Tunable Organic-Inorganic p-π-d Electron Conjugation Triggers d-π Hybridization in Quinonized MnO 2 Superlattice toward Ultrastable and High-Rate Zn-MnO 2 Batteries

• Published in: Angewandte Chemie International Edition 2025-01, p.e202423824
• Main Authors: Zhang, Anqi, Chen, Tiande, Zhao, Ran, Wang, Yahui, Yang, Jingjing, Han, Xiaomin, Wang, Xinran, Wu, Chuan, Bai, Ying
• Format: Article
• Language: English
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202423824

Zn-MnO batteries with two-electron transfer harvest high energy density, high working voltage, inherent safety, and cost-effectiveness. Zn as the dominant charge carriers suffer from sluggish kinetics due to the strong Zn -MnO coulombic interaction, which is also the origin of pestilent MnO lattice deformation and performance degradation. Current studies particularly involve H insertion-dominating chemistry, where the long-term cycle stability remains challenging due to the accumulative Zn insertion and structural collapse. Herein, a simultaneously enhanced and stabilized Zn /H co-insertion chemistry is proposed by the quinone-hybridized MnO superlattice, a first-of-this-kind structure with a distinctive organic-inorganic-extended p-π-d conjugation, which enables a tunable interlayer d-π hybridization. Theoretical and experimental results substantiate that the interlayer d-π hybridization triggers the enhancement of polarons occupancy near Fermi level, the downward shift of O p-band center, the elevated Mn t occupation and thus improved [MnO ] stability upon unprecedentedly high Zn contribution. The notable d-π hybridization endows MnO superlattice an ultrahigh specific capacity (435.9 mAh g at 0.25 A g ), state-of-the-art cycle stability (~100 % capacity retention after 30,000 cycles at 10 A g ) with substantially enhanced rate performance. Our findings enlighten a new paradigm in the adjustment of Zn /H co-insertion chemistry towards high-performance rechargeable aqueous batteries.