Twinned-magnesium metal negative electrodes enable reversible magnesium electrodeposition

Abstract The favourable thermodynamic properties of magnesium make it a promising negative electrode for rechargeable Mg-metal batteries. However, parasitic side reactions and uncontrolled deposition at the unstable electrode/electrolyte interface severely hinder reversible electrodeposition. Here we demonstrate that a high density of twin defects via cyclic-multidirectional deformation markedly increases the diffusion rate and simultaneously suppresses interfacial reactions. Comprehensive morphological characterisation combined with theoretical calculations reveals that the twinned-magnesium negative electrode exhibits significantly enhanced kinetics, leading to a reduced dimensionless electrochemical Damköhler number and indicating that magnesium deposition becomes less diffusion-limited. Furthermore, reorganisation energy analysis based on Marcus–Hush–Chidsey kinetics, in conjunction with the battery overpotential, indicates that the twin structure effectively mitigates parasitic reactions between the negative electrode and the electrolyte, thereby significantly reducing the passivation effect and enabling long-term reversible magnesium electrodeposition. Consequently, the designed twinned-magnesium electrodes in an asymmetric coin cell achieve a Coulombic efficiency of 99.53% over 2000 cycles at 30 mA cm −2 with a capacity of 2 mAh cm −2 , competitive with reported magnesium metal negative electrodes. This simple strategy has been successfully extended to the zinc metal system as a proof of concept, demonstrating the universal potential of twin engineering for achieving reversible metal electrodeposition.