Viologen compound, method for producing the same, negative electrode active material, and electricity storage device

Patent metadata

Field	Value
Publication number	US-10879015-B2
Application number	US-201816198931-A
Country	US
Kind code	B2
Filing date	Nov 23, 2018
Priority date	Dec 8, 2017
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

A viologen compound is a crystalline compound including a heterocyclic moiety in which a carboxylate of an alkali metal is bound directly or indirectly to both ends of a basic skeleton containing 4,4□-bipyridinium and an anionic moiety that pairs with 4,4□-bipyridinium. The viologen compound can be used, for example, as a negative electrode active material for an electricity storage device including a negative electrode containing the negative electrode active material, a positive electrode containing a positive electrode active material capable of giving and receiving anions, and an ion-conducting medium that is disposed between the positive electrode and the negative electrode and conducts anions.

First claim

What is claimed is:

1. A crystalline viologen compound comprising:
a heterocyclic moiety in which a carboxylate of an alkali metal is bound directly or indirectly to both ends of a basic skeleton containing 4,4′-bipyridinium; and
an anionic moiety that pairs with the 4,4′-bipyridinium,
wherein the viologen compound is represented by formula (1):

where A − is the anionic moiety, M is lithium, R is an alkylene chain or an aromatic hydrocarbon chain, and m is 0 or 1.

2. The viologen compound according to claim 1 , wherein the anionic moiety is at least one selected from the group consisting of BF 4 − , PF 6 − , SiF 6 2− , SbF 6 − , ClO 4 − , B(CN) 4 − , [(C 2 F 5 ) 3 PF 3 ] − , [(CN) 2 N] − , CF 3 SO 3 − , CF 3 CO 2 − , N(FSO 2 ) 2 − , N(CF 3 SO 2 ) 2 − , and N(C 2 F 5 SO 2 ) 2 − .

3. The viologen compound according to claim 1 , wherein the viologen compound is represented by formula (2) or formula (3):

4. A crystalline viologen compound comprising:
a heterocyclic moiety in which a carboxylate of an alkali metal is bound directly or indirectly to both ends of a basic skeleton containing 4,4′-bipyridinium; and
an anionic moiety that pairs with the 4,4′-bipyridinium,
wherein the heterocyclic moiety is a three-dimensional structure including an organic skeletal layer in which a carboxylic acid anion is bound directly or indirectly to the both ends of the basic skeleton and an alkali metal element layer in which the alkali metal is bound to oxygen contained in the carboxylic acid anion.

5. A method for producing a viologen compound, comprising:
a step (a) of providing a heterocyclic compound and an alkali metal compound, the heterocyclic compound including a heterocyclic moiety in which a carboxylic acid is bound directly or indirectly to both ends of a basic skeleton containing 4,4′-bipyridinium and an anionic moiety that pairs with the 4,4′-bipyridinium, and providing a prepared solution in which a molar ratio of alkali metal cations of the alkali metal compound to the heterocyclic compound is 2.0 or more and 2.5 or less; and
a step (b) of spray-drying the prepared solution with a spray dryer to thereby precipitate a crystalline viologen compound in which the alkali metal cations of the alkali metal compound are bound to oxygen anions of the carboxylic acid contained in the heterocyclic compound.

6. The method for producing a viologen compound according to claim 5 , wherein in the step (a), a prepared solution in which a molar ratio of the alkali metal compound to the heterocyclic compound is 2.1 or more and 2.3 or less is provided.

7. A negative electrode active material comprising a crystalline viologen compound comprising:
a heterocyclic moiety in which a carboxylate of an alkali metal is bound directly or indirectly to both ends of a basic skeleton containing 4,4′-bipyridinium; and
an anionic moiety that pairs with the 4,4′-bipyridinium.

8. An electricity storage device comprising:
a negative electrode containing the negative electrode active material according to claim 7 ;
a positive electrode containing a positive electrode active material capable of giving and receiving anions; and
an ion-conducting medium that is disposed between the positive electrode and the negative electrode and conducts anions.

Assignees

• Toyota Chuo Kenkyusho Kk

Inventors

• Kumagai Hitoshi
• Makino Yuka
• Hasegawa Masaki
• Ogihara Nobuhiro

Classifications

• C07F5/02 Primary

  Boron compounds · CPC title

• H01M10/4235

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

• H01G11/50

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

• C07F1/02

  Lithium compounds · CPC title

• H01G11/48 Primary

  Conductive polymers · CPC title