Accepted Manuscript

Liquid-involved synthesis and processing of sulfide-based solid electrolytes,

electrodes and all-solid-state batteries

Jieru Xu, Lilu Liu, Nan Yao, Fan Wu, Hong Li, Liquan Chen

PII: S2588-8420(19)30117-8
DOI: https://doi.org/10.1016/j.mtnano.2019.100048
Article Number: 100048
Reference: MTNANO 100048

To appear in: Materials Today Nano

Received Date: 21 May 2019

Revised Date: 11 July 2019
Accepted Date: 11 July 2019

Please cite this article as: Xu J., Liu L., Yao N., Wu F., Li H. & Chen L., Liquid-involved synthesis and
processing of sulfide-based solid electrolytes, electrodes and all-solid-state batteries, Materials Today
Nano, https://doi.org/10.1016/j.mtnano.2019.100048.

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 ACCEPTED MANUSCRIPT

Liquid-involved synthesis and processing of sulfide-based

solid electrolytes, electrodes and all-solid-state batteries

Jieru Xu,a, b Lilu Liu,c Nan Yao,d Fan Wu,* a, b, c, e Hong Li,* a, b, c, e Liquan Chen, a, b,
c, e

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a
Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and

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Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese
Academy of Sciences, Beijing 100190, China
b
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of

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Sciences, Beijing, 100049, China
c
Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang 213300, China
d
Princeton Institute for the Science and Technology of Materials (PRISM), Princeton University,

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70 Prospect Avenue, Princeton, NJ 08540, USA
e
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Yangtze River Delta Physics Research Center, Liyang 213300, China

*E-mail: fwu@iphy.ac.cn, hli@iphy.ac.cn.

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Content

Content .......................................................................................................................... 2

Abstract.......................................................................................................................... 3

Introduction .................................................................................................................... 3

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1. Liquid-involved synthesis and processing of sulfide solid electrolytes ............................. 5

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1.1 Liquid-phase synthesis of sulfide solid electrolytes ............................................... ＞

1.2 Processing of sulfide solid electrolyte solutions .................................................. 23

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1.3 Processing of sulfide solid electrolyte slurries ..................................................... 32

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2. Liquid-involved synthesis and processing of composite sulfide-based electrodes and solid

electrolyte layers ........................................................................................................... 3～

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2.1 Composite electrode ......................................................................................... 3～
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2.2 Solid electrolyte layer ....................................................................................... ＞0

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3. Liquid-involved processing of sulfide-based solid-state batteries ................................... ～0

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Summary ...................................................................................................................... ～8

References .................................................................................................................... 81
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Abstract

Solid-state battery has been widely accepted as the next-generation energy-storage

technology due to its better safety and potentially higher energy density. Solid electrolyte plays

the most critical role in its performance, among which sulfides show the highest lithium-ion

conductivities. In order to realize the mass production and practical application of sulfide-based

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electrolytes and all-solid-state batteries, one of the most promising methods is by in-situ

solidification of sulfide-electrolyte solution/slurries with liquid-involved processing that can be

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performed in controlled atmosphere with low temperature. This enables wet coating process for

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electrolyte/electrode layer formation and thus opens up the possibility of mass production of

sulfide solid-state batteries. In this review, liquid-involved process is carefully classified into

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liquid-phase synthesis, solution and slurry process with clear definition to avoid any confusion

among these different processes. The liquid-involved processes of sulfide solid electrolytes
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themselves on material level, sulfide-based composite electrolytes/electrodes on component level

and sulfide-based all-solid-state batteries on device level are summarized and discussed in details.
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Strategies to design and prepare solid sulfide-based electrolytes/electrode layers and batteries with
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liquid-involved process are also suggested.

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Key words: Sulfide; Solid electrolyte; Liquid-phase; Solution procedure; Slurry process
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Introduction
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Lithium-ion batteries (LIBs) have been widely applied in numerous fields, including portable
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electronics, electric vehicles, grid storage, etc. However, higher energy/power density is required

for electric vehicles with driving range beyond 500 km [1], while the energy density of

commercial LIBs is reaching the limit. Moreover, leakage and thermal instability of highly

flammable liquid electrolyte caused serious safety concerns for commercial LIBs [2, 3]. To solve

these problems, all-solid-state batteries (ASSBs) technology has been widely accepted as one of

the most promising candidates. Firstly, inorganic solid electrolytes (SEs) have no leakage problem

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and provide higher thermal stability than liquid electrolytes, thus greatly improve the safety of

LIBs. Secondly, a great increase of volumetric energy density could be achieved with a successful

integration of the lithium anode [4], which certainly deserve serious attempt. Meanwhile,

high-voltage cathode materials can also be allowed with certain SEs that are electrochemically

stable under higher voltages than liquid electrolytes. Moreover, transition metal dissolution in

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LIBs could be mitigated in ASSBs, and SEs can allow high current densities without concentration

polarization, which makes the high-power-density batteries possible in the case that the kinetic

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bottleneck of electrolyte/electrode contact was solved. Last but not least, bipolar structure and

corresponding serial connection of cells could be realized in the fabrication process of ASSBs.

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Accordingly, further advantages for high packaging efficiency and high energy density with

reduced dead space are offered. Fig. 1 demonstrates the number of commercially relevant ASSBs

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patents for 29 active organizations & alliances since 2016, showing the popularity of ASSBs
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technique in this field.

The performance of ASSBs rely heavily on the properties of SEs, which can be generally
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classified into polymers, oxides, and sulfides. Polymer SEs can be integrated into the current

mass-production process of LIBs, but suffer from low room-temperature ionic conductivities.
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Oxide SEs have good thermal stability and compatibility with oxide cathode materials, but their
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ionic conductivities plateaued at 10−3 10−4 S cm−1, and high stiffness results to bad interfacial

contact. Sulfide SEs have the highest ionic conductivity among all SEs (2.2, 12, and 25 mS
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cm−1 for Li3.25Ge0.25P0.75S4 [5], Li10GeP2S12 [6], and Li9.54Si1.74P1.44S11.7Cl0.3 [7], respectively), and

sulfides are relatively “soft” which contributes to better interfacial contact. Although sulfide SEs
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face challenges of air stability [8], electrochemical stability [9, 10], compatibility with
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positive/negative electrodes [11-15], numerous works have been performed to effectively

overcome the drawbacks and make the practical application of sulfide-based ASSBs a significant

possibility [16-18]. Moreover, NEDO in Japan has united 38 companies and research institutes in

2018 to invest 90 million US dollars for R&D and mass production of sulfide-based ASSBs,

which is now at the forefront of this field worldwide. Whoever takes the initiative of mass

production of sulfide-based ASSBs will potentially dominate the power battery market for electric

vehicles in the future.

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To realize the mass production of sulfide-based ASSBs, neither pressed powder nor layer by

dry method is feasible. One of the most practical methods is by in-situ solidification of prepared

solution/slurry of sulfide electrolytes, by which the wet coating process can be applied to form

SE layer. However, the strong reactivity of sulfides with air, moisture and most solvents make this

task nontrivial and difficult to handle. This review aims to summarize the so-far reported

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liquid-involved processes of sulfide-based SEs, composite electrode/electrolyte layers, and ASSBs,

including liquid-phase synthesis, solution process and slurry process of sulfide SEs. Liquid-phase

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synthesis is an effective way for large-scale production of sulfide SEs with nano-morphology,

while solution process and slurry process of pre-synthesized sulfide SEs play a crucial part in

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fabrication of composite electrodes and electrolyte layers, and further in construction of ASSBs

from a manufacturing viewpoint. Basic preparation strategies, selection criteria of solvents of each

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process, and processing details are elaborated and summarized to provide general guidelines for
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the mass production and practical application of sulfide-based SEs, composite

electrode/electrolyte layers and ASSBs.

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Fig. 1. Number of commercially relevant ASSBs patent families.

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1. Liquid-involved synthesis and processing of sulfide solid electrolytes

Aiming to bridge the great gap between lab-scale fabrication and industrial large-scale production

of ASSBs, tremendous effort has been made in the preparation of composite electrode fabrication,

SE layer, and the construction of a cell, among which liquid-involved synthesis and processing of

SEs are regarded as the most promising strategy. For oxide SEs, the sol-gel process can be adopted

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to synthesize Li7La3Zr2O12 (LLZO), coupled with dip-coating or spin-coating methods to produce

thin SE film [19-22]. Furthermore, LLZO thin film can be coated on steel-supported LiCoO2 via

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spin-coating and calcination at 800 °C for 10 minutes in Argon [21]. Additionally, moderate

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content of surfactant can improve the quality of the film significantly, such as 1.5 wt% of triton

X-100 [22]. Besides, attrition milling (AM) method, combined with the spray-drying (SD) method

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can be adopted to obtain secondary granulates of LLZO with uniform sizes for mass production

[23]. NASICON-type SEs can also be synthesized with the participation of solvent.
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Li1.4Al0.4Ti1.6(PO4)3 can be synthesized via evaporation induced self-assembly (EISA) method,

which is simple, applicable for large-scale production. The as-synthesized Li1.4Al0.4Ti1.6(PO4)3

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with evaporation temperature at 30 °C exhibited an ionic conductivity of 3.63 × 10−4 S cm−1 (a

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relative density of 97%) with an average particle size of 70 nm [24]. Li1.3Al0.3Ti1.7(PO4)3 powders

were prepared through a wet chemistry approach, with subsequent mixing with polyethylene oxide
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(PEO) and lithium bis(trifluoromethane)sulfonimide (LiTFSI) [25]. Li1+xAlxGe2-x(PO4)3 (LAGP)

was prepared using a precursor synthesized by the sol-gel method with citric acid, which could be
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further mixed with poly(acrylonitrile) (PAN) to prepare PAN@LAGP SE via a tape casting

method [26, 27]. Except for the synthesis of oxide materials, nanoscale LLZO slurry in
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1-methyl-2-pyrrolidinone (NMP), with the addition of dispersant, adhesives, and surfactant, could
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be adopted to prepare ultrathin electrolyte film and corresponding ASSBs via wet coating, without

cold- or hot-pressing [28]. For sulfide SEs, the processes involving liquid worth great attention,

which include liquid-phase synthesis, solution process, and slurry process of sulfide SEs, as

illustrated in Figure 2. The employment of liquid not only affects the electrochemical

performances of ASSBs, but also offers potential solutions for the mass production of ASSBs with

reduced processing time and efforts. In the following sections, the state-of-the-art strategies

employing liquid from the reported literature will be summarized and discussed.
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Fig. 2. Schematic illustrations of liquid-involved processing of sulfide solid electrolytes,

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involving (a) liquid-phase synthesis, (b) solution process, and (c) slurry process.
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1.1 Liquid-phase synthesis of sulfide solid electrolytes

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The conventional solid-phase synthesis methods of sulfide SEs include high-temperature

solid state reaction [5-7] (with quenching step [29-31] in some cases), and mechanochemical

method [32-34]. Considering the requirements of container sealing [5-7] and quenching [29-31],

as well as limited volume of ball-milling jars in mechanochemical method [32-34], it is difficult to

realize the mass production of sulfide SEs by these methods. Recently, liquid-phase synthesis has

been reported, which can be an effective way for large-scale production of sulfide SEs with

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decreasing energy costs attributable to its mild reaction conditions.

1.1.1 Procedure for liquid-phase synthesis of sulfide solid state electrolytes

(1) Li3PS4

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Li3PS4 is the most studied SE in the field of liquid-phase synthesis of sulfide SEs since Liang

et al. firstly synthesized nanoporous β-Li3PS4 by a wet-chemical method in 2013 [35]. In a typical

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synthesis, Li2S and P2S5 with a stoichiometry of 3: 1 were mixed in anhydrous tetrahydrofuran

(THF), followed by overnight stirring at room temperature and subsequent centrifugation to obtain

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Li3PS4·3THF precipitation. After the removal of THF at 80 °C, the amorphous Li3PS4 with a high

surface area of 40 m2 g−1 and a low ionic conductivity of 7.4 × 10−5 S cm−1 was formed. Further

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heating at 140 ℃ converted the amorphous Li3PS4 into crystalline β-Li3PS4 with diminished
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surface area, and the ionic conductivity was dramatically increased to 1.6 × 10−4 S cm−1 at 25 °C,

which confirmed that the transition from amorphous to crystalline β-Li3PS4 is critical for high
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ionic conductivity β-Li3PS4. Meanwhile, the ionic conductivity of nanoporous β-Li3PS4 was nearly

3 orders of magnitude higher than the intrinsic ionic conductivity of 8.93 × 10−7 S cm−1 for bulk
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β-Li3PS4 [36], which should be attributed to the high surface-to-bulk ratio by the formation of the
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nanoporous structure with an average size of 80–100 nm during the dissociation of THF. Such a

porous structure also stabilizes the preferred metastable phase and provides thermodynamical,
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chemical and electrochemical stability. In 2014, the same group employed acetonitrile (ACN) to

the liquid-phase synthesis of β-Li3PS4 nanoflakes [37]. A white precipitate was observed after the
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mixture of Li2S and P2S5 in ACN was stirred for 48 hours at room temperature. After vacuum
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filtration, the obtained precipitate was treated at 80 °C to remove the excess solvent, yielding

Li3PS4·2ACN. Further heat treatment at 200 °C produced a pure phase of β-Li3PS4 nanoflake,

with the 1–2 µm lateral size and the around 80 nm thickness, which displayed a distinct structure

from β-Li3PS4 synthesized with THF (nanoporous particles with an average size of 10 µm), as

illustrated in Fig. 3a. It is worth noting that the difference in particle size and morphology can be

attributed to the difference in solvent-solid interactions during the process of synthesis. In 2018,

Liang et al. synthesized Li3PS4 electrolytes with shape-controlled plate-like morphology via an

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exchange process from THF to ACN solvent [38]. After wet chemical reaction of Li2S and P2S5 in

THF to yield Li3PS4·3THF as firstly described by this group [35], the as-prepared Li3PS4·3THF

with an average size of about 10 µm was added to ACN to obtain Li3PS4·2ACN nanoscale plates

by exchanging the cocrystallized THF with ACN, with a well-controlled plate-like morphology

with a thickness around 80 nm.

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In 2014, a Li3PS4 SE was directly synthesized from Li2S and P2S5 by a wet chemistry

reaction using N-methylformamide (NMF) and n-hexane as reaction media by Masahiro and

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co-workers [39]. Li2S and P2S5 were mixed in a mortar and dispersed in n-hexane, then NMF was

added dropwise to the suspension of n-hexane with stirring and cooling. The wet chemical

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reaction proceeded and the product Li3PS4 directly dissolved in NMF, separated from n-hexane

phase. After the as-prepared solution was stirred for an hour with cooling, and for 5 hours under

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room temperature, 3-hour heat treatment under vacuum at 180 ℃ was operated to remove NMF
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and to obtain Li3PS4 SE, with the ionic conductivity of 2.3 × 10−6 S cm−1 at room temperature. In

2016, the same group also made a great effort in liquid-phase synthesis of Li3PS4 SE. They
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employed liquid-phase shaking method to synthesize Li3PS4 SE using dimethyl carbonate (DMC)

[40] and ethyl acetate (EA) [41] as reaction media, respectively. In this process, the mixture of
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starting materials and solvent with the presence of zirconia balls was shaken in a centrifugation
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tube at 1500 rpm with an amplitude of about 1 cm, with subsequent centrifugation and heat

treatment at low pressure (about −100 kPa). Using DMC as a reaction medium, amorphous Li3PS4
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with particle sizes smaller than 500 nm was obtained by shaking for 5 hours and heat treatment at

190 ℃. The as-prepared Li3PS4 had a lower ionic conductivity of 6.4 × 10−6 S cm−1 than that of
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glassy Li3PS4 prepared by ball-milling method [42], probably because of the residual undefined

organic substances. While in EA, preparation of crystalline Li3PS4 from Li2S and P2S5 was
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complete after shaking for 24 hours and heat treatment at 160 °C, with a high ionic conductivity of

3.3 × 10−4 S cm−1. Based on the above researches of Masahiro et al., solvent plays a decisive role

in the process of liquid-phase synthesis, which was lucubrated in their next research [43]. Li3PS4

SEs were synthesized from the reaction of Li2S and P2S5 in solvents with a carbonyl group (DMC,

EA, and Methyl Propyl Ketone (MPK)) by liquid phase shaking (shaking for 24 hours and heat

treatment at 160 ℃ for 2 hours), with ionic conductivities of 6 × 10−6 S cm−1, 2 × 10−4 S cm−1, and

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3 × 10−7 S cm−1 at room temperature, respectively. Samples prepared by three different solvents

were characterized by Thermogravimetry-differential thermal analysis (TG-DTA), Raman

spectroscopy, and X-ray diffraction (XRD), illustrating the incomplete reaction in MPK and

residual solvents of 1,2-Dimethoxyethane (DME) and MPK. Based on an estimation that O atom

in C=O bond has higher electron density in the order of DMC EA MPK on account of their

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different molecular structures, a conclusion can be made that the structures of solvents take the

most important role in the liquid synthesis of Li3PS4 SE. Therefore, this group successfully

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synthesized glass-ceramic Li3PS4 SE from Li2S and P2S5 using ethyl propionate (EP) as a

synthetic medium via liquid-phase shaking in 2017 [44]. After shaking for 6 hours and heat

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treatment at 170 ℃, the plate-like Li3PS4 (about 3 µm in length, 500 nm in width, and 100–200 nm

in thickness) was formed, which exhibited ionic conductivity of about 2.0 × 10−4 S cm−1 at room

temperature.

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Liu et al. applied successfully fabricated Li3PS4 via liquid-phase synthesis with diethylene

glycol dimethyl ether (DEGDME) solvent in 2018 [45]. The 1-day mixing of Li2S and S powders
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in DEGDME, followed by the addition of P2S5 powder and extra 3-day stirring, producing the

solution of SE by inducing a chemical reaction between soluble polysulfides and P2S5 in

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DEGDME. The deposited SE powder after pre-drying under vacuum for 2 hours and further
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drying in a vacuum furnace at 140 °C for 12 hours exhibited ionic conductivity of 2.76 × 10−5 S

cm−1, which was lower than that of commercial β-Li3PS4 (2.12 × 10−4 S cm−1) attributed to the
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residual sulfur. The same group reported a new synthesis route for sulfide electrolytes by using a

nucleophilic agent, LiSC2H5 (lithium thioethoxide, LiSEt) later this year [46]. Additives were
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firstly introduced into liquid-phase synthesis, forming the intermediate soluble compounds of
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LiSEt·P2S5 in THF. The dissolved P2S5 composite can then further react easily with Li2S, resulting

in the formation of a purified β-Li3PS4 with a conductivity of 1.32 × 10−4 S cm−1 at room

temperature, since soluble residuals or by-products can be completely removed during filtration.

In 2017, Shin et al. used liquid-phase synthesis to produce 75Li2S·25P2S5 SEs with small and

uniform particle sizes (2.2 ± 1.68 µm), with the participation of anhydrous dibutyl ether [47]. The

reaction proceeded at 165 ℃ for 24 hours under continuous stirring while monitoring the reaction

pressure, followed by heat treatment at 140 ℃ for 6 hours. The as-prepared 75Li2S·25P2S5 SEs

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exhibited ionic conductivity of about 3.1 × 10−4 S cm−1 at room temperature, with small and

uniform particle sizes, which can form intimate contact with active materials. Parameters for

liquid-phase synthesis of Li3PS4 SEs and their conductivities are summarized in Table 1-1.

(2) Li7P3S11

A Li7P3S11 crystal was synthesized from a liquid phase for the first time by Ito et al. in 2014

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[48]. Li2S and P2S5 were stirred for 3 days in DME at room temperature. After complete reaction

and removement of solvent, heat treatment proceeded at 250 ℃ for 1 hour in Ar atmosphere to

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obtain crystalline Li7P3S11 SE with high ionic conductivity of 2.7× 10−4 S cm−1 at room

temperature.

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After that, ACN is the most used reaction medium in the liquid-phase synthesis of Li7P3S11,

with appropriate polarity. In 2016, Tu et al. prepared glass-ceramic Li7P3S11 SE with different

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solvents (e.g., THF, ACN and mixed solvent of THF and ACN (THF&ACN)) [49]. The processes
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of liquid-phase synthesis are basically the like, with 24-hour stirring at room temperature and heat

treatment (250 ℃ for 2 hours to crystallize and 180 ℃ for 2 hours to further remove the residual
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solvent). Finally, Li7P3S11 glass-ceramic powders were obtained, among which, the Li7P3S11

prepared with ACN exhibited the highest ionic conductivity (9.7× 10−4 S cm−1 at 298 K) and
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wide/stable electrochemical window of 5 V, which highlighted the effects of solvents on the

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amount of impurities and the degree of crystallinity (Fig. 3b). Crystalline Li7P3S11 electrolyte

particles were synthesized by Yao et al. [50, 51] and Tu et al. [52] via the same liquid-phase
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synthesis procedure. Mixture of Li2S and P2S5 (the mole ratio of Li2S and P2S5 is 7: 3) in ACN

was stirred at 50 °C for 24 hours, followed by the removal of solvent and subsequent heat
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treatment at 260 °C for 1 hour. The as-synthesized Li7P3S11 exhibited a very high ionic

conductivity of 1.5 × 10−3 S cm−1 with a particle size of 0.4–1.0 µm, which is crucial to realizing
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high-performance ASSBs [50]. Rosero-Navarro and co-workers introduced ultrasonic irradiation

to enhance chemical reactivity in a solid-liquid system in 2017 [53], realizing the instantaneous

preparation of Li7P3S11 SE by a simple procedure involving a liquid phase process under

ultrasonic irradiation at 60 °C for 30 minutes, drying process (at 180 °C for 3 hours under

vacuum), and heat treatment at 220 °C for 1 hour. The as-synthesized Li7P3S11 exhibited high ionic

conductivity of 1 × 10−3 S cm−1, with a particle size below 500 nm. The production time was quite

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reduced, which was vital for the mass-production of sulfide SEs. Additionally, Liu and co-workers

investigated the reaction mechanism of Li7P3S11 phase in ACN in 2018 [54], by tracking the phase

change of not only the precipitates but also the dissolved phase in the supernatant liquids, with the

conclusion that crystalline Li7P3S11 was produced in two steps: (1) formation of solid Li3PS4·ACN

in precipitates and amorphous “Li2S·P2S5” phases in liquid phase and (2) solid-state reaction of

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the two phases.

In 2018, Gao et al. employed mineral spirit as reaction media in the synthesis of Li7P3S11 [55].

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A thorough mixture of Li2S and P2S5 in mineral spirit by constant stirring for 24 hours was dried at

60 °C for 24 hours and subsequently annealed at 260 °C for 1 hour under vacuum. The

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as-synthesized Li7P3S11 exhibited ionic and electronic conductivity of 2.67 × 10−3 S cm−1 and 1.91

× 10−10 S cm−1, respectively. Parameters for liquid-phase synthesis of Li7P3S11 SEs and their

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conductivities are summarized in Table 1-2.
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(3) Other Li-P-S solid electrolytes
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In 2017, sulfide SEs from Li2S and P2S5 in different ratio were synthesized and further

investigated by a liquid-phase synthesis under ultrasonic irradiation, and heat treatments at low
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temperatures [56]. Heat treatment at 220 °C was an adequate temperature to promote the
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formation of the P2S74− units (a high ionic conductivity phase), while the heat treatment at 250 °C

led to the formation of the P2S64− units resulting in a decreasing ionic conductivity. The SE with
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Li2S content of 74 mol% after the heat treatment at 220 °C exhibited the highest ionic

conductivity of 1 × 10−3 S cm−1 at 22 °C, indicating the Li2S content also played an important role.
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Wang and co-workers reported a new and rapid liquid-phase synthesis for preparing a

high-purity Li7PS6 SE in a short time (2 hours) [57]. Li2S and β-Li3PS4 (synthesized via
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liquid-phase synthesis in ACN) at a stoichiometric of 2: 1 were dissolved in anhydrous ethanol

(EtOH), followed by heat treatment at 90 °C under vacuum (not longer than 1 hour) and further

heating at 200 °C for 1 hour to obtain the final product (Li7PS6). The as-prepared Li7PS6 SE

showed an ionic conductivity of 1.1 × 10−4 S cm−1 at room temperature.

