Separator for lithium-ion battery

Abstract

The invention relates to an electrochemical device comprising an electrolyte composition and a separator consisting of at least one fluorinated polymer resin, characterized in that the ratio σe / G is between 0.02 and 200.

Description

Technical Field

[0001] This invention generally relates to the field of energy storage in Li-ion rechargeable secondary battery packs. More specifically, this invention relates to electrochemical devices comprising a separator. Background Technology

[0002] The market for membranes used in electrochemical devices is dominated by the use of polyolefins (such as Celgard® or Hipore®) produced through dry or wet extrusion and / or stretching. Membranes must simultaneously possess low thickness, sufficient mechanical strength and temperature resistance, good electrochemical tolerance to the voltages they are exposed to, optimal affinity for electrolytes, and more generally, allow for excellent ionic conductivity.

[0003] Conventional electrolytes based on carbonate solvents are unstable at high potentials. To improve the stability of high-potential electrolytes, carbonate solvents can be replaced with other solvents (ionic liquids, sulfones, nitriles) that are more stable in oxidation, or the salt concentration can be increased to reduce solvent activity. Both approaches tend to increase the viscosity of the electrolyte, which can cause wettability problems for polyolefin membranes. WO 2023 / 227 846 discloses an electrochemical device comprising a membrane and a viscous electrolyte composition. The membrane consists of a polyethylene support coated with a polymer resin. There remains a need to develop novel membranes with improved properties (i.e., a very good trade-off between the latter's wettability and its thermal stability) that overcome the aforementioned drawbacks. Summary of the Invention

[0004] According to a first aspect, the present invention relates to an electrochemical device comprising an electrolyte composition and a membrane, characterized in that σ The e / G ratio is between 0.02 and 200; σ is the conductivity of the electrolyte composition in the membrane measured at 25°C, expressed in mS / cm; e is the membrane thickness in µm; and G is the conductivity in s. -1 The air permeability of the membrane, as indicated, was measured by Gurley according to standard ISO 5636-5 (2013). This invention provides a membrane that exhibits both good thermal stability and good wettability even in the presence of viscous electrolytes. In fact, it has been surprisingly found that polyolefin membranes tend to shrink at high temperatures, which can lead to short circuits in the battery pack, especially if the battery size is large. It has also been shown that applying a polymer coating to the surface of a porous polyolefin membrane improves thermal stability and wettability, but wettability remains insufficient for some viscous electrolytes. Using a ratio σ as provided by this invention... The e / G separator overcomes the drawbacks observed under specific battery pack operating conditions (i.e., high voltage and viscous electrolyte composition).

[0005] According to a preferred embodiment, the electrolyte composition comprises at least one solvent and a lithium salt, and the electrolyte composition has a viscosity greater than 2 cP at 20°C and for 20 seconds. -1 The shear was measured.

[0006] According to a preferred embodiment, the electrolyte composition has a viscosity greater than 5 cP, preferably greater than 10 cP, particularly greater than 15 cP, at 20°C and for 20 seconds. -1 The shear was measured.

[0007] According to a preferred embodiment, the electrolyte composition comprises 5% to 70% by weight of a lithium salt and 20% to 85% by weight of at least one organic solvent.

[0008] According to a preferred embodiment, the membrane has a porosity greater than 25%, as determined by mercury porosimetry according to standard ISO 15901-1 / 2016. Porosity within the specified range maintains good mechanical strength.

[0009] According to a preferred embodiment, the diaphragm has a thickness between 5 µm and 40 µm.

[0010] According to a preferred embodiment, the diaphragm has a coefficient of thermal shrinkage of less than 10% at 150°C, measured as an absolute value according to the method described in this patent application. It has been observed that the diaphragm according to the invention has a lower coefficient of thermal shrinkage compared to diaphragms made of polyolefins.

[0011] According to a preferred embodiment, the diaphragm has a range of 0.1 and 15 seconds. -1 .µm -1 The ratio between them is G / e; G is in s -1 The value represents the air permeability of the diaphragm, measured by Gurley according to standard ISO 5636-5 (2013), and e represents the thickness of the diaphragm, expressed in µm. Above 15 s -1 .µm -1 A value of 0 would mean worse diaphragm wettability.

[0012] According to a preferred embodiment, the diaphragm comprises at least one polymer resin selected from polyarylamide, polyester, polyaryl ether ketone, polysulfone, polyethersulfone, polyetherimide, polyimide, polyacrylonitrile, polyetherimide, polycarbonate, polybenzimidazole, polyaryl ether, polyaryl sulfide, fluoropolymer, cellulose, or mixtures thereof.

[0013] According to a preferred embodiment, the diaphragm comprises at least one polymer resin comprising a fluoropolymer P1, the fluoropolymer P1 comprising repeating units derived from vinylidene fluoride and optionally repeating units derived from hexafluoropropylene; preferably, the diaphragm comprises at least one polymer resin that is a vinylidene fluoride homopolymer.

[0014] According to a preferred embodiment, the diaphragm comprises at least one cellulose-type polymer resin.

[0015] According to a preferred embodiment, the membrane further comprises a polymer P2, which includes the formula R 1 R 2 C=C(R 3 The repeating unit of C(O)R, wherein the substituent R 1 R 2 and R 3 Independently selected from H and C1-C5 alkyl groups; R selected from -NHC(CH3)2CH2C(O)CH3 or -OR', wherein R' is selected from H and C1-C5 alkyl groups optionally substituted with one or more -OH groups or 5- or 6-membered heterocycles containing at least one nitrogen atom in their ring chains. 18 alkyl.

[0016] According to a preferred embodiment, the electrochemical device further includes a positive electrode and a negative electrode, wherein the membrane is disposed between the positive electrode and the negative electrode.

[0017] According to a preferred embodiment, the negative electrode comprises an active material selected from lithium alloys, lithium metal, metal oxides, carbon materials such as graphite or hard carbon, silicon, organosilicon, silicon alloys, and Li4Ti5O. 12 .

[0018] According to a preferred embodiment, the positive electrode comprises an active material selected from LiCoO2, Li(Ni, Co,Al)O2, and Li (1+x) Ni a Mn b Co c (x represents a real number 0 or greater, a = 0.9, 0.8, 0.6, 0.5 or 1 / 3, b = 0.05, 0.1, 0.2, 0.3 or 1 / 3, c = 0.05, 0.1, 0.2 or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3O3, Li3Fe2(PO4)3, Li3V2(PO4)3, Li Mn spinel substituted with different elements, which have the characteristics of Li 1+x Mn 2-x-y M yO4 represents the composition, M represents at least one metal selected from Al, Mg, Co, Fe, Ni, and Zn, and x and y independently represent real numbers between 0 and 2. Lithium titanate Li x TiO y x and y independently represent real numbers between 0 and 2, and lithium metal phosphates with a composition represented by LiMPO4, where M represents Fe, Mn, Co or Ni, or mixtures thereof.

[0019] According to a preferred embodiment, the electrochemical device is a lithium-ion battery pack having a cutoff voltage greater than or equal to 4.4V.

[0020] According to another aspect, the present invention relates to a diaphragm having a [condition] at 0.1 and 15 s [time / time]. -1 .µm -1 The ratio between them is G / e; G is in s -1 The permeability of the diaphragm to air is measured by Gurley according to standard ISO 5636-5, and e is the thickness of the diaphragm in µm; the diaphragm comprises at least one polymer resin as defined in this patent application. Detailed Implementation

[0021] According to a first aspect, the present invention provides an electrochemical device comprising an electrolyte composition and a membrane. These are described in more detail below. In the electrochemical device according to the invention, the ratio σ The e / G value is between 0.02 and 200.

[0022] According to the method detailed below, σ represents the conductivity of the electrolyte composition in the membrane, expressed in mS / cm, measured at 25°C. e is the membrane thickness in µm. G is the membrane thickness in s. -1 The air permeability of the diaphragm was measured by Gurley according to standard ISO 5636-5 (2013).

[0023] Advantageously, the ratio σ e / G is between 0.02 and 175, preferably between 0.03 and 150, more preferably between 0.03 and 125, particularly between 0.03 and 100, even more particularly between 0.03 and 75, advantageously between 0.03 and 50, beneficially between 0.03 and 25, preferably between 0.03 and 15, and particularly beneficially between 0.03 and 10. Preferably, the ratio σ e / G is between 0.05 and 10, preferably between 0.1 and 10, more preferably between 0.15 and 10, particularly between 0.2 and 10, even more particularly between 0.2 and 8, advantageously between 0.2 and 5, beneficially between 0.2 and 3, and preferably between 0.2 and 1.

[0024] As mentioned above, diaphragms with the ratios described above offer a very good trade-off between the different properties desired for the diaphragm (i.e., mechanical strength and wettability).

[0025] Electrolyte composition

[0026] According to the present invention, the electrochemical device comprises an electrolyte composition. The electrolyte composition impregnates a diaphragm to allow impregnation of lithium ions within the device. As mentioned above, the electrolyte composition comprises a solvent and a lithium salt. The solvent may be one of the solvents mentioned below or a mixture thereof. The solvent is preferably an organic solvent. According to a first embodiment, the solvent used for the electrolyte composition has high polarity. The term "polarity" refers to the dipole moment of the electrolyte composition at 25°C. In another embodiment, the electrolyte composition has high viscosity. Viscosity was measured using a Brookfield Metek DV2T viscometer at 20°C and 20 s. -1 The result was measured under shear.

[0027] Preferably, the electrolyte composition has a viscosity greater than 2.0 cP, measured according to the method described above. 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. According to a preferred embodiment, the electrolyte composition may also have a viscosity between 2 cP and 600 cP, advantageously between 5 and 500 cP, preferably between 10 and 450 cP, more preferably between 15 and 400 cP, particularly between 20 and 350 cP, even more particularly between 25 and 300 cP, advantageously between 25 and 250 cP, and advantageously between 30 and 200 cP.

[0028] The lithium salt can be present in the electrolyte composition at a highly variable concentration. A high concentration of lithium salt will promote a high viscosity of the electrolyte composition. For example, the lithium salt can be present in the electrolyte composition at concentrations of 0.01 and 20 mol.l. -1 Between 0.01 and 15 mol.l. -1 Between 0.01 and 10 mol.l -1 The concentrations of lithium salts in the electrolyte composition vary. A high concentration of lithium salts in the electrolyte composition will improve the capacity performance of the electrochemical device.

[0029] Preferably, the electrolyte composition has a viscosity of less than 1000 cP, advantageously less than 900 cP, preferably less than 800 cP, more preferably less than 700 cP, and particularly less than 600 cP, as measured according to the method described above.

[0030] The solvent may be selected from ethers; carbonates or organic carbonates; cyclic carbonates; carboxylic acid esters; lactones; phosphate esters; nitriles; amides; lactams; nitro compounds; sulfones; sulfoxides; ionic liquids having an FSI (bis(fluorosulfonyl)imide) anion and an ammonium, imidazolium, pyrrolidineonium, piperidinium, phosphonium, sulfonium, or oxonium type cation; fluorinated solvents; organophosphorus compounds, such as phosphate esters or phosphites.

[0031] For example, the solvent may be a solvent of 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), (Ix'), (Iy), or (Iz):

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] Among them, R 4 R 5 and R 18 Selected independently from C1-C 10 Alkyl, C2-C5 alkenyl, C1-C 10 (per)fluoroalkyl and C6 aryl; R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 15 and R 16 They are selected independently from H, C1-C 10 Alkyl, C2-C5 alkenyl, C1-C 10 (per)fluoroalkyl and C6 aryl; n is an integer from 1 to 10, preferably from 1 to 5; X is O or SO2; Y 1 and Y 2 Selected from O or CR 6 R 7 R 6 and R 7 As defined above, the condition is that Y1 and Y2 are not both 0 at the same time; Y 3 It is SO2 or S=O; R 14 and R 17 They are independently selected from H, C1-C5 alkyl, C2-C5 alkenyl and C6 aryl.

[0038] In this patent application, the alkyl and alkenyl substituents described in relation to the solvent formula above are optionally replaced with the following groups: one or more fluorine atoms, C1-C5 alkoxy groups, C1-C 10 (All)fluoroalkyl, phenyl, or CN, OH, NO2, or SO2 functional groups. In this application, the C6 aryl substituents described in relation to the solvent formula above are optionally replaced with one or more fluorine atoms, C1-C... 10 Alkyl groups, C2-C5 alkenyl groups or C1-C 10 (Fully) fluoroalkyl groups.

