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Modeling Short-Range Order in Disordered Rocksalt Cathodes by Pair Distribution Function Analysis

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [3];  [4];  [5];  [6];  [7]
  1. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC
  2. University of Chinese Academy of Sciences, Beijing (China)
  3. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  4. University of Minnesota, Minneapolis, MN (United States)
  5. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  6. Florida State University, Tallahassee, FL (United States)
  7. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

Pair distribution function (PDF) analysis is a powerful technique for the characterization of short-range order (SRO) in disordered materials. Accurate interpretation of experimental PDF data is critically reliant on the development of structural models that can account for local variations in site occupancies and bond lengths. To this end, we outline an approach to model SRO using first-principles calculations based on the cluster-expansion formalism. These methods are validated on neutron scattering data from two disordered rocksalt oxyfluorides, Li1.3Mn0.4Ti0.3O1.7F0.3 and Li1.3Mn0.4Nb0.2Ti0.1O1.7F0.3. For each composition, we demonstrate that an average structure without any SRO fails to reproduce several key features in the experimental PDF. To pinpoint the origin of the suspected SRO in these materials, configurational and displacive effects were separately investigated using two disparate models. Special quasi-random structures were relaxed using density functional theory to account for local changes in bond lengths while maintaining a near-random ionic configuration. This leads to slightly improved accuracy but still misrepresents asymmetry in the first few peaks of the PDF. Monte Carlo simulations were performed to model configurational SRO on a fixed lattice, which by itself is shown to have a minimal influence on the PDF. Instead, we find that it is the bond length relaxations within environments created by SRO which controls the details of the PDF, thereby highlighting the subtle but important coupling between configurational and displacive SRO in disordered materials.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1989372
Alternate ID(s):
OSTI ID: 1997652
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 13 Vol. 35; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cations
Chemical structure
Ions
Materials
Transition metals