REVIEW

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Cyclic Voltammetry in Lithium–Sulfur Batteries—Challenges

and Opportunities
Xia Huang, Zhiliang Wang, Ruth Knibbe, Bin Luo,* Syed Abdul Ahad, Dan Sun, and
Lianzhou Wang*

lithium-air, lithium–sulfur, sodium-ion,

Lithium–sulfur batteries (LSBs) have attracted tremendous interest due to and aluminum-ion batteries.[5] Among
their high theoretical energy density and the earth-abundant sulfur feedstock. these competitors, the lithium–sulfur bat-
Multifarious characterization techniques have been applied to investigate the tery (LSB) that couples the earth-abundant
sulfur cathode with a lithium anode is
electrochemical mechanisms and the structure–property relationships in LSBs.
considered as a promising candidate.[6]
Among them, cyclic voltammetry (CV), a basic electrochemical tool, can provide
Different from the intercalation energy
indispensable thermodynamic and kinetics information of the redox processes. storage mechanism, LSBs operate on con-
However, the CV analysis in most LSB studies is sketchy—providing some well- version reactions of the sulfur cathode
known information while ignoring some specific features. To fulfill the versatile and metal striping/plating of the anode,
role of CV and thus spur further breakthroughs on LSBs, the electrochemical giving a high theoretical energy density
reactions and challenges are first described, followed by the work principles and of 2600 W h kg1 or 2800 W h L1.[7]
Although the earliest LSBs dated back to
experimental setup of LSBs for the CV technique. Then, various protocols for
1960s,[8] their practical application has been
specific research purposes in LSBs are summarized, particularly on the perfor- severely limited in niche due to the under-
mance evaluation of sulfur cathodes. Ending with challenges and the outlook of lying challenges of the multistep and
the CV technique in the LSB study, the Review provides a timely summary and multielectron processes, which involve
thus can be a guidance for future studies on batteries. complicated solid–liquid–solid phase trans-
formations.[9] As most of the challenges
originate from the cathode area, the pri-
mary research has been focused on the
1. Introduction cathode part.[10] To shift LSBs toward a practical application, a
comprehensive understanding of the electrochemical reactions
With the burgeoning energy demand and the accompanying and the structure–property relationships is imperative.[11] In this
environmental issues, the electrochemical energy storage regard, multiple characterization techniques have been applied
(EES) has gained a growing recognition.[1] Lithium-ion batteries in LSBs to illuminate the mechanisms[12]—from the basic elec-
(LIBs) have revolutionized the portable electronics over the past trochemical tools (electrochemical impedance spectroscopy and
three decades.[2] However, their theoretical energy density is lim- cyclic voltammetry [CV]) to the traditional ex situ techniques
ited by the topotactic Liþ intercalation and deintercalation energy (such as X-ray diffraction [XRD], X-ray photoelectron spectros-
storage mechanisms to 420 W h kg1 (gravimetric energy den- copy, X-ray absorption spectroscopy, Raman spectroscopy, UV-
vis spectroscopy, scanning electron microscopy, transmission
sity) or 1400 W h L1 (volumetric energy density).[3] The develop-
electron microscopy [TEM]), and then to the cutting-edge in situ
ment of electric vehicles calls for EES of higher energy density,
or operando characterizations (such as operando XRD, Raman,
longer reliability, and lower cost.[4] Thus, various “beyond
and TEM).[13] Among them, CV is one of the most basic and ver-
lithium” technologies have gained momentum, such as satile electrochemical tools[14] that is widely used to identify the
redox couples,[15] describe the electrochemical processes,[16] and
X. Huang, Dr. Z. Wang, Dr. B. Luo, Dr. D. Sun, Prof. L. Wang investigate the reaction kinetics.[17] However, due to the compli-
Nanomaterials Centre, School of Chemical Engineering and Australian cated electrochemical reactions in LSBs, ingenious CV protocols
Institute for Bioengineering and Nanotechnology
The University of Queensland and elaborate analysis are needed to obtain more details on the
St Lucia, QLD 4072, Australia redox process.[18] As a result, mostly, CV is conducted using the
E-mail: [email protected]; [email protected] regular two-electrode cells with a sketchy description of the well-
Dr. R. Knibbe, S. A. Ahad known redox process, whereas some specific features observed on
School of Mechanical and Mining Engineering the CV curves are ignored, such as the CV peak potential and cur-
The University of Queensland rent difference. These specific features may be critical in under-
St Lucia, QLD 4072, Australia
standing the mechanisms and structure–property relationships.
The ORCID identification number(s) for the author(s) of this article To fulfill the versatile role of CV and thus spur further break-
can be found under https://doi.org/10.1002/ente.201801001. throughs on the performance of LSBs, the applications of CV in
DOI: 10.1002/ente.201801001 the study of sulfur cathode for LSBs are summarized in this

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Bin Luo is currently an ARC DECRA

Research Fellow of the Nanomaterials
Centre in the Australian Institute for
Bioengineering and Nanotechnology
(AIBN), the University of Queensland
(UQ). He received his B.E. degree
from Central South University (CSU)
in 2008, and his Ph.D. from the
National Centre for Nanoscience and
Technology (NCNST), the University
of Chinese Academy of Sciences (UCAS) in 2013. His
research interest focuses on the development of 2D
nanomaterials/nanostructures for energy storage or
conversion applications, including rechargeable batteries,
supercapacitors, and photocatalysis.

