This study developed a symbiotic dual-confinement strategy integrating interstitial oxygen doping and carbon coating to enhance high-entropy alloys for high-current-density zinc-air batteries. Through the combination of theoretical cluster models with the experimental synthesis of MnFeCoNiCu@C high-entropy alloys, the synergistic suppression of demetalization and kinetic optimization was investigated. The dual-confined high-entropy alloys exhibited no significant attenuation for 1600 h in zinc-air batteries and resisted large current of 100 mA cm⁻² impacts, with density functional theory calculations confirming lower d-band centers and higher formation energies, correlating with enhanced durability and reaction kinetics. This approach simultaneously addresses atomic-scale metal dissolution and nanoscale mass transfer limitations, surpassing conventional coating strategies. The findings establish a framework for designing robust high-entropy alloys, advancing their application in high-demand electrocatalysis and energy conversion technologies.

The finite lithium-ion utilization, short cycling life, and lower capacity retention caused by irreversible dendrite growth become the maximum dilemma in lithium metal batteries’ (LMBs’) commercialization. Herein, a perfluoroalkyl-functionalized covalent organic framework (COF-F6) equipped with high stability and supernal proton conduction is introduced as an artificial solid electrolyte interface to stable the lithium metal anode. Benefiting from the strong electron-withdrawing effect of perfluoroalkyl, Li⁺ will be freed more by the competition of electronegative fluorine (F) and bis(trifluoromethanesulphonyl)imide anion (TFSI⁻). The dissociation of LiTFSI and process of Li⁺ desolvation are easier to achieve. In addition, high electronegative fluorine can also regulate local electron-cloud density to induce the fast immigration of Li⁺. All the above roles contribute to improving the Li⁺ transfer number (0.7) and achieving the goal of inhibiting Li dendrite. As a result, the perfluoroalkyl COF-F6 modified LMB presents outstanding cycling stability. The symmetric batteries accomplish an overlong life-span of more than 5000 h with a lower hysteresis voltage (11 mV) at 5 mA·cm⁻². Also, no dendrites are observed when using an in-situ optical microscope to learn the process of Li deposition. Therefore, this dendrite-free protection tactic holds broad prospects for the practical application of Li metal anodes.

Lithium metal batteries (LMBs) have attracted wide attentions because of their high theoretical specific capacity and low electrochemical potential. However, the growth of lithium dendrites seriously affects the practical application of LMBs. Thus, the lithium-philic carbonyl and carboxy dual-group-modified covalent organic framework (COF-COOH) is designed to coat the polypropylene (PP) separator (COF-COOH@PP separator), realizing the regulation of ion transport and uniform lithium deposition. The plentiful and negative charge sites in the COF-COOH can suppress the diffusion of the freely movable lithium salt anion by the electrostatic interaction. Density functional theory (DFT) calculations demonstrate that the COF-COOH possesses the function of anchoring anion and desolvation. Consequently, the Li⁺ transference number (0.7), ion conductivity (0.64 mS cm⁻¹), and desolvating of Li⁺ are obviously improved by using the COF-COOH@PP separator. The modified Li-Li symmetric battery delivers stable cycle for more than 1000 h and lower voltage hysteresis (0.02 V). This dendrite-free deposition strategy holds great promise for practical application of Li metal anodes.