www.acsaem.

org Letter

Rapid Synthesis of Highly Conductive Li6PS5Cl Argyrodite-Type Solid

Electrolytes Using Pyridine Solvent
Rajesh Rajagopal, Yuvaraj Subramanian, Yu Jin Jung, Sung Kang, and Kwang-Sun Ryu*
Cite This: ACS Appl. Energy Mater. 2022, 5, 9266−9272 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Lithium-ion highly conducting Li6PS5Cl argyrodite-

Downloaded via UNIV DE PICARDIE JULES VERNE on November 7, 2023 at 10:02:51 (UTC).

type solid electrolyte was prepared by a facile solution process

using pyridine solvent as the reaction medium. During the
synthesis process, an excess amount of P2S5 was added to suppress
impurity peaks and enhance the ionic conductivity. Powder X-ray
diffraction analyses were carried out to analyze the crystalline phase
and purity of the prepared Li6PS5Cl solid electrolyte. In addition,
laser Raman spectroscopy and XPS were employed to confirm the
formation of Li6PS5Cl solid electrolyte. Highly conductive Li6PS5Cl
solid electrolyte was obtained following a series of optimization
processes, and it was found that the Li6PS5Cl-15 P2S5 solid
electrolyte shows a high ionic conductivity value (4.3 mS cm−1) at
room temperature. We have used cyclic voltammetry (CV), DC
polarization, and galvanostatic charge−discharge techniques to
study the electrochemical performance of the selected Li6PS5Cl-15 P2S5 solid electrolyte.
KEYWORDS: solid electrolyte, argyrodite, Li6PS5Cl, high conductivity, pyridine

■ INTRODUCTION
Lithium−ion batteries (LIBs) have received much attention
contact nature. To solve this problem, researchers have
proposed several techniques including the preparation of a
due to their use in hybrid electric vehicles, electric vehicles, and solid electrolyte with a high ionic conductivity and controlled
stationary batteries, among others. In addition, LIBs have a particle size. Additionally, coating the solid electrolytes over
high energy density, have a long charge−discharge cycle life, the electrode materials also results in a good electrolyte−
and are lightweight.1 Unfortunately, flammable organic liquid electrode interface and improves the ASSLB performance.3−5
Usually, Li2S−P2S5-type solid electrolytes are prepared by
electrolytes in LIBs cause safety concerns, since the leakage of
solid-state reactions and a high energy ball-mill process. Even
flammable organic liquid electrolytes results in ignition
though these conventional methods achieve high ionic
followed by major accidents. All-solid-state lithium batteries
conductivity, they are expensive and lengthy, and their scaling
(ASSLBs) have been considered to be safer and more reliable
up is difficult. Furthermore, the large particle size and irregular
due to their nonflammable inorganic solid electrolytes.
morphology (shape) of the electrolytes are highly unfavorable
Specifically, sulfide based inorganic solid electrolytes have
to great contact between the solid electrolyte and electrode
received increasing attention because of their high ionic
materials. The liquid phase technique has been proposed as a
conductivity, mechanical stability, and wide operating temper-
suitable method to solve the above-mentioned problems.
ature. Recently, Li2S−P2S5-type solid electrolytes with various
Liquid phase techniques enable large-scale production with a
tuned compositions and metal/metalloids doping have been
controlled particle size.6,7 Unfortunately, the solid electrolytes
prepared and were reported to achieve an ionic conductivity of
prepared by liquid phase/solution techniques exhibited very
∼10−2 S cm−1.2,3
low ionic conductivity compared to that of samples prepared
Although the ionic conductivity of these sulfide based
by conventional methods, and the reason for low ionic
organic solid electrolytes is high enough to manufacture all-
solid-state lithium batteries, the ionic conductivity at the solid
electrolyte−electrode interface is poor and needs to be Received: April 18, 2022
improved. That is, high ionic conductivity is necessary at the Accepted: July 14, 2022
solid electrolyte−electrode interface for the development of Published: July 18, 2022
highly efficient all-solid-state lithium batteries. However,
creating the intimate contact between the solid electrolyte
and electrode is quite challenging due to the point-to-point