(4) LiX (X = Cl, Br, I)-based solid electrolytes

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The system of Li2S/P2S5/LiI, with rather high conductivities (1.3 × 10−3 S cm−1 at room

temperature), excellent electrochemical stabilities (both against Li metal and up to 10 V), and

good battery performances [58], has attracted wide attention recently.

Liang and co-workers firstly synthesized Li7P2S8I solid-state Li-ion conductor derived from

β-Li3PS4 and LiI via liquid-phase synthesis in 2015 [59]. Li3PS4 was synthesized using Li2S and

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P2S5 in ACN for 24 hours, with heat treatment at 80 ℃ to obtain Li3PS4·2ACN. The Li3PS4·2ACN

was further dispersed in ACN containing LiI and mixed in a turbulent mixer for 15 minutes, with

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subsequent drying and heating. Various stoichiometric compositions of Li-P-S and LiI were mixed

and heat-treated at 200 °C to investigate this new phase, while the maximum phase purity was

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observed at a 2: 1 ratio of Li3PS4: LiI, producing Li7P2S8I SE with new crystal structure (Fig. 3c).

The obtained Li7P2S8I electrolyte exhibited a room-temperature ionic conductivity of 6.3 × 10−4 S

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cm−1, with electrochemical stability up to 10 V vs. Li/Li+ attributed to the inclusion of I.
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Additionally, this sulfide electrolyte allowed low-temperature densification, which is the key to

developing industrial-scale SE membranes. In 2015, Jung et al. developed a new class of

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solution-dissolved superionic conductor, LiI-Li4SnS4 [60]. Crystalline Li4SnS4 powders,

synthesized from Li2S and SnS2 by solid-state reaction at 450 °C, were mixed with LiI in
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methanol (MeOH) for the solution process, with subsequent drying and heat-treatment to produce
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xLiI-(1−x)Li4SnS4 (0.0 ≤ x ≤ 0.5). Glass 0.4LiI-0.6Li4SnS4 was prepared at 200 °C, which

exhibited a high ionic conductivity among all inorganic SEs prepared from homogeneous solution

(4.1 × 10−4 S cm−1 at 30 °C), along with excellent deformability and dry-air-stability. In 2017, a
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solvent-based soft chemistry approach was applied to the synthesis of Li4PS4I by Janek and
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co-workers [58], via the reaction between Li2S, P2S5 and LiI in DME. The obtained Li4PS4I with a

new structure type, exhibiting a lithium ion conductivity of 1.2 × 10−4 S cm−1 at room temperature.
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Masahiro and co-workers attempted the preparation of (100−x)Li3PS4·xLiI via liquid phase

shaking method using ethyl propionate (EP) as the synthesis medium in 2017 [61]. The SE

precursors (LiI, Li2S/P2S5 = 3: 1) were mixed in one-pot, followed by shaking for 6 hours and heat

treatment. The XRD patterns illustrated that the incorporation of LiI into the sample resulted in a

structural change with the formation of Li7P2S8I as the main component. When x = 33.3%, only

peaks of Li7P2S8I were detected, as reported by Liang et al. [59], which had a lower ionic

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conductivity of 3.4 × 10−4 S cm−1 compared with the previous work.

Miura et al. prepared Li6PS5Br SE via ultrasonication of Li2S, P2S5 and LiBr in EP [62]. The

sample contained starting materials (Li2S: P2S5: LiBr = 5: 1: 1.5) in EP was ultrasonicated at 60 ℃

for 1 hour into suspension，followed by the addition of EtOH to form transparent precursor

solution, which could be applied to configurate composite electrode. Then, the solution was heated

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at 180 ℃ for 3 hours under vacuum to produce Li6PS5Br SE with a lower room-temperature

conductivity of 3.4 × 10−5 S cm−1 compared with that of Li6PS5Br prepared by mechanical milling

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(1.0 ×10−4 S cm−1), which can be attributed to rather large grain boundary resistance. In 2018,

Masahiro and co-workers employed multi-step liquid-phase synthesis to prepare Li6PS5Br SEs

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[63], via the following steps: stirring the mixture of Li2S and P2S5 with a stoichiometry of 3 to 1 in

THF to obtain Li3PS4·3THF; dissolution of Li2S and LiBr (1: 1 molar ratio) in EtOH; mixing the

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THF suspension and the EtOH solution to obtain the THF&EtOH solution of Li6PS5Br;
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subsequent drying (at 150 ℃ for 3 hours under vacuum) and heat treatment (at 550 ℃ in an dry Ar

atmosphere). Fig. 3d illustrated the unit cell of as-synthesized Li6PS5Br, in which the S2− and Br−
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anions with set disorder formed a face-centered cubic lattice and PS43− tetrahedra on the

octahedral sites. The Li+ sites (an occupancy of 0.5) formed a cage like conduction path and thus
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provided a macroscopically fast conduction pathway, showing a high ionic conductivity of 3.1 mS
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cm−1 at 25 ℃ with particle size of 1 µm, which is desirable for application in ASSBs. Synthesis

process of Li6PS5Br with THF alone or EtOH alone as a solvent was also examined, to prove the
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significance of a bi-solvent system. Nazar et al. developed a promising direct solution-engineered

approach to synthesize argyrodite phases Li6PS5X (X = Cl, Br, I) using THF&EtOH mixtures as
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reaction medium in 2018 [64]. The synthesis processes were similar to the reported work [63].

Fully crystallized Li6−yPS5−yCl1+y (y = 0–0.5), Li6PS5X (X = Cl, Br) and the mixed Cl/Br phases
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were systematically investigated, among which Li6PS5Cl0.5Br0.5 exhibited a high ionic

conductivity up to 3.9 mS cm−1 at room temperature and negligible electronic conductivity, in

excellent agreement with argyrodites obtained from solid-state reactions. In 2018, Shin and

co-workers produced Li6PS5Cl SE with liquid-phase synthesis in EA [65]. The stirring time was

24 hours with stirring of Li2S and LiCl for 1 hour and subsequent addition of P2S5 for 23 hours,

followed by drying at 30 ℃ for 12 hours under vacuum and heating at 550 ℃ for 5 hours. Thus

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rod-like Li6PS5Cl SE with a length of 20–30 µm and a width of 2–3 µm was synthesized,

exhibiting a high ionic conductivity of 1.1 × 10−3 S cm−1 at room temperature. The reduced

particle size of the as-prepared SE, with intimate contact with the active material in the composite

electrode, which was desirable for the fabrication of ASSBs.

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(5) Sodium solid electrolytes

In 2015, Masahiro and co-workers successfully synthesized a Na3PS4 SE directly from Na2S

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and P2S5 by a wet chemistry reaction using NMF and n-hexane as reaction media [66]. After the

precursor solution was obtained from Na2S and P2S5 with n-hexane and NMF as the synthesis of

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Li3PS4 in 2014 [39], the precursor solution was dried at 180 °C under vacuum to obtain the

powder and further heat treated at 260 °C to form Na3PS4 electrolytes, with the ionic conductivity

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of 2.6 × 10−6 S cm−1 at room temperature. The possible two reasons for its lower conductivity
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compared with that of cubic Na3PS4 electrolyte prepared by mechanical milling were the

coprecipitation of Na3POS3 crystal (1.57 × 10−8 S cm−1 at 80 °C) and the contribution of grain
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boundary resistance. The same group continued the synthesis Na3PS4 with DME or diethyl ether

(DEE) as reaction media in 2017 [67]. After stirring at room temperature (25 °C) for over 60 hours,
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the obtained white suspensions were dried under vacuum at room temperature to obtain the
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precursor powders. Further heating at 270 °C under vacuum formed the Na3PS4 electrolytes. The

morphology of the as-prepared Na3PS4 was affected by reaction media, as observed that fine
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particles (particle size 100 nm) were obtained in DME solvent, while Na3PS4 with 5–100 µm

particle size were obtained in DEE solvent, as illustrated in Fig. 3e. Accordingly, Na3PS4 SEs
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using DME and DEE exhibited conductivities of 2.6 × 10−5 S cm−1 (density of 99%) and 1.8 ×
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10−5 S cm−1 (density of 94%) at 25 °C, respectively. In 2018, Yao and co-workers synthesized

Na2.9PS3.95Se0.05 electrolyte via liquid-phase reaction of Na2S, P2S5, and Se in ACN [68]. The

mixture was stirred at 50 °C for 24 hours, with subsequent vacuum-distilled and drying at 80 °C

for 12 hours to remove the residual solvent. Further annealing at 270 °C under Ar atmosphere

produced Na3−2xPS4−xSex electrolyte with reduced particle size, exhibiting a high ionic

conductivity of 1.21 × 10−4 S cm−1, which was comparable with that of synthesized with a

solid-state reaction. The detailed procedure for liquid-phase synthesis of sodium sulfide SEs

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mentioned above are listed in Table 1-4.

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Fig. 3. (a) Morphology of β-Li3PS4 particles from THF is shown in the top-left panel (with an
average particle size of 10 µm) and morphology of surface of β-Li3PS4 with nanopores is
shown in the top-right panel; morphology of β-Li3PS4 particles from ACN is shown in the
bottom panel (nanoflakes with an average lateral diameter of 2 µm and a thickness of 80 nm)
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[35, 37]. (b) Raman spectra (left panel) and conductivities dependent on temperature (right
panel) of Li7P3S11 glass-ceramics synthesized from THF, ACN and THF&ACN [49]. (c) XRD
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patterns illustrating the formation of a new phase at the 2: 1 stoichiometric composition of

Li3PS4: LiI. An excess of either phase leads to the observation of the respective phase as a
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secondary impurity in addition to the newly formed phase [59]. (d) Crystal structure of
liquid-phase-synthesized Li6PS5Br. The Li, P, S, and Br sites are represented by gray, orange,
purple, and green balls, respectively [63]. (e) Scanning electron microscopy (SEM) images of
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Na3PS4 powders synthesized from solvent DME (top panel) and DEE (bottom panel) [67].
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1.1.2 Advantages of liquid-phase synthesis of sulfide solid electrolytes

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Liquid-phase synthesis provides significant advantages, which bring new opportunities to the

large-scale production of sulfide-based SEs and ASSBs.

First, this approach can achieve the cost-effective mass production of sulfide SEs through

solvent-based wet chemical reaction at mild conditions, which could reduce energy costs

compared with conventional solid-state synthesis methods with high-temperature heat treatment

[5-7, 29-31], and high-energy ball milling [32-34].

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Second, the size and morphology of the SE particles can be mediated by controlling

parameters (especially the solvent type) of liquid-phase synthesis. Synthesis of sulfide SEs with

extremely uniform particle size down to nanometer size has been realized via liquid-phase

synthesis [40, 44, 47, 50, 53, 56, 57, 63, 68], the usage of which could improve energy/power

density of ASSBs because of the increase of the loading amount of active materials in composite

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electrode and large contact area between electrode and electrolyte. Solvents as reaction media

could also influence the morphology of as-synthesized SEs [35, 37, 38, 65], such as nanoporous

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β-Li3PS4 with anomalous high ionic conductivity from THF (1.6 × 10−4 S cm−1 at 25 °C) [35], and

β-Li3PS4 nanoflakes from ACN which were desirable to fabricate thin membrane [37].

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Third, liquid-phase synthesis can provide synthetic routes for new SEs that are difficult to be

synthesized via solid-state reaction, such as Li7P2S8I from ACN (6.3 × 10−4 S cm−1 at 25 °C ) [59],

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−4
glass 0.4LiI-0.6Li4SnS4 from MeOH (4.1 × 10 S cm−1 at 30 ℃) [60], and Li4PS4I from DME
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( 6.4 × 10−5–1.2 × 10−4 S cm−1 at 25 °C) [58].

Fourth, liquid-phase synthesis has brought new strategies for the fabrication of composite
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electrode. In-situ synthesis and coating of SEs on active material particles could provide an

intimate interfacial contact between them effectively [44, 50-52, 55, 68, 69], while one-pot slurry
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with SEs precursors rather than SEs makes the use of polar solvent in composite electrode slurry a
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possible, as well as simplified fabrication processes [70].

Lastly, fabrication of thin membranes of sulfide SEs could be achieved with high efficiency
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and low cost [37, 38, 71].

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1.1.3 Disadvantages of liquid-phase synthesis of sulfide solid electrolytes

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However, there are still a lot of problems to be solved. Although some of the sulfide SEs via

liquid-phase synthesis have obtained ionic conductivity of 10−3 S cm−1 at 25 ℃, such as Li7P3S11

from ACN [50, 52, 53, 55] and mineral spirit [56], and Li6PS5X (X = Cl, Br, I) from THF&EtOH

solvent [63, 64] and EA [65], most of the as-prepared SEs exhibited conductivity of 10−4–10−5 S

cm−1 at room temperature, which may be caused by the presence of residual (such as incomplete

reactants and residual solvents) and byproducts. It is generally considered that the impurity phase

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will precipitate at the boundary of grains, thus hinder the transmission of lithium ions [49]. In

addition, higher crystallinity is critical to improving the conductivity of SE generally [35].

In-depth studies for low conductivity of liquid-phase-synthesized SEs and corresponding

approaches are needed.

Moreover, the choice of solvents is limited because of the strong reactivity of sulfides with

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most solvents. Aprotic solvents are selected to avoid the hydrolysis reaction between sulfide and

water molecules. In addition, the polarity of solvents should be appropriate to mediate

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wet-chemical reaction of reactants, but not be too high to introduce reactions between sulfide and

solvent. The boiling point of solvents should also be considered for the removal of solvents.

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Last but not least, toxicity and cost of solvents may hinder further application of liquid-phase

synthesis from a practical point of view. Therefore, the discovery of environmentally-friendly

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solvents and synthetic routes for SEs are still of interest, satisfying other requirements for
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synthesis in the meantime.
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1.1.4 Mechanism for liquid-phase synthesis of sulfide solid electrolytes

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Liquid-phase synthesis of different kinds of sulfides has three common processes: mixing

process, solvent evaporation process, and heat treatment process, but with different synthesis
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parameters, as summarized in Table 1. For Li3PS4 SE, the synthesis processes were proved by

XRD, TG-DTA, and Raman spectroscopy as follows [35]: (i) the reaction of Li2S and P2S5
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mediated by THF, forming Li3PS4·3THF at room temperature; (ii) removal of THF at 80 ℃，

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forming amorphous Li3PS4 with the decomposition of Li3PS4·3THF; (iii) the crystallization of

Li3PS4 at 140 ℃, along with further removal of THF. For Li7P3S11 SE, the suspension after

ultrasonication process, the solid powders after drying process at 180 ℃and after heat treatment at

220 ℃ were characterized via XRD and Raman spectroscopy [53], indicating that the heat

treatment at 220 ℃ promoted a structure rearrangement of PS43− units into P2S74− units. As

summarized in Table 1, the heat treatment temperature of liquid-phase synthesis of Li7P3S11 SE

(200–260 ℃) is higher than Li3PS4 SE (140–230 ℃). For new phase from LiX (X = Cl, Br,

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I)-based sulfide SEs, Li4PS4I [58], was proved to be finally synthesized at moderately elevated

temperatures, as follows:

ୈ୑୉
3Liଶ S + Pଶ Sହ ሱۛሮ 2Liଷ PSସ ∙ DME
RT

ୈ୑୉ ଶ଴଴Ԩ
Liଷ PSସ ∙ DME + LiI ሱۛሮ Liଷ PSସ ∙ DME ∙ LiI ሱۛۛሮ Liସ PSସ I
RT −DME

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Further mechanism for liquid-phase synthesis of sulfide SEs is under investigation. For the

synthesis of Li3PS4, electronegative groups in solvent molecules were proved to play a crucial role

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in reaction between Li2S and P2S5 [43]. For the case of NMF, the reaction between NMF and P2S5

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was proved to be the initial step [39, 66], while the interaction between Li in Li2S and O atom is

considered to be the first step in solvents like EA, DMC, and MPK [43]. Thus, the electron density

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of electronegative group would affect the interaction between sulfide precursors and solvent

molecules, thereby influence the reaction between Li2S and P2S5. On the other hand, the bonds
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between sulfide electrolytes and solvent molecules in their co-crystalline phases (e.g. Li3PS4·3THF,

Li3PS4·2ACN, Li3PS4·DME) are also affected by the electron density of electronegative groups,
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which further influence the drying process and properties of the as-synthesized electrolytes except
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boiling points of the solvents. In conclusion, the electron density of electronegative group in

solvent molecules should be traded off, considering proper reactivity and mild drying process.
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Wang et al. [54] reported the mechanism of formation of the Li7P3S11 phase in ACN media, which

was proved to be a different reaction pathway with that of Li3PS4. By tracking the phase change of
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deposited precursor, powder precipitate, and solution phase from the supernatant after ACN

evaporation, the deposited electrolyte precursor is verified to be a mixture of crystalline

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Li3PS4·ACN from powder precipitate and amorphous “Li2S·P2S5·ACN” form solution phase,
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which then convert into crystalline Li7P3S11 through solid-state reaction. This understanding of the

formation mechanism of Li7P3S11 may be universal for other solvents, which needs further

research.

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1.1.5 General principle and guidelines for liquid-phase synthesis of sulfide solid electrolytes

Liquid-phase synthesis has three basic processes: i) wet-chemical reaction between sulfide

precursors proceed, mediated by different organic solvents; ii) subsequent solvent evaporation

process; and iii) heat treatment process to get the aim product. Therefore, the precursors of sulfide

(reactants, additives), solvents, mixing procedure (methods, reaction time, temperature), solvent

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removing procedure (methods, time, temperature, atmosphere), and heat treatment procedure

(methods, time, temperature, atmosphere) are controllable parameters that would influence the

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product of liquid-phase synthesis, which are summarized specifically in Table 1.

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Mixing procedure is to guarantee the complete reaction between precursors, for typically

more than 24-hour stirring. The reaction time with different solvents are distinct as shown in

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Table 1, attributable to the bonds between sulfide precursors and solvent molecules. Additionally,

the reduction of reaction time has been obtained by liquid phase shaking with zirconia balls (6
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hours) [44], and ultrasonic irradiation at 60 ℃ (0.5 hours) [53, 55].

Solvent removing procedure is to eliminate the influence of organic solvent on ionic

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conductivities, including centrifugation and washing, or vacuum filtration, and further evaporation
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from 25 ℃ to 180 ℃, affected by boiling temperature of solvents, along with the bonds between

sulfide SEs and solvent molecules [43].

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Table 1 Parameters for liquid-phase synthesis of sulfide solid electrolytes

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Table 1-1 Parameters for liquid-phase synthesis of Li3PS4
Starting b. p. Conductivity
Structure Sulfide Solvent Mixing procedure Solvent evaporation Heat treatment Ea/eV Functions Ref.
materials (℃) Scm−1 (25 ℃)

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Centrifugation; −4
Crystalline β-Li3PS4 Li2S and P2S5 THF 66 Stirred, RT, overnight 140 °C, vacuum 1.6 × 10 0.356 Synthesis [35]
80 °C, vacuum
NMF and Stirred, cooling, 1 h;
Crystalline Li3PS4 Li2S and P2S5 199 180 ℃, vacuum, 3 h / 2.3 × 10−6 0.467 Synthesis [39]
n-hexane Stirred, RT, 5 h

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Centrifugation; 190 °C, low pressure −6
Crystalline Li3PS4 Li2S and P2S5 DMC 90 Shaken, 5 h 6.4 × 10 0.623 Synthesis [40]
evacuated at RT (about −100 kPa)
160 ℃, low pressure
Centrifugation;
Crystalline Li3PS4 Li2S and P2S5 EA 77.1 Shaken, 1 d (about −100 kPa), 3.3 × 10−4 0.322 Synthesis [41]
evacuated at RT

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overnight
Vacuum filtration; Thin
Crystalline β-Li3PS4 Li2S and P2S5 ACN 81.6 Stirred, 48 h 200 ℃, vacuum 1.2 × 10−4 0.36 [37]
80 ℃, membranes

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Glass-ceram Centrifugation; 170 ℃, low pressure, −4 In-situ
Li3PS4 Li2S and P2S5 EP 99.1 Shaken, 6 h 2 × 10 0.426 [44]
ic evacuated at RT 2h coating
Li2S, S and Stirred, 1 d; −5 Thin
Crystalline Li3PS4 DEGDME 162 Vacuum, 2 h 140 °C, vacuum, 12 h 2.76 × 10 0.417 [45]
P2S5 Stirred, 3 d with addition of P2S5 membranes

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Li2S, P2S5 and 140 ℃ (2 ℃ /min), 10
Crystalline β-Li3PS4 THF 66 Stirred, 12 h Centrifugation 1.32 × 10−4 0.269 Synthesis [46]
additive: LiSEt h
Glass-ceram 75Li2S·25P2 −4
Li2S and P2S5 Dibutyl ether 141 Stirred, 165 ℃ for 24 h 140 ℃, 6 h 230 ℃ (5 ℃/min), 3 h 3.1 × 10 / Synthesis [47]
ics S5

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THF: 80 °C to get
THF 66 Li3PS4·2ACN; Thin
Crystalline β-Li3PS4 Li2S and P2S5 Stirred vigorously RT, vacuum / / [38]
ACN ACN: 200 °C to get thin membranes

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81.6 EP films of β-Li3PS4
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AC

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Table 1-2 Parameters for liquid-phase synthesis of Li7P3S11 and other Li-P-S
Conductivity S cm−1
Structure Sulfide Starting materials Solvent b. p. (℃) Mixing procedure Solvent evaporation Heat treatment Ea/eV Functions Ref.
(25 ℃)

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Rotary evaporator
Crystalline Li7P3S11 Li2S and P2S5 DME 83 RT, 3 d 250 ℃, Ar, 1 h 2.7 × 10−4 0.395 Synthesis [48]
180 ℃, vacuum
250 ℃, Ar, 2 h to
ACN: 9.7 × 10−4

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ACN crystallize; 0.323
ACN: 81.6
Glass-ceramic Li7P3S11 Li2S and P2S5 THF RT, 24 h 80 ℃ 160 ℃,2 h, to THF: 2.3 × 10−4 0.354 Synthesis [49]
THF: 66
ACN&THF remove the AVN&THF: 4 × 10−4 0.311
residual solvent

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Vacuuming distilled;
Crystalline Li7P3S11 Li2S and P2S5 ACN 81.6 50 ℃ 24 h 260 ℃, 1 h 1.5 × 10−3 0.239 In-situ coating [50]
80 ℃, 12 h
Ultrasonicated, −3
Crystalline Li7P3S11 Li2S and P2S5 ACN 81.6 180 ℃, vacuum, 3 h 220 ℃, 1h 1.0 × 10 (22 ℃) 0.133 Synthesis [53]
60 ℃, 30 min
Crystalline Li7P3S11 Li2S and P2S5 ACN 81.6 50 ℃, 24 h 80 ℃, 12 h 260 ℃, 1 h / / In-situ coating [51]

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Crystalline Li7P3S11 Li2S and P2S5 ACN 81.6 RT, 24 h 80 °C 250 °C, 2 h 2 × 10−3 / In-situ coating [52]
50 °C on a hot plate, Synthesis &
8.7 × 10−4

