Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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Accelerated Formation of Surface Films on the Degradation of LiCoO2 Cathode at High Temperature

표면 피막 형성이 LiCoO2 양극의 고온 열화에 미치는 영향

  • Sung, Jong Hun (Department of Chemistry and Chemical Institute for Functional Materials, Pusan National University) ;
  • Hasan, Fuead (Department of Chemistry and Chemical Institute for Functional Materials, Pusan National University) ;
  • Yoo, Hyun Deog (Department of Chemistry and Chemical Institute for Functional Materials, Pusan National University)
  • Received : 2020.04.30
  • Accepted : 2020.05.25
  • Published : 2020.08.31
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Abstract

It is crucial to investigate the thermal degradation of lithium-ion batteries (LIBs) to understand the possible malfunction at high temperature. Herein, we investigated the effects of surface film formation on the thermal degradation of lithium cobalt oxide (LiCoO2, LCO) cathode that is one of representative cathode materials. Cycling test at 60℃ exhibited poorer cycleability compared with the cycling at 25℃. Cathodes after the initial 5 cycles at 60℃ (60-LCO) exhibited higher impedance compared to the cathode after initial 5 cycles at 25℃ (25-LCO), resulting in the lower rate capability upon subsequent cycling at 25℃, although the capacity values were similar at the lowest C-rate of 0.1C. In order to understand degradation of the LCO cathode at the high temperature, we analyzed the cathodes surface using X-ray photoelectron spectroscopy (XPS). Among various peaks, intensity of lithium hydroxide (LiOH) increased substantially after the operation at 60℃, and the C-C signal that represents the conductive agent was distinctly lower on 60-LCO compared to 25-LCO. These results pointed to an excessive formation of cathode-electrolyte interphase including LiOH at 60℃, leading to the increase in the resistance and the resultant degradation in the electrochemical performances.

리튬이온전지의 열적 열화 메커니즘을 이해하는 것은 전지의 안전성을 향상시키기 위한 필수적인 과정이다. 본 논문에서는 대표적인 양극물질의 하나인 리튬코발트산화물(LiCoO2, LCO)이 고온에서 작동할 때 형성되는 표면 필름에 의한 전기화학적 성능 열화를 조사하였다. 먼저 25℃와 60℃ 각각의 온도에서 사이클 테스트를 진행한 결과, 60℃에서 25℃에 비해 저하된 사이클 수명을 보였다. 이후 처음 5사이클을 25℃, 60℃에서 구동시킨 LCO 양극을 각각 25-LCO, 60-LCO라 명명하였으며, 이후 임피던스 및 출력 특성 분석은 25℃에서 진행하였다. 이때 두 샘플 모두 저속에서의 초기 용량은 비슷함에도 불구하고 60-LCO가 25-LCO에 비해 높은 임피던스와 낮은 출력 특성을 보였다. X-선 광전자분광 (XPS)분석 결과 60-LCO 샘플에서 cathode-electrolyte interphase의 성분 중 하나인 절연성의 수산화 리튬 (LiOH) 성분이 다량 검출되었으며, 이는 고온에서 과도한 표면 필름 형성이 양극의 표면 저항 증가 및 속도/수명 특성 저하를 가져왔음을 보여준다.

Keywords

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