Covalency-driven amorphization in dual-anion-doped Li-Zr-Cl electrolytes enables long-life all-solid-state batteries

IF 15.7 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Matter Pub Date : 2026-10-20 DOI:10.1016/j.matt.2026.103062

Zhenyu Zhu,Bohan Zhang,Ning He,Yiyan Liu,Shuoqing Zhao,Yi Pei,Shaojun Guo

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Abstract

Zirconium-based halide electrolytes are promising candidates for all-solid-state lithium batteries (ASSLBs) owing to their low cost and facile processability, but their practical application is constrained by insufficient ionic conductivity. Here, we develop a dual-anion strategy to induce covalency-driven amorphization in O2−/Br−-doped Li2ZrCl6. Covalent Zr-Br interactions promote charge delocalization and weaken electrostatic interactions, while Zr-O-Zr bridges disrupt long-range structural ordering, collectively enhancing lattice flexibility and lowering the Li+ migration barrier. The resulting Li2.25ZrCl4O0.75Br0.75 electrolyte achieves a room temperature ionic conductivity of 1.95 mS cm−1 together with enhanced oxidative and interfacial stability up to 4.5 V. When integrated into LiNi0.8Co0.1Mn0.1O2-based ASSLBs, the full cell delivers superior rate capability and retains 89.0% capacity after 1,000 cycles. This work establishes bond-covalency-mediated anion sublattice regulation as an effective strategy for coupling structural amorphization with fast ion transport, providing a design principle for high-performance halide solid-state electrolytes.

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双阴离子掺杂Li-Zr-Cl电解质的共价驱动非晶化使长寿命全固态电池成为可能

锆基卤化物电解质因其低成本和易于加工而成为全固态锂电池（ASSLBs）的有希望的候选者，但其实际应用受到离子电导率不足的限制。在这里，我们开发了一种双阴离子策略来诱导O2−/Br−掺杂的Li2ZrCl6的共价驱动非晶化。共价Zr-Br相互作用促进电荷离域，减弱静电相互作用，而Zr-O-Zr桥破坏远程结构有序，共同增强晶格柔韧性，降低Li+迁移势垒。所得li2.25 zrcl400.75 br0.75电解质的室温离子电导率为1.95 mS cm−1，氧化和界面稳定性提高至4.5 V。当集成到基于lini0.8 co0.1 mn0.1 o2的asslb时，完整的电池提供了卓越的倍率能力，并在1000次循环后保持89.0%的容量。本研究建立了键共价介导的阴离子亚晶格调控作为结构非晶化与快速离子输运耦合的有效策略，为高性能卤化物固态电解质的设计提供了一个原则。

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来源期刊

Matter MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

26.30

自引率

2.60%

发文量

367

期刊介绍： Matter, a monthly journal affiliated with Cell, spans the broad field of materials science from nano to macro levels,covering fundamentals to applications. Embracing groundbreaking technologies,it includes full-length research articles,reviews, perspectives,previews, opinions, personnel stories, and general editorial content. Matter aims to be the primary resource for researchers in academia and industry, inspiring the next generation of materials scientists.