiimide, polyoxazoline, dialdehyde such as glyoxal, acetoacetate, malonate, acetal, thiol and acrylate which are bifunctional and trifunctional, alicyclic epoxy molecules, organosilanes such as epoxy silane and amino silane, carbamate, diamine and triamine, inorganic chelating agents such as certain zinc and zirconium salts, titanium, glycouril and other aminoplasts. In certain cases, functional groups derived from other polymerization components such as surfactants, initiators, seed particles, etc. can participate in the crosslinking reaction. When two or more functional groups participate in the crosslinking process, pairs of complementary reactive groups are, for example, hydroxyl-isocyanate, acid-epoxy, amine-epoxy, hydroxyl-melamine, acetoacetate-acid. Acrylate and / or methacrylate monomers that do not contain functional groups that can participate in the crosslinking reaction after polymerization should preferably account for 70% by weight or more of the total monomer mixture, more preferably more than 90% by weight. According to one embodiment, the fluoropolymer contains a crosslinking agent selected from the group consisting of isocyanate, diamine, adipic acid, dihydrazide and combinations thereof.

[0046] According to some embodiments, PVDF homopolymers and VDF copolymers are composed of bio-based VDF. The term "bio-based" means "derived from biomass". This can improve the ecological footprint of the separator. Bio-based VDF is in accordance with the standard NF EN 16640 14As determined by the C content, it can be characterized by a content of at least 1 atomic % of renewable carbon, i.e., carbon of natural origin derived from biomaterials or biomass. The term "renewable carbon" indicates that the carbon is of natural origin and derived from biomaterials (or biomass), as shown below. According to some embodiments, the bio-carbon content of VDF exceeds 5%, preferably exceeds 10%, preferably exceeds 25%, preferably is 33% or more, preferably exceeds 50%, preferably is 66% or more, preferably exceeds 75%, preferably exceeds 90%, preferably exceeds 95%, preferably exceeds 98%, preferably exceeds 99%, and advantageously is equal to 100%.

[0047] The homopolymer fluoropolymers and VDF copolymers used in the present invention can be obtained by known polymerization methods such as emulsion polymerization or suspension polymerization.

[0048] According to one embodiment, they are prepared by an emulsion polymerization process in the absence of a fluorinated surfactant.

[0049] The polymerization of PVDF generally has a solid content of 10% to 60% by weight, preferably 10% to 50% by weight, and results in a latex having a weight average particle size of less than 1 micrometer, preferably less than 1000 nm, preferably less than 800 nm, more preferably less than 600 nm. The weight average diameter of the particles is generally at least 20 nm, preferably at least 50 nm, and advantageously the average size is in the range of 100 to 400 nm. The polymer particles can form aggregates, and the weight average size thereof is 1 to 30 micrometers, preferably 2 to 20 micrometers. The aggregates can be decomposed into separate particles during compounding and coating on the substrate.

[0050] ii) Acrylic polymer As described above, the acrylic polymer has the formula R 1 R 2 C = C(R 3 )C(O)R (wherein the substituent R 1 , R2 and R 3 are, independently of one another, H and C 1 ~C 5 selected from the group consisting of alkyl, and R is -NHC(CH 3 ) 2 CH 2 C(O)CH 3 , or OR’ (wherein R’ is selected from the group consisting of H and C 1 ~C 18 alkyl which may be substituted with one or more -OH groups, or a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain). The heterocycle may be saturated or 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 oxyindole 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 C 1 ~C 5 alkyl groups. As described above, C 1 ~C 18 alkyl may be substituted with the heterocycle. The heterocycle can be bonded to the chain via a nitrogen atom or any other atom forming the heterocycle. Preferably, the heterocycle is 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidinone or 4-imidazolidinone.

[0051] Preferably, the acrylic polymer has the formula R 1 R 2 C=C(R 3 )C(O)R (wherein the substituents R 1 , R 2 and R 3 are, independently of one another, H and C 1 ~C 5 selected from the group consisting of alkyl, and R is -NHC(CH 3 ) 2 CH2 C(O)CH 3 、 or OR’ (wherein R’ is C optionally substituted with H and one or more -OH groups 1 ~C 18 alkyl, or a 5- or 6-membered heterocycle containing at least one nitrogen atom in its cyclic chain, selected from the group consisting of), selected from the group consisting of) is based on an alkyl acrylate monomer unit. Preferably, the heterocycle is as defined above, and in particular, the heterocycle is 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidinone or 4-imidazolidinone.

[0052] According to one embodiment, the substituent R’ is selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-dodecyl, amyl, isoamyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxybutyl, hydroxypropyl, ureido, hydroxyethyl, hydroxypropyl, ethyl substituted with a hydroxybutyl group.

[0053] In particular, the acrylic polymer has the formula R 1 R 2 C=C(R 3 )C(O)R (wherein the substituents R 1 and R 2 are H, R 3 is H or CH 3 and 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 or 4-imidazolidinone) is based on an alkyl acrylate monomer.

[0054] Therefore, the alkyl acrylate may be 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, methacrylic acid, methyl methacrylate, ureido methacrylate. Among these, alkyl acrylates containing an alkyl group having 1 to 8 carbon atoms are preferred, and alkyl acrylates containing an alkyl group having 1 to 5 carbon atoms are more preferred. These compounds can be used alone or as a mixture of two or more kinds.

[0055] Here, the term "acrylate" includes acrylates and methacrylates.

[0056] Any ethylenically unsaturated compound copolymerizable with the alkyl acrylate and alkyl methacrylate includes the following. - (A) alkenyl compounds containing a functional group, - (B) alkenyl compounds having no functional group.

[0057] Examples of the alkenyl compound (A) containing a functional group include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid; vinyl ester compounds such as vinyl acetate, 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, diacetoneacrylamide; acrylic esters such as 2-hydroxyethyl acrylate, N-dialkylaminoethyl acrylate, glycidyl acrylate, n-dodecyl acrylate, fluoroalkyl acrylate; methacrylic esters such as dialkylaminoethyl methacrylate, fluoroalkyl methacrylate, 2-hydroxyethyl methacrylate, n-octyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate; maleic anhydride; alkenyl glycidyl ether compounds such as allyl glycidyl ether. Among these, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and allyl glycidyl ether are preferred. These compounds can be used alone or as a mixture of two or more.

[0058] Examples of the alkenyl compound (B) having no functional group include conjugated dienes such as 1,3-butadiene, isoprene, etc.; divinyl hydrocarbon compounds such as divinylbenzene, etc.; and alkenyl cyanides such as acrylonitrile, methacrylonitrile, etc. Among these, 1,3-butadiene and acrylonitrile are preferred. These compounds can be used alone or as a mixture of two or more.

[0059] The functional alkenyl compound (A) is used in a proportion of less than 50% by weight based on the weight of the monomer mixture, and the alkenyl compound (B) having no functional group is preferably used in a proportion of less than 30% by weight based on the weight of the monomer mixture.

[0060] The acrylic polymer used in the present invention can be obtained by polymerizing an alkyl acrylate monomer by a known polymerization method such as emulsion polymerization or suspension polymerization.

[0061] iii) A mixture of a fluoropolymer and an acrylic polymer The polymer resin can be prepared by various processes.

[0062] According to the first embodiment, the fluoropolymer and the acrylic polymer are each independently obtained by a known polymerization method such as emulsion polymerization or suspension polymerization. Then, the two polymers are mixed in the form of a powder or a latex during the preparation of the aqueous formulation, or in the presence of an organic solvent intended for use with a separator.

