Decreased Electrically and Increased Ionically Conducting Scaffolds for Long‐Life, High‐Rate and Deep‐Capacity Lithium‐Metal Anodes

Abstract Lithium (Li) metal batteries are deemed as promising next‐generation power solutions but are hindered by the uncontrolled dendrite growth and infinite volume change of Li anodes. The extensively studied 3D scaffolds as solutions generally lead to undesired “top‐growth” of Li due to their high electrical conductivity and the lack of ion‐transporting pathways. Here, by reducing electrical conductivity and increasing the ionic conductivity of the scaffold, the deposition spot of Li to the bottom of the scaffold can be regulated, thus resulting in a safe bottom‐up plating mode of the Li and dendrite‐free Li deposition. The resulting symmetrical cells with these scaffolds, despite with a limited pre‐plated Li capacity of 5 mAh cm⁻², exhibit ultra‐stable Li plating/stripping for over 1 year (11 000 h) at a high current density of 3 mA cm⁻² and a high areal capacity of 3 mAh cm⁻². Moreover, the full cells with these scaffolds further demonstrate high cycling stability under challenging conditions, including high cathode loading of 21.6 mg cm⁻², low negative‐to‐positive ratio of 1.6, and limited electrolyte‐to‐capacity ratio of 4.2 g Ah⁻¹.