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With markedly expansive demand in energy storage devices, rechargeable batteries will concentrate on achieving the high energy density and adequate security, especially under harsh operating conditions. Considering the high capacity (3860 mA h g−1) and low electrochemical potential (−3.04 V vs the standard hydrogen electrode), lithium metal is identified as one of the most promising anode materials, which has sparked a research boom. However, the intrinsically high reactivity triggers a repeating fracture/reconstruction process of the solid electrolyte interphase, side reactions with electrolyte and lithium dendrites, detrimental to the electrochemical performance of lithium metal batteries (LMBs). Even worse, when exposed to air, lithium metal will suffer severe atmospheric corrosion, especially the reaction with moisture, leading to grievous safety hazards. To settle these troubles, constructing air‐stable protective layers (ASPLs) is an effective solution. In this review, besides the necessity of ASPLs is highlighted, the modified design criteria, focusing on enhancing chemical/mechanical stability and controlling ion flux, are proposed. Correspondingly, current research progress is comprehensively summarized and discussed. Finally, the perspectives of developing applicable lithium metal anodes (LMAs) are put forward. This review guides the direction for the practical use of LMAs, further pushing the evolution of safe and stable LMBs. [ABSTRACT FROM AUTHOR]

Presenting a three-dimensional organic–inorganic composite frame material that features nitrogenous functional groups with zincophilicity as an artificial bi-functional layer coated on the zinc foil, to protect the Zn anodes and improve its electrochemical behaviors. [Display omitted] Rechargeable aqueous zinc-ion hybrid supercapacitors (ZHSs) are drawing extensive attention because of their cost-effectiveness and diminished safety hazards. Nevertheless, large-scale application of ZHSs has been hindered by the severe side reactions and rampant dendrites growth on the surface of Zn metal anodes. Herein, we propose a three-dimensional organic–inorganic composite frame material as an artificial bi-functional layer coated on the zinc foil, featuring nitrogenous functional groups with zincophilicity (abbreviated as NCFM@Zn). The nitrogen (N) site's strong adsorption capacity and synergistic effect of the sub-nanopore size promote rapid desolvation of zinc ions and reduce side reactions, while also prolonging galvanized nucleation's Sand's time and allowing for even nucleation. Moreover, the uniform distribution of N on the layer results in homogeneous zinc ions flux and supports consistent zinc plating while inhibiting dendrites generation. As a result of this unique artificial bi-functional layer, symmetric Zn cells can survive 2500 h at 2.5 mA cm−2. High-areal-capacity zinc||activated carbon hybrid supercapacitors also demonstrate 20,000 cycles at high Coulombic efficiency, thus highlighting the utter convenience and potential of this strategy for modifying rechargeable metal hybrid supercapacitor surfaces. [ABSTRACT FROM AUTHOR]

[Display omitted] • UMMT coating promotes the Zn2+ diffusion by the strong attraction of −C=O and −NH 2. • UMMT coating serves as a desolvation layer, mitigating the parasitic reactions. • The hydrogen bonding between urea and MMT strengthens MMT's mechanical properties. • The symmetric cell with UMMT@Zn anode survives over 1300 h at 6 mA cm−2 / 3 mAh cm−2. Clay minerals as artificial solid electrolyte interphase (SEI) layers have played a crucial role in protecting zinc metal anodes for aqueous Zn-ion batteries (AZIBs) due to their unique layered structure, negatively charged lamellas, ion exchange ability, and electronic insulation. However, the clay mineral layers exhibit limited ability to suppress dendrites and side reactions on the Zn anode in the water-based working environment. This limitation is attributed to the severe volumetric expansion, poor mechanical performance, and inferior zinc ion conductivity. To address these issues, montmorillonite (MMT) is intercalated with urea in this study. The resulting dense and robust UMMT coating layer enhances the diffusion of Zn2+ and increases the Zn2+ concentration at the Zn deposition surface through strong absorption of Zn2+ at −C=O and −NH 2 active sites. As a result, it facilitates the uniform deposition of Zn2+ and inhibits dendrite growth. Additionally, the UMMT coating layer acts as a desolvation layer, mitigating parasitic reactions originated from active water. Consequently, the UMMT coating layer enables stable Zn plating/stripping compared to MMT layer. In symmetric cells, MMT@Zn electrode exhibits a significantly longer lifespan of over 1300 h at 6 mA cm−2 with a capacity of 3 mAh cm−2. Furthermore, it demonstrates enhanced cyclic performance of 254 mAh g−1 at 10 A g−1 after 4000 cycles in Zn//V 2 O 5 full cells. This present work presents a strategy to intercalate small-molecule organics into clay minerals, enhancing their protective capacity and expanding their application as SEI layers in AZIBs. [ABSTRACT FROM AUTHOR]

• The MD simulation proves VRM layer can accelerate Zn2+ transport at the electrode/electrolyte interface. • The VRM layer can effectively reduce the coordination number of water molecules in the Zn2+ solvent shell. • The symmetric cell with VRM@Zn anode achieves a long cycle life of more than 580 h even at 25 mA cm−2/12.5 mAh cm−2. The zinc (Zn) metal batteries suffer from poor plating/stripping behaviors due to the severe dendrite growth and side reactions stemming from the sluggish ion migration at the electrolyte/electrode interface. Despite effectiveness by constructing artificial ion-diffusion layer to alleviate these issues, the intrinsic mechanism of zinc ion (Zn2+) diffusion within the interfacial layer is not well elucidated yet. Here, inspired by the ability of vermiculite (VRM) to promote the self-concentration kinetics of metal ions, this intrinsic issue can be tackled by elaborately constructing VRM with fast ion-transport channels on the surface of Zn metal anodes. This unique ion channel with a natural negatively charged wall can accelerate Zn2+ transport and reduce the presence of water molecules in Zn2+ solvated shell, which can be demonstrated by molecular dynamic simulation. As a proof of concept, the symmetric cell with VRM@Zn anode achieves dendrite-free plating/stripping with a stable cycling life (580 h) even at a high rate of 25 mA cm−2 with a capacity of 12.5 mAh cm−2. Meanwhile, the Zn-carbon supercapacitor with VRM@Zn anode exhibits an extended stability over 5000 cycles at 1 A g−1. This work reveals the internal mechanism of Zn2+ diffusion within the interfacial layer, and provides an avenue for constructing highly reversible Zn metal anode. [ABSTRACT FROM AUTHOR]