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Recent Research Trends in Li-S Batteries
Article in Journal of Materials Chemistry A · June 2018

DOI: 10.1039/C8TA01483C
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Recent research trends in Li–S batteries

Cite this: DOI: 10.1039/c8ta01483c Rudra Kumar, Jie Liu, Jang-Yeon Hwang and Yang-Kook Sun *
Lithium–sulfur (Li–S) batteries have recently attracted enormous attention in the energy-storage sector
owing to their high theoretical capacities (1675 mA h g1), high theoretical energy densities
(2600 W h kg1), and cost-effectiveness compared to the state-of-the-art Li-ion batteries. Despite these
merits, the practical application of Li–S battery technology is hindered by certain severe drawbacks.
Therefore, current challenges need to be diagnosed in order to find effective solutions to these Li–S
battery-commercialization obstacles. To help direct future work, we not only summarize current
research trends, but also highlight an effective solution for the practical applications of Li–S batteries. In
this review, we thoroughly summarize current research work on three kinds of Li–S battery systems
Received 11th February 2018
Accepted 5th June 2018
based on different cathode materials, namely sulfur (S8), lithium sulfide, and sulfurized-polyacrylonitrile.
In addition, we also provide insight into the current challenges associated with Li–metal anodes in Li–S
DOI: 10.1039/c8ta01483c
batteries. We then summarize and discuss an effective solution to these issues, namely the use of Li–
rsc.li/materials-a metal-free anodes or all-solid state electrolytes in Li–S full cell systems.
present in lithium–sulfur (Li–S) batteries, perform two-electron

1. Introduction conversion reactions and have high theoretical specic capac-
Rapidly growing population and associated energy problems ities (1675 mA h g1).16 As a consequence, Li–S batteries possess
are currently major global issues. An increase in the use of high energy densities and are among the most promising
traditional fossil-fuel energy raises further concerns about energy-storage devices. Moreover, the low cost of sulfur and its
environmental pollution. To reduce the dependence on fossil environmental friendliness make Li–S batteries better candi-
fuel and to mitigate its environmental impact, renewable energy dates than the state-of-the-art LIBs.17–21
sources urgently need to be developed, including solar power, In spite of these merits, the practical application of a Li–S
geothermal energy, and wind energy.1–4 However, these types of system is still hindered by the following challenges: (1) the large
energy sources only provide power intermittently, therefore volume change (80%) associated with conversion reactions that
cost-effective and environmentally friendly energy-storage take place in sulfur cathodes; (2) the insulating nature of sulfur
devices need to be developed. Rechargeable batteries, such as and its reaction products (Li2S2/Li2S); (3) the shuttle reaction
metal-hydride, lead-acid, and Li-ion batteries (LIBs) have played resulting from dissolved Li polysuldes (Li2Sx, x > 2) in elec-
signicant roles for more than a century in applications that trolytes;22–24 (4) the highly active Li metal anode, which changes
include portable electronic appliances and as backup power its morphology and structure through dendrite formation
supplies, owing to their high energy densities, good cycle lives, during continuous cycling, causing short circuiting and serious
user-friendliness, and low maintenance costs.5–7 safety issues;25–28 and (5) the evolution of gasses such as N2 and
Over the past three decades, LIBs have dominated the N2O, in addition to CH4 and H2, as volatile products, which
energy-storage market due to their high energy densities (e.g., results in the degradation of electrochemical performance.29 In
387 W h kg1 for a LiCoO2/graphite battery). However, as order to solve these problems, various strategies have been
a result of rapidly developing electric vehicles (EVs) and hybrid implemented, including: (1) the design of porous and highly
electric vehicles (HEVs), further increases in the energy densi- conductive carbon host materials that encapsulate sulfur;30 (2)
ties of LIBs are urgently being sought. Hence, electrode mate- the preparation of polar host materials that chemically trap
rials with either higher charge-storage capacities or higher cell polysuldes;31 (3) the exploitation of robust multifunctional
operating voltages are required. However, existing cathode binders;32 (4) the use of functional interlayers/separators that
materials, including LiCoO2, LiMn2O4, and LiFePO4, are mainly restrain the shuttle effect;33 (5) the construction of specially
based on insertion-type mechanisms and have low specic structured electrodes including 3D current collectors, as well as
capacities of less than 200 mA h g1, which limits the ability to sandwich and layer-by-layer structured cathodes;34 (6) the
improve LIB energy density.8–15 Sulfur cathode materials, exploitation of solid-state electrolytes for preventing polysulde
dissolution;35 (7) the preparation of anodic protection layers;36
Department of Energy Engineering, Hanyang University, Seoul 04763, Republic of
and (8) the use of Li–metal-free anodes that tackle safety
Korea. E-mail: yksun@hanyang.ac.kr concerns involving metallic Li.37
This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

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Journal of Materials Chemistry A Review
Although numerous approaches that address current and energy density, and for overcoming safety issues involving
cathode issues in Li–S batteries have been explored by both the Li–S batteries, and provide suggestions for future guidance.
scientic community and industry, problems surrounding Li– This review provides important insight into the scientic and
metal anodes still remain and urgently need to be overcome for practical issues involved with the development of Li–S batteries.
the practical application of Li–S batteries. Several approaches,
such as the application of electrolyte additives,38 gas-phase
doping on the Li metal,39 atomic layer deposition on the Li
2. Cathodes for Li–S batteries
metal,40 and polymeric coatings,41 have been used in attempts to In this section, we summarize current research and the major
protect the Li–metal surface. However, these strategies fail at issues associated with Li–S batteries based on three kinds of
high charge–discharge currents in high-sulfur-loaded Li–S cathode materials (i.e., S8, Li2S, and S–PAN). Fig. 1a–c reveals
batteries. Meanwhile, the assembly of Li–S batteries with highly steadily increasing numbers of papers published since 2010,
active Li–metal anodes is a major commercialization challenge. demonstrating that this is an actively researched eld. The most
For this reason, Li–metal-free anodes are more suitable for the commonly used cathode material in Li–S batteries is elemental
construction of reliable Li–S battery systems, and to avoid the sulfur, among which cyclo-S8 is the most thermodynamically
challenges associated with Li–metal anodes. Furthermore, stable allotrope under ambient conditions. To enable this
when a high-specic-capacity anode is used, the full cell system kinetically sluggish reaction, a series of soluble polysulde
can possess an energy density that is six-to-seven times higher intermediates (Li2Sx, x > 2) are produced during the reaction, as
than that of the existing LiCoO2/graphite system.42 Hence, this displayed in Fig. 2a.49 In this system, Li metal is oxidized to
battery technology can full the demands of sophisticated produce Li ions and electrons at the anode during the discharge
electronic equipment, technological advances in electric vehi- process. The Li ions then move to the cathode via the electrolyte
cles (travel ranges of up to 500 km), and high-energy-storage while the electrons travel through the external circuit to
grids.43–48 generate an electrical current. At the cathode side, sulfur reacts
In this review, we rst present recent developments and with the Li ions and electrons, and is reduced in a stepwise
operating mechanisms of three types of Li–S system composed manner, as shown below.
of sulfur (S8), lithium sulde (Li2S), and sulfurized- For the discharge process:
polyacrylonitrile (SPAN). We then summarize and discuss the
challenges associated with Li–metal anodes in Li–S battery S8 + 2e + 2Li+ / Li2S8 (1)
systems. Finally, we discuss strategies for enhancing capacity
3Li2S8 + 2e + 2Li+ / 4Li2S6 (2)
Fig. 1 Number of publications on Li–S batteries since 2010, based on (a) S/C, (b) Li2S/C, and (c) S–CPAN cathodes. Areal capacity vs. mass
loading for (d) sulfur and (e) Li2S.
J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

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Review Journal of Materials Chemistry A
discharging is as follows:53 During discharging, the –Sx– chain is

rst broken to form –SyLi and –SxyLi segments, whose ends are
covalently bonded to polymer backbones. Insoluble Li2S is
formed on the conducting carbon surface as discharge prog-
resses, and the values of y and (x y) in the SPAN gradually
decrease toward unity, at which point further discharging
results in the breakdown of the C–S bonds and the formation of
conjugated bonds to carbon. The nal discharge products are
mixtures of conjugated polymer backbones and Li2S. Following

charging, the conjugated polymer backbone rst loses electrons
to form delocalized radical cations that immediately trap Li2S to
form C–SLi seeds; further charging results in the growth of
sulfur chains from these C–SLi seeds. When no Li2S is available
around the reaction sites, two grown C–SLi segments close
electrochemically to form a ring that is similar to the original
structure. The SPAN redox reaction takes place between solid
Fig. 2 Charge/discharge curves for (a) a sulfur cathode, reproduced SPAN and solid Li2S during the entire discharging/charging
from ref. 49 with permission (Copyright 2015, the authors), (b) a Li2S process.
cathode with a large potential barrier at about 3.5 V at the beginning of
the first charge process (circled), reproduced from ref. 50 with
permission (Copyright 2016, the Royal Society of Chemistry), and (c) 2.1 S/C-composite cathodes
a SPAN cathode, reproduced from ref. 51 with permission (Copyright
2011, American Chemical Society). Owing to the insulating natures of sulfur and Li2S2/Li2S,
a conductive host or matrix is required for improved electron
transport.54,55 A sulfur–carbon composite is synthesized by the
2Li2S6 + 2e + 2Li+ / 3Li2S4 (3) melt-inltration method in which elemental sulfur is melted
between 119–159 C. Following inltration, the electrode
Li2S4 + 2e + 2Li+ / 2Li2S2 (4) materials are post-treated at 300 C to remove non-adsorbed
sulfur. This method provides precise control of sulfur
Li2S2 + 2e + 2Li+ / 2Li2S (5) loading.19 Vapor inltration is another promising method for
the synthesis of a C–S composite. Rings of molecular sulfur (S6–8)
For the charging process:52 are formed at 445 C, while smaller allotropes of sulfur (S2–4)
dominate at 550 C; these allotropes show valuable electro-
2S42 2e ¼ S82/S8 (6) chemical properties that are different to those of S8. This
method is benecial for the inltration of sulfur into micro-
S82/S62 2e ¼ S8 (7)
porous materials.56 Apart from liquid and vapor inltration,
Li2S, as the discharge product, can also be used as an active a C–S composite can also be synthesized by solution inltration.
material for Li–S batteries. Fig. 2b shows that an activation In this method, carbon materials are added to a sulfur-CS2
potential is rst required to charge the cell in a Li–S system.50 solution at room temperature, followed by solvent evaporation
Aer charging, Li2S is converted into elemental sulfur and Li at room temperature. The residual powder is then ground and
ions, and electrons are produced at the positive electrode. heated at 155 C to enhance sulfur distribution inside the
During the discharge process, Li ions and electrons react with carbon matrix.57
sulfur to produce Li2S again. The reactions are described as Nazar's group initially demonstrated the encapsulation of
shown below. sulfur (sulfur content < 55 wt%) in a CMK-3 carbon host, and
Charging process: reported a high specic capacity of 1320 mA h g1.19 Many
publications have since appeared that report improvements in
8Li2S / S8 + 16Li+ + 16e (8) the capacities and cycle lives of Li–S batteries using conductive
carbon matrices,58–66 while numerous S/C-composite cathodes
Discharging process: exhibit stable cycling performance up to 500 cycles.67–72 Despite
these achievements, the areal mass loadings of sulfur in the
S8 + 16Li+ + 16e / 8Li2S (9) reported S/C-composite cathodes are normally less than 2 mg
cm2.73–79 To increase the energy densities of Li–S batteries, one
Fig. 2c displays charge and discharge curves for a SPAN- trend involves enhancing the mass loading of sulfur on the
based cathode.51 The sulfur particles are in situ embedded in electrode, and increased sulfur mass loadings (2–10 mg cm2)
PAN-based carbon, which has a high melting point and elec- have been reported in recent years.80–111 However, these areal
trical conductivity. This assembled Li–S cell is in a charged state mass loadings are still incapable of generating sufficient energy
and therefore cell operation begins with a discharge process. density to meet the requirements of modern technological
The reaction mechanism for SPAN during charging and applications. As state-of-the-art LIBs require 2 mA h cm2 to

