A6008 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018)

JES FOCUS ISSUE ON LITHIUM–SULFUR BATTERIES: MATERIALS, MECHANISMS, MODELING, AND APPLICATIONS
Review—Solid Electrolytes for Safe and High Energy Density
Lithium-Sulfur Batteries: Promises and Challenges
Xabier Judez,a,b Heng Zhang, a,z Chunmei Li, a,z Gebrekidan Gebresilassie Eshetu,a,∗
José A. González-Marcos,b Michel Armand,a and Lide M. Rodriguez-Martineza
a CIC Energigune, Parque Tecnológico de Alava, 01510 Miñano, Alava, Spain
b Department of Chemical Engineering, Faculty of Science and Technology, University of the Basque Country
UPV-EHU, 48080 Bilbao, Spain

All-solid-state lithium-sulfur batteries (ASSLSBs) offer a means to enhance the energy density and safety of the state-of-art lithium-
ion batteries (LIBs), due to their high gravimetric energy density, low cost and environmental benignancy. In this work, the status
of the research advances and perspectives on several types of solid electrolytes (SEs) developed for ASSLSBs are reviewed. The
promises and challenges of utilizing SEs are discussed taking into account both theoretical calculation and experimental results, in
hope of shedding some lights on future design of high energy density, cost competitive, and safe Li-S batteries.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/),
which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any
way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0041801jes]
All rights reserved.

Manuscript submitted August 4, 2017; revised manuscript received September 25, 2017. Published October 7, 2017. This paper is
part of the JES Focus Issue on Lithium-Sulfur Batteries: Materials, Mechanisms, Modeling, and Applications.

Lithium-sulfur (Li-S) batteries have been extensively investigated
for lightweight applications (e.g., aircraft, artificial satellite, and un-
manned aerial vehicles), and large-scale stationary energy storage,
owing to their high gravimetric energy density, low cost, and en-
vironmental friendliness.1–3 The deployment of Li-S batteries into
commercial market is hampered by several seemingly intrinsic prob-
lems resulting from the complex cell chemistry. Firstly, the elec-
tronically insulating nature of elemental sulfur (S8 ) and end-product
lithium sulfide (Li2 S) leads to unstable electrochemical contact within
S cathode.4–7 Secondly, the soluble intermediates of polysulfide (PS)
can diffuse between the cathode and anode (i.e., shuttle effect of PS),
generating an active material loss in S cathode and degrading metallic
Li anode.4–9 Thirdly, the formation of ‘dead’ Li and Li dendrites upon
cycling could not only decrease the Coulombic efficiency but also
raise safety issues.10–12
In recent years, various strategies have been attempted to over-
come the above-mentioned problems. Most of the efforts have been
devoted to enhance the electrochemical performance of Li-S batteries
using well-designed cathode materials.13 The diffusion of polysulfide
species generated during discharge into electrolytes can be signif-
icantly suppressed by infusing sulfur into carbon materials in the
cathode with an adequately controlled and engineered porosity and
pore size, thus increasing the practical capacity and cyclability of Li-
S batteries. These rational and creative strategies of cathode design
have been covered by a number of recent reviews.7,14,15 Besides, new
binders (e.g., poly(ethylene oxide) (PEO)16 and carboxymethycellu-
lose (CMC)17,18 ) have been employed for guarantying the integrity of
the morphology and structure of S cathode, and enhancing the adhe-
sion to current collector. The modification of separators (e.g., multi-
wall carbon nanotubes coated polypropylene19 and lithiated Nafion20 )
have been also developed for reducing the migration of polysulfides,
thus mitigating the shuttle effect of PS.21
Apart from the strategies mentioned above, another approach,
focusing on electrolyte formulation and modification, has been
proved to be effective. The performances of Li-S batteries are
largely affected by the electrolyte recipes, such as the type and
identity of solvents, nature of Li-salts and their concentrations
and functional additives.22 To date, liquid solutions of lithium
∗ Electrochemical Society Student Member.
z
E-mail: hzhang@cicenergigune.com; cli@cicenergigune.com
bis(trifluoromethanesulfonyl)imide ([(CF3 SO2 )2 N]Li, LiTFSI) in a
mixture of linear (e.g., 1,2-dimethoxyethane (DME)) and cyclic ethers
(e.g., 1,3-dioxolane (DOL)) solvents containing small amount of
lithium nitrate (LiNO3 ) as an additive are used as archetypal elec-
trolytes. This is mainly motivated by several intrinsic features of the
electrolyte components, including (1) the highly delocalized negative
charge distribution of TFSI− , being crucial for effectively reducing
the interactions between Li+ and TFSI− and thereby increasing the
dissociation and solubility of LiTFSI in ether solvents, thus leading to
the enhancement of ionic conductivity at room temperature;23,24 (2)
the capability of DOL in forming insoluble and flexible surface films
(also called solid electrolyte interphase, SEI) of dioxolane oligomer
(–(OCH2 CH2 OCH2 )n –), which serve as a means to prevent dendrite
formation, accommodate morphology/volume changes of the elec-
trodes while allowing highly facile Li-ion transport. This ultimately
results in improving the cycling life and efficiency of Li-S batteries;25
(3) the participation of LiNO3 in formation of SEI on the surface of
Li metal anode leading to enhanced the stability of Li anode and sup-
pressed the redox shuttle effect of polysulfides and self-discharge, thus
improving the cycling performances of Li-S batteries.26–29 Besides to
form a robust passivation layer, LiNO3 has also recently reported
to catalyze the conversion of highly soluble polysulfide to slightly
soluble S8 , providing a synergetic improvement to Li-S batteries.30
Another strategy consists in the design of the so-called “sparingly
solvating” electrolytes in which the di-charged polysulfides are insol-
uble while the main salt, i.e. LiTFSI is still soluble.31,32 However, the
conductivity is one order of magnitude lower than that of DME/DOL-
electrolytes.
Despite the above advantages of liquid electrolytes, in effective,
organic solvents, may be with the exception of those sufficiently flu-
orinated and that of ionic liquids, are highly flammable and cause
safety concerns. Hence, solid-state Li-ion conductors, encompass-
ing inorganic electrolytes and organic polymer electrolytes (PEs),
have emerged as promising alternatives to these conventional liquid
electrolytes, possibly enabling the development of safe rechargeable
Li-S batteries.33,34 Several comprehensive reviews of electrolytes for
Li–S batteries have been published recently; however, little atten-
tion has been paid to solid electrolytes for all-solid-state Li-S bat-
teries (ASSLSBs).14,22,35,36 This work presents an overview of the
current status and state-of-art enlisting both inorganic and PEs, which
have been implemented in ASSLSBs. On the basis of the energy
density calculation making use of various electrolytes, the existing