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Crystalline Li7P3S11 Li2S and P2S5 ACN 81.6 150 °C on a hot plate 260 °C, Ar, 1 h 0.37 [54]
3d mechanism
Mineral 260 °C, vacuum, −3
/ 70Li2S·30P2S5 Li2S and P2S5 / Stirred 24 h 60 ℃, 24 h 2.67 × 10 / In-situ coating [55]
spirit 1h
xLi2S·(100-x)P2S Ultrasonicated,
Glass-ceramic Li2S and P2S5 ACN 81.6 180 ℃, vacuum, 3 h 220 ℃, 1 h 1.0 × 10−3 (22 ℃) / Synthesis [56]

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5 60 ℃, 30 min
Li2S and Li3PS4
90 °C, vacuum, not
Crystalline Li7PS6 (Li2S+P2S5 in EtOH 78 Dissolve 200 °C, 1 h 1.1 × 10−4 0.43 Synthesis [57]
longer than 1 h
ACN, 200 ℃)

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Table 1-3 Parameters for liquid-phase synthesis of LiX (X = Cl, Br, I)-based solid electrolytes
b. p. Conductivity
Structure Sulfide Starting materials Solvent Mixing procedure Solvent evaporation Heat treatment Ea/eV Functions Ref.
(℃) S cm−1 (25 ℃)

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24 h to obtain
Li3PS4·2ACN;
Crystalline Li7P2S8I Li2S, P2S5 and LiI ACN 81.6 dispersed in acetonitrile Ambiently, 12 h 200 ℃, vacuum 6.3 × 10−4 / Synthesis [59]
containing LiI, in a

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turbulent mixer, 15 min
0.4LiI-0.6Li Li4SnS4 powders,
Glass MeOH 64.7 Dissolve RT, vacuum 200 °C, vacuum 4.1 × 10−4 (30 ℃) 0.432 Synthesis [60]
4SnS4 LiI
50 °C, vacuum, until the

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Li3PS4·DME with LiI in 6.4 × 10−5–1.2 ×
Crystalline Li4PS4I Li2S, P2S5 and LiI DME 83 pressure was below 1 × 200 °C, at least 6 h. 0.37- 0.43 Synthesis [58]
DME, 1 d 10−4
10-3 mbar
RT;
RT (2 h)-90 ℃ (2
Crystalline Li7P2S8I Li2S, P2S5 and LiI EP 99.1 Liquid-phase shaking, 6 h 50 ℃, using a rotary 4.7 × 10−4 / Synthesis [61]
h)-170℃ (6 h)

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vacuum pump, 2 h
EP:99.1 Ultrasonicated, 60 °C, 1
Li2S: P2S5: LiBr = In-situ

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Crystalline Li6PS5Br EP&EtOH EtOH: h; dissolved in EtOH 180 ℃, vacuum, 3 h / / [62]
5: 1: 1.5 3.4 × 10−5 coating
78 solution
Synthesis
Li2S + P2S5 in THF, LP-150 (green LP-150 (green of fine
[(Li2S+ P2S5) in THF: 66 overnight; pellet): 1.3 × pellet): 0.445 SE;

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crystalline Li6PS5Br THF] + [(Li2S + THF&EtOH EtOH: suspension + Li2S + LiX, 150 ℃, vacuum, 3 h 550 ℃, dry Ar 10−4 LP-550 coating [63]
LiBr) in EtOH] 78 dissolved in EtOH LP-550 (sintered (sintered particles;
body): 3.1 × 10−3 body):0.302 infiltrate
electrode

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Li2S+ P2S5 in THF, RT,
Pressed into a
[(Li2S + P2S5) in THF: 66 for 24 h; Centrifuged;
Li6PS5X (X pellet, annealed,

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crystalline THF] + [(Li2S + THF&EtOH EtOH: suspension + Li2S + LiX dried, vacuum; 2.4 × 10−3 / Synthesis [64]
= Cl, Br, I) 550 °C (5 °C/min),
LiX) in EtOH] 78 (in EtOH), dissolved, dried 40 °C, vacuum, 20 h
vacuum, 6 h
overnight
Li2S: P2S5: LiCl = Li2S+ LiCl in EA; 550 ℃ (5 ℃/min),
crystalline Li6PS5Cl EA 77.1 30 ℃, vacuum, 12 h 1.1 × 10−3 0.27 Synthesis [65]
5: 1: 2 +P2S5 vacuum, 5 h
C EP
AC

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Table 1-4 Parameters for liquid-phase synthesis of sulfide sodium ion solid electrolytes

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Starting Solvent Heat Conductivity S
Structure Sulfide Solvent b. p. (℃) Mixing procedure Ea/eV Functions Ref.
materials evaporation treatment cm−1 (25℃)

Na2S + P2S5 in n-hexane;

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NMF and + NMF, stirred, cooling
Crystalline Na3PS4 Na2S and P2S5 NMF: 199 180 °C, vacuum 260 ℃ 2.6 × 10−6 0.395 Synthesis [66]
n-hexane in an ice bath; removing
the n-hexane phase
DME: 2.6 × 10−5

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DME or DME: 83 270 ℃, (99% density); DEE: 0.363;
Crystalline Na3PS4 Na2S and P2S5 RT, over 60 h RT, vacuum Synthesis [67]
DEE DEE: 34.6 vacuum, DEE: 1.8 × 10−5 DME: 0.34
(94% density)
Synthesis of SE

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Na2S, P2S5, Vacuum-distilled;
Crystalline Na3-2xPS4-xSex ACN 81.6 50 °C, stirred, 24 h 270 °C 1.21 × 10−4 0.229 with small particle [68]
and Se dried, 80 °C, 12 h
size; coating

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Heat treatment procedure is a crystallization process, in which solvents are further

removed at the same time. The temperature of heat treatment is typically toward the crystallization

temperature, with analyses of TG-DTA as reference.

Based on the above analyses, solvent is the most crucial one among all these parameters,

which would also influence the morphology of as-prepared sulfide via solvent-sulfide interactions.

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Requirements for solvents are as follows to achieve sulfide SEs with desirable ionic conductivity.

First, the solvents applied to liquid-phase synthesis should have appropriate polarity (4–6.5)

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to mediate wet-chemical reaction. The bonds between functional group of solvent molecules and

sulfide precursors are supposed to be moderate for trade-off of reactivity and removal of solvent.

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Moreover, the protonation of sulfur in sulfide would decompose the sulfide into H2S, HS−,

HxPS43−x, therefore aprotic solvents are needed. In addition, low-boiling-point solvents are

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required to reduce energy cost during solvent-removing procedure. Most of the solvents applied in
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liquid-phase synthesis have boiling point less than 100 ℃. Last but not least, the toxicity, cost, and

safety of solvents should also be considered for practical applications.

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1.2 Processing of sulfide solid electrolyte solutions

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Liquid-phase synthesis is a new synthesis method of sulfide SEs, while solution process is a

dissolution and precipitation process of the pre-synthesized SEs in according solvents. In order to
EP

achieve comparable electrochemical performance of bulk-typed ASSBs with LIBs with liquid

electrolyte, a low-resistance interface between electrolyte and electrode in the composite electrode
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is expected, which requires large contact area to provide adequate ionic paths and intimate contact
AC

to reduce interfacial resistances and stress/strain during cycling. Meanwhile, high concentration of

active material in the composite electrode is required for high power and energy density. Therefore,

reducing particle size of SE and coating SE on the surface of active material particles are

necessary. LiCoO2 particles coated with Li2S-P2S5 and Li4GeS4-Li3PS4 SE by the pulsed laser

deposition (PLD) method to form favorable interfaces have been reported [72-74]. However, PLD

may not be a cost-effective approach for air- or moisture-sensitive sulfide SEs. Recently, a

solution process of sulfide SEs with homogenous sulfide solution brought forward a new approach,

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which could be applied to coating and infiltration techniques to improve the interface between

electrodes and electrolytes.

1.2.1 Procedure for processing of sulfide solid electrolyte solutions

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In 2012, Huang et al. synthesized solution-processed thio-LISICON type Li3.25Ge0.25P0.75S4

via the dissolution and deposition of Li3.25Ge0.25P0.75S4 in anhydrous hydrazine [75].

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Li3.25Ge0.25P0.75S4 pre-synthesized by solid-state reaction can be completely dissolved into

anhydrous hydrazine at room temperature. After evaporation of solvent under a flow of dry

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nitrogen at 120 °C and a heat treatment at 240 °C for 2 hours under dry nitrogen, the final

amorphous Li3.25Ge0.25P0.75S4 powder with ionic conductivity of 1.13 × 10−4 S cm−1 at 30 ℃ was

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produced, which might be attributed to the stoichiometry deviation and poor crystalline nature of
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solution-processed Li3.25Ge0.25P0.75S4 , as illustrated in Fig 4a.

In 2013, Li2S-P2S5 SEs were precipitated from NMF solution of 80Li2S·20P2S5 (mol%) SEs
M

by Masahiro and co-workers [76, 77]. After the homogeneous NMF solution of 80Li2S·20P2S5

(mol%) SEs (Fig. 4b) was dried at 150 °C for 3 hours under vacuum to remove the solvent, the
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former SEs obtained by mechanical milling converted to Li2S-P2S5 SE with crystalline phase of
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Li3PS4 and Li2S. Although the obtained electrolytes exhibited the total ionic conductivity was 2.6

× 10−6 S cm−1 (nearly 2 orders of magnitude lower than the original 80Li2S·20P2S5 SEs), the
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solution process can be a processable approach to improve the interface of electrode and

electrolyte. In 2014, a Li3PS4 SE was synthesized and dissolved in NMF solvent by Masahiro and
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co-workers [39]. After NMF solvent was added dropwise into n-hexane suspension of Li2S and
AC

P2S5, sufficient reaction and complete dissolution proceeded subsequently. Further heating at 180 ℃

under vacuum produced Li3PS4 SE, with the ionic conductivity of 2.3 × 10−6 S cm−1 at room

temperature.

Liu et al. reported a novel method to synthesis the SEs mainly containing Li3PS4, which can

be directly dissolved in the same DEGDME solvent in 2018 [45]. After the complete reaction

between P2S5 powder and pre-synthesized soluble polysulfides (Li2S and S powders) in DEGDME

by total 4-day stirring, the solution of SE was obtained. The precipitated SE power from

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DEGDME was identified to mostly contain conductive β-Li3PS4 phase, which exhibited a

room-temperature ionic conductivity of 2.76 × 10−5 S cm−1.

Li6PS5X (X = Cl, Br, I) represents a series of argyrodites, which were synthesized via

solid-state reaction by Deiseroth et al. in 2008, showing promising specific Li-ion conductivities

in the range 10−2 to 10−3 S cm−1 at room temperature by preliminary impedance measurements and

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7
Li-NMR relaxation [78]. Li6PS5X electrolytes were also synthesized by ball milling process [79,

80], with high ionic conductivity and electrochemical stability. Therefore, it is a promising

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candidate of SEs, deserving further investigation.

In 2015, Li6PS5Cl SE was reprecipitated from EtOH solution by Masahiro and co-workers for

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the first time [81]. A Li6PS5Cl SE synthesized via mechanical milling (1.4 × 10−3 S cm−1 at 25 ℃)

was dissolved into an EtOH solvent, followed by a 24-hour stirring at room temperature and

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subsequent drying at 80 ℃ under vacuum for 3 hours. The as-prepared Li6PS5Cl SE exhibited the
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ionic conductivity of 1.4 × 10−5 S cm−1 at room temperature. In 2017, Rosero-Navarro and

co-workers also reprecipitated Li6PS5Cl from its EtOH solution for further application [82]. The
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initial Li6PS5Cl powders by mechanical milling provided lower ionic conductivity of 5 × 10−5 S

cm−1 compared with the reported literature [81], with the presence of Li2S phase. After
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dissolution-reprecipitation process at 80 ℃, the crystallinity of the sample was improved with a

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small loss of the ionic conductivity (1.8 × 10−5 S cm−1), which can be ascribed to the increase of

the grain boundary resistance [81]. Masahiro and co-workers studied the preparation conditions of
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argyrodite-type Li6PS5X (X = Cl, Br, I) SEs from alcohol solvents via solution process in 2018

[83]. To investigate favorable synthesis conditions such as halogen species (Cl, Br, I), alcohol
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solvents (anhydrous EtOH , deoxygenated EtOH, and 2-propanol or tertbutyl alcohol), dissolution

time (1, 3, or 24 hours), and drying temperature (80, 150, or 200 °C under vacuum for 3 hours),
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the argyrodite-type electrolytes mechanochemically synthesized in advance were reprecipitated

from the precursor solutions in different manners. In conclusion, the crystallinity and purity of the

Li6PS5Br electrolyte was improved with EtOH as a solvent and short dissolution time, thus

Li6PS5Br SEs dried at 150 or 200 °C exhibited conductivities (and activation energies) of 1.9 ×

10−4 S cm−1 (32 kJ mol−1) and 2.5 × 10−4 S cm−1 (30 kJ mol−1), respectively.

In 2018, Rosero-Navarro et al. precipitated Li6PS5Cl electrolytes from a mixed solvent of

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EtOH and ACN [84], further improved with the participation of dispersant Triton X-100. The

precipitated SEs had higher ionic conductivities than that of other argyrodites from EtOH

(Li6PS5Cl, 10−5 S cm−1 at room temperature) [81, 82], which can be attributed to the different

solvent-sulfide reactivity. Additionally, particle size and shape of sulfide SEs can be modified via

solution process and by dispersants, as larger particles (1–20 µm) obtained by mechanical milling

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was modified to 5 µm after dissolution-reprecipitation process, and to 500 nm from solution

containing dispersant, as presented in Fig. 4c. Additionally, this group further applied a mixture of

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EtOH and EA (molar ratio of 4: 6) as solvent [85]. The obtained Li6PS5Cl powder by

dissolution-reprecipitation process provided the ionic conductivity of 6 ×10−5 S cm−1 at room

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temperature, with high crystallinity.

In addition to the above report, precursors of Li6PS5X (X = Cl, Br, I) can be mixed in

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solvent with wet-chemical reaction and subsequent dissolution instead of the direct dissolution of
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sulfides that mechanochemically synthesized in advance. Miura et al. prepared Li6PS5Br SE via

ultrasonication of Li2S, P2S5 and LiBr in EP [62], followed by the addition of EtOH to form
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transparent precursor solution. The as-prepared Li6PS5Br SE exhibited a lower room-temperature

conductivity of 3.4 × 10−5 S cm−1. In 2018, Masahiro and co-workers employed multi-step
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liquid-phase synthesis to prepare Li6PS5Br solution [63], via the mixing of the THF suspension
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of Li2S and P2S5 (3: 1 molar ratio) and the EtOH solution of Li2S and LiBr (1: 1 molar ratio) to

obtain the THF&EtOH solution of Li6PS5Br. After subsequent drying and heat treatment, the

obtained Li6PS5Br showed the highest ionic conductivity of 3.1 mS cm−1 at 25 ℃ with particle
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size of 1 µm. Nazar et al. also synthesized argyrodite phases Li6PS5X (X = Cl, Br, I) using
C

THF&EtOH mixtures as reaction medium in 2018 [64], in a similar manner.

However, the dissolution of Li6PS5X (X = Cl, Br, I) in EtOH still remains further
AC

understanding, as PSx species would decompose in protic solvents such as water and EtOH by

hydrolysis or alcoholysis reactions [8, 57, 63]. In the case that precursors of Li6PS5X (X = Cl, Br,

I) were mixed in solvent with wet-chemical reaction and subsequent dissolution instead of the

direct dissolution of sulfides, excess Li2S, which is basic, plays an important role in kinetically

stabilizing the SEs in the solution, otherwise the PS43− ion was decomposed [57, 63]. Therefore,

the dissolved Li2S in EtOH might decrease the proton activity of EtOH, without side reactions

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[86]. In the case that pre-synthesized Li6PS5X were dissolved in EtOH, the partial reaction

between EtOH and the Li6PS5Br SE was characterized by X-ray photoelectron spectroscopy

(XPS) measurements, resulting in a reduction in the conductivity unfortunately [83].

Phosphorus-free SEs is another important breakthrough in solution process of sulfide SEs.

Jung and co-workers synthesized Sn-based SEs, which are phosphorus-free, thus dry-air-stable

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according to hard and soft acids and bases (HSAB) theory [87]. In 2016, glass 0.4LiI-0.6Li4SnS4

(4.1 × 10−4 S cm−1 at 30 °C) was synthesized via solution process [60]. Solutions were prepared by

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dissolving both Li4SnS4 synthesized by solid-state reaction in advance and LiI together into

anhydrous MeOH, with subsequent precipitation by heat treatment at 200 °C. Fig. 4d exhibited

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high-resolution transmission electron microscopy (HRTEM) images and their corresponding

selected-area electron diffraction (SAED) patterns for Li4SnS4 and 0.4LiI-0.6Li4SnS4 prepared at

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200 °C, respectively, which revealed a completely amorphous structure for 0.4LiI-0.6Li4SnS4, in
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sharp contrast with Li4SnS4 consisting of nanometer sized crystallites. Therefore, the

incorporation of LiI worked as the glass former, thus provided more softness and higher ionic
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conductivity than crystalline Li4SnS4, which could not be obtained by conventional synthesis.

While in 2017, a highly conductive, dry-air-stable, and coatable SE, Li4SnS4, was successfully
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prepared by a scalable aqueous-solution process, providing the ionic conductivity of 1.4 × 10−4 S
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cm−1 after heat treatment at 320 °C [88].

Additionally, a series of Na-ion electrolytes without phosphorous were prepared via solution
EP

process by Jung and co-workers, which are regarded to be dry-air-stable. In 2016, Na3SbS4 SE [89]

was synthesized via solid-state synthesis, with high conductivity of 1.1 mS cm−1 at 25 °C, which
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could be attributed to an open framework with 3D sodium ion channels (Figures 4e). More

importantly, it was the first time for sodium-ion SEs to undergo solution process, exhibiting high
AC

ionic conductivities of 0.1–0.3 mS cm−1, with 0.3–0.38 eV activation energies after precipitation

from MeOH or aqueous solutions. Na4−xSn1−xSbxS4 (0.02 ≤ x ≤ 0.33) [90] synthesized by

solid-state reaction showed excellent air stability and solution processability using water, which

was fully dissolved into deionized water without the evolution of toxic H2S gases. After

recrystallization with heat treatment at 450 °C under, the as-treated SEs exhibited a marginal

decrease in ionic conductivities. In 2017, this group reported the application of the scalable

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synthesis of Na3SbS4 from a homogenous aqueous solution using precursors of Na2S, Sb2S3, and

elemental sulfur [91]. Without evolution of toxic H2S gas, the aqueous-solution synthesized

Na3SbS4 exhibited high ionic conductivities (0.1–0.2 mS cm−1 at 25 °C).

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Fig. 4. (a) XRD patterns of Li3.25Ge0.25P0.75S4 powder synthesized by solid-state reaction (SSR)
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and final solution-processed (SP) Li3.25Ge0.25P0.75S4 powder [75]. (b) N-methylformamide

(NMF) solution of the 80Li2S·20P2S5 glass electrolyte with concentration of 10 wt% [77]. (c)
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SEM of Li6PS5Cl solid electrolyte synthesized by mechanical milling process (top-left panel),
Li6PS5Cl solid electrolyte from solution without dispersant (top-right panel), and from
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solution containing 0.1 wt% of dispersant (bottom panel) [84]. (d) HRTEM images and
SAED patterns of Li4SnS4 (left panel) and 0.4LiI-0.6Li4SnS4 (right panel) prepared at 200 °C
[60]. (e) Crystal structure of Na3SbS4 with the unit cell outlined (left panel) and 3D bond
EP

valence map isosurfaces for Na3SbS4 with an isovalue of ±0.3 v.u (right panel) [89].
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1.2.2 Conclusion
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Basically, solution process is a dissolution and precipitation process of the pre-synthesized

SEs via solid-state reaction [60, 75, 88-90], mechanochemical method [76, 77, 81-85] and

liquid-phase synthesis [39, 45, 62-64, 91] in matched solvents.

Homogeneous solutions of SEs prepared in solution process, can wet surfaces of particles and

infiltrate porous structures of composite electrodes, forming favorable solid-solid interfaces

between active material particles and the SE particles with large contact areas. Therefore, coating

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electrode active material particles or infiltrating porous composite electrodes with solution of SEs

can be promising approaches to construct composite electrodes. However, a reduction in

conductivities of sulfide SEs after solution process (to 10−4−10−6 S cm−1) is the most serious

drawback of solution process of sulfide SEs, due to the partial reaction between solvent and

sulfide [83]. The preparation conditions such as kinds of the solvents, dissolution times, and

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drying temperatures were investigated as influential factors to improve the purity and crystallinity

of sulfide SEs. For instance, sulfide SEs with reduced dissolution time have fewer impurities, and

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the crystallinity of sulfide SEs will be enhanced as the drying temperature increased. On the other

hand, although ionic conductivity of SEs can be improved with the increased temperature, high

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resistive layer between active materials and SEs by undesirable side-reaction at high temperature

and thermal instability problem of electrode components (such as binder) may appear, considering

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the application of solution process in construction of composite electrodes, which will be further
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discussed in Section 2.1.3.

For the practical application of this method, following requirements must be satisfied
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simultaneously [60, 86]. First, formation of a homogeneous solution is required for the coating

and infiltrating processes. Second, sufficient high ionic conductivities ( 10−4 S cm−1) should be
D

promised, which means higher crystallinity and fewer impurities [83]. Lastly, solvents in this
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process are supposed to be nontoxic, cost effective, and have low boiling points. Therefore only a

few combinations of solvent and SEs have been reported, which are summarized in Table 2,
EP

including Li3.25Ge0.25P0.75S4-anhydrous hydrazine [75], Li3PS4-NMF [39, 76, 77], Li6PS5X (X = Cl,

Br, I)-EtOH (with incorporation of EP/ACN/EA/THF) [62-64, 81-85], and phosphorus-free

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sulfides-water/MeOH [60, 88]. More appropriate combinations of solvents and sulfide SEs still
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deserve extensive investigation.

