Article

Cite This: Chem. Mater. 2018, 30, 990−997 pubs.acs.org/cm

Mechanism of Formation of Li7P3S11 Solid Electrolytes through Liquid

Phase Synthesis
Yuxing Wang,† Dongping Lu,*,† Mark Bowden,‡ Patrick Z. El Khoury,‡ Kee Sung Han,‡
Zhiqun Daniel Deng,† Jie Xiao,† Ji-Guang Zhang,† and Jun Liu*,†
†
Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
‡
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
*
S Supporting Information

ABSTRACT: Crystalline Li7P3S11 is a promising solid electro-

lyte for all solid-state lithium/lithium ion batteries. A
controllable liquid phase synthesis of Li7P3S11 is more desirable
than conventional mechanochemical synthesis, but recent
attempts suffer from reduced ionic conductivities. Here we
elucidate the mechanism of formation of crystalline Li7P3S11
synthesized in the liquid phase [acetonitrile (ACN)]. We
conclude that crystalline Li7P3S11 forms through a two-step
reaction: (1) formation of solid Li3PS4·ACN and amorphous
“Li2S·P2S5” phases in the liquid phase and (2) solid-state
conversion of the two phases. The implication of this two-step
reaction mechanism for morphology control and the transport
properties of liquid phase synthesized Li7P3S11 is identified and
discussed.

■ INTRODUCTION
Energy storage devices are pivotal to vehicle electrification and
renewable energy storage, which are key steps for meeting
decarbonization targets around the world. Lithium/lithium ion
batteries (LIBs) are the primary candidates especially in
applications such as electric vehicles (EVs) and portable
electronic devices where high energy densities are required.
However, the high cost and inadequate energy density of state-
of-the-art LIBs hinder further market penetration of EVs. It is
widely accepted that further enhancement of energy density
requires fundamental changes in battery chemistries.1−6 These
changes may arise from electrode materials such as a silicon
anode,7 a lithium metal anode,8,9 Li−S,10 Li−air,11 etc., or from
electrolytes.12 Solid-state electrolytes (SSEs), in particular,
inorganic lithium ion conductors, are generally considered safer
and more thermally and chemically/electrochemically stable,
although this assessment needs to be made on an individual
basis.5,13 Given the well-recognized issues with Li−metal,14 Li−
S,15 and Li−air batteries in liquid systems, an all-solid-state
design may be the solution to enable these systems.16 Other
underappreciated advantages of solid-state electrolyte systems
include the following. (1) Better thermal stability allows battery
operation at elevated temperatures and simplification of
thermal management, which is translated to enhanced pack-
level energy/power densities.17 (2) Dimensional stability allows
the use of multiple electrolyte systems with distinct
functionalities.18 (3) The single-ion conduction nature and
high carrier density improve power performance at low
temperatures and ultrahigh current densities.17
Despite many advantages, most solid-state electrolyte
systems suffer from issues such as relatively low ionic
conductivity, difficulty in forming and retaining intimate
contact with electrode materials, high processing costs,
etc.19,20 Compared with oxides and phosphate systems,
sulfide-based solid electrolytes in general have higher ionic
conductivities and lower elastic moduli (softer), making them a
more practical substitution for liquid electrolytes without much
deviation from the current battery manufacturing process.5,20 It
has been reported that some sulfide systems even have ionic
conductivity exceeding that of liquid electrolytes.17,21−23 Most
notable examples are Li10GeP2S12 (12 mS cm−1)21 and Li7P3S11
(17 mS cm−1)22,23 glass ceramics. Li7P3S11 have been shown to
form interfaces with electrode materials more kinetically stable
than those of Li10GeP2S12.24,25 Conventionally, glass ceramic
Li7P3S11 is synthesized by crystallization of 70Li2S·30P2S5
glass,26 which may be prepared by mechanochemical syn-
thesis27 or the melt quenching method,28 the former being the
preferred method. The mechanochemical synthesis involves
planetary ball-milling of precursor powders under dry or wet
conditions (no chemical interaction between the liquid medium
and the powder). Although it is effective, there are questions
about whether the process is scalable. Also, milled powders
tend to aggregate into micrometer-sized particles, and an
