A1084 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)

0013-4651/2018/165(5)/A1084/8/$37.00 © The Electrochemical Society

Symmetric Lithium Sulfide – Sulfur Cells: A Method to Study

Degradation Mechanisms of Cathode, Separator and Electrolyte
Concepts for Lithium-Sulfur Batteries
Markus Piwko, 1,2 Christine Weller,1,2 Felix Hippauf,1 Susanne Dörfler,1 Holger Althues,1
and Stefan Kaskel1,2,z
1 Fraunhofer Institute for Material and Beam Technology IWS, 01277 Dresden, Germany
2 Department of Inorganic Chemistry, Dresden University of Technology, 01062 Dresden, Germany

Novel cathode, electrolyte and separator concepts are expected to improve the capacity retention and cycle life of lithium-sulfur
batteries by avoiding the dissolution of polysulfide-intermediates into the electrolyte or preventing their diffusion to and reaction with
the lithium metal anode. However, their intrinsic evaluation is obscured by ill-defined degradation mechanisms of the lithium counter
electrode due to electrolyte and polysulfide consumption during reformation of the solid electrolyte interface. Herein, we introduce
symmetric lithium sulfide – sulfur cells to study the “cathode" specific degradation mechanisms of the cathode/electrolyte/separator-
system in order to differentiate cathode-, separator, and electrolyte and lithium metal anode degradation. Two identical carbon/sulfur-
composite cathodes, either of them one at first lithiated versus lithium, are assembled in a coin cell versus each other. The virtue of this
test cell design is demonstrated evaluating prime shuttle-suppression concepts, namely a Nafion-coated polyolefin separator and a
sparingly polysulfide-solvating electrolyte. We conclude that symmetric lithium sulfide – sulfur cells provide a valuable methodology
to analyze the intrinsic capacity decay and cycle life of cathodes for lithium-sulfur cells with limited solvation and/or blocking of
polysulfides, and it is an essential strategy to distinguish cathode from lithium anode degradation.
© 2018 The Electrochemical Society. [DOI: 10.1149/2.1131805jes]

Manuscript submitted January 2, 2018; revised manuscript received February 22, 2018. Published April 7, 2018.

Today’s trends in the automotive and aviation sector toward elec-
tric vehicles or drones, lead to a fast growing demand on low-cost and
high density energy storage in secondary batteries. Lithium-sulfur bat-
teries (LSB) are expected to exceed commercial lithium-ion batteries
(LIB) in both, due to cheap, global availability and the high theoret-
ical specific capacity (1675 mAh gsulfur −1 ) of the non-toxic sulfur.1
Although the average cell voltage is decreased to 2.15 V, this results
in an outstanding theoretic specific energy of 2.600 Wh kg−1 for LSB
compared to about 1.000 Wh kg−1 for LIB.2 Latest prototype cells
of Oxis Energy Ltd. with 400 Wh kg−1 practically support the high
prospects.3 However, the commercialization of LSB is still impeded
by the fast capacity loss which limits the cycle life of high energy
density cells below 50 cycles.
In ordinary LSBs, the electrical insulating discharge (Li2 S)
and charge (S8 ) products are formed by a complex dissolution-
precipitation mechanism of polysulfide (PS)-intermediates with high
solubility in the electrolyte.4 This results in a combination of various
degradation mechanisms which are difficult to distinguish from each
other. On the cathode side, the formation of insulating layers (Li2 S
or S8 ) on the electrical conducting carbon scaffold can decrease the
charge transfer rate and limit the active material utilization.5,6 The vol-
ume expansion during the lithiation of sulfur can even enhance this
effect by structural damaging the carbon scaffold.7 In the electrolyte,
a high PS-solubility can lead to irreversible extraction of sulfur from
the cathode, again causing severe capacity loss.8 Additionally, if the
solid electrolyte interface (SEI) at the anode is not sufficiently estab-
lished and/or not stable (typically for pure lithium metal), sulfur from
PS-intermediates can be lost by reduction to Li2 S or by incorpora-
tion during SEI reformation.9 Moreover, the reduction of solvents by
the highly reactive lithium surface can lead to gas evolution, increase
the cell impedance, and eventually cause a complete cell dry out.10
Consequently, significant research efforts have been undertaken to im-
prove each component of a lithium-sulfur cell to enhance the capacity
retention and cycle life.
