Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes
Abstract
Lithium- and manganese-rich (LMR) layered oxides are promising high-energy cathodes for next-generation lithium-ion batteries, yet their commercialization has been hindered by a number of performance issues. While fluorination has been explored as a mitigating approach, results from polycrystalline- particle-based studies are inconsistent and the mechanism for improvement in some reports remains unclear. In the present study, we develop an in situ fluorination method that leads to fluorinated LMR with no apparent impurities. Using well-defined single-crystal Li1.2Ni0.2Mn0.6O2 (LNMO) as a platform, we show that a high fluorination level leads to decreased oxygen activities, reduced side reactions at high voltages, and a broadly improved cathode performance. Detailed characterization reveals a particle-level Mn3+ concentration gradient from the surface to the bulk of fluorinated-LNMO crystals, ascribed to the formation of a Nirich LizNixMn2–xO4–yFy (x > 0.5) spinel phase on the surface and a “spinel-layered” coherent structure in the bulk where domains of a LiNi0.5Mn1.5O4 high-voltage spinel phase are integrated into the native layered framework. This work provides fundamental understanding of the fluorination effect on LMR and key insights for future development of high-energy Mn-based cathodes with an intergrown/composite crystal structure.
- Authors:
-
[2];
[2];
[1]
- Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
- Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
- Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
- OSTI Identifier:
- 2315063
- Alternate Identifier(s):
- OSTI ID: 2322412; OSTI ID: 2322511
- Report Number(s):
- PNNL-SA-195217
Journal ID: ISSN 2380-8195
- Grant/Contract Number:
- AC02-05CH11231; AC05-76RL01830; AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Name: ACS Energy Letters Journal Volume: 9 Journal Issue: 3; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- Crystal structure; Electrodes; Halogenation; Spinel; Transition metals; 25 ENERGY STORAGE; crystal structure; electrodes; halogenation; spinel; transition metals
Citation Formats
Wang, Faxing, Zuo, Peng, Xue, Zhichen, Liu, Yijin, Wang, Chongmin, and Chen, Guoying. Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes. United States: N. p., 2024.
Web. doi:10.1021/acsenergylett.3c02697.
Wang, Faxing, Zuo, Peng, Xue, Zhichen, Liu, Yijin, Wang, Chongmin, & Chen, Guoying. Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes. United States. https://doi.org/10.1021/acsenergylett.3c02697
Wang, Faxing, Zuo, Peng, Xue, Zhichen, Liu, Yijin, Wang, Chongmin, and Chen, Guoying. Tue .
"Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes". United States. https://doi.org/10.1021/acsenergylett.3c02697.
@article{osti_2315063,
title = {Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes},
author = {Wang, Faxing and Zuo, Peng and Xue, Zhichen and Liu, Yijin and Wang, Chongmin and Chen, Guoying},
abstractNote = {Lithium- and manganese-rich (LMR) layered oxides are promising high-energy cathodes for next-generation lithium-ion batteries, yet their commercialization has been hindered by a number of performance issues. While fluorination has been explored as a mitigating approach, results from polycrystalline- particle-based studies are inconsistent and the mechanism for improvement in some reports remains unclear. In the present study, we develop an in situ fluorination method that leads to fluorinated LMR with no apparent impurities. Using well-defined single-crystal Li1.2Ni0.2Mn0.6O2 (LNMO) as a platform, we show that a high fluorination level leads to decreased oxygen activities, reduced side reactions at high voltages, and a broadly improved cathode performance. Detailed characterization reveals a particle-level Mn3+ concentration gradient from the surface to the bulk of fluorinated-LNMO crystals, ascribed to the formation of a Nirich LizNixMn2–xO4–yFy (x > 0.5) spinel phase on the surface and a “spinel-layered” coherent structure in the bulk where domains of a LiNi0.5Mn1.5O4 high-voltage spinel phase are integrated into the native layered framework. This work provides fundamental understanding of the fluorination effect on LMR and key insights for future development of high-energy Mn-based cathodes with an intergrown/composite crystal structure.},
doi = {10.1021/acsenergylett.3c02697},
journal = {ACS Energy Letters},
number = 3,
volume = 9,
place = {United States},
year = {Tue Feb 27 00:00:00 EST 2024},
month = {Tue Feb 27 00:00:00 EST 2024}
}
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