Haiyan Fan, Xinxin Zhang, Jianhua Xiao, Wenjie Chen, Qiyuan Lin, Zi Shyun Ng, Yitao Lin, Yi Su, Ludi Pan, Yipeng Su, Shuaiyang Ren, Haowen Liu, Xuanzhang Li, Yuegang Zhang
{"title":"在可充电镁电池的 MgTFSI2-MgCl2/DME 电解液中使用电子缺陷型硼酸盐基添加剂定制电极-电解液界面","authors":"Haiyan Fan, Xinxin Zhang, Jianhua Xiao, Wenjie Chen, Qiyuan Lin, Zi Shyun Ng, Yitao Lin, Yi Su, Ludi Pan, Yipeng Su, Shuaiyang Ren, Haowen Liu, Xuanzhang Li, Yuegang Zhang","doi":"10.1002/eem2.12792","DOIUrl":null,"url":null,"abstract":"<p>Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase (SEI) on the anodes. Here, we used molecular dynamic simulation, density functional theory calculation, and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts, magnesium bis(trifluoromethanesulfonyl)imide (MgTFSI<sub>2</sub>), and MgCl<sub>2</sub>, with different additives in 1,2-dimethoxyethane (DME) solvent. We found that the formed [Mg<sub>3</sub>(μ-Cl)<sub>4</sub>(DME)<sub>m</sub>TFSI<sub>2</sub>] (<i>m</i> = 3, 5) inner-shell solvation clusters in MgTFSI<sub>2</sub>-MgCl<sub>2</sub>/DME electrolyte could easily decompose and form a MgO- and MgF<sub>2</sub>-rich SEI. Such electron-rich inorganic species in the SEI, especially MgF<sub>2</sub>, turned out to be detrimental for Mg plating/stripping. To reduce the MgF<sub>2</sub> and MgO contents in SEI, we introduce an electron-deficient tri(2,2,2-trifluoroethyl) borate (TFEB) additive in the electrolyte. Mg//Mg cells using the MgTFSI<sub>2</sub>-MgCl<sub>2</sub>/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of ~150 mV. Even with the presence of 800 ppm H<sub>2</sub>O, the electrolyte with TFEB additive could still preserve its good electrochemical performance. The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo<sub>6</sub>S<sub>8</sub> and Mg//CuS full cells, showing great potential for future applications.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12792","citationCount":"0","resultStr":"{\"title\":\"Tailoring Electrode–Electrolyte Interface Using an Electron-Deficient Borate-Based Additive in MgTFSI2-MgCl2/DME Electrolyte for Rechargeable Magnesium Batteries\",\"authors\":\"Haiyan Fan, Xinxin Zhang, Jianhua Xiao, Wenjie Chen, Qiyuan Lin, Zi Shyun Ng, Yitao Lin, Yi Su, Ludi Pan, Yipeng Su, Shuaiyang Ren, Haowen Liu, Xuanzhang Li, Yuegang Zhang\",\"doi\":\"10.1002/eem2.12792\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase (SEI) on the anodes. Here, we used molecular dynamic simulation, density functional theory calculation, and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts, magnesium bis(trifluoromethanesulfonyl)imide (MgTFSI<sub>2</sub>), and MgCl<sub>2</sub>, with different additives in 1,2-dimethoxyethane (DME) solvent. We found that the formed [Mg<sub>3</sub>(μ-Cl)<sub>4</sub>(DME)<sub>m</sub>TFSI<sub>2</sub>] (<i>m</i> = 3, 5) inner-shell solvation clusters in MgTFSI<sub>2</sub>-MgCl<sub>2</sub>/DME electrolyte could easily decompose and form a MgO- and MgF<sub>2</sub>-rich SEI. Such electron-rich inorganic species in the SEI, especially MgF<sub>2</sub>, turned out to be detrimental for Mg plating/stripping. To reduce the MgF<sub>2</sub> and MgO contents in SEI, we introduce an electron-deficient tri(2,2,2-trifluoroethyl) borate (TFEB) additive in the electrolyte. Mg//Mg cells using the MgTFSI<sub>2</sub>-MgCl<sub>2</sub>/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of ~150 mV. Even with the presence of 800 ppm H<sub>2</sub>O, the electrolyte with TFEB additive could still preserve its good electrochemical performance. The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo<sub>6</sub>S<sub>8</sub> and Mg//CuS full cells, showing great potential for future applications.</p>\",\"PeriodicalId\":11554,\"journal\":{\"name\":\"Energy & Environmental Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.0000,\"publicationDate\":\"2024-07-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12792\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Environmental Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/eem2.12792\",\"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":"Energy & Environmental Materials","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/eem2.12792","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}
Tailoring Electrode–Electrolyte Interface Using an Electron-Deficient Borate-Based Additive in MgTFSI2-MgCl2/DME Electrolyte for Rechargeable Magnesium Batteries
Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase (SEI) on the anodes. Here, we used molecular dynamic simulation, density functional theory calculation, and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts, magnesium bis(trifluoromethanesulfonyl)imide (MgTFSI2), and MgCl2, with different additives in 1,2-dimethoxyethane (DME) solvent. We found that the formed [Mg3(μ-Cl)4(DME)mTFSI2] (m = 3, 5) inner-shell solvation clusters in MgTFSI2-MgCl2/DME electrolyte could easily decompose and form a MgO- and MgF2-rich SEI. Such electron-rich inorganic species in the SEI, especially MgF2, turned out to be detrimental for Mg plating/stripping. To reduce the MgF2 and MgO contents in SEI, we introduce an electron-deficient tri(2,2,2-trifluoroethyl) borate (TFEB) additive in the electrolyte. Mg//Mg cells using the MgTFSI2-MgCl2/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of ~150 mV. Even with the presence of 800 ppm H2O, the electrolyte with TFEB additive could still preserve its good electrochemical performance. The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo6S8 and Mg//CuS full cells, showing great potential for future applications.
期刊介绍:
Energy & Environmental Materials (EEM) is an international journal published by Zhengzhou University in collaboration with John Wiley & Sons, Inc. The journal aims to publish high quality research related to materials for energy harvesting, conversion, storage, and transport, as well as for creating a cleaner environment. EEM welcomes research work of significant general interest that has a high impact on society-relevant technological advances. The scope of the journal is intentionally broad, recognizing the complexity of issues and challenges related to energy and environmental materials. Therefore, interdisciplinary work across basic science and engineering disciplines is particularly encouraged. The areas covered by the journal include, but are not limited to, materials and composites for photovoltaics and photoelectrochemistry, bioprocessing, batteries, fuel cells, supercapacitors, clean air, and devices with multifunctionality. The readership of the journal includes chemical, physical, biological, materials, and environmental scientists and engineers from academia, industry, and policy-making.