[0039] The solvent may also be a crown ether, such as (but not limited to), 18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether, dibenzo-18-crown-6 ether, dibenzo-24-crown-8 ether, dicyclohexyl-18-crown-6 ether, and dibenzo-12-crown-4 ether.

[0040] More preferably, the solvent is a solvent of (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (Il), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv), (Iw), (Ix), (Ix'), (Iy), or (Iz), wherein

[0041] R 4 R 5 and R 18 They are independently selected from C1-C5 alkyl, C2-C3 alkenyl, C1-C5 (per)fluoroalkyl and C6 aryl; R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 15 and R 16 They are independently selected from H, C1-C5 alkyl, C2-C3 alkenyl, C1-C5 (per)fluoroalkyl and C6 aryl; n is an integer from 1 to 10, preferably from 1 to 5; X is O or SO2; Y 1 and Y 2 Selected from O or CR 6 R 7 R 6 and R 7 As defined above, the condition is that Y1 and Y2 are not both 0 at the same time; Y 3 It is SO2 or S=O; R 14 and R 17 They are independently selected from H, C1-C5 alkyl, C2-C3 alkenyl and C6 aryl.

[0042] Specifically, the solvent is a solvent of 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), (Ix') or (Iy), wherein

[0043] R 4 R 5 and R18 They are independently selected from C1-C3 alkyl, C2-C3 alkenyl, C1-C3 (per)fluoroalkyl and C6 aryl; R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 15 and R 16 They are independently selected from H, C1-C3 alkyl, C2-C3 alkenyl, C1-C3 (per)fluoroalkyl and C6 aryl; n is an integer from 1 to 10, preferably from 1 to 5; X is O or SO2; Y 1 and Y 2 Selected from O or CR 6 R 7 R 6 and R 7 As defined above, the condition is that Y1 and Y2 are not both 0 at the same time; Y 3 It is SO2 or S=O; R 14 and R 17 They are independently selected from H, C1-C3 alkyl, C2-C3 alkenyl and C6 aryl.

[0044] More specifically, the solvent may be a solvent of formula (Ia), wherein R 4 and R 5 Independently selected from CH3, CH2F, CHF2, C2H5, CH2CH2F, CH2CHF2, CH2CF3, CH2CH2CH3, CH2CH2CH2F, CH2CHFCH3, CH2CH2CF3, CH2CF2CHF2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CF2CF2CF2CF3, and CH(CH3)2; preferably, R 4 It is CH3, C6H5, or CH2CH3 and R 5Selected from CH3, CH2F, CHF2, C2H5, CH2CH2F, CH2CHF2, CH2CF3, CH2CH2CH3, CH2CH2CH2F, CH2CHFCH3, CH2CH2CF3, CH2CF2CHF2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CF2CF2CF2CF3 and CH(CH3)2.

[0045] More specifically, the solvent may be a solvent of formula (Ib), wherein R 6 R 7 R 8 and R 9 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; preferably, R 6 R 7 and R 8 It can be H, CH3, C6H5, or CH2CH3 and R. 9 Selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0046] More specifically, the solvent may be a solvent of formula (Ic), wherein R 6 and R 7 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; preferably, R 6 It is H, CH3, C6H5 or CH2CH3 and R 7Selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0047] More specifically, the solvent may be a solvent of formula (Id), wherein R 4 and R 5 Independently selected from CH3, CH2CH3, CH2F, CHF2, CH2CH2F, CH2CF3, CH2OCH3, CH(CH3)CH2OCH3, CH(CH3)2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CHFCH3, and CH2CH2CH3; preferably, R 4 Selected from CH2CH2F, CH3, C6H5, or CH2CH3 and R 5 Selected from CH3, CH2CH3, CH2F, CHF2, CH2CH2F, CH2CF3, CH2OCH3, CH(CH3)CH2OCH3, CH(CH3)2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, CHFCH3 and CH2CH2CH3.

[0048] More specifically, the solvent may be a solvent of formula (Ie), wherein R 6 R 7 R 8 R 9 R 10 and R 11 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; preferably, R 6 R 7 and R 8 H, CH3, C6H5 or CH2CH3 and R 9 R 10 and R11 They are selected independently from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0049] More specifically, the solvent may be a solvent of formula (If), wherein R 6 R 7 R 8 R 9 R 10 R 11 R 12 and R 13 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; preferably, R 6 R 8 R 10 and R 12 It is H, CH3, C6H5 or CH2CH3 and R 7 R 9 R 11 and R 13 They are selected independently from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0050] More specifically, the solvent may be a solvent of formula (Ig), wherein R 6 R 7 R 8 R 9 R 10 and R 11Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; R 14 The components are H, CH3, C6H5, CH2CH3, and CH=CH2; preferably, R 6 R 7 and R 8 H, CH3, C6H5 or CH2CH3 and R 9 R 10 and R 11 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3, and CH=CH2; and R 14 It can be H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0051] More specifically, the solvent may be a solvent of formula (Ih), wherein R 7 R 8 R 9 and R 11 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; R 14 The components are H, CH3, C6H5, or CH2CH3 and CH=CH2; preferably R. 7 and R 8 H, CH3, C6H5 or CH2CH3 and R 9 and R 11 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2; and R14 It can be H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0052] More specifically, the solvent may be a solvent of formula (Ii), wherein R 6 R 7 R 8 R 9 R 10 R 11 R 12 and R 13 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; R 14 The components are H, CH3, C6H5, or CH2CH3 and CH=CH2; preferably R. 6 R 8 R 10 and R 12 H, CH3, C6H5 or CH2CH3 and R 7 R 9 R 11 and R 13 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2; and R 14 It can be H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0053] More specifically, the solvent may be a solvent of formula (Ij), wherein R 6 R 7 R 8 and R 9 Independently selected from each other, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3 and CH=CH2; preferably R6 R 7 and R 8 H, CH3, C6H5 or CH2CH3 and R 9 Selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0054] More specifically, the solvent may be a solvent of formula (Ik), wherein R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 15 and R 16 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; preferably R 6 R 7 R 8 R 9 and R 10 H, CH3, C6H5 or CH2CH3 and R 11 R 12 R 13 R 15 and R 16 They are selected independently from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0055] More specifically, the solvent may be a solvent of formula (Il), wherein R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13R 15 and R 16 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; R 14 The derivatives are H, CH3, C6H5, or CH2CH3 and CH=CH2; preferably R. 6 R 7 R 8 R 9 and R 10 H, CH3, C6H5 or CH2CH3 and R 11 R 12 R 13 R 15 and R 16 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2; and R 14 It can be H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0056] More specifically, the solvent may be a solvent of formula (Im), wherein R 4 and R 5 Independently selected from CH3, CH2CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CH2OCH3, CH(CH3)CH2OCH3, CH(CH3)2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CHFCH3, and CH2CH2CH3; preferably, R 4 Selected from CH3, CH2CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CH2OCH3, CH(CH3)CH2OCH3, CH(CH3)2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CHFCH3, and CH2CH2CH3, as well as R5 Selected from CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CH2OCH3, CH(CH3)CH2OCH3, CH(CH3)2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CF2CF2CF2CF3 and CHFCH3; R 6 R 7 R 8 and R 9 They are selected independently from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2.

[0057] More specifically, the solvent may be a solvent of formula (In), wherein R 4 and R 5 Independently selected from CH3, CH2CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH(CH3)2, CF3CH2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CHFCH3, and CH2CH2CH3; preferably, R 4 Selected from CH3, CH2CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH(CH3)2, CF3CH2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CHFCH3 and CH2CH2CH3; and R 5 Selected from CH2F, CHF2, CH2CH2F, CH2CHF2, CF3CH2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CF2CF2CF2CF3 and CHFCH3.

[0058] More specifically, the solvent may be a solvent of formula (Io), wherein R 4Selected from CH3, CH2CH3, CH3OCH2CH2, CH3CH2CH2, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), C6H5, CF3-C6H4, CH2 F, CHF2, CH2CH2F, CH2CHF2, CH(CH3)2, CF3CH2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, CHFCH3 and CH2CH2CH3.

[0059] More specifically, the solvent may be a solvent of formula (Ip), wherein R 6 and R 7 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3, CH3CH2CH2, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), and CH=CH2; preferably, R 6 and R 7 They are independently selected from H, F, CH3, CH2CF3, and CF. 3、 CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH2CH3, CH3CH2CH2, CH(CH3)2 and CH=CH2; and n is an integer from 1 to 10, preferably from 1 to 5.

[0060] More specifically, the solvent may be a solvent of formula (Iq), wherein R 6 R 7 R 8 R 9 R 10 R 11 R 12 and R 13 Independently selected from each other are H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3, CH3CH2CH2, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), and CH=CH2; and X is O or SO2; preferably R 6 R 7 R 8 R 9R 10 R 11 R 12 and R 13 The elements are independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH2CH3, CH3CH2CH2, CH(CH3)2 and CH=CH2; and X is O or SO2.

[0061] More specifically, the solvent may be a solvent of formula (Ir), wherein R 6 Selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3 and CH=CH2; R 14 and R 17 The components are independently selected from H, CH3, C6H5, CH2CH3, and CH=CH2; preferably, R 6 H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH(CH3)2, CH3CH2CH2, CH(CH3)2, CH2CH3 and CH=CH; and R 14 and R 17 They are independently selected from H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0062] More specifically, the solvent may be a solvent of formula (Is), wherein R 8 R 9 R 10 R 11 R 12 and R 13 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; preferably, R8 R 10 and R 12 It can be H, CH3, C6H5, or CH2CH3 and R. 9 R 11 and R 13 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2; and Y 1 and Y 2 Selected from O or CR 6 R 7 The condition is that Y1 and Y2 are not both O and R. 6 and R 7 The components are independently selected from F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3 and CH=CH2; preferably H, CH3, C6H5 or CH2CH3.

[0063] More specifically, the solvent may be a solvent of formula (It), wherein R 6 R 7 R 8 and R 9 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3, and CH=CH2; R 14 and R 17 The components are independently selected from H, CH3, C6H5, or CH2CH3 and CH=CH2; preferably, R 6 and R 8 Each of the following is independent of H, CH3, C6H5 or CH2CH3 and R. 7 and R 9Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2; and R 14 and R 17 They are independently selected from H, CH3, C6H5, or CH2CH3 and CH=CH2.

[0064] More specifically, the solvent may be a solvent of formula (Iu), wherein R 6 R 7 R 8 R 9 R 10 and R 11 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3; R 14 and R 17 The components are independently selected from H, CH3, C6H5, or CH2CH3 and CH=CH2; preferably R. 6 R 8 and R 10 Each of the following is independent of H, CH3, C6H5 or CH2CH3 and R. 7 R 9 R 11 Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3 and CH=CH2; and R 14 and R 17 They are independently selected from H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0065] More specifically, the solvent may be a solvent of formula (Iv), wherein R 6 R 7 R 8 R 9 R 10 and R 11Independently selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH2CH3, CH3CH2CH2, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), and CH=CH2; preferably, R 6 R 7 R 8 and R 9 They are independently selected from H, F, CH3, CH2CF3, and CF. 3、 CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH2CH3, CH3CH2CH2, CH(CH3)2 and CH=CH2; and n is an integer from 1 to 10, preferably from 1 to 5.

[0066] More specifically, the solvent may be a solvent of formula (Iw), wherein R 6 Selected from H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, CF2CF2CF2CF3, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CH3CH2CH2, CH(CH3)2, CH2CH3 and CH=CH2; R 14 and R 17 The components are independently selected from H, CH3, C6H5, CH2CH3, and CH=CH2; preferably, R 6 H, F, CH3, CH2F, CHF2, CH2CH2F, CH2CHF2, CH2CF3, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH(CH3)2, CH3CH2CH2, CH(CH3)2, CH2CH3 and CH=CH; and R 14 and R 17 They are independently selected from H, CH3, C6H5 or CH2CH3 and CH=CH2.

[0067] More specifically, the solvent may be a solvent of formula (Ix) or (Ix'), wherein R 4 R 5 and R 18They are independently selected from CH3, CH2F, CHF2, C2H5, CH2CH2F, CH2CHF2, CH2CF3, CH2CH2CH3, CH2CH2CH2F, CH2CHFCH3, CH2CH2CF3, CH2CF2CHF2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CF2CF2CF2CF3 and CH(CH3)2.

