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EP-4738517-A1 - NONAQUEOUS ELECTROLYTE SOLUTION AND NONAQUEOUS ELECTROLYTE BATTERY

EP4738517A1EP 4738517 A1EP4738517 A1EP 4738517A1EP-4738517-A1

Abstract

A nonaqueous electrolyte solution which contains (1) a compound represented by the general formula (1) described in the specification, (11) a solute, (111) a nonaqueous organic solvent, and hydrogen fluoride, in which a concentration of the hydrogen fluoride with respect to a total amount of the nonaqueous electrolyte solution is 0.1 ppm by mass or more and 180 ppm by mass or less, and a nonaqueous electrolyte solution battery including the nonaqueous electrolyte solution.

Inventors

  • ESAKI, Ryota
  • TERADA, RYOSUKE
  • TOKOMOTO, Junichi
  • KAWABATA, Wataru
  • TAKAHASHI, MIKIHIRO

Assignees

  • Central Glass Company, Limited

Dates

Publication Date
20260506
Application Date
20240726

Claims (19)

  1. A nonaqueous electrolyte solution, comprising: (I) a compound represented by the following general formula (1): wherein in the general formula (1), R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, and X represents an oxygen atom, a sulfur atom, or an SO 2 group; (II) a solute; (III) a nonaqueous organic solvent; and hydrogen fluoride, wherein a concentration of the hydrogen fluoride with respect to a total amount of the nonaqueous electrolyte solution is 0.1 ppm by mass or more and 180 ppm by mass or less.
  2. The nonaqueous electrolyte solution according to claim 1, further comprising (IV) at least one compound selected from the group consisting of the following compounds (2) to (9): a compound (2): at least one compound selected from the group consisting of a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2), wherein in the general formula (2-1), R 21 and R 22 are each independently a fluorine atom or an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and/or an unsaturated bond may be present in the organic group, and the general formula (2-1) includes at least one P-F bond, and in the general formula (2-2), X 21 is a fluorine atom or an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one fluorine atom, and an oxygen atom and/or an unsaturated bond may be present in the organic group, and in the general formula (2-1) and the general formula (2-2), M 1 m+ is a proton, a metal cation, or an onium cation, and m represents a valence of the corresponding cation; a compound (3): at least one compound selected from the group consisting of a compound represented by the following general formula (3-1), a compound represented by the following general formula (3-2), and a compound represented by the following general formula (3-3), wherein in the general formulae (3-1) to (3-3), R 31 to R 36 are each independently a fluorine atom or an organic group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and/or an unsaturated bond may be present in the organic group, X 31 to X 33 are each independently a fluorine atom or an organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, and/or an unsaturated bond may be present in the organic group, the general formula (3-1) includes at least one P-F bond, the general formula (3-2) includes at least one of a P-F bond and an S-F bond, the general formula (3-3) includes at least one S-F bond, and M 1 m+ is a proton, a metal cation, or an onium cation, and m represents a valence of the corresponding cation; a compound (4): at least one compound selected from the group consisting of a compound represented by the following general formula (4-1) and a compound represented by the following general formula (4-2), wherein in the general formula (4-1), W 1 represents a boron atom, a phosphorus atom, or a silicon atom, n1 is 0 to 3, n2 is 0 to 4, p is 0 or 1, R 41 represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (wherein the groups may contain a substituent or may contain a heteroatom in the structures thereof, and when n1 is 2 or more, the n1 R 41 's may be bonded to each other), R 42 represents a halogen atom, Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom, Y 3 represents a carbon atom or a sulfur atom, q oxo group (=O) is bonded to the carbon atom or the sulfur atom represented by Y 3 , q is 1 when Y 3 is a carbon atom, q is 1 or 2 when Y 3 is a sulfur atom, M a+ represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, a represents a valence of the corresponding cation, and a to d are each 1 or 2 and satisfy a × b = c × d, wherein in the general formula (4-2), R 43 represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (wherein the groups may contain a substituent or may contain a heteroatom in the structures thereof), r is 0 or 1, Y 4 represents a carbon atom or a sulfur atom, s oxo group (=O) is bonded to the carbon atom or the sulfur atom represented by Y 4 , s is 1 when Y 4 is a carbon atom, s is 1 or 2 when Y 4 is a sulfur atom, W 2 represents a boron atom or a phosphorus atom, R 44 represents a halogen atom, n3 is 2 when W 2 is the boron atom, and n3 is 4 when W 2 is the phosphorus atom; a compound (5): a compound represented by the following general formula (5), wherein in the general formula (5), R 51 's each independently represent a group having a carbon-carbon unsaturated bond, when there are a plurality of R 52 's, R 52 's each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms, the alkyl group may have at least one of a fluorine atom and an oxygen atom, and v represents an integer of 2 to 4; a compound (6): a compound represented by the following general formula (6), wherein in the general formula (6), R 61 and R 62 each independently represent a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group, any hydrogen atom of the alkyl group, the alkenyl group, and the aryl group represented by R 61 and R 62 may be substituted with a halogen atom, and n6 is 0 or 1; a compound (7): at least one compound selected from