RESEARCH ARTICLE

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Impact of Solvent Treatment of the Superionic Argyrodite

Li6PS5Cl on Solid-State Battery Performance
Justine Ruhl, Luise M. Riegger, Michael Ghidiu, and Wolfgang G. Zeier*

providing a barrier to Li dendrite growth

With growing interest in solution-based processing of electrolytes for all-solid- that plagues liquid electrolyte systems,[2–6]
state batteries comes the need to more deeply understand potential detrimental allowing the use of Li metal anodes to
effects of the solvent on electrolyte materials, as well as effects on the cell achieve the maximum energy density.
These battery systems can provide reason-
performance that may not have been evident by structural characterization alone.
able power/energy density with highly con-
Herein, the superionic solid electrolyte Li6PS5Cl is treated with five organic ductive solid-state electrolytes developed
solvents selected for a range of different physical and chemical properties. The over the past decades.[2–4,7] Nevertheless,
electrolytes treated with solvents that do not lead to obvious degradation are used for commercial production of ASSBs, scal-
in cathode composites of solid-state batteries In/LiIn│Li6PS5Cl│NCM-622: able synthesis and processing routes for the
SE are crucial. Liquid-phase synthesis has
Li6PS5Cl. After treatment in some solvents, the solid electrolyte remains seem-
thus gained interest in recent years,[8–13]
ingly unaffected, but a strong influence on the solid-state battery performance is as well as solvent-based processing of the
observed, revealing underlying effects that warrant deeper study. electrolyte into separators,[14–17] or finished
cathode composites.[3,5] This is either done
as a slurry process (where the electrolyte
is not dissolved) for mixing or as an
1. Introduction infiltration/coating process (where the electrolyte is dissolved),
with the benefit of allowing for intimate contact of the
The constant development of portable electronic devices brings materials.[18–22] For slurry processing, as opposed to dry mixing
the need for new and improved energy storage systems. Lithium- of components,[23–27] a binder is generally required, and the per-
ion batteries have been widely used for commercial applications formance of the cathode is often reduced (reductions in conduc-
since their introduction in 1992.[1] Nevertheless, lithium-ion tivity alone are often observed after exposure to seemingly inert
batteries suffer from many limitations. In addition to inherent solvents).[17,28] However, the system is a complex mixture, and
limitations to energy density,[2] safety issues due to the liquid something that is often missing is a thorough investigation of
electrolyte (leakage/bursting) are also concerning, especially the stability of various solvents against individual components
when it comes to applications in electric vehicles. The all- such as the SE. For liquid processing, the stability of the SE
solid-state battery (ASSB), utilizing a solid electrolyte (SE), tackles in the solvent is obviously of utmost importance.
these disadvantages by eliminating the flammability risks and Lithium thiophosphate solid electrolytes offer excellent
conductivities, and their mechanical softness makes them
promising candidates for easier processing into batteries.[29–31]
J. Ruhl, L. M. Riegger, Dr. M. Ghidiu
Institute of Physical Chemistry Li3PS4 is a well-studied conductor, and is often a precursor in
Justus-Liebig-University Giessen solution processing of members of the more highly conductive
Heinrich-Buff-Ring 17, D-35392 Giessen, Germany argyrodite family Li6PS5X (X¼Cl, Br, I). The argyrodites, and the
J. Ruhl, L. M. Riegger, Dr. M. Ghidiu related Li3PS4 or Li2S-P2S5 systems, are often processed in sol-
Center for Materials Research (LaMa) vents, but the chemical and structural effects of the various sol-
Justus-Liebig-University Giessen vents on the electrolyte alone are rarely methodically studied.
Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
Li3PS4 and glass-(ceramics) have been slurry-processed into cath-
Prof. W. G. Zeier
odes using a large variety of solvents. These include the fabrica-
Institute for Inorganic and Analytical Chemistry
University of Münster tion of composite electrodes with anisole[17,32–34] or n-decane.[35]
Corrensstrasse 30, D-48149 Münster, Germany In addition, the formation of separators via slurry processing was
E-mail: wzeier@uni-muenster.de reported using xylene[36] and toluene.[15] The fabrications of
The ORCID identification number(s) for the author(s) of this article active material coatings based on a suspension or solution of
can be found under https://doi.org/10.1002/aesr.202000077. electrolyte precursors or presynthesized electrolyte are widely
© 2021 The Authors. Advanced Energy and Sustainability Research pub-
reported. For suspension processes, solvents like acetonitrile
lished by Wiley-VCH GmbH. This is an open access article under the terms (ACN),[37] ethyl propionate,[38] or tetrahydrofuran (THF)[39] were
of the Creative Commons Attribution License, which permits use, used, whereas N-methylformamide (NMF),[40,41] NMF/n-hex-
distribution and reproduction in any medium, provided the original ane,[42] and diethylene glycol dimethyl ether[43] were preferred
work is properly cited. for dissolution coatings. Thin separator films can be fabricated
DOI: 10.1002/aesr.202000077 when using toluene (although exposure of the pristine electrolyte

