REVIEWS

Liquid-phase syntheses of sulfide

electrolytes for all-solid-state lithium
battery
Akira Miura1, Nataly Carolina Rosero-Navarro 1, Atsushi Sakuda 2,
Kiyoharu Tadanaga 1*, Nguyen H. H. Phuc3, Atsunori Matsuda3, Nobuya Machida4,
Akitoshi Hayashi2 and Masahiro Tatsumisago2*
Abstract | Solid sulfide electrolytes are key materials in all-solid-state lithium batteries
because of their high lithium-ion conductivity and deformability , which enable the
lithium-ion path to be connected between the material’s grain boundaries under pressure
near room temperature. However, sulfur species are moisture-sensitive and exhibit high
vapour pressures; therefore, syntheses of sulfide electrolytes need to be carefully
designed. Liquid-phase reactions can be performed at low temperatures in controlled
atmospheres, opening up the prospect of scalable processes for the preparation of sulfide
electrolytes. Here, we review liquid-phase syntheses for the preparation of sulfide-based
solid electrolytes and composites of electrolytes and electrodes, and we compare the
charge–discharge performances of the all-solid-state lithium batteries using these
components.

High energy density and long cycle life in rechargeable with electrodes in a wide voltage range. The all-solid-
batteries are in high demand, especially for electronic state cell composed of sulfide electrodes and sulfide
vehicles and for large-scale power storage to balance electrolytes can operate as a secondary battery over a
the electrical grid using renewable energy. Lithium wide temperature range of –30–+160 °C (ref.22) without
batteries can achieve high energy density per weight showing substantial degradation owing to the dissolu-
because lithium is the lightest solid element at room tion of sulfide electrodes into solid electrolytes, even at
temperature under ambient pressure and is character- high temperatures.
ized by a low reduction potential. However, the flam- Sulfide-based solid electrolytes show excellent
mable organic electrolytes in lithium-ion batteries lithium-ion conductivities, in some cases even higher
pose safety issues and limit the temperature range of than those of liquid organic electrolytes15, and are more
1
Faculty of Engineering, operation of the batteries. Past decades have seen the deformable than oxide electrolytes23. The grain bound-
Hokkaido University, development of all-solid-state lithium batteries that ary resistance of sulfide electrolytes can be decreased just
Sapporo, Japan. can solve these safety concerns by avoiding the use of by pressing the material at room temperature or at mod-
2
Department of Applied flammable electrolytes1–5. The use of solid electrodes can erate temperatures below 200 oC (refs24,25). Furthermore,
Chemistry, Graduate School of
help to achieve high lithium-ion conductivity, as only sulfide electrolytes can form low-resistive interfaces
Engineering, Osaka Prefecture
University, Sakai, Japan.
lithium ions are transported in the solid frameworks between electrodes coated with an effective buffer layer
3
Department of Electrical
without the diffusion of anions. A breakthrough in this and electrolytes in composite electrodes consisting of
and Electronic Information area was the discovery of solid electrolytes with high electrodes and electrolytes26.
Engineering, Toyohashi lithium-ion conductivities4,6–9, which include glasses Most sulfide-based electrolytes are not stable in
University of Technology, and glass ceramics10–12, Li14Zn(GeO4)4/Li4−xGe1−xPxS4 and water, leading to the evolution of H2S gas (although this
Toyohashi, Japan.
their analogues (so-called LISICON/thio-LISICON instability can be improved by modifying or changing
4
Department of Chemistry, and LGPS) 11 – 15 , Li 6PS 5Cl and isostructural com- the electrolyte compositions27–29) and making the syn-
Konan University, Kobe, Japan.
pounds (argyrodites)16,17, La2/3−xLixTiO3 and related thetic processes complex30. Usually, starting materials
*e-mail: tadanaga@
perovskites18, Li1+xAlxTi2−x(PO4)3-related compounds and products are handled in an Ar-filled glove box15,16.
[Link]; tatsu@
[Link] (so-called NASICON)19 and Li7La3Zr2O12 and isostruc- In laboratory-scale syntheses, evacuated quartz ampou­les
[Link] tural compounds (garnets)20,21. Solid electrolytes are sta- are commonly used for heat treatment to prevent the
s41570-019-0078-2 ble over a wide temperature range and can be coupled release of sulfur species with high vapour pressure.

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Reviews

a Suspension synthesis energy densities of all-solid-state batteries. Initial stud-