© 2022 American Chemical Society https://doi.org/10.1021/acsaem.2c01157

9266 ACS Appl. Energy Mater. 2022, 5, 9266−9272
ACS Applied Energy Materials
Figure 1. Schematic diagram for the preparation of Li6PS5Cl solid electrolytes.
conductivity and the formation of solid electrolyte in liquid
phase is unclear. Typically, anhydrous inorganic solvents were
used to prepare a Li2S−P2S5-type solid electrolyte by a
dissolution−precipitation method or solvent-synthesis method.
In the first case, the as-synthesized/formed solid electrolyte
was completely dissolved in the solvent and precipitated out; in
the second case, the starting materials were dissolved or
dispersed in a suitable solvent, and the solid electrolytes were
obtained after the synthesis process.
Solution synthesis is an efficient and cost-effective approach
to prepare sulfide based solid electrolytes, with a large number
of organic solvents, such as ethanol, acetonitrile (ACN), N-
methylformamide (NMF), and tetrahydrofuran (THF).1,8,9
Recently, researchers have prepared Li3PS4 solid electrolyte
using pyridine solvent and have obtained well-crystallized
material with reasonable ionic conductivity.10 Pyridine is a
well-known thionation agent and easily dissolves P2S5 to form
the P2S5·pyridine complex. Li2S can easily react with the P2S5·
pyridine complex to form Li2S−P2S5-type solid electrolytes.
On the other hand, to the best of our knowledge, lithium
argyrodite-type solid electrolytes have not been prepared by a
liquid phase technique with excess P2S5. The excess P2S5 helps
the development of the crystalline structure of Li6PS5Cl type
solid electrolytes and widens the lithium-ion transport path,
which in turn enhances the ionic conductivity and the
electrochemical performance.
In this work, we have prepared a highly conductive lithium
argyrodite solid electrolyte using pyridine solvent. The
composition of the starting material was tuned/optimized to
achieve a highly crystalline nature and enhance the ionic
conductivity. Electronic conductivity measurement was carried
out to study the electronic and ionic conductive nature of the
prepared solid electrolytes.
■ EXPERIMENTAL SECTION
Synthesis of Li6PS5Cl Solid Electrolytes Using Pyridine. The
preparation of the Li6PS5Cl solid electrolyte was carried out by a
simple cost-effective solvent-synthesis process using pyridine solvent.
To prepare Li6PS5Cl solid electrolyte, Li2S, P2S5, LiCl, and pyridine
9267
www.acsaem.org Letter
were purchased and used without any purification. Since the source
materials and resultant materials were highly moisture sensitive, all of
the experiments were conducted in an argon filled glovebox. Briefly,
0.5 g of P2S5 was dissolved in 20 mL of anhydrous pyridine under
constant stirring at room temperature to form the P2S5·pyridine
complex. Then, 0.190 g of LiCl was added to the P2S5·pyridine
complex and stirred until LiCl dissolved completely. Then, the
mixture was heated to 70 °C, and 0.516 g of Li2S was slowly added
under constant stirring (400 rpm). During this time, a green to bluish
green (cyan) color change was observed, indicating the beginning of
the chemical reaction. The above mixture was continuously stirred at
70 °C for 3 h in a closed glass bottle. Then, the product was recovered
by removing pyridine solvent using vacuum evaporation at ∼120 °C.
The product was vacuum-dried at 150 °C for 5 h for the complete
removal of organic solvent. Finally, the solid electrolyte powder
obtained was pelletized and sintered at 550 °C for 10 h at a heat rate
of 2 °C/min. After sintering, the pellet remained, referred to as the
Li6PS5Cl (LPSCl) solid electrolyte. The same experiment was
repeated with 5, 10, 15, and 20 wt % excess P2S5, and the resultant
products were named Li6PS5Cl-5 P2S5 (LPSCl-5 P2S5), Li6PS5Cl-10
P2S5 (LPSCl-10 P2S5), Li6PS5Cl-15 P2S5 (LPSCl-15 P2S5), and
Li6PS5Cl-20 P2S5 (LPSCl-20 P2S5), respectively.
Characterization of Li6PS5Cl and Metal Doped/Mixed
Li6PS5Cl Solid Electrolytes Using Pyridine. The crystalline nature
of the prepared material was assessed using an X-ray diffractometer
(XRD, Rigaku-Ultima (IV)) with Cu Kα radiation (1.5418 Å). The
XRD experiment was performed within the 2θ of 10° to 70° with a
0.01 s step size. Before XRD analysis, the samples were protected with
an airtight XRD holder. The structural units of the samples were
identified by laser Raman spectroscopy (Thermo Scientific, DXR)
with a power of 8 mW and wavelength of 532 nm. The surface
chemical functional group of the selected electrolyte was studied using
X-ray photoelectron spectroscopy (XPS), which was adopted to study
the surface functional group using an Al Kα monochromator (1.487
keV). The XPS sampling and analysis were conducted in an argon
environment, and the analysis area was fixed to 500 μm. The surface
morphology of the solid electrolytes was studied by field-emission
scanning electron microscope (FE-SEM, JSM-7610F, Japan).
Electrochemical impedance spectroscopy (EIS) analysis was
performed using a Biologic SP 300 instrument between a frequency
of 7 MHz and 1 Hz (25 °C). For this ionic conductivity
measurement, solid electrolyte (250 mg) was pressed into a pellet
using hydraulic pressure (35 MPa) (thickness = ∼2.2 mm and
https://doi.org/10.1021/acsaem.2c01157
ACS Appl. Energy Mater. 2022, 5, 9266−9272
ACS Applied Energy Materials www.acsaem.org Letter

