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Title: Extending the limits of powder diffraction analysis: Diffraction parameter space, occupancy defects, and atomic form factors

Abstract

Although the determination of site occupancies is often a major goal in Rietveld refinement studies, the accurate refinement of site occupancies is exceptionally challenging due to the many correlations and systematic errors that have a hidden impact on the final refined occupancy parameters. Through the comparison of results independently obtained from neutron and synchrotron powder diffraction, improved approaches capable of detecting occupancy defects with an exceptional sensitivity of 0.1% (absolute) in the class of layered NMC Li-ion battery cathode materials have been developed. A new method of visualizing the diffraction parameter space associated with crystallographic site scattering power through the use of f* diagrams is described and this method is broadly applicable to ternary compounds. The f* diagrams allow the global minimum fit to be easily identified and also permit a robust determination of the number and type of occupancy defects within a structure. Through a comparison of neutron and X-ray diffraction results, a systematic error in the synchrotron results was identified using f* diagrams for a series of NMC compounds. Using neutron diffraction data as a reference, this error was shown to specifically result from problems associated with the neutral oxygen X-ray atomic form factor and could be eliminatedmore » by using the ionic O2- form factor for this anion while retaining the neutral form factors for cationic species. The f* diagram method offers a new opportunity to experimentally assess the quality of atomic form factors through powder diffraction studies on chemically related multi-component compounds.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [2];  [3];  [4];  [5];  [5];  [5];  [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [1]
+ Show Author Affiliations
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Binghamton Univ., NY (United States)
  4. Univ. of California, San Diego, CA (United States)
  5. Univ. of Texas, Austin, TX (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1492520
Alternate Identifier(s):
OSTI ID: 1469791; OSTI ID: 1474182; OSTI ID: 1477122
Report Number(s):
PNNL-SA-138200; BNL-209024-2018-JAAM
Journal ID: ISSN 0034-6748
Grant/Contract Number:  
AC05-76RL01830; SC0012704; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Review of Scientific Instruments
Additional Journal Information:
Journal Volume: 89; Journal Issue: 9; Journal ID: ISSN 0034-6748
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Diffraction; occupancy defects; atomic form factors

Citation Formats

Yin, Liang, Mattei, Gerard S., Li, Zhou, Zheng, Jianming, Zhao, Wengao, Omenya, Fredrick, Fang, Chengcheng, Li, Wangda, Li, Jianyu, Xie, Qiang, Zhang, Ji-Guang, Whittingham, M. Stanley, Meng, Ying Shirley, Manthiram, Arumugam, and Khalifah, Peter G. Extending the limits of powder diffraction analysis: Diffraction parameter space, occupancy defects, and atomic form factors. United States: N. p., 2018. Web. doi:10.1063/1.5044555.
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Yin, Liang, Mattei, Gerard S., Li, Zhou, Zheng, Jianming, Zhao, Wengao, Omenya, Fredrick, Fang, Chengcheng, Li, Wangda, Li, Jianyu, Xie, Qiang, Zhang, Ji-Guang, Whittingham, M. Stanley, Meng, Ying Shirley, Manthiram, Arumugam, & Khalifah, Peter G. Extending the limits of powder diffraction analysis: Diffraction parameter space, occupancy defects, and atomic form factors. United States. https://doi.org/10.1063/1.5044555
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Yin, Liang, Mattei, Gerard S., Li, Zhou, Zheng, Jianming, Zhao, Wengao, Omenya, Fredrick, Fang, Chengcheng, Li, Wangda, Li, Jianyu, Xie, Qiang, Zhang, Ji-Guang, Whittingham, M. Stanley, Meng, Ying Shirley, Manthiram, Arumugam, and Khalifah, Peter G. Wed . "Extending the limits of powder diffraction analysis: Diffraction parameter space, occupancy defects, and atomic form factors". United States. https://doi.org/10.1063/1.5044555. https://www.osti.gov/servlets/purl/1492520.
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@article{osti_1492520,
title = {Extending the limits of powder diffraction analysis: Diffraction parameter space, occupancy defects, and atomic form factors},
author = {Yin, Liang and Mattei, Gerard S. and Li, Zhou and Zheng, Jianming and Zhao, Wengao and Omenya, Fredrick and Fang, Chengcheng and Li, Wangda and Li, Jianyu and Xie, Qiang and Zhang, Ji-Guang and Whittingham, M. Stanley and Meng, Ying Shirley and Manthiram, Arumugam and Khalifah, Peter G.},
abstractNote = {Although the determination of site occupancies is often a major goal in Rietveld refinement studies, the accurate refinement of site occupancies is exceptionally challenging due to the many correlations and systematic errors that have a hidden impact on the final refined occupancy parameters. Through the comparison of results independently obtained from neutron and synchrotron powder diffraction, improved approaches capable of detecting occupancy defects with an exceptional sensitivity of 0.1% (absolute) in the class of layered NMC Li-ion battery cathode materials have been developed. A new method of visualizing the diffraction parameter space associated with crystallographic site scattering power through the use of f* diagrams is described and this method is broadly applicable to ternary compounds. The f* diagrams allow the global minimum fit to be easily identified and also permit a robust determination of the number and type of occupancy defects within a structure. Through a comparison of neutron and X-ray diffraction results, a systematic error in the synchrotron results was identified using f* diagrams for a series of NMC compounds. Using neutron diffraction data as a reference, this error was shown to specifically result from problems associated with the neutral oxygen X-ray atomic form factor and could be eliminated by using the ionic O2- form factor for this anion while retaining the neutral form factors for cationic species. The f* diagram method offers a new opportunity to experimentally assess the quality of atomic form factors through powder diffraction studies on chemically related multi-component compounds.},
doi = {10.1063/1.5044555},
journal = {Review of Scientific Instruments},
number = 9,
volume = 89,
place = {United States},
year = {Wed Sep 26 00:00:00 EDT 2018},
month = {Wed Sep 26 00:00:00 EDT 2018}
}
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https://doi.org/10.1063/1.5044555
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Works referenced in this record:

