Electrolytic solution for nonaqueous electrolytic solution secondary batteries and nonaqueous electrolytic solution secondary battery

Patent metadata

Field	Value
Publication number	US-11114693-B2
Application number	US-201615751760-A
Country	US
Kind code	B2
Filing date	Jun 27, 2016
Priority date	Aug 12, 2015
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

A nonaqueous electrolytic solution contains a nonaqueous solvent and an electrolyte dissolved in the solvent. The solution includes a difluoro ionic complex (1-Cis) in a cis conformation represented by the formula (1-Cis), and at least one of cyclic sulfonic acid ester, cyclic sulfonic acid ester having an unsaturated bond, cyclic sulfuric acid ester, cyclic disulfonic acid ester, chain disulfonic acid ester, cyclic disulfonic acid anhydride, nitrile group-containing compound, silyl phosphate ester derivative, and silyl borate ester derivative.

First claim

The invention claimed is:

1. An electrolytic solution for nonaqueous electrolytic solution secondary batteries, the electrolytic solution comprising:
a nonaqueous solvent,
an electrolyte dissolved in the nonaqueous solvent,
(I) a difluoro ionic complex (1) represented by the general formula (1), and
(II) at least one compound selected from the group consisting of cyclic sulfonic acid ester, cyclic sulfonic acid ester having an unsaturated bond, cyclic sulfuric acid ester, cyclic disulfonic acid ester, chain disulfonic acid ester, cyclic disulfonic acid anhydride, nitrile group-containing compound, silyl phosphate ester derivative, and silyl borate ester derivative:
wherein 95 mol % or more of the difluoro ionic complex (1) is a difluoro ionic complex (1-Cis) in a cis conformation represented by the general formula (1-Cis),

wherein in (1-Cis),

wherein in the general formulas (1) and (1-Cis), A + is any one selected from the group consisting of a metal ion, a proton, and an onium ion, and M is any one selected from the group consisting of Si, P, As, and Sb;
F is a fluorine atom; O is an oxygen atom;
t is 2 when M is Si, and t is 1 when M is P, As, or Sb;
X is an oxygen atom or —N(R 1 )—; N is a nitrogen atom; R 1 is a hydrocarbon group having 1 to 10 carbon atoms and optionally having a hetero atom and/or a halogen atom (the hydrocarbon group optionally having a branched-chain or ring structure when the number of carbon atoms is 3 or more);
when X is —N(R 1 )—, and p is 0, X and W are bonded directly and optionally form a structure as shown in the general formulas (1-Cis-1) to (1-Cis-3) below; in the case of the general formula (1-Cis-2) below where the direct bond is a double bond, R 1 is not present;
Y is a carbon atom or a sulfur atom; q is 1 when Y is a carbon atom, and q is 1 or 2 when Y is a sulfur atom;
W represents a hydrocarbon group having 1 to 10 carbon atoms and optionally having a hetero atom and/or a halogen atom (the hydrocarbon group optionally having a branched-chain or ring structure when the number of carbon atoms is 3 or more), or —N(R 2 )—; wherein, R 2 represents a hydrogen atom, an alkaline metal, or a hydrocarbon group having 1 to 10 carbon atoms and optionally having a hetero atom and/or a halogen atom; when the number of carbon atoms is 3 or more, R 2 optionally has a branched-chain or ring structure; and
p is 0 or 1, q is an integer of 0 to 2, r is an integer of 0 to 2, and p+r≥1:

2. The electrolytic solution according to claim 1 , wherein in a case where the compound stated in the (II) comprises the cyclic sulfonic acid ester, the cyclic sulfonic acid ester is represented by the formula (II-1a),
in a case where the compound stated in the (II) comprises the cyclic sulfonic acid ester having an unsaturated bond, the cyclic sulfonic acid ester having an unsaturated bond is represented by the formula (II-1b),
in a case where the compound stated in the (II) comprises the cyclic sulfuric acid ester, the cyclic sulfuric acid ester is represented by the formulae (II-2a) and/or (II-2b),
in a case where the compound stated in the (II) comprises the cyclic disulfonic acid ester, the cyclic disulfonic acid ester is represented by any one or more of the groups selected from the formulae (II-3a), (II-3b), and (II-3c),
in a case where the compound stated in the (II) comprises the chain disulfonic acid ester, the chain disulfonic acid ester is represented by the formulae (II-4a) and/or (II-4b),
in a case where the compound stated in the (II) comprises the cyclic disulfonic acid anhydride, the cyclic disulfonic acid anhydride is represented by the formula (II-5a),
in a case where the compound stated in the (II) comprises the nitrile group-containing compound, the nitrile group-containing compound is represented by the formula (II-6a),
in a case where the compound stated in the (II) comprises the silyl phosphate ester derivative, the silyl phosphate ester derivative is represented by the formula (II-7a), and
in a case where the compound stated in the (II) comprises the silyl borate ester derivative, the silyl borate ester derivative is represented by the formula (II-7b):

wherein in the formula (II-1a), O represents an oxygen atom, S represents a sulfur atom, n 1 is an integer of 0 or more and 2 or less, and R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted fluoroalkyl group having 1 to 4 carbon atoms;

wherein in the formula (II-1b), O represents an oxygen atom, S represents a sulfur atom, n 2 is an integer of 1 or more and 3 or less, and R 9 , R 10 , R 11 , and R 12 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluoroalkyl group having 1 to 4 carbon atoms;

wherein in the formula (II-2a), O represents an oxygen atom, S represents a sulfur atom, C represents a carbon atom, n 3 is an integer of 0 or more and 1 or less, and R 13 , R 14 , R 15 , and R 16 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 5 carbon atoms, or a substituted or unsubstituted fluoroalkyl group having 1 to 4 carbon atoms, provided that R 13 or R 14 and R 15 or R 16 optionally form a single bond with each other when n 3 is 0;

wherein in the formula (II-2b), O represents an oxygen atom, S represents a sulfur atom, C represents a carbon atom, n 4 and n 5 are each an integer of 0 or more and 1 or less, and R 17 , R 18 , R 19 , and R 20 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluoroalkyl group having 1 to 4 carbon atoms;

wherein in the formula (II-3a), O represents an oxygen atom, S represents a sulfur atom, n 6 is an integer of 0 or more and 4 or less, and R 21 and R 22 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R 23 and R 24 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluoroalkyl group having 1 to 4 carbon atoms, and n 60 is an integer of 0 or more and 4 or less;

wherein in the formula (II-3b), O represents an oxygen atom, S represents a sulfur atom, n 7 is an integer of 0 to 3, and R 25 and R 26 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5

Assignees

• Central Glass Co Ltd

Inventors

• Itabashi Saori
• Kawabata Wataru
• Suzuki Katsutoshi
• Takeda Kazunari

Classifications

• H01M50/417

  Polyolefins · CPC title

• H01M50/429

  Natural polymers · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title

• H01M4/48

  of inorganic oxides or hydroxides · CPC title

• H01M2300/002

  Inorganic electrolyte · CPC title