ies of model active-material particles coated with a thin
Solvent
electrolyte were conducted using pulse laser deposition
(PLD)38–40. However, PLD needs to be performed under
• Li2S Mixing
• P2S5
a high vacuum, limiting the scale-up of the process.
• (Li salt) Liquid-phase processes can be scaled up relatively eas-
ily because, in these cases, solutions are used to cover
electrodes and electrode composites are formed dur-
∆ ing the subsequent heating processes. Furthermore,
b Dissolution–precipitation
mixing of electrodes, electrolytes and electron con-
Solvent Sulfide ductors does not require the use of special apparatuses,
electrolyte and low-temperature treatments prevent undesirable
Sulfide Mixing reactions between electrodes and sulfide electrolytes.
electrolyte In this Review, we report on the progress of the
liquid-phase synthesis of sulfide electrolytes for
all-solid-state lithium batteries. We categorize this into
two groups5 (Fig. 1): first, we focus on the suspension
Fig. 1 | Schematic of liquid-phase syntheses of sulfide electrolytes. a | In the synthesis of sulfide electrolytes from Li2S and P2S5 in
suspension syntheses, precursors such as Li2S and P2S5 are suspended (through mixing) organic solvents; second, we introduce the dissolu-
in organic solvents, such as 1,2-dimethoxyethane, tetrahydrofuran, acetonitrile, ethyl tion–precipitation of sulfide electrolytes using solvents
acetate, dimethyl carbonate and ethyl propionate, in which the precursors are not highly in which they are highly soluble. Finally, we summa-
soluble. Li2S and P2S5 form complexes in solution, which are allowed to precipitate rize the liquid-phase processes and the performances
through heating and consequent evaporation of the solvent. b | In the dissolution– of all-solid-state lithium batteries using composite
precipitation approach, the solid electrolyte is complexly dissolved in solvents such as ­electrodes produced by liquid-phase routes.
hydrazine, N-methylformamide, methanol and ethanol. Heating enables the
precipitation of the solid sulfide electrolytes. Δ, heat treatment.
Liquid-phase reactions for solid electrolytes
Suspension syntheses. Most of the syntheses of solid
However, the use of quartz ampoules makes the scale-up electrolytes using the suspension approach (Table 1) have
of such synthetic approaches difficult. High-energy been performed to produce Li2S–P2S5 solid electrolytes, for
ball-milling syntheses near room temperature have also which Li2S and P2S5 are the precursors. The precursors are
been developed10, but the amount of product is limited by dispersed in organic solvents such as 1,2-dimethoxyethane
the size of the ball-milling jar, and syntheses are typically (DME), tetrahydrofuran (THF), acetonitrile (ACN),
performed over 8–50 hours10,17. ethyl acetate (EA), dimethyl carbonate (DMC) and ethyl
Liquid-phase syntheses have been proposed for the propionate (EP). Dispersed Li2S and P2S5 form com-
production of metal sulfides, chalcogenides (such as plexes (Fig. 2a), although partial dissolution of precursors,
ZnS and CdSe) and their clusters for use in electronic intermediates and their complexes might occur (Fig. 2b),
devices, solar cells and biological probes31–33. Until 2012, as shown in a few studies that reported a complete dis-
limited work was conducted on liquid-phase chemistry solution of the intermediates and the precipitation of the
with thiophosphates, which are the main components products41–43. Solid–liquid separation or solvent evapora-
of Li-conducting sulfide electrolytes34,35. More recently, tion results in the formation of solid complexes such as
more attention has been paid to liquid-phase syntheses, Li3PS4·3THF, and further heating at 60–300 °C removes
and these have been used for the preparation of solid organic solvents to form sulfide electrolytes. Because Li2S
electrolytes. Liquid-phase syntheses present several and the synthesized sulfide electrolytes are highly water
advantages with respect to solid-state ones in terms of sensitive, they are handled in an inert atmosphere, typically
synthesis temperature, synthesis time and scalability. in an Ar-filled glove box.
Liquid-phase syntheses are usually performed below In 2013, Liang and co-workers reported the synthesis
300 °C, a much lower temperature than that required of nanoporous β-Li3PS4 (Fig. 2c,d) using THF as the
by solid-state synthesis, which is typically above 500 °C solvent44. Overnight stirring of Li2S and P2S5 in THF and
(refs15,16). Liquid-phase syntheses can be performed subsequent centrifugation produced a Li3PS4·3THF
in a glass container, with the vapour pressure of sul- complex. Further heating at 80 °C decomposed this com-
fur species being low. Moreover, they can lead to the plex, resulting in the formation of amorphous Li3PS4 with
formation of metastable phases with high lithium-ion an ionic conductivity of 7.4 × 10−5 S cm−1. After heating
­conductivities, such as Li7P3S11. at 140 °C, nanoporous β-Li3PS4 was formed. Three poly­
Liquid-phase processes are also attractive for pro- morphs of Li3PS4 can be attained through a solid-state
ducing composites of electrolytes and electrodes in reaction: depending on the temperature, α-Li 3PS 4
all-solid-state lithium batteries. The composite pos- (>485 °C), β-Li3PS4 (300 - 485 °C) or γ-Li3PS4 (<300 °C)
itive electrodes prepared by milling using a mortar phase can be observed45. This means that suspension syn-
and pestle typically need to be mixed with 30–60 wt% thesis leads to a thermodynamically metastable phase at
solid electrolyte to maintain lithium-ion conduction low temperature. The lithium-ion conductivity of β-Li3PS4
pathways to the electrodes36,37. Indeed, the minimum is 1.6 × 10−4 S cm−1 at 25 °C, which is higher than that of
amounts of solid electrolytes that sustain lithium-ion thermodynamically stable γ-Li3PS4 (3.0 × 10−7 S cm−1)45.
conduction pathways should be used to maximize the Faceted particles of the Li3PS4·3THF complex were a few

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Table 1 | Suspension synthesis of sulfide-based solid electrolytes and their conductivities at room temperature
Product Reactant Solvent Temperature (°C) σ (mS cm−1) Refs
a-Li3PS4 Li2S, P2S5 THF 80 0.074 44

β-Li3PS4 Li2S, P2S5 THF 140 0.16 44

β-Li3PS4 Li2S, P2S5 EA 160 0.33 50

β-Li3PS4 Li2S, P2S5 ACN 200 0.12 51

β-Li3PS4 Li2S, P2S5, LiSC2H5 THF 140 0.132 42

Li7P3S11 Li2S, P2S5 ACN 220 1.5 55,56

Li7P3S11 Li2S, P2S5 DME 250 0.27 47

Li7P3S11 Li2S, P2S5 ACN 250 0.97 48

Li7P3S11 Li2S, P2S5 ACN 260 1.5 49

Li7P2S8I Li2S, P2S5, LiI EP 170 0.46 41

Li7P2S8I Li2S, P2S5, LiI ACN 200 0.63 46

Li4PS4I Li2S, P2S5, LiI DME 200 0.12 52

σ, conductivity ; a-Li3PS4, amorphous-Li3PS4; ACN, acetonitrile; DME, 1,2-dimethoxyethane; EA , ethyl acetate; EP, ethyl propionate;
THF, tetrahydrofuran.

