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Recent advances in nanomaterials for high-performance Li-S batteries
Article in Journal of Energy Chemistry · August 2020

DOI: 10.1016/j.jechem.2019.11.018
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Journal of Energy Chemistry 47 (2020) 86–106
Contents lists available at ScienceDirect
Journal of Energy Chemistry

journal homepage: www.elsevier.com/locate/jechem
Review
Recent advances in nanomaterials for high-performance Li–S batteries

James E. Knoop a, Seongki Ahn b,∗
a
Joint School of Nanoscience and Nanoengineering, North Carolina Agricultural and Technical State University, Greensboro, NC 27401, USA
b
Research Organization for Nano and Life Innovation, Waseda University, 513, Wasedatsurumakicho, Shinjuku-ku, Tokyo 162-0041, Japan
a r t i c l e i n f o a b s t r a c t
Article history: This article reviews nanotechnology as a practical solution for improving lithium-sulfur batteries. Lithium-
Received 26 September 2019 sulfur batteries have been widely examined because sulfur has many advantageous properties such as a
Revised 19 November 2019
high crustal abundance, low environmental impact, low cost, high gravimetric (2600 W h kg−1 ) and volu-
Accepted 24 November 2019
metric (2800 W h L−1 ) energy densities, assuming complete conversion of sulfur to lithium sulfide (Li2 S)
Available online 29 November 2019
upon lithiation. However, lithium-sulfur batteries have not yet reach commercialization due to demerits
Keywords: involving the formation of soluble lithium polysulfides (Li2 Sn , n = 3–8), low electrical conductivity, and
Nanotechnology low loading density of sulfur. These issues arise mainly due to the polysulfide shuttle phenomenon and
Lithium–sulfur batteries the inherent insulating nature of sulfur. To overcome these issues, strategies have been pursued using
Carbon nanomaterials nanotechnology applied to porous carbon nanocomposites, hollow one-dimensional carbon nanomateri-
Nanocomposite sulfur als, graphene nanocomposites, and three-dimensional carbon nanostructured matrices. This paper aims to
3D nanostructured materials
review various solutions pertaining to the role of nanotechnology in synthesizing nanoscale and nanos-
tructured materials for advanced and high-performance lithium–sulfur batteries. Furthermore, we high-
light perspective research directions for commercialization of lithium–sulfur batteries as a major power
source for electric vehicles and large-scale electric energy storage.
© 2019 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by Elsevier B.V. and Science Press. All rights reserved.
James E. Knoop is currently a Ph.D. student at the Joint 1. Introduction

School of Nanoscience and Nanotechnology in the Na-
noengineering department at North Carolina Agricultural
and Technical State University. He received his M. S. in 1.1. Background of LSBs
Nanoscience from the University of North Carolina at
Greensboro in 2019 and his B.S. in Chemistry from the
Commercial lithium-ion batteries (LIBs) have dominated the
University of North Carolina at Charlotte in 2017. His
main research interest includes materials chemistry and consumer electronics market since its release in the early 1990s.
nanochemistry for reneweable energy and sustainable As a state-of-the-art secondary battery, LIBs have been used as a
technologies, including, Li–S battery cathode development
major power source for portable electronics and large-scale de-
for advanced energy storage devices and paramagnetic
ionic liquids synthesis for CO2 adsorption applications. vices such as energy storage systems (ESS) and electric vehicles
(EVs). Currently, a combination of modern technology and grow-
Seongki Ahn received his BS and MS degrees in engineer-
ing EVs market has produced an ever-increasing demand for en-
ing chemistry from Chungbuk National University, South
Korea. He received a Ph.D. degree in Applied Chemistry ergy storage devices. Unfortunately, LIBs are approaching the limit
from Waseda University, Tokyo, Japan in 2017. He is cur- of their energy density and do not adequately meet the energy
rently a post-doctoral researcher in Research Organization demands of electric vehicles [1–4]. Alternative secondary batter-
for Nano & Life Innovation, Waseda University, Japan. His
main research interest is a synthesis of nano- and micro- ies such as lithium-air batteries and lithium-sulfur batteries (LSBs)
material for electrochemical energy storage devices such have been investigated. Among them, LSBs represent a more prac-
as Li–S batteries, Li-ion batteries, and Li-ion capacitors. tical approach to state-of-the-art LIBs in terms of high energy
He also interested in suppressing the growth of lithium
dendrite and cell design for practical application. density [5]. The advantages of using sulfur as active material in
lithium batteries are derived from a high theoretical capacity of
1675 mA h g−1 and a high gravimetric and volumetric energy den-
sity of 2500 W h kg−1 and 2800 W h L−1 , respectively, compared
∗
to LIBs (Fig. 1(a)) [6]. In addition, the theoretical capacity of sulfur
Corresponding author.
is higher than common LIBs commercial cathode materials such as
E-mail address: [email protected] (S. Ahn).
https://doi.org/10.1016/j.jechem.2019.11.018
2095-4956/© 2019 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
J.E. Knoop and S. Ahn / Journal of Energy Chemistry 47 (2020) 86–106 87
Fig. 1. (a) Comparison of energy density between LIBs and LSBs, (b) cost comparison of elements for cathode materials. (Reproduced from Ref. [6] with permission from The
Royal Society of Chemistry, Copyright 2016).
Fig. 2. (a) Illustration of charge/discharge operation of LSBs (reproduced from Ref. [9] with permission from The Royal Society of Chemistry, Copyright 2017), (b) characteristic
charge/discharge curve representing the production of intermediate polysulfides (Li2 S8 , Li2 S6 , and Li2 S4 ) and insoluble polysulfides (Li2 S2 and Li2 S) in LSBs. (reprinted with
permission from Ref. [1], Copyright 2012, Springer Nature).
LiCoO2 , LiFePO4 , and LiMnO2 which have theoretical capacities of the anode and are reduced to lower-order lithium polysulfides
140, 170, and 286 mA h g−1 , respectively [7,8]. Furthermore, the where an insoluble and insulating layer of Li2 S2 /Li2 S is formed
economic feasibility of sulfur as an active material is promoted by on the lithium metal anode [10]. Meanwhile, unreacted low-order
its high abundance, non-toxicity, and low cost (Fig. 1(b)). These ad- lithium polysulfides migrate to the cathode and are re-oxidized to
vantages make LSBs a very attractive alternative to LIBs. However, form high-order lithium polysulfides to complete the cycle [11,12].
for market penetration to come to fruition, there remains certain Moreover, the exact mechanism for intermediate lithium polysul-
issues and challenges which must be addressed. fide species formed is still under heavy discussion. As a result, ca-
pacity fading from loss of sulfur in the cathode, increased cell re-
1.2. Mechanism and current issues regarding LSBs sistance due to dissolved insulating intermediate lithium polysul-
fides, lowered coulombic efficiency, and poor cyclability is experi-
Typically, LSBs are constructed from a cathode, anode, and enced during battery operation. This phenomenon presents a major
porous separator which is saturated with a lithium salt liquid elec- challenge and has prevented LSBs market penetration.
trolyte. Below, the illustration of the charge/discharge process is Furthermore, elemental sulfur has a low electrical conductivity
given (Fig. 2(a)) [9]. During the discharge process, Li-ions migrate (1 × 10−15 S m−1 ) compared to other commercially used elements
from the anode to the cathode through the porous separator and (Co: 1.7 × 107 S m−1 ; Mn: 6.2 × 105 S m−1 ; Fe: 1 × 107 S m−1 ; Ni:
vice versa. Simply, the overall mechanism is depicted by the fol- 1.4 × 107 S m−1 ). This critical issue must be addressed to achieve
lowing equations: high utilization of sulfur as a cathode material for rechargeable
secondary batteries.