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Table 2 Parameters for solution process of sulfide SEs

b. p. Solvent Heat Conductivity S
Structure Sulfide Starting materials Solvent Mixing procedure Ea/eV Function Ref.
(℃) evaporation treatment cm−1 (25 ℃)
120 ℃, a

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Li3.25Ge0.25P0.75S4 powder Anhydrous flow of dry 240 ℃, dry 1.13 ×10−4
Amorphous Li3.25Ge0.25P0.75S4 113.5 / 0.42 Thin film [75]
solid-state reaction hydrazine nitrogen nitrogen, 2 h (30 ℃)

80Li2S·20P2S5

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150 ℃,
Crystalline Li3PS4 mechanical milling NMF 199 / / 2.6 ×10−6 / Synthesis [76]
vacuum, 3 h
(2.3 ×10−4)
80Li2S·20P2S5
150 ℃,

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Crystalline 80Li2S·20P2S5 mechanical milling NMF 199 / / 2.6 ×10−6 / Coating [77]
vacuum, 3 h
(2.3 ×10−4)
Stirred, cooling, 1
NMF and h; 180 ℃, Synthesis;
Crystalline Li3PS4 Li2S and P2S5 199 / 2.3 × 10−6 0.467 [39]
n-hexane Stirred, RT, 5 h vacuum, 3 h coating

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Stirred, 1 d;
140 °C,

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Crystalline Li3PS4 (Li2S + S) + P2S5 DEGDME 162 stirred, 3 d with vacuum, 2 h 2.76 × 10−5 0.417 Thin film [45]
vacuum, 12 h
addition of P2S5
Li6PS5Cl
Crystalline Li6PS5Cl mechanical milling EtOH 78 RT, 24 h 80 ℃, 3 h / 1.4 × 10−5 0.343 Coating [81]
(1.4×10−5 S cm−1)

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Li6PS5Cl
Crystalline Li6PS5Cl mechanical milling EtOH 78 / / / 1.8 × 10−5 / Synthesis [82]
(5 × 10−5 S cm−1)

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EP: Ultrasonicated,
99.1 60 °C, 1 h; 180 ℃, In-situ
Crystalline Li6PS5Br Li2S, P2S5, LiBr EP&EtOH / 3.4 × 10−5 / [62]
EtOH: dissolved in EtOH vacuum, 3 h coating

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78 solution
Li6PS5Cl ACN: 150°C or
mechanical milling 81.6 180°C,
Crystalline Li6PS5Cl EtOH&ACN Vortex mixer / 6 × 10−4 / coating [84]
(4 × 10−5 S cm−1) + dispersant EtOH: under
EP
Triton X-100 78 vacuum, 3 h
80, 150, or
Li6PS5X (X = Cl, Li6PS5X (X = Cl, Br, I) 200 °C
Crystalline EtOH 78 1, 3, 24 h / 2.5 × 10−4 0.311 Coating [56]
Br, I) mechanical milling (2 ℃/min),
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vacuum, 3 h
EtOH:
Li6PS5Cl
78 150 °C,
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Crystalline Li6PS5Cl mechanical milling EtOH&EA Vortex mixer / 6 × 10−5 / / [85]

EA: vacuum
(4 × 10−5 S cm−1)
77.1
Li2S + P2S5 in LP-150 (green
THF: LP-150:
THF, overnight; pellet): 1.3 ×
[(Li2S + P2S5) in THF] + [(Li2S + 66 150 ℃, 0.445 Coating,
Crystalline Li6PS5Br THF&EtOH suspension + Li2S 550 ℃, dry Ar 10−4 [63]
LiBr) in EtOH] EtOH: vacuum, 3 h LP-550: infiltration
+ LiX, (in EtOH), LP-550 (sintered
78 0.302
dissolved body): 3.1 × 10−3

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Li2S + P2S5 in Centrifuged;

THF: THF, RT, for 24 h; dried, Annealed,
Li6PS5X (X = Cl, [(Li2S + P2S5) in THF] + [(Li2S + 66 suspension + Li2S vacuum; 550 °C
Crystalline THF&EtOH 2.4 × 10 −3 / Synthesis [64]
Br, I) LiX) in EtOH] EtOH: + LiX (in EtOH), dried, 40°C, (5 °C/min)

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78 dissolved, vacuum, 20 vacuum, 6 h
overnight h
200 °C;
Glass LiI-Li4SnS4 Li4SnS4, LiI MeOH 64.7 / RT, vacuum 4.1 × 10−4 (30 ℃) 0.432 Coating [60]
vacuum

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Li4SnS4 Deionized Filtration; 320 ℃, 1.4 × 10−4
Glass-ceramic Li4SnS4 100 / / Coating [88]
solid-state reaction water RT, vacuum vacuum (30 °C)
MeOH:
Na3SbS4
MeOH or 64.7 100−200 ℃,

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Crystalline Na3SbS4 solid-state reaction / RT, vacuum (1–3) × 10−4 0.3–0.38 Coating [89]
water water: vacuum
(1.1 ×10−3 S cm−1)
100
Na3.75Sn0.75Sb0.25S4 A sealed glass
Crystalline Na3.75Sn0.75Sb0.25S4 solid-state reaction Water 100 Dissolved RT, vacuum ampoule, 2 × 10−4 (30 °C) / Synthesis [90]

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(5.1 × 10−4 S cm−1 (30 °C)) 450 °C
Route-1:

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precipitated
by adding
Crystalline Na3SbS4 Na2S, Sb2S3, and S Water 100 Dissolved 200 ℃ (1–2) × 10−4 / Coating [91]
acetone;
Route-2:
RT, vacuum

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1.3 Processing of sulfide solid electrolyte slurries

Liquid-phase synthesis is a new synthesis approach for sulfide SEs, while solution process

and slurry process are post-processing of pre-synthesized sulfide SEs, which can be adopted to

fabricate composite electrode and electrolyte layers. Differently from homogeneous solutions of

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SEs prepared in solution process, slurry process of sulfide SEs is the dispersion of sulfides (with

polymeric binders) in nonpolar or low polar solvents, which has been widely investigated with

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more selections of solvents. Traditional cold/hot pressing approaches are easy to operate, but

usually result in pellets with a thickness of hundreds of micrometers to thousands of micrometers

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[5, 29, 32], which are typically used in pellet-type batteries for lab-scale evaluation, without

energy density requirements. Thin SEs layers are fabricated to satisfy the urgent needs for

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practical ASSBs, with high ionic conductivities and small thickness (~dozens of micrometers).
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Slurry process of sulfide SEs is the crucial procedure of the fabrication of thin SEs layers, thus

deserves systematic investigation.

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1.3.1 Procedure for processing of sulfide solid electrolyte slurries

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In 2002, Taro et al. compared the effects styrene-butadiene copolymer (SBR) and silicone

rubber (silicone) as polymer binder in wet process of composite electrolyte [92]. In the preparation
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of composite electrolytes with SBR via wet process, the SE powder was dispersed into toluene

solution of SBR, with gradually concentration while stirring and completely removal of solvent
C

under vacuum. While thio-LISICON powder was dispersed into n-heptane solution of the liquid
AC

silicone, which would be vulcanized at 150 °C subsequently. As a result, thio-LISICON/SBR (5

vol%) composite electrolytes had the ionic conductivity of 3.5 × 10−5 S cm−1 at 25 °C, while the

ion conductivity in thio-LISICON/silicone (5 vol%) composite electrolytes was as high as 5 × 10−4

S cm−1 at 25 °C. The great gap between ionic conductivities of thio-LISICON with different

binders should be attributed to the different texture of SBR and silicone in composite electrolytes,

which also affected mechanical properties of composite electrolytes. As illustrated in Fig. 5a, the

SBR blobs were isolated to each other, while homogeneous dispersion of silicone formed
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networks that could block the ion conduction of Li+ between electrolyte particles. The same group

further investigated pairs of sulfide SEs, polymeric binders, and solvents [93]. The ionic

conductivity at room temperature of oxysulfide glass after being immersed in various solvents

(toluene, heptane, acetone, ACN, EtOH) was compared to find chemically inert solvents for

electrolyte, with the conclusion that the glass is quite stable with hydrocarbons such as toluene or

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n-heptane. SBR composite, polypropylene oxide-polyethylene oxide (PO-EO) composite, silicone

composite electrolytes were also evaluated, in which silicone composite electrolytes exhibited the

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highest ionic conductivity (10−4 S cm−1 at room temperature). They employed the slurry of

Li3.25Ge0.25P0.75S4 with 5 vol% of silicone binder in heptane to fabricate SE layer in 2009 [94].

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The SE slurry (Li2S·P2S5 (80: 20 mol%) dispersed in 2 wt% of hydrocarbon binder dissolved

xylene solution) was used to fabricate SE layer [95]. Jung and co-workers employed anhydrous

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toluene to prepare sulfide SEs slurry of glass-ceramic Li3PS4 (pristine, 1.0 × 10−3 S cm−1 at 30 °C,
AN
after exposure to anhydrous toluene, 7.3 × 10−4 S cm−1) or tetragonal Li10GeP2S12 (, pristine, 6.0 ×

10−3 S cm−1 at 30 °C, after exposure to anhydrous toluene, 4.0 × 10−3 S cm−1) without participation
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of polymeric binder [96].

Jang et al. selected acrylonitrile butadiene rubber (NBR) and para-xylene as suitable binder
D

and solvent for sulfide glass-ceramic SE by screening a wide range of binders and solvents in
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2017 (Fig. 5c) [97]. The slurry was prepared using the 75Li2S·25P2S5 (mol%) glassy SE and

styrene butadiene styrene copolymer (SBS) at a weight ratio of 97: 3 in anisole solvent by
EP

Takeuchi and co-workers [98]. The ionic conductivities of the self-standing SE sheets compressed

at 330 MPa and 410 MPa were 1 × 10−4 S cm−1 and 2 × 10−4 S cm−1, respectively, at 25 °C.
C

Yamamoto and co-workers explored solvent and aliphatic polycarbonate binders to combine

with Li3PS4 [99]. The solvent is supposed to be chemically stable with SE, should dissolve the
AC

binder, and have a moderate vapor pressure. The chemical stability between SE and various

solvents was evaluated via the ionic conductivities and color change of Li3PS4 after exposure to

solvents (Fig. 5d), illustrating the superiority of solvents with a donor number of 9 or less (a

higher donor number indicates higher nucleophilicity), such as anisole, toluene,

1,2-dichloroethane, and n-decane. Considering the solubility of aliphatic polycarbonates in

solvents and vapor pressure of solvents at the same time, pair of poly(propylene carbonate

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(PPC)/anisole was selected to combine Li3PS4 (Li3PS4: PPC = 100: 3).

Shin et al. prepared a SE slurry with amorphous Li7P2S8I:

poly(ethylene-co-propylene-co-5-methylene-2-morbornene) (PEP-MNB) = 97: 3 (in wt%) in

heptane, with annealing at 160 °C and then pressed at 30 MPa [100]. The as-prepared

70-µm-thickness Li7P2S8I SE layer had a total Li ion conductivity of 3.63 × 10−5 S cm−1 at 25 °C,

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which was almost an order-of-magnitude lower than those of the pelletized SE (5.77 × 10−4 S

cm−1).

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Composite electrolyte consisting of Li6PS5Cl and functionalized

styrene-butadiene-block-copolymers with carboxylic acid groups (SBS-COOH) in a weight ratio

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of 98: 2 was prepared using para-xylene as a slurry solvent, exhibiting ionic conductivities on the

same order (∼10−3 S cm−1) as that of the bare Li6PS5Cl electrolytes by Choi [101]

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Gasteiger et al. systematically investigated a wide range of binders in terms of their impacts
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on processability, flexibility, density and resistivity of the resulting SE layer, with Li10SnP2S12

(LSnPS) SEs and toluene solvent [102]. As a conclusion, hydrogenated nitrile butadiene rubber
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(HNBR) binder showed the best results that the composite electrolyte with 2.5 wt% HNBR had

the highest ionic conductivity of 0.3 mS cm−1 (electrochemical impedance spectroscopy

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(EIS)-derived).
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C EP
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Fig. 5. (a) SEM images of thio-LISICON/SBR composite electrolytes (left panel) and
thio-LISICON/silicone composite electrolytes (right panel) [92]. (b) The ionic conductivities
of thio-LISICON composite electrolytes combined with different binders, as a function of the
volume fraction of the polymers [93]. (c) Lithium ion conductivities of composite SEs with
various combinations of binders and solvents [97]. (d) Ionic conductivity of solvent-exposed
Li3PS4 (σSE’) divided by that of pristine Li3PS4 (σSE), i.e. σSE’/σSE, as a function of the donor
number of solvents [99].

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1.3.2 Conclusion

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Slurry process of sulfide SEs is the first step of SE layer fabrication, influencing the

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electrochemical performance and mechanical properties of SE layer. Additionally, it is a promising

approach for mass-production of SE layers and ASSBs.

However, from a manufacturing viewpoint, there are lots of problems for further research.

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The main challenge lies in the difficulty of finding matched pairs of sulfide SEs, solvents and
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polymeric binders. The parameters for slurry process of sulfide SEs are summarized in Table 3.

For solvent, polarity and vapor pressure are the most critical parameters to consider its
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compatibility with sulfide SEs. In details, polarity of solvent determines chemical stability

between solvent and sulfide SEs, which could be examined via the ionic conductivities and color
D

change of SEs after exposure to solvents. Because of the high reactivity of sulfide SEs, nonpolar
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or low polar solvents (with polarity of 0–3) such as toluene, n-heptane, xylene, and anisole are

typical choice. Vapor pressure influences film formation of sulfide SEs, for instance, high vapor
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pressure leads to irregular films with rough surfaces because of overly fast evaporation [97, 99].

Accordingly, the solvents applied in slurry process of sulfide SEs have boiling points from 98.5 to
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155 ℃.
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For binders, the following requirements are desired: i) inert with SEs, ii) soluble in selected

solvents, iii) adhesive with SEs and current collectors, and iv) capable of maintaining the ionic

conductivities of SEs as much as possible [97]. In order to achieve the match between sulfide

electrolyte, solvent, and binder, the use of both nonpolar or low polar solvent-binder combinations

are required, because sulfide SEs tend to be reactive or even dissolved in polar solvents, thus

weakening the adhesion of SEs and current collectors. Therefore, more combinations of these

three components should be explored, such as modified binders [101]. Except for the selection of
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solvents and binders that are compatible with sulfide SEs, the impact of binder content on ionic

conductivity and viscosity of SE slurry measured by its solid content should also be considered

[102].

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C EP
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Table 3 Parameters for slurry process of sulfide SEs

Sulfide Fraction Binder Fraction Solvent b. p. (℃) Conductivity S cm−1 (25 ℃) Ref.

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−5
0.01Li3PO4-0.63Li2S-0.36SiS2 96 vol% SBR 4 vol% Toluene 110.6 7 × 10 [92]
−5
Li3.25Ge0.25P0.75S4 (thio-LISICON) 95 vol% SBR 5 vol% Toluene 110.6 3.5 × 10 [92]

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Li3.25Ge0.25P0.75S4 (thio-LISICON) 95 vol% Silicone rubber 5 vol% N-heptane 98.5 5 × 10−4 [92]
−4
0.01Li3PO4-0.63Li2S-0.36SiS2 or Li3.25Ge0.25P0.75S4 / Silicone rubber / N-heptane 98.5 10 [93]

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Li3.25Ge0.25P0.75S4 (thio-LISICON) 95 vol% Silicone rubber 5 vol% N-heptane 98.5 / [94]

Li2S·P2S5 (80: 20 mol%) 98 wt% Hydrocarbon 2 wt% Dehydrated xylene 137 140 / [95]

7.3 × 10−4

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Glass-ceramic Li3PS4 / / / Anhydrous toluene 110.6 [96]
−3
Tetragonal Li10GeP2S12 / / / Anhydrous toluene 110.6 4.0 × 10 [96]

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75Li2S·25P2S5 97 wt% NBR 3 wt% [97]
330 MPa: 1 × 10−4
75Li2S·25P2S5 97 wt% SBS 3 wt% Anisole 155 [98]
410 MPa: 2 × 10−4

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Li6PS5Cl 98.5 wt% NBR 1.5 wt% Anhydrous xylene 137 140 / [103]

Pulverized fine Li3PS4 glass 100 wt% PPC 3 wt% Anisole 155 / [99]

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−5
Li7P2S8I 97 wt% PEP-MNB 3 wt% Heptane 98.5 3.63 × 10 [100]

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SBS-
Li6PS5Cl 98 wt% 2 wt% Para-xylene solvent 138.5 ~10−3 [101]
COOH
−4
3 × 10 (EIS-derived);
Li10SnP2S12 97.5 wt% HNBR 2.5 wt% Toluene 110.6 [102]
3 × 10−3 (NMR-derived)
C EP
AC

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2. Liquid-involved synthesis and processing of composite sulfide-based electrodes and solid

electrolyte layers

ASSBs can be roughly classified into two types, including lithium ion all-solid-state batteries

(LI-ASSBs) with a conventional porous anode (Fig. 6a), and lithium metal all-solid-state batteries

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(LM-ASSBs) with a lithium-metal anode (Fig. 6b). As illustrated in Fig. 6a, the positive and

negative composite electrodes are separated by a thin SE layer in the bulk-type LI-ASSBs. In this

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section, the fabrication of composite electrode and SE layer with the participation of solvent by

liquid-phase synthesis, solution process, and slurry process will be summarized and discussed，

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respectively (Table 4).

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2.1 Composite electrode

2.1.1 Basic requirements and challenges for fabrication of composite electrode

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Generally, the composite electrode is a uniform combination of active material particles,

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ionically conductive SE particles, electronically conductive carbon additives, and binder (Fig. 6).
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Therefore, the major challenge in composite electrode fabrication is to form favorable interfaces

between these solid components to construct ionically and electronically conductive networks,
EP

which seriously affect the performance of ASSBs. Furthermore, the solid-solid interfaces greatly

depend on the architectural design of composite electrode, the requirements of which are
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summarized below.
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Fig. 6. Schematic illustrations of battery architectures for (a) lithium ion all-solid-state
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batteries (LI-ASSBs), with a partial enlargement of electrode architecture, and (b) lithium
metal all-solid-state batteries (LM-ASSBs).
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First, appropriate components are the foundation of high-performance composite electrode.

For the cathode active materials, layer-structured LiCoO2 (LCO) [39, 81, 83], LiNixCoyMnzO2
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(NCM) [44, 69, 70] and LiNixCoyAlzO2 (NCA) [104-106] have been extensively investigated in

sulfide-based ASSBs, with relatively high operating voltages but limited reversible capacities due
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to large interfacial resistances between lithium transition-metal oxide cathodes and sulfide SEs

resulted from the chemical/electrochemical instability [13], space charge layer [107], inter-atomic
AC

diffusion [108], lattice mismatch [107], poor solid-solid contact [109], etc. While transition metal

sulfides, such as NiS [110], TiS2 [111], Fe3S4 [51], Co9S8 [50] and MoS2 [52] can be admirable

cathode active materials in ASSBs with unique nanostructures to provide large contact area and

better interfacial compatibility with sulfide SEs, thus decreasing the interfacial resistance

effectively. Besides, sulfide electrodes possess high theoretical capacities and moderate operating

voltages, which are potential materials to develop high-energy-density ASSBs [51]. Additionally,

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other components including SEs, polymeric binders, carbon additives, and even current collector

should be compatible. Second, low interfacial resistance is essential for cycle performance,

especially the resistance between electrode and electrolyte. This resistance can be reduced by

increasing the contact area with small particle size or nanostructures of active materials and SEs,

as well as interfacial modification such as coatings. Third, a large ratio of the active material

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content in the composite electrode is required for high energy density. Therefore, small ratio of

SEs and carbon additives but abundant ionic and electronic conducting paths are crucial, while

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uniform distribution of every components, small particle size of SEs and active materials, as well

as SEs coating may be needed. Fourth, mechanical failure of electrodes and interfaces should be

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suppressed for good cycle performance, which requires smaller volume expansion or effective

mechanical buffering during cycling. However, contact loss always happens with the shrinkage

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and expansion of electrode particles during charging/discharging processes [109, 112, 113]. To
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solve this problem, various attempts have been made, such as reducing the particle size of

electrodes and electrolytes, introducing hot-pressing, optimizing the preparation method of

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electrode layers, and constructing reasonable interfacial architecture [114]. Liquid-involved

processing of sulfide SEs can be adopted for the construction of electrode layer, which can form
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intimate contact between active materials and SEs by SE coating on active materials via
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liquid-phase synthesis or solution process. This can enhance the homogenous distribution of every

component of composite electrode with dispersed stress/strain. Fifth, highly effective and low-cost
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manufacturing processes are essential for large-scale production, such as slurry process combined

with wet coating process.

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2.1.2 The application of liquid-phase synthesis to the fabrication of composite electrode

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Liquid-phase synthesis is an effective way for large-scale production of sulfide SEs with

decreasing energy costs, as mentioned earlier. Therefore, this method has been adopted directly to

the fabrication of composite electrode, with in-situ synthesis of sulfide SEs in composite electrode

to provide an intimate contact interface and relatively uniform volume changes of active materials.

In 2017, Matsuda and co-workers fabricated the composite electrode with in-situ synthesis of

glass-ceramic Li3PS4 SE via liquid-phase synthesis using EP as a synthetic medium [44]. The SE

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precursor suspension of Li2S and P2S5 was prepared via liquid-phase shaking with 6-hour reaction.

Subsequently, 1% LiNbO3-coated-LiNi1/3Mn1/3Co1/3O2 (NMC111) was immersed into the

as-prepared SE precursor suspension and evacuated at room temperature and at 170 °C for 2 hours

in order to obtain the composite positive electrode (NMC111: SE = 9: 1 in weight ratio). The SEM

image of cross section of the as-prepared positive electrode composite (Fig. 7a) illustrated that the

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NMC111 particles were well-dispersed in the SE matrix, forming intimate interface, thus the high

reversible capacity of 130 mAh g−1 (NMC111) was obtained at the first cycle. A new liquid-phase

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process was designed and applied to ASSBs by this group in 2018 [69]. The Li3PS4 SE was

directly produced on the cathode active materials NMC111 by applying a new liquid-phase

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shaking method, in which NMC111 (1 wt% LiNbO3 coated) was immersed in EtOH solution of

Li2S and EP solution of Li2S and P2S5 (at a molar ratio of 1: 1) step by step, producing

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90NMC·10Li3PS4 after evaporating and heat treatment. An all-solid-state cell (90NMC·10Li3PS4
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/Li3PS4/ In) was fabricated, exhibiting promising cyclability attributed to the intimate contact at

the interface between NMC111 and electrolyte during cycling.

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Yao et al. reported the coating of Li7P3S11 electrolyte particles via in-situ liquid-phase

synthesis [50]. To synthesize cobalt sulfide/Li7P3S11 nanocomposites, pre-synthesized cobalt

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sulfide (Co9S8) was mixed with Li2S and P2S5 (at a molar ratio of 7: 3) in ACN under stirring at
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50 °C for 24 hours, followed by vacuuming distillation and drying at 80 °C for 12 hours to collect

solid powders. Finally, a heat treatment at 260 °C for 1 hour produced target nanocomposites. As
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revealed by Fig. 7b, SEM studies showed that Li7P3S11 electrolyte layer uniformly anchored on

both side of Co9S8 nanosheets, with an average size of around 10 nm as illustrated by the TEM.
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Therefore, the intimate contact at the cathode-SE interface was formed, realizing

high-performance all-solid-state lithium batteries. The electrochemical performance of the

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composite electrode were investigated using laboratory-scale all-solid-state lithium cells

(employing cobalt sulfide-Li7P3S11 nanocomposites in combination with the neat Li7P3S11

electrolyte and Super P as the cathode, and lithium metal as the anode), exhibiting excellent rate

capability and cycling stability with reversible discharge capacity of 421 mAh g−1 at 1.27 mA

cm−2 after 1000 cycles. This group continued the research of in-situ liquid-phase synthesis, to

fabricate Fe3S4@Li7P3S11 nanocomposites with intimate contact at the interface of active materials

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and SEs [51]. Fe3S4@Li7P3S11 nanocomposite electrodes exhibited higher discharge capacity and

better rate capability than pristine Fe3S4 nanosheets, with the discharge capacity of 1001 mA hours

g−1 at a current density of 0.1 A g−1 after 200 cycles. MoS2 electrode was also coated by Li7P3S11

SE via in-situ liquid-phase synthesis in acetonitrile (ACN) [52], forming a MoS2/Li7P3S11

composite electrode, with intimate contact between electrode and electrolyte. The working

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electrode of testing solid-state cell consisted of MoS2/Li7P3S11 composite, Li7P3S11 SE and

acetylene black (AB) with a weight ratio of 30: 60: 10. The as-assembled ASSBs exhibited higher

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reversible capacity and better cycling stability than ASSBs with untreated MoS2. The in-situ

coating of 70Li2S-30P2S5 on Li4Ti5O12 materials was reported by Gao in 2018 [55], with better

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electrochemical performance caused by intimate contact between SEs and active materials.