In particular, after porous carbon materials had been introduced as
electronically conductive host for sulfur by Nazar et al., LSB-research
focused on improving the cathode host structure.11 Many publications
addressed specific tailoring of the carbon matrices and its porosity
in order to confine polysulfides inside the cathode structure.12–14 Be-
side the tailoring of carbon structures, other strategies to minimize
z
E-mail: Stefan.Kaskel@chemie.tu-dresden.de
the polysulfide shuttle effect have been followed so far: By tailoring
the void-structure with a yolk (sulfur) – shell (TiO2 ) nanoarchitecture,
1.000 cycles were demonstrated with capacity decay as low as 0.033%
per cycle, due to accommodation of the volume expansion of sulfur
during lithiation without damaging the scaffold structure.15 Sulfur
confinement in micropores was identified to effectively avoid PS dis-
solution in the electrolyte, changing the discharge/charge mechanism
presumably to a solid-solid transformation.16 Novel electrolyte com-
positions with sparse or even highly limited PS-solvation are expected
to overcome irreversible sulfur extraction from the cathode to the elec-
trolyte in general.17 Furthermore, ceramic or Nafion coated separators
with selective lithium ion conduction can minimize PS diffusion to
the lithium anode to a certain degree and hence, minimize irreversible
reduction.18–21 Altogether, many concepts were established to avoid
capacity decay through improvement of the cathode structure, elec-
trolyte composition and separator coatings. However, the success of
each concept is difficult to compare as the electrodes and test proce-
dures vary extremely for the respective reports. Sulfur loading, sulfur
content, electrolyte amount and current rate have a strong influence
on sulfur utilization, capacity degradation as well as cycle life.22
Electrodes with practical relevance should have a capacity loading
of several mAh cm−2 .23 Since the limit of LIB with graphite anodes in
terms of energy density may be reached soon, researchers refocus on
lithium metal anodes in order to reduce inactive weight.24 However, to
the best of our knowledge, there is no commercial viable concept to cy-
cle lithium metal anodes at high capacity loadings without continuous
dendrite and SEI formation.24,26,27 Thus, lithium metal anodes, even
with high excess, do not serve as a suitable counter electrode to an-
alyze novel cathode, electrolyte or separator concepts. They strongly
influence the cell performance through electrolyte decomposition and
finally lead to complete cell dry-out.25 High electrolyte amounts can
delay these effects, but first of all lead to a lower sulfur utilization due
to a higher concentration gradient leading to an increased polysulfide
diffusion tendency, and secondly, such test cells are too distant from
practically relevant LSB cell designs, requiring very low electrolyte
amounts of less than 3 μL mg−1 s to reach a high specific energy.28
Galvanostatic cycling of carbon/sulfur (C/S) composite cathodes
in half cells versus metallic lithium impedes clarification, whether
the capacity fade results from cathodic (e.g. pore blocking) or anodic
(e.g. sulfur incorporation in the SEI) degradation effects. In partic-
ular for novel electrolytes with low polysulfide solubility and high
prospects to increase the energy density of LSB by reducing the re-
quired electrolyte amount, the reversibility of the desired conversion

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 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)
reactions is a contentious issue. To overcome the disadvantages of
lithium metal as counter electrode and in order to study intrinsic
degradation mechanisms of sulfur cathodes, in the following we de-
scribe for the first time a symmetric lithium sulfide – sulfur cell-test.
The virtue of symmetric Li-ion cells having the same material as the
positive and negative electrode has been recently pointed out by Burns
et al. to provide vast information about reactions between electrode
materials and electrolyte.29
In the following we analyze electrolytes with high polysulfide sol-
ubility based on DME and DOL as solvents vs. sparingly polysulfide
solvating electrolytes in a symmetrical cell, Lix S|(Li+ )n Sx n− |S. With-
out the hereby eliminated sulfur loss and electrolyte decomposition
at a lithium anode, for a sparingly solvating electrolyte the capac-
ity loss is reduced from 3.6 mAh g−1 s per cycle in the half cell to
0.18 mAh g−1 s per cycle. Moreover, a cycle life of over 800 cycles
at 75% capacity retention related to the first cycle is demonstrated.
Our study clearly reveals sparingly solvating electrolytes to guarantee
highly reversible conversion of sulfur to lithium sulfide. The method-
ology provides insights into the intrinsic C/S-cathode degradation
mechanisms and enables identification of the actual bottlenecks of the
LSB cycle life.
Experimental
Preparation of electrodes.—The cathode preparation was carried
out according to a procedure reported before.30 In brief, sulfur (Sigma
Aldrich, ≥99.5%) and carbon black (Printex XE-2B, Orion Engi-
neered Carbons) were mixed in a weight ratio of 12:5, followed by a
melt-infiltration step under ambient conditions at 155◦ C. The slurry
was prepared by adding 5% CMC/SBR SBR (carboxy methylcellu-
lose/ styrene butadiene rubber)-binder and 10% multiwalled carbon
nanotubes (Nanocycl NC 7000, 90%) as conductive additive in deion-
ized water. After coating the slurry on battery-grade aluminum foil
(MTI Corp., >99,9%, 15 μm) using a comma-bar technique, the
cathode film was pre-dried using a 70◦ C/90◦ C gradient in air and
final-dried for 1 h at 50◦ C under vacuum. The cathode had a typical
density of 0.4 g cm−3 and a loading of approximately 2.5 mgcathode
cm−2 , which corresponds to 1.5 mgS cm−2 (based on the 60% sul-
fur share in the cathode). Test samples were cut out by punching the
electrodes in 12 mm disks.
