Anode active material including a multilayer metal nanotube, anode including the anode active material, lithium battery including the anode, and method of preparing the anode active material
| Title: | Anode active material including a multilayer metal nanotube, anode including the anode active material, lithium battery including the anode, and method of preparing the anode active material |
|---|---|
| Patent Number: | 9,070,943 |
| Publication Date: | June 30, 2015 |
| Appl. No: | 13/546403 |
| Application Filed: | July 11, 2012 |
| Abstract: | An anode active material, an anode including the anode active material, a lithium battery including the anode, and a method of preparing the anode active material. The anode active material includes: a multilayer metal nanotube including: an inner layer; and an outer layer on the inner layer, wherein the inner layer includes a first metal having an atomic number equal to 13 or higher, and the outer layer includes a second metal different from the first metal. |
| Inventors: | Choi, Jae-man (Hwaseong-si, KR); Hwang, Seung-sik (Seongnam-si, KR); Kwon, Moon-seok (Hwaseong-si, KR); Song, Min-sang (Seongnam-si, KR); Shon, Jeong-kuk (Hwaseong-si, KR); Kim, Myung-hoon (Seoul, KR); Kim, Han-su (Seoul, KR); Paik, Un-gyu (Seoul, KR); Song, Tae-seup (Seoul, KP) |
| Assignees: | SAMSUNG ELECTRONICS CO., LTD. (KR), INDUSTRY-UNIVERSITY COOPERATION FOUNDATION HANYANG UNIVERSITY (KR) |
| Claim: | 1. An anode active material comprising a multilayer metal nanotube comprising: an inner layer; and an outer layer on the inner layer, wherein the inner layer comprises a first metal having an atomic number equal to 13 or higher, and the outer layer comprises a second metal different from the first metal, and wherein the second metal has a resistivity which is less than a resistivity of the first metal. |
| Claim: | 2. The anode active material of claim 1 , wherein the second metal has a lithium ion diffusivity which is greater than a lithium ion diffusivity of the first metal. |
| Claim: | 3. The anode active material of claim 1 , wherein the second metal has a volume expansion during charging which is less than a volume expansion during charging of the first metal. |
| Claim: | 4. The anode active material of claim 1 , wherein the first metal is at least one selected from silicon, germanium, antimony, tin, aluminum, zinc, silver, gold, platinum, molybdenum, tungsten, and an alloy thereof. |
| Claim: | 5. The anode active material of claim 1 , wherein the first metal is a Group 14 element. |
| Claim: | 6. The anode active material of claim 1 , wherein the second metal is at least one selected from germanium, antimony, tin, aluminum, zinc, silver, gold, platinum, molybdenum, tungsten, and an alloy thereof. |
| Claim: | 7. The anode active material of claim 1 , wherein the outer layer comprises a composite of the first metal and the second metal. |
| Claim: | 8. The anode active material of claim 1 , wherein the inner layer is crystalline and the outer layer is amorphous. |
| Claim: | 9. The anode active material of claim 1 , wherein at least one of the inner layer and the outer layer further comprises a dopant. |
| Claim: | 10. The anode active material of claim 9 , wherein the dopant is a Group 13 element or a Group 15 element. |
| Claim: | 11. The anode active material of claim 1 , further comprising at least one layer disposed between the inner layer and the outer layer. |
| Claim: | 12. The anode active material of claim 1 , wherein a wall thickness of the metal nanotube is about 10 nanometers to about 200 nanometers. |
| Claim: | 13. The anode active material of claim 1 , wherein a thickness of the inner layer is about 5 nanometers to about 100 nanometers. |
| Claim: | 14. The anode active material of claim 1 , wherein a thickness of the outer layer is about 5 nanometers to about 100 nanometers. |
| Claim: | 15. The anode active material of claim 1 , wherein an outer diameter of the metal nanotube is about 30 nanometers to about 400 nanometers. |
| Claim: | 16. The anode active material of claim 1 , wherein an inner diameter of the metal nanotube is about 20 nanometers to about 200 nanometers. |
| Claim: | 17. The anode active material of claim 1 , wherein a length of the metal nanotube is about 1 μm to about 50 μm. |
| Claim: | 18. The anode active material of claim 1 , wherein an end of the metal nanotube is closed. |
| Claim: | 19. An anode comprising the anode active material according to claim 1 . |
| Claim: | 20. The anode of claim 19 , comprising: a conductive substrate; and a plurality of multilayer metal nanotubes disposed on the conductive substrate. |
