Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 42279−42285 www.acsami.org

High-Conductivity Argyrodite Li6PS5Cl Solid Electrolytes Prepared

via Optimized Sintering Processes for All-Solid-State Lithium−Sulfur
Batteries
Shuo Wang, Yibo Zhang, Xue Zhang, Ting Liu, Yuan-Hua Lin, Yang Shen, Liangliang Li,*
and Ce-Wen Nan*
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University,
Beijing 100084, China
*
S Supporting Information
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ABSTRACT: Highly Li-ion conductive Li6PS5Cl solid-state electro-

lytes (SSEs) were prepared by solid-state sintering method. The
influence of sintering temperature and duration on the phase, ionic
conductivity, and activation energy of Li6PS5Cl was systematically
investigated. The Li6PS5Cl electrolyte with a high ionic conductivity
of 3.15 × 10−3 S cm−1 at room temperature (RT) was obtained by
sintering at 550 °C for just 10 min, which was more efficient taking
into account such a short preparation time in comparison with other
reported methods to synthesize Li6PS5Cl SSEs. All-solid-state lithium
sulfur batteries (ASSLSBs) based on the Li6PS5Cl SSE were
assembled by using the nano-sulfur/multiwall carbon nanotube
composite combined with Li6PS5Cl as the cathode and Li−In alloy
as the anode. The cell delivered a high discharge capacity of 1850
mAh g−1 at RT for the first full cycle at 0.176 mA cm−2 (∼0.1C).
The discharge capacity was 1393 mAh g−1 after 50 cycles. In addition, the Coulombic efficiency remained nearly 100% during
galvanostatic cycling. The experimental data showed that Li6PS5Cl was a good candidate for the SSE used in ASSLSBs.
KEYWORDS: argyrodite Li6PS5Cl, sulfur solid electrolyte, solid-state sintering, all-solid-state battery, lithium−sulfur battery

■ INTRODUCTION
Rapid development of electrical vehicles (EVs) and mobile
electronic devices has motivated the burgeoning demands for
batteries with high energy density.1−3 Conventional lithium
batteries with oxide cathode materials (e.g., LiCoO2 and
LiFePO4) have been widely used in EVs; however, the low
theoretical capacity of these oxide cathode materials limits
their applications.4,5 Therefore, it is urgent to develop high-
energy-density and low-cost batteries. Sulfur is a promising
active cathode material due to its abundance in earth and low
cost coupled with a high theoretical capacity of 1675 mAh g−1.
Lithium−sulfur (Li−S) batteries due to their high theoretical
energy density (∼2600 W h kg−1) are recognized as a
promising candidate to meet the demands.6−9 Currently, liquid
lithium−sulfur batteries face some challenges: (1) the organic
liquid electrolytes are flammable, (2) the lithium dendrites can
penetrate the separator resulting in short circuit, and (3) the
polysulfide shuttle effects lead to poor Coulombic effi-
ciency.10−12 One of the most promising strategies to solve
these issues is to replace the liquid electrolytes with solid-state
electrolytes (SSEs).13−18
Among various kinds of inorganic SSEs, sulfide SSEs have
drawn a lot of attention because of their high Li-ion
conductivities, easy processability, and compatible interface
with sulfur-based cathodes.19 In 2011, Li10GeP2S12 was
reported to have an ultrahigh ionic conductivity of 1.2 ×
10−2 S cm−1 at room temperature (RT).20 But, the starting
material GeS2 was expensive. Argyrodites Li6PS5Cl was
reported as a promising electrolyte with a high ionic
conductivity in the range of 10−3−10−2 S cm−1 at room
temperature (RT).21 The typical preparation method for
Li6PS5Cl SSEs is ball milling.22−25 Boulineau et al. reported a
Li6PS5Cl electrolyte with a high ionic conductivity of 1.33 ×
10−3 S cm−1 synthesized by ball milling for 10 h at 600 rpm.23
To improve the crystallinity and ionic conductivity of the
Li6PS5Cl electrolyte, annealing after ball milling is adopted by
many groups. Yu et al. prepared a Li6PS5Cl electrolyte with a
conductivity of 1.1 × 10−3 S cm−1 by ball milling at 550 rpm
for 10 h followed by annealing at 550 °C for 5 h.24 The
structure and conductivity of Li6PS5Cl with different milling
times were investigated in this work. Recently, Zhang et al.
