Unveiling Phenoxazine's Unique Reversible Two-Electron Transfer Process and Stable Redox Intermediates for High-Performance Aqueous Zinc-ion Batteries.

Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 0370543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3773 (Electronic) Linking ISSN: 14337851 NLM ISO Abbreviation: Angew Chem Int Ed Engl Subsets: MEDLINE; PubMed not MEDLINE

Publication: <2004-> : Weinheim : Wiley-VCH
Original Publication: Weinheim/Bergstr. : New York, : Verlag Chemie ; Academic Press, c1962-

The low specific capacity determined by the limited electron transfer of p-type cathode materials is the main obstruction to their application towards high-performance aqueous zinc-ion batteries (ZIBs). To overcome this challenge, boosting multi-electron transfer is essential for improving the charge storage capacity. Here, as a typical heteroaromatic p-type material, we unveil the unique reversible two-electron redox properties of phenoxazine in the aqueous electrolytes for the first time. The second oxidation process is stabilized in the aqueous electrolytes, a notable contrast to its less reversibility in the non-aqueous electrolytes. A comprehensive investigation of the redox chemistry mechanism demonstrates remarkably stable redox intermediates, including a stable cation radical PNO⋅⁺ characterized by effective electron delocalization and a closed-shell state dication PNO²⁺. Meanwhile, the heightened aromaticity contributes to superior structural stability during the redox process, distinguishing it from phenazine, which features a non-equivalent hybridized sp²-N motif. Leveraging these synergistic advantages, the PNO electrodes deliver a high capacity of 215 mAh g^-1 compared to other p-type materials, and impressive long cycling stability with 100 % capacity retention over 3500 cycles. This work marks a crucial step forward in advanced organic electrodes based on multi-electron transfer phenoxazine moieties for high-performance aqueous ZIBs.
(© 2024 Wiley‐VCH GmbH.)

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No. 2011DA105287-ZR202101 State Key Laboratory of Coal Mine Disaster Dynamics and Control; Z20211350 the Technology Innovation and Application Development Special Project of Chongqing; Z20211200 Natural Science Foundation of Chongqing

Keywords: aqueous batteries; organic electrode materials; p-type materials; phenoxazine; redox chemistry

Date Created: 20240307 Latest Revision: 20240425

20260130

10.1002/anie.202319796

38451050