Polymer compound, intermediate composition, negative electrode, electrical storage device, slurry for negative electrode, method for producing polymer compound, and method for producing negative electrode

Patent metadata

Field	Value
Publication number	US-10538625-B2
Application number	US-201716076033-A
Country	US
Kind code	B2
Filing date	Jan 30, 2017
Priority date	Feb 12, 2016
Publication date	Jan 21, 2020
Grant date	Jan 21, 2020

Abstract

A polymer compound is formed by condensing a polyacrylic acid having some of carboxyl groups converted into a lithium salt with a polyfunctional amine represented by the following general formula (1). A chain structure constituted by the polyacrylic acid has free carboxyl groups and carboxyl groups converted into a lithium salt.

Y is a straight-chain alkyl group having 1 to 4 carbon atoms, a phenylene group, or an oxygen atom. R1 and R2 are each independently one or more hydrogen atoms, a methyl group, an ethyl group, a trifluoromethyl group, or a methoxy group.

First claim

The invention claimed is:

1. A polymer compound to be used as a binder for a negative electrode of a power storage device, wherein
the polymer compound is formed by condensing a polyacrylic acid having some of carboxyl groups converted into a lithium salt with a polyfunctional amine represented by the following general formula (1),
a chain structure constituted by the polyacrylic acid has free carboxyl groups and carboxyl groups converted into a lithium salt:

where
Y is a straight-chain alkyl group having 1 to 4 carbon atoms, a phenylene group, or an oxygen atom, and
R1 and R2 are each independently one or more hydrogen atoms, a methyl group, an ethyl group, a trifluoromethyl group, or a methoxy group.

2. A polymer compound to be used as a binder for a negative electrode of a power storage device, wherein
the polymer compound has a chain structure constituted by a polyacrylic acid, and a crosslinked structure connecting carboxyl groups in the chain structure or between the chain structures with each other,
the crosslinked structure is at least one crosslinked structure selected from the following general formulae (2) to (4), and
the chain structure has free carboxyl groups and carboxyl groups converted into a lithium salt

where PAA denotes the chain structure constituted by the polyacrylic acid converted into a lithium salt;
X is a structure represented by the following general formula (5):

where
Y is a straight-chain alkyl group having 1 to 4 carbon atoms, a phenylene group, or an oxygen atom, and
R1 and R2 are each independently a hydrogen atom, a methyl group, a trifluoromethyl group, or a methoxy group.

3. The polymer compound according to claim 1 , wherein a ratio of the free carboxyl groups to the carboxyl groups converted into a lithium salt is in the range of 95:5 to 25:75.

4. A method for producing a polymer compound according to claim 2 , comprising heating a polyacrylic acid having some of carboxyl groups converted into a lithium salt, and a polyfunctional amine represented by the following general formula (1) in a mixed solvent of a nonaqueous solvent with water at 150 to 230° C.:

where
Y is a straight-chain alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and
R1 and R2 are each independently one or more hydrogen atoms, a methyl group, an ethyl group, a trifluoromethyl group, or a methoxy group.

5. A negative electrode of a power storage device, comprising:
a binder for a negative electrode containing a polymer compound according to claim 1 ; and
a negative electrode active substance,
wherein the negative electrode active substance is at least one selected from carbon-based materials capable of occluding and releasing lithium, elements alloyable with lithium, and compounds having an element alloyable with lithium.

6. A power storage device comprising:
a negative electrode according to claim 5 ; and
a nonaqueous electrolyte.

7. An intermediate composition of a polymer compound to be used as a binder for a negative electrode of a power storage device, wherein
the intermediate composition contains a polyacrylic acid having some of carboxyl groups converted into a lithium salt, a polyfunctional amine represented by the following general formula (1), and a mixed solvent of a nonaqueous solvent with water,
the polyacrylic acid and the polyfunctional amine are dissolved in the mixed solvent:

where
Y is a straight-chain alkyl group having 1 to 4 carbon atoms, a phenylene group or an oxygen atom, and
R1 and R2 are each independently one or more hydrogen atoms, a methyl group, an ethyl group, a trifluoromethyl group, or a methoxy group.

8. The intermediate composition according to claim 7 , wherein a degree of lithiation is in the range of 5 to 50%, the degree of lithiation being determined by
LC /( C−A )×100

where
C represents a total number of carboxyl groups derived from the polyacrylic acid,
LC represents, out of carboxyl groups derived from the polyacrylic acid, a total number of carboxyl groups converted into a lithium salt, and
A represents a total number of amino groups derived from the polyfunctional amine, and

wherein a mixing proportion of the nonaqueous solvent to water in the mixed solvent is in the range of 2:1 to 1:2.

9. The intermediate composition according to claim 7 , wherein a degree of lithiation is in the range of 50 to 75%, the degree of lithiation being determined by:
LC /( C−A )×100

where
C represents a total number of carboxyl groups derived from the polyacrylic acid,
LC represents, out of carboxyl groups derived from the polyacrylic acid, a total number of carboxyl groups converted into a lithium salt, and
A represents a total number of amino groups derived from the polyfunctional amine, and

wherein a mixing proportion of the nonaqueous solvent to water in the mixed solvent is in the range of 1:1 to 1:2.

10. A slurry for a negative electrode to be used for production of a negative electrode of a power storage device, wherein
the slurry contains an intermediate composition according to claim 7 and a negative electrode active substance, and
the negative electrode active substance is at least one selected from carbon-based materials capable of occluding and releasing lithium, elements alloyable with lithium, and compounds having an element alloyable with lithium.

11. A method for producing a negative electrode of a power storage device, wherein a negative electrode active substance layer is formed on a current collector by using a slurry for a negative electrode according to claim 10 .

12. The polymer compound according to claim 2 , wherein a ratio of the free carboxyl groups to the carboxyl groups converted into a lithium salt is in the range of 95:5 to 25:75.

Assignees

• Toyota Jidoshokki Kk

Inventors

• Kondo Takeshi
• Sugiyama Yusuke
• Goda Nobuhiro

Classifications

• H01G11/50 Primary

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

• H01G11/28

  arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives · CPC title

• C08K5/18

  with aromatically bound amino groups · CPC title

• H01G11/06

  with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC] · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title