Zhang Mat

FEATURE ARTICLE
Lithium–Sulfur Batteries www.afm-journal.de
Heterogeneous/Homogeneous Mediators for High-Energy-

Density Lithium–Sulfur Batteries: Progress and Prospects
Ze-Wen Zhang, Hong-Jie Peng, Meng Zhao, and Jia-Qi Huang*
and low-cost solar energy harvest, ren-

Lithium–sulfur (Li–S) batteries deliver a high theoretical energy density of dering renewable electricity generation
2600 Wh kg−1, and hold great promise to serve as a next-generation high- competitive in cost and capacity to conven-
energy-density battery system. Great progress has been achieved in cathode tional thermal approaches.[2] On the other
design to deal with the intrinsic problems of sulfur cathodes, including low hand, high-performance energy storage
devices are in huge demand to store the
conductivity, the dissolution of polysulfide intermediate, and volume fluc-
renewable electricity for electrified trans-
tuation. However, aiming at the practical applications of Li–S batteries, the portation and grid storage. Therefore,
weight percentage of sulfur in cathode materials and the overall areal sulfur high-energy-density rechargeable battery
loading need to be significantly increased, which inevitably complicate the technology takes an indispensable role
process and cause heavy shuttle effect, slow redox kinetics, and more unde- in the whole picture. While lithium-ion
sirable reaction pathways. Recently, rationally designing efficient mediators, batteries (LIBs) based on intercalation
mechanisms represent the most advanced
as well as incorporating them into a working battery, emerges to be a prom-
current technology that is commercially
ising method to construct high-energy-density Li–S batteries. The influence of available, there is still a gap between state-
mediators on Li–S batteries appears to be the enhancement in redox kinetics of-the-art energy density and the request
and the increase in reaction efficiency. In this feature article, the mechanistic proposed from advancing markets of port-
understanding of redox kinetics in Li–S reactions is discussed, and then able electronics, and surging markets like
electric vehicles or stationary electricity
a comprehensive analysis of the recent advances in both heterogeneous
storage. Post LIBs technologies such as
and homogeneous mediator design is provided. A mediator perspective in lithium–sulfur (Li–S) batteries, lithium–
building high-energy-density Li–S batteries is also included. air batteries, and magnesium batteries are
widely recognized as promising solutions
to the high-energy-density quest.[3]
1. Introduction Among the alternative post LIB technologies, Li–S batteries
take a leading stand to meet the practical demands.[4] The
The conflict between mounting pressure of energy demand multielectron reactions between elemental sulfur cathode and
and growing concern of greenhouse gas emission has attracted lithium metal anode deliver a theoretical gravimetric energy
global awareness. In quest for advanced techniques to lower the density of 2600 Wh kg−1, much higher than that of conven-
carbon footprint and power up a sustainable future, research tional LIBs.[5] Other valuable characteristics of sulfur, like cost
communities along with industrial forces have made much efficiency, natural abundance, and environmental friendliness,
efforts in searching better solutions to harvest, store, and trans- are competing strengths in promising large-scale application.
port renewable energy.[1] On the one hand, the development Aside from the remarkable advantages, Li–S batteries also face
of emerging photovoltaic technologies based on polymers and several intrinsic issues, including 1) the insulating nature of
organic–inorganic hybrid perovskites contributes to efficient sulfur and lithium (di)sulfides (Li2S2/Li2S), 2) dissolution and
shuttling of lithium polysulfide (LiPS) intermediates, 3) huge
volume changes of both sulfur cathode and lithium anode, and
4) lithium dendrite growth.
Z.-W. Zhang, M. Zhao, Prof. J.-Q. Huang The successful introduction of highly ordered mesoporous
Advanced Research Institute of Multidisciplinary Science
Beijing Institute of Technology carbon to activate electrically insulating sulfur and Li2S2/Li2S
Beijing 100081, China in 2009 by Nazar and co-workers preluded a boost in Li–S
E-mail: jqhuang@bit.edu.cn battery.[6] Various methods have been proposed to tackle the
Z.-W. Zhang, H.-J. Peng problems such as shuttle phenomenon and irreversible loss of
Beijing Key Laboratory of Green Chemical Reaction active materials, and tremendous progress has been achieved
Engineering and Technology
via delicate architecture design of carbon hosts,[7] or subtle
Department of Chemical Engineering Tsinghua University
Beijing 100084, China modification of surface chemistries.[8] To date, superior battery
performance including high sulfur utilization, high sulfur con-
The ORCID identification number(s) for the author(s) of this article tent, and high rate performance has been realized.[9]
can be found under https://doi.org/10.1002/adfm.201707536.
Recently, concerns have been raised, gaining increasing
DOI: 10.1002/adfm.201707536 attention about the application prospects of Li–S batteries.
Adv. Funct. Mater. 2018, 28, 1707536 1707536 (1 of 23) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.afm-journal.de
Despite inspiring theoretical energy density and thrilling

achievements, there are many problems in translating high- Ze-Wen Zhang received his
energy-density Li–S batteries into reality. Current reported Bachelor’s Degree of mate-
results, which are almost based on low sulfur weight per- rials science and engineering
centage and areal loading, solving aforementioned inherent (2017) at Tsinghua University
problems though, would not be able to compete with commer- in China. He carried out his
cial LIBs. It is reasonable to assume that widespread practical undergraduate research with
applications of Li–S batteries (with an actual energy density of Prof. Qiang Zhang and Prof.
at least 500 Wh kg−1) require 1) a sulfur content in cathode scaf- Jia-Qi Huang in nanomate-
folds >80%, 2) an areal sulfur loading >7.5 mg cm−2, and 3) an rials based energy storage,
E/S (electrolyte/sulfur weight) ratio <2. especially lithium–sulfur bat-
The rise in weight percentage of sulfur in cathode materials teries. He is currently a PhD
and overall areal sulfur loading would inevitably complicate the student in Materials Science
situation in at least the following three aspects (Figure 1a). and Engineering at Stanford University.
Heavier Shuttle Effects: Shuttle effect, the back-and-forth
motion of LiPSs between sulfur cathode and lithium anode, is Hong-Jie Peng gained his
always the culprit for low Coulombic efficiency and unsatisfac- B.Eng. from the Department
tory cycle life of on-service Li–S batteries, and also the origin of of Chemical Engineering at
a self-discharge problem in on-shelf batteries during stocking Tsinghua University in 2013.
or delivery. By increasing the percentage and total amount of He is currently a Ph.D. candi-
sulfur in the whole cell, one would expect a multiplied LiPS date at Tsinghua University.
shuttling due to a larger sulfur concentration gradient, which His research interests focus
makes it more difficult to inhibit the hazardous LiPS crossover. on nanocarbon, advanced
Slower Redox Kinetics: The increment of areal current den- energy storage/conversion,
sity under the same C-rate (1.0 C = 1672 mA g−1) for higher- lithium–sulfur batteries, and
sulfur-loading batteries would result in increased polarization catalysis.
at electrode interfaces. An expanded voltage hysteresis indicates
an inadequacy in sulfur utilization, and also greatly harms
Jia-Qi Huang received his
the energy efficiency of the whole electricity storage/delivery
B.Eng. (2007) and Ph.D.
loop. Besides, slower redox kinetics deteriorates rate perfor-
(2012) degrees in Chemical
mance, which prevents Li–S batteries from practical application
Engineering from Tsinghua
scenarios.
University, China. He is a pro-
More Undesirable Reaction Pathways: It is widely accepted
fessor in Advanced Research
that at least two reaction pathways exist in routine Li–S bat-
Institute of Multidisciplinary
teries using a liquid electrolyte, namely, electrochemical reac-
Science (ARIMS) in Beijing
tions and chemical reactions. For electrochemical pathways,
Institute of Technology. His
LiPSs are assumed to be reduced at the electrode surface by
research interests focus on
accepting electrons from external circuits directly; while for
synthetic approaches and
chemical pathways, LiPSs undergo a disproportionation pro-
application of nanomaterials
cess in the solution, giving Li2S2/Li2S precipitates and high-
for rechargeable batteries, including Li–S batteries, Li
order LiPSs. For chemical pathways, Li2S2/Li2S are very likely
metal anodes, etc.
to precipitate from within the solution and not closely bound
to the conductive framework, inducing an irreversible loss of
active materials. The rise of the sulfur content favors the chem- term “mediator” to categorize materials that help electrons or
ical pathway, since limited electrode surfaces are available, and holes transfer directly or indirectly, and are employed in electro-
therefore more sulfur would transform via disproportionation chemical energy system to reduce electron/ion-transfer resist-
reactions. ances and facilitate redox kinetics. With rapid charge-transfer
The above-mentioned problems make it a tougher case in kinetics, better utilization and stability could be realized in high
building high-energy-density Li–S batteries with a high sulfur cycle rates.
content, a high areal sulfur loading, and a low E/S ratio.[10] In this perspective, we aim to enclose a broader context
The increases in sulfur content and areal loading are not just regarding the kinetics-promotion or reaction-intensification
a simple addition algorithm but more of an exponential magni- strategy, by using the term “mediator” rather than “catalyst” or
fying lens, exaggerating the existing problems and putting pre- “redox mediator.” Conventional catalysts work to alter the acti-
vious strategies under further inspections. More sophisticated vation energy by inducing a different transition state during
strategies are in demand to efficiently promote battery reactions reaction coordinates, and remain unchanged after the reaction.
without plaguing the overall energy density. Recently, rationally However, the surface state or composition of most so-called
designing mediators and incorporating them into a working “catalysts” in Li–S batteries might actually be different from
battery emerges to be a promising method to construct high- their initial states. For example, Li2S2/Li2S precipitates might
energy-density Li–S batteries (Figure 1b). Herein we use the cover the catalytic surface, preventing its further access to
Figure 1. Schematic of a) high sulfur loading/content dilemma of and b) a mediator perspective on high-energy-density Li–S batteries.
adsorbates and thus poisoning the catalyst. Therefore, without species transition are involved, including a LiPS–LiPS liquid–
further evidences in detailed catalytic mechanism and real liquid intertransition and a LiPS–Li2S2/Li2S liquid–solid
material status, these kinetic promoters, though with apparent transition.
