Marinite Li2Ni(SO4)2 as 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

6 Scopus citations

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)
JournalChemistry of Materials
DOIs
StatePublished - Jul 30 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-08-05
Acknowledgements: The authors acknowledge the financial support from the Technology Mission Division (Department of Science and Technology, Government of India) under the Materials for Energy Storage (MES-2018) program (DST/TMD/MES/2K18/207). S.S. and P.K.J. thank the Ministry of Human Resource Development (MHRD) for financial support. P.K.J. thanks Prof. M. Shrivastava and Prof. S. G. Gopalakrishnan for computational resources and scientific discussions, respectively. H.N.A. is grateful to the King Abdullah University of Science and Technology (KAUST) for partial financial support. A.N. and K.J. sincerely acknowledge financial support from the U.S. Department of Energy, Office of Basic Energy Sciences, Grant DE-FG02-03ER46053.

ASJC Scopus subject areas

  • Materials Chemistry
  • General Chemical Engineering
  • General Chemistry

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