Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl
Li2OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having ∼1/3 of the Li sites va...
| Main Authors: | , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/142492 |
| _version_ | 1826191866052214784 |
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| author | Wang, Fei Evans, Hayden A Kim, Kwangnam Yin, Liang Li, Yiliang Tsai, Ping-Chun Liu, Jue Lapidus, Saul H Brown, Craig M Siegel, Donald J Chiang, Yet-Ming |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Wang, Fei Evans, Hayden A Kim, Kwangnam Yin, Liang Li, Yiliang Tsai, Ping-Chun Liu, Jue Lapidus, Saul H Brown, Craig M Siegel, Donald J Chiang, Yet-Ming |
| author_sort | Wang, Fei |
| collection | MIT |
| description | Li2OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having ∼1/3 of the Li sites vacant, while the presence of the OH- anion introduces the possibility of rotational disorder that may be coupled to cation migration. Here, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li2OHCl, which undergoes an orthorhombic to cubic phase transition near 311 K (≈38 °C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 × 10-5mS/cm at 37 °C to 1.4 × 10-3 mS/cm at 39 °C). X-ray and neutron experiments conducted over the temperature range 20-200 °C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to "paddlewheel"rotation of the dynamic OH- anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility. |
| first_indexed | 2024-09-23T09:02:31Z |
| format | Article |
| id | mit-1721.1/142492 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:02:31Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1424922023-04-19T20:18:00Z Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl Wang, Fei Evans, Hayden A Kim, Kwangnam Yin, Liang Li, Yiliang Tsai, Ping-Chun Liu, Jue Lapidus, Saul H Brown, Craig M Siegel, Donald J Chiang, Yet-Ming Massachusetts Institute of Technology. Department of Materials Science and Engineering Li2OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having ∼1/3 of the Li sites vacant, while the presence of the OH- anion introduces the possibility of rotational disorder that may be coupled to cation migration. Here, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li2OHCl, which undergoes an orthorhombic to cubic phase transition near 311 K (≈38 °C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 × 10-5mS/cm at 37 °C to 1.4 × 10-3 mS/cm at 39 °C). X-ray and neutron experiments conducted over the temperature range 20-200 °C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to "paddlewheel"rotation of the dynamic OH- anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility. 2022-05-11T18:20:46Z 2022-05-11T18:20:46Z 2020 2022-05-11T18:04:49Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/142492 Wang, Fei, Evans, Hayden A, Kim, Kwangnam, Yin, Liang, Li, Yiliang et al. 2020. "Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl." Chemistry of Materials, 32 (19). en 10.1021/ACS.CHEMMATER.0C02602 Chemistry of Materials Attribution-NonCommercial-ShareAlike 4.0 International https://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf American Chemical Society (ACS) DOE repository |
| spellingShingle | Wang, Fei Evans, Hayden A Kim, Kwangnam Yin, Liang Li, Yiliang Tsai, Ping-Chun Liu, Jue Lapidus, Saul H Brown, Craig M Siegel, Donald J Chiang, Yet-Ming Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl |
| title | Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl |
| title_full | Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl |
| title_fullStr | Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl |
| title_full_unstemmed | Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl |
| title_short | Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl |
| title_sort | dynamics of hydroxyl anions promotes lithium ion conduction in antiperovskite li 2 ohcl |
| url | https://hdl.handle.net/1721.1/142492 |
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