“catalytic” effects observed, are better classified as mediators
from our perspective. Their influence on Li–S batteries appears
to be the enhancement in redox kinetics and the increase in 2.1. Liquid–Liquid Transitions: LiPSs–LiPSs
reaction efficiency, which are cautiously attributed to apparent
kinetics promotion rather than inherent catalytic regulation. The liquid–liquid phase transition (Li2S8–Li2S6–Li2S4) plateaus
In the following content, we first focus on mechanistic are where shuttle phenomenon takes place. A delayed trans-
understanding of redox kinetics in Li–S reactions, and then formation of LiPS species causes an accumulation in the elec-
discuss recent advances in mediator design, and finally offer trolyte and the ensuing shuttling. By using rotating ring-disk
a mediator perspective in building high-energy-density Li–S electrode (RRDE) voltammetry in dilute solutions, previous
batteries. Note that the sulfur cathode will be the major topic, results suggested a rapid kinetics in liquid–liquid transitions
while the overall coordination with advances in lithium metal (Figure 2a).[12] However, the case would be different in practical
anodes, electrolytes, cell configurations, and other aspects, batteries, where the sulfur concentration would be much higher
which are also the key toward high-energy-density Li–S bat- to meet the practical requirements for high-energy-density, and
teries, will not be included in this contribution but have been kinetic behaviors in a real cell might differ. Electrochemical
reviewed and discussed elsewhere.[11] impedance spectroscopy (EIS) results of Li–S asymmetric cells
and LiPS–LiPS symmetrical cells both suggested that liquid–
liquid transitions exhibit larger impedance than liquid–solid
2. Reaction Kinetics in Li–S Batteries transitions during the discharge process in Li–S batteries
(Figure 2b,c).[13] The highest impedance occurs at the highest
Conventional Li–S chemistry involves a solution pathway in sulfur concentration, where the viscosity of electrolyte reaches
commonly employed aprotic electrolytes. Two types of sulfur a peak. In other words, the accumulation of LiPSs blocks their
own reaction highway, which not only increases internal resist- poor contact with the conductive matrix. An extra overpotential
ance but also contributes to heavy bypass shuttle phenom- is required in the reverse reactions, compromising the energy
enon. Accordingly, accelerating LiPS interconversion through efficiency of cells. The detached part accounts for irreversible
enhanced liquid–liquid redox kinetics is of great significance in and continual loss of active materials. Wherefore, facilitated
Li–S chemistry, as it alleviates hazardous pileup and smoothens nucleation/growth of solid products and controlled spatial
reactions at high rate. homogeneity of sulfur species are in demand, where kinetic
control plays a vital role.[15]
While in the charge scenario, there is also a high activa-
2.2. Liquid–Solid Transitions: LiPSs–Li2S2/Li2S tion energy barrier to extract lithium ions from solid Li2S2/
Li2S. This is mostly concerned when sulfur is replaced by Li2S
In the discharge scenario, the liquid–solid phase transition as the starting cathode materials. Yang et al. have systemati-
(usually simplified as Li2S4 to Li2S) accounts for three quar- cally studied microsized Li2S particles as cathode materials, of
ters of the theoretical capacity (1254 mA h g−1). An efficient which the charging overpotential could be higher than 1 V to
transformation of LiPSs to Li2S2/Li2S matters in reaching the activate Li2S cathode under practically viable current densities
full potential of Li–S batteries. Unlike LiPS intertransitions, (Figure 3b).[16] For elemental sulfur cathodes, the overpoten-
where both reactants and products remain in liquid phase, tial would be relatively small since there are residual LiPSs in
solid phases emerge in the LiPS–Li2S2/Li2S transition as the the electrolyte after the first discharge. These residuals could
reaction proceeds. A voltage dip could be observed at the start smoothen the reoxidation as intrinsic redox mediators, which
of lower discharge plateau, and is always credited to the initial will be discussed later. Nevertheless, an activation energy bar-
nucleation barrier. Chiang and co-workers confirmed through rier would still be observed in initial cycles in coin cells using
a series of potentiostatic tests that an overpotential is needed a starting sulfur cathode, and EIS results also indicated the
in the formation of first solid nucleus to surmount the energy highest impedance at the start in the charge cycle. The high
barrier (Figure 3a).[14] A larger nucleation barrier would result internal resistance might be attributed to insulating nature
in fewer initial nuclei along with delayed formation of solid of solid Li2S2/Li2S. These results suggest that (re)oxidation of
end products, and undesirable large particles would grow from Li2S2/Li2S also needs kinetic promotion to avoid unnecessary
these nuclei, which would not be readily reoxidized due to their loss of energy efficiency and active materials.
Figure 2. Kinetics of liquid–liquid LiPS–LiPS transitions. a) RRDE experiments of 4.0 × 10−3 mol L−1 S8 dissolved in dimethyl sulfoxide (DMSO) and
1,3-dioxolane (DOL):1,2-dimethoxyethane (DME) solvents. Reproduced with permission.[12] Copyright 2014, American Chemical Society. b) EIS spectra
of symmetrical cells (S–S, Li2S6–Li2S6, and Li2S–Li2S). Reproduced with permission.[13a] Copyright 2016, American Chemical Society. c) EIS spectra of
coin cells at different depths of discharge (DOD). Reproduced with permission.[13b] Copyright 2013, Elsevier.
Figure 3. Kinetics of liquid–solid LiPS–Li2S2/Li2S transitions. a) Current–time plots for potentiostatic discharge in various solvents and com-
bined nucleation-growth rate constants resulting from fitting of current peaks. Reproduced with permission.[14] Copyright 2015, Wiley-VCH.
b) Left: relation between current rates and overpotentials. Initial potential barrier of Li2S cathodes at C/8, C/50, C/200, and C/1000 (inset).
1 C = 1166 mA g−1. Right: relation between the current rate and the overpotential. Reproduced with permission.[16] Copyright 2012, American
Chemical Society.
3. Mediators in Li–S Batteries mediators are always dissolved in the electrolyte to react with
substrates.
Mediators are a class of materials conducive to the kinetic Both heterogeneous and homogeneous mediators in Li–S
behaviors of redox reactions and capable of reducing charge chemistry could smoothen charge transfer and enhance redox
overpotentials by either facilitating charge transfer or enhancing kinetics of LiPS-related reactions, despite that they function in
ion transport. Generally, mediators can be classified as hetero- different ways. Heterogeneous mediators always act as electron
geneous and homogeneous, depending on whether the media- or hole transportation highway, reducing charge transfer resist-
tors exist in the same phase as the substrate. In a typical Li–S ance and altering reaction transition states via surface binding
battery context, substrates, namely LiPSs, are always in the toward redox intermediates. Homogeneous mediators exhibit
liquid phase. Thereupon, heterogeneous mediators are referred certain redox activities within the operating potential window
to solids embedded on the conductive framework, which could and thus work via a chemical way to overcome energy barrier
grease the wheel of LiPS transitions; while homogeneous and activate redox substrates. Here, we will make a brief review
of representative heterogeneous and homo-

geneous mediators in Li–S batteries.
3.1. Heterogeneous Mediators
In Li–S batteries, heterogeneous media-

tors include metals, metal compounds, and
emerging inorganic/organic complexes.
