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

Journal Article · · Review of Scientific Instruments
DOI: https://doi.org/10.1063/1.5044555 · OSTI ID:1469791
 [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)
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Lab. (BNL), Upton, NY (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC05-76RL01830; SC0012704
OSTI ID:
1469791
Report Number(s):
BNL--209024-2018-JAAM; PNNL-SA--138200
Journal Information:
Review of Scientific Instruments, Journal Name: Review of Scientific Instruments Journal Issue: 9 Vol. 89; ISSN 0034-6748
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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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

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25 ENERGY STORAGE
Diffraction
atomic form factors
occupancy defects