Received: November 18, 2017
Revised: January 2, 2018
Published: January 3, 2018

© 2018 American Chemical Society 990 DOI: 10.1021/acs.chemmater.7b04842

Chem. Mater. 2018, 30, 990−997
Chemistry of Materials
additional pulverization treatment may be necessary for use in
composite electrodes.29
Liquid phase synthesis has proven to be an effective method
for synthesizing nanoparticles with controllable size and
morphology.30 The richness of solution chemistry will endow
great flexibility and tunability to the material preparation
process. For instance, composites of SE and active materials or
SE and conductive carbon can be obtained directly from the
liquid phase.18,31 From a manufacturing point of view, the
liquid phase process is readily scalable and more compatible
with a conventional electrode preparation process such as
composite cathode mixing and slurry coating. The liquid phase
synthesis of sulfide solid electrolytes can be further divided into
two categories. In the first method, precursor powders are
completely dissolved in organic solvents (methanol, ethanol, N-
methylformamide, hydrazine, etc.)32−35 to form a homoge-
neous solution; in the second method, reactions between
precursor powders are mediated by polar, aprotic organic
solvents [tetrahydrofuran (THF), acetonitrile (ACN), 1,2-
dimethoxyethane (DME), ethyl propionate, etc.] to generate
precipitates.36−38 In both methods, final solid electrolyte
products are obtained by drying off the solvent and subsequent
heat treatment for crystallization. While homogeneous
solutions are suitable for coating electrode particles, the
precipitation method is conducive to producing small, uniform
particles. Unfortunately, reported ionic conductivities of solid
electrolytes using either method are lower than those obtained
by mechanochemical or solid-state methods.18,37,39
Recently, various sulfide-based solid electrolytes (β-Li3PS4,
Li7P3S11, Li7P2S8I, etc.) have been synthesized in the liquid
phase.18,36,37,40 Li7P3S11 is of particular interest because of its
extraordinarily high conductivity in its crystalline form;
crystalline Li7P3S11 has been synthesized in THF, acetonitrile,
and DME with a large variation in the reported transport
properties.18,37,39 It is unclear exactly how the Li7P3S11
crystalline phase forms from the deposited electrolyte
precursor. In this research, we improve our understanding of
the mechanism of formation of the Li7P3S11 phase in
acetonitrile by tracking the phase change of not only the
precipitates but also the dissolved phase in the supernatant
liquids. We found that the deposited electrolyte precursor is
actually a mixture of crystalline Li3PS4·ACN and amorphous
“Li2S·P2S5·ACN”, which then convert into crystalline Li7P3S11
through solid-state reaction. Implications of this formation
mechanism for the transport property and morphology of
liquid phase synthesized Li7P3S11 solid electrolytes are
discussed.
■
EXPERIMENTAL SECTION
Because of the extreme sensitivity of the sulfide compounds to
moisture, all operations were performed in an Ar-filled glovebox unless
otherwise noted. The Li7P3S11 powder was synthesized from Li2S (Alfa
Aesar, 99.9%) and P2S5 (Sigma-Aldrich, 99%) in acetonitrile
(Selectilyte BASF, battery grade). All the raw materials were used
without further treatment. Stoichiometric amounts of Li2S and P2S5
were ground first in an agate mortar and poured into the acetonitrile
solvent. The powder:solvent ratio is 1:20 in grams per milliliter. The
mixture was heated at 50 °C on a hot plate and stirred for 3 days. A
slightly greenish solution containing white precipitate was obtained.
The solvent was then allowed to evaporate on a hot plate at 150 °C.
The deposited precursor is denoted as DP. Alternatively, the solution
mixture was sealed in a tube and centrifuged at 4400 rpm for 6 min.
The powder precipitate and the supernatant were separated after
decanting. Both were then dried under vacuum. A clear gel-like
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substance was obtained after the solvent had evaporated from the
supernatant. The dried powder precipitate and the gel from the
supernatant are denoted as PP and SP, respectively. The DP, PP, and
SP samples were then heat-treated at 200 or 260 °C in a sealed PTFE
container filled with argon gas for 1 h. The sample notation is
summarized in Table 1.
