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V2O5 Polysulfide Anion Barrier for Long-Lived Li−S Batteries

Wen Li, Jocelyn Hicks-Garner, John Wang, Jun Liu,† Adam F. Gross, Elena Sherman, Jason Graetz,
John J. Vajo,* and Ping Liu‡
HRL Laboratories, LLC, 3011 Malibu Canyon Road, Malibu, California 90265, United States
*
S Supporting Information

ABSTRACT: We describe a V2O5 polysulfide anion barrier for a Li−S battery containing a Li
metal anode, an organic solvent-based electrolyte, and a nanostructured carbon−sulfur
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composite cathode that cycles without degradation from dissolution of soluble polysulfide
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anions. Degradation is prevented by the micrometer-scale V2O5 layer that physically isolates
the anode and cathode electrolytes, thus blocking diffusion of dissolved polysulfide anions
while permitting solid-state transport of Li+ cations. This divided cell architecture eliminates
the interaction of soluble polysulfide with the Li anode. Mechanical integrity of the thin V2O5
layer is achieved by depositing the layer on a commercial polymeric battery separator. In
addition, the isolated cathode electrolyte is optimized by the intentional addition of Li2S8,
which suppresses redistribution of sulfur within the nanostructured carbon−sulfur composite cathode. A 5 mA h pouch cell of
this design has been cycled >300 times over ∼1 year without noticeable degradation at capacities of 800 mA h g-sulfur−1.

■ INTRODUCTION
Concatenated molecular species of elemental sulfur (Sn, n = 2
to >8) and polyatomic sulfur anions (i.e., polysulfides, Sn2−) are
common due to the relative stability of S−S single bonds.1−3 In
addition, the relatively large size and distributed charge density
in Sn2− anions reduces the lattice energy of polysulfide salts
(e.g., Li2Sn), making salts of anions with n > ∼4 soluble in many
organic solvents.4 This solubility has thus far impeded
development of long cycle life rechargeable Li−S batteries
despite intense interest motivated by material cost and
abundance and a high theoretical specific energy density,
∼2550 W h kg−1 for the 2Li + S ↔ Li2S electrochemical
reaction.5−10
The recharging and cycle life of Li−S batteries consisting of
Li metal anodes, organic solvent-based electrolytes, and sulfur
cathodes are compromised by the dissolution of soluble
polysulfide anions formed at intermediate stages of the
electrochemical oxidation and reduction reactions.11 Dissolved
polysulfides diffuse throughout the battery electrolyte even-
tually reaching the Li metal anode. At the Li surface, chemical
reduction of polysulfides may occur. Partial chemical reduction
to lower soluble polysulfides (for example, dissolved Li2S8 being
reduced by Li to dissolved Li2S6) enables chemical diffusion of
these partially reduced polysulfides from the Li anode back to
the sulfur cathode where they can be electrochemically
reoxidized. During recharging, this diffusive anion transport
opposes the electron transport in the external circuit leading to
an endless charging current. Depending on the extent of
dissolution and the rate of recharging, this current can limit the
charging voltage preventing full recharging. The overall process,
referred to as polysulfide crossover or the polysulfide shuttle,11
is essentially an internal chemical short. More complete
chemical reduction to insoluble sulfides, such as Li2S2 or Li2S,
can passivate the Li electrode with concomitant irreversible loss
of sulfur from the cathode. Finally, even without reaction at the
Li anode, dissolution, disproportionation, and reprecipitation of
polysulfides4 within the cathode can lead to significant sulfur
redistribution that degrades the cathode kinetics and capacity.
In addition to polysulfide solubility, commercially viable Li−
S batteries have been difficult to realize due to the insulating
nature of sulfur, which limits sulfur utilization. On the basis of
the pioneering work of Ji et al.,12 this issue has been addressed
using electrically conductive porous carbon scaffolds13 with
nanometer scale pores that confine the sulfur and restrict
electron transport distances.14−24 In this approach, sulfur is
incorporated into the pore volume of nanoporous carbon
scaffolds, often by melt-infusion, to form nanostructured
carbon−sulfur composites. By adjusting the scaffold/sulfur
composition, the pore volume can be appropriately partitioned
to contain the sulfur while also accommodating volume changes
and permitting electrolyte access. Thus, cathodes based on
these carbon−sulfur composites can have high sulfur utilization
and rate capabilities.21 The presence of electrolyte within the
pore space also appears to sequester the partially reduced
soluble polysulfides, inhibiting the crossover mechanism.
Reduced diffusion of soluble polysulfides to the Li anode
enables cells based on porous nanostructured carbon−sulfur
composites to be recharged. However, a fraction of the
recharging current still originates from the polysulfide shuttle.