Li ↔ Li+ + e− (1)
To enhance the low electrical conductivity of sulfur in the cath-
ode, various materials with high electrical conductivity, such as
conductive carbons and polymers, have been investigated greatly
2Li+ + 2e− + S ↔ Li2 S (2)
as supporting matrices. Sulfur added to a conductive carbon ma-
The oxidation and reduction reaction of LSBs is shown by the trix, with ~40–50 wt% of carbon is typically the most represented
following equation: composite used for LSBs recently. Porous carbon additives have
a highly conductive carbon network which is benefited by high
2Li + S ↔ Li2 S (3) micro- and mesoporosity that dramatically heightens the contact
In the reaction, sulfur is reduced and results in the continu- between sulfur and carbon. Unfortunately, a low loading density of
ous formation of lithium polysulfides and anionic sulfur species sulfur is resultant in the composite material which use conductive
(Fig. 2(b)) [1]. These high-order lithium polysulfides migrate to carbon networks to amplify conductivity because the percentage
88 J.E. Knoop and S. Ahn / Journal of Energy Chemistry 47 (2020) 86–106
Fig. 3. Various strategies for advanced LSBs using nanotechnology: (a) sulfur/carbon core-shell nanostructure to suppress polysulfide dissolution, (reprinted with permission
from Ref. [18], Copyright 2013, WILEY), (b) sulfur/conductive carbon composite to improve sulfur conductivity (this figure by R. Chen, is licensed under CC by 3.0., 2014, AIP
Publishing LLC, [19]), (c) 3D-structured matrix for high sulfur loading density. (Reprinted with permission from Ref. [20], Copyright 2016, WILEY).
of sulfur is lowered in the material. This lowers the volumetric en- focus, we review 3D nanostructured matrices using sulfur nanopar-
ergy density of sulfur compared to other cathode materials. A high ticles as a solution to increase sulfur loading density for higher en-
loading density of sulfur is important and must be achieved to ob- ergy density LSBs. 3D nanostructured matrices provide more active
tain commercialization of LSBs. sights for sulfur coordination than 1D and 2D materials and there-
To overcome these challenges, nanotechnology should be con- fore increase sulfur loading density in the electrode. A recently
sidered a practical solution due to the merits of physical and published review article, titled “Recent advances in lithium-sulfur
chemical behavior on the nanoscale and unique constructional batteries”, demonstrated the potential of 3D structured sulfur cath-
characteristics [13,14]. odes for next-generation high capacity batteries. Comprehensively,
in this review, we describe advanced nanotechnologies for the sul-
1.3. Nanotechnology as the solution fur cathode in LSBs and provide guidance for the future develop-
ment of more efficient, advanced, and high-performance LSBs for
Nanotechnology refers to the techniques of synthesizing, as- commercial manufacturing.
sembling, manipulating, and characterizing materials in nanoscale
2. Nanotechnologies for improving LSBs
units which range from 1 to 10 0 0 nm. Since Richard Feynman
first spoke about nanoscience and nanotechnology in 1959, nano-
2.1. Early approaches in suppressing polysulfide dissolution
philosophy has been widely applied in various disciplines such
as environmental science, life science, biology, medicinal science,
In the previous section, we described the mechanism and chal-
chemistry, and other related fields. Recently, nanostructured ma-
lenges of polysulfide dissolution during battery operation of LSBs.
terials have attracted wide-attention as promising candidates for
Early approaches to overcome these challenges resulted in the use
rechargeable batteries, especially for secondary batteries with high
of 1D, 2D, and 3D carbonaceous materials due to the unique prop-
energy densities such as LIBs and LSBs. Nanostructured materi-
erties these nanostructures contribute to LSBs. For these materials
als offer unique physical, chemical, mechanical, and optical prop-
tunable pore structure and high electrical conductivity are key to
erties. These properties allow for the synthesis of self-assembled
trapping sulfur and acting as a barrier from preventing active ma-
or template-assisted nanoarchitectures which are benefitted by
terial loss to polysulfide dissolution.
high porosity, high surface area, unique functionalization, and are
Carbon nanotubes (CNTs) are 1D nanomaterials that have ex-
needed to solve the issues faced by LSBs. Thus, these properties
ceptional chemical and mechanical durability, are electrically con-
differ greatly from bulk materials and provide highly creative av-
ductive, and provide a high aspect ratio surface for sulfur coordi-
enues to addressing the challenges faced by LSBs. In addition,
nation [21]. These porous nanomaterials have been engineered as
nanomaterials applied to LSBs shorten lithium-ion diffusion path-
freestanding electrodes to suppress polysulfide dissolution or en-
ways, resulting in improved charge/discharge efficiency and high-
gineered as a shield to block polysulfide dissolution and mitigate
rate performance [15–17]. We focused on three issues in this re-
active material loss by direct coating of CNTs upon a separator
view article for the realization of high performance and advanced
[22,23].
LSBs (Fig. 3(a)–(c)) [18–20]:
Graphene is a 2D nanomaterial with high surface area and elec-
(1) Polysulfide dissolution and shuttle phenomena. trical conductivity, large pore volume, and is mechanically stable.
(2) Low electrical conductivity of sulfur. The large pore volume of graphene allows for increased sulfur
(3) Low density of sulfur in the cathode. loading. However, a large pore size may lead to loss of active mate-
rial. Partially oxidized graphene increases the polarity of graphene
In our first focus, we review the polysulfide dissolution and and increases the binding affinity to sulfur [24]. A stronger binding
shuttle phenomenon and the strategies taken to solve this is- affinity between graphene and sulfur decreases polysulfide shut-
sue. We examined the recent advancements in nanotechnology to tling. Furthermore, a mixture of pristine graphene and graphene
reduce polysulfide dissolution with metal chalcogenide additives, oxide layers would be beneficial to preventing polysulfide dissolu-
graphene oxide, passivation layers, and a unique ferromagnetic tion and maintaining a high sulfur loading capacity.
mechanism. These approaches significantly suppress intermediate Carbanaceous 3D hybrid nanomaterials often combine 1D and
lithium polysulfide dissolution through physical and chemical pro- 2D nanomaterials to create specialized nanoarchitectures for pre-
cesses. In our next focus, we cover recent advances in nanotechnol- venting polysulfide dissolution. These materials may contain com-
ogy for improving the low conductivity of sulfur in LSBs by novel binations of CNTs, graphene, carbon nanofibers, activated porous
nanoarchitectures of porous carbon–sulfur nanocomposites, hol- carbon, and polymeric carbon materials to create nanoarchitectures
low linear carbon nanostructures, core-shell nanostructures, and of differing porosity, intimate sulfur-carbon contact, high sulfur
graphene–sulfur nanocomposites. These nanoarchitectures estab- loading capabilities, and chemical and mechanical stability [25–27].
lish increased contact between sulfur and carbon due to higher Compared to approaches using 1D, 2D, and 3D carbonaceous
surface area coordination which improves conductivity. In our last materials to prevent polysulfide dissolution, there are more recent
approaches which have demonstrated progression in inhibiting 70 wt% sulfur content. Further-in, long-term cycling was demon-
polysulfide dissolution and the shuttling effect. strated for 500 cycles at 2 C.
Recently, it was reported a binder-free, porous, cobalt sulfide
2.2. Recent approaches in suppressing polysulfide dissolution (CoS2 )-reduced graphene oxide (rGO) 3D framework nanostruc-
ture via bottom-up assembly and hydrothermal treatment, fol-
In the previous section, we gave a brief overview of carbon ma- lowed by melt-diffusion at 155 °C (Fig. 4(d)) [30,31]. The cobalt
terials use to prevent polysulfide dissolution in LSBs. In this sec- sulfide nanoparticles were dispersed uniformly on graphene which
tion, we review approaches taken towards repressing intermedi- was interconnected through stacked graphene sheets (Fig. 4(e)). In
ate lithium polysulfide dissolution by metal chalcogenide additives, addition to enhanced conductivity, CoS2 significantly suppressed
graphene oxide, passivation layers, and multi-component materials lithium polysulfide dissolution and increased long-term cyclability.
to increase rate performance, cycle stability, and long-term cycla- The CoS2 /rGO composite demonstrated an initial discharge capac-
bility of sulfur cathodes. The methods, discussed below, to sup- ity of 994 mA h g−1 at 0.5 C. Additionally, it delivered a discharge
press or eliminate lithium polysulfide dissolution may contribute capacity of 807 after 110 cycles at 0.5 C demonstrating good capac-
towards market penetration of LSBs as a major power source for ity retention (Fig. 4(f)).
EVs and large-scale ESS. Babu et al. explored the catalytic phenomenon of transition
metal dichalcogenides (TMDs) as a means of lithium polysul-
2.2.1. Metal oxide/chalcogenide additives fide suppression through a liquid-based shear-exfoliation method
Metal oxide/chalcogenide molecular clusters and nanoparticles (Fig. 5(a)) [32]. Molybdenum and tungsten disulfide (MoS2 and
are transition metals which are coordinated typically to oxygen or WS2 ) nanosheets of few layers were shown to bind high-order
sulfur as applied to LSBs. The metal oxide or discrete sulfide clus- polysulfides on the nanosheet edge-sites and subsequently catalyt-
ters pack to form nanoparticles which are added to sulfur–carbon ically convert high-order lithium polysulfides to low-order poly-
nanostructures for high-performance LSBs. Metal chalcogenide ad- sulfides. This catalytically driven conversion greatly suppresses ir-
ditives (MCAs) deliver high conductivity, improved kinetics, or can reversible lithium polysulfide dissolution by congregating lithium
act as a sulfur reservoir for sulfur cathode nanomaterials. More- polysulfides at the cathode (Fig. 5(b)). As a result, the re-
over, metal chalcogenides tend to bind very strongly to formed in- versible catalytic process at the electrode/electrolyte interface im-
termediate lithium polysulfides, whereas more polar metal oxides proved cyclability with strong adsorption characteristics through
bind more favorably to sulfur; Both types of MCAs have demon- non-physical encapsulation which ensured the rate capability of
strated suppression of lithium polysulfide dissolution [28,29,38,30– lithium-ions was unhindered (Fig. 5(c)). The WS2 composite shows
37]. Metal oxides bind to sulfur more strongly to sulfur due to a specific discharge capacity of 590 mA h g−1 at 0.5 C with capac-
electrongetivity. However, strongly polar MCAs may inhibit diffu- ity retention and coulombic efficiency of 91% and 99%, respectively,
sion properties during the charge/discharge process in LSBs [28]. after 360 cycles.
