Porous silicon composite cluster structure, method of preparing the same, carbon composite using the same, and electrode, lithium battery, and device each including the same

1. A porous silicon composite cluster structure comprising:

a porous silicon composite cluster comprising a porous silicon composite secondary particle and a second carbon flake on at least one surface of the porous silicon composite secondary particle; and

a carbonaceous layer on the porous silicon composite cluster, the carbonaceous layer comprising amorphous carbon,

wherein the porous silicon composite secondary particle comprises an aggregate of two or more silicon primary particles,

each of the two or more silicon primary particles comprises silicon, a silicon suboxide of the formula SiO x , wherein 0<x<2, coated on the silicon, and a first carbon flake coated on the silicon suboxide,

the silicon suboxide is in a form of a film, a matrix, or a combination thereof, and

the first carbon flake and the second carbon flake are each independently present in a form of a film, a particle, a matrix, or a combination thereof,

wherein the first carbon flake is a first graphene flake, and

wherein the first graphene flake is

separated from the silicon suboxide by a distance of about 10 nanometers or less,

comprises 1 to about 30 graphene layers having a total thickness of about 0.3 nanometers to about 1,000 nanometers.

2. The porous silicon composite cluster structure of claim 1 , wherein the second carbon flake is directly on the surface of the porous silicon secondary particle.

3. The porous silicon composite cluster structure of claim 1 , wherein the first carbon flake and the second carbon flake each independently comprise graphene, graphite, carbon fibers, graphitic carbon, or graphene oxide.

4. The porous silicon composite cluster structure of claim 1 , wherein the amorphous carbon of the carbonaceous layer comprises pitch carbon, soft carbon, hard carbon, a meso-phase pitch carbonization product, a sintered coke, carbon fiber, or a combination thereof.

5. The porous silicon composite cluster structure of claim 1 , wherein the carbonaceous layer further comprises a crystalline carbon.

6. The porous silicon composite cluster structure of claim 4 , wherein the crystalline carbon comprises natural graphite, artificial graphite, graphene, a fullerene, carbon nanotubes, or a combination thereof.

7. The porous silicon composite cluster structure of claim 1 , wherein a ratio of a total weight of the first carbon flake and the second carbon flake of the porous silicon secondary particle to a total weight of the carbonaceous layer is in a range of about 30:1 to about 1:3 by weight.

8. The porous silicon composite cluster structure of claim 1 , wherein the carbonaceous layer comprises a first carbonaceous layer comprising the amorphous carbon, and a second carbonaceous layer comprising a crystalline carbon.

9. The porous silicon composite cluster structure of claim 1 , wherein the carbonaceous layer is a non-porous continuous coating and has a thickness in a range of about 1 nanometer to about 5000 nanometers.

10. The porous silicon composite cluster structure of claim 1 , wherein a ratio of a diameter of the porous silicon secondary particle to a diameter of the porous silicon composite cluster is in a range of about 1:1.0001 to about 1:30.

11. The porous silicon composite cluster structure of claim 1 , wherein a total amount of the first carbon flake and the second carbon flake in the porous silicon composite is in a range of about 0.1 part to about 2,000 parts by weight, based on 100 parts by weight of the silicon.

12. The porous silicon composite cluster structure of claim 1 ,

wherein the second carbon flake of the porous silicon composite secondary particle is a second graphene flake,

wherein the first graphane flake is oriented at an angle of about 0° to about 90° with respect to a major axis of the silicon, and

wherein the second graphene flake is

separated from the silicon suboxide by a distance of about 1000 nanometers or less,

comprises 1 to about 30 graphene layers having a total thickness of about 0.3 nanometers to about 1,000 nanometers, and

is oriented at an angle of about 0° to about 90° with respect to a major axis of the silicon.

13. The porous silicon composite cluster structure of claim 1 , wherein the silicon suboxide has a thickness of about 30 micrometers or less.

14. The porous silicon composite cluster structure of claim 1 , wherein the silicon is in a form of a sphere, a nanowire, a needle, a rod, a particle, a nanotube, a nanorod, a wafer, a nanoribbon, or a combination thereof.

15. The porous silicon composite of claim 1 , wherein the porous silicon secondary particle has an average particle diameter of about 200 nanometers to about 50 micrometers, a specific surface area of about 0.1 square meter per gram to about 100 square meters per gram, and a density of about 0.1 gram per cubic centimeter to about 2.8 grams per cubic centimeter.

16. The porous silicon composite cluster structure of claim 1 , wherein the silicon of the silicon primary particles has an average particle diameter of about 10 nanometers to about 30 micrometers.