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 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018)
opportunities, challenges and future work on enabling solid elec-
trolytes as the key path toward long-term and high energy density
Li-S batteries are extensively discussed.
Current Status
Since the first study on poly(ethylene oxide) (PEO) -based elec-
trolyte for Li-S cells in the late of 1980s by DeGott,37 several types
of solid electrolytes have been investigated as Li-ion conducting
materials for ASSLSBs, including those based on pure polymeric
components,38–49 ceramic electrolytes,50–67 and composite electrolytes
(mix of ceramic and other electrolytes).68–70 Generally, PEs can be
classified into two categories: solid polymer electrolytes (SPEs) and
gel polymer electrolytes (GPEs). In the former electrolyte system,
lithium salts are dissolved in high-molecular-weight polymers con-
taining high concentration of Lewis base groups such as ether (–O–),
carbonyl (–C=O), and cyano (–C≡N), which serve as ligands for
coordinating Li+ of the dissolved salt thus offering the necessary sol-
vation energy for the polymer-lithium complex formation. In GPEs,
low molecular weight components like small organic solvent (e.g.,
tetra(ethylene glycol) dimethyl ether,39,71 DOL,72 carbonates73–78 ),
and ionic liquids79,80 are added as plasticizers for improving the ionic
conductivity of a polymer electrolyte. The chemical structures of the
extensively studied lithium salt, polymer matrices, and low molecular
weight plasticizers are summarized in Fig. 1. Another important class
of solid electrolytes, the inorganic solid electrolytes, exhibit higher Li-
ion conductivities at operating temperature (e.g., 10−2 S cm−1 at 25
◦
C for Li10 GeP2 S12 81 ) compared to SPEs; while SPEs have better pro-
cessability and in principle are easier to be scaled up for large-format
batteries, as demonstrated by the application of Bluecar from Blue
Solutions in several cities (e.g., Paris, Bordeaux, Lyon, Indianapo-
lis, etc.), which are equipped with a 30 kWh LiFePO4 /PEs/Li-metal
battery pack, providing a 250 km driving range under normal urban
use.82
Looking at the existing literature related to ASSLSBs, the cyclabil-
ity and S utilization of the cells are important parameters for compar-
ing the overall performances. The detailed information of ASSLSBs
from literature is listed in Table I, in terms of the composition of the
electrodes (cathode and anode), electrolyte formulation and conduc-
tivity of the electrolyte.
Interestingly, most of the research related to ASSLSBs report cell
performances with relatively low S content (<60 wt%) and rarely
mention the S loading (areal capacity), thus hampering a sensible
comparison of the performances among all the available references.
In general, the values of S content in liquid electrolyte based cells are
higher compared to those in solid electrolytes (Fig. 2a), ascribed to
the good wettability from liquid electrolytes, which allows the liquid
solution of lithium salt and small molecular solvent to access easily
the porous structures of the S electrodes. However, in the case of solid
electrolytes, a large quantity of electrolyte is always required in the
composition of the cathode to facilitate the ionic transport, thus the S
content is hardly between 20−60 wt% in the total mass of the cathode.
Though the S utilization at the first cycle for ASSLSBs could reach
higher than 1000 mAh g−1 sulfur (Fig. 2b), long-term cyclability still
remains as a major concern. The reported cycle life for ceramic-and
polymer-based cells are mostly lower than 200 cycles (Figs. 2c and
2d), while liquid-based cells could maintain more than 1000 cycles
with good capacity retention (e.g., up to 1500 cycles with a specific
capacity of 168 mAh g−1 electrode 87 ).
ASSLSBs with relatively long cycle life have been presented in
recent studies; however, the cell performance at the end of the cycle
life is not competitive with the liquid system. Tatsumisago et al.48
reported that the Li-S cell using Li2 S-P2 S5 glass-ceramic electrolytes
could deliver a discharge capacity of 249 mAh g−1 electrode after 200
cycles. Liang et al.60 proved that the cycle life could be extended
to 300 cycles with a good capacity of 336 mAh g−1 electrode by intro-
ducing a new family of sulfur-rich compounds (Li3 PS4+n ) as active
material. Hu et al.45 reported that the polymer Li-S cell was found
to maintain good capacity retention after 200 cycles by using PEO-
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A6009
