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

Patent metadata

Field	Value
Publication number	US-10454139-B2
Application number	US-201515545187-A
Country	US
Kind code	B2
Filing date	Dec 28, 2015
Priority date	Jan 23, 2015
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

An object of the present invention is to provide an electrolytic solution for nonaqueous electrolytic solution batteries capable of showing high output characteristics at low temperature even after the batteries are used to some extent, and a nonaqueous electrolytic solution batteries. The present invention is characterized in the use of an electrolytic solution for nonaqueous electrolytic solution batteries, the electrolytic solution including a difluoro ionic complex (1-Cis) in a cis configuration represented by the general formula (1-Cis), a nonaqueous organic solvent, and a solute. Furthermore, the electrolytic solution may contain a difluoro ionic complex (1-Trans) in a trans configuration or a tetrafluoro ionic complex (5).

wherein in (1-Cis), is

First claim

The invention claimed is:

1. An electrolytic solution for nonaqueous electrolytic solution secondary batteries, the electrolytic solution including a difluoro ionic complex (1) represented by the general formula (1), a nonaqueous organic solvent, and a solute, 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),

is

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; M is any one selected from the group consisting of Si, P, As, and Sb; F is a fluorine atom; 0 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 the general formulas (2) to (4) below; in the case of the general formula (3) 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, 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; and
wherein the difluoro ionic complex (1) further includes a difluoro ionic complex (1-Trans) in a trans configuration represented by the general formula (1-Trans),
wherein in (1-Trans),

is

wherein in the general formula (1-Trans), A + is any one selected from the group consisting of a metal ion, a proton, and an onium ion, M is any one selected from the group consisting of Si, P, As, and Sb; F is a fluorine atom; 0 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 the general formulas (2) to (4) below; in the case of the general formula (3) 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; 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; and
wherein the ratio of the content of the difluoro ionic complex (1-Trans) relative to the mass of the difluoro ionic complex (1-Cis) is 0.0001 or more and 0.05 or less.

2. The electrolytic solution according to claim 1 , wherein elements in the anion moiety of the difluoro ionic complex (1-Cis) are at least one selected from the group consisting of (i), (ii), (iii), and (iv) shown below:
M=P;X═O;Y═C; p,q , and t =1; and r =0,  (i)

M=P;X═O;W═C(CF 3 ) 2 ;p and q =0; and r and t =1,  (ii)

M=Si;X═O;Y═C; p and q =1 ;t =2; and r =0,  (iii)

M=P;X═N(R 1 );Y═C;R 1 =CH 3 ;p,q , and t =1; and r =0.  (iv)

3. The electrolytic solution according to claim 1 , wherein the A+ in the difluoro ionic complex (1-Cis) is at least one ion selected from the group consisting of a lithium ion, a sodium ion, a potassium ion, and a quaternary alkylammonium ion.

4. The electrolytic solution according to claim 1 , wherein the concentration of the difluoro ionic complex (1-Cis) is in the range of 0.001 mass % or more and 20 mass % or less relative to the electrolytic solution for nonaqueous electrolytic solution batteries.

5. The electrolytic solution according to claim 1 , wherein elements in the anion moiety of the difluoro ionic complex (1-Trans) are at least one selected from the group consisting of (i), (ii), (iii), and (iv) shown below:
M=P;X═O;Y═C; p,q , and t =1; and r =0  (i)

M=P;X═O;W═C(CF 3 ) 2 ;p and q =0; and r and t =1  (ii)

M=Si;X═O;Y═C; p and q =1 ;t =2; and r =0,  (iii)

M=P;X═N(R 1 );Y═C;R 1 =CH 3 ;p,q , and t =1; and r =0.  (iv)

6. The electrolytic solution according to claim 1 , wherein the A + in the difluoro ionic complex (1-Trans) is at least one selected from the group consisting of a lithium ion, a sodium ion, a potassium ion, and a quaternary alkylammonium ion.

7. The electrolytic solution according to claim 1 , further including a tetrafluoro ionic complex (5) represented by the general formula (5),

wherein in the general formula (5), A + is any one selected from the group consisting of a metal ion, a proton, and an onium ion, M is any one selected from the group consisting of Si, P, As, and Sb; F is a fluorine atom; 0 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 the general formulas (2) to (4) below; in the case of the general formula (3) 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 ca

Assignees

• Central Glass Co Ltd

Inventors

• Takahashi Mikihiro
• Morinaka Takayoshi
• Shinmen Masutaka
• Kawabata Wataru
• Kubo Makoto
• Matsuzaki Hiroki
• Tsujioka Shoichi
• Yamamoto Kenta

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0525

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

• H01M4/48

  of inorganic oxides or hydroxides · CPC title

• H01M10/0568 Primary

  characterised by the solutes · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title