Cross-length-scale investigation reveals the spatial thermo-chemical dynamics hidden in Ni-rich layered Li-ion cathodes

Dong Hou; Jue Liu; Zhengrui Xu; Zhijie Yang; Xianghui Xiao; Feng Lin

doi:10.1016/j.matt.2023.11.025

Cross-length-scale investigation reveals the spatial thermo-chemical dynamics hidden in Ni-rich layered Li-ion cathodes

Dong Hou, Jue Liu, Zhengrui Xu, Zhijie Yang, Xianghui Xiao, Feng Lin

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Abstract

A long pursuit in developing high-energy batteries is the prognosis and improvement of thermal stability. Here, we report new understandings of the thermo-chemical transformation mechanism of delithiated Ni-rich cathodes at different spatial length scales. Using in situ neutron scattering and pair distribution function analyses, we identify that thermal degradation can be recognized as a topotactic transformation of the oxygen octahedral at angstrom scale. We highlight the importance of building a robust oxygen framework at short range to achieve higher thermal stability. Our in situ spectroscopic nano-tomography resolves the dynamic thermo-chemical interactions inside delithiated particles, illustrating the correlation between thermal performance and spatial distribution of various thermo-chemical interactions. Statistical analyses of thermally active and sluggish regions in cathode particles show that these minority regions (<2% volume fraction) govern thermal stability. We propose effective strategies to manipulate thermo-chemical interaction dynamics and to minimize the propagation of thermally active regions by “flattening the curve.”

Original language	English
Pages (from-to)	640-654
Number of pages	15
Journal	Matter
Volume	7
Issue number	2
DOIs	https://doi.org/10.1016/j.matt.2023.11.025
State	Published - Feb 7 2024

Funding

The work was supported by the National Science Foundation (NSF) under grant no. DMR-1832613 (F.L.). This research used beamline 18-ID of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used resources of the APS, a US DOE Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC0206CH11357. The authors appreciate engineering support from Kevin Beyer and Olaf Borkiewicz at APS beamline 11-ID-C. This work used shared facilities at the Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), a member of the National Nanotechnology Coordinated Infrastructure (NNCI), supported by NSF (ECCS 1542100 and ECCS 2025151). Supervision, F.L.; conceptualization, D.H. and F.L.; methodology, D.H. J.L. X.X. and F.L.; software, D.H. and X.X.; validation, D.H. Z.X. and Z.Y.; formal analysis, D.H. and F.L.; investigation, D.H. J.L. X.X. Z.X. Z.Y. and F.L.; resources, J.L. X.X. and F.L.; data curation, D.H.; writing – original draft, D.H. and F.L.; writing – review & editing, J.L. X.X. Z.X. and Z.Y.; visualization, D.H.; funding acquisition, F.L.; project administration, F.L. The authors declare no competing interests. The work was supported by the National Science Foundation ( NSF ) under grant no. DMR-1832613 (F.L.). This research used beamline 18-ID of the National Synchrotron Light Source II , a US Department of Energy ( DOE ) Office of Science User Facility , operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704 . A portion of this research used resources at the Spallation Neutron Source , a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory . This research used resources of the APS , a US DOE Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC0206CH11357 . The authors appreciate engineering support from Kevin Beyer and Olaf Borkiewicz at APS beamline 11-ID-C. This work used shared facilities at the Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), a member of the National Nanotechnology Coordinated Infrastructure ( NNCI ), supported by NSF ( ECCS 1542100 and ECCS 2025151 ).

Funders	Funder number
National Science Foundation	DMR-1832613
U.S. Department of Energy
Office of Science
Argonne National Laboratory	DE-AC0206CH11357, ECCS 1542100, ECCS 2025151
Oak Ridge National Laboratory
Brookhaven National Laboratory	DE-SC0012704
American Pain Society

Keywords

MAP 3: Understanding
Ni-rich cathode
in situ tomography
in situ total scattering
neutron diffraction
reaction heterogeneity
rechargeable batteries
thermal degradation

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10.1016/j.matt.2023.11.025

Cite this

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title = "Cross-length-scale investigation reveals the spatial thermo-chemical dynamics hidden in Ni-rich layered Li-ion cathodes",

abstract = "A long pursuit in developing high-energy batteries is the prognosis and improvement of thermal stability. Here, we report new understandings of the thermo-chemical transformation mechanism of delithiated Ni-rich cathodes at different spatial length scales. Using in situ neutron scattering and pair distribution function analyses, we identify that thermal degradation can be recognized as a topotactic transformation of the oxygen octahedral at angstrom scale. We highlight the importance of building a robust oxygen framework at short range to achieve higher thermal stability. Our in situ spectroscopic nano-tomography resolves the dynamic thermo-chemical interactions inside delithiated particles, illustrating the correlation between thermal performance and spatial distribution of various thermo-chemical interactions. Statistical analyses of thermally active and sluggish regions in cathode particles show that these minority regions (<2% volume fraction) govern thermal stability. We propose effective strategies to manipulate thermo-chemical interaction dynamics and to minimize the propagation of thermally active regions by “flattening the curve.”",

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AU - Hou, Dong

AU - Liu, Jue

AU - Xu, Zhengrui

AU - Yang, Zhijie

AU - Xiao, Xianghui

AU - Lin, Feng

PY - 2024/2/7

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N2 - A long pursuit in developing high-energy batteries is the prognosis and improvement of thermal stability. Here, we report new understandings of the thermo-chemical transformation mechanism of delithiated Ni-rich cathodes at different spatial length scales. Using in situ neutron scattering and pair distribution function analyses, we identify that thermal degradation can be recognized as a topotactic transformation of the oxygen octahedral at angstrom scale. We highlight the importance of building a robust oxygen framework at short range to achieve higher thermal stability. Our in situ spectroscopic nano-tomography resolves the dynamic thermo-chemical interactions inside delithiated particles, illustrating the correlation between thermal performance and spatial distribution of various thermo-chemical interactions. Statistical analyses of thermally active and sluggish regions in cathode particles show that these minority regions (<2% volume fraction) govern thermal stability. We propose effective strategies to manipulate thermo-chemical interaction dynamics and to minimize the propagation of thermally active regions by “flattening the curve.”

AB - A long pursuit in developing high-energy batteries is the prognosis and improvement of thermal stability. Here, we report new understandings of the thermo-chemical transformation mechanism of delithiated Ni-rich cathodes at different spatial length scales. Using in situ neutron scattering and pair distribution function analyses, we identify that thermal degradation can be recognized as a topotactic transformation of the oxygen octahedral at angstrom scale. We highlight the importance of building a robust oxygen framework at short range to achieve higher thermal stability. Our in situ spectroscopic nano-tomography resolves the dynamic thermo-chemical interactions inside delithiated particles, illustrating the correlation between thermal performance and spatial distribution of various thermo-chemical interactions. Statistical analyses of thermally active and sluggish regions in cathode particles show that these minority regions (<2% volume fraction) govern thermal stability. We propose effective strategies to manipulate thermo-chemical interaction dynamics and to minimize the propagation of thermally active regions by “flattening the curve.”

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Cross-length-scale investigation reveals the spatial thermo-chemical dynamics hidden in Ni-rich layered Li-ion cathodes

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Keywords

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