Materials Today Chemistry 23 (2022) 100675

Contents lists available at ScienceDirect

Materials Today Chemistry

journal homepage: www.journals.elsevier.com/materials-today-chemistry/

Copper sulfides and their composites for high-performance

rechargeable batteries
Y. Shi, B. Yang, X. Guo, X. Wu, H. Pang*
School of Chemisty and Chemical Engineering, Yangzhou University, Yangzhou, 225002, Jiangsu, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Copper sulfides (CuxS) are widely used as the promising electrode materials for secondary batteries
Received 16 September 2021 because of the rich abundance, low cost, excellent capacity (~337/560 mA h/g for Cu2S/CuS) as well as
Received in revised form favorable electrical conductivity (10
3 S/cm). Moreover, nanostructure designing and compounding with
27 October 2021
other conductive materials can enhance the electrochemical performance of CuxS. In this review, the up-
Accepted 4 November 2021
to-date progress in the synthesis method as well as the application for secondary batteries (lithium-ion
Available online 11 December 2021
batteries, lithium-sulfur batteries, sodium-ion batteries, magnesium-ion batteries, and so on) of CuxS and
their relevant composites have been discussed detailly. In the end, the challenges, feasible strategies, and
Keywords:
Copper sulfides
application prospects for the CuxS are also summarized.
Composites © 2021 Elsevier Ltd. All rights reserved.
Synthesis
Applications
Batteries

1. Introduction Among various materials, metal sulfides (MSs) have attracted

With the increasing demand for energy, energy shortage has
become one of the most important concerns in the 21st century.
Traditional combustion-based energy can hardly satisfy the
increasing demands, and the burning of fossil fuels has brought
serious environmental pollution. Therefore, it is urgent to explore
clean, sustainable, low-cost energy as well as efficient energy
storage devices. Nowadays, diverse electrochemical energy storage/
conversion technologies, especially rechargeable batteries, such as
lithium-ion batteries (LIBs), lithium-sulfur batteries (LSBs),
sodium-ion batteries (SIBs), magnesium-ion-batteries (MIBs), and
so on, have attracted much attention for their higher efficiency,
lower cost, and less pollution [1e4]. However, the electrochemical
performance (power density, energy density, chargeedischarge
rate, and cycling performance, etc.) of these energy storage de-
vices still have room for improvement. Hence, many studies have
demonstrated that the electrochemical performance mainly de-
pends on the electrode materials, which means that exploring
suitable materials is a major strategy to meet effective energy
storage device.
* Corresponding author.
E-mail addresses: huanpangchem@hotmail.com, panghuan@yzu.edu.cn (H. Pang).
extensive attention owing to their various structural types and
seductive electrochemical activities [5e8]. Compared with other MSs
(FeS2, Ni3S2), copper sulfides (CuxS) with a bulk bandgap of 1.2 eV,
which mainly include chalcocite (Cu2S) and covellite (CuS), have
been widely applied in secondary batteries because of the richer
abundance in nature, lower material cost, semiconductivity, and
non-toxicity. In addition, CuxS usually possesses better electrical
conductivity and higher capacity than copper oxides (CuxO) when
used as electrode materials for LIBs (Cu2S: ~335 mA h/g; CuS:
~561 mA h/g) [9e18].
Despite the previously mentioned merits, CuxS inevitably suffers
from some disadvantages, such as rapid capacity fading during
cycling, low active material utilization, poor Coulombic efficiency,
and cycle life, which limit the application and development of CuxS
[19e22]. To overcome these drawbacks, a lot of research has been
done and proved that change the morphology (nanorods, nano-
tubes, nanofibers [NFs], nanoflakes, flower-like, core shell, hollow
spheres, and so on [23e25]) and the composition (conductive
polymers [PANI] [26], carbon materials [graphene, graphene oxide
(GO), carbon nanotubes (CNTs), etc.] [27e34], and metal-based
materials [Cu2O, NiS2, MoS2, etc.]) [35e37] of the CuxS and
relevant complex can further improve the electrochemical
performance.
Up till now, numerous reviews focusing on the synthesis
and electrochemical applications of CuxS have been published.

