TY - JOUR
T1 - Tunable Organic-Inorganic p-π-d Electron Conjugation Triggers d-π Hybridization in Quinonized MnO2 Superlattice toward Ultrastable and High-Rate Zn−MnO2 Batteries
AU - Zhang, Anqi
AU - Chen, Tiande
AU - Zhao, Ran
AU - Wang, Yahui
AU - Yang, Jingjing
AU - Han, Xiaomin
AU - Wang, Xinran
AU - Wu, Chuan
AU - Bai, Ying
N1 - Publisher Copyright:
© 2025 Wiley-VCH GmbH.
PY - 2025
Y1 - 2025
N2 - 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.
AB - 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.
KW - d-π Hybridization
KW - High Zn Contribution
KW - High-Rate Zn-MnO Batteries
KW - Organic-Inorganic p-π-d Electron Conjugation
KW - Quinonized MnO Superlattice
UR - http://www.scopus.com/inward/record.url?scp=85215382703&partnerID=8YFLogxK
U2 - 10.1002/anie.202423824
DO - 10.1002/anie.202423824
M3 - Article
AN - SCOPUS:85215382703
SN - 1433-7851
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
ER -