tens of micrometres in size, being similar in size to the β-Li3PS4 was synthesized using either EA50 or ACN51,
β-Li3PS4 particles (Fig. 2c). Nonetheless, nanosized pores achieving conductivities of 3.3 × 10 −4 S cm –1 and
were observed on the surfaces of the β-Li3PS4 particles, 1.2 × 10 −4 S cm −1, respectively. Li 4PS 4I was synthe-
resulting in a high surface area. In 2014, the same group sized first by mixing the Li3PS4·DME complex and LiI
also reported the liquid-phase synthesis of a new phase, in DME to form a Li3PS4·DME·LiI complex and then
Li7P2S8I, using ACN46. The synthesis involved the for- heating the intermediates at 50–200 °C (ref.52). The ionic
mation of a Li3PS4·2ACN complex in an ACN solvent conductivity was determined to be in the range of
over 24 hours, mixing of this complex with LiI in ACN 6.4 × 10−5−1.2 × 10−4 S cm−1 at room temperature.
and subsequent heating at 200 °C. Li7P2S8I exhibited an Enhancement of the kinetics of suspension reac-
ionic conductivity of 6.3 × 10−4 S cm−1 and high stability tions to shorten the synthesis time has been achieved
towards metallic lithium. by using various mixing approaches. For example,
The preparation of a highly lithium-ion-conductive the use of zirconia balls to shake the mixture of Li2S
Li7P3S11 phase (Fig. 2c) using DME was reported by and P2S5 in DMC53 facilitated the formation of amor-
Machida et al.47 in 2014. The process included the phous Li 3PS 4 (conductivity of 6 × 10 −6 S cm −1) and
stirring of starting materials in DME for 72 hours and Li3PS4–LiI solid solutions in the presence of LiI and EP
subsequent heating at different temperatures. X-ray (conductivity of 3.4 × 10−4 S cm−1)54. The typical mixing
diffraction (XRD) patterns showed the formation of time was 1.5–6 hours, which was significantly shorter
the Li7P3S11 phase, and Raman spectra of the products than those reported above. Li7P3S11 (conductivities of
heated at 200 °C and 250 °C showed peaks at 420 cm−1 0.9–1.5 × 10−3 S cm−1) was synthesized in ACN by per-
and 405 cm−1 corresponding to the PS43- and P2S74- units, forming ultrasonication for 1 hour followed by a heat
respectively (Fig. 2e). The Li7P3S11 phase decomposed at treatment at 220 °C (refs55,56). Another approach to
300 °C and exhibited a maximum ionic conductivity of increasing the kinetics is to use a homogeneous solu-
2.7 × 10−4 S cm−1 at room temperature47. tion as an intermediate41. The reaction between P2S5
From 2015, more studies reported on electrolytes and LiI was completed without solid precipitates for
exhibiting ionic conductivities close to 10−3 S cm−1 that a LiI:P2S5 molar ratio of 2. Li2S was then added to this
were attained through mixing of the starting materials solution, shortening the mixing time to 30–60 minutes.
in a solvent for 24–72 hours. A Li7P3S11 electrolyte was The following mechanism was proposed for the reaction
prepared using ACN, ACN–THF and THF, and a max- between Li2S, P2S5 and LiI in EP:
imum ionic conductivity of 9.7 × 10−4 S cm−1 at 25 °C
was found in the product synthesized using ACN and LiI + P2S5 → LiI ⋅ P2S5 (solution) (1)
heated at 250 °C (ref.48). Another study showed that
higher conductivities of up to 1.5 × 10−3 S cm−1 at room
temperature could be attained if Li7P3S11 was instead LiI ⋅ P2S5 (solution) +3Li 2S → 2Li 3PS4+LiI (2)
heated at 260 °C (ref.49). Liu et al. proposed a two-step
mechanism for the synthesis of Li7P3S11 using ACN and β-Li3PS4 with an ionic conductivity of 1.32 × 10−4 S cm−1
heat43. First, the Li3PS4·ACN complex was formed by dis- was synthetized using the same approach with the addi-
solving Li2S·P2S5 in ACN, and a mixture of Li3PS4·ACN tion of a nucleophilic agent, LiSC2H5, and a mixing time
and Li2S·P2S5 was produced by heating the solution. of 12 hours42.
A subsequent solid-state reaction between the two com- To overview the trends of synthesis conditions in sus-
pounds resulted in the formation of Li7P3S11. The ionic pension synthesis, the ionic conductivities of electrolytes
conductivity after heating at 260 °C was 8.7 × 10−4 S cm−1. prepared near room temperature are plotted against the

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a b c β-Li3PS4 Li S Li7P3S11
THF ∆ b
1.5Li2S+0.5P2S5 Li3PS4 ·3THF β-Li3PS4
mixing
c c a
ACN ∆ a
3.5Li2S+1.5P2S5 2Li3PS4 ·ACN+0.5Li2SP2S5 Li7P3S11 b
mixing
d e 386cm–1 f
300˚C
10-3