Although Coulomb efficiencies are often not reported, it
appears that many nanostructured carbon−sulfur composites
have efficiencies (discharge capacity/recharge capacity) of 75%
to 85%.14−16 These efficiencies are high enough to permit
significant recharging; however, cycling capacities usually still
decline over ∼20 to 100 cycles. This degradation occurs
because, eventually, (1) sulfur will be irreversibly lost at the Li
Received: February 17, 2014
Revised: May 6, 2014
Published: May 15, 2014

© 2014 American Chemical Society 3403 dx.doi.org/10.1021/cm500575q | Chem. Mater. 2014, 26, 3403−3410
Chemistry of Materials
anode and (2) the continual dissolution, disproportionation,
and reprecipitation reactions, within the cathode, will lead to
sulfur deposits that are electrochemically inactive. To further
inhibit polysulfide diffusion, composite electrodes have been
coated with polymers13,17 or mixed with porous silica
adsorbents forming polysulfide reservoirs.25 Adsorbent layers
of carbon have also been overlaid on sulfur cathodes.26,27 Sulfur
has also been incorporated into an elastic polyaniline composite
in nanotube form.28 These treatments further improve
efficiencies but, nevertheless, some polysulfide diffusion and
capacity degradation still occur.
Alternative strategies have also been pursued. Lithium metal
anodes can to some extent be protected from polysulfide anions
by adding LiNO3 to the electrolyte.9 Remarkable cycling was
reported by restricting the size of the polysulfide anions formed
to only insoluble species using extreme confinement.29
However, the volume loading of 70% seems too large to
accommodate the expected volume expansion (1.8×) even
without considering electrolyte access. Nanoparticles of sulfur
have also been coated with TiO2 to create yolk−shell
structures.30 The TiO2 shell significantly reduced but did not
eliminate polysulfide dissolution into the electrolyte. Recently,
stable cycling over >500 cycles was attained by limiting the
charging capacity.31 This prevented formation of soluble
polysulfides but utilized at most only 75% of the theoretical
capacity, ∼70% of the maximum Li−S energy. A hybrid anode
was also used that contained a nonporous graphite layer acting
as a solid electrolyte over the lithium metal.32 While this
method would provide a formal barrier between the
polysulfides and the anode, direct contact of a conductive
barrier with a lithium metal anode could lead to lithium plating
and dendrites (on top of the graphite), although this was not
observed.
The continued occurrence of polysulfide diffusion in
nanostructured composites and other approaches involving
polymer or gel electrolytes is not unexpected. Diffusion in the
electrolyte contained within the pores of the composite may be
slowed by the confined volume or adsorption on the pore walls,
but it is not formally stopped. Similarly, polymers used as
coatings or electrolytes, which must be permeable to solvated
Li+ ions, will also necessarily be at least somewhat permeable to
solvated polysulfide anions. In addition, adsorbent additives
must be reversible and therefore function in equilibrium. This
equilibrium will always permit some diffusion in the presence of
a concentration gradient. Thus, these approaches will reduce
but not eliminate polysulfide diffusion.
To formally block polysulfide diffusion to the Li anode and
thereby eliminate polysulfide solubility-based degradation, a
barrier to polysulfide anions is required that transports Li+
cations without solvation. This requirement is satisfied by a
solid-state Li+ ion conductor. While solid-state electrolyte Li−S
batteries have been considered,33 an alternative approach is to
include a solid-state Li+ conducting layer within an organic
solvent electrolyte-based cell.34 This layer would completely
isolate the electrolyte at the Li anode from the electrolyte at the
sulfur cathode, thereby shutting down the polysulfide shuttle.
Ideally, this configuration would allow separate optimization of
the anode and cathodes electrolytes. The Li conducting ceramic
LISICON has been considered for this approach, but its
fragility (currently) limits the layer thickness to a minimum of
300 μm, which is too thick for practical cells.5,35
Here we describe a Li anode/organic solvent electrolyte/
nanostructured carbon−sulfur cathode Li−S battery containing
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a micrometer scale thickness V2O5 solid-state lithium ion-
conducting layer that physically separates the anode and
cathode electrolytes. A schematic illustration of this divided cell
architecture is shown in Figure 1.
Figure 1. Schematic of divided cell architecture Li−S battery. A V2O5
layer (a) coated on one side of a commercial battery separator (b)
divides the anode (c) and cathode (d) electrolytes, which are
schematically shown greatly expanded. In actuality, the V2O5 layer
contacts the sulfur cathode (e). A second separator (f) is used to
ensure electrical isolation from the Li anode (g). The V2O5 layer
transports Li+ cations but is an impermeable barrier to polysulfide
anions and solvent molecules. This barrier, therefore, stops polysulfide
crossover and enables separate optimization of the anode and cathode
electrolytes. Other configurations with the layer in contact with the
anode and isolated from both electrodes are shown in Supporting
Information Figure S1.