https://doi.org/10.1016/j.mtchem.2021.100675
2468-5194/© 2021 Elsevier Ltd. All rights reserved.
Y. Shi, B. Yang, X. Guo et al.
Fig. 1. (a) Line chart of the research trend of materials CuxS for batteries in recent years; (b) Bar chart of CuxS materials for different batteries in recent years. Source for data: Web of
Science (2006 till now). (c) Bart chart of the research trend of CuxS electrode (anode/cathode) materials; (d and e) Pie chart of CuxS electrode (anode/cathode) materials.
For instance, different synthetic methods for the fabrication of
0D, 1D, and 2D CuxS nanostructures and relevant applications
in photocatalysis, solar cells, energy storage devices, and
biomedical applications have been discussed in Roy's review
[38]. Hence, Liu et al. [39] reported transition metal sulfide
(MSs) (CuxS, FeSx, MoS2, CoSx , etc.) as anode in LIBs, which
showed enhanced electrochemical performance [40]. Howev-
er, few reviews that focus on the role of Cux S and its com-
posites for batteries have been reported. Thus, it is necessary
to summarize the advances and propose further trends of
CuxS materials. As can be seen in Fig. 1, the number of pub-
lications on CuxS materials in batteries has significantly
increased in recent years, which can be proved that great
progress has been made in the research of CuxS materials.
In this review, the crystal types of CuxS are first discussed, and
then the synthesis methods of pure CuS, Cu2S, and the relevant
complexes based on different compounded materials (carbon ma-
terials, nitrogen materials, and metal-based materials, etc.) are also
summarized. In addition, the application of CuxS and its composites
in electrochemical devices, such as LIBs, LSBs, SIBs, MIBs, solar cells,
and other devices, are discussed separately. As CuxS are used widely
in LIBs, the electrochemical performance of LIBs is discussed in
detail from three aspects (improved capacity, enhanced cycling
performance, and rate capacity). In the end, the challenges and
prospects for the development of CuxS in the battery field are
presented.
2
Materials Today Chemistry 23 (2022) 100675
2. Crystal types
Because of the influence of three-dimensional electrons, CuxS is
usually a p-type semiconductor with a direct band gap of
1.2e2.4 eV, which makes it widely used in various fields (electric
energy storage, solar radiation absorption, and so on). Because the
position of Cu atoms in the close-packed S lattice changes with the
change of x, CuxS (1  x  2) have many crystal forms, which can be
roughly divided into three systems. According to the accumulation
of sulfur in the crystal lattice, the crystal structures of these forms
can be divided into three types: cubic dense packing (aniline and
monzonite), hexagonal dense packing (djurleite and chalcocite),
and the combination of hexagonal dense packing and S atom co-
valent bond (covelline). On the other hand, CuxS can also be divided
into three categories (“sulfur-rich” systems [x ¼ 2], “1:1” system
[x ¼ 1], and “copper-rich” systems [x  1]) according to the different
values of x in CuxS. With the increase in temperature, Cu2S trans-
forms from monoclinic phase (low chalcocite) below 104 C to
hexagonal phase (high chalcocite) between 104 C and 436 C to
cubic phase (cubic chalcocite) above 436 C. In Fig. 2, crystal
structures of some selective forms of CuxS are exhibited.
3. Synthesis
In this section, numerous kinds of synthesis methods (hydro-
thermal method, solvothermal method, electrospinning method,
Y. Shi, B. Yang, X. Guo et al.
Fig. 2. Crystal structures of copper sulfides.
microwave method, template method, and others) of CuxS mate-
rials (Cu2S/CuS pristine and their hybrids) are discussed. In addi-
tion, the relationship between synthesis method and morphology/
size of materials is explored.
3.1. Cu2S pristine
Cuprous sulfide (Cu2S) is plentiful, low cost, and usually used as
a common electrode material because of the good theoretical ca-
pacity as well as high lithium activity. Recently, many Cu2S nano-
materials with numerous morphologies (such as particles [15,41],
flakes [42], nanorods [43], nanowires [43], and hierarchical petal-
like nanostructures [4]) have been reported.
0D structures often possess the size of several nanometers to
several dozen nanometers and inform nanostructures, which
induce high reactivity and stability. For instance, Leidinger et al.
[44] prepared Cu2S hollow spheres with outer diameter of
32e36 nm, wall thickness of 8e12 nm, and inner diameter of
8e16 nm through microemulsion method.
1D nanostructures have attracted more and more attention
because of their ability, which can adapt to volume changes during
repetitive chargeedischarge processes. In Gorai's report [43], two
different 1D Cu2S nanostructures (nanorods and nanowires) have
been obtained through a facile surfactant-assisted approach by
adjusting the molar ratio of cationic sodium and anionic surfactants
(dodecyl sulfate [SDS] and cetyltrimethylammonium bromide
[CTAB]). When only CTAB or SDS was added, submicron particles or
submicron wires were generated. With the increase of SDS pro-
portion in the mixed solution, the size of nanorods goes from
micron level to nanometer level. The previously mentioned results
show that anionic surfactant helped the growth of nanowires and
cationic surfactant assisted the formation of particles. Differently,
Li et al. [45] have obtained nanorod-shaped CuS and Cu2S via a
3
Materials Today Chemistry 23 (2022) 100675
facile hydrothermal method without using any template or sur-
factant. Although the rod diameters for the two samples are
roughly 100e200 nm, the Cu2S nanorods show larger diameters
and a core shell structure.
2D structures of Cu2S, including nanoflakes, nanodisks, nano-
films, and others, can be synthesized through many methods. For
instance, Cu2S flakes were obtained by implementing different
voltages between Cu and graphite electrodes in KCleNaCleNa2S
mixed solution by Li et al. [42]. When different electrolytic voltages
were used, different copper-based sulfides Cu2S, Cu7S4 as well as
Cu7KS4 (Fig. 3bee) were prepared, respectively. The thickness of
the micron-scale flakes owning smooth surfaces at voltage below
0.6 V is several micrometers, and the diameter is more than 100 mm.
Wet-chemically synthesized 2D transition MSs have been proved as
the promising materials for catalysis, batteries, as well as opto-
electronics; however, the chemical conditions for their selective
lateral growth are lack of in-depth study. In 2014, Wu et al. [46]
offer a facile route to adjust the shape of the transition MSs from
particle to plate by changing the amount of the halide ion and
introduce the method to obtain Cu2S successfully, which means
that halide-mediated slow growth kinetics have great influence on
the formation of transition MS nanoplates.
Apart from previously mentioned nanostructures, Cu2S mate-
rials with 3D nanostructures (flower-like, sandwich-like, hierar-
chical structures, and others) are synthesized widely. For instance,
Cu2S hierarchical nanostructures with diameter of 1e1.5 mm were
fabricated by Li et al. [4] by using CTAB as surfactant with the mixed
solvents of ethylene glycol (EG) and DMSO (Fig. 3 f and g). By
comparing the different morphologies of products from three types
of solvents (EG, ethanol, and cyclohexanol) at the same conditions
with that of DMSO, the results show that EG has great influence on
forming the hierarchical nanostructures as surface modifying re-
agent and guiding the growth of Cu2S. Spherical particles with big
Y. Shi, B. Yang, X. Guo et al.
Fig. 3. (a) Schematic illustration for the transformation from S to Cu2S; (bed) SEM of products obtained under electrolysis voltages of 0.6, 0.8, and 1.0 V; (e) XRD patterns image of
Cu2S obtained under electrolysis voltages of 0.6, 0.8, and 1.0 V; (f and g) SEM of Cu2S obtained with 0.02 g CTAB. (a) Reproduced with permission [47]. Copyright 2016, American
Chemical Society. (bee) Reproduced with permission [42]. Copyright 2018, American Chemical Society. (f, g) Reproduced with permission [4]. Copyright 2013, Elsevier Ltd.
size can be treated as 3D structure. For instance, Cu2S spherical
particles with the monoclinic crystal structure have been prepared
by spray pyrolysis method with heat treatment, the diameter of
which are about 0.45 mm [15].
In summary, the approaches of synthesizing pure and different
dimensions of Cu2S consist of solvothermal method, potentiostatic
electrolysis method, simple surfactant-assisted method, and so on.
Among these methods, solvothermal method is popular for its
cheap price and easy operation. And the morphology of the ob-
tained materials could be easily changed by adjusting the kinds of
raw materials, dosage, and reaction condition (temperature, time,
and solvents) in solvothermal method. However, exploring
different efficient methods to obtain various structures is still of
great importance.
3.2. CuS pristine
Compared with pure Cu2S, CuS materials are used more
frequently for easy operation. Pure CuS materials have shown
numerous morphologies, which can be divided into 0D (quantum
dots and nanoparticles) [48e50], 1D (nanotubes, nanowires, and
nanorods) [24,51e54], 2D (nanofilms, nanodisks, nanosheets, and
nanoplates) [55e61], and 3D (nanospheres, nanoflowers)
[49,62e67]. In this part, we mainly focus on the synthesis methods
and the morphologies of the pure CuS materials, and the specific
data can be obtained from Table 1.
0D CuS materials possess unique electrical properties, which
break new ways for applications in the fields of batteries. Therefore,
it is imperative to explore new strategies to obtain 0D CuS mate-
rials. Recently, the sonochemical method has attracted much
attention because of its fast reaction kinetics. Via the sonochemical
method, CuS nanoparticles synthesized by Krishnamoorthy et al.
4
Materials Today Chemistry 23 (2022) 100675
[48] exhibit spherical shape with size around 50 nm. In addition,
the dispersive particle, varying from ~200 nm to several hundreds
of nanometers, was obtained by its in situ formation in the viscous
solution of polymer electrolyte (PEO: NH4ClO4) through the sulfu-
ration of CuSO4 using H2S by Kumar et al. [50].
Nanowires, nanorods, and nanotubes, as common 1D mor-
phologies of pure CuS, have attracted more and more attention.
Feng et al. [51] prepared CuS nanowire bundles (diameter:
~6 nm, length: several micrometers) through a template and
surfactant-free approach in the mixed solvent consisting of
DMSO and EG. The CuS nanowires could only be synthesized
when the ratio of DMSO and EG was lower than 3:7, and the
products obtained in the pure DMSO or pure EG medium are
composed of nanoplates, which show that mixed solvent shows
great influence on the controlling formation of nanostructures.
Using the same raw materials (Cu(NO3)2$3H2O and thiourea) in
the solvent of b-cyclodextrin (b-CD), stick-like CuS with hierar-
chical structure are obtained by et al. [52]. As can be seen in
Fig. 4e, the diameter and length of the as-prepared CuS micro-
structures are around 3 mm and 10 mm, respectively. At the same
time, the result showed that b-CD was the key factor of con-
trolling the morphologies. With the absence of b-CD, only sphere
morphology comprised of nanoplates (Fig. 4f) can be found. Zhou
et al. [54] and Li et al. [45] have obtained the CuS nanorods with
different sizes, during the easy sol-gel method as well as hy-
drothermal method, respectively. Although the as-prepared CuS
nanorods have similar morphology, the diameter of the CuS
nanorods (diameter: 100e200 nm) in Li's study is 10 times than
of those in Zhou's study. Using Cu(Ac)2 and Na2S as raw mate-
rials, Zhou et al. [54] produced uniform CuS nanorods made of
aggregated CuS particles, with the size of less than 10 nm. In
addition, the synthesis strategy to prepare the CuS nanorods in
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Table 1
Selected summary of the synthesis and applications in batteries of pure CuS.