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to toluene was shown to reduce conductivity for Li3PS4 glass-
ceramic, but not significantly for Li10GeP2S12).[15] For making
slurries of Li3PS4 glass, a more thorough work on investigating
the stability against a variety of solvents was undertaken; the
influence of decane, 1,2-dichloroethane, anisole, 1,4-dioxane,
propylene carbonate, propanenitrile, 2-butanone, and diethylene
glycol dimethyl ether on the conductivity was studied.[33] For
those solvents with donor number higher than 14, the conduc-
tivity was adversely affected due to decomposition of the SE
caused by a nucleophilic attack. Of note, 75:25 mixtures of
Li2S:P2S5 have been shown to be chemically stable against sol-
vents such as THF, xylene, toluene, and heptane, but in some
cases, crystallinity or structure was drastically altered.[17,44]
Argyrodites have also been used with xylenes, mineral
spirit, and dibromomethane in slurry processes.[28,45–50] The
formation of a SE suspension was reported to slightly affect
the conductivity,[28,45,46] while still improving cell performance
compared with dry mixing[28] or noncoated active material.[47]
Unlike Li3PS4,[10,51] argyrodites can be dissolved in alcohols
for infiltration processes by using ethanol or mixtures of ethanol
with ethyl acetate, ethyl propionate, THF, or ACN.[16,18–22,51–58]
As a result of infiltration processing (in alcohols), higher
capacities,[20,50] high reversible capacities,[19,22] and an improve-
ment in cycling stability and rate capability[22] were achieved,
even though ethanol exposure seems to reduce the conductivity
of the argyrodite, with recovery of full conductivity not occurring
until heat treatment to high temperatures at which other
composite components may not be stable.[19,54,56,57] For argyro-
dites treated in ethanol, the grain boundary resistance was
reported to increase due to surface residues originating from
the solvent.[45,56,57] Furthermore, partial decompositions of the
argyrodite, indicated by the presence of Li2S and LiCl after recov-
ery, were reported in a mixture of ethanol and ACN.[21]
Nevertheless, ethanol seems to be a compatible solvent for solu-
tion syntheses of argyrodites, but compatibility with the argyro-
dite and other cathode components, e.g., binders or dispersants,
seems to be strongly affected by the time of exposure and the
conditions of the necessary subsequent heat treatment.[20,21,56]
To the best of our knowledge, methanol was only reported for
a 0.4LiI-0.6Li4SnS4 coating of cathode active material (CAM)
via a dissolution process which was stated to exhibit a positive
impact on the contact of electrolyte/active material.[59] There is
clearly a growing interest in solution processing of electrolytes
for cathode production, but a comprehensive knowledge here
of the chemical stability of electrolytes against solvents is needed
outside of the convoluted context of full cathode composites; this
knowledge can then be utilized more generally for solvent selec-
tions of varied processes.
In this article, we selected the lithium superionic argyrodite
Li6PS5Cl as SE due to its high ionic conductivity in the
103 S cm1 range,[60–64] the well-understood syntheses, and
the increasing interest in solvent-based synthesis and processing.
In this article, we investigate structural and chemical changes of
the electrolyte resulting from exposure to a selection of five
organic solvents, based on the prevalence of specific solvents
in the literature for synthesis and solution processing of thio-
phosphates, and to ensure a broad range of solvent properties.
Solid-state battery cells were assembled to investigate whether
effects of the solvent treatments on electrolyte properties were
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mirrored in cell performance and ionic transport, using NCM-
622 as a commonly used and well-studied active material and
untreated Li6PS5Cl as a separator.
2. Results and Discussion
Li6PS5Cl was chosen as an ideal electrolyte to study as it has
shown good performance in solid-state batteries in recent litera-
ture and is already explored for solution processing.[21,22,54,57,65–67]
Li6PS5Cl was produced according to well-established high-
temperature synthesis. To study the effects of solvent on the
electrolyte alone rather than on the entire system with active
material, the electrolytes were first treated with the solvent and
then dry-mixed with the CAMs to produce cathode composites.
For the processing of the solid electrolytes, a reasonable selec-
tion of various solvents is crucial. In this article, we chose for
stability tests the solvents ACN, THF, toluene, ethanol (EtOH)
and methanol (MeOH). This selection was based on the fre-
quently used solvents in the literature for processing. Based
on the different functional groups, the different solvents cover
the range from aprotic/polar (ACN and THF), aprotic/nonpolar
(toluene) to protic (EtOH, MeOH), as well as a variety of different
physical and chemical properties such as boiling points, flash
point, vapor pressure, and dielectric constants (see Table S1,
Supporting Information). Powders of Li6PS5Cl were subjected
to 2 days of solvent interaction to ensure enough time was given
to observe reactions and to well exceed potential contact times in
relevant industrial processes.
2.1. Chemical, Structural, and Microstructural Stability
Figure 1 shows the resulting solvent–electrolyte mixtures with a
mass loading of 10 wt% of Li6PS5Cl. Varying solubilities and
colors were observed. Treatment with ACN resulted in a blue
suspension and a region of the previously white powder was
colored yellow suggesting reacting polysulfidic species.[68] The
blue color itself stems from the S3 radical anion (see Raman
spectrum, Figure S1, Supporting Information).[69,70] Because
the argyrodite should not contain S─S bonds, observation of
polysulfides in large amounts strongly suggests redox processes
and degradation. Using THF as solvent resulted in a suspension
that was colored light yellow. A colorless suspension was
achieved by treatment with toluene, which suggests no or little
side reactions of the sulfur-containing species with the solvent.
The split image of the suspension in THF is intended to show the
Figure 1. Photographs of cuvettes with Li6PS5Cl treated with the solvents
ACN, THF, toluene, EtOH, and MeOH with a loading of 10 wt% Li6PS5Cl.
ACN, THF, and toluene result in the formation of a suspension whereas
EtOH and MeOH dissolve Li6PS5Cl. The split images of THF show the
color changes of the mixture caused by fast settling of the particles.
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change in color of the solution due to the fast precipitation of the
powder particles (within one minute), showing that stable
suspensions are not possible. This occurs also in the case of tol-
uene. Furthermore, with both EtOH and MeOH, a yellow solu-
tion of Li6PS5Cl was obtained. The changing color of the liquid
indicates underlying reactions; this is already a widely observed
phenomenon.[17,33] There is much research into colors of poly-
sulfide solutions and dependence on polysulfide chain length,
concentration, and solvent;[71] in short, the color suggests their
presence but cannot be used conclusively here.
To assess the structural impacts of the solvent treatment, the
materials were characterized by X-ray diffraction (XRD) and
Raman spectroscopy before and after treatment. Figure 2a shows
the diffraction pattern of the pristine Li6PS5Cl (red) with only
minor traces of LiCl and Li3PO4, present from the material
synthesis. After solvent treatment, the solvent was removed
under vacuum at 25  C for ACN, THF, and toluene. The com-
plete removal of EtOH and MeOH required that the temperature
be raised to 100  C, although previous reports show that lower
temperatures were sufficient.[44] Nevertheless, the required tem-
peratures for the removal of the alcohols would not be expected to
cause decomposition as Li6PS5Cl is generally synthesized or
recovered at higher temperatures (see Figure S3, Supporting
Information). Despite the aforementioned apparent reactions
taking place, the diffraction patterns shown in Figure 2a suggest
that the crystal structure after treatment in ACN, THF, and
toluene either remained relatively unchanged or was recovered.
In contrast, EtOH (yellow) and MeOH (pink) seem to decompose
Li6PS5Cl into the precursors, seen by the reflections of lithium
sulfide and lithium chloride. Figure 2b shows the Raman spectra
of the pristine argyrodite and after solvent treatment and solvent
removal. The clearly visible PS43 signal in each spectrum after
solvent removal for ACN, toluene, and THF is in agreement with
the results of XRD. These signals are located in the range of
426–427 cm1 as expected.[72] As indicated by the sharp
reduction or disappearance of the PS43 peak, the use of
EtOH and MeOH results in the partial decomposition of
Li6PS5Cl (although for EtOH, the argyrodite seems to be
reformed after heat treatments).[21] The formation of polysulfides
can be observed for both solvents approximately in the broad
range of 476–506 cm1; however, the signals in the Raman after
MeOH treatment are barely visible. A plot is shown in Figure S2,
Supporting Information. In addition, the use of EtOH seems to
result in the formation of an additional species at 390 cm1.
Although literature suggests that the argyrodite structure can
be recovered from ethanol at 80  C,[56,57] the EtOH and
MeOH treated electrolytes were excluded from further studies
on the solid-state battery performance as they no longer reflect
Li6PS5Cl under these processing conditions; higher tempera-
tures are required when using EtOH to reobtain the argyrodite
structure (Figure S3, Supporting Information). To recover full
conductivity, a potential slurry drying at 550  C is unrealistic con-
sidering the possible instability of other materials in the cathode
at higher temperatures. X-ray photoelectron spectroscopy (XPS)
measurements substantiate these findings (see Figure S4,
Supporting Information). The spectra of the pristine Li6PS5Cl
show the typical signals for the argyrodite.[24,27,73] Treatment
of Li6PS5Cl with THF shows PO43 species.[74–76] Since other
species, such as P[S]nP, are also present at these binding
energies, deconvolution is not possible for the other materials;
however, XRD confirms the presence of Li3PO4 originated from
the synthesis. The spectra of the material treated with ACN and
toluene show no significant changes compared to the pristine
sample. The detrimental impact of EtOH and MeOH becomes
evident, which is in accordance with the data of the X-ray
diffraction.
To reveal how the solvent treatment may have affected the
microstructure of Li6PS5Cl, scanning electron microscopy
(SEM) was performed on the pristine solid electrolyte, as well
as the materials treated with ACN, toluene, and THF, all of which

