{"title":"1D ZrCl4 Matrices for Enhanced Ion Transport in Glassy Chloride Electrolytes","authors":"Yongli Song, Shida Xue, Zijin Xu, Jianjun Fang, Zhaohuang Zhan, Yao-Hui Wang, Chuanxi Chen, Shunning Li, Tongchao Liu, Yong Yang, Luyi Yang, Feng Pan","doi":"10.1002/aenm.202500913","DOIUrl":null,"url":null,"abstract":"Designing a solid-state electrolyte (SSE) that combines the lithium-ion transport behavior found in liquid or solid polymer electrolytes with the high lithium-ion transference number characteristic of inorganic SSEs is an immensely appealing challenge. Herein, a cost-effective, chain-structured ZrCl<sub>4</sub> is introduced as a hosting matrix, resembling polyethylene oxide (PEO), to facilitate the dissociation of lithium salts (e.g., LiCl, Li<sub>2</sub>SO<sub>4</sub>, and Li<sub>3</sub>PO<sub>4</sub>). The dissociated free Li-ions can be coordinated by the [ZrCl<sub>6</sub>] octahedra, forming fast ion-conducting pathways along ZrCl<sub>4</sub> chains that achieve an ionic conductivity as high as 1.2 mS cm<sup>−1</sup>. Simultaneously, ZrCl<sub>4</sub> serves as a Lewis acid, trapping anions and delivering a high lithium transference number approaching unit. The proposed electrolyte exhibits stable cycling performance when integrated into LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub>||Li-In cells. Moreover, this design strategy also extends to the synthesis of sodium-ion conductors, achieving a high ionic conductivity of 0.3 mS cm<sup>−1</sup>. Demonstrating a previously unreported lithium-ion conduction mechanism, the proposed ZrCl<sub>4</sub>-based electrolytes offer a versatile approach for tailoring advanced SSEs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"140 1","pages":""},"PeriodicalIF":24.4000,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/aenm.202500913","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Designing a solid-state electrolyte (SSE) that combines the lithium-ion transport behavior found in liquid or solid polymer electrolytes with the high lithium-ion transference number characteristic of inorganic SSEs is an immensely appealing challenge. Herein, a cost-effective, chain-structured ZrCl4 is introduced as a hosting matrix, resembling polyethylene oxide (PEO), to facilitate the dissociation of lithium salts (e.g., LiCl, Li2SO4, and Li3PO4). The dissociated free Li-ions can be coordinated by the [ZrCl6] octahedra, forming fast ion-conducting pathways along ZrCl4 chains that achieve an ionic conductivity as high as 1.2 mS cm−1. Simultaneously, ZrCl4 serves as a Lewis acid, trapping anions and delivering a high lithium transference number approaching unit. The proposed electrolyte exhibits stable cycling performance when integrated into LiNi0.8Mn0.1Co0.1O2||Li-In cells. Moreover, this design strategy also extends to the synthesis of sodium-ion conductors, achieving a high ionic conductivity of 0.3 mS cm−1. Demonstrating a previously unreported lithium-ion conduction mechanism, the proposed ZrCl4-based electrolytes offer a versatile approach for tailoring advanced SSEs.
设计一种固态电解质(SSE),将液体或固体聚合物电解质中的锂离子传输行为与无机SSE的高锂离子转移数特征结合起来,是一项非常有吸引力的挑战。本文引入了一种具有成本效益的链式结构的ZrCl4作为承载基质,类似于聚乙烯氧化物(PEO),以促进锂盐(例如LiCl, Li2SO4和Li3PO4)的解离。解离的自由锂离子可以被[ZrCl6]八面体配位,沿着ZrCl4链形成快速离子导电通路,离子电导率高达1.2 mS cm−1。同时,ZrCl4作为路易斯酸,捕获阴离子并提供高锂转移数接近单位。该电解质在集成到LiNi0.8Mn0.1Co0.1O2||Li-In电池中表现出稳定的循环性能。此外,这种设计策略也扩展到钠离子导体的合成,实现了0.3 mS cm−1的高离子电导率。基于zrcl4的电解质展示了一种以前未报道过的锂离子传导机制,为定制先进的sse提供了一种通用的方法。
期刊介绍:
Established in 2011, Advanced Energy Materials is an international, interdisciplinary, English-language journal that focuses on materials used in energy harvesting, conversion, and storage. It is regarded as a top-quality journal alongside Advanced Materials, Advanced Functional Materials, and Small.
With a 2022 Impact Factor of 27.8, Advanced Energy Materials is considered a prime source for the best energy-related research. The journal covers a wide range of topics in energy-related research, including organic and inorganic photovoltaics, batteries and supercapacitors, fuel cells, hydrogen generation and storage, thermoelectrics, water splitting and photocatalysis, solar fuels and thermosolar power, magnetocalorics, and piezoelectronics.
The readership of Advanced Energy Materials includes materials scientists, chemists, physicists, and engineers in both academia and industry. The journal is indexed in various databases and collections, such as Advanced Technologies & Aerospace Database, FIZ Karlsruhe, INSPEC (IET), Science Citation Index Expanded, Technology Collection, and Web of Science, among others.