[0063] Alternatively, according to another preferred embodiment, the polymer resin is synthesized by emulsion polymerization of acrylate / methacrylate monomers using the latex of the fluoropolymer as a seed, whereby a fluoro-acrylic polymer composition in which at least a part of the fluoropolymer and at least a part of the acrylic polymer are closely mixed is obtained.

[0064] The fluoro-acrylic polymer resin is an aqueous dispersion obtained by emulsion polymerization of a monomer mixture having, in the presence of 100 parts by weight of the particles of the vinylidene fluoride polymer defined above, in an aqueous medium, 5 to 100, preferably 5 to 95 parts by weight of at least one monomer selected from the group consisting of alkyl acrylates having an alkyl group with 1 to 18 carbon atoms and alkyl methacrylates having an alkyl group with 1 to 18 carbon atoms, and optionally an ethylenically unsaturated compound copolymerizable with the alkyl acrylate and the alkyl methacrylate. The PVDF particles function as seeds for the polymerization of the acrylic monomer. The PVDF particles can be added to the polymerization system in any state as long as they are dispersed in the form of particles in the aqueous medium. Since the vinylidene fluoride polymer is generally produced as an aqueous dispersion, it is practical to use an aqueous dispersion such as the one produced as seed particles. The particle size of the vinylidene fluoride particles is preferably 0.04 to 2.9 micrometers. In a preferred embodiment, the diameter of the polymer particles is preferably 50 nm to 700 nm.

[0065] The product of the polymerization is a latex, which can usually be used in this form after filtering off the solid by-products of the polymerization process. For use in the form of a latex, the latex may be stabilized by the addition of a surfactant which may be the same as or different from the surfactant present during polymerization (where appropriate). The surfactant added later may be, for example, an ionic surfactant or a non-ionic surfactant.

[0066] The PVDF particles used as seeds can have a homogeneous or heterogeneous nature, or a gradient between the core and the surface of the particles, with respect to composition (e.g., the content of the HFP comonomer) and / or molecular weight.

[0067] In the fluoro-acrylic polymer resin, the mass ratio of PVDF / acrylic polymer varies from 95 / 5 to 5 / 95, preferably from 75 / 25 to 25 / 75, and advantageously from 60 / 40 to 40 / 60.

[0068] In the fluoro-acrylic polymer resin, the average diameter of the particles is 0.05 to 3 μm, preferably 0.05 to 1 μm, more preferably 0.1 to 1 μm. In this embodiment, the fluoro-acrylic polymer resin is characterized by a close mixing of fluoro-polymer chains and acrylic polymer chains in at least a part of the particles.

[0069] iv) VDF / AA copolymer Alternatively, the polymer resin may be a copolymer containing vinylidene fluoride monomer units and monomer units (A) of the formula R 1 R 2 C=C(R 3 )C(O)R, wherein the substituents R 1 , R 2 and R 3 are, independently of one another, selected from the group consisting of H and C 1 ~C 3 alkyl, and R is selected from the group consisting of H and C 1 ~C 5 alkyl which may be substituted with at least one -OH group.

[0070] Preferably, the monomer unit A is of the formula R 1 R 2 C=C(R 3 )C(O)R, wherein the substituents R 1 , R 2 and R 3 are, independently of one another, selected from the group consisting of H and CH 3 , and R is selected from the group consisting of H, hydroxypropyl and hydroxyethyl or a mixture thereof. The term hydroxypropyl corresponds to -CH 2 CH(OH)CH 3 . The term hydroxyethyl corresponds to -CH(CH 3 )CH 2 OH.

[0071] Preferably, the formula R 1 R 2 C=C(R 3)The monomer unit A of C(O)R is distributed along the polymer chain mainly formed by vinylidene fluoride monomer units. In this embodiment, the polymer resin contains at least 0.01 mol%, preferably at least 0.02 mol%, preferably at least 0.03 mol%, particularly 0.04 mol% of monomer unit A. Preferably, the polymer resin contains at most 5 mol%, preferably at most 4 mol%, preferably at most 2 mol%, particularly at most 1 mol%, more particularly at most 0.75 mol% of monomer unit A.

[0072] In this embodiment, the polymer resin may also contain monomer units derived from one or more fluorinated comonomers B in addition to vinylidene fluoride monomer units and monomer unit A. The comonomer B is preferably an ethylenically unsaturated comonomer containing at least one fluorine atom. Non-limiting examples of comonomer B include C 2 ~C 8 perfluoroolefins, such as tetrafluoroethylene, of the formula CH 2 =CHR 1 (wherein R 1 is C 2 ~C 6 perfluoroalkyl), perfluoroalkyl ethylene, chloro- or bromo- or iodo-C 2 ~C 6 fluoroolefins, such as chlorotrifluoroethylene, of the formula CF 2 =CFOR 2 (wherein R 2 is C 1 ~C 6 perfluoroalkyl, C 1 ~C 12 alkoxy, C 1 ~C 12 perfluoroalkoxy), perfluoroalkyl vinyl ether, of the formula CF 2 =CFOCF 2 OR 3 (wherein R 3 is C 1 ~C 6 perfluoroalkyl or C 1 ~C 6Perfluoroalkyl vinyl ethers that are perfluoroalkoxy), of the formula CF 2 =CFOR 4 (wherein R 4 is C 1 ~C 12 alkyl, C 1 ~C 12 perfluoroalkyl, C 1 ~C 12 perfluoroether, and R 4 has a carboxylic acid group or a sulfonic acid group or a salt thereof) include perfluoroalkyl vinyl ethers.

[0073] v) Inorganic particles and optional additives The coating for the separator according to the present invention can contain, in addition to the polymer resin, inorganic particles that form micropores (gaps between inorganic particles) in the coating. Further, by adding inorganic particles, it is possible to contribute to the improvement of heat resistance and 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 undergo oxidation and / or reduction within the range of the voltage used). Also, the powdery inorganic material preferably has high ionic conductivity. Low-density materials are preferred over high-density materials because they can reduce the weight of the battery to be manufactured. The dielectric constant is preferably 5 or more. According to one embodiment, the inorganic particles are BaTiO 3 , Pb(Zr,Ti)O 3 , Pb 1-x La x Zr y O 3 (0 < x < 1, 0 < y < 1), PBMg 3 Nb 2 / 3 ) 3 , PbTiO 3 , hafnia (HfO(HfO 2 ))), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, Y 2 O 3 , boehmite (y-AlO(OH)), Al2 O 3 , TiO 2 , SiC, ZrO 2 , borosilicate, BaSO 4 , nanoclay, or a mixture thereof. In this case, the proportion of the solid content of the polymer with respect to the inorganic particles is 0.5 to 40 parts by weight of the solid content of the polymer resin with respect to 60 to 99.5 parts by weight of the inorganic particles. Advantageously, the ratio of the solid content of the polymer with respect to the inorganic particles is 0.5 to 35 per 65 to 99.5 parts by weight of the inorganic particles. Preferably, the proportion of the solid content of the polymer with respect to the inorganic particles is 0.5 to 30 with respect to 70 to 99.5 parts by weight of the inorganic particles.

