Angewandte Chemie,
Год журнала:
2023,
Номер
135(21)
Опубликована: Март 23, 2023
Abstract
While
recent
work
demonstrates
the
advantages
of
weakly
solvating
solvents
in
enhancing
cyclability
LMBs,
both
new
designs
and
design
strategies
for
high
performance
solvent,
especially
physicochemical
properties,
are
still
lacking.
Here,
we
propose
a
molecular
to
tune
power
properties
non‐fluorinated
ether
solvent.
The
resulting
cyclopentylmethyl
(CPME)
have
weak
wide
liquid‐phase
temperature
range.
By
optimizing
salt
concentration,
CE
is
further
promoted
99.4
%.
Besides,
improved
electrochemical
Li−S
battery
CPME‐based
electrolytes
obtained
at
−20
°C.
Li||LFP
(17.6
mg
cm
−2
)
with
developed
electrolyte
maintains
>90
%
original
capacity
over
400
cycles.
Our
concept
solvent
molecule
provides
promising
pathway
window
high‐energy‐density
LMBs.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 23, 2023
Abstract
While
recent
work
demonstrates
the
advantages
of
weakly
solvating
solvents
in
enhancing
cyclability
LMBs,
both
new
designs
and
design
strategies
for
high
performance
solvent,
especially
physicochemical
properties,
are
still
lacking.
Here,
we
propose
a
molecular
to
tune
power
properties
non‐fluorinated
ether
solvent.
The
resulting
cyclopentylmethyl
(CPME)
have
weak
wide
liquid‐phase
temperature
range.
By
optimizing
salt
concentration,
CE
is
further
promoted
99.4
%.
Besides,
improved
electrochemical
Li−S
battery
CPME‐based
electrolytes
obtained
at
−20
°C.
Li||LFP
(17.6
mg
cm
−2
)
with
developed
electrolyte
maintains
>90
%
original
capacity
over
400
cycles.
Our
concept
solvent
molecule
provides
promising
pathway
window
high‐energy‐density
LMBs.
ACS Nano,
Год журнала:
2023,
Номер
17(10), С. 9586 - 9599
Опубликована: Май 1, 2023
In
battery
electrolyte
design
principles,
tuning
Li+
solvation
structure
is
an
effective
way
to
connect
chemistry
with
interfacial
chemistry.
Although
recent
proposed
strategies
are
able
improve
cyclability,
a
comprehensive
strategy
for
remains
imperative.
Here,
we
report
by
utilizing
molecular
steric
effect
create
"bulky
coordinating"
structure.
Based
on
this
strategy,
the
designed
generates
inorganic-rich
solid
interphase
(SEI)
and
cathode-electrolyte
(CEI),
leading
excellent
compatibility
both
Li
metal
anodes
high-voltage
cathodes.
Under
ultrahigh
voltage
of
4.6
V,
Li/NMC811
full-cells
(N/P
=
2.0)
hold
84.1%
capacity
retention
over
150
cycles
industrial
pouch
cells
realize
energy
density
495
Wh
kg-1.
This
study
provides
innovative
insights
into
engineering
offers
promising
path
toward
developing
high-energy
batteries.
Advanced Energy Materials,
Год журнала:
2023,
Номер
13(31)
Опубликована: Июнь 27, 2023
The
poor
compatibility
with
Li
metal
and
electrolyte
oxidation
stability
preclude
the
utilization
of
commercial
ester‐based
electrolytes
for
high‐voltage
lithium
batteries.
This
work
proposes
a
quasi‐localized
high‐concentration
(
q‐
LHCE)
by
partially
replacing
solvents
in
conventional
LiPF
6
based
carbonated
fluorinated
analogs
(fluoroethylene
carbonate
(FEC),
2,2,2‐trifluoroethyl
methyl
(FEMC))
weakly‐solvating
ability.
LHCE
enables
formation
an
anion‐rich
solvation
sheath,
which
functions
like
but
differs
partial
participation
cosolvent
structure.
With
this
optimized
electrolyte,
inorganic‐dominated
solid
interphases
are
achieved
on
both
cathode
anode,
leading
to
uniform
deposition,
suppressed
decomposition
deterioration.
Consequently,
supports
stable
cycling
|
LiCoO
2
(≈3.5
mAh
cm
−2
)
cells
at
4.5
V
under
whole
climate
range
(from
−20
45
°C)
limited
consumption.
