ACS Nano,
Год журнала:
2024,
Номер
18(42), С. 28810 - 28821
Опубликована: Окт. 8, 2024
Rechargeable
magnesium
batteries
are
attractive
candidates
for
large-scale
energy
storage
applications
because
of
the
low
cost
and
high
safety,
but
scarcity
inferior
performance
cathode
materials
hindering
development.
In
present
study,
a
kind
copper
tetrathiovanadate
(Cu
Abstract
Rechargeable
magnesium
batteries
(RMBs)
have
garnered
significant
attention
due
to
their
potential
provide
high
energy
density,
utilize
earth‐abundant
raw
materials,
and
employ
metal
anode
safely.
Currently,
the
lack
of
applicable
cathode
materials
has
become
one
bottleneck
issues
for
fully
exploiting
technological
advantages
RMBs.
Recent
studies
on
Mg
cathodes
reveal
divergent
storage
performance
depending
electrolyte
formulation,
posing
interfacial
as
a
previously
overlooked
challenge.
This
minireview
begins
with
an
introduction
representative
cathode‐electrolyte
phenomena
in
RMBs,
elaborating
unique
solvation
behavior
2+
,
which
lays
foundation
chemistries.
It
is
followed
by
presenting
recently
developed
strategies
targeting
promotion
desolvation
alternative
cointercalation
approaches
circumvent
step.
In
addition,
efforts
enhance
compatibility
via
development
engineering
are
highlighted.
Based
abovementioned
discussions,
this
finally
puts
forward
perspectives
challenges
establishment
stable
interface
fast
chemistry
Advanced Materials,
Год журнала:
2023,
Номер
36(9)
Опубликована: Ноя. 3, 2023
Abstract
The
development
of
advanced
magnesium
metal
batteries
(MMBs)
has
been
hindered
by
longstanding
challenges,
such
as
the
inability
to
induce
uniform
(Mg)
nucleation
and
inefficient
utilization
Mg
foil.
This
study
introduces
a
novel
solution
in
form
flexible,
lightweight,
paper‐based
scaffold
that
incorporates
gradient
conductivity,
magnesiophilicity,
pore
size.
design
is
achieved
through
an
industrially
adaptable
papermaking
process
which
ratio
carboxylated
multi‐walled
carbon
nanotubes
softwood
cellulose
fibers
meticulously
adjusted.
triple‐gradient
structure
enables
regulation
ion
flux,
promoting
bottom‐up
deposition.
Owing
its
high
flexibility,
low
thickness,
reduced
density,
potential
applications
flexible
wearable
electronics.
Accordingly,
electrodes
exhibit
stable
operation
for
over
1200
h
at
3
mA
cm
−2
/3
mAh
symmetrical
cells,
markedly
outperforming
non‐gradient
metallic
alternatives.
Notably,
this
marks
first
successful
fabrication
MMB
pouch
full
cell,
achieving
impressive
volumetric
energy
density
244
Wh
L
−1
.
simplicity
scalability
design,
uses
readily
available
materials
compatible
process,
open
new
doors
production
high‐energy‐density
batteries.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 17, 2024
Abstract
Rechargeable
magnesium‐ion
batteries
(RMBs)
have
garnered
increasing
research
interest
in
the
field
of
post‐lithium‐ion
battery
technologies
owing
to
their
potential
for
high
energy
density,
enhanced
safety,
cost‐effectiveness,
and
material
resourcefulness.
Despite
substantial
advancements
RMB
research,
a
number
intrinsic
challenges
remain
unresolved,
such
as
strong
Coulombic
interaction
between
Mg
2+
host
crystal
structure
cathode
materials,
sluggish
diffusion
kinetic,
poor
electrolyte
compatibility,
formation
passivation
films
on
anode
interface.
These
issues
hinder
commercial
applications
RMBs.
This
review
provides
comprehensive
overview
progress
key
areas
including
representative
storage
cathode/anode
materials
conducting
electrolytes.
Additionally,
recent
developments
electrode‐electrolyte
interface
regulations
pouch‐cell
fabrication
are
outlined,
highlighting
current
implementation
effective
solutions.