[0074] The coating for the separator of the present invention may optionally contain additives selected from thickeners, pH adjusters, anti-settling agents, surfactants, foaming agents, fillers, defoaming agents, and fugitive or non-fugitive adhesion promoters in an amount of 0 to 15% by weight, preferably 0.1 to 10% by weight, based on the polymer.

[0075] The separator according to the present invention comprises the above-described coating optionally disposed 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 present invention is not particularly limited as long as it is a porous substrate having pores. The support may comprise a single layer or several separate layers. When the support comprises several layers, the coating described in the present invention is disposed on the outer surface of the support, i.e., the surface that first comes into contact with the electrolyte composition. Advantageously, the application of the coating according to the present invention to the support is carried out via an aqueous route or a solvent route. The porous substrate can take the form of a membrane or a fibrous fabric. When the porous substrate is fibrous, the porous substrate can be a nonwoven web forming a porous web, for example, a web obtained by direct spinning or melt blowing (spunbond or meltblown type) or electrospinning. Examples of the porous substrate used as the support in the present invention include, but are not limited to, polyolefin, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, poly(phenylene oxide), poly(phenylene sulfide), polyethylene naphthalate, or mixtures thereof. However, other heat-resistant engineering plastics can be used without particular limitation. Nonwoven materials made of natural or synthetic materials can also be used as the substrate of the separator. The porous substrate usually has a thickness of 1 to 50 μm and is typically a membrane or a cast nonwoven obtained by extrusion drawing (wet or dry). 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.

[0076] According to another embodiment, the separator does not include a porous support. In this case, the separator consists of the coating according to the present invention containing the polymer resin. The coating is directly deposited on the cathode or anode of the electrochemical device. The absence of the porous support makes it possible to limit the manufacturing cost of the electrochemical device and the dimensions of the electrochemical device. In this case, the coating replaces the porous support. In this embodiment, the polymer resin preferably has a porosity of 5 to 95%. The average size of the pores of the polymer resin is preferably between 0.001 and 50 μm, more preferably between 0.01 and 10 μm.

[0077] According to another alternative embodiment, the separator does not include a porous support and the separator is in the form of a gel. The separator is as described in the present application. The separator is formed into a gel by ordinary techniques such as solvent casting or extrusion.

[0078] The coating for the separator of the present invention exhibits an excellent compromise of the characteristics for coating applications of the separator, namely, good dry adhesion and adhesion in the wet state, good storage integrity and good resistance to electrolyte solvents with appropriate swelling, and good Gurley air permeability. The coating for the separator of the present invention also makes it possible to improve the wettability of the separator when the electrolyte composition has a high viscosity or a high polarity, as described in the following examples.

[0079] <Electrolyte composition> According to the present invention, the electrochemical device includes an electrolyte composition. The electrolyte composition is impregnated into the separator to enable impregnation of lithium ions in the device. As described above, the electrolyte composition includes a solvent and a lithium salt. The solvent can be one of the solvents mentioned below or a mixture thereof. According to a first embodiment, the solvent used in the electrolyte composition has a high polarity. The term "polarity" refers to the dipole moment of the solvent used in the electrolyte composition at 25°C. In another embodiment, the electrolyte composition has a high viscosity. The viscosity is measured at 20°C and a shear of 20 s -1 using a Brookfield Metek DV2T viscometer.

[0080] Preferably, the electrolyte composition has a viscosity greater than 2.0 cP as measured according to the method described above.

[0081] In a preferred embodiment, the electrolyte composition may also have a viscosity greater than 3 cP, greater than 4 cP, greater than 5 cP, greater than 6 cP, greater than 7 cP, greater than 8 cP, greater than 9 cP, greater than 10 cP, greater than 11 cP, greater than 12 cP, greater than 13 cP, greater than 14 cP, greater than 15 cP, greater than 16 cP, greater than 17 cP, greater than 18 cP, greater than 19 cP, greater than 20 cP, greater than 21 cP, greater than 22 cP, greater than 23 cP, greater than 24 cP, greater than 25 cP, greater than 26 cP, greater than 27 cP, greater than 28 cP, greater than 29 cP or greater than 30 cP.

[0082] According to a preferred embodiment, the electrolyte composition may also have a viscosity between 2 cP and 600 cP, preferably between 5 and 500 cP, more preferably between 10 and 450 cP, even more preferably between 15 and 400 cP, particularly between 20 and 350 cP, more specifically between 25 and 300 cP, preferably between 25 and 250 cP, and preferably between 30 and 200 cP.

[0083] Lithium salts can be present in the electrolyte composition at very various concentrations. High concentrations of lithium salts promote a high viscosity of the electrolyte composition. For example, the lithium salt can be present in the electrolyte composition at a concentration between 0.01 and 20 mol·l -1 preferably between 0.01 and 15 mol·l -1 preferably between 0.01 and 10 mol·l -1 preferably between 0.01 and 10 mol·l. The high concentration of lithium salt in the electrolyte composition promotes the performance of the electrochemical device in terms of capacity.

[0084] Preferably, the electrolyte composition has a viscosity of less than 1000 cP, preferably less than 900 cP, preferably less than 800 cP, more preferably less than 700 cP, particularly less than 600 cP, measured according to the method described above.

[0085] For example, the solvent can be of the formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (Il), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv), (Iw), (Ix), (Iy) or (Iz).

[0086]

Chemical formula

[0087] In the present application, the alkyl substituents and alkenyl substituents described in connection with the above solvent formula may be substituted with one or more fluorine atoms, C 1 ~C 5 alkoxy groups, C 1 ~C 10 perfluoroalkyl groups, phenyl groups, or CN, OH, NO 2 or SO 2 functional groups. In the present application, the C 6 aryl substituents described in connection with the above solvent formula may be substituted with one or more fluorine atoms, C 1 ~C 10 alkyl groups, C 1 ~C 5An alkoxy group or C 1 ~C 10 may be substituted with a perfluoroalkyl group.

[0088] The solvent may be, for example, but not limited to, a crown ether such as 18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether, dibenzo-18-crown-6 ether, dibenzo-24-crown-8 ether, dicyclohexano-18-crown-6 ether, dibenzo-12-crown-4 ether, etc.

[0089] More preferably, the solvent is of the formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (Il), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv), (Iw), (Ix), (Iy) or (Iz), R 4 、R 5 and R 18 are each independently selected from the group consisting of C 1 ~C 5 alkyl, C 2 ~C 3 alkenyl, C 1 ~C 5 perfluoroalkyl and C 6 aryl, R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 15 and R 16 are each independently selected from the group consisting of H, C 1 ~C 5 alkyl, C 2 ~C 3 alkenyl, C 1 ~C 5 perfluoroalkyl and C 6 aryl, n is an integer from 1 to 10, preferably from 1 to 5, X is O or SO 2 and Y 1 and Y 2 are, with the condition that Y 1 and Y 2 are not O at the same time, selected from O or CR 6 R 7 where R 6 and R 7 are as defined above, Y 3 is SO 2 or S=O, R 14 and R 17 are, independently of each other, selected from the group consisting of H, C 1 ~C 5 alkyl, C 2 ~C 3 alkenyl, and C 6 aryl.

