Ionic organic compounds, compositions and electrolytes containing them, and their use in electrochemistry

Abstract

This technology relates to ionic organic compounds of formulas (I) and (II), compositions and solid electrolytes containing the same, and optionally inorganic particles and solid ionic bifunctional molecules for use in electrochemical applications. Electrochemical cells and electrochemical batteries comprising solid electrolytes are also described. This application relates to ionic organic compounds, compositions and solid electrolytes containing the same, and their use in electrochemical applications. More specifically, this application relates to ionic organic compounds, their manufacturing processes, and their use in electrochemical cells, particularly in all-solid-state batteries. JPEG2026525417000022.jpg2733

Description

[Technical Field]

[0001] Related applications This application claims priority under applicable law to Canadian Patent Application No. 3,206,622, filed on 14 July 2023, the contents of which that Canadian Patent Application is incorporated herein by reference in its entirety for all purposes.

[0002] Technical field This application relates to ionic organic compounds, compositions and solid electrolytes containing them, and their use in electrochemical applications. More specifically, this application relates to ionic organic compounds, processes for producing them, and their use in electrochemical cells, particularly in all-solid-state batteries. [Background technology]

[0003] background The liquid electrolyte used in lithium-ion batteries is flammable and gradually decomposes, irreversibly consuming lithium by forming a passivation layer on the surface of the lithium film or on the solid electrolyte interface (SEI for "solid electrolyte interface" or "solid electrolyte interphase"), which reduces the battery's Coulombic efficiency. Furthermore, the lithium anode undergoes significant morphological changes during battery cycles, forming lithium dendrites. Since these dendrites typically migrate through the electrolyte, they can eventually cause short circuits.

[0004] Safety concerns and requirements for higher energy density are driving research toward the development of all-solid-state rechargeable lithium batteries with polymer, ceramic, or polymer-ceramic hybrid electrolytes, all of which are more stable with respect to metallic lithium and reduce lithium dendrite growth.

[0005] However, the range of applications of solid electrolytes remains limited. Indeed, solid electrolytes present problems related to their limited electrochemical stability, limited interfacial stability, relatively low ionic conductivity, loss of reactivity, low contact between solid interfaces, etc.

[0006] Therefore, there is a need to develop an all-solid-state electrochemical system that eliminates one or more of the drawbacks of conventional all-solid-state electrochemical systems.

Summary of the Invention

Means for Solving the Problems

[0007] Summary According to some embodiments, embodiments of the present technology include the following items. Item 1. A compound of formula I or II:

Chemical formula

Chemical formula

Chemical formula

[65] ] Item 15.R 4 is a C 1~4 alkyl group, the compound according to item 11. Item 16.R5 However, hydrogen atoms or C 1~4 A compound that is an alkyl group, as described in item 11 or 15. Item 17.R + However, -P + (R 1 R 2 R 3 A compound that is a group, as described in one of items 1-5. Item 18.R 1 , R 2 and R 3 However, independently, substituted or unsubstituted linear or branched C 1~12 A compound selected from alkyl groups, as described in item 17. Item 19.R 1 , R 2 and R 3 However, independently, linear or branched C 1~12 Selected from alkyl groups, or R 1 , R 2 and R 3 The compounds described in item 17, wherein at least one of them is substituted with a halogen atom or an alkoxy, ether, ester, or siloxy group. Item 20. A compound listed in any of Items 1 to 19, wherein the compound is a compound of formula I. Item 21. A compound listed in Item 20, where n is a number in the range of 2 to 10, or 3 to 8, or 4 to 6. Item 22. A compound listed in any of Items 1 to 19, wherein the compound is a compound of formula II. Item 23.L is a linear or branched C 2~4 Alkylene or linear or branched carbon dioxide 2~3 A compound that is alkylene, as described in item 22. Item 24. A compound listed in item 22 or 23, wherein Y is O. Item 25. A compound listed in item 22 or 23, wherein Y is S. Compounds listed in one of items 22-25, where item 26.m is a number from 1 to 4, or from 1 to 3. Item 27. A compound according to one of items 1 to 26, wherein X is Cl, Br, or I, preferably Cl or Br, or X is Br. A compound according to one of items 1 to 27, having a melting point of 8.60°C or lower, or 40°C or lower, preferably 25°C or lower. Item 29.A - A compound selected from salts, 1-(6-bromohexyl)-1-methylpyrrolidinium, 1-(6-chlorohexyl)-1-methylpyrrolidinium, and 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium, preferably 1-(6-bromohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 1), 1-(6-chlorohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 2), or 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 3), as described in one of items 1 to 5. Item 30. A composition comprising a compound described in one of items 1 to 29, and an ionic bifunctional molecule. Item 31. The ionic difunctional molecule is of formula III or IV: [ka] (In the formula, A - , R + (L, Y, m, and n are defined independently in their respective appearances as defined in items 1-26.) The composition described in item 30, which is a molecule of the same name. Item 32. The composition according to item 31, wherein the ionic bifunctional molecule is 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide. Item 33. The composition according to Item 31, wherein the ionic bifunctional molecule is 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide. Item 34. The composition according to Item 31, wherein the ionic bifunctional molecule is 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide. Item 35. The composition according to Item 31, wherein the ionic bifunctional molecule is 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide. Item 36. The composition according to Item 31, wherein the ionic bifunctional molecule is 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide. Item 37. A composition according to one of items 30 to 36, wherein the weight ratio of "compound:ionic bifunctional molecule" is approximately 2:98 to approximately 50:50, or approximately 5:95 to approximately 35:65, or approximately 10:90 to approximately 30:70. Item 38. A composition according to one of items 30 to 37, which is solid at room temperature (e.g., 25°C ± 5°C). Item 39. A solid electrolyte comprising a compound described in one of Items 1-29, or a composition described in one of Items 30-38. Item 40. A solid electrolyte as described in Item 39, further comprising inorganic particles. Item 41. The solid electrolyte according to Item 40, wherein the inorganic particles include a material selected from glass, glass ceramic, ceramic, nanoceramic, and at least two combinations thereof. Item 42. The solid electrolyte according to Item 41, wherein the inorganic particles include ceramics, glass, or glass ceramics based on fluorides, phosphides, sulfides, oxysulfides, or oxides. Item 43. The solid electrolyte according to Item 41, wherein the inorganic particles include compounds of the type LISICON, thio-LISICON, silver-germanium ore, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide, fluoride, or a combination of at least two of these, in crystalline and / or amorphous forms. Item 44. The inorganic particles are of 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 (e.g., 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 a Ge b P c S d For example, M 10 GeP2S 12 );MGPSO(for example M a Ge b P c S d O e );MSiPS(for example M a Si b P c S d For example, M 10 SiP2S 12 );MSiPSO(for example M a Si b Pc S d O e );MSnPS(for example M a Sn b P c S d For example, M 10 SnP2S 12 );MSnPSO(for example M a Sn b P c S d O e );MPS(for example M a P b S c For example, M7P3S 11 );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;xM2 S-yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example a P b S c X d For example, M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (e.g., 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 Sd 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 compounds selected from inorganic compounds (where a = 2b + 3c - 5); M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two of these, and 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 thereof, and may be identical or different from X present in the compound of formula I or II; 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. Solid electrolyte as described in item 41. Item 45. A solid electrolyte as described in Item 44, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination of at least two of these. Item 46. The solid electrolyte described in Item 45, where M is Li. Item 47. A solid electrolyte according to any one of items 44 to 46, wherein the inorganic particles comprise an inorganic compound of formula MATP. Item 48. A solid electrolyte according to any one of items 44 to 46, wherein the inorganic particles comprise a sulfide or an oxysulfide. Item 49. The inorganic particles are of formula Li a P b S c X d A solid electrolyte as described in any one of items 44-46, comprising a compound selected from inorganic compounds (wherein X is Cl, Br, I or a combination of at least two of these, and a, b, c, and d are numbers such that (a+5b)=(2c+d)). Item 50. The solid electrolyte according to item 49, wherein the inorganic particles contain Li6PS5Cl. Item 51. The inorganic particles are of the formula Li a P b S c O d X e A solid electrolyte according to any one of items 44-46, comprising a compound selected from inorganic compounds (wherein X is Cl, Br, I or a combination of at least two of these, and a, b, c, d, and e are numbers such that (a+5b)=(2c+2d+e)). Item 52.a is selected from the range of 5 to 6, b is equal to 1, c is selected from the range of 3.5 to 4.8, and e is selected from the range of 1 to 2 (for example, Li 5.4 PS 4.1 O 0.3 X 1.6 or Li 5.4 PS 4.1 O0.3 ClBr 0.5 I 0.1 ), the solid electrolyte described in item 51. Item 53. The solid electrolyte according to one of items 40 to 52, wherein the inorganic particles are present in the solid electrolyte at a concentration of about 20% to about 95% by weight, or about 40% to about 95% by weight, or about 60% to about 95% by weight. Item 54. A solid electrolyte according to one of items 39 to 53, wherein the concentration of the compound in the electrolyte is in the range of about 0.2% by weight to about 5% by weight, or about 0.3% by weight to about 4% by weight, or about 0.4% by weight to about 3% by weight. Item 55. A solid electrolyte as described in one of items 39-54, further comprising a polymer. Item 56. The solid electrolyte according to Item 55, wherein the polymer is a linear or branched polymer selected from polyethers, polythioethers, polyesters, polythioesters, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylentiocarbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyimide, polyamide, polyphosphazene, polyurethane, poly(vinyl alcohol), polyacrylonitrile, polyethylacrylate and polymethacrylate, and copolymers thereof. Item 57. The solid electrolyte according to Item 56, wherein the polyether is poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), or copolymer (EO / PO). Item 58. The solid electrolyte according to item 56 or 57, wherein the polymer comprises crosslinking units derived from a crosslinkable functional group or a crosslinking equivalent thereof. Item 59. The solid electrolyte according to Item 58, wherein the crosslinkable functional group is selected from acrylate, methacrylate, vinyl, glycidyl, and mercapto functional groups. Item 60. The solid electrolyte according to Item 55, wherein the polymer is a reaction product of at least one monomer having at least one polymerizable or crosslinkable functional group and a compound having at least one SH functional group. Item 61. The solid electrolyte according to one of items 55 to 60, wherein the polymer is present in the solid electrolyte at a concentration of about 0.1% to about 20% by weight, or about 1% to about 15% by weight, or about 2% to about 13% by weight. Item 62. A solid electrolyte as described in one of items 39-61, further containing additives. Item 63. The solid electrolyte according to Item 62, wherein the additive is a fluorinated compound containing an amide functional group. Item 64. The fluorinated compound is of formula R 6 X 6 C(O)N(H)X 7 R 7 (In the formula, R 6 and R 7 X is independently an alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group. 6 is O, NH, or non-existent, X 7 is either absent or C(O), S(O)2, or Si(R) 8 R 9 ) is a group, R 8 and R 9 R is an alkyl group, 6 , R 7 , R 8 and R 9 A solid electrolyte according to item 63, which is a compound of a group (at least one of which is a group substituted with one or more fluorine atoms). Item 65.R 6 However, it is a perfluoroemission group, X 6 However, the solid electrolytes listed in item 64 are not present. Item 66. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined in one of items 39-65. Item 67. The electrochemical cell according to Item 66, wherein the positive electrode comprises a positive electrode material containing a positive electrode electrochemical active material. Item 68. The electrochemical cell described in Item 67, wherein the positive electrode material is located on the current collector. Item 69. The electrochemical cell according to item 67 or 68, wherein the positive electrode electrochemical active material is selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides. Item 70. 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, LiM''O2 (where M'' is Mn, Co, Ni, or a combination of at least two of these (e.g., NMC LiMn) x Co y Ni z An electrochemical cell as described in item 67 or 68, comprising O2 (x+y+z=1), Li(NiM''')O2 (where M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination of at least two of these), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of at least two of these if they are compatible with each other. Item 71. An electrochemical cell according to one of items 67-70, wherein the cathode material further comprises an electrically conductive material, a binder, a salt, an ionic organic compound, an ionic bifunctional molecule, and / or inorganic particles. Item 72. An electrochemical cell according to one of items 66 to 71, wherein the negative electrode comprises a negative electrode material containing a negative electrode electrochemical active material. Item 73. The electrochemical cell described in Item 72, wherein the negative electrode material is located on the current collector. Item 74. The electrochemical cell according to item 72 or 73, wherein the anode electrochemical active material comprises a metal film comprising an alkali metal or alkaline earth metal, or an alloy containing an alkali metal or alkaline earth metal. Item 75. The electrochemical cell of Item 74, wherein the alkali metal is selected from lithium and sodium. Item 76. The negative electrode electrochemical active material is an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal sulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite (exfoliated graphite), and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon dioxide (SiO₂) x ), silicon dioxide-carbon composite (SiO₂) x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and any combination thereof, as described in item 72 or 73, which are conforming to the requirements. Item 77. The metal oxide is of formula M'''' b O c (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination 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 a combination thereof) (e.g., lithium titanate (e.g., Li4Ti5O 12 ) or lithium molybdenum oxide (e.g., Li2Mo4O 13 An electrochemical cell as described in item 76, selected from the compounds of )). Item 78. An electrochemical cell according to Item 76 or 77, wherein the negative electrode material further comprises an electrically conductive material, a binder, a salt, an ionic organic compound, an ionic bifunctional molecule, and / or inorganic particles. Item 79. An electrochemical accumulator comprising at least one electrochemical cell as described in one of items 66-78. Item 80. The electrochemical storage battery according to Item 79, wherein the electrochemical storage battery is selected from the group consisting of lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, potassium-ion batteries, magnesium batteries, and magnesium-ion batteries. Item 81. The electrochemical battery described in Item 80, wherein the electrochemical battery is a lithium battery. Item 82. The electrochemical battery described in Item 80, wherein the electrochemical battery is a lithium-ion battery. [Brief explanation of the drawing]

