Developing
cost-effective
high-voltage
Ni-rich
cathodes
has
reached
a
consensus
to
replace
conventional
ultrahigh
Ni
counterparts
for
high-energy
Li-ion
batteries,
but
more
rigorous
requirements
are
put
forward
their
mechanical
and
chemical
stability.
Herein,
we
report
the
design
synthesis
of
full
concentration
gradient
LiNi0.75Mn0.20Co0.05O2
cathode
with
Mn-rich
Ni-poor
surface,
which
been
realized
by
in
situ
forming
PO43-
distribution
retard
transition-metal
ions'
interdiffusion
during
high-temperature
lithiation
process.
This
mitigates
stress
at
source
high
morphological
integrity
refrains
lattice
oxygen
loss
under
4.5
V
operation.
After
Li0.1B0.967PO4
is
coated,
surface
parasitic
reactions
further
ameliorated
stable
interface
chemistry.
The
resultant
deliver
reversible
capacity
as
212.6
mAh
g-1
2.7-4.5
an
energy
density
>800
Wh
kg-1cathode,
almost
equivalent
state-of-the-art
Ni-content
90%
2.7-4.3
V.
In
commercial-grade
cells,
superior
cycle
life
80.5%
retention
achieved
1C
within
after
1700
cycles,
exhibiting
promising
opportunities
compositional
cathodes.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(43)
Опубликована: Июнь 9, 2023
Abstract
LiNiO
2
‐based
high‐nickel
layered
oxide
cathodes
are
regarded
as
promising
cathode
materials
for
high‐energy‐density
automotive
lithium
batteries.
Most
of
the
attention
thus
far
has
been
paid
towards
addressing
their
surface
and
structural
instability
issues
brought
by
increase
Ni
content
(>90
%)
with
an
aim
to
enhance
cycle
stability.
However,
poor
safety
performance
remains
intractable
problem
commercialization
in
market,
yet
it
not
received
appropriate
attention.
In
this
review,
we
focus
on
gas
generation
thermal
degradation
behaviors
high‐Ni
cathodes,
which
critical
factors
determining
overall
performance.
A
comprehensive
overview
mechanisms
outgassing
runaway
reactions
is
presented
analyzed
from
a
chemistry
perspective.
Finally,
discuss
challenges
insights
into
developing
robust,
safe
cathodes.
Advanced Materials,
Год журнала:
2023,
Номер
35(24)
Опубликована: Март 16, 2023
Sodium-sulfur
(Na-S)
batteries
with
durable
Na-metal
stability,
shuttle-free
cyclability,
and
long
lifespan
are
promising
to
large-scale
energy
storages.
However,
meeting
these
stringent
requirements
poses
huge
challenges
the
existing
electrolytes.
Herein,
a
localized
saturated
electrolyte
(LSE)
is
proposed
2-methyltetrahydrofuran
(MeTHF)
as
an
inner
sheath
solvent,
which
represents
new
category
of
for
Na-S
system.
Unlike
traditional
high
concentration
electrolytes,
LSE
realized
low
salt-to-solvent
ratio
diluent-to-solvent
ratio,
pushes
limit
(LHCE).
The
appropriate
molecular
structure
solvation
ability
MeTHF
regulate
sheath,
features
reinforced
coordination
Na+
anions,
enlarged
-solvent
distance,
weakened
anion-diluent
interaction.
Such
configuration
found
be
key
build
sustainable
interphase
quasi-solid-solid
sulfur
redox
process,
making
dendrite-inhibited
battery
possible.
With
this
electrolyte,
pouch
cells
decent
cycling
performance
under
rather
demanding
conditions
demonstrated.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(8)
Опубликована: Янв. 26, 2024
Abstract
Gas
evolution
from
high‐nickel
layered
oxide
cathodes
(>90%
Ni)
remains
a
major
issue
for
their
practical
application.
Gaseous
species,
such
as
CO
2
,
O
and
CO,
that
are
evolved
at
high
states
of
charge
(SOC)
worsen
the
overall
safety
batteries,
pressure
build‐up
within
cell
may
lead
to
rupture.
Since
these
gasses
produced
during
cathode
degradation,
tracking
formation
is
also
important
in
diagnosing
failure.
