Insertion Type Li ₃ VO ₄ Lithiophilic Sites Boosting Dendrite‐Free Lithium Deposition in Trapping‐and‐leveling Model

Abstract Lithium (Li) metal batteries offer high energy densities but suffer from uncontrolled lithium deposition, causing serious dendrite growth and volume fluctuation. Tailorable Li nucleation and uniform early‐stage plating are essential for homogenous Li deposition. Herein, insertion type Li 3 VO 4 is first demonstrated as efficient lithiophilic sites trapping Li + ions for homogenous nucleation. By homogenizing the distribution of electric field and ions flux via an ingenious architecture design with Li 3 VO 4 nanodots grown on the carbon fibers (LVO@CNFs), leveling Li metal deposition after nucleation is also realized. These, together, result in smooth and dendrite‐free Li deposition on the LVO@CNFs via a trapping‐and‐leveling model, giving rise to unprecedented performance (highly stable Li plating/stripping exceeding 2500 h at 2 mA cm −2 under 3 mA h cm −2 capacity, high‐capacity retention of 82.5% over 500 cycles in a Li@LVO@CNFs//LiFePO 4 battery). The successful design of Li metal deposition host via insertion‐type Li 3 VO 4 may pave a new way for long lifespan Li metal batteries.