based electrolyte containing a novel type of lithium salt ([(CF3 SO2 )(n-
C4 F9 SO2 )N]Li). Recently, we evaluated the effect of lithium salt
and ceramic fillers on the cycling performance of ASSLSBs using
PEO-based electrolytes.48,49 Compared with other SPEs, the elec-
trolyte consisting of lithium bis(fluorosulfonyl)imide (LiFSI) in PEO
showed good compatibility with Li metal electrode without sacri-
ficing the ionic conductivity at the operating temperature.48,94 By
introducing Al2 O3 or Li-ion conducting glass ceramic (LICGC) as
inactive and active fillers, respectively, into the LiFSI/PEO polymer
system, the electrochemical properties could be further improved.
The composite polymer electrolyte (CPE) with nano-sized Al2 O3
showed significant improvement of the Li/electrolyte interfacial prop-
erties, resulting in a good Coulombic efficiency (ca. 99%) of the
Li-S cell, though accompanied by a relatively low S utilization (ca.
300 mAh g−1 sulfur ). More importantly, a high specific capacity of
1000 mAh g−1 sulfur (areal capacity: 1.1 mAh cm−2 ) was achieved with
CPE containing LICGC fillers. The Li-S cell with bilayer electrolytes
(Li | Al2 O3 −CPE/LICGC−CPE | S) could deliver a discharge capac-
ity of 900 mAh g−1 sulfur at the first cycle with good capacity retention.49
Future Needs and Prospects
Application of solid electrolytes in Li-S batteries does not only
facilitate the safe operation, but also benefits, in principle, the en-
ergy density at the cell level. Realistic calculations of energy density
as a function of S loading, S utilization and electrolyte thickness
will provide us useful guidance and key parameters for the design of
ASSLSBs. Our previous calculation already demonstrated that solid
electrolytes offer more room for improving the gravimetric energy
density of Li-S batteries compared to liquid electrolytes based on the
assumption that S utilization could reach 1000 mAh g−1 sulfur in all
cases.95 However, in practice, the specific capacity of Li-S batter-
ies usually decreases upon increasing the S content due to the elec-
tronically insulating properties of S and Li2 S. Therefore, we herein
performed the calculation taking into account the variation in S uti-
lization with different S contents and the results are presented in Fig.
3 (other parameters have been kept the same as our previous work79 ).
Not surprisingly, when comparing with LIB (Li0 ) cells, Li-S batter-
ies could be competitive in terms of gravimetric energy density (Wh
kg–1 ) rather than in volumetric energy density (Wh L–1 ). The latter is
likely due the low-density cathode materials, as well as the high frac-
tion of inert components (carbon) required due to the poor electronic
conductivity of elemental sulfur. The effect of electrolyte thickness
on energy density is more dominant in ceramic electrolyte than in
polymer electrolyte, since the former one normally has 2 to 5 times
higher density. For a cathode with S content of 40 wt% and achiev-
able S utilization of 1100 mAh g−1 sulfur (Fig. 3a), the minimum areal
capacities of ca. 1.5 mAh cm–2 for a polymer electrolyte with 50 μm
thickness but a ceramic electrolyte with only 10 μm thickness are re-
quired for outperforming the LIB (Li0 ) technology. In addition, with
increasing S content, both gravimetric and volumetric energy densities
display little variation (Figs. 3a–3c) due to the reduced utilization of
S. Under a possibly realistic but challenging S content (60 wt%, Fig.
3d), the gravimetric energy density for polymer electrolyte increases
significantly with extending the degree of S utilization.
ASSLSBs not only face the challenges coming from the solid
electrolytes, like other types of all-solid-state batteries (e.g., low ionic
conductivity, poor wetting properties), but also the intricate electro-
chemical redox reactions of S.34,96 The main challenges and accom-
panying possible solutions are summarized below.
(1) The quest for highly Li-ion conductive solid electrolyte with
good processability.—The Li-ion conductivity of solid electrolyte
plays a pivotal role in determining the rate performance of Li-S bat-
teries, while the effect of temperature on ionic conductivity has been
proved to be significant, especially for those PEO-based electrolytes.
For example, around room temperature region, the ionic conductiv-
ity of PEO-based PEs normally locates in the order of 10−5 –10−6 S
cm−1 ,49,97 though it can be further increased to ca. 10−4 S cm−1 above
 A6010 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018)