[0090] In particular, the solvent is of the formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (Il), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv), (Iw), (Ix), (Iy) or (Iz), and R 4 R 5 and R 18 are, independently of each other, selected from the group consisting of C 1 ~C 3 alkyl, C 2 ~C 3 alkenyl, C 1 ~C 3 perfluoroalkyl and C 6 aryl, R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 15 and R16 are, independently of each other, H, C 1 ~C 3 alkyl, C 2 ~C 3 alkenyl, C 1 ~C 3 perfluoroalkyl and C 6 selected from the group consisting of aryl, n is an integer from 1 to 10, preferably from 1 to 5, X is O or SO 2 and Y 1 and Y 2 are, Y 1 and Y 2 are not both O at the same time, O or CR 6 R 7 selected from, R 6 and R 7 are as defined above, Y 3 is SO 2 or S=O, R 14 and R 17 are, independently of each other, H, C 1 ~C 3 alkyl, C 2 ~C 3 alkenyl, and C 6 selected from the group consisting of aryl.

[0091] More specifically, the solvent is such that R 4 and R 5 are, independently of each other, CH 3 , CH 2 F, CHF 2 , C 2 H 5 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 F, CH 2CHFCH 3 , C.H. 2 CH 2 CF 3 , C.H. 2 CF 2 CHF 2 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH(CH 3 ) 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , C.H. 3 CH 2 CH(CH 3 ), C.F. 2 CF 2 CF 2 CF 3 and CH(CH 3 ) 2 and preferably R 4 But, CH 3 , C 6 H 5 or CH 2 CH 3 and R 5 But, CH 3 , C.H. 2 F, CHF 2 , C 2 H 5 , C.H. 2 CH 2 F, C.H. 2 CHF 2 , C.H. 2 CF 3 , C.H. 2 CH 2 CH 3 , C.H. 2 CH 2 CH 2 F, C.H. 2 CHFCH 3 , C.H. 2 CH2 CF 3 , C.H. 2 CF 2 CHF 2 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , C.F. 2 CF 2 CF 2 CF 3 and CH(CH 3 ) 2 It may be of formula (Ia) selected from the group consisting of:

[0092] More specifically, the solvent is R 6 , R 7 , R 8 and R 9 However, independently of each other, H, F, and CH 3 , C.H. 2 F, CHF 2 , C.H. 2 CH 2 F, C.H. 2 CHF 2 , C.H. 2 CF 3 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C.F. 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , C.H. 3 CH2 CH(CH 3 )、CH 3 CH 2 CH 2 、CH(CH 3 ) 2 、CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 , R 7 and R 8 are H, CH 3 , C 6 H 5 or CH 2 CH 3 , R 9 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 and may be of formula (Ib).

[0093] More specifically, the solvent is such that R 6 and R 7 are, independently of each other, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 )、CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 is H, CH 3 , C 6 H 5 or CH 2 CH 3 , and R 7 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2CF 3 、C 6 H 5 、CH 2 CH 3 and CH=CH 2 may be those of formula (Ic) selected from the group consisting of.

[0094] More specifically, the solvent is R 4 and R 5 are, independently of each other, CH 3 、CH 2 CH 3 、CH 2 F、CHF 2 、CH 2 CH 2 F、CH 2 CF 3 、CH 2 OCH 3 、CH(CH 3 )CH 2 OCH 3 、CH(CH 3 ) 2 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH(CH 3 ) 2 、CH 3 CH 2 CH 2 CH 2 、(CH 3 ) 2 CHCH 2 、CH 3 CH 2 CH(CH 3 )、CH 3 CH 2 CH 2 、CH(CH 3 ) 2 、CHFCH 3 and CH 2 CH2 CH 3 selected from the group consisting of, preferably R 4 is CH 2 CH 2 F, CH 3 , C 6 H 5 , or CH 2 CH 3 selected from the group consisting of, R 5 is CH 3 CH 2 CH 3 CH 2 F, CHF 2 CH 2 CH 2 F, CH 2 CF 3 CH 2 OCH 3 CH(CH 3 )CH 2 OCH 3 CH(CH 3 ) 2 CF 3 CF 2 CF 3 CF 2 CF 2 CF 3 CH(CF 3 ) 2 CF 2 CF 2 CF 2 CF 3 CHFCH 3 , and CH 2 CH 2 CH 3 and may be of formula (Id) selected from the group consisting of.

[0095] More specifically, the solvent is R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are, independently of each other, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF2 、 CH 2 CF 3 、 CF 3 、 CF 2 CF 3 、 CF 2 CF 2 CF 3 、 CH(CF 3 ) 2 、 CF 2 CF 2 CF 2 CF 3 、 C 6 H 5 、 CH(CH 3 ) 2 、 CH 3 CH 2 CH 2 CH 2 、 (CH 3 ) 2 CHCH 2 、 CH 3 CH 2 CH(CH 3 )、 CH 3 CH 2 CH 2 、 CH(CH 3 ) 2 、 CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 、 R 7 and R 8 are H, CH 3 、 C 6 H 5 or CH 2 CH 3 and R 9 、 R 10 and R 11 are, independently of each other, H, F, CH 3 、 CH 2 F, CHF 2 、 CH 2 CH 2 F, CH 2 CHF 2 、 CH 2 CF 3 、 CF 3 、 CF 2 CF 3 、 CF 2 CF2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH 2 CH 3 and CH=CH 2 may be those of formula (Ie) selected from the group consisting of.

[0096] More specifically, the solvent is R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 and R 13 are, independently of one another, H, F, CH 3 、CH 2 F, CHF 2 、CH 2 CH 2 F, CH 2 CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH 3 CH 2 CH 2 CH 2 、(CH 3 ) 2 CHCH 2 、CH 3 CH 2 CH(CH 3 )、CH 3 CH 2 CH 2 、CH(CH 3 )2 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 , R 8 , R 10 and R 12 are H, CH 3 , C 6 H 5 or CH 2 CH 3 wherein R 7 , R 9 , R 11 and R 13 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 and may be of formula (If) selected from the group consisting of.

[0097] More specifically, the solvent is R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 )、CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 is H, CH 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 and preferably R 6 , R 7 and R 8 are H, CH 3 , C 6 H 5 or CH 2 CH 3 and R 9 , R 10 and R 11 are independently of one another H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 is H, CH 3 、C 6 H 5 or CH 2 CH 3 and CH=CH 2 and may be of formula (Ig).

[0098] More specifically, the solvent is such that R 7 、R 8 、R 9 and R 11 are, independently of one another, H, F, CH 3 、CH 2 F、CHF 2 、CH 2 CH 2 F、CH 2 CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH(CH 3 ) 2 、CH 3 CH2 CH 2 CH 2 、(CH 3 ) 2 CHCH 2 、CH 3 CH 2 CH(CH 3 )、CH 3 CH 2 CH 2 、CH(CH 3 ) 2 、CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 is H, CH 3 , C 6 H 5 or CH 2 CH 3 and CH=CH 2 and preferably R 6 , R 7 and R 8 are H, CH 3 , C 6 H 5 or CH 2 CH 3 and R 9 and R 11 are independently of each other H, F, CH 3 , CH 2 F, CHF 2 , CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 and CH=CH2 selected from the group consisting of, R 14 wherein, H, CH 3 , C 6 H 5 or CH 2 CH 3 and CH=CH 2 and may be of formula (Ih).

