Additional Lithium Storage on Dynamic Electrode Surface by Charge Redistribution in Inactive Ru Metal

Abstract Beyond a traditional view that metal nanoparticles formed upon electrochemical reaction are inactive against lithium, recently their electrochemical participations are manifested and elucidated as catalytic and interfacial effects. Here, ruthenium metal composed of ≈5 nm nanoparticles is prepared and the pure ruthenium as a lithium‐ion battery anode for complete understanding on anomalous lithium storage reaction mechanism is designed. In particular, the pure metal electrode is intended for eliminating the electrochemical reaction‐derived Li₂O phase accompanied by catalytic Li₂O decomposition and the interfacial lithium storage at Ru/Li₂O phase boundary, and thereby focusing on the ruthenium itself in exploring its electrochemical reactivity. Intriguingly, unusual lithium storage not involving redox reactions with electron transfer but leading to lattice expansion is identified in the ruthenium electrode. Size‐dependent charge redistribution at surface enables additional lithium adsorption to occur on the inactive but more environmentally sensitive nanoparticles, providing innovative insight into dynamic electrode environments in rechargeable lithium chemistry.