Figure 1. The chemical structures of the extensively studied lithium salt, polymer matrices, and plasticizers for solid electrolytes.

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 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018) A6011

Table I. State of art of Li-S cell with various types of electrolytes from literature.a

Cathode Electrolyte Cycle performance

Ionic con- Voltage

ductivity / Capacity / mAh g–1 ; material window
Composition / wt% S content / wt% Anode Composition mS cm–1 considered T /◦ C C-rate /V Ref

Ceramic electrolyte
S (25) / AB (25) / SE (50) 25 Li/In 80Li2 S-20P2 S5 5 (25◦ C) 1200 (1st) vs. 996 (200th); S 25 0.14 mA cm–2 0.7−2.7 56
S/Cu (38) / AB (5) / SE 23 Li 80Li2 S-20P2 S5 5 (25◦ C) 660 (1st) vs. 650 (20th); CuS 25 0.064 mA cm–2 0.3−2.7 50,51
(57)
Li2 S/Cu (38) / AB (5) / 18 In 80Li2 S-20P2 S5 5 (25◦ C) 500 (1st) vs. 340 (20th); 25 0.064 mA cm–2 0.3−2.7 53
SE (57) Cu-Li2 S
Li3 PS4+5 (60) / carbon 28 Li/Ni Li3 PS4 0.1 (60◦ C) 1400 (1st) vs. 1200 (300th); S 60 0.015 mA cm–2 1.5−2.8 60
(30) / PVC (10)
Li2 S (25) /AB (25) / SE 18 In 80Li2 S-20P2 S5 5 (25◦ C) 650 (1st) vs. 650 (10th); Li2 S 25 0.064 mA cm–2 0.3−2.7 58
(50)
S (35) / AB (35) / SE (30) 35 Li 80Li2 S-20P2 S5 5 (25◦ C) 1000 (3rd) vs. 900 (20th); 25 0.064 mA cm–2 0.3−2.7 57
Li2 S
S (27) / Cu (21.4) / AB 27 Li4.4 Ge 60Li2 S-40SiS2 0.2 (25◦ C) 1000 (1st) vs. 1100 (20th); S 25 0.064 mA cm–2 0.3−2.6 52
(1.6) / SE (50)
Li2 S (15) / AB (15) / SE 27 In 0.01Li3 PO4 - 1.5 (30◦ C) 900 (1st) vs. 700 (20th); Li2 S 30 0.067 mA cm–2 0.4−3.0 55
(70) 0.63Li2 S-0.36SiS2
S (30) / CNF (10) / SE 30 Li 75Li2 S-25P2 S5 0.1 (30◦ C) 1600 (1st) vs. 1400 (10th), S 30 0.025 mA cm–2 1.3−2.6 65
(60)
S (25) / AB (25) / SE (50) 30 Li0.61 Al Li3.25 Ge0.25 P0.75 S4 2.2 (25◦ C) 1500 (1st) vs. 900 (10th); S 25 0.013 mA cm–2 0.5−2.7 54
S (30) / VGCF (10) / SE 30 Li4.4 Si amorphous Li3 PS4 0.1 (25◦ C) 1300 (1st) vs. 1200 (50th), S 25 0.1 mA cm–2 0.9−2.6 64
(60)
S (50) / KB (10) / SE (40) 50 Li0.79 In 60Li2 S-40P2 S5 0.02 1300 (1st) vs. 1300 (50th), S 25 1.3 mA cm–2 0.5−2.5 63
(25◦ C)
Li2 S@P2 S5 (65) / carbon 44 Li/Ni β-Li3 PS4 1 (60◦ C) 1216 (1st) vs. 852 (100th), S 60 0.02 mA cm–2 1.5−2.8 61
(25) / PVC (10)
S (23) / MCMB (23) / SP 23 Li Li2 S–P2 S5 5 (80◦ C) 400 (1st) vs. 400 (18th), S 80 84 mA g−1 . 1−5 62
(46) / SE (8)
Li2 S (25) / AB (25) / SE 25 In 75Li2 S-25P2 S5 0.1 (25◦ C) 600 (1st) vs. 600 (10th), Li2 S 80 0.064 mA cm–2 0−3 66
