Nonaqueous electrolyte solution and electricity storage device using same

Patent metadata

Field	Value
Publication number	US-9934911-B2
Application number	US-201414781792-A
Country	US
Kind code	B2
Filing date	Mar 31, 2014
Priority date	Apr 1, 2013
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

The present invention provides a nonaqueous electrolytic solution capable of improving electrochemical characteristics in a broad temperature range and an energy storage device using the same. [1] A nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution containing, as an additive, an SO 4 group-containing compound having a specified structure and [2] an energy storage device including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, wherein the nonaqueous electrolytic solution contains, as an additive, 0.001% by mass or more and less than 5% by mass of an SO 4 group-containing compound having a specified structure in the nonaqueous electrolytic solution, are disclosed.

First claim

The invention claimed is:

1. A nonaqueous electrolytic solution, comprising:
an electrolyte salt dissolved in a nonaqueous solvent; and
as an additive, at least one SO 4 group-containing compound selected from the group consisting of compounds represented by the following formulae (I) to (IV):

wherein:
L 1 represents an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, a linear or cyclic ester group having 3 to 18 carbon atoms, a sulfur atom-containing organic group having 1 to 6 carbon atoms, a silicon atom-containing organic group having 4 to 10 carbon atoms, a cyano group-containing organic group having 2 to 7 carbon atoms, a phosphorus atom-containing organic group having 2 to 12 carbon atoms, a —P(═O)F 2 group, an alkylcarbonyl group having 2 to 7 carbon atoms, or an arylcarbonyl group having 7 to 13 carbon atoms,
provided that each of the alkyl group, the alkoxyalkyl group, the alkenyl group, the alkynyl group, and the alkylcarbonyl group is straight-chain or branched, and in each of the alkyl group, the alkoxyalkyl group, the aryl group, the ester group, the sulfur atom-containing organic group, the phosphorus atom-containing organic group, the alkylcarbonyl group, and the arylcarbonyl group, at least one hydrogen atom may be substituted with a halogen atom;
L 2 represents a p-valent hydrocarbon connecting group optionally comprising contain an ether bond, a thioether bond, or an —S(═O) 2 bond, provided that at least one hydrogen atom which L 2 has may be substituted with a halogen atom;
p is an integer of 2 to 4;
L 4 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a —CR 41 R 42 C(═O)OR 43 group, or an aryl group having 6 to 12 carbon atoms,
X represents an SiR 44 R 45 group, an alkali metal belonging to the third or fourth period of the Periodic Table, or an alkaline earth metal belonging to the third or fourth period of the Periodic Table;
r is an integer of 1 or 2, provided that when X is an alkali metal belonging to the third or fourth period of the Periodic Table, then r is 1, and when X is an SiR 44 R 45 group or an alkaline earth metal belonging to the third or fourth period of the Periodic Table, then r is 2;
each of R 41 and R 42 independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
R 43 represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 3 to 6 carbon atoms;
each of R 44 and R 45 independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or an aryl group having 6 to 8 carbon atoms; and
in each of the alkyl group and the aryl group represented by L 4 and the alkyl group represented by each of R 41 to R 43 , at least one hydrogen atom may be substituted with a halogen atom.

2. The nonaqueous electrolytic solution according to claim 1 , wherein a content of the SO 4 group-containing compound in the nonaqueous electrolytic solution is 0.001 to 5% by mass in total.

3. The nonaqueous electrolytic solution according to claim 1 , wherein the SO 4 group-containing compound is a compound represented by formula (I-1) or (I-2):

wherein:
L 11 represents an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, provided that in each of the alkyl group, the alkoxyalkyl group, and the aryl group may be straight-chain or branched; and
L 12 represents a straight-chain or branched alkenyl group having 2 to 7 carbon atoms, a straight-chain or branched alkynyl group having 3 to 8 carbon atoms, a linear or cyclic ester group having 3 to 18 carbon atoms, a linear or cyclic carbonate group having 3 to 18 carbon atoms, a sulfur atom-containing organic group having 1 to 6 carbon atoms, a silicon atom-containing organic group having 4 to 10 carbon atoms, a cyano group-containing organic group having 2 to 7 carbon atoms, a phosphorus atom-containing organic group having 2 to 12 carbon atoms, a —P(═O)F 2 group, an alkylcarbonyl group having 2 to 7 carbon atoms, or an arylcarbonyl group having 7 to 13 carbon atoms, provided that each of the alkylcarbonyl group is straight-chain or branched.

4. The nonaqueous electrolytic solution according to claim 3 , comprising the SO 4 group-containing compound represented by formula (I-1), which is at least one selected from the group consisting of lithium methyl sulfate, lithium ethyl sulfate, lithium propyl sulfate, lithium butyl sulfate, lithium isopropyl sulfate, lithium sec-butyl sulfate, lithium methoxyethyl sulfate, lithium ethoxyethyl sulfate, lithium methoxypropyl sulfate, lithium phenyl sulfate, and lithium 4-methylphenyl sulfate.

5. The nonaqueous electrolytic solution according to claim 3 , comprising the SO 4 group-containing compound represented by formula (I-2), which is at least one selected from the group consisting of lithium vinyl sulfate, lithium allyl sulfate, lithium propargyl sulfate, lithium 1-oxo-1-ethoxypropan-2-yl sulfate, lithium 1-oxo-1-(2-propynyloxy)propan-2-yl sulfate, lithium 2-(acryloyloxy)ethyl sulfate, lithium 2-(methacryloyloxy)ethyl sulfate, lithium 2-((methoxycarbonyl)oxy)ethyl sulfate, lithium (2-oxo-1,3-dioxolan-4-yl)methyl sulfate, lithium 2-(methanesulfonyl)ethyl sulfate, lithium methanesulfonyl sulfate, lithium 2-(trimethylsilyl)ethyl sulfate, lithium 2-cyanoethyl sulfate, lithium 1,3-dicyanopropynyl 2-sulfate, lithium (diethoxyphosphoryl)methyl sulfate, lithium diethoxyphosphoryl sulfate, lithium dibutoxyphosphoryl sulfate, and lithium difluorophosphoryl sulfate.

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

7. The nonaqueous electrolytic solution according to claim 6 , wherein the cyclic carbonate comprises at least one selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, and a cyclic carbonate having a carbon-carbon unsaturated bond or a fluorine atom.

8. The nonaqueous electrolytic solution according to claim 7 , wherein the cyclic carbonate comprises a cyclic carbonate having a carbon-carbon unsaturated bond which is at least one selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one.

9. The nonaqueous electrolytic solution according to claim 7 , wherein the cyclic carbonate comprises a cyclic carbonate having a fluorine atom which is at one selected from the group consisting of 4-fluoro-1,3-dioxolan-2-one, and trans-4,5-difluoro-1,3-dioxolan-2-one and cis-4,5-difluoro-1,3-dioxolan-2-one.

10. The nonaqueous electrolytic solution according to claim 6 , wherein the nonaqueous solvent comprises a linear carbonate which is a symmetric linear carbonate or an asymmetric linear carbonate.

11. The nonaqueous electrolytic solution according to claim 10 , wherein the nonaqueous solvent comprises an asymmetric linear carbonate which is at least one selected from the group consisting of

Assignees

• Ube Industries

Inventors

• Shimamoto Kei
• Abe Koji
• Kotou Yuichi
• Shikita Shoji

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• H01G11/58

  Liquid electrolytes · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• Y02E60/13

  Energy storage using capacitors · CPC title