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operate HEVs, whereas EVs require 4 mA h cm2, and consid- areal capacity of 15.2 mA h cm2 was also obtained at a sulfur
ering that the operating voltage of a Li–S battery is 2.1 V, a Li–S mass loading of 21.3 mg cm2 at 1.56 mA cm2. Luo et al. re-
battery requires a higher areal specic capacity to achieve the ported the preparation of functionalized carbonized meso-
same travel range as an LIB. To further increase the trans- porous wood ber as a sulfur host electrode by atomic layer
portation, range beyond 500 km, the areal capacity of a sulfur deposition, which delivered a reversible capacity of
cathode needs to be more than 7 mA h cm2, which can be 859 mA h g1 over 450 cycles, and a capacity-decay rate of
achieved by increasing the sulfur areal mass loading to more 0.046% per cycle.120 Fang et al. prepared hollow carbon-ber
than 10 mg cm2. Fig. 1d displays the relationship between areal
foam (HCFF) by the carbonization of natural cotton and used

capacity and mass loading of sulfur over the 0.4–60 mg cm2 it as a 3D current collector that accommodated large amounts of
range. The areal capacity increases with increasing sulfur mass sulfur multiwall-carbon-nanotube–carbon-black (MWCNT–CB)
loading. However, such remarkable improvements in Li–S hybrids.118 Fig. 3c–e reveals that sulfur–MWCNT–CB clusters are
battery performance with extremely high sulfur loadings have located in the voids between the long carbon bers. Void space
only been achieved in coin-type half-cells. Moreover, the amount still remains even at a high loading of 10.8 mg cm2, which is
of electrolyte used in these Li/S systems is usually 10–15 times benecial for electrolyte uptake and the accommodation of
the weight of sulfur in the cell; this lowers the practical energy volume expansion during cycling. Therefore, the HCFF-S elec-
density and impedes Li–S-battery commercialization.112,113 trode with a sulfur mass loading of 10.8 mg cm2 exhibited an
To mitigate these issues, recent research efforts have focused areal capacity of 7.74 mA h cm2 at 0.1C aer 50 cycles (Fig. 3f).
on reducing the electrolyte volume or the use of lean electrolyte A high initial areal capacity of 23.32 mA h cm2 was achieved
conditions;114,115 however, several drawbacks, such as poor with a further increase in mass loading to 21.2 mg cm2 when
electrode wetting, electrochemical reaction kinetics, and charge the cell was cycled at 3.55 mA cm2; improved stability, with
transport between the interface also occur simultaneously.100,113 a high areal capacity of 14.8 mA h cm2, was demonstrated aer
Therefore in order to achieve good electrochemical perfor- 150 cycles (Fig. 3g). We prepared a modied high-sulfur-loaded
mance as well as high energy density, investigations into opti- electrode (MHSE) by mixing functionalized CNTs, chitosan
mizing the E/S ratio are very important.115,116 Even though high binder, and acetylene black, followed by casting onto aluminum
energy densities comparable to those of commercial LIBs can be foil. Through the use of elemental sulfur, this electrode had
obtained, research into preventing electrolyte depletion and a high sulfur loading of 10 mg cm2, and was divided into three
controlling the volatile electrolyte solution (DME/DOL-based separate components: (i) a scaffold made of a uniform mixture
electrolyte) is also needed. of N-doped acetylene black (AB) and N-doped multiwalled
Table 1 demonstrates that sulfur mass loadings of greater carbon nanotubes (MWCNTs), (ii) the chitosan binder, and (iii)
than 10 mg cm2 have been achieved by several groups in recent nitrogen-doped MWCNTs of a netting carbon lm (NCF), as
years, through the use of various lling techniques and elec- shown in Fig. 3h–j.119
trode architectures. Li et al.117 developed three-dimensionally Owing to the synergetic effects of these three components,
aligned porous-carbon microchannels fabricated through the the MHSE cell exhibited an initial discharge capacity of
carbonization of wood and its subsequent lling with reduced 1332 mA h g1 at 0.1C, a stable efficiency of 98% throughout
graphene oxide (rGO), in order to achieve high sulfur mass cycling, and a capacity fade of only 1.9 mA h g1 per cycle
loadings (Fig. 3a). The Li–S cell delivered areal capacities of 6.7 (Fig. 3k). Fig. 3l shows that good rate performance was also
and 12.6 mA h cm2 at increased sulfur mass loadings of 7.8 obtained. The cells were cycled at rates between 0.1C and 2C,
and 15.2 mg cm2, respectively (Fig. 3b). A remarkably high
Table 1 Performance of Li–S batteries based on cathodes with high sulfur mass loadings (>10 mg cm2)
S Loading (mg cm2) Initial capacity (mA h g1) Areal capacity (mAh cm2) Cycling stability (%) Ref.
19.1 1010 (0.1C) 19.3 44 (@0.1C, 100th) 56

21.3 715 (0.07C) 15.2 73.7 (@0.07C, 50th) 114
16.5 989 (0.1C) 16 75 (@0.1C, 50th) 118
10 1332 (0.1C) 13.32 91 (@1/3C, 50th) 119
10 800 (0.5C) 8 60 (@0.5C, 200th) 121
10.1 1000 (1C) 10.1 44.8 (@1.0C, 1000th) 122
17.3 873 (0.05C) 15.1 79.5 (@0.1C, 20th) 123
11.1 1011 (0.05C) 11.22 80 (@0.05C, 12th) 124
9.6 625 (0.1C) 6 75.5 (@0.1C, 300th) 125
15.7 800 (0.04C) 12.5 83.8 (@0.04C, 10th) 126
13 778 (0.04C) 10.1 76.9 (@0.04C, 20th) 127
13.9 1050 (0.5C) 14.6 70.5 (@0.5C, 100th) 128
17 1199.1 (0.01C) 20.4 78.4 (@0.01C, 10th) 129
30.7 1173 (0.1C) 36 67 (@0.1C, 100th) 130
40 725 (0.05C) 29 62 (@0.05, C 100th) 131

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Fig. 3 (a) Illustrating the preparation and structure of the S@C-wood composite electrode. (b) Cycling performance of the S@C-wood
composite electrode with different sulfur mass loadings; reproduced from ref. 117 with permission (Copyright 2017, American Chemical Society).
(c) SEM images, (d) 3D XRM image, (e) partial 2D projections, and (f) cycling performance of the HCFF-S electrode with a 10.8 mg cm2 sulfur
loading. (g) Cycling performance of the 21.2 mg cm2 sulfur-loaded cathode with a thin HCFF interlayer; reproduced from ref. 118 with
permission (Copyright 2016, Wiley-VCH). (h) Schematic design of the modified high sulfur-loading electrode (MHSE). SEM images of (i) NCF and
(j) mixed N-doped MWCNT and N-doped AB by mixer-milling. (k) Cycle performance at 1/3C rate and (l) rate capabilities (0.1C, 0.2C, 1/3C, 0.5C,
1C, 1.5C, and 2C) of the MHSE cell (sulfur loading: 10 mg cm2); reproduced from ref. 119 with permission (Copyright 2016, American Chemical
Society).
and their capacities did not plummet, even at high currents (2C parameters are required. The Li2S–C composite is synthesized
discharge capacity, 845 mA h g1; 2C/0.1C, 63%). by a solution-based chemical process. A solution of Li2S is
mixed with carbon to form the Li2S–C composite, aer which it
is dried at 40–60 C inside a glove box.147 The Li2S–C composite
2.2 Li2S/C-composite cathodes can also be synthesized through a one-step solid-state reaction,
Fully lithiated Li2S, with a high theoretical capacity in which lithium–metal foil is reacted with CS2 vapor carried by
(1160 mA h g1) and energy density, is also a promising argon gas in a tubular furnace at 650 C.148 In this section, we
candidate for cathode materials in Li–S cells. Li2S possesses highlight recent research progress on Li2S cathodes for use in
a high decomposition temperature (>900 C); therefore, to Li–S batteries. The electrochemical performance of a Li2S
improve conductivity, Li2S/C composites can be synthesized cathode-based Li–S cell is usually related to the mass loading
through pyrolysis with a carbon precursor. Moreover, lithiated and content of Li2S, the electrolyte dosage, and the starting
sulfur can easily be paired with Li–metal-free anodes. Although active materials. Low Li2S mass loadings (<2 mg cm2) and
a Li2S-based cathode has these advantages, the electronic- and contents (<60 wt%), and abundant electrolyte dosages were
ionic-insulating nature of Li2S requires a high activation initially used.24,133,149–151 In order to obtain high energy densities,
potential during the rst charging process, which leads to low many research groups have reported good cell performance
active-material use in subsequent cycles.132–138 In addition, the with high mass loadings.139,152–158 Fig. 1e displays the relation-
Li2S-based cathode also suffers from an 80% volume change ship between Li2S mass loading and the areal specic capacity,
and the shuttle effect during cycling. In order to enhance the which increases with increasing mass loading, suggesting that
electrochemical performance of Li2S cathodes, numerous the energy density of the cell increases. Table 2 lists the
developments in the design of advanced electrodes have taken performance of several Li–S batteries with high Li2S mass
place; high capacities in excess of 500 mA h g1 and long cycle loadings (>3 mg cm2).
lives of 1000 cycles, have been achieved.139–146 However, to Recently, Yu et al.156 designed a low-cost freestanding and
further improve the capacities and energy densities of Li2S- exible Li2S-based paper electrode, which was prepared by an
cathode-based Li–S batteries, optimized cell-design electrospinning method. This exible paper was carbonized by