Generally, these mediator materials are
also categorized as “polar” or “chemisorp-
tive” host materials, as a few review papers
indicated previously.[17] Tailored surface
polarity or chemisorptivity to polysulfides
and Li2S2/Li2S is indeed a prerequisite for
efficient kinetic mediation. Nevertheless,
heterogeneous charge transport and rea-
sonable desorption/surface diffusion also
need to be considered for the entire interfa-
cial redox reactions. Simple though strong
chemisorption inevitably leads to undesir-
able adsorption saturation of polysulfides
without subsequent rapid transformation
to scavenge adsorbed polysulfides. On the
contrary, fast conversion of polysulfides and
regeneration of empty sites will be expected
if a mediator possesses both a moderate
chemisorption ability to redox intermedi-
ates and the capability of expediting redox
reactions through one of following mecha-
nisms or combined: 1) weakening internal
molecular bonds in LiPS to make it easily
break; 2) controlling adsorbed orientation to
better fit the reaction nature; 3) facilitating
Figure 4. Heterogeneous metal mediators. a) Schematic of Pt mediator anchored on graphene
surface ion transport to surmount diffusion and its interaction with LiPSs during charge/discharge processes. Reproduced with permis-
barrier; 4) forming active complex to bypass sion.[20] Copyright 2015, American Chemical Society. b) Schematic of a synergistic Co–N-GC
slow redox pathways. Basically, heteroge- mediator and its interaction with LiPSs during the charge/discharge processes. Reproduced
neous mediator is an evolutionary paradigm with permission.[22] Copyright 2016, Royal Society of Chemistry.
of polar host, as it hardly suffers from the
limitation of bulk chemisorption capacity and can operate well well as to suppress shuttle effect (Figure 4a).[20] Sulfur cathode
even with a tiny addition, which, in principle, benefits a high with Pt-nanoparticle-modified graphene exhibited superior
sulfur content. redox kinetic behaviors, where a 40% enhancement in the spe-
cific capacity over pristine graphene was observed, along with
good stability over 100 cycles at a current rate of 0.2 C. Post-
3.1.1. Metals mortem analysis of cycled electrodes suggested a promoted
conversion from short-chain LiPSs to long-chain LiPSs. Gold
Elemental metals are widely employed as industrial catalysts for nanoparticles were also found to chemically interact with
various chemical reactions. Partially occupied d-orbitals lead to sulfur/LiPSs and thereby mediate the deposition.[21] Beyond
superior coordination with the substrates, therefore facilitating noble metal particles, cobalt (Co) has also been investigated
the following transitions. The occupation depth of d-orbitals in the Li–S systems. Zheng and co-workers derived cobalt and
always accounts for distinct catalytic activities. nitrogen-doped graphitic carbon (Co–N-GC) composites from
Tao et al. first suggested the decoration of sulfur by porous metal–organic framework (MOF) precursors for high-energy-
platinum (Pt) nanostructure that effectively stabilized sulfur density Li–S batteries, suggesting that Co and N dopants work
and suppressed shuttle effect.[18] Zheng et al. also validated synergistically as dual-functional redox promoters for both LiPS
enhanced sulfur immobilization by embedding copper nano- oxidation and reduction (Figure 4b).[22] By applying Co–N-GC
particles in carbon matrix.[19] Nevertheless, the concept of as the sulfur host, a specific capacity of 565 mA h g−1 was real-
metal-catalyzed sulfur conversion has not been brought out ized at a 5.0 C rate with a sulfur content of 70% in the sulfur/
until when Arava and co-workers adopted elemental metal nan- Co–N-GC composite. Other carbon matrixes modified with cobalt
oparticles into Li–S chemistry to modify LiPS transformation as or nickel nanoparticles, despite their various nanostructures,
exhibited analogous function that embedded metal mediators nonconductive oxides supported on conductive materials such
facilitated Li–S reactions.[23] as carbon, Cui and co-workers pointed out the importance of
Metals exert great impetus in Li–S chemistry as shown above. balance between surface adsorption and diffusion process
Unique d-band structure and intrinsic metallic conductivity of LiPSs after a systematic investigation on a series of metal
enable them to evidently promote kinetics in LiPS transitions. oxides (Al2O3, CeO2, La2O3, MgO, and CaO) and their interac-
Detailed study of interaction mechanisms and sophisticated tions with LiPSs (Figure 5a).[32] It was elucidated that strong
structural designs are in demand to optimize redox tuning per- binding and good surface diffusion properties must be simulta-
formance. Nonetheless, it is important to notice that currently neously provided by an optimal nonconductive oxide mediator.
high price of noble metals such as Pt as redox mediators is not It is also viable to design intrinsically conductive oxide
compatible with cost efficiency claim for Li–S systems. Besides, mediators. The creation of inherent defects or vacancies is able
some studies evidenced that some metal mediators such as plat- to alter an insulating or semiconducting oxide into a conduc-
inum,[20] gold,[21] and nickel[24] undergo phase transformations tive one. For example, Nazar and co-workers first introduced
from pristine metal to metal sulfide during Li–S reactions. Magnéli-phase Ti4O7 as a conductive polar host for sulfur
Thus, it is also very important to probe the actual mediator cathode.[33] The surface unsaturated Ti3+ sites provided strong
phase and clarify the kinetic promotion mechanism toward coordination toward polar sulfur species. And unlike TiO2, the
rational design of metal mediators. intrinsic metallic conductivity of Ti4O7 (2 × 103 S cm−1 at 298 K)
expedited following electron transfer to surface-coordinated
sulfur species, thus promoting surface-dominated reactions
3.1.2. Metal Compounds (Figure 5b). The introduction of Ti4O7 into the sulfur cathode
enabled substantial capacity retention over 250 cycles at 0.5 C
Metal compounds are a big group of redox mediators with a with a decay rate of 0.08% per cycle, and an initial capacity of
comparable ability in kinetic tuning to noble metals. Unsatu- 850 mA h g−1 at 2.0 C was attained, along with a decay rate
rated surface sites in these compounds provide similar coor- of 0.06% per cycle over 500 cycles. Almost at the same time,
dination with intermediates as their elemental counterparts. Tao et al. correlated the performance enhancement of sulfur
Their adjustable surface exposure and edge chemical states cathodes by the use of Magnéli-phase TinO2n−1 scaffolds to the
offer more possibilities for kinetic mediating. Moreover, unlike number of low-coordination Ti sites.[34] The more unsaturated
elemental metals, metal compounds are intrinsically polar sites there are, the stronger binding to LiPSs and the higher
materials due to their mostly ionic bonding nature, which are electrical conductivity are offered. It thus provides a mechanistic
expected to exhibit stronger interactions with LiPSs. Also, the insight into why Ti4O7 is among the best overall Magnéli-phase
low-cost characteristic for non-noble metal compounds endows TinO2n−1 and a rational guidance to design Ti3+-rich or even
them with brighter prospect in large-scale practical applications. Ti2+-rich TiOx (1 ≤ x < 2) mediators.[35] Another method to
Oxides and Hydroxides: Metal oxides are among the first improve the bulk electrical conductivity is to dope the oxide
group of mediators that has been broadly investigated. Metal with foreign metals. For example, Yao et al. clearly evidenced
oxides and hydroxides are typical ionic compounds with strong that solid Li2S2/Li2S species deposit preferentially onto tin-
surface polarity, which favors the interaction with polar redox doped indium oxide instead of carbon.[36] The further decora-
intermediates. tion of carbon nanofiber scaffolds with tin-doped indium oxide
The introduction of Mg0.6Ni0.4O as a LiPS adsorbent sets nanoparticles significantly improved the capacity, stability, and
off the zest in redox mediating by inorganic compounds. rate capability of Li–LiPS catholyte cells. Other heterodoped
Song et al. first incorporated nanosized Mg0.6Ni0.4O in the oxides such as cheaper aluminum-doped zinc oxide were also
sulfur cathode to exert LiPS adsorbing and catalytic effects demonstrated as favorable mediators with high LiPS affinity
of promoting Li–S reactions.[25] Although worked out in and metallic conductivity.[37]
improving the capacity retention of sulfur cathode, insulating The second strategy is to utilize oxides of transition metals
nature of widely employed (hydro)oxide additives, such as with a myriad of possibilities to regulate the electronic struc-
Mg0.6Ni0.4O,[25,26] SiO2,[27] MgO,[28] Al2O3,[29] MgBO2(OH),[30] ture, surface properties, and binding scenarios through d-band
Mg–Al layered double hydroxide (LDH),[31] prevents continual engineering. These transition metal (hydro)oxides include
enhancement of high-rate and high-loading batteries. Most of Mn (MnO2,[38] Mn3O4,[39] and MnO[40]), Fe (Fe2O3[41] and
them have rarely been elucidated with unambiguous kinetic Fe3O4[42]), Co (Co3O4,[43] CoO,[44] and Co(OH)2[45]), Ni (NiO[46]
promotion or reaction mediating effect, possibly because of and Ni(OH)x[47]), other transition metal-based (VO2/V2O5,[48]
1) high charge transfer resistance that impedes direct surface Nb2O5,[49] etc.[50]), and multi metal-based (NiFe2O4,[51] Ni–Co/
redox reactions on oxides and/or 2) the lack of transition metal Fe LDH,[52] and La0.6Sr0.4CoO3−δ/Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovs-
sites with highly tunable valence and coordination to alter LiPS kites[53]) materials. These transition metal oxides and hydrox-
binding schemes and reaction pathways. ides possess intrinsically polar surface units of O–M–O(H) to
Two strategies are proposed to solve the above problems bind LiPSs and the ability of transition metal sites to form deli-
and fully exert the potential of oxide as efficient Li–S mediator. cate electronic interactions with LiPSs make them promising
One is to enhance the charge transport through either accel- heterogeneous mediators.
erating surface diffusion of LiPSs to conductive substrate or Among them, MnO2 has gathered the most considerable
engineering the intrinsic electrical conductivity of oxide itself. attention because it dominates a unique reaction-regulating
The transport of surface-bound LiPSs between nonconduc- mechanism distinct from others as first elucidated by Nazar and
tive oxide and carbon is thus of notable significance. For those co-workers (Figure 5c).[38a] The uniqueness of MnO2-mediated
Figure 5. Heterogeneous metal oxide/hydroxide mediators. a) Schematic of the LiPS adsorption and diffusion on the surface of various nonconductive
metal oxides. Reproduced with permission.[32] Copyright 2016, Nature Publishing Group. b) Diagram illustrating surface-mediated reduction of Li2S
from LiPSs on Ti4O7. Reproduced with permission.[33] Copyright 2014, Nature Publishing Group. c) XPS study of the interaction between LiPSs and
MnO2 nanosheets and schematic showing the surface-bound “Wackenroder” mechanism. Reproduced with permission.[38a] Copyright 2015, Nature
Publishing Group. d) Schematic of the cooperative interface of Ni–Fe LDH@NG. Reproduced with permission.[52b] Copyright 2016, Wiley-VCH.