Morphology Size Synthesis method Applications Ref.

Nanoparticles 50 nm Sonochemical method LIBs/Solar cells [48]

Nanoparticles more than 200 nm In situ formation method LIBs [50]
Quantum dots 5e7 nm Homogeneous precipitation methods LSBs [49]
Nanotubes 5e7 mm; 100 nm diameter Self-sacrificed templates method LIBs [24,53]
Nanowire bundles 6 nm diameter Template method LIBs [51]
Nanorods sub-10 nm Sol-gel method LIBs [54]
Nanofilms 35 nm Electrodeposition method Semi-3DCMBs [57]
Films 50 nm thickness, 1 mm width Electrodeposition method LIBs [56]
Nanodisks 200e500 nm Hydrothermal method SIBs [55]
Nanosheets 3.2 nm thickness Soft colloidal template method LIBs [59]
Sheets/particles 500 mm~1 mm In situ melt-diffusion method LIBs [68]
Ball-like structures 0.25~1 mm diameter Hydrothermal method LIBs [67]
Dandelion-like structures e Solvothermal method LIBs [67]
Sphere-like nanostructures 20 nm Solvothermal method LIBs [60]
Flower-like structures 0.65e1.1 mm Self-assembled method LIBs [62]
Porous spheres 4 nm and 10 nm Bubble template method LIBs [66]
Hollow spheres 1.9 mm diameter Bubble template method LIBs [66]
Microspheres 1 mm diameter Microwave irradiation method SIBs [64]
Microspheres 2 mm diameter Hydrothermal method SIBs [69]

Fig. 4. SEM images of (a) CuS particles prepared at room temperature (25 C); (b) CuS nanobuds prepared at 80 C; (c) The energy-dispersive X-ray (EDX) spectra of the CuS sheets;
(d) (I) SEM images of CuS nanosheets prepared at 140 C; (II) Copper element, (III) sulfur element; (e and f) SEM image and HRTEM image of the CuS prepared at 120 C for 12 h; (g)
SEM image of CuS films prepared for 60 min; (h) SEM image in the [00w] zone axis of the flakes from the electrodeposited CuS films (Cu(TFSI)2: S8 ¼ 1:2, t ¼ 60 min, T ¼ 120 C); (i)
SEM image of as-prepared CuS material; (j) SEM image of the as-prepared CuS hollow spheres. The higher magnification image is also inserted; (k) Scheme illustrating the proposed
mechanism for the formation of CuxS hollow spheres with phase-engineered composition at the water-to-toluene phase boundary of a micelle; (l) Schematic illustration of the
formation of hollow and porous CuS spheres. (aed) Reproduced with permission [70]. Copyright 2016, Elsevier B.V. (e and f) Reproduced with permission [52]. Copyright 2014,
Elsevier B.V. (g and h) Reproduced with permission [56]. Copyright 2012, The Royal Society of Chemistry. (i) Reproduced with permission [65]. Copyright 2017, Elsevier B.V. (j and k)
Reproduced with permission [66]. Copyright 2012, Elsevier B.V. (l) Reproduced with permission [44]. Copyright 2011, The Royal Society of Chemistry.

Li's study [45] is easy and efficient, without any surfactant and Qian's report by using [Cu(tu)]Cl$12H2O (tu: thiourea) nanowire
template. Differently, hollow CuS nanotubes made up of CuS precursors as self-sacrificial templates [24,53].
nanoparticles, the diameter and length of which is about 100 nm The above is the introduction of the synthesis methods and
and several micrometers respectively, have been prepared in morphologies of 1D materials. In this part, the synthesis strategies

