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Optimizing Li‐Excess Cation‐Disordered Rocksalt Cathode Design Through Partial Li Deficiency

Journal Article · · Advanced Energy Materials
 [1];  [2];  [3];  [2];  [1];  [2];  [2];  [2];  [2];  [1];  [4];  [2];  [3];  [2]
  1. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
+ Show Author Affiliations
Li-excess disordered rocksalts (DRXs) are emerging as promising cathode materials for Li-ion batteries due to their ability to use earth-abundant transition metals. In this work, a new strategy based on partial Li deficiency engineering is introduced to optimize the overall electrochemical performance of DRX cathodes. Specifically, by using Mn-based DRX as a proof-of-concept, it is demonstrated that the introduction of cation vacancies during synthesis (e.g., Li1.3-xMn2+0.4-xMn3+xNb0.3O1.6F0.4, x = 0, 0.2, and 0.4) improves both the discharge capacity and rate performance due to the more favored short-range order in the presence of Mn3+. Density functional theory calculations and Monte Carlo simulations, in combination with spectroscopic tools, reveal that introducing 10% vacancies (Li1.1Mn2+0.2Mn3+0.2Nb0.3O1.6F0.4) enables both Mn2+/Mn3+ redox and excellent Li percolation. However, a more aggressive vacancy doping (e.g., 20% vacancies in Li0.9Mn3+0.4Nb0.3O1.6F0.4) impairs performance because it induces phase separation between an Mn-rich and a Li-rich phase.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
2427335
Alternate ID(s):
OSTI ID: 1905668
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 4 Vol. 13; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
Li-ion batteries
cation vacancies
cation-disordered cathodes
percolation properties
short-range order