17. A carbon composite comprising:

the porous silicon composite cluster structure of claim 1 ; and

a carbonaceous material.

18. An electrode comprising the porous silicon composite cluster structure of claim 1 or comprising a carbon composite which comprises the porous silicon composite cluster structure of claim 1 and a carbonaceous material.

19. The electrode of claim 18 , wherein the carbonaceous material comprises graphene, graphite, fullerene, carbon fiber, graphitic carbon, carbon nanotube, or a combination thereof, and

wherein an amount of the carbonaceous material is about 0.001 to about 99.999 parts by weight, based on 100 parts by weight of the carbon composite.

20. A lithium battery comprising the electrode of claim 18 .

21. A porous silicon composite cluster structure comprising:

a porous silicon composite cluster comprising a porous silicon composite secondary particle and

a second carbon flake on at least one surface of the porous silicon composite secondary particle; and

a carbonaceous layer on the porous silicon composite cluster, the carbonaceous layer comprising amorphous carbon,

wherein the porous silicon composite secondary particle comprises an aggregate of two or more silicon primary particles, wherein

each of the two or more silicon primary particles comprises silicon, a silicon suboxide of the formula SiO x , wherein 0<x<2, coated on the silicon, and a first carbon flake coated on the silicon suboxide, and

the silicon suboxide is in a form of a film, a matrix, or a combination thereof, and

wherein the first carbon flake and the second carbon flake are each independently present in a form of a film, a particle, a matrix, or a combination thereof, and

wherein the second carbon flake of the porous silicon composite secondary particle is a second graphene flake, and wherein the second graphene flake is separated from the silicon suboxide by a distance of about 1000 nanometers or less, and comprises 1 to about 30 graphene layers having a total thickness of about 0.3 nanometers to about 1,000 nanometers.

22. The porous silicon composite cluster structure of claim 21 , wherein the second graphene flake is oriented at an angle of about 0° to about 90° with respect to a major axis of the silicon.

23. A carbon composite comprising:

the porous silicon composite cluster structure of claim 21 ; and

a carbonaceous material.

24. An electrode comprising the porous silicon composite cluster structure of claim 21 or comprising a carbon composite which comprises the porous silicon composite cluster structure of claim 21 and a carbonaceous material.

25. The electrode of claim 24 , wherein the carbonaceous material comprises graphene, graphite, fullerene, carbon fiber, graphitic carbon, carbon nanotube, or a combination thereof, and

wherein an amount of the carbonaceous material is about 0.001 to about 99.999 parts by weight, based on 100 parts by weight of the carbon composite.

26. A lithium battery comprising the electrode of claim 24 .

27. A porous silicon composite cluster structure comprising:

a porous silicon composite cluster comprising a porous silicon composite secondary particle and a second carbon flake on at least one surface of the porous silicon composite secondary particle; and

a carbonaceous layer on the porous silicon composite cluster, the carbonaceous layer comprising amorphous carbon,

wherein the porous silicon composite secondary particle comprises an aggregate of two or more silicon primary particles, wherein

each of the two or more silicon primary particles comprises silicon, a silicon suboxide of the formula SiOx, wherein 0<x<2, coated on the silicon, and a first carbon flake coated on the silicon suboxide, and

the silicon suboxide is in a form of a film, a matrix, or a combination thereof, and

wherein the first carbon flake and the second carbon flake are each independently present in a form of a film, a particle, a matrix, or a combination thereof,

wherein a ratio of a total weight of the first carbon flake and the second carbon flake of the porous silicon secondary particle to a total weight of the carbonaceous layer is in a range of about 10:1 to about 1:0.9 by weight.

28. The porous silicon composite cluster structure of claim 27 , wherein the carbonaceous layer further comprises a crystalline carbon, and the crystalline carbon comprises natural graphite, artificial graphite, graphene, a fullerene, carbon nanotubes, or a combination thereof.

29. The porous silicon composite cluster structure of claim 27 , wherein the carbonaceous layer comprises a first carbonaceous layer comprising the amorphous carbon, and a second carbonaceous layer comprising a crystalline carbon.

30. The porous silicon composite cluster structure of claim 27 , wherein the carbonaceous layer is a non-porous continuous coating and has a thickness in a range of about 1 nanometer to about 5000 nanometers.

31. The porous silicon composite cluster structure of claim 27 , wherein a ratio of a total weight of the first carbon flake and the second carbon flake of the porous silicon secondary particle to a total weight of the carbonaceous layer is in a range of about 6:4 to about 1:0.9 by weight.

32. A carbon composite comprising:

the porous silicon composite cluster structure of claim 27 ; and

a carbonaceous material.

