Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries
Nonaqueous metal–gas batteries have emerged as a growing family of primary and rechargeable batteries with high capacities and energy densities. We herein report a high-capacity primary Li–gas battery that uses a perfluorinated gas, nitrogen trifluoride (NF3), as the cathode reactant. Gravimetric ca...
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| Format: | Article |
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American Chemical Society (ACS)
2019
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| Online Access: | https://hdl.handle.net/1721.1/121525 |
| _version_ | 1811089757035298816 |
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| author | He, Mingfu Li, Yuanda Guo, Rui Gallant, Betar |
| author2 | Massachusetts Institute of Technology. Department of Mechanical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Mechanical Engineering He, Mingfu Li, Yuanda Guo, Rui Gallant, Betar |
| author_sort | He, Mingfu |
| collection | MIT |
| description | Nonaqueous metal–gas batteries have emerged as a growing family of primary and rechargeable batteries with high capacities and energy densities. We herein report a high-capacity primary Li–gas battery that uses a perfluorinated gas, nitrogen trifluoride (NF3), as the cathode reactant. Gravimetric capacities of ∼1100 and 4000 mAh/gC are achieved at 25 and 55 °C, respectively (at 20 mA/gC), with discharge voltages up to 2.6 V vs Li/Li⁺. NF₃ reduction occurs by a 3e–/NF₃ process, yielding polycrystalline lithium fluoride (LiF) on a carbon cathode. The detailed electrochemical NF₃ conversion mechanism is proposed and supported by solid- and liquid-phase characterization and theoretical computation, revealing the origin of observed discharge overpotentials and elucidating the significant contribution of N–F bond cleavage. These findings indicate the value of exploring fluorinated gas cathodes for primary batteries; moreover, they open new avenues for future targeted electrocatalyst design and cathode materials synthesis applications benefiting from conformal coatings of LiF. |
| first_indexed | 2024-09-23T14:24:13Z |
| format | Article |
| id | mit-1721.1/121525 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T14:24:13Z |
| publishDate | 2019 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1215252022-10-01T21:09:43Z Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries He, Mingfu Li, Yuanda Guo, Rui Gallant, Betar Massachusetts Institute of Technology. Department of Mechanical Engineering Nonaqueous metal–gas batteries have emerged as a growing family of primary and rechargeable batteries with high capacities and energy densities. We herein report a high-capacity primary Li–gas battery that uses a perfluorinated gas, nitrogen trifluoride (NF3), as the cathode reactant. Gravimetric capacities of ∼1100 and 4000 mAh/gC are achieved at 25 and 55 °C, respectively (at 20 mA/gC), with discharge voltages up to 2.6 V vs Li/Li⁺. NF₃ reduction occurs by a 3e–/NF₃ process, yielding polycrystalline lithium fluoride (LiF) on a carbon cathode. The detailed electrochemical NF₃ conversion mechanism is proposed and supported by solid- and liquid-phase characterization and theoretical computation, revealing the origin of observed discharge overpotentials and elucidating the significant contribution of N–F bond cleavage. These findings indicate the value of exploring fluorinated gas cathodes for primary batteries; moreover, they open new avenues for future targeted electrocatalyst design and cathode materials synthesis applications benefiting from conformal coatings of LiF. National Science Foundation (U.S.) (Award DMR-14-19807) 2019-07-08T21:11:57Z 2019-07-08T21:11:57Z 2018-07-27 2018-06 Article http://purl.org/eprint/type/JournalArticle 1948-7185 https://hdl.handle.net/1721.1/121525 He, Mingfu et al. "Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries." Journal of Physical Chemistry Letters 9, 16 (July 2018): 4700-4706 © 2018 American Chemical Society http://dx.doi.org/10.1021/acs.jpclett.8b01897 Journal of Physical Chemistry Letters Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Gallant via Elizabeth Soergel |
| spellingShingle | He, Mingfu Li, Yuanda Guo, Rui Gallant, Betar Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries |
| title | Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries |
| title_full | Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries |
| title_fullStr | Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries |
| title_full_unstemmed | Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries |
| title_short | Electrochemical Conversion of Nitrogen Trifluoride as a Gas-to-Solid Cathode in Li Batteries |
| title_sort | electrochemical conversion of nitrogen trifluoride as a gas to solid cathode in li batteries |
| url | https://hdl.handle.net/1721.1/121525 |
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