Unsaturated polymer electrolytes and methods for producing them and for use in electrochemical applications.

Abstract

The present invention relates to a process for producing polymers containing unsaturated units, the polymers thus obtained, and compositions, such as electrolytes or electrode materials, and their use in electrochemical cells and batteries. For example, the polymer is present in an electrolyte, which may optionally contain salts. For example, the electrolyte may be in solid form or in the form of a gel electrolyte membrane. For example, the solid electrolyte may be a solid polymer electrolyte or a composite containing particles.

Description

[Technical Field]

[0001] Related applications This application claims priority under applicable law to Canadian Provisional Patent Application No. 3,199,962, filed on 19 May 2023, the contents of which Canadian Provisional Patent Application are incorporated herein by reference in their entirety for all purposes.

[0002] Technical field This application relates to the field of polymers and their use in electrochemical applications. More specifically, this application relates to the field of solid polymers, electrolytes and electrode materials containing them, methods for producing them, and their use in electrochemical cells, particularly in so-called all-solid-state batteries. [Background technology]

[0003] background Solid polymer electrolytes are promising materials for numerous technological applications because they enable the development of all-solid-state electrochemical systems that are substantially safer, lighter, more flexible, and more efficient than their liquid counterparts.

[0004] Despite their significant advantages, they still face the challenge of ionic conductivity at room temperature.

[0005] Therefore, the development of new materials for use in all-solid-state electrochemical systems with improved properties is necessary. [Overview of the project] [Means for solving the problem]

