Unlocking Four‐electron Conversion in Tellurium Cathodes for Advanced Magnesium‐based Dual‐ion Batteries

Magnesium (Mg) batteries hold promise as a large-scale energy storage solution, but their progress has been hindered by the lack of high-performance cathodes. Here, we address this challenge by unlocking the reversible four-electron Te⁰/Te⁴⁺ conversion in elemental Te, enabling the demonstration of superior Mg//Te dual-ion batteries. Specifically, the classic magnesium aluminum chloride complex (MACC) electrolyte is tailored by introducing Mg bis(trifluoromethanesulfonyl)imide (Mg(TFSI)₂), which initiates the Te⁰/Te⁴⁺ conversion with two distinct charge-storage steps. Te cathode undergoes Te/TeCl₄ conversion involving Cl^- as charge carriers, during which a tellurium subchloride phase is presented as an intermediate. Significantly, the Te cathode achieves a high specific capacity of 543 mAh g_Te ^-1 and an outstanding energy density of 850 Wh kg_Te ^-1, outperforming most of the previously reported cathodes. Our electrolyte analysis indicates that the addition of Mg(TFSI)₂ reduces the overall ion-molecule interaction and mitigates the strength of ion-solvent aggregation within the MACC electrolyte, which implies the facilized Cl^- dissociation from the electrolyte. Besides, Mg(TFSI)₂ is verified as an essential buffer to mitigate the corrosion and passivation of Mg anodes caused by the consumption of the electrolyte MgCl₂ in Mg//Te dual-ion cells. These findings provide crucial insights into the development of advanced Mg-based dual-ion batteries.