优化Li||NCM811电池电解液溶剂化和电极电解液界面的阴离子受体添加剂策略

doi:10.3866/PKU.WHXB202306039

摘要/Abstract

摘要：

锂金属电池的循环稳定性和倍率能力受制于多个因素，如阳极/阴极电解液界面的品质和电解液溶剂化特性。在该工作中，我们提出了阴离子受体电解液添加剂策略，通过六氟苯添加剂对Li⁺溶剂化结构进行调控，实现了PF₆⁻的稳定性并提高了电解液的导电性，优化了阳极/阴极电解液界面中间相的组分/结构特征，有效抑制了锂枝晶的生长和提升了阴极表面的Li⁺传输，Li||Li对称电池在1 mA∙cm⁻²的电流密度下实现超过400 h的稳定循环，并且Li||NCM811电池在200 mA∙g⁻¹的电流密度下经过100次循环后的容量保持率达到75%。

关键词: 电解液, 六氟苯, 阴离子受体, 锂金属电池, 锂负极, 阳极/阴极电解质界面

Abstract:

Metallic lithium (Li) offers Li metal batteries (LMBs) with an opportunity to meet the high-energy demand in many fields. At present, the main cathode materials used for high-energy-density batteries are nickel-rich layered oxides, including nickel cobalt lithium manganese oxides (NCM) with intercalation chemistry. According to this plan, NMC811 demonstrates great merits in this aspect. However, there are still many problems with Li metal anode. The failure of Li anode is mainly caused by the high reactivity of Li metal, which can cause irreversible continuous reactions between Li and electrolyte to shorten cycling life. Due to multiple electroplating and stripping processes, Li anode undergoes significant volume and morphology change, increasing side reactions and the growth of Li dendrites caused by the first two factors. Electrolyte engineering, as a simple and effective modification method, can effectively solve the above problems. Among them, using electrolyte additives is a simple, efficient, and economical electrolyte engineering strategy. Herein, we proposed an anion acceptor electrolyte additive strategy for optimizing the component/structural characteristics of solid/cathode electrolyte interphases to inhibit the growth of Li dendrites and Li⁺ transition on cathode surface for enhancing cycling and rate performance of Li|| NCM811 battery, which is also ascribed to the regulation of Li⁺ solvation structure by hexafluorobenzene (HFBen) to realizing the stability of PF₆⁻ and the conductivity enhancement of electrolyte. As expected, Li||Li cells with 1% (wt) HFBen-contained electrolyte could achieve a stable cycling above 400 h at 1 mA∙cm⁻², and the capacity retention rate of Li||NCM811 battery could reach 75% after 100 cycles at 200 mA∙g⁻¹. Finally, the cycling and rate performance of Li||NMC811 batteries were significantly enhanced at 4.5 V with the help of HFBen. This work demonstrates that HFBen as an additive can effectively improve the electrochemical performance of LMBs. Moreover, the interfacial reaction mechanism across the batterywas analyzed and studied. This study provides new insights for the interface reaction between electrolyte and Li anode.

Key words: Electrolyte, Hexafluorobenzene, Anion acceptor, Lithium metal battery, Lithium anode, Anode/cathode electrolyte interphases

刘建东, 李鑫, 吴达雄, 王华平, 黄俊达, 马建民. 优化Li||NCM811电池电解液溶剂化和电极电解液界面的阴离子受体添加剂策略[J]. 物理化学学报, 2024, 40(6), 2306039. doi: 10.3866/PKU.WHXB202306039

Jiandong Liu, Xin Li, Daxiong Wu, Huaping Wang, Junda Huang, Jianmin Ma. Anion-Acceptor Electrolyte Additive Strategy for Optimizing Electrolyte Solvation Characteristics and Electrode Electrolyte Interphases for Li||NCM811 Battery[J]. Acta Phys. -Chim. Sin. 2024, 40(6), 2306039. doi: 10.3866/PKU.WHXB202306039

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202306039

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I6/2306039

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