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Title: Computational Investigation and Experimental Realization of Disordered High-Capacity Li-Ion Cathodes Based on Ni Redox

Journal Article · · Chemistry of Materials
ORCiD logo [1];  [2];  [1];  [3];  [4];  [1];  [1];  [5];  [3];  [1];  [4];  [6];  [1]
  1. Department of Materials Science and Engineering, University of California Berkeley, Berkeley, California 94720, United States; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  2. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
  3. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  4. Materials Department, University of California Santa Barbara, Santa Barbara, California 93106, United States
  5. X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory Argonne, Lemont Illinois 60439, United States
  6. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, New Jersey 07030, UnitedStates
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In cation-disordered rocksalt Li-ion cathode materials, an excess of Li with respect to the transition metal content is necessary for the creation of percolating pathways for Li transport. Because of the lower amount of redox-active transition metal, a substantial part of the charge transfer must occur via less reversible oxygen redox. Fluorination can be used to minimize this dependence on oxygen redox by increasing the amount of low-valent transition metal in the compound, but it adds complexity to materials design. Here, we investigate the feasibility of using computationally constructed phase diagrams to facilitate the search for optimal oxyfluorides. We use the phase diagram of LiF-Li3NbO4-NiO to identify Li1.13Ni0.57Nb0.3O1.75F0.25 and Li1.19Ni0.59Nb0.22O1.46F0.54 as two promising compositions and demonstrate that they can be successfully synthesized. These compounds exhibit significantly reduced hysteresis and higher energy density than the previously reported Li1.3Ni0.27Nb0.43O2 compound in this space. Although we generally attribute the improved performance to the increased Ni content enabled by fluorination, a more nuanced relation between fluorination and the cycling behavior is revealed through electrochemical tests, X-ray absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and density functional theory. We find that fluorination increases the voltage, improves cycle life, but reduces the accessibility of Ni redox. Consideration of these effects will facilitate the future design of optimized disordered-rocksalt oxyfluoride cathodes.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1507617
Alternate ID(s):
OSTI ID: 1507791; OSTI ID: 1508812; OSTI ID: 1580830
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Vol. 31 Journal Issue: 7; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

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