Modulating electronic structure of metal-organic frameworks derived zinc manganates by oxygen vacancies for superior lithium storage

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2022-04, Vol.433, p.133770, Article 133770
• Main Authors: Lin, Jia, Huang, Taoping, Lu, Man, Lin, Xiaoming, Reddy, R. Chenna Krishna, Xu, Xuan
• Format: Article
• Language: English
• Subjects: DFT calculation; Lithium storage; Metal-organic framework; Oxygen vacancies; Zinc manganates
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2021.133770

A conceptual vacancy protocol for Metal-organic framework (MOF)-derived ZnMn2O4 is proposed for manipulating electronic structure of anodes in LIBs. Unraveled by experimental and theoretical investigations, the OV-ZMOs derived from dicarboxybenzene-, tricarboxybenzene-, and isonicotinic-based Zn-Mn-MOFs (BDC-OV-ZMO, BTC-OV-ZMO, and IN-OV-ZMO) achieve superior electrochemical performance for lithium storage. [Display omitted] •A conceptual vacancy protocol for MOF-derived ZnMn2O4 is proposed for manipulating electronic structure.•Experimental and theoretical investigations unravel that all the OV-ZMOs achieve superior electrochemical performance.•The enriched oxygen vacancies facilitate boosted diffusion kinetics, and preferable Li adsorption. Electronic structure manipulation of transition metal oxides in crystal lattices renders as a prevailing methodology for high-performance Lithium-ion battery (LIB) electrodes. Thereinto, oxygen defective oxides can self-adaptively regulate the electronic property and active sites to reconcile the subpar electronic conductivity and substantial volume fluctuation. Herein, a conceptual protocol for constructing oxygen vacancies enriched ZnMn2O4 derived from various Zn-Mn-based Metal-organic frameworks (MOFs) is proposed as versatile anode materials towards lithium storage. Experimental implementation and theoretical calculation systematically unravel that the enriched OV is conducive to boosted electronic conductivity, extra active sites, preferable Li+ adsorption, and accelerated diffusion kinetics of OV-ZMOs. As expected, all the OV-ZMOs derived from dicarboxybenzene-, tricarboxybenzene-, and isonicotinic-based Zn-Mn-MOFs (BDC-OV-ZMO, BTC-OV-ZMO, and IN-OV-ZMO) achieve exalted electrochemical performance with superior specific capacity, distinguished rate capacity, and pre-eminent cyclability. This work envisions a conceptual vacancy protocol for MOF-derived electrode materials for LIBs.