prepared a Li6PS5Cl electrolyte with a high ionic conductivity
of 1.29 × 10−3 S cm−1 by ball milling at 500 rpm for 24 h
followed by annealing at 300 °C for 10 h.25 These two
Received: August 31, 2018
Accepted: November 19, 2018
Published: November 19, 2018

© 2018 American Chemical Society 42279 DOI: 10.1021/acsami.8b15121

ACS Appl. Mater. Interfaces 2018, 10, 42279−42285
ACS Applied Materials & Interfaces
processes above are complex and time-consuming. Another
method to prepare Li6PS5Cl is the liquid-phase technique. This
method was facile, but the ionic conductivity was low, in the
order of only 10−5−10−4 S cm−1 at RT.26−28 The solid-state
sintering is an easy method suitable for mass production.
Deiseroth et al. reported a Li6PS5Cl electrolyte synthesized by
sintering at 550 °C for 7 days.21 Zhang et al. prepared a
Li6PS5Cl electrolyte by heating a mixture of Li2S, P2S5, and
LiCl to 600 °C at 0.3 °C min−1, and the ionic conductivity of
Li6PS5Cl was 1.8 × 10−3 S cm−1 at RT.29 Most recently, Yu et
al. prepared a Li6PS5Cl electrolyte with a very high ionic
conductivity of 4.96 × 10−3 S cm−1 at 26.2 °C by sintering the
mixed precursors at 550 °C for 10 h.30
Various cathode active materials such as LiCoO 2 ,
LiNi1/3Co1/3Mn1/3O2, S, and Li2S have been used in the all-
solid-state batteries with Li 6 PS 5 Cl as the electro-
lyte.15,23−26,31,32 Han et al. assembled high-performance all-
solid-state lithium sulfur batteries (ASSLSBs) using a mixed
conducive Li2S nanocomposite as the cathode and Li6PS5Cl as
the electrolyte.15 The cell delivered a large reversible capacity
of 830 mAh g−1 at 50 mA g−1 for 60 cycles at RT. Yu et al.
combined S with Li6PS5Cl to assemble an all-solid-state
battery. This battery displayed a high initial discharge capacity
of 1400 mAh g−1, and the capacity decayed rapidly below 400
mAh g−1 after 20 cycles.24
In the previous work, the effects of sintering temperature
and duration on the phase and ionic conductivity of Li6PS5Cl
have rarely been studied systematically; there is lack of an
efficient method to synthesize high-conductivity Li6PS5Cl in a
short period of time; in addition, the cycling performance of
the ASSLSBs with Li6PS5Cl electrolyte is poor. In this study,
we systematically investigated the influence of sintering
temperature and duration on the phase and ionic conductivity
of Li6PS5Cl and obtained a Li6PS5Cl electrolyte with a high
ionic conductivity of 3.15 × 10−3 S cm−1 by sintering at 550 °C
for just 10 min. The conductivity of Li6PS5Cl was enhanced to
3.38 × 10−3 S cm−1 with process optimization. We fabricated
ASSLSBs using the nano-sulfur/multiwall carbon nanotube
(MWCNT) composite as the cathode, Li6PS5Cl as the
electrolyte, and Li−In alloy as the anode. The discharge
capacity reached 1850 mAh g−1 at RT for the first cycle at
0.176 mA cm−2 and remained at 1393 mAh g−1 after 50 cycles.
This excellent performance demonstrated that the Li6PS5Cl
electrolyte was a good candidate for the SSE used in ASSLSBs.
