提高锂电极稳定性的方法及其在锂氧电池中的应用

doi:10.11896/cldb.19050012

材料导报

2020, Vol. 34

Issue (19): 19067-19074 https://doi.org/10.11896/cldb.19050012

无机非金属及其复合材料

提高锂电极稳定性的方法及其在锂氧电池中的应用

罗志虹¹, 冀晨皓¹, 朱广彬¹, 李富杰¹, 周立¹, 罗鲲²

1 桂林理工大学材料科学与工程学院,桂林 541004
2 常州大学材料科学与工程学院,常州 213164

Research Progress on Methods for Improving the Stability of Li Metal and the
Application in Li-O₂ Batteries

LUO Zhihong¹, JI Chenhao¹, ZHU Guangbin¹, LI Fujie¹, ZHOU Li¹, LUO Kun²

1 College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China
2 School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China

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摘要以金属锂为负极的二次电池具有高的能量密度(3 860 mAh/g),被誉为电池设计制造业的“圣杯”。但是由于金属锂与电解液反应形成的固态电解质(SEI)组成和结构不均匀、稳定性较差,使得在电池循环过程中,金属锂的沉积和析出伴随着枝晶与“死锂”的生成以及体积膨胀,容易造成电池短路、循环稳定性差、能量效率低等问题。此外,在具有高能量密度的锂氧电池中,锂负极还面临着与正极交互作用(如与正极活性物质氧气、放电中间体分解电解液产生的水分等反应)带来的腐蚀问题。
本文对金属锂枝晶及腐蚀问题进行评述,涉及合金化锂负极、三维结构锂负极、表面处理、电解液成分、隔膜改性以及固态电解质等提高金属锂稳定性的方法。其具体包括锂与硅、锡、铝等金属形成的合金化电极;采用多孔金属(如镍、铜等)、多孔碳材料(如碳纳米管、石墨烯、碳纤维等)构筑三维结构电极及其亲锂性的改善方法;通过化学预处理、电化学预处理、抛光和制备保护膜等表面处理方式提高金属锂的稳定性;通过调整电解液溶剂、溶质、添加剂的成分或浓度等方法调控固态电解质的组成和结构,以增强其稳定性;采用高聚物和/或无机纳米材料的复合材料对传统电池隔膜进行改性以防止正负极交互作用;以及使用高锂离子电导率的固态电解质等。本文充分探讨了各种锂保护方法的基本原理,详细阐述了其改善金属锂稳定性的根本原因,阐明了各种锂保护手段对电池性能的影响及其存在的不足与相应的改进方法,并对锂电极保护在新型锂氧电池中的应用及前景进行了展望。

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关键词: 金属锂固态电解质膜枝晶腐蚀锂氧电池

Abstract: The secondary batteries with lithium metal as negative electrode possess high energy density (3 860 mAh/g), which is considered as “Holy grail” for battery design and manufacture. However, due to the unstable SEI originated from the reaction between Li anode and electrolyte with uneven component and structure, the plating and stripping of Li is accompanied with the formation of dendrite and “dead Li” during the battery cycling process, as well as volume expansion, which lead to the short circuit of battery, poor cyclic performance and low energy efficiency. In addition, in the operation of Li-O₂ batteries with extremely high energy, Li metal encounters corrosion caused by the interplay of positive and negative electrodes, for example, Li metal will react with O₂ of cathode and water from discharge intermediates decomposing electrolyte.
This contribution focuses on the dendrite and corrosion issues of Li metal electrode, including Li alloy anode, three dimensional structural anode, surface treatment, electrolyte component, separator modification and solid state electrolyte. Typically, this paper reviews the following methods: the formation of Li alloy anode by Li metal reacting with Si, Sn, Al etc; employing porous metals and porous carbon materials as structural electrode, such as Ni, Cu, carbon nanotubes, graphene and carbon fibers etc, as well as providing pathways for improving the lithiophilicity; improving the stability of Li anode by surface treatment, such as chemical pretreatment, electrochemical pretreatment, polishing and coating artificial film; adjusting the component and concentration of solvent, salt, additives of electrolyte to regulate the component and structure of SEI and enhance its stability; modifying the conventional separator with composites of polymer and/or inorganic nanoparticles to prevent the interplay between anode and cathode; adopting solid state electrolyte with high Li⁺ conductivity. The mechanism of various methods is discussed adequately, the primary reason for the enhancement of Li anode stability is illustrated in detail; the effects of these methods on the battery performance, as well as the merits and demerits are clarified. Moreover, a comprehensive overview on the application and prospect of protective strategies in the new type Li-O₂ batteries is presented.

Key words: Li metal solid electrolyte interface dendrite corrosion Li-O₂ batteries

发布日期: 2020-11-05

ZTFLH:

TB321

基金资助: 国家自然科学基金(51874051);广西自然科学基金(2018GXNSFAA281184;2019GXNSFAA245046)

通讯作者: luokun@cczu.edu.cn

作者简介: 罗志虹,桂林理工大学材料科学与工程学院,讲师,硕士研究生导师。于2014年获得华中科技大学博士学位。从事锂空气电池、超级电容器、燃料电池等的研究,取得了多项创新性成果,在Chem. Commun.、J. Mater. Chem. A.、ChemElectroChem等期刊发表学术论文20多篇。
冀晨皓,2018年毕业于太原工业学院,获得高分子材料与工程专业工学学士学位。现为桂林理工大学硕士研究生,在罗鲲教授和罗志虹博士的指导下进行研究。目前主要研究领域为新能源材料。
罗鲲,常州大学,教授,博士研究生导师,曾于2008—2018年在桂林理工大学任教。分别于2000年和2004年获得中国科学院材料科学与工程专业硕士学位和博士学位。从事新能源储能材料研究,已在Adv. Mater.、Chem. Commun. 、Chem.Mater., 、J. Mater. Chem. A.等期刊发表研究论文100余篇。

引用本文:

罗志虹, 冀晨皓, 朱广彬, 李富杰, 周立, 罗鲲. 提高锂电极稳定性的方法及其在锂氧电池中的应用[J]. 材料导报, 2020, 34(19): 19067-19074.
LUO Zhihong, JI Chenhao, ZHU Guangbin, LI Fujie, ZHOU Li, LUO Kun. Research Progress on Methods for Improving the Stability of Li Metal and the
Application in Li-O₂ Batteries. Materials Reports, 2020, 34(19): 19067-19074.

链接本文:

http://www.mater-rep.com/CN/10.11896/cldb.19050012 或 http://www.mater-rep.com/CN/Y2020/V34/I19/19067

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