{"title":"一种用于可充电镁电池的基于全无机盐的无调节特性的非亲核电解质","authors":"","doi":"10.1016/j.jma.2023.06.007","DOIUrl":null,"url":null,"abstract":"<div><div>Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries (RMBs). In the present work, a non-nucleophilic electrolyte (denoted as MLCH) based on all-inorganic salts of MgCl<sub>2</sub>, LiCl and CrCl<sub>3</sub> for RMBs is prepared by a straightforward one-step reaction. As a result, the MLCH electrolyte shows the noticeable performance of high ionic conductivity (3.40 mS cm<sup>−1</sup>), low overpotential (∼46 mV <em>vs</em> Mg/Mg<sup>2+</sup>), high Coulombic efficiency (∼93%), high anodic stability (SS, ∼2.56 V <em>vs</em> Mg/Mg<sup>2+</sup>) and long-term (more than 500 h) cycling stability, especially the conditioning-free characteristic. The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of [LiCl<sub>2</sub>(THF)<sub>2</sub>]<sup>−</sup> and solvated dimers of [Mg<sub>2</sub>(µ-Cl)<sub>3</sub>(THF)<sub>6</sub>]<sup>+</sup>. The addition of LiCl can assist the dissolution of MgCl<sub>2</sub> and activation of the electrode/electrolyte interface, resulting in a superior Mg plating/stripping efficiency. The synergistic effect of LiCl, CrCl<sub>3</sub>, a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte. Moreover, the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS. The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g<sup>−1</sup> at 0.1 C and the capacity can retain ∼72% after 40 cycles. Notably, the MLCH electrolyte has other superiorities such as the broad sources of materials, low-cost and easy-preparation, leading to the potential prospect of commercial application.</div></div>","PeriodicalId":16214,"journal":{"name":"Journal of Magnesium and Alloys","volume":null,"pages":null},"PeriodicalIF":15.8000,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2213956723001317/pdfft?md5=37987d472cd94fd7d2f694ee14a9b521&pid=1-s2.0-S2213956723001317-main.pdf","citationCount":"0","resultStr":"{\"title\":\"A non-nucleophilic electrolyte based on all-inorganic salts with conditioning-free characteristic for rechargeable magnesium batteries\",\"authors\":\"\",\"doi\":\"10.1016/j.jma.2023.06.007\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries (RMBs). In the present work, a non-nucleophilic electrolyte (denoted as MLCH) based on all-inorganic salts of MgCl<sub>2</sub>, LiCl and CrCl<sub>3</sub> for RMBs is prepared by a straightforward one-step reaction. As a result, the MLCH electrolyte shows the noticeable performance of high ionic conductivity (3.40 mS cm<sup>−1</sup>), low overpotential (∼46 mV <em>vs</em> Mg/Mg<sup>2+</sup>), high Coulombic efficiency (∼93%), high anodic stability (SS, ∼2.56 V <em>vs</em> Mg/Mg<sup>2+</sup>) and long-term (more than 500 h) cycling stability, especially the conditioning-free characteristic. The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of [LiCl<sub>2</sub>(THF)<sub>2</sub>]<sup>−</sup> and solvated dimers of [Mg<sub>2</sub>(µ-Cl)<sub>3</sub>(THF)<sub>6</sub>]<sup>+</sup>. The addition of LiCl can assist the dissolution of MgCl<sub>2</sub> and activation of the electrode/electrolyte interface, resulting in a superior Mg plating/stripping efficiency. The synergistic effect of LiCl, CrCl<sub>3</sub>, a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte. Moreover, the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS. The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g<sup>−1</sup> at 0.1 C and the capacity can retain ∼72% after 40 cycles. Notably, the MLCH electrolyte has other superiorities such as the broad sources of materials, low-cost and easy-preparation, leading to the potential prospect of commercial application.</div></div>\",\"PeriodicalId\":16214,\"journal\":{\"name\":\"Journal of Magnesium and Alloys\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":15.8000,\"publicationDate\":\"2024-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2213956723001317/pdfft?md5=37987d472cd94fd7d2f694ee14a9b521&pid=1-s2.0-S2213956723001317-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Magnesium and Alloys\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2213956723001317\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"METALLURGY & METALLURGICAL ENGINEERING\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Magnesium and Alloys","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2213956723001317","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"METALLURGY & METALLURGICAL ENGINEERING","Score":null,"Total":0}
A non-nucleophilic electrolyte based on all-inorganic salts with conditioning-free characteristic for rechargeable magnesium batteries
Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries (RMBs). In the present work, a non-nucleophilic electrolyte (denoted as MLCH) based on all-inorganic salts of MgCl2, LiCl and CrCl3 for RMBs is prepared by a straightforward one-step reaction. As a result, the MLCH electrolyte shows the noticeable performance of high ionic conductivity (3.40 mS cm−1), low overpotential (∼46 mV vs Mg/Mg2+), high Coulombic efficiency (∼93%), high anodic stability (SS, ∼2.56 V vs Mg/Mg2+) and long-term (more than 500 h) cycling stability, especially the conditioning-free characteristic. The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of [LiCl2(THF)2]− and solvated dimers of [Mg2(µ-Cl)3(THF)6]+. The addition of LiCl can assist the dissolution of MgCl2 and activation of the electrode/electrolyte interface, resulting in a superior Mg plating/stripping efficiency. The synergistic effect of LiCl, CrCl3, a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte. Moreover, the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS. The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g−1 at 0.1 C and the capacity can retain ∼72% after 40 cycles. Notably, the MLCH electrolyte has other superiorities such as the broad sources of materials, low-cost and easy-preparation, leading to the potential prospect of commercial application.
期刊介绍:
The Journal of Magnesium and Alloys serves as a global platform for both theoretical and experimental studies in magnesium science and engineering. It welcomes submissions investigating various scientific and engineering factors impacting the metallurgy, processing, microstructure, properties, and applications of magnesium and alloys. The journal covers all aspects of magnesium and alloy research, including raw materials, alloy casting, extrusion and deformation, corrosion and surface treatment, joining and machining, simulation and modeling, microstructure evolution and mechanical properties, new alloy development, magnesium-based composites, bio-materials and energy materials, applications, and recycling.