[0099] More specifically, the solvent is R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ), CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3and CH=CH 2 selected from the group consisting of, R 14 is H, CH 3 C 6 H 5 or CH 2 CH 3 and CH=CH 2 and preferably R 6 R 8 R 10 and R 12 are H, CH 3 C 6 H 5 or CH 2 CH 3 and R 7 R 9 R 11 and R 13 are, independently of one another, H, F, CH 3 CH 2 F, CHF 2 CH 2 CH 2 F, CH 2 CHF 2 CH 2 CF 3 CF 3 CF 2 CF 3 CF 2 CF 2 CF 3 CH(CF 3 ) 2 CF 2 CF 2 CF 2 CF 3 C 6 H 5 CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 is H, CH 3 C 6 H 5 or CH 2 CH 3 and CH=CH 2 and may be of formula (Ii).

[0100] More specifically, the solvent is R 6 R7 and R 8 and R 9 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ) 3 , CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 , R 7 and R 8 are H, CH 3 , C 6 H 5 or CH 2 CH 3 and R 9 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2CHF 2 , C.H. 2 CF 3 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C.F. 2 CF 2 CF 2 CF 3 , C 6 H 5 , C.H. 2 CH 3 and CH=CH 2 It may be of formula (Ij) selected from the group consisting of:

[0101] More specifically, the solvent is R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 15 and R 16 However, independently of each other, H, F, and CH 3 , C.H. 2 F, CHF 2 , C.H. 2 CH 2 F, C.H. 2 CHF 2 , C.H. 2 CF 3 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C.F. 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , C.H. 3 CH 2 CH 2 CH2 、 (CH 3 ) 2 CHCH 2 、 CH 3 CH 2 CH(CH 3 )、 CH 3 CH 2 CH 2 、 CH(CH 3 ) 2 、 CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 、 R 7 、 R 8 、 R 9 and R 10 are H, CH 3 、 C 6 H 5 or CH 2 CH 3 wherein R 11 、 R 12 、 R 13 、 R 15 and R 16 are, independently of each other, H, F, CH 3 、 CH 2 F、 CHF 2 、 CH 2 CH 2 F、 CH 2 CHF 2 、 CH 2 CF 3 、 CF 3 、 CF 2 CF 3 、 CF 2 CF 2 CF 3 、 CH(CF 3 ) 2 、 CF 2 CF 2 CF 2 CF 3 、 C 6 H 5 、 CH 2 CH 3 and CH=CH 2 and may be of formula (Ik) selected from the group consisting of.

[0102] More specifically, the solvent is R6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 15 and R 16 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 , CH(CH 3 )、CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH 2 is selected from the group consisting of, R 14 is H, CH 3 , C 6 H 5 or CH 2 CH 3 and CH=CH 2 and preferably R 6 , R7 , R 8 , R 9 and R 10 are H, CH 3 , C 6 H 5 or CH 2 CH 3 and R 11 , R 12 , R 13 , R 15 and R 16 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 and are selected from the group consisting of, and R 14 is H, CH 3 , C 6 H 5 or CH 2 CH 3 and CH=CH 2 and may be of formula (Il).

[0103] More specifically, the solvent is such that R 4 and R 5 are, independently of one another, CH 3 , CH 2 CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH2 CHF 2 , C.H. 2 CF 3 , C.H. 2 OCH 3 , CH(CH 3 )CH 2 OCH 3 , CH(CH 3 ) 2 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C.F. 2 CF 2 CF 2 CF 3 , C 6 H 5 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , C.H. 3 CH 2 CH(CH 3 ), CHFCH 3 and C.H. 2 CH 2 CH 3 and preferably R 4 But, CH 3 , C.H. 2 CH 3 , C.H. 2 F, CHF 2 , C.H. 2 CH 2 F, C.H. 2 CHF 2 , C.H. 2 CF 3 , C.H. 2 OCH 3 , CH(CH 3 )CH 2 OCH 3 , CH(CH 3 ) 2 , C.F. 3 , C.F. 2 CF 3 , C.F. 2CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CHFCH 3 and CH 2 CH 2 CH 3 selected from the group consisting of, R 5 is CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CH 2 OCH 3 , CH(CH 3 )CH 2 OCH 3 , CH(CH 3 ) 2 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CF 2 CF 2 CF 2 CF 3 and CHFCH 3 selected from the group consisting of, R 6 , R 7 , R 8 and R 9 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 may be those of formula (Im) selected from the group consisting of.

[0104] More specifically, the solvent is R 4 and R 5 are each independently CH 3 , CH 2 CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH(CH 3 ) 2 , CF 3 CH 2 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ), CHFCH 3 and CH 2 CH 2 CH 3selected from the group consisting of, preferably R 4 is CH 3 CH 2 CH 3 CH 2 F, CHF 2 CH 2 CH 2 F, CH 2 CHF 2 CH(CH 3 ) 2 CF 3 CH 2 CF 3 CF 2 CF 3 CF 2 CF 2 CF 3 CH(CF 3 ) 2 CF 2 CF 2 CF 2 CF 3 C 6 H 5 CHFCH 3 and CH 2 CH 2 CH 3 selected from the group consisting of, R 5 is CH 2 F, CHF 2 CH 2 CH 2 F, CH 2 CHF 2 CF 3 CH 2 CF 3 CF 2 CF 3 CF 2 CF 2 CF 3 CH(CF 3 ) 2 C 6 H 5 CF 2 CF 2 CF 2 CF 3 and CHFCH 3 and may be of formula (In) selected from the group consisting of.

[0105] More specifically, the solvent is R4 is CH 3 、CH 2 CH 3 、CH 3 OCH 2 CH 2 、CH 3 CH 2 CH 2 、CH(CH 3 ) 2 、CH 3 CH 2 CH 2 CH 2 、(CH 3 ) 2 CHCH 2 、CH 3 CH 2 CH(CH 3 )、C 6 H 5 、CF 3 -C 6 H 4 、CH 2 F、CHF 2 、CH 2 CH 2 F、CH 2 CHF 2 、CH(CH 3 ) 2 、CF 3 CH 2 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、CHFCH 3 and CH 2 CH 2 CH 3 It may be of formula (Io) selected from the group consisting of

[0106] More specifically, the solvent is R 6 and R 7 are, independently of each other, H, F, CH 3 、CH 2 F, CHF2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ) and CH=CH 2 selected from the group consisting of, preferably R 6 and R 7 are, independently of each other, H, F, CH 3 , CH 2 F, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH 2 CH 3 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 and CH=CH 2It can be a compound of formula (Ip) selected from the group consisting of, where n is an integer from 1 to 10, preferably from 1 to 5.

[0107] More specifically, the solvent is R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 and R 13 are, independently of each other, H, F, CH 3 、CH 2 F、CHF 2 、CH 2 CH 2 F、CH 2 CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH 2 CH 3 、CH 3 CH 2 CH 2 、CH(CH 3 ) 2 、CH 3 CH 2 CH 2 CH 2 、(CH 3 ) 2 CHCH 2 、CH 3 CH 2 CH(CH 3 ) and CH=CH 2 selected from the group consisting of, where X is O or SO 2 , preferably R 6 、R 7 、R 8 、R 9 、R 10 、R11 , R 12 and R 13 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH 2 CH 3 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 and CH=CH 2 selected from the group consisting of, and X is O or SO 2 and may be of formula (Iq).

[0108] More specifically, the solvent is such that R 6 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2, CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ) 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 and R 17 are, independently of each other, H, CH 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH, and R 14 and R 17 are, independently of each other, H, CH 3 , C 6 H5 or CH 2 CH 3 and CH=CH 2 and may be selected from the group consisting of formula (Ir).