As described above, the initial reduction of sulfur with Li
produces intermediate polysulfide anions that are soluble in
organic solvent-based electrolytes. These anions diffuse
throughout the electrolyte and in conventional cells eventually
reach the Li anode. In the divided cell, the dense and
nonporous V2O5 layer presents a formal barrier to polysulfide
anion diffusion. Dissolved polysulfide anions diffuse freely
within the electrolyte contained in the cathode but are
prevented from crossing into the anode electrolyte and
reaching the anode. In contrast, V2O5 is a well-known Li
battery cathode material and a good solid-state conductor of Li+
cations. Thus, by desolvating and resolvating at the V2O5/
electrolyte interfaces, Li+ cations can be transported between
the anode and cathode through the V2O5 layer. Although V2O5
is a good solid-state lithium ion conductor, the diffusion
coefficient for Li+ in V2O5 is much lower than in liquid
electrolyte, ∼3 × 10−12 cm2 s−1 to 4 × 10−9 cm2 s−1 depending
on Li content.36 Thus, to support the Li+ ion fluxes required for
practical batteries (∼1 mA cm−2) without excessive resistance,
i.e., IR losses, the V2O5 layer must have a thickness on the order
of 1 μm. This restriction on thickness prevents use of
freestanding layers. To use layers with micrometer scale
thicknesses while maintaining the mechanical integrity
necessary for handling and assembly in a practical battery, the
V2O5 is deposited onto one side of a commercial polymeric
battery separator.
In addition to Li ion conductivity, V2O5 is also electronically
conductive, a characteristic crucial in its performance as a
cathode. Thus, to guard against an electrical short between the
Li anode and sulfur cathode from any V2O5 that may have been
deposited through the holes in the separator, a second
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Chemistry of Materials
(uncoated) separator is placed between the Li anode and the
coated separator. In general, the V2O5 layer can be utilized in
three configurations (Supporting Information Figure S1): (1)
in contact with the sulfur cathode; (2) fully isolated by using
two additional separators, one on each side of the coated
separator; or (3) in contact with the Li anode. Choosing to
place the layer in contact with the sulfur cathode, as shown in
Figure 1, allows the V2O5 to at least partially charge and
discharge along with the sulfur cathode.
Assembling a divided cell requires separately supplying
electrolyte to the anode and cathode. This enables the
electrolyte for each electrode to be optimized separately. For
example, for the sulfur cathode, dissolution of soluble
polysulfide will still occur within the electrode structure.
Dissolved polysulfide anions can precipitate elsewhere in the
cathode through disproportionation reactions or through
oxidation during battery charging. Dissolution and precipitation
redistributes sulfur within the cathode. This redistribution can
lead to loss of electrochemically active sulfur through the
formation of sulfur deposits that are electrically isolated or
agglomerates that are too large for sufficient electron
conduction. Redistribution of sulfur within the cathode may
be suppressed by intentionally adding polysulfide anions (eg, as
Li2S8) to the cathode electrolyte. Addition of Li2S8 does not
change the rate constants for dissolution or diffusion but rather
reduces the free energy for net dissolution.
Following this design we demonstrate micrometer thick
V2O5 films deposited on commercial polypropylene separators
with the adhesion and mechanical robustness required for use
as solid-state lithium ion conducting layers. We show the
effectiveness of these layers at preventing soluble polysulfide
crossover and the advantage of optimizing the isolated cathode
electrolyte using added polysulfide anions. These features are
utilized together in 5 mA h pouch cells that have been cycled
>300 times over ∼1 year without noticeable degradation at
capacities of 800 mA h g-sulfur−1.
■
MATERIALS AND METHODS
Solid-state Li ion conducting layers were fabricated by coating
commercial polymeric battery separators with a V2O5 sol−gel. Sol−
gels of V2O5 were prepared by adding 1.62 g of V2O5 powder (99.6%,
Aldrich) to 100 mL of 30 wt % H2O2 in water (Aldrich). This mixture
was magnetically stirred for ∼80 min in a room temperature water
bath. Hydrolysis and gelation began after ∼20 min. The sol−gel was
then stored in a Nalgene bottle at room temperature for at least one
week prior to use. Sols diluted from 1:2 up to 1:6 with deionized water
by volume were prepared as needed and used immediately.
Polypropylene separators containing surfactant coatings (Celgard,
3401 and 3501) were used as substrates for the V2O5 coatings.
Substrates were prepared by taping pieces of separator around 4 in. ×
4 in. glass slides, so that the separator was under tension. The
separator was then rinsed with deionized water from a wash bottle
until its appearance became translucent, ∼3 to 5 min. The slide was
secured on a spin-coater (Chemat Technology, KW-4A) using double
sided tape. Next, 3 mL of the V2O5 sol was applied to the center of the
separator and spun for 15 s at 2000 rpm. This process was repeated to
achieve the desired layer thickness. Layer thicknesses between 500 nm
and 6 μm were used. The sol−gel layers were dried overnight in air
and then heated for 4 h in air at 100 °C. Coated separators were stored
at room temperature in a vacuum desiccator.
Nanostructured carbon−sulfur composites were fabricated by
infiltrating sulfur into electrically conductive carbon foam scaffolds.
Scaffolds were synthesized in the form of monoliths using
condensation of resorcinol-formaldehyde gels templated by silicone
oil-based emulsions, as described previously.37 Following the
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nomenclature in ref 37, the foam used in this work is designated
30%/100−1200 indicating synthesis using 30 wt % resorcinol−
formaldehyde precursor solution with 100 cP viscosity silicone oil and
a final firing temperature of 1200 °C. This composition produced a
foam in which the spherical voids originating from the silicone oil
droplets were partially collapsed (Supporting Information Figure S2).