Conductivity (S cm–1)
250˚C

Intensity (a.u.)
10μm 405cm–1
250˚C
10–4
420cm–1
Dried Li7P3S11 Li7P2S8I
Wet Li3PS4 Li4PS4I
10–5
10μm 500nm 500 400 300 0 100 200 300
(cm–1) Heating temperature(˚C)
Fig. 2 | Suspension synthesis of sulfide electrolyte. a | Suspension reactions for the synthesis of representative solid
sulfide electrolytes43,44. b | Photo of suspension for the Li7P3S11 precursors. c | In the left panel, the crystal structure of
β-Li3PS4 is shown, with the tetrahedrons denoting PS43– (refs45,79). In the right panel, the crystal structure of Li7P3S11
with PS43– and P2S74– units is shown79,80. d | Faceted Li3PS4·3THF particles (shown in the top-left panel)44, β-Li3PS4 particles,
which have a morphology similar to that of Li3PS4·3THF particles (shown in the bottom-left panel)44 and a β-Li3PS4 surface
featuring nanopores (shown in the right panel)44. e | Raman spectra of the various steps of the suspension synthesis of
Li2S–P2S5 powder47. Peaks at 420 cm−1, 405 cm−1 and 386 cm−1 are attributed to PS43–, P2S74− and P2S64−, respectively. PS43−
and P2S74− in the Li7P3S11 phase are detected after drying and subsequent heating at 200 °C and 250 °C, respectively.
f | Heating temperatures for suspension synthesis and the corresponding conductivities of synthesized electrolytes near
room temperature41,42,44,46–52,54–56,59. Δ, heat treatment; ACN, acetonitrile; THF, tetrahydrofuran. Part d is adapted with
permission from ref.44, ACS. Part e is adapted with permission from ref.47, Elsevier.

maximum heating temperatures (Fig. 2e). Ionic conduc- mechanism of metastable phases. An accurate struc-
tivities presented in this Review are mostly measured tural analysis of complexes and products can enable
using alternating current (AC) impedance measurements further understanding. We believe that this method has
under an inert atmosphere. Some previous research the potential to produce new sulfide electrolytes that
confirmed the ionic transport number to be unity using cannot be obtained by other approaches. In addition,
additional direct current (DC) measurements of a the conductivity of some of the synthesized electrolytes
Li–electrolyte–Li cell50,54,57. The range of synthesis tem- through this method is greater than 1 × 10−3 S cm−1,
peratures is 80–300 °C, and the maximum ionic con- which makes these electrolytes suitable for use in
ductivity of electrolytes is 1.5 × 10−3 S cm−1. Because all-solid-state batteries.
suspension approaches require lower temperatures than
those required in solid-state syntheses (typically above Dissolution–precipitation. In addition to suspen-
500 °C), metastable phases such as β-Li3PS4 and Li7P3S11 sion syntheses, dissolution–precipitation approaches
have been observed. New phases in Li2S–P2S5–LiI were in which a solid electrolyte is completely dissolved in
attained as a result of such suspension syntheses, sug- a homogeneous solution have been reported (Fig. 3a;
gesting that this approach could be used to explore new Table 2) . Generally, solid electrolytes attained by
materials. The synthesized powders were submicrometre solid-state synthesis or ball milling are first dissolved in
to a few micrometres in size44,55,56,58 and exhibited highly organic solvents such as hydrazine, N-methylformamide
porous structures44, which were favourable for produc- (NMF), methanol and ethanol, in which they are
ing dense membranes by cold sintering or warm sinter- highly soluble. Then, the solvent is removed by evapo-
ing46,55,59. Although the ionic conductivity of β-Li3PS4 ration, leaving the solid product, the phases of which are
synthesized using suspension approaches is approx- usually the same as those before dissolution. Handling
imately three orders of magnitude higher than that of the electrolyte is usually performed in an Ar-filled
achieved by solid-state synthesis44, the conductivities of glove box or under a vacuum to prevent exposure to
other phases are lower than those achieved by solid-state air and water. Homogeneous solutions (Fig. 3b) are
syntheses. The broad range of conductivity of electrolytes suitable for producing thin layers after evaporation of
attained through liquid-phase syntheses suggests that the solvent.
optimization of the synthesis conditions is ­necessary to In 2012, Huang and co-workers reported the dis-
achieve electrolytes with high conductivities. solution–precipitation of Li3.25Ge0.25P0.75S4 dissolved
Overall, an advantage of the suspension synthesis in anhydrous hydrazine57. Subsequent heating in dry
is that highly lithium-conductive and metastable solid nitrogen at 240 °C produced a powder or thin film of
electrolytes are synthesized from commercially availa- Li3.25Ge0.25P0.75S4. The lithium-ion conductivities of the
ble Li2S and P2S5. Knowledge of both the kinetics and powder and thin film at 30 °C were 1.1 × 10−4 S cm−1 and
thermodynamics of the formation and decomposition 1.8 × 10−4 S cm−1, respectively. Hayashi, Tatsumisago
of complexes is necessary to understand the reaction and co-workers produced a Li2S–P2S5 solid electrolyte

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a Ethanol Li6PS5Cl ∆ using NMF as the solvent60. Dissolving 80Li2S·20P2S5

Li6PS5Cl Li6PS5Cl
mixing solution glass synthesized by ball milling in NMF produced
b a yellow solution, and further heating at 150 °C under a
vacuum led to a Li2S–P2S5 solid electrolyte with an ionic

Intensity (a.u.)
conductivity of 2.6 × 10−6 S cm−1 at 25 °C. Instead, Li3PS3
with a conductivity of 2.3 × 10−6 S cm−1 was first dis-
solved in NMF and then precipitated after the s­ olution
was heated at 180 °C (ref.61).
500 400 300
–1
) Argyrodites, such as Li6PS5Cl, consist of Li+, PS43–
c S
and monovalent anions and are attractive sulfide elec-
Cl
trolytes because of their high lithium-ion conductivity
of 10−2−10−3 S cm−1 at room temperature16. A Li6PS5Cl–
ethanol solution was attained by dissolving Li6PS5Cl
synthesized by ball milling in anhydrous ethanol.
Raman spectra of the transparent ethanol solution
Li
clearly revealed the presence of PS43– ions62 (Fig. 3b).
c After solvent evaporation, a Li6PS5Cl phase exhibiting
b
a a PS43- unit was precipitated62–65 (Fig. 3c). The conduc-
tivities of the dried product at 80 °C and 150 °C were
d Before dissolution e Precipitated with dispersant 1.4 × 10−5 S cm−1 (ref.62) and 1.9 × 10−4 S cm−1 (ref.64),
respectively. Before dissolution, particles of Li6PS5Cl
synthesized by high-energy ball milling were irregular
in shape (Fig. 3d). The heating at 180 °C and the addition
1μm 1μm of dispersant in the mixture of ACN and ethanol helped
in achieving homogeneous and submicrometre-sized
f Precipitated without dispersant Li6PS5Cl particles65 (Fig. 3e), whereas aggregates of a
few micrometres in size were attained without the
addition of the dispersant (Fig. 3 f). The conductivities
of the electrolyte synthesized with and without dis-
1μm persant reached 6 × 10−4 S cm−1 and 3 × 10−4 S cm−1,
respectively. Isostructural argyrodites, Li6PS5X (X = Cl,
g Br and I), were also synthesized using ethanol, which
Li6PS5X Li4SnS4–LiI
Li4SnS4 Li3.25Ge0.25P0.75S4 was evaporated by heating at 80 °C or 150 °C. The con-
10-3
ductivities of these precipitates were in the range of
10−5–10−4 S cm−1 (ref.64).
Conductivity (Scm–1)