[0068] More specifically, the solvent may be a solvent of formula (Iy), wherein R 4 and R 5 Independently selected from CH3, CH2F, CHF2, C2H5, CH2CH2F, CH2CHF2, CH2CF3, CH2CH2CH3, CH2CH2CH2F, CH2CHFCH3, CH2CH2CF3, CH2CF2CHF2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CF2CF2CF2CF3, and CH(CH3)2; Y 3 It is SO2 or S=O.

[0069] More specifically, the solvent may be a solvent of formula (Iz), wherein R 4 Selected from CH3, CH2F, CHF2, C2H5, CH2CH2F, CH2CHF2, CH2CF3, CH2CH2CH3, CH2CH2CH2F, CH2CHFCH3, CH2CH2CF3, CH2CF2CHF2, CF3, CF2CF3, CF2CF2CF3, CH(CF3)2, C6H5, CH(CH3)2, CH3CH2CH2CH2, (CH3)2CHCH2, CH3CH2CH(CH3), CF2CF2CF2CF3 and CH(CH3)2.

[0070] In a non-limiting manner, the solvent is selected from, for example, propylene carbonate, ethylene carbonate, butyl carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, γ-butyrolactone, 3-fluoro-γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, γ-caprolactone, butyrolactam, valerolactone, N-methylbutyrolactam, N-methylvalerolactone, 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. Fluorobutyl ether, methyl isopropyl carbonate, ethyl isopropyl carbonate, ethyl propyl 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 carbonate, 1,1,1-trifluoroethyl ethyl carbonate, vinylene carbonate, vinylene carbonate, ethyl acetate, ethyl 1-fluoroethyl acetate Ethyl 1,1-difluoroethyl acetate, 1-fluoroethyl acetate, methyl acetate, 1-methoxyisopropyl acetate, 1-fluoroethyl propionate, ethyl 2-fluoropropionate, methyl butyrate, ethyl butyrate, methyl methoxyacetate, 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, 2,3-dimethyl ethylene carbonate, vinylene carbonate, 2-vinyl ethylene carbonate, methyl benzoate, ethyl benzoate, 5-pentanolide, trimethyl phosphate, ethyl phosphate Dimethyl ester, 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-methylpyrrolidone, 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, methylbenzonitrile, 1,3-dimethyl-2-imidazolium ketone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1,H)-pyrimidinone, 3-methyl-2-oxazolidinone, nitromethane, nitrobenzene, nitrobanane, nitrobanane, nitrobanane, tris(2,2,2-trifluoroethyl) phosphite, tris(2,2,2-trifluoroethyl) phosphate. These solvents can be used independently or in combination.

[0071] Alternatively, the solvent may be an ionic liquid. Preferably, the ionic liquid is an ionic liquid of the formula (cationic)FSI or (cationic)TFSI, wherein FSI is bis(fluorosulfonyl)imide and TFSI is bis(trifluoromethanesulfonyl)imide. Preferably, the cation is ammonium, imidazolium, pyrrolidineonium, piperidinium, phosphonium, sulfonium, or oxonium. References may be made in a non-limiting manner to (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), (1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide), (1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imide), (1-propyl-3-methylpyrrolidine 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(fluorosulfonyl)imide), (1-ethyl -3-methylimidazolium bis(trifluoromethanesulfonyl)imide, (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide), (1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide), (1-propyl-3-methylpyrrolidine 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).

[0072] Alternatively, the solvent used in this electrolyte composition has a dipole moment greater than 2 Debyes at 25°C. Preferably, the solvent has a dipole moment greater than 2.5 Debyes, more preferably greater than 3.0 Debyes, more preferably greater than 3.5 Debyes, and particularly greater than 4.0 Debyes at 25°C. For example, in a non-limiting manner, the solvent may be selected from 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, carbonate, etc. Fluorinated ethylene ester, vinylene 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 methyl carbonate -Tetrafluoropropyl ethyl ester, 1,1,1,2,2-pentafluoropropyl ethyl ester carbonate, nitromethane, 18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether, 18-crown-6 dibenzo[a]ether, 24-crown-8 dibenzo[a]ether, dicyclohexyl-18-crown-6 ether, dibenzo-12-crown-4 ether, nitromethane, nitrobenzene, nitrobenzene, nitrobenzene, 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-methylpyrrolidone, N-methylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfone, ethylmethyl sulfone, diethyl sulfone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, benzonitrile, methylbenzonitrile, 1,3-dimethyl-2-imidazolium, 3-methyl-2-oxazolium.

[0073] Among the solvents mentioned in this patent application, sulfones, sulfoxides, nitriles, ionic liquids, fluoroethers, organophosphorus compounds (e.g., phosphate esters or phosphites), and fluorocarbonates are preferred. The nitriles may be selected from acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, sebaconitrile, 2-methylglutaronitrile, valeronitrile, butyronitrile, isobutyronitrile, benzonitrile, and methylbenzonitrile. The sulfones may be selected from dimethyl sulfone, ethylmethyl sulfone, diethyl sulfone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, and sulfolane. The sulfoxides may be selected from dimethyl sulfoxide, methyl ethyl sulfoxide, and diethyl sulfoxide. The ionic liquid may be selected from EMIM-FSI (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), BMIM-FSI (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), PYR14-FSI (1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imide), PYR13-FSI (1-propyl-3-methylpyrrolidine bis(fluorosulfonyl)imide), PIP14-FSI (1-butyl-1-methylpiperidinium bis(fluorosulfonyl)imide), PIP13-FSI (1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide), P1444-FSI (methyl(tri-n-butyl)phosphonium bis(fluorosulfonyl)imide) and P1222-FSI (methyl(tri-n-ethyl)phosphonium bis(fluorosulfonyl)imide). The fluorinated solvent may be selected from fluoroethers, fluoroesters, fluoroformates, fluorocarbonates, fluorophosphates, fluorophosphites, or fluorosulfates.In a non-exhaustive manner, the following may be mentioned: 1,1,2,2-tetrafluoroethyl methyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, hexafluoroisopropyl methyl ether, 1,1,3,3,3-pentafluoro-2-trifluoromethylpropyl methyl ether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 1,1,2,3,3,3-hexafluoropropyl ethyl ether, 1,1,1,3,3,3-hexafluoro-2-(2,2,2-trifluoroethoxy)propyl Alkane, bis(2,2,2-trifluoroethyl) ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, methoxynonafluorobutane, ethoxynonafluorobutane, 1,2-(1,1,2,2-tetrafluoroethoxy)ethane, 2,2,3,3-tetrafluoro-1,4-dimethoxybutane, 2-(2-ethoxyethyl)-1,1,1-trifluoroethane, 2-(2-(2,2-difluoroethoxy)ethoxy)-1,1-difluoroethane, 2-(2-(2,2-difluoroethoxy)ethoxy)-1,1,1-trifluoroethane, 1,1,1-trifluoroethane Fluoro-2-(2-(2-trifluoroethoxy)ethoxy)ethane, 2,2-difluoroethyl acetate, 2,2,2-trifluoroethyl acetate, 2,2-difluoroethyl propionate, 3,3-difluoropropyl acetate, 3,3-difluoropropyl propionate, ethyl 4,4-difluorobutyrate, difluoroethyl formate, trifluoroethyl formate, 2,2,2-trifluoroethyl orthoformate, 4-fluoro-1,3-dioxolane-2-one (F1EC), 4,5-difluoro-1,3-dioxolane-2-one (F2EC), ethyl (1-fluoroethyl) carbonate (F1DE) C) 1-fluoroethyl (2,2,2-trifluoroethyl) carbonate (F4DEC), bis(2,2,2-trifluoroethyl) carbonate (BFEC), 2,2,2-trifluoroethyl methyl carbonate (F3EMC), trifluoropropylene carbonate, difluorodimethyl carbonate, methyl 2,2,2-trifluoroethyl carbonate, 2,2-difluoroethyl methyl carbonate, trifluoroethyl ethyl carbonate, methyl hexafluoro-i-propyl carbonate, ethyl hexafluoro-i-propyl carbonate, bis(trifluoroethyl) carbonate, propyl trifluoroethyl carbonate, fluorotoluene, and 1,4-dimethoxytetrafluorotoluene. Among the ionic liquids, pyrrolidone, piperidinium, and phosphonium are preferred. Among the organophosphorus compounds (e.g., phosphates or phosphites), tris(2,2,2-trifluoroethyl) phosphite and tris(2,2,2-trifluoroethyl) phosphate are preferred. Sulfones, and especially sulfolane, are preferred. The content of organic solvent in the electrolyte composition according to the invention is preferably between 30% and 85% by weight, more preferably between 40% and 85% by weight, more preferably between 50% and 80% by weight, and even more preferably between 60% and 75% by weight, relative to the total weight of the electrolyte composition.

[0074] As mentioned above, the electrolyte composition further comprises a lithium salt. For example, the lithium salt may be LiPF6, LiF, FSO3Li, LiiOSO2CF3, LiN(SO2CF3)2, LiN(SO2F)2, LiBF4, LiClO4, lithium 2-trifluoromethyl-4,5-dicyanimidazolium, lithium difluorophosphate (LiPO2F2), lithium bis(oxalate)borate (LiB(C2O4)2), lithium difluoro(oxalate)borate (LiF2B(C2O4)2), or LiNO3 or mixtures thereof. In particular, the lithium salt comprises lithium bis(fluorosulfonyl)imide (LiFSI-LiN(SO2F)2). The electrolyte composition may have a lithium salt content of 5% to 70% by weight, relative to the total weight of the electrolyte composition. The lithium salt content in the composition can be determined by NMR. The content can be from 10% to 60% by weight, preferably from 15% to 50% by weight, more preferably from 20% to 40% by weight, relative to the total weight of the electrolyte composition. The electrolyte composition according to the invention is preferably non-aqueous or substantially non-aqueous. In the context of the invention, the term "substantially non-aqueous" means that the water content in the electrolyte composition is less than or equal to 50 ppm of water, preferably less than or equal to 20 ppm of water. The electrolyte composition preferably has an organic solvent content of 20% to 85% by weight, relative to the total weight of the electrolyte composition.

[0075] The electrolyte composition according to the invention may optionally contain one or more additives. The additives are particularly selected from lithium salts other than LiFSI, organic compounds containing silicon, organic compounds containing boron, organic compounds containing phosphorus, phosphazenes, acid anhydrides, and compounds containing aluminum.

