In:
Angewandte Chemie, Wiley, Vol. 133, No. 8 ( 2021-02-19), p. 4215-4220
Abstract:
The recent developments in rechargeable aqueous batteries have witnessed a burgeoning interest in the mechanism of proton transport in the cathode materials. Herein, for the first time, we report the Grotthuss proton transport mechanism in α‐MnO 2 which features wide [2×2] tunnels. Exemplified by the substitution doping of Ni (≈5 at.%) in α‐MnO 2 that increases the energy density of the electrode by ≈25 %, we reveal a close link between the tetragonal‐orthorhombic (TO) distortion of the lattice and the diffusion kinetics of protons in the tunnels. Experimental and theoretical results verify that Ni dopants can exacerbate the TO distortion during discharge, thereby facilitating the hydrogen bond formation in bulk α‐MnO 2 . The isolated direct hopping mode of proton transport is switched to a facile concerted mode, which involves the formation and concomitant cleavage of O−H bonds in a proton array, namely via Grotthuss proton transport mechanism. Our study provides important insight towards the understanding of proton transport in MnO 2 and can serve as a model for the compositional design of cathode materials for rechargeable aqueous batteries.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202011588
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
505868-5
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
514305-6
detail.hit.zdb_id:
505872-7
detail.hit.zdb_id:
1479266-7
detail.hit.zdb_id:
505867-3
detail.hit.zdb_id:
506259-7
Permalink