TY - JOUR
T1 - Marinite Li2Ni(SO4)2 as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes
AU - Singh, Shashwat
AU - Jha, Pawan Kumar
AU - Avdeev, Maxim
AU - Zhang, Wenli
AU - Jayanthi, K.
AU - Navrotsky, Alexandra
AU - Alshareef, Husam N.
AU - Barpanda, Prabeer
N1 - 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.
PY - 2021/7/30
Y1 - 2021/7/30
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/670389
UR - https://pubs.acs.org/doi/10.1021/acs.chemmater.1c01669
U2 - 10.1021/acs.chemmater.1c01669
DO - 10.1021/acs.chemmater.1c01669
M3 - Article
SN - 0897-4756
JO - Chemistry of Materials
JF - Chemistry of Materials
ER -