■
EXPERIMENTAL SECTION
Synthesis of Li6PS5Cl. Li6PS5Cl SSEs were prepared by solid-state
sintering method. Reagent-grade Li2S (Alfa, 99.9%), LiCl (Aladdin,
99.9%), and P2S5 (Aladdin, 99%) powders were used as starting
materials. All of the reagents were weighed according to a Li2S/LiCl/
P2S5 molar ratio of 5:2:1 and mixed by ball milling using a planetary
ball mill apparatus (Fritsch Pulverisette 7) at a rotation speed of 100
rpm for 1 h. The total weight of the mixture was about 1 g.
Subsequently, the mixture was placed in a quartz tube for sintering.
All the procedures were conducted under Ar atmosphere in a dry
glovebox (O2 < 0.1 ppm, H2O < 0.1 ppm). The mixture was heated at
350, 400, 440, 460, 480, 500, 520, 550, 570, or 620 °C for 10 h. The
heating rate was 1.5 °C min−1. The tube was slowly cooled down to
room temperature after sintering. The samples sintered at different
temperature were named as 350-10 h, 400-10 h, 440-10 h, 460-10 h,
480-10 h, 500-10 h, 520-10 h, 550-10 h, 570-10 h, and 620-10 h,
respectively. After the optimal reaction temperature was achieved, the
reaction duration was changed to optimize the process. For example,
the ball-milled mixture was heated at 550 °C for 10 min, 1 h, 2 h, 3 h,
5 h, 10 h, 15 h, or 20 h. These samples were designated as 550-10
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min, 550-1 h, 550-2 h, 550-3 h, 550-5 h, 550-10 h, 550-15 h, and 550-
20 h, respectively.
Materials Characterization. X-ray diffractometry (XRD) was
carried out using Rigaku D/max-2500 diffraction meter with a Cu Kα
radiation source to identify the phases of the samples at RT. The
samples were sealed in an airtight container covered with a polyimide
thin film to avoid reaction with moisture and oxygen and mounted on
the X-ray diffractometer. Scanning election microscopy (SEM, Zeiss
Merlin field-emission) was used to observe the microstructure of the
samples. Raman spectra were obtained using a Raman spectrometer
(LabRAM HR Evolution) at an excitation of 532 nm. All the samples
were sealed in a chamber with a glass window in the glovebox.
Electrochemical Performance Measurements. The powder
was pressed into pellets with a diameter of 12 mm under 150 MPa for
ionic conductivity measurement. Two stainless steel disks were
attached to the pellets as current collectors. The alternating current
impedance measurement was conducted using an impedance analyzer
(ZAHNER-elektrik IM6) in the frequency range of 1 Hz to 1 MHz
with an applied voltage of 50 mV. The ionic conductivity σ was
calculated by the equation σ = L/RS, where R was the total resistance
of the solid electrolyte, L was the sample thickness, and S was the area
of the solid electrolyte.
The Ea was determined from the slope of the Arrhenius plot.
Impedance spectra were recorded at 5 °C intervals during heating
from 35 to 60 °C. To evaluate the electrochemical stability of the
Li6PS5Cl electrolyte, lithium metal∥Li6PS5Cl electrolyte∥stainless
steel cell was conducted by cyclic voltammetry (CV) using a
potentiostat (Biologic VMP3) at a scan rate of 0.2 mV s−1 at voltages
ranging from −0.5 to 5 V at RT. The blocking stainless
steel∥Li6PS5Cl∥stainless steel cell was used for the direct-current
(DC) polarization test with a constant voltage of 2 V to determine the
electronic conductivity.