[0006] overview In a particular embodiment, the technical embodiments described herein include the following: 1. Repeating unit of Equation 1: [ka] [In the formula, R 1~12 , 1~12 , 1~12 , 1~12 and R 2 is, independently and in each occurrence, selected from a hydrogen atom and, optionally substituted, C 1~3 alkyl group, preferably R 1 is a hydrogen atom, more preferably R 1 and R 2 are both hydrogen atoms, R 3 , R 4 , R 5 , and R 6 is, independently and in each occurrence, selected from a hydrogen atom, a halogen atom (such as F and Cl), and, optionally substituted, C 1~12 alkyl group, L1 and L2 are selected from C2-C6 alkylene, C(O)C1-C6 alkylene, C1-C6 alkylene C(O), C(O)C2-C6 alkylene C(O), (C2-C6 alkylene O) 1~12 C2-C6 alkylene, C(O)(C2-C6 alkylene O) 1~12 C2-C6 alkylene, (C2-C6 alkylene O) 1~12 C2-C6 alkylene C(O), C(O)(C2-C6 alkylene O) 1~12 C2-C6 alkylene C(O) group, polyether, polyester, polycarbonate chain, and a copolymer of at least two units selected from alkyl ether, ester, and carbonate, X 1 , X 2 , X 3 , and X 4 is, independently and in each occurrence, selected from O, NH, NR, and S, or or, X 1 is a -N(R)- group, L 1 , X 2 is absent, where R is selected from a polyether, polyester, polycarbonate chain, and a copolymer of at least two units selected from alkyl ether, ester, and carbonate, --- represents a bond with a hydrogen atom, a bond with another repeating unit of the polymer, or a bond with a terminal group. A polymer containing [this component]. 2. X 3 and X 4 A polymer according to item 1, in which, independently and in each occurrence, is selected from O and NH, preferably O. 3. L 2 However, (C2~C6 alkylene O) 1~12 A polymer that conforms to item 1 or 2, having a C2-C6 alkylene group (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, etc.). 4. Repeating units of Equation 2: [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , L 1 , X 1 , and X 2 This is as defined in item 1, n is a number between 1 and 20. A polymer that includes items according to item 1. 5. R 1 and R 2 A polymer that is a hydrogen atom, and conforms to one of items 1 through 4. 6. X 1 and X 2 However, a polymer that is selected from O and NH, and conforms to any one of items 1 to 5. 7. L 1 However, (C2~C6 alkylene O) 1~12 A polymer according to any one of items 1 to 6, selected from copolymers containing C2-C6 alkylene groups, polyethers, polyesters, or ether and ester units. 8. X 1 -L 1 -X 2 Parts, structure: [ka] [ka] [Here, R 3 , R 4 , R 5 , and R 6 This is as defined in item 1, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 These are, independently and in each instance, hydrogen atoms, halogen atoms (such as F and Cl), and C which is substituted as needed. 1~12 Selected from alkyl groups, j is a number that is independently selected and, in each instance, is chosen within the range of 2 to 30. k is a number from 1 to 20. m is a number selected within the range of 2 to 150. p is a number between 0 and 12, preferably between 0 and 6. q is a number between 0 and 8, preferably between 0 and 6, provided that p and q are not both zero at the same time. r is a number selected within the range of 2 to 4. [s is a number selected within the range of 5 to 30] A polymer selected from, conforming to any one of items 1 through 5. 9. The repeating unit is given by equations 3 to 6: [ka] [ka] [In the formula, R 1 , R2 , R 3 , R 4 , R 5 , and R 6 This is as defined in item 1, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 These are, independently and in each instance, hydrogen atoms, halogen atoms (such as F and Cl), and C which is substituted as needed. 1~12 Selected from alkyl groups, j is a number that is independently selected from the range of 2 to 30 in each occurrence. k is a number from 1 to 20. m is a number selected within the range of 2 to 150. n is a number between 1 and 20. p is a number between 0 and 12, preferably between 0 and 6. q is a number between 0 and 8, preferably between 0 and 6, provided that p and q are not both zero at the same time. r is a number selected within the range of 2 to 4. [s is a number selected within the range of 5 to 30] A polymer selected from, conforming to any one of items 1 through 5. 10. A polymer according to item 8 or 9, wherein the sum (p+q) is within the range of 2 to 9, preferably within the range of 3 to 6. 11. R 11 However, it is a hydrogen atom, R 12 A polymer that follows any one of items 8 to 10, where p is a C1-C6 alkyl group which is substituted as needed, and p is equal to 1. 12. R 11 and R 12A polymer according to any one of items 8 to 10, wherein all are hydrogen atoms and p is selected within the range from 1 to 6. 13. R 13 and R 14 are both hydrogen atoms and q is selected within the range from 2 to 6, a polymer according to any one of items 8 to 12. 14. R 13 and R 14 at least one of which is a C1 - C6 alkyl group optionally substituted in at least one occurrence, a polymer according to any one of items 8 to 12. 15. When r is 2 or 3, preferably 2, R 15 and R 16 are both hydrogen atoms in each occurrence, or one of R<所给内容有误,推测为 15 and R<所给内容有误,推测为 16 is methyl in one occurrence and R<所给内容有误,推测为 15 and R<所给内容有误,推测为 16 are both hydrogen atoms in other occurrences, a polymer according to item 8 or 9. 16. R 7 、R 8 、R<000确定为 9 、and R 10 are independently and in each occurrence selected from a hydrogen atom, a fluorine atom, and an optionally substituted C 1~3 alkyl group, preferably, R 7 、R 8 、R 9 、and R 10 are all hydrogen atoms, or one of R 7 、R 8 、R 9 、and R 10 is a methyl group and the others are all hydrogen atoms, a polymer according to item 8, 9 or 15. 17. R 3 、R 4 、R 5 、and R 6 are independently and in each occurrence selected from a hydrogen atom, a fluorine atom, and an optionally substituted C<此处有误,推测为 1~3 alkyl group, preferably, R3 , R 4 , R 5 , and R 6 However, all of them are either hydrogen atoms or R 3 , R 4 , R 5 , and R 6 A polymer that conforms to any one of items 4 through 16, wherein one of the groups is a methyl group and the others are all hydrogen atoms. 18. A polymer according to any one of items 1 through 17, comprising terminal groups selected from hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkenyl, optionally substituted alkynyl, acrylate, methacrylate, or at least two combinations thereof. 19. A polymer that conforms to any one of items 1 to 18, having a number-average molecular weight in the range of 500 to 5 million, or 500 to 1,000,000, or 500 to 500,000, or 500 to 250,000, or 500 to 100,000, or 500 to 75,000, or 500 to 70,000, or 500 to 65,000, or 500 to 60,000, or 500 to 55,000, or 500 to 50,000, or 1,000 to 50,000, or 1,500 to 50,000, or 2,000 to 50,000, as determined by triple detection gel permeation chromatography. 20. An electrolyte comprising a polymer as defined in any one of items 1 through 19, and optionally a salt. 21. An electrolyte according to item 20, wherein the electrolyte is in the form of a solid or gel electrolyte membrane. 22. An electrolyte according to item 20 or 21, comprising the salt, preferably an alkali metal salt, preferably a lithium salt, in an electrolyte at a concentration preferably from about 5% to about 40% by weight, or from about 15% to about 40% by weight, or from about 20% to about 35% by weight. 23. The salt comprises an alkali metal (preferably Li) cation and a hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI - ), 4,5-dicyano-1,2,3-triazolate (DCTA - ), bis(pentafluoroethylsulfonyl)imide (BETI - ), difluorophosphate (DFP - ), tetrafluoroborate (BF4 - ), bis(oxalato) borate(BOB - ), nitrates (NO3 - ), chloride (Cl - ), bromide (Br - ), fluoride (F - ), perchlorate (ClO4 - ), hexafluoroarsenate (AsF6 - ), trifluoromethanesulfonate (SO3CF3 - )(Tf - ), fluoroalkyl phosphate [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate [B(C6O2)2] - (BBB - ), difluoro(oxalato)borate (BF2(C2O4) - )(FOB - ), formula BF2O4R x - (In the formula, R x =C 2~4An electrolyte according to item 22, comprising an alkyl anion and an anion selected from at least two combinations thereof (e.g., LiTFSI or LiFSI). 24. An electrolyte according to any one of items 20 to 23, further containing additional polymers. 25. An electrolyte according to item 24, wherein the additional polymer is selected from polyethers, substituted polyethylenes, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl (meth)acrylate), poly(methyl (meth)acrylate of poly(ethylene glycol)methyl ether) (PEGMA), poly(2,2,2-trifluoroethyl (meth)acrylate), poly((meth)acrylic acid), and copolymers thereof, and optionally comprises crosslinking units derived from crosslinkable functional groups, wherein the additional polymer is linear or branched. 26. Electrolytes according to item 24, wherein the additional polymer is selected from rubber polymers such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), and ACM (polyacrylic rubber); fluorinated polymers such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and HFP (polyhexafluoropropylene); and at least two combinations thereof. 27. An electrolyte according to any one of items 20 to 26, further comprising, for example, an oxide, sulfide, or oxysulfide-based, preferably amorphous, ceramic, or glass-ceramic type, inorganic particles, wherein the inorganic compound is natural or synthetic. 28. The inorganic particles are of the formula MLZO (for example, M7La3Zr2O 12 M (7-a) La3Zr2Al b O 12 M (7-a) La3Zr2Ga b O 12 M (7-a)La3Zr (2-b) Ta b O 12 , and M (7-a) La3Zr (2-b) Nb b O 12 );MLTaO(for example, M7La3Ta2O 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO(for example, M7La3Sn2O 12 );MAGP(for example, M 1+a Al a Ge 2-a (PO4)3);MATP(for example, M 1+a Al a Ti 2-a (PO4)3);MLTiO(for example, M 3a La (2 / 3-a) TiO3); MZP (for example, M a Zr b (PO4) c );MCZP(for example, M a Ca b Zr c (PO4) d );MGPS(for example, M 10 GeP2S 12 M etc. a Ge b P c S d );MGPSO(for example, M a Ge b P c S d O e );MSiPS(for example, M 10 SiP2S 12 M etc. a Si b P c S d );MSiPSO(for example, M a Si b P c S d O e );MSnPS(for example, M 10 SnP2S 12 M etc. a Sn b Pc S d );MSnPSO(for example, M a Sn b P c S d O e );MPS (for example, M7P3S 11 M etc. a P b S c );MPSO (for example, M a P b S c O d );MZPS(for example, M a Zn b P c S d );MZPSO(for example, M a Zn b P c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 M models such as X, M7P2S8X, and M6PS5X a P b S c X d );MPSOX(for example, M a P b S c O d X e );MGPSX(M a Ge b P c S d X e );MGPSOX(M a Ge b P c S d O e X f );MSiPSX(M a Si b P c S d X e);MSiPSOX(M a Si b P c S d O e X f );MSnPSX(M a Sn b P c S d X e );MSnPSOX(M a Sn b P c S d O e X f );MZPSX(M a Zn b P c S d X e );MZPSOX(M a Zn b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c It includes natural or synthetic ceramics selected from inorganic compounds (where a = 2b + 3c - 5), During the ceremony, M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two of these, where if M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality. X is selected from F, Cl, Br, I, or at least two combinations of these. a, b, c, d, e, and f are non-zero numbers, independently chosen in each equation to achieve electrical neutrality. v, w, x, y, and z are non-zero numbers, independently selected in each formula to obtain a stable compound. Electrolytes according to item 27. 29. The MLZO ceramic is of the formula Li 7-b La3Zr2M i b O 12In the formula, b is 0 ≤ b ≤ 1, and M i is Al, Ga, Ta, Fe, or Nb, or is absent, preferably b is 0, and M i Electrolytes that do not exist, according to item 28. 30. The inorganic particles are Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., those based on aluminosilicates, mesoporous silica, etc.), sulfide-based ceramics (e.g., Li6PS5Cl, Li7P3S 11 Electrolytes in accordance with item 27, including glass ceramics (e.g., LIPON, etc.), other similar ceramics, and natural or synthetic ceramics selected from at least two combinations thereof. 31. An electrolyte according to item 30, wherein the ceramic is an aluminosilicate-based compound. 32. An electrolyte according to item 27 or 28, wherein the ceramic is a sulfide-based or oxysulfide-based ceramic. 33. An electrolyte according to any one of items 27 to 32, wherein the inorganic particles are in the form of spherical particles, rods, needles, nanotubes, or a combination thereof. 34. An electrolyte according to any one of items 27 to 33, wherein the electrolyte contains inorganic particles in an amount ranging from about 5% to about 99% by weight, or from about 5% to about 90% by weight, or from about 10% to about 80% by weight, or from about 15% to about 40% by weight. 35. An electrolyte according to any one of items 20 to 34, further comprising a plasticizer in the electrolyte, preferably in a concentration of about 5% to about 50% by weight, or about 10% to about 40% by weight, or about 20% to about 30% by weight. 36. An electrolyte according to item 35, wherein the plasticizer is selected from glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and other similar liquids, preferably glycol diether liquids (such as TEGDME). 37. An electrolyte according to any one of items 20 to 36, further containing organic additives. 38. An electrolyte according to item 37, wherein the organic additive is selected from ionic organic compounds (e.g., ionic soft crystals, ionic soft salts, ionic liquids, etc.) and halogenated amides. 39. Electrode materials comprising polymers, electrochemical active materials, and optionally conductive materials, binders, salts, or at least two combinations thereof, as defined in any one of items 1 through 19. 40. An electrode material according to item 39, wherein the polymer acts as a binder. 41. An electrode material according to item 39, wherein the polymer acts as a coating on the particles of the electrochemical active material. 42. An electrode material according to any one of items 39 to 41, wherein the electrochemical active material is selected from metal phosphates, lithified metal phosphates, metal oxides, and lithified metal oxides. 43. The electrochemical active material is LiM'PO4 (where M' is Fe, Ni, Mn, Co, or a combination of at least two of these), LiV3O8, V2O5F, LiV2O5, LiMn2O4, Li 1+w M''O 2-a X b (where M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or at least two of these, and X is F, S, or at least two of these), Li 1+w(NiM''')O2 (where M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or at least two combinations thereof), carbon-based active materials such as sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, graphite, organic cathode active materials, and electrode materials according to any one of items 39 to 41, selected from at least two combinations thereof, where applicable. 44. An electrode material according to any one of items 39 to 41, wherein the electrochemical active material comprises a metal film comprising an alkali or alkaline earth metal or an alloy containing an alkali or alkaline earth metal, the polymer is present in a thin layer on the metal film, and preferably the alkali metal is selected from lithium and sodium, or an alloy containing lithium or sodium, preferably lithium or an alloy containing lithium. 45. The electrochemical active material may be an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTi2(PO4)3), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), or silicon dioxide (SiO₂). x ), silicon dioxide-carbon composite material (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite material (SnO x -C), and, where applicable, electrode materials conforming to any one of items 39 to 41, including at least two combinations of these. 46. ​​The aforementioned metal oxide is of formula M'''' b O c(wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof; b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM'''''O (wherein M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof) (e.g., lithium titanate (Li4Ti5O) 12 (etc.), or lithium and molybdenum oxide (Li2Mo4O 13 Electrode material selected from compounds such as those specified in item 45. 47. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive electrode or the negative electrode comprises an electrode material as defined in any one of items 39 to 46. 48. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined in any one of items 20 to 38, and at least one of the positive electrode or the negative electrode comprises an electrode material as defined in any one of items 39 to 46. 49. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined in any one of items 20 to 38. 50. An electrochemical cell according to item 49, comprising a positive electrode material, wherein the positive electrode contains an electrochemical active material of the positive electrode and, if necessary, is located on a current collector. 51. An electrochemical cell according to item 50, wherein the electrochemical active material of the positive electrode is selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides. 52. The electrochemical active material of the positive electrode is LiM'PO4 (where M' is Fe, Ni, Mn, Co, or a combination of at least two of these), LiV3O8, V2O5F, LiV2O5, LiMn2O4, Li1+w M''O 2-a X b (where M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or at least two of these, and X is F, S, or at least two of these), Li 1+w An electrochemical cell in accordance with item 50, comprising (NiM''')O2 (where M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or at least two of these), a carbon-based active material such as sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, graphite, an organic cathode active material, or, where applicable, at least two of these. 53. An electrochemical cell according to any one of items 50 to 52, wherein the positive electrode material further comprises a conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles. 54. An electrochemical cell according to any one of items 49 to 53, wherein the negative electrode comprises a negative electrode material containing an electrochemical active material of the negative electrode, and optionally located on a current collector. 55. An electrochemical cell in accordance with item 54, wherein the electrochemical active material of the negative electrode comprises a metal film comprising an alkali or alkaline earth metal, or an alloy containing an alkali or alkaline earth metal. 56. An electrochemical cell according to item 55, wherein the alkali metal is selected from lithium and sodium, or an alloy containing lithium or sodium, preferably lithium or an alloy containing lithium. 57. The electrochemical active material of the negative electrode may be an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTi2(PO4)3), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), or silicon dioxide (SiO2).x ), silicon dioxide-carbon composite material (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite material (SnO x -C), and, where applicable, an electrochemical cell in accordance with item 54, including at least two combinations of these. 58. The metal oxide is of formula M'''' b O c (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof; b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM'''''O (wherein M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof) (e.g., lithium titanate (Li4Ti5O) 12 (etc.), or lithium and molybdenum oxide (Li2Mo4O 13 An electrochemical cell according to item 57, selected from compounds such as)). 59. An electrochemical cell according to item 57 or 58, wherein the negative electrode material further comprises a conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles. 60. A battery comprising at least one electrochemical cell as defined in any one of items 47 through 59. 61. A battery according to item 60, wherein the battery is selected from lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, potassium-ion batteries, magnesium batteries, and magnesium-ion batteries. 62. A battery according to item 60, wherein the battery is a lithium battery. 63. A battery according to item 60, wherein the battery is a lithium-ion battery. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 shows the proton nuclear magnetic resonance (1H NMR) spectrum obtained for polymer 5, as described in Example 2.

[0008] [Figure 2] Figure 2 shows the 1H NMR spectrum obtained for polymer 6, as described in Example 2.

[0009] [Figure 3] Figure 3 shows the 1H NMR spectrum obtained for polymer 7, as described in Example 2.

[0010] [Figure 4] Figure 4 shows the 1H NMR spectrum obtained for polymer 9, as described in Example 2.

[0011] [Figure 5] Figure 5 shows the 1H NMR spectrum obtained for polymer 15, as described in Example 2.

[0012] [Figure 6] Figure 6 shows the 1H NMR spectrum obtained for polymer 19, as described in Example 2.

[0013] [Figure 7] Figure 7 shows the 1H NMR spectrum obtained for polymer 21, as described in Example 2.

