Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(21)
Опубликована: Март 16, 2024
Diluents
have
been
extensively
employed
to
overcome
the
disadvantages
of
high
viscosity
and
sluggish
kinetics
high-concentration
electrolytes,
but
generally
do
not
change
pristine
solvation
structure.
Herein,
a
weakly
coordinating
diluent,
hexafluoroisopropyl
methyl
ether
(HFME),
is
applied
regulate
coordination
Na
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(2)
Опубликована: Ноя. 12, 2022
Hard
carbon
(HC)
is
a
promising
anode
material
for
sodium-ion
batteries,
yet
still
suffers
from
low
initial
Coulombic
efficiency
(ICE)
and
unstable
solid
electrolyte
interphase
(SEI).
Herein,
sodium
diphenyl
ketone
(Na-DK)
applied
to
realize
dual-function
presodiation
HC
anodes.
It
compensates
the
irreversible
Na
uptake
at
oxygen-containing
functional
groups
reacts
with
defects
of
five/seven-membered
rings
quasi-metallic
in
HC.
The
as-formed
induces
robust
NaF-rich
SEI
on
1.0
M
NaPF6
diglyme,
favoring
interfacial
reaction
kinetics
stable
Na+
insertion
extraction.
This
renders
presodiated
(pHC)
high
ICE
≈100
%
capacity
retention
82.4
after
6800
cycles.
demonstrated
couple
Na3
V2
(PO4
)3
cathodes
full
cells
show
700
work
provides
in-depth
understanding
chemical
new
strategy
highly
batteries.
ACS Energy Letters,
Год журнала:
2023,
Номер
8(4), С. 1752 - 1761
Опубликована: Март 13, 2023
The
commercialization
of
high-voltage
lithium
(Li)
metal
batteries
(LMBs)
has
been
severely
hindered
due
to
the
lack
advanced
electrolytes
that
can
simultaneously
support
a
stable
anode
(LMA)
and
cathode
(>4
V
vs
Li+/Li).
Here,
we
propose
tetrahydropyran
(THP)-based
weakly
solvating
electrolyte
(WSE)
regulate
Li+
solvation
structures
interfacial
behaviors.
anion-rich
in
THP-based
WSE
effectively
promotes
formation
inorganic-rich
solid
interphase
(SEI)
layers,
firm
(CEI)
films,
protective
passivation
films
on
an
Al
current
collector.
optimized
behaviors
contribute
highly
compact
Li
deposition,
stability,
inhibition
transition
ion
dissolution
corrosion.
Finally,
Li||LiNi0.5Co0.2Mn0.3O2
full
cell
delivered
cycling
performance
at
high
cutoff
voltages
4.3
even
4.5
V.
This
study
demonstrates
exciting
approach
enable
ether-based
for
LMBs
could
be
developed
other
battery
systems.
Advanced Functional Materials,
Год журнала:
2023,
Номер
34(5)
Опубликована: Апрель 27, 2023
Abstract
NaF‐rich
electrode–electrolyte
interphases
play
crucial
roles
in
determining
the
cycling
stability
of
sodium
metal
batteries
(SMBs)
because
their
electronic
insulation
and
mechanical
stability.
In
this
work,
perfluorobenzene
(PFB)
is
proposed
as
additive
to
contribute
formation
solid
electrolyte
(SEI).
PFB
at
periphery
solvation
layer
can
pull
out
a
part
EC
with
lowest
energy
by
Van
der
Waals
forces,
thus
allowing
more
participate
Na
+
form
an
anion‐aggregated
sheath,
promoting
decomposition
produce
NaF.
addition,
has
higher
highest
occupied
molecular
orbital
lower
unoccupied
level,
which
also
preferentially
decomposes
NaF
both
electrodes.
Benefiting
from
intensified
ratio
SEI,
Na||Na
symmetric
cells
such
achieves
superior
life
over
350
h
1
mA
cm
−2
,
3
V
2
(PO
4
)
O
F
realize
ultrahigh
performance
88.8%
capacity
retention
after
500
cycles.