Lianzhou Wang is currently a

Figure 1. Versatile role of CV in the LSB study. Professor in the School of Chemical
Engineering and Director of the
Nanomaterials Centre, of the
Review, as schematically shown in Figure 1. Basic chemistry University of Queensland (UQ),
and challenges in LSBs are introduced first, followed by the Australia. He received his Ph.D.
CV principles and experimental setup. Then, the applications degree from Shanghai Institute of
of CV by different protocols are summarized according to Ceramics, Chinese Academy of
the research purposes and CV setup, including mechanism Sciences in 1999. Before joining UQ
studies mainly using three-electrode CV and application-oriented in 2004, he has worked at two
structure–property relationship studies mainly by two-electrode national institutes (NIMS and AIST) of Japan for 5 years.
CV, which consists of the regular cell and specially designed Wang’s research interests include the design and
(symmetrical and asymmetrical) cells. Finally, the challenges development of functional nanomaterials for renewable
and opportunities of CV in LSB studies are briefly discussed. We energy conversion and storage applications including
believe that this Review will provide a timely summary and con- photocatalysis, low-cost solar cells, and EES devices.
siderable guidance for using CV in the LSB research.

2. Electrochemical Reactions and Challenges

in LSBs
2.1. Electrochemical Reactions

LSBs operate on conversion reactions on the sulfur cathode and

metal striping/plating on the lithium anode, demonstrating an
overall reaction of Equation (1).[19]

S8 þ 16 Li ⇌ 8 Li2 S (1)

However, the actual redox reactions are much more compli-

cated, generating a series of soluble lithium polysulfide inter-
mediates (LiPS, Li2Sn, 2 < n < 8). Figure 2 shows the typical
two-plateau galvanostatic discharge/charge curves and the
related species transformation in a traditional LSB. S8 (solid) is
first reduced to catholyte Li2S8 (solid-to-liquid), showing the first
voltage plateau at 2.2–2.3 V. Then, Li2S8 is further reduced to
short-chain Li2S6 and Li2S4, featuring a steep voltage slope
(liquid-to-liquid). Theoretically, these two steps contribute to
one-quarter of the overall capacity (419 mA h g1).[20] Then,
the dissolved short-chain LiPS is reduced to an insoluble lithium
sulfide (Li2S and/or Li2S2), generating the second longer and Figure 2. Typical galvanostatic discharge/charge curves and the related
lower voltage plateau at 1.9–2.1 V. These steps contribute to chemistry in a traditional liquid LSB. Reproduced with permission.[22]
the remaining capacity of 1256 mA h g1.[20a] Copyright 2015, The Royal Society of Chemistry.

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Apart from the electrochemical reductions, there are chemical complete reactions. Since then, some primary research efforts
reactions as described by Equations (2) and (3).[21] have been focused on the material design that features a
high conductivity with good sulfur distribution, physical
Li2 Sn þ Li2 S ! Li2 Snm þ Li2 S1þm (2) confinement/chemical interaction to polysulfide, and/or catalysis
1 to the redox process. Various (modified) carbons, functional pol-
Li2 Sn ! Li2 Sn1 þ S8 (3) ymers, metal oxides/carbides/sulfides, and their hybrids have
8
been developed, which further enhance the sulfur utilization,
The aforementioned LSBs redox process provides a general rate performance, and cycling stability.[26] However, it has been
guidance for material design and specific electrochemical pro- recognized that high areal sulfur loading (>5 mg S cm2), low
cess analysis. However, the sensitivity of redox intermediates electrolyte/sulfur (<4 μL mg1) ratio, and low lithium excess
and redox products to experimental conditions and the moisture, are essential for achieving high energy density LSBs that can
air, and characterization atmosphere makes it difficult to sepa- compete with LIBs.[27] In such situations, the strategies that
rate and thus identify all the products unambiguously. Thus, achieved high specific capacity and long cycling life in low sulfur
more efforts are still needed to figure out the redox mechanisms. loading, flooded electrolyte, and superfluous lithium systems
may not achieve similar or comparable performance, as the
2.2. Challenges aforementioned challenges are greatly aggravated and new chal-
lenges emerge.[28]
The practical application of LSB has been hindered by several Thus, breakthroughs are urgently needed to promote the prac-
intrinsic challenges.[23] tical application of LSBs, where a better understanding of the
First, sulfur and its reduced products, e.g., lithium sulfide, relationships between redox mechanisms and structure–property
are both ionic and electronic insulating, leading to poor active- are imperative. CV, a basic electrochemical tool that can provide
material utilization. Various conductive cathode hosts have information on both thermodynamics and kinetics, is thus indis-
been developed, which greatly enhanced the specific capacity. pensable to achieve these goals. To fulfill its versatile role, a better
However, too much conductive additives will sacrifice the overall understanding of its principles and the experimental setup is
energy density. Moreover, during the reciprocating charge/ needed.
discharge processes, the insulating sulfur and lithium sulfide
tend to accumulate on and passivate the cathode surface, result-
ing in the fast capacity degradation or even in the “sudden death”
3. CV Principles and Experimental Setup
of the battery.[7b,24]
Second, although the dissolved LiPS intermediates in the 3.1. Theory of CV
electrolyte can facilitate the kinetics, it also suffers from the noto-
rious “shuttle effect.” The long-chain LiPS can diffuse from CV is operated based on the Nernst equation and observed as a
the cathode to anode and is thus chemically reduced by lithium peaked current–potential curve.[29] Figure 3 is a representative
to short-chain LiPS or solid lithium sulfide, as described in CV curve for a simple reversible process of Equation (5).
Equation (4). The short-chain LiPS can diffuse back to the
cathode, leading to a low coulombic efficiency. Lithium sulfide O þ ne ⇌ R (5)
deposits on the lithium surface, thereby aggregating the cell
polarization. In short, the shuttle effect is the origin of active- where O is the oxidized species, R is the reduced species.
material loss, electrolyte degradation, lithium corrosion, and pas-
sivation, leading to an unsatisfied capacity and a short cycling
stability.[20b]