In 2018, Yao and co-workers synthesized core-shell Fe1−xS@Na2.9PS3.95Se0.05 nanorods for

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room temperature all-solid-state sodium batteries with high energy density by an in-situ
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liquid-phase coating approach [68]. After the preparation of Fe1−xS, a mixture of Fe1−xS and

Na2.9PS3.95Se0.05 precursors (Na2S, P2S5, and Se) in ACN solvent was stirred at 50 °C for 24 hours,
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thus the Fe1−xS@Na2.9PS3.95Se0.05 precursor suspension was obtained with complete wet chemical

reaction. Further vacuum-distillation and annealing at 270 °C produced core-shell structured

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Fe1−xS@Na2.9PS3.95Se0.05 nanorods, with ionic conductivity electrolyte (1.21 × 10−4 S cm−1) and
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intimate interfacial contact to realize high-performance all-solid-state sodium batteries. The

Fe1−xS@Na2.9PS3.95Se0.05/ Na2.9PS3.95Se0.05/Na all-solid-state sodium battery exhibited excellent

EP

rate capability at room temperature, showing reversible discharge capacities of 899.2, 795.5, 655.1,

437.9, and 300.4 mAh g−1 at current densities of 20, 50, 100, 150, and 200 mA g−1, respectively.
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Based on the above review, liquid-phase synthesis can be applied to in-situ coating of sulfide

SEs on the active material particles with great advantages for the fabrication of composite
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electrode. First, the in-situ synthesis and coating provide an intimate interfacial contact between

active materials and SEs effectively, thus reducing interfacial resistance and stress-strain during

cycling. Second, fine particle size of the as-prepared SE promoted an increased contact area

between SE and active materials. Therefore, ASSBs with higher energy density could be achieved,

with small ratio of SEs to provide ionic conduction paths. Third, the fabrication process of

composite electrode could be simplified, with the participation of SE precursors, rather than SEs.

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However, the evaluations of in-situ coating of sulfide electrolytes have mainly been

demonstrated in the pellet-type electrodes in pellet-type batteries without the participation of

polymeric binders and even carbon additives for lab-scale evaluation, while its application to more

practical sheet-type composite electrodes is expected.

In 2017, Jung and co-workers reported the application of liquid-phase synthesis in the

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slurry-based fabrication process to produce sheet-type electrodes in a single step [70]. As

illustrated in Fig. 7c, the one-pot slurry for producing composite electrodes was prepared by

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stirring a mixture of the active materials (LiNi0.6Co0.2Mn0.2 (NCM622) or graphite), SE precursors

(Li2S and P2S5), polymeric binders NBR or polyvinyl chloride (PVC)), and carbon additives

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(Super C65) in THF overnight at room temperature, followed by subsequent spreading on a piece

of current collector foil via a conventional doctor blade method. Further heating at 140 ℃ removed

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the THF and promoted crystallization of Li3PS4, yielding the sheet-type composite electrode,
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along with the synthesis of Li3PS4 at the same time. Therefore, the fabrication processes of

sheet-type composite electrode were simplified. Additionally, the effects of the SE precursors
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particle size and kinds of polymeric binders on the electrochemical performance of composite

electrode was investigated, with the conclusion that electrodes with ball-milled precursors (~1 µm
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particle size) and NBR binder exhibited better performance. At 30 ℃, the single-step-fabricated
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NCM622 electrode (weight ratios of NCM622: SE (Li3PS4): super C65: binder = 70.0: 27.5: 1.0:

1.5) exhibited a capacity of 140 mAh g−1 at 0.1 C; and the as-prepared graphite electrode ( weight
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ratios of graphite: SE (Li3PS4): super C65: binder = 50.0: 47.5: 0.0: 2.5) exhibited a capacity of

320 mAh g−1 at 0.2 C in an all-solid-state half-cell (electrode/SE-Li6PS5Cl/Li0.5In). Excellent

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cycling stability and rate capability were demonstrated for NCM622/graphite ASSBs at 30 ℃, and

100 ℃.
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2.1.3 The application of solution process to the fabrication of composite electrode

Solution process with dissolution-precipitation could be employed to coating and infiltration

techniques to form intimate contact between electrodes and electrolytes and increase the amount

of active materials in composite electrode.

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(1) Solid electrolytes-coated active materials with solid electrolyte solution

In 2013, LCO particles were coated with Li2S-P2S5 SE via the NMF solution of

80Li2S·20P2S5 glass electrolyte by Masahiro et al. for the first time [77]. The NMF solutions (10

wt% 80Li2S·20P2S5) was mixed with LiNbO3-coated LCO particles, followed by 3-hour drying at

150 ℃ under vacuum. The as-prepared SE-coated LCO particles (the weight ratio of LCO: SE

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coatings is 92.5: 7.5) were mixed with the glass-ceramic 80Li2S·20P2S5 to prepare composite

cathode (the weight ratio of LCO: total SE (SE coatings + glass-ceramic 80Li2S·20P2S5) is 70: 30).

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All-solid-state half cells (In/80Li2S·20P2S5 glass-ceramic/LCO composite electrode) with

SE-coated LCO exhibited better electrochemical performance than the cells using uncoated

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LiCoO2. In 2014, the Li3PS4 SE was directly synthesized from Li2S and P2S5 via liquid-phase

synthesis using NMF and n-hexane, with subsequent addition of LCO particles into solution and

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drying at 180 °C [39]. The all-solid-state half cells with as-prepared cathode particles exhibited
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almost the same discharge capacity (~30 mAh g−1) as the cells with SE-coated LCO by using a

NMF solution of pre-synthesized 80Li2S·20P2S5 (mol%) via ball-milling, which illustrated the
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feasibility of this method.

Besides, the EtOH solution of argyrodite-type Li6PS5X (X = Cl, Br, I) SEs was also prepared
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to coat SEs on active material particles by the same group [81, 83]. In 2015, LiNbO3-coated LCO
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was dispersed into EtOH solution of pre-synthesized Li6PS5Cl in the weight ratio of 92.5: 7.5,

with subsequent drying at 80 ℃ under vacuum for 3 hours to remove EtOH [81]. The as-prepared
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SE-coated LCO was evaluated in all-solid-state half cells (In/80Li2S·20P2S5 (mol%)

glass-ceramic/SE-coated LCO), without additional SEs, carbon additives and binders in composite

electrode, providing initial discharge capacity of 45 mAh g−1. In 2018, Li6PS5Br-coated LCO was
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also prepared by a solution process (Fig. 7d) [83]. The mixture of EtOH solution of Li6PS5Br and
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LCO powder was dried at 150 or 200 °C under vacuum for 3 hours to obtain Li6PS5Br-coated

LCO particles (the conductivities of as-synthesized Li6PS5Br were 1.9 × 10−4 and 2.5 × 10−4 S

cm−1, respectively). The high performance of as-prepared composite electrode was compared with

the conventional mixed electrode by the hand-mixing of LCO and Li6PS5Br particles (6.4 × 10−4 S

cm−1 by mechanical milling technique) in bulk-type all-solid-state In/Li3PS4/LCO half cells with

two types of composite electrodes, in which weight ratio of LCO: Li6PS5Br is 92.5: 7.5. The cell

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with Li6PS5Br-coated LCO particles (dried at 150 °C) exhibited a capacity of 70 mAh g−1, which

is higher than that of cell with conventional mixed electrode (27 mAh g−1) and cell with Li6PS5Cl

electrolyte (with ionic conductivity of 1.4 × 10−5 S cm−1) in their previous work [81]. This result

illustrated that intimate contact between active material particles and electrolyte particles and high

ionic conductivity are necessary for the electrochemical performance of cells. However, the cell

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with Li6PS5Br-coated LCO particles dried at 200 °C (with higher conductivity) had lower capacity,

which might be attributed to the formation of resistive layer between electrode and electrolyte by

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undesirable side-reaction at rising temperature. Therefore, the optimized temperature is quite

important in the preparation of SE-coated active material particles via a solution process. After

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that, EtOH solution of Li6PS5Br via liquid-phase synthesis and subsequent solution process was

used to prepare Li6PS5Br-coated NCM111 powder by the same group [63]. The slurry of EtOH

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precursor solution and NCM111 powder was dried at 150 °C under vacuum for 3 hours to solidify
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the electrolyte, producing NCM111 particles coated with Li6PS5Br SE (90NCM111: 10Li6PS5Br

in weight ratio). The cell with the Li6PS5Br-coated NCM electrode presented a capacity of 119
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mAh g−1, whereas the cell with the conventional mixed NCM111 electrode produced a capacity of

65 mAh g−1 at the 4th discharge process.

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A new class of dissoluble superionic conductor, glass 0.4LiI-0.6Li4SnS4 and Li4SnS4, which
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could be directly coated on active material particles via solution process, was reported by Jung and

co-workers [60, 88]. Glass 0.4LiI-0.6Li4SnS4 prepared at 200 °C exhibited the highest ionic
−4 −1
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conductivity (4.1 × 10 S cm at 30 °C), with great deformability [60]. Therefore,

low-boiling-point MeOH solvent was employed to produce 0.4LiI-0.6Li4SnS4-coated LCO

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(weight ratio of LCO: SE is 85: 15) with high surface coverage on LCO (81%). As illustrated in

Fig. 7e, the voids observed in Field Emission Scanning Electron Microscopy (FESEM) image of
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the conventional mixed electrode reflected poor spatial distribution of SEs and their limited

contacts with LCO particles, while the SE-coated LCO electrode exhibited a smooth and flat

surface, in which the SEs are well distributed by filling the spaces between the LCO particles. The

Li4SnS4-coated LCO powders (the weight ratio of LCO: SE is 85: 15) were also prepared by

aqueous-solution process in the presence of LCO powders with heat treatment at 320 °C [88], with

better electrochemical performance compared with conventional mixed composite electrode. It is

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notable that adding LCO powders to the pre-dissolved Li4SnS4 solution instead of adding LCO

and Li4SnS4 powders together in deionized water is necessary for the preparation of

Li4SnS4-coated LCO, in order to avoid direct exposure of LCO to fresh water.

Solution-process of sodium-ion SEs was also demonstrated by Jung and co-workers [89]. A

new type of sodium superionic conductor, Na3SbS4, could be precipitated from MeOH or aqueous

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solutions, exhibiting high ionic conductivities (0.1–0.3 mS cm−1). Na3SbS4-coated NaCrO2

particles were produced via solution process, with MeOH solution and corresponding heat

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treatment at 200 °C. As-prepared Na3SbS4-coated NaCrO2 (13 wt% Na3SbS4) composite electrode

with intimate ionic contact exhibited improvement in the utilization of NaCrO2 over conventional

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mixed electrodes in all-solid-state NaCrO2/Na-Sn cells, which was almost the same value as that

of the liquid-electrolyte cell. Jung et al. also introduced a scalable aqueous-solution synthesis of

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Na3SbS4 using precursors of Na2S, Sb2S3, and elemental sulfur into solution process to prepare
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coating solution, instead of direct dissolution of Na3SbS4 [91]. The aqueous-solution route could

be applied to high surface-coverage coating of Na3SbS4 on FeS2, the as-prepared composite

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electrode exhibited promising electrochemical performance in FeS2/Na-Sn half cells. In 2018,

Na3PS4-coated Mo6S8 using a solution method was obtained to achieve an intimate contact
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between Mo6S8 and the SEs by Wang and co-workers [115]. To prepare Na3PS4-coated Mo6S8,
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Mo6S8 powders were dispersed into NMF solution of Na3PS4 under 12-hour stirring, with

subsequent drying at 150 °C and heat treatment at 270 °C. The as-prepared Na3PS4-coated Mo6S8
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was mixed with additional Na3PS4 SEs and carbon additives (the weight ratio of Mo6S8: Na3PS4

coating layer and additional Na3PS4: AB is 38: 57: 5) to fabricate composite cathode, and
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evaluated in all-solid-state half cells, with Na3PS4 as SEs and the Na-Sn-C composite as anode.

The as-fabricated cell could be stable after 500-time cycling at 60 °C, which was much better than
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the liquid-electrolyte sodium batteries with the Mo6S8 cathode.

(2) Wet-mixing of every components of electrode in solid electrolyte solution

In 2016, Wang et al. fabricated a sulfur nanocomposite electrode consisting of a

homogeneous distribution of nanosized active material, SE, and carbon by dispersing Li2S,

Li6PS5Cl , and polyvinylpyrrolidone (PVP) in EtOH, followed by a coprecipitation and

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high-temperature carbonization process, simultaneously improving the ionic and electronic

conductivity of sulfur cathodes at nanoscale for ASSBs [116]. In 2017, Rosero-Navarrol and

co-workers employed solution process to wet-mixing process [82]. The EtOH solution of Li6PS5Cl

SEs allowed the incorporation of ethyl cellulose as a binder to improve the cycle life of ASSBs.

Meanwhile, effects of the binder content on the electrochemical performance of composite

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cathode was investigated. As a result, the composite cathode consisting of 89 wt% of NCM111

and 0.5 wt% of ethyl cellulose maintained a capacity retention rate of 91.7% after ten cycles.

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Akira et al. also synthesized and dissolved Li6PS5Br SEs in EP&EtOH solvent via a combination

of liquid-phase synthesis and solution process [62]. A mixture of Li6PS5Br precursors (Li2S, P2S5

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and LiBr), NCM111, and vapor grown carbon fiber (VGCF) in EP&EtOH solvent was

ultrasonicated and heated at 80 ℃. The laboratory-scale cell using the as-prepared composite

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cathode (the mass ratio of NCM111: Li6PS5Br: VGCF = 84: 14: 2) exhibited the capacity of 109
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mAh g−1 for the first discharge, which was much higher than that of composite cathode prepared

by ball-milling process. The composite cathode was also prepared by solution process dispersing
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NCM111, Li6PS5Cl and VGCF in ACN&EtOH [84], and in EtOH&EA (molar ratio of 4: 6) [85].

With the addition of dispersants (such as Triton X-100), particle size and shape of sulfide SE can
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be modified, thus could improve the total discharge capacity, capacity efficiency and cycle
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retention of the ASSBs with high content of active material up to 89 wt% [84].
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(3) Infiltration of solid electrolyte solution into electrode layer

The reports above prepared SEs-coated active materials and composite electrodes from
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solution of SEs via solution process, which formed intimate contact between SE particles and

electrode particles, along with high content of active materials. However, most reports remained in
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lab-scale pellet type batteries with pellet-type electrodes by manual pressing, which is difficult to

develop large-scale production.

The use of a slurry process for ASSBs electrodes requires the homogenous distribution of

four components (active materials, SEs, conducting additives, and binders), which is quite

complex because of the limited choice of solvents and polymeric binders. Therefore, Jung and

co-workers reported an alternative fabrication approach for composite electrodes via solution

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process, in which conventional porous electrodes of LIBs were infiltrated with homogenous SE

solution in 2017 [117]. As illustrated in Fig. 7f, the Li6PS5Cl /EtOH solution infiltrated into

conventional composite LIB electrodes (LCO and graphite electrodes) by a dip-coating method,

with subsequent removal of solvent and heat treatment at 180 ℃, considering thermal stability of

polyvinylidene fluoride (PVdF). Afterwards, the solution-infiltrated electrodes were densified by

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cold-pressing under 770 MPa during the subsequent fabrication process for all-solid-state cells,

ensuring more intimate ionic contacts with low porosities of 6–8%. It was notable that the amount

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of binder was decisive of the rate capabilities for electrodes, which effected ionic contact between

SEs and active materials.

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In 2019, Masahiro et al. infiltrated the conventional NCM111 electrode with THF&EtOH

solution of Li6PS5Br via dipping the electrode into the precursor solution [63]. The obtained

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composite electrode was dried at 150 ℃ under vacuum to prepare composite electrode, with
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densification by pressing at 360 MPa to form favorable electrode-electrolyte interfaces. The

as-prepared electrode (weight ratio of NMC111, Li6PS5Br, AB, and PVdF was 82.2: 15.3: 1.7: 0.8)
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exhibited a high reversible capacity of 154 mAh g−1. However, the cell with conventional mixed

electrode using electrolyte with higher ionic conductivity presented better rate performance than
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the cell with the infiltrated NCM111 electrode, thus indicated the importance of effective ionic
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conductivity of the electrode layer, in addition to forming a favorable interface. The Li4Ti5O12 and

carbon nanotube (LTO@CNT) porous electrode infiltrated with Li6PS5Br-THF&EtOH solution

EP

[118], and Si composite electrode infiltrated with Li6PS5Cl-EtOH solution [119] were also

reported.
C

(4) Conclusion
AC

With solution process, new approaches to fabricate composite electrodes were inspired,

including SEs-coated active materials with SE solution, wet-mixing of every components of

electrode in SE solution, and infiltration of SE solution into electrode layer. The composite

electrodes fabricated using these methods exhibited high reversible capacity attributed to intimate

contact between electrodes and electrolytes. Although improved ionic conductivity of SEs via

solution process can be obtained as the drying temperature increased, with fewer impurities and

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higher crystallinity, formation of high-resistance interfacial layer between active materials and SEs

by undesirable side-reaction at high temperature [63, 83], and thermal instability problem of

electrode components (such as binder) [117] would destroy the electrochemical performances of

as-assembled ASSBs. Therefore, high ionic conductivity and a stable interface are both crucial for

electrochemical performances of the composite electrode, which deserve careful trade-off to

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determine the optimal heat treatment temperature. In addition, high-conductivity SEs at mild heat

treatment temperature and pre-processing of active materials (such as LiNbO3 coating) may be

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potential solutions.

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2.1.4 The application of slurry process to the fabrication of composite electrode

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The major application of liquid-phase synthesis and solution process to the fabrication of
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composite electrodes focuses on SE coating on active materials, which is an additional process of

active materials for their usage in composite electrodes of ASSBs. Infiltrating conventional
M

electrodes with SE solution is a new proof-of-concept approach with applicability to the scalable

roll-to-roll fabrication process [63, 117]. While for the typical fabrication process of sheet-type
D

electrodes in sheet-type all-solid-state cells, slurry process is the first step, followed by wet
TE

coating on current collectors and removal of solvents, which is critical for the fabrication of

all-solid-state cells.
EP

Slurry process is regarded as an effective mixing method to fabricate composite electrode

powder, which contribute to a better distribution and thus a higher capacity [62, 82, 84, 85, 116,
C

120]. LTO particles, solid-phase synthesized Li6PS5Cl SE, and VGCFs with the weight ratio of 5:
AC

4: 1 were dispersed into 200#Paint solvent, with subsequent stirring and drying to obtain LTO@

Li6PS5Cl /VGCFs composites electrode by Gao and co-workers [120].

On the other hand, slurry process is regarded as a typical fabrication process for sheet-type

electrodes, with subsequent casting on current collectors. LTO@70Li2S·30P2S5 material, Li3PS4

SE, VGCFs and polybutadiene (PB) with the weight ratio of 5: 4: 1: 0.5 in mineral spirit was

stirred, casted on Cu foil and dried at 60 ℃ to fabricate sheet-type composite electrode by Gao and

co-workers [55]. The combination of PB binder and mineral sprit solvent made sheet-type

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electrode a feasible process for ASSBs. Shin et al. prepared composite electrode with Li6PS5Cl SE

via slurry process [65]. The composite cathode slurry was prepared by mixing LiNbO3-coated

NCM622, Li6PS5Cl SE, Super P carbon and NBR at a weight ratio of 68: 29: 1.5: 1.5 in xylene,

with which the cell exhibited a capacity of 145 mAh g−1 for the first discharge at 0.1 C.

(1) The influential factors of slurry process

PT
Differently from the LIBs electrodes with liquid electrolytes soaking the polymeric binders to

provide Li+ conducting pathways, involving of SEs are necessary during the slurry process for the

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fabrication of sheet-type electrodes of ASSBs. Therefore, the selections of sulfide SEs, solvents,

binders, and carbon additives compatible with each other in appropriate proportion have been

SC
investigated to obtain sheet-type electrodes with adequate electronic and ionic conductivities and

favorable interfaces.

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The appropriate combinations of solvents and binders are widely studied. Sakuda and
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co-workers systematically investigated the fabrication of ASSBs using sheet-type electrode with

high NCM111 content [121]. As a result, n-decane was selected as the solvent for slurry process
M

because it had little effect on conductivity of 75Li2S·25P2S5, with appropriate vapor pressure.

Pre-compression of the electrode sheet at 37 MPa, along with low fabrication pressure of 111 MPa
D

exhibited high initial discharge despite the high internal resistance, due to the pulverization and
TE

cracking of NCM111 particles induced by high fabrication pressure.

Choi et al. reported a systematic investigation on selection of binders and solvents for
EP

slurry-casting process [97]. NBR binder and para-xylene solvent were compatible with

glass-ceramic 75Li2S·P2S5 SE, facilitating homogeneous dispersion of the SE and offering

C

appropriate lithium ionic conductivity. The as-prepared sheet-type cathode (containing

LiNi0.8Co0.1Mn0.1O2 (NCM811)) on Al foil exhibited decent rate capability and cyclability due to
AC

homogeneous distribution of the electrode components compared with that of dry-mixing

electrode, attributed to the appropriate combination of solvent and binder. Takeuchi and

co-workers compared different combination of solvent and binder (styrene ethylene butylene

styrene copolymer (SEBS) in heptane vs. SBS in anisole) [98]. All-solid-state half cells with

positive electrode sheets prepared using SBS in anisole displayed higher reversible capacities of

158 mAh g−1 with a lower resistance than that of another one, which should be the better selection.

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Uchimoto et al. [122] further analyzed the reaction distribution in composite electrodes using

different binder materials, namely, SBR and SEBS in the in-plane and cross-sectional directions

via 2D-XAS measurements, as illustrated in Fig. 7g. The analysis results revealed that the

dispersion state of the cathode active materials and SE in the composite electrodes greatly affected

battery performance via reaction distribution, originating from a suitable combination between the

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binder and solvent. Choi and co-workers [101] adopted the thiol-ene “click” reaction to

functionalize SBS with an optimal level of carboxylic acid groups (-COOH), which formed

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hydrogen bonds with metal oxide active materials and current collector to provide adhesion of

electrode (Fig. 7h). Meanwhile, it was chemically compatible with Li6PS5Cl sulfide electrolyte

SC
and para-xylene solvent in a slurry, preserving of the ionic conductivity within the electrode. The

half cells with the optimal binder (10% grafting, namely C10), exhibited clearly improved

U
capacity retention compared to that of the butadiene rubber (BR)-based control cell: 78.7% vs.
AN
57.8% retention after 45 cycles.

The effects of different contents of binders in composite cathodes on the electrochemical

M

performance was also investigated. Zhang et al. demonstrated a facile strategy to fabricate

composite sheet-type cathode for ASSBs via the slurry coating method with mixture of NCM811,
D

Li6PS5Cl, ethyl cellulose and carbon black in EtOH [123], in which a moderate content of binder
TE

played the important role to ensure the fast ion migration and stable interface between active

particles and SE. In particular, the composite electrode with 1 wt% ethyl cellulose exhibited the
EP

best electrochemical performance, including reversible capacity, cycling stability and rate

capability.
C

Considering that polymeric binders would hinder ionic conduction by blocking favorable

contacts between active materials and SEs, some researchers adopted heat treatment to remove
AC

binders after the construction of sheet-type electrodes with them [99, 124]. Yamamoto et al.

reported the first fabrication of a binder-free sheet-type battery [99]. Volatile PPC was selected as

binder, which could be easily removed by heat treatment after the fabrication of slurry-type

electrode, leading to enhanced electrochemical performances, including rate capability, excellent

cycle stability, and a 2.6-fold increase in the cell-based-energy-density over previously reported

sheet-type batteries. The same group also heated bilayer sheet (the Si-composite sheet and glassy

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75Li2S·25P2S5 powder after pressing) at 225 °C for 15 minutes under vacuum in the fabrication

process of half cells, in order to remove the PPC binder to reduce internal resistance [124]. In

addition, the influence factors for fabricating silicon-composite electrodes in ASSBs, including

different types of SEs, the ratio of conductive additives, silicon powders with different sizes, and

different wet-mixing methods were investigated. As a result, the wet-mixing technique using a

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shaker was effective in increasing the contact area between Si and the Li3PS4.

