Most
catalysts
cannot
accelerate
uninterrupted
conversion
of
polysulfides,
resulting
in
poor
long-cycle
and
high-loading
performance
lithium-sulfur
(Li-S)
batteries.
Herein,
rich
p-n
junction
CoS2
/ZnS
heterostructures
embedded
on
N-doped
carbon
nanosheets
are
fabricated
by
ion-etching
vulcanization
as
a
continuous
efficient
bidirectional
catalyst.
The
built-in
electric
field
the
heterostructure
not
only
accelerates
transformation
lithium
polysulfides
(LiPSs),
but
also
promotes
diffusion
decomposition
for
Li2
S
from
to
ZnS
avoiding
aggregation
sulfide
(Li2
S).
Meanwhile,
possesses
strong
chemisorption
ability
anchor
LiPSs
superior
affinity
induce
homogeneous
Li
deposition.
assembled
cell
with
/ZnS@PP
separator
delivers
cycling
stability
capacity
decay
0.058%
per
cycle
at
1.0
C
after
1000
cycles,
decent
areal
8.97
mA
h
cm-2
an
ultrahigh
sulfur
mass
loading
6
mg
.
This
work
reveals
that
catalyst
continuously
efficiently
converts
via
abundant
fields
promote
Li-S
chemistry.
Abstract
Interface
engineering
of
heterostructures
has
proven
a
promising
strategy
to
effectively
modulate
their
physicochemical
properties
and
further
improve
the
electrochemical
performance
for
various
applications.
In
this
context
related
research
newly
proposed
amorphous‐crystalline
have
lately
surged
since
they
combine
superior
advantages
amorphous‐
crystalline‐phase
structures,
showing
unusual
atomic
arrangements
in
heterointerfaces.
Nonetheless,
there
been
much
less
efforts
systematic
analysis
summary
examine
complicated
interfacial
interactions
elusory
active
sites.
The
critical
structure‐activity
correlation
electrocatalytic
mechanism
remain
rather
elusive.
review,
recent
advances
energy
conversion
storage
fields
are
amply
discussed
presented,
along
with
remarks
on
challenges
perspectives.
Initially,
fundamental
characteristics
introduced
provide
scientific
viewpoints
structural
understanding.
Subsequently,
superiorities
current
achievements
as
highly
efficient
electrocatalysts/electrodes
hydrogen
evolution
reaction,
oxygen
supercapacitor,
lithium‐ion
battery,
lithium‐sulfur
battery
applications
elaborated.
At
end
future
outlooks
opportunities
also
put
forward
promote
development
application
field
clean
energy.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(42)
Опубликована: Авг. 30, 2023
Abstract
The
serious
shuttle
effect
and
intrinsically
sluggish
oxidation–reduction
reaction
kinetics
of
polysulfides
severely
hinder
the
practical
commercialization
lithium–sulfur
(Li–S)
batteries.
Herein,
oxygen‐defect‐rich
WO
3−
x
–W
3
N
4
Mott–Schottky
heterojunctions
are
designed
as
efficient
catalysts.
Based
on
theoretical
calculations
comprehensive
experimental
characterization,
exhibits
a
lower
free
energy
change
(1.03
eV)
Li
2
S
decomposition
barrier
(0.92
than
W
,
which
significantly
enhances
sulfur
reduction
(SRR)
activity.
Furthermore,
relationship
between
catalytic
activity
gaps
in
d
p
bands
centers
(Δ
d–p
)
is
also
established,
with
low
Δ
heterojunction
leading
to
antibonding
state
energy,
promotes
electron
transfer
interfacial
redox
kinetics.
Oxygen
vacancies
can
improve
without
affecting
adsorption.
Hence,
Li–S
battery
using
@CC/S
exhibited
outstanding
rate
duration
performance
(913.9
mAh
g
–1
at
C,
stable
400
cycles
1
C).
Impressively,
achieves
high
areal
capacity
5.0
cm
−2
under
loading
4.98
mg
.
