The chemical and electrochemical
reactions at the positive electrode–electrolyte
interface in Li-ion batteries are hugely influential on cycle life
and safety. Ni-rich layered transition metal oxides exhibit higher
interfacial reactivity than their lower Ni-content analogues, reacting
via mechanisms that are poorly understood. Here, we study the pivotal
role of the electrolyte solvent, specifically cyclic ethylene carbonate
(EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial
reactivity at charged LiNi
0.33
Mn
0.33
Co
0.33
O
2
(NMC111) and LiNi
0.8
Mn
0.1
Co
0.1
O
2
(NMC811) cathodes by using both single-solvent
model electrolytes and the mixed solvents used in commercial cells.
While NMC111 exhibits similar parasitic currents with EC-containing
and EC-free electrolytes during high voltage holds in NMC/Li
4
Ti
5
O
12
(LTO) cells, this is not the case for
NMC811. Online gas analysis reveals that the solvent-dependent reactivity
for Ni-rich cathodes is related to the extent of lattice oxygen release
and accompanying electrolyte decomposition, which is higher for EC-containing
than EC-free electrolytes. Combined findings from electrochemical
impedance spectroscopy (EIS), TEM, solution NMR, ICP, and XPS reveal
that the electrolyte solvent has a profound impact on the degradation
of the Ni-rich cathode and the electrolyte. Higher lattice oxygen
release with EC-containing electrolytes is coupled with higher cathode
interfacial impedance, a thicker oxygen-deficient rock-salt surface
reconstruction layer, more electrolyte solvent and salt breakdown,
and higher amounts of transition metal dissolution. These processes
are suppressed in the EC-free electrolyte, highlighting the incompatibility
between Ni-rich cathodes and conventional electrolyte solvents. Finally,
new mechanistic insights into the chemical oxidation pathways of electrolyte
solvents and, critically, the knock-on chemical and electrochemical
reactions that further degrade the electrolyte and electrodes curtailing
battery lifetime are provided.
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Ni-rich
lithium nickel manganese cobalt (NMC) oxide cathode materials
promise Li-ion batteries with increased energy density and lower cost.
However, higher Ni content is accompanied by accelerated degradation
and thus poor cycle lifetime, with the underlying mechanisms and their
relative contributions still poorly understood. Here, we combine electrochemical
analysis with surface-sensitive X-ray photoelectron and absorption
spectroscopies to observe the interfacial degradation occurring in
LiNi
0.8
Mn
0.1
Co
0.1
O
2
–graphite
full cells over hundreds of cycles between fixed cell voltages (2.5–4.2
V). Capacity losses during the first ∼200 cycles are primarily
attributable to a loss of active lithium through electrolyte reduction
on the graphite anode, seen as thickening of the solid-electrolyte
interphase (SEI). As a result, the cathode reaches ever-higher potentials
at the end of charge, and with further cycling, a regime is entered
where losses in accessible NMC capacity begin to limit cycle life.
This is accompanied by accelerated transition-metal reduction at the
NMC surface, thickening of the cathode electrolyte interphase, decomposition
of residual lithium carbonate, and increased cell impedance. Transition-metal
dissolution is also detected through increased incorporation into
and thickening of the SEI, with Mn found to be initially most prevalent,
while the proportion of Ni increases with cycling. The observed evolution
of anode and cathode surface layers improves our understanding of
the interconnected nature of the degradation occurring at each electrode
and the impact on capacity retention, informing efforts to achieve
a longer cycle lifetime in Ni-rich NMCs.
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