Tailoring Coordination in Conventional Ether‐Based Electrolytes for Reversible Magnesium‐Metal Anodes

Rechargeable magnesium (Mg) batteries based on conventional electrolytes are seriously plagued by the formation of the ion-blocking passivation layer on the Mg metal anode. By tracking the Mg2+ solvation sheath, this work links the passivation components to the Mg2+ -solvents (1,2-dimethoxyethane, DME) coordination and the consequent thermodynamically unstable DME molecules. On this basis, we propose a methodology to tailor solvation coordination by introducing the additive solvent with extreme electron richness. Oxygen atoms in phosphorus-oxygen groups compete with that in carbon-oxygen groups of DME for the coordination with Mg2+ , thus softening the solvation sheath deformation. Meanwhile, the organophosphorus molecules in the rearranged solvation sheath decompose on the Mg surface, increasing the Mg2+ transport and electrical resistance by three and one orders of magnitude, respectively. Consequently, the symmetric cells exhibit superior cycling performance of over 600 cycles with low polarization.