Therefore, while polar materials are good for inhibiting polysulfide Recently, MCAs have been identified as great polysulfide immo-
dissolution, the most polar material is not always best. We focus bilizers due to strong chemical coordination between oxygen and
here on the effects of MCAs on regulating lithium polysulfide dis- sulfur species with lithium polysulfides. Furthermore, there are a
solution in LSBs. plethora of metal chalcogenide molecular clusters or nanoparticles
Tao et al. revealed that the balance between Li2 Sn (n = 1– which have not been fully investigated [39]. Moreover, MCAs offer
8) adsorption and diffusion properties on the metal oxides sur- beneficial properties such as high conductivity in conjunction with
face is necessary to improve the electrochemical performance of polysulfide binding properties. One potential downfall of MCAs is
LSBs [28]. Metal oxides such as CeO2 , Al2 O3 , La2 O3 , MgO, and the determination of the most optimal metal chalcogenide species
CaO were prepared via Pechini sol–gel method and adorned with for LSBs. There are many MCAs which exhibit different properties
carbon nanoflakes to improve conductivity. First principle calcu- and differences in binding energies between lithium polysulfides
lations using density functional theory (DFT) were performed to and therefore identification of the most suitable properties for LSBs
investigate the binding energies between lithium polysulfides and will take time. We suggest further investigation into metal chalco-
metal oxides. They determined Al2 O3 bound more strongly than genide discrete molecular clusters or metal chalcogenide nanopar-
the other metal oxides and exhibited stable bonding with Li2 S ticles using first-principle calculations to quickly identify and ex-
where two oxygen atoms participated in coordination. However, al- pand the library of MCAs for mitigating polysulfide dissolution.
though Al2 O3 demonstrated strong adsorption, the diffusion prop- Graphene oxide: Graphene has been used immensely as an elec-
erties of this metal oxide were poor and resulted in low cyclability. tron conducting material for energy storage devises because of its
This binding interaction showed that the strongest binding metal physical and electrochemical advantages such as large surface area,
oxide is not necessarily the best and a balance between adsorp- mechanical strength, flexibility, and unique electron and phonon
tion of intermediate lithium polysulfides and diffusion properties transport mechanisms due to sp2 bonded carbon atoms arranged
of MCAs is needed for better performance. in a hexagonal 2D lattice [40,41]. To our knowledge, graphene has
Pang et al. deviated from a typical carbon-sulfur cathode the highest conductivity of any organic material to date. Recently,
and prepared a highly polar tetratitanium heptoxide (Ti4 O7 )– various designs of sulfur and graphene nanocomposites have been
sulfur cathode to prevent the dissolution of polysulfides through synthesized for LSBs to entrap or alleviate polysulfide dissolution
metal oxide and lithium polysulfide coordination [29]. Titanium(IV) through chemical or physical means [42–46].
ethoxide and polyethylene glycol were mixed and heated (950 °C), Ji et al. synthesized surface-functionalized graphene oxide for
followed by melt-diffusion of sulfur and Ti4 O7 (155 °C). The mech- sulfur immobilization (Fig. 6(a)) [42]. Graphene oxide was synthe-
anisms of binding between lithium polysulfides and metal ox- sized via Hummer’s method followed by chemical vapor deposi-
ide were not yet revealed but they determined strong interaction using sodium sulfide (Na2 S) to produce the graphene–sulfur
tion of terminal and bridging sulfur were coordinated to the Ti4 O7 nanocomposite (GO–S). This novel graphene-sulfur nanocomposite
surface by x-ray photoelectron spectroscopy (XPS) (Fig. 4(a) and was characterized by transmission electron microscopy (TEM) and
(b)). A visual test for polysulfide adsorption was conducted and electron energy-loss spectrum (EELS) (Fig. 6(b)). The TEM micro-
demonstrated high adsorption by Ti4 O7 after one hour (Fig. 4(c)). graph and EELS results depict a thin layer of sulfur particles were
The Ti4 O7 –sulfur cathode delivered a high discharge capacity of uniformly dispersed on the surface of the flake-like GO–S with a
1070 mA h g−1 at 0.5 C, stable cycling up to 100 cycles, and a thickness of ~10 nm. The obtained GO–S delivered a discharge ca-
Fig. 4. (a) Bridging and terminal bonding of Ti4 O7 and Li2 S4 , (b) visual test of polysulfide adsorption, (c) XPS of Li2 S4 and Ti4 O7 coordination. (reprinted with permission
from Ref. [29], Copyright 2014, Springer Nature), (d) schematic of free-standing CoS2 /rGO cathode, (e) TEM morphology of CoS2 /rGO, (f) characteristic of charge/discharge
curves of CoS2 /rGO at 1st and 50th cycle. (Reprinted with permission from Ref. [30], Copyright 2018, Elsevier).
pacity of 10 0 0 mA h g−1 after 55 cycles at 0.1 C (Fig. 6(c)). The au- ation while functional groups acted as intermediate lithium poly-
thors attributed the high capacity to the inner space between the sulfide immobilizers. This GO-S composite shows improved cycle
deposited sulfur nanoparticles and carbonyl and carboxylic func- stability and high discharge capacity at various C-rates (Fig. 6(d)).
tional groups on the graphene surface. The inner space between Yu et al. prepared a carbon-sulfur nanocomposite wrapped in
sulfur accommodated the volume expansion of sulfur upon lithi- reduced graphene oxide (rGO) as an encapsulation layer to prevent
Fig. 5. (a) Schematic of catalytic binding of high-order polysulfides to edge-sites of MS2 (M = Mo, W), (b) UV–Vis of polysulfide binding with increased concentration of
WS2 , (c) characteristic charge/discharge curves of WS2 demonstrating cyclability through 50 cycles at 0.2 C, (d) long-term cycling of WS2 0.5 C. (reprinted with permission
from Ref. [31], Copyright 2017, American Chemical Society).
polysulfide dissolution [43]. Most interestingly, human hair was binding intermediate lithium polysulfides due to surface func-
used as a carbon source to synthesize the nanocomposite (GW- tionalized oxygen atoms which impart polarity on the surface of
C/S) by a facile carbonization/activation method (Fig. 6(e)). Sulfur graphene. The polar surface of graphene oxide is excellent for bind-
infiltrated the micropores of the hair-derived activated carbon via ing polar, dissolved lithium sulfide species and plays an integral
melt-diffusion at 155 °C. Electrostatic self-assembly caused the rGO role in suppressing lithium polysulfide dissolution. Unfortunately,
layers to wrap around the carbon-sulfur nanocomposite. Scanning graphene oxide is not as conductive as pristine graphene and its
transmission electron microscopy (STEM) and energy-dispersive X- conductivity is highly dependent on the degree of oxidation upon
ray spectroscopy (EDX) imaging demonstrated the homogeneous the nanosheet. This may be detrimental when improving the ca-
distribution of sulfur within the nanocomposite (Fig. 6(f)). The pacity of the sulfur cathode. A combination of graphene oxide and
electrochemical test of GW-C/S composite delivered great cycle sta- a more conductive additive will most likely provide the realization
bility for 300 cycles under various C-rates (Fig. 6(g)). The core-shell of high-performance LSBs for commercial application.
nanoarchitecture cause physical entrapment of the carbon-sulfur
nanoparticles by the rGO nanosheets and demonstrate and increase 2.2.2. Passivation layer
in conductivity and a decrease in polysulfide dissolution. Nanoscale surface modification technique is an effective way
In addition, Wang et al. reported amino-functionalized reduced to increase the electrochemical performance of LSBs by suppress-
graphene oxide (AF-rGO) as an intermediate lithium polysulfide ing lithium polysulfide dissolution. Herein, we review approaches
immobilizer through covalent stabilization of sulfur [44]. Ethylene- taken and their effects in synthesizing a nanoscale passivating
diamine (EDA) was used as the amino-functionalization agent be- layer on cathodes for LSBs using atomic layer deposition (ALD) of
cause of its unique molecular structure. Strong reactivity enhances metal oxides, carbon layers, and conductive polymer layers. The
covalent binding strength between polar lithium polysulfides and addition of a passivation layer adds a physical barrier to suppress
nonpolar carbon. SEM and TEM micrographs of AF-rGO/S con- lithium polysulfide dissolution through physical and chemical en-
firm a coating of lithium polysulfides that formed a thick uniform trapment and therefore improves upon the electrochemical per-
layer instead of aggregating (Fig. 7(a)–(h)). First principle calcula- formance of LSBs. Recently, ALD techniques have been widely ap-
tions using DFT verified strong binding strengths between lithium plied to develop advanced electrodes for secondary batteries due
sulfide and AF-rGO (Fig. 7(i)–(k)). The C–N binding energy was to facile nanoscale deposition of transition metal oxides on vari-
2.58 eV with a bonding length of 1.5 Å, demonstrating strong co- ous electrode substrates [47–52]. The layered thickness of transi-
ordination between rGO and EDA. After discharge, strong binding tion metal oxides is manipulated by the number of oxidative cycles
remained at the surface of AF-rGO (2.08–2.30 eV). Furthermore, and time of precursor deposition.
