Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution
Abstract
We report the recent discovery of Li-excess cation-disordered rock salt cathodes has greatly enlarged the design space of Li-ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn3+–Nb5+-based cation-disordered oxyfluorides, Li1.2Mn3+0.6+0.5xNb5+0.2-0.5xO2-xFx (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition-metal redox (Mn3+/Mn4+) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn3+-induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn-redox capacity to the overall capacity.
- Authors:
-
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES); Robert Bosch GmbH; Umicore
- OSTI Identifier:
- 1493873
- Alternate Identifier(s):
- OSTI ID: 1482427
- Grant/Contract Number:
- AC02-06CH11357; AC02‐05CH11231; AC02-05CH11231; NSF DMR 1720256
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Energy Materials
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 1614-6832
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; cyclability; DFT; fluorination; Jahn–Teller distortion; Li‐excess cation‐disordered cathodes
Citation Formats
Lun, Zhengyan, Ouyang, Bin, Kitchaev, Daniil A., Clément, Raphaële J., Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, Lei, Teng, Shi, Tan, McCloskey, Bryan D., Lee, Jinhyuk, and Ceder, Gerbrand. Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution. United States: N. p., 2018.
Web. doi:10.1002/aenm.201802959.
Lun, Zhengyan, Ouyang, Bin, Kitchaev, Daniil A., Clément, Raphaële J., Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, Lei, Teng, Shi, Tan, McCloskey, Bryan D., Lee, Jinhyuk, & Ceder, Gerbrand. Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution. United States. https://doi.org/10.1002/aenm.201802959
Lun, Zhengyan, Ouyang, Bin, Kitchaev, Daniil A., Clément, Raphaële J., Papp, Joseph K., Balasubramanian, Mahalingam, Tian, Yaosen, Lei, Teng, Shi, Tan, McCloskey, Bryan D., Lee, Jinhyuk, and Ceder, Gerbrand. Fri .
"Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution". United States. https://doi.org/10.1002/aenm.201802959. https://www.osti.gov/servlets/purl/1493873.
@article{osti_1493873,
title = {Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution},
author = {Lun, Zhengyan and Ouyang, Bin and Kitchaev, Daniil A. and Clément, Raphaële J. and Papp, Joseph K. and Balasubramanian, Mahalingam and Tian, Yaosen and Lei, Teng and Shi, Tan and McCloskey, Bryan D. and Lee, Jinhyuk and Ceder, Gerbrand},
abstractNote = {We report the recent discovery of Li-excess cation-disordered rock salt cathodes has greatly enlarged the design space of Li-ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn3+–Nb5+-based cation-disordered oxyfluorides, Li1.2Mn3+0.6+0.5xNb5+0.2-0.5xO2-xFx (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition-metal redox (Mn3+/Mn4+) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn3+-induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn-redox capacity to the overall capacity.},
doi = {10.1002/aenm.201802959},
journal = {Advanced Energy Materials},
number = 2,
volume = 9,
place = {United States},
year = {Fri Nov 16 00:00:00 EST 2018},
month = {Fri Nov 16 00:00:00 EST 2018}
}
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