Online
electrochemical
mass
spectrometry
(OEMS)
powerful
situ
technique
study
gas
high‐voltage
charge.
However,
differences
OEMS
experimental
setups
between
different
groups
make
it
challenging
compare
results
groups.
In
this
perspective,
various
factors
influence
based
on
collected
group
presented.
The
focus
conditions
release,
with
particular
emphasis
reactive
oxygen
subsequent
chemical
reactions
electrolyte.
Promising
strategies,
electrolytes,
compositional
tuning,
surface
coatings
effective
suppressing
highlighted.
Critical
insights
into
mitigating
degradation
provided
guide
development
safer,
high‐energy
batteries.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 13, 2025
Abstract
Li‐ion
and
Na‐ion
batteries
are
promising
systems
for
powering
electric
vehicles
grid
storage.
Layered
3d
transition
metal
oxides
A
x
TMO
2
(A
=
Li,
Na;
TM
metals;
0
<
≤
2)
have
drawn
extensive
attention
as
cathode
materials
due
to
their
exceptional
energy
densities.
However,
they
suffer
from
several
technical
challenges
caused
by
crystal
structure
degradation
associated
with
ions
migration,
such
poor
cycling
stability,
inferior
rate
capability,
significant
voltage
hysteresis,
serious
decay.
Aiming
tackle
these
challenges,
this
review
provides
an
in‐depth
discussion
comprehensive
understanding
of
the
migration
behaviors
in
.
First,
key
thermodynamics
kinetics
that
impact
discussed,
covering
ionic
radius,
electronic
configuration,
arrangement,
barrier.
In
particular,
details
provided
regarding
universal
specific
characteristics
Ni,
Co,
Mn,
Fe,
Cr,
V
layered
materials.
Subsequently,
impacts
migrations
on
electrochemical
performance
emphasized
terms
fundamental
science
behind
issues,
strategies
modulate
advanced
development
summarized.
Besides,
characterization
techniques
probing
present,
like
neutron
diffraction
(ND),
scanning
transmission
electron
microscopy
(STEM),
nuclear
magnetic
resonance
(NMR),
others.
Finally,
future
directions
regard
comprehensively
concluded.
This
offers
valuable
insights
into
basic
design
oxide
batteries.
Abstract
Layered
Cobalt
(Co)‐free
Nickel
(Ni)‐rich
cathode
materials
have
attracted
much
attention
due
to
their
high
energy
density
and
low
cost.
Still,
further
development
is
hampered
by
material
instability
caused
the
chemical/mechanical
degradation
of
material.
Although
there
are
numerous
doping
modification
approaches
improve
stability
layered
materials,
these
still
in
laboratory
stage
require
research
before
commercial
application.
To
fully
exploit
potential
a
more
comprehensive
theoretical
understanding
underlying
issues
necessary,
along
with
active
exploration
previously
unrevealed
mechanisms.
This
paper
presents
phase
transition
mechanism
Co‐free
Ni‐rich
existing
problems,
state‐of‐the‐art
characterization
tools
employed
study
transition.
The
causes
crystal
structure
degradation,
interfacial
instability,
mechanical
elaborated,
from
material's
its
atomic
orbital
splitting.
By
organizing
summarizing
mechanisms,
this
aims
establish
connections
among
common
problems
identify
future
priorities,
thereby
facilitating
rapid
materials.
Abstract
High‐nickel
layered
oxide
cathodes
and
lithium‐metal
anode
are
promising
candidates
for
next‐generation
battery
systems
due
to
their
high
energy
density.
Nevertheless,
the
instability
of
electrode–electrolyte
interphase
is
hindering
practical
application.
Localized
high‐concentration
electrolytes
(LHCEs)
present
a
solution
achieving
uniform
lithium
deposition
stable
cathode–electrolyte
interphase.
However,
limited
choice
diluents
cost
restricting
implementation.
Four
novel
cost‐effective
performance
with
highly
reactive
LiNiO
2
cathode
Li‐metal
reported
here.
The
results
show
that
all
LHCE
cells
exhibit
Coulombic
efficiency
>99.38%
in
Li
|
Cu
capacity
retention
>85%
after
250
cycles.