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Table 2 Performance of Li–S batteries with Li2S-based cathodes average areal capacity of 7.5 mA h cm2 cycled between 0.8 and
3.0 V at a rate of 0.1C (Fig. 4e). Although Li2S/C based cathodes
Initial
with high mass loadings and superior electrochemical proper-
Li2S loading capacity Areal capacity Cycling
(mg cm2) (mA h g1) (mA h cm2) stability (%) Ref. ties for use in Li–S batteries have been reported in the litera-
ture,134,152,159,160 approaches that use Li2S as the cathode material
5.73 920 (0.01C) 5.27 81 (@0.01, 10th) 139 in Li–S batteries still need further modication in terms of
3.18 700 (0.03C) 2.23 84.3 (@0.03C, 10th) 152 morphological control, uniform lithiation, and cost-effective
4.8–5.3 666 (0.5C) 3.0 77 (@0.5C, 400th) 154
3.6 648 (0.04C) 2.33 128 (@0.04C, 60th) 155

scalable synthesis.
4 1052.1 (0.2C) 4.21 94.5 (@0.2C, 300th) 153
3.5–4 800 (0.1C) 2.9–3.4 48.2 (@0.1C, 150th) 157
2.0–3.0 915 (0.5C) 7.5 53.3 (@0.5C, 150th) 158 2.3 S/PAN-composite cathodes
Liquid sulfur inltration, which involves the melting of
elemental sulfur at 155 C and its subsequent inltrate into
porous carbon architectures, has been widely used to prepare
a carbothermal reduction process, in which Li2SO4 was reduced carbon–sulfur-based composites. Apart from liquid inltration,
to Li2S (Li2SO4 + 2C / Li2S + 2CO2) to form Li2S-embedded vapor inltration has also been used to synthesize sulfur–
nitrogen-doped carbon nanobers (Li2S@NCNFs), as shown in carbon composites; however, this method results in weak
Fig. 4a. The electrochemical performance of Li2S@NCNF interactions between elemental sulfur and the carbon matrix,
between 1.7 and 2.8 V, at a rate of 1C, is shown in Fig. 4b. An leading to unevenly distributed sulfur and poor electrochemical
initial discharge capacity of 560 mA h g1 (3.36 mA h cm2) and performance of the corresponding Li–S battery.161,162 In addi-
a capacity retention of 76% were obtained aer 200 cycles with tion, polysulde dissolution causes the viscosity of the electro-
a Li2S loading of 6.0 mg cm2. Even with a Li2S loading of lyte to increase, while lowering ionic conductivity and clogging
9.0 mg cm2, a high initial capacity of 520 mA h g1 the separator membrane. In order to resolve these issues,
(4.68 mA h cm2) could still be achieved with stable capacity sulfurized polymer-composite-cathode materials show great
retention (>65%) over 200 cycles. A higher Li2S mass loading of promise for incorporation into high-performance Li–S cell
10.7 mg cm2 was achieved by Balach et al.158 Li2S 15 nm designs. The SPAN composite, which is a sulfurized polymer,
nanoparticles were formed by the full lithiation and irreversible uses interactions between the nitrile groups of the polymer and
decomposition of MoS2 at a low potential (Fig. 4c). elemental sulfur to destabilize PAN and promote dehydroge-
The charge/discharge curves for the rst few cycles following nation and ring formation.163 Aer thermal treatment at high
activation are shown in Fig. 4d, which are similar to those of the temperature in an inert atmosphere, sulfur species are cova-
SPAN composite and sulfur-conned ultramicroporous carbon- lently bound throughout the composite, which results in
cathode systems that are governed by solid-state chemical a combination of physical entrapment and chemical conjuga-
reactions. This behavior explains the lack of soluble polysulde tion of elemental sulfur in the host PAN matrix.164 In addition,
formation and, therefore, its good performance in a carbonate- the lone electron pairs present in the nitrile groups of PAN
based electrolyte. Consequently, the Li2S–Li cell delivered an readily interact with Li through coordination bonding. Inter-
actions between Li2S and the PAN polymer result in a stiffening
of the PAN framework as the Li2S is uniformly dispersed. Here
Li2S acts as a cross-linking agent that interconnects the PAN
network. Such a material-design strategy improves the electro-
chemical performance of Li–S batteries. In this section, we
present recent developments in the eld of SPAN-based
composite cathodes for Li–S batteries.
Low sulfur content in SPAN-based composites is a major
barrier to achieving high areal capacity and energy density. In
addition, the low operating voltage of 1.8 V further reduces the
energy density of SPAN-based Li–S batteries. In this context, an
optimized cell design with a high mass loading of sulfur that
improves the specic areal capacity, or a reduction in additional
Fig. 4 (a) FESEM image of Li2S@NCNF paper. (b) Cycling performance
electrode weight in order to increase gravimetric specic
and coulombic efficiency of Li2S@NCNF electrodes with Li2S loadings
of 3.0, 6.0, and 9.0 mg cm2 at 1.0C; reproduced from ref. 156 with capacity, is required. Research on SPAN-cathode-based Li–S
permission (Copyright 2017, Wiley-VCH). (c) The in-cell formation of batteries began with Wang et al. who delivered a battery with
Li2S nanoparticles through full lithiation and the irreversible decom- a specic capacity of 1000 mA h g1 using a 65% sulfur content
position of MoS2 nanoparticles. (d) Galvanostatic charge/discharge in the composite.165 The same group explored SPAN composites
voltage profiles of the half cell with MoS2 nanoparticles as the starting
in a PVDF-gel electrolyte that delivered a specic capacity of
cathode material. (e) Cycling performance of the Li–Li2S half-cell
containing a high areal Li2S loading of 10.7 mg cm2, cycled between 600 mA h g1 aer 50 cycles, which is ve times higher than that
0.8 and 3.0 V vs. Li/Li+ at a current rate of 0.1C; reproduced from ref. of a LiCoO2-based cathode.166 Yu et al. also synthesized con-
158 with permission (Copyright 2017, Elsevier). ducting sulfur-containing electrodes by heating PAN with sulfur

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at a high temperature, which delivered a specic capacity of S/DPAN/rGO composite exhibited a capacity of 1490 mA h gS1
480 mA h g1 aer 240 cycles with a capacity retention of in the second cycle, whereas the S/DPAN composite produced
92%.167,168 Fanous et al. showed that a SPAN composite only 1000 mA h gS1. Capacity retentions of 92% and 94% for
synthesized at 330 C with S–C bonds delivered a specic the S/DPAN/rGO and S/DPAN composites, respectively, were
capacity of more than 1000 mA h g1, based on the sulfur mass, achieved aer 100 cycles, which is ascribable to C–S bonds
aer 40 cycles in carbonate-based electrolytes.169 Other SPAN- present in the S/DPAN composite even aer extensive cycling.
based cathode materials for Li–S batteries have also been Guo et al. provided experimental evidence that soluble LiPS
employed in order to further enhance capacity and cycling reacts with PAN/DMF solution to form a gel-like structure that is
stability.51,170–172 cross-linked by Li2S.175 Due to the uniform dispersion of Li2S in
Recently, Frey et al.173 developed a simple and scalable the carbon and the trapping of the high-order Li polysulde, the
synthesis method for poly(methyl methacrylate)/ composite materials prepared by this strategy show high elec-
poly(acrylonitrile) (PMMA/PAN) bers. Fibrous SPAN was ob- trochemical performance. Recently, our group proposed a novel
tained by the thermal conversion of PMMA/PAN with sulfur at cell design that included a poly(acrylic acid) (PAA) binder for
a high temperature and a 46% mass-loading of sulfur. The improved integrity of the composite electrode, and uoro-
brous morphology with cylindrical macropores helped to form ethylene carbonate (FEC) as an electrolyte additive that stabi-
electronic conduction networks in the cathode, providing lized the surface of the lithium metal.176 A sulfurized PAN
directed diffusion pathways for ions. As compared to particulate electrode was synthesized by the mixer milling of PAN and
SPAN (400 mA h g1 at 2C), the brous SPAN composite sulfur at 350 C, followed by carbonization at 600 C. By
exhibited a better rate capability (800 mA h g1 at 2C), and applying this strategy, the resulting battery delivered an initial
a good capacity retention of >800 mA h g1 at 0.5C was observed specic capacity of 1500 mA h g1 and a 98.5% cycling stability
aer 1200 cycles. Konarov et al.174 prepared a dehydrogenated aer 100 cycles at 0.5C with a sulfur loading of 3.0 mg cm2. In
polyacrylonitrile–sulfur (S/DPAN) composite attached to order to examine the viability of Li–S cells prepared using this
reduced graphene oxide (rGO) (S/DPAN/rGO) for use in Li–S strategy under more realistic conditions, we assembled pouch
batteries. The S/DSPAN composite was attached to rGO through cells for further testing. Furthermore, different types of SPAN–
a self-assembly method. The attachment of reduced graphene C-composite electrodes have been fabricated by many research
oxide helped to improve the conductivity to 104 S cm1 (from groups; Table 3 summarizes SPAN-based cathode materials that
1012 S cm1) and improve electrochemical performance. The have recently been used in Li–S batteries.
Table 3 Li–S battery performance based on SPAN-based cathodes
Material Initial capacity (mAh g1) C-rate Cycle number Cycling stability (%) Ref.
Sulfur/polyacrylonitrile/carbon 860 100 mA g1 100 57.4 177

composite
pPAN@C/S 1269 0.5C 100 64.38 178
S/PAN/Graphene 285 2C 100 100 180
Li2S–C composite 500 200 mA g1 20 100 175
SPAN 1400 0.4C 1000 71.4 51
Sulfur-cPAN (SPC) 1647(sulfur) 0.5C 100 79.17 181
S@pPAN 1542 200 mA g1 100 88 182
Li2S–C 888 0.1C 100 50.7 141
pPAN-KB/S 1600 0.5C 100 54.1 183
S/CPAN 1585 0.1C 100 54.38 184
S/MCPs–PAN 1518.6 160 mA g1 200 84.4 185
S/DPAN/MWCNT 1457 0.2C 260 85.8 186
PAN-NC 1279 200 mA g1 100 80.45 187
dSPAN 810.5 100 mA g1 50 98.1 188
S–PAN 1600 60 mA g1 50 1276 189
S0.6Se0.4@CNFs 350 1 A g1 1000 98.9 190
C/S/PAN 1183 200 mA g1 400 61.7 191
pPANS@GNS 1449.3 0.2C 300 88.8 192
SPAN/G–PET 113 (mAh) 5 mA 30 96.8 193
S/PAN/Mg0.6Ni0.4O 1223 0.1C 100 100 194
pPAN@S 1500 0.1C 150 93.3 195
S/DPAN/rGO 1490 0.2C 100 92 174
(PAN + PMMA)/S 1080 0.05C 100 68.5 196
S/DPAN 1343 0.2C 80 74 197
SPAN/rGO 1467 0.1C 200 75.5 198
S–PAN 500 — 200 75 199
Fibrous SPAN 1150 0.5 1350 64.7 173

