Journal of the Korean Ceramic Society (한국세라믹학회지)

The Korean Ceramic Society (한국세라믹학회)
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Preparation of Spherical Li4Ti5O12 and the Effect of Y and Nb Doping on the Electrochemical Properties as Anode Material for Lithium Secondary Batteries

리튬이온이차전지용 구형 Li4Ti5O12 음극 합성 및 Y와 Nb 도핑에 따른 전기화학적 특성

  • Ji, Mi-Jung (Electronic Materials Laboratory, Korea Institute of Ceramic Engineering & Technology) ;
  • Kwon, Yong-Jin (Electronic Materials Laboratory, Korea Institute of Ceramic Engineering & Technology) ;
  • Kim, Eun-Kyung (Electronic Materials Laboratory, Korea Institute of Ceramic Engineering & Technology) ;
  • Park, Tae-Jin (Electronic Materials Laboratory, Korea Institute of Ceramic Engineering & Technology) ;
  • Jung, Sung-Hun (Electronic Materials Laboratory, Korea Institute of Ceramic Engineering & Technology) ;
  • Choi, Byung-Hyun (Electronic Materials Laboratory, Korea Institute of Ceramic Engineering & Technology)
  • 지미정 (한국세라믹기술원 전자소재팀) ;
  • 권용진 (한국세라믹기술원 전자소재팀) ;
  • 김은경 (한국세라믹기술원 전자소재팀) ;
  • 박태진 (한국세라믹기술원 전자소재팀) ;
  • 정성헌 (한국세라믹기술원 전자소재팀) ;
  • 최병현 (한국세라믹기술원 전자소재팀)
  • Received : 2012.10.26
  • Accepted : 2012.11.15
  • Published : 2012.11.30
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Abstract

Yttrium (Y) and niobium (Nb) doped spherical $Li_4Ti_5O_{12}$ were synthesized to improve the energy density and electrochemical properties of anode material. The synthesized crystal was $Li_4Ti_5O_{12}$, the particle size was less than $1{\mu}m$ and the morphology was spherical and well dispersed. The Y and Nb optimal doping amounts were 1 mol% and 0.5 mol%, respectively. The initial capacity of the dopant discharge and charge capacity were respectively 149mAh/g and 143 mAh/g and were significantly improved compared to the undoped condition at 129 mAh/g. Also, the capacity retention of 0.2 C/5 C was 74% for each was improved to 94% and 89%. It was consequently found that Y and Nb doping into the $Li_4Ti_5O_{12}$ matrix reduces the polarization and resistance of the solid electrolyte interface (SEI) layer during the electrochemical reaction.

