Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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Effect of Lithium Bis(oxalate)borate as an Electrolyte Additive on Carbon-coated SiO Negative Electrode

탄소가 코팅된 일산화규소(SiO) 음극에서 전해질 첨가제로서 Lithium Bis(oxalato)borate의 영향

  • Kim, Kun Woo (Technology team, Samsung SDI Co., Ltd.) ;
  • Lee, Jae Gil (Department of Chemical and Biological Engineering, Seoul National University) ;
  • Park, Hosang (Department of Chemical and Biological Engineering, Seoul National University) ;
  • Kim, Jongjung (Department of Chemical and Biological Engineering, Seoul National University) ;
  • Ryu, Ji Heon (Graduate School of Knowledge-based Technology and Energy, Korea Polytechnic University) ;
  • Kim, Young-Ugk (Energy 1-Lab., Samsung SDI Co. Ltd.) ;
  • Oh, Seung M. (Department of Chemical and Biological Engineering, Seoul National University)
  • 김건우 (삼성SDI 전지사업부) ;
  • 이재길 (서울대학교 화학생물공학부) ;
  • 박호상 (서울대학교 화학생물공학부) ;
  • 김종정 (서울대학교 화학생물공학부) ;
  • 류지헌 (한국산업기술대학교 지식기술기반 에너지대학원) ;
  • 김영욱 (삼성SDI 중앙연구소) ;
  • 오승모 (서울대학교 화학생물공학부)
  • Received : 2013.12.23
  • Accepted : 2014.01.22
  • Published : 2014.02.28
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Abstract

As an electrolyte additive, the effects of lithium bis(oxalate)borate (LiBOB) on the electrochemical properties of a carbon-coated silicon monoxide (C-coated SiO) negative electrode are investigated. The used electrolyte is 1.3M $LiPF_6$ that is dissolved in ethylene carbonate (EC), fluoroethylene carbonate (FEC), and diethyl carbonate (DEC) (5:25:70 v/v/v) with or without 0.5 wt. % LiBOB. In the LiBOB-free electrolyte, the film resistance is not so high in the initial period of cycling that lithiation is facilitated to generate the crystalline $Li_{15}Si_4$ phase. Due to repeated volume change that is caused by such a deep charge/discharge, cracks form in the active material to cause a resistance increase, which eventually leads to capacity fading. When LiBOB is added into the electrolyte, however, more resistive surface film is generated by decomposition of LiBOB in the initial period. The crystalline $Li_{15}Si_4$ phase does not form, such that the volume change and crack formation are greatly mitigated. Consequently, the C-coated SiO electrode exhibits a better cycle performance in the later cycles. At an elevated temperature ($45^{\circ}C$), wherein the effect of film resistance is less critical, the alloy ($Li_{15}Si_4$ phase) formation is comparable for the LiBOB-free and added cell to give a similar cycle performance.

탄소가 코팅된 일산화규소(C-coated SiO) 전극에서 전해질 첨가제로서 lithium bis(oxalato)borate(LiBOB)의 영향을 조사하였다. 전해질 조성은 1.3M $LiPF_6$/ethylene carbonate (EC), fluoroethylene carbonate (FEC), diethyl carbonate (DEC) (5:25:70 v/v/v)이며, 여기에 LiBOB을 0.5 wt.% 첨가한 것과 첨가하지 않은 2가지 전해질을 사용하였다. LiBOB을 첨가하지 않은 전해질에서 C-coated SiO 전극은 초기에 저항이 작은 피막이 형성되어 결정질의 $Li_{15}Si_4$를 형성할 때까지 합금화가 진행되며 동시에 큰 부피 변화를 보였다. 따라서 입자의 균열이 발생하고, 전극의 저항이 증가하여 충방전이 진행됨에 따라 용량이 빠르게 감소하였다. 반면에 LiBOB이 첨가된 전해질에서는 초기에 LiBOB의 환원분해에 의해 저항이 큰 피막이 형성되어, 합금화 반응이 원활히 진행되지 못하였다. 따라서 결정질 $Li_{15}Si_4$도 생성되지 못하였고, 결과적으로 부피변화도 적게 발생하므로 입자의 균열과 전극 저항의 증가도 적게 나타났다. 이러한 효과로 싸이클 후반부에서 용량감소가 적었고, 싸이클 성능도 좋은 결과를 보였다. 반면 피막 저항에 의한 영향이 줄어드는 $45^{\circ}C$ 에서는 LiBOB 첨가에 관계없이 합금화 반응이 유사하게 진행되며 비슷한 싸이클 성능을 나타내었다.

Keywords

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