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3. Lithium metal anode: challenges electrode/electrolyte interface, which damages the SEI layer on
the Li–metal surface, intensies dendritic Li growth, and also
Li–metal foil is generally used as the anode in a Li–S battery due diminishes the role of the LiNO3 additive.205,206 As this process is
to its high theoretical specic capacity of 3860 mA h g1 and its repeated, the contact area between the electrolyte and the Li
low negative electrochemical potential of 3.040 V. However, metal increases, which causes further electrolyte consumption,
some serious problems associated with Li–metal anodes used in which enhances the viscosity of the electrolyte while increasing
Li–S batteries remain; they include: (1) the formation of solid- Li-ion diffusion resistance and cell polarization.201 Irreversible
electrolyte-interphase (SEI) layers at Li/electrolyte boundaries electrolyte consumption during continuous cycling can also dry
during electrochemical reactions that are not mechanically the cell, resulting in severe capacity fading. Even if the cell is
robust, leading to continuous formation/dissolution and inef- relled with electrolyte, the Li–S pouch cell remains inoperative
cient Li–S-battery performance. (2) Exothermic reactions due to the fatal deterioration of the Li–metal anode. In addition,
between Li metal and non-aqueous ammable electrolyte dendritic Li becomes detached from the anode surface and
solvents that create risks of overheating, while the low melting dead Li powder is formed, which reduces reactivity during
point of Li may cause thermal runaway or battery explosion. (3) cycling when side reactions between the electrolyte/Li poly-
The formation of Li dendrites and their detachment from the Li sulde and the Li–metal anode take place.207–210 Various
metal can cause losses of active material and coulombic effi- research groups have proposed growth mechanisms for
ciency. (4) Dendritic Li growth can pierce the separator and dendrite formation.208,209 Bai et al.208 grew Li dendrites in a glass
extend to the cathode, resulting in short circuiting and the risk capillary cell and demonstrated that a change of mechanism,
of explosion. from root-growing mossy Li to tip-growing dendritic Li, occurs
at the onset of limited electrolyte diffusion. They also showed
that mossy Li is blocked by nanoporous ceramic separators,
3.1 S–CPAN-composite cathodes while dendritic Li can easily penetrate nanopores, resulting in
The Li–metal anodes used in Li–S batteries suffer from huge a short circuit. Lopez examined the morphological transition of
volume changes, a consequence of the heterogeneous deposi- a Li–metal surface, from at and smooth into a rough struc-
tion of Li during continuous cycling, which results in changes ture.209 This study revealed that three different surface
in surface morphology. The degradation of the Li–metal anode morphologies form during the cycling process, namely
also generates a rough surface and Li-dendrite growth in a dendritic layer at the top, a porous intermediate layer, and
random directions. Changes in the surface properties of the Li a residual layer. This study also showed that cell failure is
metal cause the formation of dendrites that grow further and related to electrolyte depletion and the production of a porous
can pierce the separator, resulting in a short circuit; this is layer during the reaction of active metallic Li.
a serious safety issue for Li–S batteries. Even if SPAN-based cathodes can avoid the shuttle
Generally, low sulfur mass loading masks the Li–metal- phenomenon and polysulde dissolution, thereby preventing
anode issue. When a high-loaded sulfur cathode is used to the loss of active sulfur, the high mass loadings of sulfur in
generate high energy density, the instability of the Li–metal SPAN composites still present problems similar to those
anode is more pronounced. The interphase growth of Li metal encountered in conventional Li–S batteries. The practical
has been demonstrated to be extremely porous, and this application of Li–S batteries requires high sulfur mass loadings
condition becomes more severe with increasing current density. that generate high charge–discharge currents, which (again)
Moreover, the interphase grows toward the inside of fresh Li causes Li–metal degradation. A variety of techniques have been
metal and accumulates on the Li–metal anode, which can cause used to resolve the dendrite issue, including electrolyte addi-
an increase in cell impedance.88,200 Cracks appear and Li-anode tives that form stable SEIs on Li–metal surfaces. The formation
corrosion takes place. The formation of a thick interphase due of an SEI layer can reduce the precipitation of Li2S- and Li2S2-
to side reactions between the newly formed porous Li metal, the reaction products on the surface of the Li–metal anode and
electrolyte, and the soluble polysuldes lead to the loss of alleviate dendritic growth, thereby enhancing the cycling
sulfur, an increase in cell impedance, and electrolyte performance of a Li–S battery. Electrolyte additives such as
consumption. This is a major drawback and a key challenge that lithium nitrate (LiNO3),24,28,211,212 phosphorus pentasulde
needs to be addressed when improving the energy densities of (P2S5),145 lithium iodide (LiI),213 and indium iodide (InI3),214
Li–S battery systems.6 among others, have recently been used to protect Li–metal
Furthermore, the role of the Li–metal anode is much more anodes and prevent dendritic growth. An anodic protection
important when a Li–S pouch cell is constructed. In such layer has also been used to cover the Li–metal surface and
a pouch cell, the high areal mass loading of sulfur generates produce a stable articial SEI layer. Li nitride (Li3N),87 PEDOT-
high current and causes serious polysulde shuttling, which co-PEG,112 and Al2O3 layers,215 have all recently been used to
damages the Li–metal anode. The high current generated in protect Li anodes.
a pouch cell creates an inhomogeneous distribution on the Electrolyte additives and the formation of an anodic
surface of the Li–metal anode, where some specic sites accu- protection layer can reduce Li–metal corrosion from poly-
mulate more current, resulting in the formation of more suldes and alleviate dendritic growth through the formation of
dendritic Li and electrolyte decomposition.201–204 High areal a stable SEI layer, however assembling Li–S batteries using Li–
current also leads to a large Li-ion concentration gradient at the metal anodes is a major challenge for the commercialization of

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Li–S batteries. Furthermore, future requirements of high- some additives. The voltage window in a Li–S battery is less than
energy-density Li–S batteries require high areal sulfur mass 3 V, which facilitates the use of organic solvents as electrolytes.
loadings, which enhance the polysulde concentration in the Numerous polysuldes are formed during the charging and
electrolyte and the current density on the anode surface. discharging processes, and these polysuldes can react with
Therefore, it is very difficult to commercialize Li–S batteries organic solvents. Consequently, the available range of solvents
based on Li–metal anodes for applications in high power and for Li–S batteries is very narrow. One approach to improving Li–
energy equipment. Consequently, the development of Li–metal- S battery performance involves the design of effective electro-
free anodes for Li–S batteries is a worthwhile objective. lytes that provide good capacity and cycling stability. Electrolyte
species, such as the type of solvent, concentration, nature of the
lithium salt, and functional additives, can improve the perfor-
3.2 Prevention of lithium-dendrite growth
mance of Li–S batteries. Generally, electrolytes consisting of
The lithium–metal anode is important for the safe operation of lithium bis(triuoromethanesulfonyl)imide ([(CF3SO2)2N]Li,
a Li–S battery; therefore, its degradation and dendritic growth, LiTFSI) in a solvent mixture of 1,2-dimethoxyethane (DME) and
which deteriorate electrochemical performance, need to be 1,3-dioxolane (DOL), containing lithium nitrate (LiNO3) as an
prevented. Dendritic lithium growth is suppressed by circum- additive, have been used. The advantage of TFSI is mainly
venting lithium dendrite nucleation, which can be inhibited at associated with its highly delocalized negative-charge distribu-
the root.24,216 Modication of the three-dimensional anode tion, which increases the dissociation and solubility of LiTFSI
architecture by tuning the surface energy is another way of and improves ionic conductivity. Furthermore, the DOL-based
suppressing dendritic growth.218,227 Surface treatment of the solvent forms an SEI layer, which prevents dendritic growth
anode circumvents potentially active dendritic-growth sites. and accommodates electrode volume changes, resulting in
Recently, a multi-layered graphene (MLG) coating improved good cycling performance. The lithium nitrate additive used in
lithium-anode performance due to the separated formation of the Li–S battery facilitates SEI-layer formation on the surface of
the SEI layer and the suppression of lithium-dendrite growth.219 the lithium–metal anode, which stabilizes the lithium metal
A Li3PO4 thin-lm coating also suppressed lithium-dendrite and suppresses polysulde redox shuttling, thereby increasing
growth,220 while a cross-linked polymer, as an interfacial layer, the battery's coulombic efficiency and cycling stability.
was also employed to suppress lithium-dendrite formation Recently, Zhang et al.229 demonstrated the catalytic effect of
through surface coverage.221 A protective lm of Li3N, which is LiNO3 on the conversion of highly soluble polysuldes into
formed through the reaction of lithium and nitrogen gas at slightly soluble sulfur. Different concentrations of the lithium
room temperature, has also been used to suppress lithium- nitrate additive have been used to enhance battery perfor-
dendrite formation, while Ma et al.87 showed that a three- mance.230–233 Furthermore, the low solubilities of lithium poly-
dimensional porous anode architecture is another modica- suldes in uorinated electrolytes, which limit parasitic
tion that improves Li–S battery performance.222,223 In contrast, reactions of lithium and alleviate self-discharge, have seen
the growth of 3D atomic crystals of boron nitride and graphene these electrolytes recently used in Li–S batteries. The use of the
on copper has been used to hinder lithium–metal dendrite LiNO3 additive in a uorinated electrolyte also suppresses self-
formation. Metallic Ni foam has also been employed to pre- discharge owing to the formation of SEI layers on the lithium
store lithium, which formed a Li–Ni-composite anode and anode and the sulfur cathode. The synergistic effect between the
prevented lithium-dendrite growth;224 this three-dimensional additive and the uorinated electrolyte prevents redox shut-
architecture provided an abundant electrode/electrolyte inter- tling, thereby improving the coulombic efficiency of the Li–S
face that lowered current density and enhanced electron battery.234–236
transfer and ion diffusion. A novel, mechanically strong, porous Organo-uorine compounds, such as 1,1,2,2-
separator was also employed to prevent lithium-dendrite tetrauoroethyl-2,2,3,3-tetrauoropropyl ether (TTE), have been
formation.217,225,226 Recently, PE separators coated with ZrO2/ applied as electrolyte solvents in Li–S batteries, leading to
POSS multilayers, through layer-by-layer techniques, have been reduced shuttling, and improved cycling stability and
used to improve cycle lives. This novel separator reduced elec- coulombic efficiency. The SEI was formed through the partici-
trode polarization and suppressed lithium-dendrite growth, pation of TTE in redox reactions on both electrodes, which
which increased coulombic efficiency.227 Cellulose-based inhibited parasitic reactions and resulted in the better use of
membranes containing nanopores and nanobers have also electrode materials.234 A uorinated-electrolyte mixture
been used as separators that inhibit lithium-dendrite formation composed of TTE and LiNO3, as the additive, was used by Azimi
and improve electrochemical performance.228 et al.;236 this electrolyte combination exhibited good electro-
chemical performance with no self-discharges observed aer
4. Electrolytes for Li–S batteries long hours of rest at elevated temperatures. A uorinated
bis(2,2,2-triuoroethyl)-ether-containing (BTFE-containing)
Apart from the electrode, the electrolyte is another important electrolyte also alleviated self-discharge at elevated tempera-
component in a Li–S battery. The main function of an electro- tures, at both low and high sulfur loadings, due to the forma-
lyte is the transfer of ions between the electrodes, while also tion of a vigorous protective lm on the anode.235 Recently, Gao
facilitating the formation of an SEI layer on the electrode. An et al.237 demonstrated a Li–S battery containing a porous
organic liquid electrolyte mainly consists of solvents, salts, and carbon/S-composite electrode and a symmetrical uorinated

