Enciso-Maldonado, Leopoldo, Dyer, Matthew S ORCID: 0000-0002-4923-3003, Jones, Michael D, Li, Ming, Payne, Julia L, Pitcher, Michael J ORCID: 0000-0003-2044-6774, Omir, Mona K, Claridge, John B ORCID: 0000-0003-4849-6714, Blanc, Frederic ORCID: 0000-0001-9171-1454 and Rosseinsky, Matthew J ORCID: 0000-0002-1910-2483
(2015)
Computational Identification and Experimental Realization of Lithium Vacancy Introduction into the Olivine LiMgPO<sub>4</sub>.
CHEMISTRY OF MATERIALS, 27 (6).
pp. 2074-2091.
Text
LiMgPO4_paper_cm504518q.pdf - Author Accepted Manuscript Access to this file is embargoed until Unspecified. Download (13MB) |
Abstract
Calculation of the energetics of aliovalent substitution into the olivine LiMgPO4 suggests that replacement of Mg2+ by In3+ is the most effective way to introduce lithium vacancies and thus generate Li ion conductivity. Experimental synthesis accesses materials with up to 17% Li vacancy content. An order-of-magnitude increase in the high-temperature hopping rates probed by 7Li NMR spin-lattice relaxation, and over 2 orders of magnitude increase in the room-temperature Li+ ion conductivity measured by impedance spectroscopy is observed upon the introduction of In3+ ions and Li vacancies. NMR spectroscopy and calculations reveal that the energy barrier to site-to-site hopping is 0.3-0.5 eV, comparable with best-in-class nonoxide systems such as argyrodite, but NMR-derived hopping rates, and impedance spectroscopy shows that longer range transport is less facile with activation energies in the range of 0.7-1 eV. Calculations suggest that this is because the Li vacancies are strongly bound to the In3+ dopants, suggesting that high lithium mobilities in oxides are accessible but high conductivities require strategies to separate defect from dopant.
Item Type: | Article |
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Subjects: | ?? QD ?? |
Depositing User: | Symplectic Admin |
Date Deposited: | 02 Mar 2015 11:30 |
Last Modified: | 17 Oct 2023 01:58 |
DOI: | 10.1021/cm504518q |
Related URLs: | |
URI: | https://livrepository.liverpool.ac.uk/id/eprint/2007506 |