ðn  1Þ Li2 Sn þ 2Li ! nLi2 Sn1 (4)

Third, the volume change of the cathode during charge/

discharge processes can lead to structure pulverization.[7a]
Finally, lithium dendrites formation aggregates electrolyte
degradation and battery failure, which can also cause safety
issues.[25]
To handle these challenges, significant efforts have been
devoted to LSBs. However, it was not until 2009 that a major
breakthrough was reported by Nazar and co-workers. A highly
ordered carbon–sulfur nanostructure coated with polyethylene
glycol (PEG) enables a high capacity of 1320 mA h g1 at
168 mA g1, which is much higher than the typically reported
300–550 mA h g1 at that time. The conductive mesoporous car-
bon framework guarantees the electrical contact and Liþ access to
sulfur, which also helps in trapping polysulfide. PEG coating fur- Figure 3. A schematic CV curve for a simple reversible reaction, with the
ther retards the diffusion of polysulfide, which facilitates more inset showing the voltage change during the CV scan.

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During the CV test, a linearly swept potential (incentive) at a When│E λ  E p,c │ > 35 n1 mV1 is applied, ΔE p equals
scan rate of v is applied to the electrode, and the redox reactions at 2.3RT=nF (59 n1 mV1 at 25  C), which is independent of
the electrode/electrolyte interface are detected by measuring the the scan ratev. 2) For the electrochemical reversible process with
resultant current (response). The applied potential is swept in the stable products (chemical reversible), ip,a =ip,c equals 1, which is
opposite direction at time (λ), when the set potential (Eλ) is independent of v and E λ .
reached (Figure 3 inset). At the beginning of the cathodic scan However, practical situations are much more complicated. An
(usually starts from open circuit voltage [OCV]), the voltage is electrochemical reversible system can show an increase in the
higher than the reduction potential and only capacitive current peak potential separation due to the uncompensated resistance
flows (non-Faraday currents). As voltage approaches the reduc- (Ru) between the working electrode (WE) and the reference elec-
tion potential, reduction begins, consuming O at the electrode trode (RE). The system may show reversible curves at smallv,
surface. Thus, a concentration gradient between the electrode while irreversible curves at high v. For systems with high
surface and bulk solution forms and diffusion begins. The dif- electron-transfer barriers (quasi-reversible system, when ip is not
1
fusion flux forms cathodic current—which is proportional to proportional to v2 ), more negative potentials are needed for
the concentration gradient. As the scanning voltage continues reduction and more positive for oxidation—which produces a
to be more negative, surface concentration of O decreases, larger ΔE p and a rounder peak summit.[29b] Furthermore, com-
and the flux increases. When the surface concentration of O is plex electrode processes with different species may be involved
exhausted, the flux reaches a peak. This peak corresponds to the (e.g., the LSB system). Thus, additional attentions are needed
cathodic peak current, ip,c, and cathodic peak potential,E p,c . Then, on the experimental design and data analysis, especially for
the current begins to decrease due to the depletion effect. During the mechanism study. For the material-based LSB study,
the opposite scan (anodic scan), where oxidation happens, the Equation (7) is usually used for the calculation of lithium-ion dif-
anodic peak current, ip,a , and oxidation potential, E p,a , are fusion coefficient, which is reasonable for the qualitative compar-
obtained along with the increasing potential.[29a] ison of the order of magnitude.[30]
For an electrochemical reversible system (the potentials and
concentrations follow the Nernst equation or its derived equa-
1 3.2. Different CV Setups for a Specific Research Purpose
tions), the current,i, is proportional to v2 : (The property also fea-
tures a diffusion-controlled redox species, which differs from As mentioned earlier, CV is a potential scan technology; thus, it
an electrode-adsorbed one that i is proportional to v.) Especially, is important to accurately monitor the applied potential and the
the peak current ip is described by Randles–Sevick equation resultant current. A three-electrode cell setup makes this possi-
(Equation (6)).[29a] ble, which consists of the target electrode as WE, a potential sta-
1 ble electrode as RE, and a counter electrode (CE) to form a
nFvD2
ip ¼ 0.4463nFAC (6) current circuit with the WE (Figure 4a).[31] For the WE, since it
RT is referred to a stable potential, the accurate potential loaded on it
where n is the electrons involved in the reaction, F is the can be finely controlled. This allows us to focus on the surface
Faraday’s constant, A is the electrode surface area, C is the bulk reaction on the target electrode without considering the reaction
concentration of the oxidized species, v is the scan rate, R is the kinetics or potential change in the CE. All those electrodes should
universal gas constant, T is the temperature, and D is the diffu- be redox insert so they do not affect the redox processes.
sion coefficient of the oxidized species. Furthermore, an ideal electrolyte solvent should have a high sol-
At 298.15  K, for A in cm2, D in cm2 sec1, C in mol cm3, v in ubility of the active species.[31] Thus, the three-electrode system
V sec1, and ip in amperes (A) provides a great convenience on the fundamental mechanism
study of the electrochemical process. Three-electrode split flat
3 1 1
ip ¼ 268600n2 AD2 Cv2 (7) cells as shown in Figure 4b have been developed for the electro-
chemical process study in the battery research, which is more
For the totally irreversible process, i at any point of the CV closer to the actual working state of the battery.
curve In most application-oriented studies, more concerns are on
the impact of the cathode structure, sulfur loading, separator,
3 1 1
ip ¼ 299000nðαna Þ2 AD2 Cv2 (8) and electrolyte on the redox process and their kinetics. The
two-electrode coin cells are predominately applied for the CV
1
is still proportional to v2 , when ip is calculated by Equation (8), test, although only two electrodes can be used—the anode and
where the units are the same as that for Equation (7). cathode. Therefore, we have to adopt the two-electrode system
Equations (7) and (8) are usually used for diffusion coefficient with one electrode functioning as both CE to form a current cir-
1
calculation, as n, A, and C can be measured, and ip and v2 are cuit and RE to loading bias (Figure 4c). In this case, the potential
directly obtained from the CV test. of CE (e.g., E(Li/Liþ)) may not keep constant during the reaction
CV provides a valuable information for the initial electrochem- when the concentration of Liþ changes. However, the concentra-
ical research on the new system, where two parameters are usu- tion of Liþ can be considered as constant during the test.
ally used—peak potential separation (ΔE p ¼ E p,a  E p,c ) and peak Furthermore, the potential difference, i.e., the bias, is under
current derivation (ip,a =ip,c ). 1) For electrochemical reversible pro- control during the potential scan. Thus, it is reasonable to
cess, the electron transfer is fast (low barrier), and the response apply the two-electrode coin cells for the CV experiment to inves-
between the potential and the concentration (or current) is quick. tigate the effect of battery components on the redox process

