Engineering Triple‐Phase Interfaces around the Anode toward Practical Alkali Metal–Air Batteries

Abstract Alkali metal–air batteries (AMABs) promise ultrahigh gravimetric energy densities, while the inherent poor cycle stability hinders their practical application. To address this challenge, most previous efforts are devoted to advancing the air cathodes with high electrocatalytic activity. Recent studies have underlined the solid–liquid–gas triple‐phase interface around the anode can play far more significant roles than previously acknowledged by the scientific community. Besides the bottlenecks of uncontrollable dendrite growth and gas evolution in conventional alkali metal batteries, the corrosive gases, intermediate oxygen species, and redox mediators in AMABs cause more severe anode corrosion and structural collapse, posing greater challenges to the stabilization of the anode triple‐phase interface. This work aims to provide a timely perspective on the anode interface engineering for durable AMABs. Taking the Li–air battery as a typical example, this critical review shows the latest developed anode stabilization strategies, including formulating electrolytes to build protective interphases, fabricating advanced anodes to improve their anti‐corrosion capability, and designing functional separator to shield the corrosive species. Finally, the remaining scientific and technical issues from the prospects of anode interface engineering are highlighted, particularly materials system engineering, for the practical use of AMABs.