Table 1. Samples and Treatment Conditions
samplea treatment
DP deposited precursor from the precipitate and solution mixture
after acetonitrile evaporation
PP powder precipitate after centrifugation and decanting
SP dried solution phase from the supernatant after acetonitrile
evaporation
DP-200 DP annealed at 200 °C for 1 h
DP-260 DP annealed at 260 °C for 1 h
a
PP-200, PP-260, SP-200, and SP-260 are defined in the same manner.
Thermogravimetric analysis (TGA) and differential thermal analysis
(DTA) were performed on samples DP, PP, and SP with a Netzsch
STA 449F1 instrument. Sample loading and weighing were performed
inside glovebox. The sample was transferred quickly into the TG
instrument in a sealed container, and the chamber was flushed
promptly. The samples were heated from 25 to 300 °C under argon.
The morphology of the samples was observed with a dual-focus ion
beam (FIB) scanning electron microscope (Environmental, FEI
Helios) at 5 kV.
Powder X-ray diffraction (PXRD) was used for phase character-
ization. Samples were sealed in thin-walled glass capillary tubes (500
μm diameter, 10 μm wall thickness, Charles Supper Co.) under argon.
A Rigaku D/Max Rapid II microdiffraction system with a rotating Cr
target (λ = 2.2910 Å) operated at 35 kV and 25 mA was used to collect
the diffraction patterns. A parallel X-ray beam collimated to a 300 μm
diameter was directed onto the specimen, and the diffracted intensities
were recorded on a large two-dimensional image plate during a 10 min
exposure. Alternatively, a desktop diffractometer (Rigaku MiniFlex II)
was employed with a scan speed of 2° min−1 and a step size of 0.05°.
The sample was covered with an 8 μm Kapton film during the
measurement.
The Raman spectra were collected using a Raman spectrometer
(Horiba LabRAM HR) coupled with an inverted optical microscope
(Nikon Ti-E). The incident CW laser light source (633 nm) was
attenuated using a variable neutral density filter wheel (to ∼5 μW/
μm2), reflected off a dichroic beam splitter, and focused onto the
sample using a 10× microscope objective. The back-scattered light was
collected through the same objective, transmitted though the beam
splitter cube, and dispersed through a 600 g/mm grating onto a CCD
detector. Spectra were acquired as time series (10 sequentially
recorded spectra, each of which was time-integrated for 5 s) to ensure
the integrity of our sample. As such, the final spectra shown are time-
averaged and otherwise not subjected to further data analysis
procedures.
31
P solid-state magic angle spinning (MAS) nuclear magnetic
resonance (NMR) spectra were obtained at a spinning speed of 20
kHz and 295 K with a 3.2 mm HXY probe on a 600 MHz NMR
spectrometer (Bruker). The spectra were obtained by the Fourier
transformation of free induction decay after a single-pulse excitation
with a 90° pulse length of 4 μs and a repetition delay of 100 s. The 31P
chemical shift (δ) was calibrated using 0 ppm of 85% H3PO4 as an
external reference. Spinning sidebands at multiples of the spinning
speed were determined by comparison between the spectra obtained
at various spinning speeds (15, 20, and 23 kHz).
Electrochemical impedance spectroscopy (EIS) was employed to
characterize the transport properties of the samples; 100 mg of the
sample powder was pelletized by cold pressing in a 10 mm diameter
pressing die at 380 MPa. Indium electrodes were formed by pressing
In foils onto both sides of the pellet at 130 MPa. The pellet was
sandwiched by two stainless steel rods inside a Swagelok setup for
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Chemistry of Materials
Figure 1. (a) Images of the deposited precursor (DP), the powder precipitate (PP), and the supernatant containing the solution phase. (b) TGA and
DTA data of PP, DP, and SP samples.
impedance measurement. The measured temperature range was −40
to 100 °C. Low-temperature testing was performed inside an
environmental chamber using an electrochemical interface (Solartron
1287, Solartron Analytical) and a frequency response analyzer
(Solartron 1260, Solartron Analytical); high-temperature testing was
performed inside a heating oven using a Biologic potentiostat
(VMP3). The frequency range was 1 MHz to 1 Hz.