lithium in lithium polysulfides will coordinate strongly to sulfur Kim et al. reported aluminum oxide (Al2 O3 ) prepared by
and nitrogen on the AF-rGO surface. AF-rGO/S composite illus- plasma-enhanced atomic layer deposition (PE-ALD) on the surface
trated great cycle stability up to 350 cycles at 0.5 C with a high of sulfur impregnated activated carbon fiber (S-ACF) (Fig. 8(a)) [47].
sulfur loading of 69 wt% (Fig. 7(l)). PE-ALD offers many advantages such as low-temperature process-
The inherent properties of graphene, such as large surface area, ing (<200 °C) and fast deposition rates which provide uniform and
present more opportunity for surface coordination with lithium homogenous layers. Furthermore, non-infiltrating sulfur nanoparti-
polysulfides. Consequently, graphene oxide is more suitable to cles deposited on the outer surface of ACF were removed through
Fig. 6. (a) SEM micrograph of the GO–S nanocomposite with the illustration of GO immobilizing with sulfur, (b) TEM bright field (BF) micrograph and the elemental
mapping for carbon and sulfur including EELS spectrum. The scale bars are 50 nm, (c) cyclability at 0.1 C after initial activation processes at 0.02C for two cycles, (d)
C-rate performance. (reprinted with permission from Ref. [42], Copyright 2011, American Chemical Society). (e) Schematic of the g-C/S composite synthesizing process, (f)
STEM micrographs of the g-C/S composite and the elemental mapping images of carbon, nitrogen, oxygen, and sulfur with scale bars of 500 nm, (g) cyclability of the g-C/S
composite at various current densities. (Reproduced from Ref. [43] with permission from The Royal Society of Chemistry, Copyright 2015).
heat treatment at 230 ͦC. Beneficially, volume expansion of sul- posite without PE-ALD of Al2 O3 , indicating polysulfide dissolution.
fur during lithiation was accommodated by mesopores which were However, 30-ALD and 50-ALD demonstrated good cyclability up to
created by the PE-ALD process (Fig. 8(b)). The cyclability of the 800 cycles. This demonstrates that metal oxide PE-ALD will sup-
Al2 O3 layered S-ACF composite with 0, 30, and 50 cycles of ALD, press the polysulfide dissolution effectively. Furthermore, interme-
namely no-ALD, 30-ALD, and 50-ALD, was tested for 800 cycles at diate polysulfide deposition was observed by SEM after cycling
0.2 C (Fig. 8(c)). Rapid fading was observed for the S-ACF com- (Fig. 8(d)).
Fig. 7. (a) TEM and (b) SEM micrographs of AF-rGO/S nanocomposite after 350 cycles with scale bar of 100 nm and 5 μm, respectively. (c) and (d) Elemental mapping of
carbon and sulfur in the composite, respectively. (e) TEM and (f) SEM micrographs of rGO–S nanocomposite 150 cycles with scale bar of 100 nm and 5 μm, respectively.
(g) and (h) Elemental mapping of carbon and sulfur, respectively. DFT calculation showing the interaction bonding between Li2 S and (i) graphene or (j) and (k) EFG. (l)
Cyclability of each sample. (Reprinted with permission from Ref. [44], Copyright 2014, Springer Nature).
Chung et al. proposed a facile suppression of polysulfide disso- the mesoporous carbon/sulfur composite (MC/S). As a result, the
lution through a carbon-coated separator (Fig. 8(e)) [48]. The car- initial discharge capacity of 1140 mAh g−1 using the PEDOT:PSS
bon coating layer was synthesized by the addition of conductive coating was improved compared to the uncoated MC/S compos-
carbon (Super P) to a polymeric separator (Celgard). Moreover, the ite initial discharge capacity of 1051 mAh g−1 . Furthermore, the
thin one-sided carbon layer offered great flexibility (Fig. 8(f)). The PEDOT:PSS-coated MC/S composite showed less pronounced capac-
carbon layer consisted of porous nanoparticle clusters which acted ity fading compared to the uncoated composite indicating the ben-
as a barrier to hinder and immobilize intermediate polysulfide. efit of conductive polymer coating in reducing polysulfide dissolu-
The LSBs carbon-coated separator demonstrated outstanding cycle tion (Fig. 9(b)). In addition, the PEDOT:PSS-coated MC/S compos-
stability and high performance with discharge capacities of 1389, ite demonstrated higher coulmbic efficiency greater than 95% for
1289, 1220, and 1045 mA h g−1 at 0.2, 0.5, 1, and 2 C, respectively, 100 cycles while the uncoated C/S composite demonstrated lower
compared to the uncoated separator (Fig. 8(g)). The stability pro- coulombic efficiency under 95% (Fig. 9(c)).
vided by the carbon layer is further corroborated by cyclic voltam- Surface passivation is a great strategy to prevent polysulfide
metry which shows concurrent reduction and oxidation peaks dur- dissolution by physical or chemical means. Even more, this ap-
ing cycling (Fig. 8(h)). proach utilizes a uniform coating with the opportunity to tune
Yang et al. reported a conductive polymer layer of poly(3,4- the passivating layer thickness, in the case of ALD. However, this
ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) for approach is rather dynamic. In pursuit of high-performance LSBs,
polysulfide confinement and adsorption (Fig. 9(a)) [49]. The CMK- one needs to consider the increase of resistivity between the
3 PEDOT:PSS-coated nanocomposite improved the performance of passivating layer and electrode interface. Moreover, a conductive
Fig. 8. (a) Schematic of synthesizing of ALD coated S-ACFs, (b) illustration of alumina coating around S-ACF, (c) sulfur to carbon ratio during charge/discharge process, (d)
SEM micrograph of non-Al2 O3 sample, showing the dissolved and deposited polysulfide particle. (Reprinted with permission from Ref. [47], Copyright 2013, WILEY). (e) Roll
of carbon layer coated on separator (f) Flexibility of carbon coated separator, (g) cycle abilities and (h) cyclic voltammogram of sample with carbon coated (reprinted with
permission from ref. [48], Copyright 2014, WILEY).
coating has more beneficial properties regarding electron transport 2.2.3. Multi-component materials
but may not optimally prevent polysulfide dissolution. For this In this section, we discussed the multi-component materials
strategy, matching between the chemical coating species and the such as ferromagnetic nanoparticles, metal oxide, sulfides, nitrides,
sulfur matrix interface will most likely lead to more advanced and and so on. Magnetism is an interesting avenue, which is not
high-performance LSBs. In addition, it is not easy to design large- fully explored, towards increasing the performance of secondary
sized Li–S battery using ALD technique. For pratical application, batteries, mainly LSBs. There are many materials that are con-
above issues have to be addressed. ductive and yield magnetic properties, for example, spinel-type
Fig. 9. (a) Scheme of PEDOT:PSS coated mesoporous C/S composite, (b) cyclability of bare C/S composite and PEDOT:PSS coated C/S composite, (c) Coulombic efficiency
comparison of both samples in the first 100 cycles. (Reprinted with permission from Ref. [49], Copyright 2011, American Chemical Society).
iron(II, III) oxide (Fe3 O7 ) is one such species that demonstrates (Fig 10(c)). If reproduced successfully, this mechanism-type may
high conductivity and magnetic properties. Recently, a rotating lead to new advanced nanostructures for high-performance LSBs.
magnetic field induced onto graphite flakes functionalized with It was reported that the metal oxides such as VO2 –VN and
highly paramagnetic nanoparticles has been demonstrated to TiO2 –TiN can suppress the polysulfide dissolution from cathode to
increase the lithium-ion loading in graphite electrodes for LIBs electrolyte by trapping and immobilization mechanism. The Sul-
and thus increase the electrochemical performance [53]. Likewise, fur cathode fabricated with a twinborn TiO2 –TiN heterostructure
there are further reports of using induced magnetic fields to in- composite can deliver an outstanding cyclability with good dis-
crease the capacity of nanocomposites in graphene electrodes and charge capacity of 704 mAh g−1 at 20 0 0th cycle [59,60]. Fur-
electrochemical capacitors [54,55]. Notably, an applied magnetic thermore, perovskite-based materials such as La0.6 Sr0.4 CoO3-δ and
field was shown to concentrate lithium polysulfides in a flow Ba0.5 Sr0.5 Co0.8 Fe0.2 O3−δ can immobilize the polysulfide by chemi-
battery [56]. Xie et al. applied this phenomenon to LSBs with cal bonding between lithium and oxygen or sulfiphilic and sulfur,
ferromagnetic spontaneous polarization and demonstrated a new resulting in high rate performance with low capacity decay rate of
approach for polysulfide trapping by ferroelectric barium titanate 0.062% for 200 cycles [61,62].
