EC : MA 혼합전해질에서 카본 전극의 용량 특성 II. 초기 비가역 용량에 대한 첨가제의 효과

Properties of Capacity on Carbon Electrode in EC : MA Electrolyte II. Effect of Additives on Initial Irreversible Capacity

  • 박동원 (전남대학교 자연과학대학 화학과 & RRC/HECS & IBS) ;
  • 김우성 (대정화금(주) 중앙연구소) ;
  • 손동언 (전남대학교 자연과학대학 화학과 & RRC/HECS & IBS) ;
  • 최용국 (전남대학교 자연과학대학 화학과 & RRC/HECS & IBS)
  • Park, Dong-Won (Department of Chemistry & RRC/HECS & IBS, Chonnam National University) ;
  • Kim, Woo-Seong (R & D Center, DaeJung Chemicals & Metals Co., LTD) ;
  • Son, Dong-Un (Department of Chemistry & RRC/HECS & IBS, Chonnam National University) ;
  • Choi, Yong-Kook (Department of Chemistry & RRC/HECS & IBS, Chonnam National University)
  • 투고 : 2006.01.02
  • 심사 : 2006.11.08
  • 발행 : 2006.12.10

초록

리튬의 삽입과 탈리가 가능한 탄소전극은 첫 싸이클 동안 카본전극 계면에 solid electrolyte interface가 형성된다. 초기 충전과정에서의 용매분해로 형성된 막은 전지의 성능에 영향을 미치게 되며, 이러한 용매분해는 초기 비가역 용량의 주된 요인중의 하나이다. 본 연구에서는 초기 비가역 반응을 억제하기위해 카본 표면 위에 부동태 막 형성을 위한 첨가제로서 $Li_{2}CO_{3}$을 사용하였다. $Li_{2}CO_{3}$ 첨가 효과를 시간대 전압법, 순환 전압-전류법, 그리고 임피던스법을 이용하여 조사하였고, 또한 SEM, EDX 그리고 XRD를 통해 표면 현상과 조성의 변화를 관찰하였다. 1 M $LiPF_{6}$/EC : MA (1 : 3, v/v) 전해질 용액에 $Li_{2}CO_{3}$의 첨가는 전극 표면에서의 용매분해 억제를 통하여 초기 비가역 용량을 감소시킴을 확인하였다.

Solid electrolyte interface is formed on a carbon electrode used as an anode in Li-ion battery, which can be of $Li^{+}$ intercalation/deintercalation during the first cycle. The passivation film formed by a solvent decomposition during the initial charge process affects cell performance and it was one of the main reason of an initial irreversible capacity. This paper describes the use, for the first time, of $Li_2CO_3$ as the additive for the formation of a passivation film on the carbon surface to suppress the initial irreversible reaction. Chronopotentiometry, cyclic voltammetry, and impedance spectroscopy were used to investigate the effects of the $Li_{2}CO_{3}$ additive. Scanning electron microscopy, energy dispersive X-ray analysis, and X-ray diffraction were also used to monitor changes in the surface morphology and composition of the passivation film formed by solvent decomposition and the precipitation of $Li_{2}CO_{3}$. The addition of $Li_{2}CO_{3}$ to a solution of 1 M $LiPF_{6}$/EC:MA (1:3, v/v) resulted in a decrease in the initial irreversible capacity and it was due to the suppression of the solvent decomposition on the electrode surface.

키워드

과제정보

연구 과제 주관 기관 : 과학기술부

참고문헌

  1. J. O. Besenhard, M. Winter, J. Yang, and W. Biberacher, J. Power Sources, 54, 228 (1995) https://doi.org/10.1016/0378-7753(94)02073-C
  2. D. Aurbach, Y. Gofer, M. Ben-Zion, and P. Aped, J. Electroanal. Chem., 339, 451 (1992) https://doi.org/10.1016/0022-0728(92)80467-I
  3. U. von Sacken, E. Nodwell, A. Sundger, and J. R. Dahn, Solid State Ionics, 138, 2207 (1991)
  4. M. Kikuchi, Y. Ikezawa, and T. Takamura, J. Electroanal. Chem., 396, 451 (1995) https://doi.org/10.1016/0022-0728(95)04082-Y
  5. D. Aurbach, Y. Ein-Eli, O. Chusid (Youngman), Y. Carmeli, M. Babai, and H. Yamin, J. Electrochem. Soc., 141, 603 (1994) https://doi.org/10.1149/1.2054777
  6. T. Abe, N. Kawabata, Y. Mizutani, M. Inaba, and Z. Ogumi, J. Electrochem. Soc., 150, A257 (2003) https://doi.org/10.1149/1.1541004
  7. M. Egashira, S. Okada, and J. Yamaki, J. Power Sources, 124, 237 (2003) https://doi.org/10.1016/S0378-7753(03)00601-3
  8. D. Aurbach, Y. Ein-Eli, B. Markovsky, A. Zaban, S. Luski, Y. Carmeli, and H. Yamin, J. Electrochem. Soc., 142, 2882 (1995) https://doi.org/10.1149/1.2048659
  9. Y. Ein-Eli, S. R. Thomas, and V. R. Koch, J. Electrochem. Soc., 144, 1159 (1997) https://doi.org/10.1149/1.1837566
  10. T. Osaka, T. Momma, Y. Matsumoto, and Y. Uchida, J. Electrochem. Soc., 144, 1709 (1997) https://doi.org/10.1149/1.1837665
  11. M. Winter, R. Imhof, F. Joho, and P. Novk, J. Power Sources, 81, 818 (1999) https://doi.org/10.1016/S0378-7753(99)00116-0
  12. Y.-K. Choi, K.-I. Chung, W.-S. Kim, Y.-E. Sung, and S.-M. Park, J. Power Sources, 104, 132 (2002) https://doi.org/10.1016/S0378-7753(01)00911-9
  13. K.-I. Chung, J.-G. Park, W.-S. Kim, Y.-E. Sung, and Y.-K. Choi, J. Power Sources, 112, 626 (2002) https://doi.org/10.1016/S0378-7753(02)00421-4
  14. W.-S. Kim, K.-I. Chung, J.-H. Cho, D.-W. Park, C.-Y, Kim, and Y.-K. Choi, J. Ind. Eng. Chem., 9, 699 (2003)
  15. D. Aurbach and A. Zaban, J. Electroanal. Chem., 348, 155 (1993) https://doi.org/10.1016/0022-0728(93)80129-6
  16. D.-W. Park, W.-S. Kim, D.-U. Son, S.-P. Kim, and Y.-K. Choi, J. Korean Ind. Eng. Chem., 12, 183 (2006)