Advanced Energy Materials,
Год журнала:
2023,
Номер
13(36)
Опубликована: Авг. 9, 2023
Abstract
Aqueous
Zn−ion
batteries
(AZIBs)
promise
appealing
advantages
including
safety,
affordability,
and
high
volumetric
energy
density.
However,
rampant
parasitic
reactions
dendrite
growth
result
in
inadequate
Zn
reversibility.
Here,
a
biocompatible
additive,
L‐asparagine
(Asp),
low‐cost
aqueous
electrolyte,
is
introduced
to
address
these
concerns.
Combining
substantive
verification
tests
theoretical
calculations,
it
demonstrated
that
an
Asp‐containing
ZnSO
4
electrolyte
can
create
robust
nanostructured
solid‐electrolyte
interface
(SEI)
by
simultaneously
modulating
the
2+
solvation
structure
optimizing
metal‐molecule
interface,
which
enables
dense
deposition.
The
optimized
supports
excellent
reversibility
achieving
dendrite‐free
plating/stripping
over
240
h
at
utilization
of
85.5%
symmetrical
cell
average
99.6%
Coulombic
efficiency
for
1600
cycles
asymmetrical
cell.
Adequate
full‐cell
performance
with
poly(3,4‐ethylenedioxythiophene)
intercalated
vanadium
oxide
(PEDOT‐V
2
O
5
)
cathode,
delivers
areal
capacity
4.62
mAh
cm
−2
holds
84.4%
retention
200
under
practical
conditions
ultrathin
anode
(20
µm)
low
negative/positive
ratio
(≈2.4).
This
engineering
strategy
provides
new
insights
into
regulating
anode/electrolyte
interfacial
chemistries
toward
high‐performance
AZIBs.
Proceedings of the National Academy of Sciences,
Год журнала:
2023,
Номер
120(15)
Опубликована: Апрель 6, 2023
Aqueous
zinc-ion
batteries
are
emerging
as
one
of
the
most
promising
large-scale
energy
storage
systems
due
to
their
low
cost
and
high
safety.
However,
Zn
anodes
often
encounter
problems
dendrite
growth,
hydrogen
evolution
reaction,
formation
by-products.
Herein,
we
developed
ionic
association
electrolytes
(LIAEs)
by
introducing
2,
2-trifluoroethanol
(TFE)
into
30
m
ZnCl
2
electrolyte.
Owing
electron-withdrawing
effect
-CF
3
groups
in
TFE
molecules,
LIAEs,
2+
solvation
structures
convert
from
larger
aggregate
clusters
smaller
parts
will
construct
H-bonds
with
H
O
structure
simultaneously.
Consequently,
migration
kinetics
significantly
enhanced
ionization
solvated
is
effectively
suppressed
LIAEs.
As
a
result,
LIAE
display
fast
plating/stripping
Coulombic
efficiency
99.74%.
The
corresponding
full
exhibit
an
improved
comprehensive
performance
such
high-rate
capability
long
cycling
life.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(47)
Опубликована: Окт. 9, 2023
The
solvation
structure
of
Li+
plays
a
significant
role
in
determining
the
physicochemical
properties
electrolytes.
However,
to
date,
there
is
still
no
clear
definition
solvating
power
different
electrolyte
solvents,
and
even
solvents
that
preferentially
participate
remain
controversial.
In
this
study,
we
comprehensively
discuss
process
ions
using
both
experimental
characterizations
theoretical
calculations.
Our
findings
reveal
dependent
on
strength
-solvent
(ion-dipole)
interaction.
Additionally,
uncover
anions
tend
enter
sheath
most
systems
through
-anion
(ion-ion)
interaction,
which
weakened
by
shielding
effect
solvents.
competition
between
interactions
ultimately
determines
final
structures.
This
insight
into
fundamental
understanding
provides
inspiration
for
design
multifunctional
mixed-solvent
electrolytes
advanced
batteries.
Advanced Materials,
Год журнала:
2023,
Номер
35(32)
Опубликована: Май 11, 2023
Severe
issues
including
volume
change
and
dendrite
growth
on
sodium
metal
anodes
hinder
the
pursuit
of
applicable
high-energy-density
batteries.