(BaTiO3 ) nanoparticles [57]. By trapping lithium polysulfides with We have described recent advancements to suppress polysulfide
spontaneous polarization in an electric field, ferromagnetism was dissolution using metal chalcogenide additives, graphene-oxide,
pursued in LSBs to realize polysulfide trapping with magnetism. passivating layers, and a novel ferromagnetic mechanism. These
Gao et al. discovered a new mechanism coined the shield- approaches demonstrated lower capacity fading and higher cycling
ing effect for suppressing polysulfide dissolution through magnetic stability because of improved coordination with intermediate poly-
field trapping via ferromagnetic nanoparticles [58]. They prepared sulfides that led to stronger binding properties. In the next section,
an in-situ activated cotton textile with iron/iron carbide (Fe/Fe3 C) we discuss recent advancements towards enhancing the low con-
nanoparticles wrapped by graphene nanosheets (Fe/Fe3 C/G). The ductivity of sulfur through sulfur-porous carbon nanocomposites,
possible mechanism proceeds by altering the diffusion behavior hollow linear carbon nanostructures, core-shell nanoarchitectures,
of intermediate polysulfides formed by an induced magnetic field and graphene-sulfur nanomaterials. The synthetic approaches, dis-
upon the surface of sulfur nanoparticles which are uniformly discussed below, are likely to contribute towards new novel and ro-
tributed on the Fe/Fe3 C/G nanoparticles during cycling. The au- bust nanostructures which demonstrate higher discharge capac-
thors suggest Lorentz force as the mechanism which causes dis- ity, higher coulombic efficiency, and cycle stability for future high-
solved polysulfides to diffuse back to the cathodic region where performance LSBs.
they remained trapped. The synthesis is a two-step process that
combines the cotton textile soaked in iron nitrate (Fe(NO3 )3 ) that 2.3. Improvement of low conductivity of sulfur
is dried and heated at 10 0 0 °C for 1 h (Fig 10(a)). The high-
temperature heating treatment activates the cotton textile, and a 2.3.1. Sulfur-porous carbon composite
graphene shell is formed around the Fe/Fe3 C nanoparticles. Sul- Porous carbon materials have been investigated heavily because
fur is loaded via melt-diffusion at 155 °C and becomes well dis- of their ability to confine sulfur while enhancing conductivity.
tributed on the surface of Fe/Fe3 C/G. Notably, the cell demonstrates These materials may contain micro-, meso–, or macropores which
a specific discharge capacity of 764 mA h g−1 , outstanding rate have diameters of less than 2 nm, between 2 and 50 nm, and
performance, and long-term cycling up to 600 cycles (Fig. 10(b)). above 50 nm, respectively. Synthesis of porous carbon nanos-
The possible polysulfide trapping mechanism due to ferromagnetic tructures has been widely applied to LSBs and many novel
nanoparticles is visually observed and demonstrates a concentrated micro/mesoporous nanostructures have been realized for high-
area of intermediate polysulfides contained in the cathodic region performance LSBs [63–71]. Generally, the distribution of sulfur
Fig. 10. (a) Schematic of ACT@Fe/Fe3 C nanoparticles, (b) long-term cycling performance of ACT@Fe/Fe3 C at 0.4 C from 50 to 600 cycles, (c) visual test of polysulfide trapping
concentrated at the cathode after 4 h operation. (Reprinted with permission from Ref. [58], Copyright 2018, WILEY).
within micropores increases the capacity of LSBs greatly due to a unique supercritical CO2 fluid method for sulfur loading (Fig.
high contact of sulfur and carbon. Sulfur distributed within carbon 11(a)). Surface modification of nickel(II) hydroxide was carried out
mesopores has more contact between the electrolyte which im- through chemical deposition in a base bath. The cell performance
proves ion-mobility of lithium. Aside from tuning the porosity of of the surface-modified nanocomposite was compared to the un-
carbon nanomaterials, there should be attention paid towards pro- modified nanocomposite and the melt-diffusion loaded nanocom-
moting kinetics through electrocatalysis. To increase reaction kinet- posite, respectively (Fig. 11(b)). The results from the characteristic
ics, one could improve the ion transport throught carbon matrices curve show a high capacity of 1335 mA h g−1 at 0.1 C and low-
[72,73]. This would accelerate the conversion of sulfur species by ered activation energy compared to the control nanocomposites.
continuous lithium-ion transport. Furthermore, one could lower The lower activation energy is an indicator of higher charge mobil-
the energy barrier and increase redox reaction efficiency of sulfur ity and demonstrates superior ionic transport pathways compared
species by addition of polar catalytic sites in the cathode [74,75]. to the control. Furthermore, this nanocomposite demonstrates ex-
Recently, Xin et al. demonstrated confinement of intermedi- ceptional rate performance (Fig. 11(c)). The effects of surface mod-
ate low-order polysulfide species in which conversion of low- ification show strong binding of Ni(OH)2 with intermediate poly-
order polysulfides to high-order polysulfides was inhibited (Li2 Sn , sulfides and suppression of polysulfide dissolution is demonstrated
n = =3–8) [76]. While micropores hinder the formation of high- after 100 cycles (Fig. 11(d)) [122].
order polysulfides and accommodate the volume expansion of sul- Wu et al. synthesized a ‘swiss cheese-shaped’ nitrogen-doped
fur upon lithiation, the formation of soluble polysulfides in carbon sulfur/carbon nanomaterial with a 3D porous structure of multi-
mesopores, although suppressed, is still an issue to be addressed. porosity [64]. This hierarchical porous nanocomposite was synthe-
Herein, we review nanoscale sulfur-porous carbon composite ma- sized from a sacrificial zinc chloride (ZnCl) salt template and sili-
terials and comment on the strategies using nanotechnology to im- con oxide (SiO2 ) hard template (Fig. 11(e)). Sulfur was loaded into
prove the low conductivity of sulfur. the nanostructure through dissolution and evaporation with a car-
Xia et al. synthesized a porous carbon nanocomposite mate- bon disulfide (CS2 ) medium. The morphology and dispersity of sul-
rial from natural yeasts as a carbon source and biological tem- fur were measured by SEM and elemental mapping (Fig. 11(f) and
plate. In addition, this nanocomposite material was surface mod- (g)). The balance of micro- and mesoporosity allowed for high uti-
ified with nickel(II) hydroxide (Ni(OH)2 ). The synthesis proceeds lization of sulfur, high coulombic efficiency, and outstanding cycla-
through hydrothermal synthesis and heat treatment followed by bility. The inner space of this structure accommodates the volume
Fig. 11. (a) Schematic of Ni(OH)2 @PYC/S synthesis, (b) characteristic charge/discharge of Ni(OH)2 @PYC/S, PYC/S, and PYC/S-155, (c) rate performance of Ni(OH)2 @PYC/S, (d)
visual test of polysulfide binding by PYC@S and Ni(OH)2 @PYC/S. (Reprinted with permission from Ref. [122], Copyright 2018, Elsevier), (e) schematic of HPNC-S nanocom-
posite, (f) SEM micrograph of HPNC-S composite and its (g) elemental mapping, (h) long-term cycling performance of HPNC-S at 0.2 C. (Reprinted with permission from Ref.