Figure 2. Influence of solvent treatment on the composition of Li6PS5Cl. a) XRD of the untreated Li6PS5Cl (pristine, red) and after treatment with ACN
(green), toluene (blue), THF (orange), EtOH (yellow), and MeOH (pink). Black lines in (a) indicate peak positions of Li6PS5Cl from Kraft et al.[64]
The diffractogram is displayed with sqrt intensity to highlight the low intensity reflections. b) Raman spectroscopy of the same; the Raman spectra
show negligible changes in the wavenumber of the characteristic PS43 unit in the range of 426–427 cm1 for ACN, toluene, and THF. The partially
decomposed EtOH and MeOH spectra are shown in Figure S2, Supporting Information.

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leave the phase itself intact. Scanning electron micrographs are
shown in Figure S5, Supporting Information. The SEM image of
the pristine Li6PS5Cl exhibits a broad particle size distribution
compared to the solvent-treated materials. The influence of
ACN on the microstructure results in an apparent increase in
smaller particles. In contrast, more medium-sized particles
and larger particles are formed by the influence of THF.
Toluene treatment gave the most unusual appearance, of the
particles seemingly bound together in a matrix. In general,
the handling consistency of the powders also changed noticeably
after the treatment with some solvents. Although the material
treated with ACN exhibited a loose powdery consistency, the
material treated with THF seemed to have a much finer powder
consistency, but when pressed, the powder seemed to stick
together readily, making it difficult to handle and process.
Using toluene resulted in a similar behavior.
At this point, we feel a short discussion on the source of the
argyrodite is needed. Li6PS5Cl can be synthesized by a high-
temperature reaction of mixtures of P4S10, Li2S, and LiCl as
was done here,[61,64] by ball milling the same precursors
(followed by short heat treatments),[77–79] or by solution chemis-
try from Li2S, LiX, and Li3PS4 (which itself can be ball milled or
made via solution) in a solvent such as ethanol.[51,80] It can also be
bought commercially from a few suppliers, where the synthesis
route is not always clear. It is striking that, although Raman and
XRD analyses suggest the materials to be structurally identical,
very different behaviors can be observed—for example, some
reports mention dissolution of the argyrodite in ethanol leading
to brown-colored solutions,[19,56,57] whereas others give yellow/
clear solutions.[51,67,80] This could be indicative of some impuri-
ties or nonhomogeneity between samples not noted in more
limited characterization, which in turn itself may present differ-
ent properties and reactivities during any solvent processing.
2.2. Investigation of Transport Properties
To reveal the influence of the solvent treatment on the conduc-
tivity of the SE Li6PS5Cl, temperature-dependent impedance
spectroscopy was performed. In Figure 3a, the Nyquist plots
of the pristine Li6PS5Cl (red) as well as the spectra of the materi-
als treated with ACN (green), toluene (blue), and THF (orange) at
25  C with their corresponding fits are shown. For fitting these
spectra, a fit model consisting of two resistors and constant phase
elements (R/CPEs) and a CPE element was used; representatives
of the data and fitting were shown for the toluene-treated mate-
rial in Figure 3b. In addition, the Nyquist plots of the conductivity

Figure 3. Temperature-dependent electrochemical impedance measurements of Li6PS5Cl pristine (red) and after treatment with ACN (green), toluene
(blue), and THF (orange). a) Nyquist plots of the obtained impedance spectra with corresponding fit at 25  C, normalized to the pellet thickness.
b) Exemplary fit of the impedance spectrum at 25  C of Li6PS5Cl treated with toluene. c) Arrhenius plots of the materials reflect that with increasing
resistance due to the solvent treatment, a decrease in total conductivity can be observed. d) Activation energies and conductivities at 25  C.

