Composite for anode active material, anode including the composite, lithium secondary battery including the anode, and method of preparing the composite
A composite anode active material includes: a silicon anode active material, a metal nitride; and a metal fluoride, wherein the metal nitride and the metal fluoride are each independently disposed on at least one surface of the silicon anode active material.
1. A composite anode active material comprising:
a silicon anode active material comprising silicon;
a metal nitride; and
a metal fluoride,
wherein the metal nitride and the metal fluoride are each independently disposed directly on at least one surface of the silicon anode active material.
2. The composite anode active material of claim 1 , wherein the silicon anode active material comprises
a metal silicide core, which comprises a metal silicide, and
a silicon shell, which comprises silicon.
3. The composite anode active material of claim 2 , wherein the metal nitride and the metal silicide comprise a same metal.
4. The composite anode active material of claim 2 , wherein the metal silicide comprises Ti, V, Cu, Zn, Mo, Ni, Al, Ca, Mg, Fe, Cr, an alloy of at least two thereof, or a combination thereof.
5. The composite anode active material of claim 2 , wherein a content of the metal nitride in the composite anode active material is about 0.5 mole or less, based on 1 mole of the silicon contained in the silicon shell.
6. The composite anode active material of claim 2 , wherein a content of the metal silicide in the composite anode active material is about 0.5 mole or less, based on 1 mole of silicon contained in the silicon shell.
7. The composite anode active material of claim 2 , wherein the metal silicide is TiSi x wherein 0<x≤2.
8. The composite anode active material of claim 1 , wherein the silicon anode active material comprises a silicon core without a shell, wherein the silicon core comprises silicon.
9. The composite anode active material of claim 8 , wherein a content of the metal nitride in the composite anode active material is about 0.5 mole or less, based on 1 mole of silicon contained in the silicon core.
10. The composite anode active material of claim 1 , wherein the metal nitride comprises Ti, V, Cu, Zn, Mo, Ni, Al, Ca, Mg, Fe, Cr, an alloy of at least two thereof, or a combination thereof.
11. The composite anode active material of claim 1 , wherein the metal nitride is TiO x N y , wherein 0≤x<1 and y=1−x.
12. The composite anode active material of claim 1 , wherein the metal fluoride comprises Al, Li, Sb, Ba, Bi, B, Ca, Co, Cu, Ge, Fe, La, Mg, Mn, Mo, Ni, Si, Ag, Na, Sr, Sn, Ti, W, Y, Zn, Zr, an alloy of at least two thereof, or a combination thereof.
13. The composite anode active material of claim 1 , wherein the metal fluoride comprises AlF x O y wherein 0<x≤3 and y=3−x, LiF x O y wherein 0<x≤ 1 and y=1−x, or a combination thereof.
14. The composite anode active material of claim 1 , wherein a content of the metal fluoride is in the range of about 1 to about 70 parts by weight, based on 100 parts by weight of a total weight of the composite anode active material.
15. An anode comprising the composite anode active material according to claim 1 .
16. The anode of claim 15 , further comprising an additional anode active material.
17. A lithium secondary battery comprising the anode according to claim 15 .
18. A method of preparing a composite anode active material, the method comprising:
milling a metal silicide;
heat-treating the milled metal silicide in a nitrogen atmosphere to form a heat-treated metal silicide comprising a metal nitride on a surface thereof; and
contacting the heat-treated metal silicide with a metal fluoride to dispose the metal fluoride directly on a surface of the heat-treated metal silicide and to form a coating comprising the metal fluoride disposed directly on the surface of the heat-treated metal silicide to prepare the composite anode active material.
19. The method of claim 18 , wherein the composite anode active material comprises a core comprising the metal silicide, and
wherein the metal nitride and the metal fluoride are each independently disposed on a surface of the core.
20. The method of claim 18 , wherein the composite anode active material comprises a core and a shell,
wherein the core comprises the metal silicide,
wherein the shell comprises silicon, and
wherein the metal nitride and the metal fluoride are each independently disposed on a surface of the active material.
21. The method of claim 18 , wherein the contacting comprises milling a mixture of the heat-treated metal silicide and the metal fluoride.
22. The method of claim 18 , wherein the contacting comprises combining the heat-treated metal silicide with a solution comprising the metal fluoride.
23. The method of claim 18 , wherein the heat-treating is performed at a temperature of about 800° C. to about 1200° C.