New advances in solid-state electrolytes: from halides to oxyhalides
Inorganic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5810 - 5832
Опубликована: Янв. 1, 2024
This
review
summarizes
the
types,
crystal
structures,
ion
conduction
mechanisms,
and
modification
methods
of
halides,
extends
to
oxyhalides,
proposes
cutting-edge
topics.
Язык: Английский
Advancements in the emerging rare-earth halide solid electrolytes for next-generation all-solid-state lithium batteries
Coordination Chemistry Reviews,
Год журнала:
2025,
Номер
528, С. 216432 - 216432
Опубликована: Янв. 11, 2025
Язык: Английский
Decoding Structural Disorder, Synthesis Methods, and Short- and Long-Range Lithium-Ion Transport in Lithium Argyrodites (Li6–xPS5–xBr1+x)
Chemistry of Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 28, 2025
By
varying
the
bromine
content
and
cooling
method,
we
are
able
to
induce
site
disorder
in
Li6–xPS5–xBr1+x
(x
=
0,
0.3,
0.5)
system
via
two
routes,
allowing
us
disentangle
impact
of
chemical
composition
on
conductivity.
Through
solid-state
nuclear
magnetic
resonance
(NMR),
can
explore
environment
as
well
short-range
lithium-ion
dynamics
compare
these
results
obtained
from
neutron
diffraction
electrochemical
impedance
spectroscopy
(EIS).
We
find
that
method
has
a
profound
effect
7Li
31P
cannot
be
explained
through
4d
alone.
The
configurational
entropy
(Sconf)
is
used
more
complete
descriptor
structural
linked
distortions
both
phosphorus
lithium
environment.
These
correlated
increased
intercage
movement
T1
spin–lattice
relaxation
(SLR)
NMR.
Further
analysis
prefactors
SLR
NMR
EIS
allows
obtain
migrational
(ΔSm).
For
movement,
ΔSm
correlates
with
Sconf,
implying
related
distortion
cages
decrease
distance.
Comparison
shows
an
increase
translates
into
long-range
straightforward
manner
for
slow-cooled
samples.
However,
quench-cooled
samples,
this
correlation
lost.
Lattice
softness
phonon–ion
interactions
suggested
play
important
role
conduction
which
only
becomes
apparent
when
disentangled.
This
work
by
altering
one
synthesis
step,
relationship
between
site-occupancy-based
descriptors
(site
or
Sconf)
changed
profoundly.
Furthermore,
it
seen
same,
changes
length
scale
probed.
Finally,
challenges
implicit
assumption
diffusivity
automatically
diffusivity.
Язык: Английский
Energy Transport in Superionic Crystals
Physical Review Letters,
Год журнала:
2025,
Номер
134(14)
Опубликована: Апрель 9, 2025
In
this
Letter,
we
propose
a
rigorous
concept
based
on
the
Onsager
reciprocal
theorem
to
describe
thermal
transport
behaviors
in
superionic
crystals.
Our
results
show
that
energy
crystals
can
be
transferred
through
conduction
of
atomic
vibrations,
enthalpy
diffusion
caused
by
ions'
and
thermodiffusion
coupling.
The
conductivity
resulting
from
heat
pathway
decreases
with
temperature
as
scatterings
among
vibrations
between
ions
become
stronger.
However,
due
increases
temperature,
which
is
because
diffuse
farther
at
high
temperatures.
owing
coupling
negligible
since
chemical
potential
gradient
under
steady
state
small.
apparent
therefore
determined
competition
these
two
pathways,
exhibit
diverse
behavior
negative,
weak,
positive
dependence
observed
experiments.
This
Letter
unveils
mechanisms
crystals,
explains
long-standing
confusing
Язык: Английский
Elucidating Anisotropic Ionic Diffusion Mechanism in Li3YCl6 with Molecular Dynamics Simulations
ACS Applied Energy Materials,
Год журнала:
2024,
Номер
7(16), С. 7019 - 7024
Опубликована: Авг. 2, 2024
Halide-based
solid
electrolytes
have
emerged
as
promising
materials
for
the
development
of
solid-state
batteries,
due
to
their
high
ionic
conductivity
and
excellent
chemical
properties.
Li3YCl6
is
a
prototype
halide-based
superionic
material
that
features
anisotropic
diffusion.
Elucidating
transport
optimizing
in
such
are
crucial
enhancing
performance
batteries.
In
this
work,
by
using
molecular
dynamics
simulations
with
machine
learning
force
field,
we
systematically
study
ion
diffusion
behavior,
including
directional
contribution,
concerted
migration,
disorder–order
transition
Li3YCl6.
Our
results
prove
fast
c-direction
major
contributor
total
diffusivity,
especially
at
room
temperature.
The
hexagonal
close-packed
anion
arrangement
leads
mechanism.
Lithium
along
exhibits
highly
feature,
which
absent
ab-plane
A
lithium
sublattice
can
occur
below
critical
show
ordering
occurs
regular
pattern
ions.
strongly
influenced
yttrium
cation
be
suppressed
if
small
amount
Li/Y
antisite
defects
present.
These
understandings
help
provide
guidance
future
materials.
Язык: Английский
Superior Li‐Ion Transport in LiNb0.5Ta0.5Cl6
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 24, 2024
Abstract
Halide‐based
solid‐state
electrolytes
have
emerged
as
promising
candidates
for
all‐solid‐state
lithium
batteries.
Among
them,
amorphous
LiTaCl
6
and
LiNbCl
shown
remarkable
conductivities
at
room
temperature,
up
to
11.0
13.5
mS
cm
−1
298.15
K,
respectively.
Surpassing
these
values,
molecular
dynamics
simulations
based
on
machine‐learning
force
fields
predict
that
the
Li‐ion
conductivity
in
LiNb
0.5
Ta
Cl
can
reach
15.7
K
with
an
activation
energy
of
0.146
eV.
mobility
is
found
correlate
degree
anharmonic
cation‐anion
coupling:
shows
strongest
coupling
low‐frequency
modes
Cl‐ion
vibration
modes.
Despite
many
similarities
between
Nb
Ta,
this
work
demonstrates
when
both
are
present,
synergy
result
significantly
enhanced
superionic
,
surpassing
observed
.
Язык: Английский