摘要
Owing to their high capacity and energy density,
lithium- and manganese-rich transition metal layered oxides
(LMR-NMC) are considered promising cathode materials for
lithium-ion batteries to power electrical vehicles (EVs) in the
future. Especially,
Li1.2Ni0.15Mn0.55Co0.1O2,
which can also be expressed in the two-component notation as
0.5Li2MnO3∙0.5LiNi0.375Mn0.375Co0.25O2,
is drawing a lot of interest worldwide. Therefore, evaluation of
this material in practical lithium-ion battery systems is
important. In this work, I have conducted research on a lithium-ion
battery system bearing
Li1.2Ni0.15Mn0.55Co0.1O2/graphite
during extended cycling. The data indicate that this system shows
significant performance degradation, including severe capacity
fade, large impedance rise and voltage fade. A series of
comprehensive materials characterization techniques, including
scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray
absorption spectroscopy (XAS), Raman spectroscopy, secondary ion
mass spectrometry (SIMS), and X-ray photoelectron spectroscopy
(XPS), are applied to analyze the harvested electrodes and
electrolyte. The data show that capacity fade is mainly caused by
lithium trapping in the continuous solid-electrolyte interphase
(SEI) formation on the surface of the graphite-based negative
electrode. Impedance rise and voltage fade are coming from the
Li1.2Ni0.15Mn0.55Co0.1O2-based
positive electrode. Recognizing the origin of performance
degradation has enabled us to develop effective strategies to
extend the cell life.
The strategies,
such as using alumina powder as an additive for the positive
electrode, applying atomic layer deposition (ALD) alumina coatings
onto the whole positive electrode, or applying a
pulsed-sonochemical method to coat the oxide particles with
alumina, have been used to enhance the performance of full-cells.
All of these strategies effectively improve the capacity retention
of the full-cells. ALD coating of the whole positive electrode and
pulsed-sonochemical coating of the individual oxide particles also
successfully mitigate the impedance rise of the cell. However, for
all those strategies, there is little-to-no effect on voltage fade,
which is a characteristic of this cathode material. In order to
understand the effects of voltage fade on the total energy density,
a method, which uses a resistance-corrected average voltage, is
proposed to track and quantify voltage fade of this LMR-NMC
material. In addition to that, the effects of cycling window,
temperature and the voltage fade behaviors of different cathode
materials at high voltages are discussed and compared. Possible
voltage fade mechanisms are also summarized to provide possible
strategies to mitigate voltage fade in the future. Detailed
discussions regarding all these topics are…