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Figure 4. Typical CV setups. a) Traditional type three-electrode cells. Reproduced with permission.[31] Copyright 2017, American Chemical Society. b) Split
flat cells. c) Regular two-electrode cells. d) Symmetrical and e) asymmetrical cells.

and the kinetics. There are generally three kinds of two-electrode CV, absorption spectroscopy, and controlled-potential electroly-
coin cells used for CV tests. The regular cells comprised the sis.[35] They found that sulfur is initially reduced through a
sulfur-contained cathode (catholyte or Li2S) and lithium (or non- two-electron process, generating S2 8 and other LiPS, followed
lithium) as the anode (Figure 4c). Another two kinds of special by a second reduction of four-electron per S8 with S2 4 as the
two-electrode cells are mainly used for kinetic studies— major stable species. Although the reduced sulfur can be reoxi-
symmetrical (Figure 4d) and asymmetrical cells (Figure 4e). A dized, the processes are considered as irreversible because the
symmetrical cell couples two identical electrodes with lithium ΔE p is larger than 56 mV, and the peak potentials are scan-rate
polysulfide (Li2S8, Li2S6, or Li2S4) as the active material. The elec- dependent.
trodes are the target cathode host that may feature with specific In 1985, Yamin et al. systematically studied the redox processes
structure (facilitate the ion diffusion) or electrocatalysis that can of sulfur and polysulfide of various concentrations in THF by
affect the redox process. The only difference of an asymmetrical CV.[15b,36] A schematic of the CV setup is shown in Figure 5d.
cell from the symmetrical cell is that the active material (sulfur Three cathodic peaks and one anodic peak are observed in the sys-
or Li2S) is involved in one electrode. How these CV tests are tems of 4 mM Li2S12, S8, and Li2S8 in THF with 0.8 m LiCIO4, as
used for kinetic research will be introduced in the following shown in Figure 5. The ΔE p (between the first cathodic peak and
related parts. the anodic peak) reaches up to 350 mV—indicating an irreversible
redox process. After a series of the rate-dependent CV experiments
combined with the kinetic analysis, a complex redox process was
4. Three-Electrode CV Studies proposed. The single anodic peak is the result of polysulfide oxi-
dation (to sulfur), where the charge transfer is preceded by a slow
As mentioned, CV is widely used to identify the redox couples for chemical reaction. The first cathodic peak is attributed to the
new systems. In early fundamental LSB studies, the three- reduction of the high-order polysulfides (Li2Sn, n > 6); the second
electrode CV test was conducted to investigate the electrochemical cathodic peak is mostly due to the reduction of S2 2
6 to S5 , and this
process. An electrolyte solvent that can dissolve with the active spe- charge transfer is preceded by a slow disproportion of S2 6 to S5
2