Finally,
future
directions
proposed
guide
development
high‐performance
RMBs
with
practical
applications.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(17)
Опубликована: Янв. 4, 2024
Abstract
Mg(SO
3
CF
)
2
(Mg(OTf)
is
a
simple
and
cost‐effective
magnesium
salt,
which
can
promote
the
future
applications
of
rechargeable
batteries
(RMBs).
However,
Mg(OTf)
/ether
electrolytes
suffer
from
poor
electrochemical
properties
due
to
low
solubility
serious
decomposition
passivation
[Mg
2+
‐OTf
−
]
ion
pair
on
Mg.
Herein,
OTf
anion
successfully
grafted
low‐cost
fluoride
boronic
esters
(B(OC
x
H
y
F
2x‐y+1
obtain
asymmetric
weak‐coordination
boron‐center
[B(OC
OTf]
in
ether
electrolytes.
The
‐OCH
(TFE)
groups
B(TFE)
effectively
realize
charge
delocalization
B‐O
plane,
restraining
independent
pair.
co‐decomposition
[B(TFE)
induces
formation
B‐containing
organic/inorganic
interphase,
thus
achieving
reversible
Mg
plating/stripping.
After
further
solubilization
reaction,
obtained
electrolyte
exhibits
high
average
coulombic
efficiency
98.13%
long‐term
cycling
stability
(1000
h).
Notably,
long
life
(capacity
retention
90.2%
after
600
cycles
at
1
C)
high‐rate
capacity
(43.0
mAh
g
−1
5
Mg/Mo
6
S
8
full
cell
demonstrate
favorable
electrolyte/cathode
compatibility.
This
work
brings
new
insights
design
new‐type
Mg‐salts
high‐performance
for
commercial
RMBs.
ACS Nano,
Год журнала:
2024,
Номер
18(23), С. 15239 - 15248
Опубликована: Май 29, 2024
Simple
magnesium
(Mg)
salt
solutions
are
widely
considered
as
promising
electrolytes
for
next-generation
rechargeable
Mg
metal
batteries
(RMBs)
owing
to
the
direct
Mg2+
storage
mechanism.
However,
passivation
layer
formed
on
anodes
in
these
is
key
challenge
that
limits
its
applicability.
Numerous
complex
halogenide
additives
have
been
introduced
etch
away
layer,
nevertheless,
at
expense
of
electrolyte's
anodic
stability
and
cathodes'
cyclability.
To
overcome
this
dilemma,
here,
we
design
an
electrolyte
with
a
weakly
coordinated
solvation
structure
which
enables
passivation-free
deposition
while
maintaining
high
cathodic
compatibility.
In
detail,
successfully
introduce
hexa-fluoroisopropyloxy
(HFIP–)
anion
into
Mg2+,
[Mg–HFIP]+
contact
ion
pair
facilitates
transportation
across
interfaces.
As
consequence,
our
shows
outstanding
compatibility
RMBs.
The
Mg||PDI–EDA
Mg||Mo6S8
full
cells
use
demonstrating
decent
capacity
retention
∼80%
over
400
cycles
500
cycles,
respectively.
This
represents
leap
cyclability
simple
RMBs
rest
can
barely
cycle.
work
offers
system
compatible
brings
deeper
understanding
modifying
toward
practical
electrolytes.
ACS Nano,
Год журнала:
2024,
Номер
18(18), С. 11740 - 11752
Опубликована: Апрель 22, 2024
Rechargeable
magnesium
batteries
(RMBs)
have
garnered
significant
attention
for
their
potential
in
large-scale
energy
storage
applications.
However,
the
commercial
development
of
RMBs
has
been
severely
hampered
by
rapid
failure
large-sized
Mg
metal
anodes,
especially
under
fast
and
deep
cycling
conditions.
Herein,
a
concept
proof
involving
ion-reinforced
phytic
acid
(PA)
layer
(100
cm
×
7.5
cm)
with
an
excellent
water-oxygen
tolerance,
high
Mg2+
conductivity,
favorable
electrochemical
stability
is
proposed
to
enable
uniform
plating/stripping
anode.
