Interfacial Coordination Engineering to Boost Li‐Ion Conduction in Economic Zr‐Based Halide Electrolytes

IF 27.4 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Advanced Materials Pub Date : 2025-07-15 DOI:10.1002/adma.202509928

Mengyi Wu, Han Su, Yu Zhong, Fanya Zhao, Jiangping Tu, Xiuli Wang

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引用次数: 0

Abstract

Halide solid electrolytes (HSEs) have seen rapid progress in the development of all‐solid‐state lithium batteries (ASSLBs), offering favorable lithium‐ion transport properties, broad electrochemical stability, and strong interfacial compatibility with high‐voltage oxide cathodes. However, developing HSEs that simultaneously offer high ionic conductivity and low cost remains a significant challenge. Most high‐conductivity halides rely on expensive metal elements, whereas cost‐effective Zr‐based halides are limited by their relatively low ionic conductivity. In this study, a new composite electrolyte (LA/LZCO) is developed via an interfacial coordination reaction between Zr‐based oxychlorides (LZCO) and Li1.3Al0.3Ti1.7(PO4)3 (LATP). The coordination between PO43− groups in LATP and Zr4+ in LZCO induces local structural disorder, promoting LZCO amorphization. As a result, the ionic conductivity of LA/LZCO composite electrolyte is enhanced by more than twofold compared to LZCO, reaching 2.81 mS cm−1, among one of the highest reported for Zr‐based halide electrolytes. When integrated into ASSLBs with NCM83125 cathodes, the composite electrolyte enables excellent cycling stability, with 92.4% and 87.5% capacity retention after 1000 cycles at 0.5 and 2 C under 4.25 V. Even at an elevated cut‐off voltage of 4.5 V, 85.1% capacity is retained after 380 cycles, highlighting the promise of this composite strategy for high‐energy, long‐life ASSLBs.

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界面配位工程促进经济的Zr基卤化物电解质中Li离子的传导

卤化物固体电解质（HSEs）在全固态锂电池（ASSLBs）的发展中取得了快速进展，具有良好的锂离子传输性能，广泛的电化学稳定性以及与高压氧化物阴极的强界面相容性。然而，开发同时提供高离子电导率和低成本的hse仍然是一个重大挑战。大多数高导电性卤化物依赖于昂贵的金属元素，而具有成本效益的Zr基卤化物则受到其相对较低的离子导电性的限制。本研究通过Zr基氧氯化物（LZCO）与Li1.3Al0.3Ti1.7(PO4)3 （LATP）的界面配位反应，制备了一种新型复合电解质LA/LZCO。LATP中的PO43−基团与LZCO中的Zr4+之间的配位导致了LZCO的局部结构紊乱，促进了LZCO的非晶化。结果表明，LA/LZCO复合电解质的离子电导率比LZCO提高了两倍以上，达到2.81 mS cm−1，是目前报道的Zr基卤化物电解质中离子电导率最高的电解质之一。当与NCM83125阴极集成到asslb时，复合电解质具有出色的循环稳定性，在0.5和2 C下4.25 V下循环1000次后，容量保持率分别为92.4%和87.5%。即使在4.5 V的高截止电压下，380次循环后仍能保持85.1%的容量，这突出了这种复合策略对高能、长寿命assb的承诺。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Advanced Materials 工程技术-材料科学：综合

CiteScore

43.00

自引率

4.10%

发文量

2182

审稿时长

2 months

期刊介绍： Advanced Materials, one of the world's most prestigious journals and the foundation of the Advanced portfolio, is the home of choice for best-in-class materials science for more than 30 years. Following this fast-growing and interdisciplinary field, we are considering and publishing the most important discoveries on any and all materials from materials scientists, chemists, physicists, engineers as well as health and life scientists and bringing you the latest results and trends in modern materials-related research every week.