■
RESULTS AND DISCUSSION
White precipitates appear immediately after the mixture of Li2S
and P2S5 (originally yellowish) is added to acetonitrile. The
colorless solution turns bluish within 1 min. The bluish color is
preserved after the mixture is stirred at 50 °C for 3 days. The
obtained DP sample (without centrifugation) appears slightly
yellowish, whereas the PP sample (with centrifugation) appears
entirely white (Figure 1a). Interestingly, the color of the
supernatant changes from bluish to yellowish slowly after
decanting. It is consistently found that the yields of DP and PP
are ∼0.7 of ∼1.15 g, respectively; a clear gel-like substance
remains after the evaporation of acetonitrile. These pieces of
evidence clearly suggest that some of the Li2S and P2S5
precursors remain in the supernatant and the DP is actually a
combination of PP and SP.
According to TGA and DTA (Figure 1b), both samples PP
and DP exhibit one major thermal event around 200 °C. Close
inspection reveals that the onset and peak temperatures of the
DP sample are 10 °C higher than those of the PP sample (200
and 220 °C vs 190 and 210 °C, respectively). Both samples
experience large weight losses during the event. Rangasamy et
al. reported that Li2S and P2S5 at a 3:1 molar ratio combine
with acetonitrile to form an unknown crystalline phase, which
the authors assigned as Li3PS4·2ACN.40 For sample PP, the
weight loss below 100 °C can be attributed to absorbed
acetonitrile; minimal weight loss was observed between 100
and 190 °C and above 230 °C, suggesting that the complex
phase is stable below 190 °C but decomposes and releases all
acetonitrile above 190 °C in an endothermic reaction. This is in
stark contrast to Li3PS4·3THF (tetrahydrofuran), which
decomposes at ∼100 °C.36 However, on the basis of the
weight loss of the PP sample at 200 °C, we believe the formula
of the acetonitrile complex should be Li3PS4·ACN rather than
Li3PS4·2ACN. The TG and DTA curves of sample SP show a
rather smooth continuous trend throughout the temperature
range. Most features are too small to explain. Noticeably, there
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appears to be a small exothermic peak in the DTA curve, and a
slight change in slope in the TG curve at 260 °C. Similar
features can be seen in the TG and DTA curves of sample DP.
The origin of these peaks will be discussed below. In addition,
sample DP continued to lose weight after the major thermal
event, similar to sample SP but to a lesser degree. The TGA
and DTA results suggest sample DP has characteristics of
samples PP and SP.
The morphologies of PP-260, DP-260, and SP-260 were
characterized by scanning electron microscopy (SEM) (Figure
2). PP-260 and DP-260 samples were in the powder form; SP-
Figure 2. Scanning electron microscopy images of samples (a) PP-260,
(b) DP-260, and (c) SP-260.
260 was obtained by casting the supernatant onto an aluminum
substrate followed by annealing. Sample PP-260 consists of
submicrometer primary particles (Figure 2a). Determination of
the exact particle size is complicated by slight agglomeration of
primary particles. Nevertheless, these particles are much more
uniform and smaller than those synthesized via mechanochem-
ical synthesis.29,41 Sample SP-260 before annealing (Figure
S1d) shows a featureless, complete coverage of an amorphous
phase on the substrate; after annealing, the amorphous feature
remains in most of the regions while cracks and particles appear
(Figure 2c), probably due to shrinkage induced by acetonitrile
evaporation. The morphology of DP-260 is similar to that of
PP-260, but there seems to be more agglomeration or
secondary amorphous phase binding of the primary particles
(Figure 2b). From the low-magnification images (Figure S1), it
can be seen that some primary particles agglomerate into very
large secondary particles in the extreme case. In contrast,
particles in sample PP-260 seem to be more dispersible. These
results indicate the amorphous solution phase has a critical
effect on the morphology of Li7P3S11.