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measurements at 40  C for all materials can be found in
Figure S6, Supporting Information. The impedance data show
that treating the SE with any type of solvent results in an increase
in the resistance.[15,22,28,81] In all Nyquist plots, the first (R/CPE)
element is assigned to the total resistance (Rtotal) of the SE as
grain and grain boundary contributions cannot be deconvoluted
for Li6PS5Cl at the investigated temperatures.[82] The correspond-
ing capacitances of these processes show increasing capacitances
with the solvent treatment from 1011 F (pristine) to 1010 F
(ACN, toluene) and 109 F (THF), suggesting a significant
impact of the organic solvent on the grain boundary resistance
and the total conductivity. Low-temperature measurements
would be needed,[82] however, due to the handling characteristics
of the powders from THF and toluene, it was not possible to
prepare free-standing pellets. The second contribution of the
resistance can be assigned to the sample–electrode interface
roughness based on the averaged modeled capacitances in the
106 F range.[83,84]
Figure 3c shows the Arrhenius behavior of the ionic conduc-
tivity of the different materials and Figure 3d shows the total
conductivity at 25  C and the extracted activation energies of
the pristine material as well as the solvent-influenced solid
electrolyte. A clear drop of the total conductivity can be observed
after treatment with all of the solvents; from a pristine conduc-
tivity of 1.7 mS cm1, ACN treatment decreased the conductivity
to 0.75 mS cm1 and THF resulted in a reduction to
0.46 mS cm1. The highest and most surprising impact in terms
of conductivity resulted from treatment with toluene, a reduction
to 0.066 mS cm1. This drastic change can potentially be
correlated with the fact that toluene showed the most unusual
morphological change under SEM.
Activation energies were moderately impacted. From 0.40 eV
for the pristine material, a minor increase to 0.42 eV can be
observed in the case of ACN. In addition, the activation energy
further increased due to the treatment with THF and toluene to
0.44 eV in both cases. However, considering the general
Figure 4. Nyquist plots of the first cycle (solid-state cells) with the corresponding fits for a) pristine, b) ACN-, c) toluene-, and d) THF-treated Li6PS5Cl.
The illustrated semicircles represent the assigned processes: RSE,bulk (light gray), RSE,grain (light brown), RSE/CAM (light pink), and RSE/anode (light purple).
The respective fit model is also shown in the graphs.
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uncertainty of measured activation barriers,[82] we cannot draw
any conclusion as to a change in the activation barriers here,
although the solvent treatment clearly detrimentally influences
the ionic conductivity. The trend of the Arrhenius prefactor sup-
ports the persistence of the argyrodite structure by XRD and
Raman spectroscopy (Figure S7, Supporting Information). The
prefactor remains constant in the range of 108–109 K S cm1.
2.3. Interfacial Resistances in Solid-State Batteries
Clearly, the nature of the solvent affects the microstructure and
ionic transport properties of Li6PS5Cl. To test if the solvent
processing also affects solid-state battery performance,
In/LiIn│Li6PS5Cl│NCM-622:Li6PS5Cl solid-state cells were
assembled and cycled. As mentioned earlier, the separator con-
sists of untreated Li6PS5Cl whereas the electrolyte in the cathode
composite is Li6PS5Cl after solvent treatment (with the pristine
untreated electrolyte as control). Electrochemical impedance
spectra were recorded before cycling and after each charge
and discharge to identify the underlying interfacial processes
in a frequency range of 7 MHz–100 mHz. Figure 4 shows the
Nyquist plots and the corresponding fits of the impedance data
after charging in the first cycle. To support the quality of the
employed fits, Bode plots of cycles 1, 5, and 10 are shown
representatively in Figure S8, Supporting Information. In the
measured impedance spectra, the presence of four processes
can be identified corresponding to the bulk resistance of the
SE RSE,bulk, the grain resistance of the SE in the composite
RSE,grain, the resistance at the interface/interphase between the
SE and CAM RSE/CAM, as well as the interface between the elec-
trolyte and the anode RSE/anode as recently discussed in
literature.[23]
These previously found processes can be distinguished based
on their frequency ranges and capacitances (see Table S2,
Supporting Information).[23–25] One process is located in the
high-frequency (HF) region. In the middle-frequency (MF)
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range, two processes can be found in the 103 Hz and 100 Hz
region. The low-frequency (LF) part shows one semicircle in
the approximately hertz range. In the case of the cell with only
untreated Li6PS5Cl, it was necessary to fit the obtained spectrum
with a pre-resistance and three (R/CPE) elements[25] to ensure a
reasonable fit.
Recently, these different processes were assigned to the
possible interfaces in a solid-state battery.[23–25] The process in
the HF range of all impedance spectra stems from the bulk
resistance of the SE (RSE,bulk). This is applicable in all spectra
a–d, independent of whether the fit was performed with a pre-
resistance or a (R/CPE) element. The assignment to the RSE,bulk
is corroborated based on the resulting capacitances of the
solvent-treated Li6PS5Cl.[24,85]
The second observable semicircle shows the resulting capaci-
tances of this process to be strongly influenced by the solvent
treatment. Although the process of the cell made with pristine
Li6PS5Cl exhibits a lower average capacitance, an increase can
be observed after using an organic solvent. The dimension of
the capacitance suggests grain boundary contributions,[84] and