Advanced
characterizations
unveil
cell
operation
well‐tuned
interphases
morphology.
In
addition,
online
electrochemical
mass
spectroscopy
differential
scanning
calorimetry
reveal
gas
generation
heat‐release
greatly
reduced
LHCEs
presented.
Overall,
study
provides
new
insights
into
role
offers
valuable
guidance
further
optimization
density
batteries.
ACS Energy Letters,
Год журнала:
2023,
Номер
8(12), С. 5143 - 5148
Опубликована: Ноя. 17, 2023
Gas
release
from
high-Ni
layered
oxide
cathodes
(LiNixMn1-x-y-zCoyAlzO2;
x
>
0.8)
can
jeopardize
the
overall
performance
and
safety
characteristics
of
cell.
A
comprehensive
assessment
rational
cathode
design
with
common
dopants,
such
as
Ni,
Co,
Al,
Mn,
to
suppress
gas
evolution
is
crucial
for
battery
safety,
yet
it
remains
be
conducted.
Here,
we
present
an
in
situ
analysis
nine
materials
online
electrochemical
mass
spectrometry
(OEMS).
We
show
that,
regardless
dopant,
reactive
oxygen
lattice
a
critical
process
evolution.
series
comparisons
reveals
that
intensity
onset
point
are
strongly
dependent
on
composition.
Notably,
Al
Mn
most
effective
dopants
at
4.4
V.
further
highlight
stability
limits,
across
these
compositions,
between
85%
93%
state-of-charge.
Chemistry of Materials,
Год журнала:
2024,
Номер
36(12), С. 6226 - 6236
Опубликована: Июнь 4, 2024
High-nickel
layered
oxide
cathodes
make
up
a
promising
family
of
materials
for
next-generation
lithium-ion
batteries
(LIBs).
Deleterious
phase
transitions
and
surface
instabilities,
however,
have
hindered
their
mass
adoption.
Al
doping
Mn
both
been
shown
to
improve
cyclability
at
the
expense
initial
capacity.
However,
effects
these
dopants
on
performance
high-voltage
H2–H3
transition
remain
unexplored.
Herein,
we
examine
in
Li[Ni0.95Al0.05]O2
Li[Ni0.95Mn0.05]O2
comparison
that
undoped
LiNiO2
(LNO).
We
find
5%
suppress
delay
higher
voltage
but
appear
affect
its
reversibility
only
minimally.
further
reduce
increase
impedance
with
when
passing
through
do
so
Cyclic
step
chronoamperometry
shows
rate
compared
LNO.
This
is
attributed
widened
lithium
diffusion
channels
high
states
charge
enabled
by
dopants,
which
verified
X-ray
diffraction.
work
provides
insights
into
transition,
necessary
optimized
cycling
protocols
LIBs,
improves
our
general
understanding
crucial
energy
materials.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 10, 2024
Abstract
High‐nickel
layered
cathodes
exhibit
great
promise
in
advancing
high‐energy‐density
batteries
owing
to
their
significant
advantages
high
energy
capacity
and
low
cost,
but
they
suffer
severe
structural
interfacial
deterioration
during
cycling,
resulting
safety
risk
reduced
cycle
life.
Herein,
drawing
inspiration
from
the
melting
point
infusion
capability
of
Sb
2
Se
3
,
a
three‐pronged
strategy
aimed
at
simultaneously
achieving
coating
on
primary
secondary
particles
surface,
doping
elongated
slimed
particle
morphology
is
proposed
developed
fortify
stability
high‐nickel
LiNi
0.9
Co
0.05
Mn
O
(NCM90)
cathode.
The
“melted
infused”
plays
beneficial
role
defensive
effect
particle's
surfaces,
mitigating
deterioration.
In
addition,
enhanced
achieved
by
both
5+
regulated
morphology,
contributing
alleviated
breakage
ultimately
reinforced
cycling
stability.
Consequently,
‐NCM90
electrodes
significantly
improve
performance,
which
maintain
higher
retentions
96.6%
4.3
V
after
100
cycles
80.2%
1C/5C
500
cycles.
coating‐doping‐microstructure
regulation
three‐in‐one
for
improving
NCM
offers
innovative
ideas
design
advancement
lithium‐ion
batteries.