Marinite Li2Ni(SO4)2 as a new member of the bisulfate family of high-voltage lithium battery cathodes

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dc.contributor.authorSingh, Sen_AU
dc.contributor.authorJha, PKen_AU
dc.contributor.authorAvdeev, Men_AU
dc.contributor.authorZhang, WLen_AU
dc.contributor.authorJayanthi, Ken_AU
dc.contributor.authorNavrotsky, Aen_AU
dc.contributor.authorAlshareef, HMen_AU
dc.contributor.authorBarpanda, Pen_AU
dc.date.accessioned2021-09-14T03:18:09Zen_AU
dc.date.available2021-09-14T03:18:09Zen_AU
dc.date.issued2021-07-31en_AU
dc.date.statistics2021-09-09en_AU
dc.description.abstractDevelopment 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. © 2021 American Chemical Societyen_AU
dc.identifier.citationSingh, S., Jha, P. K., Avdeev, M., Zhang, W., Jayanthi, K., Navrotsky, A., Alshareef, H. M., & Barpanda, P. (2021). Marinite Li2Ni(SO4)2 as a new member of the bisulfate family of high-voltage lithium battery cathodes. Chemistry of Materials, 33(15), 6108–6119. doi:10.1021/acs.chemmater.1c01669en_AU
dc.identifier.issn1520-5002en_AU
dc.identifier.issue15en_AU
dc.identifier.journaltitleChemistry of Materialsen_AU
dc.identifier.pagination6108-6119en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.chemmater.1c01669en_AU
dc.identifier.urihttps://apo.ansto.gov.au/dspace/handle/10238/11698en_AU
dc.identifier.volume33en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectPhase transformationsen_AU
dc.subjectGranular materialsen_AU
dc.subjectNeutron diffractionen_AU
dc.subjectLithium ion batteriesen_AU
dc.subjectRedox reactionsen_AU
dc.subjectCathodesen_AU
dc.subjectAntiferromagnetismen_AU
dc.subjectX-ray diffractionen_AU
dc.subjectMagnetic propertiesen_AU
dc.subjectTemperature range 0065-0273 Ken_AU
dc.titleMarinite Li2Ni(SO4)2 as a new member of the bisulfate family of high-voltage lithium battery cathodesen_AU
dc.typeJournal Articleen_AU
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