it is therefore reasonable to assume that this process stems from
the grain boundaries of the SE in the composite cathode rather
than the separator, as the separator was untreated. However,
pure grain boundary capacitance should be of a different order
of magnitude and the stated capacitances of these processes
seem to reflect surface layer contributions.[84] Nevertheless, it
is reasonable to assume that the grain surface is influenced
by the organic solvents, which is well in line with the observed
microstructural changes. Thus, an influence on the grain bound-
ary contribution is the consequence.
The capacitances of the third process in the MF region exhibit
only minor variations; these are therefore negligible. Similar to
previous reports, this process can be assigned to the solid
electrolyte/CAM interface.[23–25] Although the variations in the
capacitances are small, a significant increase in the resistance
of this process can be found after solvent treatment. Although
the overall cell resistance of cycle one in case of the pristine
Li6PS5Cl can be determined as 58 Ω, the treatment with
ACN results in an increase to 92 Ω. Remarkably, the previous
treatment of the SE in the composite cathode with toluene and
THF induces a stark increase to 330 and 347 Ω, respectively.
Finally, the fourth semicircle in the LF region of 101–103 Hz
can be attributed to the solid electrolyte/anode resistance
(RSE/anode). This interface contribution is often reported to be
in the lower frequency region and is known to exhibit capacitan-
ces in the millifarad range,[23,25] which are also found here for all
cells.
Clearly, solvent treatment of the SE Li6PS5Cl leads to strong
differences in its grain resistance in the composite, RSE,grain, and
even moreso in the resistance at the interface/interphase
between the SE and CAM RSE/CAM. This can potentially be
explained in the case of toluene by the unusual microstructure
revealed by SEM; it seems that some component has been
partially dissolved and has coated smaller particles. In the case
of THF, there is precedent in the literature that for Li3PS4 (which
may be a degradation product of the argyrodite or present as an
amorphous impurity), reaction with THF can lead to the creation
of amorphous Li3PS4 with the potential to coat particles.[17]
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2.4. Cycling of Solvent-Treated Electrolyte Composites
Although solvent treatment of the electrolyte has varied affects on
ionic conductivity, the influence on the long-term battery perfor-
mance also needs elucidation. Figure 5 shows the charge and
discharge curves (dashed and solid, respectively) of the cells
assembled with the pristine Li6PS5Cl (red) and those treated with
solvents ACN (green), toluene (blue), and THF (orange).
Remarkably, all cells exhibited a high first charge capacity; the
use of a solvent seems to have a smaller impact on the charge
capacity of the first cycle, despite the changes to the overall cell
resistance. The solvent treatment results in a change of the
capacity, relative to pristine at 166, to 163 mAh g1 (ACN),
169 mAh g1 (toluene), and 160 mAh g1 (THF). Comparing this
to the first discharge capacities of the solid-state batteries, the
trend slightly changes (pristine 143 mAh g1, ACN
140 mAh g1, toluene 119 mAh g1, and THF 119 mAh g1),
showing that solvent treatment can detrimentally affect the per-
formance in the discharge. When considering the different resis-
tances of the solid electrolyte–CAM interface, the largest
overpotentials are found in the cells with the largest resistances,
i.e., after treatment with THF or toluene (Figure S9, Supporting
Information). Remarkably, the cells assembled with the pristine
and ACN-treated electrolyte show similar overpotentials; this is
also found by toluene and THF.
To explore stability during cyclization, the trend of the
charge/discharge curves after the 5th, 10th, 20th, 30th, 40th, and
50th cycle was compared. The Coulombic efficiencies of all cell
types are shown in Figure S10, Supporting Information. The cell
assembled with the pristine electrolyte shows the smallest fading
behavior when comparing the charge capacities of the first and
the 50th cycle. ACN results in a slightly higher decrease in
capacities from the first to 50th cycle; however, it is similar to
the perforrmance of the cell with the pristine electrolyte. For
the following cycles, the capacities remain in the same region
indicating a stable cycling behavior. In contrast, the toluene-
treated sample exhibits the strongest fading of the charge capaci-
tities. THF treatment resulted in a moderate stability of the cell; a
relatively high fading in the charge capacities can be observed.
Therefore, the charge capacities seem to be more affected than
the discharge, where the fading is approximately in the same
range.
Figure 6 shows the development of the charge (dark color) and
discharge capacities (light color) of the cell with the pristine
material (red) and with the ACN- (green), toluene- (blue), and
THF-treated (orange) materials. The cell with pristine
Li6PS5Cl exhibits the highest capacities over 50 cycles, but does
show some capacity fading after 20–30 cycles as previously
observed.[73,86] Remarkably, the treatment with ACN results in
lower capacities, but shows very stable behavior up to 50 cycles,
even with a steady slight increase in capacity. Toluene and THF
resulted in the lowest attainable capacities. Nevertheless, the dis-
charge capacities of the 50th cycle are 127 mAh g1 (pristine),
118 mAh g1 (ACN), 102 mAh g1 (THF), and 97 mAh g1
(toluene).
In addition to the charge/discharge behavior, the development
of the overall cell resistance was investigated and shown for cycle
1–10 as well as 20, 30, 40, and 50 of the prepared solid-state
© 2021 The Authors. Advanced Energy and Sustainability Research
published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advenergysustres.com