The PXRD patterns of sample PP (Figure S3) before
annealing match well with those of the crystalline phase
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“Li3PS4·2ACN”;40 after annealing at 200 or 260 °C, the
patterns (Figure 3) match well with those of the reported β-
Figure 3. PXRD patterns of samples DP, PP, and SP after heat
treatment at 200 or 260 °C. The raw patterns and detailed pattern
fitting can be found in Figure S2.
42
Li3PS4. Peaks corresponding to Li2S were observed in both
patterns, indicating small amounts of Li2S were present in both
samples. The crystallinity of sample PP is higher with a higher
annealing temperature; small unknown peaks also disappear in
sample PP-260. We can unambiguously conclude from the
XRD and TGA/DTA data that the main phase of sample PP is
Li3PS4·ACN, which undergoes decomposition and transforms
into β-Li3PS4 phase at >190 °C.
For sample DP, the XRD pattern before annealing is similar
to that of PP (Figure S3), suggesting that the SP coverage on
PP is indeed amorphous. After annealing, the pattern of DP-
260 matches well with that of the high-conductivity Li7P3S11
phase, whereas DP-200 is a combination of Li7P3S11, β-Li3PS4,
and some unknown phase. It should be noted that Bragg peaks
reflect only crystalline phases, and amorphous phases could also
be present in the sample. The completely different phases of
DP-260 and PP-260 indicate the critical role of the solution
phase (SP) in converting the powder precipitate (PP) into the
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desired Li7P3S11 phase. The conversion occurs at a temperature
that is slightly higher (∼10 °C) than that of the conversion of
sample PP into β-Li3PS4, as seen from TG and DTA, which
explains the presence of both β-Li3PS4 and Li7P3S11 phases in
sample DP-200. As DP is basically PP particles coated by SP,
two processes need to occur during the conversion: (1)
decomposition of PP and formation of β-Li3PS4 with the release
of ACN and (2) solid-state reaction of SP with PP or PP
derivatives. It is inconclusive whether the two processes occur
concurrently or sequentially; the presence of β-Li3PS4 suggests
the latter mechanism is more likely. It can also be inferred that
due to the need for solid-state diffusion and reaction, the
formed crystalline Li7P3S11 may suffer from local inhomoge-
neity and nonstoichiometry. According to the SEM image
(Figure 2b), the conversion did not consume the SP coating
completely, as some amorphous coverage was still observed in
sample DP-260.
PXRD is useful in the identification of crystalline phases, but
amorphous components of the sample cannot be characterized.
Raman and 31P MAS NMR spectroscopy were employed as
complementary tools to improve our understanding of the local
structures of the samples. The Raman spectra of PP-200 and
PP-260 are similar (Figure 4). A single peak at 426 cm−1 can be
Figure 4. Raman (left) and 31P MAS NMR (right) spectra of samples
DP, PP, and SP annealed at different temperatures. The asterisk
denotes a spinning sideband.
assigned to the local structural unit of PS43− tetrahedra,
confirming that only the Li3PS4 phase is present.43 The
spectrum of sample DP-260 shows a major peak at 410 cm−1
corresponding to the local structural unit of P2S74− and a
shoulder peak at 426 cm−1 corresponding to PS43−, consistent
with the crystalline structure of the Li7P3S11 phase.27 The 426
cm−1 peak is stronger in sample DP-200. This is expected as the
residual β-Li3PS4 phase is present in the XRD pattern of DP-
200. The Raman spectrum of SP-260 is not presented because
of the large fluorescence background, which hinders the
determination of its local structure.