(50)
S (30) / CMK-3 (20) / SE 30 Li0.61 Al Li3.25 Ge0.25 P0.75 S4 2.2 (25◦ C) 1600 (1st) vs. 700 30th); S 25 0.13 mA cm–2 0.5−2.7 59
(50)
S (35) / AC (15) / SE (50) 35 Li4.4 Si 70Li2 S–30P2 S5 N.A. 300 (1st ) vs. 250 (6th ); S 25 0.13 mA cm–2 0.5−2.7 67
Solid polymer electrolytes
S (50) / carbon (16) / SE 50 Li LiTFSI/PEO (1/49, 0.49 722 (1st) vs. 270 (10th); 90 0.050 mA cm–2 1.5−2.7 38
(34) weight) (90◦ C) electrode
S (50) / AB (5) / PEO 50 Li PEO10 LiTf + 0.22 1650 (1st) vs. 490 (10th); S 90 0.14 mA cm–2 1.7−3.2 39
(40) / LiTf (5) Tix O2x-1 (x = 1, 2, (90◦ C)
85/15, weight)
S/C (80) / SP (10) / PVdF 40 Li PEO20 LiTf + 10 0.1 (70◦ C) 400 (1st) vs. 500 (30th); S 70 30 mA g–1 1.5−3.2 42
(10) wt% S-ZrO2 + Li2 S.
S composite (60) / AB 40 Li PEO18 LiTFSI–10 0.5 (70◦ C) 1266 (1st) vs. 823 (25th); S 70 0.1 mA cm–2 1−3 43
(20) / PEO (20) wt% SiO2
S / AB / PEO N. A. Li PEO6 LiBF4 –10 wt% 0.3 (80◦ C) 1600 (1st) vs. 40 (10th); S 80 0.07 mA cm –2
1.7−3 41
Al2 O3
S (24) / AB (10) / PEO 24 Li P(EO)20 LiTFSI–10 > 0.1 452 (1st) vs. 184 (50th); 75 0.1 mA cm–2 1.5−3.2 40
(56) / PVdF (10) wt% γ-LiAlO2 (75◦ C) electrode,
◦
CMK3-S (65) / SP (10) / 45 Li P(EO)20 LiTNFSI 0.1 (60 C) 450 (6th) vs. 450 (200th); 60 0.2 C 1.6−2.5 45
SE (20) / PVdF (5) electrode
S composite (80) / SP 30 Li P(EO)15 LiTFSI + 10 0.1 800 (1st), 745 (100th); S 25 0.1 C 1.2−3.0 47
(10) / binder (10) wt% HNT (25 ◦ C)
S composite (80) / SP 43 Li P(EO)15 LiTFSI + N.A. 1000 (1st) vs. 558 (1000th); S 60 0.5 C 1.0−3.0 44
(10) / binder (10) 6.5 wt% MIL-53(Al)
S (60) / SP (30) / PAA 60 Li P(EO)15 LiTFSI + 10 0.6 1450 (1st) vs. 792 (50th); S 80 0.5 C 1.5−2.8 46
(10) wt% MIL-53(Al) (80 ◦ C)
S (40) / carbon (15) / SE 40 Li P(EO)20 LiFSI 0.74 900 (1st) vs. 600 (50th); S 70 0.1 C 1.6−2.8 48
(45) (70◦ C)
S (40) / carbon (15) / SE 40 Li P(EO)20 LiFSI + 3 0.6 (70◦ C) 1000 (1st) vs. 600 (50th); S 70 0.1 C 1.6−2.8 49
(45) vol% LICGC
Gel polymer electrolytes
Li2 S (35) / SP (35) / 35 Sn/C PEO20 LiTf + 10 5 (25◦ C) 1200 (1st) vs. 800 (30th); 25 0.038 mA cm–2 0.2−4.0 74
PEO20 LiTf (30) wt% S-ZrO2 in Li2 S
EC/DMC + Li2 S
S (50) / carbon (5) / 50 Li LiBF4 + PVdF-HFP 0.62 1450 (1st) vs. 400 (10th); S 25 0.14 mA cm–2 1.7−3.2
PVdF-HFP (40) / LiBF4 + TEGDME (25◦ C)
(5)
S (50) / carbon (5) / 50 Li LiPF6 + PVdF-HFP 1.89 1500 (1st) vs. 500 (10th); S 25 0.14 mA cm–2 1.7−3.2 83
PVdF-HFP (40) / LiPF6 + TEGDME (25◦ C)
(5)