5
Y. Shi, B. Yang, X. Guo et al.
of 2D materials, such as films, nanoplates, and nanodisks, will be
detailly discussed. Recently, numerous methods (chemical vapor/
bath deposition, supporting, thermal evaporation, spray pyrolysis,
and so on) have been applied to obtain CuS thin film, among which
the electrodeposition method owning the special ability to realize
conformal deposit structures stands out. Mazor et al. [57] and Chen
et al. [56] have obtained the CuS thin film by the electrodeposition
method, which was carried out in the electrolyte of 1,2-propanediol
and ionic liquid [EMIm]TFSI (99.5%, Solvionic), respectively. In
Mazor's report [57], the CuS film on nickel films and nickel/gold-
coated silicon substrates was obtained successfully. Under slow
stirring or no stirring, Cu2S films were obtained, while when the
solution was quickly stirred, bluish-black CuS films were deposited.
More significantly, the materials can show excellent ability when
using ionic liquids, for the reason that aqueous/organic media often
exhibit wide electrochemical window and extremely low vapor
pressures. Via electrodeposition in ionic liquid, Chen et al. have
successfully prepared single-phase CuS thin films comprised of
uniform nanoflakes [56]. The flakes with wideness of 1 mm and
thickness of about 50 nm are stacked face to face and perpendicular
to the substrate. The results suggested that the temperature, stir-
ring rate, sulfur concentration, deposition current, or potential all
show a certain influence on the morphology as well as the stoi-
chiometry of the CuS thin films. For instance, with the increase of
temperature from 120 C to 200 C, the morphologies of the ob-
tained materials are changed from flakes to particles (Fig. 4g and h).
CuS nanodisks (CuS-NDs) were synthesized via stirring oleyl amine
(OM), S, and CuCl by Kim et al. [55], and the products had a lateral
size of 200e500 nm and thicknesses of several nanometers. In
addition, the obtained CuS-NDs show a highly ordered internal
structure as well as a thin, amorphous outer layer with a thickness
of several nanometers. Using the similar raw materials, Du et al.
[59] used a general soft colloidal template method to prepare the
hexagonal CuS nanosheets, which have a thickness of 3.2 nm.
Moreover, He et al. [58] synthesized ultrathin CuS nanoflakes
through the soft-template method, which displayed a clear geo-
metric structure with hexagonal bottom of around 200 nm and
thickness of 5e20 nm. Through a simple single-mode microwave
method, Xiao et al. [70] have synthesized three different mor-
phologies (nanoparticle [Fig. 4a], nanobud [Fig. 4b], and nanosheet
[Fig. 4c and d]) of CuS under different irradiation temperatures
(25 C, 80 C, and 140 C), respectively. When the irradiation tem-
perature is 140 C, the leaf-like CuS nanosheets seem to attach to
the Cu foil with alike orientation, forming an interconnected
nanosheet-assembled network. Auyoong et al. [61] investigated the
formation of CuS hexagonal plates with the average length of 1 mm
and thickness of 100 nm through hydrothermal method without
appending any assistant agent.
Compared with 1D and 2D materials, 3D materials, such as
spheres, flowers, and cubes, are easier to synthesize and have the
largest number. In this paragraph, 3D CuS spheres [49,63,64] and
flowers [62,65] have been discussed detailly. In Li's work [64], CuS
microspheres with the size of around 2 mm are successfully pre-
pared by an easy method under microwave irradiation without any
template or additive. In comparison with the micromaterials,
nanomaterials exhibit the advantages of the smaller particle size,
enhanced surface energy, larger specific surface area, and propor-
tion of surface atoms. Because of this, Li et al. [63] have synthesized
monodispersed CuS nanospheres (diameter: ~200 nm) from
Cu(Ac)2$H2O and CS2 by solvothermal method. Moreover, to further
increase the specific surface area, Han et al. [60] and Shi et al. [65]
have obtained sphere-like CuS hierarchical structures composed of
self-assembled nanoplates (thickness: ~20 nm) as well as flower-
like CuS microspheres consisting of nanosheets (thickness:
~50 nm) (Fig. 4i) by solvo/hydrothermal method, respectively. In
6
Materials Today Chemistry 23 (2022) 100675
Han's report [60], sphere-like CuS was prepared by strictly con-
trolling the molar ratio of raw materials as well as reaction tem-
perature. Hollow nanostructures also exhibit large specific surface
area, low density, and rich internal space, which have been widely
applied in batteries, supercapacitors, and energy catalysis. Nagar-
athinam et al. [62], Zhao et al. [66], and Leidinger et al. [44] all
prepared the hollow CuS spheres by hydrothermal method, bubble
template synthesis method, and w/o-microemulsion method,
respectively. Nagarathinam et al. [62] used self-assembled method
in the synthesis of internally hollow CuS nanospheres. Based on the
already completed synthesis of precursors, the products can be
achieved by hydrothermal reactions. Predefined shapes of CuS can
be obtained by sacrificing the precursor. When the [Cu3(HSser)3(-
H2O)2]3$2H2O was used as the precursor (Ser: serine), the size of
the synthesized flower-like CuS materials was in the range of
0.65e1.1 mm. In Zhao's study [66], glutathione (GSH) was used as
sulfur source, bubble template source, as well as assembling re-
agent. Two different morphologies could be synthesized by pre-
cisely changing the volume ratio of H2O/CH3OH in the solution. As
Fig. 4k indicated, the Cu source, Cu(NO3)2$3H2O, was homoge-
neously dissolved in the mixture of deionized water, methanol, and
GSH. The volume ratio of the solvent system H2O/CH3OH used to
produce hollow spheres with the thickness of the shell was about
50 nm was 1:2, whereas for the porous spheres, it was 2:1. Lei-
dinger et al. [44] prepared CuS as nanoscale hollow spheres with a
homogeneous size of 35e40 nm through a w/o-microemulsion
method, which react at the liquid-to-liquid phase boundary.
Meanwhile, Cu1.8S and Cu2S can be obtained by changing the raw
materials and have similar structure to CuS (Fig. 4l). The signifi-
cance of the method is tailoring phase-specific properties can be
obtained through precise adjustment. In fact, the solution can make
great difference to the structure. Hosseinpour et al. [67] synthe-
sized ball-like CuS in water and dandelion-like CuS in water-EG
mixture (1 : 3 v/v) at 70 C through the reaction between sodium
thiosulfate (Na2S2O3) and copper nitrate (Cu(NO3)2). When the
solvent was EG solution, spaghetti-like CuS was formed because of
the complexation of Cu ion with S precursor.
In conclusion, there are various common methods to obtain
different dimensions of CuS, such as template method, micro-
emulsion method, and microwave method, among which hydro/
solvothermal method with the virtue of good reproducibility and
simple operation stands out. Via changing the reaction conditions
(solvents, temperature, time, and so on), the morphology of the
product can also be easily adjusted by hydro/solvothermal method.
In hydro/solvothermal method, different reaction solvents and
different ratios of mixed solvent have been proved to make great
difference in the size and structure of product. In addition, other
synthetic methods also have their own advantages. For instance,
template method, using template as carrier to control the size,
shape, structures, and properties of nanomaterials, is also a valid
pathway to synthesize the well-designed nanostructures, such as
nanorods, nanospheres, and hollow structures. Moreover, electro-
deposition and microwave methods are more simple, fast, and
convenient.
3.3. Cu2S hybrids
In this part, hybrids of Cu2S, including Cu2S/metal-based ma-
terials and Cu2S/carbon materials, are chiefly summarized, and the
specific morphology, size, and synthesis method of the materials
are shown in Table 2. Moreover, preparing Cu2S/metal-based ma-
terials through growing on metal substrate (mainly including Cu
foil and Al film) has been reported too. Compounding with carbon
materials is discussed in detail for their various structures and
excellent electroconductivity performance.
Y. Shi, B. Yang, X. Guo et al.
Table 2
Selected summary of the synthesis and applications in batteries of Cu2S and its composites, categorized by their morphologies.
Materials Morphology Size
Cu2S Spheres 0.45 mm
Cu2S Nanorods/nanowires 0.09e1.75 mm
Cu2S Nanorods 100 nm
Cu2S Flakes 100 mm diameter
Cu2S Hierarchical petal-like structures 1e1.5 mm diameter
Cu2S@Cu Cu2S film on Cu foil 2 mm thickness
Cu2S@ Cu Cu2S nanowire arrays 40e120 nm diameter
Cu2SeMoS2 Hierarchical microspheres ~2 mm
Cu2S@C Octahedral shape 20 mm
Cu2S/C Carbon layer on Cu2S nanowires ~250 nm
SWCNT-n-Cu2S Core shell structures e Atomic layer deposition method
Cu2S/CNT Mesoporous structures e Air atmospheric solution combustion
Cu2S@rGO Cu2S nanoflower and rGO matrix ~2 mm
Growing on metal substrate is an easy-operate method, and
metal materials could further improve the electroconductivity of
the hybrids. In 2012, Ni et al. [71] have prepared Cu2S film on the Cu
film through a simple hydrothermal method, and the film possesses
possible hollow structure and average thickness of about 2 mm.
However, the hydrothermal reaction is carried out at high tem-
perature and high pressure and has a long reaction time. One year
later, Ni et al. [72] successfully solved this problem and adopted a
new method (dry thermal sulfuration method) under a lower
temperature to synthesize Cu2S film on Cu foil. Although the
temperature and reaction time have been decreased, the temper-
ature is still higher than 100 C. Lai et al. [73] have used a common
solvothermal method to obtain highly ordered massive Cu2S
nanowire arrays at 80 C and deposit them on the Cu metal current
collector substrate at room temperature. The experimental results
have proved that the higher the reaction temperature is, the faster
the vulcanization rate is, and the increase or decrease of sulfur
makes the size of the product increase. The synthesis methods of
the above three papers [71e73] are common and have been widely
