Halogen-based
redox-active
materials
represent
an
important
class
of
in
aqueous
electrochemistry.
The
existence
versatile
halogen
species
and
their
rich
bonding
coordination
create
great
flexibility
designing
new
redox
couples.
Novel
reaction
mechanisms
electrochemical
reversibility
can
be
unlocked
specifically
configurated
electrolyte
environments
electrodes.
In
this
review,
the
halogen-based
couples
appealing
chemistries
batteries,
including
flow
batteries
traditional
static
that
have
been
studied
recent
years,
are
discussed.
New
electrochemistry
provides
hope
to
outperform
state-of-the-art
systems
facing
resources
performance
limitation,
enrich
existing
battery
chemistries.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 25, 2025
The
advancement
of
aqueous
zinc-based
batteries
is
greatly
restricted
by
zinc
dendrites.
One
potential
solution
to
this
challenge
lies
in
the
employment
high-modulus
separators.
However,
achieving
both
high
modulus
and
large
ionic
conductivity
a
single
separator
remains
formidable
task.
Inspired
wood
architecture,
study
breaks
trade-off
designing
an
anisotropic
biodegradable
separator.
This
design
significantly
improves
along
oriented
direction
while
simultaneously
facilitating
fast
Zn2+
ion
transport
through
aligned
vertical
channels.
Additionally,
configuration
resolves
contradiction
between
low
thickness
good
dendrite-inhibition
capability.
These
benefits
are
supported
finite
element
simulations
comprehensive
experimental
validation,
which
also
underscore
critical
role
enhancement
for
By
employing
separator,
prolonged
life
span
realized
Zn||Zn
cells,
with
improved
cyclability
full
batteries.
work
presents
strategy
modification
towards
dendrite-free
metal
plays
crucial
mitigating
dendrites
side
reactions
zinc-ion
Here,
authors
break
ability.
The
multielectron
conversion
electrochemistry
of
I–/I0/I+
enables
high
specific
capacity
and
voltage
in
zinc–iodine
batteries.
Unfortunately,
the
I+
ions
are
thermodynamically
unstable
highly
susceptible
to
hydrolysis.
Current
endeavors
primarily
focus
on
exploring
interhalogen
chemistry
activate
I0/I+
couple.
However,
practical
working
is
below
theoretical
level.
In
this
study,
redox
couple
fully
activated,
efficiently
stabilized
by
a
chelation
agent
cost-effective
urea
conventional
aqueous
electrolyte.
A
record-high
plateau
1.8
V
vs
Zn/Zn2+
has
been
realized.
Theoretical
calculations
combined
with
spectroscopy
studies
electrochemical
tests
reveal
that
coordination
between
electron-deficient
electron-rich
O
N
atoms
molecules
favorable
for
inhibits
self-disproportionation
I+,
which
turn
promotes
rapid
kinetics
excellent
reversibility
I0/I+.
Moreover,
decreases
water
activity
electrolyte
forming
hydrogen
bonds
further
suppress
hydrolysis
I+.
Accordingly,
419
mAh
g–1
delivered
at
1C,
147
retained
after
10,000
cycles
5C.
This
work
offers
effective
insights
into
formulating
halogen-free
electrolytes
high-performance
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
The
integration
of
water-based
electrolytes
into
zinc-ion
batteries
encounters
challenges
due
to
the
limited
voltage
window
water,
interfacial
side
reactions
mobile
counterions,
and
growth
zinc
metal
(Zn0)
dendrites
during
charge.
In
this
study,
we
introduce
a
nonfluorinated,
cation-conducting
polyelectrolyte
membrane
(PEM)
designed
alleviate
these
by
suppressing
reactivities
both
water
counterions.
This
PEM
forms
hydrogen
bonds
with
molecules
through
its
proton-accepting
chains,
thus
shifting
lowest
unoccupied
molecular
orbital
(LUMO)
energy
from
−0.37
−0.14
eV
inducing
negative
shift
in
onset
potential
for
evolution
110
mV.
Additionally,
it
immobilizes
counteranions
onto
polymer
backbones
via
covalent
bonding,
hence
making
Zn2+
transference
number
nearly
unity
(0.96).
Meanwhile,
high
modulus
establishes
solid-state
diffusion
barrier
homogenize
flux,
leading
3D
in-plane
compact
Zn0
plating
within
(002)
plane.
Atomic
resolution
scanning
transmission
electron
microscopy
(STEM)
reveals
corrosion-free
deposition
without
electrolyte
degradation,
while
operando
transition
X-ray
(TXM)
further
illustrates
real-time
dendrite-free
process
at
5
mA/cm2.
Consequently,
unique
properties
water-binding
anion-tethering
enable
enhanced
electrochemical
performance
employing
highly
fluorinated
expensive
anions.
demonstrates
durability
3800
h
Zn0–Zn0
symmetric
cells
lifetime
6000
cycles
Zn0–LiV3O8
full
cells.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 2, 2024
Abstract
The
zinc
(Zn)
anode
in
zinc‐ion
batteries
suffers
from
potential
defects
such
as
wild
dendrite
growth,
severe
Zn
corrosion,
and
violent
hydrogen
evolution
reaction,
inducing
erratic
interfacial
charge
transfer
kinetics,
which
eventually
leads
to
electrochemical
failure.