[0109] More specifically, the solvent is R 8 R 9 R 10 R 11 R 12 and R 13 are each independently H, F, CH 3 CH 2 F, CHF 2 CH 2 CH 2 F, CH 2 CHF 2 CH 2 CF 3 CF 3 CF 2 CF 3 CF 2 CF 2 CF 3 CH(CF 3 ) 2 CF 2 CF 2 CF 2 CF 3 C 6 H 5 CH 3 CH 2 CH 2 CH 2 (CH 3 ) 2 CHCH 2 CH 3 CH 2 CH(CH 3 ) 3 CH 2 CH 2 CH(CH 3 ) 2 CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 8 R 10 and R 12 are H, CH 3 C 6 H5 or CH 2 CH 3 and R 9 、R 11 and R 13 are, independently of one another, H, F, CH 3 、CH 2 F, CHF 2 、CH 2 CH 2 F, CH 2 CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH 2 CH 3 and CH=CH 2 and are selected from the group consisting of, Y 1 and Y 2 are O or CR 6 R 7 and are selected from, provided that Y 1 and Y 2 are not O at the same time, and R 6 and R 7 are, independently of one another, H, F, CH 3 、CH 2 F, CHF 2 、CH 2 CH 2 F, CH 2 CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2CF 3 、C 6 H 5 、CH 3 CH 2 CH 2 CH 2 、(CH 3 ) 2 CHCH 2 、CH 3 CH 2 CH(CH 3 )、CH 3 CH 2 CH 2 、CH(CH 3 ) 2 、CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably, H, CH 3 、C 6 H 5 or CH 2 CH 3 and may be of formula (Is).

[0110] More specifically, the solvent is R 6 、R 7 、R 8 and R 9 are, independently of one another, H, F, CH 3 、CH 2 F、CHF 2 、CH 2 CH 2 F、CH 2 CHF 2 、CH 2 CF 3 、CF 3 、CF 2 CF 3 、CF 2 CF 2 CF 3 、CH(CF 3 ) 2 、CF 2 CF 2 CF 2 CF 3 、C 6 H 5 、CH(CH 3 ) 2 、CH 3 CH 2 CH2 CH 2 、 (CH 3 ) 2 CHCH 2 、 CH 3 CH 2 CH(CH 3 )、 CH 3 CH 2 CH 2 、 CH(CH 3 ) 2 、 CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 and R 17 are, independently of each other, H, CH 3 、 C 6 H 5 、 or CH 2 CH 3 、 CH=CH 2 selected from the group consisting of, preferably, R 6 and R 8 are, independently of each other, H, CH 3 、 C 6 H 5 、 or CH 2 CH 3 and R 7 、 R 9 are, independently of each other, H, F, CH 3 、 CH 2 F、 CHF 2 、 CH 2 CH 2 F、 CH 2 CHF 2 、 CH 2 CF 3 、 CF 3 、 CF 2 CF 3 、 CF 2 CF 2 CF 3 、 CH(CF 3 ) 2 、 CF 2 CF 2 CF 2 CF 3 、 C 6 H 5 、 CH 2 CH 3 and CH=CH 2selected from the group consisting of R 14 and R 17 are, independently of each other, H, CH 3 C 6 H 5 or CH 2 CH 3 and CH=CH 2 and may be of formula (It).

[0111] More specifically, the solvent is R 6 R 7 R 8 R 9 R 10 and R 11 are, independently of each other, H, F, CH 3 CH 2 F, CHF 2 CH 2 CH 2 F, CH 2 CHF 2 CH 2 CF 3 CF 3 CF 2 CF 3 CF 2 CF 2 CF 3 CH(CF 3 ) 2 CF 2 CF 2 CF 2 CF 3 C 6 H 5 CH(CH 3 ) 2 CH 3 CH 2 CH 2 CH 2 (CH 3 ) 2 CHCH 2 CH 3 CH 2 CH(CH 3 ) 3 CH 2 CH 2 CH(CH 3 ) 2 CH 2 CH 3and CH=CH 2 selected from the group consisting of, R 14 and R 17 are, independently of one another, H, CH 3 , C 6 H 5 or CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 , R 8 and R 10 are, independently of one another, H, CH 3 , C 6 H 5 , or CH 2 CH 3 wherein R 7 , R 9 , R 11 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, R 14 and R 17 are, independently of one another, H, CH 3 , C 6 H 5 , or CH 2 CH 3 and CH=CH 2 and may be of formula (Iu).

[0112] More specifically, the solvent is R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are, independently of one another, H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 , CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH 2 CH 3 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ) and CH=CH 2 is selected from the group consisting of, preferably R 6 , R 7 , R 8 and R 9 are, independently of one another, H, F, CH 3 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF3 , CH(CF 3 ) 2 , C 6 H 5 , CH 2 CH 3 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 and CH=CH 2 and can be of formula (Iv) wherein n is an integer from 1 to 10, preferably from 1 to 5, and is selected from the group consisting of

[0113] More specifically, the solvent is such that R 6 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ), CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH2 selected from the group consisting of, R 14 and R 17 are, independently of one another, H, CH 3 , C 6 H 5 , CH 2 CH 3 and CH=CH 2 selected from the group consisting of, preferably R 6 is H, F, CH 3 , CH 2 F, CHF 2 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 , CH(CH 3 ) 2 , CH 2 CH 3 and CH=CH, and R 14 and R 17 are, independently of one another, H, CH 3 , C 6 H 5 or CH 2 CH 3 and CH=CH 2 and may be of formula (Iw) selected from the group consisting of.

[0114] More specifically, the solvent is such that R 4 , R 5 and R 18 are, independently of one another, CH 3 , CH 2 F, CHF 2 , C 2 H 5, CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 F, CH 2 CHFCH 3 , CH 2 CH 2 CF 3 , CH 2 CF 2 CHF 2 , CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH(CH 3 ) 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , CH 3 CH 2 CH(CH 3 ), CF 2 CF 2 CF 2 CF 3 and CH(CH 3 ) 2 It may be one of formula (Ix) selected from the group consisting of.

[0115] More specifically, the solvent is R 4 and R 5 are, independently of each other, CH 3 CH 2 F, CHF 2 , C 2 H 5 , CH 2 CH 2 F, CH 2CHF 2 , C.H. 2 CF 3 , C.H. 2 CH 2 CH 3 , C.H. 2 CH 2 CH 2 F, C.H. 2 CHFCH 3 , C.H. 2 CH 2 CF 3 , C.H. 2 CF 2 CHF 2 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH(CH 3 ) 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , C.H. 3 CH 2 CH(CH 3 ), C.F. 2 CF 2 CF 2 CF 3 and CH(CH 3 ) 2 and Y is selected from the group consisting of 3 But, SO 2 Or it may be of formula (Iy) where S=O.