[0008] [Figure 1a] Figures 1(a) to 1(c) show the proton NMR spectra of compounds 1, 2, and 3 as described in Example 2, respectively. [Figure 1b] Figures 1(a) to 1(c) show the proton NMR spectra of compounds 1, 2, and 3 as described in Example 2, respectively. [Figure 1c] Figures 1(a) to 1(c) show the proton NMR spectra of compounds 1, 2, and 3 as described in Example 2, respectively.

[0009] [Figure 2a-b] Figures 2(a) to 2(c) show the results of differential scanning calorimetry (DSC) analysis obtained for compounds 1, 2, and 3 as described in Example 3, respectively. [Figure 2c] Figures 2(a) to 2(c) show the results of differential scanning calorimetry (DSC) analysis obtained for compounds 1, 2, and 3 as described in Example 3, respectively.

[0010] [Figure 3a] Figures 3(a) to 3(c) show the thermogravimetric analysis (TGA) results obtained for compounds 1, 2, and 3 as described in Example 3, respectively. [Figure 3b-c] Figures 3(a) to 3(c) show the results of thermogravimetric analysis (TGA) obtained for Compounds 1, 2, and 3 as described in Example 3, respectively.

[0011] [Figure 4] Figure 4 shows the results of differential scanning calorimetry (DSC) analysis obtained for Compositions 1, 2, and A1 to A3 as described in Example 4.

[0012] [Figure 5] Figure 5 shows the results of ionic conductivity measured as a function of temperature for Cells 1 (■), 2 (●), 3 (▲), 4 (▼), 5 (<), 6 (>), and 7 (★) as described in Example 5(b).

[0013] [Figure 6] Figure 6 shows the results of ionic conductivity measured as a function of temperature for Cells 1 (■), 3 (▲), 6 (>), 7 (★), 8 (△), and 9 (◆) as described in Example 5(b).

[0014] [Figure 7] Figure 7 shows the results of ionic conductivity measured as a function of temperature for Cells 1 (■), 2 (●), 10 (★), and 11 (▲) as described in Example 5(b).

Mode for Carrying Out the Invention

[0015] Detailed Description All technical and scientific terms and expressions used herein have the same definitions as those generally understood by those skilled in the art of this technology. Nevertheless, the definitions of certain specific terms and expressions used are described below.

[0016] Where the term "approximately" is used herein, it means approximately, within a range, or roughly. For example, when the term "approximately" is used in relation to a number, it modifies the number by a variation of 10% above or below its nominal value. This term may also take into account, for example, experimental errors or rounding errors of measuring instruments.

[0017] Where a range of values ​​is referred to in this application, the lower and upper limits of the range are always included in the definition unless otherwise specified. Where a range of values ​​is referred to in this application, all intermediate and subranges, as well as the individual values ​​that fall within the range of values, are included in the definition.

[0018] Where the article “a” is used in this application to introduce an element, it does not mean “only one,” but rather “one or more.” Naturally, where the description states that a particular step, component, element, or feature “may be” included or “may be included,” that particular step, component, element, or feature does not have to be included in every embodiment.

[0019] The chemical structures described herein are drawn in accordance with the rules of the art. Furthermore, where an atom such as a carbon atom appears to have an incomplete valence, the valence is assumed to be filled by one or more hydrogen atoms, even if hydrogen atoms are not explicitly depicted.

[0020] As used herein, the term "alkyl" refers to a saturated hydrocarbon group having 1 to 12 carbon atoms, optionally substituted (unless otherwise specified). Examples of alkyl groups, though not limited to these, may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, and isobutyl groups. When the alkyl group is located between functional groups, the term alkyl also includes alkylene groups such as methylene, ethylene, propylene, and butylene.m ~C n "Alkyl" and "C m ~C n The term "alkylene" refers to an alkyl or alkylene group having carbon atoms ranging from the indicated number "m" to the indicated number "n".

[0021] As used herein, the term “alkenyl” refers to an unsaturated hydrocarbon having 2 to 12 carbon atoms and at least one double bond between any two carbon atoms, and which may be optionally substituted, and includes linear or branched alkenyl groups. Examples of alkenyl groups, though not limited to these, 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 The term "alkenylene" refers to an alkenyl or alkenylene group having carbon atoms ranging from the indicated number "m" to the indicated number "n".

