盐包水杂化电解质的结构研究。

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI:10.1039/d5cp00680e

Raúl Lois-Cuns,Antía Santiago-Alonso,Martín Otero-Lema,Juan J Parajó,Josefa Salgado,Hadrián Montes-Campos,Trinidad Méndez-Morales,Luis M Varela

{"title":"盐包水杂化电解质的结构研究。","authors":"Raúl Lois-Cuns,Antía Santiago-Alonso,Martín Otero-Lema,Juan J Parajó,Josefa Salgado,Hadrián Montes-Campos,Trinidad Méndez-Morales,Luis M Varela","doi":"10.1039/d5cp00680e","DOIUrl":null,"url":null,"abstract":"Water-in-salt electrolytes are promising candidates for next-generation lithium-ion batteries due to their enhanced safety and cost-effectiveness. However, optimizing the performance of hybrid aqueous/non-aqueous water-in-salt electrolytes remains a challenge. This work investigates the structural characteristics of mixtures of a LiTFSI water-in-salt based electrolyte (21 m) with several common solvents (e.g. carbonates, dimethyl sulfoxide, acetonitrile) using molecular dynamics simulations combined with experimental measurements. Our analysis reveals a correlation between the ability of a given cosolvent to solvate lithium cations and its Lewis basicity. A strong Lewis basicity favours the formation of free water cluster aggregates in the system, which reduces the electrochemical performance of the electrolyte. Moreover, the relative permittivity of the cosolvents also plays an important role in modifying the ionic interaction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":2.9000,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"On the structure of hybrid water-in-salt electrolytes.\",\"authors\":\"Raúl Lois-Cuns,Antía Santiago-Alonso,Martín Otero-Lema,Juan J Parajó,Josefa Salgado,Hadrián Montes-Campos,Trinidad Méndez-Morales,Luis M Varela\",\"doi\":\"10.1039/d5cp00680e\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Water-in-salt electrolytes are promising candidates for next-generation lithium-ion batteries due to their enhanced safety and cost-effectiveness. However, optimizing the performance of hybrid aqueous/non-aqueous water-in-salt electrolytes remains a challenge. This work investigates the structural characteristics of mixtures of a LiTFSI water-in-salt based electrolyte (21 m) with several common solvents (e.g. carbonates, dimethyl sulfoxide, acetonitrile) using molecular dynamics simulations combined with experimental measurements. Our analysis reveals a correlation between the ability of a given cosolvent to solvate lithium cations and its Lewis basicity. A strong Lewis basicity favours the formation of free water cluster aggregates in the system, which reduces the electrochemical performance of the electrolyte. Moreover, the relative permittivity of the cosolvents also plays an important role in modifying the ionic interaction.\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":\"6 1\",\"pages\":\"\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-06-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5cp00680e\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5cp00680e","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

摘要

由于盐水电解质具有更高的安全性和成本效益，因此有望成为下一代锂离子电池的候选材料。然而，优化含水/非含水盐电解质的性能仍然是一个挑战。本研究利用分子动力学模拟和实验测量相结合的方法，研究了LiTFSI盐中水基电解质（21 m）与几种常见溶剂（如碳酸盐、二甲亚砜、乙腈）的混合物的结构特征。我们的分析揭示了给定助溶剂溶剂化锂阳离子的能力与其路易斯碱度之间的相关性。较强的路易斯碱度有利于在体系中形成自由水团簇，从而降低了电解质的电化学性能。此外，共溶剂的相对介电常数对离子相互作用的改变也起着重要的作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

On the structure of hybrid water-in-salt electrolytes.

Water-in-salt electrolytes are promising candidates for next-generation lithium-ion batteries due to their enhanced safety and cost-effectiveness. However, optimizing the performance of hybrid aqueous/non-aqueous water-in-salt electrolytes remains a challenge. This work investigates the structural characteristics of mixtures of a LiTFSI water-in-salt based electrolyte (21 m) with several common solvents (e.g. carbonates, dimethyl sulfoxide, acetonitrile) using molecular dynamics simulations combined with experimental measurements. Our analysis reveals a correlation between the ability of a given cosolvent to solvate lithium cations and its Lewis basicity. A strong Lewis basicity favours the formation of free water cluster aggregates in the system, which reduces the electrochemical performance of the electrolyte. Moreover, the relative permittivity of the cosolvents also plays an important role in modifying the ionic interaction.

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

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.