Negative electrode material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using the same
View Patent ↗A negative electrode material for a nonaqueous electrolyte secondary battery, where the negative electrode contains a carbon material A and a carbon material B. Carbon material A is a multilayer-structure carbon material containing a graphitic particle having an amorphous carbon surface covering, where the interplaner spacing of 002 planes, by wide-angle XRD, is 3.37 Å or less, Lc is 900 Å or more, the tap density is 0.8 g/cm 3 or more, and the Raman R value is from 0.25 to 0.6. Carbon material B is a graphitic particle where the interplanar spacing of 002 planes, by wide-angle XRD, is 3.37 Å or less, Lc is 900 Å or more, the tap density is 0.8 g/cm 3 or more, the Raman R value is from 0.2 to 0.5, and the average degree of circularity, determined by a flow-type particle analyzer, is 0.9 or more.
1. A negative electrode material for nonaqueous electrolyte secondary battery, comprising a carbon material (A) and a carbon material (B),
wherein the carbon material (A) is a multilayer-structure carbon material comprising a graphitic particle and an amorphous carbon covering the surface of the graphitic particle, and wherein the carbon material (A) has:
an interplanar spacing (d002) of 002 planes by the wide-angle X-ray diffraction method of 3.37 Å or less;
a crystallite size (Lc) of 900 Å or more;
a tap density of 0.8 g/cm 3 or more; and
a Raman R value, as a ratio of a peak intensity near 1,360 cm −1 to a peak intensity near 1,580 cm −1 in the argon ion laser Raman spectrum, from 0.25 to 0.6, and
wherein the carbon material (B), which is not a multilayer-structure carbon material, comprises a graphitic particle, and wherein the carbon material (B) has:
an interplanar spacing (d002) of 002 planes by the wide-angle X-ray diffraction method of 3.37 Å or less;
a crystallite size (Lc) of 900 Å or more;
a tap density of 0.8 g/cm 3 or more;
a Raman R value, as a ratio of a peak intensity near 1,360 cm −1 to a peak intensity near 1,580 cm −1 in the argon ion laser Raman spectrum, from 0.2 to 0.5; and
an average degree of circularity, as determined by a flow-type particle analyzer, of 0.9 or more.
2. The negative electrode material of claim 1 , wherein a ratio in the average particle diameter between the carbon material (A) and the carbon material (B) (average particle diameter of carbon material (A)/average particle diameter of carbon material (B)) is from 0.7 to 1.3.
3. The negative electrode material of claim 1 , wherein a ratio of the carbon material (B) is from 30 to 70 wt %, based on a total amount of the carbon material (A) and the carbon material (B).
4. The negative electrode material of claim 1 , wherein in the graphitic particle employed for the carbon material (A) has:
an interplanar spacing (d002) of 002 planes by the wide-angle X-ray diffraction method of 3.37 Å or less;
a crystallite size (Lc) of 900 Å or more;
a tap density of 0.8 g/cm 3 or more; and
a Raman R value, as a ratio of a peak intensity near 1,360 cm −1 to a peak intensity near 1,580 cm −1 in the argon ion laser Raman spectrum, from 0.2 to 0.5.
5. The negative electrode material of claim 1 , having a tap density of 0.8 g/cm 3 or more.
6. The negative electrode material of claim 1 , wherein the carbon material (B) has a true density of 2.21 g/cm 3 or more.
7. The negative electrode material of claim 1 , wherein a specific surface area of the carbon material (A) is from 0.5 to 8 m 2 /g.
8. The negative electrode material of claim 1 , wherein the average degree of circularity of the graphitic particle employed for the carbon material (A), as determined by a flow-type particle analyzer, is 0.88 or more.
9. The negative electrode material of claim 1 , wherein the pore volumes in the range of 10 to 100,000 nm of the carbon material (A) and the carbon material (B), as measured by the mercury intrusion method, are 0.4 ml/g or more.
10. The negative electrode material of claim 1 , wherein an average particle diameter of the carbon material (A) is from 2 to 30 μm.
11. A negative electrode for nonaqueous electrolyte secondary battery, comprising:
a current collector; and
a negative electrode layer disposed on the current collector,
wherein the negative electrode layer comprises the negative electrode material of claim 1 and a binder resin.
12. A nonaqueous electrolyte secondary battery, comprising:
the negative electrode of claim 11 ;
a positive electrode, which stores and releases lithium ion; and
a nonaqueous electrolytic solution.
13. The negative electrode material of claim 1 , wherein a ratio of the carbon material (B) is from 10 to 90 wt %, based on a total amount of the carbon material (A) and the carbon material (B).
14. The negative electrode material of claim 1 , wherein the ratio in the average particle diameter between the carbon material (A) and the carbon material (B) is from 0.8 to 1.2.
15. The negative electrode material of claim 1 , wherein a ratio of the carbon material (B) is from 30 to 50 wt %, based on a total amount of the carbon material (A) and the carbon material (B).
16. The negative electrode material of claim 1 , wherein in the graphitic particle employed for the carbon material (A) has:
an interplanar spacing (d002) of 002 planes by the wide-angle X-ray diffraction method of 3.36 Å or less;
a crystallite size (Lc) of 950 Å or more;
a tap density of 0.85 g/cm 3 or more; and
a Raman R value, as a ratio of a peak intensity near 1,360 cm −1 to a peak intensity near 1,580 cm −1 in the argon ion laser Raman spectrum, from 0.25 to 0.5.
17. The negative electrode material of claim 5 , having a tap density of 0.85 g/cm 3 or more.
18. The negative electrode material of claim 6 , wherein the true density of the carbon material (B) is 2.23 g/cm 3 or more.
19. The negative electrode material of claim 7 , wherein the specific surface area of the carbon material (A) is from 1 to 6 m 2 /g.
20. The negative electrode material of claim 9 , wherein the pore volumes in the range of 10 to 100,000 nm of the carbon material (A) and the carbon material (B), as measured by the mercury intrusion method, are 0.5 ml/g or more.