LiF-Rich Interfacial Protective Layer Enables Air-Stable Lithium Metal Anodes for Dendrite-Free Lithium Metal Batteries

Abstract

Lithium (Li) metal is considered as a promising anode candidate for high-energy-density batteries. However, the high reactivity of Li metal leads to poor air stability, limiting its practical application. Additionally, the interfacial instability, such as dendrite growth and an unstable solid electrolyte interphase layer, further complicates its utilization. Herein, a dense lithium fluoride (LiF)-rich interfacial protective layer is constructed on the Li surface through a simple reaction between Li and fluoroethylene carbonate (denoted as LiF@Li). The LiF-rich interfacial protective layer consists of both organic (ROCO₂Li and C-F-containing species, which only exist on the outer layer) and inorganic (LiF and Li₂CO₃, distribute throughout the layer) components with a thickness of ∼120 nm. Specifically, chemically stable LiF and Li₂CO₃ play an important role in blocking air and hence improve the air durability of LiF@Li anodes. Notably, LiF with high Li⁺ diffusivity facilitates uniform Li⁺ deposition, while organic components with high flexibility relieve volume change upon cycling, thereby enhancing the dendrite inhibition capacity of LiF@Li. Consequently, LiF@Li exhibits remarkable stability and excellent electrochemical performance in both symmetric cells and LiFePO₄ full cells. Moreover, LiF@Li maintains its initial color and morphology even after air exposure for 30 min, and the air-exposed LiF@Li anode still retains its superior electrochemical performance, further establishing its outstanding air-defendable capability. This work proposes a facile approach in constructing air-stable and dendrite-free Li metal anodes toward reliable Li metal batteries.