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

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 O 2- 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:
 [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [4] ;  [5] ;  [5] ;  [5] ;  [2] ;  [3] ;  [4] ;  [5] ; ORCiD logo [1]
  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:
Report Number(s):
BNL-209024-2018-JAAM
Journal ID: ISSN 0034-6748
Grant/Contract Number:
SC0012704; AC02-05CH11231
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)
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Diffraction; occupancy defects; atomic form factors
OSTI Identifier:
1469791
Alternate Identifier(s):
OSTI ID: 1474182

Yin, Liang, Mattei, Gerard S., Li, Zhou, Zheng, Jianming, Zhao, Wngao, Omenya, Fredrick, Fang, Chengcheng, Li, Wangda, Li, Jianyu, Xie, Qiang, Zhang, Ji-Guang, Whittingham, M. Stanley, Meng, Ying Shirley, Manthiram, Arumugam, and Khalifah, Peter. Extending the limits of powder diffraction analysis: diffraction parameter space, occupancy defects, and atomic form factors. United States: N. p., Web. doi:10.1063/1.5044555.
Yin, Liang, Mattei, Gerard S., Li, Zhou, Zheng, Jianming, Zhao, Wngao, Omenya, Fredrick, Fang, Chengcheng, Li, Wangda, Li, Jianyu, Xie, Qiang, Zhang, Ji-Guang, Whittingham, M. Stanley, Meng, Ying Shirley, Manthiram, Arumugam, & Khalifah, Peter. Extending the limits of powder diffraction analysis: diffraction parameter space, occupancy defects, and atomic form factors. United States. doi:10.1063/1.5044555.
Yin, Liang, Mattei, Gerard S., Li, Zhou, Zheng, Jianming, Zhao, Wngao, Omenya, Fredrick, Fang, Chengcheng, Li, Wangda, Li, Jianyu, Xie, Qiang, Zhang, Ji-Guang, Whittingham, M. Stanley, Meng, Ying Shirley, Manthiram, Arumugam, and Khalifah, Peter. 2018. "Extending the limits of powder diffraction analysis: diffraction parameter space, occupancy defects, and atomic form factors". United States. doi:10.1063/1.5044555.
@article{osti_1469791,
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, Wngao 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},
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 = {2018},
month = {9}
}

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Lithium Batteries and Cathode Materials
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