Reciprocal Salt Flux Growth of LiFePO<sub>4</sub> Single
Crystals with Controlled Defect Concentrations
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Abstract
Improved
methods for the flux growth of single crystals of the
important battery material LiFePO<sub>4</sub> have been developed,
allowing the facile preparation of single crystals up to 1 cm across
with well-developed facets at relatively low temperatures. The structural
characterization of these samples by both powder X-ray diffraction
and single crystal diffraction (X-ray and neutron) indicates that
the samples are typically stoichiometric with a very low concentration
of Fe defects on the Li site, though crystals with larger concentrations
of defects can be specifically grown using Fe-rich fluxes. These defects
occur through the formation of a Fe-rich (Li<sub>1–2<i>x</i></sub>Fe<sub><i>x</i></sub>)FePO<sub>4</sub> partial
solid solution, in contrast to the antisite defects more commonly
discussed in the literature which would preserve the ideal LiFePO<sub>4</sub> stoichiometry. The LiFePO<sub>4</sub> defects are shown to
be sarcopside-like (2 Li<sup>+</sup> → Fe<sup>2+</sup> + vacancy)
based on compositions refined from single crystal diffraction data,
the observed dependence of unit cell parameters on defect concentration,
and their observed phase behavior (defects only appear in growths
from fluxes which are Fe-rich relative to stoichiometric LiFePO<sub>4</sub>). The distribution of defects has been studied by aberration
corrected scanning transmission electron microscopy and was found
to be highly inhomogenous, suggesting that defect-containing crystals
may consist of endotaxial intergrowths of olivine LiFePO<sub>4</sub> and sarcopside Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> in a manner
that minimizes the detrimental influence of Fe<sub>Li</sub> defects
on the rate of Li-ion transport within crystallites