Carbon material, carbon material-active material composite, electrode material for lithium-ion secondary battery, and lithium-ion secondary battery

Patent metadata

Field	Value
Publication number	US-10644318-B2
Application number	US-201615556993-A
Country	US
Kind code	B2
Filing date	May 10, 2016
Priority date	May 14, 2015
Publication date	May 5, 2020
Grant date	May 5, 2020

Abstract

Provided is a carbonaceous material capable of enhancing the initial charge and discharge efficiency and the cycle characteristics of lithium ion secondary batteries. The carbonaceous material is used as an electrode material for a lithium ion secondary battery and has a volume resistivity of 0.7 Ω·cm or less as measured at a pressure of 13 MPa in the form of a mixture of 5 wt % of the carbonaceous material and 95 wt % of lithium cobaltate.

First claim

The invention claimed is:

1. A carbonaceous material used as an electrode material for a lithium ion secondary battery, having a volume resistivity of 0.7 Ω·cm or less as measured at a pressure of 13 MPa in the form of a mixture of 5 wt % of the carbonaceous material and 95 wt % of lithium cobaltate,
wherein the carbonaceous material has a graphene-layered structure and an exfoliated plate shape.

2. The carbonaceous material according to claim 1 , having a volume resistivity of 0.5 Ω·cm or less as measured at a pressure of 13 MPa in the form of a mixture of 5 wt % of the carbonaceous material and 95 wt % of lithium cobaltate.

3. The carbonaceous material according to claim 1 , having a volume resistivity of 0.4 Ω·cm or less as measured at a pressure of 38 MPa in the foifu of a mixture of 5 wt % of the carbonaceous material and 95 wt % of lithium cobaltate.

4. The carbonaceous material according to claim 1 , having a volume resistivity of 0.04 Ω·cm or less as measured at a pressure of 38 MPa in the form of a mixture of 3 wt % of the carbonaceous material and 97 wt % of lithium cobaltate.

5. The carbonaceous material according to claim 1 , having a volume resistivity of 0.1 Ω·cm or less as measured at a pressure of 38 MPa in the form of a mixture of 2 wt % of the carbonaceous material and 98 wt % of lithium cobaltate.

6. The carbonaceous material according to claim 1 , having a volume resistivity of 5.5 Ω·cm or less as measured at a pressure of 38 MPa in the form of a mixture of 1 wt % of the carbonaceous material and 99 wt % of lithium cobaltate.

7. The carbonaceous material according to claim 1 , having a D/G ratio of 0.5 or less when a peak intensity ratio between a D band and a G band is referred to as the D/G ratio in a Raman spectrum obtained by Raman spectroscopy.

8. The carbonaceous material according to claim 1 , satisfying y <0.1055e 0.0169x (x≥60) when a thickness of a sheet consisting of 5 wt % of the carbonaceous material, 92 wt % of lithium cobaltate, and 3 wt % of polyvinylidene fluoride is referred to as x μm, and a volume resistivity of the sheet is referred to as y Ωcm.

9. The carbonaceous material according to claim 1 , having a BET specific surface area (m 2 /g) of 25 m 2 /g or more and 500 m 2 /g or less.

10. The carbonaceous material according to claim 1 , the carbonaceous material being obtained by pyrolysis of a resin in a composition in which the resin is grafted or fixed by adsorption onto graphite or primary exfoliated graphite, and having a structure in which the graphite is partially exfoliated.

11. A carbonaceous material-active material complex comprising:
the carbonaceous material according to claim 1 ; and
an active material.

12. The carbonaceous material-active material complex according to claim 11 , wherein
the active material is lithium cobaltate.

13. The carbonaceous material-active material complex according to claim 11 , wherein
a content of the carbonaceous material is 0.5 wt % or more and 10 wt % or less.

14. The carbonaceous material-active material complex according to claim 11 , being a positive electrode material fora lithium ion secondary battery.

15. A lithium ion secondary battery comprising:
an electrode constituted by the carbonaceous material-active material complex according to claim 11 .

16. An electrode material for a lithium ion secondary battery, comprising:
an active material;
a conduction aid containing the carbonaceous material according to claim 1 ; and
a binder resin, wherein
a percentage of the conduction aid in 100 wt % of the electrode material is 1 wt % or more and 10 wt % or less,
a percentage of the binder resin in 100 wt % of the electrode material is 1 wt % or more and 4 wt % or less, and
when an amount of methylene blue adsorbed per gram of the carbonaceous material (pmol/g) is referred to y, the amount of methylene blue adsorbed being measured based on a difference between an absorbance of a methanol solution of methylene blue at a concentration of 10 mg/L and an absorbance of a supernatant obtained by placing the carbonaceous material in the methanol solution of methylene blue, followed by centrifugation, and a BET specific surface area (m 2 /g) of the carbonaceous material is referred to as x, a ratio y/x is 0.14 or more, and the BET specific surface area of the carbonaceous material is 25 m 2 /g or more and 500 m 2 /g or less.

17. The electrode material for a lithium ion secondary battery according to claim 16 ,
the carbonaceous material being obtained by pyrolysis of a resin in a composition in which the resin is grafted or fixed by adsorption onto graphite or primary exfoliated graphite, having a structure in which the graphite is partially exfoliated, and being a resin-remaining partially exfoliated graphite in which the resin partially remains.

18. The electrode material for a lithium ion secondary battery according to claim 16 , wherein
an electrode density is 0.8 times or more and 1.5 times or less with respect to a specific gravity of the active material.

19. The electrode material for a lithium ion secondary battery according to claim 16 , wherein
the active material is lithium cobaltate.

20. The electrode material for a lithium ion secondary battery according to claim 16 , wherein
the binder resin comprises at least one selected from the group consisting of styrene butadiene rubber, carboxymethylcellulose, polyvinylidene fluoride, polyimide resin, acrylic resin, butyral resin, and modified products thereof.

21. The electrode material for a lithium ion secondary battery according to claim 16 , being a positive electrode material for a lithium ion secondary battery.

22. A lithium ion secondary battery comprising:
an electrode constituted by the electrode material for a lithium ion secondary battery according to claim 16 .

Assignees

• Sekisui Chemical Co Ltd
• Sekesui Chemical Co Ltd

Inventors

• Wada Takuya
• Masuda Hiroki
• Sasagawa Naoki
• Nakasuga Akira
• Nozato Shoji

Classifications

• H01M4/36

  Selection of substances as active materials, active masses, active liquids · CPC title

• H01M4/625 Primary

  Carbon or graphite · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/525 Primary

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M2004/028

  Positive electrodes · CPC title