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

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

Energy & Environmental Materials ›› 2024, Vol. 7 ›› Issue (6) : e12792 DOI: 10.1002/eem2.12792

RESEARCH ARTICLE

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

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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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electrolyte additives / interfacial chemistry / magnesium metal batteries / solvation structure

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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. Tailoring Electrode–Electrolyte Interface Using an Electron-Deficient Borate-Based Additive in MgTFSI₂-MgCl₂/DME Electrolyte for Rechargeable Magnesium Batteries. Energy & Environmental Materials, 2024, 7(6): e12792 DOI:10.1002/eem2.12792

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