After firing, the foam was found to contain 43 wt % SiO2 from
decomposition of residual silicone oil that was not fully washed out
prior to firing. Trying to remove this SiO2 compromised the integrity
of the foam, and so it was left in place. The pore size distribution,
determined from N2 adsorption and Hg intrusion, was bimodal with
peaks at ∼8 and 100 nm (Supporting Information Figure S3). The
total pore volume was 1.23 cm3 g−1. The conductivity of the monolith
measured using a 4-point probe method was 0.39 ± 0.07 S cm−1. This
conductivity is lower than desired for optimal electrode performance,38
possibly due to the SiO2. Formation of the nanostructured carbon−
sulfur composite was achieved by melt infiltration while heating the
monolith with sulfur powder (purified by sublimation, −100 mesh,
Aldrich), to 110 °C for 0.5 h in a sealed evacuated flask. After cooling,
bulk sulfur on the exterior of the monolith was removed by scrapping.
By weight, the composite was determined to be 61.8 wt % sulfur,
corresponding to a volume loading of ∼60%. The composite monolith
was subsequently hand-ground to a fine powder.
Electrodes were formulated by mixing the nanostructured carbon
foam/sulfur composite, SuperP carbon (MMM), and polyvinylidene
fluoride (PVDF) binder (Kyner Flex 2801, Arkema) in a 80:10:10
weight ratio in N-methylpyrrolidinone (NMP) (99+%, Aldrich) until
homogeneous slurries were obtained. Additional slurries containing
bulk sulfur were prepared by mixing powder sulfur, TiS2 (99.9%, −200
mesh, Aldrich), to improve nucleation of Li2S, KS6 graphite
(TIMCAL) to improve conductivity, SuperP carbon, and PVDF
binder in a 60:10:10:10:10 weight ratio. Slurries of these mixtures were
coated on Al foil (12 μm thick, Furukawa) and dried at 50 °C under
vacuum (10−3 Torr) overnight to remove the solvent. These electrode
tapes were then calendared. Areal sulfur densities were 1.25 mg-sulfur
cm−2 for the nanostructured electrode and 3 mg-sulfur cm−2 for the
bulk electrode. Electrochemical testing was performed using 2032 coin
or 2 cm × 2 cm pouch half-cells. Cells were assembled in an argon
filled glovebox using Li metal foil (Lectro Max 100, FMC Lithium),
polypropylene separators (Celgard 3501), and 1 M lithium bis-
(trifluoromethanesulfonyl)-imide (LiTFSI) in 1:1 dioxolane (DOL)/
dimethoxyethane (DME) (Novolyte) electrolyte. Cells containing
V2O5 layers supported on Celgard 3401 separators were assembled by
first wetting the barrier layer side only with electrolyte and then
placing the V2O5 layer facing the sulfur cathode. A second separator
with no coating (Celgard 3501) was used to ensure electrical isolation
from the Li anode. For cells without V2O5 layers, two separator layers
were used to match the V2O5 layer cell design. Cells with added
lithium polysulfide were assembled with barriers wetted with
polysulfide by floating the separator containing the V2O5 layer (with
the V2O5 layer facing down) on the surface of electrolyte containing
0.5 M Li2S8. The separator was carefully lifted off the polysulfide
solution (excess electrolyte was allowed to drip off) and placed on the
sulfur cathode with the V2O5 layer in contact with the sulfur electrode.
From elemental analysis, the effective areal density of added sulfur was
determined to be 0.4 mg/cm−2.
Cells were assembled by stacking the component layers including
the separator containing the V2O5 layer without attempting to seal the
edges of the V2O5 layer. For coin cells, the separator containing the
V2O5 layer was slightly larger than the cathode (1.5 cm vs 1.0 cm
diameter). One or two drops of electrolyte were placed on the cathode
(nanostructured or bulk) and one drop was placed on both the back
(uncoated) anode side of the separator containing the barrier and on
the second separator. Pouch cells were constructed using 2 cm × 2 cm
sulfur cathodes with Al current collector tabs. Electrolyte was added
dropwise (∼four or five drops) to the cathode just to wetness, with the
edge still slightly dry. This was done to try to prevent electrolyte and
thereby polysulfide from being pressed around the edges of the barrier
layer. Separators coated with V2O5 layers were 3 cm × 3 cm. The
second separator was 4 cm × 4 cm. Approximately three drops of
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Chemistry of Materials Article

electrolyte were added to the anode side of the separator supporting

the barrier and the second separator. The lithium anode was 3.5 cm ×
3.5 cm and was pressed into a Ni grid custom etched from a Ni foil
(99.8%, AMETEK 899L) with a Ni foil current collector tab. The
stacked assembly was placed in a polyethylene bag and heat-sealed
around the current collector tabs slightly over the edge of the second
separator and up to the edge of the V2O5. This sealing and the much
larger electrode area of the pouch cells likely reduced any electrolyte
contact between the anode and cathode around the edge of the V2O5
although formally the edge was still not sealed. The sealed
polyethylene bag was further sealed in a metallized bag. A schematic
of the assembly is shown in Supporting Information Figure S4.
