[논문]과전압 거동 분석을 통한 리튬 금속 음극의 전착/탈리 현상 이해

한지원; 진다희; 김수환; 이용민

doi:10.5229/jkes.2022.25.1.1

과전압 거동 분석을 통한 리튬 금속 음극의 전착/탈리 현상 이해
A Review on the Deposition/Dissolution of Lithium Metal Anodes through Analyzing Overpotential Behaviors 원문보기

전기화학회지 = Journal of the Korean Electrochemical Society, v.25 no.1, 2022년, pp.1 - 12

한지원 (대구경북과학기술원에너지공학과) , 진다희 (대구경북과학기술원에너지공학과) , 김수환 (대구경북과학기술원에너지공학과) , 이용민 (대구경북과학기술원에너지공학과)

초록
AI-Helper

리튬이온전지의 성능과 안전성을 뛰어넘는 다양한 차세대전지 개발이 진행되고 있다. 특히, 흑연을 대신할 고용량 음극 소재로 리튬 금속을 사용하는 연구는 여전히 활발히 이뤄지고 있지만, 높은 충전 전류 밀도에서 형성되는 덴드라이트는 리튬 금속 전극 상용화에 가장 큰 걸림돌이다. 이에 따라, 전해질 첨가제, 보호막 도입, 리튬 형상 제어 등 다양한 접근법으로 덴드라이트 문제를 개선하기 위한 연구가 진행되어 왔으며, 중요한 실험 결과 중 하나로서 가장 많이 보고되는 것이 리튬 대칭셀을 이용한 과전압 거동 분석이다. 이 과전압 거동은 크게 세 단계로 구분될 수 있지만, 대부분의 연구에서는 단순히 제어 변수에 따른 과전압 감소나 대칭셀 수명 차이로 각 접근법이 덴드라이트 형성 제어에 효과적임을 주장하고 있다. 또한, 각 과전압 거동을 자세히 살펴보면, 리튬 핵 생성 및 성장되는 전착 과정이나 탈리 조건에 크게 영향을 받고 있음에도, 이에 대한 해석은 제한적으로 이뤄지고 있다. 뿐만 아니라, 전착/탈리 과정이 장기간 반복됨에 따라, Dead 리튬 형성으로 인한 물질전달 제한이 과전압에 영향을 주고 있음이 명확히 언급되고 있지 않다. 따라서, 본 총설에서는 이러한 리튬 대칭셀 과전압 분석에 있어, 각 과전압 거동에 대한 이론적 배경을 자세히 설명하고, 전해질 조성, 분리막, 리튬 형상 제어, 리튬 표면 개질에 따른 과전압 거동 분석 결과를 재조명한다.

Abstract ▼ AI-Helper

Lithium metal is the most promising anode for next-generation lithium-ion batteries due to its lowest reduction potential (-3.04 V vs. SHE) and high specific capacity (3860 mAh/g). However, the dendritic formation under high charging current density remains one of main technical barriers to be used for commercial rechargeable batteries. To address these issues, tremendous research to suppress lithium dendrite formation have been conducted through new electrolyte formulation, robust protection layer, shape-controlled lithium metal, separator modification, etc. However, Li/Li symmetric cell test is always a starting or essential step to demonstrate better lithium dendrite formation behavior with lower overpotential and longer cycle life without careful analysis. Thus, this review summarizes overpotential behaviors of Li/Li symmetric cells along with theoretical explanations like initial peaking or later arcing. Also, we categorize various overpotential data depending on research approaches and discuss them based on peaking and arcing behaviors. Thus, this review will be very helpful for researchers in lithium metal to analyze their overpotential behaviors.

주제어

표/그림 (14)

