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Valence Fluctuations of ^(57)Fe in Disordered Li_(0.6)FePO_4

Dodd, J. L. and Halevy, I. and Fultz, B. (2007) Valence Fluctuations of ^(57)Fe in Disordered Li_(0.6)FePO_4. Journal of Physical Chemistry C, 111 (4). pp. 1563-1566. ISSN 1932-7447.

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The local electronic structure around iron ions in Li_(0.6)FePO)4 was studied by ^(57)Fe Mössbauer spectrometry at temperatures from 25 to 240 °C. The equilibrium two-phase, triphylite plus heterosite, material was compared to a disordered solid solution that was obtained by quenching from a high temperature. Substantial electronic relaxations were found in the disordered solid solution compared to the two-phase material at temperatures of 130 °C and above. Fluctuations in the electric field gradient showed an approximately Arrhenius behavior, with an activation energy of 335 ± 25meV and a prefactor of 5 × 10^(11) Hz, whereas Arrhenius plots for the isomer shift showed activation energies of approximately 600 meV. It is suggested that these spectral relaxations are caused by the motions of Li^+ ions. A slight relaxation at 180 °C in 10% of the two-phase material can be attributed to defects in the heterosite and triphylite phases. Overall, the disordered solid solution phase shows faster electronic dynamics than the two-phase material.

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Fultz, B.0000-0002-6364-8782
Additional Information:© 2007 American Chemical Society. Received 20 November 2006. Published online 6 January 2007. Published in print 1 February 2007. The authors thank K. Amine, I. Belharouak, and Argonne National Laboratory for providing the LiFePO_4 material, and we also thank R. Yazami and L. F. Nazar for helpful discussions. This work was supported by the U.S. Department of Energy under Grant DE-FG03-00ER15035.
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Department of Energy (DOE)DE-FG03-00ER15035
Record Number:CaltechAUTHORS:20170609-091425287
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Official Citation:Valence Fluctuations of 57Fe in Disordered Li0.6FePO4 J. L. Dodd, I. Halevy, and B. Fultz The Journal of Physical Chemistry C 2007 111 (4), 1563-1566 DOI: 10.1021/jp067710x
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78051
Deposited By: Ruth Sustaita
Deposited On:09 Jun 2017 16:24
Last Modified:09 Jun 2017 16:24

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