Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 6, 2024
Abstract
Phosphate‐based
localized
high‐concentration
electrolytes
(LHCE)
feature
high
flame
retardant
and
satisfactory
cathodic
stability
for
lithium
metal
batteries.
However,
stable
cycling
of
those
at
ultra‐high
upper
cut‐off
voltages
long‐term
remains
challenging.
Herein,
an
ether‐modified
phosphate,
diethyl
(2‐methoxy
ethoxy)
methylphosphonate
(DMEP),
is
designed
high‐voltage
applications.
The
ether
modification
enhances
the
Li
+
‐DMEP‐FSI
−
coordination
structure,
promoting
formation
cation‐anion
aggregates
(AGG)
dominated
solvation
which
favors
generation
LiF‐rich
cathode
electrolyte
interphase
layers
compared
to
triethyl
phosphate
(TEP)‐based
LHCE.
Consequently,
degradation,
including
transition‐metal
dissolution
electrode
cracking,
well‐suppressed.
LiNi
0.8
Co
0.1
Mn
O
2
(NCM811)||Li
full
cells
using
DMEP‐based
LHCEs
show
more
than
90.7%
capacity
retention
ultrahigh
voltage
4.7
V
after
100
cycles.
Notably,
DMEP‐LHCE
exhibits
enhanced
safety
that
TEP‐LHCE,
suggesting
its
versatility
potential
next‐generation
ACS Nano,
Journal Year:
2023,
Volume and Issue:
17(13), P. 12759 - 12773
Published: June 23, 2023
Further
popularization
of
ultrahigh-Ni
layered
cathodes
for
high-energy
lithium-ion
batteries
(LIBs)
is
hampered
by
their
grievous
structural
and
interfacial
degeneration
upon
cycling.
Herein,
leveraging
the
strong
electronegativity
low
solubility
properties
Sb
element,
a
multifunctional
modification
that
couples
atomic/microstructural
reconstruction
with
shielding
well
designed
to
improve
LiNi0.94Co0.04Al0.02O2
(NCA)
cathode
combining
Sb5+
doping
Li7SbO6
coating.
Notably,
robust
O
framework
established
regulating
local
coordination
owing
incorporation
Sb-O
covalence
bond,
leading
inhibited
lattice
evolution
at
high
voltage,
as
revealed
synchrotron
X-ray
absorption
spectroscopy.
Moreover,
radially
aligned
primary
particles
(003)
crystallographic
texture
refined/elongated
sizes
are
achieved
pinning
on
grain
boundaries
confirmed
scanning
transmission
electron
microscopy,
resulting
in
fast
Li+
diffusion
mitigated
particle
cracking.
Additionally,
situ
construction
ionic
conductive
layer
can
effectively
boost
stability
kinetics.
As
result,
optimal
Sb-modified
NCA
delivers
capacity
retention
94.6%
after
200
cycles
1
C
good
rate
183.9
mAh
g-1
10
C,
which
expected
be
applied
next-generation
advanced
LIBs.
Proceedings of the National Academy of Sciences,
Journal Year:
2024,
Volume and Issue:
121(10)
Published: Feb. 28, 2024
Micro-sized
single-crystalline
Ni-rich
cathodes
are
emerging
as
prominent
candidates
owing
to
their
larger
compact
density
and
higher
safety
compared
with
poly-crystalline
counterparts,
yet
the
uneven
stress
distribution
lattice
oxygen
loss
result
in
intragranular
crack
generation
planar
gliding.
Herein,
taking
LiNi
0.83
Co
0.12
Mn
0.05
O
2
an
example,
optimal
particle
size
of
3.7
µm
is
predicted
by
simulating
distributions
at
various
states
charge
relationship
fracture
free-energy,
then,
fitted
curves
calcination
temperature
time
further
built,
which
guides
successful
synthesis
target-sized
particles
(
m
-NCM83)
highly
ordered
layered
structure
a
unique
high-temperature
short-duration
pulse
lithiation
strategy.
The
-NCM83
significantly
reduces
strain
energy,
Li/O
loss,
cationic
mixing,
thereby
inhibiting
formation,
gliding,
surface
degradation.
Accordingly,
m-NCM83
exhibits
superior
cycling
stability
structural
integrity
dual-doped
shows
excellent
88.1%
capacity
retention.
Industrial & Engineering Chemistry Research,
Journal Year:
2023,
Volume and Issue:
62(2), P. 1029 - 1034
Published: Jan. 3, 2023
Developing
olivine-type
lithium
ferromanganese
phosphates
with
high
ionic/electronic
conductivity
is
vital
to
promote
their
practical
application
in
long-life
and
high-rate
lithium-ion
batteries
(LIBs).
Herein,
we
propose
a
dual
modification
strategy
combining
C-coating
Nb-doping
apply
it
enhance
LiFe0.5Mn0.5PO4
cathode
materials.
The
uniform
compact
layer
successfully
fabricates
the
high-speed
conductive
network
among
primary
particles
meantime
prevents
attack
of
electrolytes.
strong
Nb–O
coordination
can
effectively
accelerate
ion
diffusion
electron
transport
within
nanoparticles
while
suppressing
Jahn–Teller
effect
Mn3+.
modifications
synergistically
improve
materials
superior
lithium-storage
capacities
152
115
mAh
g–1
at
0.1
5
C,
respectively.
Furthermore,
exhibits
an
impressive
cycling
performance
ultrahigh
capacity
retention
95.4%
after
1000
cycles
1
C.
These
findings
extend
surface-to-bulk
co-modification
developing
novel
used
high-performance
LIBs.
Journal of Materials Chemistry A,
Journal Year:
2023,
Volume and Issue:
11(37), P. 19955 - 19964
Published: Jan. 1, 2023
Configuration
entropy
is
increased
by
doping
with
multiple
cations,
whereby
the
material
defects
and
active
sites
are
phase
transition
inhibited
at
high
voltage.
Meanwhile,
sodium-ion
diffusion
rate
was
improved
co-doping
strategy.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
36(1)
Published: Nov. 13, 2023
Abstract
Raising
the
charging
cut‐off
voltage
of
layered
oxide
cathodes
can
improve
their
energy
density.
However,
it
inevitably
introduces
instabilities
regarding
both
bulk
structure
and
surface/interface.
Herein,
exploiting
unique
characteristics
high‐valence
Nb
5+
element,
a
synchronous
surface‐to‐bulk‐modified
LiCoO
2
featuring
Li
3
NbO
4
surface
coating
layer,
Nb‐doped
bulk,
desired
concentration
gradient
architecture
through
one‐step
calcination
is
achieved.
Such
multifunctional
facilitates
construction
high‐quality
cathode/electrolyte
interface,
enhances
+
diffusion,
restrains
lattice‐O
loss,
Co
migration,
associated
layer‐to‐spinel
phase
distortion.
Therefore,
stable
operation
Nb‐modified
half‐cell
achieved
at
4.6
V
(90.9%
capacity
retention
after
200
cycles).
Long‐life
250
Wh
kg
−1
4.7
V‐class
550
pouch
cells
assembled
with
graphite
thin
anodes
are
harvested
(both
beyond
87%
1600
This
modification
strategy
establishes
technological
paradigm
to
pave
way
for
high‐energy
density
long‐life
lithium‐ion
cathode
materials.