cies to a high concentration is preferable.[31] Thus, high dielectric 2

and S7 ; and the third cathodic peak is caused by the reduction of
2
solvents with high sulfur/LiPS solubility are predominately inves- S2 2
5 to S2 or S or their mixture. These latter species are insolu-
tigated, such as dimethyl sulfoxide (DMSO),[32] tetrahydrofuran ble in THF, and, thus, passivate the electrode and shift (more neg-
(THF),[9a,15b,33] and dimethyl formamide (DMF).[34] ative) the reduction potential.
In 1970, Merritt and Sawyer studied the electrochemical In 2002, Levillain and co-workers summarized the character-
reduction behavior of sulfur on a gold electrode in DMSO using istics of sulfur and polysulfide in a nonaqueous solvent and

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Figure 5. CV of 4 mM. a) Li2S12 and b) S8, in THF with 0.8 m LiClO4. Reproduced with permission.[36] Copyright 1985, Elsevier B.V. c) Li2S8 in THF with
0.8 m LiClO4. d) Three-electrode setup used for the CV experiment. Reproduced with permission.[15b] Copyright 1988, The Electrochemical Society.

analyzed their redox processes, emphasizing that polysulfide pathways, and the effect of different electrolyte solvents. How-
identification played a vital role in understanding the electro- ever, these systems are usually different from the application-
chemical mechanisms.[37] An example of the combination of CV oriented studies, which mainly focus on the structure–property
and spectroelectrochemial studies is shown in Figure 6. relationships of the battery components on the performance,
High dielectric solvents have been thoroughly studied, such as the sulfur cathode, separator, electrolyte, and anode.
whereas the low dielectric solvents have received less attention.
This is despite the fact that the low dielectric solvents are typically
used as electrolyte solvents in practical LSBs. In 2014, Lu et al. 5. Two-Electrode CV Studies
probed the reaction kinetics and reaction mechanisms of sulfur
in DMSO (high dielectric solvent) and 1,3–dioxolane (DOL)/ In application-oriented studies, the regular two-electrode coin
dimethoxymethane (DME) (low dielectric solvent) through CV cells or the special symmetrical/asymmetrical cells are usually
and rotating-ring disk electrode studies.[38] Sulfur demonstrates applied for the CV analysis.
different redox potentials in the two solvent systems, as shown in
Figure 7a. The authors ascribed the difference to different Liþ 5.1. Regular Cells
solvation energies—which was calculated from the donor num-
bers of the solvents. In combination with operando UV-vis spec- 5.1.1. Electrochemical Process Description
troscopy,[32b] the solvent-dependent sulfur reduction pathways
were proposed, as shown in Figure 7b. The direct electrochemi- In combination with the discharge/charge curves, the CV is gen-
cal reduction of sulfur only contributes in part to the capacity, erally used to describe the electrochemical redox processes.
and the subsequent polysulfide chain-growth/disproportion Figure 8 is a representative CV curve observed in a typical
reactions generate the remaining capacity. The chain-growth/ LSB.[16c] The first reduction peak at 2.4–2.2 V involves the reduc-
disproportion reactions are faster in DOL: DME compared with tion of solid S8 to soluble Li2Sn (3 ≤ n ≤ 8), and the second reduc-
that in DMSO, corresponding to the better rate capability. tion peak at 2.1–1.9 V is related to the reduction of Li2Sn to Li2S2/
In fundamental studies, strict CV tests are conducted, mainly Li2S.[16c] The two-step reduction process is reflected in the two-
focusing on the reversibility of different reactions, kinetics, redox plateau discharge curve, as shown in Figure 2. During the anodic

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Figure 6. a) CV of 2.5 mM S8 in DMF (293 K; 1 V s-1; Pt-WE; pseudo-RE Pt-wire). b) Spectra-electrochemical experiment of (a). Reproduced with per-
mission.[37] Copyright 2002, Elsevier B.V.

Figure 7. a) CVs of a glass carbon electrode in 4 mM S8-0.2 m LiClO4 in DMSO and 4 mM S8-1.0 m LiTFSI DOL:DME (1:1) at 50 mV s1 Potential vs
Li/Liþ. Reproduced with permission.[38] Copyright 2014, American Chemical Society. b) Proposed sulfur reduction pathways in different solvents.
Reproduced with permission.[32b] Copyright 2016, American Chemical Society.