Hard carbon anodes were prepared by doctor-blading of a slurry
containing 90 wt% commercial hard carbon powder (HC; Carbotron
P; Kureha GmbH), 5 wt% MWCNT and 5 wt% styrene butadiene
rubber (SBR; 15 wt% in water; Targray) onto a copper foil (SE-Cu
58, Schlenk GmbH, 10 μm). After drying overnight at 25◦ C in air,
circular electrodes (Ø 12 mm) were punched out. The electrodes had
a typical weight of 12.8–13.8 mg cm−2 and were dried for 12 h under
vacuum at 80◦ C before cell assembly.
Preparation of Nafion-coated separator.—The preparation of a
Nafion-coated polyolefin separator was performed by slot-dye proce-
dure (wet film thickness: 35 μm) in a roll-to-roll process (0.3 m min−1 )
from LITHion Dispersion (10 m-% Li-Nafion, Ion Power Inc.) and
dried at 40◦ C for 15 min in air. A dense and smooth Nafion film with
a loading of 0.3 mg cm−2 was achieved. The Nafion-coated separator
disks (Ø 19 mm) were punched out and dried at room temperature
under vacuum for 30 min before they were used.
Cell assembly and electrochemical testing.—For the half-cells,
the carbon/sulfur cathode were assembled with 8 μL mgs −1 elec-
trolyte in a coin cell (MTI Corp., CR2016) under argon atmo-
sphere (MBraun glove box, < 0.1 ppm O2 and H2 O) versus a
lithium chip (MTI Corp., 99.0%, diameter: 15.6 mm, thickness:
250 μm) as the reference/counter electrode separated by a poly-
olefin separator. The D/D - electrolyte consisted of 1 M lithium
bis(trifluoromethylsulfonyl) imide (LiTFSI, Sigma Aldrich, 99.95%)
+ 0.25 M lithium nitrate (LiNO3 , Alfa Aesar, 99.98%, anhy-
drous) in 1,2-dimethoxy ethane (DME, Sigma Aldrich, 99.5%, an-
hydrous) and 1,3-dioxolane (DOL, Sigma Aldrich, 99.8%, anhy-
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A1085
drous) with a solvent-ratio of 1:1, by volume. The T/T - elec-
trolyte consisted of 1.5 M lithium bis(trifluoromethylsulfonyl) imide
(LiTFSI, Sigma Aldrich, 99.95%) in sulfolane (tetrahydrothiophen-
1,1-dioxide, tetramethylensulfone, TMS, 99% Sigma Aldrich) and
1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE, 99%,
Synquest Labs) with a solvent-ratio of 1:1, by volume. The half-
cells were cycled with a rate of C/10 (1C = 1672 mA g−1 S ) between
2.6 V and 1.8 V for D/D- and between 2.6 and 1.5 V for T/T- elec-
trolyte. For T/T-electrolyte, a slow C/20 formation cycle to 1.5 V was
carried out initially. A BaSyTec Cell Test System (CTS) was used for
galvanostatic cycling measurements at 24◦ C (± 2◦ C).
For the lithiated hard carbon-sulfur cell, the hard carbon anode was
prelithiated in T/T-electrolyte versus lithium with one full cycle and
on discharge/lithiation cycle by a constant current – constant voltage
(CC-CV) procedure: CC discharge at 0.2 mA cm−2 to a voltage of
10 mV vs. Li/Li+ plus CV step to a current of 0.04 mA cm−2 and
CC charge at 0.2 mA cm−2 to a 1.5 V vs. Li/Li+ . After disassembling
this cell, the lithiated hard carbon was reassembled as anode versus
the C/S-cathode analogous to half-cells. The cycling was carried out
at C/10 between 2.6 V and 0.5 V. A CV step to 0.04 mA cm−2 was
implemented at 2.6 V during charge.