[0076] Other lithium salts besides LiFSI can be selected from LiPF6 (lithium hexafluorophosphate), LiTDI (lithium 2-trifluoromethyl-4,5-dicyanimidazolium), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium difluorophosphate (LiPO2F2), lithium bis(oxalate)borate (LiB(C2O4)2), lithium difluoro(oxalate)borate (LiF2B(C2O4)2), lithium tetrafluoroborate (LiBF4), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium fluoride (LiF), and lithium fluorosulfonate (FSO3Li). Organochemical compounds containing silicon are particularly selected from diphenylsilanediol, dimethoxyphenylsilane, tetra(trimethylsilyl)silane, trimethylsilyl acetate, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, bis(trimethylsilyl) sulfate, and tert-butyldimethylsilyl trifluoromethanesulfonate. Organochemical compounds containing phosphorus are particularly selected from tri(trimethylsilyl) phosphate, tri(hexafluoroisopropyl) phosphate, ethyl polyphosphate, bis(2,2,2-trifluoroethyl) phosphate, trimethyl phosphite, and tri(trimethylsilyl) phosphite (TMSPi). Organochemical compounds containing sulfur are particularly selected from propane sulpholol (PS), prop-1-ene-1,3-sulpholol (PES), methylene methane disulfonate (MMDS), ethylene sulfite, ethylene sulfate, 1,4-butane sulpholol, and methyl methanesulfonate. Organic compounds containing boron are particularly selected from trimethyl borate, triethyl borate, triisopropyl borate; tributyl borate, tris(2,2,2-trifluoroethyl) borate, tris(trimethylsilyl) borate, tris(pentafluorophenyl)borane, trimethoxyboroxine, triisopropylboroxine, and triphenylboroxine. Anhydrides are particularly selected from maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, pentene anhydride, itaconic anhydride, diethylene glycol anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic anhydride, and phenylsuccinic anhydride. Phosphazene compounds are particularly selected from ethoxy(pentafluoro)cyclotriphosphazene, hexafluorocyclotriphosphazene, and pentafluoro(phenoxy)cyclotriphosphazene. The compound containing aluminum (preferably in salt form) may be selected from aluminum tris[bis(fluorosulfonyl)imide] (Al(FSI)3=Al[(N(SO2F)2]3), aluminum tris[bis(trifluoromethanesulfonyl)imide] (Al(TFSI)3=Al[(N(SO2CF3)2]3), aluminum acetate, aluminum acetylacetone, aluminum carbonate, aluminum nitrate, aluminum chlorate, alkyl aluminum (e.g., triethylaluminum), and aluminum alkoxide (e.g., triacetylene oxide), preferably Al(FSI)3. The additive content in the electrolyte composition may be from 0% to 10% by weight, preferably from 0% to 5% by weight, relative to the total weight of the electrolyte composition.Preferably, the electrolyte composition of the present invention comprises dissolved aluminum salt, thereby having a concentration in the electrolyte composition between 0.5 and 10000 ppm, preferably between 0.5 and 9000 ppm, preferably between 0.5 and 8000 ppm, preferably between 0.5 and 7000 ppm, preferably between 0.5 and 6000 ppm, preferably between 0.5 and 5000 ppm, preferably between 0.5 and 4000 ppm, preferably between 0.5 and 3000 ppm, preferably between 0.5 and 2000 ppm, preferably between 0.5 and 1000 ppm, preferably between 0.5 and 900 ppm, preferably between 0.5 and 800 ppm, preferably between 0.5 and 700 ppm, preferably between 0.5 and 600 ppm, preferably between 0.5 and 500 ppm, preferably between 0.5 and 400 ppm, preferably between 0.5 and 3000 ppm. The aluminum content is between ppm, preferably between 0.5 and 200 ppm, preferably between 0.5 and 100 ppm, preferably between 0.5 and 90 ppm, preferably between 0.5 and 80 ppm, preferably between 0.5 and 70 ppm, preferably between 0.5 and 60 ppm, preferably between 0.5 and 50 ppm, preferably between 0.5 and 40 ppm, preferably between 0.5 and 30 ppm, preferably between 0.5 and 20 ppm, and preferably between 0.5 and 10 ppm by weight. The aluminum content in the electrolyte composition can be determined by any method known to those skilled in the art, and particularly by ICP-MS (inductively coupled plasma mass spectrometry), ICP-AES (inductively coupled plasma atomic emission spectrometry), or X-ray fluorescence spectrometry, preferably by ICP-MS.

[0077] In a particular embodiment that can be combined with preferred and other embodiments of the invention, the electrolyte composition according to the invention has a pH greater than or equal to 3.5, as determined by dilution to a 1:1 mass ratio in distilled water having a pH of 6.5 at 25°C. The pH may be greater than or equal to 4, and preferably 4 to 8. The pH may be 3.5 to 4; or 4 to 4.5; or 4.5 to 5; or 5 to 5.5; or 5.5 to 6; or 6 to 6.5; or 6.5 to 7; or 7 to 7.5; or 7.5 to 8; or 8 to 8.5; or 8.5 to 9; or 9 to 9.5; or 9.5 to 10; or 10 to 10.5; or 10.5 to 11; or 11 to 11.5; or 11.5 to 12; or 12 to 12.5; or 12.5 to 13; or 13 to 13.5; or 13.5; or 13.5 to 14. The pH can be measured by any method known to those skilled in the art. The pH can be measured, for example, using a glass electrode whose potential varies according to the Nernst equation as a function of hydrogen ion concentration. This potential can be measured relative to a reference electrode using a high-impedance potentiometer (commonly referred to as a pH meter). An example of a usable pH meter is the pHM210 model from Radiometer. The pH meter can be pre-calibrated using three buffer solutions (e.g., at pH = 4.0, 7.0, and 10.0). The aqueous solution can be stirred during pH measurement. The pH is preferably measured within one hour of dilution in distilled water. The fact that the aqueous solution (prepared by dissolving lithium bis(fluorosulfonyl)imide in distilled water) has a pH greater than or equal to 3.5 advantageously maintains the stability of the electrolyte with a high salt concentration at high voltages (greater than 4.5 V). The electrolyte composition can be prepared by mixing a lithium salt, an organic solvent, and optionally one or more additives. Preferably, the desired amount of lithium salt is dissolved in an organic solvent, and then the optional additives are added.

[0078] diaphragm

[0079] The membrane comprises at least one polymer resin. The membrane may also comprise inorganic particles. The membrane is preferably in the form of a layer consisting of the at least one polymer resin and optionally the inorganic particles. Alternatively, the inorganic particles may be deposited on the layer consisting of the at least one polymer resin.

[0080] According to a preferred embodiment, the membrane has a porosity greater than 25%, advantageously greater than 26%, preferably greater than 27%, preferably greater than 28%, more preferably greater than 29%, particularly greater than 30%, more particularly greater than 31%, preferably greater than 32%, advantageously greater than 33%, advantageously greater than 34%, preferably greater than 35%, more preferably greater than 36%, particularly greater than 37%, more particularly greater than 38%, and more particularly greater than 39%. This porosity is measured by mercury porosimetry according to standard ISO 15901-1:2016. However, excessively high porosity (above 90%, preferably above 70%) can lead to the risk of dendrite formation. According to a preferred embodiment, the membrane may have a porosity less than 90%, advantageously less than 88%, preferably less than 86%, and particularly less than 85%. According to a preferred embodiment, the membrane has a porosity of less than 70%, advantageously less than 69%, preferably less than 68%, preferably less than 67%, more preferably less than 66%, particularly less than 65%, more particularly less than 64%, advantageously less than 63%, advantageously less than 62%, preferably less than 61%, more preferably less than 60%, as determined by mercury porosimetry according to standard ISO 15901-1:2016. According to a preferred embodiment, the membrane has a porosity between 25% and 90%, advantageously between 25% and 80%, preferably between 25% and 80%, more preferably between 25% and 70%, between 30% and 65%, particularly between 35% and 65%, more particularly between 40% and 60%, as determined by mercury porosimetry according to standard ISO 15901-1:2016. The porosity can vary as a function of the material used to prepare the membrane, preferably greater than 25%, and is determined by mercury porosimetry according to standard ISO 15901-1:2016.

[0081] According to a preferred embodiment, the diaphragm preferably has a thickness between 5µm and 40µm. Advantageously, the diaphragm may have a thickness between 6µm and 38µm, preferably between 7µm and 36µm, more preferably between 8µm and 34µm, particularly between 9µm and 32µm, and even more particularly between 10µm and 30µm. According to a preferred embodiment, the diaphragm may have a thickness between 10µm and 28µm, advantageously between 10µm and 26µm, preferably between 10µm and 24µm, particularly between 10µm and 22µm, and even more particularly between 10µm and 20µm. Alternatively, the diaphragm may have a thickness between 40µm and 150µm, or between 40µm and 130µm, or between 50µm and 100µm.

[0082] As mentioned above, the diaphragm according to the invention has very good thermal stability, characterized by a low coefficient of thermal shrinkage at 150°C. Advantageously, the diaphragm has a coefficient of thermal shrinkage of less than 10% at 150°C, measured as an absolute value according to the method described in this patent application. Preferably, the diaphragm has a coefficient of thermal shrinkage of less than 9% at 150°C, more preferably less than 8%, particularly less than 7%, even more particularly less than 6%, advantageously less than 5%, advantageously less than 4%, and preferably advantageously less than 3%, measured as an absolute value according to the method described in this patent application.

[0083] The diaphragm has a range of 0.1 and 15 s. -1 .µm -1 The ratio G / e is given by the standard ISO 5636-5, where G is the air permeability of the membrane, measured by Gurley, and e is the thickness of the membrane. Advantageously, the ratio G / e is between 0.1 and 14 s. -1 .µm -1 Between 0.1 and 13 s -1 .µm -1 Between 0.1 and 12 s -1 .µm -1 Between 0.1 and 11 s -1 .µm -1 Between 0.1 and 10 s -1 .µm -1 Between 0.1 and 9 s -1 .µm -1 Between 0.1 and 8 s -1 .µm -1 Between 0.1 and 7 s -1 .µm -1 Between 0.1 and 6 s -1 .µm -1 Between 0.1 and 5 s -1 .µm -1 between.

[0084] The at least one polymer resin may be selected, alone or in combination, from the polymer resins described below. The at least one polymer resin may be selected from polyarylamides, polyesters, polyaryl ether ketones, polysulfones, polyethersulfones, polyetherimides, polyimides, polyacrylonitrile, polycarbonates, polybenzimidazoles, polyaryl ethers, polyaryl sulfides, fluoropolymers, cellulose, or mixtures thereof. In particular, the at least one polymer resin may be selected from polyarylamides, polyesters, polyaryl ether ketones, polysulfones, polyethersulfones, polyetherimides, polyimides, polyacrylonitrile, fluoropolymers, cellulose, or mixtures thereof. More particularly, the at least one polymer resin contained in the separator may be polyarylamides, polyesters, polyaryl ether ketones, polyetherimides, polyimides, fluoropolymers, cellulose, or mixtures thereof.

[0085] According to a preferred embodiment, the at least one polymer resin comprises a fluoropolymer P1, wherein the fluoropolymer P1 contains at least one fluorinated monomer M1a in its chain. The at least one fluorinated monomer M1a is selected from compounds containing vinyl groups capable of opening for polymerization, and contains at least one fluorine atom, a fluoroalkyl group, or a fluoroalkoxy group directly attached to the vinyl group. The fluoropolymer P1 may contain polar groups. These polar groups may be present in the fluoropolymer P1 via monomers containing said polar groups. Alternatively, the polar groups may be grafted onto the fluoropolymer according to known techniques to provide the fluoropolymer P1. Preferably, the polar groups are introduced into the fluoropolymer P1 via monomers containing said polar groups (e.g., via monomer M1c described in the following patent application).

[0086] Preferably, the fluoropolymer P1 comprises repeating units derived from monomer M1a, wherein monomer M1a is selected from vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers, such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE), and perfluoro(propyl vinyl) ether (PPVE); Fluorine (1,3-dioxacyclopentene); perfluoro(2,2-dimethyl-1,3-dioxacyclopentene) (PDD); products of the formula CF2=CFOCF2CF(CF3)OCF2CF2X, where X is SO2F, CO2H, CH2OH, CH2OCN, or CH2OPO3H; products of the formula CF2=CFOCF2CF2SO2F; products of the formula F(CF2)nCH2OCF=CF2, where n is 1, 2, 3, 4, or 5; products of the formula R 1 The product of CH2OCF=CF2, wherein R1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; formula R 2The product of OCF=CH2, in which R 2 The composition is F(CF2)p and p is 1, 2, 3 or 4; perfluorobutylethylene (PFBE); trifluoropropylene, tetrafluoropropylene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropylene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropylene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene, or mixtures thereof. In trifluoropropylene, 3,3,3-trifluoropropylene may be mentioned. In tetrafluoropropylene, 2,3,3,3-tetrafluoropropylene or 1,3,3,3-tetrafluoropropylene may be mentioned. In pentafluoropropylene, 1,1,3,3,3-pentafluoropropylene or 1,2,3,3,3-pentafluoropropylene may be mentioned. Chlorofluoroethylene may represent 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The isomer 1-chloro-1-fluoroethylene is preferred. Chlorotrifluoropropylene is preferably 1-chloro-3,3,3-trifluoropropylene or 2-chloro-3,3,3-trifluoropropylene.

[0087] Specifically, the fluoropolymer P1 comprises repeating units derived at least from monomer M1a, which is vinylidene fluoride. The fluoropolymer P1 may be a vinylidene fluoride homopolymer or a vinylidene fluoride copolymer. Therefore, the fluoropolymer P1 may comprise repeating units derived from monomer M1a, which is vinylidene fluoride, repeating units derived from fluorinated monomer M1b, and / or repeating units derived from monomer M1c. In the fluoropolymer P1, the mass content of repeating unit M1a is at least 50%, preferably at least 60%, more preferably greater than 70%, and advantageously greater than 80%.