A low-temperature post-sintering at the crystallization temperature of sulfide SEs for the

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slurry-cast composite electrodes was also reported, in order to overcome the poor interfacial

contact induced by binder [100, 125]. Shin and co-workers evaluated the electrochemical

SC
performance of pellet-type and slurry-type all-solid-state cells with LiNbO3-coated

LiNi0.6Co0.2Mn0.2O2 (NCM622@LNO)/Li7P2S8I composite cathode and Li metal anode [100]. The

U
heptane slurry of LiNbO3-coated NCM622, amorphous Li7P2S8I, conducting agent (Super P) and
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polymeric binder(poly(ethylene-co-propylene-co-5-methylene-2-norbornene (PEP-MNB)) at a

ratio of 70: 25: 2.5: 2.5 (wt%) was coated on a current collector, with subsequent annealing at 160 ℃
M

to develop the glass-ceramic structure of Li7P2S8I SE. Ha et al. reported a low-temperature

post-sintering method for the fabrication of slurry-cast composite electrodes [125], in order to
D

mitigate the binder-induced detrimental effect on the interfacial robustness. The effects of this
TE

method on the interfacial resistance and robustness were characterized by EIS and galvanostatic

intermittent titration technique (GITT), as illustrated in Fig. 7i. The composite electrode via
EP

slurry-casting was post-sintered at 160 °C, thus the LiI-doped Li3PS4 SEs with low glass-transition

and crystallization temperatures, along with PEP-MNB binder with high thermal stability were
C

suitable for this method. The slurry-cast post-sintering electrode presented better electrochemical

performances compared with the pre-annealing electrode. Additionally, the size reduction and
AC

accordingly more homogeneous dispersion of SE particles also improve utilization of the active

materials.

The effect of carbon additives on sheet-type electrodes was also investigated [124, 126]. Shin

and co-workers investigated the effect of binary carbon additives (VGCF/Super P) on sheet-type

NCM622 composite cathodes of ASSBs [126]. As a result, the 70 wt% of NCM622 composite

cathode with VGCF exhibited superior rate performance attributed to the connection between long

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range positioned NCM622 particles. As for the composite electrode with 80 wt% of NCM622,

VGCF/ Super P (1: 2 wt%) was more appropriate with nano-sized Super P to fill in the closer

intervals between NCM622 particles.

Weight fractions of active materials and the mass loadings were also influence factors. The

electrochemical performance of conventional dry-mixed electrodes and slurry-mixed electrodes

PT
were systematically compared by Jung et al. [103], along with different weight fractions of active

materials and the mass loadings. The slurry-mixed electrodes exhibited worse electrochemical

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performance than that of dry-mixed electrodes, due to the presence of insulating polymeric binders

in slurry that partially block contacts between active materials and SEs. Additionally, premixing of

SC
active materials (NCM622) and SEs by ball-milling before wet-slurry fabrication was attempted to

ensure favorable ionic contacts with low fraction of SEs and participation of polymeric binders,

U
which improved reversible capacity. However, high-rate performance was not affected
AN
significantly, highlighting the importance of high-conductivity SEs.

Besides, Jung and co-workers introduced SE precursors (Li2S and P2S5) into slurry process,
M

instead of pre-synthesized SEs, with in-situ liquid-phase synthesis of Li3PS4 during slurry process,

which simplified the fabrication processes of composite electrodes and widened options of
D

solvents and binders [70].

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(2) Conclusion
EP

To conclude, slurry process with proper combination of solvent and binder is demonstrated to

largely decrease the aggregation of active material particles and SE particles in composite
C

electrode compared with dry-mixing process [97], which is close to the fabrication process of

conventional LIBs electrodes. Without the injection of liquid electrolyte, slurry process of ASSBs
AC

electrodes requires the homogeneous distribution of four components (active materials, SEs,

carbon additives, and binders), in which the employment of SEs generated new challenges while

constructing Li+ conducting pathways.

First, solvents and binders should be compatible with reactive sulfide SEs, thus be restricted

to nonpolar or less polar solvent-binder combinations, such as NBR, PB, and BR binders in xylene

[65, 97, 101, 103, 126], SBS, PPC, and SEBS binders in anisole [98, 99, 122, 124], ethyl cellulose

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binder in EtOH [82, 123], SEBS binder in n-decane [121], PEP-MNB binder in heptane [100, 125]

and PB binder in mineral spirit [55]. Chemical compatibility with sulfide SEs, vapor pressure, and

toxicity of solvents are generally considered. Second, ratio of active materials/SE directly

determines Li+ conducting pathways, while to achieve the high energy density of cells with

sheet-type electrodes, the fraction of active materials should be more than 80 wt%. Therefore,

PT
reduced size (approximately 1 µm) and more homogeneous dispersion of SE particles are required

to ensure the utilization of the active materials [121]. Third, the addition of polymeric binders and

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carbon additives in composite electrodes influences Li+ conduction (Fig. 6a). The insulative

polymeric binders provides mechanical adhesion, but would partially block contacts between

SC
active material particles and SE particles, thus the ionic conductivity of electrode with the

participation of binder is also a crucial parameter to judge the effectiveness of binders, except for

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chemical compatibility with SE, solubility in solvent, and adhesion of electrode, which requires
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suitable types [97, 98, 122], appropriate content [123], or even modification of binders [101]. In

addition, some researchers adopted binder-free electrodes [99, 124] and low-temperature
M

post-sintering in fabrication process [100, 125] to alleviate the detrimental effect of binders on the

interface between active materials and SEs. Carbon additives are employed to form effective
D

electronic conducting network in composite electrode, but in competition with ionic conducting
TE

pathways. Therefore, morphology and content of carbon additives should also be considered in the

construction of composite electrodes [124, 126]. Fourth, the homogeneous distribution of four
EP

components without agglomeration are important to form electronic/ionic conducting network and

mechanical properties with a large proportion of active materials, such as using a shaker with ZrO2
C

balls in slurry process [124]. Fifth, the liquid-phase synthesis could be employed in slurry

process, with precursors of sulfide SEs directly involved into the slurry process to widen the
AC

options of solvent-binder combinations [70]. The participation of solution process with dissolved

SEs may reduce the complexity of mixing of four components despite the limited potions of

sulfide SE-solvent.

In conclusion, the compatible four components (active materials, SEs, carbon additives, and

polymeric binders) in appropriate proportion, along with engineering methods to ensure their

homogeneous distribution are required in slurry process to achieve effective utilization of active

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materials with high active materials fraction.

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U SC
AN
M
D
TE
C EP
AC

Fig. 7. (a) SEM image of cross section of the positive electrode composite containing 90
NCM111-10SE (glass-ceramic 75Li2S·25P2S5) via liquid-phase shaking [44]. (b) SEM image
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(left panel) and TEM image (right panel) of cobalt sulfide-Li7P3S11 nanocomposites via
in-situ liquid-phase synthesis [50]. (c) Schematic illustration of the single-step
wet-fabrication of sheet-type composite electrodes from SE precursors (conductive additives
(Super C65) are not shown in the scheme), along with photographs of each step from one-pot
slurry to the as-fabricated electrode [70]. (d) Field-emission scanning electron microscopy
(FE-SEM) image of Li6PS5Br-coated LCO particle (left panel) and its energy dispersive
X-ray spectroscopy (EDX) maps of cobalt, niobium, sulfur, and bromine (right panel) [83]. (e)
FE-SEM surface images of 0.4LiI-0.6Li4SnS4/LiCoO2 mixture electrode (left panel) and

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0.4LiI-0.6Li4SnS4-coated LiCoO2 electrode (right panel), in which the arrows indicate void
spaces [60]. (f) Schematic illustration of the infiltration of conventional LIB composite
electrodes with homogeneous solution of the Li6PS5Cl /EtOH [117]. (g) X-ray transmission

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images and reacted area mapping results for different SOCs in the in-plane direction (left
panel) and cross-sectional direction (top-right panel) for the SBR electrode and SEBS

SC
electrode via an operando two-dimensional imaging X-ray absorption spectroscopy (2D-XAS)
method; schematic illustration of structure of composite cathodes using SBR and SEBS
binders (bottom-right panel) [122]. (h) Proposed working mechanism of the click binder in
the electrode to form hydrogen bonding between the LiNi0.7Co0.15Mn0.15O2 active material

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and the modified binder [101]. (i) EIS spectra at SOC = 100% (left panel) and transient
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discharge voltage profiles (from the GITT experiments) from SOC = 50% (right panel) of
the pre-annealing and post-annealing electrodes [125].
M
D
TE
C EP
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Table 4-1 Parameters for SE coating of active materials via liquid-phase synthesis and their performance
Active materials/Electrolyte composite via in-situ liquid-phase synthesis
Carbon
Active wt wt
Mixing Solvent Heat wt% Electrolyte additiv Electrode type Test condition Performance Ref.
% %

PT
materials/Electrolyte Solvent b. p. (℃)
procedure evaporation treatment es
composite
90NMC111 (1%
3.85–1.50 V
LiNbO3-coated)·10SE 170 ℃, 2 Pellet-type (dry-mixing) 130 mAh g−1,
EP 99.1 / RT 100 / 0 / 0 (vs. Li-In); at [44]

RI
(glass-ceramic h 330 MPa 1st
0.1 C
75Li2S·25P2S5)
90NMC111 (1% 170 °C,
stirring (500
LiNbO3-coated EtOH EtOH:78 reduced Pellet-type (dry mixing) 95 mAh g−1,
rpm), RT 100 / 0 / 0 0.1 C [69]

SC
NCM111)·10SE EP EP: 99.1 pressure, 330 MPa 9th
50 °C, 6 h
(β-Li3PS4) 2 h,
Vacuuming Li7P3S11 0.5–3.0 V (vs.
Co9S8@Li7P3S11 260 °C, 1 Pellet-type (dry mixing) 633 mAh g−1,
ACN 81.6 50 °C, 24 h distilled; 40 (liquid-phase 50 Super P 10 Li/Li+), at 0.38 [50]
nanocomposites h 240 MPa 1st
80 °C, 12 h synthesized) mA cm−2

U
Li7P3S11 0.5–3.0 V (vs.
Fe3S4@Li7P3S11 260 °C, 1 Pellet-type (dry mixing) 842.6 mAh
ACN 81.6 50 °C, 24 h / 45 (liquid-phase 50 Super P 5 Li/Li+), at 0.1 [51]
g−1, 1st

AN
nanocomposites h 240 MPa
synthesized) A g−1
0.1–3.0 V (vs.
Li7P3S11 (liquid
MoS2@Li7P3S11 250 °C, 2 Pellet-type (dry mixing) Li/Li+), at 0.1 868.4 mAh
ACN 81.6 RT, 24 h 80 °C, 24 h 60 phase 30 AB 10 [52]
composite h 380 MPa C (0.102 mA g−1, 1st
synthesized)
cm−1)

M
260 ℃, Sheet-type (wet mixing 2.5–1.0 V (vs.
Li4Ti5O12@70Li2S·30P2 mineral 198 mAh g−1,
/ 24 h 60 ℃, 24 h vacuum, 1 50 70Li2S·30P2S5 40 VGCF 10 in mineral spirit) Li/Li+), at 0.05 [55]
S5 spirit 1st
h 300 MPa for 45 min C, at 80 ℃

D
0.5–3.0 V (vs.
Fe1-xS@Na2.9PS3.95Se0.05 Vacuum-dist Pellet-type (dry mixing) 695.5 mAh
ACN 81.6 50 °C, 24 h 270 °C 40 Na2.9PS3.95Se0.05 50 AB 10 Li/Li+), at 20 [68]
nanocomposite illed 240 MPa g−1, 1st
mA g−1

TE
Table 4-2 Parameters for slurry process of composite electrode via liquid-phase synthesis and their performance
EP
Active Carbon b. p. Mixing Solvent Heat Electrode Test
wt% Electrolyte wt% wt% Binder wt% Solvent Performance Ref.
materials additives (℃) procedure evaporation treatment type condition
Li3PS4
precursors Sheet-type 3.0–4.3 V, 140 mAh g−1,
C

NCM622 70 27.5 Super C65 1 NBR 1.5 THF 66 / 140 ℃, vacuum [70]
(Li2S and 370 MPa 0.1 C 1st
P2S5)
AC

Li3PS4
precursors Sheet-type 0–1.9 V, 320 mAh g−1,
Graphite 50 47.5 / 0 NBR 2.5 THF 66 / 140 ℃, vacuum [70]
(Li2S and 370 MPa 0.2 C 1st
P2S5)

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Table 4-3 Parameters for SE coating of active materials via solution process and their performance

Active materials/Electrolyte composite via solution process

wt Carbon wt

PT
Active
b. p. Mixing Solvent Heat wt% Electrolyte Electrode type Test condition Performance Ref.
materials/Electrolyte Solvent % additives %
(℃) procedure evaporation treatment
composite
70
2.0–3.6 V (vs.
150 ℃, 107 mAh g−1,

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92.5LCO·7.5SE NMF (only Pellet-type (dry-mixing)
199 / / 80Li2S·20P2S5 30 / 0 Li-In), at 0.13 [77]
(Li2S-P2S5) vacuum, 3 h LCO) 360 MPa reversible
mA cm−2
Pellet-type 2.0–3.6 V (vs.
Using a 180 ℃, 32 mA h g−1,

SC
92.5LCO·7.5Li3PS4 NMF 199 / 100 / 0 / 0 (dry mixing) Li-In), at 0.13 [39]
mortar vacuum, 3 h 1st
360 MPa mA cm−2
−1
2.0–3.6 V (vs. 45 mAh g ,
80 ℃, Pellet-type (dry-mixing)
92.5LCO·7.5Li6PS5Cl EtOH 78 / / 100 / 0 / 0 Li-In), at 0.13 1st [81]
vacuum, 3 h 360 MPa
mA cm−2

U
−1
2.0–3.6 V (vs. 70 mAh g ,
150 ℃, Pellet-type (dry-mixing)
92.5LCO·7.5Li6PS5Br EtOH 78 / / 100 / 0 / 0 Li-In), at 0.13 1st [83]

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vacuum, 3 h 360 MPa
mA cm−2
1.9–3.8 V (vs.
90NCM111·10Li6PS5 150 ℃, Pellet-type (dry-mixing) 119 mAh g−1,
EtOH 78 / / 100 / 0 / 0 Li-In), at 0.13 [63]
Br vacuum, 3 h 360 MPa 4th, discharge
mA cm−2

M
3.0–4.3 V (vs.
135 mAh g-1,
85LCO·15Glass Pellet-type (dry-mixing) Li/Li+), at 0.11
MeOH 64.7 / 200 ℃ 200 ℃ 100 / 0 / 0 1st [60]
0.4LiI-0.6Li4SnS4 370 MPa mA cm−2 (0.1
C), at 30 ℃

D
3.0–4.3 V (vs. 97 mAh g−1,
Deionized Pellet-type (dry-mixing)
85LCO·15Li4SnS4 100 / 320 ℃ 320 ℃ 100 / 0 / 0 Li/Li+), at 1st [88]
water 370 MPa
30 ℃.

TE
1.2–4.0 V (vs.
108 mAh g−1,
Pellet-type (dry-mixing) Na/Na+) 50
87LCO·13Na3SbS4 MeOH 64.7 / 200 ℃ 200 ℃ 100 / 0 / 0 1st [89]
370 MPa mA cm−2, at
30 ℃.
EP
Adding
acetone, 0.6–3.0 V, at
431 mAh g−1,
Deionized being Pellet-type (dry-mixing) 50 µA cm−2,
83FeS2·17Na3SbS4 100 / 200 ℃ 100 / 0 / 0 1st [91]
water washed 370 MPa under 75 MPa,
C

using at 30 ℃
ethanol
Under 0.6–3.0 V, at
AC

324 mAh g−1,

Deionized vacuum, at Pellet-type (dry-mixing) 50 µA cm−2,
87FeS2·13Na3SbS4 100 / 200 ℃ 100 / 0 / 0 1st [91]
water room 370 MPa under 75 MPa,
temperature at 30 ℃
38 0.9–1.9 V (vs. 90 mAh g−1,
150°C, 270 ℃, Na3PS4/57 Pellet-type (dry-mixing)
Mo6S8@Na3PS4 NMF 199 12 h (only 0 AB 5 Na/Na+), 5 mA 1st [115]
vacuum Ar, 1 h 360 MPa
Mo6S8) g−1, at 60 ℃.

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Table 4-4 Parameters for slurry process of composite electrode with solid electrolytes solution and their performance

Active Carbon wt b. p. Mixing Solvent Heat Electrode

wt% Electrolyte wt% wt% Binder Solvent Test condition Performance Ref.
materials additives % (℃) procedure evaporation treatment type

PT
carbon 0.5 3.0 V (vs.
100 °C, 550 °C, 489 mAh g−1,
Li2S 59.6 Li6PS5Cl 29.8 (from 10.6 / 0 EtOH 78 / Pellet-type Li-In), at 0.064 [116]
vacuum Ar 1st
PVP) mA cm−2

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Capacity
2.0 3.8 V vs.
Ethyl Ultrasonicat 180 °C, Pellet-type retention rates
NCM111 89 Li6PS5Cl 9 VGCG 2 0.5 EtOH 78 / Li-In, at 0.064 [82]
cellulose ed, for 3 min vacuum, 3 h 360 MPa of 91.7% after
mA cm−2 10 cycles

SC
EP:
Ultrasonicat
EP& 99.1 453 K, Pellet-type 2.0 3.8 V, at 109 mAh g−1,
NCM111 84 Li6PS5Br 14 VGCG 2 / 0 ed, 300 K, 5 / [62]
EtOH EtOH: vacuum, 3 h 320 MPa 0.1 mA 1st
min
78

U
THF:
2.0 3.8 V (vs.
THF& 66 180 °C, Pellet-type 115 mAh g−1,
NCM111 89 Li6PS5Cl 9 VGCG 2 / 0 / / Li-In), at 0.13 [84]

AN
EtOH EtOH: vacuum, 3 h 360 MPa 1st
78 mA cm−2
EA:
2.0 3.8 V (vs.
EA& 77.1 150 °C, Pellet-type 160 mAh g−1,
NCM111 84 Li6PS5Cl 14 VGCG 2 / 0 / / Li-In), at 0.13 [85]
EtOH EtOH: vacuum 360 MPa 1st

M
78 mA cm-2

Table 4-5 Parameters for infiltration of solid electrolyte solution into electrode layer via solution process

D
Electrolyte solution

TE
Active Carbon wt Electrode
wt% Mixing Solvent Heat wt% Binder wt% Test condition Performance Ref.
materials Electrolyte Solvent b. p. (℃) additives % type
procedure evaporation treatment
Sheet-typ 3.0 4.3 V (vs.
180 ℃, 141 mAh g−1,
LCO 86.3 Li6PS5Cl EtOH 78 / Vacuum 11 Super P 1.8 PVdF 0.9 e 770 Li/Li+), at 0.14 [117]
EP
vacuum 1st
MPa mA cm−2
0.005 2.0 V
Sheet-typ
180 ℃, (vs. Li/Li+), at 364 mAh g−1,
Graphite 73.6 Li6PS5Cl EtOH 78 / Vacuum 20.5 / 0 PVdF 3.9 e 770 [117]
vacuum 0.14 mA cm−2, 1st
C

MPa
at 30 ℃
AC

Sheet-typ 1.9 3.8 V (vs.

THF: 66 150 ℃, 154 mAh g−1,
NCM111 82.2 Li6PS5Br EtOH / / 15.3 AB 1.7 PVdF 0.8 e 360 Li-In), at 0.13 [63]
EtOH:78 vacuum 1st
MPa mA cm−2

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Table 4-6 Parameters for slurry process of composite electrode and their performance

PT
Solvent
Active Carbon wt wt b. p. Mixing Heat Electrode
wt% Electrolyte wt% Binder Solvent evaporati Test condition Performance Ref.
materials additives % % (℃) procedure treatment type
on

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1.0–2.5 V (vs.
200# 60 ℃, Pellet-type Li/Li+), at 0.05 C 179.6 mAh
LTO 50 Li6PS5Cl 40 VGCF 10 / 0 / RT, 24 h / [120]
Paint 24 h 300 MPa (1 C = 175 mA g−1, 1st
g−1), at 80 ℃.

SC
Sheet-type,
pre-compres
Planetary 2.0–3.7 V (vs.
sion at 37
Glass mixer; RT, Li-In), at 64 µA 131-150 mAh
NCM111 80 20 AB 2 SEBS 1 N-decane 174.2 / MPa, [121]
75Li2S·25P2S5 ultrasonicate, 24 h. cm−2 (0.05 C g−1

U
fabrication
1 min rate)
pressure at

AN
111 MPa
60 ℃, 1.9–3.6 V (vs.
Glass-ceramic Denka Para-xyle 138.3 Mortar and 138.2 mAh
NCM811 60 35 2 NBR 3 RT, 1 h vacuum, Sheet-type Li-In), at 0.1 C [97]
75Li2S·25P2S5 black ne 7 pestle g−1, 1st
24 h (17.8 mA g−1)
A planetary
158 mAh g−1,

M
Glass Sheet-type
NCM111 70 30 AB 3 SBS 3 Anisole 155 centrifugal / / 3.7 V (vs. Li-In) [98]
75Li2S·25P2S5 330 MPa 1st
mixer
A planetary
Glass Sheet-type 289 mAh g−1,
Graphite 58 42 AB 1 SBS 3 Anisole 155 centrifugal / / / [98]

D
75Li2S·25P2S5 330 MPa 1st
mixer
Li3PS4

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precursors Super 140 ℃, Sheet-type 140 mAh g−1,
NCM622 70 27.5 1 NBR 1.5 THF 66 / / 3.0–4.3 V, 0.1 C [70]
(Li2S and C65 vacuum 370 MPa 1st
P2S5)
120 °C;
137 Sheet-type 3.0–4.3 V, at 0.1 133 mAh g−1,
NCM622 68.1 Li6PS5Cl 29.2 Super P 1.3 NBR 1.4 Xylene / subsequent dried, vacuum, [103]
EP
−140 370 MPa C, at 30 °C 1st
overnight
−1
Sheet-type 2.0–3.7 V (vs. 151 mAh g ,
NCM111 80 Fine-Li3PS4 20 AB 2 PPC 3 Anisole 155 / RT / [99]
110 MPa Li-In) 1st
Sheet-type, −0.57 to 0.88 V 308 mAh g−1,
C

Graphite 58 Fine-Li3PS4 42 AB 1 PPC 3 Anisole 155 / RT / [99]

110 MPa (vs. Li-In) 1st
Amorphous PEP-M 160 ℃, Ar, Sheet-type 2.5–4.3 V, at 120 mAh g−1,
NCM622 70 25 Super P 2.5 2.5 Heptane 98.42 / / [100]
AC

Li6PS5I NB 3h 30 MPa 55 °C 1st

LTO@70 Sheet-type 2.5–1.0 V (vs.
Mineral
Li2S·30P2 50 70Li2S·30P2S5 40 VGCFs 10 PB 5 / / 60 °C / 300 MPa, Li/Li+), at 0.05 198 mAh g−1, [55]
spirit
S5 for 45 min C, at 80 ℃ 1st
ethyl
Carbon 80 °C, Sheet-type 2.5–4.0 V, at 111.7 mAh
NCM811 75 Li6PS5Cl 15 10 cellulos 1 EtOH 78 / / [123]
black overnight 350MPa 0.05 C, at 30 ℃ g−1, 1st
e
NCM622 70 LiI-doped 25 Super P 2.5 PEP-M 2.5 Heptane 98.42 / RT 160 °C, Sheet-type 2.5–4.3 V (vs. 170.1 mAh [125]

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Li3PS4 NB vacuum, 3 h 250 MPa Li/Li+, at 55 ℃ g−1, 1st

Sheet-type −0.62 to 0.88 V
Glass 25 °C, 24 330 MPa vs. Li-In, 0.19 3058 mAh g−1,
µm-Si 60 40 AB 6 PPC 3 Anisole 155 A shaker / [124]
75Li2S·25P2S5 h 225 ℃ to mA cm−2 (~0.03 1st

PT
remove PPC C)
120 °C,
Sheet-type 2.38–3.68 V (vs. 148 mAh g−1,
NCM622 68.1 Li6PS5Cl 9.2 VGCF 1.3 NBR 1.4 O-xylene 144.4 / vacuum, / [126]
45 MPa Li-In), at 0.1 C 1st
2h

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VGCF: 120 °C,
Sheet-type 2.38–3.68 V (vs. 141 mAh g−1,
NCM622 77.8 Li6PS5Cl 19.5 Super P 1.3 NBR 1.4 O-xylene 144.4 / vacuum, / [126]
45 MPa Li-In), at 0.1 C 1st
(1:2) 2h
120 °C,

SC
137– Mortar and Sheet-type 3.0–4.3 V (vs. 145.8 mAh
NCM622 68 Li6PS5Cl 29 Super P 1.5 NBR 1.5 Xylene vacuum, / [65]
140 pestle 135 MPa Li/Li+), at 0.1 C g−1, 1st
2h
LiNi0.7Co RT, 1 h; 1.9–3.6 V vs
SBS-C Para-xyle 102.5 mAh
0.15Mn0.15 77.3 Li6PS5Cl 19.2 super P 1.5 2 138.4 / 60 °C, / Sheet-type Li-In, at 0.1C [101]
OOH ne g−1, after 45th

U
O2 24 h (10.5 mA g−1)
2.0–3.7 V (vs
Glass Sheet-type

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NCM111 70 30 AB 3 SBR 3 Anisole 155 / RT, 72 h / Li-In), at 64 µA / [122]
75Li2S·25P2S5 330 MPa
cm−2 (1/40 C).
2.0–3.7 V (vs
Glass Sheet-type
NCM111 70 30 AB 3 SEBS 3 Anisole 155 / RT, 24 h / Li-In), at 64 µA / [122]
75Li2S·25P2S5 330 MPa
cm−2 (1/40 C).

