Nonaqueous electrolyte, capacitor device using same, and carboxylic acid ester compound used in same

Patent metadata

Field	Value
Publication number	US-2019198928-A1
Application number	US-201916286914-A
Country	US
Kind code	A1
Filing date	Feb 27, 2019
Priority date	Dec 19, 2013
Publication date	Jun 27, 2019
Grant date	—

Abstract

The present invention provides a nonaqueous electrolytic solution capable of improving electrochemical characteristics in the case of using an energy storage device at a high temperature and at a high voltage and further capable of inhibiting the gas generation while maintaining a capacity retention rate after storage at a high temperature and at a high voltage and also provides an energy storage device using the same. Disclosed is a nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution containing a carboxylic acid ester compound represented by the following general formula (I).

In the formula, each of R 1 and R 2 independently represents a hydrogen atom, a —C(═O)—OR 4 group, or the like, and R 1 and R 2 may be bonded to each other to form a ring structure. R 3 represents a hydrogen atom or the like, and n represents an integer of 1 to 3. When n is 1, then L and R 4 represent an alkyl group having 1 to 6 carbon atoms or the like; and when n is 2 or 3, then L represents an n-valent connecting group, X represents a —C(═O)— group, an —S(═O)— group, an —S(═O) 2 — group, an —S(═O) 2 —R 5 —S(═O) 2 — group or a CR 6 R 7 group, R 5 represents an alkylene group having 1 to 4 carbon atoms, and each of R 6 and R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

First claim

1 : A nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution comprising from 0.001 to 10% by mass of a carboxylic acid ester compound represented by the following general formula (I):

wherein:
each of R 1 and R 2 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a —C(═O)—OR 4 group, and when R 1 and R 2 are each an alkyl group, then R 1 and R 2 may be bonded to each other to form a ring structure; R 3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; n represents an integer of 1 to 3;
when n is 1, then L and R 4 may be the same as or different from each other and represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 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 6 carbon atoms, a cyanoalkyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and when n is 2 or 3, then L represents an n-valent connecting group constituted of a carbon atom and a hydrogen atom, which may contain an ether bond, a thioether bond, or an SO 2 bond and R 4 is the same as described above; and
X represents a —C(═O)— group, an —S(═O)— group, an —S(═O) 2 — group, an —S(═O) 2 —R 5 —S(═O) 2 — group or a CR 6 R 7 group, R 5 represents an alkylene group having 1 to 4 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R 6 and R 7 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom,
when X is a —C(═O)— group, R 1 and/or R 2 is a —C(═O)—OR 4 group, and
wherein at least one hydrogen atom of the alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 3 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the alkynyl group having 3 to 6 carbon atoms, the alkoxyalkyl group having 2 to 6 carbon atoms, the cyanoalkyl group having 2 to 6 carbon atoms, the aralkyl group having 7 to 13 carbon atoms, or the aryl group having 6 to 12 carbon atoms as R 1 , R 2 , R 4 , or L, may be substituted with a halogen atom; and
further comprising 0.07 to 7% by volume of one or more selected from vinylene carbonate, vinyl ethylene carbonate and 4-ethynyl-1,3-dioxolan-2-one, relative to a total volume of the nonaqueous solvent.

2 : The nonaqueous electrolytic solution according to claim 1 , wherein in the general formula (I), X is a —C(═O)— group, and n is an integer of 1 to 3.

3 . (canceled)

4 : The nonaqueous electrolytic solution according to claim 1 , wherein in the general formula (I), X is an —S(═O)— group, an —S(═O) 2 — group, or a —CR 6 R 7 group, and n is 1.

5 : The nonaqueous electrolytic solution according to claim 4 , wherein in the general formula (I), the compound wherein X is an —S(═O)— group, an —S(═O) 2 — group, or a —CR 6 R 7 group is a carboxylic acid ester compound represented by the following general formula (I-2):

wherein:
each of R 21 and R 22 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, or a —C(═O)—OR 25 group, and when R 21 and R 22 are each an alkyl group, then R 21 and R 22 may be bonded to each other to form a ring structure;
R 23 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms;
R 24 and R 25 may be the same as or different from each other and represent an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, an alkenyl group having 2 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, an alkynyl group having 3 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a cyanoalkyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, or an aryl group having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom; and
X 1 represents an —S(═O) group, an —S(═O) 2 group, or a —CR 26 R 27 group and each of R 26 and R 27 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom.

6 : The nonaqueous electrolytic solution according to claim 1 , wherein in the general formula (I), X is an —S(═O) 2 —R 5 —S(═O) 2 — group, and n is 1 or 2.

7 : The nonaqueous electrolytic solution according to claim 6 , wherein in the general formula (I), the compound wherein X is an —S(═O) 2 —R 5 —S(═O) 2 — group, and n is 1 or 2 is a carboxylic acid ester compound represented by the following general formula (I-3):

wherein:
each of R 31 and R 32 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, or a —C(═O)—OR 34 group; R 33 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; m represents 1 or 2;
when m is 1, then L 3 and R 34 may be the same as or different from each other and represent an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, an alkenyl group having 2 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, an alkynyl group having 3 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a cyanoalkyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, or an aryl group having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, and when m is 2, then L 3 represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 4 to 8 carbon atoms, or an alkynylene group having 4 to 8 carbon atoms, and at least one hydrogen atom of L 3 may be substituted with a halogen atom and R 34 is

Assignees

• Ube Industries

Inventors

• Shimamoto Kei
• Abe Koji
• Shikita Shoji
• Miyoshi Kazuhiro

Classifications

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C07D317/36

  Alkylene carbonates; Substituted alkylene carbonates · CPC title

• C07D327/10

  two oxygen atoms and one sulfur atom, e.g. cyclic sulfates · CPC title

• Y02E60/13

  Energy storage using capacitors · CPC title