used in the synthesis of Cu2S, even the transformation MSs. More
significantly, Zhang et al. [74] used a novel method (electro-
chemical order synthesis), which is similar to a dynamic equilib-
rium process. Under the condition of open circuit, pure copper
transforms into nanocrystalline Cu2S in the thin region of copper
needle in a mixed solution of NaCl (0.1 M) and Na2S (5  10
4 M).
Differently, a rough Cu2S layer is formed in the active region of
electrochemical polarization, which is transformed into a passive
layer with uniform thickness at higher potential. Using Cu foil and
dimethyl sulfoxide (DMSO as S source) as raw materials in sol-
vothermal approach, Li et al. [4] prepared 3D hierarchical petal-like
Cu2S nanostructures with a diameter of about 1 mm, which are
composed of nanoslices with a thickness of 15 nm via solvothermal
approach. Molybdenum disulfide (MoS2) is a promising material to
compound with CuxS for the tunable band gap, whereas Cu and
graphene can bring significant enhancement in the electrochemical
activities of MoS2 [75e78]. Therefore, Kadam et al. [79] synthesized
3D hierarchical Cu2SeMoS2 microsphere with a size of 2 mm
through a solvothermal method. Moreover, the composites con-
sisted of 2D ordered ultrathin layered nanosheets with a size of
150 nm as well as a thickness of 10 nm.
Among the materials compounded with Cu2S, carbon materials
used widely for carbon materials with different morphologies can be
compounded with Cu2S, and the composite function acted as a
conductive agent can offer fast channels for electronic transportation
to improve electrochemical performance [85e88]. Via a hydrother-
mal method, Liu et al. [81] successfully coated a 20e40 nm thick
amorphous carbon layer on the surface of Cu2S with glucose as
carbon source. In recent years, metal organic framework (MOF) is
7
Materials Today Chemistry 23 (2022) 100675
Synthesis method Applications Ref.
Spray pyrolysis method LIBs [15]
Surfactant-assisted pathway e [43]
Surfactant-assisted pathway e [43]
Electrolysis method SIBs [42]
Solvothermal method LIBs/solar cells [4]
Hydrothermal method LIBs [71]
Hydrothermal method LIBs [73]
Solvothermal method LIBs [79]
MOF-derived sulfurization method Mg2þ/Liþ batteries [80]
Hydrothermal method LIBs [81]
LIBs [82]
LIBs [83]
Hydrothermal method LIBs [84]
widely used as a precursor/template for the synthesis of MOs and
MSs because of the large specific surface area as well as the
porousness [33,89,90]. In Wang's study [80], Cu2S@C derived from
the MOFs was synthesized the process of low-temperature sulfu-
ration at 300 C and subsequent high-temperature carbonation at
600 C (Fig. 5a). Analyzing from Fig. 5b and c, Cu-MOF has regular,
octahedral structures as well as high monodispersity, and Cu2S@C
composite can retain well-defined structure after high-temperature
sulfurization process. So far, in situ generation techniques have
been widely used in the preparation of structure/morphology-
controlled nanomaterials and attracted more attention. Hence, the
tubular mesoporous carbon with the large pore volume, open pore
structure, and thin pore wall is considered as a remarkable carbon
matrix to encapsulate numerous nanoparticles to enhance lithium
storage performance [91]. Combining the previously mentioned two
points, Han et al. [92] have obtained a Cu2S/C material through the
chargeedischarge reactions of an S/C compound on a Cu foil current
collector. Hence, the Cu2S nanoparticles are homogeneously
dispersed in the carbon, which owning tubular mesoporous struc-
ture. In addition to the previously mentioned synthesis methods,
films, obtained by atomic layer deposition (ALD) approach, are
grown layer by layer at the atomic scale and conformally deposit
within high-aspect-ratio and porous nanostructures [93]. Using this
method, Meng et al. [82] synthesized core-shell single-walled carbon
nanotubes (SWCNTs)-Cu2S. The results exhibited that with the in-
crease of the ALD cycles, Cu2S morphology changed from discon-
tinuous nanoparticles of about 15 nm (100 cycles; Fig. 5d) into
coalesced nanoparticles of about 30 nm (200 cycles) and finally into
continuous films (400 and 600 cycles). In Fig. 5e, core-shell Cu2S
particles with the average size of 15 nm were chained by SWCNTs,
which can ensure close contact and high porosity between the two
components to achieve effective charge transfer. Moreover, Wang
et al. [83] obtained mesoporous MSs/CNT composites via solution
combustion synthesis (Fig. 5f), which is seldom applied in the syn-
thesis of MS, and the reaction should be protected in inert gas.
Moreover, reaction temperature should be high enough (550 C) to
start the combustion reaction and carbonization, and the reaction
time should be short enough to prevent oxidation. Moreover,
through using L-cysteine as S source and fuel, CO2 and NH3 can be
produced and make a contribution to the formation of the pore
structures. In addition, reduced GO (rGO) materials can also com-
pound with Cu2S because of the stability and superior performance.
Zhang et al. [84] prepared Cu2S@rGO hybrid composites through
hydrothermal method and freeze-drying process. Through the
scanning electron microscope (SEM) images of Cu2S and Cu2S@rGO
(Fig. 5g), it can be seen Cu2S has a flower-like structure with a
diameter of 1.0 mm, and the thickness is about 20 nm. More
significantly, the 3D matrix consisting of rGO sheets (Fig. 5h) can
Y. Shi, B. Yang, X. Guo et al.
Fig. 5. (a) Schematic illustration of the preparation process of the Cu2S@C composite; (b and c) SEM images of Cu-MOF octahedral precursor and Cu2S@C composite; (d) SEM images
of the ALD-coated SWCNTs following 100 Cu2S ALD cycles; (e) TEM images of the 100-ALD cycle SWCNT-n-Cu2S; (f) Proposed air atmospheric solution combustion synthesis of the
MSs/CNT composites (M ¼ Co, Ni, and Cu); (g and h) SEM images of Cu2S and Cu2S@rGO. (aec) Reproduced with permission [80]. Copyright 2019, Elsevier B.V. (d and e) Reproduced
with permission [82]. Copyright 2015, Elsevier B.V. (f) Reproduced with permission [83]. Copyright 2018, American Chemical Society. (g and h) Reproduced with permission [84].
Copyright 2019 Elsevier B.V.
encapsulate Cu2S and relieve the change of structure and
morphology of Cu2S particles during chargeedischarge processes.
Therefore, the rGO bridge can also increase the effective area for
electrons and Liþ to reach at the same time, thus improving the
specific capacity of Cu2S nanoflowers.
Compounding with carbon materials is a good route to explore
new structures and excellent performance for the various structures
and good electroconductivity of carbon materials. Among these ma-
terials, GO, rGO, and CNTs are used widely to construct 3D structure
because of the good electroconductivity, high surface area, flexible
structure, and ultrathin thickness. During the reaction, temperature is
important because the high temperature would destroy the structure,
whereas low temperature goes against the reaction. Moreover,
microwave-assisted solvothermal method are used to disperse the
raw materials and obtain homogeneous product. Compared with
other methods, hydrothermal is still the main method; the main Cu
source is CuSO4$5H2O, and S sources are Na2S2O3$5H2O, thiourea, and
others. It is noted that appropriate dispersing agent or stabling agent
is often used in hydrothermal method.
3.4. CuS hybrids
In this section, we mainly discussed the synthesis method and
the related morphologies of CuS hybrids. Hence, the detailed in-
formation has been summarized in Table 3.
3.4.1. CuS/metal-based materials hybrids
The synthesis reactions of CuS materials are usually compli-
cated, and the conductive additives are necessary for the prepara-
tion of electrode binders. Therefore, more and more researches are
devoted to the growth of nanomaterials on the metal substrate (Cu
foam, Ni foam, and stainless steel), which can be directly tested as
electrodes without binders and conductive enhancers. Moreover,
8
Materials Today Chemistry 23 (2022) 100675
3D structures with interconnected porous networks can improve
the utilization of active materials, promote the immersion of elec-
trolytes, and provide a quick path for ions transportation. Both
Cheng et al. [68] and Tang et al. [94] have obtained CuS directly
grown on the Cu foam through a simple in situ melt-diffusion
method and H2O2-aided electrochemical corrosion method,
respectively. In Cheng's study [68], the CuS sheets and particles
have been formed by combining copper ions with sulfur ions on the
surface of Cu foam, which ensures effective immersion of electro-
lyte and makes lithium ion and charge rapidly transform. On the
other hand, a 3D porous CuS@Cu-independent structure exhibiting
homogeneous film-like morphology was obtained by Tang et al.
[94]. Except for the Cu foam, a three-layer CuS/rGO/Ni3S2 nano-
structure grown on nickel foam (NF) was obtained through a one-
step hydrothermal-assisted technique [95]. During the synthesis
process, the Ni element reacts with GO on the foam surface and
then vulcanized to form the bottom Ni3S2 layer and the interme-
diate rGO layer. Hence, the upper layer of CuS, composed of spheres
as well as fiber-like blocks, was formed by the adsorption of Cu2þ
under electrostatic action and then fixed on the surface of rGO.
Owing to the coupling interface at the atomic level, small lattice
distortion and a large number of vacancy defects, the CuS/NiS2
interface nanocrystals (CuS/NiS2 INs) were successfully obtained in
An's research [35] and applied as highly efficient bifunctional oxygen
electrocatalysts for high power density Zn-air batteries. What is more,
hierarchical hollow CuS@MoS2 microcubes with shell thickness of
about 20e30 nm were prepared by Zhou et al. [36]. The synthesis
mechanism (Fig. 6a) is on the basis of the transformation from Cu2O to
CuS and the precipitation formation of MoS2 at the same time.
3.4.2. CuS/C hybrids
Similar to the Cu2S materials, CuS materials can be compounded
with various materials. Except for metal materials, C materials are
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Table 3
Selected summary of the synthesis and applications in batteries of CuS hybrids.