[0014] [Figure 8] Figure 8 shows the results of differential scanning calorimetry (DSC) analysis obtained for polymer 9, as described in Example 2.

[0015] [Figure 9]Figure 9 shows the results of the DSC analysis obtained for Polymer 19 as described in Example 2.

[0016] [Figure 10] Figure 10 shows the results of the DSC analysis obtained for Polymer 21 as described in Example 2.

[0017] [Figure 11] Figure 11 is a graph showing the ionic conductivity results (S·cm-1) for Cell 1 during temperature increase (◆) and decrease (■) as a function of temperature (1000 / T, K-1) as described in Example 5(a).

[0018] [Figure 12] Figure 12 is a graph showing the voltage (V) and current density (mA·cm-2) for Cell 1 as a function of time (hours) as described in Example 5(a).

[0019] [Figure 13] Figure 13 is a graph showing the ionic conductivity results (S·cm-1) for Cell 2 during temperature increase (◆) and decrease (■) as a function of temperature (1000 / T, K- / ) as described in Example 5(a).

[0020] [Figure 14] Figure 14 is a graph showing the ionic conductivity results (S·cm-1) for Cell 2 during temperature increase (◆) and decrease (■) as a function of temperature (1000 / T, K-1) as described in Example 5(a).

[0021] [Figure 15] Figure 15 is a graph showing the ionic conductivity results (S·cm-1) for Cell 3 during temperature increase (◆) as a function of temperature (1000 / T, K-1) as described in Example 5(a).

[0022] [Figure 16]FIG. 16 is a graph showing the ionic conductivity results (S·cm-1) for cell 4 during temperature rise (◆) as a function of temperature (1000 / T, K-1), as described in Example 5(a).

[0023] [Figure 17] FIG. 17 shows a graph of relative capacity (%) as a function of cycle number for cell 5, as described in Example 5(b).

[0024] [Figure 18] FIG. 18 shows a graph of Coulomb efficiency (%) as a function of cycle number for cell 5, as described in Example 5(b).

MODE FOR CARRYING OUT THE INVENTION

[0025] Detailed Description The following detailed description and examples are presented for illustrative purposes only and should not be construed as further limiting the scope of the invention. On the contrary, they are intended to cover all alternatives, modifications, and equivalents that may be included as defined herein. The polymers of the invention containing unsaturated units, the processes for their preparation, as well as the electrodes, electrode materials, electrolytes, electrochemical cells, and electrochemical storage batteries containing them, their purposes, advantages, and other features will become clearer and better understood by reading the following non-limiting description of the invention and referring to the accompanying drawings.

[0026] All technical and scientific terms and expressions used herein have the same definitions as those generally understood by a person skilled in the art in relation to the technology of the invention. Nevertheless, for the purpose of clarity, the definitions of some terms and expressions used herein are provided below.

[0027] When the term "approximately" is used herein, it means roughly, around, or about that. When the term "approximately" is used in relation to a number, it modifies it, for example, by a rate of change of plus or minus 10% of its nominal value. This term may also take into account the probability of random error in experimental measurements due to rounding of numbers or, for example, limitations of the instrument.

[0028] Where a range of values ​​is referred to in this application, the lower and upper limits of that range are always included in the definition unless otherwise indicated. Where a range of values ​​is referred to in this application, all intermediate ranges and subranges included in that range, as well as individual values, are included in the definition. For example, "between x and y" or "up to x and y" means a range that includes the limits x and y, unless otherwise indicated. For example, the range "between 1 and 50" includes the values ​​1 and 50.

[0029] Where the article “a” is used in this application to introduce an element, it means “one or more” rather than “only one.” Where this specification states that a particular step, component, feature, or characteristic “may,” “may,” “may,” or “may be,” it should be understood that that particular step, component, feature, or characteristic does not have to be included in all substitutes.

[0030] When a trademark name is used herein, it is intended to independently include both the product identified by that trademark name and the active ingredient of that trademark product.

[0031] The term "polymer" refers to a macromolecule containing multiple repeats of units or motifs derived from one or more monomers and / or macromonomers. Similarly, "polymer chain" refers to the polymeric portion of a polymer or macromonomer.

[0032] The term "repeating unit" refers to a monomer or motif that is repeated within a polymer chain.

[0033] The expression "crosslinkable functional group" or "crosslinkable group" in a polymer refers to a group having at least one functional moiety that can react to form crosslinks between the main chain and / or branches of the polymer, thereby forming a three-dimensional network structure.

[0034] The term "(meth)acrylate" or "(meth)acrylic" refers to an acrylate or acrylic group that is optionally substituted with a methyl group, i.e., an acrylate group, methacrylate group, acrylic group, or methacrylic group.

[0035] The term "alkyl," as used herein, refers to saturated hydrocarbons having between 1 and 12 carbon atoms, including linear or branched alkyl groups. Non-limiting examples of alkyl groups may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, etc. The term alkyl also includes alkylene groups such as methylene, ethylene, and propylene, when the alkyl group is located between two functional groups. m ~C n "Alkyl" and "C m ~C n "Alkylene" refers to an alkyl or alkylene group having between the specified number "m" and the specified number "n" carbon atoms.

[0036] The term "alkenyl," as used herein, refers to an unsaturated hydrocarbon having between 2 and 12 carbon atoms and containing at least one double bond between any two carbon atoms, and which may be optionally substituted, and includes linear or branched alkenyl groups. Non-limiting examples of alkenyl groups may include vinyl, allyl, 1-propen-2-yl, 1-buten-3-yl, 1-buten-4-yl, 2-buten-4-yl, 1-penten-5-yl, 1,3-pentadiene-5-yl, etc. When the alkenyl group is located between two functional groups, the term alkenyl also includes alkenylene groups such as vinylene, allylene, 1-propen-2-ylene, 1-buten-3-ylene.m ~C n "Alkenil" and "C m ~C n "Alkenylene" refers to an alkenyl or alkenylene group having between the specified number "m" and the specified number "n" carbon atoms.

[0037] The term "alkynyl," as used herein, refers to an unsaturated hydrocarbon having between 2 and 12 carbon atoms and containing at least one triple bond between two carbon atoms, and which is optionally substituted, and includes linear or branched alkynyl groups. Non-limiting examples of alkynyl groups may include ethynyl, 1-propyne-3-yl, 1-butyne-4-yl, 2-butyne-4-yl, 1-pentyne-5-yl, and 1,3-pentadiinyne-5-yl. When the alkynyl group is located between two functional groups, the term alkynyl also includes alkynylene groups such as ethynylene, 1-propyne-3-ylene, and 1-butyne-4-ylene. m ~C n "Alkinyl" and "C m ~C n "Alkynylene" refers to an alkynyl or alkynylene group having between the specified number "m" and the specified number "n" carbon atoms.

[0038] The term "cycloalkyl," as used herein, refers to a group containing one or more saturated or partially unsaturated (non-aromatic) carbocyclic rings with 3 to 15 members in a monocyclic or polycyclic system (including spiro (sharing atoms), condensed (sharing at least one bond), or cross-linked carbocyclic rings), which may be substituted as necessary. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-2-yl, cyclopenten-3-yl, cyclohexyl, cyclohexen-1-yl, cyclohexen-2-yl, cyclohexen-3-yl, cycloheptyl, etc. The term cycloalkylene may also be used when the cycloalkyl group is located between two functional groups. m ~C n"Cycloalkyl" and "C m ~C n "Cycloalkylene" refers to a cycloalkyl or cycloalkylene group having between the indicated number "m" and the indicated number "n" carbon atoms, respectively.

[0039] The term "heterocycloalkyl," as used herein, refers to a group containing a saturated or partially unsaturated (non-aromatic) carbocyclic ring with 3 to 15 members in a monocyclic or polycyclic system (including spiro (sharing one atom), condensed (sharing at least one bond), or bridging carbocyclic ring), which may be substituted as necessary, and which contains a carbon atom and 1 to 4 heteroatoms (e.g., N, O, S, or P) or a group containing such heteroatoms (e.g., NH, NR). x (R x The group includes alkyl, acyl, aryl, heteroaryl, or cycloalkyl groups, PO2, SO, SO2, and other similar groups. Heterocycloalkyl groups may be linked to carbon atoms or heteroatoms (e.g., via nitrogen atoms) if linkage is possible. The term heterocycloalkyl includes both unsubstituted and substituted heterocycloalkyl groups. The term heterocycloalkylene may also be used when the heterocycloalkyl group is located between two functional groups. m ~C n "heterocycloalkyl" and "C m ~C n "Hypercycloalkylene" refers to a heterocycloalkyl or heterocycloalkylene group, respectively, that has a number of ring atoms ranging from m to n, including carbon atoms and heteroatoms.

[0040] As used herein, the term "aryl" refers to a functional group comprising a ring having aromatic characteristics due to 6 to 14 ring atoms, preferably 6 ring atoms. The term "aryl" refers to both monocyclic and conjugated polycyclic systems. The term "aryl" also includes substituted and unsubstituted groups. Examples of aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indenyl, benzocyclooctenyl, benzocycloheptenyl, azlenyl, acenaphthirenyl, fluorenyl, phenantrenyl, anthracenyl, and perilenyl. m ~C n "Aryl" and "C m ~C n "Arylene" refers to an aryl or arylene group having between the specified number "m" and the specified number "n" carbon atoms.

[0041] The terms "heteroaromatic" or "heteroaryl" refer to groups having, for example, 5 to 18 ring atoms, preferably 5, 6, or 9 ring atoms, and containing 1 to 5 heteroatoms selected from oxygen, nitrogen, and sulfur in addition to carbon atoms, or groups containing such heteroatoms (e.g., NH, NR). x (R x A polycyclic system is defined as an aromatic group having 4n + 2π (pi) conjugated electrons, including alkyl, acyl, aryl, heteroaryl, or cycloalkyl groups, SO, and other similar groups, where n is an integer from 1 to 3. A polycyclic system contains at least one heteroaromatic ring. Heteroaryls may be directly bonded or linked by C1-C3 alkyl (also called heteroarylalkyl or heteroaralkyl) groups. Heteroaryl groups may be linked to carbon atoms or heteroatoms of the ring (e.g., via nitrogen atoms) where possible. m ~C n "heteroaryl" and "C m ~C n"Heteroarylene" refers to a heteroaryl or heteroarylene group having from the indicated number "m" to the indicated number "n" of ring atoms, including carbon atoms and heteroatoms, respectively.

