Tunneling Proton Grotthuss Transfer Channels by Hydrophilic‐Zincophobic Heterointerface Shielding for High‐Performance Zn‐MnO2 Batteries

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-09, Vol.20 (38), p.e2403136-n/a
• Main Authors: Wang, Yahui, Wang, Xinran, Zhang, Anqi, Han, Xiaomin, Yang, Jingjing, Chen, Wenxing, Zhao, Ran, Wu, Chuan, Bai, Ying
• Format: Article
• Language: English
• Subjects: aqueous zinc‐ion batteries; Atomic structure; Channels; Degradation; Diffusion rate; Electrode materials; grotthuss transfer; Hydrophilicity; Insertion; Interface stability; Kinetics; Low currents; Manganese dioxide; Oxygen enrichment; oxygen vacancy; proton intercalation; Protons; Shielding
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202403136

Hollandite‐type manganese dioxide (α‐MnO2) is recognized as a promising cathode material upon high‐performance aqueous zinc‐ion batteries (ZIBs) owing to the high theoretical capacities, high working potentials, unique Zn2+/H+ co‐insertion chemistry, and environmental friendliness. However, its practical applications limited by Zn2+ accommodation, where the strong coulombic interaction and sluggish kinetics cause significant lattice deformation, fast capacity degradation, insufficient rate capability, and undesired interface degradation. It remains challenging to accurately modulate H+ intercalation while suppressing Zn2+ insertion for better lattice stability and electrochemical kinetics. Herein, proton Grotthuss transfer channels are first tunneled by shielding MnO2 with hydrophilic‐zincophobic heterointerface, fulfilling the H+‐dominating diffusion with the state‐of‐the‐art ZIBs performance. Local atomic structure and theoretical simulation confirm that surface‐engineered α‐MnO2 affords to the synergy of Mn electron t2g–eg activation, oxygen vacancy enrichment, selective H+ Grotthuss transfer, and accelerated desolvation kinetics. Consequently, fortified α‐MnO2 achieves prominent low current density cycle stability (≈100% capacity retention at 1 C after 400 cycles), remarkable long‐lifespan cycling performance (98% capacity retention at 20 C after 12 000 cycles), and ultrafast rate performance (up to 30 C). The study exemplifies a new approach of heterointerface engineering for regulation of H+‐dominating Grotthuss transfer and lattice stabilization in α‐MnO2 toward reliable ZIBs. Reconstructed MnO2 surface enables hydrophilic‐zincophobic shielding and simultaneous oxygen vacancy generation that facilitates H+ preferential Grotthuss transfer and accelerated desolvation kinetics while suppressing Zn2+ accommodation, synergistically boosting ultrastable cycle stability, improved rate capability, significantly reduced dissolution, and strengthened lattice stability for high‐performance Zn‐MnO2 batteries.