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diethoxyethane electrolyte. The electrolyte solvent, composed of as Li–S-battery anodes. High capacity Si- and Sn-alloy electrodes
a mixture of 1,2-bis(1,1,2,2-tetrauoroethoxy)ethane (TFEE) and are superior for use as high-energy-density Li–S-battery anodes;
DOL suppressed polysulde dissolution and shuttling, result- however, they undergo huge volume expansions during cycling,
ing in a capacity retention of 99.5% per cycle over 100 cycles. which damages the electrode structure and thickens the SEI
Talian et al.238 compared Li–S battery performance using a tet- layer on the anode, resulting in impeded performance. There-
raglyme electrolyte with that using a TFEE-based electrolyte at fore, a great deal of effort has been directed toward achieving
low electrolyte loading. Polysulde solubility was lower in the high-energy-density and long-cycling-life Li–S full cells that are
TFEE-based electrolyte owing to the different Li+-solvation
also very safe. Li–S full cells that are based on sulfur cathodes
mode. 1,1,2,2-Tetrauoroethyl 2,2,2-triuoroethyl ether (HFE), and Li–metal-free anodes are summarized in Table 4.
1,1,2,3,3,3-hexauoropropyl ethyl ether (HEE), and ethyl 1,1,2,2- Recently, Xu et al.241 studied electrochemically pre-lithiated
tetrauoroethyl ether (ETE) have also been used in Li–S graphite anodes for the preparation of a Li–S full cell with
batteries.239 Apart from uorinated electrolytes, the develop- a MWCNT–S cathode; such a full cell exhibited a charge capacity
ment of highly concentrated electrolytes for use in Li–S batteries of 1113 mA h g1 at 0.2C, with a specic energy of 485 W h kg1.
has also been studied. The salt concentration in a liquid elec- Zeng et al. reported Li–S full-cell performance using a pre-
trolyte is usually less than 1.2 mol L1. Recently, Suo et al. lithiated graphite anode and a sulfur–carbon-composite
introduced a high-concentration electrolyte, referred to as cathode in a super-concentrated ether electrolyte; this full cell
a “solvent-in-salt” electrolyte, which exhibited a high lithium- delivered a capacity of 686 mA h gsulfur1 at 0.1C aer 105
ion transference number (0.73) in a Li–S battery. This electro- cycles.252 The sulfur–carbon-composite cathode was prepared by
lyte synergistically enhanced cycling performance and safety by melt diffusion 155 C. Graphite was pre-lithiated by electro-
inhibiting dendritic lithium growth. In addition, the inhibition chemical cycling in an electrolyte. Agostini et al.244 fabricated
of lithium polysulde dissolution further enhanced the cycling a Li–S full cell using a graphite anode, a S/C-composite cathode,
performance and coulombic efficiency of the Li–S battery.240 and a DOL–DME–LiTFSI electrolyte, with LiNO3 and Li2S8 as
additives. Li2S8 suppresses the dissolution of sulfur and LiNO3
5. Li–S full cells reduces polysulde shuttling. This full cell exhibited a stable
capacity of 500 mA h g1 and operated at about 2 V. To improve
In this section, we highlight current Li–S full-cell congurations the performance of Li–S full cells with graphite-based anodes,
with Li–metal-free anodes such as carbon, silicon (Si), and tin polyacrylic acid sodium salt (PAA-Na) was applied to the anode
(Sn), in combination with elemental sulfur, Li2S, or SPAN- as a protective binder, which impedes graphite exfoliation and
composite cathodes, in order to overcome safety issues and acts as a protective layer with better surface coverage at the
enhance the electrochemical performance of the battery. electrode–electrolyte interface. Therefore, the cell prepared with
the PAA-Na binder provided improved cycling performance and
5.1 Li–S full cells: S/C-composite cathodes coulombic efficiency (99%) when compared to the cell with the
Safety is the main reason for replacing high theoretical-capacity poly(vinylidene diuoride) (PVDF) binder (>95%).253 Brückner
Li–metal anodes in Li–S batteries. A variety of carbonaceous et al.37 demonstrated improved wettability of the cathode by
materials that have been used as anode materials in LIBs, due to optimizing the carbon nanotube/PTFE ratio. Hard carbon, with
their low lithiation voltages, small volume changes, high a small amount of MWCNT pasted on a carbon-ber network,
coulombic efficiencies, and long cycle lives, are good candidates was used as the anode in a full cell Li–S battery. a-Si on a carbon-
Table 4 Performance of Li–S full-cell batteries composed of sulfur-based cathodes, and carbon, Si, or Sn-based anodes
Sulfur loading Initial capacity Cycle Energy density

Anode//cathode (mg cm2) (mAh g1) no. C-rate (W h kg1) Ref.
Graphite//S–MWCNT — 757 50 0.2C 485 241

Prelithiated MCMB/S–C composite 3 1000 450 0.1C — 242
Hard carbon//S-carbide derived carbon 2.3–2.9 1050 4100 0.1, 0.5, 1.0C — 243
Si–C//S–MWCNT 1.64 765 (5th) 1390 0.1C — 37
Hard carbon//S–MWCNT 1.3–1.5 1471 (2nd) 550 0.2C — 37
MCMB//S–MCMB 1.3 900 200 1.0C 300 244
Naon coated porous Si//S–CNF — 800 100 0.1C 590 179
Si@graphite//S-CMK3 1.7 1146.6 200 0.3C 175 245
Si–SiOx nanosphere//S-activated carbon 0.8 750 500 1.0C 497 246
Si nanowire array//S–CNT 3.0–4.4 950 200 0.1, 0.2C 300 247
Si nanowire-carbon composite//S–C composite — 1027 460 0.2C 410 248
Si–C microspheres//S–C composite — 926.4 50 0.1C — 27
Si nanoparticle//S–C composite 3.7–5.0 400 100 0.1C — 249
Sn–G–rGO//S–C composite 1.5–2.0 978 40 0.1C 336 250
Li4Sn–C//S–AOMC 3.0 550 300 0.2C 280 251
SnO2–graphene//S-CMK3 2.0 800 500 1C — 35

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ber anode was prepared by the DC-magnetron sputtering of p- full cell in an electrolyte containing 1 M LiTFSI and 0.25 M
doped silicon onto carbon ber. The anode was combined with LiNO3 (E/S ¼ 12 mL mg1), which delivered a nal specic
a hollow carbon-sphere/MWCNT–S composite with 53% sulfur capacity of 422 mA h g1 at 0.1C. This result corresponds to an
content and delivered a capacity of 1470 mA h g(sulfur)1 (720 overall capacity decay of only 48.1%, or 0.0118% per cycle (over
mA h gcathode1) in a minimal amount of electrolyte. Recently, 4076 cycles), relative to the capacity at the 24th cycle. To further
Chen et al.242 demonstrated a Li–S full cell composed of a pre- verify stable capacity by electrolyte pre-saturation, a full cell
lithiated graphite anode and a sulfur cathode in a multifunc- with a PS-additive electrolyte (0.8 M LiTFSI + 0.25 M LiNO3 +
tional uorinated ether-based (BTFE-based) electrolyte (1.0 M 0.15 M Li2S6, E/S ¼ 12 mL mg1) was also prepared; this full cell
LiTFSI in DOL/BTFE (1 : 1, v/v)). The cathode was prepared by delivered a specic capacity of 1134 mA h g1 over the rst 24
the thermal treatment of elemental sulfur and a commercial cycles and 554 mA h g1 aer 4100 cycles at 0.1C. Even though
Ketjenblack mixture at 159 C. Such an electrolyte has low ultralong cycling performance can be obtained, the low capac-
viscosity and good wettability, which improves reaction kinetics ities of Li–S full cells using these carbon anodes is the main
and leads to high sulfur usage; it also diminishes polysulde drawback to their use in high-energy-density applications.
solubility and impedes polysulde shuttling, thereby improving In addition to carbonaceous anode materials for Li–S full-cell
the cyclability of the electrode. In addition, it facilitates the batteries, Sn is another very promising anode material, due to
formation of a stable SEI on the graphite anode, leading to its high theoretical capacity and ability to form different Li–Sn
improved cyclability of the anode. A discharge capacity of intermetallics, including Li22Sn5, Li7Sn2, Li3Sn, Li5Sn, LiSn, and
950 mA h g1 (3 mA h cm2) in the second cycle, with >95% Li2Sn5. Pairing the high capacity of a Sn anode with a sulfur
coulombic efficiency and a capacity retention of >65% aer 450 cathode enhances the overall capacity and energy density of
cycles, were obtained. A hierarchal porous carbide-derived a Li–S full-cell battery. In this section, we shed some light on Li–
carbon (DUT-107), which has a high surface area and pore S full cells based on tin- or tin-oxide-anode materials paired
volume, was used as a scaffold for sulfur impregnation. A Li–S with sulfur cathodes that have recently been published. Mohan
full cell was assembled using DUT-107-S as the cathode and pre- et al.250 studied a Li–S full cell composed of a 3D porous Sn/G/
lithiated hard carbon on carbon paper (LIHC@GDL) as the rGO composite as the anode and S/C as the cathode. The
anode.243 DUT-107 was prepared by a template-assisted method, anode was fabricated by a method involving electroplating and
in which a silica template was inltrated with polycarbosilane, drop casting onto a carbon-paper substrate. The advantage of
aer which it was pyrolyzed in an inert atmosphere and then pristine graphene in the anode is enhanced electron conduc-
chemically etched. Fig. 5a shows a SEM image of the DUT-107/S tion, while the addition of rGO sheets protects the surface of the
composite, while Fig. 5b displays the cycling performance of the electrode from direct contact with the electrolyte and minimizes
Fig. 5 (a) SEM image of the DUT-107/S composite. (b) Cycling performance of the DUT-107/S cathode in a full-cell setup (vs. LiHC@GDL) with
12.0 mLE mgS1 at an alternating rate in an R-E electrolyte. The inset compares the initial (cycles 1–24) and final (cycles 4076–4100) discharge
capacities at 0.1C; reproduced from ref. 243 with permission (Copyright 2015, the Royal Society of Chemistry). (c) XPS spectra of SnO2 anodes
obtained from cycled SnO2/LE/S and SnO2/GPE/S cells. (d) Cycling performance of the SnO2/LE/S and SnO2/GPE/S cells at 0.3C; reproduced
from ref. 35 with permission (Copyright 2016, Elsevier). (e) Illustrating the honeycomb-like sulfur copolymer on a 3D graphene network (3D cpS-
G). (f) Long cycle performance of a lithiated full silicon–sulfur battery fabricated from a 3D cpS-G-network cathode and a 3D-lithiated Si–G
anode; reproduced from ref. 254 with permission (Copyright 2016, the Royal Society of Chemistry).