Herein,
an
in
situ
reaction
approach
is
developed
that
takes
metal-organic
frameworks
as
nano-reactor
pore-former
to
produce
a
mesoporous
host
comprised
nitrogen-doped
carbon
fibers
embedded
with
monodispersed
Sn
clusters
(SnNCNFs).
The
hybrid
shows
outstanding
sodiophilicity
enables
rapid
Na
infusion
ultralow
nucleation
overpotential
2
mV.
Its
porous
structure
holds
high
content
guides
uniform
deposition.
Such
provides
favorable
plating/stripping
average
Coulombic
efficiency
99.96%
over
2000
cycles
(at
3
mA
cm-2
h
).
Na-infused
SnNCNF
anode
delivers
extreme
utilization
86%
symmetric
cells
10
),
rate
capability
cycle
life
Na-SnNCNF||Na3
V2
(PO4
)3
full
1
A
g-1
for
1000
capacity
retention
92.1%).
Furthermore,
high-energy/power-density
anode-less
anode-free
are
achieved.
This
work
presents
effective
heteroatom-doping
fabricating
multifunctional
materials
developing
high-performance
JACS Au,
Год журнала:
2023,
Номер
3(3), С. 953 - 963
Опубликована: Фев. 17, 2023
Electrolytes
are
critical
for
the
reversibility
of
various
electrochemical
energy
storage
systems.
The
recent
development
electrolytes
high-voltage
Li-metal
batteries
has
been
counting
on
salt
anion
chemistry
building
stable
interphases.
Herein,
we
investigate
effect
solvent
structure
interfacial
reactivity
and
discover
profound
designed
monofluoro-ether
in
anion-enriched
solvation
structures,
which
enables
enhanced
stabilization
both
cathodes
anodes.
Systematic
comparison
different
molecular
derivatives
provides
an
atomic-scale
understanding
unique
structure-dependent
reactivity.
interaction
between
Li+
monofluoro
(-CH2F)
group
significantly
influences
electrolyte
promotes
monofluoro-ether-based
reactions
over
chemistry.
With
in-depth
analyses
compositions,
charge
transfer,
ion
transport
at
interfaces,
demonstrated
essential
role
tailoring
highly
protective
conductive
interphases
(with
enriched
LiF
full
depths)
electrodes,
as
opposed
to
anion-derived
ones
typical
concentrated
electrolytes.
As
a
result,
solvent-dominant
high
Li
Coulombic
efficiency
(∼99.4%)
anode
cycling
rate
(10
mA
cm-2),
together
with
greatly
improved
stability
4.7
V-class
nickel-rich
cathodes.
This
work
illustrates
underlying
mechanism
competitive
reaction
schemes
offers
fundamental
insights
into
rational
design
future
high-energy
batteries.
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.
Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(5)
Опубликована: Янв. 22, 2024
High-performance
sodium
storage
at
low
temperature
is
urgent
with
the
increasingly
stringent
demand
for
energy
systems.
However,
aggravated
capacity
loss
induced
by
sluggish
interfacial
kinetics,
which
originates
from
Na
+
desolvation.
Herein,
all-fluorinated
anions
ultrahigh
electron
donicity,
trifluoroacetate
(TFA
−
),
are
introduced
into
diglyme
(G2)-based
electrolyte
anion-reinforced
solvates
in
a
wide
range.
The
unique
solvation
structure
TFA
and
decreased
G2
molecules
occupying
inner
sheath
accelerates
desolvation
of
to
exhibit
4.16
3.49
kJ
mol
−1
24.74
16.55
beyond
below
−20
°C,
respectively,
compared
that
1.0
M
NaPF
6
-G2.
These
enable
cell
Na||Na
3
V
2
(PO
4
)
deliver
60.2%
its
room-temperature
high
retention
99.2%
after
100
cycles
−40
°C.
This
work
highlights
regulation
chemistry
highly
stable
sodium-ion
batteries
temperature.