ASSLSBs were fabricated by employing nano-sulfur/MWCNT
composites combined with Li6PS5Cl as the cathode, Li6PS5Cl as the
solid electrolyte, and the Li−In foil as the anode (see Figure 1). For
Figure 1. Schematic diagram of a nano-sulfur/MWCNT composite
cathode∥Li6PS5Cl∥Li−In ASSLSB. Yellow spheres, red spheres, and
dark short rods denote the Li6PS5Cl particles, sulfur particles, and
MWCNTs, respectively.
the composite cathode, the nano-sulfur/MWCNT composite was
prepared according to the method reported by Chen et al.33 The
weight ratio of nano-sulfur to MWCNT was around 6:4. Then, the as-
synthesized nano-sulfur/MWCNT powder was mixed with Li6PS5Cl
SSE with a weight ratio of 4:6 by ball-milling at 300 rpm for 1 h. The
all-solid-state cells were fabricated as follows. First, 130 mg of
Li6PS5Cl powder was pressed under 150 MPa to form a solid
electrolyte pellet. Then, the cathode composite powder (about 5 mg)
was pressed on the top of the pellet at 150 MPa. Next, the Li−In foil
was attached on the other side of the pellet as the anode at 100 MPa.
Finally, the formed three-layered pellet was cold-pressed under 150
MPa. All the processes were conducted in a poly(ether-ether-ketone)
mold (diameter: 12 mm) with stainless steel rods as current
collectors. The charge−discharge behavior of the cells was tested
using a battery test system (LAND, C2001A) under a cutoff voltage of
0.0−3.0 V (vs Li−In) at RT. The current density was set as 0.044 mA
cm−2 for the first two cycles and 0.176 mA cm−2 for the following
cycles. The CV measurements of the solid-state batteries were
DOI: 10.1021/acsami.8b15121
ACS Appl. Mater. Interfaces 2018, 10, 42279−42285
ACS Applied Materials & Interfaces
performed under the voltage of 0.0−3.0 V with a sweep speed of 0.5
mV s−1.
■
RESULTS AND DISCUSSION
Figure 2a shows the XRD patterns of the Li6PS5Cl samples
synthesized by solid-state sintering at 350, 400, 440, 460, 480,
Figure 2. XRD patterns (a) and Raman spectra (b) of the Li6PS5Cl
samples synthesized by solid-state sintering at different temperatures
for 10 h.
550, and 620 °C for 10 h. The diffraction pattern of the
mixture without sintering correspond to the starting materials,
Li2S, LiCl, and P2S5. Regarding the 350-10 h sample, the main
diffraction peaks are indexed as crystalline Li6PS5Cl, and the
minor peaks of Li2S, LiCl, and Li4P2S6 impurities are also
detected. The intensity of the diffraction peaks of the
impurities gradually decreases with increasing sintering
temperature. It can be observed that the Li4P2S6 impurity
phase is transformed to Li6PS5Cl phase when the sintering
temperature increases. The major peaks of the 460-10 h sample
can be indexed to the Li6PS5Cl crystal structure, except a weak
peak for Li2S at 27° that disappears when the sintering
temperature is 480 °C. As for the 480-10 and 550-10 h
samples, a pure Li6PS5Cl crystalline phase is obtained. When
the sintering temperature increases to 620 °C, weak peaks for
LiCl, Li2S, and unknown phase appear; therefore, a temper-
ature higher than 620 °C is not suitable for obtaining pure
Li6PS5Cl electrolytes. Thus, 550 °C is the optimal sintering
temperature to obtain Li6PS5Cl electrolytes with a pure
Li6PS5Cl phase.
The Raman spectra of Li6PS5Cl samples synthesized by
solid-state sintering at different temperatures for 10 h are
shown in Figure 2b. A main peak at 484 cm−1 and a small peak
at 382 cm−1 are observed in the 350-10 h sample. The peak at
484 cm−1 is attributed to the stretching of PS43−, which
indicates the presence of the high ionic conductivity phase
Figure 3. Ionic conductivities of Li6PS5Cl samples at room temperature as a function of sintering temperature (a) and sintering duration (b).
