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Title: Probing Dopant Redistribution, Phase Propagation, and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes

Abstract

Achieving the targeted control of layered oxide properties calls for more fundamental studies to mechanistically probe their evolution during their synthesis. Herein, dopant distribution, phase propagation, and local chemical changes as well as their interplay in multielement-doped LiNiO2 materials are investigated using spectroscopic, imaging, and scattering techniques. It is shown that dopants undergo dynamic redistribution in the Ni(OH)2 host lattice at the early stage of calcination (below 300 °C). Such redistribution behavior exhibits strong dopant-dependent characteristics, allowing for targeted surface and bulk doping control. The Ni oxidation process exhibits depth-dependent characteristics and the most rapid Ni oxidation takes place between 300 and 700 °C. Using Ni oxidation state as the proxy for the phase transformation, the buildup of heterogenous phase propagation in the early stage of calcination is shown, especially along the radial direction of secondary particles. Furthermore, the radial heterogenous phase distribution gradually decreases upon completing the calcination. However, a high degree of mosaic-like heterogeneity may still be present in the final product, departing from the perfect layered oxide. Overall, the present study offers fundamental insights into manipulating multiscale materials properties during calcination for obtaining stable, high-energy layered oxide cathodes.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4];  [5];  [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1737417
Alternate Identifier(s):
OSTI ID: 1779452; OSTI ID: 1785564
Report Number(s):
BNL-220701-2020-JAAM
Journal ID: ISSN 1614-6832
Grant/Contract Number:  
SC0012704; EE0008444; AC02-76SF00515; AC02-06CH11357; AC05-00OR22725; CHE-1531834; CHE‐1531834
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; calcination; Co free; dopant distribution; layered oxides; Li-ion batteries

Citation Formats

Yang, Zhijie, Mu, Linqin, Hou, Dong, Rahman, Muhammad Mominur, Xu, Zhengrui, Liu, Jue, Nordlund, Dennis, Sun, Cheng‐Jun, Xiao, Xianghui, and Lin, Feng. Probing Dopant Redistribution, Phase Propagation, and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes. United States: N. p., 2020. Web. https://doi.org/10.1002/aenm.202002719.
Yang, Zhijie, Mu, Linqin, Hou, Dong, Rahman, Muhammad Mominur, Xu, Zhengrui, Liu, Jue, Nordlund, Dennis, Sun, Cheng‐Jun, Xiao, Xianghui, & Lin, Feng. Probing Dopant Redistribution, Phase Propagation, and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes. United States. https://doi.org/10.1002/aenm.202002719
Yang, Zhijie, Mu, Linqin, Hou, Dong, Rahman, Muhammad Mominur, Xu, Zhengrui, Liu, Jue, Nordlund, Dennis, Sun, Cheng‐Jun, Xiao, Xianghui, and Lin, Feng. Fri . "Probing Dopant Redistribution, Phase Propagation, and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes". United States. https://doi.org/10.1002/aenm.202002719. https://www.osti.gov/servlets/purl/1737417.
@article{osti_1737417,
title = {Probing Dopant Redistribution, Phase Propagation, and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes},
author = {Yang, Zhijie and Mu, Linqin and Hou, Dong and Rahman, Muhammad Mominur and Xu, Zhengrui and Liu, Jue and Nordlund, Dennis and Sun, Cheng‐Jun and Xiao, Xianghui and Lin, Feng},
abstractNote = {Achieving the targeted control of layered oxide properties calls for more fundamental studies to mechanistically probe their evolution during their synthesis. Herein, dopant distribution, phase propagation, and local chemical changes as well as their interplay in multielement-doped LiNiO2 materials are investigated using spectroscopic, imaging, and scattering techniques. It is shown that dopants undergo dynamic redistribution in the Ni(OH)2 host lattice at the early stage of calcination (below 300 °C). Such redistribution behavior exhibits strong dopant-dependent characteristics, allowing for targeted surface and bulk doping control. The Ni oxidation process exhibits depth-dependent characteristics and the most rapid Ni oxidation takes place between 300 and 700 °C. Using Ni oxidation state as the proxy for the phase transformation, the buildup of heterogenous phase propagation in the early stage of calcination is shown, especially along the radial direction of secondary particles. Furthermore, the radial heterogenous phase distribution gradually decreases upon completing the calcination. However, a high degree of mosaic-like heterogeneity may still be present in the final product, departing from the perfect layered oxide. Overall, the present study offers fundamental insights into manipulating multiscale materials properties during calcination for obtaining stable, high-energy layered oxide cathodes.},
doi = {10.1002/aenm.202002719},
journal = {Advanced Energy Materials},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {11}
}

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