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

doi:10.1021/acs.chemmater.1c01669

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 journal › Article › peer-review

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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.

Original language	English (US)
Journal	Chemistry of Materials
DOIs	https://doi.org/10.1021/acs.chemmater.1c01669
State	Published - 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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@article{90de71242027488a852152ff9d4994f9,

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

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.",

author = "Shashwat Singh and Jha, {Pawan Kumar} and Maxim Avdeev and Wenli Zhang and K. Jayanthi and Alexandra Navrotsky and Alshareef, {Husam N.} and Prabeer Barpanda",

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.",

year = "2021",

month = jul,

day = "30",

doi = "10.1021/acs.chemmater.1c01669",

language = "English (US)",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

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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 -

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

Abstract

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