Electrode active material, electrode comprising the same, lithium battery comprising the electrode, and method of preparing the electrode active material
| Title: | Electrode active material, electrode comprising the same, lithium battery comprising the electrode, and method of preparing the electrode active material |
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| Patent Number: | 9,343,732 |
| Publication Date: | May 17, 2016 |
| Appl. No: | 13/548746 |
| Application Filed: | July 13, 2012 |
| Abstract: | An electrode active material, an electrode including the electrode active material, a lithium battery including the electrode, and a method of preparing the electrode active material. The electrode active material includes a core having at least one of a metal or a metal oxide that enables intercalation and deintercalation of lithium ions and a crystalline carbon thin film that is formed on at least a portion of a surface of the core. The electrode active material has a nano-structure. |
| Inventors: | Shon, Jeong-kuk (Cheonan-si, KR); Choi, Jae-man (Hwaseong-si, KR); Hwang, Seung-sik (Seongnam-si, KR); Kwon, Moon-seok (Hwaseong-si, KR); Song, Min-sang (Seongnam-si, KR); Kim, Myung-hoon (Seoul, KR); Kim, Ji-man (Suwon-si, KR); Park, Gwi-ok (Pyeongtaek-si, KR) |
| Assignees: | SAMSUNG ELECTRONICS CO., LTD. (KR) |
| Claim: | 1. An electrode active material comprising: a core comprising at least one of a metal and a metal oxide which enable intercalation and deintercalation of lithium ions; a crystalline carbon thin film that is formed on at least a portion of a surface of the core; and the electrode active material has a nano-structure, wherein the core comprises pores and a skeleton that forms a wall between adjacent pores, the electrode active material has a bimodal pore size distribution, the crystalline carbon thin film is formed on an exposed surface of the core and an inner wall of the pore by forming a carbon-based moiety represented by Formula 2 below and converting the carbon-based moiety into the crystalline carbon thin film having a thickness of 2 nanometers or less, wherein the metal comprises at least one of tin (Sn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), molybdenum (Mo), and bismuth (Bi), and the metal oxide comprises at least one of tin oxide, iron oxide, cobalt oxide, nickel oxide, zinc oxide, manganese oxide, molybdenum oxide, and bismuth oxide: [chemical expression included] wherein ring A is benzene, naphthalene, phenalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentaphene, hexacene, pyridine, pyrazine, pyrimidine, pyridazine, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, phenanthridine, phenanthroline, or phenazine; b is an integer of 1 to 5; and * denotes a binding site with the surface of the core. |
| Claim: | 2. The electrode active material of claim 1 , wherein the electrode active material is in the form of a particle, rod, wire, or tube. |
| Claim: | 3. The electrode active material of claim 1 , wherein the pores are connected to each other to form a channel. |
| Claim: | 4. The electrode active material of claim 1 , wherein the core comprises at least one of SnO 2 and MoO 2 . |
| Claim: | 5. The electrode active material of claim 1 , wherein the peak intensity ratio of I D /I G is 0.7 or lower, wherein in a Raman spectrum of the crystalline carbon thin film, I D represents an intensity of peak D that is present at a wave number of 1360±10 cm −1 and I G represents an intensity of peak G that is present at a wave number of 1580±10 cm −1 . |
| Claim: | 6. The electrode active material of claim 1 , wherein a powder resistance value of the electrode active material at 31.83 Mpa is in a range of about 2.0×10 −5 S/cm to about 1.0×10 −2 S/cm. |
| Claim: | 7. The electrode active material of claim 1 , wherein B/A is 7.69×10 −3 g 2 /m 2 or less, A represents a specific surface area of the core, and B represents a mass of the carbon thin film. |
| Claim: | 8. The electrode active material of claim 1 , wherein a specific surface area of the electrode active material is in a range of about 50 m 2 /g to about 250 m 2 /g. |
| Claim: | 9. An electrode comprising the electrode active material of claim 1 . |
| Claim: | 10. A lithium battery comprising the electrode of claim 9 . |