[64], Copyright 2018, Elsevier).
expansion of the conversion of sulfur to lithium sulfide. Even more, ning and hydrothermal treatment (Fig. 12(a)). The source of sul-
this lithium-sulfur half-cell delivered a high discharge capacity of fur came from thioacetamide before hydrothermal synthesis. The
623 mA h g−1 at 2 C and maintained a capacity of 520 mA h g−1 hollow interior containing CNTs allows for facile sulfur loading
after 300 cycles at 0.2 C indicating a capacity loss of 0.13% per cy- through capillary effect with uniform distribution (Fig. 12(b)). The
cle (Fig. 11(h)). conductivity of sulfur is not only enhanced by the CNTs but
Porous–sulfur composite materials are among the most heav- is also increased by the catalytic reactivity of CoS nanostraws.
ily investigated nanomaterials for LSBs. These composites are used Furthermore, the CoS nanostraws provides strong chemisorption
prominently because sulfur distributes within the pores of the binding sites for lithium polysulfides. Moreso, the increased elec-
composites with ease and intimate contact between sulfur and the trocatalytic conversion of intermediate lithium polysulfides is
conductive porous carbon matrix is increased. This approach usu- demonstrated by smaller hysteresis of S@CNTs/CoS–NS character-
ally yields high-performance LSBs when a combination of micro- istic charge/discharge curves compared to S/CoS–NS and S/CNTs
and mesoporosity in the composite is obtained. For this approach, characteristic charge/discharge curves. The tubular S@CNTs/CoS–NS
a balance is needed between micro-, meso–, and macroporosity. nanostructure delivered excellent rate capability with a capacity
Preferably, the templated-synthesis of a porous carbon composite of 573 mA h g−1 compared to 165 and 100 mA h g−1 for S/CoS-
with few macropores in the core of the carbon matrix, a higher NS and S/CNTs, respectively. This cell demonstrated long-term cy-
amount of mesopores surrounding the macropores, and an even clability with very high stability (Fig. 12(c)). Furthermore, their
greater volume of micropores surrounding the meso–/macropores lithium-sulfur half-cell had a capacity of 675 and 572 mA h g−1
should be most ideal. Few macropores in the core would al- after 10 0 0 cycles at 1 C and 2 C-rates, respectively, with a high
low for high sulfur loading but would need to prohibit sulfur and stable coulombic efficiency.
agglomeration. Ni et al. synthesized MnO2 nanosheet-coated hollow carbon
Engineering mesoporous carbon with ionic tunnels would coaxial nanofibers through an electrospinning and carbonization
greatly improve rate performance through mass Li-ion transport process which was followed by an in-situ redox mechanism
and while still allowing for high sulfur loading and quick con- for MnO2 nanosheet growth [79]. Sulfur was loaded into the
version of sulfur species. A high density of micropores in the nanofibers via melt-diffusion at 155 °C (Fig. 12(d)). They confirmed
outer composite would prevent high-order polysulfides from form- the hollow nanofiber structure and uniform distribution of sulfur
ing while still retaining intimate contact between sulfur and the sandwiched between carbon and the MnO2 nanosheets using SEM
conductive carbon matrix. The use of natural carbon from biomass and EDX (Fig. 12(e)). This strategy to enhance the electric conduc-
may provide a cheap path towards engineering ionic tunnels tivity of sulfur while suppressing polysulfide dissolution was very
within the carbon matrix. effective. A specific discharge of 1248 mA h g−1 at 0.1 C and an
exceptional rate capability of 670 mA h g−1 at 2 C was demon-
2.3.2. Hollow carbon materials strated (Fig. 12(f)). After 300 cycles, a capacity of 600 mA h g−1
Hollow carbon fibers are investigated due to their excellent me- at 1 C was achieved (Fig. 12(g)). Even better, the cell maintained
chanical properties, high electrical conductivity, and unique surface long-term cycling up to 10 0 0 cycles at a rate of 1 and 2 C. This
states. These nanomaterials facilitate surface functionalization and strategy yielded stable long-term cycling by manipulation on the
can be tailored to specific applications. In addition, a hollow inner- nanoscale and paved the way for longer-lasting LSBs.
tube increases the surface area greatly for these materials and is Hollow carbon nanomaterials provide more surface area and in-
beneficial for improving the sulfur loading amount in LSBs. Surface creased conductivity due to higher sulfur adsorption to the car-
functionalization of hollow carbon fibers combined with a high bon surface compared to linear carbon materials. These nanos-
sulfur loading reduces capacity fading from the entrapment of in- tructures offer an interconnected network that creates abundant
termediate polysulfides and increases in the capacity and cycle sta- electron transport pathways and, in turn, increases reaction ki-
bility. Herein, we review nanoscale hollow carbon materials and netics. To maximize the capacity of LSBs, sulfur cathodes utiliz-
comment on how nanomaterials of these structures improve LSBs ing this strategy should strive for long linear hollow carbon ma-
performance [77–87]. trices with a small tubular diameter. This approach will facilitate
Liu et al. reported sulfur-loaded hollow porous carbon sulfur nanoparticle adsorption within the hollow tubes/fibers. Fur-
nanotubes functionalized with manganese(II) oxide nanoflakes thermore, a decreased diameter of the hollow structure helps pre-
(p-CNT@Void@MnO2 /S) using a sacrificial template and melt- vent sulfur agglomeration and thus lower the resistance experi-
diffusion method [77]. The p-CNT@Void@MnO2 /S has a large inner enced during battery operation.
void of 79%. It offers enough space for a high density of sul-
fur and accommodates the volume change of sulfur cathode dur- 2.3.3. Core-shell nanostructure
ing charge/discharge. Furthermore, manganese(II) oxide does not Core-shell nanostructures represent an ideal material for LSBs
have a high conductivity but is known to oxidize polysulfides because they accommodate the volume expansion of sulfur, im-
into surface-bound thiosulfates and suppress polysulfide dissolu- prove capacity significantly through intimate contact between sul-
tion. This proceeds through strong chemisorption with interme- fur and the matrix, increase the cycle stability for longer-lasting
diate polysulfides through disproportionation reactions to yield a secondary batteries, and physically entrap or stop intermediate
poly-thiosulfate layer [88,89]. A dual-effect of polysulfide suppres- polysulfide formation [90–99]. Even better, the sulfur content and
sion and enhanced capacity are achieved by the close contact and loading are greatly increased compared to carbon nanotubes or
surface functionalization of MnO2 and the hollow CNTs. They noted nanofibers. Core-shell nanostructures are unique because of the
that the long-term cycle stability of p-CNT@Void@MnO2 /S might variability in shell and core compositional morphologies that can
be attributed to a reduction in sulfur agglomeration at the surface range from zero to three dimensional systems. Core-shell nanos-
sites of the CNT. This was confirmed by electrochemical impedance tructures may also be further coated to form dual or multi-shell
spectroscopy. The p-CNT@Void@MnO2 /S demonstrated a discharge complexes. Typically, the shell is reported as transition metal
capacity of 562 mA h g−1 after 100 cycles at 1 C. Even more, high chalcogens, conductive polymers, metal nanoparticles, graphene
coulombic efficiency and good cyclability were achieved. nanosheets, or carbon with micro/mesoporosity. This protective
Ma et al. prepared crisscrossed CNTs fortified with hollow CoS coating benefits LSBs because intermediate polysulfide formed are
nanostraws for improving the capacity and stability of LSBs [78]. physically trapped and are not dissolved into the electrolyte [100].
The CNTs/CoS-NS nanostructure was synthesized via electrospin- Likewise, conversion of sulfur to lithium sulfide, an approximately
Fig. 12. (a) Schematic of S@CNT/CoS-NS synthesis and sulfur loading, (b) SEM and EDX imaging of S@CNT/CoS-NS, (c) long-term cycling performance of S@CNT/CoS-NS for
10 0 0 cycles at 1 and 2 C-rates. (Reprinted with permission from Ref. [78], Copyright 2018, American Chemical Society), (d) schematic of the synthesis process of S@C/MnO2 ,
(e) TEM micrograph of S@C/MnO2 nanofiber and EDX elemental mapping of C, O, Mn, and S, (f) rate performances of S@CMnO2 and bare sulfur at various C-rates, (g)
long-term cycling performance and coulombic efficiency of S@CMnO2 for 300 cycles at 1 C. (Reprinted with permission from Ref. [79], Copyright 2017, WILEY).
~80% increase in volume, will be accommodated in the case of Jin et al. recently prepared a multi core-shell nanocomposite
core-shell materials with a yolk-shell architecture. Herein, we re- material using the metal-organic framework (MOF) MIL-101(Cr)
view the recent nanotechnologies using core-shell nanostructures as the main core component [91]. Notably, MIL-101(Cr) was syn-
and comment on the strategies taken for advanced and high- thesized by a one-step hydrothermal treatment (Fig. 13(c)) and
performance LSBs. would be beneficial in the industry as a cheap and fast production
Recently, Li et al. demonstrated hollow polypyrrole functional- option. Moreover, MOFs are characterized by their well-defined
ized MnO2 nanospheres as a sulfur host for a high-performance shapes (Fig. 13(d)). In this study, sulfur was loaded into MIL-
core-shell nanostructure for LSBs [90]. The in-situ synthesis was 101(Cr) via melt-diffusion (155 °C) and was doped with poly(3,4-
facile and involved redox reaction between manganese(I) carbon- ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) mul-
ate (MnCO3 ) and potassium permanganate (KMnO4 ), acid etching, tiple times to obtain a uniform coating. In addition, the sul-
melt-diffusion to load sulfur, and coating with polypyrrole (Fig. fur distribution was uniform throughout the MOF nanostructure
13(a)). The conductive polypyrrole coating of ~55 nm enhanced observed by TEM and elemental mappings (Fig. 13(e)–(g)). Even
the capacity of the sulfur nanoparticles that were confined within more, the structure of MIL-101(Cr) enables a high sulfur content
the core through high interfacial contact. In addition, this nanos- due to mesoporosity and high surface area. The conductive PE-
tructured demonstrated a superior rate performance and long- DOT:PSS polymer layer confines and suppresses polysulfide disso-
cycle life, outstanding cycling retention, and high coulombic effi- lution through steric blocking. As suspected, the conductive layer
ciency. The cell exhibited a specific discharge of 1488 mA h g−1 at enhances the discharge capacity of the MIL-101(Cr)/S nanocom-
0.1 C. Furthermore, a capacity decay rate of 0.048% per cycle was posite (Fig. 13(h)). This cell demonstrated a high specific dis-
achieved during 500 cycles at 0.5 C with a high areal capacity of charge of ~1440 mA h g−1 and exhibited a reversible capacity of
3.3 mg cm−2 (Fig. 13(b)). 607 mA h g−1 after 192 cycles at 0.1 C, respectively.