The
notorious
shuttle
effect
and
sluggish
conversion
of
polysulfides
seriously
hinder
the
practical
application
Lithium-sulfur
(Li-S)
batteries.
In
this
study,
a
novel
architecture
MoS2
/MoO3
heterostructure
uniformly
distributed
on
carbon
nanotubes
(MoS2
@CNT)
is
designed
introduced
into
Li-S
batteries
via
decorating
commercial
separator
to
regulate
redox
reactions
polysulfides.
Systematic
experiments
theoretical
calculations
showed
that
not
only
provides
sufficient
surface
affinity
capture
acts
as
an
active
catalyst
promote
polysulfides,
but
also
highly
conductive
CNT
enables
rapid
electron/ion
migration.
As
result,
with
@CNT-PP
deliver
impressive
reversible
capacity
(1015
mAh
g-1
at
0.2
A
after
100
cycles),
excellent
rate
(873
5
),
low
self-discharge
loss
(94.6%
retention
7
days
standing).
Moreover,
even
elevated
temperature
70
°C,
it
still
exhibits
high-capacity
(800
1
cycles).
Encouragingly,
when
sulfur
load
increased
8.7
mg
cm-2
,
high
areal
6.61
can
be
stably
maintained
cycles,
indicating
potential
for
application.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(33)
Опубликована: Апрель 10, 2024
Abstract
Catalyzing
polysulfides
conversion
for
lithium‐sulfur
batteries
is
an
efficient
strategy
to
overcome
the
sluggish
kinetics
of
as
well
its
serious
shuttling
effect.
Due
multistep
and
complicated
phase
transformation
sulfur
species,
monofunctional
catalyst
can
hardly
promote
overall
redox
process.
Herein,
a
molybdenum‐based
heterostructure
proposed,
that
facilitates
entire
reduction
process
by
tandemly
catalyzing
liquid‐liquid
liquid‐solid
conversion.
It
uncovered
MoC
physiochemically
immobilizes
soluble
long‐chain
polysulfide
accelerates
between
S
8
Li
2
4
through
adsorbing
extending
S─S
bond
distance.
Then,
precipitation
enhanced
facilitating
migration
from
MoSe
.
This
driven
internal
electric
field
at
heterogeneous
interface
low
diffusion
energy
barrier
on
Li2S
Moreover,
MoC‐MoSe
exhibits
smallest
degree
disproportionation
throughout
Consequently,
cell
with
/C/S
cathode
delivers
initial
discharge‐specific
capacity
841.1
mAh
g
−1
long‐term
cycling
stability
attenuation
rate
0.08%
per
cycle
1.0
C.
work
presents
novelty
view
design
rational
multifunction
sequentially
accelerating
stepwise
polysulfides.
Abstract
Lithium‐sulfur
batteries
(LSBs)
are
recognized
as
the
prospective
candidate
in
next‐generation
energy
storage
devices
due
to
their
gratifying
theoretical
density.
Nonetheless,
they
still
face
challenges
of
practical
application
including
low
utilization
sulfur
and
poor
cycling
life
derived
from
shuttle
effect
lithium
polysulfides
(LiPSs).
Herein,
a
hollow
polyhedron
with
heterogeneous
CoO/Co
9
S
8
/nitrogen‐doped
carbon
(CoO/Co
/NC)
is
obtained
through
employing
zeolitic
imidazolate
framework
precursor.
The
/NC
balances
redox
kinetics
Co
chemical
adsorption
CoO
toward
LiPSs,
effectively
inhibiting
LiPSs.
mechanisms
verified
by
both
experiment
density
functional
theory
calculation.
Meanwhile,
structure
acts
chamber,
which
mitigates
volumetric
expansion
maximizes
sulfur.
Benefiting
above
advantages,
lithium‐sulfur
battery
S‐CoO/Co
achieves
high
initial
discharge
capacity
(1470
mAh
g
−1
)
at
0.1
C
long
cycle
(ultralow
attenuation
0.033%
per
after
1000
cycles
1
C).