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SEI formation. A Li–S full cell (Sn/G/rGO–S) devoid of anode or a seven-fold increase in specic capacity compared to
cathode lithiation was constructed with a thin piece of Li–metal a graphite–LiMO2 system. Si anodes perform well in carbonate-
foil on the anode side. The mass loadings of the Li–metal foil, based electrolytes; however, the S cathode performs very poorly
anode, and cathode were 2, 4.8, and 1.6 mg cm2, respectively. in these electrolytes due to side reactions between polysuldes
The fabricated cell delivered a specic capacity of 413 mA h g1 and the electrolyte, which causes abrupt fade in capacity. Si–S
aer 40 cycles with a coulombic efficiency of 90%. It operated at full cells also exhibit poor electrochemical performance even in
1.6 V and delivered specic energies of 660 W h kg1, ether-based electrolytes. The failure mechanism for Si–S full
336 W h kg1, and 146 W h kg1 based on the mass of sulfur, the
cells has been described by Shen et al.179 During the cycling

total mass of the cathode (S/C), and the total mass of both process, Si becomes lithiated because it has a lower potential
electrodes, respectively. Moreno et al.251 also demonstrated the than a polysulde. The reaction between lithiated Si (LixSi) and
fabrication of a Li–S full cell consisting of a lithiated nano- a polysulde results in the transfer of Li ions from LixSi to the
structured tin–carbon anode (Li4Sn–C) and an activated meso- polysulde, which leads to capacity fading during cycling. One
porous carbon–sulfur cathode (AOMC–S) in an electrolyte strategy that protects the Si anode from this polysulde reaction
composed of 1 M LiTFSI and 0.4 M LiNO3 in DME/DOL (1 : 1, v/ involves coating the surface of the Si anode with a uoropol-
v). AOMC was synthesized by sol–gel polymerization and high- ymer-copolymer based on Naon. The negatively charged
temperature carbonization followed by CO2 activation. The S– sulfonate groups electrostatically repel the negatively charged
carbon composite was formed by in situ sulfur deposition from anions. A Si–S full cell composed of a Naon-coated lithiated
an aqueous solution of sodium thiosulfate acidied with porous Si anode and a S cathode delivered a specic capacity of
hydrochloric acid. The full cell operated at 1.7 V and delivered 330 mA h g1 and an energy density of 590 W h kg1 based on
a specic capacity of 600 mA h g1 over 300 cycles with 100% the total mass of S and Si aer 100 cycles. Krause and co-
coulombic efficiency, and a practical energy density of workers fabricated Si nanowires on a 3D carbon-mesh current
280 W h kg1. collector and used them as anode materials.248 This anode was
A SnO2 anode was also paired with a sulfur cathode to coupled to a C/S cathode to fabricate a Li–S full cell in an ether-
prepare a Li–S full cell. SnO2 has advantages over Sn as an anode and Li-triate-based electrolyte; such a full cell delivered an
material due to its conversion and alloying mechanism, its areal capacity of 2.3 mA h cm2, a cyclability that surpassed 450
ability to be reduced to Sn, and the formation of a Li2O scaffold cycles, and a capacity retention of 80% aer 150 cycles (capacity
that buffers the volumetric changes experienced by Sn during loss < 0.4% per cycle). The low degradation during cycling is
Li-ion insertion/extraction. Liu et al.35 reported a Li–S polymer ascribable to a lower level of polysulde self-reduction, as
battery composed of a lithiated SnO2 anode, a CMK-3-S cathode, determined by in-operando X-ray diffraction. Hassoun et al.
and a bifunctional gel-polymer electrolyte (GPE). A SnO2/LE/S reported a Li–metal-free full cell composed of a sulfur–carbon-
full cell was rst constructed with an ether-based electrolyte, composite cathode formed by hard carbon spherules, a lithi-
graphene as the conducting agent, and carboxymethylcellulose ated silicon–carbon-nanocomposite anode, and a glycol-based
(CMC) as the binder. The formation of a passivation layer and electrolyte. The battery delivered an average specic capacity
polysulde dissolution restricted the ability to achieve high of 300 mA h gS1 when operated at 2 V, and exhibited a long
capacity and long-term cycling. The GPE-based full cell exhibi- cycle life and high safety.256 A room-temperature ionic-liquid
ted enhanced capacity, rate capability, and cycling stability, due electrolyte (N-methyl-N-allylpyrrolidinium bis(tri-
to the prevention of polysulde dissolution in the electrolyte. uoromethanesulfonyl)imide (RTIL P1A3TFSI)) was also used
The surfaces of the SnO2 anodes were examined by XPS in a Li–S full-cell battery system (pre-lithiated Si/C microspheres
following disassembly of the SnO2/LE/S and SnO2/GPE/S cells as the anode and a S/C composite as the cathode).27 This cell
aer cycling. Fig. 5c reveals two peaks in the S 2p spectrum, at delivered a high specic discharge capacity of 926.4 mA h g1 in
165.9 and 162.1 eV, which are assigned to sulfur signals from the rst cycle, which remained as high as 670 mA h g1 aer 50
Li2S–SO3 and sulde (Li2S) deposited on the surface of the cycles. Weinberger et al.249 demonstrated a Li–S full cell that
anodic SEI. The sulfur signals from the SnO2/LE/S cell show consisted of a Si-nanoparticle anode and a carbon–sulfur
clearly stronger peak densities, indicating that the side depo- cathode. Si nanoparticles were prepared by ball milling and the
sition of sulfur species is much more severe than in this cell that anode was prepared by mixing carbon black, Si nanoparticles,
in the SnO2/GPE/S cell. This explains why the SnO2/GPE/S cell and aqueous lithiated polyacrylic acid. The cathode was
delivered a specic capacity of 755.7 mA h g1 at a rate of 0.3C a carbon/sulfur composite prepared by the melt impregnation
aer 300 cycles with a capacity retention of 83.3%, whereas the of sulfur into activated charcoal. The full-cell conguration
SnO2/LE/S cell retained only 49.1% (Fig. 5d). In addition, the exhibited an initial discharge capacity of 400–500 mA h g1,
SnO2/GPE/S cell exhibited superior rate capability based on the mass of the cathode, and was stable up to 50
(608.2 mA h g1 at 5C) and good cycle retention at 1C (82.1% cycles. They further demonstrated a pouch-cell conguration
aer 500 cycles). with an effective electrode area of 24 cm2, which delivered an
Silicon electrodes have been widely studied due to their high initial discharge capacity of 45 mA h at a current density of
theoretical capacities (4200 mA h g1), low discharge potentials 20 mA g1. A full cell that employed a honeycomb-like sulfur
(0.2 V vs. Li/Li+), the abundance of Si in the Earth's crust, and copolymer on 3D graphene (3D cpS-G) as the cathode (with
its environmentally friendly nature. The combination of a Si a sulfur mass loading of 5 mg cm2) and a 3D lithiated Si–G
anode and a S cathode, in a full cell, can theoretically provide network as the anode (with a Si mass loading of 3.9 mg cm2)

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was fabricated.254 A three-dimensional lithiated Si/graphene contrast, a S@CMK-3/liquid-electrolyte/Si@graphite cell only

anode with ultrathin nanowalls was fabricated by a template- exhibited a specic capacity of 361.6 mA h g1 and a cycling
assisted method; this anode exhibited good electrical conduc- retention of 46.2%. In addition, the rate performance of the
tivity and accommodated a large Si-volume change during S@CMK-3/OSE/Si@graphite cell was far superior to that of the
prolonged cycling. As shown in Fig. 5e, the sulfur copolymer S@CMK-3/liquid-electrolyte/Si@graphite cell in all current
was attached to a honeycomb-like three-dimensional graphene ranges examined. Moreover, the OSE-based cell has the advan-
network with multi-sized pores as a cathode material, in order tage of high safety, which is attributed to its low ammability
to facilitate the fast diffusion of electrons and Li ions; this through the elimination of Li metal.
structure also efficiently trapped polysuldes with strong cova- In Sun's group, Si–SiOx-nanosphere materials were prepared
lent bonds, and accommodated large volume changes during by the pyrolysis of hydrogen silsesquioxane nanospheres that
lithiation/delithiation processes. The cycling performance of were obtained by the sol–gel reaction of triethoxysilane, and
this lithiated Si–S cell is shown in Fig. 5f; the capacity remained a Li–S full cell was constructed by employing this lithiated Si–
at 578 mA h g1, even aer 500 cycles at 0.27 A g1, and SiOx-nanosphere anode with a dual-type sulfur cathode,
demonstrated very low capacity decay (86% capacity was composed of a solid sulfur electrode and a polysulde cath-
maintained aer 500 cycles). Zhou et al.245 fabricated a Si–S full olyte.246 Such a Li–S full cell displayed good electrochemical
cell with an optimized solid-like electrolyte (OSE). The OSE was performance, with an estimated energy density of 497 W h kg1
prepared by the organic-template method. The Si@graphite at a rate of 1C based on the weight of the electrode materials.
anode was prepared by mixing Si@graphite powder, carbon The energy density of this full cell was more than twice that of
black, and carboxymethylcellulose (CMC) binder in DI water, a commercially available LIB. More importantly, Fig. 6a reveals
followed by coating onto Cu foil. The S-CMK-3 cathode was that the full cell maintained about 85.5% of its specic capacity
prepared by the melt-diffusion method. The electrolyte con- over 500 cycles with cycling efficiencies in excess of 98.2%,
sisted of two functional components: a hollow SiO2-nanosphere except for the rst cycle (86%), indicating that the cycle life of
layer and uoroethylene carbonate (FEC) in an ether-based this full cell was almost that of a commercial LIB. The better
solvent. The hollow SiO2 layer prevented the diffusion of poly- cycling performance of the cell arises from both the newly
suldes while the FEC additive reduced the anode/electrolyte designed anode, as well as the dual-type sulfur cathode used in
interface resistance through the formation of a thin, dense this work. Cross-sectional images of the Si/SiOx electrode show
SEI. The assembled Si–S full cell, which was composed of that it was about 4 mm thicker following pre-lithiation (Fig. 6b
S@CMK-3 mesoporous carbon (as the cathode) and Si@gra- and c), due to Si/SiOx-nanosphere expansion. The dimensional
phite (as the anode) in OSE (S@CMK-3/OSE/Si@graphite cell), stability of the lithiated Si/SiOx electrode was also investigated
delivered a high reversible capacity of 824.2 mA h g1 (with by observing thickness changes in the electrode aer cycling.
a capacity retention of 76.7%) aer 200 cycles at 0.3C. In Fig. 6c and d reveal that the lithiated Si/SiOx electrode retained
Fig. 6 (a) Cyclic responses of lithiated Si–SiOx/DME/DOL (1 : 1 v/v), Li2S8 (0.05 M), LiTFSI (1 M), LiNO3 (0.4 M)/AC-S full cell cycled at 1C rate.
Inset: magnification of coulombic efficiency. FESEM images of Si/SiOx electrode (b) before prelithiation, (c) before cycling, and (d) after 20 cycles;
reproduced with permission from ref. 246 Copyright 2015 American Chemical Society. (e) Cycling performance at 0.5C and (f) rate performance
of Li–S pouch cells containing composite sulfur cathodes and Li–metal anodes within 1.8–2.7 V. (g) Cycling performance of Si–Li–S pouch cells
comprising composite sulfur cathodes and composite Si anodes; reproduced with permission from ref. 255 Copyright 2016 Wiley-VCH.