[0022] As used herein, the term "alkynyl" refers to an unsaturated hydrocarbon having 2 to 12 carbon atoms and at least one triple bond between any two carbon atoms, and includes linear or branched alkynyl groups. Examples of alkynyl groups that are not limited to these 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 nThe term "alkynylene" refers to an alkynyl or alkynylene group having carbon atoms ranging from the indicated number "m" to the indicated number "n".

[0023] Generally, the terms "cycle" and "heterocyclic" refer to "cycloalkyl" and "aryl" groups, and "heterocycloalkyl" and "heteroaryl" groups, respectively.

[0024] As used herein, the term "cycloalkyl" means a group comprising one or more saturated or partially unsaturated (non-aromatic) carbocyclic rings containing 3 to 15 ring members in a monocyclic or polycyclic ring system, including spiro (sharing one atom), condensed (sharing at least one bond), or bridging carbocyclic rings, and 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 The term "cycloalkylene" refers to a cycloalkyl or cycloalkylene group having carbon atoms ranging from the indicated number "m" to the indicated number "n".

[0025] As used herein, the term "heterocycloalkyl" means a group comprising a saturated or partially unsaturated (non-aromatic) carbocyclic ring containing 3 to 15 ring members in a monocyclic or polycyclic system, including spiro (sharing one atom), condensed (sharing at least one bond), or bridging carbocyclic rings, which may be substituted as necessary, and which comprises 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 xA heterocycloalkyl group has (which is an alkyl, acyl, aryl, heteroaryl, or cycloalkyl group), PO2, SO, SO2, and other similar groups. Heterocycloalkyl groups can be linked to carbon atoms or heteroatoms (e.g., via nitrogen atoms) where 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 The term "heterocycloalkylene" refers to a heterocycloalkyl or heterocycloalkylene group having a ring atom containing carbon atoms and heteroatoms ranging from the indicated number "m" to the indicated number "n".

[0026] The terms "aryl" or "aromatic" refer to aromatic groups having 4n+2 (where n is a number between 1 and 3) conjugated π electrons within a monocyclic group, or condensed bicyclic or tricyclic systems having a total of 6 to 15 ring members, in which case at least one of the rings in the system is aromatic. The terms "aryl" or "aromatic" refer to both monocyclic and conjugated polycyclic systems. The terms "aryl" or "aromatic" also include substituted or 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, perilenyl, etc. m ~C n "Aryl" and "C m ~C n The term "arylene" refers to an aryl or arylene group having carbon atoms ranging from the indicated number "m" to the indicated number "n".

[0027] The terms "heteroaryl," "heteroarylene," or "heteroaromatic" refer to aromatic groups having 4n+2 (where n is a number from 1 to 3) conjugated π electrons, for example, having 5 to 18 ring atoms, preferably 5, 6, or 9 ring atoms, in a conjugated monocyclic or polycyclic system (condensed or uncondensed), and containing 1 to 6 heteroatoms selected from oxygen, nitrogen, and sulfur in addition to carbon atoms, or groups containing such heteroatoms or groups containing such heteroatoms (e.g., NH and NR). x (R x A polycyclic ring system refers to an aromatic group having an alkyl, acyl, aryl, heteroaryl, or cycloalkyl group (SO, and other similar groups). A polycyclic ring system contains at least one heteroaromatic ring. Heteroaryls can be directly bonded or linked by C1-C3 alkyl groups (also called heteroarylalkyl or heteroaralkyl). Heteroaryl groups can, where possible, be linked through carbon atoms of the ring or to heteroatoms (e.g., via nitrogen atoms). m ~C n "heteroaryl" and "C m ~C n The term "heteroarylene" refers to a heteroaryl or heteroarylene group having a ring atom containing carbon atoms and heteroatoms ranging from the indicated number "m" to the indicated number "n".

[0028] Generally, the term "substituted" means that one or more hydrogen atoms of the designated group are replaced by suitable substituents. The substituents or combinations of substituents contemplated in this description result in the formation of chemically stable compounds. Examples of substituents include halogen atoms (e.g., F, Cl, Br, I), and hydroxyl group, oxo group, alkyl group, alkoxyl group, alkoxyalkyl group, nitrile group, azide group, aldehyde group, carboxylic acid group, metal or alkyl carboxylate group, alkoxycarbonyl group, alkylcarbonyl group, primary, secondary or tertiary amine group, amide group, nitro group, silane group, siloxane group, thiocarboxylate group, thiol group, alkylthiol group, sulfonyl group, sulfonic acid group, metal or alkyl sulfonate group, sulfonamide group, metal or dialkyl phosphate group, metal or dialkyl phosphonate group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, heterocycloalkyl group, or combinations thereof.

[0029] This technology relates to formula I or II:

Chemical formula

Chemical formula

[0030] According to some examples, the compound is the compound of formula I, where X is Br and A -gabis(trifluoromethanesulfonyl)imide (TFSI - ) and R + If n is a 3-methyl-1-imidazolium group, then n is different from 5.

[0031] The compound of formula I or II is preferably an ionic liquid at or near room temperature. For example, the compound of formula I or II preferably has a melting point of 60°C or lower, or 40°C or lower, preferably 25°C or lower.

[0032] Delocalized anion A - The anion is preferably selected from anions comprising phosphates, imides, sulfonylimides, sulfonates, sulfates, borates, nitrates, arseneates, or triazolates. For example, the delocalized anion is hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI - ), 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 - ), perchlorate (ClO4 - ), hexafluoroarsenieate (AsF6 - ), trifluoromethanesulfonate (CF3SO3 - or - OTf), fluoroalkyl phosphate ([PF3(CF2CF3)3] - or FAP -), tetrakis(trifluoroacetoxy)borate ([B(OCOCF3)4] - or TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate([B(C6O2)2] - or BBB - ), difluoro(oxalato)borate (BF2(C2O4) - or FOB - ), and formula BF2O4R x (R x =C 2~4 The group consisting of alkyl anions can be selected. For example, the delocalized anion is hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI - ), tetrafluoroborate (BF4 - ), and trifluoromethanesulfonate (CF3SO3 - or - Selected from the group consisting of OTf), preferably bis(trifluoromethanesulfonyl)imide (TFSI - )

[0033] For example, R + is, formula -N + (R 1 R 2 R 3 )(wherein, R 1 , R 2 and R 3 These are independently substituted or unsubstituted linear or branched C 1~12 It is the base (selected from alkyl groups).

[0034] In another example, R + is, formula -N + (R 1 R 2 R 3 )(wherein, R 1 , R 2and R 3 These are independently linear or branched C 1~12 Selected from alkyl groups, or R 1 , R 2 and R 3 At least one of these groups is a halogen atom or a group that is substituted with an alkoxy, ether, ester, or siloxy group.

[0035] In another example, R + is, formula -N + (R 1 R 2 R 3 )(wherein, R 1 and R 2 It combines with a nitrogen atom to form a heterocycle having one or more rings and 3 to 12 ring members, R 3 This is as previously defined, preferably R 3 C 1~12 Alkyl or C 1~4 It is the group of an alkyl group. According to an example of interest, R 3 is unsubstituted C 1~4 Alkyl (e.g., methyl, ethyl, n-propyl or i-propyl, n-butyl, i-butyl, s-butyl and t-butyl), preferably R 3 This is a methyl group.

[0036] In another example, R + is, formula -N + (R 1 R 2 R 3 )(wherein, R 1 , R 2 and R 3 It is a group that, together with a nitrogen atom, forms a heteroaromatic or partially unsaturated heterocycle having one or more rings and 5 to 12 ring members.

[0037] In another example, R + teeth, [ka] (Here, R 3 It is as defined above; R 4 This refers to substituted or unsubstituted linear or branched C12C. 1~12 Alkyl, C 1~12 Alkenyl or C 1~12 It is an alkynyl group; R 5 This is a hydrogen or halogen atom, or a substituted or unsubstituted linear or branched carbon atom. 1~12 Alkyl, C 1~12 Alkenil or C 1~12 It is an alkynyl group; (Heterocyclic rings are substituted as needed.) Selected from.

[0038] According to a preferred example, R + The formula is: [ka] (In the formula, R 3 (This is as previously defined.) That is the case.

[0039] R 3 The group, when present in the heterocycle, is selected from, for example, a methyl group, an ethyl group, an n-propyl or i-propyl group, and an unsubstituted C group, i-butyl, i-butyl, s-butyl or t-butyl group. 1~4 It can be alkyl.

[0040] R 4 If a base exists, it is C 1~4 It can be an alkyl group. 5 Also, if present, hydrogen atoms or C 1~4 It can be an alkyl group.

[0041] In another example, R + is, equation -P + (R 1 R 2 R 3 )(wherein, R 1 , R 2and R 3 These are independently substituted or unsubstituted linear or branched C 1~12 It is the base (selected from alkyl groups).