Li4SnS4 and their derivatives are attractive because

of their high stability in water. Jung and co-workers
10–4
reported on LiI–Li4SnS4 dissolved in methanol28 and
water 29. Li 4SnS 4 synthesized by solid-state synthe-
sis was dissolved in methanol (with LiI) or deionized
water (without LiI), releasing in both cases a negligible
10–5
0 100 200 300 quantity of H2S. The high stability of the SnS44– in water
Heating temperature(˚C) could be explained by the lower affinity of O2− for Sn4+
than for P5+. The precipitates from methanol at 200 °C
Fig. 3 | Dissolution–precipitation of sulfide electrolyte. exhibited an amorphous phase and a maximum conduc-
a | Dissolution–precipitation reaction for the synthesis of a tivity of 4.1 × 10−4 S cm−1 (ref.28). The precipitates from
representative sulfide-based solid electrolyte. b | Picture
the aqueous solution heated at and above 320 °C were
of Li6PS5Cl–ethanol solution and the corresponding Raman
spectrum showing PS43− (ref.62). PS43− unit dissolved in indexed as Li4SnS4 and their maximum conductivity was
ethanol is stable and can be precipitated by removing the 1.4 × 10−4 S cm−1 (ref.29).
solvent. c | Crystal structure of Li6PS5Cl, with tetrahedrons A combined approach of suspension synthesis and
denoting PS43− (refs16,79). d | Irregular-shaped Li6PS5Cl subsequent dissolution–precipitation was proposed for
particles synthesized by high-energy ball-milling process65. the solution synthesis using Li2S and P2S5 as starting
e | Homogeneous and submicrometre-sized Li6PS5Cl materials66,67. In the first step, the mixing of Li2S, P2S5
particles precipitated from a Li6PS5Cl–ethanol solution and LiBr powders in EP or THF led to an electrolyte
with dispersant65. f | Irregular-shaped Li6PS5Cl particles suspension of PS43– complexes. The addition of etha-
precipitated from a Li6PS5Cl–ethanol solution without nol to this suspension produced a transparent solution,
dispersant65. g | Heating temperatures of dissolution–
and subsequent heating at 180 °C precipitated Li6PS5Br
precipitation processes and corresponding conducti­vities
(near room temperature) of precipitated electro­ powder with a conductivity of 3.4 × 10−5 S cm−1 (ref.66).
lytes28,29,57,62–64,66. Δ, heat treatment; Li6PS5X, isostructural The conductivity of the precipitated electrolyte sintered
argyrodite (X = Cl, Br and I). Part b is adapted with at 550 °C reached 3.1 × 10−3 S cm−1 (ref.67); the sintering
permis­sion from ref.62, Elsevier. Parts d–f are adapted temperature and conductivity were comparable to those
with permissions from ref.65, Elsevier. prepared by a solid-state reaction16.

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Table 2 | Dissolution–precipitation of sulfide-based solid electrolytes and conductivities at room temperature

Product Synthesis Solvent Temperature (°C) σ (mS cm−1) Refs
LGPS SS Hydrazine 240 0.113 57

Li2S·P2S5 BM NMF 150 0.0026 60

Li6PS5Cl BM Ethanol 80 0.014 62

Li6PS5Cl BM Ethanol 150 0.19 64

Li6PS5Cl BM ACN–ethanol 180 0.6 65

Li6PS5Br SP EP–ethanol 180 0.034 66

Li4SnS4 SS Methanol 200 0.09 28

Li4SnS4 SS Water 320 0.14 30

0.6Li4SnS4·0.4LiI SS Methanol 200 0.41 28

σ, conductivity ; ACN, acetonitrile; BM, ball-milling; EP, ethyl propionate; LGPS, Li3.25Ge0.25P0.75S4; NMF, N-methylformamide; SP,
suspension; SS, solid-state.

