Negative electrode material for nonaqueous secondary cells, negative electrode for nonaqueous secondary cells, and nonaqueous secondary cell
View Patent ↗A negative electrode material for a nonaqueous secondary battery capable of realizing a nonaqueous secondary battery having a small charging/discharging irreversible capacity at an initial cycle and exhibiting an excellent high-rate charging/discharging characteristics and an excellent cycle performances is provided. The main component of the material is graphite particles. The median diameter is 5 μm or more, and 40 μm or less in the volume-basis particle size distribution based on the laser diffraction/scattering particle size distribution measurement. The tapping density is 0.7 g/cm 3 or more. The specific surface area measured by a BET method is 0.2 m 2 /g or more, and 8 m 2 /g or less. The average circularity is 0.83 or more, and 1.00 or less. When an electrode is produced by a predetermined method for manufacturing an electrode and, the resulting electrode is subjected to X-ray diffraction, the graphite crystal orientation ratio I 110 /I 004 on the electrode is 0.08 or more, where I 110 represents the wide angle X-ray diffraction peak area of the (110) peak peak in the region of 2θ=76.5 to 78.5 degrees of the graphite particles on the electrode and I 004 represents the wide angle X-ray diffraction peak area of the (004) peak peak in the region of 2θ=53.5 to 56 degrees.
1. A negative electrode material for a nonaqueous secondary battery, comprising:
as the main component, graphite particles having a median diameter of from 5 μm to 40 μm in the volume-basis particle size distribution based on the laser diffraction/scattering particle size distribution measurement;
a tapping density of 0.7 g/cm 3 or more;
a specific surface area measured by a BET method of from 0.2 m 2 /g, to 8 m 2 /g;
an average circularity of the graphite particles of from 0.83 to 1.00; and
when an electrode is produced by a method for manufacturing an electrode and the resulting electrode is subjected to X-ray diffraction, the graphite crystal orientation ratio I 110 /I 004 on the electrode is 0.08 or more, where I 110 represents the wide angle X-ray diffraction peak area of the (110) peak in the region of 2θ=76.5 to 78.5 degrees of the graphite particles on the electrode and I 004 represents the wide angle X-ray diffraction peak area of the (004) peak in the region of 2θ=53.5 to 56 degrees, said method for manufacturing an electrode comprising:
adding 1 part by weight of aqueous dispersion of styrene-butadiene rubber in terms of solid content and 1 part by weight of carboxymethyl cellulose having a molecular weight of from 250,000 to 300,000 present in an aqueous solution in terms of solid content to 100 parts by weight of the negative electrode material to form a slurry,
applying said slurry to a current collector formed from copper foil having a thickness of 18 μm by using a doctor blade in such a way that 10±0.1 mg/cm 2 of the negative electrode material in terms of weight after drying is adhered, followed by drying, and
pressing once with a roll press while a press load is adjusted in such a way that the electrode density, exclusive of the copper foil, becomes 1.63±0.03 g/cm 3 .
2. The negative electrode material according to claim 1 , wherein the negative electrode material comprises graphite granulated particles, in which a plurality of graphite particles are bonded to each other, as a main component.
3. The negative electrode material according to claim 1 , wherein the total number of graphite particles is 30×10 6 /g or less, determined by a number-basis equivalent circle diameter distribution measurement based on the flow particle image analysis with a lower limit of detection of 0.6 μm.
4. The negative electrode material according to claim 1 , wherein the negative electrode material is produced from carbonaceous primary particles, as a raw material, having a median diameter of from 5 μm to 40 μm in the volume-basis particle size distribution based on the laser diffraction/scattering particle size distribution measurement.
5. The negative electrode material according to claim 1 , wherein the negative electrode material is produced from carbonaceous primary particles, as a raw material, having an average circularity of from 0.82 to 1.00.
6. The negative electrode material according to claim 1 , wherein said median diameter of said graphite particles is from 10 μm to 30 μm.
7. The negative electrode material according to claim 1 , wherein said tapping density is from 0.9 g/cm 3 to 1.3 g/cm 3 .
8. The negative electrode material according to claim 1 , wherein said specific surface area is from 0.3 m 2 /g to 4 m 2 /g.
9. The negative electrode material according to claim 1 , wherein said average circularity is from 0.90 to 0.96.
10. The negative electrode material according to claim 1 , wherein said graphite crystal orientation ratio I 110 /I 004 on the electrode is from 0.08 to 0.20.
11. The negative electrode material according to claim 1 , wherein said graphite crystal orientation ratio I 110 /I 004 on the electrode is from 0.09 to 0.18.
12. The negative electrode material according to claim 1 , wherein said graphite crystal orientation ratio I 110 /I 004 on the electrode is from 0.10 to 0.16.
13. A negative electrode for a nonaqueous secondary battery, comprising a negative electrode active material layer, which comprises the negative electrode material according to claim 1 as an active material, wherein said negative electrode active material is present on a current collector.
14. A nonaqueous secondary battery comprising
a positive electrode capable of absorbing and emitting lithium ions,
the negative electrode according to claim 13 , which is capable of absorbing and emitting lithium ions, and
an electrolyte.
15. The nonaqueous secondary battery according to claim 14 , exhibiting an irreversible capacity of at most 31 mAh/g.
16. The nonaqueous secondary battery according to claim 14 , exhibiting a rate performance of at least 85%.