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ABSTRACT: Vanadyl ion substituted LiFePO4 cathodes of the form
LiFe1-x(VO)xPO4 for 0exe0.25 have been synthesized by a rapid
microwave-solvothermal process at <300 C within 10 min. Clear
evidence of vanadyl ion substitution is demonstrated, despite a large
size difference between Fe2þ and (VO)2þ, by characterizing the
products structurally, spectroscopically, and electrochemically. The
vanadyl ion substitution is accompanied by the formation of iron
vacancies in the lattice and Fe3O4 impurity phase, which increases
with increasing (VO)2þ substitution for Fe2þ and could be removed
with a magnetic stir bar. The formation of iron vacancies, along with
the oxidation of some Fe2þ to Fe3þ to maintain charge neutrality,
results in a decrease in the unit cell volume with increasing x despite
the substitution of larger (VO)2þ for Fe2þ. Charge-discharge data
of the vanadyl ion substituted samples suggest suppression of the
two-phase plateau behavior that is characteristic of LiFePO4. Electrochemical
data collected without any carbon coating reveal that the capacity and rate capability decreases, but the capacity
retention improves with (VO)2þ substitution.

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