Non-aqueous electrolyte, power storage device using same, and lithium salt used for same

Patent metadata

Field	Value
Publication number	US-2017271091-A1
Application number	US-201515309840-A
Country	US
Kind code	A1
Filing date	May 13, 2015
Priority date	May 14, 2014
Publication date	Sep 21, 2017
Grant date	—

Abstract

A nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution containing a lithium salt having a specific α,β-dihydroxy carboxylic acid ester structure, phosphono hydroxy carboxylic acid structure, alkoxycarbonyl hydroxy carboxylic acid structure, or formyloxy structure; an energy storage device using the nonaqueous electrolytic solution; and a lithium salt used for the nonaqueous electrolytic solution. This nonaqueous electrolytic solution makes it possible not only to improve the electrochemical characteristics when the energy storage device is used at a high temperature and a high voltage and to improve the capacity retention rate after high-voltage and high-temperature storage, but also to suppress gas generation.

First claim

1 : A nonaqueous electrolytic solution that comprises an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution comprising:
one or more selected from the group consisting of lithium salts represented by formula (I), (III), or (IV):

wherein R 1 , R 5 , and R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or —C(═O)—OR 9 group, R 2 , R 3 , R 6 , and R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, C(R 5 )(R 6 ) and C(R 7 )(R 8 ) may each independently represents C(═O), R 4 and R 9 each independently represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and L represents a single bond or an alkylene group having 1 to 4 carbon atoms, provided that at least one hydrogen atom of the alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, or the alkylene group may be substituted with a halogen atom; and
M represents a boron atom or phosphorus atom, m represents 0 or 1, and n represents 0, 2, or 4, provided that in a case where M is a boron atom, 2m+n=2 and in a case where M is a phosphorus atom, 2m+n=4:

wherein R 11 and R 13 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a —C(═O)—OR 1′ group, a —P(═O)(—OR 16 ) (—OR 17 ) group, a —P(═O)(—R 18 ) (—OR 19 ) group, or a —P(═O)(—R 20 ) (—R 21 ) group, R 14 represents —C(═O)—ORS group, a —P(═O)(—OR 16 ) (—OR 17 ) group, a —P(═O)(—R 18 ) (—OR 19 ) group, or a —P(═O)(—R 20 ) (—R 21 ) group, C(R 11 )(R 12 ) may represent C(═O), R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 each independently represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and L represents a single bond or an alkylene group having 1 to 4 carbon atoms, provided that at least one hydrogen atom of the alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, or the alkylene group may be substituted with a halogen atom; and
M represents a boron atom or phosphorus atom, q represents 0 or 1, and r represents 0, 2, or 4, provided that in a case where M is a boron atom, 2q+r=2 and in a case where M is a phosphorus atom, 2q+r=4:

wherein R 31 and R 32 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, C(R 31 )(R 32 ) may represent C(═O), L represents a single bond or an alkylene group having 1 to 4 carbon atoms, M represents a boron atom or phosphorus atom, s represents an integer of 0 to 2, t represents an integer of 0 to 5, and u represents an integer of 1 to 6, provided that at least one hydrogen atom of the alkyl group or the alkylene group may be substituted with a halogen atom, in a case where M is a boron atom, s=1 and 2s+t+u=4, and in a case where M is a phosphorus atom, 2s+t+u=6.

2 : The nonaqueous electrolytic solution according to claim 1 , wherein the lithium salt represented by the general formula (I) is one or more selected from the group consisting of lithium bis(dimethyl-2,3-di(hydroxy-kO) butane dioate) borate, lithium bis(diethyl-2,3-di(hydroxy-kO) butane dioate) borate, lithium (dimethyl-2,3-di(hydroxy-kO) butane dioate) (oxalate) borate, lithium (diethyl-2,3-di(hydroxy-kO) butane dioate) (oxalate) borate, lithium difluoro(dimethyl-2,3-di(hydroxy-kO) butane dioate) borate, lithium (diethyl-2,3-di(hydroxy-kO) butane dioate) difluoroborate, lithium bis(dimethyl-2,3-di(hydroxy-kO) butane dioate) difluorophosphate, lithium bis(diethyl-2,3-di(hydroxy-kO) butane dioate) difluorophosphate, lithium difluoro(dimethyl-2,3-di(hydroxy-kO) butane dioate) (oxalate) phosphate, lithium difluoro(diethyl-2,3-di(hydroxy-kO) butane dioate) (oxalate) phosphate, lithium (dimethyl-2,3-di(hydroxy-kO) butane dioate) tetrafluorophosphate, and lithium (diethyl-2,3-di(hydroxy-kO) butane dioate) tetrafluorophosphate.