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Li6PS5Cl.31,34,35 This result is consistent with the previous
reports that argyrodite-type solid electrolyte Li6PS5Cl was
composed of PS43− units.21 In addition, the peak at 382 cm−1 is
for P2S64−, which belongs to the Li4P2S6 phase.34,35 With the
increasing sintering temperature, the intensity of the P2S64−
peak gradually decreases and disappears at 460 °C. From 460
to 620 °C, only the PS43− peak shows up. The Raman results
are in accordance with the XRD data above.
The Nyquist spectra of the Li6PS5Cl SSEs measured at 25
°C are presented in Figure S1a. The resistance of the Li6PS5Cl
electrolyte decreases as the sintering temperature increases.
When the temperature increases to 620 °C, the resistance
increases. The ionic conductivities of the Li6PS5Cl SSEs
sintered at different temperatures were calculated and shown in
Figure 3a. The ionic conductivity of the 350-10 h sample is
5.42 × 10−4 S cm−1. With the increase in the sintering
temperature, the ionic conductivity of the Li6PS5Cl electrolyte
increases rapidly until 460 °C, then rises slowly, reaches the
maximum at 550 °C, and then decreases. The ionic
conductivity of the 550-10 h sample is as high as 3.34 ×
10−3 S cm−1 at RT. From 350 to 460 °C, the rapid increase in
the ionic conductivity might be due to the reduction of the
LiCl, Li2S, and Li4P2S6 impurities with poor ionic con-
ductivity.19,36 When the temperature continues to increase,
these impurities disappear and the crystallinity of the Li6PS5Cl
SSEs increases, leading to the slow increase in the ionic
conductivity. As for the 620-10 h sample, its conductivity
decreases due to the formation of LiCl and Li2S impurities.
Thus, the optimized sintering temperature is 550 °C.
The Arrhenius plots of the Li6PS5Cl SSEs sintered at
different sintering temperatures are shown in Figure 4a. Figure
4b shows the activation energy Ea calculated from the slope of
the linear Arrhenius plot according to the Arrhenius equation
σ(T) = A exp(−Ea/kT), where T is the absolute temperature, A
is a pre-exponential factor, and k is the Boltzmann constant.
For the 350-10 h sample, the Ea value is 0.34 eV. As the
sintering temperature increases, the Ea values of the 400-10 h
and 440-10 h samples become 0.32 and 0.29 eV, respectively,
which are lower than that of the 350-10 h sample. The
reduction of LiCl, Li2S, and Li4P2S6 impurities results in the
decrease in Ea. When the temperature is more than 440 °C, Ea
remains constant at 0.29 eV, which is low in comparison with
other reported SSEs.23,29,37 Thus, a sintering temperature of
550 °C offers both higher ionic conductivity and lower Ea.
Figure 5a shows the XRD patterns of the Li6PS5Cl samples
synthesized by solid-state sintering at 550 °C for 10 min, 1 h, 2
h, 3 h, 5 h, 10 h, 15 h, and 20 h. As for the 550-10 min sample,
a weak peak attributed to Li2S impurity is detected besides the
DOI: 10.1021/acsami.8b15121
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ACS Applied Materials & Interfaces
Figure 4. (a) Arrhenius plots of the Li6PS5Cl samples synthesized by solid-state sintering at different temperatures for 10 h and (b) the dependence
of the activation energy of Li6PS5Cl samples on the sintering temperature.
Figure 5. XRD patterns (a) and Raman spectra (b) of the Li6PS5Cl
samples synthesized by solid-state sintering at 550 °C for different
sintering durations.
main diffraction peaks for Li6PS5Cl. The Li2S peak intensity
decreases when the sintering time increases. After a heat
treatment duration of 3 h or more, the Li2S peak disappears
and a pure Li6PS5Cl phase is obtained. Figure 5b shows the
Raman spectra of the Li6PS5Cl samples synthesized by solid-
state sintering at 550 °C for different sintering durations. The
Raman bands around 424 cm−1 associated with the PS43−
group are observed in all the samples, indicating a Li6PS5Cl
phase.