[0088] The fluoropolymer M1b is different from the monomer M1a. Therefore, the fluorinated monomer M1b is selected from: fluoroethylene; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers, such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE), and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxacyclopentene); perfluoro(2,2-dimethyl-1,3-dioxacyclopentene) (PDD); products of the formula CF2=CFOCF2CF(CF3)OCF2CF2X, wherein X is SO2F, CO2H, CH2OH, CH2OCN, or CH2OPO3H; products of the formula CF2=CFOCF2CF2SO2F; products of the formula F(CF2)nCH2OCF=CF2, wherein n is 1, 2, 3, 4, or 5; products of the formula R 1 The product of CH2OCF=CF2, in which R 1 For hydrogen or F(CF2)m and m is 1, 2, 3 or 4; Formula R 2 The product of OCF=CH2, in which R 2The fluoropolymer P1 comprises F(CF2)p and p being 1, 2, 3, or 4; perfluorobutylethylene (PFBE); trifluoropropylene, tetrafluoropropylene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropylene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropylene, and 2-trifluoromethyl-3,3,3-trifluoro-1-propene, or mixtures thereof. Preferably, the fluoropolymer P1 comprises repeating units derived from monomer M1a, which is vinylidene fluoride, and repeating units derived from fluorinated monomer M1b, said fluorinated monomer M1b being selected from vinyl fluoride; trifluoroethylene; chlorotrifluoroethylene; 1,2-difluoroethylene; tetrafluoroethylene; hexafluoropropylene; perfluoro(alkyl vinyl) ethers, such as perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether, or perfluoro(propyl vinyl) ether; perfluoro(1,3-dioxacyclopentene); perfluoro(2,2-dimethyl-1,3-dioxacyclopentene); formula CF The product of formula CF2=CFOCF2CF(CF3)OCF2CF2X, where X is SO2F, CO2H, CH2OH, CH2OCN, or CH2OPO3H; the product of formula CF2=CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF2, where n is 1, 2, 3, 4, or 5; the product of formula R'CH2OCF=CF2, where R' is hydrogen or F(CF2)z and z is 1, 2, 3, or 4; the product of formula R''OCF=CH2, where R... 2The fluoropolymer P1 is F(CF2)z, where z is 1, 2, 3, or 4; trifluoropropylene, tetrafluoropropylene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropylene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropylene, or 2-trifluoromethyl-3,3,3-trifluoro-1-propene or mixtures thereof. Specifically, the fluoropolymer P1 comprises repeating units derived from monomer M1a, which is vinylidene fluoride, and repeating units derived from fluorinated monomer M1b, which is selected from trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, and hexafluoropropylene or mixtures thereof. Preferably, when it contains either one, the fluoropolymer P1 comprises 1% to 40% by weight, preferably 1% to 30% by weight, and particularly 2% to 20% by weight of repeating units derived from said monomer M1b, based on the total weight of the polymer. The fluoropolymer P1 may be, for example, a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and trifluoroethylene, a copolymer of vinylidene fluoride and tetrafluoroethylene, a copolymer of vinylidene fluoride and chlorotrifluoroethylene, a ternary polymer of vinylidene fluoride, chlorotrifluoroethylene and tetrafluoroethylene, a ternary polymer of vinylidene fluoride, chlorotrifluoroethylene and trifluoroethylene, a ternary polymer of vinylidene fluoride, trifluoroethylene and hexafluoropropylene, a ternary polymer of vinylidene fluoride, tetrafluoroethylene and 1,1-chlorofluoroethylene, or a ternary polymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. The fluoropolymer P1 may be a copolymer of vinylidene fluoride and hexafluoropropylene, wherein the hexafluoropropylene content is 1% to 40% by weight, preferably 1% to 30% by weight, particularly 2% to 20% by weight, based on the total weight of the fluoropolymer P1. The fluoropolymer P1 may be poly(vinylidene fluoride-trifluoroethylene and / or tetrafluoroethylene), preferably poly(vinylidene fluoride-copolymer-trifluoroethylene). These fluoropolymers preferably have a molar content of 25% to 95%, preferably 55% to 80%, for example 25% to 35%, or 35% to 45%, or 45% to 55%, or 55% to 65%, or 65% to 80%, or 80% to 95% of vinylidene fluoride units; and / or a molar content of 5% to 75%, preferably 20% to 45%, for example 5% to 10%, or 10% to 20%, or 20% to 30%, or 30% to 45%, or 45% to 55%, or 55% to 65%, or 65% to 75% of trifluoroethylene and / or tetrafluoroethylene units. The fluoropolymer P1 may be poly(vinylidene fluoride-trifluoroethylene and / or tetrafluoroethylene-chlorofluoroethylene and / or chlorotrifluoroethylene), preferably poly(vinylidene fluoride-tert-trifluoroethylene-tert-chlorofluoroethylene) or poly(vinylidene fluoride-tert-trifluoroethylene-tert-chlorotrifluoroethylene).These fluoropolymers preferably have a molar content of 25% to 80%, preferably 35% to 70%, for example 25% to 35%, or 35% to 45%, or 45% to 55%, or 55% to 70%, or 70% to 80% of vinylidene fluoride units; and / or between 3% and 60%, preferably 14% to 40%, for example 3% to 5%, 5% to 10%, 10% to 14%, 14% to 20%, or 20% to 30%, or 30% to 40%, or 40% to 50%. Or 50% to 60% molar content of trifluoroethylene and / or tetrafluoroethylene units; and / or 2% to 20%, preferably 3% to 15%, preferably 4% to 12%, for example 2% to 3%, or 3% to 4%, or 4% to 5%, or 5% to 6%, or 6% to 7%, or 7% to 8%, or 8% to 9%, or 9% to 10%, or 10% to 12%, or 12% to 15%, or 15% to 18%, or 18% to 20% molar content of chlorofluoroethylene and / or chlorotrifluoroethylene units.

[0089] The monomer M1c can be represented by formula R. a R b C=C(R c (X) 3 ) p′ C(O)R d The monomer of ) wherein the substituent R a R b and R c Independently selected from H, CO2H, and C1-C5 alkyl groups; R d Selected from -NHC(CH3)2CH2C(O)CH3 or -OR d ', where R d Selected from H and optionally using one or more -OH, -CO2H, -SO3H, -PO3H or -OC(O)R d '' or -C(O)OR d '' group or a five- or ten-membered heterocyclic substituted group containing at least one nitrogen atom in its ring chain, C1-C 18 Alkyl; R d Selected from C6-C atoms optionally substituted with one or more -OH, -CO2H, -SO3H or -PO3H groups. 12 Aryl and C1-C6 alkyl; p'' is 0 or 1; X 3 Selected from -[-C(O)OC(R) 26’ (R) 27’ )C(R 28’ (R) 29’ )-] w2 - and optionally C1-C with one or more -OH, -CO2H or ester groups. 10Alkyl hydrocarbon group; wherein w2 is an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, particularly from 1 to 5; for each unit w2 independently, R 26’ R 27’ R 28’ R 29’ The heterocycles are independently selected from H and C1-C5 alkyl groups. The heterocycles can be saturated, unsaturated, or aromatic. The heterocycles can be monocyclic or bicyclic. The heterocycles can be pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, oxindole, indigo, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidinone, or 4-imidazolidinone rings. The heterocycles can be substituted with one or more C1-C5 alkyl groups. As mentioned above, C1-C... 18 The alkyl group is optionally replaced with the heterocycle. The latter may be attached to the alkyl chain via a nitrogen atom or any other atom that forms the heterocycle. Preferably, the heterocycle is a 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidineone, or 4-imidazolidineone.

[0090] Advantageously, the monomer M1c can be of formula R a R b C=C(R c (X) 3 ) p′ C(O)R d The monomer of ) wherein the substituent R a R b and R c Independently selected from H, CO2H, and C1-C5 alkyl groups; R d For -OR d ', where R d Selected from H and optionally using one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)R d '' or -C(O)OR d '' group or a five- or ten-membered heterocyclic substituted group containing at least one nitrogen atom in its ring chain, C1-C 18 Alkyl; R d Selected from C6-C atoms optionally substituted with one or more -OH, -CO2H, -SO3H or -PO3H groups. 12 Aryl and C1-C6 alkyl; p'' is 0 or 1; X 3 Selected from -[-C(O)OC(R) 26’ (R) 27’ )C(R 28’ (R) 29’ )-] w2- and optionally C1-C with one or more -OH, -CO2H or ester groups. 10 Alkyl hydrocarbon group; wherein w2 is an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, particularly from 1 to 5; for each unit w2 independently, R 26’ R 27’ R 28’ and R 29’ They are independently selected from H and C1-C5 alkyl groups.

[0091] Preferably, the monomer M1c can be of formula R a R b C=C(R c (X) 3 ) p′ C(O)R d The monomer of ) wherein the substituent R a R b and R c Independently selected from H, CO2H, and C1-C5 alkyl groups; R d For -OR d ', where R d Selected from H and optionally using one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)R d '' or -C(O)OR d '' group substitution C1-C 15 Alkyl; R d Selected from C6-C atoms optionally substituted with one or more -OH, -CO2H, -SO3H or -PO3H groups. 10 Aryl and C1-C5 alkyl; p'' is 0 or 1; X 3 Selected from -[-C(O)OC(R) 26’ (R) 27’ )C(R 28’ (R) 29’ )-] w2 - and optionally C1-C with one or more -OH, -CO2H or ester groups. 10 Alkyl hydrocarbon group; wherein w2 is an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, particularly from 1 to 5; for each unit w2 independently, R 26’ R 27’ R 28’ and R 29’ They are independently selected from H and C1-C5 alkyl groups.

[0092] More preferably, the monomer M1c can be of formula R a R b C=C(R c(X) 3 ) p′ C(O)R d The monomer of ) wherein the substituent R a R b and R c Independently selected from H, CO2H, and C1-C3 alkyl groups; R d For -OR d ', where R d Selected from H and optionally using one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)R d '' or -C(O)OR d '' group substitution C1-C 10 Alkyl; R d '' is selected from C6 aryl and C1-C5 alkyl groups optionally substituted with one or more -OH, -CO2H, -SO3H or -PO3H groups; p'' is 0 or 1; X 3 Selected from -[-C(O)OC(R) 26’ (R) 27’ )C(R 28’ (R) 29’ )-] w2 - and optionally a C1-C5 alkyl group having one or more -OH, -CO2H or ester groups; wherein w2 is an integer from 1 to 5; for each unit w2 independently, R 26’ R 27’ R 28’ and R 29’ They are independently selected from H and C1-C3 alkyl groups.

[0093] Specifically, the monomer M1c can be of formula R a R b C=C(R c )C(O)R d The monomer, wherein the substituent R a R b and R c Independently selected from H, CO2H, and C1-C3 alkyl groups; R d For -OR d ', where R d Selected from H and optionally using one or more -OH, -CO2H, -SO3H, -PO3H, -OC(O)R d '' or -C(O)OR d '' group substitution C1-C 10 Alkyl; R d '' is selected from C6 aryl and C1-C5 alkyl groups that are optionally substituted with one or more -OH, -CO2H, -SO3H or -PO3H groups.

[0094] The monomer M1c can also be of formula R. e R f C=C(R g )(OC(O)R h ), R I R j C=CR k C(O)OC(O)CR l =CR m R n R o R p C=CR q (CN), R r R s C=CR t (C(O)NR u R v monomers; in: R h It is a C1-C5 alkyl group; R e R f R g R h R I R j R k R l R m R n R o R p R q R r R s R t R u and R v The components are independently selected from H and C1-C5 alkyl groups, preferably from H and CH3.

[0095] The monomer M1c can also be a monomer of the following formula. or

[0096] Where R aa R ab R ac R ad R ae R af R ag R ah R ai R aj R ak and R alThe components are independently selected from H and C1-C5 alkyl groups, preferably from H and CH3.

[0097] According to a particularly preferred embodiment, the monomer M1c may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-dodecyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-dodecyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate Esters, n-octyl methacrylate, urea methacrylate, maleic anhydride, vinyl acetate, acrylamide, acrylonitrile; methacrylic anhydrides of the formula CH2=C(CH3)C(O)OC(O)C(CH3)=CH2; monomers of the formulas CH2=CH(CO2CH2CH2CO2H), CH2=CH(CO2CH2CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH2CH2CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH(CH3)CH2-OC(O)-CH2CH2CO2H), CH2=CH(CO2CH2CH2-OC(O)-C6H4CO2H), CH2=CH(CO2CH2CH2CH2CH(CO2H)CH2CH2CO2H); and mixtures thereof. Among these, the monomer M1c having an alkyl group containing 1 to 8 carbon atoms is preferred, and an alkyl group containing 1 to 5 carbon atoms is more preferred. The fluoropolymer P1 may comprise one or more repeating units derived from the monomer M1c as defined herein. Preferably, when it contains any one of these, the fluoropolymer P1 comprises 0.01% to 10% by weight, preferably 0.05% to 5% by weight, and particularly 0.1% to 5% by weight of repeating units derived from the monomer M1c, based on the total weight of the fluoropolymer P1.