For the symmetric cells, a typical half-cell was assembled with the
electrolyte of the latter symmetric cell. After 1 cycle and a followed
discharge, the lithiated electrode was recovered by cell-disassembling
and reassembled without washing (to avoid wash out of sulfur as
polysulfides) versus a C/S-cathode with similar mass loading (max.
deviation ± 0.1 mg/cm2 ). Again 8 μL mgs −1 (with respect to the total
sulfur mass in both electrodes) were used as electrolyte amount. The
symmetric cells were cycled at C/10 (1C = 1672 mA g−1 S ) related
to the C/S-electrode between the calculated cutoff cell voltage. The
specific capacity of the symmetric cells is always related to the sulfur
mass of the C/S-electrode only. The CE is calculated as discharge
capacity (lithiation of the initial S8 -electrode) over charge capacity
(delithiation of the initial S8 -electrode) multiplied by 100%.
Results and Discussion
Recently, a novel electrolyte with reduced polysulfide solubility
based on sulfolane (TMS) and a fluorinated ether (TTE) was discov-
ered with promising performance for lithium-sulfur batteries using
either lithium or lithiated silicon as anode.30,31 In order to study the
cycling stability and possible degradation effects for this sparingly
PS-solvating electrolyte system (T/T) in comparison to a conven-
tional electrolyte based on DME/DOL (D/D), initial test-cells were
set-up with C/S-cathodes, Li-metal anodes and 8 μL mgs −1 elec-
trolyte. For both electrolytes we observe a continuous capacity fade
(loss of 3.6 mAh g−1 s or 0.34% per cycle) (Figure 1a), but there
are obvious differences observed for the coulombic efficiency (CE).
Firstly, for the cell with T/T-electrolyte, after the first formation cy-
cle the CE stabilizes at an almost constant value (96%). In contrast,
for D/D the CE decreases from 98.1% (cycle 5) to 93.1% (cycle
175). This can be attributed to the decomposition of the SEI-forming
additive LiNO3 during cycling resulting in an enhanced polysulfide
shuttle.32 Secondly, while the cell with D/D-electrolyte completely
failed after about 200 cycles due to dry out, the cell with T/T is still
cycling.
The discharge voltage profiles highlight the differences between
both electrolyte compositions (Figures 1b, 1c). The first discharge
plateau, which is directly related to the concentration of dissolved
long-chain PS), is remarkably shortened for the T/T-electrolyte. To
illustrate the reduced polysulfide solubility and analyze the influence
on the lithium metal anode, the half-cells with both electrolytes were
disassembled after 100 cycles (Figure 2). For the T/T-electrolyte,
the separator showed only slight yellowish discoloration, while the
orange discoloration indicates a higher polysulfide accumulation in
the D/D-electrolyte.8 The greyish surface of the lithium metal an-
ode cycled in T/T-electrolyte is a clear indication for corrosion side
reactions, while the surface of the lithium metal anode cycled in D/D-
electrolyte exhibits much less discoloration. The reduced solubility of
 A1086 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)
Figure 1. The specific discharge capacity and coulombic efficiency (CE) with
D/D- and T/T–electrolyte (a) and their respective discharge voltage profiles for
C/S-cathode in half cells versus lithium metal anode with D/D- (b) and T/T-
(c) electrolyte.
polysulfides is responsible for the high cycle stability of T/T-
compared with D/D-electrolyte in high energy density pouch
cells.31
However, the electrochemical performance of the battery is af-
fected by both, anode and cathode chemistry. Analyzing the voltage
profiles of the half cells (Figures 1b, 1c), no increase in the overpo-
tential during cycling is observed for T/T-electrolyte. Thus, one may
rule out the formation of insulating Li2 S or S8 layers on the cathode,
independently also confirmed by analyzing residual porosity in cy-
cled cathodes via nitrogen physisorption.33 A further value extracted
here from the voltage profiles is the ratio of the capacity in the first
Figure 2. Lithium metal anode (left) and separator (right) of half cells with
T/T- (a) and D/D- (b) electrolyte after 100 cycles.
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Figure 3. The specific discharge capacity and CE of C/S-cathode versus
lithium metal and versus lithiated hard carbon anode with T/T-electrolyte.
plateau (until the voltage knee) and the second plateau (until the end
of discharge). For the cell with D/D-electrolyte, the ratio is 2.2 in
the first cycle dropping down to 1.75 (- 21%) in cycle 150. For the
cell with T/T-electrolyte, the ratio is 6.8 in the first cycle and 3.62
(- 47%) in cycle 150. Thus, for T/T the capacity loss is faster in the
second plateau while the capacity for D/D-electrolyte is rather lost in
both plateaus. Therefore, we assume a high and complex dependency
of this ratio from electrolyte characteristics and electrolyte specific
degradation mechanism like: sulfur losses at the cathode (pore block-
ing, insulation films), the anode (sulfur incorporation in the SEI) or
in the electrolyte (wash out of PS) and electrolyte decomposition
(reduction of the liquid electrolyte amount in the cell-stack by gas
formation).