Fig. 13. (a) Schematic of PPy@MnO2 @S synthetic route, (b) long-term cycle performance. (Reprinted with permission from Ref. [90], Copyright 2018, Elsevier). (c) Schematic
of BPCS synthesis, (d) SEM micrograph of MIL-101(Cr), (e)-(g) TEM micrograph of BPCS and EDX micrographs of C and S, respectively, (h) charge/discharge curve of BPCS (red)
and MIL-101(Cr)/S@PEDOT:PSS. (This figure by W.W. Jin, is licensed under CC by 3.0., 2018, [91] The Royal Society of Chemistry), (i) HRTEM micrograph of Fe3 O4 @S-CNT-2
showing core-shell structures, (j) long-term cycling performance of Fe3 O4 @S-CNT-1 Fe3 O. (Reprinted with permission from Ref. [92], Copyright 2018, Elsevier).
Gao et al. reported an iron (II,III) oxide (Fe3 O4 )/sulfur core-shell sulfur battery demonstrated a high capacity of ~775 mA h g−1 at
nanostructure where sulfur was layered around Fe3 O4 nanopar- 1 C. Moreover, long-term cycle stability was established with a ca-
ticles (8–10 nm) [92]. Interestingly, sulfur was the shell compo- pacity of ~450 mA h g−1 after 500 cycles at 1 C and coulombic ef-
nent. These core-shell nanostructures, about 20–30 nm in size, ficiency of ~95%. During the charge/discharge process, the capacity
were embedded and coated on oxidized CNTs (Fig. 13(i)). The ra- reduced from 914 to 649 mA h g−1 1 after 20 cycles with a capacity
tio of Fe3 O4 /S core-shell nanostructure and CNTs were 0.5, 1.0, and retention of ~70% was achieved from 20 to 500 cycles (Fig. 13(j)).
1.5 mL of Fe3 O4 /S in the oxidized CNT suspension (0.01 g mL−1 ), Core-shell carbon nanocomposites are likely to offer the best
respectively. All ratios that were investigated showed superior rate approach to achieving high-performance LSBs. These types of
performance. Notably, the 1.5 mL CNT ratio demonstrating a high nanostructures facilitate sulfur nanoparticle loading with increased
capacity of ~480 mA h g−1 at 5 C. However, Fe3 O4 /S core-shell capacity and long-term cycle stability. Equally important, the is-
nanoparticles added to the 1.0 mL CNT suspension exhibited the sue of volume expansion is resolved with this type of approach
highest capacity and long-term cyclability at 1 C. This lithium- due to the encapsulation of sulfur within a large void. The best
Fig. 14. (a) Schematic of N-doped graphene with sulfur, TEM micrograph of (b) N-doped graphene and (c) sulfur composite, (d) charge/discharge curve of N-doped graphene-
sulfur composite, and (e) cyclability for 20 0 0 cycles. (Reprinted with permission from Ref. [102], Copyright 2014, American Chemical Society).
approach, utilizing core-shell nanostructures may be realized with this nanostructure ideal for lithium polysulfide chemisorption. The
the synthesis of hierarchical core structures and conductive shell lithium-sulfur cell demonstrated strong chemisorption character-
which strongly binds intermediate polysulfides. Hierarchical core- istics with polysulfides, fast sulfur-conversion kinetics, high cycle
conductive shell nanostructures have demonstrated increased sul- stability, superior rate capability, and a high sulfur loading. The
fur loading with contact between carbon and sulfur while improv- cycle performance of PNG was compared against nitrogen-doped
ing the ionic and electronic charge transfer pathways, respectively. graphene and plain graphene. This cell had a cycle decay rate of
Notably, the properties of the conductive shell should have poly- 0.099% after 300 cycles at 0.5 C, an impressive rate capability of
sulfide binding properties that ensure the suppression of dissolved 988 mA h g−1 at 2 C, and a sulfur loading and areal capacity of
polysulfides. 8.9 mg cm−2 and 8.81 mA h cm−2 were achieved, respectively.
Qiu et al. studied nitrogen-doped graphene (S@NG) nanocom-
posite for ultra-long cycling LSBs where 20 0 0 cycles were achieved
2.3.4. Graphene–sulfur nanocomposites
[102]. The nitrogen-functionalization of graphene demonstrated
Graphene has been used in a variety of nanomaterials to en-
strong polysulfide binding (Fig. 14(a)). Moreso, the graphene
hance sulfur conductivity in LSBs due to the high surface area
nanosheets wrapped around the sulfur nanoparticles and this
and superior conductivity. The large surface area of graphene
configuration positively impacted the nanomaterials’ performance
allows for increased kinetics during LSBs operation while the
(Fig. 14(b) and (c)). Furthermore, a high sulfur content of 60%
supreme conductivity of graphene improves the electron transport
was achieved by applying a nanostructure and lead to a high spe-
within the cathode. Also, graphene is easily oxidized or reduced
cific discharge capacity with outstanding rate performance at 5 C
for surface-functionalized modification. Graphene is also mechan-
(Fig. 14(d)). The high performance exhibited by the 7 lithium–
ically and chemically stable. These characteristics make graphene
sulfur cell might be attributed to the high surface area and conduc-
an ideal host for increasing the conductivity of sulfur [101–109].
tivity of graphene in addition to polysulfide binding by nitrogen.
In fact, many graphene nanomaterials with unique configurations
They demonstrated high cell performance with a specific discharge
and surface functionality that have improved the electrochemical
capacity of 1058 and 606 mA h g−1 at 0.5 and 5 C, respectively.
performance of LSBs are reported [110–114]. Herein, we review
Even better, the cell has shown long-term cycling up to 20 0 0 cy-
graphene-incorporated nanomaterials for enhancing the low con-
cles with a low capacity decay-rate of 0.028% per cycle at 2 C (Fig.
ductivity of sulfur for high-performance LSBs.
14(e)).
Kong et al. synthesized porphyrin-functionalized graphene
nanosheets to enhance the conductivity of sulfur [101]. A thin
layer was grown on graphene through the nucleated growth of 2.4. Increasing density of sulfur
the porphyrin organic framework (POF). This layer was conformal
due to strong π -π orbital overlap between the POF and graphene In the previous section, we described different synthetic ap-
nanosheets. After the pyrolysis of POF, graphene was nitrogen- proaches which yielded novel nanostructures to improve the low
doped because of the nitrogen-rich backbone in the POF. The por- capacity of sulfur for more advance LSBs. Herein, we examine dif-
phyrin nanosheet (PNG) not only strongly adsorbs intermediate ferent strategies for increasing the density of sulfur in cathodes
polysulfides but is highly conductive and adds to the superior of LSBs by 3D structured materials. 3D structured materials offer
conductivity of graphene. More so, a polar surface of PNG makes more surface area and complex hierarchical architectures which al-
Fig. 15. (a) A schematic diagram of fabricating the 3D Ni/S composite by electrodeposition, (b) SEM micrographs of Ni foam, sulfur deposited Ni foam with the elemental
mapping, (c) cycling performance of 3D Ni/S cathodes with different S content and bulk S cathode, (d) cycling performance with coulombic efficiency of 3D Ni/S cathodes
(0.45 mg/cm2 ) and bulk S (0.50 mg/cm2 ). (Reprinted with permission from Ref. [120], Copyright 2015, American Chemical Society), (e) a lightweight N,S-doped graphene
sponge standing on a dandelion, (f) the formation process of the N,S-doped graphene electrode prepared by polysulfide catholyte, (g) cycling performance and coulombic
efficiency of N, S-doped graphene with sulfur at 0.5 C rate for 200 cycles. (This figure by Q. Zhou, is licensed under CC by 4.0., 2015, [120] Springer Nature).