Figure 2. (a) X-ray diffraction pattern and (b) laser Raman spectra of prepared Li6PS5Cl and P2S5 excess Li6PS5Cl solid electrolytes.

Figure 3. (a, b) XPS spectra Li6PS5Cl-15 P2S5 solid electrolyte with deconvoluted P 2p and S 2p spectra and (c) FE-SEM images of prepared
Li6PS5Cl and P2S5 excess Li6PS5Cl solid electrolytes at different magnifications.

diameter = 10 mm), and indium foil (50 μm thick) was attached on
both sides. For the electronic conductivity measurement, we
assembled the pressure cell similar to that used for the ionic
conductivity measurement, except with indium foil with the
constantly applied voltage of 1 V. For the electronic conductivity
measurement, the pellet thickness was 0.8 mm (100 mg). Cyclic
voltammetry (CV) analysis was performed by preparing a 2032-type
coin cell. The CV measurement was carried out using a Biologic SP
300 instrument between the potential window of −0.5 to 5.0 V at a
scan rate of 1 mV s−1. For CV measurement, 0.2 g of solid electrolyte
was pressed into a pellet with ∼1 mm thickness and 16 mm diameter
and assembled as a Li/solid electrolyte/stainless steel coin cell. In
addition, we also conducted the CV test for the LPSCl-15 P2S5 +
VGNF/LPSCl-15 P2S5/Li cell at the scan rate of 0.1 mV s−1 between
2 and 4.8 V. For the LPSCl-15 P2S5 + VGNF cathode preparation,
LPSCl-15 P2S5 and VGNF were mixed with the weight ratio of 90:10
and ground for 15 min to obtain uniform mixing and create sufficient
electronic pathways. The prepared LPSCl-15 P2S5 + VGNF cathode
(15 mg) was uniformly spread over the LPSCl-15 P2S5 solid
electrolyte layer and assembled as a 2032-type coin cell. A Li/solid
electrolyte/Li symmetry cell was assembled and performed for the
galvanostatic polarization test using a MACCOR-battery analyzing
system with a current density of 0.05−0.4 mA cm−2. Finally, we
assembled the ASSLBs using the selected solid electrolyte and studied
the galvanostatic charge−discharge characteristics. First, we mixed the
NCM 811 (6 μm), solid electrolyte, and Super-P with the weight ratio
of 70:28:2 and used this as the cathode composite. Then, the solid
electrolyte layer or pellet (0.2 g, 16 mm diameter) was prepared in a

