Stable Zinc Anode Facilitated by Regenerated Silk Fibroin-modified Hydrogel Protective Layer.

Inherent dendrite growth and side reactions of zinc anode caused by its unstable interface in aqueous electrolytes severely limit the practical applications of zinc-ion batteries (ZIBs). To overcome these challenges, a protective layer for Zn anode inspired by cytomembrane structure is developed with PVA as framework and silk fibroin gel suspension (SFs) as modifier. This PVA/SFs gel-like layer exerts similar to the solid electrolyte interphase, optimizing the anode-electrolyte interface and Zn2+ solvation structure. Through interface improvement, controlled Zn2+ migration/diffusion, and desolvation, this buffer layer effectively inhibits dendrite growth and side reactions. The additional SFs provide functional improvement and better interaction with PVA by abundant functional groups, achieving a robust and durable Zn anode with high reversibility. Thus, the PVA/SFs@Zn symmetric cell exhibits an ultra-long lifespan of 3150 h compared to bare Zn (182 h) at 1.0 mAh cm-2-1.0 mAh cm-2, and excellent reversibility with an average Coulombic efficiency of 99.04% under a large plating capacity for 800 cycles. Moreover, the PVA/SFs@Zn||PANI/CC full cells maintain over 20 000 cycles with over 80% capacity retention under harsh conditions at 5 and 10 A g-1. This SF-modified protective layer for Zn anode suggests a promising strategy for reliable and high-performance ZIBs.

Molecular insight into the initial hydration of tricalcium aluminate.

Portland cement (PC) is ubiquitously used in construction for centuries, yet the elucidation of its early-age hydration remains a challenge. Understanding the initial hydration progress of tricalcium aluminate (C3A) at molecular scale is thus crucial for tackling this challenge as it exhibits a proclivity for early-stage hydration and plays a pivotal role in structural build-up of cement colloids. Herein, we implement a series of ab-initio calculations to probe the intricate molecular interactions of C3A during its initial hydration process. The C3A surface exhibits remarkable chemical activity in promoting water dissociation, which in turn facilitates the gradual desorption of Ca ions through a metal-proton exchange reaction. The dissolution pathways and free energies of these Ca ions follow the ligand-exchange mechanism with multiple sequential reactions to form the ultimate products where Ca ions adopt fivefold or sixfold coordination. Finally, these Ca complexes reprecipitate on the remaining Al-rich layer through the interface-coupled dissolution-reprecipitation mechanism, demonstrating dynamically stable inner-sphere adsorption states. The above results are helpful in unmasking the early-age hydration of PC and advancing the rational design of cement-based materials through the bottom-up approach.