| Claim: | 21. The anode of claim 20 , wherein the multilayer metal nanotubes are disposed at a regular interval on the conductive substrate. |
| Claim: | 22. The anode of claim 20 , wherein the multilayer metal nanotubes extend away from a surface of the conductive substrate. |
| Claim: | 23. The anode of claim 20 , wherein the metal nanotubes extend in in a direction which is perpendicular to a surface of the conductive substrate. |
| Claim: | 24. The anode of claim 20 , wherein the conductive substrate comprises at least one selected from stainless steel, copper, iron, nickel, aluminum, and cobalt. |
| Claim: | 25. A lithium battery comprising the anode of claim 19 . |
| Claim: | 26. A method of preparing an anode active material, the method comprising: growing a metal oxide nanorod which extends away from a surface of a conductive substrate; forming a first metal layer comprising a first metal on the metal oxide nanorod to form a coated metal oxide nanorod; thermally treating the coated metal oxide nanorod to selectively remove the metal oxide nanorod and form a first metal nanotube; and forming a second metal layer comprising a second metal on the first metal nanotube to form a multilayer metal nanotube to prepare the anode active material, wherein the anode active material comprises a multilayer metal nanotube comprising an inner layer, and an outer layer on the inner layer, wherein the inner layer comprises a first metal having an atomic number equal to 13 or higher, and the outer layer comprises a second metal different from the first metal, and wherein the second metal has a resistivity which is less than a resistivity of the first metal. |
| Claim: | 27. The method of claim 26 , wherein the metal oxide is at least one selected from ZnO, Al 2 O 3 , SiO 2 , ZrO 2 , TiO 2 , and MgO. |
| Claim: | 28. The method of claim 26 , wherein the first metal layer comprises at least one selected from silicon, germanium, antimony, tin, aluminum, zinc, silver, gold, platinum, molybdenum, tungsten, and an alloy thereof. |
| Claim: | 29. The method of claim 26 , wherein the second metal layer comprises at least one selected from germanium, antimony, tin, aluminum, zinc, silver, gold, platinum, molybdenum, tungsten, and an alloy thereof. |
| Claim: | 30. The method of claim 26 , wherein the forming of the first metal layer comprises contacting the metal oxide nanorod with a first metal precursor gas. |
| Claim: | 31. The method of claim 30 , wherein the first metal precursor gas is at least one selected from SiH 4 , SiCl 4 , GeH 4 , and GeF 4 . |
| Claim: | 32. The method of claim 30 , wherein the first metal precursor gas further includes a dopant precursor gas. |
| Claim: | 33. The method of claim 30 , wherein the contacting of the first metal precursor gas and the metal oxide nanorod is performed at about 200° C. to about 800° C. for about 1 minute to about 1000 minutes. |
| Claim: | 34. The method of claim 26 , wherein the thermally treating the coated metal oxide nanorod to selectively remove the metal oxide nanorod is performed in an atmosphere of at least one selected from hydrogen, argon, nitrogen, neon, and helium. |
| Claim: | 35. The method of claim 26 , wherein the thermally treating the coated metal oxide nanorod to selectively remove the metal oxide nanorod is performed at a temperature of about 200° C. or greater. |
| Claim: | 36. The method of claim 26 , wherein the forming of the second metal layer comprises contacting the first metal nanotube with a second metal precursor gas. |
| Claim: | 37. The method of claim 36 , wherein the second metal precursor gas is at least one selected from SiH 4 , SiCl 4 , GeH 4 , and GeF 4 . |
| Claim: | 38. The method of claim 36 , wherein the second precursor gas further comprises a dopant precursor gas. |
| Claim: | 39. The method of claim 36 , wherein the first metal nanotube is contacted with the second metal precursor gas at about 200° C. to about 800° C. for about 1 minute to about 1000 minutes. |
| Patent References Cited: | 2011/0104551 May 2011 Yang et al. 2011/0159365 June 2011 Loveness et al. 2011/0159367 June 2011 Kim et al. 1020030020298 March 2003 1020100032059 March 2010 1020100093465 August 2010 1020100136073 December 2010 2010129910 November 2010 2010138617 December 2010 |
| Other References: | Extended European Search Report for corresponding European Patent Application No. 12 17 6104, dated Nov. 15, 2012, 7 pages. cited by applicant Park, Mi-Hee, et al., “Silicon Nanotube Battery Anodes”, Nano Letters, 2009, vol. 9, No. 11, pp. 3844-3847. cited by applicant |
| Primary Examiner: | Walls, Cynthia K |
| Attorney, Agent or Firm: | Cantor Colburn LLP |
| Accession Number: | edspgr.09070943 |
| Database: | USPTO Patent Grants |
| Language: | English |
|---|