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发展高比容量负极材料是提升锂电池能量密度的重要技术路线。然而，高比容量负极材料在充放电循环过程中存在不可逆体积膨胀大和界面副反应剧烈等问题挑战，从而劣化下一代高比能锂电池的寿命和安全。近年来，随着先进表征技术的发展，研究发现循环后的锂电池负极中存在大量氢化锂，但目前关于氢化锂的存在及其作用机制仍存在较大争议。本文通过综述相关文献，首先总结了氢化锂的基本物理化学性质，然后系统回顾了氢化锂在非锂金属负极、金属锂负极中的研究进展以及氢化物在非锂电池负极中的研究进展。最后，针对氢化锂诱导负极失效和保护机制提出一些思考和探讨，并对高容量负极材料、界面和电解液的优化改进提出展望，旨在推动下一代高比能锂电池的快速发展。
Abstract：Lithium batteries are widely and profoundly applied in different fields(i.e., portable electronic devices and electric vehicles) due to their high energy density and environmental friendliness. However, high-capacity electrode materials become a key to the development of the next generation of high-energy lithium batteries with the increasing demand for extended driving ranges in new energy electric vehicles. The chemical environment in these next-generation high-energy lithium batteries is complex, with intensified electrode/electrolyte interfacial reactions. Among these challenges, some issues such as the volume expansion of high-capacity anode materials and severe side reactions at the interface have a significant negative impact on the cycle life and safety of the battery. Recent studies reveal the presence of significant amounts of lithium hydride(Li H) in the anode of lithium batteries after cycling. However, there is a considerable debate regarding the existence of Li H and its underlying mechanisms. The formation and evolution of Li H, as well as its role in inducing anode failure, remain major research gaps. This review summarizes the fundamental physicochemical properties of Li H based on the existing literature and systematically represents the research work on lithium hydride in non-lithium metal anodes, lithium metal anodes, and non-lithium battery anodes. Furthermore, this review discusses the mechanisms by which Li H induces anode failure and protection, to provide a targeted guidance for the optimization and improvement of high-capacity anode materials, interfaces, and electrolytes, thus facilitating the commercialization of the next generation of high-energy lithium batteries. This review firstly introduced the fundamental physicochemical properties of Li H. As a hydride of metallic lithium, Li H is the lightest ionic compound in nature and exhibits strong alkalinity. Furthermore, this review summarizes the conventional synthesis methods for Li H and the conventional chemical reactions in which it can participate. These related chemical reactions can provide valuable insights and considerations for research on Li H in battery anodes. From the ongoing advancement in the understanding of the interfacial chemistry of battery anodes and advanced characterization techniques, the presence of Li H is confirmed in both non-lithium metal anodes(i.e., graphite, germanium, and silicon) and lithium metal anodes, which serves as a new component of the anode solid electrolyte interphase(SEI) film. However, the existing research mainly focuses on confirming the existence of Li H, while the distribution of Li H in the anode surface/interface or bulk phase, its formation and evolution mechanisms, and its effects on different anode materials remain unclear. In addition to the presence of Li H in lithium battery anodes, related hydrides(such as sodium hydride(Na H), magnesium hydride(Mg H2), etc.) are also identified in non-lithium battery anodes. The formation and decomposition of these hydrides can have significant effects on the performance of the anode materials and even the overall battery performance. Summary and prospects High-capacity anode materials are a preferred option for the development of the next generation of high-energy lithium batteries. However, some issues such as the volume expansion of high-capacity anode materials and severe side reactions at the interface significantly hinder their further development. The discovery of Li H on the anode provides a perspective for investigating the problems related to anode materials and interfacial failure. However, there remains considerable controversy due to the limited scope of the existing research. Firstly, most studies on the physicochemical properties of Li H focus on bulk particles(bulk-Li H), whereas what is generated at the battery anode interface is predominantly in the form of nanoparticles(nano-Li H). It is thus crucial to fully understand the nanoparticle effects of nano-Li H. Also, there is a need for in-depth studies on the formation and decomposition mechanisms of Li H on different anode materials, as well as the various effects and mechanisms by which Li H interacts with these materials. It is important to investigate the reactivity of the nano-sized lithium hydride formed at the anode with various components of the battery, as well as its correlation with battery failure phenomena. A clarification is needed to determine whether Li H accelerates battery failure or failure issues trigger the formation of Li H. Research on these issues can deepen the understanding of Li H and provide valuable insights for the study of hydrides in other battery anodes. Furthermore, the research will offer some targeted strategies for optimizing and improving high-capacity anode materials, interfaces, and electrolytes.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20240771
中图分类号:TQ131.11;TM912
引用信息:
[1]杨立萱,庄想春,李杰东等.锂电池负极中氢化锂研究的一些思考和探讨[J].硅酸盐学报,2025,53(06):1685-1699.DOI:10.14062/j.issn.0454-5648.20240771.
基金信息:
国家自然科学基金(22102206); 山东省自然科学基金(ZR2024YQ008)