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Solvent-Anion Counterpoised Electrolyte Enables High-Rate Magnesium Metal Batteries
Meng Zhang1, Ruimin Li1,2, Wanyu Zhao1
1School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, P. R. China.
Abstract:
Magnesium batteries are compelling post-lithium energy storage candidates but suffer from sluggish charge transfer kinetics, fundamentally restricted by the high energy barrier of Mg2+ desolvation. Herein, we address the compact and tenacious solvation sheath induced by the high charge density of Mg2+, characterized by strong electrostatic binding. To effectively weaken the coordination strength and lower the desolvation barrier, we utilize machine learning to identify electrolytes that energetically balance Mg2+-solvent and Mg2+-anion interactions. This counterpoise state leads to a comprehensive weakening of the solvation shell. As corroborated by in situ Raman spectroscopy, this environment facilitates a synchronous desolvation pathway and induces a robust MgH2-based solid-electrolyte interphase, fundamentally accelerating interfacial kinetics. The screened amine-based electrolyte empowers low-overpotential Mg2+ reduction of 0.06 V at 1 mA cm-2, and full cells with high-rate performance sustain 50 C cycling, and a Mg/fluorinated carbon cell delivers 918 mAh g-1 at 0.5 C. This paradigm shifts the design focus from individual solvation to collective energy equilibration in multivalent electrolytes.
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