Work‐Function‐Induced Interfacial Electron/Ion Transport in Carbon Hosts toward Dendrite‐Free Lithium Metal Anodes

Coupled electron/ion transport is a decisive feature of Li plating/stripping, wherein the compatibility of electron/ion transport rates determines the morphology of deposited Li. Local Li + hotspots form due to inhomogeneous interfacial charge transfer and lead to uncontrolled Li deposition, which decreases the Li utilization rate and safety of Li metal anodes. Herein, we report a method to obtain dendrite‐free Li metal anodes by driving electron pumping and accumulating and boosting Li ion diffusion by tuning the work function of a carbon host using cobalt‐containing catalysts. The results reveal that increasing the work function provides an electron deviation from C to Co, and electron‐rich Co shows favorable binding to Li + . The Co catalysts boost Li + diffusion on the carbon fiber scaffolds without local aggregation by reducing the Li + migration barrier. The as‐obtained dendrite‐free Li metal anode exhibits a Coulombic efficiency of 99.0 %, a cycle life of over 2000 h, a Li utilization rate of 50 %, and a capacity retention of 83.4 % after 130 cycles in pouch cells at a negative/positive capacity ratio of 2.5. These findings provide a novel strategy to stabilize Li metal by regulating the work function of materials using electrocatalysts.