scan, the peaks may be overlapped at 2.2–2.6 V, corresponding

to the oxidation of lithium sulfide to LiPS/sulfur. In most of
the cases, the redox reactions experience a similar process as
described earlier, leading to similar descriptions of the CV
curves.
For LSBs with Li2S as the starting material, it is generally
charged to 3.5 V first, when the original Li2S electrode has to
get over a large overpotential barrier to get oxidized to a short-
chain polysulfide, reflecting a broad oxidation peak at 3.0–3.2 V
(Figure 9a).[39] The short-chain polysulfide is then further oxi-
dized to a long-chain polysulfide, corresponding to a long charge
process (Figure 9b).[39] The following electrochemical redox pro-
cesses are the same as that with the S8 cathode, which can be
seen from both the CV curves and voltage profiles in Figure 9.
Instead of the general two-step reduction that corresponds to a
two-peak CV cathodic scan and a two-plateau discharge curve,
Figure 8. CV curves of a typical LSB at a scanning rate of 0.1 mV s1. some sulfur forms demonstrate different redox processes
Reproduced with permission.[16c] Copyright 2012, Elsevier B.V. (Figure 10). A microsphere carbon-encapsulated sulfur electrode

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Figure 9. a) CV curves and b) voltage profiles of the Li2S-graphene electrode. Reproduced with permission.[39] Copyright 2017, Springer Nature Limited.

Figure 10. a) CV curves and b) voltage profiles of sulfur encapsulated in microsphere carbon. Reproduced with permission.[16a] Copyright 2013, The Royal
Society of Chemistry. c) CV curves and d) voltage profiles of S-PAN electrode. Reproduced with permission.[41a] Copyright 2012, The Royal Society of
Chemistry.

demonstrates an almost negligible upper reduction peak cycling stability as well. The confined small sulfur gives a single
(Figure 10a) and shows a very short potential at 2.25 V vs Liþ/Li reduction peak at CV curves and a single-plateau on the voltage
(Figure 10b). In the following cycles, only one reduction peak and profiles, avoiding the unfavorable polysulfide transformation
[16b]
one lower discharge plateau are observed in the CV and voltage from S8 to S24 . LSB operated under the confinement effect
profiles, respectively.[16a] The encapsulated sulfur electrode usually achieved a high stability and high rate performance,
shows a stable cycling performance of up to 500 cycles, which which can also work well in both ether- and carbonate-based elec-
is mainly attributed to the confinement effect of the micropores trolytes. However, one of the shortfalls is that only limited sulfur
on the electrochemical reactions. Lately, Guo and co-workers can be confined in the nanopores or 2D interlayers.[40]
developed a microporous carbon-confined small sulfur mole- One cathodic peak can also be observed in the sulfur/
cules (S24), which achieved high capacity, high rate, and long polyacrylonitrile system (S-PAN), as shown in Figure 10c,d.

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1
Sulfur is widely known as a dehydrogenation reagent. An S-PAN linearly with the square root of the scan rate (v2 ). DLiþ was
composite is obtained through the dehydrogenation process that calculated by Randles–Sevick equation, showing that the MOF-
sulfur and PAN are under heat treatment at 300  C, forming a based separator did not impede Liþ diffusion obviously. Huang
conductive main chain, followed by cyclizing of the polar —CN et al.[17d] constructed a GO-based separator. The negatively
group, and embedding with elemental sulfur.[41] Similarly, the charged GO is supposed to suppress the diffusion of polysulfide
S-PAN system can achieve a high rate and long-cycling perfor- anions due to the electrostatic effect, while not hindering the Liþ
mance, while the sulfur content is low (<50%). diffusion. The former is confirmed by an enhanced cycling sta-
bility, and the latter is confirmed by the rate-dependent CV test,
in which a battery with and without a GO film demonstrates a
5.1.2. Kinetic Comparison
similar DLiþ .[17d] In Zhou and Huang’s works, the obtained DLiþ
are in the same order of magnitudes, 109.
The peak potentials of the CV curves can be related to the charge-
It has been realized that high sulfur-loading electrodes are
transfer barrier in a same system, and thus it is used for qualitative
essential in achieving high energy density LSBs. However,
comparison of the kinetic. Li and co-workers[42] developed a con-
the ion diffusion is obviously hindered in thick electrodes,
ductive porous vanadium nitride/graphene (VN/G) composite to
due to the difficulty in constructing continuous conductive
accommodate the Li2S6 catholyte. This composite decreases the
pathways.[44] Manthiram and co-workers[45] developed a carbon-
polarization and facilitates the polysulfide conversion, demonstrat-
cotton cathode with a high sulfur content (80%) and a high area
ing higher reduction peaks and lower oxidization potentials than
sulfur loading (61.4 mg cm2). The rate-dependent CV experi-
that of the reduced graphene oxide (RGO) cathode (Figure 11).
ments (Figure 12d–f) show that the DLiþ is at the same order of
The lithium-ion diffusion coefficient (DLiþ ) is used to compare
magnitude with the reference (108–109), indicating a smooth
the redox reaction kinetics. Although accurate DLiþ measurement
Liþ diffusion in a thick electrode.
is not easy, qualitative comparison at the magnitude level can
Instead of suppressing the LiPS diffusion, accelerating LiPS
be achieved by CV experiments at different scan rates (rate-
conversion reactions by electro catalyst has been proved to be
dependant CV).[13b] The measured current (i) obeys a power–
an efficient approach to migrate the shuttle effect.[10b] The electro
law relationship with the scan rate (v), as
catalyst can also prevent the accumulation of insulating sulfur
i ¼ avb (9) species on the cathode, which further enhances the kinetics.[10c]
The catalytic effect is usually evaluated by either comparing
It is a positive correction between b and the lithium-ion diffu- the peak potential positions (as have been demonstrated in
sion kinetics. By plotting log i vs log v, b is obtained from the Figure 11) or DLiþ . Long and co-workers systematically studied
slope. When b ¼ 1, it relates to a totally surface-controlled reac- the catalytic effect of Nb2O5 on the redox reaction kinetics by
tion (capacitive behavior), while b ¼ 0.5 corresponds to a semi- rate-dependent CV tests (Figure 12g–i).[17b] The plots of
infinite diffusion-controlled process.[29a] For the latter, DLiþ is log i vs log i show a good linear relationship at the low scan rate
usually calculated by Randles–Sevick equation (Equation (7)). (<1 mV s1), and the obtained b is in the range of 0.5–1. As is
Separator coating or adding an interlayer between the cathode known, the first cathodic peak (peak ¼ 1 \* ROMANI) corre-
and separator is an efficient approach to migrate the shuttle sponds to a solid–liquid reaction (S8 to Li2S6/Li2S4), whereas
effect. Ideally, LiPS diffusion is suppressed, whereas Liþ diffu- the second cathodic peak (peak ¼ 2 \* ROMANII) relates to a
sion is not hindered. Zhou and co-workers[43] developed a metal– liquid–solid transformation (Li2S6/Li2S4 to Li2S2/Li2S). For both
organic framework (MOF)-based separator, which selectively hosts with and without Nb2O5, the obtained b value from
sieved Liþ ions while suppressed LiPS diffusion. Rate-dependent peak ¼ 1 \* ROMANI (b ¼ 1 \* ROMANI) is always higher than
CV experiments (Figure 12a–c) show that for both the general that from peak ¼ 2 \* ROMANII (b ¼ 2 \* ROMANII), indicat-
and MOF-based separators, the peak currents (ip ) increase ing that the liquid–solid transformation is slower than the