Materials Morphology Size Synthesis method Applications Ref.

CuS@Cu CuS sheets on Cu foam CuS: 10 mm width Melt-diffusion strategy without binder LIBs [68]
CuS@Cu Porous architecture Several nanometers' thickness H2O2-aided electrochemical corrosion method LIBs [94]
CuS/RGO/Ni3S2 Three-layer nanostructure Several nanometers' thickness One-pot hydrothermal method Supercapacitors [95]
CuS@MoS2 Hierarchical microcubes 500 nm Transformation LIBs [36]
CuS/graphene Hierarchical CuS/graphene layers CuS: 8 mm diameter Solvothermal method followed by calcination LIBs [96]
CuS@CQDs@C Hollow nanospheres ~40 to 45 nm Hydrothermal method Supercapacitors [97]
CuS-CNT CuS nanoparticles CuS: 2 nm Microwave-assisted solvothermal method LIBs [98]
CuS@CNT Nanoneedles 5e7 nm diameters Template-based hydrothermal conversion Supercapacitors [99]
S@CuS@CNT Nanoneedles Several nanometers' diameters Heat melt-diffusion method LSBs [99]
CuS/graphene CuS spheres graphene sheets CuS: ~800 nm One-pot microwave irradiation method LIBs [100]
GR/PANI/CuS Hexagonal structure 1 mm diameter Hydrothermal and in situ polymerization LIBs [26]
CuS NWs/rGO rGO nanosheets/CuS nanowires e One-pot and template-free solution LIBs [27]
CuS/rGO rGO nanosheets/CuS particles CuS: 300e500 nm Solvothermal method Supercapacitor [101]
CuS/rGO Double-sandwich-like structures CuS: 15e50 nm Hydrothermal method LIBs [102]
CuS-RGO CuS nanosheets into RGO e Hydrothermal method SIBs [103]
Vs-CuS/RGO Mesoporous structures CuS: 3e5 nm Thermal annealing method LIBs [104]

Fig. 6. (a) Schematic diagram of as-prepared hollow CuS@MoS2 microcubes formation; (bed) FE-SEM, HR-TEM, TEM (inset: selected area electron diffraction [SAED] pattern) of the
CuS@CQDs@C HNS; (e) Schematic illustration of the formation of CuS nanoneedles on CNT backbone (CuS@CNT) by a multistep conversion route; (f) SEM image of CuS@CNT; (g)
HMSEM image of S@CuS@CNT; (h) Schematic illustration of the formation of CuS-G; (i) SEM image and (j) TEM image of CuS-G; (k) illustration of the formation process of CuSNWs/
rGO nanocomposites; (l) SEM image of CuS microsphere/rGO composites. (a) Reproduced with permission [36]. Copyright 2017, Elsevier Ltd. (bed) Reproduced with permission
[97]. Copyright 2016, American Chemical Society. (eeg) Reproduced with permission [99]. Copyright 2017, Springer-Verlag Berlin Heidelberg. (hej) Reproduced with permission
[100]. Copyright 2016, Elsevier Ltd. (k, l) Reproduced with permission [27]. Copyright 2015, American Chemical Society.