Figure S1b shows the RT Nyquist spectra of the Li6PS5Cl
SSEs synthesized at 550 °C for various durations. The
resistance of the Li6PS5Cl electrolyte decreases slowly to the
lowest value and then increases with the increasing sintering
duration. The ionic conductivities for these samples were
calculated and are shown in Figure 3b. With the increase in
duration, the ionic conductivity of Li6PS5Cl increases slowly,
reaches the maximum at 15 h, and then decreases. The ionic
conductivity of the 550-10 min sample with minor Li2S
impurity is 3.15 × 10−3 S cm−1. When the duration increases to
3 h, the ionic conductivity of Li6PS5Cl increases to 3.20 × 10−3
S cm−1 with pure Li6PS5Cl. The ionic conductivity reaches the
maximum of 3.38 × 10−3 S cm−1 at 15 h and then decreases at
a longer duration. The decrease in the ionic conductivity may
be due to the evaporation of lithium when the sintering
duration is more than 15 h.38 In general, the ionic conductivity
is not sensitive to the sintering duration. A duration of 10 min
is sufficient to obtain a high ionic conductivity of over 3 × 10−3
S cm−1.
The ionic conductivity data of the Li6PS5Cl SSEs prepared
through various methods that have been recently reported are
compared and summarized in Table 1. The ionic conductivity
of our 550-10 min sample with minor Li2S impurity is 3.15 ×
10−3 S cm−1. The electronic conductivity of this sample is 3.40
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× 10−9 S cm−1 (Figure S2). The Li+ transference number was
very close to 1, according to Figure S3, which is considerably
higher than those of liquid electrolytes39,40 and polymer
electrolytes.41 As for the 550-15 h sample with pure Li6PS5Cl,
the ionic conductivity is 3.38 × 10−3 S cm−1. Clearly, the
conductivity of the 550-15 h sample is one of the highest
values compared with others obtained by liquid phase chemical
synthesis, ball milling followed by annealing, and solid-state
sintering.22−30 Taking into account both the ionic conductivity
of Li6PS5Cl and preparation time, a high ionic conductivity of
over 3 × 10−3 S cm−1 can be obtained by sintering at 550 °C
for just 10 min. Furthermore, a duration time of 10 min is
much shorter in comparison to that in others works. Such a
short time duration can save energy and increase production
efficiency.
The SEM images of the 550-15 h sample are shown in
Figure S4. The morphology of the Li6PS5Cl powder (Figure
S4a) shows that the size of the particles is inhomogeneous.
Most particles have a size of 1−3 μm, and few particles have a
size of around 10 μm. The average size of the particles is small,
which is beneficial to increase the contact area between the
active material and the electrolyte in the composite cathode. It
can be seen that a good contact between particles is achieved
in the Li6PS5Cl pellet prepared by cold pressing without
sintering (Figure S4b).
The electrochemical window is important to evaluate the
stability of the Li6PS5Cl electrolyte against lithium metal. The
CV curve of the stainless steel∥Li6PS5Cl∥Li cell is shown in
Figure 6. Cathodic and anodic currents that correspond to
lithium deposition (Li+ + e− → Li) and dissolution (Li → Li+
+ e−), respectively, are observed around 0 V vs Li/Li+ in the
voltammogram. Meanwhile, there is no significant current due
to electrolyte decomposition in the potential range from −0.5
to 5 V vs Li/Li+. Therefore, the Li6PS5Cl electrolyte exhibits a
high stability against Li metal with an electrochemical window
of more than 5 V.
