Electrolyte for non-aqueous electrolyte cell, and non-aqueous electrolyte cell wherein same is used

Patent metadata

Field	Value
Publication number	US-11424486-B2
Application number	US-202017064930-A
Country	US
Kind code	B2
Filing date	Oct 7, 2020
Priority date	Dec 22, 2015
Publication date	Aug 23, 2022
Grant date	Aug 23, 2022

Abstract

Provided is an electrolyte for a non-aqueous electrolyte battery, which can provide, when used in a non-aqueous electrolyte battery, in a good balance, an effect to suppress an increase in an internal resistance at a low temperature and an effect to suppress an increase in an amount of gas generated at a high temperature, as well as a non-aqueous electrolyte battery containing such an % electrolyte. The non-aqueous electrolyte comprises a non-aqueous solvent and at least a hexafluorophosphate and/or tetrafluoroborate as a solute, and further comprises at least one imide anion-containing salt represented by the following general formula [1] but does not contain a silane compound represented by the following general formula [2] or an ionic complex represented by, for example, the following general formula [3].

First claim

The invention claimed is:

1. An electrolyte for a non-aqueous electrolyte battery, comprising:
a non-aqueous solvent and at least one of hexafluorophosphate and tetrafluoroborate as a solute, and
at least one imide anion-containing salt represented by the following formula [1]:

wherein in the formula [1],
R 1 , R 2 and R 3 each independently represent a fluorine atom or an organic group selected from the group consisting of a linear or branched C 1-10 alkyl group, a linear or branched C 1-10 alkoxy group, a C 2-10 alkenyl group, a C 2-10 alkenyloxy group, a C 2-10 alkynyl group, a C 2-10 alkynyloxy group, a C 3-10 cycloalkyl group, a C 3-10 cycloalkoxy group, a C 3-10 cycloalkenyl group, a C 3-10 cycloalkenyloxy group, a C 6-10 aryl group and a C 6-10 aryloxy group, wherein a fluorine atom, an oxygen atom or an unsaturated bond may be present in the organic group and wherein at least one of R 1 , R 2 and R 3 represents a fluorine atom;
M m+ represents an alkali metal cation, an alkaline-earth metal cation or an onium cation; and
m is an integer equivalent to the valence of the corresponding cation;
wherein the electrolyte excludes a silane compound represented by the following formula [2], and the electrolyte excludes an ionic complex represented by any one of the following formula [3], formula [4] and formula [5]:
Si(R 4 ) a (R 5 ) 4-a   [2]

wherein in the formula [2],
each R 4 independently represents a group having a carbon-carbon unsaturated bond;
each R 5 independently represents a linear or branched C 1-10 alkyl group, which may contain a fluorine atom and/or an oxygen atom; and
a is an integer of 2, 3 or 4;

wherein in the formula [3],
A b+ represents at least one selected from the group consisting of a metal ion, a proton and an onium ion;
F represents a fluorine atom;
M represents at least one element selected from the group consisting of Al, B, Si, P, As and Sb;
O represents an oxygen atom;
S represents a sulfur atom;
R 6 represents a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 6 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more), or —N(R 7 )—;
R 7 represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 7 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more);
Y represents a carbon atom or a sulfur atom; in the case wherein Y represents a carbon atom, r is 1; in the case wherein Y represents a sulfur atom, r is 1 or 2; and
b is 1 or 2; o is 2 or 4; n is 1 or 2; p is 0 or 1; q is 1 or 2; r is 0, 1 or 2; and in the case wherein p is 0, a direct bond is formed between S and Y;

wherein in the formula [4],
A b+ represents at least one type selected from the group consisting of a metal ion, a proton and an onium ion;
F represents a fluorine atom;
M represents at least one element selected from the group consisting of Al, B, Si, P, As and Sb;
O represents an oxygen atom;
N represents a nitrogen atom;
Y represents a carbon atom or a sulfur atom; in the case wherein Y represents a carbon atom, q is 1; in the case wherein Y represents a sulfur atom, q is 1 or 2;
R 6 represents a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 6 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more), or —N(R 7 )—;
R 7 represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 7 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more);
R 8 represents a hydrogen atom, a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 8 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more), or —N(R 7 )—; and
b is 1 or 2; o is 2 or 4; n is 1 or 2; p is 0 or 1; q is 1 or 2; r is 0 or 1; in the case wherein p is 0, Y and a carbon atom positioning at both sides of R 6 form a direct bond; and in the case wherein r is 0, a direct bond is formed between M and N;

wherein in the formula [5],
D represents at least one selected from the group consisting of a halogen ion, a hexafluorophosphate anion, a tetrafluoroborate anion, a bis(trifluoromethanesulfonyl)imide anion, a bis(fluorosulfonyl)imide anion, a (fluorosulfonyl)(trifluoromethanesulfonyl)imide anion and a bis(difluorophosphonyl)imide anion;
F represents a fluorine atom;
M represents one element selected from the group consisting of Al, B, Si, P, As and Sb;
O represents an oxygen atom;
N represents a nitrogen atom;
Y represents a carbon atom or a sulfur atom; in the case wherein Y represents a carbon atom, q is 1; in the case wherein Y represents a sulfur atom, q is 1 or 2;
X represents a carbon atom or a sulfur atom; in the case wherein X represents a carbon atom, r is 1; in the case wherein X represents a sulfur atom, r is 1 or 2;
R 6 represents a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 6 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more), or —N(R 7 )—;
R 7 represents a hydrogen atom, an alkali metal, a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 7 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more); and
R 9 and R 10 independently represent a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms (R 9 and R 10 can also have a branched chain or a ring structure when a number of carbon atoms is 3 or more); a ring structure specified by the following formula [6] is optionally contained:

c is 0 or 1; in the case wherein n is 1, c is 0 (in the case wherein c is 0, D does not exist); in the case wherein n is 2, c is 1;
o is 2 or 4; n is 1 or 2; p is 0 or 1; q is 1 or 2; r is 1 or 2; s is 0 or 1; in the case wherein p is 0, a direct bond is formed between Y and X; and
in the case wherein s is 0, N(R 9 )(R 10 ) is directly bonded to R 6 ; in this case, any one of the following structures of formula [7], formula [8], formula [9] and formula [10] may be formed; in the case wherein the direct bond is a double bond as in the formula [8] or formula [10], R 10 does not exist; a structure having a double bond outside the ring may be formed; in this case, R 11 and R 12 independently represent a hydrogen atom, or a hydrocarbon group which may have a ring, a heteroatom, or a halogen atom, the hydrocarbon group having 1 to 10 carbon atoms, wherein when a number of carbon atoms is 3 or more, R 11 and R 12 can also have a branched chain or a ring structure,

wherein the solute is contained in an amount not lower than

Assignees

• Central Glass Co Ltd

Inventors

• Morinaka Takayoshi
• Kubo Makoto
• Kawabata Wataru
• Shinmen Masutaka
• Matsuzaki Hiroki
• Takahashi Mikihiro

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01G11/50 Primary

  specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation · CPC title

• H01G11/64

  characterised by additives · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title