Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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Electrochemical Performance of High-Voltage Lithium-Ion Batteries with NCM Cathode Varying the Thickness of Coating Layer by Atomic Layer Deposition

Atomic Layer Deposition의 두께 변화에 따른 NCM 양극에서의 고전압 리튬 이온 전지의 전기화학적 특성 평가

  • Im, Jinsol (Department of Materials Science and Chemical Engineering, Hanyang University) ;
  • Ahn, Jinhyeok (Department of Materials Science and Chemical Engineering, Hanyang University) ;
  • Kim, Jungmin (School of Chemical Engineering, Sungkyunkwan University) ;
  • Sung, Shi-Joon (Convergence Research Center for Solar Energy, DGIST) ;
  • Cho, Kuk Young (Department of Materials Science and Chemical Engineering, Hanyang University)
  • 임진솔 (한양대학교재료화학공학과) ;
  • 안진혁 (한양대학교재료화학공학과) ;
  • 김정민 (성균관대학교화학공학과) ;
  • 성시준 (DGIST 태양에너지융합연구센터) ;
  • 조국영 (한양대학교재료화학공학과)
  • Received : 2019.04.16
  • Accepted : 2019.04.30
  • Published : 2019.05.31
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Abstract

High-voltage operation of the lithium ion battery is one of the advantageous approaches to obtain high energy capacity without changing the conventional cell components and structure. However, operating at harsh condition inevitably results in severe side reactions at the electrode surface and structural disintegration of active material particles. Herein we coated layers composed of $Al_2O_3$ and ZnO on the electrode based on NCM using atomic layer deposition (ALD). Thicker layers of novel Al-doped ZnO (AZO) coating compared to conventional ALD coated layers are prepared. Cathode based on NCM with the varying AZO coating thickness are fabricated and used for coin cell assembly. Effect of ALD coating thickness on the charge-discharge cycle behavior obtained at high-voltage operation was investigated.

이차 전지의 고전압 구동은 기존 셀 구조의 변화 없이도 고용량을 구현할 수 있는 유용한 접근 방법 중에 하나이나, 전극 표면에서의 극심한 부반응과 전극 활물질의 구조 붕괴 등과 같은 문제를 야기하게 된다. 본 연구에서는 니켈-망간-코발트 삼성분계(NCM) 활물질을 도입한 양극의 고전압 구동을 위해 원자층 증착법 (Atomic Layer Deposition, ALD)을 통해 전극판 표면에 $Al_2O_3$와 ZnO층으로 구성된 코팅 층을 형성하였다. 기존 ALD법으로 제조되는 박막에 비해 유사한 조건에서도 두꺼운 Al-doped ZnO (AZO)층을 최초로 형성하였고, 코팅된 AZO층의 두께를 달리한 NCM 기반의 양극판을 제조하였다. ALD 코팅된 양극이 도입된 코인셀을 제조하여 두껍게 형성된 코팅 층의 두께에 따른 고전압에서 충방전 거동을 확인하였다.

Keywords

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Fig. 1. (a) Schematic of ALD coating process: mainly ZnO deposition and only one layer of Al2O3 deposition. TEM image of ZnO:Al2O3 ALD coating layer on glass. (b) ZnO:Al2O3 = 5:1 (AZO6), (c) ZnO:Al2O3 = 9:1 (AZO10), (d) ZnO:Al2O3 = 19:1 (AZO20), and (e) ZnO:Al2O3 = (19:1)×2 (AZO40)

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Fig. 2. EDS mapping of ALD coated NCM523 at AZO20: (a) SEM image of analysis site, and mapping image of elements of (b) Al (aluminum), and (c) Zn (zinc). (d) Element intensity of Zn.

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Fig. 3. EDS elemental line concentration profile of ALD coated NCM523 at AZO20: (a), (b) SEM image of analysis area point, (c) intensity, and (d) atomic %.

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Fig. 4. Cyclic voltammetry on ALD coated cathode half cell: (a) AZO6, (b) AZO10, (c) AZO20, and (d) AZO40.

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Fig. 5. Electrochemical result of cells using ALD coated and non-coated cathode: cycle performance of the cell operated at the cut off voltage of 4.5 V. (a) cycle rate of 0.2 C, (b) cycle rate of 0.5 C, (c) coulombic efficiency, (d) capacity retention plot using the result of (a), and (e) rate capability.

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Fig. 6. Nyquist plots of coated cathode and anode full cell systems: (a) non-coated, (b) AZO6, (c) AZO10, (d) AZO20, (e) AZO40, and (f) equivalent circuit used to model the impedance spectra of cells.

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