Li–S reactions is that through a mild surface oxidation pro- sulfur-rich environment. Formation of surface sulfides might
cess, LiPSs can be oxidized into a surface-bound specie of account for the enhanced affinity toward LiPSs in this case,
thiosulfate (OSO2S), which further catenates soluble although detailed surface chemistry examination is in demand
LiPSs to produce immobilized intermediates of polythionates to reveal the subtle interaction.
(OSO2SxSO2O). Unlike the routine mechanism that Sulfides: Metal sulfides possess an incomparable competing
short-chain LiPSs disproportionate into Li2S2/Li2S and long- strength in Li–S chemistry due to their special surface compo-
chain LiPSs, Li–S reactions proceed through a surface “Wack- sition, which provides unique affinity toward LiPSs. Normally,
enroder” mechanism to greatly suppress the bypass shuttle the electrical conductivity of a certain metal sulfide is higher
effect and improve interfacial kinetics. The existence of thio- than its oxide counterpart because S2− is a softer base than O2−
sulfate and polythionate was evidenced by X-ray photoelectron so it weakens the ionic nature of M–S bonds and reduces the
spectroscopic (XPS) results. With 75% sulfur content in the electron localization. Moreover, transition metal disulfides have
sulfur/MnO2 composite, MnO2-based cathodes delivered a been employed as industrial hydrodesulfurization catalysts for
reversible capacity of over 1000 mA h g−1 at 2.0 C and exhib- decades, and recent results further suggested their superior
ited a low decay rate over 2000 cycles of 0.036% per cycle. A catalytic capability for various redox reactions.[54]
wide range of transition metal oxides was further investigated The application of metal sulfides for sulfur or Li2S cathodes
to reveal a universal principle: MnO2-like redox mediators share was first demonstrated by Garsuch et al., who introduced tita-
a common feature that their redox potentials are higher than nium disulfide (TiS2) as a second active component in sulfur
that of soluble LiPSs to trigger the surface oxidation to form cathode.[55] Seh et al. further employed this kind of conductive
thiosulfate while not too high to overoxidize LiPSs into non- layered metal disulfides including TiS2, VS2, and ZrS2 to encap-
active sulfates.[48a] The redox potential window (vs Li/Li+) was sulate Li2S cathodes.[56] The polar nature contributed to strong
identified as 2.4–3.05 V for screening potential candidates chemical confinement, and the good electrical conductivity
capable of expediting a surface “Wackenroder” mechanism. accounted for improved rate performance. Since then, the devel-
Explored candidates include MnO2, VO2, and CuO; while other opment of metal sulfides as encapsulating or scaffolding mate-
transition metal (hydro)oxides like Nb2O5 enhance the redox rials for the cathode of Li–S batteries is booming, as many of
kinetics rather through the strong chemisorption of LiPS spe- them reported, including bulk-type sulfides generally based on
cies instead of thiosulfates/polythionates.[49] Group VIII elements (FeS2,[57] CoSx,[13a,58] and NiSx[59]) and lay-
The aforementioned two strategies can be exerted in a combi- ered sulfides based on either early transition metals (i.e., TiS2,[60]
natorial manner to provide complementary benefits. Peng et al. VS2,[61] MoS2,[62] NbS2,[63] and WS2[64]) or nontransition metals
have proposed a cooperative interface design to rationalize the (i.e., SnS2[65]). Despite the general advantages, some of them
strongly coupled surface interactions, diffusions, and reactions also exhibited as very promising heterogeneous mediators.
(Figure 5d).[52b] By building such a cooperative interface from For bulk-type sulfides, Co-based compounds, such as
“lithiophilic” N-doped graphene and “sulfiphilic” Ni–Fe LDHs, CoS2,[13a] Co3S4,[58b,d] and Co9S8,[58a,c] attract the most atten-
on the one hand, the lithiophilic N-doping sites and sulfiphilic tion because of the superior conductivity surpassing those of
metal sites synergistically bind the bipolar head (SLi) of Fe-based and Ni-based ones. Zhang and co-workers first pro-
LiPSs, smoothening the surface conversion of LiPSs; while on posed the strategy to bypass LiPS shuttle by intensifying liquid–
the other hand, the strong coupling between N-doped graphene liquid transitions via the use of sulfiphilic semimetallic CoS2
and LDHs, as well as the Fe doping, introduces desirable sur- mediator (Figure 6a).[13a] Simply inducing CoS2 microparticles
face strains to fully expose the binding sites and regulate the via mechanical milling to graphene electrodes largely amplified
electronic properties. As a result, the Li–S cell modified with electrochemical current response and reduced charge transfer
a N-doped graphene/Ni–Fe LDH interlayer exhibited signifi- resistance in LiPS symmetrical cells. These elevated electro-
cantly improved reaction rates, and reduced shuttle as a low chemical behaviors well bolstered an expedited redox kinetics
capacity decay rate of 0.060% per cycle at 2.0 C was achieved through CoS2 tuning. A high initial capacity of 1368 mA h g−1 at
for 1000 cycles. Moreover, a promising specific capacity of 800 0.5 C, an increase of 10% in energy efficiency, and a low decay
mA h g−1 was retained at an areal sulfur loading of 4.3 mg cm−2 rate of 0.034% per cycle for 2000 cycles at 2.0 C were realized
after 100 cycles. This concept was further explored by designing through the incorporation of mechanically milled CoS2 with a
nanosized Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite mediators with low specific surface area. More importantly, it was found that
sulfiphilic Sr sites and lithiophilic O-vacancy sites, of which the CoS2 served as a mediator rather the conductive substrate, as it
incorporation into a cathode with a sulfur loading of 3.8 mg only propelled the LiPS interconversion and facilitated the prior
cm−2 enabled its very stable cycling at 0.2 C for 200 cycles.[53b] formation of Li2S nuclei, while Li2S was mainly precipitated on
It is noteworthy that the interaction mechanism varied in nonpolar graphene host around the CoS2 mediator. Pang et al.
metal (hydro)oxide mediators. Transition metal oxides are of also synthesized a graphene-like metallic Co9S8 host for sulfur
particular interests because of their tunable electronic proper- cathode, suggesting the important role of exposed facet orienta-
ties and binding affinities. The electrical conductivity must be tions in binding LiPSs and tuning their reactions.[58a] Regarding
well engineered. Regarding the enhancing mechanism, which the synthetic methodology, conversion from MOF precursors is
remains exclusive except that of MnO2-like materials,[38a,48a] it highly efficient in generating various Co-based sulfide/nano-
is reasonable to assume that surface chemistry of certain oxides porous carbon hybrids with advantages in reducing the size of
might undergo structural and/or constitutional changes due sulfide mediators and enlarging the conductive surface.[58b,c]
to higher affinity between metal and sulfur atoms than that of Unlike bulk-type sulfides with various and hardly controlled
oxygen atoms or hydroxyl groups in an oxygen-deficient but surface crystal orientations, 2D transition metal dichalcogenides
Figure 6. Heterogeneous metal sulfide mediators. a) Schematic of CoS2-accelerated LiPS redox to bypass shuttle. Reproduced with permission.[13a]
Copyright 2015, American Chemical Society. b) Schematic of defect-rich MoS2-x/graphene mediator and the enhanced LiPS redox kinetics of symmetric
LiPS–LiPS cells by introducing abundant defects. Reproduced with permission.[62c] Copyright 2017, Royal Society of Chemistry. c) Schematic of the
sulfur conversion process and the catalytic oxidation of Li2S on the surface of the substrate. Reproduced with permission.[68] Copyright 2017, National
Academy of Sciences.
