Asymmetric Lithium Extraction and Insertion in High Voltage Spinel at Fast Rate

Muhammad Mominur Rahman; Kangxuan Xia; Xiao Qing Yang; Kingo Ariyoshi; Enyuan Hu

doi:10.1021/acs.nanolett.3c02042

Asymmetric Lithium Extraction and Insertion in High Voltage Spinel at Fast Rate

Muhammad Mominur Rahman, Kangxuan Xia, Xiao Qing Yang, Kingo Ariyoshi, Enyuan Hu

Emerging and Solid-State Batteries

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

5 Scopus citations

Abstract

Spinel-structured ordered-LiNi_0.5Mn_1.5O₄ (o-LNMO) has experienced a resurgence of interest in the context of reducing scarce elements such as cobalt from the lithium-ion batteries. O-LNMO undergoes two two-phase reactions at slow rates. However, it is not known if such phenomenon also applies at fast rates. Herein, we investigate the rate-dependent phase transition behavior of o-LNMO through in operando time-resolved X-ray diffraction. The results indicate that a narrow region of the solid solution reaction exists for charge and discharge at both slow and fast rates. The overall phase transition is highly asymmetric at fast rates. During fast charge, it is a particle-by-particle mechanism resulting from an asynchronized reaction among the particles. During fast discharge, it is likely a core-shell mechanism involving transition from Li_0+xNi_0.5Mn_1.5O₄ to Li_1+xNi_0.5Mn_1.5O₄ in the outer layer of particles. The Li_0.5Ni_0.5Mn_1.5O₄ phase is suppressed during fast discharge and appears only through Li redistribution upon relaxation.

Original language	English
Pages (from-to)	7135-7142
Number of pages	8
Journal	Nano Letters
Volume	23
Issue number	15
DOIs	https://doi.org/10.1021/acs.nanolett.3c02042
State	Published - Aug 9 2023

Funding

The work at BNL is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy (EERE), Vehicle Technology Office (VTO) of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program under contract no. DE-SC0012704. This research used beamline X14A of the National Synchrotron Light Source, a U.S. DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704.

Keywords

fast charge
high voltage cathode
in situ XRD
ordered-LiNiMnO
phase transition

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10.1021/acs.nanolett.3c02042

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title = "Asymmetric Lithium Extraction and Insertion in High Voltage Spinel at Fast Rate",

abstract = "Spinel-structured ordered-LiNi0.5Mn1.5O4 (o-LNMO) has experienced a resurgence of interest in the context of reducing scarce elements such as cobalt from the lithium-ion batteries. O-LNMO undergoes two two-phase reactions at slow rates. However, it is not known if such phenomenon also applies at fast rates. Herein, we investigate the rate-dependent phase transition behavior of o-LNMO through in operando time-resolved X-ray diffraction. The results indicate that a narrow region of the solid solution reaction exists for charge and discharge at both slow and fast rates. The overall phase transition is highly asymmetric at fast rates. During fast charge, it is a particle-by-particle mechanism resulting from an asynchronized reaction among the particles. During fast discharge, it is likely a core-shell mechanism involving transition from Li0+xNi0.5Mn1.5O4 to Li1+xNi0.5Mn1.5O4 in the outer layer of particles. The Li0.5Ni0.5Mn1.5O4 phase is suppressed during fast discharge and appears only through Li redistribution upon relaxation.",

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author = "Rahman, \{Muhammad Mominur\} and Kangxuan Xia and Yang, \{Xiao Qing\} and Kingo Ariyoshi and Enyuan Hu",

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year = "2023",

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doi = "10.1021/acs.nanolett.3c02042",

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AU - Rahman, Muhammad Mominur

AU - Xia, Kangxuan

AU - Yang, Xiao Qing

AU - Ariyoshi, Kingo

AU - Hu, Enyuan

PY - 2023/8/9

Y1 - 2023/8/9

N2 - Spinel-structured ordered-LiNi0.5Mn1.5O4 (o-LNMO) has experienced a resurgence of interest in the context of reducing scarce elements such as cobalt from the lithium-ion batteries. O-LNMO undergoes two two-phase reactions at slow rates. However, it is not known if such phenomenon also applies at fast rates. Herein, we investigate the rate-dependent phase transition behavior of o-LNMO through in operando time-resolved X-ray diffraction. The results indicate that a narrow region of the solid solution reaction exists for charge and discharge at both slow and fast rates. The overall phase transition is highly asymmetric at fast rates. During fast charge, it is a particle-by-particle mechanism resulting from an asynchronized reaction among the particles. During fast discharge, it is likely a core-shell mechanism involving transition from Li0+xNi0.5Mn1.5O4 to Li1+xNi0.5Mn1.5O4 in the outer layer of particles. The Li0.5Ni0.5Mn1.5O4 phase is suppressed during fast discharge and appears only through Li redistribution upon relaxation.

AB - Spinel-structured ordered-LiNi0.5Mn1.5O4 (o-LNMO) has experienced a resurgence of interest in the context of reducing scarce elements such as cobalt from the lithium-ion batteries. O-LNMO undergoes two two-phase reactions at slow rates. However, it is not known if such phenomenon also applies at fast rates. Herein, we investigate the rate-dependent phase transition behavior of o-LNMO through in operando time-resolved X-ray diffraction. The results indicate that a narrow region of the solid solution reaction exists for charge and discharge at both slow and fast rates. The overall phase transition is highly asymmetric at fast rates. During fast charge, it is a particle-by-particle mechanism resulting from an asynchronized reaction among the particles. During fast discharge, it is likely a core-shell mechanism involving transition from Li0+xNi0.5Mn1.5O4 to Li1+xNi0.5Mn1.5O4 in the outer layer of particles. The Li0.5Ni0.5Mn1.5O4 phase is suppressed during fast discharge and appears only through Li redistribution upon relaxation.

KW - fast charge

KW - high voltage cathode

KW - in situ XRD

KW - ordered-LiNiMnO

KW - phase transition

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DO - 10.1021/acs.nanolett.3c02042

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JO - Nano Letters

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ER -

Asymmetric Lithium Extraction and Insertion in High Voltage Spinel at Fast Rate

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