popular for the excellent performance and different structures,
including amorphous C, CNTs, and graphene materials [26,96,100].
In addition, the synergistic effect between CuS and C materials can
improve the performance greatly. CNTs have unique 1D structure as
well as excellent electrical and mechanical properties, which are
considered as ideal scaffolds for 1D hybrid structures. CuS/CNTs
composites were obtained by Liu et al. [98] via a one-pot, micro-
wave-assisted solvothermal strategy. It was shown that the CuS
nanosheets with a mean size of around 2 nm coated on CNTs ho-
mogeneously. At the same time, a template transformation
9
pathway to form ultrafine CuS nanoneedles arrays on the CNT
framework (CuS@CNT) and further synthesize S@CuS@CNT was
reported by Hou et al. [99]. The synthesis process is illustrated in
Fig. 6e. In CuS@CNT (Fig. 6f), CuS nanoneedles with a diameter of
5e7 nm were firmly attached to the framework of CNTs. Moreover,
the result shows that the CuS@CNT nanomaterials have a large
surface area (49.3 m2/g), which is beneficial to increase the ion
transfer rate as well as contact area. In addition, the S@CuS@CNT
complex (Fig. 6g) was synthesized through heating the mixture of
CuS@CNT and S powder.
Y. Shi, B. Yang, X. Guo et al.
As another common carbon material, 2D graphene sheets exhibit
excellent mechanical strength, which can relieve the volume change
during the chargeedischarge process. In addition, graphene can also
improve the conductivity as well as rate performance of the hybrid
electrodes. For instance, CuS/graphene composite was obtained by Li
et al. [100] through one-pot microwave irradiation approach
(Fig. 6h). As can be seen in Fig. 6i and j, CuS spheres with the diameter
of ~800 nm are wrapped in or distributed onto the surface of gra-
phene sheets. Moreover, a graphene/polyaniline/CuS nano-
composite (GR/PANI/CuS NC) has been obtained by Iqbal et al.
through in situ polymerization reaction [26]. The results show that
GR has almost transparent and flexible 2D uniform ultrathin
NS features mainly lie in a wrinkled form with the PANI NFs growth
on the edges of CuS NPs in the composites. Hence, there are no
separate GR or PANI agglomerates can be found, and the structure
can maintain without broken and collapsed, which means that the
reaction is effective. GO sheets, monatomic layer structure, are ob-
tained through chemical oxidation and exfoliation of graphene. In
comparison with graphene, GO sheets have richer surface functional
groups and higher catalytic activity due to oxidation. For example,
Liu et al. [69] obtained a flexible and adhesive-free CuS/GO film
possessing 3D sandwich-like structure through a vacuum filtration
method. The CuS microsphere with average diameter of 2 mm
consists of irregular nanosheets (thickness: ~20 nm).
Moreover, rGO can be used to decorate CuS materials. Feng et al.
[27] developed an easy and one-pot method to synthesize CuSNWs/
rGO nanomaterial in solution of DMSO and EG. The surfaces of CuS
NWs are rough and coated by rGO nanosheets (Fig. 6k). In compar-
ison with pristine CuS NWs, the NWs are uniformly distributed, and
the length becomes shorter. The results show that rGO nanosheets
can protect CuS from aggregating. In addition, in the presence of
thiourea, CuS microspheres were found to be dispersed in the rGO
nanosheets homogeneously (Fig. 6l). He et al. [101] synthesized CuS/
rGO hybrid via a solvothermal method and used EG as the reducing
agent. Microsphere CuS particles disperse on the rGO layers, and the
composite possesses size with diameters of 300e500 nm. Ren et al.
[102] reported double-sandwich-like CuS/rGO composite through
hydrothermal method. In the first hydrothermal step, GO sheets can
combine CuS by the electrostatic attraction, and NaBH4 acts as
reducing agent in the next step, which oxidizes GO to rGO. Li et al.
[103] synthesized the CuS/rGO composite via microwave-assisted
reduction through incorporating rGO into CuS nanosheets. More-
over, the as-prepared CuS nanoparticles were turned into nano-
sheets and further dispersed on the surface of rGO nanosheets when
adding the rGO. Zhang et al. [104] synthesized microflower-like
vacancy defective CuS/rGO composites through a thermal anneal
in air, which can generate S vacancies.
2D graphene and 1D carbon nanotubes, as the most common
carbon allotropes, have been widely applied in energy storage.
Nevertheless, 0D carbon quantum dots have been recognized as new
endowments of carbon in the field of electrochemistry because of
their good conductivity, excellent chemical stability, and environ-
mental friendliness. De et al. [97] prepared core-shell CuS@Carbon
Quantum Dots@Carbon hollow nanospheres (CuS@CQDs@C HNS),
which possess a hierarchical hollow sphere-like structure with high
microporosity, through a facile and scalable in situ one-step hydro-
thermal approach (Fig. 6bed). In addition, the uniform spherical-
shaped CuS NPs with the size of 40e45 nm are encapsulated by a
carbon shell in the CuS@CQDs@C, and the mean size of carbon hol-
low nanospheres (CQDs) is found to be around 3 nm.
3.5. Summary
Among various method to synthesize CuxS and relevant mate-
rials, hydrothermal/solvothermal method is used the most
10
Materials Today Chemistry 23 (2022) 100675
frequently one because of its simple operation and low price.
Moreover, the technology can increase the solubility of the reactant
in the solvent, accelerate the reaction, and achieve rapid super-
saturation at high temperature and pressure so that the nano-
structures can be obtained. In addition, the morphology and size of
CuxS can be changed easily through altering the kind/quality of
precursors, the temperature/pressure/time of reaction, the kind/
volume/ratio of solution, and other parameters. Specially, poly-
mers, surfactants, and other additives can be added to control the
morphology.
Besides hydro/solvothermal approaches, one-pot hot-injection
method is also a common strategy for synthesizing monodisperse
CuxS nanocrystals of good quality. In the presence of surface, the
sudden addition of cold reactants (room temperature) into thermal
solution can facilitate the nucleation of materials. Thermolysis in-
volves the formation of CuxS nanostructures by thermal decom-
position of CuxS composites as single-source precursor. Both the
formation of multilayer superlattices (nanorods, nanodisks, nano-
platelets, and others) and oriented growth of CuxS depends on the
differences in surface energy of (001) and (100), (110) facets. Mi-
crowave irradiation is the method that uses microwave of
0.3e2.45 GHz to convert electromagnetic energy into thermal en-
ergy along with the chemical reaction. Similarly, different choices
of reaction parameters can influence the structures of CuxS. Elec-
trochemical deposition is a high-throughput technique that can
synthesis CuxS materials onto the substrate directly. Generally, the
Cu/S source is contained in the electrolyte. Many studies have
confirmed that the time of deposition duration, the content of
electrolyte, and the voltage range are mainly influence factors.
4. Applications
As a result of the rich abundance, low cost, excellent capacity
(~337/560 mA h/g for Cu2S/CuS, respectively) as well as favorable
electrical conductivity (10
3 S/cm), CuxS and its relevant compos-
ites are widely employed as the promising electrode materials for
batteries. In this part, we mainly focus on the reaction mechanism
and application of CuxS and the relevant composites in recharge-
able secondary batteries, such as LIBs, LSBs, SIBs, MIBs, and so on.
4.1. Lithium-ion batteries
4.1.1. LIB anode
LIBs are an effective device for energy storage for the excellent
performance (capacity, cycling performance, rate capability, and
others). However, the low energy caused by the poor surface area of
the electrodes and the low power caused by sluggish diffusivity of
Liþ are still the main problems to be solved [105]. Exploring
effective materials as electrode is the main method to obtain
excellent performance. CuxS and relevant composites, conversion
reactionebased MSs, have attracted more and more attention for
their excellent electroconductivity, rich redox chemistry, and high
specific capacity (theoretical capacity CuS: 560 mA h/g as well as
Cu2S: 337 mA h/g) [106,107]. Thus, in this part, the CuxS materials
with different structures and the electrochemical performance of
LIBs are discussed in detail. The effect of CuxS and its composites for
electrochemical performance are discussed divided into improved
capacity, cycling performance, and rate capacity (see Tables 4e6
and Fig. 7). Moreover, the application of LIBs cathodes is dis-
cussed in the next section because of the different mechanisms. All
enhanced electrochemical properties of LIBs can be assigned in two
ways: nanostructure designing and compounding with other
materials.
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Table 4
The initial chargeedischarge capacity data of CuxS and its composites in LIBs.