33. An electrode comprising the porous silicon composite cluster structure of claim 27 or comprising a carbon composite which comprises the porous silicon composite cluster structure of claim 27 and a carbonaceous material.

34. The electrode of claim 33 ,

wherein the carbonaceous material comprises graphene, graphite, fullerene, carbon fiber, graphitic carbon, carbon nanotube, or a combination thereof, and

wherein an amount of the carbonaceous material is about 0.001 to about 99.999 parts by weight, based on 100 parts by weight of the carbon composite.

35. A lithium battery comprising the electrode of claim 33 .

36. A device comprising the porous silicon composite cluster structure of claim 1 or comprising a carbon composite which comprises the porous silicon composite cluster structure of claim 1 and a carbonaceous material.

37. A device comprising the porous silicon composite cluster structure of claim 21 or comprising a carbon composite which comprises the porous silicon composite cluster structure of claim 21 and a carbonaceous material.

38. A device comprising the porous silicon composite cluster structure of claim 27 or comprising a carbon composite which comprises the porous silicon composite cluster structure of claim 27 and a carbonaceous material.

39. A method of preparing the porous silicon composite cluster structure of claim 1 , the method comprising:

contacting a dispersing agent, a solvent, and a particle comprising silicon and a silicon suboxide of the formula SiO x wherein 0<x<2, coated on the silicon, to obtain a porous silicon cluster;

thermally treating a combination of a carbon source gas and the porous silicon cluster to obtain the porous silicon secondary particle; and

mixing a composition comprising the porous silicon secondary particle, amorphous carbon, and a solvent in a dry manner to prepare the porous silicon composite.

40. A method of preparing the porous silicon composite cluster structure of claim 21 , the method comprising:

contacting a dispersing agent, a solvent, and a particle comprising silicon and a silicon suboxide of the formula SiO x wherein 0<x<2, coated on the silicon, to obtain a porous silicon cluster;

thermally treating a combination of a carbon source gas and the porous silicon cluster to obtain the porous silicon secondary particle; and

mixing a composition comprising the porous silicon secondary particle, amorphous carbon, and a solvent in a dry manner to prepare the porous silicon composite.

41. A method of preparing the porous silicon composite cluster structure of claim 27 , the method comprising:

contacting a dispersing agent, a solvent, and a particle comprising silicon and a silicon suboxide of the formula SiO x wherein 0<x<2, coated on the silicon, to obtain a porous silicon cluster;

thermally treating a combination of a carbon source gas and the porous silicon cluster to obtain the porous silicon secondary particle; and

mixing a composition comprising the porous silicon secondary particle, amorphous carbon, and a solvent in a dry manner to prepare the porous silicon composite.

42. A porous silicon composite cluster structure comprising:

a porous silicon composite cluster comprising

a core comprising a porous silicon composite secondary particle, and

a shell disposed on the core, the shell comprising a second carbon flake; and

a carbonaceous layer on the porous silicon composite cluster, the carbonaceous layer comprising amorphous carbon,

wherein the porous silicon composite secondary particle comprises an aggregate of silicon composite primary particles, and each of the silicon composite primary particles in the aggregate comprises:

at least one silicon oxide selected from i) a silicon suboxide (SiOx, wherein 0<x<2), and ii) a thermal treatment product of a silicon suboxide (SiOx, wherein 0<x<2); and

a first carbon flake disposed on the at least one silicon suboxide,

wherein the silicon suboxide is in a form of a film, a matrix, or a combination thereof, and the first carbon flake and the second carbon flake are each independently present in a form of a film, particles, a matrix, or a combination thereof,

wherein the thermal treatment product is a product of thermally treating the silicon suboxide in an atmosphere of a carbon source gas or a gas mixture comprising a carbon source gas and a reducing gas, and the thermal treatment product of the silicon suboxide comprises a silicon oxide of the formula SiOy, wherein 0<y≤2, and silicon disposed in the silicon oxide, or

the thermal treatment product comprises a structure comprising a silicon oxide of the formula SiO2, a silicon suboxide of the formula SiOy wherein 0<y<2, or a combination thereof, and silicon disposed in the structure,

wherein the first carbon flake is a first graphene flake, and

wherein the first graphene flake is

separated from the silicon suboxide by a distance of about 10 nanometers or less,

comprises 1 to about 30 graphene layers having a total thickness of about 0.3 nanometers to about 1,000 nanometers.

43. The porous silicon composite cluster structure of claim 42 ,

wherein the first graphene flake is oriented at an angle of about 0° to about 90° with respect to a major axis of the silicon suboxide.