[0042] In another example, R + is, equation -P + (R 1 R 2 R 3 )(wherein, R 1 , R 2 and R 3 These are independently linear or branched C 1~12 Selected from alkyl groups, or R 1 , R 2 and R 3 At least one of these groups is a halogen atom or a group that is substituted with an alkoxy, ether, ester, or siloxy group.

[0043] In some embodiments, the compound is a compound of formula I. In some examples, n can be a number in the range of 2 to 10, or 3 to 8, or 4 to 6, including upper and lower limits.

[0044] According to other embodiments, the compound has formula II. In some examples, L is linear or branched C 2~4 Alkylene or linear or branched carbon dioxide 2~3 It is an alkylene. According to a preferred embodiment, the variable Y may be an oxygen atom. Alternatively, the variable Y may be a sulfur atom. In some examples, m is a number from 1 to 4, or from 1 to 3.

[0045] According to some examples, X is a chlorine, bromine, or iodine atom, or X is a chlorine or bromine atom, or X is a bromine atom.

[0046] Examples of compounds described herein, etc., are not limited to the following, but include the cations 1-(6-bromohexyl)-1-methylpyrrolidinium, 1-(6-chlorohexyl)-1-methylpyrrolidinium, or 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium, for example, 1-(6-bromohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 1), 1-(6-chlorohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 2), or 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 3) and their delocalized anion A. - Includes.

[0047] This technology also includes a composition comprising at least one compound as described herein. Preferably, the composition further comprises an ionic solid such as an ionic bifunctional molecule.

[0048] According to some embodiments, the ionic bifunctional molecule is defined by formula III or IV: [ka] (In the formula, A - , R + L, Y, m, and n are defined above for each compound independently in their respective appearances, and they include separately the examples, embodiments, and substitutes. It is a molecule of the compound. The variable A of the compound. - , R + It should be noted that L, Y, m, and n may independently differ from or be identical to these variables in the ionic bifunctional molecule of the same composition.

[0049] According to some examples, the ionic bifunctional molecules are selected from 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, and 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide. According to an example of interest, the bifunctional ionic molecule is 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

[0050] According to some preferred forms, the weight ratio of "compound:ionic bifunctional molecule" is approximately 2:98 to approximately 50:50, or approximately 5:95 to approximately 35:65, or approximately 10:90 to approximately 30:70. For example, the composition is solid at room temperature (e.g., approximately 25°C ± 5°C).

[0051] This technology also relates to solid electrolytes comprising ionic organic compounds as defined herein, or compositions as previously defined, preferably compositions as defined herein.

[0052] In some examples, the solid electrolyte further comprises inorganic particles. For example, the inorganic particles may be selected from all known solid inorganic electrolyte material particles, or they may be selected based on their compatibility with various components of a possible electrochemical cell. For example, the inorganic particles may include materials such as glass, glass ceramics, ceramics, nanoceramics, and combinations of at least two of these.

[0053] For example, inorganic particles may include ceramics, glass, or glass ceramics based on fluorides, phosphides, sulfides, oxysulfides, or oxides.

[0054] In another example, inorganic particles may include compounds of the form of lithicon, thio-lithicon, silver-germanium ore, garnet, nasicon, perovskite, oxide, sulfide, oxysulfide, phosphide, fluoride, or a combination of at least two of these in crystalline and / or amorphous forms.

[0055] In another example, inorganic particles are given by 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 (e.g., M7La3Ta2O) 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 ); - MLSnO (e.g., M7La3Sn2O) 12 ); - MAGP (e.g., 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, Ma Zr b (PO4) c ); - MCZP (for example, M a Ca b Zr c (PO4) d ); - MGPS (for example, M a Ge b P c S d For example, M 10 GeP2S 12 ); - MGPSO (for example, M a Ge b P c S d O e ); - MSiPS (for example, M a Si b P c S d For example, M 10 SiP2S 12 ); - MSiPSO (for example, M a Si b P c S d O e ); - MSnPS (for example, M a Sn b P c S d For example, M 10 SnP2S 12 ); - MSnPSO (for example, M a Sn b P c S d O e ); - MPS (for example, M a P b S c For example, M7P3S 11 ); - MPSO (for example, M a P b S c O d ); - MZPS (for example, M a Zn bP 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, M a P b S c X d For example, M7P3S 11 X, M7P2S8X, and M6PS5X); - MPSOX (for example, M a P b S c O d X e ); - MGPSX (for example, M a Ge b P c S d X e ); - MGPSOX (for example, M a Ge b P c S d O e X f ); - MSiPSX (for example, M a Si b P c S d X e ); - MSiPSOX (for example, M a Si bP c S d O e X f ); - MSnPSX (for example, M a Sn b P c S d X e ); - MSnPSOX (for example, M a Sn b P c S d O e X f ); - MZPSX (for example, M a Zn b P c S d X e ); - MZPSOX (for example, M a Zn b P c S d O e X f ); - M3OX; - M2HOX; - M3PO4; - M3PS4; and - M a PO b N c (Here, a = 2b + 3c - 5) It comprises a compound selected from the inorganic compounds; M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two of these, and 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 thereof, and may be identical or different from X present in the compound of formula I or II; 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.

[0056] For example, M can be selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or at least two combinations of these. According to one modification of interest, M is Li.

[0057] According to one modification of interest, the inorganic particles include an inorganic compound of formula MATP as defined herein.

[0058] According to another variation of interest, inorganic particles contain sulfides or oxysulfides.

[0059] For example, inorganic particles are given by formula Li a P b S c X d The inorganic compounds include a compound selected from the inorganic compounds of the formula Li6PS5Cl (wherein X is Cl, Br, I, or a combination of at least two of these, and a, b, c, and d are numbers such that (a+5b)=(2c+d)). For example, the inorganic particles may include the inorganic compound of the formula Li6PS5Cl. The inorganic compound may be in the form of silver-germanium sulfide ore.

[0060] In another example, inorganic particles are given by formula Li a P b S c O d X e The formula includes compounds selected from inorganic compounds such that (a+5b)=(2c+2d+e), where X is Cl, Br, I or a combination of at least two of these, and a, b, c, d, and e are numbers such that (a+5b)=(2c+2d+e). In some cases, a is selected from the range of 5-6, b is equal to 1, c is selected from the range of 3.5-4.8, and e is selected from the range of 1-2 (e.g., Li 5.4 PS 4.1 O 0.3 X 1.6 or Li 5.4 PS 4.1 O0.3 ClBr 0.5 I 0.1 ).

[0061] Inorganic particles may be present in the solid electrolyte at concentrations ranging from approximately 20% to 95% by weight, including upper and lower limits. For example, inorganic particles may be present in the solid electrolyte at concentrations ranging from approximately 40% to 95% by weight, or from approximately 60% to 95% by weight, including upper and lower limits.

[0062] The concentration of the compound in the electrolyte may be approximately within the range of about 0.2% to about 5% by weight, or about 0.3% to about 4% by weight, or about 0.4% to about 3% by weight, including upper and lower limits. If the composition as defined above is present in the electrolyte, it may be present at a concentration of about 1% to about 15% by weight, or about 2% to about 10% by weight, or about 4% to about 8% by weight, of the total mass of the solid electrolyte.

[0063] The solid electrolyte as defined herein may further include a polymer. For example, the polymer may be selected for its compatibility with various components of the electrochemical cell. Any known compatible polymer is intended. The polymer may be selected from linear or branched polymers. Examples of polymers, not limited to these, include polyethers (e.g., poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), or polyethers based on a combination of these two (e.g., EO / PO copolymers)), polythioethers, polyesters, polythioesters, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylentiocarbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyimides, polyamides, polyphosphazenes, polyurethanes, poly(vinyl alcohol), polyacrylonitrile, polyethylacrylate and polymethacrylate, and copolymers thereof, and optionally include crosslinking units from crosslinkable functional groups (e.g., acrylate, methacrylate, vinyl, glycidyl, mercapto, etc.) or their crosslinking equivalents.

[0064] For example, when present in an electrolyte, the polymer may be the product of a reaction between at least one monomer containing at least one polymerizable or crosslinkable functional group and a compound containing at least one SH functional group.

[0065] In another example, the polymer may be present in the solid electrolyte at a concentration ranging from about 0.1% to about 20% by weight, including upper and lower limits. For example, the polymer may be present in the solid electrolyte at a concentration ranging from about 1% to about 15% by weight, or from about 2% to about 13% by weight, including upper and lower limits.

[0066] For example, ionic organic compounds or compositions as defined herein act as binders between inorganic particles in the solid electrolyte, and therefore the binders may also further include polymers as defined herein.

[0067] Solid electrolytes as defined herein may also include additives as needed.

[0068] As an example, when present in an electrolyte, the additive may be a fluorinated compound containing an amide functional group. The fluorinated compound is represented by formula R 6 X 6 C(O)N(H)X 7 R 7 (In the formula, R 6 and R 7 X is independently an alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group. 6 is O, NH, or non-existent, X 7 is either absent or C(O), S(O)2, or Si(R) 8 R 9 ) is a group, R 8 and R 9 R is an alkyl group, 6 , R 7 , R 8 and R 9 The compound may be one of which is a group substituted with one or more fluorine atoms. For example, R6 X is a perfluoroemission group, 6 It is non-existent.