Guided
even
distributions
flux
electric
field,
as-prepared
PA-Al@Mg
electrode
(5.8
4.5
exhibits
no
perforation
after
cycling.
Consequently,
ultralong
lifespan
(2400
h
at
3
mA
cm-2
1
mAh
cm-2)
current
tolerance
(300
9
symmetric
cell
using
anode
could
be
achieved.
Notably,
PA-Al@Mg//Mo6S8
full
demonstrates
exceptional
stability,
operating
8000
cycles
5
C
capacity
retention
99.8%,
surpassing
that
bare
(3000
cycles,
74.7%).
Moreover,
successfully
contributes
stable
pouch
(200
750
0.1
C),
further
confirming
its
practical
utilization.
This
work
provides
valuable
theoretical
insights
technological
support
implementation
RMBs.
ACS Energy Letters,
Год журнала:
2025,
Номер
unknown, С. 552 - 561
Опубликована: Янв. 1, 2025
Mg
anodes
are
hindered
by
a
huge
overpotential
and
limited
cycling
life,
stemming
primarily
from
the
unstable
interphase
between
electrolyte.
An
effective
approach
lies
in
establishing
an
anion-derived,
inorganic-rich
solid–electrolyte
(SEI)
that
mitigates
continuous
reduction
of
Nevertheless,
high
charge
density
divalent
cations
poses
significant
challenge
balancing
coordination
dissociation
anions
within
Mg2+
solvation
sheath.
Herein,
selecting
small-sized
OTf–,
diglyme
solvent,
trimethyl
phosphate
(TMP)
as
cosolvents
with
similar
donor
number
(DN)
values,
electrolyte-dominated
Mg2+–OTf–
contact
ion-pair
configuration
is
achieved,
further
deriving
stable
inorganic
SEI
containing
fluoride
phosphide
components.
Among
them,
TMP
can
break
lattice
energy
magnesium
salts,
while
OTf–
low
electron
delocalization
ensure
degree
Mg2+,
jointly
realizing
anion
chemistry.
MgF2
MgS,
dominated
decomposition
at
potential
0.6
V
(vs
Mg/Mg2+),
enhance
electronic
insulation
interphase.
Consequently,
exhibit
superior
performance
over
3200
h
polarization
(<0.1
V)
excellent
plating/stripping
Coulombic
efficiency
1000
cycles
0.1
mA
cm–2.
Developing
chlorine-free
electrolytes
enabling
fast
Mg2+
transport
through
a
solid/cathode-electrolyte
interphase
(SEI/CEI)
remains
critical
for
rechargeable
magnesium
batteries
(RMBs).
However,
single-anion
often
lack
the
necessary
redox
properties
this
requirement.
Here,
we
propose
dual-anion
electrolyte
combining
bis(trifluoromethanesulfonyl)imide
and
1-butyl-1-methylpiperidinium
trifluoromethylsulfonate
(PP14CF3SO3)
in
diglyme
2-methoxyethylamine
(MOEA)
solvent,
achieving
efficient
Mg
plating/stripping,
cathode
compatibility,
high
anodic
stability.
The
electrostatic
interactions
between
MOEA
Mg2+/CF3SO3–
stabilize
Mg-anode
SEI
while
fostering
CxNy-rich
CEI
formation.
This
leads
to
significantly
improved
performance
Mg∥Mg
stainless
steel
(SS)∥Mg
cells,
with
an
extended
lifespan
over
2500
h
average
Coulombic
efficiency
of
98.1%,
respectively.
Mo6S8∥Mg
full
cells
exhibit
excellent
rate
performance,
poly(6,6′,6″-(benzene-1,3,5-triyl)tris(9,10-anthracenedione))
(PBAQ)∥Mg
operate
at
2.8
V
(1
A
g–1)
∼70%
capacity
retention
after
200
cycles.
work
highlights
anion-mediated
solvation
regulation,
providing
insights
into
advanced
engineering
high-performance
RMBs.