Nonaqueous electrolyte solution and electricity storage device using same

Patent metadata

Field	Value
Publication number	US-2016027592-A1
Application number	US-201414781792-A
Country	US
Kind code	A1
Filing date	Mar 31, 2014
Priority date	Apr 1, 2013
Publication date	Jan 28, 2016
Grant date	—

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

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 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;
ρ is an integer of 2 to 4;
each of R 31 to R 33 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;
q is an integer of 1 to 4;
when q is 1, then R 31 may be —OSO 3 —R 37 , and R 37 is synonymous with R 31 ;
when q is 1, then L 3 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 34 R 35 C(═O)OR 36 group, or an aryl group having 6 to 12 carbon atoms;
when q is 2 to 4, then L 3 represents a q-valent hydrocarbon connecting group which may contain an ether bond, a thioether bond, or an —S(═O) 2 — bond;
each of R 34 and R 35 independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and R 36 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;
in each of the alkyl group and the aryl group represented by L 3 and the alkyl group represented by each of R 34 to R 36 , at least one hydrogen atom may be substituted with a halogen atom;
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 C 42 C(═O)OR 43 group, or an aryl group having 6 to 12 carbon atoms,
X represents an SiR 44 R 45 group, a quaternary onium, 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 a quaternary onium or 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 , comprising the SO 4 group-containing compound represented by the general formula (I), which is a compound represented by formula (I-1), (I-2), or (I-3):

wherein:
L 11 represents an alkyl group having 1 to 12 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, at least one hydrogen atom may be substituted with a halogen atom;
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 alkenyl group, the alkynyl group, and the alkylcarbonyl group is straight-chain or branched, and in each of 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; and
L 13 represents an alkyl group having 1 to 12 carbon atoms, in which at least one hydrogen atom is substituted with a halogen atom, an alkoxyalkyl group having 2 to 12 carbon atoms, in which at least one hydrogen atom is substituted with a halogen atom, or an aryl group having 6 to 12 carbon atoms, in which at least one hydrogen atom is substituted with a halogen atom.

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 pentyl sulfate, lithium hexyl sulfate, lithium heptyl sulfate, lithium octyl sulfate, lithium isopropyl sulfate, lithium sec-butyl sulfate, lithium trifluoromethyl sulfate, lithium 2,2,2-trifluoroethyl sulfate, lithium 2,2,3,3-tetrafluoropropyl sulfate, lithium 1,1,1,3,3,3-hexafluoro-2-propyl sulfate, lithium methoxyethyl sulfate, lithium ethoxyethyl sulfate, lithium methoxypropyl sulfate, lithium phenyl sulfate, lithium 4-methylphenyl sulfate, lithium 4-fluorophenyl sulfate, and lithium perfluorophenyl sulfate.

5 . The nonaqueous electrolytic solution according to claim 3 , comprising the SO 4 group-containing compound repr

Assignees

• Ube Industries

Inventors

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

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title