[0069] The technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode, positive electrode, and electrolyte comprises an ionic organic compound or composition as defined herein, and preferably the electrolyte is as defined above.

[0070] The positive electrode optionally includes a positive electrode material on the current collector, and the positive electrode material includes a positive electrode electrochemical active material. Not limited examples of electrochemically active positive electrode materials include metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides.

[0071] For example, the metal of the electrochemical active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), antimony (Sb), and, if compatible, at least two combinations of these. According to one variation of interest, the metal of the electrochemical active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), and, if compatible, at least two combinations of these.

[0072] Examples of positive electrode electrochemical active materials, though not limited to these, generally include metal phosphates and lithium metal phosphates (e.g., LiM'PO4 and M'PO4 (where M' is Fe, Ni, Mn, Co, or a combination of at least two of these)), vanadium oxides and lithium vanadium oxides (e.g., LiV3O8, V2O5F, LiV2O5, and other similar vanadium oxides and lithium vanadium oxides), and materials of the formulas LiMn2O4, LiM''O2 (where M'' is selected from Mn, Co, Ni, or a combination of at least two of these) (e.g., NMC, LiMn x Co y Ni z O 2、 The formula includes lithium metal oxides of x+y+z=1, Li(NiM''')O2 (wherein M''' is selected from Mn, Co, Al, Fe, Cr, Ti, Zr, another similar metal and at least two combinations thereof), and at least two combinations thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or at least two combinations thereof where they are compatible with each other.

[0073] The cathode material as defined herein may further comprise an electrically conductive material, a binder, a salt, the ionic organic compound, an ionic difunctional molecule (e.g., an ionic difunctional molecule as defined above), and / or inorganic particles.

[0074] The negative electrode includes a negative electrode material, which optionally contains a negative electrode electrochemical active material located on the current collector.

[0075] For example, the negative electrode electrochemical active material may include a metal film containing an alkali metal or alkaline earth metal, or an alloy containing an alkali metal or alkaline earth metal. For instance, the alkali metal may be selected from lithium and sodium.

[0076] According to another example, the negative electrode electrochemical active material can 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 sulfide, a carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), a silicon-carbon composite (Si-C), or silicon dioxide (SiO2). x ), silicon dioxide-carbon composite (SiO₂) x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, if applicable.

[0077] For example, metal oxides are given by formula M'''' b O c (wherein M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination 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 a combination thereof) (e.g., lithium titanate (e.g., Li4Ti5O 12 ) or lithium molybdenum oxide (e.g., Li2Mo4O 13 The compounds can be selected from the following:

[0078] In another example, the negative electrode material may further include an electrically conductive material, a binder, a salt, the ionic organic compound, an ionic bifunctional molecule (e.g., an ionic bifunctional molecule as previously defined), and / or inorganic particles.

[0079] This technology also relates to a process for preparing a solid electrolyte as described herein. This process may include the step of mixing a compound or composition as defined herein with inorganic particles and, optionally, a polymer and / or a solvent. The resulting mixture is then applied to a surface and dried, if a solvent is present. The surface may be a temporary inert surface, which is ultimately removed when assembling an electrochemical cell containing the solid electrolyte. In this case, the solid electrolyte forms a film, which is then combined with at least one positive electrode and at least one negative electrode.

[0080] In an alternative example, the surface to which the mixture is applied is the surface of an electrode, which is either the positive or negative electrode, and in this process, the other electrode is subsequently applied to the free surface of the solid electrolyte.

[0081] Another preparation method may include the steps of applying a powder mixture containing inorganic particles onto a surface, then applying a mixture containing the compound or composition in a solvent as needed, and then evaporating the solvent.

[0082] This technology also relates to an electrochemical battery comprising at least one electrochemical cell as defined herein. For example, the electrochemical battery is selected from the group consisting of lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, potassium-ion batteries, magnesium batteries, and magnesium-ion batteries. According to one modification of interest, the electrochemical battery is a lithium battery or a lithium-ion battery.

[0083] The presence of ionic organic compounds as defined herein in solid electrolytes, such as inorganic solid electrolytes or polymer-ceramic hybrid solid electrolytes, can significantly improve some of their physical and / or electrochemical properties. For example, these compounds exhibit positive interactions with ionic solids, such as the ionic bifunctional molecules described above. In another example, the presence of these compounds, particularly in combination with ionic bifunctional molecules, can substantially improve the ionic conductivity and / or electrochemical stability of solid electrolyte films, as well as their mechanical strength. [Examples]

[0084] The following embodiments are for illustrative purposes only and should not be construed as further limiting the scope of the invention as intended. These embodiments are better understood by referring to the accompanying drawings. Example 1 Preparation of ionic organic compounds (i) Preparation of 1-(6-bromohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 1) [ka]

[0085] 1,6-dibromohexane (20.8 g, 85.6 mmol) is introduced into a 100 mL round-bottom flask sealed with a septum, and cooled to 0°C under N2. A solution of 1-methylpyrrolidine (3.6 g, 42.8 mmol) in 20 mL of tetrahydrofuran is added dropwise to the flask with stirring. The solution is then stirred at room temperature for 12 hours. The precipitate is then separated by filtration and washed three times with tetrahydrofuran. The resulting product, 1-(6-bromohexyl)-1-methylpyrrolidinenium bromide, is dried under vacuum at 50°C for 24 hours.

[0086] Anion exchange with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is carried out in deionized water at room temperature for 3 hours. The precipitate is removed by filtration, the organic phase is extracted with dichloromethane, and then washed with deionized water. After washing, the organic solution is dried over sodium sulfate. The solvent is then evaporated, and the final product is dried under vacuum at 60°C for 48 hours. Compound 1(1-(6-bromohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide) is obtained as an oily substance. (ii) Preparation of 1-(6-chlorohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 2) [ka]

[0087] In a 100 mL round-bottom flask sealed with a septum, 1,6-dichlorohexane (13.3 g, 85.6 mmol) is introduced and cooled to 70°C under N2. A solution of 1-methylpyrrolidine (3.6 g, 42.8 mmol) in 20 mL of acetonitrile is added dropwise to the flask with stirring. The solution is then stirred at 70°C for 12 hours. The solvent is evaporated. The solid is introduced into a mixture of acetone and methanol (20 mL in a volume ratio of 10 / 1.05). The precipitate is then removed by filtration and the solvent is evaporated. This process is repeated twice. The resulting product, 1-(6-chlorohexyl)-1-methylpyrrolidinenium chloride, is dried under vacuum at 50°C for 24 hours.

[0088] Anion exchange with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is carried out in deionized water at room temperature for 3 hours. The organic phase is extracted with dichloromethane and then washed with deionized water. After washing, the organic solution is dried with sodium sulfate. The solvent is then evaporated and the final product is dried under vacuum at 60°C for 48 hours. Compound 2(1-(6-chlorohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide) is obtained as a yellow liquid. (iii) Preparation of 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 3) [ka]

[0089] In a 100 mL round-bottom flask sealed with a septum, 1,2-bis(2-chloroethoxy)ethane (20 g, 107 mmol) is introduced and cooled to 70°C under N2. A solution of 1-methylpyrrolidine (3.6 g, 42.8 mmol) in 20 mL of acetonitrile is added dropwise to the flask with stirring. The solution is then stirred at 70°C for 12 hours. The solvent is evaporated. The viscous solid is washed three times with diethyl ether. The product, 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium chloride, is dried under vacuum at 50°C for 24 hours.

[0090] Anion exchange with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is carried out in deionized water at room temperature for 3 hours. The organic phase is extracted with dichloromethane and then washed with deionized water. After washing, the organic solution is dried with sodium sulfate. The solvent is then evaporated and the final product is dried under vacuum at 60°C for 48 hours. Compound 3(1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide is obtained as a yellow liquid. Example 2 Characterization by nuclear magnetic resonance (NMR)

[0091] Compounds 1, 2, and 3 prepared in Example 1 were subjected to proton nuclear magnetic resonance ( 1 The samples were characterized by 1H NMR.