(TMDs) with an ideal crystal structure only have two specific further exploited the role of exposed edge sites in TMD (WS2
atom configurations: at the basal plane (terrace) and at the and MoS2) flakes as preferential active centers in sulfur/LiPS
edge. The edge sites primarily,[66] as well as the defects of basal redox activity.[64a] The facile redox kinetics over monolayer or
plane recently,[67] have been validated as the catalytic centers few-layered TMDs were evidenced via comparison in redox
for many reactions such as electrocatalytic hydrogen evolution. current, onset potential, and exchange current density through
Similarly, this understanding has been implemented in Li–S a three-electrode configuration experiment. The WS2-based
chemistry. Wang et al. first elucidated the edge selectivity of electrode demonstrated a higher exchange current density of
Li2S deposition on MoS2 flakes due to the stronger binding of 11.8 µA cm−2 compared to 8.5 µA cm−2 of a carbon electrode
LiPSs to edges than terrace surfaces.[62a] Arave and co-workers and reduced polarization in onset potentials. Beyond the edge
site, Lin et al. engineered sulfur-deficient MoS2 to expose the of metal phosphides (Fe2P, Co2P, and Ni2P) as heterogeneous
active sites to the maximum through the introduction of basal- mediators and confirmed their role in promoting the oxidation
plane defects (Figure 6b).[62c] In symmetrical cell test, sulfur- of Li2S, which, together with desirable LiPS adsorption, led to
deficient MoS2 electrode exhibited a clear and sharp two-peak significant performance enhancement.[75b] Compared to metal
redox pattern in both cathodic and anodic scanning under low (hydro)oxides and sulfides, metal carbides, nitrides, and phos-
scan rate and big voltage window, corresponding to facile con- phides have a dominant advantage, namely superior metal-like
version kinetics and good electrochemical reversibility. The conductivity; while generally the polarity is poorer, referring to
presence of plentiful sulfur defects contributes greatly to high- weaker binding energies to LiPSs.
rate performance as well as cycle stability in Li–S cells. A spe- There are two major strategies to overcome the above issue
cific capacity of 827 mA h g−1 at 8.0 C and a capacity fading rate of weak binding ability for metal carbide/nitride/phosphide
of 0.083% per cycle for 600 cycles at 0.5 C were achieved. mediators. One is to engineer rational heterostructures of
The principles of designing bulk-type and layered sulfide strong-binding metal (hydro)oxide and weak-binding but highly
mediators have also been rationalized and unified despite conductive metal carbide/nitride/phosphide. Zhou et al. dem-
their distinct electronic properties and active sites. Cui and onstrated such a concept by constructing twinborn TiO2–TiN
co-workers studied catalytic oxidation of Li2S on various metal heterostructures to enable smooth trapping–diffusion–conversion
sulfide surfaces, including both bulk-type (FeS, CoS2, and of LiPSs across the interface (Figure 7b).[76] It was suggested
Ni3S2) and layered-type (TiS2, VS2, and SnS2) and suggested that with an optimal ratio of adsorptive TiO2 and conducting
that the diffusion of lithium ions on mediator surfaces is essen- TiN in the heterostructure (7TiN:3TiO2), the highest poten-
tial to Li2S oxidation (Figure 6c).[68] VS2, TiS2, and CoS2 func- tiostatic discharge capacity was obtained, corresponding to
tion as effective kinetic enhancer to lower the overpotential in the largest deposition amount of Li2S. Li–S cells with a hybrid
oxidation process owing to relatively low diffusion barriers for interlayer of 7TiN:3TiO2 on graphene exhibited good long-term
lithium ions on them. In the first charge cycle of Li2S-based cycling stability with 73 and 67% of initial capacities retained
composite electrodes with VS2, TiS2, or CoS2, the overpotential after 2000 cycles at 1.0 C when sulfur loadings were 3.1 and
at the beginning before the phase transition plateau is largely 4.3 mg cm−2, respectively. Li and co-workers investigated a
reduced, indicating an improved conductivity and charge heterostructured MoC@MoOx material as a polar conductive
transfer process. This general understanding was further redox mediator for Li–S chemistry, where MoC functioned as
implemented in the study of first-row transition metal mono- redox promotor and MoOx provided strong surface binding
sulfide mediators,[69] and is expected to merge the gap between toward LiPSs.[77] A largely increased current response along
theoretical understanding and practical design. with a decreased resistance was observed in symmetrical cells,
Metal sulfides are among the most promising groups of which well supported expedited LiPS transitions. The universal
heterogeneous mediators for Li–S chemistry in the sense that effect of heterostructures was further validated by Wang and
metal sulfide materials like CoS2 microparticles and large TMD co-workers, as they suggested that the strong binding of LiPSs
flakes without further engineering also worked well in Li–S to a class of transition metal phosphides and chalcogenides
batteries.[13a,64a] Therefore, sophisticated design and synthesis (CoP as a representative) was derived from a surface oxidation
of metal sulfide based mediators with controlled structure and layer.[78]
optimized exposure of active sites promise better performance Another strategy is to transform bulk metal carbide/nitride/
in high-energy-density Li–S batteries. phosphide into low-dimensional structures. This strategy has
Carbides, Nitrides, and Phosphides: Metal carbides, nitrides, two merits of 1) maximizing the exposed binding sites and 2)
and phosphides are noble-metal-like compounds and prom- regulating the electronic structure of a routine semiconductor
ising low-cost alternatives to noble metals for many bulk with metallic feature. In this regard, mesoporous spheres con-
applications such as water splitting. These interstitial alloys sisting of Co4N nanosheets were synthesized and employed as
are therefore perceived as potential candidates for kinetics the sulfur host with 72 wt% of sulfur in the composite.[79] The
control. The inclusion of interstitial atoms, with a moderate composite Co4N/sulfur cathode exhibited remarkable high-rate
polarity compared to oxygen and sulfur, in close packed metal cyclability at 5.0 C, with a capacity of 585 mA h g−1 obtained after
lattices will modify electronic structure of metal hosts through 300 cycles. The sulfur contents can be even increased to 90 and
chemical bonding process and/or concomitant structural modi- 95 wt% with superb electrochemical performance preserved. It
fication like strain, rendering metal carbides, nitrides, and is also interesting to find that Co4N nanosheets even exhibited
phosphides favorable characteristics in redox kinetics tuning. stronger adsorptivity of LiPSs than Co3O4, highly indicating
Many conductive metal carbides, nitrides, and phosphides are the superiority of low-dimensionalization of metal nitrides in
exploited for Li–S batteries, including TiC,[70] NbC,[71] TiN,[72] enhancing the surface atom exposure and LiPS affinity. Other
VN,[11c,73] MoP,[74] and Ni2P.[75] Among them, Peng et al. low-dimensional metal carbide/nitride mediators, such as TiC/
have systemically investigated TiC as conductive polar redox Mo2C/W2C nanocrystals[80] and VN nanobelt arrays,[81] have
matrix, indicating that compared with highly polar but semi- also demonstrated that effective materials engineering leads to
conducting TiO2, moderately polar but metallic conductive TiC superior LiPS-mediating properties.
better facilitated both liquid–liquid transitions between LiPSs The aforementioned two strategies can be simultaneously
and nucleation–solid nucleation growth of Li2S (Figure 7a).[70a] realized through investigating an emerging family of 2D transi-
Sun et al. synthesized conductive porous VN nanoribbon/gra- tion metal carbides, carbonitrides, and nitrides, namely MXene,
phene composite to provide strong anchoring of LiPSs and fast as the Li–S mediator. MXene is indeed an uprising option for
LiPS conversion.[11c] Tao and co-workers investigated a series electrochemical kinetic tuning, since it meets the two critical
Figure 7. Heterogeneous metal carbide/nitride mediators. a) Role of polar conductor in enhancing surface reaction and nucleation. Reproduced with
permission.[70a] Copyright 2016, Wiley-VCH. b) Schematic of twinborn TiO2–TiN heterostructures and different Li2S nucleation behaviors with different ratio
of TiO2 and TiN. Reproduced with permission.[76] Copyright 2017, Royal Society of Chemistry. c) Schematic demonstrating the two-step interaction between a
representative hydroxyl-decorated MXene phase and LiPSs, as well as corresponding XPS spectra. Reproduced with permission.[84] Copyright 2016, Wiley-VCH.
requirements of high conductivity and rich surface function- a monolayer of surface polar groups such as F and OH.
ality. Derived from selective etching and exfoliation process, Thus, MXene is regarded as a 2D atomic heterostructure of
MXenes are featured with 2D metallic carbide basal plane and metal carbide/carbonitride/nitrides and metal fluoride/(hydro)
oxide. This unique structure renders MXene with exotic prop- is to search for specific active sites and understand the interplay
erties and desirable materials in energy storage and chemical between LiPSs and these active sites, with emerging analytical
catalysis.[82] and characterization tools.
Liang et al. pioneered the use of MXene in Li–S batteries and Inorganic Polymers/Heteroatom-Doped Carbons: Inorganic
took Ti2C as the first example to show the effectiveness of the polymers, mainly represented by graphitic carbon nitride
MXene family as heterogeneous mediators.[83] MXene species (g-C3N4) polymer, and heteroatom-doped carbons have been
were able to bond sulfur species via STiC bonds formed studied as sulfur hosts or functional additives in Li–S bat-
during the thermal treatment, when surface reactive OH teries for a long time.[86] Compared to pristine carbon mate-
groups were replaced by sulfur; while electron transfer via Ti2C rials such as graphene, the presence of electronegative (O, N,
surface expedited surface redox reactions. The binding mech- and S) or electropositive (B) atoms induces the electronic struc-
anism of sulfur species on MXene was further elucidated by ture reconfiguration of carbon, contributing to enhanced
examining the interaction between LiPSs and different MXene binding energies to polar LiPSs, as many theoretical works
phases of Ti2C, Ti3C2, and Ti3CN with various surface function- suggested.[8a,87] Nevertheless, the role of g-C3N4 and heter-
alities through XPS analysis and theoretical calculation.[84] A oatom-doped carbons as heterogeneous Li–S mediators has
two-step interaction mechanism was proposed accordingly: for rarely been elucidated.