Even
under
loading
3.0
mg
cm
−2
,
shows
satisfactory
electrochemical
performance.
This
work
may
provide
an
idea
elevate
performance
LSBs
constructing
metal
oxide/sulfide/nitrogen‐doped
structure.
Lithium-sulfur
battery
(LSB)
is
widely
regarded
as
the
most
promising
next-generation
energy
storage
system
owing
to
its
high
theoretical
capacity
and
low
cost.
However,
practical
application
of
LSBs
mainly
hampered
by
electronic
conductivity
sulfur
cathode
notorious
"shuttle
effect",
which
lead
voltage
polarization,
severe
over-charge
behavior,
rapid
decay.
To
address
these
issues,
a
novel
reservoir
synthesized
coating
polypyrrole
(PPy)
thin
film
on
hollow
layered
double
hydroxide
(LDH)
(PPy@LDH).
After
compositing
with
sulfur,
such
PPy@LDH-S
shows
multi-functional
effect
reserve
lithium
polysulfides
(LiPSs).
In
addition,
unique
architecture
provides
sufficient
inner
space
encapsulate
volume
expansion
enhances
reaction
kinetics
sulfur-based
redox
chemistry.
Theoretical
calculations
have
illustrated
that
PPy@LDH
has
shown
stronger
chemical
adsorption
capability
for
LiPSs
than
those
porous
carbon
LDH,
preventing
shuttling
enhancing
nucleation
affinity
liquid-solid
conversion.
As
result,
electrode
delivers
stable
cycling
performance
superior
rate
capability.
Flexible
demonstrated
this
can
work
properly
treatments
bending,
folding,
even
twisting,
paving
way
wearable
devices
flexible
electronics.
Advanced Materials,
Год журнала:
2024,
Номер
36(26)
Опубликована: Апрель 15, 2024
High-energy-density
lithium
metal
batteries
(LMBs)
are
limited
by
reaction
or
diffusion
barriers
with
dissatisfactory
electrochemical
kinetics.
Typical
conversion-type
sulfur
battery
systems
exemplify
the
kinetic
challenges.
Namely,
before
diffusing
reacting
in
electrode
surface/interior,
Li(solvent)
Advanced Functional Materials,
Год журнала:
2022,
Номер
33(8)
Опубликована: Дек. 19, 2022
Abstract
Lithium–sulfur
(Li–S)
batteries
hold
great
promise
for
the
next‐generation
energy
storage
system.
However,
their
commercial
applications
are
severely
hindered
by
myriads
of
drawbacks
such
as
poor
electrical
conductivity
sulfur,
sluggish
redox
reaction
kinetics
sulfur
species,
“shuttling
effect”
soluble
lithium
polysulfides
(LiPSs)
and
uncontrollable
dendritic
Li
growth.
Herein,
it
is
conceptually
demonstrated
that
conversion
LiPSs
markedly
stimulated
exquisite
heterointerface
modulation
at
nanoscale
level
over
transition
metal
carbides
nitrides.
In
this
scenario,
N‐doped
carbon
coupled
with
molybdenum
nitride/carbide
(Mo
2
N‐MoC/NC)
hybrid
nanocomposites
designed
through
a
one‐step
carbonization‐nitridation
process,
wherein
component
regulation
induced
dense
heterointerfaces
in
situ
produced.
Benefiting
from
high
conductivity,
strong
chemical
adsorption,
superior
catalytic
activity
afforded
heterointerfaces,
Mo
N‐MoC/NC
modified
separators
significantly
restrict
shuttling
simultaneously
suppress
dendrite
generation.
The
assembled
Li–S
exhibit
remarkable
electrochemical
performance.
Integrated
experimental
theoretical
results
substantiate
boosted
chemisorption
endowed
heterointerfaces.
work
will
open
new
vista
rationally
constructing
multifarious
heterostructured
materials
communities
Li‐S
batteries.