M
D
TE
C EP
AC

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2.2 Solid electrolyte layer

SE layer is the most important component of ASSBs, which separates electrodes and provides

lithium ion transporting paths. Therefore, SE layer determines the energy density, rate

performance, and long cyclability of ASSBs. The basic requirements are summarized below.

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First, SE is supposed to be safe, with non-fluidity, non-flammability, and high-temperature

stability. Second, fast ionic conduction greatly affects the electrochemical performance of the

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ASSBs, which requires high ionic conductivity, single-ion conducting nature, and thin thickness of

SE layer (dozens of micron) [37, 38, 71]. Third, the mechanical properties of SE layer determine

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the fabrication of ASSBs and their long-term reliability. Sulfide SE is supposed to be “soft” with

deformable particles, and mediate Young’s moduli between the oxide and other chalcogenide

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glasses [127]. Finally, there should be a versatile approach to fabricate the SE layer.
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Based on the present reports, a lot of strategies have been adopted to fabricate sulfide SE

layer, involving the application of slurry process, SE layer with scaffold, fabrication of thin SE
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membrane, and sulfide-polymer hybrid electrolyte, with different applications. Specific fabrication

methods and applications will be discussed in the following sections.

D
TE

2.2.1 The application of slurry process

EP

Slurry process of sulfide SEs can be applied effectively to the fabrication of sulfide SE layer,

in which “polarity matching combinations” of sulfide SE, solvent, and binder has been
C

summarized in Section 1.3 hereinbefore. Fabrication of the sulfide SE layers in this way begins
AC

with coating of the sulfide SE slurry on a release sheet and involves subsequent drying, followed

by exfoliating from the release sheet to obtain the free-standing sulfide SE layer in some cases.

(1) Direct coating of solid electrolytes slurry on the electrode layer

Direct coating of sulfide SE slurry on the prepared electrode layer is the most conventional

process to fabricate electrolyte layer, with improved interface between two layers.

In 2009, Kanno and co-workers fabricated the electrolyte sheet by a simple coating method
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[94]. The slurry of Li3.25Ge0.25P0.75S4 with 5 vol% silicone binder was coated on an aluminum foil

as electrolyte/anode-aluminum sheet, which was placed on the cathode sheet subsequently. Aihara

coated a SE slurry (98 wt% of Li2S·P2S5 (80: 20 mol%) and 2 wt% of hydrocarbon binder in

xylene) on the surface of the graphite anode [95]. It is notable that the binder in anode here was

conventional PVdF, considering that the same binder in anode and electrolyte layer was not

PT
applicable to the printing process due to its common solubility with xylene by Aihara. Choi and

co-workers adopted appropriate combination of solvent and binder (para-xylene and NBR) to

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fabricate glass-ceramic 75Li2S·25P2S5 SE layer [97], with ionic conductivity of 4.2 × 10−4 S cm−1

close to that of pelletized bare 75Li2S·25P2S5 (4.5 × 10−4 S cm−1). The electrolyte layer was

SC
fabricated via direct coating of sulfide slurry (of 97 wt% of 75Li2S·25P2S5 and 3 wt% of NBR in

para-xylene) on the surface of the cathode layer (with para-xylene and NBR). Although the

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cathode layer was wet by the solvent (para-xylene) of the electrolyte layer, its mechanical and
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chemical properties were not changed after drying, because of the usage of same solvent and

binder. Jung et al. also directly coating xylene-NBR based Li6PS5Cl slurry on the graphite
M

electrode by the doctor-blade method before combining with the NCM622 electrode [103]. SE

slurry (weight ratio of fine-Li3PS4: PPC is 100: 3 in anisole) was directly casted on electrode layer
D

by Yamamoto and co-workers [99], as illustrated in Fig. 8a, along with heat treatment at 225 °C
TE

for 30 minutes under vacuum to remove PPC, in order to suppress ionic conduction blocking. Shin

and co-workers coated a heptane slurry of amorphous Li7P2S8I and polymeric binder PEP-MNB
EP

(with a weight ratio of 97: 3) on the composite cathode layer of LiNbO3-coated NCM622,

amorphous Li7P2S8I, conducting agent (Super P) and PEP-MNB binder to prepare the
C

cathode/electrolyte assembly [100], with subsequent annealing at 160 ℃ to develop the

glass-ceramic structure of Li7P2S8I. The as-prepared slurry-type [NCM622@LiNbO3 + Li7P2S8I

AC

composite cathode]/Li7P2S8I/Li half cells presented initial discharge capacity of 120 mAh g−1 at

55 ℃, retaining 80% of a pellet-type test cell, which should be attributed to decreased ionic

conductivity (1.75 × 10−4 S cm−1 at 55 ℃) than those of the pelletized SE. Choi also casted

electrolyte slurry (Li6PS5Cl: binder = 98: 2) directly on the composite electrode layer after its

drying process [101]. Additionally, the binder was modified-SBS with an optimal level of

carboxylic acid groups (-COOH), with which the electrolyte layer showed ionic conductivities on

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the same order (∼10−3 S cm−1) as that of the bare Li6PS5Cl.

To conclude, the SE layers are prepared via wet coating of solid electrolytes slurry on the

electrode layer, with subsequent removal of solvents and post-processing technologies to further

improve ionic conducting in some cases. It is notable that the corresponding electrode layer

generally uses the same solvent and binder as those of electrolyte layer to maintain the mechanical

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and chemical properties in the wet coating process and drying process.

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(2) Free-standing electrolyte layer exfoliated from the release sheet

Although the direct coating of SE layer on dry electrode layer is convenient, it still suffers

SC
from several technical issues: i) precise thickness control of SE layers on large-area electrodes; ii)

poor mechanical properties of SE layers; and iii) interlayer-mixing between electrode layers and

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SE layers during the coating of SE slurry [86]. Therefore, some researchers developed
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free-standing SE layers.

Self-standing SE sheet was fabricated via a slurry coating process and subsequent exfoliation
M

by Takeuchi et al. in 2017 [98]. The slurry was prepared using the glassy 75Li2S·25P2S5 SE and

SBS at a weight ratio of 97: 3 in anisole solvent, with slurry casting on release sheet and drying at
D

25 ℃. The SE sheets were pressed at 330 MPa or 410 MPa and exfoliated from the release sheet,
TE

with ionic conductivities of 1 × 10−4 S cm−1 and 2 × 10−4 S cm−1 at 25℃, respectively. A

PPC-containing SE slurry could also be fabricated into a bendable free-standing SE sheets for
EP

further stacking according to study of Yamamoto (Fig. 8b) [99]. Gasteiger and co-workers

fabricated free-standing LSnPS sheets by slurry process [102], and systematically evaluated the
C

influences of the binder on the processability, flexibility, density and resistivity of SE thin layers.

Controllable parameters, including LSnPS-to-binder ratio, solids content in the slurry, applicator
AC

gap size and compression method in the fabrication process of free-standing SE layer were also

investigated.

2.2.2 Solid electrolyte layer with scaffold

Although the application of slurry process with coating layer or exfoliated coating layer is

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easy to scale up for practical applications, the mechanical strength of theses electrolyte layers was

not strong enough for further preparation of sheet-type full cells. Therefore, the participation of

scaffold can be a potential approach for free-standing and stackable SE layer for ASSBs.

In 2009, Kanno et al. firstly designed the self-standing sulfide SEs sheet with a combination

of the SE and an adhesive polymer mesh (with the thickness less than 20 µm and an opening area

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ratio over 70%) [94]. The adhesive polymer mesh was fabricated by coating a modified-PET on

the surface of the mesh string, with a thickness of 3–5 µm. Polymer-free sulfide particles occupied

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the openings of plastic mesh, forming tight bound with mesh string after a heat treatment above

the melting point (tm) of the binder, thus providing the 100-µm self-standing SE sheet with enough

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mechanical strength to support further fabrication process. Additionally, this new method

separated two different solvents for coating the mesh string with binder and for preparing sulfide

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SE slurry, thus allowed the usage of polar solvents (unstable with sulfide) with binder and
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provided much more candidate materials for the binder, accordingly.

In 2015, Jung and co-workers prepared a bendable and thin sulfide SE films reinforced with a
M

mechanically compliant poly(paraphenylene terephthalamide) (PPTA) nonwoven (NW) scaffold

via a “transfer” method [96]. The fabrication processes were illustrated in Fig. 8c, which begins
D

with coating the toluene slurry of sulfide SE on a Ni foil with subsequent drying. The as-prepared
TE

SE-coated Ni foil is then cold-pressed onto the NW substrate with a 16-µm thickness and a high

porosity (70%) as well as large opening sizes (∼40 µm), transferring the SE layer from the Ni foil
EP

to the NW substrate. The as-prepared freestanding SE-NW-SE and NW-SE-NW films were ∼70

µm, with the marginal decrease in conductivity of the NW-SE films (0.20 mS cm−1 for

Li3PS4-NW-Li3PS4 and 0.16 mS cm−1 for NW-Li3PS4-NW). Additionally, a free-standing

C

Li10GeP2S12-Li3PS4 bilayer SE film could be fabricated via this method (Li3PS4-NW-Li10GeP2S12

AC

or NW-Li10GeP2S12-Li3PS4-NW) to overcome the poor stability problem of Li10GeP2S12 in contact

with Li. Besides, the poor ionic contact at electrode/(NW-SE-NW) interface was supposed to

decrease the utilization of active materials, thus PEO-LiTFSI was coated on the NW scaffold,

yielding a PEO/LiTFSI-coated NW scaffold (pNW), with improved capacity in pNW-SE-pNW

LCO/LTO cell. While In 2018, SE powder was directly pressed at 20 MPa in a

polytetrafluoroethylene (PTFE) mold to fabricate self-standing SE layer [126]. In 2019, a thin

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Li3PS4 layer with a ∼100 µm thickness reinforced by a Kevlar nonwoven scaffold was prepared

by dropping toluene suspension of Li3PS4 into a Kevlar nonwoven scaffold, followed by drying

overnight under vacuum [128].

To summarize, thin thickness, high porosity, favorable adhesion are crucial factors of

scaffolds to achieve self-standing, high-ionic-conduction, and bendable SE layer for ASSBs with

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high energy density. Additionally, thermal, chemical, and electrochemical stability should also be

considered in order to serve as a mechanically compliant scaffold that provides flexibility and

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toughness. The as-prepared self-standing and bendable SE layers make the large-scale cell

assembly for ASSBs a significant possibility.

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2.2.3 Fabrication of thin solid electrolyte membranes
AN
There is a huge demand for thin SE membranes which are necessary to achieve high-energy

density of ASSBs, although their fabrication faces multiple difficulties, lacking high-efficient and
M

low-cost processing methods. Traditional thin film techniques, such as pulsed laser deposition

(PLD), atomic layer deposition (ALD), and radio frequency (RF) magnetron sputtering, require
D

high-cost and time-consuming ultrahigh vacuum conditions. Furthermore, they suffer from
TE

deviation from the stoichiometry of synthesized thin SE membranes, especially for volatile

elements such as Li, P, and S [38]. Therefore, scalable strategies were adopted with the
EP

participation of solvents, which are discussed below.

In 2014, Liang et al. synthesized β-Li3PS4 nanoflakes via liquid-phase synthesis in ACN,
C

with subsequent EISA technique to produces ultrathin β-Li3PS4 membranes for the first time [37].
AC

β-Li3PS4 nanoflake synthesized using wet chemistry reaction method presented the morphology

with 1–2-µm lateral size and around 80-nm thickness, which tended to easily form thin, dense

membranes upon solvent evaporation because of the large aspect ratio, as illustrated in Fig. 8d.

The as-prepared membranes had thicknesses between 8 and 50 µm, which could be controlled by

adjusting the suspension concentrations. After that, liquid-phase shaking with EP was further

applied to the preparation of Li3PS4 electrolyte film by Masahiro and co-workers [71]. It was

prepared using colloidal process by employing electrophoretic deposition (EPD) technique

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followed by warm pressing, with Li3PS4 suspension synthesized by liquid-phase shaking. The

homogeneous film with thickness of 10–100 µm was controllably prepared, which exhibited high

conductivity (1.98 × 10−4 S cm−1 at room temperature). In 2018, Liang et al. reported a new, facile

strategy for generating ultrathin, dense films of SEs with desirable ionic conductivities based on

their previous works [38]. The synthesis based on exchanging the co-crystalized THF with ACN,

PT
was the key to produce well-controlled plate-like Li3PS4·2ACN with a thickness around 80 nm

that could serve as building blocks for the fabrication of ultrathin films. Sub-micrometer-thick

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membranes of β-Li3PS4 were fabricated using the Li3PS4·2ACN, with subsequent heat treatment at

80 ℃ under vacuum and warm pressed at a temperature of 200 °C at 200 MPa, providing an ionic

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conductivity of 7.2 × 10−5 S cm−1 at 20 °C.

Except for liquid phases synthesis process, solution process was also widely employed to

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prepare SE thin film. In 2012, Huang and co-workers reported a new method to deposit
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Li3.25Ge0.25P0.75S4 thin film via solution process at low temperature [75]. After the spin-casting of

hydrazine solution of Li3.25Ge0.25P0.75S4 on substrate, annealing at 240 °C for 30 minites proceeded

M

to deposit Li3.25Ge0.25P0.75S4 thin film. The as prepared thin film showed an ionic conductivity of

1.82 × 10−4 S cm−1 at 30 ℃, and a lithium-ion transference number of > 0.999. The
D

solution-process method might be an applicable approach to form thin films onto porous
TE

electrodes, constructing favorable contact between electrode and electrolyte. Liu et al. applied

successfully fabricated thin Li3PS4 membrane via liquid-phase synthesis with DEGDME solvent
EP

in 2018 [90]. The DEGDME solution of SE, from a chemical reaction between soluble

polysulfides and P2S5, was coated on Li chip (15 mm diameter) and proceeded heat treatment (in a
C

vacuum for 2 hours and in a vacuum furnace at 140 °C for 12 hours) to form a SE layer (thickness

of ≈ 50 µm) with the measured conductivity of about 10−7 S cm−1, which was proved to have
AC

favorable interfacial contact with Li metal.

Preparation of thin sulfide-based SE membranes can be achieved via liquid-phase synthesis

with production of sulfide with desirable morphology to form thin, dense membranes, as well as

solution process. These new approaches are convenient, low-cost, and high-efficiency, which

could be further applied in mass-production of thin sulfide-based SE membranes.

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2.2.4 Sulfide-polymer hybrid electrolyte

Hybrid SEs consisting of polymer electrolytes and inorganic fillers (such as inorganic solid

electrolytes) have attracted tremendous interest, among which hybrid SEs with oxide SEs as active

fillers have been widely reported, providing high room-temperature ionic conductivity (10−4 S

cm−1), high mechanical stability, high chemical stability, and excellent processability [129]. In this

PT
review article, we will discuss hybrid SEs with sulfide SEs, which are classified into polymer in

sulfide, and sulfide in polymer, with large amounts and low amounts of sulfide SEs, respectively.

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(1) Polymer in sulfide

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Sulfide SEs are single-ion conductors, with high ionic conductivity (over 10−4 S cm−1) [5-7],

which are promising electrolytes for ASSBs. However, low adhesion between sulfide SEs and

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active materials hinders its further application, which may cause contact loss during charge and

discharge. Therefore, sulfide SEs combined with sticky polymer were investigated.
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Sulfide-polymer hybrid electrolytes were firstly synthesized via mechanochemical method

using 70Li2S·30P2S5 glass and oligomers, such as diethylene glycol (DEG), poly(ethylene glycol)s
M

(PEG), polyethylene glycol dimethyl ether (PEGDME), and aklanediols HO(CH2)nOH with
D

different chain lengths by Masahiro and co-workers [130, 131]. The reaction between sulfide and

polymer to prepare hybrid electrolytes was illustrated via the formation of P-O-C bonds by Fourier
TE

transform infrared spectroscopy (FT-IR) and Raman spectra. As illustrated in Fig. 8e, the

proportion of aklanediols had an influence on the conductivity of hybrid electrolytes that high
EP

proportion of insulative aklanediols would decrease Li+ concentration and block continuous Li+

conducting paths. The chain length of aklanediols also affected the increase of conductivity of
C

hybrid electrolytes, that alkanediols with shorter chain length was more effective. The hybrid
AC

electrolyte with 2 mol% 1,4-butanediol exhibited the ambient conductivity of 9.7×10−5 S cm−1

[130], and the hybrid electrolyte using ethyleneglycol (n = 2) showed the highest conductivity of

1.1×10−4 S cm−1 at room temperature [131], which were much higher than the pristine glass

(6.3×10−5 S cm−1 at room temperature). The increase of conductivity of the hybrid electrolytes

might be attributed to the decrease of Tg.

Composite LSnPS/PEO-LiI films, containing 25 to 50 wt% polymer, was fabricated via

cost-effective EPD from acetone-based suspension by Golodnitsky and co-workers [132]. In the
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as-prepared film, PEO/LiI electrolyte filled in the spatial gaps between ceramic particles, which

could suppress polysulfide shuttle and lithium dendrites, thus was regarded as a possible

candidate for polysulfide barriers in Li/S batteries.

DeSimone and co-workers emphasized the types of polymers in hybrid electrolytes, with the

conclusion that single ion-conducting polymer electrolytes would neither block the Li+ conducting

PT
paths nor reduce the single-ion conduction property of sulfide SEs [133]. Single ion-conducting

hybrid SEs were synthesized via mechanochemical reactions between sulfide glass

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(75Li2S·25P2S5), hydroxy-terminated perfluoropolyether (PFPE-diol), and LiTFSI by ball-milling.

The final product, a hybrid SE 77(75Li2S·25P2S5)·23PFPE can be made into 150-µm-thick or even

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thinner membranes using a manual press, with hallmarks of elastic solids as revealed in Fig. 8f,

exhibiting improved adhesive properties (low shear modulus of 2.6 MPa), high ionic conductivity

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close to glassy sulfide (about 10−4 S cm−1 at room temperature), cation transference number close
AN
to the unity, and a wide electrochemical stability window (up to 5 V).

In 2018, Li7P3S11/PEO hybrid SEs with excellent interfacial compatibility for ASSBs was
M

synthesized via in-situ liquid phase procedure by Ci and co-workers [134]. The mixture of Li2S,

P2S5, PEO and LiClO4 with different ratio in ACN were stirred for 72 hours, with subsequent
D

drying to produce PEO-LiClO4 layer wrapped Li7P3S11 hybrid electrolyte. The as-synthesized
TE

hybrid electrolyte with the optimum 3 wt% PEO-LiClO4 exhibited the highest conductivity (2.1

mS cm−1 at room temperature), with PEO-LiClO4 as conductive bridge between the Li7P3S11
EP

particles. Moreover, the PEO-LiClO4 suppressed reaction between SE and lithium, providing

interfacial stability with lithium.

C

Nazar et al. prepared a hybrid membrane with rational structure by two-step process [135].
AC

First, a dense β-Li3PS4 framework provided Li+ conducting paths, which was synthesized via

liquid-phase synthesis, casting, drying and pressing. Second, the infiltration of diluted

polydimethylsiloxane (PDMS) solution with curing agent by spin coating and subsequent

cross-linking via heat treatment filled the voids of β-Li3PS4 framework, preventing direct

electrolyte penetration and offering structure flexibility. The rationally designed electrolyte

membrane with fast and single-ion-conducting channel, suppressed lithium dendritic plating

underneath the membrane.

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PEO reinforced Li6PS5Cl hybrid SE with enhanced electrochemical performance, mechanical

property and interfacial stability was synthesized by Zhang et al. in 2019 [136]. The Li6PS5Cl-x%

PEO (x represents the mass ratio of PEO) hybrid electrolyte was prepared via liquid-phase process,

in which pre-synthesized Li6PS5Cl and PEO (with different mass ratio) was fully mixed in

anhydrous ACN and dried at 60 °C. Pristine Li6PS5Cl had the highest ionic conductivity (1.30 ×

PT
10−3 S cm−1 at 25 °C), and the ionic conductivity decreased 1–3 orders of magnitude with 5–20 wt%

of PEO. However, the addition of PEO in Li6PS5Cl provided enhanced mechanical property and

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stable interface with lithium, especially with the optimal 5 wt% PEO.

Based on the above reports, the addition of polymer aims to improve the mechanical

SC
properties of sulfide SEs, which could obtain intimate electrode-electrolyte interface with

increased adhesion. However, the type of additive polymers should be considered. With the

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addition of polymer without salt, the ionic conductivity would decrease dramatically because the
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insulating polymer blocks the Li+ conducting paths. There would be no obvious decrease in ionic

conductivity for the hybrid electrolyte with small ratio of polymer, while the improvement in
M

mechanical properties would be quite limited [130, 136]. The total ionic conductivity of hybrid

electrolyte may be increased with the addition of salt, such as PEO-LiTFSI, but the single-ion
D

conduction property of the inorganic electrolyte would be reduced, along with the large interfacial
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impedance between conventional electrolytes and single-ion conductors [137]. Therefore,

single-ion conducting polymer with salt is an appropriate polymer to combine with sulfide SE,
EP

with which the hybrid electrolyte could exhibit high ionic conductivity, transference number close

to unity, and improved mechanical flexibility [133].

C

(2) Sulfide in polymer

AC

Sulfide SEs were also selected to disperse into polymer SEs in order to prepare a composite

SE with improved ionic conductivity and electrochemical stability.

