In Situ Dynamic Interphase‐Supported Cement Zinc Batteries for Sustainable Power Supply Ecosystem

Abstract Integrating storage into cementitious media is limited by interfacial instability and sluggish transport. It is reported that an interface‐engineered, recyclable cement Zinc batteries in which the cement electrolyte recovered from symmetric cells after electrochemical testing, is milled and reconstituted to refine pore architecture and percolation, thereby driving the in situ formation of a conformal calcium zincate interphase (CZOH) on Zn during curing. DFT shows the hydrogen adsorption free energy (ΔG_H) increases from 0.47 eV on metallic Zn to 2.78 eV on CZOH, rendering H* formation thermodynamically unfavorable and intrinsically suppressing the hydrogen‐evolution reaction. In situ pH reveals attenuated local alkalization, and in situ EIS/DRT indicates reduced and more stable charge‐transfer and diffusion resistances, evidencing interfacial stabilization. COMSOL analyses across 10/100/1000 nm pores show that moderate pore refinement coupled with connectivity homogenizes Zn 2+ flux and smooths the interfacial potential. The electronically insulating yet ion‐permissive CZOH thereby preserves ordered Zn 2+ transport and deposition. Consequently, the recycled cement quasi‐solid electrolyte (RCQE) based symmetric cells operate ≈2500 h at 0.1 mA cm −2 /0.1 mAh cm −2 , and Zn ‖ MnO 2 full cells retain 175.6 mAh g −1 after 500 cycles at 0.1 A g −1 . These results establish interphase regulation as a prerequisite for durable cement‐based Zn batteries and outline a sustainable pathway for structural energy‐storage systems.