Thus, it is likely that different degradations mechanisms are the
reason for the (similar) overall values of capacity fade of half-cells
with D/D- and T/T-electrolyte. We conclude that half cells with lithium
metal are not suitable to study the reversibility of the conversion of
sulfur to lithium sulfide in sparingly solvating electrolytes due to the
influence of anodic degradation mechanisms.
In order to achieve a deeper understanding of the lithium anode
contribution to the observed degradation effects, the substitution of
the lithium anode by a lithiated hard carbon anode is a promising
approach.34 Due to the low volume change of hard carbons during
lithiation/delithiation, the SEI is much more stable than on metallic
lithium. Thus, fewer polysulfides are consumed for SEI reformation.
A higher CE is observed and the capacity fade of a C/S-cathode versus
lithiated hardcarbon anode in the T/T-electrolyte is lower compared
to the conventional half-cell (Figure 3). Despite the advantages of
hard carbons suppressing the superimposed degradation of metallic
lithium, that system does not fully exclude degradation mechanisms
and side reactions at the hard carbon anode.
A symmetric cell design instead offers the possibility to study
the degradation mechanism of the cathode without any anodic
influences.29 In the symmetric sulfur cell setup, proposed here, two
C/S-“cathodes” with identical composition and comparable active ma-
terial loading and porosity were chosen. One of them was assembled
in a typical half-cell versus lithium counter electrode and electro-
chemically lithiated to form Li2 S in a controlled manner in order to
create a pseudo-anode with identical porosity and morphology as the
non-lithiated sulfur cathode. Hereafter, the lithiated C/Li2 S-electrode
was reassembled versus the non-lithitated C/S-electrode, resulting in
the symmetric lithium sulfide – sulfur cell setup. In this setup the cell
voltage approaches zero and is practically useless, but the superim-
posed degradation mechanism of lithium metal causing capacity fade
are eliminated.
To allow a comparable test procedure to the conventional half-
cell system, the cutoff cell voltages have to be adopted for D/D- and
T/T-electrolyte (Figures 4a, 4b). They can be calculated by subtrac-
tion of the upper and lower cutoff potentials of the half cells with
lithium metal anode as they have been chosen to allow full lithia-
tion and delithiation of sulfur. Because the electrodes have similar
capacity loading, the calculated upper and lower cell voltage in the
symmetrical system have the same values, only with opposite sign.
 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)
In the same manner, the expected cell voltage plot during delithiation
of the C/Li2 S-electrode and lithiation of the C/S-electrode can be cal-
culated by the subtraction of the delithiation and lithiation plots of
half-cell measurements and are symmetric for both current directions
(“charge”/”discharge”) (Figures 4c, 4d).
We assume that the lithium-sulfur system is ideal for the symmetric
cell setup, due to its unique discharge and charge voltage profiles. The
rapid potential rise/decay when the final charge (S8 ) or discharge
(Li2 S) products are reached will result in an even higher slope of the
cell voltage compared to the potential slope in half cells. Therefore,
the end of the lithiation/delithiation processes of the active material
in the symmetric cell is very well defined. Thus, side reactions by
decomposition of electrolyte components (e.g. LiNO3 ) below 1.8 V
or above 2.6 V vs. Li/Li+ will become visible by a further plateau or
a less steep voltage cutoff.
The main issue of symmetric lithium sulfide – sulfur cells is the
dissolution and diffusion of sulfur as polysulfides in the electrolyte and
the precipitation as sulfur or lithiumsulfide at the opposite electrode
leading to unrealistic capacity values given that only the originally ad-
justed sulfur loading is taken for the calculation of the capacity values.
High polysulfide solubility can lead not only to exchange of sulfur as
active material, but also to reactions between polysulfides from both
electrodes and to polysulfide shuttle (Figure 5a). Experimentally, a
symmetric lithium sulfide – sulfur cell with D/D-electrolyte and con-
ventional porous polysulfide permeable separator does not reach the
cutoff cell voltages within the theoretic capacity of sulfur as already
mentioned above (Figure 5b). Interestingly, during the first “recharge”
process, the cutoff cell voltage was almost reached but at nearly the
double capacity as for a half cell. This suggests that sulfur of both
electrodes can be used as active material due to the exchange by poly-
sulfides based on a concentration gradient. In the subsequent cycles,
this phenomenon was not observed again though, probably because
the polysulfide concentration in the electrolyte was saturated by dis-
solution resulting in an enhancement of the charge balancing shuttle
process.