the group consisting of a compound represented by the following general formula (7-1) and a compound represented by the following general formula (7-2), wherein in the general formula (7-1), R 70 to R 73 each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms, and n71 represents an integer of 1 to 3, and in the general formula (7-2), R 74 to R 79 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms, and n72 represents an integer of 0 to 2; a compound (8): a compound represented by the following general formula (8), wherein in the general formula (8), R 81 represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom may be included in a carbon atom-carbon atom bond in the alkylene group, any hydrogen atom of the alkylene group may be substituted with an alkyl group, and any hydrogen atom of the alkylene group and the alkyl group may be substituted with a halogen atom; and a compound (9): a compound represented by the following general formula (9), wherein in the general formula (9), R 91 and R 92 each independently represent an alkyl group having 1 to 6 carbon atoms.
  3. The nonaqueous electrolyte solution according to claim 1, wherein the concentration of the hydrogen fluoride with respect to the total amount of the nonaqueous electrolyte solution is 1 ppm by mass or more and 70 ppm by mass or less.
  4. The nonaqueous electrolyte solution according to claim 1, wherein a content of the (I) with respect to the total amount of the nonaqueous electrolyte solution is 0.01% by mass or more and 10% by mass or less.
  5. The nonaqueous electrolyte solution according to claim 1, wherein a content of the (IV) with respect to the total amount of the nonaqueous electrolyte solution is 0.01% by mass or more and 10% by mass or less.
  6. The nonaqueous electrolyte solution according to claim 1, wherein the compound represented by the general formula (1) is at least one compound selected from the group consisting of diglycolic anhydride, methyldiglycolic anhydride, dimethyldiglycolic anhydride, ethyldiglycolic anhydride, vinyldiglycolic anhydride, tetrafluorodiglycolic anhydride, allyldiglycolic anhydride, thiodiacetic anhydride, and sulfodiacetic anhydride.
  7. The nonaqueous electrolyte solution according to claim 2, wherein the compound (2) is at least one compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, and lithium trifluoromethanesulfonate.
  8. The nonaqueous electrolyte solution according to claim 2, wherein the compound (3) is at least one compound selected from the group consisting of lithium bis(fluorosulfonyl)imide, lithium (fluorosulfonyl)(difluorophosphoryl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(difluorophosphoryl)imide, lithium bis(pentafluoroethanesulfonyl)imide, and lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide.
  9. The nonaqueous electrolyte solution according to claim 2, wherein the compound (4) is at least one compound selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium tris(oxalato)phosphate, lithium difluorobis(oxalato)phosphate, lithium tetrafluoro(oxalato)phosphate, lithium difluoro(malonato)borate, lithium tetrafluoro(malonato)phosphate, tetrafluoro(picolinato)phosphate, and difluoro(picolinato)borate.
  10. The nonaqueous electrolyte solution according to claim 2, wherein the compound (5) is at least one compound selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane.
  11. The nonaqueous electrolyte solution according to claim 2, wherein the compound (6) is at least one compound selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide and 1,3,2-dioxathiane-2,2-dioxide.
  12. The nonaqueous electrolyte solution according to claim 2, wherein the compound (8) is at least one compound selected from the group consisting of 1,2-ethanedisulfonic anhydride and 1,3-propanedisulfonic anhydride.
  13. The nonaqueous electrolyte solution according to claim 2, wherein the compound (9) is at least one compound selected from the group consisting of methanesulfonic anhydride and ethanesulfonic anhydride.
  14. The nonaqueous electrolyte solution according to claim 1, wherein the (II) is at least one selected from the group consisting of LiPF 6 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiCl, and Lil or at least one selected from the group consisting of NaPF 6 , NaSbF 6 , NaAsF 6 , NaClO 4 , NaAlO 2 , NaAlCl 4 , NaCl, and Nal.
  15. The nonaqueous electrolyte solution according to claim 1, wherein the (III) contains at least one selected from the group consisting of a cyclic ester, a chain ester, a cyclic ether, a chain ether, a sulfone compound, a sulfoxide compound, and an ionic liquid.
  16. The nonaqueous electrolyte solution according to claim 15, wherein the cyclic ester is a cyclic carbonate, and the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.
  17. The nonaqueous electrolyte solution according to claim 15, wherein the chain ester is a chain carbonate, and the chain carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.
  18. A nonaqueous electrolyte solution battery, at least comprising: a positive electrode; a negative electrode; a separator; and the nonaqueous electrolyte solution according to any one of claims 1 to 17.
  19. A method for decreasing the initial resistance of a nonaqueous electrolyte solution battery including a nonaqueous electrolyte solution, comprising: using, as the nonaqueous electrolyte solution, a nonaqueous electrolyte solution containing (I) a compound represented by the following general formula (1): wherein in the general formula (1), R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, and X represents an oxygen atom, a sulfur atom, or an SO 2 group (II) a solute, (III) a nonaqueous organic solvent, and hydrogen fluoride; and adjusting a concentration of the hydrogen fluoride with respect to a total amount of the nonaqueous electrolyte solution to 0.1 ppm by mass or more and 180 ppm by mass or less.