[0098] Preferably, the fluoropolymer P1 is heated at 230°C and for 100 seconds. -1The melt viscosity at the shear rate is greater than or equal to 5 kP, as measured according to standard ASTM D3835. Advantageously, the melt viscosity of the fluoropolymer P1 is greater than or equal to 8 kP, preferably greater than or equal to 10 kP, more preferably greater than or equal to 13 kP, particularly greater than or equal to 15 kP, even more particularly greater than or equal to 20 kP, and advantageously greater than or equal to 25 kP, according to standard ASTM D3835 at 230°C and 100 s. -1 The measured shear rate was [value missing]. Higher melt viscosity can improve the mechanical strength of the diaphragm made from the fluoropolymer P1 mentioned above.

[0099] The at least one polymer resin may be a polyarylamide. Polyarylamides comprise repeating units, each containing one or more amide functional groups adjacent to an aromatic ring. Therefore, polyarylamides may contain the formula -[-C(O)-NH-A 1 -NH-C(O)-A 2 -]- repeating units, where A 1 and A 2 Independently selected from one or more of the following: halogen, SO3H, CO2H, OH, PO3H, C1-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C2-C 15 C6-C substitution of ester groups 18 Aryl group. Preferably, the polyarylamide contains the formula -[-C(O)-NH-A 1 -NH-C(O)-A 2 -]- repeating units, where A 1 and A 2 They were selected independently from C6-C. 18 Aryl. Specifically, A 1 and A 2 =Phenyl; More specifically, A 1 and A 2 They are attached to their adjacent groups (C(O) or NH) in interposition or para position.

[0100] In this patent application, the term halogen refers to F, Cl, Br, or I; the term Cl-C 10 The alkoxy group refers to the -OR group, where R is C1-C. 10 Alkyl; term C2-C 15 Ethers refer to hydrocarbon groups (alkyl or aryl) containing 2 to 15 carbon atoms and the ether functional group -O-; the term C1-C 10 The carboxyl group refers to a hydrocarbon group (alkyl or aryl) containing 1 to 10 carbon atoms and a -C(O)- functional group; the term C1-C 10Ester refers to a hydrocarbon group (alkyl or aryl) containing 1 to 10 carbon atoms and a -C(O)O- functional group. The term alkyl includes straight-chain and branched alkyl. The term aryl includes hydrocarbons containing 6 to 8 carbon atoms and containing at least one monocyclic (phenyl, tolyl, benzyl, methylbenzyl, etc.) or polycyclic (bisphenyl, anthracene, naphthyl, etc.) aromatic ring.

[0101] The at least one polymer resin may be a polyester. The polyester comprises repeating units, each containing one or more -C(O)-O functional groups. The polyester may contain the formula [-A...] 1 -C(O)-O-]、[-A 1 -C(O)-OA 2 -]、[-OC(O)-A 1 -C(O)-O-] or [-OC(O)-A 1 -C(O)-OA 2 -] repeating units, where A 1 and A 2 Independently selected from one or more of the following: halogen, SO3H, CO2H, OH, PO3H, C1-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl and C1-C 10 Alkyl groups. For example, the polyester may contain the formula [-OC(O)-A]. 1 -C(O)-OA 2 -] repeating units, where A 1 For C6-C 18 aryl, preferably phenyl, and A 2 For C1-C 10 Alkyl group, preferably C1-C5 alkyl group. Specific examples are polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate.

[0102] The at least one polymer resin may be a polyaryl ether ketone. The polyaryl ether ketone comprises repeating units, wherein the repeating units comprise ether and ketone functional groups. The polyaryl ether ketone may contain the formula [-OA]. 1 -OA 2 -C(O)-A 3 -]、[-OA 1 -C(O)-A 2 -]、[-OA 1 -C(O)-A 2 -C(O)-A 3 -]、[-OA1 -OA 2 -C(O)-A 3 -C(O)-A 4 -] or [-OA 1 -C(O)-A 2 -OA 3 -C(O)-A 4 -C(O)-A 5 -] repeating units, where A 1 A 2 A 3 A 4 and A 5 Independently selected from one or more of the following: halogen, SO3H, CO2H, OH, PO3H, C1-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl and C1-C 10 Alkyl group. Preferably, in the above formula, A 1 A 2 A 3 A 4 and A 5 It is a phenyl substituent. Specific examples are polyetheretherketone (PEEK or polyphenylene etheretherketone), polyetherketone (PEK), polyetheretherketoneketone (PEEKK), polyetherketoneketone (PEKK), and polyetherketoneetherketoneketone (PEKEKK).

[0103] The at least one polymer resin may be polysulfone. Polysulfone comprises repeating units, each containing one or more sulfone functional groups (SO2). Preferably, polysulfone may contain [-A...]. 1 [-SO2-] repeating unit, where A 1 Selected optionally from one or more of halogens, SO3H, CO2H, OH, PO3H, C1-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl and C1-C 10 Alkyl; preferably, A 1 Optionally, one or more elements selected from halogens, SO3H, CO2H, OH, PO3H, and C1-C are used. 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups18 Aryl; in particular, A 1 It is phenyl. A specific example is polyphenylene sulfone.

[0104] The at least one polymer resin may be polyethersulfone. Polyethersulfone comprises repeating units, wherein the repeating units comprise ether and sulfone functional groups. Polyethersulfone may contain the formula [-A] 1 -OA 2 -SO2-] or [-A] 1 -SO2-A 2 -OA 3 The repeating unit of -O-], where A 1 and A 2 Independently selected from one or more of the following: halogen, SO3H, CO2H, OH, PO3H, C1-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl and C1-C 10 Alkyl group. Preferably, A 1 and A 2 Independently selected from one or more of the following: halogen, SO3H, CO2H, OH, PO3H, C1-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl. A particular example is [-A] 1 -OA 2 -SO2-](where A 1 and A 2 (for phenyl) or formula [-A 1 -SO2-A 2 -OA 3 -O-](where A 1 and A 2 For phenyl and A 3 It is a polyethersulfone (C6H4-C(CH3)2-C6H4).

[0105] The at least one polymer resin may be a polyetherimide. A polyetherimide comprises repeating units, each containing one or more ether and imide functional groups. An example of a polyetherimide is poly(bisphenol A-copolymer-4-nitrophthalic anhydride-copolymer-1,3-phenylenediamine).

[0106] The at least one polymer resin may be a polyimide. The polyimide comprises repeating units, each containing one or more imide functional groups -C(O)-N(R)-C(O)-. The imide groups may be linear or cyclic. The polyimide may contain formula A as described below. 1 Or A 2 Repeating unit

[0107] in: n1 is an integer from 0 to 5; n2 is an integer from 0 to 5; R1 and R2 are independently selected from one or more of the following: halogens, SO3H, CO2H, OH, PO3H2, Cl-C 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl, C1-C 10 Alkyl and C2-C 15 ether.

[0108] The at least one polymer resin may be polyacrylonitrile. Polyacrylonitrile includes the formula [-CR] 1 R 2 CR 3 (CN)-] repeating units, where R 1 R 2 and R 3 The elements are independently selected from H, or optionally from one or more halogens, SO3H, CO2H, OH, PO3H, and C1-C. 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl and C1-C 10 Alkyl group. Preferably, the polyacrylonitrile contains at least 50% by weight of [-CR] as defined above. 1 R 2 CR 3 (CN)-] repeating units.

[0109] The at least one polymer resin may be polycarbonate. Polycarbonate comprises repeating units, each containing one or more carbonate functional groups -OC(O)-O-. Polycarbonate may contain the formula [-A 1 The repeating unit of -OC(O)-O-], where A 1 Optionally, one or more elements selected from halogens, SO3H, CO2H, OH, PO3H, and C1-C are used. 10Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl; in particular, A 1 It can be C6H4-C(CH3)2-C6H4.

[0110] The at least one polymer resin may be polybenzimidazole. Polybenzimidazole comprises repeating units, each of which contains one or more benzimidazole groups. A particular example may be poly[2,2'-(m-phenylene)-5,5'-bisbenzimidazole].

[0111] The at least one polymer resin may be of the inclusion formula [-A] 1 Polyaryl ethers of repeating units of [-O-], wherein A 1 Optionally, one or more elements selected from halogens, SO3H, CO2H, OH, PO3H, and C1-C are used. 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl; especially A 1 It is phenyl, tolyl, or methylbenzyl. A particular example is poly[oxy(2,6-dimethyl-1,4-phenylene)].

[0112] The at least one polymer resin may be of the inclusion formula [-A] 1 Polyaryl sulfides of repeating units of [-S-], wherein A 1 Optionally, one or more elements selected from halogens, SO3H, CO2H, OH, PO3H, and C1-C are used. 10 Alkoxy, C2-C 15 Ethers, C1-C 10 Carboxyl group and C1-C 10 C6-C substitution of ester groups 18 Aryl; especially A 1 It can be phenyl, tolyl, or methylbenzyl.

[0113] The at least one polymer resin may be cellulose-type, that is, it contains repeating units of the following formula.

[0114] Where R is independently selected for each substituent -OR from C1-C, optionally substituted with OH groups. 10 Alkyl; n is an integer between 10 and 100,000.

[0115] Preferably, the at least one polymer resin comprises repeating units of the following formula.

[0116] Where R is independently selected from C1-C5 alkyl groups with respect to each substituent -OR, and optionally substituted with OH groups; n is an integer between 10 and 50,000.

[0117] The diaphragm may also comprise a polymer P2 other than the at least one polymer resin detailed above, wherein the polymer P2 comprises repeating units of monomer M2 or mixtures thereof derived from formulas (I), (II), (III), (IV), (V), (VI), and (VII).

[0118] R 1 R 2 C=C(R 3 (X) 2 ) P’ -C(O)R 4 (I)

[0119] R 5 R 6 C=C(R 7 )(OC(O)R 8 (II)

[0120] R 9 R 10 C=CR 11 C(O)OC(O)CR 12 =CR 13 R 14 (III)

[0121] R 30 R 31 C=CR 32 (CN) (VI)

[0122] R 33 R 34 C=CR 35 (C(O)NR 36 R 37 (VII)

[0123] in: R 1 R 2 and R 3 They are independently selected from H, CO2H, and C1-C5 alkyl groups; R 4 Selected from -NHC(CH3)2CH2C(O)CH3 and -OR25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 25’ -OC(O)R 25’ C1-C groups and five- or six-membered heterocyclic substituted groups containing at least one nitrogen atom in their ring chains 18 alkyl; R 25’ Selected from C6-C with one or more CO2H functional groups substituted. 12 Aryl and C1-C5 alkyl groups; X 2 Selected from -[-C(O)OC(R) 26 (R) 27 )C(R 28 (R) 29 )-] w1 - and optionally C1-C with one or more -OH, -CO2H or ester groups. 10 Alkyl hydrocarbon group; w1 is 1 to 50, advantageously 1 to 25, preferably 1 to 10, particularly an integer from 1 to 5; for each unit w1 independently, R 26 R 27 R 28 and R 29 They are independently selected from H and C1-C5 alkyl groups; p' is 0 or 1; R 5 R 6 and R 7 They are independently selected from H and C1-C5 alkyl groups; R 8 It is a C1-C5 alkyl group; R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 30 R 31 R 32 R 33 R 34 and R 35The components are independently selected from H and C1-C5 alkyl groups, preferably from H and CH3; R 36 and R 37 Independently selected from H and optionally using one or more -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 38 or -OC(O)R 38 C1-C substituent 10 Alkyl; R 38 Selected from C1-C5 alkyl groups and C6-C groups substituted with one or more CO2H functional groups. 12 Aryl.

[0124] Advantageously, the polymer P2 comprises repeating units of monomer M2 or mixtures thereof derived from formulas (I), (II), (III), (IV), and (V).