Cycling was performed on a BT-2000 battery cycler (Arbin
Instruments) between 3.0 and 1.0 V. Some cells were charged to 3.0
V with a subsequent voltage hold at 3.0 V until the current decreased
by a factor of 10× or for a maximum of 5 h. A summary of the cells Figure 2. Secondary electron image of V2O5 layer on polymeric
tested is given in Supporting Information Table S1. battery separator. The sample was prepared by peeling a portion of the

■ RESULTS AND DISCUSSION

Achieving well-adhered crack-free V2O5 coatings is essential for
preventing polysulfide anion crossover. Using surfactant coated
polypropylene separators designed for aqueous electrolytes and
then, crucially, rinsing the separator with deionized water
enabled coatings with excellent adhesion. We speculate that the
rinse removed excess surfactant, enabling the sol to interact
with a monolayer of surfactant bound to the polypropylene.
Surfactant removal by the water was indicated visually by the
formation of stable bubbles in the rinsing solution and
chemically by FTIR spectroscopy following drying a sample
of the rinsed water. Complete wetting of the separator by the
water indicated retention of at least a monolayer of surfactant
because uncoated polypropylene separators are highly hydro-
phobic. The required duration of the rinse was determined by a
change in appearance of the separator from opaque to
translucent when sufficient surfactant was removed to permit
water to enter the pores. Without rinsing, the sol still wet the
separator well. However, the films cracked easily and exhibited
poor adhesion as expected for a mechanically weak thick
surfactant layer between the coating and the substrate. The
porosity of the separator was also important for adhesion. The
V2O5 coating must bridge the separator’s open pores. A
porosity of 41% (Celgrad 3401) gave well adhered coatings
while much poorer adhesion was found with a porosity of 55%
(Celgard 3501) likely because of cracks initiated over the larger
open pores. In addition to the substrate properties, the dilution
of the sol also affected adhesion. Coatings without diluting the
stock sol gave thick highly stressed layers, ∼5 μm per
application that adhered poorly. Dilutions of 1:2 or 1:3, sol
to deionized water, gave ∼0.5 μm thick layers per application
with good adhesion. Dilutions > ∼1:4 gave incomplete layers
even after multiple applications. Figure 2 shows a secondary
electron image of a V2O5 layer in cross section after two
applications of a 1:2 diluted sol on a water rinsed Celgard 3401
separator.
A portion of the layer was intentionally cracked and peeled
away from the separator to expose the cross section. Although
polycrystalline and rough, the layer is dense, nonporous, and
pinhole free. The thickness is uniformly ∼1 μm. Qualitatively,
the adhesion is good with no delamination at the fractured
interface. As shown, a shard of V2O5 remained attached to the
substrate where the layer fractured internally, not at the
interface. Additional images of the cross section and surface of
the film are shown in Supporting Information Figures S5 and
S6. The roughness originates from the holes and roughness of
layer showing the V2O5 surface, V2O5 cross section, and the separator
surface. The layer thickness is ∼1 μm. The arrow designates a portion
of the layer that fractured internally and remained adhered to the
separator.
the separator because layers deposited on glass are smoother
(Supporting Information Figure S6d). After deposition, the
coated separators, up to 10 cm × 10 cm, could be handled and
even moderately bent without peeling or noticeable cracking. In
addition, after wetting the barrier layer with the highly colored
polysulfide solution, no color was observed on the back,
uncoated, side of the separator.
Layers thinner than ∼0.5 μm did not sufficiently cover the
roughness and holes of the separator. However, only
commercial separators were tried as substrates. We expect
that layers with thicknesses of ∼0.1 μm should be possible on
separators with surfaces optimized for barrier layer deposition.
First cycle charge/discharge profiles of coin cells assembled
using bulk sulfur electrodes, with and without V2O5 lithium ion
conducting polysulfide anion barrier layers, are shown in Figure
3. Even for an extremely slow discharge rate of C/120 (1C =
1675 mA g−1), the discharge capacities for both cells are low
(<700 mA h g-sulfur−1) due to the relatively poor utilization of
sulfur in bulk electrodes. However, the capacity is greater with
the V2O5 layer suggesting that a portion of the poor capacity for
the cell without the layer originated from loss of sulfur,
Figure 3. Charge/discharge profiles of Li anode/bulk sulfur cathode
cells with and without V2O5 barrier layer. The first cycle is shown at a
rate of ∼C/120 (1C = 1675 mA g−1), a current of 14 mA g-sulfur−1.
Without the barrier (blue), the cell could not be recharged to 3.0 V.
Including the barrier (red) increases the discharge capacity and enables
recharging.

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presumably as soluble polysulfide. Upon charging without the
barrier layer, the voltage did not rise above 2.35 V.
This indicates a high rate of polysulfide anion crossover,
sufficient to continuously sustain a charging current of 14 mA
g-sulfur−1. Such crossover is not surprising for a bulk sulfur
electrode, which readily liberates soluble polysulfide anions into
the electrolyte. In contrast, using the same electrode with the
V2O5 polysulfide anion barrier layer, crossover appears to be
completely blocked. The voltage rises sharply to the 3.0 V
cutoff. Otherwise, the voltage profiles including the plateau
voltages of the two cells are similar, demonstrating that
inclusion of the V2O5 layer does not alter the cell character-
istics. For sufficiently thick V2O5 layers, > ∼5 μm, a plateau at
3.0 V from discharge of the V2O5 is noticeable (Supporting
Information Figure S7). From this plateau, we estimate the
capacity of an ∼1 μm thick layer to be small, ∼15 mA g−1, and
to occur only on the first cycle because the cells were only
charged to 3 V.