| Claim: | 11. A lithium battery of claim 10 , wherein the electrode is a negative electrode. |
| Claim: | 12. A method of preparing the electrode active material of claim 1 , the method comprising: forming a carbon-based moiety represented by Formula 2 below on at least a portion of a surface of a core including at least one of a metal and a metal oxide that enable intercalation and deintercalation of lithium ions by mixing i) the core, ii) a carbon-based precursor represented by Formula 1 below, and iii) a solvent; and converting the carbon-based moiety into a crystalline carbon thin film having a thickness of 2 nm or less by heating in an inert atmosphere the core on which the carbon-based moiety is formed, [chemical expression included] in Formulae 1 and 2, the ring A is benzene, naphthalene, phenalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentaphene, hexacene, pyridine, pyrazine, pyrimidine, pyridazine, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, phenanthridine, phenanthroline, or phenazine; a and b are each independently an integer of 1 to 5; and * denotes a binding site with the surface of the core, wherein the metal comprises at least one of tin (Sn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), molybdenum (Mo), and bismuth (Bi), and the metal oxide comprises at least one of tin oxide, iron oxide, cobalt oxide, nickel oxide, zinc oxide, manganese oxide, molybdenum oxide, and bismuth oxide. |
| Claim: | 13. The method of claim 12 , wherein a and b each are 1 or 2. |
| Claim: | 14. The method of claim 12 , wherein the forming of the carbon-based moiety on at least a portion of the surface of the core further comprises heating at a temperature of about 100° C. to about 500° C. for about 1 hour to about 5 hours to promote dehydration between a hydroxyl group at the core surface and a hydroxyl group of the carbon-based precursor. |
| Claim: | 15. The method of claim 12 , wherein the heating of the core on which the carbon-based moiety is formed, is performed at a temperature of about 300° C. to about 600° C. for about 1 hour to about 5 hours. |
| Claim: | 16. The electrode active material of claim 1 , wherein the thickness of the crystalline carbon thin film is smaller than the thickness of the skeleton. |
| Claim: | 17. The electrode active material of claim 1 , wherein the carbon-based moiety is 2,3-dihydroxynaphthalene. |
| Claim: | 18. The electrode active material of claim 1 , wherein the carbon-based moiety is formed using a carbon-based precursor represented by Formula 1 below [chemical expression included] wherein the ring A is a substituted or unsubstituted C 5 -C 30 aromatic ring or a substituted or unsubstituted C 2 -C 30 heteroaromatic ring; and a is an integer of 1 to 5. |
| Patent References Cited: | 2004/0234859 November 2004 Lee et al. 2006/0234127 October 2006 Kim et al. 10-2011-0004500 January 2011 10-2011-0035003 April 2011 10-2011-0036447 April 2011 2004049473 June 2004 |
| Other References: | Sugnaux (EP 1207572) (a raw machine translation) (Abstract and Detailed Description) (May 22, 2002). cited by examiner Yuan, et al., Nano-structured SnO2—carbon composites obtained by in situ spray pyrolysis method as anodes in lithium batteries, Journal of Power Sources 146 (2005) pp. 180-184. cited by applicant Extended European Search Report for Application No. 12181559.1-2119 dated Dec. 18, 2012. cited by applicant Xiaoxu Ji et al., “Carbon-Coated SnO2 Nanorod Array for Lithium-Ion Battery Anode Material,” Nanoscale Res Lett, vol. 5, 2010, p. 649-653. cited by applicant Hirotomo Nishihara et al., “Carbon-coated mesoporous silica with hydrophobicity and electrical conductivity,” Carbon, vol. 46, 2008, p. 48-53. cited by applicant Taeri Kwon et al., “Carbon-coated mesoporous silica as an electrode material,” Microporous and Mesoporous Materials, vol. 132, 2010, p. 421-427. cited by applicant Mijung Noh et al., “Amorphous Carbon-Coated Tin Anode Material for Lithium Secondary Battery,” Chem. Mater, vol. 17, 2005, p. 1926-1929. cited by applicant |
| Assistant Examiner: | Lyles-Irving, Carmen |
| Primary Examiner: | Ryan, Patrick |
| Attorney, Agent or Firm: | Cantor Colburn LLP |
| Accession Number: | edspgr.09343732 |
| Database: | USPTO Patent Grants |
| Language: | English |
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