9268 https://doi.org/10.1021/acsaem.2c01157
ACS Appl. Energy Mater. 2022, 5, 9266−9272
ACS Applied Energy Materials
Figure 4. (a) Nyquist plot and (b) calculated ionic conductivity value of prepared Li6PS5Cl and P2S5 excess Li6PS5Cl solid electrolytes using
pyridine solvent.
polyether ether ketone (PEEK) mold by applying 30 MPa pressure.
Next, the cathode composite layer was formed by sprinkling the
cathode composite (10 mg) over the solid electrolyte pellet/layer and
pressing (30 MPa) for 3 min. Then, the indium foil (50 μm thick)
current collector was stuck on the cathode side. Another piece of
indium foil was stuck on the opposite side and assembled in a 2032-
type coin cell.
■ RESULTS AND DISCUSSION
During the synthesis of the Li6PS5Cl solid electrolyte, we have
optimized the process to reduce the preparation time and
boost the complete reaction to obtain a high ionic
conductivity. For this purpose, P2S5 samples were dissolved
in pyridine to form a soluble complex, and LiCl was dissolved
subsequently to get a clear solution. Then, Li2S were added
and stirred for 3 h at 400 rpm. During this reaction time, we
maintained the reaction temperature at 70 °C to boost the
reaction. Finally, the vacuum drying process was done to
eliminate the pyridine solvent prior to the sintering process.
The schematic diagram for the synthesis process of Li6PS5Cl
solid electrolyte is shown in Figure 1. The structural
characteristics and the formation of argyrodite structure were
confirmed by various characterization analysis techniques.
First, powder XRD analysis was performed for the prepared
solid electrolytes, and the corresponding XRD patterns were
shown in Figure 2. Crystalline peaks were obtained after the
sintering process at 550 °C for 10 h. Characteristic peaks at 2θ
= 15.3 ± 3°, 17.8 ± 3°, 25.4 ± 3°, 29.9 ± 3°, 31.2 ± 3°, 44.9 ±
3°, 47.7 ± 3°, and 52.3 ± 3° for the prepared Li6PS5Cl solid
electrolyte were observed from the XRD analysis. The
observed peak positions coincided with the cubic crystal
structure with the F4̅3m space group. This confirmed the
successful formation of Li-argyrodite type solid electro-
lyte.11−13 In addition, Li3PO4 impurity peaks were observed
at 2θ = 22.0°, 22.9°, 24.5°; Li2S and LiCl impurity peaks were
observed at 26.8° and 49.9°, respectively.14 Usually, impurity
peaks of Li3PO4, Li2S, and LiCl are observed during the
preparation of argyrodite solid electrolyte by solution syn-
thesis. To remove these impurity peaks, excess P2S5 was added
during the synthesis process. Increasing the concentration of
P2S5 gradually decreased the intensity of Li3PO4, Li2S, and LiCl
impurity peaks. The Li2S and LiCl impurity peaks greatly
decreased during the addition of 15 and 20 wt % excess P2S5.
However, few Li3PO4 impurity peaks were observed at 20 wt %
excess P2S5 LPSCl solid electrolyte. This might be related to
9269
www.acsaem.org Letter
the pyridine solvent which contained a small amount of water
(0.1%). For comparison, we also performed the Rietveld
refinement for the selected Li6PS5Cl-15 P2S5 solid electrolyte
and confirmed the formation of the argyrodite structure. In
addition, laser Raman analysis was performed for all the
prepared solid electrolytes. All of the Li6PS5Cl and excess P2S5
Li6PS5Cl solid electrolytes exhibited characteristic peaks at 420
and 570 cm−1, indicating the successful formation of the PS43−
structure. These characteristic peaks were related to the
stretching vibration of the tetrahedral PS43− anion and
confirmed the formation of the Li3PS4 structure.15,16
The chemical states of the surface functional group of
Li6PS5Cl-15 P2S5 solid electrolyte were identified by XPS
analysis, and the corresponding deconvoluted P 2p and S 2p
spectra are shown in Figure 3a,b, respectively. The
deconvoluted XPS spectra of P 2p displayed peaks at 130.9
and 131.8 eV, corresponding to P 2p3/2, and P 2p1/2,
