A two-electron transfer mechanism of the Zn-doped δ-MnO2 cathode toward aqueous Zn-ion batteries with ultrahigh capacity

Zhao, Wen; Fee, Jared; Khanna, Harshul; March, Seth; Nisly, Nathaniel; Rubio, Samantha B.; Cui, Can; Li, Zhuo; Suib, Steven L.

doi:10.1039/d1ta10864f

A two-electron transfer mechanism of the Zn-doped δ-MnO₂ cathode toward aqueous Zn-ion batteries with ultrahigh capacity

Journal Article · Mon Feb 14 00:00:00 EST 2022 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d1ta10864f· OSTI ID:1978847

Zhao, Wen ^[1]; Fee, Jared ^[2]; Khanna, Harshul ^[2]; March, Seth ^[2]; Nisly, Nathaniel ^[2]; Rubio, Samantha B. ^[2]; Cui, Can ^[2]; Li, Zhuo ^[3]; ^[2]

Univ. of Connecticut, Storrs, CT (United States); OSTI
Univ. of Connecticut, Storrs, CT (United States)
Huazhong Univ. of Science and Technology, Wuhan (China)

Neutral aqueous zinc-ion batteries (ZIBs) have attracted considerable attention due to their safe and green features. As one typical cathode, birnessite MnO₂ (δ-MnO₂) suffers from low conductivity and structural instability, and its energy storage mechanism is still not well established yet. Herein, we developed a Zn-doped δ-MnO₂ material via a facile and effective microwave-assisted method for the cathode in aqueous ZIBs. By incorporating Zn to modify the microstructure and promote reaction kinetics, the Zn-doped δ-MnO₂ electrode demonstrates significantly enhanced electrochemical performance with an ultrahigh reversible capacity of 455 mA h g^–1 and excellent specific energy of 628 W h kg^–1. In addition, the successive insertion of H⁺ and Zn²⁺ and deep two-electron transfer routes are revealed systematically by ex situ experiments. In this study, the two-electron transfer route (Mn⁴⁺/Mn³⁺ and Mn³⁺/Mn²⁺) mechanism of Zn-doped δ-MnO₂ electrodes explains the exceedingly high capacity and opens new opportunities to develop high-energy aqueous ZIBs.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Connecticut, Storrs, CT (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-86ER13622

OSTI ID:: 1978847

Alternate ID(s):: OSTI ID: 1846309

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 12 Vol. 10; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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