In 2015, Xu and co-workers firstly incorporated Li10GeP2S12 sulfide SEs into PEO matrix to

fabricate composite solid polymer electrolyte membranes [138]. PEO and LiTFSI were mixed and

dissolved in ACN, into which pre-synthesized Li10GeP2S12 power with different weight ratio (1%,

5% or 10%) was added respectively, followed by conventional solution-casting technique and

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drying to prepare composite electrolyte membrane (150–200 µm thickness) (Fig. 8g). The

as-prepared electrolytes with the optimum 1% Li10GeP2S12 content presented the maximum ionic

conductivity (1.18 × 10−5 S cm−1 at 25 °C), which might be related to inhibition of crystallization

and reduced interactions between the lithium ions and the PEO chains. PEO-LiTFSI-1%

Li10GeP2S12-10%SN was also successfully prepared via the same conventional method by the

PT
same group, with ionic conductivity of 9.1 × 10−5 S cm−1 at 25 °C [139]. Subsequently, inorganic

electrolytes (Li10GeP2S12, and 75 Li2S·24P2S5·1P2O5 (LPOS)) were selected as active fillers

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incorporated into PEO matrix to fabricate composite SEs [140]. The optimal conductivities are

1.60 × 10−5, and 1.18 × 10−5 S cm−1 at room temperature for PEO-1% Li10GeP2S12, and

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PEO-1%LPOS, respectively. The improvement of ionic conductivity should be attributed to active

fillers, which suppressed polymer crystallization, thus increased the amorphous range in polymer.

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Nano-sized fillers are regarded to be more effective in improving ionic conductivities due to
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their large specific surface areas, however, nano-sized particles tend to agglomerate together.

Therefore, Xu and co-workers put forward a new strategy to prepare sulfide-polymer composite
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SE via in-situ liquid-phase synthesis of nano-sized Li3PS4 fillers with homogeneous distribution in

PEO-matrix [141]. As illustrated in Fig. 8h, precursors of Li3PS4 (Li2S and P2S5) were dispersed in
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ACN and mixed with PEO and LiTFSI, with subsequent casting and annealing at 230 °C. The
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in-situ prepared hybrid electrolyte containing 2 vol% Li3PS4 presented higher ionic conductivity

(8.01 × 10−4 S cm−1 at 60 °C) than that of PEO with pre-synthesized Li3PS4.
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Cui et al. synthesized a composite of poly(vinyl carbonate) (PVC) and LSnPSsolid-state

electrolyte successfully via in situ polymerization [136]. 3 wt % of LSnPS was dispersed into the
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vinylene carbonate (VC) solution of difluoro(oxalate)borate (LiDFOB) and azobisisobutyronitrile

(AIBN) initiator, which was injected into a cellulose separator with subsequent heat treatment at
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60 °C for 120 hours to ensure complete polymerization. The as-prepared composite SE was

estimated to be 2 × 10−4 S cm−1 at room temperature, with intimate contact at electrode-electrolyte

interface.

In conclusion, the composite SEs above are prepared via homogeneous distribution of small

amount of sulfide SEs into polymer matrix, with improved ionic conductivities due to the

suppression of polymer crystallization by sulfide active fillers.

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NMP

Fig. 8. (a) An anisole slurry of 100fine-Li3PS4: 3PPC and a two-layered sheet prepared by
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coating the SE slurry on the electrode sheet (right panel) [99]. (b) A flexible and
free-standing PPC-containing SE sheet [99]. (c) Schematic illustrations of the fabrication of
bendable sulfide NW-SE films with two different structures (SE-NW-SE and NW-SE-NW),
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with FESEM images and photo images [96]. (d) Schematic illustration of EISA of β-Li3PS4
nanoflakes under argon [37]. (e) Temperature dependence of electrical conductivities for the
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(100−x) (70Li2S·30P2S5 glass)·x(1,4-butanediol) hybrid electrolytes [131]. (f) Linear rheology

measurements of the prepared hybrid SE 77(75Li2S·25P2S5) · 23PFPE. Frequency (ω)

dependency of (●) storage (G′) and (○) loss (G″) moduli for hybrid electrolyte measured at
30 °C [133]. (g) A photo of PEO-LiTFSI-Li10GeP2S12 hybrid SE membrane [138]. (h)
Schematic illustration of in-situ preparation process of PEO/Li3PS4 hybrid polymer
electrolytes [141].

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3. Liquid-involved processing of sulfide-based solid-state batteries

Comparison of conventional LIBs and ASSBs at the cell, stack, and pack levels with

potentials for increased energy density were illustrated in Fig. 9, which are quite different from

each other [142]. In a conventional LIB, the liquid electrolyte immerses all components of the cell,

forming parallel connection inside the cell stack. In contrast, in an ASSB, the immobile electrolyte

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enables the bipolar stacking with single cells connected in series, which could greatly increase the

voltage of cell and optimize the packaging design of cell with reduced amount of current

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collectors. Additionally, no cooling system is required for ASSBs due to the lack of flammable

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organic electrolytes. However, the scale-up of ASSBs with sulfide SEs from laboratory research to

industrial mass production still faces huge challenges, with only few publications actually

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attempted to fabricate ASSBs with scalable production processes, as summarized and discussed

below.
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Fig. 9. Comparison of conventional LIBs and ASSBs at the cell, stack, and pack levels with
potentials for increased energy density [142].

In 2009, Kanno and co-workers constructed the ASSBs with lithium inorganic SE

Li3.25Ge0.25P0.75S4 for the first time [94]. Based on the Li-Al/ Li3.25Ge0.25P0.75S4/Mo6S8 system,
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sheet-type battery with a dimension of 30 mm × 30 mm was fabricated via the following four

steps, (i) cathode fabrication on current collector, in which the cathode mixture obtained by ball

milling of Mo6S8, thio-LISICON Li3.25Ge0.25P0.75S4 and carbon additives (AB) in a weight ratio of

70: 30: 3.5 was coated on both the aluminum foil and grid current collector, (ii)

cathode-electrolyte stacking, in which the heptane slurry of Li3.25Ge0.25P0.75S4 and 5 vol% of

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silicone binder was directly coated on the aluminum foil to form electrolyte/anode-aluminum

sheet, followed by stacking on the cathode sheet, (iii) sintering of the cell at 100 ℃ under 100 MPa,

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causing closer contact and higher lithium-ion conduction, (iv) packaging. On the other hand, an

adhesive polymer mesh coated by modified-PET was incorporated to obtain 100-µm electrolyte

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sheet, in which two different solvents could be separately used for coating with binder and SE

slurry. Aihara et al. also adopted electrode-supported strategy to construct practical size cell with

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88 mm × 53 mm electrode active area in 2013 [95]. It was notable that the anode electrode was
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prepared from typical NMP solution of 95 wt% artificial graphite and 5 wt% PVdF, which was

insoluble in xylene solvent used in electrolyte slurry, in order to maintain the separation of the
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anode and the electrolyte at the interface. As illustrated in Fig. 10a, the as-prepared Li2O-ZrO2

coated LiNi0.8Co0.15Al0.05O2/ Li2S·P2S5 (80: 20 mol%)/artificial graphite single cell provided

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capacity retentions of 82% and 85% of initial capacities after 100 cycles at 25 and 60 ℃,
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respectively, which strongly indicated the high temperature stability of the sulfide-based ASSBs,

thus would be appropriate for the electric vehicle and energy storage system applications.
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Meanwhile, a 1 Ah class battery was constructed via stacked battery (three parallel stacks of single

cells). Choi et al. employed electrode-supported strategy via slurry coating [97], in which the SE
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slurry consisting of 97 wt% of 75Li2S·25P2S5 and 3 wt% of NBR binder dispersed in para-xylene

solvent was directly coated on the preassembled composite cathode-current collector layer by wet
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coating, followed by placement of In and Li foils. As illustrated in Fig. 10b, the fabrication

processes of slurry-based ASSBs were different from dry-mixing-based ASSBs, providing more

homogeneous dispersion of cell components in electrode/electrolyte film compared with the

dry-mixing one, attributed to the appropriate combination of binder and solvent.

Takeuchi and co-workers combined three separate layers of the positive electrode, negative

electrode, and self-standing SE sheet to fabricate ASSBs [98]. The free-standing SE sheet was

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prepared by wet coating on copper foil as the release sheet, followed by drying, pressing and

exfoliation from the release sheet, which was sandwiched between cathode and anode composite

electrodes and pressed at 330 MPa and 25 ℃ for cell construction. A relatively dense cross-section

is observed after 10 cycles by the cross-sectional SEM image of the sheet-type all-solid-state full

cell (Fig. 10c). Jung and co-workers [70] assembled the NCM622/graphite full-cell using the

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electrodes prepared by single-step wet-chemical fabrication and thin SE-NW composite film (~70

µm) [96], as illustrated in Fig. 10d. Because of the bendability of the as-prepared electrodes and

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electrolyte layer, the fabrication strategy shed light on scalable roll-to-roll process for practical

production of ASSBs. Yamamoto also stacked the positive/negative electrodes and SE sheet,

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which were fabricated via wet coating strategy using PPC/anisole [99]. Finally, the binder is

removed from the three-layered sheet by heat treatment.

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SE layers were coated on the graphite electrodes via wet coating of SE slurry before
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combined with the NCM622 electrodes by Jung and co-workers [103]. The as-fabricated 80 mm ×

60 mm pouch-type cell provided the first-cycle discharge capacity of 112 mAh gNCM622−1 and a
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stable cycling performance at 0.025 C. The safety performance of the pouch-type

NCM622/graphite full cell was assessed by cutting with scissors and heating at 111 °C on a hot
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plate for > 1 hour, exhibiting mechanical robustness and thermal stability (Fig. 10e).
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Fig. 10. (a) Discharge curves of a Li2O-ZrO2 (LZO)-coated LiNi0.8Co0.15Al0.05O2/ Li2S·P2S5

(80: 20 mol%)/artificial graphite single cell at 25 and 60 °C at every 20 cycles until 100 cycles
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[94]. (b) Fabrication procedures of the ASSBs fabricated by dry-mixing and slurry-mixing
(top panel) and their respective cross-sectional prepared using focused ion beam (FIB)
images (bottom panel) [97]. (c) Cross-sectional SEM image of a sheet-type all-solid-state full
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cell after 10 cycles [98]. (d) Schematic illustration of the free-standing LiNi0.6Co0.2Mn0.2O2
(NCM622)/SE-NW/graphite ASSBs [99]. (e) Photographs of 80 mm × 60 mm pouch-type
NCM622/graphite all-solid-state full-cells after cutting with scissors (left panel) and being
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placed on the hot plate at 111 °C for > 1 h (right panel) [103].
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Based on the above reported publications, processes for the fabrication of sulfide-based

ASSBs via solvent approach include SE separator fabrication, anode fabrication, cathode

composite fabrication, and cell assembly. The parameters for liquid-involved fabrication of

all-solid-state batteries are listed in details in Table 5.

Anodes are divided into anode composite electrodes and lithium-based anodes. The latter

could be fabricated via foil processing, melt processing, vapor-based processing and plating [142],

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which was not the main point of this article, while composite anode could be fabricated by slurry

process and subsequent wet coating, the same as composite cathode. The composite electrode

fabrication via wet process includes three steps concluded by Schnell [142] (Fig. 11a), (i)

composite mixing, which has been discussed in Chapter 2.2.1, (ii) layer forming, which is a wet

coating process, with the sulfide slurry directly coated onto a current collector before removal of

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solvent, (iii) layer compaction, in which a calendering step is recommended for composite

electrodes with ductile sulfide SEs.

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The fabrication of a SE separator layer also includes composite mixing, layer forming and

layer compaction, which can either be directly coated on the electrodes [94, 95, 97, 103] or be

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fabricated into bendable and self-standing SE layer [70, 94, 98, 99] depending on the cell design,

as illustrated in Fig. 11b.

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After the fabrication of each component of ASSBs, the cell assembly procedure was
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proceeded, including layer cutting, cell stacking, and stack pressing, cell contacting, cell

packaging, which was roughly outlined by Schnell [142].

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The feasible processes for the production of sulfide-based ASSBs based on major

publications were selected to approach the processes for a conventional LIB pouch cell, as
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depicted in Fig. 11c, while Jung and co-workers combined infiltration of solution-processable SEs
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into conventional LIB electrodes [117] with bendable and free-standing SE-NW film (∼70 µm)

[96] to fabricate sulfide-based ASSBs. The Li6PS5Cl-infiltrated LCO/ Li6PS5Cl/graphite ASSBs

assembled with the SE-NW film exhibited 94 mAh gLCO−1 at 0.1 C (0.14 mA cm−2) between 2.0–
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4.2 V at 30 °C. Although the electrochemical performances of the as-prepared ASSBs were not
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impressive compared with the conventional liquid LIBs, this proof-of-concept combination of the

SE-infiltrated electrodes and a bendable and thin SE-NW film was supposed to be applicable in
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roll-to-roll fabrication processes of ASSBs. In this way, fabrication processes of conventional

liquid LIBs could be fully adapted to production of ASSBs, in which the sulfide SE solution was

injected into the preassembled electrodes-separator assemblies, followed by solidification with

removal of solvent and densification via compaction.

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Fig. 11. (a) Processes for composite electrode fabrication via wet process. (b) Processes for
SE separator fabrication via wet process. (c) Schematic illustration of the processes for the
production of sulfide-based ASSBs (pouch format) [142].
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Table 5 Parameters for liquid-involved fabrication of all-solid-state batteries

Electrodes Electrolyte
Active Carbon Cell Test
Electrolyte/ Binder/ Solvent/ Binder/ Solvent/ Performance Ref.
materials additives/ Method SE/wt% Method construction conditions

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wt% wt% b. p. wt% b. p.
/wt% wt%
Wet Sintering at
Silicone/ Heptane/ At a current 11 mAh g−1,
Cathode Mo6S8/70 Li3.25Ge0.25P0. AB/3.5 / / Dry mixing Li3.25Ge0.25P0.75S4/ coating on 100℃ under
5 vol% 98.42 ℃ of 0.1 mA 8th discharge

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75S4/30 95 vol% Al foil 100 MPa
At a current [94]
Modified Adhesive density of 40 mAh g−1,
Anode Al foil Li3.25Ge0.25P0.75S4 / /
-PET mesh 0.64 mA 8th discharge

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cm−2
Li2O-ZrO
Dehydrate
2-coated Amorphous Carbon Wet coating on
d xylene/
Cathode LiNi0.8Co 80Li2S·20P2 nanotube/ NBR/2 carbon-coated Dehydrat
137−140

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0.15Al0.05O S5/34 5 Al foil ed Wet
℃ 80Li2S·20P2S5/ 110 mAh, 1st
2/59 NBR/2 xylene/ coating on Compression 2.5–4.0 V [95]
98 discharge

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Artificial 137−140 anode
graphite/ NMP/ Wet coating on ℃
Anode / / PVdF/5
204 ℃ nickel foil
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Glass-cerami 1.9–3.6 V 140.4 mAh g−1

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NCM811 Para-xyle
c Denka Wet coating on Para-xyle Wet (vs. Li-In), after 40 cycles,
Cathode / NBR/2 ne/ 75Li2S·25P2S5/
75Li2S·25P2 black/3 Al foil NBR/3 ne/ coating on / at 0.1 C with 101.6% [97]
60 138.5 ℃ 97
S5/35 138.5 ℃ cathode (17.8 mA capacity
Anode In and Li foils g−1) retention

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Glass
NCM111 Anisole/
Cathode 75Li2S·25P2 AB/3 SBS/3 Wet coating Wet Stacked and
/70 155 ℃ 0.064 mA 114 mAh

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S5/30 Anisole/ coating on pressed at
75Li2S·25P2S5/97 SBS/3 cm−2 (~1/24 gNCM−1, 1st [98]
Glass 155 ℃ copper 330 MPa and
Graphite/ Anisole/ C) diacharge
Anode 75Li2S·25P2 AB/1 SBS/3 Wet coating foil 25 ℃
58 155 ℃
S5/42
SE
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NCM622 precursors Super NBR/ THF/ Wet coating on
Cathode
/70 (Li2S and C65/1 1.5 66 ℃ Al foil
Stacking and 2.5–4.2 V, 124 mAh
P2S5)/27.5 PPTA
Li3PS4/100 / / pressing at 370 at 0.025 C gNCM622−1, 1st [70]
SE NW
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MPa and 30 ℃ discharge

Graphite/ precursors Super NBR/ THF/ Wet coating on
Anode
50 (Li2S and C65/0 2.5 66 ℃ Cu foil
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P2S5)/47.5
LiNbO3-
Rod-like Anisole/ Stacking and
Cathode NCM111 AB/2 PPC/3 Wet coating
Li3PS4/20 155 ℃ Anisole/ heat treatment
/80 Li3PS4/100 PPC/3 / / / [99]
155 ℃ to remove
Graphite/ Rod-like Anisole/
Anode AB/2 PPC/3 Wet coating binder
58 Li3PS4/42 155 ℃
NCM622 Li6PS5Cl/29. Super NBR/ Xylene/13 Xylene/ Wet Pressing 2.5–4.2 V, 112 mAh
Cathode Wet coating Li6PS5Cl /98.5 NBR/1.5 [103]
/68.1 2 C65/1.3 1.4 7–140℃ 137– coating on subsequently at 0.025 C gNCM622−1, 1st

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140 ℃ graphite at 492 MPa and 25 °C discharge

Li6PS5Cl/39. Super NBR/ Xylene/13
Anode Graphite/ Wet coating anode
1 C65/0 2.3 7–140℃
58.6
EtOH/ Wet coating, 2.0–4.2 V,

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Cathode LCO Li6PS5Cl Super P PVdF
78 ℃ infiltration at 0.1 C
PPTA
SE / / / (0.14 mA 94 mAh gLCO−1 [117]
EtOH/ Wet coating, NW
Anode Graphite Li6PS5Cl Super P PVdF cm−2), at
78 ℃ infiltration
30 °C

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Summary

Liquid-involved methods are promising to realize the mass production of sulfide-based SEs

and ASSBs. In this review, we comprehensively summarize the current liquid-involved synthesis

of sulfide-based SE materials and processing of composite electrode/electrolyte layers and ASSBs,

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which are categorized into liquid-phase synthesis, solution process and slurry process.

Liquid-phase synthesis can achieve the cost-effective mass production of sulfide SEs through

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solvent-based wet chemical reaction at mild conditions. Size and morphology of the SE particles

can be mediated by controlling parameters of the procedure. For fabrication of composite

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electrodes and SE layers, liquid-phase synthesis can be applied to in-situ coating of sulfide SEs on

the active material particles with great advantages due to the controllable particle size and

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morphology, which can provide an intimate solid-solid contact between active materials and SEs
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and promote an increased contact area between SE and active materials, thus decreasing the

electrode resistance effectively. Solution process is a dissolution and precipitation process of the
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pre-synthesized SEs via solid state reaction, mechanochemical method and liquid-phase synthesis

in matched solvents. Homogeneous solutions of SEs prepared in solution process, can wet any
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surfaces of particles and infiltrate any porous structures of composite electrodes, forming
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favorable solid-solid interfaces between active material particles and the SE particles with large

contact areas. With solution process, new approaches to fabricate composite electrodes were
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inspired, including SEs-coated active materials with SE solution, wet-mixing of every components

of electrode in SE solution, and infiltration of SE solution into electrode layer, which can lead to a
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high reversible capacity due to the improved interfacial contact between electrodes and electrolyte.
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Slurry process of sulfide SEs is the first step of SE layer fabrication, influencing the

electrochemical performance and mechanical properties of SE layer. Additionally, it is regarded as

an effective mixing method to fabricate composite electrode layer due to a better distribution of all

the components. The aggregation of active materials and SE particles in composite electrodes

prepared with slurry process is demonstrated to be largely decreased compared with dry-mixing

method. In summary, liquid-phase synthesis of sulfide SEs is a scalable synthesis method for

cost-effective mass production of sulfide SEs, while solution/slurry process of pre-synthesized

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sulfide SEs play a crucial part in fabricating sheet-type composite electrodes and electrolyte layers,

and further in construction of ASSBs from a perspective of manufacturing.

Liquid-involved synthesis and processing of sulfide SEs have three common processes:

mixing process, solvent evaporation process, and heat treatment process, but with different

synthesis/processing parameters. Selection of solvents is the most crucial one among all these

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parameters, which has different criteria for liquid-phase synthesis, solution process, and slurry

process, respectively. For liquid-phase synthesis (Table 1), the solvents should be aprotic to avoid

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the hydrolysis reaction between sulfides and solvent molecules, with appropriate polarity (4–6.5)

to mediate wet-chemical reaction. Additionally, low-boiling-point solvents are required to reduce

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energy cost during solvent-removing procedure. Most of the solvents applied in liquid-phase

synthesis have boiling point less than 100 ℃. For solution process of sulfide SEs (Table 2), only a

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few combinations of solvent and SEs have been reported without distinct rule, including
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Li3.25Ge0.25P0.75S4-anhydrous hydrazine [75], Li3PS4-NMF [39, 76, 77], Li6PS5X (X = Cl, Br,

I)-EtOH (with incorporation of EP/ACN/EA/THF) [62-64, 81-85], and phosphorus-free

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sulfides-water/MeOH [88]. For slurry process of sulfide SEs (Table 3), polarity of solvents is

generally low (0–3), thus toluene, n-heptane, xylene, and anisole are typical choice. Vapor
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pressure influences film formation of sulfide SEs, with corresponding boiling points from 98.5 to
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155 ℃.

However, there are still many shortcomings to be improved in the state-of-the-art

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liquid-involved methods. A reduction in conductivities of sulfide SEs after a liquid-involved

process is the most serious drawback, which may be caused by the presence of residual (such as
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incomplete reactants and residual solvents) and byproducts, along with low crystallinity of sulfide

SEs at decreased heat treatment temperature. Considering the further application of

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liquid-involved processing of sulfide-based sheet-type electrode/electrolyte layer and ASSBs,

further efforts are required to obtain sulfide SEs with relatively high ionic conductivities at mild

heat treatment temperature. This development is significant to avoid formation of high-resistance

interfacial layer between active materials and SE by undesirable side-reaction at high temperature

[63, 83], and thermal instability problem of electrode components (such as binder) [117]. In the

meantime, toxicity and costs of solvents may hinder further application of liquid-involved

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synthesis and processing of sulfide SEs from a practical point of view. Therefore, new solvents

with more environmentally-friendly properties are remained to be developed.

At the same time, there are still many intrinsic issues to be solved for the practical application

of sulfide-based ASSBs, in terms of chemical stability in air, electrochemical stability, and

compatibility between SEs and electrodes. Low chemical stability in moisture is the most serious

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drawback of sulfide SEs that hydrolysis reaction between sulfides and water in air generates

harmful H2S gas, which accelerates degradation of sulfides, causes safety issues and increases

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processing costs [8]. Low electrochemical stability is another challenge for sulfide SEs, which

directly limits their application in high-energy-density ASSBs with high-voltage cathode and

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lithium metal anode [12]. Additionally, the successful application of ASSBs relies on the

compatibility between SEs and electrodes, such as lithium metal anode and high-voltage

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transitional metal oxides cathode (LixMO2). For sulfide SEs with lithium metal, the most pressing
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issues are lithium dendrites growth along the grain boundaries [143] and even inside bulk SE

[144], along with chemical instability at sulfide SEs/lithium interface [12]. For cathode part,
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ASSBs with bare LixMO2 cathodes exhibited lower capacity with theoretical one and high

interfacial resistances, due to imperfect solid-solid contact, and formation of interfacial layer. This
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can be attributed to low electrochemical stability of sulfide SEs [9], electrochemical reaction at
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interface [13], space charge layer [107], inter-atomic diffusion [108], lattice mismatch [107]

between cathodes and sulfide SEs, etc.

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Acknowledgements

This work is supported by National Key R&D Program of China (Grants No. 2016YFB0100100),
Beijing Municipal Science & Technology Commission (Grants No. D181100004518003), and
100-Person Plan of Chinese Academy of Sciences.

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Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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