[0125] R 1 R 2 C=C(R 3 (X) 2 ) P’ -C(O)R 4 (I)

[0126] R 5 R 6 C=C(R 7 )(OC(O)R 8 (II)

[0127] R 9 R 10 C=CR 11 C(O)OC(O)CR 12 =CR 13 R 14 (III)

[0128] R 30 R 31 C=CR 32 (CN) (VI)

[0129] R 33 R 34 C=CR 35 (C(O)NR 36 R 37 (VII)

[0130] in: R 1 R 2 and R 3They are independently selected from H, CO2H, and C1-C5 alkyl groups; R 4 Selected from -NHC(CH3)2CH2C(O)CH3 and -OR 25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 25’ -OC(O)R 25’ The group is substituted with a five- or six-membered heterocycle containing at least one nitrogen atom in its ring chain. 15 alkyl; R 25’ Selected from C6-C with one or more CO2H functional groups substituted. 12 Aryl and C1-C5 alkyl groups; X 2 Selected from -[-C(O)OC(R) 26 (R) 27 )C(R 28 (R) 29 )-] w1 - and optionally C1-C with one or more -OH, -CO2H or ester groups. 10 Alkyl hydrocarbon group; w1 is an integer from 1 to 10, particularly from 1 to 5; for each unit w1 independently, R 26 R 27 R 28 and R 29 They are independently selected from H and C1-C5 alkyl groups; p' is 0 or 1; R 5 R 6 and R 7 They are independently selected from H and C1-C3 alkyl groups; R 8 It is a C1-C3 alkyl group; R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 30 R31 R 32 R 33 R 34 and R 35 The components are independently selected from H and C1-C3 alkyl groups, preferably from H and CH3; R 36 and R 37 Independently selected from H and optionally using one or more -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 38 or -OC(O)R 38 Group-substituted C1-C5 alkyl groups; R 38 Selected from C6 aryl and C1-C3 alkyl groups substituted with one or more CO2H functional groups.

[0131] Preferably, the polymer P2 comprises repeating units of monomer M2 or mixtures thereof derived from formulas (I), (II), (III), (IV), (V), (VI), and (VII).

[0132] R 1 R 2 C=C(R 3 (X) 2 ) P’ -C(O)R 4 (I)

[0133] R 5 R 6 C=C(R 7 )(OC(O)R 8 (II)

[0134] R 9 R 10 C=CR 11 C(O)OC(O)CR 12 =CR 13 R 14 (III)

[0135] R 30 R 31 C=CR 32 (CN) (VI)

[0136] R 33 R 34 C=CR 35 (C(O)NR 36 R 37 (VII)

[0137] in: R1 R 2 and R 3 They are independently selected from H, CO2H, and C1-C5 alkyl groups; R 4 Selected from -NHC(CH3)2CH2C(O)CH3 and -OR 25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, -SO3H, -OPO3 2- -C(O)OR 25’ -OC(O)R 25’ C1-C groups and five- or six-membered heterocyclic substituted groups containing at least one nitrogen atom in their ring chains 18 alkyl; R 25’ Selected from C6-C with one or more CO2H functional groups substituted. 12 Aryl and C1-C5 alkyl groups; X 2 Selected from -[-C(O)OC(R) 26 (R) 27 )C(R 28 (R) 29 )-] w1 - and optionally C1-C with one or more -OH, -CO2H or ester groups. 10 Alkyl hydrocarbon group; wherein w1 is an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, particularly from 1 to 5; for each unit w1 independently, R 26 R 27 R 28 and R 29 They are independently selected from H and C1-C5 alkyl groups; p' is 0 or 1; R 5 R 6 and R 7 They are independently selected from H and C1-C5 alkyl groups; R 8 It is a C1-C5 alkyl group; R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R22 R 23 R 24 R 30 R 31 R 32 R 33 R 34 and R 35 The components are independently selected from H and C1-C5 alkyl groups, preferably from H and CH3; R 36 and R 37 Independently selected from H and optionally using one or more -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 38 or -OC(O)R 38 C1-C substituent 10 Alkyl; R 38 Selected from C6-C with one or more CO2H functional groups substituted. 12 Aryl and C1-C5 alkyl groups.

[0138] More preferably, the polymer P2 is of formula (I), (III), or (IV), wherein R 1 R 2 and R 3 They are independently selected from H, CO2H, and C1-C3 alkyl groups; R 4 For -OR 25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 25’ -OC(O)R 25’ C1-C groups and five- or six-membered heterocyclic substituted groups containing at least one nitrogen atom in their ring chains 15 alkyl; R 25’ Selected from C6-C with one or more CO2H functional groups substituted. 12 Aryl and C1-C5 alkyl groups; X 2 Selected from -[-C(O)OC(R) 26 (R) 27 )C(R 28 (R) 29 )-] w1 - and optionally C1-C with one or more -OH, -CO2H or ester groups. 10 Alkyl hydrocarbon group; w1 is an integer from 1 to 50, advantageously from 1 to 25, preferably from 1 to 10, particularly from 1 to 5; for each unit w1 independently, R26 R 27 R 28 and R 29 They are independently selected from H and C1-C5 alkyl groups; p' is 0 or 1; R 9 R 10 R 11 R 12 R 13 R 14 R 15 and R 16 The components are independently selected from H and C1-C5 alkyl groups, preferably from H and CH3.

[0139] Specifically, the polymer P2 is of formula (I), (III), or (IV), wherein R 1 R 2 and R 3 They are independently selected from H, CO2H, and C1-C3 alkyl groups; R 4 For -OR 25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 25’ -OC(O)R 25’ C1-C groups and five- or six-membered heterocyclic substituted groups containing at least one nitrogen atom in their ring chains 10 alkyl; R 25’ Selected from C6 aryl and C1-C5 alkyl groups substituted with one or more CO2H functional groups; X 2 Selected from -[-C(O)OC(R) 26 (R) 27 )C(R 28 (R) 29 )-] w1 - and optionally a C1-C5 alkyl group with one or more -OH, -CO2H or ester groups; w1 is an integer from 1 to 5; for each unit w1 independently, R 26 R 27 R 28 and R 29 They are independently selected from H and C1-C5 alkyl groups; p' is 0 or 1; R 9 R 10 R 11 R 12 R 13 R14 R 15 and R 16 The components are independently selected from H and C1-C5 alkyl groups, preferably from H and CH3.

[0140] More specifically, the polymer P2 comprises repeating units of monomer M2 derived from formula (I), (III), or (IV), wherein

[0141] R 1 R 2 and R 3 They are independently selected from H, CO2H, and C1-C3 alkyl groups; R 4 For -OR 25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 25’ and -OC(O)R 25’ C1-C groups substituted 10 alkyl; R 25 Selected from C6 aryl and C1-C5 alkyl groups substituted with one or more CO2H functional groups; X 2 Selected from -[-C(O)OC(R) 26 (R) 27 )C(R 28 (R) 29 )-] w1 - and optionally a C1-C5 alkyl group with one or more -OH, -CO2H or ester groups; w1 is an integer from 1 to 5; for each unit w1 independently, R 26 R 27 R 28 and R 29 They are independently selected from H and C1-C5 alkyl groups; p' is 0 or 1; R 9 R 10 R 13 R 14 R 15 R 16 For H; R 11 and R 12 It is CH3.

[0142] Preferably, the polymer P2 comprises a derivative of formula (I)R 1 R 2 C=C(R 3 )(C(O)R 4(I) Repeating units of monomer M2 as defined above (III) or as defined above (IV), wherein

[0143] R 1 R 2 and R 3 They are independently selected from H, CO2H, and C1-C3 alkyl groups; R 4 For -OR 25 , where R 25 Selected from H and optionally one or more selected from -OH, -CO2H, SO3H, -OPO3 2- -C(O)OR 25’ and -OC(O)R 25’ C1-C5 alkyl groups substituted with radicals; R 25’ Selected from C1-C3 alkyl groups and C6 aryl groups substituted with one or more CO2H functional groups; R 9 R 10 R 13 R 14 R 15 R 16 For H; R 11 and R 12 It is CH3.

[0144] According to one embodiment, the polymer P2 is a homopolymer of monomer M2 according to any one of formulas (I) to (VII) above. According to another embodiment, the polymer P2 is a copolymer of several monomers M2 according to any one of formulas (I) to (VII) above. The term copolymer means a repeating unit obtained from at least two monomers M2 according to any one of formulas (I) to (VII) above.

[0145] According to a preferred embodiment, the polymer P2 has a weight-average molar mass between 500 g / mol and 5,000,000 g / mol, advantageously between 1,000 g / mol and 4,000,000 g / mol, preferably between 2,000 g / mol and 3,000,000 g / mol, more preferably between 3,000 g / mol and 2,500,000 g / mol, particularly between 4,000 g / mol and 2,000,000 g / mol, even more particularly between 5,000 g / mol and 1,500,000 g / mol, and advantageously between 10,000 g / mol and 1,000,000 g / mol. The molecular weight or molar mass is determined by size exclusion chromatography (SEC). A test sample corresponding to a polymer solution of 90 mg dry matter is introduced into a 10 mL flask. A mobile phase supplemented with 0.04% dimethylformamide (DMF) is added to a total mass of up to 10 g. The mobile phase composition was as follows: NaHCO3: 0.05 mol / L, NaNO3: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3: 0.03% by mass. The SEC line consisted of a Waters 510 isocratic pump (flow rate adjusted to 0.8 ml / min), a Waters 717+ autosampler, an oven containing a Waters Ultrahydrogel Guard Column pre-column (6 cm long, 40 mm inner diameter) and a subsequent Waters Ultrahydrogel linear column (30 cm long, 7.8 mm inner diameter). Detection was performed using a Waters 410 RI differential refractometer. The oven was heated to 60°C and the differential refractometer to 45°C. The SEC apparatus was supplied by PolymerStandards Service with a flow rate of 1000 g / mol and 1×10⁻⁶ g / mol. 6 The calibration was performed using a series of sodium polyacrylate standards with peak molecular weights between g / mol and polydispersity indices between 1.4 and 1.7. The calibration curves were linear and corrections were taken into account using the flow marker: dimethylformamide (DMF).

[0146] Preferably, in the separator, the at least one polymer resin as described above is the main component. Therefore, according to a preferred embodiment, the separator contains at least 45% by weight, advantageously at least 50% by weight, preferably at least 55% by weight, more preferably at least 60% by weight, particularly at least 65% by weight, and even more particularly at least 70% by weight of the at least one polymer resin according to the invention, based on the total weight of the separator. When the at least one polymer resin is as described above and is the main component of the separator, it can achieve a higher σ compared to separators made of polyolefins. The e / G ratio results in better final properties.

[0147] There are no particular limitations on the method used to obtain the diaphragm. Typically, the diaphragm can be prepared via a phase-inversion or dry stretching method. The dry stretching method involves producing a dense film by coating a polymer dissolved in a solvent or by coating a molten polymer and then uniaxially stretching the polymer. The phase-inversion method involves coating a solution of polymer dissolved in a solvent onto a glass substrate using a highly controlled doctor blade, then transferring the wet film to a bath of water and isopropanol (70 / 30) and subsequently to a water bath.

[0148] According to a preferred embodiment, the membrane further comprises inorganic particles selected from BaTiO3, Pb(Zr,Ti)O3, and Pb 1-x La x Zr y O3(0 <x<1,0<y<1)、PbMg3Nb 2 / 3 O3, PbTiO3, hafnium oxide (HfO or HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, Y2O3, boehmite (y-AlO(OH)), Al2O3, TiO2, SiC, ZrO2, boron silicate, BaSO4 and nano clay, or mixtures thereof.

[0149] use

[0150] The electrochemical device according to the invention comprises a positive electrode, a negative electrode, and a separator according to the invention; the latter is disposed between the positive electrode and the negative electrode. The term "negative electrode" refers to an electrode that acts as the anode when the battery conducts current (i.e., during discharge) and as the cathode when the battery is charging. The negative electrode typically comprises an electrochemically active material, optionally a conductive material, and optionally a binder. The term "positive electrode" refers to an electrode that acts as the cathode when the battery conducts current (i.e., during discharge) and as the anode when the battery is charging. The positive electrode typically comprises an electrochemically active material, optionally a conductive material, and optionally a binder. The term "electrochemically active material" refers to a material capable of reversibly inserting ions. The term "conductive material" refers to a material capable of conducting electrons.

[0151] Preferably, the negative electrode comprises an active material selected from lithium alloys, lithium metal, metal oxides, carbon materials (e.g., graphite or hard carbon), silicon, organosilicon, silicon alloys, and Li4Ti5O. 12 When the negative electrode contains lithium, the lithium may be in the form of a lithium metal film or a lithium-containing alloy. Examples of usable lithium-based alloys include lithium-aluminum alloys, lithium-silicon dioxide alloys, lithium-tin alloys, Li-Zn, Li3Bi, Li3Cd, and Li3SB. Examples of negative electrodes may comprise a bright lithium film prepared by rolling a lithium strip between rolls.

