Marinite Li2Ni(SO4)2as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes

Singh, S and Jha, PK and Avdeev, M and Zhang, W and Jayanthi, K and Navrotsky, A and Alshareef, HN and Barpanda, P (2021) Marinite Li2Ni(SO4)2as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes. In: Chemistry of Materials, 33 (15). pp. 6108-6119.

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Abstract

Development of sustainable, economic, and high-voltage cathode materials forms the cornerstone of cathode design for Li-ion batteries. Sulfate chemistry offers a fertile ground to discover high-voltage cathode materials stemming from a high electronegativity-based inductive effect. Herein, we have discovered a new polymorph of high-voltage m-Li2NiII(SO4)2 bisulfate using a scalable spray drying route. Neutron and synchrotron diffraction analysis revealed a monoclinic structure (s.g. P21/c, #14) built from corner-shared NiO6 octahedra and SO4 tetrahedra locating all Li+ in a distinct site. Low-temperature magnetic susceptibility and neutron diffraction measurements confirmed long-range A-type antiferromagnetic ordering in m-Li2NiII(SO4)2 below 15.2 K following the Goodenough-Kanamori-Anderson rule. In situ X-ray powder diffraction displayed an irreversible (monoclinic � orthorhombic) phase transformation at �400 °C. The m-Li2NiII(SO4)2 framework offers two-dimensional Li+ migration pathways as revealed by the bond valence site energy (BVSE) approach. The electronic structure obtained using first-principles (DFT) calculation shows a large electronic band gap (Eg �3.8 eV) with a trapped state near the Fermi energy level triggering polaronic conductivity. As per the DFT study, m-Li2NiII(SO4)2 can work as a 5.5 V (vs Li+/Li0) cathode for Li-ion batteries, with suitable electrolytes, coupling both cationic (NiII/III) and anionic (O-) redox activity. ©

Item Type:	Journal Article
Publication:	Chemistry of Materials
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society
Keywords:	Antiferromagnetism; Calculations; Cathode materials; Cathodes; Chemical bonds; Design for testability; Electronegativity; Electronic structure; Energy gap; Lithium-ion batteries; Magnetic susceptibility; Nickel compounds; Redox reactions; Sulfur compounds; Temperature; X ray powder diffraction, A-type antiferromagnetic order; Electronic band gaps; High voltage cathode; Lithium battery cathodes; Monoclinic structures; Neutron diffraction measurements; Situ X-ray powder diffraction; Synchrotron diffraction, Lithium compounds
Department/Centre:	Division of Chemical Sciences > Materials Research Centre
Date Deposited:	02 Dec 2021 13:01
Last Modified:	02 Dec 2021 13:01
URI:	http://eprints.iisc.ac.in/id/eprint/70086

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