To investigate the full potential of using V2O5 barrier layers,
cells assembled with high capacity sulfur cathodes were tested.
These cathodes are less likely to degrade from mechanisms
such as volume expansion-induced cracking, enabling the
performance of the barrier to be studied. Figure 4 shows first
and second cycle discharge profiles and discharge cycling
behavior for three coin cells containing nanostructured
carbon−sulfur composite cathodes. Using constant current
cycling between 1.0 and 3.0 V (cell designated: Without hold),
Figure 4. Discharge profiles and capacity retention for cells containing
high capacity nanostructured carbon−sulfur composite cathodes and
V2O5 polysulfide anion barrier layers. (a) First and second cycle
discharge profiles at ∼C/20 (90 mA g−1) for cells charged to 3.0 V
(blue, labeled “Without hold”), charged to 3.0 V with a voltage hold at
3.0 V (green, labeled “With hold”), and containing Li2S8 added to the
cathode electrolyte and charged to 3.0 V with a voltage hold (red,
labeled “With hold and polysulfide addition”). (b) Fractional discharge
capacity retention relative to 100% on the first cycle for the cells in (a).
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first and second cycle discharge capacities of 1100 mA h g-
sulfur−1 and 800 mA h g-sulfur−1, respectively, were obtained.
The first cycle capacity is high, similar to other nanostructured
carbon−sulfur composite cathodes.12,14,16,20 These high
capacities likely originate from the nanoscale size of the sulfur
but also possibly from the relatively larger amount of electrolyte
in the lower areal loading of the nanostructured electrode.
However, although this cell charged without apparent crossover
(Supporting Information Figure S8), the second cycle capacity
is significantly degraded, only 73% of the first cycle. In the
absence of crossover, this degradation was likely due to
redistribution of sulfur within the cathode. To attempt to
recover an optimal distribution of sulfur, a constant voltage
hold was included upon reaching 3.0 V during charge. We
hypothesized that this voltage hold would permit low current
oxidative electrochemical deposition of sulfur that had been
chemically redistributed within the cathode. We note, however,
that low current cell charging also permits low-level crossover
to occur. The results in Figure 4 show some improvement with
the second cycle discharge capacity 84% of the first cycle.
Effective recovery of chemically redistributed sulfur may not
be possible if redistribution continually competes with recovery.
Another option that relies on the physical separation of the
anode and cathode electrolytes by the V2O5 layer is to modify
the cathode electrolyte to suppress net dissolution of
polysulfide anions. This may be accomplished by adding Li
polysulfide to the cathode electrolyte, which reduces the free
energy for dissolution. This cell shows (Figure 4) a high first
cycle capacity that actually increases on the second cycle. These
capacities are influenced by additional sulfur from the added
polysulfide, which was ∼30% of the sulfur in the cathode. This
amount is relatively high due to the relatively high amount of
electrolyte required for these laboratory cells. We estimate
needing ∼4× the amount of electrolyte used in a commercially
manufactured cell. Thus, optimally, the amount of added sulfur
would be <10%. Overall, the capacity during cycling (Figure
4b) increased and rate of capacity degradation decreased using
the added Li polysulfide and the 3.0 V constant voltage hold
with 80% capacity retention after ∼50 cycles.
For the coin cells in Figures 3 and 4, the various cell
components including the separator containing the V2O5 layer
were simply stacked, without trying to seal the edges. Thus,
crossover of electrolyte from the cathode to the anode could
still occur around the edges of the separator layers. While
developing techniques to seal the edges are beyond the intent
of this work, we sought to simply reduce the edge to area ratio
by using pouch cells with 2 cm × 2 cm electrode areas. Sections
of separator up to 3 cm × 3 cm were coated with V2O5 and
readily handled without cracking or delamination. Although still
not formally sealed, cells were assembled by heat-sealing a
polyethylene bag up to the edge of the V2O5 layer. Charge/
discharge profiles and cycling capacity and efficiency at ∼C/15
(100 mA g-sulfur−1) are shown in Figure 5. The plateau voltage
and slope are constant with cycling while the capacity increases
up to the third cycle. After approximately 20 cycles, the capacity
stabilized at 800 mAh g-sulfur−1 for ∼300 cycles performed
over ∼1 yr. This capacity includes the 30% additional sulfur
added as polysulfide to the cathode electrolyte. Fully including
this added sulfur gives a lower estimate of the capacity because
(1) likely not all of the added sulfur is active and (2) as
discussed above a commercially manufactured cell would have
much less electrolyte. Without accounting for the added sulfur,
the capacity would be 1025 mA h g-sulfur−1. A linear fit of the
dx.doi.org/10.1021/cm500575q | Chem. Mater. 2014, 26, 3403−3410
Chemistry of Materials
Figure 5. Behavior of long life 5 mA h Li−S pouch cell. The cell
contained a high capacity nanostructured carbon−sulfur composite
cathode, a V2O5 polysulfide anion barrier layer, and Li2S8 added to the
cathode electrolyte and was charged with a voltage hold at 3.0 V. (a)
Charge/discharge profiles at C/15 for selected cycles, as labeled. The
capacities do not include the sulfur added to the electrolyte. (b)
Discharge capacity and efficiency over 250 cycles collected during ∼1
yr. This capacity does include the 30% additional sulfur added as Li2S8.
capacity over 225 cycles actually showed a slight increase of
0.002% per cycle. The efficiency (discharge capacity/recharge
capacity) including the constant voltage hold at 3.0 V is ∼82%.