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 A6012 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018)

Table I. (Continued).

Cathode Electrolyte Cycle performance

Ionic Voltage
conductivity Capacity / mAh g–1 ; material window
Composition / wt% S content / wt% Anode Composition / mS cm–1 considered T /◦ C C-rate /V Ref

S (50) / carbon (5) / 50 L LiTf + PVdF-HFP + 0.33 (25◦ C) 1200 (1st) vs. 450 (10th); S 25 0.14 mA cm–2 1.7−3.2
PVdF-HFP (40) / LiPF6 TEGDME
(5)
S (50) / SP (15) / 50 Li LiClO4 + PEO + 0.34 (25◦ C) 320 (1st) vs. 160 (10th); S 25 0.05 mA cm–2 1.7−2.7 71
PEO8 LiClO4 (35) TEGDME
S composite (60) / AB 30 Li PVdF-HFP + LiTFSI + 0.25 (25◦ C) 1218 (1st) vs. 818 (20th); S 25 0.050 mA cm–2 1.0−3.0 80
(30) / PVdF (10) PY14 TFSI
S (60) / carbon (25) / 60 Li LiTf + PVdF + N.A. 1268 (1st); S 22 0.14 mA cm–2
1.7−3.5 84
PEO (15) TEGDME
S (42) / carbon (28) / SP 42 Li Cellulose + LiTFSI + 1.2 (20◦ C) 730 (1st) vs. 730 (60th); S 20 0.58 mA cm–2 1.5−3.0 72
(20) / PVdF (10) TEGDME + DOL +
LiNO3
S (40) / MCMB (40) / SP 4 Lix Sn-C PEO20 LiTf + 10 wt% 1.3 (25◦ C) 600 (1st) vs. 500 (20th); S 25 0.335 mA cm–2 0.2−3.8 78
(10) / PVdF (10) ZrO2 in EC/DMC
S (52) / GNS (28) / AB 52 Li PVdF-HFP/PMMA/SiO2 3.1 (25◦ C) 809 (1st) vs. 413 (50th); S 25 0.335 mA cm–2 1−3 85
(10) / PVdF (10) in LiTFSI-TEGDME
S (30) / AC (40) / AB 21 Li PVdF-HFP/SiO2 in 1.2 (25◦ C) 560 (1st) vs. 300 (25th); 25 0.3 mA cm–2 1−3 73
(20) / PTFE (10) LiPF6 -PC/EC/DEC electrode
S (38) / PAN (38) / 38 Li PVdF-HFP + silicates in 4.9 (25◦ C) 900 (1st) vs. 500 (300th); S 25 0.2 C 1−3 86
Mg0.6 Ni0.4 O (4) / AB LiPF6 -EC/DEC
(10) /PVdF (10)
Li2 S (35) / C (35) / 35 Sn-C PEO20 LiTf + 10 wt% 4.9 (25◦ C) 200 (1st) vs. 200 (80th); 25 0.15 mA cm–2 1−3 75
PEO20 LiTf (30) ZrO2 in EC/ DMC Li2 S-C
S (49) / CNF (21) / SP 49 Li PAN/PMMA + LiTFSI- 3.8 (25◦ C) 1200 (1st) vs.900 (50th); S 25 0.15 mA cm–2 1−3 79
(20) / CMC (4) / SBR (6) PY14 TFSI/PEGDME
S (32) / PAN (48) / AB 32 Li PMMA/PVdF-HFP in > 1 (25◦ C) 1600 (1st) vs. 1000 (110th); S 25 0.2 C 1−3 76
(10) / PVdF (10) LiPF6 -EC/DEC
Representative liquid electrolytes
S/MnO2 (75) / SP (15) / 56 Li 1 M LiTFSI-DME/DOL 15 (25◦ C) 1300 (1st) vs. 380 (1200th); S 25 0.2 C 1.7−3.0 87
PVdF (10) (1:1, v/v) + 2 wt%
LiNO3
S composites (75) / SP 56 Li 1 M LiTFSI-DME/DOL 15 (25◦ C) 900 (1st) vs. 300 (1500th); S 25 0.5 C 1.8−3.0 88
(15) / PVdF (10) (1:1, v/v) + 2 wt%
LiNO3
S composites (80) / CB 48 Li 1 M LiTFSI-DME/DOL 15 (25◦ C) 600 (1st) vs. 400 (1000th); S 25 5C 1.7−2.8 89
(10) / PTFE (10) (1:1, v/v) + 0.5 wt%
LiNO3
S/C (80) / SP (10) / PVdF 61 Li 1 M LiTFSI-DME/DOL 15 (25◦ C) 700 (1st) vs. 600 (300th); S 25 0.5 C 1.8−2.7 90
(10) (1:1, v/v) + 2 wt%
LiNO3
S (60) / SP (20) / PVdF 60 Li 1.85 M LiTf-DME/DOL N.A. 864 (1st) vs. 527 (400th); S 25 1C 1.8−2.8 91
(20) (1:1, v/v) + 0.1 M LiNO3
◦
S composites (80) / CB 76 Li 1 M LiTFSI-DME/DOL 15 (25 C) 727 (1st) vs. 698 (500th); S 25 1C 1.7−2.7 92
(15) / PVdF (10) (1:1, v/v) + 2 wt%
LiNO3
S composites (60) / SP 60 Li 1 M LiTFSI-DME/DOL 15 (25◦ C) 1000 (1st) vs. 700 (500th); S 25 0.25 C 1.7−2.6 93
(30) / PEO (10) (1:1, v/v) + 2 wt%
LiNO3

a The abbreviations are listed as below: AB (acetylene black), AC (active carbon), CMC (carboxy methylated cellulose), CMK-3(mesoporous carbon),
CNF (carbon nano fibers), GNS (graphene nanosheet), HNT (halloysite nanotubes), KB(Ketjen black), LiCGC (Li-ion conducting glass ceramic), MCMB
(meso porous carbon micro beads), MIL-53(Al) (aluminum 1,4-benzenedicarboxylate metal-organic framework), PTFE (poly(tetrafluroethylene)), PVC
(poly(vinyl chloride)), SBR (styrene butadiene rubber), SP (super P), TEGDME (tetra(ethylene glycol) dimethyl ether), VGCF (vapor-grown carbon fiber).