Figure 11. a) CV curves of the VN/G and RGO cathodes at a scan rate of 0.1 mV s1 in a potential window from 1.7 to 2.8 V. b) Galvanostatic charge–
discharge curves of the VN/G and RGO cathodes at 0.2  C. Reproduced with permission.[42] Copyright 2017, Springer Nature Limited.

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Figure 12. Rate-dependent CV experiments. CVs at different scan rates of LSBs with a) pristine separator (Celgard 2400) and b) MOF@GO separators.
c) The linear fits of the CV peak currents of LSBs with pristine separator (α1, β1, γ1) and with MOF@GO separators (α2, β2, γ2). Reproduced with
permission.[43] Copyright 2016, Springer Nature Limited. d–f) LSBs based on a carbon–cotton cathode with high sulfur loading. Reproduced with per-
mission.[45] Copyright 2016, American Chemical Society. g–i) LSBs with and without Nb2O5 carbon host. Reproduced with permission.[17b] Copyright
2016, The Royal Society of Chemistry.

solid–liquid transformation. The introduction of Nb2O5 the contribution of capacitive currents (without lithium polysulfide
increases the b values, indicating enhanced lithiation kinetics. active material), the polarization curves can be directly related to
Furthermore, the author has conducted CV tests at different tem- the redox current of lithium polysulfide. Thus, a higher current
peratures and calculated the activation energy for sulfur lithiation density indicates faster reaction kinetics.[47] Zhang and co-workers
reactions. Hosts with Nb2O5 nanocrystals demonstrate a lower constructed a CoS2/graphene sulfur host and conducted a sym-
activation energy. Their work demonstrated a versatile role of metrical Li2S6 cell CV test (Figure 13a).[47] In coupling CoS2 into
CV in evaluating the electrocatalytic effect. graphene as the electrode, an order of magnitude higher current
density is obtained than that with the graphene-only electrode,
5.2. Special Cells indicating that CoS2 dynamically accelerates the electrochemical
reactions. Similarly, the catalytic effects of VS2,[17c] MXene/
5.2.1. Symmetrical Cells MoS2 composite,[48] and TiC[46] have also been demonstrated
using a similar protocol. Helms and co-workers demonstrated that
To investigate the kinetics, the CV test based on symmetrical cells a supramolecular perylene bisimide (PBI) can act as an active
is considered as a more straightforward approach.[13b] It consists of mediator for soluble long-chain polysulfide.[17a] Two redox peaks
two identical electrodes with lithium polysulfide (Li2S8, Li2S6, or centered at 2.5 and 2.1 V correspond to the processes of S8-S2
4 and
2
Li2S4) as the active material, showing an OCV of 0 V. The CV S2
4 -S , respectively. By adding PBI to the Li2S8 solution, a four-
experiments are generally scanned from OCV to a symmetrical fold increase of the current density is observed (Figure 13b), con-
voltage interval, such as from 0.8 to 0.8 V.[46] By subtracting firming its role in accelerating the redox process.