CV was used to reveal the electrochemical reaction
mechanism of the nano-sulfur/MWCNT cathode, as shown
in Figure 7a. In the first cycle, a remarkable cathode peak can
be observed at 0.93 V (vs Li−In) due to the reduction of S8
molecules to Li2S. Meanwhile, an anode peak is detected at
2.12 V (vs Li−In), representing the oxidation of Li2S back to
S8.16,42 The CV curves after the first cycle are almost identical
to each other, demonstrating a good electrochemical
reversibility of the nano-sulfur/MWCNT composite cathode.
Cycling performance of a nano-sulfur/MWCNT composite
cathode∥Li6PS5Cl∥Li−In ASSLSB between 0.0 and 3.0 V (vs
Li−In) is shown in Figure 7b. The current density is 0.044 mA
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ACS Appl. Mater. Interfaces 2018, 10, 42279−42285
 Table 1. Summary of the Conductivities of Li6PS5Cl SSEs Synthesized through Different Preparation Methods
ionic
conductivity
references (mS cm−1) temperature preparation processes
26 0.014 RT ball milling at 600 rpm for 45 h to obtain Li6PS5Cl precursor. Then, the precursor is dissolved into EtOH solution followed by stirring for 24 h and drying at 80 °C for 3 h
27 0.06 RT ball milling at 600 rpm for 40 h to obtain Li6PS5Cl precursor. Then, the precursor is dissolved into a mixture solution followed by stirring and drying at 150 °C
28 0.6 25 °C ball milling at 600 rpm for 40 h to obtain Li6PS5Cl precursor. Then, the precursor is dissolved into a mixture solution followed by stirring and drying at 180 °C
24 1.1 RT high-energy ball milling at 550 rpm for 10 h followed by annealing at 550 °C for 5 h
25 1.29 RT ball milling at 500 rpm for 24 h followed by annealing at 300 °C for 10 h
23 1.33 25 °C ball milling at 600 rpm for 10 h with Li2S impurity
29 1.8 RT a mixture of Li2S, P2S5, and LiCl was heated to 600 °C at 0.3 °C min−1 and cooled down
22 1.9 RT ball milling for 20 h followed by annealing at 550 °C for 5 h
30 4.96 26.2 °C a mixture of Li2S, P2S5, and LiCl was heated at a reaction temperature of 550 °C for 10 h and cooled down
ACS Applied Materials & Interfaces

our work 3.15 25 °C a mixture of Li2S, P2S5, and LiCl was heated at a reaction temperature of 550 °C for 10 min and cooled down
our work 3.38 25 °C a mixture of Li2S, P2S5, and LiCl was heated at a reaction temperature of 550 °C for 15 h and cooled down

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Figure 6. CV curve of the stainless steel∥Li6PS5Cl∥Li cell.

voltage profiles of the cells at 2nd, 3rd, 20th, and 50th cycles.
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ACS Appl. Mater. Interfaces 2018, 10, 42279−42285
the capacity during the initial several cycles is due to the
material as solid electrolytes.15,23−26,29,32,43,44 The increase in
highest capacity achieved in all-solid-state cells using Li6PS5Cl
corresponding to a capacity retention of 75%. This is the
cm−2 (∼0.02C) for the first two cycles and 0.176 mA cm−2
discharge capacity, and Coulombic efficiency as a function of the cycle

capacity of the all-solid-state cell in the first 35 cycles is even

reported for the Li−S batteries.15,45 Note that the reversible
activation process for the sulfur cathode, which has been
the 5th cycle and declines to 1393 mAh g−1 after 50 cycles,
mA cm−2. The discharge capacity increases to 1866 mAh g−1 at
(∼0.1C) for the following cycles. The initial discharge capacity
of the cell is 1850 mAh g−1 at RT for the first full cycle at 0.176
number at 0.176 mA cm−2. (c) The corresponding discharge−charge
composite cathode∥Li6PS5Cl∥Li−In all-solid-state cells. (b) Charge,
Figure 7. (a) Cycling performance of nano-sulfur/MWCNT

higher than the theoretical capacity of sulfur. The extra

ACS Applied Materials & Interfaces
capacity of the battery could be attributed to the Li6PS5Cl
electrolyte in the composite cathodes that may act as active
cathode material.14,16 It has been reported that the Li6PS5Cl
electrolyte shows some reversible electrochemical activity,
which could contribute to the reversible capacity of the
battery.43 The cell delivers a high Coulombic efficiency of
nearly 100% after three cycles, demonstrating a high
reversibility. All these results show that the Li6PS5Cl electrolyte
is applicable as an electrolyte for ASSLSBs.
