As the economy started to recover from the COVID pandemic, the price of Li2CO3 is skyrocketed to the highest. This situation has aggravated concerns on the supply chain for lithium-ion...
While
lithium, manganese-rich (LMR) layered oxide cathode materials
offer high energy density (>900 Wh kg–1) and
low
cost, LMR is susceptible to continuous capacity and voltage decay
from the oxygen migration and side reaction with aqueous electrolyte
at high voltage. Herein, the integration of Na/F co-doping (CD) and
AlF3 coating on LMR is achieved without the need of complex
atomic layer deposition. Akin to pristine and CD samples, CD with
1 wt % AlF3 (CD-1.0 wt %) shows excellent electrochemical
performance with the capacity and voltage retentions of 93 and 91%
after 150 cycles at 0.5C, respectively, and increased ionic conductivity.
Spectroscopic analysis indicates that the coating mainly influences
the Co distribution, where Co is enriched on the surface, and partial
diffusion of Al3+ ions toward the bulk, leading to a slight
change of transition-metal (TM) valence states at the nanometer scale
and the formation of a stable Li
x
(CoAl)O
y
phase. Post-cycling analysis reveals that CD-1.0
wt % can alleviate the formation of rock-salt structure and Mn dissolution.
Besides, little to no metal segregation is detected for the cycled
CD-1.0 wt % sample. This finding presents the first instance to apply
co-doping and AlF3 coating as a new strategy to enhance
the structural homogeneity and takes another step toward their commercial
viability.
With the proliferation of market
demand for lithium-ion batteries
(LIBs) over the past decades, battery recycling has aroused extensive
attention due to the environmental, supply, and economic issues caused
by waste batteries. The hydrometallurgical recycling method has been
widely adopted to recover cathode materials as a result of its wide
applicability and high productivity. However, it is hard to completely
eliminate impurities such as copper, aluminum, and carbon, which could
bring significant impacts on recovered materials. Here, the influence
of the carbon impurity on recovered LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode material is systematically
investigated. It shows that the carbon impurity promotes nucleation
during coprecipitation and forms holes in the cathode secondary particles
after sintering which could enhance cyclability of the NCM622 cathode.
The cathode with 0.2 atom % of carbon impurity displays the highest
capacity of 159.9 mAh/g with a striking capacity retention rate of
97.9% after 100 cycles at 0.33C, but performs worse at high rates.
Nonetheless, excess carbon (5 atom %) results in severe cation disorder
and lattice distortion which significantly deteriorates the electrochemical
properties of the NCM622 cathode. Therefore, it is important to strictly
control carbon impurity during the recycling process for spent LIBs.
Iron
impurities are generally included in the obtained leaching
liquor solution during the hydrometallurgical recycling method of
spent lithium-ion batteries (LIBs) due to the usage of iron in battery
casings and machinery parts of recycling equipment, which would definitely
affect the physical and electrochemical features of the recovered
active materials. In this work, the effects of iron impurity with
different valence states (Fe2+ and Fe3+) and
gradient concentrations (0.2, 1.0, and 5.0 at. %) for the obtained
LiNi0.6Co0.2Mn0.2O2 (NCM622)
cathodes are fully studied. It is found that Fe3+ impurity
could easily lower the tap density and average size of NCM622 particles
and even introduce some impurity phases in the NCM622 structure at
high concentration (5.0 at. %), leading to much lower specific capacity,
worse rate capability, and cycling performance of the Fe3+-based NCM622 cathode. On contrast, with certain concentrations of
Fe2+ impurity (0.2 and 1.0 at. %), the NCM622 cathode material
exhibits comparable and much better electrochemical properties compared
with the virgin NCM622 materials. Based on these results, the valence
of Fe impurity should be considered and controlled as well as its
concentration during the recycling process design for spent LIBs.
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