3 : The nonaqueous electrolytic solution according to claim 1 , wherein the lithium salt represented by the general formula (III) is one or more selected from the group consisting of lithium bis(1-dimethoxyphosphoryl-2-oxo-ethanediolate) borate, lithium bis(1-diethoxyphosphoryl-2-oxo-ethanediolate) borate, lithium (1-dimethoxyphosphoryl-2-oxo-ethanediolate) (oxalate) borate, lithium (1-diethoxyphosphoryl-2-oxo-ethanediolate) (oxalate) borate, lithium (1-(di(2,2,2-trifluoroethoxy) phosphoryl)-2-oxo-ethanediolate) (oxalate) borate, lithium difluoro(1-dimethoxyphosphoryl-2-oxo-ethanediolate) borate, lithium (1-diethoxyphosphoryl-2-oxo-ethanediolate) difluoroborate, lithium (1-methoxycarbonyl-2-oxo-ethanediolate) (oxalate) borate, lithium (1-ethoxycarbonyl-2-oxo-ethanediolate) (oxalate) borate, lithium (1-((2,2,2-trifluoroethoxy) carbonyl)-2-oxo-ethanediolate) (oxalate) borate, lithium bis(1-dimethoxyphosphoryl-2-oxo-ethanediolate) difluorophosphate, lithium bis(1-diethoxyphosphoryl-2-oxo-ethanediolate) difluorophosphate, lithium difluoro(1-dimethoxyphosphoryl-2-oxo-ethanediolate) (oxalate) phosphate, lithium (1-diethoxyphosphoryl-2-oxo-ethanediolate) (oxalate) difluorophosphate, lithium difluoro(1-(di(2,2,2-trifluoroethoxy) phosphoryl)-2-oxo-ethanediolate) (oxalate) phosphate, lithium (1-dimethoxyphosphoryl-2-oxo-ethanediolate) tetrafluorophosphate, lithium (1-diethoxyphosphoryl-2-oxo-ethanediolate) tetrafluorophosphate, lithium (1-methoxycarbonyl-2-oxo-ethanediolate) (oxalate) difluorophosphate, lithium (1-ethoxycarbonyl-2-oxo-ethanediolate) (oxalate) difluorophosphate, and lithium (1-((2,2,2-trifluoroethoxy) carbonyl)-2-oxo-ethanediolate) (oxalate) difluorophosphate.

4 : The nonaqueous electrolytic solution according to claim 1 , wherein the lithium salt represented by the general formula (IV) is one or more selected from the group consisting of lithium bis(formyloxy) (oxalate) borate, lithium bis(formyloxy) (malonate) borate, or lithium bis(formyloxy) (2,2-difluoromalonate) borate, lithium formyloxypentafluorophosphate, lithium tetrakis(formyloxy) (oxalate) phosphate, lithium bis(formyloxy) bis(oxalate) phosphate, lithium tetrakis(formyloxy) (malonate) phosphate, and lithium bis(formyloxy) bis(malonate) phosphate.

5 : The nonaqueous electrolytic solution according to claim 1 , comprising: 0.001 to 10% by mass of one or more selected from the group consisting of at least one lithium salt represented by general formula (I), (III), and (IV).

6 : The nonaqueous electrolytic solution according to claim 1 , wherein the nonaqueous solvent comprises a cyclic carbonate and a linear ester.

7 : The nonaqueous electrolytic solution according to claim 6 , wherein the cyclic carbonate comprises one or more selected from the group consisting of ethylene carbonate, propylene carbonate, 4-fluoro-1,3-dioxolan-2-one, vinylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one.

8 : The nonaqueous electrolytic solution according to claim 6 , comprising both symmetric linear carbonate and asymmetric linear carbonate as the linear ester, wherein a content of the symmetric linear carbonate is more than a content of the asymmetric linear carbonate.

Assignees

• Ube Industries

Inventors

• Abe Koji
• Shikita Shoji
• Chika Junichi
• Shimamoto Kei
• Sato Yosuke

Classifications

• H01G11/06 Primary

  with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC] · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01G11/64

  characterised by additives · CPC title

• C07F9/6596

  having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms · CPC title