The 31P MAS NMR spectra of samples PP-260 and DP-260
(Figure 4) match well with the reported spectra of 75Li2S·
25P2S5 and 70Li2S·30P2S5 glass ceramics.44 The two strong
peaks at 91 and 87 ppm can be assigned to the structural units
of P2S74− and PS43− in the crystalline phases, respectively.45
Seino et al. analyzed the degree of crystallization in the 70Li2S·
30P2S5 glass ceramics using 31P MAS NMR.46 They showed
that broad peaks related to P2S74− and PS43− units in the
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Chemistry of Materials
Figure 5. Schematic illustration of the mechanism of formation of Li7P3S11 synthesized in acetonitrile.
amorphous component convolute with sharp peaks corre-
sponding to P2S74− and PS43− in the crystalline component in
poorly crystalline samples. Minimal broadening at the base of
sharp crystalline peaks was observed in the spectra of samples
PP-260 and DP-260, suggesting that both samples are mostly
crystalline. Two small peaks at 109 and 105 ppm in the
spectrum of DP-260 can be assigned to the structural unit of
P2S64− in the crystalline Li4P2S6 phase. The Li4P2S6 phase is
known to arise from decomposition of glassy Li4P2S7 with
release of elemental S.45 It is also reported that prolonged
heating of Li7P3S11 will lead to formation of the Li4P2S6 phase.47
We can safely conclude from XRD, Raman, and 31P NMR
analysis that the crystalline Li7P3S11 phase is formed by
conversion of Li3PS4 or Li3PS4·ACN and the solution phase
through solid-state reaction. There remains a question about
what the solution phase is. To answer the question, we
conducted a similar synthesis but varied the Li2S:P2S5 molar
ratio. Interestingly, the quantity of powder precipitates
decreases with an increase in the amount of P2S5; e.g., at a
55:45 ratio, only 0.2 g of PP was obtained from a total of 1 g of
precursors. The XRD pattern of PP at a 55:45 ratio is similar to
that at a 75:25 ratio (Figure S3), also matching the dried
precursor:Li7P3S11 ratio of Yao et al.18 and that of the “Li3PS4·
2ACN” phase of Rangasamy et al.,40 indicating that all the
powder precipitates are essentially the same compound. At a
1:1 ratio, Li2S and P2S5 dissolve quickly to form a clear
yellowish solution. Indeed, Liang et al. have shown that the 1:1
Li2S/P2S5 solution can be used to coat Li2S particles.48,49
Therefore, the solution phase is some amorphous form of
“Li2S·P2S5·xACN”. The term “Li2S·P2S5” is used in a vague
sense to refer to the phase with a Li2S:P2S5 molar ratio of 1:1
that either dissolves in or precipitates out of the solution,
because the solvated form of the solution phase or the structure
of the amorphous solids after solvent removal was not directly
determined. It should be noted that neither Li2S nor P2S5 is
soluble in acetonitrile, so the dissolution of Li2S and P2S5 (1:1)
is probably due to the formation of a new structural P2S62− unit
that is soluble in acetonitrile. We believe that Li2S and P2S5 (in
an x:100 − x molar ratio, where 50 < x < 75) participate in the
reaction in acetonitrile as follows:
x Li 2S + (100 − x)P2S5 + ACN
→ 2(x − 50)Li3PS4 ·ACN(p) + 2(75 − x)Li 2S· P2S5(s)
When x < 50, soluble “Li2S·P2S5” forms and some P2S5 remains
undissolved; when x > 75, the Li3PS4·ACN precipitate forms
and some Li2S remains undissolved. In the case of 70Li2S·
30P2S5 under equilibrium conditions, 80 mol % Li3PS4·ACN
(PP) precipitates out while 20 mol % “Li2S·P2S5” dissolves in
the solution.
After acetonitrile evaporation, the Li3PS4·ACN precipitates
are coated by the amorphous “Li2S·P2S5” phase and then
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converted to the high-conductivity Li7P3S11 phase after
annealing. The proposed mechanism of formation of Li7P3S11
is illustrated in Figure 5. This precipitation−solid-state
conversion reaction mechanism may be universal to the liquid
phase synthesis of thiophosphate compounds and their
derivatives, as the Li3PS4·ACN phase may be the only stable
precipitate. For instance, the Li7P2S8I phase has been
synthesized by solid-state reaction of liquid phase-synthesized
“Li3PS4·2ACN” and LiI.40 It follows that the morphology of
these liquid-synthesized thiophosphate compounds is largely
determined by that of the Li3PS4·ACN precipitate. Therefore,
the mechanism of formation of the Li3PS4·ACN precipitate is
critically important, which has not been elucidated. Given the
insoluble nature of Li2S and high solubility of “Li2S·P2S5”, the
formation of Li 3 PS 4 ·ACN most likely occurs through
conversion of Li2S particles from outside to inside by the
“Li2S·P2S5” solution. Under such an assumption, the morphol-
ogy of Li2S particles will determine the morphology of the
Li3PS4·ACN precipitate. When the Li2S precursor particles are
large, the conversion may never reach completion because of
the passivation of the outer Li3PS4·ACN, which can explain the
presence of Li2S in samples PP-200 and PP-260.
