Tailoring Electrode–Electrolyte Interface Using an Electron-Deficient Borate-Based Additive in MgTFSI2-MgCl2/DME Electrolyte for Rechargeable Magnesium Batteries

IF 13 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Energy & Environmental Materials Pub Date : 2024-07-06 DOI:10.1002/eem2.12792
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
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Abstract

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.

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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
可充电镁金属电池需要一种能在阳极上形成稳定且具有离子导电性的固体电解质相(SEI)的电解质。在此,我们利用分子动力学模拟、密度泛函理论计算和 X 射线光电子能谱分析,研究了双盐、双(三氟甲磺酰)亚胺镁(MgTFSI2)和氯化镁(MgCl2)与不同添加剂在 1,2 二甲基乙烷(DME)溶剂中的溶解结构和 SEI 成分。我们发现,在 MgTFSI2-MgCl2/DME 电解质中形成的[Mg3(μ-Cl)4(DME)mTFSI2](m = 3,5)内壳溶簇很容易分解并形成富含氧化镁和 MgF2 的 SEI。SEI 中的这种富电子无机物,尤其是 MgF2,对镁的电镀/剥离非常不利。为了降低 SEI 中的 MgF2 和 MgO 含量,我们在电解液中引入了缺电子的三(2,2,2-三氟乙基)硼酸盐(TFEB)添加剂。使用 MgTFSI2-MgCl2/DME-TFEB 电解液的镁/镁电池可在约 150 mV 的小极化电压下稳定循环 400 小时以上。即使存在 800 ppm H2O,添加了 TFEB 的电解液仍能保持良好的电化学性能。优化后的电解液还能使镁/钼6S8 和镁/铜S全电池实现稳定循环和高倍率能力,显示出未来应用的巨大潜力。
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来源期刊
Energy & Environmental Materials
Energy & Environmental Materials MATERIALS SCIENCE, MULTIDISCIPLINARY-
CiteScore
17.60
自引率
6.00%
发文量
66
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.
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