The ionic conductivities near room temperature the formation of the electrode–electrolyte composite
of electrolytes prepared by dissolution–precipitation particles (Fig. 4a). Liquid-phase processes lead to elec-
are plotted against the maximum heating temperature trolyte layers on electrodes, minimizing the amount of
(Fig. 3g). Most heating temperatures are between 80 °C solid electrolyte and thus enhancing the energy density
and 320 °C, and the conductivities of electrolytes in of all-solid-state batteries.
this temperature range are below 1 × 10−3 S cm−1. Most Also for the production of electrode composites,
of the synthesized phases are thermodynamically sta- we categorize the liquid-phase processes into suspen-
ble, in contrast to those obtained by suspension syn- sion and dissolution–precipitation processes. Table 3
thesis. The precipitated solid electrolytes retained the shows the conditions tested for the preparation of com-
same phase of the dissolved compounds, but the con- posite electrodes using liquid-phase processes and the
ductivities of the precipitated electrolytes were not as ­capacities of the cells including the composites.
high as those before dissolution. For instance, most of
the Li6PS5X synthesized by dissolution–precipitation Suspension syntheses. Suspension syntheses are pro-
and heating below 300 °C exhibited conductivities of cesses in which electrodes and additives are mixed in
10−5–10−4 S cm−1, which are at least one order of magni- suspensions of solid electrolytes (or their precursors),
tude smaller than the conductivities of the electrolytes usually synthesized from Li2S and P2S5. After evapora-
synthesized by a solid-state reaction (~10−3 S cm−1)17. tion of the solvent, a composite electrode containing
Using water as the solvent for the synthesis of Li4SnS4 an active material that features lithium-ion and elec-
was advantageous in reducing the environmental tron paths is obtained. To maximize the energy density
cost but, in most cases, higher heating temperatures of all-solid-state batteries, minimum amounts of solid
were needed to remove the solvents. electrolytes that sustain lithium conduction pathways
One of the advantages of the dissolution–precipitation should be used.
process is that it affords homogeneous solid electrolytes Phuc, Matsuda and co-workers used suspension syn-
derived from a homogeneous solution. Therefore, this thesis to prepare Li3PS4 (conductivity of 2 × 10−4 S cm−1
approach is preferred for the syntheses of electrolytes for at room temperature) from Li2S and P2S5 in EP with
composite electrodes because the homogeneous solu- zirconium balls to achieve fast mixing. A suspension
tion penetrates electrode particles with relative ease. for a positive composite electrode was then prepared
Additionally, the particle size and shape of precipitates by adding 90 wt% LiNi 1/3 Co 1/3 Mn 1/3 O 2 , so-called
can be controlled through removal of the solvents and NCM111, as the active material68. This suspension
surface modification based on nucleation and crystal was heated at 170 °C for 2 hours under a vacuum.
growth in a homogeneous solution. Although notable The active-material particles were well dispersed in the
advancements have been made in regard to the disso- solid-electrolyte matrix for the composite electrode
lution–precipitation process using different solvents, (Fig. 4b), resulting in a high initial discharge capacity
reducing the heating temperature while completely of up to 130 mA h g −1 in bulk-type all-solid-state
removing the organic solvent and maintaining high con- batteries (Fig. 4c).
ductivity continue to be a challenge; as it stands, no study The Li3PS4–THF suspension has also been used to
using heating temperatures below 300 °C has reported prepare sheet-type all-solid-state batteries. A solid-
conductivities higher than 1 × 10−3 S cm−1. electrolyte layer was added onto LiNi0.6Co0.2Mn0.2O2,
NCM622, and graphite electrodes69. Polymeric binders,
Liquid-phase processes for electrode composites such as nitrile–butadiene rubber or polyvinyl chloride,
In this section, we introduce the liquid-phase processes compatible with THF were used to improve the adhe-
used to prepare composite electrodes. In these processes, sion and mechanical properties of the positive composite
electrodes and additives are first immersed in suspen- electrode. Although there were cracks in the compos-
sions or solutions of solid electrolytes (or their precur- ite electrodes, both the electrodes displayed high ini-
sors), and the evaporation of the solvent then leads to tial discharges of 150 mA h g−1 and 320 mA h g−1 for

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a Solvent
Active materials
Mixing ∆
=
• Li2S
• P2S5 (Li salt)
or sulfide Composite
electrolyte electrodes

b d Co e Co

LiNi1/3Co1/3Mn1/3O2 5μm 5μm 20μm 20μm

S S
Li3PS4

5μm 5μm 20μm

c 4.5 f
4.5
Cell voltage (V vs Li)

4.0 4.0

Cell voltage (V)

3.5 + 3.5
Cathode
3.0 3.0
Solid electrolyte
2.5 2.5
–
2.0 Anode
2.0

0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160

Capacity (mA h g–1) Capacity (mA h g–1)

Fig. 4 | Liquid-phase processes for composite electrodes of all-solid-state lithium batteries. a | Scheme of
liquid-phase process of composite electrodes. b | Cross-section image of composite electrodes of LiNi1/3Co1/3Mn1/3O2 and
Li3PS4 prepared by suspension synthesis68. c | First charge–discharge curve of bulk-type all-solid-state battery using the
positive electrode composite of LiNi1/3Co1/3Mn1/3O2 and Li3PS4 prepared by suspension synthesis; a Li–In alloy is used as a
negative electrode, and the cathode is made of a composite of LiNi1/3Co1/3Mn1/3O2 and Li3PS4 (ref.68). d | Scanning electron
microscopy and energy dispersive X-ray analysis mapping (Co and S) images of a LiCoO2 particle coated with Li6PS5Cl
solid electrolyte precipitated from a Li6PS5Cl–ethanol solution62. e | Scanning electron microscopy and energy dispersive
X-ray analysis mapping (Co and S) images of composite of LiCoO2 and Li6PS5Cl precipitated from Li6PS5Cl–ethanol
solution73. f | Charge–discharge curves of sheet-type all-solid-state battery fabricated by dissolution–precipitation
process; active materials of positive and negative electrodes are LiCoO2 and graphite, respectively, and a Li6PS5Cl–ethanol
solution is used as the electrolyte73. Δ, heat treatment. Parts b and c are adapted from ref.68, Springer Nature Limited. Part d
is adapted with permission from ref.62, Elsevier. Parts e and f are adapted with permission from ref.73, ACS.

