Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi0.5Mn1.5O4 Spinel Cathodes for Lithium-Ion Batteries

Gemeng Liang; Vanessa K. Peterson; Zhibin Wu; Shilin Zhang; Junnan Hao; Cheng Zhang Lu; Cheng Hao Chuang; Jyh Fu Lee; Jue Liu; Grzegorz Leniec; Sławomir Maksymilian Kaczmarek; Anita M. D'Angelo; Bernt Johannessen; Lars Thomsen; Wei Kong Pang; Zaiping Guo

doi:10.1002/adma.202101413

Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathodes for Lithium-Ion Batteries

Gemeng Liang, Vanessa K. Peterson, Zhibin Wu, Shilin Zhang, Junnan Hao, Cheng Zhang Lu, Cheng Hao Chuang, Jyh Fu Lee, Jue Liu, Grzegorz Leniec, Sławomir Maksymilian Kaczmarek, Anita M. D'Angelo, Bernt Johannessen, Lars Thomsen, Wei Kong Pang, Zaiping Guo

Powder Diffraction

Research output: Contribution to journal › Article › peer-review

68 Scopus citations

Abstract

The development of reliable and safe high-energy-density lithium-ion batteries is hindered by the structural instability of cathode materials during cycling, arising as a result of detrimental phase transformations occurring at high operating voltages alongside the loss of active materials induced by transition metal dissolution. Originating from the fundamental structure/function relation of battery materials, the authors purposefully perform crystallographic-site-specific structural engineering on electrode material structure, using the high-voltage LiNi_0.5Mn_1.5O₄ (LNMO) cathode as a representative, which directly addresses the root source of structural instability of the Fd (Formula presented.) m structure. By employing Sb as a dopant to modify the specific issue-involved 16c and 16d sites simultaneously, the authors successfully transform the detrimental two-phase reaction occurring at high-voltage into a preferential solid-solution reaction and significantly suppress the loss of Mn from the LNMO structure. The modified LNMO material delivers an impressive 99% of its theoretical specific capacity at 1 C, and maintains 87.6% and 72.4% of initial capacity after 1500 and 3000 cycles, respectively. The issue-tracing site-specific structural tailoring demonstrated for this material will facilitate the rapid development of high-energy-density materials for lithium-ion batteries.

Original language	English
Article number	2101413
Journal	Advanced Materials
Volume	33
Issue number	44
DOIs	https://doi.org/10.1002/adma.202101413
State	Published - Nov 2 2021

Funding

The authors acknowledge support from the Australian Research Council for FT160100251, DP200101862, and DP210101486. The authors thank the Australian Institute of Nuclear Science and Engineering (AINSE) Limited for providing financial assistance in the form of a Post Graduate Research Award (PGRA) to carry out this work. This work was performed in part on the Powder Diffraction Beamline, the wiggler XAS Beamline (12ID), and the Soft X‐ray Beamline at the Australian Synchrotron. The authors appreciate the operational support of ANSTO staff for in operando sXRPD and NPD experiments. The neutron PDF studies (at NOMAD) used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by ORNL. The authors acknowledge the Electron Microscopy Centre (EMC) at the University of Wollongong for their support and equipment assistance. The authors acknowledge support from the Australian Research Council for FT160100251, DP200101862, and DP210101486. The authors thank the Australian Institute of Nuclear Science and Engineering (AINSE) Limited for providing financial assistance in the form of a Post Graduate Research Award (PGRA) to carry out this work. This work was performed in part on the Powder Diffraction Beamline, the wiggler XAS Beamline (12ID), and the Soft X-ray Beamline at the Australian Synchrotron. The authors appreciate the operational support of ANSTO staff for in operando sXRPD and NPD experiments. The neutron PDF studies (at NOMAD) used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by ORNL. The authors acknowledge the Electron Microscopy Centre (EMC) at the University of Wollongong for their support and equipment assistance.

Keywords

crystallographic-site-specific
high-voltage spinel cathodes
lithium-ion batteries
structural engineering
structure/function relation of materials

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/adma.202101413

Cite this

Liang, G., Peterson, V. K., Wu, Z., Zhang, S., Hao, J., Lu, C. Z., Chuang, C. H., Lee, J. F., Liu, J., Leniec, G., Kaczmarek, S. M., D'Angelo, A. M., Johannessen, B., Thomsen, L., Pang, W. K., & Guo, Z. (2021). Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathodes for Lithium-Ion Batteries. Advanced Materials, 33(44), Article 2101413. https://doi.org/10.1002/adma.202101413

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title = "Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi0.5Mn1.5O4 Spinel Cathodes for Lithium-Ion Batteries",

abstract = "The development of reliable and safe high-energy-density lithium-ion batteries is hindered by the structural instability of cathode materials during cycling, arising as a result of detrimental phase transformations occurring at high operating voltages alongside the loss of active materials induced by transition metal dissolution. Originating from the fundamental structure/function relation of battery materials, the authors purposefully perform crystallographic-site-specific structural engineering on electrode material structure, using the high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode as a representative, which directly addresses the root source of structural instability of the Fd (Formula presented.) m structure. By employing Sb as a dopant to modify the specific issue-involved 16c and 16d sites simultaneously, the authors successfully transform the detrimental two-phase reaction occurring at high-voltage into a preferential solid-solution reaction and significantly suppress the loss of Mn from the LNMO structure. The modified LNMO material delivers an impressive 99% of its theoretical specific capacity at 1 C, and maintains 87.6% and 72.4% of initial capacity after 1500 and 3000 cycles, respectively. The issue-tracing site-specific structural tailoring demonstrated for this material will facilitate the rapid development of high-energy-density materials for lithium-ion batteries.",

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author = "Gemeng Liang and Peterson, {Vanessa K.} and Zhibin Wu and Shilin Zhang and Junnan Hao and Lu, {Cheng Zhang} and Chuang, {Cheng Hao} and Lee, {Jyh Fu} and Jue Liu and Grzegorz Leniec and Kaczmarek, {S{\l}awomir Maksymilian} and D'Angelo, {Anita M.} and Bernt Johannessen and Lars Thomsen and Pang, {Wei Kong} and Zaiping Guo",

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Liang, G, Peterson, VK, Wu, Z, Zhang, S, Hao, J, Lu, CZ, Chuang, CH, Lee, JF, Liu, J, Leniec, G, Kaczmarek, SM, D'Angelo, AM, Johannessen, B, Thomsen, L, Pang, WK & Guo, Z 2021, 'Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathodes for Lithium-Ion Batteries', Advanced Materials, vol. 33, no. 44, 2101413. https://doi.org/10.1002/adma.202101413

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AU - Liang, Gemeng

AU - Peterson, Vanessa K.

AU - Wu, Zhibin

AU - Zhang, Shilin

AU - Hao, Junnan

AU - Lu, Cheng Zhang

AU - Chuang, Cheng Hao

AU - Lee, Jyh Fu

AU - Liu, Jue

AU - Leniec, Grzegorz

AU - Kaczmarek, Sławomir Maksymilian

AU - D'Angelo, Anita M.

AU - Johannessen, Bernt

AU - Thomsen, Lars

AU - Pang, Wei Kong

AU - Guo, Zaiping

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KW - structural engineering

KW - structure/function relation of materials

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