Tuning Desolvation Kinetics with Perovskite‐Type Ion‐Conductive Modulators toward Low‐Temperature Zn Metal Batteries

Aqueous zinc metal batteries (AZMBs) are regarded as the promising candidates for low-cost, sustainable, but safe energy storage systems. Unfortunately, Zn metal anodes suffer from incomplete desolvation and random dendrite formation, which is attributed to sluggish diffusion kinetics resulted from the strong ion (Zn$^{2+}$)-dipole (H$_2$O) interactions. Herein, to promote the Zn$^{2+}$ desolvation and diffusion kinetics, the strategy of constructing perovskite-type ion-conductive kinetic modulators of ZnSn(OH)$_6$ is initially designed and coated on the Zn metal anode (PIC-ZSH@Zn), regulating ion behaviors against dendrite growth and side reactions of active water. As confirmed by theoretical simulations, COMSOL, time-of-flight second-ionic mass spectroscopy, Raman and various electrochemical analyses, the abundant active sites synergistically weaken Zn$^{2+}$-H$_2$O interactions to accelerate desolvation to release free Zn$^{2+}$, effectively homogenizing the Zn$^{2+}$ flux distribution to preferentially nucleate and plate metallic Zn. Consequently, the as-fabricated cell maintains reversible stability of 800 h at 10 mA cm$^{−2}$ with high Coulombic efficiency over 99% under low temperature of 0°C. ... mehrThe paired full cell with PIC-ZSH@Zn presents a high-capacity retention of nearly 80% after 1000 cycles at 1.0 A g$^{−1}$ at 0°C, reinforcing the operation robustness of AZMBs under low temperature environments.