Description

TECHNICAL FIELD The present disclosure relates to a nonaqueous electrolyte solution and a nonaqueous electrolyte solution battery. BACKGROUND ART In recent years, there is a rapidly increasing demand for batteries that have a high capacity, high output, and a high energy density and that can be mounted as an auxiliary power source for electric vehicles, hybrid vehicles, and fuel-cell vehicles in addition to a power storage system for a compact and high energy density application, such as information-related devices and communication devices, that is, personal computers, video cameras, digital cameras, mobile phones, and smartphones. In addition, there is an increasing demand for batteries that can be used for a long period of time even in power storage systems for large and power applications such as power storage. Nonaqueous electrolyte solution batteries such as lithium secondary batteries have been actively developed as candidates for these various power storage systems. A nonaqueous electrolyte solution battery generally includes a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte solution. Patent Literature 1 proposes improving the residual characteristics and the suppression of an increase in resistance during high-temperature storage by using an electrolyte solution in which hydrofluoric acid is added, as an additive, to diglycolic anhydride. Patent Literature 2 proposes to improve the cycle characteristics by using an acid anhydride having a specific ring structure and a carbonate having a fluorine atom in an electrolyte solution. Patent Literature 3 proposes to improve the cycle characteristics and the low-temperature characteristics by using a silicon compound in an electrolyte solution. Patent Literature 4 proposes to improve the storage characteristics by using a nonaqueous electrolyte solution containing lithium bis(fluorosulfonyl)imide as a solute. Patent Literature 5 proposes to suppress self-discharge and improve the storage characteristics after charging by using lithium monofluorophosphate or lithium difluorophosphate in an electrolyte solution. Patent Literature 6 proposes using a fluorosulfonic acid salt in a nonaqueous electrolyte solution to maintain high input/output characteristics and impedance characteristics even after a durability test. Patent Literature 7 proposes that the decomposition on the carbon negative electrode with the progress of charge-discharge cycles can be suppressed by using a cyclic sulfate ester in a nonaqueous electrolyte solution. Patent Literature 8 proposes that the reductive decomposition of the electrolyte solution during high-temperature storage is greatly suppressed and that, as a result, a battery having low self-discharge, in which deterioration of load characteristics and resistance is significantly suppressed and in which the amount of gas generated in the battery is low can be obtained by using a cyclic sultone (unsaturated sultone) in a nonaqueous electrolyte solution. Patent Literature 9 proposes to improve the charge-discharge efficiency and cycle characteristics by using a sulfonic anhydride in an electrolyte solution. CITATION LIST PATENT LITERATURE Patent Literature 1: JP2002-008717APatent Literature 2: JP5412705BPatent Literature 3: JP3497812BPatent Literature 4: JP4847675BPatent Literature 5: JP3439085BPatent Literature 6: JP5353923BPatent Literature 7: JP3760540BPatent Literature 8: JP4190162BPatent Literature 9: JP4379567B SUMMARY OF INVENTION TECHNICAL PROBLEM Patent Literature 1 discloses that when 0.1% by weight of hydrogen fluoride is contained in a nonaqueous electrolyte solution, the high-temperature storage characteristics of a secondary battery including the nonaqueous electrolyte solution are improved. However, the studies by the present disclosers have revealed that the secondary battery described in Patent Literature 1 has a problem of high initial resistance. The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a nonaqueous electrolyte solution capable of lowering the initial resistance of a nonaqueous electrolyte solution battery and a nonaqueous electrolyte solution battery having low initial resistance. SOLUTION TO PROBLEM As a result of intensive studies to solve such a problem, the present disclosers have found that a nonaqueous electrolyte solution battery having low initial resistance can be provided when a concentration of hydrogen fluoride is reduced to less than one fifth of the concentration described in Patent Literature 1 in a nonaqueous electrolyte solution containing a specific acid anhydride compound, a nonaqueous organic solvent, and a solute. Specifically, the above problem can be solved by the following configuration. [1] A nonaqueous electrolyte solution containing (I) a compound represented by the following general formula (1), (II) a solute, (III) a nonaqueous organic solvent, and hydrogen fluoride in which a concentr