1 research outputs found
High-Voltage, High-Energy Layered-Spinel Composite Cathodes with Superior Cycle Life for Lithium-Ion Batteries
The unique structural characteristics and their effect
on the electrochemical
performances of the layered-spinel composite cathode system <i>x</i>LiÂ[Li<sub>0.2</sub>Mn<sub>0.6</sub>Ni<sub>0.17</sub>Co<sub>0.03</sub>]ÂO<sub>2</sub>–(1 – <i>x</i>)ÂLiÂ[Mn<sub>1.5</sub>Ni<sub>0.425</sub>Co<sub>0.075</sub>]ÂO<sub>4</sub> (0 ≤ <i>x</i> ≤ 1) have been investigated by a systematic analysis
of the X-ray diffraction (XRD) data, neutron diffraction data (ND),
electrochemical charge–discharge profiles, and electrochemical
differential–capacity measurements. In the 0.5 ≤ <i>x</i> < 1 samples, the capacity and energy density of the
composite cathodes gradually increase during 50 cycles with a change
in the shape of the charge–discharge profiles. Ex situ X-ray
diffraction data reveal two important findings, which account for
the superior cycle performance: (i) the layered phase in the composite
cathodes (<i>x</i> = 0.5 and 0.75) undergoes an irreversible
phase transformation to a cubic spinel phase during extended electrochemical
cycling, and the newly formed spinel phase exhibits only a 3 V plateau
without any 4 or 4.7 V plateau as both Mn and Ni are present in the
4+ state; (ii) the parent 5 V cubic spinel phase undergoes a cubic
to tetragonal transition during discharge, but the volume change is
small (∼5%) for the <i>x</i> = 0.5 and 0.75 compositions.
Both the small volume change associated with the cubic to tetragonal
transition and the excellent stability of the newly evolved 3 V spinel-like
phase lead to remarkable cycle life despite a wide voltage range (2–5
V) involving phase transitions