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

  • Sathiya, M.; Rousse, G.; Ramesha, K.
  • Nature Materials, Vol. 12, Issue 9
  • DOI: 10.1038/nmat3699

Absolute Measurement of the Atomic Scattering Factors of Aluminum on Powder in Transmission
journal, February 1969

Absolute Measurement of X-Ray Scattering Factors of Copper
journal, December 1966

  • Hosoya, Sukeaki; Yamagishi, Tomoe
  • Journal of the Physical Society of Japan, Vol. 21, Issue 12
  • DOI: 10.1143/jpsj.21.2638

Lithium Batteries and Cathode Materials
journal, October 2004

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
  • DOI: 10.1021/cr020731c

Neutron scattering lengths and cross sections
journal, January 1992

Absolute X-Ray Measurement of the Atomic Scattering Factor of Nickel
journal, November 1969

Absolute Measurement of the Atomic Scattering Factors of Iron, Copper, and Aluminum
journal, April 1961

  • Batterman, Boris W.; Chipman, David R.; DeMarco, John J.
  • Physical Review, Vol. 122, Issue 1
  • DOI: 10.1103/physrev.122.68

Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries
journal, January 2001

  • Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 12
  • DOI: 10.1149/1.1413182

Sensitivity and Limitations of Structures from X-ray and Neutron-Based Diffraction Analyses of Transition Metal Oxide Lithium-Battery Electrodes
journal, January 2017

  • Liu, Hao; Liu, Haodong; Lapidus, Saul H.
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.0271709jes

Comparative study of LiCoO2, LiNi12Co12O2 and LiNiO2 for 4 volt secondary lithium cells
journal, June 1993

T2 and O2 Li[sub 2/3][Co[sub x]Ni[sub 1/3−x/2]Mn[sub 2/3−x/2]]O[sub 2] Electrode Materials
journal, January 2002

  • Lu, Zhonghua; Donaberger, R. A.; Thomas, C. L.
  • Journal of The Electrochemical Society, Vol. 149, Issue 8
  • DOI: 10.1149/1.1491236

The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • DOI: 10.1016/j.nimb.2012.05.037

Reversible Oxygen Participation to the Redox Processes Revealed for Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2
journal, January 2013

  • Koga, Hideyuki; Croguennec, Laurence; Ménétrier, Michel
  • Journal of The Electrochemical Society, Vol. 160, Issue 6
  • DOI: 10.1149/2.038306jes

Absolute X-Ray Measurement of the Atomic Scattering Factor of Chromium
journal, May 1972

Lithium Batteries and Cathode Materials
journal, December 2004

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    Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics
    journal, January 2019

    • Friedrich, Franziska; Strehle, Benjamin; Freiberg, Anna T. S.
    • Journal of The Electrochemical Society, Vol. 166, Issue 15
    • DOI: 10.1149/2.0821915jes
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