Fast Li-Ion Conduction in Spinel-Structured Solids
Spinel-structured solids were studied to understand if fast Li<sup>+</sup> ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/9/2625 |
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| author | Jan L. Allen Bria A. Crear Rishav Choudhury Michael J. Wang Dat T. Tran Lin Ma Philip M. Piccoli Jeff Sakamoto Jeff Wolfenstine |
| author_facet | Jan L. Allen Bria A. Crear Rishav Choudhury Michael J. Wang Dat T. Tran Lin Ma Philip M. Piccoli Jeff Sakamoto Jeff Wolfenstine |
| author_sort | Jan L. Allen |
| collection | DOAJ |
| description | Spinel-structured solids were studied to understand if fast Li<sup>+</sup> ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically active solid solution of the Li<sup>+</sup> stuffed spinel with spinel-structured Li-ion battery electrodes. This could enable a single-phase fully solid electrode eliminating multi-phase interface incompatibility and impedance commonly observed in multi-phase solid electrolyte–cathode composites. Materials of composition Li<sub>1.25</sub>M(III)<sub>0.25</sub>TiO<sub>4</sub>, M(III) = Cr or Al were prepared through solid-state methods. The room-temperature bulk Li<sup>+</sup>-ion conductivity is 1.63 × 10<sup>−4</sup> S cm<sup>−1</sup> for the composition Li<sub>1.25</sub>Cr<sub>0.25</sub>Ti<sub>1.5</sub>O<sub>4</sub>. Addition of Li<sub>3</sub>BO<sub>3</sub> (LBO) increases ionic and electronic conductivity reaching a bulk Li<sup>+</sup> ion conductivity averaging 6.8 × 10<sup>−4</sup> S cm<sup>−1</sup>, a total Li-ion conductivity averaging 4.2 × 10<sup>−4</sup> S cm<sup>−1</sup>, and electronic conductivity averaging 3.8 × 10<sup>−4</sup> S cm<sup>−1</sup> for the composition Li<sub>1.25</sub>Cr<sub>0.25</sub>Ti<sub>1.5</sub>O<sub>4</sub> with 1 wt. % LBO. An electrochemically active solid solution of Li<sub>1.25</sub>Cr<sub>0.25</sub>Mn<sub>1.5</sub>O<sub>4</sub> and LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> was prepared. This work proves that Li-stuffed spinels can achieve fast Li-ion conduction and that the concept is potentially useful to enable a single-phase fully solid electrode without interphase impedance. |
| first_indexed | 2024-03-10T11:47:12Z |
| format | Article |
| id | doaj.art-631433e1ed3e4fa1a6cefb8c1c36cb44 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T11:47:12Z |
| publishDate | 2021-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-631433e1ed3e4fa1a6cefb8c1c36cb442023-11-21T17:57:31ZengMDPI AGMolecules1420-30492021-04-01269262510.3390/molecules26092625Fast Li-Ion Conduction in Spinel-Structured SolidsJan L. Allen0Bria A. Crear1Rishav Choudhury2Michael J. Wang3Dat T. Tran4Lin Ma5Philip M. Piccoli6Jeff Sakamoto7Jeff Wolfenstine8Energy Sciences Division, Sensors & Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD 20783, USADepartment of Chemistry, Howard University, Washington, DC 20059, USADepartment of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USADepartment of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USAEnergy Sciences Division, Sensors & Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD 20783, USAEnergy Sciences Division, Sensors & Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD 20783, USADepartment of Geology, University of Maryland, College Park, MD 20742, USADepartment of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USASolid Ionic Consulting, 9223 Matthews Ave, Seattle, WA 98115, USASpinel-structured solids were studied to understand if fast Li<sup>+</sup> ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically active solid solution of the Li<sup>+</sup> stuffed spinel with spinel-structured Li-ion battery electrodes. This could enable a single-phase fully solid electrode eliminating multi-phase interface incompatibility and impedance commonly observed in multi-phase solid electrolyte–cathode composites. Materials of composition Li<sub>1.25</sub>M(III)<sub>0.25</sub>TiO<sub>4</sub>, M(III) = Cr or Al were prepared through solid-state methods. The room-temperature bulk Li<sup>+</sup>-ion conductivity is 1.63 × 10<sup>−4</sup> S cm<sup>−1</sup> for the composition Li<sub>1.25</sub>Cr<sub>0.25</sub>Ti<sub>1.5</sub>O<sub>4</sub>. Addition of Li<sub>3</sub>BO<sub>3</sub> (LBO) increases ionic and electronic conductivity reaching a bulk Li<sup>+</sup> ion conductivity averaging 6.8 × 10<sup>−4</sup> S cm<sup>−1</sup>, a total Li-ion conductivity averaging 4.2 × 10<sup>−4</sup> S cm<sup>−1</sup>, and electronic conductivity averaging 3.8 × 10<sup>−4</sup> S cm<sup>−1</sup> for the composition Li<sub>1.25</sub>Cr<sub>0.25</sub>Ti<sub>1.5</sub>O<sub>4</sub> with 1 wt. % LBO. An electrochemically active solid solution of Li<sub>1.25</sub>Cr<sub>0.25</sub>Mn<sub>1.5</sub>O<sub>4</sub> and LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> was prepared. This work proves that Li-stuffed spinels can achieve fast Li-ion conduction and that the concept is potentially useful to enable a single-phase fully solid electrode without interphase impedance.https://www.mdpi.com/1420-3049/26/9/2625solid electrolytefast Li<sup>+</sup> ion conductorLi-ion batteryspinelsolid-state batterycathode-electrolyte interface |
| spellingShingle | Jan L. Allen Bria A. Crear Rishav Choudhury Michael J. Wang Dat T. Tran Lin Ma Philip M. Piccoli Jeff Sakamoto Jeff Wolfenstine Fast Li-Ion Conduction in Spinel-Structured Solids Molecules solid electrolyte fast Li<sup>+</sup> ion conductor Li-ion battery spinel solid-state battery cathode-electrolyte interface |
| title | Fast Li-Ion Conduction in Spinel-Structured Solids |
| title_full | Fast Li-Ion Conduction in Spinel-Structured Solids |
| title_fullStr | Fast Li-Ion Conduction in Spinel-Structured Solids |
| title_full_unstemmed | Fast Li-Ion Conduction in Spinel-Structured Solids |
| title_short | Fast Li-Ion Conduction in Spinel-Structured Solids |
| title_sort | fast li ion conduction in spinel structured solids |
| topic | solid electrolyte fast Li<sup>+</sup> ion conductor Li-ion battery spinel solid-state battery cathode-electrolyte interface |
| url | https://www.mdpi.com/1420-3049/26/9/2625 |
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