This efficiency is low due to parasitic side reactions during the
voltage hold. This hold occurred at currents down to as low as
C/150, which greatly facilitates reactions that reduce the
efficiency (see discussion below). We note that the usefulness
of the voltage hold when using the added Li polysulfide is
uncertain. Several cycles (∼20) run without the hold showed
little change in the established trend. Without including the
integrated current during the hold, the efficiency is ∼95%.
The cycling behavior shown in Figure 5 was intentionally
conducted at a relatively low rate (C/15) and over an extended
time to enhance the influence of any polysulfide crossover,
thereby highlighting the efficacy of the V2O5 layer. As shown in
Figure 6, at cycling rates up to C/1.5, the capacity decreased
from 800 mA h g−1 to 480 mA h g−1 but fully recovered upon
reducing the rate to C/15. This moderate rate capability is
assuring considering (1) that the V2O5 was relatively thick,
because it was deposited on a commercial separator that was
not designed to be a layer substrate; and (2) the conductivity of
the carbon scaffold used for the sulfur cathode was not
optimized for high rates. As discussed above, use of separators
optimized for deposition of lithium conducting layers may
allow 10× thinner layers (∼0.1 μm) to be used. This would
significantly reduce any rate limitations from the V2O5 layer.
Finally, while the capacity was reduced, the efficiency at C/1.5
increased to 99% including a voltage hold to C/15. This
3408
Article
Figure 6. Cycling rate behavior of Li−S pouch cell. The cycling shown
in Figure 5 was continued with varying charge and discharge rates.
After cycling at C/15 for 275 cycles, approximately 10 cycles were
performed at C/7.5, C/3, C/1.5, and C/15, as labeled. For each charge
cycle, the voltage was held at 3.0 V until the charge current decreased
by 10×. (a) Selected discharge profiles. (b) Discharge capacity
including the added sulfur and efficiency.
substantiates that the low efficiencies at C/15 were significantly
influenced by low current side reactions.
The majority of the capacity degradation with increasing rate
shown in Figure 6a occurred in the second plateau, beginning at
∼300 mA h g-sulfur−1. This indicates that the capacity was
likely limited by the formation of electrically insulating phases,
such as Li2S2 and Li2S, within the cathode and not flux of Li+
through the V2O5 layer. However, both plateau voltages also
decreased, which may be an indication of the V2O5 layer
resistance. On the first discharge plateau, at a capacity of 50 mA
h g-sulfur−1 (∼2.3 V), the decrease in voltage is ohmic with a
resistance of 24 Ω (Supporting Information Figure S9). At the
beginning of the second plateau, 300 mA h g-sulfur−1 (∼2.0 V),
the resistance is 33 Ω (Supporting Information Figure S9).
Considering the concentration dependence of the Li
diffusion coefficient in the V2O5 layer reveals the origin of
the cell resistance and the operation of the barrier layer. For Li
concentrations, x, in LixV2O5 from ∼0.5 to 3, the diffusion
coefficient for Li varies from ∼4 × 10−9 cm2 s−1 to 3 × 10−12
cm2 s−1.36 Using this dependence and the Nernst−Einstein
relation, we calculate that, for a 1 μm thick layer, the resistance
varies from 1 Ω (at x = 0.5) to 200 Ω (at x = 3). This
calculation is described in detail in Supporting Information
Figure S10. From the V2O5 discharge curve in ref 36, the Li
content of the V2O5 is x = 2.0 at the first Li/S plateau (2.3 V)
while for the second plateau (2.0 V), x = 2.3. At x = 2.0 the
calculated resistance of a 1 μm thick V2O5 layer is 10 Ω; for x =
2.3 the resistance is 30 Ω. The similarity of the calculated V2O5
layer resistances and measured cell resistances suggest that a
significant portion of the cell resistance originates from the
dx.doi.org/10.1021/cm500575q | Chem. Mater. 2014, 26, 3403−3410
Chemistry of Materials
V2O5 layer. Furthermore, the Li content and thereby the
diffusion coefficient and resistance of the barrier vary as the
sulfur cathode charges and discharges. This is the expected
behavior given that the V2O5 is a Li cathode material and that it
is electrically connected to the sulfur. Finally, the behavior of
the Li diffusion coefficient with Li content, ref 36 and
Supporting Information Figure S10, indicate that lower
resistances are possible. Isolating the barrier (Supporting
Information Figure S1b) and fixing the Li concentration in
the barrier at x ∼ 0.5 would reduce the resistance to ∼1 Ω.