[0152] Preferably, the positive electrode comprises an active material selected from LiCoO2, Li(Ni, Co, Al)O2, and Li (1+x) Ni a Mn b Co c (x represents a real number 0 or greater, a = 0.9, 0.8, 0.6, 0.5 or 1 / 3, b = 0.05, 0.1, 0.2, 0.3 or 1 / 3, c = 0.05, 0.1, 0.2 or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3O3, Li3Fe2(PO4)3, Li3V2(PO4)3, Li Mn spinel substituted with different elements, which have the characteristics of Li 1+x Mn 2-x-y M y O4 represents the composition, M represents at least one metal selected from Al, Mg, Co, Fe, Ni, and Zn, and x and y independently represent real numbers between 0 and 2. Lithium titanate Li x TiO y x and y independently represent real numbers between 0 and 2, and lithium metal phosphates with a composition represented by LiMPO4, where M represents Fe, Mn, Co or Ni, or mixtures thereof.

[0153] Each electrode may also contain (in addition to electrochemically active and conductive materials) a carbon source, including, for example, carbon black, Ketjen® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (e.g., vapor-grown carbon fibers or VGCF), non-powdered carbon obtained by carbonization of organic precursors, or combinations of two or more thereof. Other additives may also be present in the material of the positive electrode, such as lithium salts or ceramic or glass-type inorganic particles, or other compatible active materials (e.g., sulfur).

[0154] Each electrode may also contain an adhesive. Non-limiting examples of adhesives include linear, branched, and / or crosslinked polyether polymer adhesives (e.g., polymers based on polyethylene oxide (PEO) or polypropylene oxide (PPO) or mixtures of both (or EO / PO copolymers), and optionally containing crosslinkable units), water-soluble adhesives (e.g., SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epimercaptochloropropylene rubber), ACM (acrylate rubber)), or fluoropolymer adhesives (e.g., PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene)) and combinations thereof. Some adhesives (e.g., water-soluble ones) may also contain additives, such as CMC (carboxymethyl cellulose).

[0155] The metal support for the electrodes acting as current collectors is typically made of aluminum for the cathode and copper for the anode. The metal support may be surface-treated and have a conductive primer. The conductive primer may contain carbon-based materials, metallic materials, and polymeric materials. The support may also be a woven or non-woven fabric made of carbon fiber.

[0156] The electrochemical device may be a Li-ion battery pack, particularly for portable electronic devices (e.g., mobile phones or laptops), electric vehicles, or for storing renewable energy sources (e.g., photovoltaic or wind power).

[0157] Preferably, the electrochemical device is a Li-ion battery pack having a cutoff voltage of 4.4V or greater, more preferably 4.5V or greater.

[0158] Example

[0159] Transitivity Measurement Methods

[0160] The ionic conductivity of the electrolyte in the membrane was determined in a CR2032 coin cell by electrochemical impedance spectroscopy. Membranes cut to a diameter of 16 mm were immersed in 100 µL of electrolyte and then placed between two 16 mm diameter stainless steel wedges in a sealed CR2032 coin cell. The coin cell was connected to a potentiostat (Biologic, VMP3) and placed in an oven at 25°C. The resistance of the electrolyte-impregnated membrane was measured by impedance spectroscopy (PEIS technique): a sinusoidal voltage with an amplitude of 10 mV was applied near the open-circuit potential, sweeping frequencies from 200 kHz to 100 kHz. The resistance “R” of the electrolyte-impregnated membrane was extracted from the obtained Nyquist plot by reading the intersection of the x-axis with the extrapolation of the straight line obtained at high frequencies. The conductivity σ of the electrolyte-impregnated membrane was obtained according to the following formula: σ [mS / cm] = (e 1000) / (S R)

[0161] in

[0162] e [cm]: Diaphragm thickness

[0163] S [cm²]: Surface area of ​​the stainless steel wedge

[0164] R [Ohms]: Resistance of the electrolyte-impregnated diaphragm, measured by impedance.

[0165] Method for measuring the coefficient of thermal shrinkage at 150°C

[0166] Cut the sample into 100 mm pieces in the MD direction and 100 mm pieces in the TD direction. Lightly press a 59 mm (MD) x 44 mm (TD) rectangular mark into the center. Then, place the sample in an oven at 150°C for 1 hour. During this time, sandwich the sample between two sheets of cardboard. After removing the sample from the oven and allowing it to cool, measure the length (mm) of the rectangular mark in each direction. Repeat this process with four different samples, and take the average length in each direction as the length after heating. The coefficient of thermal shrinkage in each direction is calculated using the following formula, and the larger value is recorded as the coefficient of thermal shrinkage.

[0167] Coefficient of thermal shrinkage (%) = [(Initial length – Length after heating) / Initial length] x 100

[0168] Methods for measuring diaphragm thickness

[0169] The diaphragm thickness was measured using a gap gauge (Mitutoyo, Digimatic ID-H comparator).

[0170] The performance of the diaphragm was evaluated using an electrolyte composition consisting of 73.4 wt% sulfolane and 26.6 wt% LiFSI (i.e., a concentration of 2.5 mol / L). This composition had a viscosity of 88 cP at 20°C and measured over 20 s⁻¹. -1 The shear was measured.

[0171] Polymers P1 to P3 and polymers C1 and C2 (comparative examples) according to the present invention are used to prepare membranes. Ratio σ e / G and G / e are provided in Table 1 below.

[0172] Polymer P1: has properties at 230°C and 100 s -1 The melt viscosity of poly(vinylidene fluoride) homopolymer at a shear rate of 34 kP, measured according to standard ASTM D3835, and at a melting point of 162°C.

[0173] Polymer P2: has properties at 230°C and 100 s -1 The melt viscosity of poly(vinylidene fluoride) homopolymer at a shear rate of 30.5 kP, as measured according to standard ASTM D3835, and at a melting point of 165°C.

[0174] Polymer P3: has a concentration of 0.4 g / cm³. 3 Cellulose with a density of 73% and a porosity of 73%.

[0175] Polymer P4: has a concentration of 0.4 g / cm³. 3 The density and porosity of the polyimide (Blueshift-AeroZero standard membrane) are high.

[0176] Polymer C1: Polyethylene

[0177] Polymer C2: Polyethylene coated with a 3 µm thick layer of vinylidene fluoride-hexafluoropropylene copolymer.

[0178] [Table 1]

[0179] The separator according to the invention provides an optimal trade-off for use in high-voltage electrochemical devices in the presence of high-viscosity electrolyte compositions. Separators made of polyolefins (polymer C1) exhibit low thermal stability, expressed here as a coefficient of thermal shrinkage greater than 50%, which can cause short circuits in battery packs. The presence of a coating layer on the polyolefin separator (polymer P2) improves the coefficient of thermal shrinkage, but it has been surprisingly demonstrated that by specifically selecting the separator prepared from the polymer resin, a ratio σ greater than 0.02 can be obtained in the presence of viscous electrolyte compositions. e / G can greatly improve wettability, which is essential for high-voltage applications.

Claims

1. An electrochemical device comprising an electrolyte composition and a membrane, characterized in that... σ The e / G ratio is between 0.02 and 200; σ is the conductivity of the electrolyte composition in the membrane measured at 25°C, expressed in mS / cm; e is the membrane thickness in µm; and G is the conductivity in s. -1 The air permeability of the membrane is indicated by measurement by Gurley according to standard ISO 5636-5.

2. The electrochemical device according to the preceding claims, characterized in that... The electrolyte composition comprises at least one solvent and a lithium salt, and the electrolyte composition has a viscosity greater than 2 cP at 20°C and for 20 s. -1 The shear was measured.

3. The electrochemical device according to any one of the preceding claims, characterized in that... The electrolyte composition has a viscosity greater than 5 cP, preferably greater than 10 cP, and particularly greater than 15 cP, at 20°C and for 20 seconds. -1 The shear was measured.

4. The electrochemical device according to any one of the preceding claims, characterized in that... The electrolyte composition comprises 5% to 70% by weight of a lithium salt and 20% to 85% by weight of at least one solvent.

5. The electrochemical device according to any one of the preceding claims, characterized in that... The membrane has a porosity greater than 25%, as determined by mercury porosimetry according to standard ISO 15901-1:2016.

6. The electrochemical device according to any one of the preceding claims, characterized in that... The diaphragm has a coefficient of thermal shrinkage of less than 10% at 150°C, which is measured as an absolute value according to the method described in this patent application.

7. The electrochemical device according to any one of the preceding claims, characterized in that... The diaphragm has a range of 0.1 and 15s. -1 .µm -1 The ratio between them is G / e; G is in s -1 The value of e represents the air permeability of the diaphragm, measured by Gurley according to standard ISO 5636-5, and e represents the thickness of the diaphragm in µm.

8. The electrochemical device according to any one of the preceding claims, characterized in that... The diaphragm comprises at least one polymer resin selected from polyarylamide, polyester, polyaryl ether ketone, polysulfone, polyethersulfone, polyetherimide, polyimide, polyacrylonitrile, polycarbonate, polybenzimidazole, polyaryl ether, polyaryl sulfide, fluoropolymer, cellulose, or mixtures thereof.

9. The electrochemical device according to any one of the preceding claims, characterized in that... The diaphragm comprises at least one polymer resin, which includes a fluoropolymer P1, the fluoropolymer P1 comprising repeating units derived from vinylidene fluoride and optionally repeating units derived from hexafluoropropylene; preferably, the diaphragm comprises at least one polymer resin that is a vinylidene fluoride homopolymer.

10. The electrochemical device according to any one of the preceding claims, characterized in that... The diaphragm comprises at least one cellulose-type polymer resin.

11. The electrochemical device according to any one of the preceding claims, characterized in that... The diaphragm comprises at least one polyimide polymer resin.

12. The electrochemical device according to any one of claims 8 to 11, characterized in that... The membrane also comprises polymer P2, which includes formula R 1 R 2 C=C(R 3 The repeating unit of C(O)R, wherein the substituent R 1 R 2 and R 3 Independently selected from H and C1-C5 alkyl groups; R selected from -NHC(CH3)2CH2C(O)CH3 or -OR', wherein R' is selected from H and C1-C5 alkyl groups optionally substituted with one or more -OH groups or 5- or 6-membered heterocycles containing at least one nitrogen atom in their ring chains. 18 alkyl.

13. The electrochemical device according to any one of the preceding claims, characterized in that... It also includes a positive electrode and a negative electrode, wherein the diaphragm is disposed between the positive electrode and the negative electrode.

14. The electrochemical device according to the preceding claims, characterized in that... The negative electrode comprises an active material selected from lithium alloys, lithium metal, metal oxides, carbon materials such as graphite or hard carbon, silicon, organosilicon, silicon alloys, and Li4Ti5O. 12 .

15. The electrochemical device according to any one of claims 13 and 14, characterized in that... The positive electrode comprises an active material selected from LiCoO2, Li(Ni, Co, Al)O2, and Li (1+x) Ni a Mn b Co c (x represents a real number 0 or greater, a = 0.9, 0.8, 0.6, 0.5 or 1 / 3, b = 0.05, 0.1, 0.2, 0.3 or 1 / 3, c = 0.05, 0.1, 0.2 or 1 / 3), LiNiO2, LiMn2O4, LiCoMnO4, Li3NiMn3O3, Li3Fe2(PO4)3, Li3V2(PO4)3, Li Mn spinel substituted with different elements, which have the characteristics of Li 1+x Mn 2-x-y M y O4 represents the composition, M represents at least one metal selected from Al, Mg, Co, Fe, Ni, and Zn, and x and y independently represent real numbers between 0 and 2. Lithium titanate Li x TiO y x and y independently represent real numbers between 0 and 2, and lithium metal phosphates with a composition represented by LiMPO4, where M represents Fe, Mn, Co or Ni, or mixtures thereof.

16. The electrochemical device according to the preceding claims, characterized in that... It is a lithium-ion battery pack with a cutoff voltage of 4.4V or higher.

17. A diaphragm having a [value] at 0.1 and 15 s -1 .µm -1 The ratio between them is G / e; G is in s -1 The permeability of the diaphragm to air is measured by Gurley according to standard ISO 5636-5, and e is the thickness of the diaphragm in µm; the diaphragm comprises at least one polymer resin as defined in any one of claims 8 to 12.

Images