respectively. Similarly, the deconvoluted XPS spectra of S 2p
showed characteristic peaks at 160.6 and 161.8 eV,
corresponding to S 2p3/2 and S 2p1/2, respectively. The
observed peaks of P and S elements belonged to the PS43−
system.17 The particle size and surface morphology were
studied by FE-SEM analysis, and the corresponding images are
presented in Figure 3c. Here, we observed that the prepared
solid electrolyte particles measured between 5 and 10 μm.
From the XRD analysis, we confirmed that highly crystalline
argyrodite materials were prepared by solution synthesis using
pyridine solvent. Thus, we argued that the prepared solid
electrolytes might exhibit a high ionic conductivity. Figure 3
shows the calculated ionic conductivity value of the
synthesized solid electrolytes from the Nyquist plot obtained
by an EIS measurement at room temperature. From Figure 4,
we observed that the calculated ionic conductivity value of the
prepared Li6PS5Cl (LPSCl) solid electrolyte is 2.6 mS cm−1.
This value was lower than that for Li6PS5Cl solid electrolyte
prepared by a ball-mill process due to the presence of Li3PO4,
Li2S, and LiCl impurities. However, the ionic conductivity
value obtained was slightly higher than that of Li6PS5Cl solid
electrolytes prepared by other solvent-synthesis processes.13,15
Previously, the solid electrolyte was optimized under normal
drying and vacuum drying processes after solvent removal.
During the normal drying process, Li3PO4 and LiCl impurity
peaks (Figure S1 a) were not observed. We believe that this
was due to insufficient drying, and the presence of residual
https://doi.org/10.1021/acsaem.2c01157
ACS Appl. Energy Mater. 2022, 5, 9266−9272
ACS Applied Energy Materials
Figure 5. (a) CV graph (inset: CV graph of LPSCl-15 P2S5 + VGNF/LPSCl-15 P2S5/Li cell with the scan rate of 0.1 mV s−1), (b) DC graph of
LPSCl-15 P2S5 solid electrolyte, (c) DC charge−discharge graph, and (d) cycle stability of In/LPSCl-15 P2S5/NCM811 ASSLBs at room
temperature.
carbon and unreacted P2S5 from a pyridine−P2S5 complex
might have hindered minor impurity peaks. The presence of
residual carbon and unreacted P2S5 might be related to the
formation of a wide semicircle in the Nyquist plot. The
conductivity of the Li6PS5Cl solid electrolyte was related to the
combination of electronic conductivity and ionic conductivity.
Thus, the solid electrolyte prepared by normal drying showed
high conductivity (4.6 mS cm−1) at room temperature and was
comparable to the ball-mill method.11,19 In the case of vacuum
drying, we observed impurity peaks in the XRD pattern, and
no semicircles were observed in the Nyquist plot, indicating a
complete drying process (Figures S1 and S2). Thus, vacuum
drying successfully removed pyridine solvent and enhanced
ionic conductivity.
Further to remove Li3PO4 and LiCl impurities, excess P2S5
was added during the synthesis process. As expected (from
XRD analysis), the ionic conductivity gradually increased while
increasing the concentration of excess P2S5. As a result, the
Li6PS5Cl-15 P2S5 solid electrolyte exhibited a high ionic
conductivity (4.3 mS cm−1) value similar to that of the
Li6PS5Cl solid electrolyte prepared by the ball-mill process and
was nearly twice that of the Li6PS5Cl solid electrolyte prepared
without excess P2S5. This is reasonable, since according to
XRD analysis, Li2S and LiCl impurities were completely
removed at a high excess P2S5 concentration. Furthermore, the
ionic conductivity value decreased to 3.9 mS cm−1 when the
excess P2S5 concentration was increased to 20 wt %; this might
9270
www.acsaem.org Letter
be due to the presence of excess P2S5 (XRD peaks were not
detected).18 In addition, we prepared LiCl excess Li6PS5Cl
solid electrolyte to improve the ionic conductivity and remove
impurity peaks using the optimized synthesis procedure
(Supporting Information). Unfortunately, the impurity peaks
