Protons intercalation induced hydrogen bond network in δ-MnO₂ cathode for high-performance aqueous zinc-ion batteries

Birnessite-type MnO₂ (δ-MnO₂) exhibits great potential as a cathode material for aqueous zinc-ion batteries (AZIBs). However, the structural instability and sluggish reaction kinetics restrict its further application. Herein, a unique protons intercalation strategy was utilized to simultaneously modify the interlayer environment and transition metal layers of δ-MnO₂. The intercalated protons directly form strong O  H bonds with the adjacent oxygens, while the increased H₂O molecules also establish a hydrogen bond network (O  H···O) between H₂O molecules or bond with adjacent oxygens. Based on the Grotthuss mechanism, these bondings ultimately enhance the stability of layered structures and facilitate the rapid diffusion of protons. Moreover, the introduction of protons induces numerous oxygen vacancies, reduces steric hindrance, and accelerates ion transport kinetics. Consequently, the protons intercalated δ-MnO₂ (H-MnO_2-x) demonstrates exceptional specific capacity of 401.7 mAh/g at 0.1 A/g and a fast-charging performance over 1000 cycles. Density functional theory analysis confirms the improved electronic conductivity and reduced diffusion energy barrier. Most importantly, electrochemical quartz crystal microbalance tests combining with ex-situ characterizations verify the inhibitory effect of the interlayer proton environment on basic zinc sulfate formation. Protons intercalation behavior provides a promising avenue for the development of MnO₂ as well as other cathodes in AZIBs.