NCM622 and graphite, respectively. In addition, a full electrode particles. After solvent removal, homogeneous
sheet-type all-solid-state battery showed high discharge composites, which are difficult to obtain by simply mix-
capacity and a capacity retention of 120 mA h g−1 at 30 °C ing the particles of the electrode and solid electrolyte,
and 100 °C. can be formed.
The high ionic conductor Li7P3S11 was used to pre- LiCoO2 particles were coated with 80Li2S·20P2S5
pare a buffer layer for sulfide-type electrodes such as (ref.61) and Li6PS5Cl (ref.62) and dissolved in NMF and
Co9S8, Fe3S4 and MoS2 to achieve close contact with ethanol, respectively. The formation of a solid-electrolyte
the additional Li7P3S11 solid electrolyte. Sulfide-type layer coating LiCoO2 particles was verified by scanning
electrodes coated with Li7P3S11 were mixed with addi- electron microscopy and energy dispersive X-ray analy-
tional Li7P3S11 powders by hand milling. Compared with ses (Fig. 4d). Bulk-type all-solid-state batteries constructed
uncoated electrodes, bulk-type all-solid-state batteries with coated particles exhibited better charge–discharge
featuring a Li7P3S11 layer showed improved charge and capacity than uncoated positive electrodes, with the
discharge capacities higher than 600 mA h g−1 (refs49,70,71). former achieving 30–50 mA h g−1 (refs61,62). Several mix-
tures of protic and aprotic solvents helped to produce
Dissolution–precipitation. Homogeneity of composite a layer of solid electrolyte on LiNi1/3Co1/3Mn1/3O2 that
materials is important; therefore, the dissolution–repre- promoted a better interface between the active mate-
cipitation process using a homogeneous solution would rial and solid electrolyte in a bulk-type all-solid-state
be critical to the fabrication of composite materials for battery63,65,72. For example, a combination of EA and
positive and negative electrodes. The liquid precursor ethanol led to a very high initial discharge capacity of
of sulfide electrolytes can easily cover the surfaces of the 160 mA h g−1 in a composite electrode prepared with a

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Reviews

14 wt% layer of solid electrolyte. Bulk-type all-solid-state advancements have been made concerning reactions for
batteries fabricated with composite positive electrodes the synthesis of sulfide electrolytes and the preparation
derived from liquid-phase processes containing disper- of composites used in all-solid-state lithium batteries.
sants show high initial discharge capacities of 110 mA h g−1, All-solid-state batteries using different solid electro-
better than those attained without the use of dispersants lytes for negative electrodes, an electrolyte layer and
(40 mA h g−1)65. Infiltration of the Li6PS5Cl solution into positive electrodes can now be designed. This flexible
tortuous porous structures of sheet-type electrodes pro- design, however, requires the use of a variety of electro-
duced adequate ionic conduction pathways, providing lytes and synthesis approaches to achieve the specific
intimate ionic contacts and favourable ionic percola- requirements of each of the components of all-solid-
tion73 (Fig. 4e). The capacity of a full sheet-type all-solid state batteries. For example, given that ion conductiv-
lithium battery was ~100 mA h g−1 (Fig. 4 f). ity for a solid-electrolyte layer often needs to be in the
Electrolyte solutions of 0.4LiI–0.6Li4SnS4 and Li4SnS4 range of 10−3–10−2 S cm−1, suspension synthesis for pro-
using methanol and water as solvents, respectively, were ducing a high-conductivity phase would be suitable for
produced and used with LiCoO2 for the preparation of such an electrolyte layer. On the other hand, for com-
composite electrodes28,29. Bulk-type all-solid-state batter- posite electrodes, dissolution–precipitation processes
ies fabricated with these positive composite electrodes provide the advantage of producing homogeneously
(15 wt% solid electrolyte) achieved good electrochem- distributed electrodes and electrolytes as well as a large
ical performances, as testified by high initial discharge interfacial contact between them; however, the scope
capacities of 135 mA h g−1. for improvement remains in the conductivity of the
precipitated electrolyte achieved with such processes.
Summary and outlook The requisite electrochemical window for electrolytes
With the recent increased attention on sulfide-based for positive electrodes is in the high-potential range,
all-solid-state lithium batteries, liquid-phase appro­ typically 3–5 V versus Li/Li+, whereas that for nega-
aches for the production of sulfide electrolytes have tive electrodes is in the low-potential range, typically
assumed greater importance. In the past years, notable 0–1 V versus Li/Li+. Suppressing Li dendrite formation

Table 3 | Synthesis conditions of composite electrodes prepared by suspension synthesis and their capacities
Electrolyte wt% Active wt% Others wt% Solvent Temperature Capacitya Refs
material (°C) (mA h g−1)
Suspension synthesis
Li3PS4 10 NCM111 90 – – EP 170 130 (BT) 68