Fig. 16. (a) Illustration of synthesis of N-graphene nano-hollows as sulfur host, (b) TEM micrograph, (c) SEM micrograph and element mapping, (d) cyclability for 160 cycles
depending on sulfur loading amounts. (Reproduced from Ref. [118] with permission from The Royal Society of Chemistry, Copyright 2018), (e) schematic of 3d Graphene-
Foam, (f) and (g) XRM 3D projections of the reconstructed GF–rGO/S cathode, (h) cyclability of GF-rGO/S (reprinted with permission from Ref. [20], Copyright 2016, WILEY).
low for greater sulfur loading in a nanoconfined space. These types was tested at sulfur loadings of 2.3, 5.5, and 10.1 mg cm−2 . All
of structures will increase the energy density of sulfur cathodes lithium–sulfur cells of different loading demonstrated outstanding
and enable the LSBs to penetrate the EVs and large-scale electric cell stability during 160 cycles (Fig. 16(d)). The PSSN/S nanocom-
energy storage market. posite material represents new success in achieving LSBs with high
sulfur density, increased capacity, and suppressed polysulfide dis-
2.4.1. 3D structured materials solution using nanotechnology.
We discussed the low electrical conductivity of sulfur and how Hu et al. prepared a 3D graphene foam by a chemical vapor
carbon materials of high electrical conductivity are then applied deposition [20]. This free-standing 3D structure offers chemical
to sulfur-based cathodes to take advantage of the insulating na- and physical advantages such as strong lithium polysulfide bind-
ture of sulfur. However, sulfur cathodes which contain carbon addi- ing, high electrical conductivity, porosity, and an interconnected
tives that demonstrate high-capacity typically have low sulfur den- conductive network as shown in Fig. 16(e). In the X-ray microto-
sity compared to other commercial electrode materials which have mography micrographs (XRM), a 3D visual of uniform sulfur distri-
good electrical conductivity and a higher active material density. To bution and infiltration is observed (Fig. 16(f) and (g)). The lithium-
solve this issue, 3D structured materials, such as 3D metal foams, sulfur cell demonstrated a high sulfur loading of 14.36 mg cm−2
have been investigated to increase the density of sulfur for higher and a high areal capacity ~10 mAh cm−2 . Moreso, after cycling, the
volumetric energy density in LSBs [115–119]. In this section, vari- areal capacity was ~6 mAh cm−2 after 350 cycles at 0.2 C which
ous 3D structured materials that improve upon the sulfur density is higher than LiCoO2 , a common cathode for LIBs, with an areal
for higher electrochemical performance in LSBs will be introduced. capacity between 3 and 4 mA g cm−2 . The cyclability of GF-Go/S
To increase the low sulfur density, Nara et al. prepared a 3D was compared to LIBs for over 350 cycles (Fig. 16(h)). Synthesizing
structured aluminum foam current collector to increase the load- 3D structured graphene-based materials is considered a promising
ing density of sulfur for high areal capacity [115]. The 3D struc- strategy to improve the sulfur loading density and volumetric en-
tured aluminum foam was loaded with sulfur via melt diffu- ergy density of LSBs.
sion at 155 °C. A 3D single-layered pouch cell was fabricated 3D structured materials have demonstrated the ability to
using a lithium/copper anode and demonstrated a high sulfur achieve higher sulfur densities due to the increased surface area
loading amounts of 17.7 mg cm−2 with a high areal capacity of for greater sulfur coordination. Increasing sulfur density in the
21.9 mA h cm−2 . The sulfur–carbon composite using 3D aluminum cathode is importance as this will contribute to a higher energy
foam established the possibility of an improved energy density of density and allow LSBs to surpass conventional LIBs in the market
greater than 200 W h kg−1 . The high loading density of sulfur with place. A majority of LSBs cathode possess less than 2 mg cm−2
high areal capacity was obtained using micro-scale 3D structured areal sulfur loading [121]. Furthermore, an areal sulfur loading
aluminum foam, but poor cyclability still remains a challenge. To greater than 8 mg cm−2 is needed to be compete with current
solve this issue, the nano-scale sulfur dot was applied. Zhao et al. LIBs, a low electrolyte/sulfur ratio is needed due to high molec-
prepared a 3D structured nickel foam for increased sulfur density ular weight of the electrolyte, a high fraction of sulfur in the ac-
[120]. Sulfur nanoparticles were loaded in the 3D nickel foam by tive material to achieve a high volumetric density. These are tough
electrodeposition (Fig. 15(a)). A uniform distribution of sulfur in- challenges to overcome due to a lower operating potential voltage
filtration was confirmed by SEM and EDX (Fig. 15(b)). The aver- for LSBs compared to commercialized LIBs.
age diameter of distributed sulfur nanoparticle was ~2.0 nm. This To the density of sulfur, we recommend using a combination
lithium-sulfur cell exhibited a high sulfur density of 4.79 mg cm−2 of 1D and 2D materials to form a free-standing electrode. Free-
with a good areal capacity of 2.01 mAh cm−2 after 50 cycles at standing materials do’ not require a binder and therefore allow a
0.2 C (Fig. 15(c) and (d)). higher density of sulfur within the cathode. Moreover, mimicking
Zhou et al. prepared a nitrogen and sulfur (N/S) co-doped 3D 3D structures in nature may provide a good route towards the de-
structured graphene sponge from plant material for high energy sign of high sulfur density cathodes. There are many nanoscale hi-
density LSBs (Fig. 15(e)) [117]. This strategy offered a light-weight erarchical structures in nature, when mimicked, that deliver highly
material for improving sulfur density, large pore volume for high ordered and high surface area structures. For example, the morpho
sulfur loading, and reduced polysulfide dissolution through strong butterfly wing contains a unique hierarchical nanostructure with
nitrogen-sulfur adsorption properties. The rGO sponge was syn- high surface area that may be advantageous for LSBs.
thesized by a combination of a hydrothermal and freeze-drying
method (Fig. 15(f)). The N/S co-doped rGO sponge provides a 3. Conclusions and perspectives
strong bonding strength between intermediate polysulfides and
rGO surface, high electrical conductivity, and acts as a buffer to In this review, we have systematically discussed the back-
volume expansion of sulfur during the charge/discharge process. ground, electrochemical mechanism, and current challenges faced
As a result, the lithium-sulfur cell demonstrated outstanding cy- with LSBs. We have concentrated on a nanotechnological approach
cle stability with 0.078% capacity fading per cycle for 500 cycles for solving issues towards the commercialization of LSBs for EVs
and a high sulfur loading amount of 8.5 mg cm−2 (Fig. 15(g)). and large-scale electric energy storage. As mentioned in the intro-
Tang et al. reported a functionalized pomegranate-like carbon duction, nanoscience and nanoengineering have been widely used
hollow-nanostructure through self-assembly (PSSN) [118]. With in chemistry, biology, environmental science, medical science, and
this 3D nanostructure, an ultra-high surface area and sulfur load- other fields because of the unique properties materials exhibit on
ing of 10.1 mg cm−2 was demonstrated. Prussian blue (PB) and glu- the nanoscale. For that reason, we focused on strategies that ad-
cose (1: 0.3 wt%) were mixed together, forming a uniform micro- vanced LSBs with nanotechnology. Furthermore, we categorized
sphere, followed by Kirkendall method, heat-treatment, and acid the strategies for enhancing the electrochemical performance of
etching, to obtain the pomegranate-like microporous core-shell γ - LSBs into three themes in this review.
Fe2 O3 @graphene composite (Fig. 16(a)). Sulfur was infiltrated via The first theme covered intermediate polysulfide dissolu-
melt-diffusion (155 °C) to obtain PSSN/S. The layered nanoporous tion which is caused by the generation of soluble long-chain
structure of PSSN was observed by TEM (Fig. 16(b)). The uni- polysulfides (Li2 Sn , n = 3–8) during lithiation. As a solution,
form distribution of sulfur in the nanocomposite was confirmed by nanoscale materials such as metal oxides/chalcogenides nanopar-
SEM and EDX (Fig. 16(c)). Furthermore, strong intermediate lithium ticles/nanoclusters, graphene oxide, nano-layer passivation, and
polysulfide adsorption was confirmed by XPS. Cell performance ferromagnetic nanoparticles were discussed. The interesting as-
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Declaration of Competing Interest 9609–9615.
[44] Z. Wang, Y. Dong, H. Li, Z. Zhao, H. Bin Wu, C. Hao, S. Liu, J. Qiu, X. Wen,
D. Lou, Nat. Commun. (2014) 5.
The authors declare that they have no known competing finan- [45] D. Qu, M. Zheng, P. Du, Y. Zhou, L. Zhang, D. Li, H. Tan, Z. Zhao, Z. Xie, Z. Sun,
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Recent advances in nanomaterials for high-performance Li-S batteries

Article in Journal of Energy Chemistry · August 2020

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Journal of Energy Chemistry

Recent advances in nanomaterials for high-performance Li–S batteries

James E. Knoop is currently a Ph.D. student at the Joint 1. Introduction

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