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Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes
Abstract
Abstract Mn‐redox‐based oxides and oxyfluorides are considered the most promising earth‐abundant high‐energy cathode materials for next‐generation lithium‐ion batteries. While high capacities are obtained in high‐Mn content cathodes such as Li‐ and Mn‐rich layered and spinel‐type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn‐rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation‐disordered rocksalt (DRX) cathode (Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 , an ultrahigh capacity of ≈320 mAh g −1 (energy density of ≈900 Wh kg −1 ) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn 4+ and Li + vacancies promotes local cation ordering, leading to the formation of domains of a “ δ phase” within the disordered framework. On deep discharge, Mn 4+ reduction, along with Li + insertion transform the structure to a partially orderedmore »
- Authors:
-
[1];
[2];
[2];
[3];
[3];
[2];
[1]
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Univ. of California, Santa Barbara, CA (United States)
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Environmental Molecular Sciences Laboratory (EMSL), Richland, WA (United States)
- Sponsoring Org.:
- 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). Scientific User Facilities (SUF); National Science Foundation (NSF); USDOE
- OSTI Identifier:
- 2234110
- Alternate Identifier(s):
- OSTI ID: 1983536
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; AC05-76RLO1830; DGE-650114; DE‐AC05‐76RLO1830; DE‐AC02‐05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Energy Materials
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 23; Journal ID: ISSN 1614-6832
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; capacity rise with cycling; disordered rocksalts; lithium-ion batteries; Mn-rich cathode materials; structural transformation
Citation Formats
Ahn, Juhyeon, Giovine, Raynald, Wu, Vincent C., Koirala, Krishna Prasad, Wang, Chongmin, Clément, Raphaële J., and Chen, Guoying. Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes. United States: N. p., 2023.
Web. doi:10.1002/aenm.202300221.
Ahn, Juhyeon, Giovine, Raynald, Wu, Vincent C., Koirala, Krishna Prasad, Wang, Chongmin, Clément, Raphaële J., & Chen, Guoying. Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes. United States. https://doi.org/10.1002/aenm.202300221
Ahn, Juhyeon, Giovine, Raynald, Wu, Vincent C., Koirala, Krishna Prasad, Wang, Chongmin, Clément, Raphaële J., and Chen, Guoying. Mon .
"Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes". United States. https://doi.org/10.1002/aenm.202300221.
@article{osti_2234110,
title = {Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes},
author = {Ahn, Juhyeon and Giovine, Raynald and Wu, Vincent C. and Koirala, Krishna Prasad and Wang, Chongmin and Clément, Raphaële J. and Chen, Guoying},
abstractNote = {Abstract Mn‐redox‐based oxides and oxyfluorides are considered the most promising earth‐abundant high‐energy cathode materials for next‐generation lithium‐ion batteries. While high capacities are obtained in high‐Mn content cathodes such as Li‐ and Mn‐rich layered and spinel‐type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn‐rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation‐disordered rocksalt (DRX) cathode (Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 , an ultrahigh capacity of ≈320 mAh g −1 (energy density of ≈900 Wh kg −1 ) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn 4+ and Li + vacancies promotes local cation ordering, leading to the formation of domains of a “ δ phase” within the disordered framework. On deep discharge, Mn 4+ reduction, along with Li + insertion transform the structure to a partially ordered DRX phase with a β ′‐LiFeO 2 ‐type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high‐Mn DRXbut also provide guidance for the future development of Mn‐based, high‐energy density oxide, and oxyfluoride cathode materials.},
doi = {10.1002/aenm.202300221},
journal = {Advanced Energy Materials},
number = 23,
volume = 13,
place = {United States},
year = {Mon May 01 00:00:00 EDT 2023},
month = {Mon May 01 00:00:00 EDT 2023}
}
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