用于稳定全固态锂电池卤化物固体电解质中锂离子间隙位置的阴离子工程学

IF 8.3 2区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Applied Materials & Interfaces Pub Date : 2023-12-11 DOI:10.1021/acsami.3c13002

Kern-Ho Park, Se Young Kim, Mina Jung, Su-Bin Lee, Min-Jeong Kim, In-Jun Yang, Ji-Hoon Hwang, Woosuk Cho, Guoying Chen, KyungSu Kim* and Jisang Yu*,

{"title":"用于稳定全固态锂电池卤化物固体电解质中锂离子间隙位置的阴离子工程学","authors":"Kern-Ho Park, Se Young Kim, Mina Jung, Su-Bin Lee, Min-Jeong Kim, In-Jun Yang, Ji-Hoon Hwang, Woosuk Cho, Guoying Chen, KyungSu Kim* and Jisang Yu*, ","doi":"10.1021/acsami.3c13002","DOIUrl":null,"url":null,"abstract":"Halide solid electrolytes (SEs) have been highlighted for their high-voltage stability. Among the halide SEs, the ionic conductivity has been improved by aliovalent metal substitutions or choosing a ccp-like anion-arranged monoclinic structure (C2/m) over hcp- or bcc-like anion-arranged structures. Here, we present a new approach, hard-base substitution, and its underlying mechanism to increase the ionic conductivity of halide SEs. The oxygen substitution to Li2ZrCl6 (trigonal, hcp) increased the ionic conductivity from 0.33 to 1.3 mS cm–1 at Li3.1ZrCl4.9O1.1 (monoclinic, ccp), while the sulfur and fluorine substitutions were not effective. A systematic comparison study revealed that the energetic stabilization of interstitial sites for Li migration plays a key role in improving the ionic conductivity, and the ccp-like anion sublattice is not sufficient to achieve high ionic conductivity. We further examined the feasibility of the oxyhalide SE for practical and all-solid-state battery applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"15 50","pages":"58367–58376"},"PeriodicalIF":8.3000,"publicationDate":"2023-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Anion Engineering for Stabilizing Li Interstitial Sites in Halide Solid Electrolytes for All-Solid-State Li Batteries\",\"authors\":\"Kern-Ho Park, Se Young Kim, Mina Jung, Su-Bin Lee, Min-Jeong Kim, In-Jun Yang, Ji-Hoon Hwang, Woosuk Cho, Guoying Chen, KyungSu Kim* and Jisang Yu*, \",\"doi\":\"10.1021/acsami.3c13002\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Halide solid electrolytes (SEs) have been highlighted for their high-voltage stability. Among the halide SEs, the ionic conductivity has been improved by aliovalent metal substitutions or choosing a ccp-like anion-arranged monoclinic structure (C2/m) over hcp- or bcc-like anion-arranged structures. Here, we present a new approach, hard-base substitution, and its underlying mechanism to increase the ionic conductivity of halide SEs. The oxygen substitution to Li2ZrCl6 (trigonal, hcp) increased the ionic conductivity from 0.33 to 1.3 mS cm–1 at Li3.1ZrCl4.9O1.1 (monoclinic, ccp), while the sulfur and fluorine substitutions were not effective. A systematic comparison study revealed that the energetic stabilization of interstitial sites for Li migration plays a key role in improving the ionic conductivity, and the ccp-like anion sublattice is not sufficient to achieve high ionic conductivity. We further examined the feasibility of the oxyhalide SE for practical and all-solid-state battery applications.\",\"PeriodicalId\":5,\"journal\":{\"name\":\"ACS Applied Materials & Interfaces\",\"volume\":\"15 50\",\"pages\":\"58367–58376\"},\"PeriodicalIF\":8.3000,\"publicationDate\":\"2023-12-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Materials & Interfaces\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsami.3c13002\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Materials & Interfaces","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsami.3c13002","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

摘要

卤化物固体电解质（SE）因其高压稳定性而备受瞩目。在卤化物固态电解质中，离子电导率已通过别价金属置换或选择类ccp阴离子排列的单斜结构（C2/m）而不是类hcp或bcc阴离子排列的结构得到了改善。在此，我们提出了一种新方法--硬碱置换，及其提高卤化物 SE 离子电导率的内在机制。在 Li3.1ZrCl4.9O1.1（单斜，ccp）中，氧取代 Li2ZrCl6（三棱，hcp）可将离子电导率从 0.33 mS cm-1 提高到 1.3 mS cm-1，而硫和氟取代则无效。通过系统比较研究发现，锂迁移间隙位点的能量稳定在提高离子电导率方面起着关键作用，而ccp类阴离子亚晶格不足以实现高离子电导率。我们进一步研究了氧卤化物 SE 在实际和全固态电池应用中的可行性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Anion Engineering for Stabilizing Li Interstitial Sites in Halide Solid Electrolytes for All-Solid-State Li Batteries

查看原文本刊更多论文

Anion Engineering for Stabilizing Li Interstitial Sites in Halide Solid Electrolytes for All-Solid-State Li Batteries

Halide solid electrolytes (SEs) have been highlighted for their high-voltage stability. Among the halide SEs, the ionic conductivity has been improved by aliovalent metal substitutions or choosing a ccp-like anion-arranged monoclinic structure (C2/m) over hcp- or bcc-like anion-arranged structures. Here, we present a new approach, hard-base substitution, and its underlying mechanism to increase the ionic conductivity of halide SEs. The oxygen substitution to Li₂ZrCl₆ (trigonal, hcp) increased the ionic conductivity from 0.33 to 1.3 mS cm^–1 at Li_3.1ZrCl_4.9O_1.1 (monoclinic, ccp), while the sulfur and fluorine substitutions were not effective. A systematic comparison study revealed that the energetic stabilization of interstitial sites for Li migration plays a key role in improving the ionic conductivity, and the ccp-like anion sublattice is not sufficient to achieve high ionic conductivity. We further examined the feasibility of the oxyhalide SE for practical and all-solid-state battery applications.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

ACS Applied Materials & Interfaces 工程技术-材料科学：综合

CiteScore

16.00

自引率

6.30%

发文量

4978

审稿时长

1.8 months

期刊介绍： ACS Applied Materials & Interfaces is a leading interdisciplinary journal that brings together chemists, engineers, physicists, and biologists to explore the development and utilization of newly-discovered materials and interfacial processes for specific applications. Our journal has experienced remarkable growth since its establishment in 2009, both in terms of the number of articles published and the impact of the research showcased. We are proud to foster a truly global community, with the majority of published articles originating from outside the United States, reflecting the rapid growth of applied research worldwide.