Here,
collagen,
a
biomacromolecule,
is
added
achieve
the
reconstruction
of
electrolyte
hydrogen‐bonding
network
modification
derived
interface.
Benefiting
electronegativity
advantage
amino
groups
(‐NH
2
)
(002)
crystal
plane
preferentially
exposed
solid
interface
(SEI)
rich
ZnF
3
N
promotes
rapid
anode.
Thence,
an
impressive
cumulative
capacity
7,500
mAh
cm
−2
at
30
mA
achieved
assembled
Zn|VO
cell
exhibited
robust
cycle
reversibility
even
when
subject
maximum
current
100
A
g
−1
ultra‐long
life
20,000
cycles
50
,
with
single‐cycle
loss
low
0.0021%.
Such
convenient
strategy
solvent
sheathing
regulation
manipulation
opening
up
promising
universal
approach
toward
long‐life
high‐rate
anodes.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(46)
Опубликована: Авг. 17, 2024
Abstract
The
reversibility
and
stability
of
zinc
(Zn)
metal
anode
are
closely
related
to
inner
Helmholtz
plane
(IHP)
chemistry.
H
2
O‐rich
IHP
raises
severe
parasitic
reactions
irregular
Zn
deposition,
impeding
the
practical
utility
in
aqueous
Zn‐ion
batteries
(AZIBs).
In
this
study,
tetrahydropyran
(THP),
a
five‐carbon
heterocyclic
ether
with
permanent
dipole
moment
hydrophobic
characteristic,
is
introduced
as
self‐adsorptive
additive
reshape
IHP.
It
squeezes
out
partial
O
molecules
forms
O‐lean
IHP,
benefitting
for
alleviating
active
decomposition
improving
anode.
Moreover,
adsorbed
THP
induces
preferential
nucleation
(002)
plane,
facilitating
dendrite‐free
growth
Consequently,
Zn||Zn
symmetric
cell
enables
cycle
over
3600
h
at
5
mA
cm
−2
@
1
mAh
.
Zn||Cu
half‐cell
can
stably
400
cycles
99.9%
coulombic
efficiency
even
under
harsh
test
conditions
(10
@5
)
30
µm
foil.
Zn||NH
4
V
10
full
maintains
92.6%
capacity
retention
after
800
A
g
−1
Zn||I
perform
steadily
10000
decay
rate
merely
0.003%
per
C.
Advanced Energy Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
Abstract
Zn‐I
2
battery
with
four‐electron
reaction
path
(I
−
/I
+
)
in
the
cathode
delivers
high
energy
density,
which
however
is
thermodynamically
not
favored
as
I
metastable.
Herein,
it
demonstrated
that
conjugated
2P
valence
electrons
graphitic
framework
can
be
relocated,
offering
chances
to
stabilize
species.
Combinations
of
elements
(B,
N,
C,
O)
various
configurations
are
first
screened
computationally,
identifying
O─B─C─N
optimal
structure.
In
this
B‐centered
domain,
adjacent
O
and
meta‐positioned
owing
more
higher
electronegativity,
found
withdraw
from
surrounding
C
atoms
enrich
z
orbital
electron‐deficient
B
site
at
Fermi
level;
weak
electronically
enriched
tends
donate
reactants,
thus
also
enhance
adsorption
iodine
species
on
carbon
host.
Carbon
nanosheets
abundant
domains
developed
accordingly;
relevant
shows
a
large
capacity
420.3
mAh
g
−1
coulombic
efficiency
98.9%
under
0.8
A
;
moreover,
stand
for
9000
cycles
retention
88.8%.
This
computation‐guided
study
presents
how
interplay
2p‐elements
manipulated
pursue
an
efficient
host
novel
batteries.
Zinc-ion
secondary
batteries
have
been
competitive
candidates
since
the
"post-lithium-ion"
era
for
grid-scale
energy
storage,
owing
to
their
plausible
security,
high
theoretical
capacity,
plentiful
resources,
and
environment
friendliness.
However,
many
encumbrances
like
notorious
parasitic
reactions
Zn
dendrite
growth
hinder
development
of
zinc-ion
remarkably.
Faced
with
these
challenges,
eutectic
electrolytes
aroused
notable
attention
by
virtue
feasible
synthesis
tunability.
This
review
discusses
definition
advanced
functionalities
in
detail
divides
them
into
nonaqueous,
aqueous,
solid-state
regard
state
component
electrolytes.
In
particular,
corresponding
chemistry
concerning
solvation
structure
regulation,
electric
double
layer
(EDL)
structure,
solid-electrolyte
interface
(SEI)
charge/ion
transport
mechanism
is
systematically
elucidated
a
deeper
understanding
Moreover,
remaining
limitations
further
are
discussed
electrolyte
design
extended
applications.
