Effectively Regulating More Robust Amorphous Li Clusters for Ultrastable Dendrite‐Free Cycling

A disordered phase in Li‐deposit nanostructure is greatly attractive, but plagued by the uncontrollable and unstable growth, and the nanoscale characterization in the structure. Here, fully characterized in cryogenic transmission electron microscopy (cryo‐TEM), more robust amorphous‐Li (ALi) clusters are revealed and effectively regulated on heteroatom‐activating electronegative sites and an advanced solid electrolyte interphase (SEI) layer. Heteroatom‐activating electronegative sites capably enhance the electrostatic interaction of Li+ and heteroatom‐doping graphene‐like film (HDGs), meaning lower Li diffusion barrier and larger binding energy that is confirmed by small nucleation overpotentials of 13.9 and 10 mV at 0.1 mA cm−2 in the fluoroethylene carbonate‐adding ester‐based (FEC‐ester) and LiNO3‐adding ether‐based (LiNO3‐ether) electrolytes. Orderly multilayer SEI structure comprised of inorganic‐rich components enables fast ion transports and durable capabilities to construct highly reversible and long‐term plating/stripping cycling. ALi cluster anodes exhibit non‐crystalline morphologies and perform ultrastable dendrite‐free cycling over 2800 times. Stable ALi clusters are also grown in LiFePO4 (LFP) (LFP‐ALi‐HDGs‐N||LiFePO4 [LFP]) full cells with advantageous capacities up to 165.5 and 164.3 mAh g−1 in these optimized electrolytes at 0.1 C; the remarkable capacity retentions maintain to 93% and 91% after 150 cycles at 0.2 C. Structure viability, electrochemical reversibility, and excellent performance in ALi clusters are effectively regulated. Structure viability, electrochemical reversibility, and excellent performance in amorphous Li (ALi) clusters are effectively regulated on the heteroatom‐activating electronegative sites and advanced, multilayer‐ordered, and robust solid electrolyte interphase systems for a more robust ALi cluster anode that exhibits non‐crystalline morphologies and performs ultrastable dendrite‐free cycling over 2800 cycles. Stable ALi clusters are also grown in LFP‐ALi‐HDGs‐N||LiFePO4 (LFP) full cells with advantageous capacities.