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

Shashwat Singh, Pawan Kumar Jha, Maxim Avdeev, Wenli Zhang, K. Jayanthi, Alexandra Navrotsky, Husam N. Alshareef, Prabeer Barpanda

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish (US)
Pages (from-to)6108-6119
Number of pages12
JournalChemistry of Materials
Volume33
Issue number15
DOIs
StatePublished - Aug 10 2021

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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