Li7P3S11 50 b
Co9S8 40 c
Super P 10 ACN 260 650 (BT) 49

Li7P3S11 50b Fe3S4 45c Super P 5 ACN 260 1,001 (BT) 70

Li7P3S11 60 b
MoS2 30 c
AB 10 ACN 250 700 (BT) 71

Li3PS4 27.5 NCM622 70 Super C65 1 THF 140 150 (ST) 69

Li3PS4 27.5 NCM622 70 NBR 1.5 THF 140 150 (ST) 69

Li3PS4 47.5 Graphite 50 NBR 1.5 THF 140 320 (ST) 69

Dissolution–precipitation
Li3PS4 7.5 LiCoO2 92.5 – – NMF 180 32 (BT) 61

Li6PS5Cl 7.5 LiCoO2 92.5 – – Ethanol 80 45 (BT) 62

Li4SnS4·LiI 15 LiCoO2 85 – – Methanol 200 135 (BT) 28

Li4SnS4 15 LiCoO2 85 – – Water 320 130 (BT) 29

Li6PS5Cl 14 NCM111 84 VGCF 2 Ethanol 80 44 (BT) 63

Li6PS5Cl 3 LiCoO2 97 Super P 2 Ethanol 180 150 (ST) 73

Li6PS5Cl 3 LiCoO2 97 PVDF 1 Ethanol 180 150 (ST) 73

Li6PS5Cl 5 Graphite 95 PVDF 5 Ethanol 180 320 (ST) 73

Li6PS5Br 14 NCM111 84 VGCF 2 EP + ethanol 180 109 (BT) 66

Li6PS5Cl 14 NCM111 84 VGCF 2 EA + ethanol 150 160 (BT) 72

Li6PS5Cl 9 NCM111 89 VGCF 2 ACN + ethanol 150 115 (BT) 65

Li6PS5Cl 9 NCM111 89 Triton 0.1 ACN + ethanol 150 115 (BT) 65

Li6PS5Br 10 NCM111 90 – – THF + ethanol 150 120 (BT) 67

AB, acetylene carbon black; ACN, acetonitrile; BT, bulk-type all-solid-state lithium battery cell; EA , ethyl acetate; EP, ethyl
propionate; NBR , nitrile–butadiene rubber (as a binder); NCM111, LiNi1/3Co1/3Mn1/3O2; NCM622, LiNi0.6Co0.2Mn0.2O2; NMF,
N-methylformamide; PVDF, polyvinylidene difluoride; ST, sheet-type all-solid-state lithium battery cell; Super C65 and Super P,
carbon additives; THF, tetrahydrofuran; VGCF, vapour-grown carbon fibre. aCapacity per weight of active material. bAdded by
hand-milling the mixture to produce a composite. cIncludes the content of the Li7P3S11 layer.

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is essential for the use of lithium metal as a negative than 10 wt% electrolyte show discharge capacities above
electrode. Combining sulfide electrolytes with other 100 mA h g−1. Liquid-phase reactions are also used for
electrolytes, such as oxides and halides, also expands the production of Na ion conductors74–76 and applied in
the flexibility of design. Evidently, solution chem- all-solid-state sodium batteries77. For lithium batteries
istry needs to be further enriched in order to opti- that use organic electrolytes, the negative composite
mize the configurations and fabrication processes of electrode coated with Li7P3S11 was also prepared in this
all-solid-state batteries. suspension reaction78.
In this Review, we categorize liquid-phase reactions Liquid-phase chemistry concerning sulfide elec-
into suspension syntheses for the production of sulfide trolytes is growing rapidly, and synthesized composite
electrolytes, typically from Li2S and P2S5, and dissolution– electrodes are being used in sulfide-based all-solid-state
precipitation using solid electrolytes synthesized typi- lithium batteries. Liquid-phase chemistry offers a syn-
cally by solid-state synthesis or the ball-milling process. thesis tool for optimizing the properties of solid elec-
Suspension syntheses involve the mixing of starting trolytes by controlling chemical reactions through the
precursors in organic solvents to form complexes and selection of starting materials and synthesis protocols.
their thermal decomposition to produce nanoporous However, many challenges remain. A synthesis mech-
sulfide electrolytes. An increase in reaction kinetics anism based on the suspension of starting materials to
was achieved by modifying the mixing methods, such produce sulfide electrolytes has not yet been clarified,
as shaking with zirconium balls and ultrasonication, and the conductivities of most electrolytes prepared
and by using highly soluble intermediates. The syn- using liquid-phase processes are not as high as those
thesized phases are often thermodynamically meta- prepared by solid-state reactions. Further efforts are
stable and include Li7P3S11 with conductivities above required to lower the temperatures to completely remove
1 × 10−3 S cm−1. Newly discovered compounds in the the organic solvent. This development is important to
Li–P–S–I system expand the chemical space useful for simplify the process and to avoid undesirable reactions
sulfide-based electrolytes. Dissolution–precipitation in composites. Manufacturing the sheet electrolyte and
uses highly polar solvents such as ethanol. The stability composite electrodes devoid of cracks is important for
of the P–S unit in such solutions enables the precipita- all-solid-state batteries. In order to scale up for industrial
tion of solid electrolytes from organic solvents. In most applications, a process carried out using dry air with a
reported cases, the crystal structures of precipitates are dew point of –40 °C to –20 °C needs to be established.
thermodynamically stable phases. Nonetheless, we believe that sulfide liquid-phase chem-
Both suspension reaction and dissolution–precip- istry has made big leaps in the past few years and has the
itation are used for the fabrication of composite elec- potential to be extended to not only the manufacture of
trodes for all-solid-state batteries. These approaches all-solid-state lithium batteries and other chalcogenides
are scalable, as they include the mixing of electrodes, but also other applications.
electrolytes and electron conductors without the use
of special apparatuses. Composites produced with less Published online 19 February 2019

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solid electrolyte from 1,2-dimethoxyethane solvent. prepared by a liquid-phase technique using ethanol Author contributions
J. Power Sources 271, 342–345 (2014). as a solvent. ACS Appl. Energy Mater. 1, 3622–3629 [Link]., N.C.R.N., A.S. and K.T. wrote the draft. N.H.H.P.,
This paper describes the suspension synthesis (2018). [Link]., N.M., A.H. and M.T. discussed the Review. All the
of Li7P3S11. 65. Rosero-Navarro, N. C., Miura, A. & Tadanaga, K. authors agreed upon the final version of the manuscript.
48. Xu, R. C. et al. Preparation of Li7P3S11 glass-ceramic Composite cathode prepared by argyrodite precursor
electrolyte by dissolution-evaporation method for solution assisted by dispersant agents for bulk-type Competing interest
all-solid-state lithium ion batteries. Electrochim. Acta all-solid-state batteries. J. Power Sources 396, 33–40 The authors declare no competing interests.
219, 235–240 (2016). (2018).
49. Yao, X. et al. High-energy all-solid-state lithium The morphology of precipitated Li6PS5Cl particles Publisher’s note
batteries with ultralong cycle life. Nano Lett. 16, is controlled by a dispersant in a homogeneous Springer Nature remains neutral with regard to jurisdictional
7148–7154 (2016). solution. claims in published maps and institutional affiliations.

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