Figure 5. Charge (dashed) and discharge (solid) curves of cells assembled with a) pristine Li6PS5Cl (red) and those treated with b) ACN (green),
c) toluene (blue), and d) THF (orange) at 0.1 C and 25  C. The curves of the first, 5th, 10th, 20th, 30th, 40th, and 50th cycle are shown for all cells,
displayed in order of darker to lighter color, starting with black.

batteries depending on the solvent-treated SE (Figure S11,

Supporting Information). As is often observed, the overall cell
resistance increases with increasing cycle number, which is
usually related to contact loss during cycling[23,85] as well as elec-
trochemically induced side reactions.[24] This increase in this
resistance is observable for every Li6PS5Cl, treated or untreated,
independent of the chemical/physical properties of the solvent.
The resistances of the pristine and the ACN-treated Li6PS5Cl
remained below 170 Ω, whereas treatment with toluene and
THF resulted in a tremendous increase from cycle 1–50.
Clearly, the nature of the solvent affects the solid-state battery
performance, which likely stems directly from the changes to
conductivity and microstructure of the solid electrolyte. Even sol-
vents that do not seem to strongly affect structure or composition
of the electrolyte seem to have unexpected effects on transport.
Solvents may generally have to be tested with the individual SE to
match specific processing conditions for solid-state battery
applications.