were not removed, and the intensities of the Li3PO4 and LiCl
impurity peaks slightly increased (Figure S3). Thus, the ionic
conductivity value of LiCl excess Li6PS5Cl solid electrolyte
remained unchanged due to the presence of impurity peaks
(Figure S4). Finally, we evaluated the electrical conductivity of
the solid electrolyte to understand the conduction mechanism.
The chronoamperometry graphs of the prepared solid
electrolytes are shown in Figure S5. The calculated electronic
conductivity values of all synthesized solid electrolytes are
∼10−8 S cm−1. This value was very small and suggested that
the value obtained from EIS analysis was mainly related to the
ionic conductivity rather than the electronic conductivity.
Various electrochemical analyses of highly conductive
LPSCl-15 P2S5 solid electrolyte were carried out. First, cyclic
voltammetry analysis was carried out to determine the
electrochemical stability window of the solid electrolyte, and
the results are shown in Figure 5a. The selected solid
electrolyte exhibited strong reduction and oxidation peaks
near 0 V, indicating the deposition and dissolution of Li. Apart
from this characteristic peak, no other peaks were observed up
to 5 V, thus confirming the stability of LPSCl-15 P2S5 solid
electrolyte.18 The electrochemical stability window of the
https://doi.org/10.1021/acsaem.2c01157
ACS Appl. Energy Mater. 2022, 5, 9266−9272
ACS Applied Energy Materials
LPSCl-15 P2S5 + VGNF/LPSCl-15 P2S5 /Li cell shows that
the solid electrolytes are starting to oxidize at approximately
2.8 V (Figure 5a, inset). This oxidation attributed to the
oxidation of PS43− into −S0− and P2S74−. Further, the
oxidation and reduction process is a completely reversible
process. Furthermore, we determined the critical current
density of the solid electrolyte by DC polarization analysis, and
the corresponding graph is shown in Figure 5b. The prepared
solid electrolyte was stable up to (critical current density) 0.35
mA cm−2. The recorded value was almost similar to the
Li6PS5Cl solid electrolyte prepared by the ball-mill process.20,21
Finally, we assembled the In/LPSCl-15 P2S5/NCM811 coin
cell (2032)-type all-solid-state battery to evaluate the potential
application of the prepared solid electrolyte. The galvanostatic
charge−discharge graph of the assembled ASSB with the
potential window of 2−3.8 V is shown in Figure 5c. The
fabricated device exhibited the initial charge and discharge
capacity of 179.6 mAh g−1 and 111 mAh g−1, respectively, with
a Coulombic efficiency of 61.8% at a 0.1 C rate. The obtained
discharge capacity values were comparable to reported
argyrodite-type solid electrolytes prepared by the solution
method.5,22 The Coulombic efficiency of the device reached
100% after a few initial cycles and was stable up to 50 cycles.
Figure 5d shows the calculated specific discharge capacity and
Coulombic efficiency of the fabricated device up to 50 cycles.
The discharge specific capacity gradually decreased with
respect to cycle number, and the assembled In/LPSCl-15
P2S5/ NCM811 battery exhibited the specific capacity value of
86.2 mAh g−1 at the end of 50 cycles with a specific capacity
retention of 78%.
■ CONCLUSION
In this work, highly conductive Li6PS5Cl solid electrolyte was
prepared by a solution technique using pyridine solvent. X-ray
diffraction, laser Raman spectroscopy, and XPS analysis
confirmed the successful formation of lithium argyrodite-type
structure. During the synthesis process, an excess amount of
P2S5 was added to suppress Li3PO4, Li2S, and LiCl impurity
peaks. The surface morphology and the particle size of the
solid electrolytes were studied by FE-SEM analysis. The
prepared Li6PS5Cl-15 P2S5 solid electrolyte exhibited high
ionic conductivity (4.3 mS cm−1) at room temperature and was
comparable to the ball-mill technique. Cyclic voltammetry