그림 Fig. 1. (a) Potential profile of a Li/Li symmetric cell at 2 mA cm^-2 with a cut-off capacity of 1 mAh cm^-2. Magnified views of (a): (b) in the second cycle, (c) in the 40^th cycle, and (d) in the 57^th cycle. Reproduced with permission.²²⁾ Copyright 2018, Wiley-VCH.
그림 Fig. 2. (a) Overpotential behavior of a Li/Li symmetric cell during the first deposition/dissolution process in 1M LiPF₆ in EC/DMC(1/1) at 5 mA cm^-2 and (b) schematic cartoon and (c) activation energies of nucleation and growth processes in the (a). Reproduced with permission.¹⁶⁾ Copyright 2016, American Chemical Society.
그림 Fig. 3. (a) Overpotential behavior of a Li/Li symmetric cell after the first deposition/dissolution in 1M LiPF₆ in EC/ DMC(1/1) at 5 mA cm^-2. Reproduced with permission.¹⁶⁾ Copyright 2016, American Chemical Society. (b) Schematic cartoon of dead lithium formation. Reproduced with permission.²³⁾ Copyright 1998, Elsevier B.V. (c) Schematic cartoons to describe Li dissolution process in Li pits. Reproduced with permission.²⁴⁾ Copyright 2021, Wiley-VCH.
그림 Fig. 5. (a) Morphological evolution of dead Li layer with SEM images in the cycle number (2^nd, 22^nd, 36^th, and 42^nd), (b) schematic cartoon to compare the tortuosity of the Li ion paths before and after the formation of thick dead lithium layer, and (c) correlation between concentration gradient (red line) and overpotential (black line) during mid-cycles (upper). Li-ion concentration at the reducing electrode surface(x=α) as a function of time (t₁ < t₂ < t₃ < t₄) (lower). Reproduced with permission.¹⁷⁾ Copyright 2017, Royal Society of Chemistry.
그림 Fig. 4. Correlation between concentration gradient (red line) and overpotential (black line) during initial cycles (upper). Li-ion concentration at the reducing electrode surface(x=α) as a function of time (t₁ < t₂ < t₃ < t₄) (lower). Reproduced with permission.¹⁷⁾ Copyright 2017, Royal Society of Chemistry.
그림 Fig. 6. Potential profiles of Li/Li symmetric cells having (a) 1 M LiTFSI-DME/DOL electrolyte or (b) 5 M LiTFSIDME/ DOL at 0.25 mA cm^-2. Reproduced with permission.²⁵⁾ Copyright 2017, Elsevier B.V.
그림 Fig. 7. Potential profiles of Li/Li symmetric cells with and without an electrolyte additive, 2-fluoropyridine, in 1M LiPF₆ in EC/DEC (1/1, v/v) at 1 mA cm^-2. Reproduced with permission.⁹⁾ Copyright 2020, Elsevier B.V.
그림 Fig. 8. (a) Overpotential behavior of visualization Li/Li symmetric cells at 1 mA cm^-2 after 20 cycles and (b) schematic representation of nucleation barriers depending on electrolyte types (1 M LiPF₆+EC/DMC(1/ 1); 4 M LiFSI+DME; 1 M LiTFSI+DOL/DME (1/1)+ 0.18 M Li₂S₈ +2 wt% LiNO₃). Reproduced with permission.¹⁶⁾ Copyright 2016, American Chemical Society.
그림 Fig. 10. Effects of nano-Si-coated layer on polypropylene separator on potential profiles of Li/Li symmetric cells with 1 M LiPF₆ in EC/DMC (1/1, v/v) at 1 mA cm^-2 and 1 mAh cm^-2. Reproduced with permission.²⁷⁾ Copyright 2019, American Chemical Society.
그림 Fig. 11. Schematic cartoons of micro-patterning process with (a) a micro-needle roller and (b) a micro-stamp and (c) potential profiles of Li/Li symmetric cells with microneedle treated Li (upper) and bare Li (lower) using 1 M LiPF₆ in EC/DEC (1/1, v/v) at 0.53 mA cm^-2. Reproduced with permission.^{14, 28)} Copyright 2014, Wiley-VCH.
그림 Fig. 9. (a) Schematic configuration of Li/Li symmetric cells having polypropylene separators with or without anodic aluminum oxide layer and 1.2 M LiPF₆ in EC/ EMC (3/7, w/w) and (b) their potential profiles at 1 mA cm^-2 and 0.5 mAh cm^-2. Reproduced with permission.²⁶⁾ Copyright 2020, American Chemical Society.
그림 Fig. 12. Overpotential behaviors of Li/Li symmetric cells with bare Li and coated Li powder (CLiP) using 1 M LiPF₆ in EC/DMC (1/1) under the current densities of (a) 0.354 mA cm^-2 and (b) 0.885 mA cm^-2. Reproduced with permission.¹⁵⁾ Copyright 2013, Wiley-VCH.
그림 Fig. 13. Schematic cartoons to describe Li deposition processes on (a) bare Li metal and (b) Ag/Li composite. Potential profiles of Li/Li symmetric cells with (c) bare Li metal (d) Ag/Li composite using 1 M LiTFSI in DME/DOL (1/1, v/v) at 0.1 mA cm^-2 and 1 mA cm^-2. Reproduced with permission.²⁹⁾ Copyright 2019, Royal Society of Chemistry.
그림 Fig 14. (a) Schematics of bare Li foil and Li₃P/LiCl-protected Li foil and (b) potential profiles of Li/Li symmetric cells having bare and coated Li foils with 1 M LiPF₆ in EC/DMC/EMC (1/1/1, v/v/v) containing 5 wt% FEC at various current densities. Reproduced with permission.³⁰⁾ Copyright 2019, Royal Society of Chemistry.

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