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Mössbauer Spectrometry Study of Thermally-Activated Electronic Processes in Li_xFePO_4

Tan, H. J. and Dodd, J. L. and Fultz, B. (2009) Mössbauer Spectrometry Study of Thermally-Activated Electronic Processes in Li_xFePO_4. Journal of Physical Chemistry C, 113 (6). pp. 2526-2531. ISSN 1932-7447.

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The solid solution phase of Li_xFePO_4 with different Li concentrations, x, was investigated by Mössbauer spectrometry at temperatures between 25 and 210 °C. The Mössbauer spectra show a temperature dependence of their isomer shifts (E_(IS)) and electric quadrupole splittings (E_Q), typical of thermally activated, electronic relaxation processes involving ^(57)Fe ions. The activation energies for the fluctuations of E_Q and E_(IS) for Fe^(3+) are nearly the same, 570 ± 9 meV, suggesting that both originate from charge hopping. For the Fe^(2+) components of the spectra, the fluctuations of E_Q occurred at lower temperatures than the fluctuations of E_(IS), with an activation energy of 512 ± 12 meV for E_Q and one of 551 ± 7 meV for E_(IS). The more facile fluctuations of E_Q for Fe^(2+) are evidence for local motions of neighboring Li^+ ions. It appears that the electron hopping frequency is lower than that of Li^+ ions. The activation energies of relaxation did not have a measurable dependence on the concentration of lithium, x.

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Fultz, B.0000-0002-6364-8782
Additional Information:© 2009 American Chemical Society. Received: September 26, 2008; Revised Manuscript Received: November 27, 2008. Publication Date (Web): January 15, 2009. The authors thank Dr. Amine, Dr. Belharouak, and Argonne National Laboratory for providing the LiFePO_4 material. H.T. thanks J. Y. Y. Lin and L. Mauger for their help with the computational work. The authors thank General Motors for financial support.
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Issue or Number:6
Record Number:CaltechAUTHORS:20090902-083907646
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Official Citation:Mössbauer Spectrometry Study of Thermally-Activated Electronic Processes in LixFePO4 H. J. Tan, J. L. Dodd, B. Fultz The Journal of Physical Chemistry C 2009 113 (6), 2526-2531.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15549
Deposited By: Tony Diaz
Deposited On:09 Sep 2009 18:34
Last Modified:03 Oct 2019 00:59

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