OH-terminated MXene phases, the OH groups first undergo g-C3N4 is a typical medium-bandgap semiconductor. Its
redox reactions with LiPSs to form surface thiosulfate groups valuable characteristics like thermal stability, chemical sta-
and further expose the Ti atoms through Wackenroder reac- bility, defect-richness, polarized surface, and free of metal
tions, which is analogous to the case of MnO2; then the meta- render g-C3N4 a promising material in sustainable chemistry
stable Ti atoms react with additional LiPSs to form STiC/N and multifunctional catalytic applications.[88] Zhang and co-
bonds by Lewis acid–base interactions (Figure 7c). Interwoven workers first employed oxygenated C3N4 in sulfur cathodes to
MXene nanosheet/carbon nanotube hybrids were thereafter demonstrate a Li–S cell with an ultralong cycle life over 2000
prepared to host more than 79 wt% of sulfur in the final com- cycles.[86a] Liang et al. further investigated polymeric g-C3N4
posites, enabling high-loading cathodes with sulfur loadings of as a redox promoter for Li–S chemistry to not only localize
3.6 and 5.5 mg cm−2 to stably cycled for 250 cycles at 0.2 C. the LiPS species through intrinsic polarized C3N4 surface but
Enlightened by these pioneering works, many other sulfur cath- also kinetically speed up the conversion of LiPSs.[86b] Hybrid-
odes based on MXenes were reported, showing the effective- ized with conductive graphene substrate, the polymeric g-C3N4
ness of MXene both to adsorb LiPSs and improve their redox rendered the sulfur cathode with low kinetic polarization and
reactions.[85] small resistance.
Metal carbides, nitrides, and phosphides are attractive For heteroatom-doped carbons, especially N-doped carbons,
options for advanced mediators in the sense that they possess the role of pyridinic-N or pyrrolic-N was revisited as kinetic
superior conductivity that facilitates surface charge transport mediators due to the use of in situ characterization techniques
and expedites redox reactions. They also possess a moderate and new analytical methods. For example, Dong and co-
surface polarity which balances surface binding and diffu- workers employed in operando Raman spectroscopy and theo-
sion; while in order to improve the bulk LiPS adsorptivity, retical calculation to specify the LiPS intermediates in working
constructing heterostructures with highly adsorptive materials Li–S cells. It was observed that LiPSs cannot be fully charged
such as metal (hydro)oxides could work well. In particular, back to elemental sulfur on routine carbon electrode due to the
the MXene is probed to be an ideal heterogeneous mediator weak binding of unstable Li2S8; while this key intermediate can
owing to its exotic 2D characteristic, superb metallic conduc- be strongly anchored on Lewis basic sites like pyridinic-N or
tivity, and abundant and tunable surface functionalities. A pyrrolic-N, facilitating their conversion to sulfur.[89] Yuan et al.
controlled surface orientation and increased active surface area prepared a series N-doped carbon/Li2S electrode and correlated
are in great demand to optimize redox tuning behavior, which the height of the first charging barrier to the concentration of
is worthy being studied in the future with both theoretical and pyridinic-N dopants, suggesting the promotion of Li2S oxida-
experimental advance. tion by pyridinic-N.[90] It is believed that with further advance-
ment in characterization techniques and research methods,
deeper understanding into the role of heteroatom dopants
3.1.3. Metal-Free Mediators such as pyridinic-N or highly polarized surface such as C3N4
is expected for guiding the design of metal-free heterogeneous
Despite transition metals and metal compounds are effective Li–S mediators.
in mediating Li–S redox, transition metals are generally heavy Organic Polymers/Supramolecules: Analogous to heteroatom-
elements, inevitably increasing the weight percentage of these doped carbon, organic polymeric and supramolecular mate-
mediators in the whole electrode. Moreover, the use of noble rials, especially those conductive ones like polyaniline,[91] poly
metals (i.e., Pt and Au), heavy metals (i.e., Co, Ni, Cu, and Sn), pyrrole,[92] poly(3,4-ethylenedioxythiophene):poly(styrene sul-
and toxic metal compounds (i.e., V2O5) will either reduce the fonate),[93] etc., are a class of intensively studied coating or mod-
cost efficiency of Li–S batteries or increase the environmental ifying materials for Li–S batteries due to their diverse surface
burden. So, it is of substantial interests and importance to functionalities and tailorable electrical properties. Neverthe-
explore metal-free mediators including both inorganic poly- less, their function as a Li–S reaction mediator has rarely been
mers/heteroatom-doped carbons or organic polymers/supra- validated with unambiguous experimental or theoretical evi-
molecules. The key for designing efficient metal-free mediators dences. Recently, desirable organic polymeric/supramolecular
mediators were explored with the progress in sophisticated structural units such as unsaturated bonds or sulfydryl groups
molecular design and method innovation. to form covalent bonds with polysulfuric chains, and the redox
These polymeric/supramolecular mediators can be derived of sulfur would proceed through the breakage of SS bonds
from exotic binding sites tailoring or unique structure design within the immobilized polysulfuric chain. Unlike routine
of conventional conductive polymer. For example, Zhang and Li–S reactions producing mobile LiPSs, this reaction scheme
co-workers rationally incorporated phytic acid as a cross-linker restrains the formation of highly soluble LiPSs and thereby mit-
in polyaniline, enriching the quinonoid imine group that pos- igates the shuttle effect. The greatly suppressed shuttle effect
sesses stronger binding energies to LiPSs than the naturally was validated by Yan and co-workers, who designed a series of
existed amine group (Figure 8a).[94] The transition between thiol-functionalized or allyl-functionalized nanocarbon hosts
deprotonated and protonated states of quinonoid imine trig- that adopted the above short-chain-LiPS redox mechanism and
gers facile adsorption and desorption of LiPSs, thus signifi- employed in situ ultraviolet/visible light (UV/Vis) spectroscopy
cantly promoting the kinetic conversion of LiPSs into Li2S to monitor the specie evolution (Figure 8b).[102] For example,
and corresponding to enhanced capacity and rate performance cysteamine was employed to functionalize reduced graphene
of sulfur cathodes employing the quinonoid-imine-enriched oxide with sulfydryl groups, which was further tethered with
mediator. Chen and co-workers reported a radical polymer, short sulfur chains.[102a] The modified cathode materials exhib-
poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate) ited high capacity retention of 87% after 450 cycles at 1.0 C.
(PTMA), that can be in situ activated into positively charged Moreover, the Coulombic efficiency remained as high as 99.5%
PTMA+ when first charged to 4.0 V. The in situ activation is for 500 cycles at 1.0 C with no lithium nitrate additive to pas-
critical as it produces more efficient NO+ cation sites than sivate the anode. Along with the in situ UV/Vis observation,
NO• radicals, and the capacity of a sulfur cathode modified the drastically restrained shuttle effect was unambiguously
with PTMA+ was nearly 80% higher than the control cathode evidenced.
with pristine PTMA. Helms and co-workers elucidated the Another type of organic heterogeneous mediators possess
molecular-level underpinnings that a rationally designed poly- intrinsic redox activities. Different from organic (poly)sulfide
electrolyte binder, poly[(N,N-diallyl-N,N-dimethylammonium) mediators that function through immobilized polysulfuric
bis(trifluoromethanesulfonyl)imide], allowed dual-ion regu- chains, these intrinsic redox-active mediators could react with
lation of improving lithium ion transport and retarding poly- sulfur species chemically and restore their redox activities elec-
sulfide diffusion through anion metathesis.[95] As a result, the trochemically. As an indispensable feature, the redox potential
deposition kinetics of Li2S was drastically enhanced, leading to of these mediators must sit within the working voltage window
superior sulfur at a high loading of up to 8.1 mg cm−2. Aside of Li–S batteries. Thus, Helms and co-workers employed
from the binding-site engineering, the structure of polymer high-throughput computational methods to screen more than
mediators can be optimized through molecular imprinting.[96] 80 polycyclic aromatic hydrocarbons (PAHs) with suitable redox
The use of long-chain LiPSs as the molecular template during potentials.[103] PAHs have a remarkable advantage in offering
the synthesis of molecular imprinted polymers (MIPs) ben- exceptionally low reorganization energy, which is a favorable
efits the recognition and rebinding of long-chain LiPSs by MIP characteristic for an ideal redox mediator. In addition, PAHs
mediators. Therefore, the MIP mediator exhibited the strongest with well-tailored molecular structures can also be assembled
adsorption of long-chain LiPSs and the highest activity to facili- into supramolecules through noncovalent interactions. Perylene
tate LiPS conversion. bisimide[103a] and N-aryl-substituted benzo[ghi]peryleneimide
Beyond the enhanced binding capability through molec- (BPI)[103b] were found to be redox active within a voltage
ular engineering, there are two types of special polymeric/ window of ≈2.0–2.5 V (vs Li/Li+). Among them, BPI exhibited
supramolecular mediators capable of mediating the LiPS thrilling capability to mediate the growth of Li2S from dissolve
reactions directly. One type is based on the surface-immo- LiPSs (Figure 8c).[103b] With the presence of BPI, the 3D precipi-
bilized polysulfuric catenation reactions, resemble to that tation pathway was opened for Li2S on the carbon paper current
occurring on oxidative inorganic mediators like MnO2. The collector, quite distinct from the routine 2D growth model. The
concept of organic (poly)sulfide mediators can be traced to the extended dimension of deposition rendered 600% and 220%
use of phenyl polysulfides by Wang et al. in 2004.[97] Pyun and enhancement in Li2S formation and total sulfur utilization
co-workers further explored the idea of inverse pulverization to with the BPI mediator, respectively. The search for intrinsically
synthesis sulfur-rich polymers in 2013.[98] Since then, sulfur- redox-active organic mediators can also be inspired from con-
rich polymeric materials have attracted considerable attention ventional organic electrode materials for lithium and sodium
due to their relatively better cycling stability than elemental storage. Chen and co-workers described a simple yet effective
sulfur when serving in Li–S batteries. The kernel of this con- strategy of utilizing anthraquinone (AQ), one of the mostly
cept is to design organic/polymeric cross-linkers to covalently investigated organic electrode materials, as a redox-active medi-
bond polysulfuric chains.[99] Benefited from flourishing organic ator for Li–S batteries.[104] AQ can be stabilized on reduced gra-
chemistries, various cross-linkers, including benzene,[97,99i] phene oxide through π–π stacking and LiPSs reacted with the
phenyl diene,[98,99b] linear carbine/diene,[99a,h] trithiocyanuric benzoquinonyl (CO) group to form SO groups, presumably
acid,[99c] covalent triazine frameworks,[99d] benzoxazine,[99e] proceeding a surface-bound redox reaction as both theoretical
limonene,[100] and methylsulfonyl methanethione radical,[101] etc., calculation and in situ X-ray diffraction (XRD) indicated. The
were developed, aiming to improve the electrical/ionic conduc- abundance in explored organic electrode materials and the
tivity and the distribution of polysulfuric domains. These cross- extraordinary design flexibility of organic materials promise a
linkers share a common characteristic that they possess reactive myriad of opportunities for organic heterogeneous mediators.
