Unusual Size Effect in Ion and Charge Transport in Micron‐Sized Particulate Aluminum Anodes of Lithium‐Ion Batteries

Aluminum is a promising anode material for lithium-ion batteries owing to its high theoretical capacity, excellent conductivity, and natural abundance. An anomalous size effect was observed for micron-sized aluminum powder electrodes in this work. Experimental and theoretical investigations reveal that the insulating oxide surface layer is the underlying cause, which leads to poor electrical conductivity and limited capacity utilization when the particle is too small. Additionally, poor electrolyte wettability also accounts for the hindered reaction kinetics due to the weak polarity feature of the oxide layer. Surface grafting of polar amino groups was demonstrated to be an effective strategy to improve electrolyte wettability. The present work revealed the critical limitations and underlying mechanisms for the aluminum anode, which is crucial for its practical application. Our results are also valuable for other metallic anodes with similar issues.