Thus, both the thickness and the cell design may be further
optimized to reduce the barrier layer resistance to levels that
should not limit cell performance.
After completing the cycling shown in Figure 6, the cell was
disassembled in order to look for any physical evidence for
sulfur crossover through the V2O5 barrier layer. Upon peeling
up the Li foil anode (Figure 1g) and the second separator
(Figure 1f) there was no visual evidence of sulfur deposits in
the anode electrolyte. In addition, UV spectroscopy of
tetraethylene glycol dimethyl ether (tetraglyme) in which a
piece of the second separator was soaked showed no discernible
signature from polysulfide anions, although this measurement
was not quantified. Finally, energy dispersive X-ray (EDX)
elemental analysis was conducted on the dried second
separator. Sulfur was detected, but this sulfur appeared to
originate from the LiTFSI electrolyte because the sulfur to
fluorine elemental ratio was equal to the ratio for a piece of
pristine separator soaked in LiTFSI solution (the TFSI anion
contains both sulfur and fluorine in a 1:3 atomic ratio). Overall,
after being assembled for >1 yr and undergoing >300 cycles, no
clear indication of sulfur crossover was seen.
The effectiveness of V2O5 (or LixV2O5) as a polysulfide anion
barrier suggests the possibility that other diffusion barriers
could be formed from dense (pinhole-free) films composed of
fast Li+ conductors, such as conventional electrodes (e.g.,
lithiated carbon) or solid electrolytes (e.g., LiPON).
Importantly, this concept of dividing the cell and restricting
electrolyte crossover to Li+ ions may be used to improve
capacity retention in more conventional lithium cells. For
example, when paired with graphite, a number of high-energy
lithium batteries suffer from severe capacity fade due to the
dissolution and crossover of transition metal ions from the
cathode (e.g., Mn2+, Ni2+, Cu2+).39−41 This problem is
particularly acute with the Mn-based cathodes, which have a
tendency to form soluble divalent Mn cations during cycling.
Although there is some debate over the mechanisms involved,42
the interaction of Mn2+ with the graphite surface increases the
loss of active Li+ (attributed to side reactions with the
electrolyte), forms a thicker, more resistive solid electrolyte
interphase, and results in significant capacity fade.43 Implement-
ing a barrier layer by, for example, coating the separator with a
thin lithium ion conductor would be a simple and effective
method of eliminating the unwanted cation crossover and
thereby improving capacity retention.
In addition to preventing unwanted ion crossover, the use of
a solid-state Li+ conducting barrier also enables divided cell
architectures, providing a potentially useful extension of
traditional battery designs. For example, in addition to
separately optimizing the anode and cathode electrolytes, as
described in this work, different organic solvents could be used
for each electrolyte. This could enable higher voltage Li/metal-
oxide cells with different electrolyte solvents compatible with Li
metal anodes and high voltage cathodes, respectively. Another
3409
Article
example could be a combined aqueous/organic solvent-based
battery34,35 if the layer material was compatible with both
electrolytes. These designs may be further extended to cells
with dissolved or liquid cathodes. Addition of polysulfide to the
sulfur cathode described here is to some extent along these
lines because the Li2S8 added to the electrolyte can function as
a dissolved cathode.44,45 Use of dissolved or liquid cathodes
enables extension to flow battery designs10 where a reservoir of
cathode material maybe distantly separated from the separator
and the anode, a design with inherent safety advantages.
■ SUMMARY
In summary, we have described a micrometer-scale V2O5
barrier layer to separate the anode and cathode electrolytes of
an organic electrolyte Li−S battery. This layer stops diffusion of
dissolved polysulfide anions between the sulfur cathode and the
Li anode while permitting solid-state transport of Li+ cations.
Blocking diffusion of polysulfide anions to the Li anode
eliminates polysulfide anion crossover, which is one of the
major degradation mechanisms that plague Li−S batteries.
Separation of the anode and cathode electrolytes also enables
each electrolyte to be optimized individually. We optimized the
cathode electrolyte with the addition of Li2S8 to reduce
redistribution of sulfur within the cathode. The required
mechanical integrity of such a thin V2O5 layer was achieved by
coating the layer on one side of a commercial polymeric battery
separator. We implemented this design with a high capacity
nanostructured carbon−sulfur composite cathode based on a
nanoporous carbon foam. A 2 cm × 2 cm pouch cell was
demonstrated that cycled with a capacity of 5 mA h (800 mA h
g-sulfur−1) without noticeable degradation for >300 cycles over
∼1 year.
■
*
ASSOCIATED CONTENT
S Supporting Information
Alternate cell configurations, SEM images of the carbon foam
and pore size distribution plots, SEM images of the V2O5 layer,
and additional cell discharge profiles. This material is available
free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jjvajo@hrl.com (J.J.V.).
Present Addresses
†
MK Tech. Ltd., Suzhou, Jiangsu Province, 215125 China
(J.L.).
‡
Advanced Research Projects Agency - Energy (ARPA-E), 1000
Independence Avenue Southwest, Washington, DC 20585,
United States (P.L.).
Notes
The authors declare no competing financial interest.
■
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