The shuttle of polysulfides can be suppressed introducing of a
Nafion-coated separator.20 Due to the negatively charged SO3 − groups
this polymer is a lithium-ion selective conductor. Thus, the charac-
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A1087
Figure 4. Adjustment of the cutoff voltages in the symmet-
ric cells based on half-cells with lithium metal anode (a, b)
and resulting cell voltage plot of a symmetric cell for D/D-
(c) and T/T-electrolyte (d).
teristic electrochemical reactions during charging (Li2 S to S8 ) and
discharging (S8 to Li2 S) are separated in the electrode-electrolyte sys-
tem on both sides of the cell. Only the lithium-ions are exchanged
from the initially Li2 S- to the initially S8 -electrode to drive the elec-
trochemical oxidation and reduction reactions (Figure 6a). Due to the
drastic reduction of the polysulfide shuttle and sulfur active mate-
rial exchange between the electrodes hereby the calculated cutoff cell
voltage is reached (Figure 6c). This indicates the complete conversion
of Li2 S and S8 , respectively, resulting in the rapid increase/decrease of
the potentials versus Li/Li+ at the end of charge/discharge. Moreover,
reasonably high capacity values (1109 mAh/g in cycle 1 Figure 6)
reveal ideal separation of catholyte and anolyte.
To monitor the electrode potentials versus Li/Li+ , a third reference
electrode may be used. However, we have not used this approach so
far, as it might be scope for future work since the required higher elec-
trolyte amount would also influence or rather change the concentration
gradients and cell chemistry.22
During cycling, the symmetric cell containing D/D-electrolyte and
Nafion-coated separator showed a similar capacity decrease compared
to the half-cell versus lithium (Figure 6b). This indicates that in the
typical D/D-electrolyte system with high polysulfide solubility, ca-
thodic degradation mechanisms such as irreversible precipitation of
Li2 S or sulfur are most probably the main reasons for the capacity fade
in the first cycles (until about cycle 100).6 However, during longer cy-
cling, the electrolyte decomposition by SEI-reformation at the lithium
anode dominates the capacity fade until the complete cell dry out. In
the symmetric cell, this cell dry out was avoided and the capacity fade
continued linearly due to cathodic degradation only. By suppressing
the polysulfide shuttle, the CE was increased from maximum 98.1%
(cycle 5) if the half cell to about 100% in the symmetric cell. The slight
deviation of ± 0.4% may result from slight temperature changes, as
the cell was cycled in a climate controlled room, where changes be-
tween ± 2◦ C are possible. Further measurements should be carried
out in a climate chamber with stable temperature control to allow
an interpretation of the CE in regard to the capacity fade. Neverthe-
less, the CE during the first cycles, between 106.4% (1st ) and 100.7%
(5th ), implies enhanced losses in the beginning of cycling which might
be attributed to several effects, e.g. irreversible Li2 S-formation at the
 A1088 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)
uncycled S8 -cathode, irreversible dissolution of sulfur active material,
or reaction of lithium-ions with trace water impurities.
The enlarged view of the capacity and potential around the volt-
age knee in the discharge voltage profile reveals more details of the
degradation effects of the symmetric cell (Figure 6d). During the
entire cycle life, the capacity of the first discharge plateau does not
change significantly indicating a constant polysulfide concentration in
the electrolyte. However, the capacity of the second discharge plateau
drops and the cell impedance increases, leading to an overall increas-
ing overpotential (about 100 mV at the voltage knee from cycle 2 to
cycle 500). A well accepted degradation mechanism for LSB-cells
explaining this behavior is the agglomeration of the electrical insulat-
ing discharge (Li2 S) and/or charge (S8 ) products as particles/films at
the electrode surface grow.33 Thereby sulfur species become electro-
Figure 6. Symmetric lithium sulfide – sulfur cell with Nafion-coated sepa-
rator: Scheme of separated reduction/oxidation reactions of polysulfides (a),
specific discharge capacity and CE versus cycle number compared to half-cell
tests (b), corresponding voltage profiles of symmetrical cell charge/discharge
(c), and detailed exposure of the respective discharge profiles (d).
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Figure 5. Schematic representation of sulfur active material ex-
change and charge balancing (a) and the plot of the cell voltage
over specific capacity (b) for a symmetric lithium sulfide – sulfur
cell with a high polysulfide soluble electrolyte (D/D-electrolyte) and
porous separator.
chemically inactive and can increase the cell impedance by blocking
the carbon porosity and, hence, active surface area for the electron
transfer from the carbon scaffold to the sulfur species. Thus, the in-
sufficient reversibility of the conversion reactions in the carbon/sulfur
cathode in the D/D-electrolyte is limiting the capacity retention of
LSB-cells. However, the cell dry out can be attributed to electrolyte
decomposition at the lithium metal anode.