A
practical
ampere‐hour
level
graphite
pouch
cell
aggressive
LiNi
0.5
Mn
1.5
O
4
5.0
excellent
capacity
retention
further
reveals
effectiveness
LHCE.
refinement
old‐fashioned
provides
new
perspectives
toward
battery
systems.
Advanced Energy Materials,
Год журнала:
2023,
Номер
13(15)
Опубликована: Март 4, 2023
Abstract
Enhancing
the
charge
cut‐off
voltage
of
LiCoO
2
at
4.6
V
can
improve
battery
density,
however,
structural
instability
is
a
critical
challenge
(e.g.,
electrolyte
decomposition,
Co
dissolution,
and
phase
transition).
Here,
robust
electrode
interphases
(EEIs)
with
high
Li
+
conductivity
offered
by
polar
amide
groups
3
N/LiF
heterostructure
constructed.
3‐(trifluoromethyl)
phenyl
isocyanate
(3‐TPIC)
rationally
designed
as
an
additive
for
sustaining
Li||LiCoO
such
CEI,
which
effectively
address
instability.
The
group
achieve
de‐solvation
increase
transport.
in
cathode
interphase
(CEI)
speed
up
insertion/extraction
improving
Coulombic
efficiency
weakening
polarization
V.
In
addition,
solid
(SEI)
similar
structure
on
anode
surface
contributes
to
uniform
deposition
suppressing
dendrite
growth.
As
expected,
batteries
superior
EEIs
deliver
excellent
electrochemical
performance.
Advanced Energy Materials,
Год журнала:
2023,
Номер
13(37)
Опубликована: Авг. 3, 2023
Abstract
Lithium
metal‐based
batteries
(LMBs)
have
garnered
significant
attention
due
to
their
exceptional
energy
density
and
lightweight
characteristics.
However,
the
electrochemical
performance
of
LMBs
often
falls
short,
particularly
in
extreme
temperature
conditions.
To
address
these
challenges,
development
electrolytes
capable
withstanding
wide
ranges
has
emerged
as
a
highly
promising
strategy
for
enhancing
operational
capabilities
LMB
across
diverse
weather
This
comprehensive
review
aims
explore
degradation
mechanisms
wide‐temperature
electrolytes,
establishing
fundamental
understanding
failure
that
impede
at
harsh
temperatures.
Essential
properties
required
are
elucidated,
latest
advancements
electrolyte
technologies
tailored
specifically
all‐climate
operations
comprehensively
discussed.
Particular
emphasis
is
placed
on
unique
role
solvation
structure
interfacial
offers
valuable
insights
proposes
directions
practical
implementation
LMBs,
contributing
significantly
existing
knowledge
base
while
concurrently
paving
way
developing
robust
rigors
environments.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 6, 2024
Abstract
Constraining
the
electrochemical
reactivity
of
free
solvent
molecules
is
pivotal
for
developing
high-voltage
lithium
metal
batteries,
especially
ether
solvents
with
high
Li
compatibility
but
low
oxidation
stability
(
<4.0
V
vs
+
/Li).
The
typical
concentration
electrolyte
approach
relies
on
nearly
saturated
coordination
to
molecules,
which
confronted
severe
side
reactions
under
voltages
>4.4
V)
and
extensive
exothermic
between
reactive
anions.
Herein,
we
propose
a
molecular
anchoring
restrict
interfacial
in
diluted
electrolytes.
hydrogen-bonding
interactions
from
effectively
suppress
excessive
enhances
nickel
rich
cathodes
at
4.7
V,
despite
extremely
/ether
molar
ratio
(1:9)
absence
anion-derived
interphase.
Furthermore,
processes
thermal
abuse
conditions
are
mitigated
due
reduced
anions,
postpones
battery
runaway.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(7)
Опубликована: Янв. 3, 2024
Abstract
High‐energy
Li
metal
batteries
(LMBs)
consisting
of
anodes
and
high‐voltage
cathodes
are
promising
candidates
the
next
generation
energy‐storage
systems
owing
to
their
ultrahigh
energy
density.
However,
it
is
still
challenging
develop
nonflammable
electrolytes
with
superior
anode
cathode
compatibility
for
LMBs.