the melting transition of PEO (60−65◦ C). This requires an operating
temperature higher than 60◦ C for the PEO-based ASSLSBs, as seen in
Table I.38–43,45,46,48,49 In comparison, the dependence of conductivity
on temperature for ceramic electrolytes generally follows a continu-
ous Arrhenius trend. For example, the lithium superionic conductor,
Li10 GeP2 S12 , holds an extremely high bulk conductivity of > 10−2 S
cm−1 at 25 ◦ C, and reaches 10−1 S cm−1 at 100 ◦ C with an activation
energy of 24 kJ mol−1 for ionic conduction.98
Overall, PEs provide good elastomeric properties, but relatively
lower ionic conductivity compared to ceramic electrolytes at the
room temperature. Both the structural modification of polymer
matrix and the development of new lithium salts are highly desired
for enhancing the ionic conductivity of PEs. Recently, a high
ionic conductivity of 4.5 × 10−5 S cm−1 at room temperature
was achieved by a new type of comb polymer material based on
polyether amines oligomer side chains (i.e., Jeffamine compounds),99
which can thus be a good candidate for operating polymer-based
ASSLSBs around room temperature. On the other hand, ceramic
electrolytes hold the advantages in Li-ion conductivity and ab-
sence of solubility for polysulfide species, but their application
is plagued by the poor processability. Combining the merits of
polymer and ceramic together, the blend electrolytes of polymer and

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 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018) A6013

Figure 2. The state-of-art Li-S cells with various kinds of electrolyte: (a) S content vs. type of electrolyte; (b) first cycle discharge capacity in mAh g−1 sulfur vs.
cycle life; end of cycle life discharge capacity in (c) mAh g−1 sulfur and (d) mAh g−1 electrode vs. cycle life. The numbers in squares correspond to the references
listed in Supplementary Information and color code corresponds to type of electrolyte.

ceramic solid electrolytes could lead to a possible breakthrough in
ASSLSBs batteries, boosting a synergetic effect of both systems.
Effectively, several types of ceramic electrolytes have recently
been integrated into polymer electrolytes for enhancing their
physiochemical and electrochemical properties, such as
those using NASICON (Li1.4 Al0.4 Ge1.7 (PO4 )3 ,100 LICGC
(Li1+x+y Alx Ti2-x Siy P3-y O12 ),49 and Li1.3 Al0.3 Ti1.7 (PO4 )3
(LATP)97,101 ), perovskite (Li0.33 La0.557 TiO3 (LLTO)102,103 ), and
garnet (Li7 La3 Zr2 O12 (LLZO).104,105
(2) A good contact of solid/solid interphase.—Decreasing the
charge-transfer resistance between the electrodes and solid electrolyte
etc. presents an enormous challenge, which requires a good contact of
the two solid/solid components, especially when considering the vol-
ume expansion and contraction of the S cathode undergoes upon dis-
charge/charge cycles. This challenge will be magnified in ASSLSBs
with true ceramic electrolyte, as clearly seen from Table I and Fig.
2 that high C-rate discharge/charge and long-term cycling are less
revealed in the state-of-art work.
In order to improve the contact between electrodes and solid elec-
trolytes, the composite electrolytes comprising of ceramic electrolyte
layer and either liquid or polymer electrolytes are proposed. Hagen
et al.106 utilized a composite electrolyte consisting of a glass ceramic
electrolyte (Li2 O-Al2 O3 -SiO2 -P2 O5 -TiO2 -GeO2 ) and 1 M LiTFSI-
DME/DOL liquid electrolyte. Though successful operation of the
corresponding Li-S cell was achieved, only several cycles at a low
rate of C/100 was reported. Follow the similar concept, Wen et al.68
exhibited that with LATP and 1 M LiTFSI-DME/DOL composite
electrolytes, the shuttle effect of PS was suppressed and the contact
of solid/solid interphase was significantly improved. Very recently,
Wachsman and Hu et al.107–109 proposed several surface treatment
methods on Li metal anode for reducing the interfacial impedance be-
tween Li metal anode and solid electrolytes, such as Al2 O3 107,108 and
germanium layers.109 Besides, they conceived a three-dimensional bi-
layer electrolyte framework for enhancing the interfacial contact of
ASSLSBs.69 The dense garnet layer with a few microns thickness
retained good mechanical stability, and blocked polysulfide diffusion
and impeded Li dendrite formation; the thick porous garnet layer acted
as a mechanical support for the thin dense layer, as well as enabled
continuous Li+ /electron pathways to host the sulfur cathode. These
methods offer an excellent chance to increase the cycle-life and S
loading of ASSLSBs.
Apart from the strategies mentioned above, we suggest that the in-
tegration of polymeric components into ceramic electrolyte could help
to minimize the contact problem, e.g., with a mixture of ceramic and
polymer in the S cathode, and surface treatment of ceramic electrolyte
with organic functional moieties.110,111
(3) An in-depth understanding of ASSLSBs.—The dis-
charge/charge mechanism can be affected by the identity and quantity
of solvent and lithium salt, as proved by the several recent reports
in liquid electrolytes.31,32,112 However, an in-depth understanding in
the reaction mechanism of ASSLSBs, a necessary step for improving
further the cycling performances, is seldom presented in the literature.
In addition, the surface characterizations on Li metal and S cathode
have been well studied in liquid system, but far less so with solid
electrolyte, especially for those PEs-based Li-S cells.