analysis and DC polarization analysis showed the electro-
chemical stability of the solid electrolytes. The fabricated In/
LPSCl-15 P2S5/ NCM811 coin cell (2032)-type all-solid-state
battery exhibited an initial discharge capacity value of 111.0
mAh g−1 at C-rate of 0.1 C. We also studied the cycle stability
of the assembled ASSB device and exhibited the specific
capacity value of 86.2 mAh g−1 at the end of 50 cycles with a
specific capacity retention of 78%.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.2c01157.
Experiments, powder XRD analysis, impedance analysis,
and chronoamperometry graph of prepared Li6PS5Cl
and LiCl excess Li6PS5Cl solid electrolytes using
pyridine solvent (PDF)
9271
www.acsaem.org Letter
■ AUTHOR INFORMATION
Corresponding Author
Kwang-Sun Ryu − Department of Chemistry, University of
Ulsan, Ulsan 44776, Korea; Energy Harvest Storage
Research Center (EHSRC), University of Ulsan, Ulsan
44610, Korea; orcid.org/0000-0002-8758-0495;
Phone: +82-52-712-8003; Email: ryuks@ulsan.ac.kr;
Fax: +82-52-712-8002
Authors
Rajesh Rajagopal − Department of Chemistry, University of
Ulsan, Ulsan 44776, Korea; Energy Harvest Storage
Research Center (EHSRC), University of Ulsan, Ulsan
44610, Korea
Yuvaraj Subramanian − Department of Chemistry, University
of Ulsan, Ulsan 44776, Korea
Yu Jin Jung − Research Center for Advanced Specialty
Chemicals, Korea Research Institute of Chemical Technology
(KRICT), Ulsan 44412, Korea
Sung Kang − Research Institute of Industrial Science &
Technology, Pohang 37673, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.2c01157
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study was supported by the National Research
Foundation of Korea (NRF), funded by the Ministry of
Education, Science and Technology (MEST) of the Korean
Government (NRF-2019R1A6A1A11053838).
■ REFERENCES
(1) Teragawa, S.; Aso, K.; Tadanaga, K.; Hayashi, A.; Tatsumisago,
M. Liquid-Phase Synthesis of a Li3PS4 Solid Electrolyte Using N-
Methylformamide for All-Solid-State Lithium Batteries. J. Mater.
Chem. A 2014, 2 (14), 5095−5099.
(2) Zhou, L.; Minafra, N.; Zeier, W. G.; Nazar, L. F. Innovative
Approaches to Li-Argyrodite Solid Electrolytes for All-Solid-State
Lithium Batteries. Acc. Chem. Res. 2021, 54 (12), 2717−2728.
(3) Wang, S.; Fang, R.; Li, Y.; Liu, Y.; Xin, C.; Richter, F. H.; Nan,
C.-W. Interfacial Challenges for All-Solid-State Batteries Based on
Sulfide Solid Electrolytes. J. Materiomics 2021, 7 (2), 209−218.
(4) Li, Y.; Zhang, D.; Xu, X.; Wang, Z.; Liu, Z.; Shen, J.; Liu, J.; Zhu,
M. Interface Engineering for Composite Cathodes in Sulfide-Based
All-Solid-State Lithium Batteries. J. Energy Chem. 2021, 60, 32−60.
(5) Chida, S.; Miura, A.; Rosero-Navarro, N. C.; Higuchi, M.; Phuc,
N. H. H.; Muto, H.; Matsuda, A.; Tadanaga, K. Liquid-Phase
Synthesis of Li6PS5Br Using Ultrasonication and Application to
Cathode Composite Electrodes in All-Solid-State Batteries. Ceram.
Int. 2018, 44 (1), 742−746.
(6) Ito, S.; Nakakita, M.; Aihara, Y.; Uehara, T.; Machida, N. A
Synthesis of Crystalline Li7P3S11 Solid Electrolyte from 1,2-
Dimethoxyethane Solvent. J. Power Sources 2014, 271, 342−345.
(7) Choi, S.; Lee, S.; Park, J.; Nichols, W. T.; Shin, D. Facile
Synthesis of Li2S-P2S5 Glass-Ceramics Electrolyte with Micron Range
Particles for All-Solid-State Batteries via a Low-Temperature Solution
Technique (LTST). Appl. Surf. Sci. 2018, 444, 10−14.
(8) Phuc, N. H. H.; Morikawa, K.; Totani, M.; Muto, H.; Matsuda,
A. Chemical Synthesis of Li3PS4 Precursor Suspension by Liquid-
Phase Shaking. Solid State Ion. 2016, 285, 2−5.
(9) Rajagopal, R.; Ryu, K.-S. Facile Synthesis of 3Li2S-P2S5:XLiCl:
(1-x)LiI Glass Ceramic Solid Electrolyte for Solid-State Lithium-Ion
Batteries. J. Alloys Compd. 2019, 798, 235−242.
https://doi.org/10.1021/acsaem.2c01157
ACS Appl. Energy Mater. 2022, 5, 9266−9272
ACS Applied Energy Materials www.acsaem.org Letter