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Figure 13. Polarization curves of a) L2S6 symmetrical graphene electrode with different content CoS2. Reproduced with permission.[47] Copyright 2016,
American Chemical Society. b) L2S8 symmetrical cell with and without the redox mediator. Reproduced with permission.[17a] Copyright 2015, American
Chemical Society.

5.2.2. Asymmetrical Cells fundamental mechanisms underneath the performance

enhancement is also indispensable to direct the practical-
Although the symmetric-cell CV test is a more direct approach to oriented research. CV has played a critical role in understanding
measure the kinetic enhancement, the obtained information the structure–property relationships as well as the underneath
reflects the combined catalytic effect on the reduction and oxida- mechanisms. The Review has summarized the principles and
tion processes. In a symmetric cell, once the reduction happens on experimental setup of CV, followed by its application in LSB
one electrode, oxidation happens on the CE. As can be seen from based on the research purpose. Three-electrode CV is usually
the CV curves of the regular cells, the separated two cathodic peaks involved in fundamental studies, especially in the early stages
can be distinguished clearly when compared with the anodic of the research on LSBs. Two-electrode CV test is mainly used
peak(s).[18] The difference between charge and discharge processes in the material-based studies. Two-electrode regular-cell CV test
is also reflected on the charge and discharge curves. A typical two- is generally used to describe the redox process and compare the
plateau discharge curve is usually observed, while the charge curve kinetics based on the peak potentials or lithium-ion diffusion
may show one or two plateaus. However, the charge process is coefficient measurement. Two-electrode symmetric cell CV pro-
usually taken as the reverse of the discharge process, which could vides a more straightforward approach to compare the LiPS
inevitably hinder the understanding of the mechanism as well as
conversion kinetics by measuring the polarization currents.
the property–performance relationship.[13b]
The two-electrode asymmetric cell CV test provides a way to
To illuminate the catalytic effect on the oxidation and reduc-
study the catalytic effect on the reduction and oxidation processes
tion individually, Lee and co-workers constructed two asymmet-
individually.
ric cells, asymmetric cell-S and cell-Li2S. WO3x and WO3 were
However, there are some challenges in the CV applications
used as the catalysts for comparison.[18] In the asymmetric cell-S
in LSBs:
CV test (Figure 14a), the Li2S6 catholyte was sandwiched by the
two different electrodes, a catalyst-only WE and a sulfur-catalyst
mixture CE. In the asymmetric cell-Li2S, a Li2S-catalytic mixture (1) In most cases, the CV test with two-electrode regular cells is
was used as the CE and the other parameters kept the same sketchy, which may result in ignoring the important infor-
as asymmetric cell-S. The cell was scanned from the OCV (0 V) mation on the mechanisms and structure–property
to 1 V and then to 1 V. By careful analysis of the CV peaks, the understanding.
authors proposed LiPS transformation pathways during the (2) For fundamental mechanism studies, dominant efforts have
reduction (Figure 14c) and oxidation processes, showing that been focused on investigating the electrochemical reactions
WO3x is an efficient bidirectional electrocatalyst for the LiPS in different solvents. However, most of these solvents are
conversion, which is more effective for the LiPS-S8 oxidation pro- different from that of the material-based research.
cess. This work demonstrates a new method to evaluate the cata- Furthermore, fundamental mechanism studies rarely con-
lytic effect on the reduction and oxidation process separately. sider the effect of the cathode structure, anode, and separa-
tor, while those parameters are the research focus of
material-based study, which greatly affect the redox process
6. Summary and Outlook and battery performance. In such situations, it is difficult
to translate the information between fundamental- and
With the intense research efforts, both the performance and material-based studies.
mechanisms of understanding of LSBs have been greatly pushed (3) Kinetics data from the CV are usually limited for the qualita-
forward. However, when considering the total energy density, tive comparison within the same system, making it difficult to
cycling life, and cost, breakthroughs on the material-based compare with different works. This is due to the underlying
research are still needed. A better understanding of the CV character as well as the lack of the standard LSB systems.

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Figure 14. Elucidation of the catalytic effects of WO3x nanoplates with the asymmetric cell-S. a) Schematic of an asymmetric cell-S. b) CV of the WO3x
asymmetric cell-S at 3 mV s1. c) Illustration of the electrode reactions for the redox peaks. Reproduced with permission.[18] Copyright 2018, Wiley-VCH
Verlag GmbH & KGaA.

As is known, LSBs’ performance can be greatly influenced by Conflict of Interest

electrode characters (such as sulfur content, sulfur loading,
current collector, and binder), battery parameters (such as The authors declare no conflict of interest.
electrolyte amount, separator, lithium amount), the assem-
bling process, and battery testing conditions (such as
discharge/charge rates and temperature). Those parameters
vary with works, while the performance evaluation tends to Keywords
demonstrate the good side only. cyclic voltammetry, fundamental mechanisms, lithium–sulfur batteries,
structure–property relationships
Representative CV protocols for specific research purpose have
Received: November 1, 2018
been summarized here, which can be a guideline for fulfilling the
Revised: December 30, 2018
potentials of CV in LSBs. More “practical” fundamental research Published online: April 10, 2019
based on the applied LSBs is needed, which will better direct the
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