[0092] Compound prepared in Example 1 1The 1H NMR spectra were obtained in DMSO-d6 (deuterated dimethyl sulfoxide) as the solvent. The obtained spectra are shown in Figures 1(a) to 1(c), and include the assignment of each peak. During DMSO-d6 1 1H NMR (δppm):

[0093] Compound 1. 1.33 -CH2-C2H4-N; 1.45 -CH2-C2H4-Br; 1.72 -CH2-CH2-CH2-N; 1.84 -CH2-CH2-CH2-Br; 2.09 -CH2-C2H4-CH2-N cyclic; 2.98 -CH3; 3.25-3.34 CH2-CH2-N; 3.34-3.51 -CH2-N-CH2-cyclic; 3.55 -CH2-Br. (See Figure 1(a))

[0094] Compound 2. 1.34 -CH2-C2H4-N; 1.45 -CH2-C2H4-Cl; 1.62-1.82 -CH2-CH2-CH2-N and -CH2-CH2-CH2-Cl; 2.09 -CH2-C2H4-CH2-N cyclic; 2.98 -CH3; 3.24-3.36 CH2-CH2-N; 3.36-3.55 -CH2-N-CH2-cyclic; 3.65 -CH2-Cl. (See Figure 1(b)) Compound 3.22.09 -CH2-C2H4-CH2-N cyclic; 3.05 -CH3; 3.47-3.58 -CH2-N-CH2-cyclic; 3.60 -O-CH2-CH2-N; 3.61 -O-CH2-CH2-O-; 3.66-3.78 -CH2-O-CH2-CH2-O-CH2-; 3.82-3.90 -CH2-Cl. (See Figure 1(c)) Example 3 Thermal and thermogravimetric analysis

[0095] Figures 2(a) to 2(c) show the results of differential scanning calorimetry (DSC) analysis obtained for compounds 1, 2, and 3 prepared in Example 1. The DSC analysis was performed over a temperature range of approximately -80°C to approximately 150°C at a heating rate of 10°C / min. As shown in Figure 4, compound 1 has a crystallization temperature of -51°C and a melting temperature of -29°C. No crystallization was observed in compounds 2 and 3 between approximately -80°C and approximately 150°C.

[0096] Figures 3(a) to 3(c) show the results of thermogravimetric analysis (TGA) obtained for compounds 1, 2, and 3 prepared in Example 1. Thermogravimetric analysis was performed within a temperature range of approximately 30°C to 600°C. As shown in Figure 3(a), compound 1 has a decomposition point at approximately 269°C. Compounds 2 and 3 have decomposition points at approximately 296°C (see Figures 3(b) and 3(c), respectively). Example 4 Preparation and characterization of organic compound compositions containing ionic solids

[0097] Various compositions were prepared, which include compound 1 or 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (compound IL) combined with the ionic solid 1,1'-hexamethylenebis(1-methylpyrrolidinium)bis(trifluoromethylsulfonyl)imide (compound SI) in the proportions shown in Table 1. [Table 1]

[0098] Figure 4 shows the DSC curves for the compositions in Table 1 with different mass ratios. DSC analysis was performed over a temperature range of approximately -80°C to approximately 148°C at a heating rate of 10°C / min. The data extracted from the DSC measurements are shown in Table 2 below. [Table 2]

[0099] Composition A2 exhibits the lowest melting point at approximately 47°C. However, the melting point of composition 1, having the same weight ratio, is 57°C, which is relatively 10°C higher. This difference indicates that the intermolecular interaction between compound 1 and the ionic solid (compound SI) is stronger than the intermolecular interaction of the mixture of compound IL in a 20 / 80 ratio. Furthermore, the weak intermolecular interaction between compound IL and compound SI can lead to phase separation and, therefore, can inhibit the electrochemical properties of the mixture, as shown in Example 5. Example 5 Preparation and characterization of composite solid electrolyte films

[0100] The crosslinkable polymer used in the following examples is a highly branched polyether containing crosslinkable units as described in U.S. Patent No. 7,897,674 (hereinafter referred to as "US'674 polymer"). a) Preparation of ceramic-cobonder composite solid electrolyte films

[0101] Composite solid electrolyte films containing sulfide-based ceramics, the ionic solid salt compound SI as defined above, and compound 1 were prepared in various compositions. Composite solid electrolyte films containing sulfide-based ceramics and the ionic solid salt compound SI, with or without a halogen-free ionic liquid (compound IL), were also prepared for comparison. The halogen-free ionic liquid is compound IL as previously defined and therefore has a structure similar to compound 1, but has a tetracarbon chain and does not have halogens at the ends of the chain.

[0102] Other composite solid electrolyte films (E10 and E11) containing sulfide-based ceramics, ionic solid salts SI and halogenated ionic liquids (compounds 2 or 3) were prepared and compared with film E2 (equivalent to compound 1) or with composite solid electrolyte films containing sulfide-based ceramics and ionic solid salts (SI), with or without halogen-free ionic liquids.

[0103] All operations were performed in the glove compartment under an argon atmosphere (0.1 ppm H2O; 0.1 ppm O2).

[0104] Two sizes of ceramic sulfide-based inorganic solid electrolyte particles (Li6PS5Cl) (approximately 3 μm and less than 1 μm) were mixed in a 90:10 mass ratio using a vortex mixer.

[0105] The binder is formed from a mixture of (a) a US'674 polymer containing 4.0 wt% TBT(4,4'-thiobisbenzenethiol) and (b) an ionic solid compound SI containing or not containing a halogenated (compound 1, 2, or 3) or non-halogenated (compound IL) ionic liquid dissolved in dichloromethane, in a ratio of 40 / 60 by mass.

[0106] The weight ratio of the sulfide-based ceramic to the binder was 90 / 10 by mass. The amount of dichloromethane was adjusted to obtain a mixture with appropriate viscosity. The resulting mixture was coated onto previously degreased aluminum foil. The film was dried in a glove box.

[0107] The composition of the ceramic-ionic binder composite solid electrolyte film is shown in Table 3. [Table 3] b) Ionic conductivity of ceramic-cobonder composite solid electrolyte films

[0108] Pellets with a diameter of 10 mm were cut from the ceramic-coionic binder composite solid electrolyte film prepared in Example 6(a). The pellets were placed in a 10 mm diameter mold and compressed under a pressure of 2.8 tons using a press. The pellets were then placed in a closed conductivity cell under a pressure of 5 MPa in an inert argon atmosphere. The electrodes were made of stainless steel. The configuration of each cell is shown below: Cell X: Electrode / Electrolyte / Electrode

[0109] Cells 1-11 were prepared using the corresponding electrolytes E1-E11 as described in (a) above.

[0110] The ionic conductivity of the cell assembled in this example was measured using a VMP-300 multi-channel potentiostat (Bio-Logic TM The measurements were performed using [specific equipment / tool / method]. Measurements were taken within a temperature range of -20°C to 70°C (increasing in 10°C increments) and a temperature decrease of 70°C to 20°C (in 10°C increments), within a frequency range of 7MHz to 200mHz, and with an amplitude of 50mV.

[0111] Impedance measurements were obtained after a stabilization period of approximately one hour. Two impedance measurements were recorded at each temperature, with a 15-minute interval between each measurement. Figure 5 shows the cell. 1(■), 2(●), 3(▲), 4(▼), 5(<), 6(>), and 7(★) The results of ionic conductivity measured as a function of temperature are shown below.

[0112] The ionic conductivity after passing through 70°C and returning to 20°C is relatively high due to the liquefaction and recrystallization of the ionic solid (compound SI).

[0113] From Figure 5, it can be observed that the ionic conductivity before and after heating to 70°C increases with increasing amounts of added ionic halide liquid, demonstrating the interaction between the co-binding agent, composed of the ionic solid and ionic halide liquid, and the sulfide ceramic particles. It should be noted that stabilization of ionic conductivity is observed from approximately 20% ionic halide liquid relative to the ionic solid. Furthermore, only linear activation energy curves appear during both temperature increases and decreases, supporting the interaction between the ionic halide liquid and other solid components (e.g., ionic solid and sulfide ceramic solid electrolyte). Thus, the ionic halide liquid mixes with other components without phase separation.

[0114] Figure 6 shows the effect of adding a halogenated ionic liquid compared to adding a non-halogenated ionic liquid, in a cell. 1(■), 3(▲), 6(>), 7(★), 8(△), and 9(◆) The results of ionic conductivity measured as a function of temperature are shown below.

[0115] In Figure 6, it can be observed that at approximately 10% concentration, the ionic conductivity is identical with the addition of halogenated or non-halogenated ionic liquids. At a 20% composition, a significant decrease in ionic conductivity is observed when using the non-halogenated ionic liquid compared to the halogenated ionic liquid, and the halogenated ionic liquid enables the achievement of the maximum ionic conductivity tested at 20%. Furthermore, with increasing temperature, two intersecting activation energy gradients can be observed at approximately 45°C. This temperature corresponds to the temperature observed in the DSC in Figure 4 and Table 2 of Example 4. Thus, phase separation occurs between the non-halogenated ionic liquid and the ionic solid, resulting in differentiation of activation energies. This is not observed with the use of halogenated ionic liquids such as Compound 1, supporting their greater interaction with ionic solids and potential as co-binding agents for ceramic applications in solid electrolytes. Furthermore, improved mechanical strength during cutting was observed in the electrolyte film with the addition of the halogenated ionic liquid.

[0116] Figure 7 shows the effects of adding the halogenated ionic liquids of compounds 1, 2, and 3 compared to the effect when only the ionic solids are present, in a cell. 1(■), 2(●), 10(★), and 11(▲) The results of ionic conductivity measured as a function of temperature are shown below.

[0117] Any of the embodiments described above may be modified in some way without departing from the intended scope of the present invention. References, patents, or scientific documents referenced herein are incorporated herein by reference in their entirety for all purposes.

