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Electronic and Electrochemical Properties of Li<sub>1β<i>x</i></sub>Mn<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>4</sub> Spinel Cathodes As a Function of Lithium Content and Cation Ordering
The
electronic and electrochemical properties of the high-voltage
spinel LiMn<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>4</sub> as a function
of cation ordering and lithium content have been investigated. Conductivity
and activation energy measurements confirm that charge transfer occurs
by small polaron hopping, and the charge carrier conduction is easier
in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data
reveal that the Ni<sup>2+/3+</sup> and Ni<sup>3+/4+</sup> redox couples
are combined in a single 3d band, and that maximum charge carrier
concentration occurs where the average Ni oxidation state is close
to 3+, corresponding to <i>x</i> = 0.5 in Li Li<sub>1β<i>x</i></sub>Mn<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>4</sub>. Accordingly,
maximum electronic conductivity is found at <i>x</i> = 0.5,
regardless of cation ordering. The thermodynamically stable phases
formed during cycling were investigated by recording the X-ray diffraction
(XRD) of chemically delithiated powders. The more ordered spinels
maintained two separate two-phase regions upon lithium extraction,
while the more disordered samples exhibited a solid-solubility region
from LiMn<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>4</sub> to Li<sub>0.5</sub>Mn<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>4</sub>. The conductivity and
phase-transformation data of four samples with varying degrees of
cation ordering were compared to the electrochemical data collected
with lithium cells. Only the most ordered spinel showed inferior rate
performance, while the sample annealed for a shorter time performed
comparable to the unannealed or disordered samples. The results presented
here challenge the most common beliefs about high-voltage spinel:
(i) low Mn<sup>3+</sup> content is responsible for poor rate performance
and (ii) thermodynamically stable solid-solubility is critical for
fast kinetics