Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery

Patent metadata

Field	Value
Publication number	US-11101499-B2
Application number	US-201716315076-A
Country	US
Kind code	B2
Filing date	Jul 4, 2017
Priority date	Jul 6, 2016
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

An object of the present invention is to provide a nonaqueous electrolytic solution and a nonaqueous electrolytic solution secondary battery capable of showing high output characteristics at a low temperature even after the battery is used to some extent, and capable of showing good high-rate properties, and further capable of improving safety of batteries. The nonaqueous electrolytic solution includes 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 a specific cyclic phosphazene compound, siloxane compound, aromatic compound, cyclohexene compound, phosphoric acid ester compound, fluorinated linear ether compound, fluorinated cyclic ether compound, and boric acid ester compound, and 95 mol % or more of the difluoro ionic complex (1) is a difluoro ionic complex (1-Cis) in a cis configuration represented by the general formula (1-Cis).

First claim

The invention claimed is:

1. A nonaqueous electrolytic solution for nonaqueous electrolytic solution secondary batteries, the nonaqueous 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 a cyclic phosphazene compound represented by the general formula (II-1) below, a siloxane compound represented by the general formula (II-2) below, an aromatic compound represented by the general formula (II-3) below, a cyclohexene compound represented by the general formula (II-4) below, a phosphoric acid ester compound represented by the general formula (II-5) below, a fluorinated linear ether compound represented by the general formula (II-6) below, a fluorinated cyclic ether compound represented by the general formula (II-7) below, and a boric acid ester compound represented by the general formula (II-8) below,
wherein 95 mol % or more of the difluoro ionic complex (1) is a difluoro ionic complex (1-Cis) in a cis configuration represented by the general formula (1-Cis),

wherein in (1-Cis),

wherein in the general formula (1) and the general formula (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; and 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 at least one selected from 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; 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;
p is 0 or 1, q is an integer of 0 to 2, r is an integer of 0 to 2, and further, p+r≥1,

wherein
in the general formula (II-1), R 1 to R 6 are each independently a substituent selected from the group consisting of a halogen atom, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms; n 1 is an integer of 1 to 10; and the alkyl group, the alkoxy group, and the aryloxy group optionally have a hetero atom and/or a halogen atom;
in the general formula (II-2), R 7 to R 12 are each independently a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms, said groups optionally having a hetero atom and/or a halogen atom; n 2 is an integer of 1 to 10; when n 2 is 2 or more, R 11 's and R 12 's independently are optionally the same as or different from one another; a group represented by OR 7 and a group represented by OR 8 are optionally bonded to each other to form a siloxane bond; and the siloxane compound represented by the general formula (II-2) includes a siloxane compound represented by the general formula (II-2′); and
in the general formula (11-2′), R 13 and R 14 are each independently a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms, said groups optionally having a hetero atom and/or a halogen atom; n 3 is an integer of 2 to 10; R 13 's and R 14 's independently are optionally the same as or different from one another;

wherein
in the general formula (II-3), R 15 to R 20 are each independently a substituent selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 12 carbon atoms; and at least two of R 15 to R 20 are optionally bonded to one another to form a ring; and
in the general formula (II-4), R 21 to R 24 are each independently a substituent selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 12 carbon atoms; and at least two of R 21 to R 24 are optionally bonded to one another to form a ring;

wherein
in the general formula (II-5), R 25 to R 27 are each independently a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms, said groups optionally having a hetero atom and/or a halogen atom; and any two or all of R 25 , R 26 , and R 27 are optionally bonded to one another to form a ring structure;
in the general formula (II-6), R 28 and R 29 are each independently a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated cycloalkyl group having 3 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and having an ethereal oxygen atom between the carbon atoms, and a fluorinated alkyl group having 1 to 10 carbon atoms and having an ethereal oxygen atom between the carbon atoms; and at least one of R 28 and R 29 contains a fluorine atom;
in the general formula (II-7), R 32 is a substituent selected from the group consisting of an alkylene group having 1 to 5 carbon atoms, a fluorinated alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 5 carbon atoms and having an ethereal oxygen atom between the carbon atoms, and a fluorinated alkylene group having 1 to 5 carbon atoms and having an ethereal oxygen atom between the carbon atoms; R 30 and R 31 are each independently a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluorinated alkyl group having

Assignees

• Central Glass Co Ltd

Inventors

• Itabashi Saori
• Harada Shuji
• Suzuki Katsutoshi
• Takeda Kazunari

Classifications

• H01M50/417

  Polyolefins · CPC title

• H01M50/429

  Natural polymers · CPC title

• H01M2300/002

  Inorganic electrolyte · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title