(10) Ghidiu, M.; Schlem, R.; Zeier, W. G. Pyridine Complexes as

Tailored Precursors for Rapid Synthesis of Thiophosphate Superionic
Conductors. Batter. Supercaps 2021, 4 (4), 607−611.
(11) Wang, H.; Gao, L.; Lu, Z.; Tang, Y.; Ye, D.; Zhao, G.; Zhao, H.;
Zhang, J. Borohydride Substitution Effects of Li6PS5Cl Solid
Electrolyte. ACS Appl. Energy Mater. 2021, 4 (11), 12079−12083.
(12) Ruhl, J.; Riegger, L. M.; Ghidiu, M.; Zeier, W. G. Impact of
Solvent Treatment of the Superionic Argyrodite Li6PS5Cl on Solid-
State Battery Performance. Adv. Energy Sustain. Res. 2021, 2 (2),
2000077.
(13) Rosero-Navarro, N. C.; Niwa, H.; Miura, A.; Tadanaga, K.
Two-Step Liquid-Phase Synthesis of Argyrodite Li6PS5Cl Solid
Electrolyte Using Nonionic Surfactant. Bol. Soc. Esp. Cerámica Vidr.
2021, DOI: 10.1016/j.bsecv.2021.12.001.
(14) Ishigaki, N.; Akimoto, J. Room Temperature Synthesis and
Phase Transformation of Lithium Phosphate Li3PO4 as Solid
Electrolyte. J. Asian Ceram. Soc. 2021, 9 (2), 452−458.
(15) Zhang, J.; Zheng, C.; Li, L.; Xia, Y.; Huang, H.; Gan, Y.; Liang,
C.; He, X.; Tao, X.; Zhang, W. Unraveling the Intra and Intercycle
Interfacial Evolution of Li6PS5Cl-Based All-Solid-State Lithium
Batteries. Adv. Energy Mater. 2020, 10 (4), 1903311.
(16) Randrema, X.; Barcha, C.; Chakir, M.; Viallet, V.; Morcrette, M.
A Detailed Characterisation Study of Li6PS5Cl Ionic Conductors from
Several Synthetic Routes. Solid State Sci. 2021, 118, 106681.
(17) Subramanian, Y.; Rajagopal, R.; Senthilkumar, B.; Park, Y. J.;
Kang, S.; Jung, Y. J.; Ryu, K.-S. Tuning of Li-Argyrodites Ionic
Conductivity through Silicon Substitution (Li6+xP1‑XSixS5Cl0.5Br0.5)
and Their Electrochemical Performance in Lithium Solid State
Batteries. Electrochim. Acta 2021, 400, 139431.
(18) Rangasamy, E.; Liu, Z.; Gobet, M.; Pilar, K.; Sahu, G.; Zhou,
W.; Wu, H.; Greenbaum, S.; Liang, C. An Iodide-Based Li7P2S8I
Superionic Conductor. J. Am. Chem. Soc. 2015, 137, 1384−1387.
(19) Lee, J. M.; Park, Y. S.; Moon, J.-W.; Hwang, H. Ionic and
Electronic Conductivities of Lithium Argyrodite Li6PS5Cl Electrolytes
Prepared via Wet Milling and Post-Annealing. Front. Chem. 2021, 9,
778057.
(20) Wan, H.; Zhang, J.; Xia, J.; Ji, X.; He, X.; Liu, S.; Wang, C. F Recommended by ACS
and N Rich Solid Electrolyte for Stable All-Solid-State Battery. Adv.
Funct. Mater. 2022, 32, 2110876.
(21) Zou, C.; Yang, L.; Luo, K.; Liu, L.; Tao, X.; Yi, L.; Liu, X.; Luo, Cathode Properties of xLiF–LiCrO2 Composites (x = 0–1.5)
Z.; Wang, X. Ionic Conductivity and Interfacial Stability of Li6PS5Cl− Prepared by Dry Ball-Milling Method for Lithium Ion
Li6.5La3Zr1.5Ta0.5O12 Composite Electrolyte. J. Solid State Electrochem. Batteries
2021, 25 (10), 2513−2525. Ayuko Kitajou, Shunsuke Muto, et al.
(22) Rosero-Navarro, N. C.; Kinoshita, T.; Miura, A.; Higuchi, M.; FEBRUARY 07, 2023
Tadanaga, K. Effect of the Binder Content on the Electrochemical THE JOURNAL OF PHYSICAL CHEMISTRY C READ
Performance of Composite Cathode Using Li6PS5Cl Precursor
Solution in an All-Solid-State Lithium Battery. Ionics 2017, 23 (6), High Ionic Conductivity with Improved Lithium Stability of
1619−1624.
CaS- and CaI2-Doped Li7P3S11 Solid Electrolytes Synthesized
by Liquid-Phase Synthesis
Kazuhiro Hikima, Atsunori Matsuda, et al.
MAY 06, 2022
ACS OMEGA READ

Sputter-Deposited Amorphous Li3PO4 Solid Electrolyte Films

Tsuyoshi Ohnishi and Kazunori Takada
JUNE 08, 2022
ACS OMEGA READ

Engineered Li7La3Zr2O12 (LLZO) for Pseudo-Solid-State

Lithium Metal Batteries (SSLMBs): Tailor-Made Synthesis,
Evolution of the Microstructure, Suppression of Dendritic...
Kuntal Ghosh and Mir Wasim Raja
MARCH 21, 2023
ACS APPLIED ENERGY MATERIALS READ

Get More Suggestions >

9272 https://doi.org/10.1021/acsaem.2c01157
ACS Appl. Energy Mater. 2022, 5, 9266−9272