Claims

1. Compounds of formula I or II: 【Chemistry 13】 And in the formula, A － is a delocalized anion; R ＋ is selected from a -N ＋ (R １ R ２ R ３ ) group and a -P ＋ (R １ R ２ R ３ ) group; R １ , R ２ and R ３ When adjacent to N, it independently comprises a hydrogen atom and a linear or branched C. １～１２ Alkyl or C ６ Selected from aryl groups, the alkyl or aryl group is substituted or unsubstituted, R １ , R ２ and R ３ If one of them is a hydrogen atom, then the other two are not hydrogen atoms; R １ , R ２ and R ３ When adjacent to P, it independently forms a linear or branched C １～１２ Alkyl, OC １～１２ Alkyl or SC １～１２ Alkyl alkyl groups, and C ６ Ariel, OC ６ Aryl or SC ６ Selected from aryl groups, the alkyl or aryl group may be substituted or unsubstituted; Alternatively, R １ and R ２ It, together with a nitrogen or phosphorus atom, forms a heterocycle having one or more rings and 3 to 12 ring members, R ３ This is as previously defined, or R １ , R ２ and R ３ Together with a nitrogen or phosphorus atom, these atoms form one or more rings and 5 to 12 ring members to form a heteroaryl or partially unsaturated heterocycloalkyl group, wherein the heteroaryl or heterocycloalkyl group is substituted or unsubstituted; L is independently linear or branched in each instance. ２～８ It is alkylene; X is a halogen atom; Y is either O or S; m is a number equal to or greater than 1, or within the range of 1 to 6; n is a number equal to or greater than 1, or within the range of 1 to 11; Preferably, the compound is a compound of formula I, where X is Br and A － ga bis(trifluoromethanesulfonyl)imide (TFSI) － ) and R ＋ If n is a 3-methyl-1-imidazolium group, then n is different from 5. compound.

2. A － The compound according to claim 1, wherein the anion is selected from an anion comprising a phosphate, imide, sulfonylimide, sulfonate, sulfate, borate, nitrate, arsenate, or triazolate.

3. A － However, the following anions, hexafluorophosphates (PF ６ － ), bis(trifluoromethanesulfonyl)imide (TFSI － ), bis(fluorosulfonyl)imide (FSI － ), (fluorosulfonyl) (trifluoromethanesulfonyl)imide (FTFSI － ), 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 － ), nitrate (NO ３ － ), perchlorate (ClO ４ － ), hexafluoroarsenieate (AsF ６ － ), trifluoromethanesulfonate (CF ３ SO ３ － or － OTf), fluoroalkyl phosphate ([PF ３ (CF ２ CF ３ ) ３ ] － or FAP － ), tetrakis(trifluoroacetoxy) borate ([B(OCOCF ３ ) ４ ] － or TFAB － ), bis(1,2-benzenediolate(2-)-O,O')borate([B(C ６ O ２ ) ２ ] － or BBB － ), difluoro(oxalato)borate (BF ２ (C ２ O ４ ) － or FOB － ), and formula BF ２ O ４ R ｘ (R ｘ = C ２～４ A compound according to claim 1 or 2, selected from an anion of an alkyl group.

4. The delocalized anion is hexafluorophosphate (PF ６ － ), bis(trifluoromethanesulfonyl)imide (TFSI － ), bis(fluorosulfonyl)imide (FSI － ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI － ), tetrafluoroborate (BF ４ － ), and trifluoromethanesulfonate (CF ３ SO ３ － or － OTf), and the compound according to claim 3.

5. The delocalized anion is bis(trifluoromethanesulfonyl)imide (TFSI) － The compound according to claim 4, which is the compound described in claim 4.

6. R ＋ However, -N ＋ (R １ R ２ R ３ The compound according to any one of claims 1 to 5, wherein the compound is a group.

7. R １ , R ２ and R ３ However, independently, substituted or unsubstituted linear or branched C １～１２ A compound according to claim 6, selected from alkyl groups.

8. R １ , R ２ and R ３ However, independently, linear or branched C １～１２ Selected from alkyl groups, R １ , R ２ and R ３ The compound according to claim 6, wherein at least one of the members is substituted with a halogen atom or an alkoxy, ether, ester, or siloxy group.

9. R １ and R ２ However, together with a nitrogen atom, it forms a heterocycle having one or more rings and 3 to 12 ring members, R ３ However, as defined in claim 1, preferably R ３ However, C １～１２ Alkyl or C １～４ The compound according to claim 6, wherein it is alkyl.

10. R １ , R ２ and R ３ The compound according to claim 6, wherein it combines with a nitrogen atom to form a heteroaromatic or partially unsaturated heterocycle having one or more rings and 5 to 12 ring members.

11. R ＋ However, heterocyclic: 【Chemistry 14】 Selected from, here, R ３ This is as defined in claim 1; R ４ This refers to substituted or unsubstituted linear or branched C12C. １～１２ Alkyl, C １～１２ Alkenyl or C １～１２ It is an alkynyl group; R ５ This is a hydrogen or halogen atom, or a substituted or unsubstituted linear or branched carbon atom. １～１２ Alkyl, C １～１２ Alkenil or C １～１２ It is an alkynyl group; The aforementioned heterocycle is substituted as needed. The compound according to claim 6.

12. R ＋ However, the formula is: 【Chemistry 15】 And in the formula, R ３ This is as defined in claim 1, The compound according to claim 11.

13. R ３ However, non-substituted C １～４ A compound according to any one of claims 1 to 9, 11, or 12, wherein the compound is an alkyl group.

14. R ３ The compound according to claim 13, wherein the group is selected from a methyl group, an ethyl group, an n-propyl or i-propyl group, and an n-butyl, i-butyl, s-butyl or t-butyl group.

15. R ４ However, C １～４ The compound according to claim 11, wherein it is an alkyl group.

16. R ５ However, hydrogen atoms or C １～４ The compound according to claim 11 or 15, wherein it is an alkyl group.

17. R ＋ However, -P ＋ (R １ R ２ R ３ The compound according to any one of claims 1 to 5, wherein the compound is a group.

18. R １ , R ２ and R ３ However, independently, substituted or unsubstituted linear or branched C １～１２ A compound according to claim 17, selected from alkyl groups.

19. R １ , R ２ and R ３ However, independently, linear or branched C １～１２ Selected from alkyl groups, or R １ , R ２ and R ３ The compound according to claim 17, wherein at least one of the members is substituted with a halogen atom or an alkoxy, ether, ester, or siloxy group.

20. The compound according to any one of claims 1 to 19, wherein the compound is a compound of formula I.

21. The compound according to claim 20, wherein n is a number in the range of 2 to 10, 3 to 8, or 4 to 6.

22. The compound according to any one of claims 1 to 19, wherein the compound is a compound of formula II.

23. L is a linear or branched C ２～４ Alkylene or linear or branched carbon dioxide ２～３ The compound according to claim 22, which is alkylene.

24. The compound according to claim 22 or 23, wherein Y is O.

25. The compound according to claim 22 or 23, wherein Y is S.

26. The compound according to any one of claims 22 to 25, wherein m is a number from 1 to 4 or from 1 to 3.

27. The compound according to any one of claims 1 to 26, wherein X is Cl, Br, or I, preferably Cl or Br, or X is Br.

28. The compound according to any one of claims 1 to 27, having a melting point of 60°C or lower, or 40°C or lower, preferably 25°C or lower.

29. A － A compound according to any one of claims 1 to 5, selected from a salt, 1-(6-bromohexyl)-1-methylpyrrolidinium, 1-(6-chlorohexyl)-1-methylpyrrolidinium, and 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium, preferably 1-(6-bromohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 1), 1-(6-chlorohexyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 2), or 1-(2-(2-(2-chloroethoxy)ethoxy)ethyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (compound 3).

30. A composition comprising a compound according to any one of claims 1 to 29, and an ionic bifunctional molecule.

31. The aforementioned ionic difunctional molecule is defined by formula III or IV: 【Chemistry 16】 【Chemistry 17】 It is the numerator, and in the formula, A － , R ＋ L, Y, m, and n are, in their respective occurrences, independently as defined in claims 1 to 26. The composition according to claim 30.

32. The composition according to claim 31, wherein the ionic bifunctional molecule is 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

33. The composition according to claim 31, wherein the ionic bifunctional molecule is 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

34. The composition according to claim 31, wherein the ionic bifunctional molecule is 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

35. The composition according to claim 31, wherein the ionic bifunctional molecule is 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

36. The composition according to claim 31, wherein the ionic bifunctional molecule is 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide.

37. The composition according to any one of claims 30 to 36, wherein the weight ratio of "compound:ionic bifunctional molecule" is about 2:98 to about 50:50, or about 5:95 to about 35:65, or about 10:90 to about 30:

70.

38. The composition according to any one of claims 30 to 37, which is solid at room temperature (e.g., 25°C ± 5°C).

39. A solid electrolyte comprising a compound according to any one of claims 1 to 29, or a composition according to any one of claims 30 to 38.

