Tunable Organic-Inorganic p-π-d Electron Conjugation Triggers d-π Hybridization in Quinonized MnO2 Superlattice toward Ultrastable and High-Rate Zn−MnO2 Batteries

Anqi Zhang, Tiande Chen, Ran Zhao, Yahui Wang, Jingjing Yang, Xiaomin Han, Xinran Wang*, Chuan Wu*, Ying Bai*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Zn-MnO2 batteries with two-electron transfer harvest high energy density, high working voltage, inherent safety, and cost-effectiveness. Zn2+ as the dominant charge carriers suffer from sluggish kinetics due to the strong Zn2+−MnO2 coulombic interaction, which is also the origin of pestilent MnO2 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 Zn2+ insertion and structural collapse. Herein, a simultaneously enhanced and stabilized Zn2+/H+ co-insertion chemistry is proposed by the quinone-hybridized MnO2 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 t2g occupation and thus improved [MnO6] stability upon unprecedentedly high Zn2+ contribution. The notable d-π hybridization endows MnO2 superlattice an ultrahigh specific capacity (435.9 mAh g−1 at 0.25 A g−1), state-of-the-art cycle stability (~100 % capacity retention after 30,000 cycles at 10 A g−1) with substantially enhanced rate performance. Our findings enlighten a new paradigm in the adjustment of Zn2+/H+ co-insertion chemistry towards high-performance rechargeable aqueous batteries.

Original languageEnglish
JournalAngewandte Chemie - International Edition
DOIs
Publication statusAccepted/In press - 2025

Keywords

  • d-π Hybridization
  • High Zn Contribution
  • High-Rate Zn-MnO Batteries
  • Organic-Inorganic p-π-d Electron Conjugation
  • Quinonized MnO Superlattice

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Zhang, A., Chen, T., Zhao, R., Wang, Y., Yang, J., Han, X., Wang, X., Wu, C., & Bai, Y. (Accepted/In press). Tunable Organic-Inorganic p-π-d Electron Conjugation Triggers d-π Hybridization in Quinonized MnO2 Superlattice toward Ultrastable and High-Rate Zn−MnO2 Batteries. Angewandte Chemie - International Edition. https://doi.org/10.1002/anie.202423824