[0042] The chemical structures described herein are drawn according to the conventions of the art. Also, when an atom such as a carbon atom appears to have an incomplete valence as depicted, the valence is assumed to be satisfied by one or more hydrogen atoms even if the hydrogen atoms are not explicitly drawn.

[0043] Generally, the term "substituted" means that one or more hydrogen atoms in the specified group are replaced by suitable substituents. The substituents or combinations of substituents contemplated herein result in the formation of chemically stable compounds. Examples of substituents include halogen atoms (such as fluorine), and hydroxyl, oxo, alkyl, alkoxy, alkoxyalkyl, cyano, azide, carboxylate, alkoxycarbonyl, alkylcarbonyl, primary, secondary, or tertiary amines, amides, nitro, silane, siloxane, thiocarboxylate, sulfonyl, sulfonate, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl groups, or combinations of at least two of these.

[0044] According to a first aspect, the technology of the present invention is a repeating unit of formula 1:

Chemical formula

[0045] Preferably, X 3 and X 4 Independently and in each occurrence, is selected from O and NH, preferably O. 2 Preferably, (C2-C6 alkylene O) 1~12These are C2-C6 alkylene groups (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.).

[0046] According to some examples, polymers are repeating units of formula 2: [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , L 1 , X 1 , and X 2 This is as defined above, n is a number between 1 and 20. Includes.

[0047] In some examples of equations 1 and 2, R 1 and R 2 These are all hydrogen atoms. In other examples of equations 1 and 2, X 1 and X 2 is selected from O and NH, and / or L 1 (C2~C6 alkylene O) 1~12 The copolymer is selected from C2-C6 alkylene groups, polyethers, polyesters, and copolymers containing ether and ester units.

[0048] X 1 -L 1 -X 2 A non-restrictive example of a part is structure: [ka] [Here, R 3 , R 4 , R 5 , and R 6 As defined above, R 7 , R 8 , R 9 , R10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 These are, independently and in each instance, hydrogen atoms, halogen atoms (such as F and Cl), and C which is substituted as needed. 1~12 Selected from alkyl groups, j is a number that is independently selected and, in each instance, is chosen within the range of 2 to 30. k is a number from 1 to 20. m is a number selected within the range of 2 to 150. p is a number between 0 and 12, preferably between 0 and 6. q is a number between 0 and 8, preferably between 0 and 6, provided that p and q are not both zero at the same time. r is a number selected within the range of 2 to 4. [s is a number selected within the range of 5 to 30] Includes.

[0049] For example, the repeating units of the polymer of the present invention are given by formulas 3 to 6: [ka] [In the formula, R 1 From R 16 [j, k, m, n, p, q, r, and s are as defined above.] It may be any one of them.

[0050] In some examples, the sum (p+q) is within the range of 2 to 9, preferably within the range of 3 to 6. In other examples, R 11 R is a hydrogen atom, 12 is a C1-C6 alkyl group which is substituted as needed, and p is equal to 1 or R 11 and R 12These are all hydrogen atoms, and p is selected within the range of 1 to 6. According to another example, R 13 and R 14 These are all hydrogen atoms, and q is selected from the range of 2 to 6, or R 13 and R 14 At least one of them is a C1-C6 alkyl group that is substituted as necessary in at least one occurrence.

[0051] According to another example, if r is 2 or 3, preferably 2, then R 15 and R 16 In each appearance, it is either a hydrogen atom or R 15 and R 16 One of them is methyl in a single appearance, R 15 and R 16 In all other appearances, it is a hydrogen atom.

[0052] According to some definitions, R 7 , R 8 , R 9 , and R 10 Independently and in each occurrence, hydrogen atoms, fluorine atoms, and C as needed are substituted. 1~3 Selected from alkyl groups, preferably R 7 , R 8 , R 9 , and R 10 These are all either hydrogen atoms or R 7 , R 8 , R 9 , and R 10 One of them is a methyl group, and the others are all hydrogen atoms.

[0053] In any of the above formulas, R 3 , R 4 , R 5 , and R 6 Independently and in each occurrence, hydrogen atoms, fluorine atoms, and C as needed are substituted. 1~3 Selected from alkyl groups, preferably R 3 , R4 , R 5 , and R 6 These are all either hydrogen atoms or R 3 , R 4 , R 5 , and R 6 One of them is a methyl group, and the others are all hydrogen atoms.

[0054] The polymer of the present invention includes terminal groups. For example, the terminal groups may be selected from hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkenyl, optionally substituted alkynyl, acrylate, methacrylate, or at least two combinations thereof.

[0055] The number-average molecular weight of the polymer of the present invention, when determined by triple detection gel permeation chromatography, may fall within the ranges of 500 to 5,000,000, or 500 to 1,000,000, or 500 to 500,000, or 500 to 250,000, or 500 to 100,000, or 500 to 75,000, or 500 to 70,000, or 500 to 65,000, or 500 to 60,000, or 500 to 55,000, or 500 to 50,000, or 1,000 to 50,000, or 1,500 to 50,000, or 2,000 to 50,000. Preferably, the number-average molecular weight of the polymer of the present invention may fall within the range of 2,000 to 50,000.

[0056] The technology of the present invention is a process for preparing a polymer as defined herein, wherein the process comprises the following steps: (i) Unsaturated monomer of formula A: [ka] [In the formula, L 2 , R 2 , X 3 and X 4This is as defined above. The steps of preparing and (ii) A comonomer of formula B containing at least two functional groups from an unsaturated monomer of formula A: [ka] [In the formula, L 1 , X 1 and X 2 This is as defined above. and polymerization step This also relates to the process, including the process itself.

[0057] According to one example, the step of preparing an unsaturated monomer of formula A is: formula HX 3 -L 2 -X 4 This can be carried out by the reaction of a -H compound, such as a diol (or glycol), with an acetylene carboxylic acid (such as propiolic acid, also called propynoic acid). Non-limiting examples of diols include ethylene glycol (1,2-ethanediol), diethylene glycol (or ethylenediglycol), triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, and other similar glycols and diols, or at least two of these in combination.

[0058] For example, the synthesis of unsaturated monomers of formula A can be carried out by esterification from diols and acetylene carboxylic acids. In one example, esterification is carried out by a Fischer esterification reaction or a Steglich esterification reaction. According to an example for a certain purpose, the step of preparing an unsaturated monomer of formula A is a process illustrated in Scheme 1 below: [ka] This can be done by [method].

[0059] In another example, the step of preparing the unsaturated monomer of formula A can be carried out in the presence of at least one catalyst. Any suitable catalyst is intended. For example, the catalyst may be an acid catalyst. Non-limiting examples of acid catalysts include p-toluenesulfonic acid (or tosylic acid, TsOH) and sulfuric acid (H2SO4). In an example for a certain purpose, the acid catalyst may be TsOH.

[0060] In another example, the polymerization step can be carried out in the presence of at least one polymerization catalyst. In one example, the polymerization catalyst may be a nucleophile such as 1,4-diazabicyclo[2.2.2]octane (DABCO) and 4-dimethylaminopyridine (DMAP). In one example for a particular purpose, the nucleophile is DABCO.

[0061] In another example, the polymerization step can be carried out in the presence of at least one organic solvent, such as a polar aprotic solvent. For example, the solvent can be selected from the group consisting of N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile (ACN), and at least two miscible combinations thereof.

[0062] In another example, the polymerization step can be carried out at a temperature within the range of approximately 40°C to approximately 80°C (including upper and lower limits). For example, the polymerization step can be carried out at a temperature within the range of approximately 45°C to approximately 75°C, or approximately 45°C to approximately 70°C, or approximately 50°C to approximately 70°C (including upper and lower limits). In an example for a certain purpose, the polymerization step can be carried out at a temperature within the range of approximately 50°C to approximately 70°C (including upper and lower limits).

[0063] In another example, the polymerization step can be carried out over a duration that falls within the range (including upper and lower limits) of approximately 30 to 80 minutes, or approximately 30 to 75 minutes, or approximately 30 to 70 minutes, or approximately 30 to 65 minutes, or approximately 30 to 60 minutes. In an example for a certain purpose, the polymerization step can be carried out over a duration that falls within the range (including upper and lower limits) of approximately 30 to 60 minutes.

[0064] In another example, the process further includes a step of crosslinking the polymer as defined above. For example, the polymer includes at least one functional group that enables the crosslinking of the polymer. In another example, the crosslinking step can be carried out by UV irradiation, heat treatment, microwave irradiation, under an electron beam, by gamma ray irradiation, or by X-ray irradiation. In an example for a certain purpose, the crosslinking step is carried out by UV irradiation. In another example, the crosslinking step can be carried out in the presence of a crosslinking agent, a thermal initiator, a photoinitiator, a catalyst, a plasticizer, or a combination of at least two of these. For example, the photoinitiator is 2,2-dimethoxy-2-phenylacetophenone (Irgacure® 651). [ka]

[0065] The polymer's unique structure allows for the elimination of crystallinity, which limits ionic conductivity at low temperatures (as demonstrated by DSC). Conductivity at 20°C and 50°C is higher than that reported for carbonate polymers. Furthermore, under certain conditions, the insertion of double bonds into the chain can enable ester stabilization, thereby substantially increasing electrochemical stability. Finally, the presence of functional groups at the chain ends (terminal groups) allows for modification of the polymer, thereby increasing its lithium ion transport number (t + This can increase the amount of or make it crosslinkable. In addition, the polymerization method is relatively simple and can be carried out in a rapid one-step process.

[0066] The technology of the present invention also relates to compositions comprising polymers as defined herein. For example, such compositions may be present in electrolytes or electrode materials.

[0067] For example, the polymer is present in the electrolyte, which may contain salts as needed. For instance, the electrolyte may be in solid form or in the form of a gel electrolyte membrane. For example, the solid electrolyte may be a solid polymer electrolyte or a composite containing particles.

