Dual‐Aspect Control of Lithium Nucleation and Growth with Hydroxyapatite and Liquid Crystal Polymers for High‐Performance Lithium Metal Batteries

Abstract Lithium (Li) metal is a promising anode material for next‐generation high‐energy‐density batteries. However, safety concerns and the limited lifespan due to Li dendrite formation hinder its practical application. The complex dendrite formation process involves nonuniform nucleation and radial growth, requiring a holistic strategy to simultaneously regulate both processes. In this work, a dual‐aspect control strategy is developed by designing a protective layer composed of hydroxyapatite (HA) and a liquid crystal polymer (LCP). Electrochemical, microstructural, and computational analyses revealed that HA provides homogenous Li 0 adsorption sites, enhancing Li nucleation kinetics and uniformity. Meanwhile, the LCP self‐assembles into cation‐selective channels, promoting Li‐ion diffusion and regulating growth direction. This dual‐aspect control significantly improved Li plating kinetics and mitigated Li dendrite formation. Benefiting from this strategy, the symmetric cell achieved a critical current density of 5 mA cm −2 and maintained a lifespan of 500 h at 3 mA cm −2 . Furthermore, in Li–sulfur batteries, the cell exhibited exceptional high‐rate cycling performance (>10 mA cm −2 ) with an average capacity decay rate of only 0.056% over 1000 cycles. These results highlight the effectiveness of dual‐aspect control in suppressing Li dendrites and improving high‐rate cycling stability.