With annealing of the precipitates and solution phase
mixture, a majority of the solution phase will be “assimilated”
during the solid-state reaction but a small amount may remain
on the surface of Li7P3S11 particles. Therefore, the state into
which the solution phase transforms at the annealing
temperature will influence the transport property of DP-260.
The PXRD patterns of SP-200 and SP-260 have large
amorphous backgrounds, consistent with the SEM observation
that the sample remains mostly amorphous. Bragg peaks in SP-
200 can be attributed to P2S5, and peaks in SP-260 can be
attributed to Li4P2S6 and Li2P2S6 phases.50,51 The small
exothermic peak in the DTA data of sample SP can then be
attributed to crystallization of the amorphous phase. The 31P
NMR spectrum of SP-260 is quite complex. Most peaks are
broad, confirming the amorphous nature. The peak at 109 ppm
is associated with P2S64− in the Li4P2S6 phase; the peak at 83
ppm is due to glassy Li2S−P2S5.45 Two peaks of small chemical
shifts are unidentified. Nevertheless, none of the crystalline
Li 4 P 2S 6 , Li 2 P 2 S 6 , or glassy Li 2 S−P 2 S 5 has good ionic
conductivity,50−52 so the presence of the residual solution
phase is expected to lower the overall ionic conductivity of
sample DP-260.
The ionic conductivity of sample DP-260 was characterized
by electrochemical impedance spectroscopy over the temper-
ature range of −40 to 100 °C. The impedance plots are shown
in Figure S4, and detailed fitting information can be found in
the Supporting Information. At or above room temperature (22
°C), the impedance plots show a straight line intercepting or
trending toward the x-axis at low and intermediate frequencies
whereas the bending at high frequencies is due to stray
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capacitance and stray inductance. The straight line represents a
contribution from the electrodes, and the intercepts give the
impedance of the materials. It cannot be determined from these
data what components contribute to the impedance; therefore,
we denote it as total impedance (Rt). At low temperatures (≤0
°C), a semicircle appeared whose left intercept did not go to
zero. Apparently, there are at least two processes that
significantly contribute to overall impedance. Literature
references of low-temperature impedance measurement of
Li7P3S11 solid electrolytes are scarce, so it is difficult to
determine the origin of the low-frequency semicircle. We
assume that the process at high frequency corresponds to
intragrain (bulk) transport and the process at lower frequency
corresponds to intergrain transport. The intergrain impedance
may be due to secondary phases or simply grain boundary
impedance. The intragrain resistance and the intergrain
resistance were obtained by fitting, and the ionic conductivities
were calculated from the resistance and the sample geometry.
The room-temperature conductivity of sample DP-260 is 8.7 ×
10−4 S cm−1.
The activation energy was calculated on the basis of the
Arrhenius equation: σ = σ0/T exp(−Ea/kT). It can be seen
(Figure 6) that the total ionic conductivity shows a good
Figure 6. Arrhenius plot for the total and intergrain ion conductivity of
Li7P3S11 (260 °C, DP-260).
Arrhenius behavior in the entire temperature range with an
activation energy of 0.37 eV (36 kJ mol−1). This value is close
to that of 70Li2S·30P2S5 glass obtained by mechanical milling
and much lower than that of 70Li2S·30P2S5 glass ceramics (0.18
eV). Seino et al. showed that the activation energy of 70Li2S·
30P2S5 glass ceramics from mechanical milling is roughly
negatively correlated with the degree of crystallization.