[0068] If present, the salt is preferably an alkali metal salt, preferably a lithium salt, and may be present in the electrolyte at concentrations of about 5% to about 40% by weight, or about 15% to about 40% by weight, or about 20% to about 35% by weight. Non-limiting examples of salts include alkali metal (preferably Li) cations and hexafluorophosphate (PF6). - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI - ), 4,5-dicyano-1,2,3-triazolate (DCTA - ), bis(pentafluoroethylsulfonyl)imide (BETI - ), difluorophosphate (DFP - ), tetrafluoroborate (BF4 - ), bis(oxalato) borate(BOB - ), nitrate (NO3 - ), chloride (Cl - ), bromide (Br - ), fluoride (F - ), perchlorate (ClO4 - ), hexafluoroarsenate (AsF6 - ), trifluoromethanesulfonate (SO3CF3 - )(Tf- ), fluoroalkyl phosphate [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate [B(C6O2)2] - (BBB - ), difluoro(oxalato)borate (BF2(C2O4) - )(FOB - ), formula BF2O4R x - (In the formula, R x =C 2~4 It comprises an alkyl anion and an anion selected from at least two combinations thereof, for example, LiTFSI or LiFSI.

[0069] The electrolyte may also include a second polymer in addition to the polymer of the present invention. For example, this additional polymer may be selected from polymers typically used in electrolytes or as electrode binders. For example, the additional polymer may be selected from polyethers, substituted polyethylenes, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethanes, poly(vinyl alcohol), polyacrylonitrile, poly(methyl (meth)acrylate), poly(methyl (meth)acrylate of poly(ethylene glycol)methyl ether) (PEGMA), poly(2,2,2-trifluoroethyl (meth)acrylate), poly((meth)acrylic acid), and copolymers thereof, and may optionally include crosslinking units derived from crosslinkable functional groups, and the additional polymer may be linear or branched. According to an alternative, the additional polymer may be selected from rubber-based polymers such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR), and polyacrylic rubber (ACM). According to another alternative, the additional polymer may be selected from fluorinated polymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyhexafluoropropylene (HFP). According to yet another alternative, the additional polymer may be a combination of at least two of the polymers mentioned above.

[0070] In another example, the electrolyte further comprises inorganic particles, preferably amorphous, ceramic, or glass-ceramic, based on oxides, sulfides, or oxysulfides, and the inorganic compounds are natural or synthetic. The electrolyte may contain inorganic particles in amounts ranging from about 5% to about 99% by weight, or from about 5% to about 90% by weight, or from about 10% to about 80% by weight, or from about 15% to about 40% by weight.

[0071] A non-restrictive example of inorganic particles is the formula MLZO (e.g., M7La3Zr2O 12 M (7-a)La3Zr2Al b O 12 M (7-a) La3Zr2Ga b O 12 M (7-a) La3Zr (2-b) Ta b O 12 , and M (7-a) La3Zr (2-b) Nb b O 12 );MLTaO(for example, M7La3Ta2O 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO(for example, M7La3Sn2O 12 );MAGP(for example, M 1+a Al a Ge 2-a (PO4)3);MATP(for example, M 1+a Al a Ti 2-a (PO4)3);MLTiO(for example, M 3a La (2 / 3-a) TiO3); MZP (for example, M a Zr b (PO4) c );MCZP(for example, M a Ca b Zr c (PO4) d );MGPS(for example, M 10 GeP2S 12 M etc. a Ge b P c S d );MGPSO(for example, M a Ge b P c S d O e );MSiPS(for example, M 10 SiP2S 12 M etc. a Si b P c S d );MSiPSO(for example, M a Si b P c Sd O e );MSnPS(for example, M 10 SnP2S 12 M etc. a Sn b P c S d );MSnPSO(for example, M a Sn b P c S d O e );MPS (for example, M7P3S 11 M etc. a P b S c );MPSO (for example, M a P b S c O d );MZPS(for example, M a Zn b P c S d );MZPSO(for example, M a Zn b P c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 M models such as X, M7P2S8X, and M6PS5X a P b S c X d );MPSOX(for example, M a P b S c O d X e );MGPSX(M a Ge b P c S d X e );MGPSOX(M a Ge b P c S d Oe X f );MSiPSX(M a Si b P c S d X e );MSiPSOX(M a Si b P c S d O e X f );MSnPSX(M a Sn b P c S d X e );MSnPSOX(M a Sn b P c S d O e X f );MZPSX(M a Zn b P c S d X e );MZPSOX(M a Zn b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c It includes natural or synthetic ceramics selected from inorganic compounds (where a = 2b + 3c - 5), During the ceremony, M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two of these, where if M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality. X is selected from F, Cl, Br, I, or at least two combinations of these. a, b, c, d, e, and f are non-zero numbers, independently chosen in each equation to achieve electrical neutrality. v, w, x, y, and z are non-zero numbers and are independently selected in each formula to obtain a stable compound.

[0072] For example, the ceramic may be of the MLZO type, and the formula Li 7-b La3Zr2M i b O 12 It can be such that, in the formula, b is such that 0 ≤ b ≤ 1, and M i is Al, Ga, Ta, Fe, or Nb, or is absent, preferably b is 0, and M i It does not exist. Other examples of inorganic particles are Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., those based on aluminosilicates, mesoporous silica, etc.), sulfide-based ceramics (e.g., Li6PS5Cl, Li7P3S 11 This includes glass ceramics (e.g., LIPON), other similar ceramics, and natural or synthetic ceramics selected from at least two combinations thereof. For example, the ceramic may be an aluminosilicate-based compound or a sulfide-based or oxysulfide-based ceramic.

[0073] The inorganic particles may take various forms, such as spherical particles, rods, needles, nanotubes, or combinations thereof.

[0074] According to some alternatives, the electrolyte further contains a plasticizer, preferably in a concentration of about 5% to about 50% by weight, or about 10% to about 40% by weight, or about 20% to about 30% by weight. Non-limiting examples of plasticizers include glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and other similar liquids, preferably glycol diether liquids (such as TEGDME).

[0075] The electrolyte may further include organic additives selected from, for example, ionic organic compounds (e.g., ionic soft crystals, ionic soft salts, ionic liquids, etc.) and halogenated amides.

[0076] When the polymer of the present invention is present in an electrode material, the latter also includes an electrochemical active material and, optionally, a conductive material, a binder, a salt, or a combination of at least two of these. For example, the polymer may exist as an additive, as a binder, or as a coating on particles of the electrochemical active material.

[0077] According to some examples, when an electrochemical active material is included in the positive electrode, this material can be selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides. For example, electrochemical active materials include LiM'PO4 (where M' is Fe, Ni, Mn, Co, or a combination of at least two of these), LiV3O8, V2O5F, LiV2O5, LiMn2O4, Li 1+w M''O 2-a X b (where M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or at least two of these, and X is F, S, or at least two of these), Li 1+w (NiM''')O2 (where M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or at least two combinations thereof), carbon-based active materials such as sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, and graphite, as well as organic cathode active materials, and at least two combinations thereof may be selected if they are compatible with each other.

[0078] According to some examples, when an electrochemical active material is included in the negative electrode, this material may include a metal film containing an alkali or alkaline earth metal or an alloy containing an alkali or alkaline earth metal, and the polymer is present in a thin layer on the metal film, preferably the alkali metal is selected from lithium and sodium, or an alloy containing lithium or sodium, preferably lithium or an alloy containing lithium. According to alternatives, the electrochemical active material may be an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTi2(PO4)3), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, a carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon dioxide (SiO₂) x ), silicon dioxide-carbon composite material (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite material (SnO x -C), and, where applicable, a combination of at least two of these. For example, a metal oxide is given by formula M'''' b O c (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof; b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM'''''O (wherein M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof) (e.g., lithium titanate (Li4Ti5O) 12 (etc.), or lithium and molybdenum oxide (Li2Mo4O 13 Selected from compounds such as)).

[0079] The electrode material may further include a binder. The binder polymer may contain ionic solvation units, particularly lithium ion solvation units. Non-limiting examples of solvation polymers include linear or branched polyethers (e.g., poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), or copolymers (EO / PO)), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, polymethyl methacrylate, and copolymers thereof, as well as optionally including crosslinking units derived from crosslinkable functional groups (e.g., acrylate, methacrylate, vinyl, glycidyl, mercapto functional groups, etc.). According to alternatives, the binder may consist of polymers as described for additional polymers of the electrolyte.

[0080] Examples of conductive materials that may be included in electrode materials include carbon black (e.g., Ketjen® carbon, Denka® carbon, Schawinigan carbon, acetylene black, etc.), graphite, graphene, carbon nanotubes, carbon fibers (including carbon nanofibers, vapor-grown carbon fibers (VGCF), etc.), non-powdered carbon obtained by carbonization of organic precursors (e.g., in the form of a coating on particles), or a combination of at least two of these.

[0081] The technology of the present invention also relates to an electrochemical cell comprising the polymer of the present invention. For example, the electrochemical cell comprises a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive or negative electrode comprises an electrode material as defined above. Alternatively, the electrolyte may be as defined herein, or the electrolyte and at least one of the positive or negative electrode may comprise an electrode material as defined herein.

[0082] If the electrolyte or electrode material does not contain one of the polymers defined herein, the electrolyte or electrode material is as defined above, and there is no addition of the polymers of the present invention.

[0083] The technology of the present invention also relates to a battery or electrochemical storage battery comprising at least one electrochemical cell as defined herein. For example, the battery may be selected from lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, potassium-ion batteries, magnesium batteries, and magnesium-ion batteries. Preferably, the battery is a lithium battery or a lithium-ion battery.

[0084] The batteries and electrochemical storage batteries described herein are intended for use in portable devices such as mobile phones, cameras, tablets, or laptop computers, in electric or hybrid vehicles, or in renewable energy storage. [Examples]

[0085] The following examples are for illustrative purposes only and should not be construed as further limiting the scope of the invention as intended. These examples will be better understood by referring to the accompanying figures. Example 1 Preparation of monomers 1 and 2 [ka]

[0086] (i) Monomer 1 (n=3)

[0087] In a 1-liter flask, 15 g of tetraethylene glycol was weighed and 300 mL of chloroform was added in a fume hood. Using a funnel, 44 g of p-toluenesulfonic acid monohydrate (TsOH) was added, followed by 100 mL of chloroform to rinse the funnel walls. The resulting solution was stirred. Then, 11.5 mL of propiolic acid (stored at 4°C) was added at room temperature. A liquefaction apparatus was attached to the flask, and the reaction mixture was heated under reflux for 48 to 72 hours.