Keywords

References

  1. Z. Yang, D. Choi, S. Kerisit, K.M. Rosso, D. Wang, J. Zhang, G. Graff, and J. Liu, "Nanostructures and Lithium Electrochemical Reactivity of Lithium Titanites and Titanium Oxides: A Review," J. Power Sources, 192 [2] 588-98 (2009). https://doi.org/10.1016/j.jpowsour.2009.02.038
  2. K. Hasegawa and Y. Arakawa, "Safety Study of Electrolyte Solutions for Lithium Batteries by Accelerating-rate Calorimetry," J. Power Sources, 44 [1-3] 523-29 (1993). https://doi.org/10.1016/0378-7753(93)80198-X
  3. I. Belharouak and K. Amine, "$Li_2MTi_6O_{14}$ (M = Sr, Ba): New Anodes for Lithium-ion Batteries," Electrochem. Commun, 5 [6] 435-38 (2003). https://doi.org/10.1016/S1388-2481(03)00090-0
  4. Panero S, Satolli D, Salomon M, and Scrosati B, "A New Type of Lithium-ion Cell based on the $Li_4Ti_5O_{12}/Li_2Co_{0.4}Fe_{0.4}Mn_{3.2}O_8$ High-voltage, Electrode Combination," Electrochem. Commun, 2 [11] 810-13 (2000). https://doi.org/10.1016/S1388-2481(00)00127-2
  5. K. Nakahara, R. Nakajima, T. Matsuchima, and H. Majima, "Preparation of Particulate $Li_4Ti_5O_{12}$ Having Excellent Characteristics as an Electrode Active Material for Power Storage Cells," J. Power Sources, 117 [1-2] 131-36 (2003). https://doi.org/10.1016/S0378-7753(03)00169-1
  6. H. Zhao, Y. Li , Z. Zhu, J. Lin, Z. Tian, and R. Wang, "Structural and Electrochemical Characteristics of $Li_4xAlxTi_5O_{12}$ as Anode Material for Lithium-ion Batteries," Electrochem. Acta, 53 [24] 7079-83 (2008). https://doi.org/10.1016/j.electacta.2008.05.038
  7. J. Shu, "RETRACTED: Li-Ti-O Compounds and Carboncoated Li-Ti-O Compounds as Anode Materials for Lithium Ion Batteries," Electrochem. Acta, 54 [10] 2869-76 (2009). https://doi.org/10.1016/j.electacta.2008.11.016
  8. C. Shen, X. Zhang, Y. Zhou, and H. Li, "Preparation and Characterization of Nanocrystalline $Li_4Ti_5O_{12}$ by Sol-gel Method," Materials Chemistry and Physics, 78 [2] 437-41 (2002).
  9. Y. Tang, L. Yang, S. Fang, and Z. Qiu, "$Li_4Ti_5O_{12}$ Hollow Microspheres Assembled by Nanosheets as an Anode Material for High-rate Lithium Ion Batteries," Electrochem. Acta, 54 [26] 6244-49 (2009). https://doi.org/10.1016/j.electacta.2009.05.092
  10. J. Kim and J. Cho, "Spinel $Li_4Ti_5O_{12}$ Nanowires for High-Rate Li-Ion Intercalation Electrode," Electrochem. Solid-State Letters, 10 [3] A81-A84 (2007). https://doi.org/10.1149/1.2431242
  11. B. H. Choi, M. J. Ji, Y. J. Kwon, E. K. Kim, and S. Nahm, "Electrochemical Properties of Lithium Secondary Battery and the Synthesis of Spherical $Li_4Ti_5O_{12}$ Powder by Using $TiCl_4$ As a Starting Material," Kor. J. Mater. Res., 20 [12] 669-75 (2010). https://doi.org/10.3740/MRSK.2010.20.12.669
  12. J. Gao, C. Jiang, J. Ying, and C. Wan, "Preparation and Characterization of High-density Spherical $Li_4Ti_5O_{12}$ Anode Material for Lithium Secondary Batteries," J. Power Sources, 155 [2] 364-67 (2006). https://doi.org/10.1016/j.jpowsour.2005.04.008
  13. S. H. Ju and Y. C. Kang, "Effects of Preparation Conditions on the Electrochemical and Morphological Characteristics of $Li_4Ti_5O_{12}$ Powders Prepared by Spray Pyrolysis," J. Power Sources, 189 [1] 185-90 (2009). https://doi.org/10.1016/j.jpowsour.2008.09.107
  14. S.Y. Yin, L.Song, X.Y.Wang, M.F.Zhang, K.L.Zhang, and Y.X.Zhang, "Synthesis of Spinel $Li_4Ti_5O_{12}$ Anode Material by a Modified Rheological Phase Reaction," Electrochem. Acta, 54 [24] 5629-33 (2009). https://doi.org/10.1016/j.electacta.2009.04.067
  15. Y. Hao, Q. Lai, J. Lu, D. Liu, and X. Ji, "Influence of Various Complex Agents on Electrochemical Property of $Li_4Ti_5O_{12}$ Anode Material," J. Alloy Compounds, 439 [1-2] 330-36 (2007). https://doi.org/10.1016/j.jallcom.2006.08.082
  16. Y. Hao, Q. Lai, Y. Chen, J. Lu, and X. Ji, "In Situ Deposition Method Preparation of $Li_4Ti_5O_{12}-SnO_2$ Composite Materials for Lithium Ion Batteries," J. Alloys Compounds, 462 [1-2] 404 (2008). https://doi.org/10.1016/j.jallcom.2007.08.061
  17. E. K. Kim, B. H. Choi, M. J. Ji, Y. J. Kwon, H. Seo, Y. J. Kim, and K. B. Kim, "Synthesis and Electrochemical Characteristics of $Li_4Ti_5O_{12}$ Nanofibers by Hydrothermal Method," J. Kor. Ceram. Soc., 47 [6] 627-32 (2010). https://doi.org/10.4191/KCERS.2010.47.6.627
  18. J.L. Allen, T.R. Jow, and J. Wolfenstine, "Low Temperature Performance of Nanophase $Li_4Ti_5O_{12}$," J. Power Sources, 159 [2] 1340-45 (2006). https://doi.org/10.1016/j.jpowsour.2005.12.039
  19. B. H. Choi, D. J. Lee, M. J. Ji, Y. J. Kwon, and S. T. park, "Study of the Electrochemical Properties of $Li_4Ti_5O_{12}$ Doped with Ba and Sr Anodes for Lithium-Ion Secondary Batteries," J. Kor. Ceram. Soc., 47 [6] 638-42 (2010). https://doi.org/10.4191/KCERS.2010.47.6.638
  20. J. W. Lee, J. I. Kim, K. C. Roh, S. M. Park, M. J. Ji, and B. H. Choi, "Hydrothermal Synthesis and Electrochemical Performance of Array of $Li_4Ti_5O_{12}$ Nanoparticles," Appl. Chem., 13 [2] 213-16 (2009).
  21. J. Gao, J. Ying, C. Jiang, and C. Wan, "Preparation and Characterization of Spherical La-doped $Li_4Ti_5O_{12}$ Anode Material for Lithium Ion Batteries," Ionics, 15 597-601 (2009). https://doi.org/10.1007/s11581-008-0306-0
  22. Z. Zhong, "Synthesis of $Mo^{4+}$ Substituted Spinel $Li_4Ti_{5x}Mo_xO_{12}$," Electrochem. Solid-State Lett., 10 [12] A267-A269 (2007). https://doi.org/10.1149/1.2784142
  23. S. Huang, Z. Wen, X. Zhu, and Z. Gu, "Preparation and Electrochemical Performance of Ag Doped $Li_4Ti_5O_{12}$," Electrochem. Commun, 6 [11] 1093-97 (2004). https://doi.org/10.1016/j.elecom.2004.08.013
  24. B. Tian, H. Xiang, L. Zhang, and H. Wang, "Effect of Nb-doping on Electrochemical Stability of $Li_4Ti_5O_{12}$ Discharged to 0 V," J. Solid State Electrochem, 16 [1] 205-11 (2012). https://doi.org/10.1007/s10008-011-1305-z