Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

Krishna Prasad Koirala; Lin Jiang; Shripad Patil; Paolo Longo; Zhao Liu; Bert Freitag; Juri Barthel; Ethan C. Self; Yingge Du; Lee Pullan; Ted Tessner; Leslie J. Allen; Wu Xu; Wei Tong; Jagjit Nanda; Chongmin Wang

doi:10.1021/acsenergylett.3c02154

Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

Krishna Prasad Koirala, Lin Jiang, Shripad Patil, Paolo Longo, Zhao Liu, Bert Freitag, Juri Barthel, Ethan C. Self, Yingge Du, Lee Pullan, Ted Tessner, Leslie J. Allen, Wu Xu, Wei Tong, Jagjit Nanda, Chongmin Wang

Energy Storage & Conversion

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

3 Scopus citations

Abstract

Cation-disordered rocksalt (DRX) oxides are promising candidates as next-generation cathodes for lithium-ion batteries. Partial fluorination of the DRX oxides enhances their cyclability. However, the lattice position, concentration, and spatial distribution of fluorine within DRX lattices remain elusive. Here, we use atom location by channeling-enhanced microanalysis, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and integrated differential phase contrast imaging in a scanning transmission electron microscope to gain atomic-level insights into DRX with nominal composition of Li_1.2Mn_0.7Ti_0.1O_1.7F_0.3 and Li_1.15Ni_0.45Ti_0.3Mo_0.1O_1.85F_0.15. We reveal that fluorine substitutes oxygen in the DRX lattices. The O/F ratio in terms of O+F = 2 is in the range from 1.92:0.08 to 1.82:0.18. Spatially, fluorine is distributed in the proximity of the Li-rich regions but distinct from lithium fluoride. Additionally, we observe that incorporation of fluorine in the DRX lattice induces a larger variation in cation-anion separation. These observations provide insight into the guided design of oxyfluoride DRX cathodes for high-performance batteries.

Original language	English
Pages (from-to)	10-16
Number of pages	7
Journal	ACS Energy Letters
Volume	9
Issue number	1
DOIs	https://doi.org/10.1021/acsenergylett.3c02154
State	Published - Jan 12 2024

Funding

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO), of the U.S. Department of Energy (DOE) with Contract No. DE-LC-000L096 under the Cation-disordered Rocksalt (DRX) Cathode Materials (DRX+) consortium. Part of the work was conducted at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the Department of Energy under Contract DE-AC05-76RL01830. Work conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. DOE was sponsored by the VTO under the Office of EERE.

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title = "Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes",

abstract = "Cation-disordered rocksalt (DRX) oxides are promising candidates as next-generation cathodes for lithium-ion batteries. Partial fluorination of the DRX oxides enhances their cyclability. However, the lattice position, concentration, and spatial distribution of fluorine within DRX lattices remain elusive. Here, we use atom location by channeling-enhanced microanalysis, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and integrated differential phase contrast imaging in a scanning transmission electron microscope to gain atomic-level insights into DRX with nominal composition of Li1.2Mn0.7Ti0.1O1.7F0.3 and Li1.15Ni0.45Ti0.3Mo0.1O1.85F0.15. We reveal that fluorine substitutes oxygen in the DRX lattices. The O/F ratio in terms of O+F = 2 is in the range from 1.92:0.08 to 1.82:0.18. Spatially, fluorine is distributed in the proximity of the Li-rich regions but distinct from lithium fluoride. Additionally, we observe that incorporation of fluorine in the DRX lattice induces a larger variation in cation-anion separation. These observations provide insight into the guided design of oxyfluoride DRX cathodes for high-performance batteries.",

author = "Koirala, {Krishna Prasad} and Lin Jiang and Shripad Patil and Paolo Longo and Zhao Liu and Bert Freitag and Juri Barthel and Self, {Ethan C.} and Yingge Du and Lee Pullan and Ted Tessner and Allen, {Leslie J.} and Wu Xu and Wei Tong and Jagjit Nanda and Chongmin Wang",

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AU - Koirala, Krishna Prasad

AU - Jiang, Lin

AU - Patil, Shripad

AU - Longo, Paolo

AU - Liu, Zhao

AU - Freitag, Bert

AU - Barthel, Juri

AU - Self, Ethan C.

AU - Du, Yingge

AU - Pullan, Lee

AU - Tessner, Ted

AU - Allen, Leslie J.

AU - Xu, Wu

AU - Tong, Wei

AU - Nanda, Jagjit

AU - Wang, Chongmin

PY - 2024/1/12

Y1 - 2024/1/12

N2 - Cation-disordered rocksalt (DRX) oxides are promising candidates as next-generation cathodes for lithium-ion batteries. Partial fluorination of the DRX oxides enhances their cyclability. However, the lattice position, concentration, and spatial distribution of fluorine within DRX lattices remain elusive. Here, we use atom location by channeling-enhanced microanalysis, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and integrated differential phase contrast imaging in a scanning transmission electron microscope to gain atomic-level insights into DRX with nominal composition of Li1.2Mn0.7Ti0.1O1.7F0.3 and Li1.15Ni0.45Ti0.3Mo0.1O1.85F0.15. We reveal that fluorine substitutes oxygen in the DRX lattices. The O/F ratio in terms of O+F = 2 is in the range from 1.92:0.08 to 1.82:0.18. Spatially, fluorine is distributed in the proximity of the Li-rich regions but distinct from lithium fluoride. Additionally, we observe that incorporation of fluorine in the DRX lattice induces a larger variation in cation-anion separation. These observations provide insight into the guided design of oxyfluoride DRX cathodes for high-performance batteries.

AB - Cation-disordered rocksalt (DRX) oxides are promising candidates as next-generation cathodes for lithium-ion batteries. Partial fluorination of the DRX oxides enhances their cyclability. However, the lattice position, concentration, and spatial distribution of fluorine within DRX lattices remain elusive. Here, we use atom location by channeling-enhanced microanalysis, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and integrated differential phase contrast imaging in a scanning transmission electron microscope to gain atomic-level insights into DRX with nominal composition of Li1.2Mn0.7Ti0.1O1.7F0.3 and Li1.15Ni0.45Ti0.3Mo0.1O1.85F0.15. We reveal that fluorine substitutes oxygen in the DRX lattices. The O/F ratio in terms of O+F = 2 is in the range from 1.92:0.08 to 1.82:0.18. Spatially, fluorine is distributed in the proximity of the Li-rich regions but distinct from lithium fluoride. Additionally, we observe that incorporation of fluorine in the DRX lattice induces a larger variation in cation-anion separation. These observations provide insight into the guided design of oxyfluoride DRX cathodes for high-performance batteries.

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Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

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