[0088] Next, the mixture was cooled to room temperature and the solid was filtered by washing with the minimum necessary amount of dichloromethane. The filtrate was required to be free of solids. The filtrate was evaporated to dryness using a rotary evaporator, and the residue was separated by chromatography using a stepwise elution protocol with a mixture of dichloromethane and ethyl acetate on an 80 g silica cartridge. The protocol included a gradient to 100% dichloromethane over approximately 5 minutes, 5% ethyl acetate and 95% dichloromethane over approximately 15 minutes, and then to a maximum of 70% ethyl acetate over approximately 15 minutes. The first peak showing a UV signal was evaporated to dryness using a rotary evaporator. The thus obtained product was evaporated in deuterated chloroform (CDCl3) 1 Analysis was performed by 1H NMR (approximately 50% yield, approximately 99% purity). (ii) Monomer 2 (n=2)

[0089] Monomer 2 was prepared by substituting tetraethylene glycol (15 g) with triethylene glycol (11.6 g) in accordance with the protocol described in (i). Analysis confirmed that monomer 2 was obtained. Example 2 Polymer preparation and properties

[0090] The polymers were prepared by copolymerization of monomer 1 or 2 and by copolymerization of comonomers (diols, diamines, etc.) according to the conditions shown in Tables 1 and 2.

[0091] For example, tetraethylene glycol (comonomer) and an anhydrous solvent (e.g., THF, DMF, ACN) were added to a clean, dry 25 mL flask. The mixture was then stirred under nitrogen. Next, a catalyst (e.g., DABCO or DMAP) was added to the flask and the mixture was stirred. Then, monomer 1 or monomer 2 was added under a stream of nitrogen, and the mixture was heated under nitrogen at a temperature of approximately 40°C for approximately 1 hour.

[0092] If necessary, additional monovalent compounds (such as monoalcohols) were added along with the comonomers as shown in the table below, via the diaphragm using a syringe, and the mixture was stirred for an additional 15 minutes.

[0093] Next, the reaction mixture was cooled to room temperature and poured into 10 volumes of diethyl ether at a temperature of approximately 20°C. A red precipitate then formed. The mixture was stirred for approximately 10 minutes, and the supernatant was decanted. The resulting solid was then dried at a temperature of approximately 60°C for approximately 3 hours.

[0094] The polymer obtained in this way is then used in CDCl3 1 Analysis was performed by 1H NMR, gel permeation chromatography (GPC) in THF, and digital scanning (DSC) (from -70 to 150°C at 10°C / min). [Table 1-1] [Table 1-2]

[0095] [Table 2]

[0096] [Table 3]

[0097] Figures 1 to 7 show the results obtained for polymers 5, 6, 7, 9, 15, 19, and 21, respectively. 1 The 1H NMR spectrum is shown.

[0098] Figures 8 to 20 show the results of DSC analysis obtained for polymers 9, 19, and 21, respectively. Isothermal (at 150.00°C and -70.00°C) and non-isothermal (10.00°C / min slope) measurements were performed. Repeated DSC heating-cooling cycles were carried out according to the thermal procedure: (1) an isotherm over 3 minutes at -70.00°C, (2) a 10.00°C / min slope from -70.00°C to 150.00°C, (3) an isotherm over 3 minutes at 150.00°C, (4) a 10.00°C / min slope from 150.00°C to -70.00°C, (5) an isotherm over 3 minutes at -70.00°C, and (6) a 10.00°C / min slope from -70.00°C to 150.00°C. Example 3 Preparation of electrolyte membranes

[0099] Ionic conductivity, critical current density (CCD), and stability measurements were obtained for the electrolyte membrane containing the polymer prepared in Example 2.

[0100] The electrolyte membrane was obtained using the following procedure: 2.0 g of the polymer prepared in Example 2 and 0.51 g of LiTFSI were dissolved in 1.0 g of THF using a vortex. The resulting mixture was stirred using a roll mill for approximately 12 hours. If crosslinking was required, 0.015 g of Irgacure® was added to the mixture and dissolved using a vortex.

[0101] Next, for ionic conductivity measurement, the mixture thus obtained was coated using a coating system with 6 mil slits at 8 mm.s. -1 It was applied to the stainless steel sheet at the following speed.

[0102] The coating was performed in an anhydrous chamber at room temperature. Subsequently, the electrolyte membrane was irradiated with UV light under a nitrogen atmosphere for approximately 5 minutes to achieve crosslinking. The electrolyte membrane was then air-dried for approximately 1 hour, and then placed in an oven at 80°C under vacuum for approximately 12 hours.

[0103] After drying, the electrolyte membrane was again irradiated with UV light for approximately 5 minutes under a nitrogen atmosphere. The resulting electrolyte membrane had a thickness of approximately 40 μm.

[0104] The same procedure was used for the electrolyte membrane for CCD measurement, by replacing the stainless steel sheet with a metallic lithium concentrator having a thickness of approximately 40 μm during the coating step.

[0105] The same procedure was used for the electrolyte membrane for stability testing by adding 20% ​​by mass of carbon black and a sufficient amount of THF to the mixture to obtain a viscosity suitable for coating. No crosslinking was performed. Example 4 Cell preparation and electrochemical properties

[0106] The electrolyte membrane prepared in Example 3 was placed between two stainless steel electrodes for ionic conductivity measurement and assembled into a symmetric cell for CCD measurement.

[0107] The electrochemical properties of electrolyte membranes obtained from polymers P6, P16, P17, P18, P24, P25, and P26 are shown in Table 4. [Table 4] Example 5 Cell preparation and electrochemical properties a) Ionic conductivity

[0108] Ionic conductivity results were also obtained for the electrolyte membranes containing polymers P25 and P26 prepared in Example 2.

[0109] The electrolyte membrane was prepared using the composition indicated in Table 5, following the procedure described in Example 3. [Table 5]

[0110] Figure 11 shows a graph presenting the ionic conductivity results for cell 1 as a function of temperature during temperature increase (◆) and decrease (■).

[0111] Figure 12 shows graphs presenting the voltage and current density for cell 1 as a function of time.

[0112] Figures 13 and 14 show graphs presenting the ionic conductivity results for cell 2 as a function of temperature during temperature increases (◆) and decreases (■).

[0113] Figure 15 shows a graph presenting the ionic conductivity results for cell 3 as a function of temperature during temperature increase (◆).

[0114] Figure 16 shows a graph presenting the ionic conductivity results for cell 4 as a function of temperature during temperature increase (◆). b) Electrochemical behavior of electrolyte membranes

[0115] The electrochemical properties of the electrolyte membrane prepared in Example 2 were studied.

[0116] The composition of the electrochemical cell is shown in Table 6. [Table 6]

[0117] Cell 5 was cycled at a temperature of 60°C according to the following cycling protocol: (1) two formation cycles (charge / discharge) at C / 10 between 3.65 and 2.0V; (2) charging at C / 6 (cutoff at 3.65V or 0.15mA over 1 hour under constant voltage); charging at C / 6 (cutoff at 2.0V).

[0118] Figure 17 shows a graph of the relative capacity as a function of the number of cycles obtained for cell 5.

[0119] Figure 18 shows a graph of the Coulomb efficiency as a function of the number of cycles obtained for cell 5.

[0120] Numerous modifications can be made to any of the embodiments described above without departing from the scope of the invention as intended. References, patents, or scientific documents referenced herein are incorporated herein by reference in their entirety for all purposes.

Claims

1. Repeating unit of Equation 1: 【Chemistry 16】 A polymer containing, in the formula, R １ and R ２ Independently and in each instance, hydrogen atoms and, if necessary, substituted C １～３ Selected from alkyl groups, preferably R １ is a hydrogen atom, and more preferably R １ and R ２ These are all hydrogen atoms, R ３ 、R ４ 、R ５ 、and R ６ are, independently and in each occurrence, selected from a hydrogen atom, a halogen atom (such as F and Cl), and an optionally substituted C １～１２ alkyl group, L １ and L ２ C ２ ~C ６ Alkylene, C(O)C １ ~C ６ Alkylene, C １ ~C ６ Alkylene C(O), C(O)C ２ ~C ６ Alkylene C(O), (C ２ ~C ６ Alkilen O) １～１２ C ２ ~C ６ Alkylene, C(O)(C) ２ ~C ６ Alkilen O) １～１２ C ２ ~C ６ Alkylene, (C ２ ~C ６ Alkilen O) １～１２ C ２ ~C ６ Alkylene C(O), C(O)(C ２ ~C ６ Alkilen O) １～１２ C ２ ~C ６ Selected from alkylene C(O) groups, polyethers, polyesters, polycarbonate chains, and copolymers of at least two units selected from alkyl ethers, esters, and carbonates, X １ , X ２ , X ３ , and X ４ Independently and in each occurrence, is selected from O, NH, NR, and S, Or, X １ is a -N(R)- group, L １ , X ２ There is no such thing as, where R is selected from polyethers, polyesters, polycarbonate chains, and copolymers of at least two units selected from alkyl ethers, esters, and carbonates. --- represents a bond with a hydrogen atom, a bond with another repeating unit of the polymer, or a bond with a terminal group. polymer.

2. X ３ and X ４ The polymer according to claim 1, wherein, independently and in each occurrence, is selected from O and NH, preferably O.

3. L ２ However, (C ２ ~C ６ Alkilen O) １～１２ C ２ ~C ６ The polymer according to claim 1 or 2, wherein the polymer is an alkylene group (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.).

4. Repeating unit of Equation 2: 【Chemistry 17】 A polymer according to claim 1, comprising, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , L １ , X １ , and X ２ This is as defined in claim 1, n is a number between 1 and 20. polymer.

5. R １ and R ２ The polymer according to any one of claims 1 to 4, wherein the atom is a hydrogen atom.

6. X １ and X ２ The polymer according to any one of claims 1 to 5, wherein the polymer is selected from O and NH.

7. L １ However, (C ２ ~C ６ Alkilen O) １～１２ C ２ ~C ６ A polymer according to any one of claims 1 to 6, selected from alkylene groups, polyethers, polyesters, or copolymers comprising ether and ester units.