Figure 6. Capacities up to 50 cycles of cells assembled with pristine 3. Conclusion

Li6PS5Cl (red) and those treated with ACN (green), toluene (blue), and
THF (orange). Charge capacities are highlighted in darker colors com- In summary, we provide a systematic study of the influence of
pared with the discharge capacities in lighter colors. various organic solvents on the phase, microstructure, and

Adv. Energy Sustainability Res. 2021, 2000077 2000077 (7 of 10) © 2021 The Authors. Advanced Energy and Sustainability Research
published by Wiley-VCH GmbH
www.advancedsciencenews.com
conductivity of the superionic argyrodite Li6PS5Cl (synthesized
via classical high-temperature technique) as well as the resulting
effects on performance in cathodes with NCM as CAM. X-ray
diffraction, Raman spectroscopy, and XPS suggest that the elec-
trolyte may be stable against the solvents ACN, toluene, and
THF, in contrast to the alcohols EtOH and MeOH, where a clear
decomposition can be observed. Impedance spectroscopy shows
the detrimental influence of the solvents on the total ionic con-
ductivity. Toluene, despite having little impact on structure,
decreased the conductivity more than 20-fold. In addition, the
changing microstructures after solvent treatments and the
changing consistency may influence the solid-state battery per-
formance. In/LiIn│Li6PS5Cl│NCM-622:Li6PS5Cl cells revealed
that the predominant increase in resistance stems from the
SE/CAM interface. The worst cycling performance was seen
in the cells using THF- and toluene-treated solid electrolytes,
whereas ACN treatment led to stable cycling similar to the
pristine Li6PS5Cl.
This work shows the importance of the selection of the solvent
for processing cathode composites for solid-state batteries.
Although typically optimization of solid-state battery comprises
the mixing, particle size distribution, and protective coatings,
alongside the search for faster solid ion conductors, the careful
choice of a solvent for a slurry processing needs to not only be
considered, but fully tested.
4. Experimental Section
Solid Electrolyte Synthesis: The synthesis of Li6PS5Cl as well as the
solvent treatment was conducted in an Ar filled glovebox (MBraun,
O2 < 0.1 ppm, H2O < 0.1 ppm). Li6PS5Cl was prepared using a typical
solid-state synthesis approach.[61,64] Stoichiometric amounts of the pre-
cursors lithium sulfide (Li2S, 5 equiv., 28.0 (m)M, Alfa Aesar, 99.9%),
diphosphorus pentasulfide (P4S10, 0.5 equiv., 5.59 (m)M, Merck, 99%),
and lithium chloride (LiCl, 2 equiv., 11.3 (m)M, anhydrous, Alfa Aesar,
99%) were hand ground in an agate mortar for 15 minutes. After obtaining
3 g of a homogenous powder, the precursor mixture was pressed into pel-
lets and filled into a quartz glass ampule (10 mm diameter). To prevent
side reactions, the ampule was coated with carbon and preheated under
dynamic vacuum at 800  C for 2 h. After adding the precursors, the ampule
was sealed under vacuum and heated in a furnace for 2 weeks at 550  C.
The obtained Li6PS5Cl pellets were then hand ground for the subsequent
analysis and solvent treatments.
Solvent Treatment: ACN (Sigma Aldrich, anhydrous, 99.8%), toluene
(Sigma Aldrich, anhydrous, 99.8%, prior to use: distilled over CaH2),
THF (Sigma Aldrich, anhydrous, ≥99.9%, inhibitor-free), EtOH
(ACROS Organics, extra dry, absolute, ≥99.5%), and MeOH (Sigma
Aldrich, ACS spectrophotometric grade, 99.9%) were added to
Li6PS5Cl, respectively, to obtain a 10 wt% suspension of the solid electro-
lyte. All solvents were purchased in an anhydrous state and stored in a
glovebox. To ensure more than enough contact time of the SE with the
solvent, 2 days of exposure were chosen. Afterward, the solvent was
removed under vacuum at room temperature using a conventional
Schlenk line. For proper drying, the materials were kept under vacuum
at room temperature for one hour to obtain the solvent-treated
Li6PS5Cl. In case of the MeOH- and EtOH-treated Li6PS5Cl, a temperature
of 100  C was needed during this drying process to fully remove the
solvent.
Raman Spectroscopy: For Raman spectroscopic analysis, the obtained
materials were placed on a microscopy glass slide and sealed with
Kapton tape to prevent reactions with ambient air and humidity. The mea-
surement was performed by focusing through the glass slide. A Bruker
Senterra Raman microscope equipped with a 532 nm excitation laser
Adv. Energy Sustainability Res. 2021, 2000077 2000077 (8 of 10)
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was used for the measurements. Furthermore, a laser power of 2 mW
was used. An integration time and a coaddition of 5 and 10 s was used,
respectively. Raman spectra in the range of 47–1548 cm1 were recorded
with a spectral resolution of 3–5 cm1. The obtained data were processed
using the OPUS 7.5 software.
X-Ray Powder Diffraction: For investigating the changes of the crystal
structure, all materials were placed on a (911)–oriented silicon sample