An alternative concept to improve the cycle life of LSB by re-
ducing PS shuttle is the use of electrolytes with reduced polysulfide
solubility.8,17,31,35 As the formation and diffusion of long-chain poly-
sulfides is reduced in this kind of electrolyte, one can also expect
reduced mass transport of sulfur species in symmetric lithium sul-
fide – sulfur cells. In other words, the catholyte and anolyte can be
separated by the intrinsic electrolyte properties without an additional
implementation of a Nafion membrane.
Thus, the characteristic oxidation and reduction reactions at both
electrodes proceed without using a Nafion-coated separator, by the use
of our previously introduced T/T-electrolyte with low polysulfide sol-
ubility (Figure 7). After evaluation of the rate capability, we performed
a cycle test with C/5 until cycle 800. A pause of 2 days was imple-
mented after cycle 500 to measure the self-discharge characteristics.
Similar to the cell with D/D-electrolyte and Nafion-coated separator,
the CE during cycling is about 100%. Contrariwise, it only differs
in the first cycle (103.8%), indicating reduced irreversible losses due
to electrolyte decomposition. While increasing the C-rate to C/2, the
retained capacity is not drastically lowered and no capacity fade was
observed during cycling 20 cycles (Figure 7c). The increase to 1C
resulted in a huge capacity loss. The high capacity can be retrieved
at subsequent cycling at C/10. An overall increased polarization is
observed in the voltage profiles (Figure 7d), when raising the C-rate
that can be explained by concentration polarization. While the second
plateau is still formed until C/2, the cell voltage drops at 1C almost
immediately. At 1C, also an asymmetry of the charge and discharge
voltage profile is detected lowering the CE.
After the rate capability test, we continued a cycle stability test
at C/5 as compromise to retain a high capacity in a reasonable time
for each cycle. A linear capacity decrease of 0.18 mAh gs −1 per cy-
cle was observed until cycle 800 (Figure 7a). The reduced discharge
capacity after a pause of 2 days only related to the loss of the first
discharge plateau, which is characteristic for self-discharge of LSB.36
This indicates the formation of Li2 S6 and Li2 S4 takes place in analogy
to half cells, allowing a comparison of the self-discharge behavior of
both cells. The corresponding voltage profiles underline the improved
capacity retention of the C/S-cathodes by using the T/T-electrolyte
(Figure 7b). Compared to the symmetric cell with D/D-electrolyte and
Nafion-coated separator, almost no increase in overpotential during
cycling is observed. While the capacity of the first discharge plateau
is stable for both systems over the entire cycle life, the drop of the
cell voltage at the end of the first discharge plateau is less pronounced
for the cell with T/T- (65 mV) compared to D/D- (91 mV) electrolyte.
And, much more important, the overpotential of the second plateau is
drastically reduced for the cell with T/T-electrolyte. In combination
with the lower capacity loss, we therefore assume that the agglomera-
tion of electrochemical inactive insulating films/particles (Li2 S or S8 )
 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)
Figure 7. The specific discharge capacity and CE during cycling (a, c) and the corresponding voltage profiles (b, d) for the symmetric lithium sulfide – sulfur cell
with T/T-electrolyte and a porous separator.
on the electrode surface and pore blocking effects are reduced by re-
ducing the polysulfide dissolution in the T/T-electrolyte. Restraining
the active polysulfide species inside the porous carbon structure close
to the electrode interface, the structural reorganization of Li2 S or S8
species is suppressed.
To finally compare the capacity retention of the symmetric- and
half-cell measurements with T/T-electrolyte, we cycled a symmetric
cell with constant rate, identical to the half-cell test conditions (C/10)
(Figure 8). A very low capacity fade of about 0.25 mAh gs −1 per
cycle between cycle 50 and 250 was observed, comparable to the
previously combined rate/cycle life measurements in the symmetric
cell system with T/T-electrolyte. The capacity in the first cycle is
slightly (100 mAh gs −1 ) higher than that of the half-cell maybe due
to a slight PS diffusion to the counter electrode. For a pronounced
polysulfide shuttle or sulfur active material exchange we expect this
difference to be much higher. From the corresponding voltage profiles
(Figure 8b), the high capacity retention is accompanied by the stability
(voltage and capacity) at the end of the first discharge plateau and the
stability of the overall discharge voltage. A careful analysis of the
voltage profile reveals changes from cycle 2 to cycle 50 where the
decrease/increase of the cell voltage at the end of the second plateau
becomes sharper, when PS exist in the electrolyte. This was also
observed in the half-cells during cycle 1 to 10. We attribute this effect
to the accumulation of polysulfides in the electrolyte affecting the
precipitation-dissolution-kinetics of Li2 S and sulfur.