Figure 8. Heterogeneous organic mediators. a) Schematic of the phytic acid-induced enrichment of quinonoid imine and the theoretically calculated
binding energies of various nitrogen groups in polyaniline. Reproduced with permission.[94] Copyright 2017, Wiley-VCH. b) Schematic of copolymeriza-
tion of S8 with sulfydryl-functionalized reduced graphene oxide (GSH) and in situ UV/Vis spectra of S-GSH cathode at various voltages. Reproduced
with permission.[102a] Copyright 2017, American Chemical Society. c) Schematic representation of the electrodeposition of Li2S onto carbon cloth in the
absence and presence of BPI and electrochemical performance with BPI. Reproduced with permission.[103b] Copyright 2016, American Chemical Society.
Organic polymers and supramolecules are very attractive het- from organic chemistry and polymer/supramolecular chem-
erogeneous mediators as there are almost infinite opportunities istry. The advance in high-throughput computational design
to regulate their properties by rationally exerting the knowledge and delicate molecular engineering will create a plenty of room
for the development of heterogeneous organic mediators. through one of following mechanisms or combined: 1) accel-
Future directions might focus on pursuing an in-depth under- erating electron transfer between the active materials and the
standing of mediating mechanism, designing more efficient electrodes via a solution pathway instead of a direct surface
active sites, and improving their electronic properties. route; 2) creating uniform distribution of active materials in
reaction to circumvent spatial inhomogeneity as well as fol-
lowing irreversible reactions.
3.1.4. Others
Elemental materials with exotic surface and electronic prop- 3.2.1. Intrinsic Mediators: LiPSs
erties can also serve as Li–S mediators.[105] Phosphorene is
a single layer of black phosphorous, a new atomically thin LiPSs are natural RMs in Li–S chemistry. Bare sulfur and
2D material that has been extensively studied in electronics Li2S are poor electrode materials as inherent ionic/electronic
and optoelectronics due to its unique direct bandgap between insulators. Their capability of being battery materials is in
zero-gap graphene and 2D TMDs.[106] Koratkar and co-workers fact realized through the generation of soluble LiPS inter-
employed few-layer phosphorene (FLP) nanosheets to promote mediates, which easily diffuse to the conductive surface and
LiPS conversion.[107] Reduced polarizations of reduction and oxi- undergo a series of complicated reactions. Despite the com-
dation peaks as well as onset potential shifts could be observed plexity of the reaction nature between LiPSs, recently devel-
in cyclic voltammetric profiles of LiPS catholyte with a FLP-dec- oped in situ and in operando characterization techniques
orated carbon nanofiber current collector. The specific capacity revealed that both electrochemical and chemical (dispro-
of FLP-carbon nanofiber cathodes remained 660 mA h g−1 after portionation and comproportionation) reactions exist in the
500 cycles at 1.0 C, corresponding to a 0.05% decay rate per cycle. whole reaction scheme in aprotic electrolytes.[108] Although
Heterogeneous mediators are extensively studied in Li–S chem- electrolyte properties significantly influence the main existing
istry due to their tunable surface chemistry, tremendous compo- forms of LiPSs, being either dianions (e.g., S62− and S42−)
sitional variety, controllable crystal structure, and adjustable elec- or radicals (e.g., S3•−), and the correlation between existing
tronic properties. A leap of cathode scaffold performance could be forms of LiPSs and dominant reaction mechanism remained
realized with inorganic compound mediators. However, most of elusive, it is irrefutable to consider LiPSs as natural RMs in
these compounds contain heavy metal elements. Their incorpora- Li–S batteries.
tion into the cathode might impair the overall gravimetric energy In contrast to the mounting efforts on disclosing in-opera-
density of battery, and this effect needs to be fairly evaluated from tion speciation and time-dependent evolution of LiPSs, the
a cell-level perspective. Developing efficient organic heteroge- spatial distribution of LiPSs and its influence on the electro-
neous mediators is a promising direction in propelling the Li–S chemical behaviors are less concerned. Peng et al. have pro-
battery reaction kinetics and performance, as there will be marve- posed a universal self-healing mechanism in Li–S batteries
lous opportunities endowed by well-established modern organic using preloaded LiPSs as extrinsic “healing” agents to enable a
chemistry and polymer/supramolecular chemistry. stable cycling of micrometer-sized sulfur cathodes.[15] Distinct
from electrochemically produced LiPSs, the preloaded LiPSs in
electrolyte could eliminate the initial spatial inhomogeneity of
3.2. Homogeneous Mediators LiPS distribution in the working cells before solid products pre-
cipitated from within the electrolyte far from conductive sur-
To date, heterogeneous mediators take a dominant role in face, substantially reducing irreversible loss of active materials
Li–S battery research field. However, homogeneous mediators (Figure 9a). A uniform initial distribution of LiPS RMs would
are also promising candidates to offer a solution toward high- lead to a homogeneous deposition and smooth reoxidization
energy-density Li–S batteries, though less commonly con- of discharge products. The absence of ultralarge solid particles
cerned. Homogeneous mediators are often referred to as redox and clogged conductive surface would be ideal for a facilitated
mediators (RMs), a class of redox couples that undergo surface liquid–solid phase transfer. By adopting external LiPS-con-
electroredox and diffuse to react with the active materials chem- taining electrolyte (with 0.33 mol [S] L−1) in the Li–S batteries,
ically. This unique feature stands out in Li–S batteries because an unprecedented cycle life of 7500 cycles was achieved with
immobile solid phases such as sulfur and Li2S2/Li2S are the a decay rate of 0.010% per cycle. Increasing the concentration
end products of oxidation and reduction reactions, respectively, of preloaded LiPS to 1.0 mol [S] L−1 further realized truly self-
making it difficult for them to achieve ideal contact with hetero- healed cycling performance with no capacity decay for 2000
geneous mediators and thereafter to be “catalyzed” or “medi- cycles.
ated.” Learning from conventional understanding of catalysis, The superiority of LiPSs as inherent RMs to facilitate
the catalyst must have access to immobile phases if the reaction the Li–S reactions becomes even more significant in an
involves solid reactants. Therefore, homogeneous mediators electrolyte-lean scenario, as proposed for building practical
are indispensable in facilitating solid-phase-involved redox reac- high-energy-density Li–S cells with a low E/S ratio.[109] For
tions, such as the formation of Li2S and its inverse oxidation. example, Balasubramanian and co-workers worked on a LiPS-
The use of homogeneous mediators might be an ultimate solu- sparingly-solvating electrolyte based on a fully complexed
tion to achieve an expedited full reaction scheme. solvate of ACN2LiTFSI (ACN: acetonitrile; LiTFSI: lithium
In Li–S batteries, homogeneous mediators always readily bis(trifluoromethane)sulfonamide) and a noncoordinating
react with active materials, and expedite redox reactions solvent of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl
Figure 9. Intrinsic homogeneous mediators of LiPSs. a) Left: schematic of how spatial heterogeneity impacts the solution–solid phase transfer based
on Gibbs–Thomson theory. Right: scanning electron microscopy images and corresponding energy dispersive spectroscopic mapping of elemental
nickel and sulfur of a nickel foam/sulfur microparticle cathode discharged in routine electrolyte (RE) and LiPS-preloaded self-healing electrolyte (SHE).