[0116] More specifically, the solvent is R 4 But, CH 3 , C.H. 2 F, CHF 2 , C 2 H 5 , C.H. 2 CH 2 F, C.H. 2 CHF 2 , C.H. 2CF 3 , C.H. 2 CH 2 CH 3 , C.H. 2 CH 2 CH 2 F, C.H. 2 CHFCH 3 , C.H. 2 CH 2 CF 3 , C.H. 2 CF 2 CHF 2 , C.F. 3 , C.F. 2 CF 3 , C.F. 2 CF 2 CF 3 , CH(CF 3 ) 2 , C 6 H 5 , CH(CH 3 ) 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CHCH 2 , C.H. 3 CH 2 CH(CH 3 ), C.F. 2 CF 2 CF 2 CF 3 and CH(CH 3 ) 2 It may be of formula (Iz) selected from the group consisting of:

[0117] In a non-limiting manner, the solvent is, for example, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, γ-butyrolactone, 3-fluoro-γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, γ-caprolactone, butyrolactam, valerolactam, N-methyl-butyrolactam, N-methyl-valerolactam, fluoroethylene carbonate, fluoropropylene carbonate, monofluoromethyl methyl carbonate, methyl-2,2,2-trifluoroethyl carbonate, trifluoroethyl ethyl carbonate, bis(2,2,2-trifluoroethyl carbonate), propyl-2,2,2-trifluoroethyl carbonate, methyl nonafluorobutyl ether, hexafluoroisopropyl methyl ether, bis(2,2,2-trifluoroethyl) ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, methyl isopropyl carbonate, ethyl isopropyl carbonate, propyl ethyl carbonate, methyl propyl carbonate, 1-fluoropropyl methyl carbonate, 2-fluoropropyl methyl carbonate, 1,1,1-trifluoropropyl methyl carbonate, 1,1,1,2,2-pentafluoropropyl methyl carbonate, 1,1,2,2-tetrafluoropropyl methyl carbonate, 1,1,1-trifluoroethyl methyl carbonate, 1,1-difluoroethyl methyl carbonate, 1-fluoroethyl methyl carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl fluoromethyl carbonate, 1-fluoroethyl ethyl carbonate, 1,1-difluoroethyl ethyl carbonate, 1,1,1-trifluoroethyl ethyl carbonate, vinyl ethylene carbonate, vinylene carbonate, ethyl ethanoate, ethyl 1-fluoroethanoate, ethyl 1,Selected from the group consisting of 1-difluoroethanoate, 1-fluoroethyl ethanoate, methyl ethanoate, 1-methoxyisopropyl ethanoate, 1-fluoroethyl propanoate, ethyl 2-fluoropropanoate, methyl butanoate, ethyl butanoate, methyl methoxyethanoate, N-methyl-2-oxazolidinone, ethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,4-dioxane, 1,3-dioxolane, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate, methyl phenyl carbonate, ethylene 2,3-dimethyl carbonate, vinylene carbonate, ethylene 2-vinyl carbonate, methyl benzoate, ethyl benzoate, 5-valerolactone, trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, triethyl phosphate, acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methylglutaronitrile, valeronitrile, butyronitrile, isobutyronitrile, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, N-methylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, benzonitrile, toluonitrile, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1,H)-pyrimidinone, 3-methyl-2-oxazolidinone, nitromethane, nitroethane, nitropropane, nitrobutane. These solvents may be used alone or in combination.,

[0118] Alternatively, the solvent may be an ionic liquid. Preferably, the ionic liquid is of the formula (cation) FSI or (cation) TFSI (wherein FSI is bis(fluorosulfonyl)imide and TFSI is bis(trifluoromethanesulfonyl)imide). Preferably, the cation is of the ammonium, imidazolium, pyrrolidinium, piperidinium, phosphonium, sulfonium or oxonium type. In a non-limiting manner, (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), (1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide), (1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide), (1-propyl-3-methylpyrrolidinium bis(fluorosulfonyl)imide), (1-butyl-1-methylpiperidinium bis(fluorosulfonyl)imide), (1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide), (methyl(tri-n-butyl)phosphonium bis(fluorosulfonyl)imide), (methyl(tri-n-ethyl))phosphonium bis(fluorosulfonylimide), (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide), (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide), (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), (1-propyl-3-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), (1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide), (1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide), (methyl(tri-n-butyl)phosphonium bis(trifluoromethanesulfonyl)imide)(methyl(tri-n-ethyl)phosphonium bis(trifluoromethanesulfonyl)imide) can be mentioned.

[0119] Alternatively, the solvent used in the present electrolyte composition has a dipole moment exceeding 2 Debye at 25°C. Preferably, the solvent has a dipole moment exceeding 2.5 Debye, preferably exceeding 3.0 Debye, more preferably exceeding 3.5 Debye, and particularly exceeding 4.0 Debye at 25°C.

[0120] For example, in a non-limiting manner, the electrolyte is propylene carbonate, 1-fluoroethyl methyl carbonate, 1-fluoroethyl ethyl carbonate, 1,1-difluoroethyl methyl carbonate, 1,1-difluoroethyl ethyl carbonate, 1,1,1-trifluoroethyl methyl carbonate, 1,1,1-trifluoroethyl ethyl carbonate, perfluoroethyl methyl carbonate, perfluoroethyl ethyl carbonate, propyl methyl carbonate, propyl ethyl carbonate, dimethoxymethane, ethylene carbonate, isopropyl methyl carbonate, isopropyl ethyl carbonate, fluoroethylene carbonate, vinylidene carbonate, butylene carbonate, vinyl ethylene carbonate, fluoropropylene carbonate, fluoro-γ-butyrolactone, δ-valerolactone, γ-butyrolactone, fluoropropyl methyl carbonate, 2-fluoropropyl methyl carbonate, 1,1,1-trifluoropropyl methyl carbonate, 1,1,2,2-tetrafluoropropyl methyl carbonate, 1,1,1,2,2-pentafluoropropyl methyl carbonate, fluoropropyl ethyl carbonate, 2-fluoropropyl ethyl carbonate, 1,1,1-trifluoropropyl ethyl carbonate, 1,1,2,2-tetrafluoropropyl ethyl carbonate, 1,1,1,2,2-pentafluoropropyl ethyl carbonate, nitromethane, 18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether, dibenzo-18-crown-6 ether, dibenzo-24-crown-8 ether, dicyclohexano-18-crown-6 ether, dibenzo-12-crown-4 ether, nitromethane, nitroethane, nitropropane, nitrobutane, trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, triethyl phosphate, acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methylglutaronitrile, valeronitrile, butyronitrile, isobutyronitrile, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,It may be selected from the group consisting of N-dimethylacetamide, N-methylpyrrolidinone, N-methylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfone, ethylmethyl sulfone, diethyl sulfone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfoxide, methylethyl sulfoxide, diethyl sulfoxide, benzonitrile, toluonitrile, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidinone.,

[0121] As described above, the electrolyte composition also contains a lithium salt. For example, the lithium salt is LiPF 6 , LiOSO 2 CF 3 , LIN(SO 2 CF 3 ) 2 , LIN(SO 2 F) 2 , LiBF 4 , LiClO 4 , lithium 2-trifluoromethyl-4,5-dicyanoimidazolate, lithium difluorophosphate (LiPO 2 F 2 ), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ), lithium difluoro(oxalato)borate (LiF 2 B(C 2 O 4 ) 2 ), or LiNO 3 and may be.,

Examples

[0122] The following examples illustrate the scope of the present invention in a non-limiting manner. The examples according to the present invention and the comparative examples described below were carried out according to the same protocol.,

[0123] Preparation of latex Three different latexes are shown in Table 1 below together with their main characteristics, namely the HFP content in the P(VDF-HFP) copolymer, the PVDF / acrylic ratio, and the solids content. The polymer resins used in Tests 3 and 4 are according to the present invention. The polymer resin according to the present invention was prepared from a P(VDF-HFP) copolymer latex used as a seed for synthesizing the corresponding fluoro-acrylic polymer composition by an emulsion polymerization process according to the protocol described in WO2007 / 018783.

