New Insights into Structural Evolution of LiNiO2 Revealed by Operando Neutron Diffraction

Po Hsiu Chien; Xianyang Wu; Bohang Song; Zhijie Yang; Crystal K. Waters; Michelle S. Everett; Feng Lin; Zhijia Du; Jue Liu

doi:10.1002/batt.202100135

New Insights into Structural Evolution of LiNiO₂ Revealed by Operando Neutron Diffraction

Po Hsiu Chien, Xianyang Wu, Bohang Song, Zhijie Yang, Crystal K. Waters, Michelle S. Everett, Feng Lin, Zhijia Du, Jue Liu

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

17 Scopus citations

Abstract

LiNiO₂ (LNO) represents the end member in the compositional space of the LiNi_1-x-yMn_xCo_yO₂ (as x and y approach zero) cathode system. Despite its high theoretical specific capacity (275 mAh/g), LNO suffers from phase transitions with large volume change and unfavorable reactions upon electrochemical cycling, which restricts its practical use in the application of lithium-ion batteries. While the contributing factor to the structural instability is commonly linked to the undesired volume collapse associated with the H2-H3 phase transition, detailed analysis of structural evolution following the entire route of phase transitions (H1-M-H2-H3) in real time under battery operating conditions remains a challenging task. In this work, we employ operando neutron diffraction to study the structural changes (crystal lattice, Li/Ni−O bond length, O−Ni−O bond angles, and LiO₂/NiO₂ layer thickness) of LNO cathode in a home-built Li_xNiO₂||graphite full cell during Li⁺ de-/intercalation. In particular, the anomalous increase(decrease) of Ni−O(Li−O) bond length at high SOC (>∼85 %) in the H3 phase is discussed in the context of O²⁻ (2p)→Ni⁴⁺(3d) negative charge transfer.

Original language	English
Pages (from-to)	1701-1707
Number of pages	7
Journal	Batteries and Supercaps
Volume	4
Issue number	11
DOIs	https://doi.org/10.1002/batt.202100135
State	Published - Nov 2021

Funding

Research conducted at the NOMAD beamlines at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U.S. Department of Energy. This research at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) under contract DE-AC05-00OR22725, was sponsored by the Office of Energy Efficiency and Renewable Energy (EERE) and Vehicle Technologies Office (VTO). The work at Virginia Tech is supported by the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (EERE) under the award number: DE-EE0008444 (Technology Manager: Peter Faguy).

Keywords

LiNiO
lithium-ion batteries
operando neutron diffraction
phase transition
structural evolution

UN SDGs

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

Access to Document

10.1002/batt.202100135

Cite this

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title = "New Insights into Structural Evolution of LiNiO2 Revealed by Operando Neutron Diffraction",

abstract = "LiNiO2 (LNO) represents the end member in the compositional space of the LiNi1-x-yMnxCoyO2 (as x and y approach zero) cathode system. Despite its high theoretical specific capacity (275 mAh/g), LNO suffers from phase transitions with large volume change and unfavorable reactions upon electrochemical cycling, which restricts its practical use in the application of lithium-ion batteries. While the contributing factor to the structural instability is commonly linked to the undesired volume collapse associated with the H2-H3 phase transition, detailed analysis of structural evolution following the entire route of phase transitions (H1-M-H2-H3) in real time under battery operating conditions remains a challenging task. In this work, we employ operando neutron diffraction to study the structural changes (crystal lattice, Li/Ni−O bond length, O−Ni−O bond angles, and LiO2/NiO2 layer thickness) of LNO cathode in a home-built LixNiO2||graphite full cell during Li+ de-/intercalation. In particular, the anomalous increase(decrease) of Ni−O(Li−O) bond length at high SOC (>∼85 %) in the H3 phase is discussed in the context of O2− (2p)→Ni4+(3d) negative charge transfer.",

keywords = "LiNiO, lithium-ion batteries, operando neutron diffraction, phase transition, structural evolution",

author = "Chien, {Po Hsiu} and Xianyang Wu and Bohang Song and Zhijie Yang and Waters, {Crystal K.} and Everett, {Michelle S.} and Feng Lin and Zhijia Du and Jue Liu",

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year = "2021",

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AU - Chien, Po Hsiu

AU - Wu, Xianyang

AU - Song, Bohang

AU - Yang, Zhijie

AU - Waters, Crystal K.

AU - Everett, Michelle S.

AU - Lin, Feng

AU - Du, Zhijia

AU - Liu, Jue

PY - 2021/11

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N2 - LiNiO2 (LNO) represents the end member in the compositional space of the LiNi1-x-yMnxCoyO2 (as x and y approach zero) cathode system. Despite its high theoretical specific capacity (275 mAh/g), LNO suffers from phase transitions with large volume change and unfavorable reactions upon electrochemical cycling, which restricts its practical use in the application of lithium-ion batteries. While the contributing factor to the structural instability is commonly linked to the undesired volume collapse associated with the H2-H3 phase transition, detailed analysis of structural evolution following the entire route of phase transitions (H1-M-H2-H3) in real time under battery operating conditions remains a challenging task. In this work, we employ operando neutron diffraction to study the structural changes (crystal lattice, Li/Ni−O bond length, O−Ni−O bond angles, and LiO2/NiO2 layer thickness) of LNO cathode in a home-built LixNiO2||graphite full cell during Li+ de-/intercalation. In particular, the anomalous increase(decrease) of Ni−O(Li−O) bond length at high SOC (>∼85 %) in the H3 phase is discussed in the context of O2− (2p)→Ni4+(3d) negative charge transfer.

AB - LiNiO2 (LNO) represents the end member in the compositional space of the LiNi1-x-yMnxCoyO2 (as x and y approach zero) cathode system. Despite its high theoretical specific capacity (275 mAh/g), LNO suffers from phase transitions with large volume change and unfavorable reactions upon electrochemical cycling, which restricts its practical use in the application of lithium-ion batteries. While the contributing factor to the structural instability is commonly linked to the undesired volume collapse associated with the H2-H3 phase transition, detailed analysis of structural evolution following the entire route of phase transitions (H1-M-H2-H3) in real time under battery operating conditions remains a challenging task. In this work, we employ operando neutron diffraction to study the structural changes (crystal lattice, Li/Ni−O bond length, O−Ni−O bond angles, and LiO2/NiO2 layer thickness) of LNO cathode in a home-built LixNiO2||graphite full cell during Li+ de-/intercalation. In particular, the anomalous increase(decrease) of Ni−O(Li−O) bond length at high SOC (>∼85 %) in the H3 phase is discussed in the context of O2− (2p)→Ni4+(3d) negative charge transfer.

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