Atomic-scale storage mechanism in ultra-small size (FeCuCrMnNi)3O4/rGO with super-stable sodium storage and accelerated kinetics

[Display omitted] •The facile and mass-producible synthesis for (FeCuCrMnNi)3O4/rGO architecture.•Ultra-small size causes pseudo-capacitive behaviour revealing accelerated kinetics.•The oxygen vacancies promote the desorption of Na+ during the charge process.•Highly reversible transformation of spin...

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Published in:Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2023-08, Vol.469, p.143951, Article 143951
Main Authors: Li, Huijun, Duan, Yunrui, Zhao, Zhenxin, Cheng, Xiaoqin, Bian, Wenshu, Xiao, Zehua, Wang, Xiaomin
Format: Article
Language:English
Subjects:
Accelerated kinetics
High-Entropy oxides
Oxygen vacancies
Storage mechanism
Ultra-small size
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Summary:[Display omitted] •The facile and mass-producible synthesis for (FeCuCrMnNi)3O4/rGO architecture.•Ultra-small size causes pseudo-capacitive behaviour revealing accelerated kinetics.•The oxygen vacancies promote the desorption of Na+ during the charge process.•Highly reversible transformation of spinel to rock salt is observed by in situ XRD. Transition-metal high-entropy oxides show superior electrochemical properties and excellent long-term cycling stability in secondary batteries due to their entropy stabilization effect. However, the effects on storage mechanisms of Na+ batteries remains an open question, especially considering its larger ionic radius, sluggish kinetics movement, and serious volumetric expansion. In this work, ultra-small size spinel-structured (FeCuCrMnNi)3O4 composition of hollow porous microspheres is dispersed on the reduced graphene oxide net work. The architecture can effectively suppress the continuous volume expansion and maintain valid interface contact between electrode and electrolyte, thus achieving highly reversible sodium storage. Moreover, oxygen vacancies promote the desorption of Na+ during the charge process due to weak chemical bonding and migration barrier, improving cycling stability. Furthermore, highly reversible structural transformation of spinel to monometallic oxides and then to rock salt structure is observed by in situ XRD. The results provide an in-depth understanding of Na+ storage mechanism in HEOs with self-supporting electrode materials.
ISSN:1385-8947
DOI:10.1016/j.cej.2023.143951