Here,
we
propose
an
active
diluent‐anion
synergy
strategy
achieve
outstanding
by
using
1,2‐difluorobenzene
(DFB)
high
activity
yielding
LiF
as
diluent
regulate
dimethylacetamide
(DMAC)‐based
localized
concentration
electrolyte
(LHCE‐DFB).
DFB
bis(fluorosulfonyl)imide
(FSI
−
)
anion
cooperate
construct
robust
LiF‐rich
solid
interphase
(SEI)
(CEI),
which
effectively
stabilize
DMAC
from
intrinsic
reactions
enhance
interfacial
stability
LiNi
0.8
Co
0.1
Mn
O
2
(NCM811)
cathodes.
LHCE‐DFB
enables
Coulombic
efficiency
(98.7
%),
dendrite‐free,
extremely
stable
long‐term
cycling
in
||
Cu
cells
cells.
The
fabricated
NCM811
display
remarkably
enhanced
excellent
rate
capability.
This
work
provides
a
designing
high‐energy
batteries.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(26)
Опубликована: Фев. 25, 2024
Abstract
High‐voltage
sodium‐ion
batteries
(SIBs)
are
one
of
the
most
promising
energy
storage
technologies
for
abundant
resources
and
cost‐efficiency.
However,
their
low
density
compared
with
lithium‐ion
(LIBs)
hinders
practical
applications.
The
high
reactivity
high‐voltage
cathodes,
primary
factor,
leads
to
deterioration
electrode/electrolyte
interphase.
Herein,
a
novel
anion/cation
solvation
strategy
is
innovatively
proposed
ternary
low‐concentration
electrolyte
that
tackles
critical
bottleneck
unstable
Especially,
intermolecular
interaction
within
as‐designed
remodeled
by
weakly
polar
fluorinated
co‐solvent
(ethoxy(pentafluoro)cyclotriphosphazene,
PFPN)
traditional
carbonate‐based
electrolytes.
PFPN
can
not
only
stabilize
propylene
carbonate
(PC),
reduce
Na
+
‐PC,
ClO
4
−
,
accelerating
desolvation,
but
also
weaken
anions
form
stable
organic/inorganic
composite
cathode
interphase
(CEI).
In
this
work,
ionic
conductivity
increases
6.12
mS
cm
−1
oxidation
stability
successfully
extended
4.84
V.
And
3
V
2
(PO
)
F
(NVPF)||Na
half‐cells
present
excellent
cycling
performance
average
coulombic
efficiency
99.5%
after
2000
cycles
at
4.5
NVPF||hard
carbon
(HC)
full
cells
relatively
(≈450
Wh
kg
competitive
commercial
LIBs,
which
expected
be
coupled
higher
voltage
cathodes
achieve
in
future.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(21)
Опубликована: Март 10, 2024
Abstract
Anion‐derived
solid‐electrolyte
interphase
(SEI)
has
received
growing
attention
owing
to
its
appealing
properties
like
fast
ion
transport
and
excellent
passivation
effect.
However,
a
sophisticated
understanding
of
anion‐derived
SEI
is
lacking.
To
common
wisdom,
features
an
inorganic‐rich
composition.
Herein,
it
reveal
that
the
freshly
formed
consists
polymer‐rich
outer
layer
inorganic
inner
layer.
Then,
organic
components
dissolve
during
discharge
process,
while
species
with
low
solubility
are
retained
in
empty
husk.
The
accumulation
husks
cycling
forms
reacted
lithium
(Li)
layer,
which
much
higher
content
than
newly
SEI.
Therefore,
acknowledged
“anion‐derived
SEI”
actually
refers
Li
instead
This
work
provides
fruitful
insights
on
compositional
ACS Nano,
Год журнала:
2024,
Номер
18(16), С. 10726 - 10737
Опубликована: Апрель 11, 2024
Ether-based
high-voltage
lithium
metal
batteries
(HV-LMBs)
are
drawing
growing
interest
due
to
their
high
compatibility
with
the
Li
anode.
However,
commercialization
of
ether-based
HV-LMBs
still
faces
many
challenges,
including
short
cycle
life,
limited
safety,
and
complex
failure
mechanisms.
In
this
Review,
we
discuss
recent
progress
achieved
in
electrolytes
for
propose
a
systematic
design
principle
electrolyte
based
on
three
important
parameters:
electrochemical
performance,
industrial
scalability.
Finally,
summarize
challenges
commercial
application
suggest
roadmap
future
development.