[0124] Preparation of PVDF / acrylic polymer blend: An acrylic latex having the same composition as the acrylic part of the P(VDF-HFP) copolymer latex and the polymer resin of Test 4 is prepared independently of each other by an emulsion polymerization process as described above. Then, the two latexes are mixed at a ratio of 70 / 30.

[0125] Preparation of coating composition For each of Tests 2 to 4, the indicated latexes are added to a thickener (CMC250k in 3.5% aqueous solution) and, if necessary, the remainder in the form of demineralized water to obtain the same solids content close to 25.4% regardless of the initial solids content of the latex alone. Mixing is carried out at 200 rpm / 10 minutes under medium shear in a Thinky mixer. Then, other additives - a wetting agent (BYK 349), an adhesion promoter (BYK LPC-22346, already supplied in a 50% solution) are added only to the composition that does not yet contain acrylic in the latex (= Test 2), and then mixing is carried out again at 200 rpm / 10 minutes.

[0126] Coating application Each coating composition is applied to a porous PE separator (Gelon, thickness 12 microns) at a speed of about 25 mm / second using a coater equipped with a spiral bar for depositing 6 μm (wet thickness), and then dried at ambient temperature for 24 hours.

[0127]

Table 1

[0128] Wettability test Deposit a droplet of 2 ml of the electrolyte composition onto the separator. Visual inspection can be used to determine whether good wettability is observed, i.e., whether the electrolyte composition impregnates the separator, or conversely, whether no wettability is observed, i.e., whether the droplet of the electrolyte composition does not impregnate the separator. Perform a visual inspection after 30 minutes for all samples. Very good wettability is scored 2, good wettability is scored 1, and lack of wettability is scored 0.

[0129] The electrolyte composition is prepared by mixing the solvent in question and the lithium salt in amounts calculated to achieve the desired concentration. In the following examples, the lithium salt concentration is 4 mol·l with respect to the two solvents considered, namely propylene carbonate (PC) and diethyl carbonate (DEC). -1 is.

[0130] Perform Test 1 in the presence of a separator made of only a polyethylene support without coating. Perform Test 2 in the presence of a separator comprising a polyethylene support coated with a PVDF film without an acrylic part. Perform Tests 3 and 4 in the presence of a separator comprising a polyethylene support coated with a fluoro-acrylic polymer latex (prepared by the emulsion shown above). The results are shown in Table 2 below.

[0131]

Table 2

[0132] As shown by the above results, the polymer resin according to the present invention (Tests 3 and 4) is more likely to impregnate the separator than the polymer resin without an acrylic component.

Claims

1. An electrochemical device comprising a separator and an electrolyte composition, i) The separator includes a vinylidene fluoride monomer unit and a formula R １ R ２ C═C(R ３ ).C(O)R (wherein the substituents R １ , R ２ and R ３ are each independently selected from the group consisting of H and C １ -C ５ alkyl, and R is selected from the group consisting of -NH-C(CH ３ ). ２ CH ２ C(O)CH ３ , or OR' (where R' is selected from the group consisting of H and C １ -C １８ alkyl which may be substituted with one or more -OH groups, or a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom in its cyclic chain)), and includes at least one coating containing a polymer resin containing these monomer units ii) The electrolyte composition comprises a solvent and a lithium salt, and the electrolyte composition is at 20°C and 20s －１ The solvent has a viscosity greater than 2 cP when measured by shear, or the solvent has a dipole moment greater than 2 Debye at 25°C. An electrochemical device characterized by the following features.

2. The electrolyte composition is at 20°C and 20s －１ The electrochemical device according to claim 1, characterized in that it has a viscosity of more than 5 cP, preferably more than 10 cP, and particularly more than 15 cP, as measured by shear.

3. The electrochemical device according to claim 1, characterized in that the solvent has a dipole moment of more than 2.5 Debye, preferably more than 3.0 Debye, more preferably more than 3.5 Debye, and particularly more than 4.0 Debye, at 25°C.

4. The polymer resin is composed of monomer units of vinylidene fluoride and formula R １ R ２ C = C(R ３ ) A copolymer containing monomer units of C(O)R, or the polymer resin is a fluoropolymer containing monomer units of vinylidene fluoride and formula R １ R ２ C = C(R ３ )C(O)R (wherein, the substituent R 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' (wherein R' may be substituted with H and one or more -OH groups) １ ~C １８ The electrochemical device according to claim 1, characterized by being a mixture of an acrylic polymer containing monomer units (selected from the group consisting of alkyl groups or five-membered or six-membered heterocycles containing at least one nitrogen atom in their cyclic chain).

5. The polymer resin is a fluoropolymer containing monomer units of vinylidene fluoride, and formula R １ R ２ C = C(R ３ )C(O)R (wherein, the substituent R 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' (wherein R' may be substituted with H and one or more -OH groups) １ ~C １８ An electrochemical device according to claim 1, wherein the fluoropolymer is a mixture of an acrylic polymer containing monomer units (selected from the group consisting of alkyl or a five-membered or six-membered heterocycle having at least one nitrogen atom in its cyclic chain), and the fluoropolymer is selected from the group consisting of polyvinylidene fluoride homopolymer and copolymers based on vinylidene fluoride and at least one comonomer compatible with vinylidene fluoride.

6. The electrochemical device according to claim 5, characterized in that the comonomer is selected from the group consisting of vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, perfluoroalkyl vinyl ether, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, chlorotrifluoropropene, and ethylene.

7. The electrochemical device according to claim 5, characterized in that the fluoropolymer is a polyvinylidene hexafluoropropylene copolymer having a weight percentage of 2% to 25% by weight, preferably 4% to 15% by weight, of hexafluoropropylene monomer units relative to the weight of the copolymer.

8. The electrochemical device according to claim 5, characterized in that the fluoropolymer contains monomer units having at least one of the following functional groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, epoxy group, amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenol, ester, ether, siloxane, sulfonic acid, sulfuric acid, phosphoric acid, or phosphonic acid.

9. The electrochemical device according to claim 5, characterized in that the acrylic polymer contains a monomer selected from the group consisting of 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, hydroxybutyl acrylate, hydroxypropyl methacrylate, methyl acrylic acid, methyl methacrylate, ureidomethacrylate, and combinations thereof.

10. The coating is BaTiO ３ , Pb(Zr,Ti)O ３ Pb １－ｘ La ｘ Zr ｙ O ３ (0<x<1, 0<y<1), PBMg ３ Nb ２／３ ) ３ , PbTiO ３ , hafnia (HfO (HfO ２ )), SrTiO ３ , SnO ２ , CEO ２ , MgO, NiO, CaO, ZnO, Y ２ O ３ , Boehmite (y-AlO(OH)), Al ２ O ３ , TiO ２ , SiC, ZrO ２ , borosilicate, BaSO ４ The electrochemical device according to claim 1, characterized by comprising inorganic particles selected from the group consisting of nanoclay or mixtures thereof.

11. The device according to any one of claims 1 to 10, characterized in that it is selected from the group consisting of Li-ion batteries, capacitors, electric double-layer capacitors, and membrane electrode assemblies (MEAs) for fuel cells, and is preferably a Li-ion battery.

12. A device according to any one of claims 1 to 10, characterized in that it is a Li-ion secondary battery and also includes an anode and a cathode.