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almost its original thickness, even aer 20 cycles, and exhibited 5.2 Li–S full cells: Li2S/C-composite cathodes
no cracking. These results clearly demonstrate that the nano-
Li2S is introduced into Li–S-battery systems as a cathode
scale engineering of Si, and the use of amorphous SiOx as the
material can easily be paired with Li–metal-free anodes to avoid
matrix, effectively mitigated the mechanical strain induced by
the safety issues. In this section, we focus on Li–S full-cell
the huge volume changes experienced by Si during cycling. The
batteries fabricated with carbon-, Si-, and Sn-based electrodes
strains and stresses induced by periodic volume changes are
paired with Li2S-based cathodes; Table 5 summarizes such Li–S
very signicant and potentially detrimental because the total
full cells.
active material per unit geometrical area increases with Li et al.257 reported a Li–S full cell constructed with a graphite
increasing Si/SiOx areal loading; therefore a relative low loading anode and a Li2S cathode (mass loading of 2.2 mg cm2) in
of 1 mg cm2 was applied in this study. To further accelerate the
a solvate ionic-liquid electrolyte ([Li(G4)1]-[TFSA]/HFE). A sche-
practical application of Li–S full cells, we concentrated on the
matic diagram depicting the charging process in such a Li2S–
challenges of upscaling Li–S battery prototypes from small
graphite full cell is shown in Fig. 7a. The CV trace (Fig. 7b)
laboratory coin cells to much larger pouch cells containing C-
displays an initial oxidation peak at 1.9 V, which corresponds to
coated Si/SiOx anodes with an increased loading of 4.3 mg
Li extraction from Li2S. The peaks at 2.8 and 3.5 V correspond to
cm2.255 Fig. 6e displays the cycling performance of these pouch
different electrochemical-activation processes. A peak at 2.4 V,
cells using a Li–metal anode (average sulfur loading of 2.8 mg corresponding to Li2S oxidation, appeared in subsequent scans,
cm2) at a rate of 0.5C between 1.8 and 2.7 V over 60 cycles. The while the two peaks at 2.1 and 1.9 V correspond to the stepwise
pouch cells delivered high discharge capacities of around
reduction of sulfur. The composition of the electrolyte ([Li(G4)x]
1170 mA h g1 during initial cycling, and were stable up to the
[TFSA]/HFE, x ¼ 0.6, 0.8, and 1) was further optimized by
40th cycle. However, the cell showed dramatic capacity fading
varying the G4-to-LiTFSA molar ratio. Cells containing [Li(G4)1]
(capacity decay rate of 1.4% per cycle) beyond the 40th cycle.
[TFSA]/HFE, [Li(G4)0.8][TFSA]/HFE, and [Li(G4)0.6][TFSA]/HFE
Fig. 6f also reveals that these pouch cells suffer from fast
electrolytes delivered specic capacities of 343, 410, and
capacity fading at high rates, which is mainly due to the
231 mA h g1 aer 100 cycles at a 1/12C rate. The improved
morphological failures of their Li anodes, which is not as electrochemical performance of the [Li(G4)0.8][TFSA]/HFE-
pronounced in small coin cells. The Li–S pouch cell with a Si/ based electrolyte is attributed mainly to balanced ionic
SiOx anode (Si–Li–S cell) delivered an initial capacity of around
conductivity and the Li+ intercalation/deintercalation proper-
800 mA h g1 (based on the mass of sulfur) at a rate of 0.5C. As
ties of the electrolytes. Wang et al.258 developed a Li–S full-cell
seen in Fig. 6g, the cell capacity decreased to around
battery with graphite as the anode, a Li2S@porous-carbon
500 mA h g1 during initial cycling, and then exhibited stable
(Li2S@PC) composite as the cathode, and DOL/DME with
capacity retention during hundreds of cycles (62.7% of the
LiNO3 as the electrolyte. The Li2S@PC composite was prepared
initial capacity aer 400 cycles), with coulombic efficiencies
by reacting Li2SO4 and pyrolytic carbon from sucrose. Li2S
higher than 99.5% during prolonged cycling. This study nanoparticles were uniformly distributed into the porous-
demonstrated that the use of highly loaded pre-lithiated C- carbon matrix, which was capable of trapping dissolved poly-
coated Si/SiOx anodes that do not suffer from dendritic Li
sulde. The process for the synthesis of the Li2S@PC composite
growth, can be upscaled to Li–S pouch cells with long cycling
is schematically depicted in Fig. 7c. The cycling performance
lives; we encourage further research in the upscaling of battery
and charge–discharge prole of the full cell is shown in Fig. 7d,
prototypes aer initial studies on the small scale, in order to
which reveals voltage plateaus at 1.9 V. The full cell delivered
understand real and important bottlenecks involved in the
a specic discharge capacity of 268 mA h g1 at 0.1C aer 30
commercialization of battery technology.
cycles with a coulombic efficiency of 82%, and 173 mA h g1 at
Table 5 Performance of Li–S full-cell batteries composed of Li2S-based cathodes, and carbon, Si, or Sn-based anodes
Initial capacity
Anode//cathode Li2S loading (mg cm2) (mA h g1) Cycle no. C-Rate Energy density (W h kg1) Ref.
Graphite anode //Li2S@porous carbon 1 516 100 0.5C 1197 (by Li2S) 258
cathode
Graphite anode//Li2S/graphene 2.2 740 20 1/12C — 257
composite cathodes
Lithiated Si–O–C anode//Li2S-MCMB — 280 50 0.2C 390 227
cathode
Silicon nanowire anode//Li2S/CMK-3 1.1–1.4 423 20 C/3 630 (by Li2S) 262
carbon composite cathodes
Lithiated nano Si@C composite anode// — 788 150 250 mA g1 — 158
Mo/Li2S-based cathode
Sn-C anode//Li2S–C cathode — 600 80 0.2C 1200 (by Li2S) 260
SnO2 anode//Li2S cathode 2.4 983 200 0.5C 352 38

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Fig. 7 (a) Schematically illustrating the charging process in a Li2S/graphite full cell using solvate ionic-liquid electrolytes ([Li(G4)x][TFSA]/HFE, x ¼
0.6, 0.8, and 1). (b) Typical cyclic voltammograms of a Li2S/graphite full cell with a ball-milled Li2S/graphene cathode, a graphite anode, and the
[Li(G4)1][TFSA]/HFE electrolyte at a scan rate of 0.04 mV s1; reproduced from ref. 257 with permission (Copyright 2016, American Chemical
Society). (c) Schematically illustrating the Li2S@PC-composite fabrication process. (d) Charge/discharge curves for graphite–Li2S@PC full cells at
0.1C, and cycling performance at 0.1C and 0.5C (inset); reproduced from ref. 258 with permission (Copyright 2017, Elsevier). (e) Schematic of
Li2S@graphene capsules. (f) Cycling performance of graphite/Li2S@graphene cells at a current density of 160 mA g1; reproduced from ref. 148
with permission (Copyright 2017, Nature Publishing Group). (g) SEM image of carbonized commercial wipes (inset: optical image of the free-
standing carbon matrix). (h) Cycling performance of SnO2/Li2S batteries employing an ether-based electrolyte with 50 mM InI3 as additive;
reproduced from ref. 38 with permission (Copyright 2017, Elsevier). (i) Cross-sectional STEM image of an electrodeposited Si–O–C electrode. (j)
Cycling response of the Li2S–MCMB/LiCF3SO3(TEGDME)4/Si–O–C full cell; reproduced from ref. 140 with permission (Copyright 2014,
American Chemical Society).
0.5C aer 100 cycles with a coulombic efficiency of 95%. Tan prevention of Li polysulde dissolution and the avoidance of
et al.148 reported a Li2S cathode with Li2S nanoparticles enclosed capacity loss. The use of a Sn/C-composite anode, with a nano-
by few-layer graphene sheets (Li2S@graphene nanocapsules) structured morphology of Sn particles conned in an amor-
(Fig. 7e). The cathode, with a high Li2S mass loading (10 mg phous carbon matrix, circumvented the volume changes
cm2), in a half-cell conguration, delivered a reversible associated with nanometric Sn, which helped to achieve high
capacity of 1160 mA h g(Sulfur)1 and an aerial capacity of energy densities. The test cell was operated at 60 C and no
8.1 mA h cm2. Fig. 7f displays the cycling performance of the polysulde dissolution was observed. The conversion reaction
full cell assembled using this Li2S@graphene-nanocapsule of Li polysulde is as follows:
cathode and a graphite anode. The full cell delivered an initial
specic charge capacity of 1600 mA h g1 and a discharge 2.2Li2S/C / 2.2S + C + 4.4Li+ + 4.4e (10)
capacity of 730 mA h g1 when it was charged and discharged
between 3.5 and 1.4 V. Aer the rst cycle, the cell delivered In addition, the Li ion reacts with the tin/carbon composite
90% coulombic efficiency with cycling stability, retaining to forms alloys, as shown in the following equation:
a specic capacity of 440 mA h g1 aer 200 cycles at 160 mA g1
4.4Li+ + Sn/C +4.4e / Li4.4Sn + C (11)
with a Li2S mass loading of 2 mg cm2.
Hassoun and Scrosati et al.259 rst introduced the Sn–Li The cell delivered an initial specic capacity of 600 mA h g1
polysulde polymer Li–S battery, which consists of a Sn/C at a C/20 rate and was cycled 33 times. Hassoun260 also reported
anode, a Li2S/C cathode, and a gel-polymer electrolyte (GPE). a Sn–C/Li2S polymer battery that operated at about 2 V and
The electrolyte was composed of an ethylene carbonate/ exhibited specic capacities of 600 mA h g1 and 1200 mA h g1
dimethyl carbonate solution of Li hexauorophosphate based on the Li2S–C and Li2S masses, respectively. The cell
(EC : DMC LiPF6) saturated with Li2S in a polyethylene oxide/Li delivered a total energy density of 1200 W h kg1 and was cycled
triuoromethanesulfonate (PEO/LiCF3SO3) polymer matrix. The 110 times. In situ XRD of the cell revealed that Li2S is converted
polymer electrolyte has several advantages, including the into sulfur during the charging process, while the sulfur is

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converted back to sulde during the discharging process. Liu

et al.38 developed a Li–S full cell equipped with a SnO2 anode,
a Li2S cathode, and a LiTFSI-based electrolyte with a bifunc-
tional electrolyte additive (indium triiodide (InI3)), which not
only acted as a redox mediator to activate the Li2S cathode, but
also formed an in situ passivation layer that protected the anode
from polysulde corrosion. Li2S nanoparticles were incorpo-
rated into commercial wipe-derived carbon, as the cathode

