Negative electrode active material for nonaqueous electrolyte secondary batteries
Proposed is a novel negative electrode for nonaqueous electrolyte secondary batteries in which the battery capacity does not decrease even when charging and discharging are repeated. Proposed is a silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries, comprising negative electrode active material particles which are provided with a surface layer containing carbon and titanium or aluminum on the entirety or a portion of the surface of the active material.
1. A silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries, wherein the negative electrode active material particles comprise a surface layer comprising carbon and titanium or aluminum on an entirety or a portion of a surface of a core portion,
wherein the core portion comprises: pure silicon; a silicon alloy selected from SiB 4 or SiB 6 , Cu 5 Si, FeSi 2 , or Mg 2 Si; or a silicon compound selected from Si 3 N 4 or SiC in an amount of 90% by mass or more, and
a content of titanium or aluminum in the surface layer is 0.002 to 0.07% by mass of the silicon-containing negative electrode active material particles.
2. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein a content of carbon in the surface layer is 0.004 to 0.5% by mass of the silicon-containing negative electrode active material particles.
3. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein said surface layer is formed from an organic compound comprising carbon and titanium or aluminum, which is a coupling agent containing the titanium or aluminum.
4. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 3 , wherein said negative electrode active material particles are subjected to heating at 300 to 500° C.
5. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 3 , wherein said coupling agent containing titanium or aluminum further has an amino group at a side chain.
6. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein D50 measured by a laser diffraction scattering type particle size distribution measurement method is 0.1 μm to 5.0 μm.
7. A negative electrode for nonaqueous electrolyte secondary batteries, comprising the active material for nonaqueous electrolyte secondary batteries according to claim 1 , and a binder.
8. A negative electrode for nonaqueous electrolyte secondary batteries, comprising the active material for nonaqueous electrolyte secondary batteries according to claim 1 as a first negative electrode active material, a graphite as a second negative electrode active material, and a binder.
9. The negative electrode for nonaqueous electrolyte secondary batteries according to claim 7 , wherein the binder is a polyimide.
10. A nonaqueous electrolyte secondary battery comprising the negative electrode according to claim 7 .
11. A nonaqueous electrolyte secondary battery comprising the negative electrode according to claim 8 .
12. A nonaqueous electrolyte secondary battery comprising the negative electrode according to claim 9 .
13. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein a content of the carbon in the surface layer is 0.004 to 0.5% by mass.
14. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein said surface layer is formed from an organic compound comprising carbon and titanium or aluminum, which is a coupling agent containing the titanium or aluminum.
15. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 2 , wherein said surface layer is formed from an organic compound comprising carbon and titanium or aluminum, which is a coupling agent containing the titanium or aluminum.
16. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 14 , wherein said negative electrode active material particles are subjected to heating at 300 to 500° C.
17. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 15 , wherein said negative electrode active material particles are subjected to heating at 300 to 500° C.
18. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 4 , wherein said coupling agent containing titanium or aluminum further has an amino group at a side chain.
19. The negative electrode for nonaqueous electrolyte secondary batteries according to claim 8 , wherein the binder is a polyimide.
20. The negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein the surface layer containing the carbon and the titanium or aluminum is provided as the outermost layer of the core portion.
21. The negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein the total content of iron (Fe), calcium (Ca), phosphorus (P), and oxygen (O) in the negative electrode active material is from 0.1 to 2.5% by mass.
22. The silicon-containing negative electrode active material for nonaqueous electrolyte secondary batteries according to claim 1 , wherein the negative electrode active material particles are materials in which the additive elements are solid-solubilized in one of the silicon-containing materials, as a silicon solid solution.