Negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, lithium ion secondary battery, method for producing negative electrode material for lithium ion secondary batteries, and method for producing negative electrode for lithium ion secondary batteries

Patent metadata

Field	Value
Publication number	US-9735428-B2
Application number	US-201314416873-A
Country	US
Kind code	B2
Filing date	Jun 28, 2013
Priority date	Jul 24, 2012
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

Provided is a negative electrode material for a lithium ion secondary battery, which has excellent high-temperature storage characteristics and cycle characteristics. The negative electrode material for a lithium ion secondary battery has a high molecular weight polymer adsorbed on a carbon material, the O/C value of surface functional group quantity is 4.5% or more and 25% or less in the negative electrode material for a lithium ion secondary battery, and the S/C value of surface functional group quantity is 0.05% or more and 2.5% or less in the negative electrode material for a lithium ion secondary battery. Also provided are a negative electrode for a lithium ion secondary battery, lithium ion secondary battery, and methods for producing the negative electrode material, the negative electrode, and the battery.

First claim

The invention claimed is:

1. A negative electrode material for a lithium ion secondary battery, the material having a high molecular weight polymer adsorbed on a carbon material,
wherein an O/C value of surface functional group quantity, the value expressed by the following formula 1, is 4.5% or more and 25% or less in the negative electrode material for a lithium ion secondary battery, and
a S/C value of surface functional group quantity, the value expressed by the following formula 2, is 0.05% or more and 2.5% or less in the negative electrode material for a lithium ion secondary battery
O/C Value (%)= O Atom Concentration figured out on the basis of Peak Area of O is Spectrum in X-ray photoelectron spectroscopy (XPS) Analysis/ C Atom Concentration figured out on the basis of Peak Area of C 1 s Spectrum in XPS Analysis×100  Formula 1

S/C Value (%)= S Atom Concentration figured out on the basis of Peak Area of S 2 p Spectrum in X-ray photoelectron spectroscopy (XPS) Analysis/ C Atom Concentration figured out on the basis of Peak Area of C 1 s Spectrum in XPS Analysis×100.  Formula 2

2. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein the O/C value of surface functional group quantity is 4.7% or more and 20% or less in the negative electrode material for a lithium ion secondary battery, and
the S/C value of surface functional group quantity is 0.20% or more and 2.0% or less in the negative electrode material for a lithium ion secondary battery.

3. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein the O/C value of surface functional group quantity is 6.0% or more and 16% or less in the negative electrode material for a lithium ion secondary battery, and
the S/C value of surface functional group quantity is 0.30% or more and 1.5% or less in the negative electrode material for a lithium ion secondary battery.

4. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein an O is peak appearing around 525 eV to 540 eV has therein a peak derived from SO 3 , the peak appearing around 531.5 eV.

5. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein the peak area derived from SO 3 accounts for 10% or more in the O 1s, when the O is peak is subjected to curve fitting with peaks derived from SO 3 , and peaks representing C—O appearing around 533.5 eV and 532 eV, to find the peak area.

6. The negative electrode material for a lithium ion secondary battery according claim 4 ,
wherein the peak area derived from SO 3 accounts for 30% or more in the O is, when the O is peak is subjected to curve fitting with peaks derived from SO 3 , and peaks representing C—O appearing around 533.5 eV and 532 eV, to find the peak area.

7. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein the high molecular weight polymer comprises any one or more of a sulfonic acid group, a sulfonate group, and a sulfonyl group.

8. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein the high molecular weight polymer comprises a functional group in the form of a salt.

9. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
Wherein carbon (002) plane spacing is 0.334 nm to 0.338 nm when the carbon material is measured with an X-ray diffractometer (XRD).

10. The negative electrode material for a lithium ion secondary battery according to claim 1 ,
wherein the high molecular weight polymer is one or more of a polyvinyl sulfonic acid, polystyrene sulfonic acid, a polyvinyl sulfonic acid Na, and or polystyrene sulfonic acid Na.

11. A negative electrode for a lithium ion secondary battery, the electrode comprising the negative electrode material for a lithium ion secondary battery according to claim 1 , the negative electrode including a binder,
wherein the binder is an aqueous solvent binder.

12. A lithium ion secondary battery comprising the negative electrode for a lithium secondary battery according to claim 11 .

13. A method for producing a negative electrode material for a lithium ion secondary battery, the method comprising:
providing the material having a high molecular weight polymer adsorbed on a carbon material,
providing an O/C value of surface functional group quantity where the value expressed by the following formula 1, is 4.5% or more and 25% or less in the negative electrode material for a lithium ion secondary battery,
providing a S/C value of surface functional group quantity where the value expressed by the following formula 2, is 0.05% or more and 2.5% or less in the negative electrode material for a lithium ion secondary battery, and
dispersing the carbon material in 50 mass % purified water so that the purified water has pH of 6 or more
O/C Value (%)= O Atom Concentration figured out on the basis of Peak Area of O is Spectrum in X-ray photoelectron spectroscopy (XPS) Analysis/ C Atom Concentration figured out on the basis of Peak Area of C 1 s Spectrum in XPS Analysis×100  Formula 1

S/C Value (%)= S Atom Concentration figured out on the basis of Peak Area of S 2 p Spectrum in X-ray photoelectron spectroscopy (XPS) Analysis/ C Atom Concentration figured out on the basis of Peak Area of C 1 s Spectrum in XPS Analysis×100.  Formula 2

14. A method for producing a negative electrode for a lithium ion secondary battery, the negative electrode comprising:
a negative electrode material for a lithium ion secondary battery, the material having a high molecular weight polymer adsorbed on a carbon material; and
a binder,
wherein an O/C value of surface functional group quantity, the value expressed by the following formula 1, is 4.5% or more and 25% or less in the negative electrode material for a lithium ion secondary battery,
a S/C value of surface functional group quantity, the value expressed by the following formula 2, is 0.05% or more and 2.5% or less in the negative electrode material for a lithium ion secondary battery,
wherein the method comprises the steps of:
preparing negative electrode combination slurry for a lithium ion secondary battery by kneading the carbon material, the high molecular weight polymer, and the binder,
applying the negative electrode combination slurry for a lithium ion secondary battery onto a negative electrode collector
O/C Value (%)= O Atom Concentration figured out on the basis of Peak Area of O is Spectrum in X-ray photoelectron spectroscopy (XPS) Analysis/ C Atom Concentration figured out on the basis of Peak Area of C 1 s Spectrum in XPS Analysis×100  Formula 1

S/C Value (%)= S Atom Concentration figured out on the basis of Peak Area of S 2 p Spectrum in X-ray photoelectron spectroscopy (XPS) Analysis/ C Atom Concentration figured out on the basis of Peak Area of C 1 s Spectrum in XPS Analysis×100.  Formula 2

Assignees

• Hitachi Ltd

Inventors

• Tanaka Akihide
• Nishimura Etsuko
• Hoshi Kento

Classifications

• H01M4/0416

  involving impregnation with a solution, dispersion, paste or dry powder (H01M4/0438 takes precedence) · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M4/622

  being polymers · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M10/052

  Li-accumulators · CPC title