holder and covered with Kapton foil. Diffractograms were obtained on
a PANalytical Empyrean powder diffractometer in Bragg–Brentano geom-
etry in the 2θ range of 10 –90 (step size 0.013, integration time/step
150 s). The Pawley fits to obtain the lattice parameters were conducted
using the TOPAS-Academic V6 software.[87]
X-Ray Photoelectron Spectroscopy: For the XPS measurements, the sam-
ples were prepared in a glovebox and tranferred to the analysis chamber
using an argon flushed transfer shuttle. The measurement was performed
with a PHI 5000 Versaprobe Scanning ESCA Microprobe from Physical
Electronics with a monochromatized Al Kα X-ray source (beam diameter
200 μm, X-ray power of 50 W). The data collection was conducted with a
step size of 0.2 eV, 50 ms per step, and 23.5 eV analyzer pass energy.
Measurements were performed within a vacuum of 106 Pa on charge
neutralized samples which was achieved with slow electrons and argon
ions. For the raw data analysis, the CasaXPS software (version 2.3.23,
Casa Software Ltd) was used. The spectra were analyzed using a
Gaussian–Lorentzian line shape (GL30), a Shirley background, and a
charge correction on the PS43 signal at 161.7 eV.[24,27,73]
Scanning Electron Microscopy: With a Merlin SEM from Carl Zeiss AG,
the changes of the microstructure caused by the solvent treatment
were investigated. To transfer the sample under air-tight conditions to the
microscope, the Leica EM VCT500 transfer module (Leica Microsystems
GmbH) was used. For imaging the structural information, a secondary
electron detector with a pixel average scanning mode was utilized.
Electrochemical Impedance Spectroscopy: Press cells such as those
reported in previous studies [25] were used to measure the conductivity
of the obtained materials. 70 mg of each powder was pressed into pellets
manually. After applying 380 MPa for 3 min with an automatic press
(Specac Atlas Autotouch 25 T), the press cell was fixed with
70 MPa[23,24,82] in an Al frame. Electrochemical impedance spectra were
measured with an impedance potentiostat SP-300 (Biologic) in a fre-
quency range of 7 MHz to 100 mHz (amplitude 10 mV) in a temperature
range of 40 to 40  C using a climate chamber (Weiss Klimatechnik).
Assembly of ASSBs: To investigate the influence of solvent-treated
Li6PS5Cl on the battery performance, ASSBs for cell cycling were assem-
bled. A solid-state battery cell setup as previously reported was used.[25]
The battery composition of In/LiIn│Li6PS5Cl│NCM-622:Li6PS5Cl was
chosen to monitor the battery cyclability and the developing impedance.
For the composite cathode, the as-prepared Li6PS5Cl was used as well as
the ones which were treated with ACN, toluene, and THF, respectively. The
separator was composed of Li6PS5Cl that had not been solvent treated. For
the composite cathode, Ni0.6Co0.2Mn0.2O2 (NCM–622) was used as an
active material and dried at 250  C over night using a Büchi oven
B–585. NCM-622 and the Li6PS5Cl (treated and untreated for reference)
were weighted in a 70:30 ratio and hand ground for 15 min. For the cell
assembly, 60 mg of the untreated Li6PS5Cl was filled into the press cell as
separator. After hand pressing, 12 mg of the composite cathode was dis-
tributed homogeneously on the separator. This amount of NCM related to
an area capacity of 2.14 mAh cm2, based on a theoretical specific capacity
of 200 mAh gCAM1.[88] The homogeneous distribution of the composite
mixture became more difficult for the electrolytes treated with toluene
and THF due to the sticky consistency; this affected the addressed active
material. The cell arrangement was pressed manually. Furthermore, a
pressure of three tons was applied for 3 min (Specac Atlas Autotouch
25 T). As anode a lithium (200 μm thickness, 4 mm diameter) and indium
foil (chemPUR, 100 μm thickness, 9 mm diameter, 99.999%) were used to
ensure a stable alloy during cycling (32.3 at% Li[89]). After finishing the cell
assembly, the battery was resting for 2 h to achieve microstructural relax-
ation. Before starting the electrochemical measurements, the press cells
were fixed in an Al frame. For the long-term cell cycling, the cells were
charged to 3.7 V and discharged to 2.0 V versus In/LiIn at room
© 2021 The Authors. Advanced Energy and Sustainability Research
published by Wiley-VCH GmbH
www.advancedsciencenews.com
temperature by applying a current density of 0.214 mA cm2, correspond-
ing to a C-rate of 0.1 C. Electrochemical impedance spectroscopy measure-
ments were performed at room temperature by adopting the parameters
stated earlier.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
The research was supported by the Federal Ministry of Education and
Research (BMBF) within the project FESTBATT under grant number
03XP0177A and 03XP0176D.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
organic solvents, slurry processing, solid electrolytes, solid-state batteries
Received: December 7, 2020
Published online:
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