Negative electrode active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including the material
Provided are a negative electrode active material for a lithium secondary battery and a method of preparing the same, wherein since the negative electrode active material includes porous polycrystalline silicon and the porous polycrystalline silicon includes pores disposed at grain boundaries, the negative electrode active material may exhibit a buffering action by internally absorbing changes in volume of the active material during charge and discharge. As a result, lifetime characteristics of a negative electrode and a battery may be improved.
1. A negative electrode active material for a lithium secondary battery, the negative electrode active material comprising:
porous polycrystalline silicon, wherein the porous polycrystalline silicon is an aggregate of silicon single crystals, the silicon single crystals are silicon nanograins having an average grain size of 3 nm to 300 nm,
wherein the porous polycrystalline silicon comprises pores disposed at grain boundaries, and
wherein the porous polycrystalline silicon has an average particle diameter (D50) of 0.01 μm to 50 μm.
2. The negative electrode active material for a lithium secondary battery of claim 1 , wherein the porous polycrystalline silicon further comprises pores formed on a surface of the porous polycrystalline silicon.
3. The negative electrode active material for a lithium secondary battery of claim 1 , wherein the porous polycrystalline silicon has a porosity of 5 vol % to 80 vol %.
4. The negative electrode active material for a lithium secondary battery of claim 1 , wherein the porous polycrystalline silicon comprises a metal impurity in an amount of 2,000 ppm or less.
5. The negative electrode active material for a lithium secondary battery of claim 1 , wherein the porous polycrystalline silicon does not comprise a metal impurity.
6. The negative electrode active material for a lithium secondary battery of claim 1 , further comprising a coating layer including a carbon-based material on a surface of the porous polycrystalline silicon.
7. The negative electrode active material for a lithium secondary battery of claim 6 , wherein the carbon-based material comprises amorphous carbon.
8. The negative electrode active material for a lithium secondary battery of claim 6 , wherein the coating layer including a carbon-based material is included in an amount of 50 wt % or less based on a total weight of the negative electrode active material.
9. A method of preparing a negative electrode active material for a lithium secondary battery, the method comprising:
performing a heat treatment on polycrystalline silicon including a metal impurity and cooling the polycrystalline silicon to prepare polycrystalline silicon including the metal impurity at grain boundaries; and
preparing porous polycrystalline silicon, in which pores are formed at grain boundaries, by performing an acid treatment on the polycrystalline silicon including the metal impurity at grain boundaries to dissolve the metal impurity.
10. The method of claim 9 , wherein the metal impurity comprises one selected from the group consisting of nickel (Ni), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), magnesium (Mg), calcium (Ca), phosphorus (P), aluminum (Al), germanium (Ge), tin (Sn), antimony (Sb), bismuth (Bi), and lithium (Li), or a mixture of two or more thereof.
11. The method of claim 9 , wherein the heat treatment is performed in a temperature of 750° C. to 1,400° C.
12. The method of claim 9 , wherein the cooling is performed by cooling to a temperature of 20° C. to 30° C. within 10 minutes.
13. The method of claim 9 , wherein the acid comprises one selected from the group consisting of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or a mixture of two or more thereof.
14. The method of claim 9 , further comprising forming a coating layer including a carbon-based material on a surface of the porous polycrystalline silicon, after the preparation of the porous polycrystalline silicon.
15. A negative electrode for a lithium secondary battery comprising the negative electrode active material of claim 1 .
16. A lithium secondary battery comprising the negative electrode of claim 15 .
17. A battery module comprising the lithium secondary battery of claim 16 as a unit cell.
18. A battery pack comprising the battery module of claim 17 .