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

A dual-aspect control strategy is developed to simultaneously regulate lithium (Li) nucleation and growth by integrating a protective layer composed of hydroxyapatite and a sulfonate-abundant liquid crystal polymer. This strategy effectively suppresses Li dendrite formation while significantly enhancing the cycling stability of symmetric batteries. Moreover, Li–sulfur batteries incorporating this protective layer exhibit exceptional high-rate and long-term cycling performance.

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 Li⁰ 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.