In order to study the capacity of both electrodes after cycling, the
symmetric cell was disassembled after 250 cycles and both anode
and cathode reassembled vs. a fresh lithium anode. Both electrodes,
one lithiated (C/Li2 S) and one delithiated (C/S) electrode, were re-
assembled in herein named post-mortem half-cells versus a standard
lithium metal anode and T/T-electrolyte without additional washing
step. Dissolved PS was added to the T/T-electrolyte in the satura-
tion concentration (0.033 M Li2 S8 ), only slightly increasing the spe-
cific electrode capacity, for three reasons:31 Firstly, the electrolyte
is pre-saturated with polysulfides to allow same conditions as in the
disassembled symmetric cell. Secondly, the electrochemical oxida-
tion (Li2 S) and reduction (S8 ) reactions are activated. Thirdly, the
concentration gradient for PS retained in the electrode is reduced
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A1089
to avoid the dissolution of electrode active material (S8 or Li2 S) in
the electrolyte. The capacity of the initial half cycle at C/20 (charge
for the C/Li2 S- and discharge for the C/S-electrode) was reduced to
800 mAh gS −1 based on the sulfur amount of the electrode determined
before electrochemical characterization. For the C/S-electrode, the de-
creased capacity of the first discharge resulted from the absence of
the first discharge plateau (Figure 8c). For the C/Li2 S-electrode, no
overpotential from Li2 S-activation is observed (Figure 8d). Therefore,
we attribute the lowered capacity to a partial dissolution of electrode
active material in the electrolyte because the PS concentration in the
electrolyte at the end of the conversion reaction in the symmetric cell
is not saturated. During the following discharge of the post-mortem
half-cells, the capacity increased for both cells because the charac-
teristic processes can proceed. Following the cycling procedure the
capacity retention of the post-mortem half cells is similar to that of
conventional half –cells. Hence, the reversibility of the conversion re-
actions in the carbon/sulfur cathode is much higher than measured in a
half cell (Figure 8a). Thus, a non-negligible capacity loss could be as-
signed to the degradation mechanisms at the lithium metal anode. The
slight difference in the specific capacity (150 mAh gs −1 ) eventually
results from sulfur distribution during the cycling in the symmetric
cell that cannot be excluded by using a conventional porous separator
without selective ion transport properties. However, this decay may
also be attributed to the handling during disassembling the cells to
recover the electrodes, as cathode material is lost from the edges of
the electrodes where mechanical stability is poor due to the punching
process.
Conclusions
In conclusion, symmetric lithium sulfide – sulfur cells were demon-
strated to provide a valuable methodology to differentiate the degra-
dation mechanisms resulting from novel cathode/electrolyte/separator
concepts and degradation derived from the lithium metal anode. Es-
pecially at high capacity loadings needed for practical cells with high
energy density the repeated electrolyte consumption and incorpora-
tion of sulfur active material during SEI reformation at the lithium
metal anode dominates the electrochemical capacity fade. Instead, the
 A1090 Journal of The Electrochemical Society, 165 (5) A1084-A1091 (2018)
Figure 8. The capacity retention and CE in half-cell, symmetric cell, and post-mortem half-cell with electrodes from the symmetric cell and TT-electrolyte (a)
and the corresponding voltage profile of the symmetric cell (b) and post-mortem half-cells with C/S- (c) and C/Li2 S-electrode.
intrinsic performance characteristics of the sulfur cathode are moni-
tored by substituting the lithium metal anode by a prelithiated sulfur
cathode (factual Li2 S) resulting in a symmetric cell. Without poly-
sulfide shuttle suppression, in the symmetric cell continuous self-
discharge and sulfur active material exchange between both elec-
trodes occur and impede the full conversion reaction (Li2 S to S8 ).
By blocking the polysulfide shuttle with a Nafion-coated separator
or using an electrolyte with limited PS solubility, the characteristic
reduction/oxidation reactions during Li2 S and S8 formation can be
analyzed separately. Thus, sulfur reduction and oxidation can be eval-
uated independently from lithium metal anode degradation. Utilizing
this test cell design, the advantages of recently developed TMS/TTE-
based electrolyte system showing highly reversible cathodic conver-
sion reactions during charge and discharge of a LSB in comparison
with conventional ether based electrolyte systems were demonstrated.
Stable 800 cycles could be shown indicating that the lithium anode
is for both electrolytes the crucial component leading to cell failure.
Avoiding the negative impacts of lithium metal degradation on the
determined cell performance, in our view symmetric lithium sulfide –
sulfur cells are ideal systems to analyze and develop highly reversible
cathode/electrolyte/separator concepts for future lithium sulfur bat-
teries with high specific energy and long cycle life.
ORCID
Markus Piwko https://orcid.org/0000-0002-1983-6137
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