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Thermodynamic and Kinetic Stability of the Solid Solution Phase in Nanocrystalline Li_(x)FePO_4

Tan, H. J. and Dodd, J. L. and Fultz, B. (2009) Thermodynamic and Kinetic Stability of the Solid Solution Phase in Nanocrystalline Li_(x)FePO_4. Journal of Physical Chemistry C, 113 (48). pp. 20527-20530. ISSN 1932-7447 http://resolver.caltech.edu/CaltechAUTHORS:20091208-135031033

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Abstract

Samples of nanostructured Li_(x)FePO_4 with characteristic crystal sizes of 26 nm, and compositions of x = 0.35 and 0.65, were synthesized by ball-milling and chemical delithiation. X-ray powder diffraction showed that the solid solution phase started to form whenever two-phase materials were heated above 200 °C. The solid solution phase of nanocrystalline Li_(0.65)FePO_4 was quick to form above 200 °C but did not unmix at lower temperatures. Unmixing below 200 °C was found after long-time annealing of nanocrystalline Li_(0.35)FePO_4, however, consistent with the equilibrium phase diagram of bulk Li_(x)FePO_4. The stability of the solid solution of nanocrystalline Li_(x)FePO_4 is kinetic in origin, perhaps originating with effects of crystal surfaces.


Item Type:Article
Additional Information:© 2009 American Chemical Society. Received: July 27, 2009; Revised manuscript received: October 27, 2009. Publication Date (Web): November 6, 2009. We acknowledge help from C. M. Garland with TEM work. The authors thank K. Amine, I. Belharouak, and Argonne National Laboratory for providing LiFePO4 material. This work was supported by General Motors.
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General MotorsUNSPECIFIED
Record Number:CaltechAUTHORS:20091208-135031033
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20091208-135031033
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Official Citation:Thermodynamic and Kinetic Stability of the Solid Solution Phase in Nanocrystalline LixFePO4 H. J. Tan, J. L. Dodd, B. Fultz The Journal of Physical Chemistry C 2009 113 (48), 20527-20530
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16907
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:08 Dec 2009 22:26
Last Modified:26 Dec 2012 11:37

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