IP Library Granted Patent US 9,293,770
Granted Patent B2
US 9,293,770 · App. 13/826,710 · Granted Mar 22, 2016

Graphene oxide, positive electrode for nonaqueous secondary battery using graphene oxide, method of manufacturing positive electrode for nonaqueous secondary battery, nonaqueous secondary battery, and electronic device

Inventors: Hiroatsu Todoriki (Nagano, JP); Mikio Yukawa (Kanagawa, JP); Yumiko Saito (Kanagawa, JP); Masaki Yamakaji (Kanagawa, JP); Rika Yatabe (Kanagawa, JP); Tatsuya Ikenuma (Kanagawa, JP)
Assignee: SEMICONDUCTOR ENERGY LABORATORY CO., LTD.
H01M4/625C01B31/043H01M4/131H01M4/133H01M4/136H01M4/5825H01M4/624H01M4/64H01M4/366Y02E60/122
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Quick Facts
Patent No.
US 9,293,770
App. No.
13/826,710
Granted
Mar 22, 2016
Kind
B2
Abstract

A graphene oxide used as a raw material of a conductive additive for forming an active material layer with high electron conductivity with a small amount of a conductive additive is provided. A positive electrode for a nonaqueous secondary battery using the graphene oxide as a conductive additive is provided. The graphene oxide is used as a raw material of a conductive additive in a positive electrode for a nonaqueous secondary battery and, in the graphene oxide, the atomic ratio of oxygen to carbon is greater than or equal to 0.405.

Claims (45)

1. A method of manufacturing a positive electrode for a nonaqueous secondary battery, comprising:

forming a paste including a dispersion medium, a plurality of active materials, a plurality of graphene oxides and a binding agent, wherein an atomic ratio of oxygen to carbon in the plurality of graphene oxides is 0.405 or more;

applying the paste on a current collector; and

reducing the plurality of graphene oxides after or at the same time when the dispersion medium included in the applied paste is volatilized, whereby an active material layer comprising a plurality of graphenes is formed over the current collector.

2. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 1 ,

wherein the paste is manufactured by the following steps:

dispersing the plurality of graphene oxides into the dispersion medium,

adding the plurality of active materials to the dispersion medium into which the plurality of graphene oxides are dispersed and performing mixing to form a mixture; and

adding the binding agent to the mixture and performing mixing.

3. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 1 ,

wherein the plurality of graphene oxides comprise one or more groups selected from an epoxy group, a carbonyl group, a carboxyl group, and a hydroxyl group.

4. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 1 ,

wherein the plurality of active materials are lithium iron phosphate.

5. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 1 ,

wherein a compounding ratio of A:B:C=X:Y:Z is satisfied in the paste, where A is the plurality of graphene oxides, B is the plurality of active materials, C is the binding agent, X is 2 to 10, Y is 85 to 93, and Z is 1 to 5.

6. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 1 ,

wherein a compounding ratio of A:B:C=P:Q:R is satisfied in the active material layer, where A is the plurality of graphenes, B is the plurality of active materials, C is the binding agent, P is 1 to 5, Q is 90 to 94, and R is 1 to 5.

7. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 1 ,

wherein, in the active material layer:

at least one of the plurality of graphenes is larger than an average particle diameter of the plurality of active materials,

the plurality of graphenes are dispersed in the active material layer such that at least one of the plurality of graphenes makes surface contact with one or more adjacent graphenes, and

at least one of the plurality of graphenes makes surface contact with at least one of the plurality of active materials in such a way as to wrap part of a surface thereof.

8. A method of manufacturing a positive electrode for a nonaqueous secondary battery, comprising:

forming a paste including a dispersion medium, a plurality of active materials, a plurality of graphene oxides and a binding agent, wherein an atomic ratio of oxygen to carbon in the plurality of graphene oxides is 0.405 or more;

applying the paste on a current collector; and

electrochemically reducing the plurality of graphene oxides after the dispersion medium included in the applied paste is volatilized, whereby an active material layer comprising a plurality of graphenes is formed over the current collector,

wherein, as bonding states of carbon included in the active material layer, a proportion of a C═C bond is 35% or more and a proportion of a C—O bond is 5% or more and 20% or less.

9. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 8 ,

wherein the paste is manufactured by the following steps:

dispersing the plurality of graphene oxides into the dispersion medium,

adding the plurality of active materials to the dispersion medium into which the plurality of graphene oxides are dispersed and performing mixing to form a mixture; and

adding the binding agent to the mixture and performing mixing.

10. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 8 ,

wherein, in the active material layer:

at least one of the plurality of graphenes is larger than an average particle diameter of the plurality of active materials,

the plurality of graphenes are dispersed in the active material layer such that at least one of the plurality of graphenes makes surface contact with one or more adjacent graphenes, and

at least one of the plurality of graphenes makes surface contact with at least one of the plurality of active materials in such a way as to wrap part of a surface thereof.

11. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 8 ,

wherein the plurality of graphene oxides comprise one or more groups selected from an epoxy group, a carbonyl group, a carboxyl group, and a hydroxyl group.

12. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 8 ,

wherein the plurality of active materials are lithium iron phosphate.

13. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 8 ,

wherein a compounding ratio of A:B:C=X:Y:Z is satisfied in the paste, where A is the plurality of graphene oxides, B is the plurality of active materials, C is the binding agent, X is 2 to 10, Y is 85 to 93, and Z is 1 to 5.

14. The method of manufacturing a positive electrode for a nonaqueous secondary battery according to claim 8 ,

wherein a compounding ratio of A:B:C=P:Q:R is satisfied in the active material layer, where A is the plurality of graphenes, B is the plurality of active materials, C is the binding agent, P is 1 to 5, Q is 90 to 94, and R is 1 to 5.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 7, 2013
From: TODORIKI, HIROATSU; YUKAWA, MIKIO; SAITO, YUMIKO; YAMAKAJI, MASAKI; YATABE, RIKA; IKENUMA, TATSUYA
To: SEMICONDUCTOR ENERGY LABORATORY CO., LTD.
Reel/Frame 030363/0221 →
Priority Claims (2)
JP 2012-089346 · Apr 10, 2012 · national
JP 2012-125138 · May 31, 2012 · national
Continuity (1)
Related Publication 20130266859A1 · Oct 10, 2013