Li3N对固态电解质Li2ZrCl6与锂金属界面优化作用的研究

全固态锂金属电池由于具有较高的安全性能和高能量密度被认为是最有应用前景的下一代储能和动力电池。开发出性能优良的固态电解质是发展全固态锂金属电池的难点之一。氯化物固态电解质Li₂ZrCl₆（LZC）由于其高室温离子电导率、高氧化稳定性和低成本等特性而受到了国内外学者的广泛关注，但是由于LZC还原稳定性较差，和锂金属接触后会直接发生反应，这限制了其在全固态锂金属电池中的应用。为了攻克该难题，本文首次系统研究了LZC和锂金属界面的失效机制并开展了利用Li₃N进行界面保护的研究工作。

本文利用球磨的方式合成了LZC，对其电化学性能进行了测试。重点研究了LZC和Li金属的反应现象，对反应产物进行了表征分析，监测了电化学循环过程中LZC和锂金属负极界面的演化过程。发现界面不但无法自限，而且会持续恶化导致失效。通过对LZC和锂金属的界面失效机制的分析，提出了一种优化策略。

本文选择Li₃N作为保护层来进行界面优化的策略。基于固态烧结方法制备的α-Li₃N具有较高的室温离子电导率，并且与Li接触非常稳定，对于LZC和Li金属界面同时产生优化作用，可有效防止LZC和Li金属在电池循环中发生反应。在α-Li₃N保护层的作用下，LZC能够在对称锂金属电池中实现稳定的循环，并能够与常用正极材料组装成全固态锂金属电池，并实现更好的循环性能。

综上所述，本文通过合理的材料选择和界面优化，较好地解决了LZC还原稳定性差、锂金属负极循环不稳定等问题。本工作为利用LZC电解质和锂金属负极开发高性能全固态锂金属电池提供了有效的策略。

All-solid-state lithium-metal batteries (ASSLMBs) are considered to be the most promising next-generation batteries due to their high safety performance and high energy density. The development of solid electrolytes with excellent performance is the key to the development of ASSLMBs. The chloride solid-state electrolyte Li₂ZrCl₆ (LZC) has attracted extensive attention because of its high ionic conductivity at room temperature, high oxidation stability and low cost. However, owing to poor reduction stability, LZC will be reduced upon contact with lithium metal, limiting the application in ASSLMBs. To solve this problem, we studied the degradation mechanism of interface between LZC and lithium metal, and proposed using Li₃N as an interface protection strategy.

In this work, LZC was synthesized by mechanochemical milling. Its electrochemical performance was analyzed, focusing particularly on the reaction products of LZC and lithium metal, and the interface between LZC and lithium-metal anode during cycling. During cycling, the interface deteriorated continuously. By analyzing the mechanism of its interface degradation, an optimization strategy was proposed.

To solve the problem of the LZC/lithium-metal interface, Li₃N was selected as a protective layer. α-Li₃N prepared by sintering has high ionic conductivity at room temperature. It effectively prevents the reaction between LZC and lithium metal during cycling. Moreover, α-Li₃N shows an excellent optimization effect on the LZC/lithium-metal anode interface. The use of an α-Li₃N protective layer enables LZC to form ASSLMBs with common cathode materials, and achieve better cycling performance. The use of an α-Li₃N protective layer also enables LZC to achieve stable cycling in symmetrical lithium-metal batteries, and to form state-of-the-art ASSLMBs with common cathode materials.

In summary, through reasonable material selection and interface optimization, the problems of poor reduction stability of LZC and unstable cycling of lithium-metal anode are well solved. This work provides an effective strategy for the development of high-performance ASSLMBs with LZC electrolyte and lithium-metal anode.

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