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 A6014 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018)

Figure 3. Estimated gravimetric (left) and volumetric (right) energy density of Li-S cells in solid electrolytes: (a) 40 wt% S content and 1100 mAh g−1 sulfur S
utilization, (b) 50 wt% S content and 900 mAh g−1 sulfur S utilization, (c) 60 wt% S content and 600 mAh g−1 sulfur S utilization, and (d) 60 wt% S content and
various S utilizations.

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 Journal of The Electrochemical Society, 165 (1) A6008-A6016 (2018) A6015

In recent years, a few advanced techniques have been developed to Acknowledgments

probe sulfur speciation and to understand the exact redox chemistry
This work was supported by GV-ELKARTEK-2016 from the
as well as capacity fading of ceramic electrolyte-based ASSLSBs.
Basque Government, and MINECO RETOS (Ref: ENE2015-64907-
Kanno et al.113 reported the ex situ X-ray scattering study of Li-S
C2-1-R) from Spanish Government. X. J. thanks the Government of
cell with thio-LISICON (Li3.25 Ge0.25 P0.75 S4 ) electrolyte. The forma-
the Basque Country for funding through a Ph.D. Fellowship, and C.L.
tion of two Li2 S phases during the discharge reaction and the strong
thanks the Juan de la Cierva scholarship (Ref: FJCI-2015-23898).
interaction between sulfur and carbon layer was confirmed. This sug-
gests that modifying the structure of the sulfur/carbon composite
is important for improving the capacity and cycling characteristics
of ASSLSBs. Tatsumisago et al.58 employed cross-sectional trans-
mission electron microscopy (TEM) and electron-energy-loss spec- Heng Zhang
troscopy (EELS) to reveal the importance of realizing intimate contact Chunmei Li
among electrode components and reducing the particle size of active
composite electrodes. Through high-resolution TEM and energy dis-
persed X-ray (EDX) spectroscopy experiments, Tatsumisago et al.66
also showed reversible structural and morphological changes at the 1.
nano-scale during the discharge/charge cycles in ceramic electrolyte- 2.
based ASSLSBs. To avoid possible side effects and inaccuracy ema- 3.
4.
nating from post-treatment of samples, various advanced in situ and
operando techniques have been recently applied for Li-S cell using 5.
liquid electrolytes. These tools provide the real-time dynamic picture
of the electrochemical process on operating Li-S cells. Nelson et al.114 6.
reported on the use of operando XRD and transition X-microscopy 7.
on Li-S system and demonstrated results that contradict to those ob- 8.
tained by ex situ studies. Operando X-ray absorption spectroscopy
(XAS),115 in situ X-ray absorption near-edge structure (XANES),116 9.
and in situ X-ray fluorescence (XRF)16 have been used to investi- 10.
gate the sulfur speciation in operating Li-S system. Other operando
characterization tools such as ultraviolet-visible spectroscopy (UVS), 11.
electron paramagnetic resonance (EPR) as well as in situ7 Li 12.
NMR,18 high-performance liquid chromatography-mass spectroscopy 13.
(HPLC-MS)117 etc to gain an in-depth understanding of the Li-S
system. 14.
Though the emerging of in situ, operando techniques and other 15.
combination of arsenal tools have advanced the knowledge on Li- 16.
S, the utilization theoretical studies and chemical simulations are of
paramount importance to have further in-depth understanding of the 17.
ASSLSBs. For instance, using results obtained from DME-based liq-
18.
uid solution could be used to mimic and thereby correlate the ones
from PEO-based PEs, owing to the fact that DME is the low-molecular
weight analogue of PEO. Still, the techniques to understand the ex- 19.
act reaction mechanism between the Li/PEs or ceramics and cath-
20.
ode/PEs or ceramics are missed and deserve further exploration in the
future. 21.
22.
Conclusions 23.
24.
Li-S batteries have emerged as important candidates for future en-
ergy storage systems; especially for applications which remand high 25.
gravimetric energy densities. All-solid-state Li-S batteries (ASSLSBs) 26.
offer a chance not only to be safer than those using liquid electrolytes, 27.
but also to achieve higher gravimetric energy densities than the state- 28.
of-art Li-ion batteries. Current research works on ASSLSBs using 29.
either inorganic or organic polymer electrolytes or their compos-
30.
ite mixture showed sufficiently high S utilization at initial cycles; 31.
however, the cyclability and areal capacity of ASSLSBs are still far
from the practical requirements. The future development of ASSLSBs 32.
needs to overcome the challenges including in most cases low Li-ion
33.
conductivity, poor processability and solid-solid contact, lack of in-
depth understanding of S redox chemistry in solid electrolytes, and 34.
the choice of ad-hoc techniques to probe in details the interfacial 35.
properties. With the possible solutions mentioned in this review and 36.
great efforts that are being dedicated to this field, we could anticipate 37.
that ASSLSBs will be an excellent choice for safe and high gravi-
metric energy storage system in the future. Moreover, we strongly 38.
believe that new findings, understandings, and insights into the Li-S
39.
chemistry, interfacial processes and cathode-anode interactions will
synergistically bring ASSLSBs much closer to commercial reality. 40.
ORCID
https://orcid.org/0000-0002-8811-6336
https://orcid.org/0000-0003-4438-0458
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