40. The solid electrolyte according to claim 39, further comprising inorganic particles.

41. The solid electrolyte according to claim 40, wherein the inorganic particles include a material selected from glass, glass ceramic, ceramic, nanoceramic, and at least two combinations thereof.

42. The solid electrolyte according to claim 41, wherein the inorganic particles include ceramics, glass, or glass ceramics based on fluorides, phosphides, sulfides, oxysulfides, or oxides.

43. The solid electrolyte according to claim 41, wherein the inorganic particles include compounds of the type LISICON, thio-LISICON, silver-germanium ore, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide, fluoride, or a combination of at least two of these in crystalline and / or amorphous forms.

44. 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 (e.g., M ７ La ３ Sn ２ O １２ ); MAGP (for example M １＋ａ Al ａ Ge ２－ａ (PO ４ ) ３ );MATP (e.g., 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 ａ Ge ｂ P ｃ S ｄ For example, M １０ GeP ２ S １２ ); MGPSO (for example M ａ Ge ｂ P ｃ S ｄ O ｅ ); MSiPS (for example M ａ Si ｂ P ｃ S ｄ For example, M １０ SiP ２ S １２ ); MSiPSO (for example M ａ Si ｂ P ｃ S ｄ O ｅ ); MSnPS (e.g., M ａ Sn ｂ P ｃ S ｄ For example, M １０ SnP ２ S １２ ); MSnPSO (for example, M ａ Sn ｂ P ｃ S ｄ O ｅ ); MPS (for example, M ａ P ｂ S ｃ For example, M ７ P ３ S １１ ); MPSO (e.g., 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 ａ P ｂ S ｃ X ｄ For example, M ７ P ３ S １１ X, M ７ P ２ S ８ X, and M ６ PS ５ X); 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 It includes a compound selected from inorganic compounds (where a = 2b + 3c - 5); M is an alkali metal ion, an alkaline earth metal ion, or a combination of at least two of these, and 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 thereof, and may be the same as or different from X present in the compound of formula I or II; 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. The solid electrolyte according to claim 41.

45. The solid electrolyte according to claim 44, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or at least two combinations thereof.

46. The solid electrolyte according to claim 45, wherein M is Li.

47. The solid electrolyte according to any one of claims 44 to 46, wherein the inorganic particles comprise an inorganic compound of formula MATP.

48. The solid electrolyte according to any one of claims 44 to 46, wherein the inorganic particles include a sulfide or an oxysulfide.

49. The inorganic particles, formula Li ａ P ｂ S ｃ X ｄ A solid electrolyte according to any one of claims 44 to 46, comprising a compound selected from the inorganic compounds, wherein X is Cl, Br, I or a combination of at least two of these, and a, b, c, and d are numbers such that (a + 5b) = (2c + d).

50. The inorganic particles are Li ６ PS ５ A solid electrolyte according to claim 49, comprising Cl.

51. The inorganic particles, formula Li ａ P ｂ S ｃ O ｄ X ｅ A solid electrolyte according to any one of claims 44 to 46, comprising a compound selected from the inorganic compounds, wherein X is Cl, Br, I or a combination of at least two of these, and a, b, c, d, and e are numbers such that (a + 5b) = (2c + 2d + e).

52. a is selected from the range of 5 to 6, b is equal to 1, c is selected from the range of 3.5 to 4.8, and e is selected from the range of 1 to 2 (for example, Li ５．４ PS ４．１ O ０．３ X １．６ or Li ５．４ PS ４．１ O ０．３ ClBr ０．５ I ０．１ ), the solid electrolyte according to claim 51.

53. The solid electrolyte according to any one of claims 40 to 52, wherein the inorganic particles are present in the solid electrolyte at a concentration of about 20% to about 95% by weight, or about 40% to about 95% by weight, or about 60% to about 95% by weight.

54. The solid electrolyte according to any one of claims 39 to 53, wherein the concentration of the compound in the electrolyte is in the range of about 0.2% by weight to about 5% by weight, or about 0.3% by weight to about 4% by weight, or about 0.4% by weight to about 3% by weight.

55. A solid electrolyte according to any one of claims 39 to 54, further comprising a polymer.

56. The solid electrolyte according to claim 55, wherein the polymer is a linear or branched polymer selected from polyethers, polythioethers, polyesters, polythioesters, poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylentiocarbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyimide, polyamide, polyphosphazene, polyurethane, poly(vinyl alcohol), polyacrylonitrile, polyethylacrylate, and polymethacrylate, as well as copolymers thereof.

57. The solid electrolyte according to claim 56, wherein the polyether is poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), or copolymer (EO / PO).

58. The solid electrolyte according to claim 56 or 57, wherein the polymer comprises crosslinking units derived from a crosslinkable functional group or a crosslinking equivalent thereof.

59. The solid electrolyte according to claim 58, wherein the crosslinkable functional group is selected from acrylate, methacrylate, vinyl, glycidyl, and mercapto functional groups.

60. The solid electrolyte according to claim 55, wherein the polymer is a reaction product of at least one monomer containing at least one polymerizable or crosslinkable functional group and a compound containing at least one SH functional group.

61. The solid electrolyte according to any one of claims 55 to 60, wherein the polymer is present in the solid electrolyte at a concentration of about 0.1% to about 20% by weight, or about 1% to about 15% by weight, or about 2% to about 13% by weight.

62. A solid electrolyte according to any one of claims 39 to 61, further comprising an additive.

63. The solid electrolyte according to claim 62, wherein the additive is a fluorinated compound containing an amide functional group.

64. The fluorinated compound is of formula R ６ X ６ C(O)N(H)X ７ R ７ It is a compound of which, in the formula, R ６ and R ７ X is independently an alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group. ６ is O, NH, or non-existent, X ７ is non-existent or C(O), S(O) ２ , or Si(R ８ R ９ ) is a group, R ８ and R ９ is an alkyl group, R ６ , R ７ , R ８ and R ９ The solid electrolyte according to claim 63, wherein at least one of the groups is a group substituted with one or more fluorine atoms.

65. R ６ However, it is a perfluoroemission group, X ６ The solid electrolyte according to claim 64, wherein the solid electrolyte is absent.

66. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined in any one of claims 39 to 65.

67. The electrochemical cell according to claim 66, wherein the positive electrode comprises a positive electrode material containing a positive electrode electrochemical active material.

68. The electrochemical cell according to claim 67, wherein the positive electrode material is located on a current collector.

69. The electrochemical cell according to claim 67 or 68, wherein the positive electrode electrochemical active material is selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides.

70. The electrochemical active material of the positive electrode is LiM'PO ４ (Here, M' is Fe, Ni, Mn, Co, or a combination of at least two of these), LiV ３ O ８ , V ２ O ５ F, LiV ２ O ５ LiMn ２ O ４ LiM''O ２ (Here, M'' is Mn, Co, Ni, or a combination of at least two of these (for example, NMC LiMn) ｘ Co ｙ Ni ｚ O ２ And here x + y + z = 1), Li(NiM''')O ２ The electrochemical cell according to claim 67 or 68, wherein M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination of at least two of these), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active material such as graphite, organic cathode active material, or a combination of at least two of these if they are compatible with each other.

71. The electrochemical cell according to any one of claims 67 to 70, wherein the positive electrode material further comprises an electrically conductive material, a binder, a salt, an ionic organic compound, an ionic bifunctional molecule, and / or inorganic particles.

72. The electrochemical cell according to any one of claims 66 to 71, wherein the negative electrode comprises a negative electrode material containing a negative electrode electrochemical active material.

73. The electrochemical cell according to claim 72, wherein the negative electrode material is located on the current collector.

74. The electrochemical cell according to claim 72 or 73, wherein the negative electrode electrochemical active material includes a metal film comprising an alkali metal or an alkaline earth metal, or an alloy containing an alkali metal or an alkaline earth metal.

75. The electrochemical cell according to claim 74, wherein the alkali metal is selected from lithium and sodium.

76. The negative electrode electrochemical active material 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 sulfides, 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 (SiO ｘ -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO ｘ ), tin oxide-carbon composite (SnO ｘ -C), and any combination thereof, as described in claim 72 or 73.

77. 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 a combination 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 (e.g., 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 a combination thereof) (e.g., lithium titanate (e.g., Li ４ Ti ５ O １２ ) or lithium molybdenum oxide (e.g., Li ２ Mo ４ O １３ An electrochemical cell according to claim 76, selected from the compounds of )).

78. The electrochemical cell according to claim 76 or 77, wherein the negative electrode material further comprises an electrically conductive material, a binder, a salt, an ionic organic compound, an ionic bifunctional molecule, and / or inorganic particles.

79. An electrochemical battery comprising at least one electrochemical cell according to any one of claims 66 to 78.

80. The electrochemical battery according to claim 79, wherein the electrochemical battery is selected from the group consisting of lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, potassium-ion batteries, magnesium batteries, and magnesium-ion batteries.

81. The electrochemical battery according to claim 80, wherein the electrochemical battery is a lithium battery.

82. The electrochemical battery according to claim 80, wherein the electrochemical battery is a lithium-ion battery.

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