8. Foreword X １ -L １ -X ２ Part, structure: [Chemistry 18] 【Chemistry 19】 Selected from, here, R ３ , R ４ , R ５ , and R ６ This is as defined in claim 1, R ７ 、R ８ 、R ９ 、R １０ 、R １１ 、R １２ 、R １３ 、R １４ 、R １５ 、and R １６ are, independently and in each occurrence, selected from a hydrogen atom, a halogen atom (such as F and Cl), and, optionally substituted, C １～１２ alkyl group, j is a digit independently selected within the range of 2 to 30 in each occurrence. k is a number from 1 to 20. m is a number selected within the range of 2 to 150. p is a number between 0 and 12, preferably between 0 and 6. q is a number between 0 and 8, preferably between 0 and 6, provided that p and q are not both zero. r is a number selected within the range of 2 to 4. 's' is a number selected within the range of 5 to 30. The polymer according to any one of claims 1 to 5.

9. The aforementioned repeating unit is given by equations 3 to 6: 【Chemistry 20】 【Chemistry 21】 Selected from, in the formula, R １ 、R ２ 、R ３ 、R ４ 、R ５ 、and R ６ are as defined in claim 1, R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ Independently and in each instance, hydrogen atoms, halogen atoms (such as F and Cl), and C as needed are present. １～１２ Selected from alkyl groups, j is a number that is independently selected from the range of 2 to 30 in each occurrence. k is a number from 1 to 20. m is a number selected within the range of 2 to 150. n is a number between 1 and 20. p is a number between 0 and 12, preferably between 0 and 6. q is a number between 0 and 8, preferably between 0 and 6, provided that p and q are not both zero. r is a number selected within the range of 2 to 4. 's' is a number selected within the range of 5 to 30. The polymer according to any one of claims 1 to 5.

10. The polymer according to claim 8 or 9, wherein the sum (p + q) is within the range of 2 to 9, preferably within the range of 3 to 6.

11. R １１ However, it is a hydrogen atom, R １２ However, C is replaced as needed. １ ~C ６ The polymer according to any one of claims 8 to 10, wherein the alkyl group is equal to p, and p is equal to 1.

12. R １１ and R １２ The polymer according to any one of claims 8 to 10, wherein all are hydrogen atoms and p is selected within the range of 1 to 6.

13. R １３ and R １４ The polymer according to any one of claims 8 to 12, wherein all are hydrogen atoms, and q is selected within the range of 2 to 6.

14. R １３ and R １４ At least one of C is substituted as necessary in at least one occurrence. １ ~C ６ The polymer according to any one of claims 8 to 12, wherein the polymer is an alkyl group.

15. When r is 2 or 3, preferably 2, １５ and R １６ However, in each instance, it is either a hydrogen atom or R １５ and R １６ One of them is methyl in a single appearance, R １５ and R １６ The polymer according to claim 8 or 9, wherein in all other appearances, is a hydrogen atom.

16. R ７ , R ８ , R ９ , and R １０ However, independently and in each instance, hydrogen atoms, fluorine atoms, and C atoms substituted as needed are present. １～３ Selected from alkyl groups, preferably R ７ , R ８ , R ９ , and R １０ Either all of them are hydrogen atoms, or R ７ , R ８ , R ９ , and R １０ The polymer according to claim 8, 9, or 15, wherein one of the members is a methyl group and the others are all hydrogen atoms.

17. R ３ , R ４ , R ５ , and R ６ However, independently and in each instance, hydrogen atoms, fluorine atoms, and C atoms substituted as needed are present. １～３ Selected from alkyl groups, preferably R ３ , R ４ , R ５ , and R ６ However, all of them are either hydrogen atoms or R ３ , R ４ , R ５ , and R ６ The polymer according to any one of claims 4 to 16, wherein one of the members is a methyl group and the others are all hydrogen atoms.

18. The polymer according to any one of claims 1 to 17, comprising a terminal group selected from hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkenyl, optionally substituted alkynyl, acrylate, methacrylate, or at least two combinations thereof.

19. The polymer according to any one of claims 1 to 18, having a number-average molecular weight in the range of 500 to 5,000,000, or 500 to 1,000,000, or 500 to 500,000, or 500 to 250,000, or 500 to 100,000, or 500 to 75,000, or 500 to 70,000, or 500 to 65,000, or 500 to 60,000, or 500 to 55,000, or 500 to 50,000, or 1,000 to 50,000, or 1,500 to 50,000, or 2,000 to 50,000, as determined by triple detection gel permeation chromatography.

20. An electrolyte comprising a polymer according to any one of claims 1 to 19, and optionally a salt.

21. The electrolyte according to claim 20, wherein the electrolyte is in the form of a solid or a gel electrolyte membrane.

22. The electrolyte according to claim 20 or 21, wherein the salt, preferably an alkali metal salt, preferably a lithium salt, is contained in the electrolyte in a concentration preferably from about 5% to about 40% by weight, or from about 15% to about 40% by weight, or from about 20% to about 35% by weight.

23. The salt comprises an alkali metal (preferably Li) cation and hexafluorophosphate (PF ６ － ), bis(trifluoromethanesulfonyl)imide (TFSI － ), bis(fluorosulfonyl)imide (FSI － ), (fluorosulfonyl) (trifluoromethanesulfonyl)imide ((FSI) (TFSI) － ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI － ), 4,5-dicyano-1,2,3-triazolate (DCTA － ), bis(pentafluoroethylsulfonyl)imide (BETI － ), difluorophosphate (DFP － ), tetrafluoroborate (BF ４ － ), bis(oxalato)borate (BOB － ), nitrates (NO ３ － ), chloride (Cl － ), bromide (Br － ), fluoride (F － ), perchlorate (ClO ４ － ), hexafluoroarsenate (AsF ６ － ), trifluoromethanesulfonate (SO ３ CF ３ － ) (Tf － ), fluoroalkyl phosphate [PF ３ (CF ２ CF ３ ) ３ － ] (FAP － ), tetrakis(trifluoroacetoxy) borate [B(OCOCF ３ ) ４ ] － (TFAB) － ), bis(1,2-benzenediolato(2-)-O,O')borate [B(C ６ O ２ ) ２ ] － (BBB) － ), difluoro(oxalato)borate (BF ２ (C ２ O ４ ) － ) (FOB － ), formula BF ２ O ４ R ｘ － (In the formula, R ｘ = C ２～４ The electrolyte according to claim 22, comprising an alkyl anion and an anion selected from at least two combinations thereof (e.g., LiTFSI or LiFSI).

24. The electrolyte according to any one of claims 20 to 23, further comprising an additional polymer.

25. The electrolyte according to claim 24, wherein the additional polymer is selected from polyethers, substituted polyethylenes, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, poly(methyl (meth)acrylate), poly(methyl (meth)acrylate of poly(ethylene glycol) methyl ether) (PEGMA), poly(2,2,2-trifluoroethyl (meth)acrylate), poly((meth)acrylic acid), and copolymers thereof, and optionally comprises crosslinking units derived from crosslinkable functional groups, wherein the additional polymer is linear or branched.

26. The electrolyte according to claim 24, wherein the additional polymer is selected from rubber-based polymers such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), and ACM (polyacrylic rubber); fluorinated polymers such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and HFP (polyhexafluoropropylene); and at least two combinations thereof.

27. For example, an electrolyte according to any one of claims 20 to 26, further comprising inorganic particles, preferably amorphous, ceramic, or glass-ceramic, based on an oxide, sulfide, or oxysulfide, wherein the inorganic compound is natural or synthetic.

28. The inorganic particles are of formula MLZO (for example, M ７ La ３ Zr ２ O １２ M （７－ａ） La ３ Zr ２ Al ｂ O １２ M （７－ａ） La ３ Zr ２ Ga ｂ O １２ M （７－ａ） La ３ Zr （２－ｂ） Ta ｂ O １２ , and M （７－ａ） La ３ Zr （２－ｂ） Nb ｂ O １２ );MLTaO (for example, M ７ La ３ Ta ２ O １２ M ５ La ３ Ta ２ O １２ , and M ６ La ３ Ta １．５ Y ０．５ O １２ ); MLSnO (for example, M ７ La ３ Sn ２ O １２ ); MAGP (for example, M １＋ａ Al ａ Ge ２－ａ (PO ４ ) ３ );MATP (for example, M １＋ａ Al ａ Ti ２－ａ (PO ４ ) ３ );MLTiO (for example, M ３ａ La （２／３－ａ） TiO ３ ); MZP (for example, M ａ Zr ｂ (PO ４ ) ｃ ); MCZP (for example, M ａ Ca ｂ Zr ｃ (PO ４ ) ｄ ); MGPS (for example, M １０ GeP ２ S １２ etc. M ａ Ge ｂ P ｃ S ｄ ); MGPSO (for example, M ａ Ge ｂ P ｃ S ｄ O ｅ ); MSiPS (for example, M １０ SiP ２ S １２ etc. M ａ Si ｂ P ｃ S ｄ ); MSiPSO (for example, M ａ Si ｂ P ｃ S ｄ O ｅ ); MSnPS (for example, M １０ SnP ２ S １２ etc. M ａ Sn ｂ P ｃ S ｄ ); MSnPSO (for example, M ａ Sn ｂ P ｃ S ｄ O ｅ ); MPS (for example, M ７ P ３ S １１ etc. M ａ P ｂ S ｃ ); MPSO (for example, M ａ P ｂ S ｃ O ｄ ); MZPS (for example, M ａ Zn ｂ P ｃ S ｄ ); MZPSO (for example, M ａ Zn ｂ P ｃ S ｄ O ｅ ); xM ２ S-yP ２ S ５ ;xM ２ S-yP ２ S ５ -zMX;xM ２ S-yP ２ S ５ -zP ２ O ５ ;xM ２ S-yP ２ S ５ -zP ２ O ５ -wMX;xM ２ S-yM ２ O-zP ２ S ５ ;xM ２ S-yM ２ O-zP ２ S ５ -wMX;xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ ;xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ -vMX;xM ２ S-ySiS ２ ;MPSX (for example, M ７ P ３ S １１ X, M ７ P ２ S ８ X, and M ６ PS ５ X etc. M ａ P ｂ S ｃ X ｄ ); MPSOX (for example, M ａ P ｂ S ｃ O ｄ X ｅ ); MGPSX (M ａ Ge ｂ P ｃ S ｄ X ｅ );MGPSOX(M ａ Ge ｂ P ｃ S ｄ O ｅ X ｆ );MSiPSX(M ａ Si ｂ P ｃ S ｄ X ｅ );MSiPSOX(M ａ Si ｂ P ｃ S ｄ O ｅ X ｆ ); MSnPSX(M ａ Sn ｂ P ｃ S ｄ X ｅ ); MSnPSOX(M ａ Sn ｂ P ｃ S ｄ O ｅ X ｆ ); MZPSX (M ａ Zn ｂ P ｃ S ｄ X ｅ );MZPSOX(M ａ Zn ｂ P ｃ S ｄ O ｅ X ｆ ); M ３ OX;M ２ HOX;M ３ PO ４ M ３ PS ４ ; and M ａ PO ｂ N ｃ (Here, it includes natural or synthetic ceramics selected from inorganic compounds of the form a = 2b + 3c - 5) During the ceremony, M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two of these, where, if M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality. X is selected from F, Cl, Br, I, or at least two combinations of these. a, b, c, d, e, and f are non-zero numbers, independently chosen in each equation to achieve electrical neutrality. v, w, x, y, and z are non-zero numbers, independently selected in each formula to obtain a stable compound. The electrolyte according to claim 27.