However, the observed high activation energy cannot be
explained by this correlation because the XRD and NMR data
indicated that sample DP-260 is mostly crystalline. This
observation highlights the key differences between Li7P3S11
solid electrolytes obtained via solid-state route and liquid phase
synthesis. Glass ceramics obtained by a solid-state route arise
from crystallization of a homogeneous single-phase glass,
whereas liquid phase synthesized samples arise from reaction
of at least two phases. Notably, the reported activation energies
of Li7P3S11 via liquid phase synthesis, despite all having the
superionic crystal phase, have large variation, ranging from 23
to 38 kJ mol−1.18,37,39 This is not surprising considering the
complexity of the formation mechanism in the liquid phase as
995
Article
elucidated by this study and hence how sensitive the transport
properties can be to experimental conditions. Identifying the
two-step reaction mechanism provides crucial clues for further
improving the quality of Li7P3S11 from the liquid phase
synthesis. Measures that could potentially improve the
transport property of liquid phase-synthesized Li7P3S11 should
focus on facilitating complete conversion of the two solid
phases, for instance, (1) optimizing the solvent extraction
process so the two phases are more uniformly mixed, (2)
optimizing the annealing process for better solid-state
conversion, and (3) reducing the size of the Li3PS4·ACN
particle to shorten diffusion length, etc.
It is evident that the intergrain process has an activation
energy much higher than that of the intragrain process.
Although indeterminable from the impedance spectrum, the
intergrain resistance at 22 and 50 °C can be calculated by
extrapolation to be 10 and 1 Ω, respectively; the intergrain
resistance is negligible at high temperatures.
■
CONCLUSIONS
The mechanism of formation of crystalline Li7P3S11 solid
electrolytes synthesized in acetonitrile was revealed by
analyzing the intermediate products during the reaction. It is
found that the precursors (70:30 Li2S:P2S5 molar ratio) in
acetonitrile form Li3PS4·ACN (75:25 Li2S:P2S5) precipitates
and soluble “Li2S·P2S5” (50:50 Li2S:P2S5). Unlike the β-Li3PS4
crystalline phase that forms directly from the decomposition of
Li3PS4·ACN precipitates, crystalline Li7P3S11 forms through the
solid-state reaction of the Li3PS4·ACN precipitates and the
amorphous “Li2S·P2S5” phase from the supernatant. The
soluble species “Li2S·P2S5” appears as amorphous coverage on
the precipitate particles after acetonitrile evaporation. The
liquid phase-synthesized Li7P3S11 has a total conductivity of
0.87 mS cm−1 at room temperature. The understanding of the
formation mechanism provides clues for further optimizing the
transport properties and morphologies of liquid phase-
synthesized Li7P3S11 solid electrolytes.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.7b04842.
Additional SEM images and XRD data, impedance
spectra, and detailed fitting information (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: dongping.lu@pnnl.gov.
*E-mail: jun.liu@pnnl.gov.
ORCID
Dongping Lu: 0000-0001-9597-8500
Patrick Z. El Khoury: 0000-0002-6032-9006
Kee Sung Han: 0000-0002-3535-1818
Ji-Guang Zhang: 0000-0001-7343-4609
Jun Liu: 0000-0001-8663-7771
Notes
The authors declare no competing financial interest.
DOI: 10.1021/acs.chemmater.7b04842
Chem. Mater. 2018, 30, 990−997
Chemistry of Materials
■ ACKNOWLEDGMENTS
This work was supported by the Energy Efficiency and
Renewable Energy (EERE) Office of Vehicle Technologies of
the U.S. Department of Energy (DOE) under Contract
DEAC02-05CH11231 and DEAC02-98CH10886 for the
Advanced Battery Materials Research (BMR) Program and
the U.S. DOE EERE Water Power Technologies Office and the
U.S. Army Corps of Engineers Portland District. SEM, solid-
state NMR, and Raman characterization were conducted in the
William R. Wiley Environmental Molecular Sciences Labo-
ratory (EMSL). PNNL is operated by Battelle for the DOE
under Contract DE-AC05-76RLO1830.
■
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997 DOI: 10.1021/acs.chemmater.7b04842

Chem. Mater. 2018, 30, 990−997