Figure 7c shows the charge−discharge curves of the nano-
sulfur/MWCNT composite cathode∥Li6PS5Cl∥Li−In cell. The
current density of the second cycle is 0.044 mA cm−2 and that
of the other cycles is 0.176 mA cm−2. Only one discharge
plateau at 1.5 V (vs Li−In) is detected due to the
transformation from S8 to S2−. Meanwhile, only one charge
plateau at 1.8 V (vs Li−In) is observed, corresponding to the
transformation from Li2S to S8. These results indicate a direct
reaction between sulfur and Li2S during the discharge/charge
process in the ASSLSB, which is in accordance with the CV
scan in Figure 7a. Compared to the Li−S batteries with an
organic liquid electrolyte, the sulfur redox chemistry is
distinguished in ASSLSB and there is no other charge or
discharge plateau related to the formation of polysulfides in the
ASSLSBs, which is in accordance with the reported
works.14−16,18,36 Due to the elimination of polysulfide shuttle
effect, the nano-sulfur/MWCNT composite cathode∥-
Li6PS5Cl∥Li−In cell exhibits a high reversibility. Overlapping
of the 3rd and the 20th discharge curves indicates a good
cycling performance with little attenuation during the initial
galvanostatic cycling. Although the discharge capacity rapidly
decreases after 20 cycles, the discharge capacity of the 50th
cycle is still as high as 1393 mAh g−1.
■ CONCLUSIONS
Li6PS5Cl SSEs with high ionic conductivities were synthesized
by solid-state sintering. The influence of sintering temperature
and duration on the phase, ionic conductivity, and activation
energy of Li6PS5Cl was investigated. It was found that a
duration of 10 min at 550 °C was enough to obtain the
Li6PS5Cl with minor Li2S impurity and a high ionic
conductivity of 3.15 × 10−3 S cm−1. Such a short preparation
time can increase the production efficiency and reduce the
energy consumption. The ASSLSBs based on Li6PS5Cl SSEs
were assembled. An ultrahigh discharge capacity of 1850 mAh
g−1 was achieved at RT for the first full cycle at 0.176 mA
cm−2. After 50 cycles, the discharge capacity was 1393 mAh
g−1. The Coulombic efficiency remained nearly 100% during
the charge−discharge cycles. These results show that the
Li6PS5Cl SSEs possess good potential for applications in
ASSLSBs.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b15121.
Nyquist spectra measured at 25 °C for Li6PS5Cl SSEs
synthesized at various sintering temperatures for 10 h
and at 550 °C for different durations; direct-current
(DC) polarization of a blocking stainless steel∥-
Li6PS5Cl∥stainless steel cell; current−time curves of
the 550-10 min sample; SEM images of the 550-15 h
42284
Research Article
Li6PS5Cl powder and the surface of a Li6PS5Cl pellet
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: liliangliang@mail.tsinghua.edu.cn. Phone: +86-10-
62797162. Fax: +86-10-62771160 (L.L.).
*E-mail: cwnan@mail.tsinghua.edu.cn. Phone: +86-10-
62773587. Fax: +86-10-62771160 (C.-W.N.).
ORCID
Xue Zhang: 0000-0002-2531-4263
Liangliang Li: 0000-0001-7808-7052
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by Basic Science Center Program of
National Natural Science Foundation of China (NSFC) under
Grant No. 51788104 and NSFC projects under Grant Nos.
51572149, 51532002, 51572141, and 51625202.
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