host, by an inltration method (Fig. 7g). The SnO2/Li2S cell
delivered a stable specic capacity of 647 mA h g1 at 0.5C aer
200 cycles, which corresponds to an energy density of
352 W h kg1 based on the mass of the entire material (Fig. 7h).
The non-uniformity of each unit cell in a practical battery pack
results in the overcharging or overdischarging of certain cells in
some cases, which is a common issue under real working
conditions. The cycle life and capacity of a battery are shortened
by overcharging or overdischarging in some cases, especially for
Fig. 8 (a) Schematic illustration of a lithium-ion sulfur battery,
a lithium-based battery. Therefore, a comparative study of SnO2/
including the discharging and charging processes. (b) TEM image of
Li2S full cells and Li/Li2S half-cells under abusive test condi- S@pPAN. (c) Electrochemical performance of the lithium-ion sulfur
tions (overcharging and overdischarging) was also conducted. battery fabricated with a S@pPAN cathode and a pre-lithiated SiOx/C
Aer such testing, the cycling time dropped to only 1.47 h for anode in a carbonate-based electrolyte at 100 mA g1; reproduced
the Li/Li2S cell, which represents a large capacity loss, whereas from ref. 263 with permission (Copyright 2017, Elsevier).
a steady cycling time (2.8–2.9 h) was maintained by the SnO2/
Li2S full cell. These results demonstrate the fragile responses of
traditional Li–S batteries to overcharging and overdischarging, (mesophase-carbon-microbead) composite in a tetraglyme
while establishing the advantages of combining a Li–metal-free electrolyte.140 The Li2S–MCMB cathode was prepared by high-
anode and a Li2S cathode. energy ball milling. A 500–650 nm-thick thin lm containing
Balach et al.158 prepared a Li–S full cell composed of a Mo/ silicon (content: 60%), oxygen, and carbon, was prepared
Li2S cathode and a nanostructured Si anode in a carbonate- through an electrodeposition method and used as the anode, as
based electrolyte. Li2S nanoparticles were synthesized by the shown in Fig. 7i. Fig. 7j reveals that this full cell delivered
electrochemical decomposition of MoS2 at a low potential. The a stable capacity of 280 mA h gLi2S1 for over 50 cycles, which
advantages of the Mo/Li2S cathode include the avoidance of corresponds to an energy density of the order of 390 W h kg1.
soluble polysuldes and the ability to operate in carbonate-
based electrolytes. A Si@C–Li2S full cell, with a Li2S mass
loading of 10.7 mg cm2, delivered an initial discharge capacity 5.3 Li–S full cells: S/PAN-composite cathodes
of 780 mA h g1 and areal capacity of 7.5 mA h cm2, based on In this section, we focus on the merits of a Li–S full cell
the mass of sulfur. A reversible capacity of 410 mA h g1 was composed of a sulfurized-polymer cathode coupled with a Li–
retained at a current density of 250 mA g1 aer 150 cycles, with metal-free anode. Sulfur-based cathodes are chemically
a degradation rate of 0.32% per cycle. The advantages of using incompatible with carbonate-based electrolytes, which severely
nanosized Li2S over microsized Li2S include its higher specic reduces Li–S-battery performance in a carbonate-based elec-
capacity, cycling stability, and capacity retention. Furthermore, trolyte. Carbonate-based electrolytes react with Li polysuldes
the cell was operated in a carbonate-based electrolyte without by nucleophilic addition or substitution reactions, resulting in
any additive and in the absence of polysulde shuttling, which the loss of active sulfur material and, consequently, capacity
is ascribable to the formation of a stable polymer gel-like SEI fading of the battery. However, polysuldes have very low
layer. Such an SEI layer protects against the loss of active solubilities in carbonate-based electrolytes; hence the shuttle
materials, while allowing Li-ion permeation. In addition, Yang effect can be avoided. SPAN-polymer-cathode materials are
et al.262 demonstrated a Li–metal-free Li–S full cell consisting of compatible with carbonate-based electrolytes; they exhibit high
a Si-nanowire anode and a Li2S/mesoporous-carbon-composite specic capacities, good conductivities, and good cycling
cathode with a theoretical specic energy of 1550 W h kg1. stabilities. Shi et al.263 demonstrated a Li–S full-cell battery
The mesoporous carbon composite was prepared by the inl- consisting of a pre-lithiated SiOx/C anode and a S@pPAN
tration of resorcinol-formaldehyde into the pores between cathode in a carbonate-based electrolyte. The charge and
close-packed nanospheres at 85 C, followed by carbonization. discharge processes are schematically illustrated in Fig. 8a. The
The silicon nanowires were directly synthesized on a stainless- TEM image of a S@pPAN composite is shown in Fig. 8b, which
steel substrate by a vapor–liquid–solid method. An initial reveals that the S@pPAN has a regular nanospherical
specic discharge energy of 630 W h kg1 was obtained. They morphology with an average diameter of about 200 nm. The
constructed a Li–S full cell based on the combination of a high- S@pPAN particles are also seen to agglomerate to some extent,
capacity Si–O–C anode and a high-rate Li2S–MCMB which is probably due to interconnecting sulfurized

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polyacrylonitrile molecular chains that form larger particles 1000 mA h g1 at 0.064 mA cm2 (25 C). Trevey et al.281 reported
during heating. The full cell delivered a highly reversible a PAN–S-based electrode with a sulde-based solid electrolyte
capacity of 616 mA h g1 and relatively good cycling stability, for use in an all-solid-state battery that delivered a specic
with a capacity retention of about 84% aer 100 cycles, capacity of 605 mA h g1 over 50 cycles. An inorganic solid
compared to the 2nd cycle (Fig. 8c). Moreover, the coulombic electrolyte, a-60Li2S$40SiS2, was also employed with a sulfur
efficiency of this cell remained at almost 100% during cycling. electrode in an all-solid-state lithium battery.276 When the
The energy density of this full cell is estimated to be about Li10GeP2S12 SE electrolyte was used, this battery exhibited
661 W h kg1 (based on the active materials on the cathode and
higher discharge capacities at higher current densities than that

anode) aer 100 cycles, which is more than twice that of using the 75Li2S$25P2S5 glass electrolyte.265 The main limita-
a commercial LIB. Similar to S/CPAN chemistry, the sulfur/ tions of solid-state Li–S batteries are the insufficient amount of
lithium-ion battery has been constructed by employing sulfur and the use of very small current densities, which limits
a lithium/Sn–C composite anode, a carbyne polysulde practical applications. Recently, a high mass loading of elec-
cathode, and a carbonic ester electrolyte solution.261 This full trode materials in an ASSLSB was reported by Nagata et al.282
cell exhibited a reversible capacity of 500 mA h g1 at a current this battery was composed of a positive composite electrode
density of 200 mA g1 aer 50 cycles, with a specic energy of with a high P/S (number of phosphorus atoms/number of sulfur
410 W h kg1; carbyne polysulde possesses a higher electrical atoms) ratio and the Li1.5PS3.3 solid electrolyte. The cell deliv-
conductivity than elemental sulfur. The half-cell conguration ered an energy density of 500 W h kg1 at a mass loading of 7.5–
with a carbyne polysulde cathode delivered a specic capacity 9.0 mg cm2. A high power density at 50% state-of-charge was
of 520 mA h g1 at 200 mA g1 aer 50 cycles, with a capacity achieved in an all-solid-state Li/S cell prepared with a positive
retention of 96%. The carbyne polysulde electrode has activated-carbon-based composite electrode. The cell delivered
a unique discharge prole, exhibiting only one discharge a good reversible capacity of 1600 mA h g1 aer 100 cycles at
voltage plateau at 1.8 V; it also reacts with Li+ ions to form Li2S2 1.3 mA cm2 (1C) and 25 C.283 However, ASSLSB performance is
and Li2S without polysulde dissolution. till far below those required for high-power applications
because of their low electrical conductivities at room tempera-
6. All-solid-state Li–S batteries ture and complex synthesis processes compared to those of
liquid electrolytes. The major problem associated with low
Solid-polymer electrolytes (SPEs), with and without ller, have conductivity is the impediment to fast C-rate charging and
been reported by various groups.267–270 In order to enhance discharging, which restricts the ability to deliver the high energy
conductivity, nanosized inorganic llers have been used to and power required from all-solid-state Li–S batteries. Apart
balance charge-carrier mobility, which are attributed to inter- from these drawbacks, the main benets of these electrolytes
actions between the surface groups of the ller and the PEO includes low polysulde solubility and shuttling, fundamental
oxygen atoms.268 Recently, Li–S batteries containing SPEs, with safety owing to a lack of leakage and thermal stability, better
nanosized ZrO2 (10 wt%) as the electrolyte additive, have been lithium–metal-ion stabilities, and the lack of dendrite
reported by Hassoun et al.271 these batteries exhibited enhanced formation.
ionic conductivities and lithium-ion transference numbers. An
all solid-state lithium–sulfur battery (ASSLSB) composed of an 7. Conclusions and perspective
S/C-composite cathode, ZrO2, and a Li2S-doped LiTf-PEO CPE,
delivered a specic capacity of 900 mA h g1 with a cycling In conclusion, we summarized recent progress in Li–S batteries
efficiency of 100% up to 50 cycles. based on three types of cathodes, namely S8, Li2S, and SPAN,
Liang et al. reported the use of an all-solid-state PEO18- which are either paired with Li–metal anodes or Li–metal-free
Li(CF3SO2)2N–10 wt%–SiO2 electrolyte in a Li–S battery anodes. We emphasize the various kinds of electrolytes used
composed of mesoporous carbon spheres.272 The cell delivered in Li–S batteries and also discuss all-solid-state lithium–sulfur
a reversible discharge capacity of 800 mA h g1 aer 25 cycles. batteries that use solid electrolytes. For practical application,
Apart from solid-polymer electrolytes in ASSLSBs, various high-loading electrodes are a precondition to achieving high
research groups have developed highly conductive glassy solid- energy densities. Hence, we rst presented recent developments
state electrolytes for use in Li–S batteries. Numerous inorganic in high-loading sulfur cathodes based on S8, Li2S, and SPAN.
solid electrolytes (SEs), such as Li2S–P2S5 glass Although numerous approaches have been used to address
ceramics,152,264,266,273,274 Li2S–SiS2 glass,275,276 and thio-LISICONs current cathode issues, problems associated with Li–metal
(lithium superionic conductors) in Li4GeS4–Li3PS4 systems,277 anodes still remain and urgently require solutions in order for
with high Li+-ion conductivities of over 104 S cm1 at 25 C, Li–S batteries to be applied in practical settings. We summarize
have been reported for use in all-solid-state Li/S batteries. and discuss challenges facing Li–metal anodes and the
Further improvements in lithium-ion conductivity, to values in prevention of lithium–metal-dendrite growth in Li–S-battery
excess of 103 S cm1 at 25 C, have been reported with SEs such systems. Finally, we focus on issues related to all-solid-state
as Li7P3S11,278 Li2S–P2S5–LiI,279 Li2S–P2S5–LiBH4,280 and Li2S– lithium–sulfur batteries and the current status. We conclude
GeS2–P2S5.58 Recently, Nagao et al.152 reported all solid-state that the use of Li–metal-free anodes for the construction of Li–S
cells composed of Li2S–C-composite electrodes and Li2S–P2S5 full cells is an effective solution that alleviates the issues asso-
glass–ceramic SEs. These cells delivered charge capacities of ciated with Li–metal anodes, and summarize and discuss

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Recent Research Trends in Li-S Batteries

Article in Journal of Materials Chemistry A · June 2018

Rudra Kumar Jie Liu

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Recent research trends in Li–S batteries

present in lithium–sulfur (Li–S) batteries, perform two-electron

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

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discharging is as follows:53 During discharging, the –Sx– chain is

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foam (HCFF) by the carbonization of natural cotton and used

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Journal of Materials Chemistry A Review

3.6 648 (0.04C) 2.33 128 (@0.04C, 60th) 155

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

Table 3 Li–S battery performance based on SPAN-based cathodes

Sulfur/polyacrylonitrile/carbon 860 100 mA g1 100 57.4 177

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

Sulfur loading Initial capacity Cycle Energy density

Graphite//S–MWCNT — 757 50 0.2C 485 241

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

cells has been described by Shen et al.179 During the cycling

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

was fabricated.254 A three-dimensional lithiated Si/graphene contrast, a S@CMK-3/liquid-electrolyte/Si@graphite cell only

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

converted back to sulde during the discharging process. Liu

rated into commercial wipe-derived carbon, as the cathode

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

higher discharge capacities at higher current densities than that

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

various scenarios for the commercial development of Li–metal- References

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018

Review Journal of Materials Chemistry A

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A

Journal of Materials Chemistry A Review

54, 12886–12890. Carbon, 2017, 118, 120–126.

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2018