29. The aforementioned MLZO ceramic is, formula Li ７－ｂ La ３ Zr ２ M ｉ ｂ O １２ In the formula, b is 0 ≤ b ≤ 1, and M ｉ is Al, Ga, Ta, Fe, or Nb, or is absent, preferably b is 0, and M ｉ The electrolyte according to claim 28, wherein the element is absent.

30. The inorganic particles are Al ２ O ３ Mg ２ B ２ O ５ Na ２ O.2B ２ O ３ xMgO・yB ２ O ３ ・zH ２ O, TiO ２ , ZrO ２ , ZnO, Ti ２ O ３ SiO ２ , Cr ２ O ３ , CEO ２ , B ２ O ３ , B ２ O, SrBi ４ Ti ４ O １５ , LLTO, LLZO, LAGP, LATP, Fe ２ O ３ , BaTiO ３ γ-LiAlO ２ , molecular sieves and zeolites (e.g., those based on aluminosilicates, mesoporous silica, etc.), sulfide-based ceramics (e.g., Li ６ PS ５ Cl, Li ７ P ３ S １１ The electrolyte according to claim 27, comprising glass ceramics (e.g., LIPON, etc.), other similar ceramics, and natural or synthetic ceramics selected from at least two combinations thereof.

31. The electrolyte according to claim 30, wherein the ceramic is an aluminosilicate-based compound.

32. The electrolyte according to claim 27 or 28, wherein the ceramic is a sulfide-based or oxysulfide-based ceramic.

33. The electrolyte according to any one of claims 27 to 32, wherein the inorganic particles are in the form of spherical particles, rods, needles, nanotubes, or a combination thereof.

34. The electrolyte according to any one of claims 27 to 33, wherein the electrolyte contains inorganic particles in an amount ranging from about 5% by weight to about 99% by weight, or from about 5% by weight to about 90% by weight, or from about 10% by weight to about 80% by weight, or from about 15% by weight to about 40% by weight.

35. The electrolyte according to any one of claims 20 to 34, further comprising a plasticizer in the electrolyte, preferably in a concentration of about 5% to about 50% by weight, or about 10% to about 40% by weight, or about 20% to about 30% by weight.

36. The electrolyte according to claim 35, wherein the plasticizer is selected from glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and other similar liquids, preferably glycol diether liquids (such as TEGDME).

37. The electrolyte according to any one of claims 20 to 36, further comprising an organic additive.

38. The electrolyte according to claim 37, wherein the organic additive is selected from ionic organic compounds (e.g., ionic soft crystals, ionic soft salts, ionic liquids, etc.) and halogenated amides.

39. An electrode material comprising a polymer, an electrochemical active material, and optionally a conductive material, a binder, a salt, or at least two combinations thereof, according to any one of claims 1 to 19.

40. The electrode material according to claim 39, wherein the polymer acts as a binder.

41. The electrode material according to claim 39, wherein the polymer acts as a coating on the particles of the electrochemical active material.

42. The electrode material according to any one of claims 39 to 41, wherein the electrochemical active material is selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides.

43. The electrochemical active material is LiM'PO ４ (where M' is Fe, Ni, Mn, Co, or at least two of these), LiV ３ O ８ , V ２ O ５ F, LiV ２ O ５ LiMn ２ O ４ Li １＋ｗ M''O ２－ａ X ｂ (where M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or at least two combinations thereof, and X is F, S, or at least two combinations thereof), Li １＋ｗ (NiM''')O ２ Electrode material according to any one of claims 39 to 41, including (wherein M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or at least two combinations thereof), carbon-based active materials such as sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, graphite, organic cathode active materials, and, where applicable, selected from at least two combinations thereof.

44. The electrode material according to any one of claims 39 to 41, wherein the electrochemical active material comprises a metal film comprising an alkali or alkaline earth metal or an alloy containing an alkali or alkaline earth metal, the polymer is present in a thin layer on the metal film, and preferably the alkali metal is selected from lithium and sodium, or an alloy containing lithium or sodium, preferably lithium or an alloy containing lithium.

45. The electrochemical active material is an intermetallic compound (for example, SnSb, TiSnSb, Cu ２ Sb, AlSb, FeSb ２ FeSn ２ , and CoSn ２ ), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi ２ (PO ４ ) ３ ), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxide (SiO2) ｘ ), silicon dioxide-carbon composite material (SiO ｘ -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO ｘ ), tin oxide-carbon composite material (SnO ｘ -C), and, if applicable, an electrode material according to any one of claims 39 to 41, comprising at least two combinations thereof.

46. The aforementioned metal oxide is given by formula M'''' ｂ O ｃ (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof; b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO ３ MoO ２ MoS ２ , V ２ O ５ , and TiNb ２ O ７ ), spinel oxide (for example, NiCo ２ O ４ ZnCo ２ O ４ MnCo ２ O ４ , CdCo ２ O ４ , and CoFe ２ O ４ ), and LiM'''''O (wherein M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two of these) (e.g., lithium titanate (Li ４ Ti ５ O １２ (etc.), or lithium and molybdenum oxide (Li ２ Mo ４ O １３ The electrode material according to claim 45, selected from the compounds of the following:

47. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive electrode or the negative electrode comprises an electrode material according to any one of claims 39 to 46.

48. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as described in any one of claims 20 to 38, and at least one of the positive electrode or the negative electrode comprises an electrode material as described in any one of claims 39 to 46.

49. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as described in any one of claims 20 to 38.

50. The electrochemical cell according to claim 49, wherein the positive electrode includes a positive electrode material that contains an electrochemical active material of the positive electrode and is optionally located on a current collector.

51. The electrochemical cell according to claim 50, wherein the electrochemical active material of the positive electrode is selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides.

52. The electrochemical active material of the positive electrode is LiM'PO ４ (where M' is Fe, Ni, Mn, Co, or at least two of these), LiV ３ O ８ , V ２ O ５ F, LiV ２ O ５ LiMn ２ O ４ Li １＋ｗ M''O ２－ａ X ｂ (where M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or at least two combinations thereof, and X is F, S, or at least two combinations thereof), Li １＋ｗ (NiM''')O ２ The electrochemical cell according to claim 50, wherein M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or at least two combinations thereof), a carbon-based active material such as sulfur, elemental selenium, elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, graphite, an organic cathode active material, or, where applicable, at least two combinations thereof.

53. The electrochemical cell according to any one of claims 50 to 52, wherein the positive electrode material further comprises a conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles.

54. The electrochemical cell according to any one of claims 49 to 53, wherein the negative electrode comprises a negative electrode material containing an electrochemical active material of the negative electrode and is optionally located on a current collector.

55. The electrochemical cell according to claim 54, wherein the electrochemical active material of the negative electrode includes a metal film comprising an alkali or alkaline earth metal, or an alloy containing an alkali or alkaline earth metal.

56. The electrochemical cell according to claim 55, wherein the alkali metal is selected from lithium and sodium, or an alloy containing lithium or sodium, preferably lithium or an alloy containing lithium.

57. The electrochemical active material of the negative electrode is an intermetallic compound (e.g., SnSb, TiSnSb, Cu) ２ Sb, AlSb, FeSb ２ FeSn ２ , and CoSn ２ ), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi ２ (PO ４ ) ３ ), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxide (SiO2) ｘ ), silicon dioxide-carbon composite material (SiO ｘ -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO ｘ ), tin oxide-carbon composite material (SnO ｘ -C), and, if applicable, an electrochemical cell according to claim 54, comprising at least two combinations thereof.

58. The aforementioned metal oxide is given by formula M'''' ｂ O ｃ (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two combinations thereof; b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO ３ MoO ２ MoS ２ , V ２ O ５ , and TiNb ２ O ７ ), spinel oxide (for example, NiCo ２ O ４ ZnCo ２ O ４ MnCo ２ O ４ , CdCo ２ O ４ , and CoFe ２ O ４ ), and LiM'''''O (wherein M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or at least two of these) (e.g., lithium titanate (Li ４ Ti ５ O １２ (etc.), or lithium and molybdenum oxide (Li ２ Mo ４ O １３ An electrochemical cell according to claim 57, selected from the compounds of the following:

59. The electrochemical cell according to claim 57 or 58, wherein the negative electrode material further comprises a conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles.

60. A battery comprising at least one electrochemical cell as described in any one of claims 47 to 59.

61. The battery according to claim 60, wherein the battery is selected from lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, potassium-ion batteries, magnesium batteries, and magnesium-ion batteries.

62. The battery according to claim 60, wherein the battery is a lithium battery.

63. The battery according to claim 60, wherein the battery is a lithium-ion battery.

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