Reproduced with permission.[15] Copyright 2017, American Chemical Society. b) Left: first cycle voltage profiles of separate ACN2LiTFSI–TTE cells using
bulk sulfur electrodes using C/30 rate and at indicated temperatures. Right: The evolution of sulfur species as a function of capacity, monitored by
operando XRD. Reproduced with permission.[109a] Copyright 2017, American Chemical Society.
ether (TTE).[109a] The Li–S cell with ACN2LiTFSI–TTE elec- 3.2.2. Extrinsic Mediators
trolyte behaved distinctively from that with a conventional
ether-based electrolyte (1,3-dioxolane:1,2-dimethoxyethane; Analogous to organic heterogeneous mediators, extrinsic
DOL:DME), showing a great potential for Li–S batteries with homogeneous mediators can be classified into two groups: one
an ultralow E/S ratio targeting to 1 mLelectrolyte gsulfur−1. At an is based on sulfur-chain catenation reactions in the electrolyte;
elevated temperature of 55 °C, the LiPS nonsolvating ACN– the other is so-called RM with intrinsic redox activity within
TTE electrolyte switched to a LiPS-sparingly-solvating one the working voltage window of Li–S batteries. Their advantages
with a certain tiny solubility of LiPSs (e.g., Li2S6), which redi- essentially resemble to those discussed for their heterogeneous
rected the reaction pathway by fundamentally changing the counterparts; but as mainly in dissolved state, they possess
rates of competing reactions of direct electrochemical reduc- higher diffusivity and better access to the solid products of
tion and LiPS-mediated chemical disproportionation. The sulfur/Li2S.
largely reduced cell polarization and enhanced kinetics were The first class of extrinsic mediators generally exert the thiol
attributed to this tiny amount of LiPS RMs, as suggested by chemistry and polysulfuric chemistry in aprotic solvent, medi-
operando XRD, X-ray absorption spectroscopy, and theoretical ating the SS bond cleavage and recombination through var-
modeling (Figure 9b). ious thiol radicals. The replacement of terminal lithium ions
with organic groups brings about different

redox activity of terminal S• radicals, poten-
tially rendering a more facile dissociation of
SS bonds. Wang and co-workers introduced
dimethyl disulfide (DMDS, CH3SSCH3) as a
cosolvent for Li–S batteries, enabling an alter-
native reaction pathway for sulfur cathode
by forming soluble dimethyl polysulfide
(DMPS, CH3SSmSCH3) species instead of
LiPSs.[110] DMPSs and the reduction products
of lithium organosulfides (herein CH3SLi)
showed better electrochemical kinetics and
reversibility than LiPSs and Li2S, respec-
tively. Fu and co-workers proposed a similar
concept but investigated dimethyl trisulfide
(DMTS, CH3SSSCH3) instead, since DMTS
possesses an even lower dissociation energy
of the SS bond than DMDS.[111] Inspired by
biocatalysts, Yang and co-workers designed a
series of biomolecules as LiPS-scission rea-
gents to suppress the shuttle effect.[112] These
LiPS-scission reagents, including vitamin
C, glutathione, and dithiothreitol (DTT),
share a common feature of sulfydryl groups
to slice the SS bond within LiPSs, thus
rapidly erasing the accumulation of LiPSs
and directing to more favorable kinetics
(Figure 10a). Inserted with a graphene/DTT
interlayer, the Li–S cells exhibited a very high
initial capacity of 1643 mA h g−1 at 0.2 C and
a low capacity decay rate of 0.036% per cycle
for over 1100 cycles at 5.0 C.
The other class of extrinsic mediators
known as RMs generally work through
redox reactions of their own redox cou-
ples, in an electrochemical activation and Figure 10. Extrinsic homogeneous mediators. a) Schematic of electrode configuration for
[112]
ensuing chemically functional manner. Li–S battery with a graphene/DTT interlayer. Reproduced with permission. Copyright 2017,
The design principle for homogeneous and American Chemical Society. b) Comparison between the first voltage profiles of Li2S electrodes
charged at C/5 using different electrolyte solutions containing various RMs, as well as XRD
heterogeneous RMs is generally the same. patterns of the charged electrodes. Reproduced with permission.[113] Copyright 2014, American
One critical design parameter is the redox Chemical Society.
potential of RMs. Aurbach and co-workers
investigated various RMs in typical Li–S
batteries.[113] Categorized by oxidization potential compared precipitation and oxidation processes. For instance, indium
with active materials, redox mediators were divided into iodide was demonstrated to provide both the lithium iodide/
three types, namely, ERM < ELi2S (cobaltocene), ERM ≈ ELi2S iodine RM couple for Li2S oxidation and an indium-based
(dibenzenechromium), and ERM > ELi2S (decamethylferro- protective film on the lithium anode.[114c] Lee and co-workers
cene, lithium iodide, and ferrocene). They found that the introduced two metallocenes as tandem RMs in Li–S flow bat-
third type of RMs, whose ERM > ELi2S, would enable a supe- teries with the chromium-based one propelling the reduction
rior utilization of active materials. With a fixed redox poten- reactions while the nickel-based on promoting the oxidation
tial much lower than activation energy of solid Li2S cathodes, reactions.[114a] Such a tandem-RM concept can be realized
RMs would facilitate the conversion of solid Li2S into LiPSs by using only one RM (e.g., ethyl viologen diperchlorate),
in a solution pathway, and the as-produced LiPSs further pro- which possesses multielectron redox activities occurring
moted the oxidation of Li2S as intrinsic RMs. Upon cycling, at different potentials to mediate the successive multistep
little trace of solid Li2S could be observed in the cathode at a Li–S reactions.[114d]
fully charged state, indicating a thorough conversion of solid Homogeneous mediators are ideal options in that a small
species (Figure 10b). Since then, the research into homo- number of redox couples would be enough to homogenize and
geneous RMs for Li–S batteries and flow cells is becoming reactivate massive active materials, improve the utilization of
progressively concerned.[114] Some of them even described active materials, as well as increase the reversibility of cathode
multifunctional RMs or RM combo to facilitate both Li2S reactions without impairing gravimetric energy density.
However, it should also be noticed that the incorporation of 1. Moderate affinity toward LiPS species balances surface
RMs would inevitably induce another redox shuttle couple charge transfer and subsequent diffusion process, which
in the system. The redox couple would readily react with the promotes surface transition and also prevents the blockage of
lithium metal anode, ending up with a severer shuttle pheno active mediating sites.
menon and harsher anode corrosion. These unwanted side 2. Superior conductivity guarantees facile electron transfer
reactions might speed up the dying of a cell and vitiate the pathway, especially in high-loading or high-rate conditions,
overall Coulombic efficiency to some extent. So, this concept where high current densities might introduce undesired
must be considered along with advanced anode protection large overpotential at the electrode interface.
strategies. 3. Optimized structure contributes to full exposure of active
surfaces and sites, and expedites ion transport. Achieving
higher kinetic promotion with less mediators helps to build
batteries with high energy density based on the gross weight.
4. Conclusions and Perspectives
4. Chemical and electrochemical stability of mediators are es-
4.1. Design Principles for Efficient Mediators sential for allowing favorable long-term cycling performance.
Stability in active states of mediators is crucial in persistent
Efficient mediators pave a promising road for the design of kinetic promotion for practical applications.
high-energy-density Li–S battery. By expediting ion and charge
transfer process, thereby facilitating redox conversions, media- Therefore, to fully explore the potential of these heterogeneous
tors can reduce the overpotential and internal resistance of Li–S mediators in building high-energy-density Li–S batteries, sophis-
redox reactions and increase the energy density and energy effi- ticated synthesis techniques and in-depth mechanistic investiga-
ciency of Li–S batteries. This is especially critical for high sulfur tion of mediator-controlled kinetics are of paramount importance.
loading and high sulfur content scenarios, where redox kinetics For homogeneous mediators, suitable redox potential, good
are heavily impaired due to sluggish transport phenomenon solubility/diffusivity, excellent chemical/electrochemical sta-
and hazardous accumulation of active materials. Several key bility, and concurrent efficient strategies to protect lithium
points are therefore proposed here for highly efficient mediator metal anodes are in great demand. Insights from lithium–
design (Figure 11). oxygen/air batteries are somewhat instructive, but the redox
For heterogeneous mediators, moderate surface affinity toward potential window is usually mismatched.
LiPSs, superior conductivity, optimized structure, and excellent
chemical/electrochemical stability are in paramount pursuit. 1. Suitable redox potential enables smooth phase transitions
without exerting extra energy beyond necessary to activate
dead materials as well as preserving electrolyte stability from
undesirable parasitic reaction such as electrooxidation, which
is crucial to energy efficiency.
2. Good solubility and diffusivity guarantee that sufficient RMs
could be added to the battery system and transported to inac-
tive and immobile phases, especially in high sulfur loading
and low E/S ratio context.
3. Chemical/electrochemical stability ensures sustained function
of RMs and enables superb long-term cycling performance.
4. Efficient anode protection strategies prevent anode corro-
sion, benefiting a high Coulombic efficiency and cell safety.
Notably, for both heterogeneous and homogeneous media-

tors, low cost is another key factor in promoting practical appli-
cations of high-energy-density Li–S materials. Last but not the
least, there is no demonstration of either heterogeneous or
homogeneous mediators in Li–S pouch cells with practically a
high sulfur loading and a low E/S ratio. Whether the concept of
Li–S redox mediation can be translated in reality requires fur-
ther validation in practical conditions; otherwise, tremendous
attempts of using coin cells will probably be an unfortunate
fairy tale.
4.2. Combined Strategy for Building High-Energy-Density

Li–S Batteries
Figure 11. Design principles for efficient heterogeneous and homoge-
neous mediators. The two outmost circles indicate the common working
range of heterogeneous (cyan) and homogeneous mediators (pink). “s” Both heterogeneous and homogeneous mediators hold great
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