Materials Electrode Initial chargeedischarge capacity Current density Ref.

CuS@Cu Anode 580/380 mA h/g 0.5 A/g [94]

Cu2S/C Anode ~330/~460 mA h/g 0.1 A/g [81]
Cu2-xS@C Anode ~350/408 mA h/g 0.337 A/g [130]
CuS/CNTs Anode ~ 420/~460 mA h/g 0.4 A/g [136]
CuSNWs/rGO Anode 620/900 mA h/g 0.28 A/g [27]
CuS@SFC Anode -/903 mA h/g 0.05 A/g [119]
CoeCu2S@C Anode 858/1,356 mA h/g 0.5 A/g [108]
CuS@MoS2 Anode 1,080/1,150 mA h/g 0.5 A/g [36]
Ball-like CuS Cathode ~320/390 mA h/g 0.56 A/g [67]
Dandelion-like CuS Cathode ~ 450/500 mA h/g 0.56 A/g [67]
CuS nanospheres Cathode -/628 mA h/g 0.01 A/g [63]
CuS hollow spheres Cathode -/480 mA h/g 0.05 A/g [66]
Cu2S@CFP Cathode 379/532 mA h/g 0.1 A/g [150]
SWCNT-n-Cu2S Cathode 239/709 mA h/g 0.1 A/g [82]
CuxS/C Cathode ~560/~740 mA h/g 0.25 A/g [149]

Table 5
The cycling performance of CuxS and its composites in LIBs.

Materials Electrode Current density Cycle performance Cycle numbers Ref.

Cu2S nanowire bundles Anode 0.1 A/g 313 mA h/g 100 [51]
CuS nanorods Anode 0.112 A/g ~390 mA h/g 250 [54]
CuS nanorods Anode 0.1 A/g 472 mA h/g 100 [45]
Cu2-xS@C nanorods Anode 0.337 A/g 270 mA h/g 600 [130]
CuS/CNTs hybrid Anode 0.4 A/g 558 mA h/g 450 [136]
CuS/N,S co-doped rGO Anode 2 A/g 530 mA h/g 1,000 [154]
Cu2S on Cu foil Cathode 0.337 A/g 250 mA h/g 100 [15]
Cu2S particles Cathode 0.337 A/g 270 mA h/g 50 [153]

Table 6 Recently, many reports have shown that cation doping can
The rate performance of CuxS and its composites in LIBs.
effectively improve the lithium storage kinetics of MS electrode
Materials Electrode Current density Rate performance Ref. through introducing edge/surface defects and local charge polari-
CuS@Cu-BTC Anode 1 A/g ~490 mA h/g [132] zation, which plays an important role in promoting the charge and
GR/PANI/CuS NC Anode 5 A/g 374 mA h/g [26] electron transfer of the electrode [109,110]. Tang et al. [94] prepared
CuS@Cu Anode 2 A/g 414 mA h/g [94] 3D porous CuS@Cu with the commercial Cu foam as the source;
Cu2S/C Cathode 3.37 A/g 225 mA h/g [92]
when directly used as anode for LIBs, the composite delivered
CuS/graphene Cathode 1 A/g 143 mA h/g [96]
CuxS/rGO Cathode 7 A/g 205 mA h/g [157]
initial discharge/charge capacity of 580/380 mA h/g at 0.5 A/g.
CuS 3D network Cathode 1.12 A/g 376 mA h/g [160] However, the discharge/charge capacity can increase to 845/
Cu2S nanowire arrays Cathode 6.7 A/g 145 mA h/g [73] 834 mA h/g after 500 cycles, which can be attributed to the elec-
trochemical reconstruction during the reaction [111]. Except for the
cation doping, 2D nanostructure can also enhance the rate capa-
4.1.1.1. Increased capacity. The commercial anode for LIBs is bility, as its high surface-to-volume ratio can readily trigger the
graphite (theoretic capacity: 372 mA h/g), and the energy density charge transfer reactions consisting of surface or near-surface
is low. In recent years, CuxS are expected to be promising anode redox reactions in comparison with the 3D counterparts [112e117].
materials in LIBs because of remarkable theoretical specific ca- Qing et al. [108] synthesized 2D nanosheet-like Co-Cu2S@C hybrid
pacity, and the capacity can be further improved by cooperating composites with HKUST-1 as the precursor (Fig. 8d). When used as
with other materials (carbon, metal oxides, MSs, etc.) owning anode of LIBs, the electrode shows initial charge/discharge capacity
high theoretical capacity, strong conductivity, and many active of 858/1,356 mA h/g, respectively (Fig. 8e). After 300 cycles, the 2D
sites. Co-Cu2S@C nanosheet can still maintain the capacity of 670 mA h/g,
2D MSs exhibit higher active edge sites and larger specific which is much higher than 3D Cu2S@C (234 mA h/g) and pure Cu2S
surface area, among which MoS2 with analogous structure as (206 mA h/g). The remarkable capacity performance can be
2D graphene stands out because of its enhanced theoretical attributed to the Co doping as well as C coupling, which can provide
capacity (670 mA h/g) as well as excellent conductivity. For shorter pathway for Liþ transportation and the large surface of
instance, Zhou et al. [36] successfully synthesized hierarchical nanosheet for Liþ adsorption.
hollow CuS@MoS 2 microcubes consisting of MoS 2 nanosheets Except for cation doping, the introduction of carbon-based
and hollow CuS nanostructures (Fig. 8a and b). The 3D hollow materials (carbon nanotubes, amorphous carbon, graphene, and
composites have obvious internal voids and large specific sur- other) can provide a feasible way to design target materials with
face area, which can adapt to the large changes of electrode multifunctional or enhanced properties because of their excellent
volume in the process of electrochemical cycling. Therefore, the conductivity as well as large surface area. First, carbon coating has
obtained electrode can deliver enhanced initial charge/ been proved to reduce volume expansion, suppress the aggregation
discharge capacity of 1,000/1,150 mA h/g at 0.5 A/g (Fig. 8c), and of active particles, and enhance the conductivity of electrodes [118].
the specific discharge capacity can retain 912 mA h/g after 200 Hence, as a common carbon source, glucose is used widely to obtain
cycles. amorphous carbon coating through calcining for period of time
11
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Fig. 7. Initial discharge capacity of pure CuxS, CuxS/carbon, CuxS/metal-based composites, and CuxS/other transition materials. (Digit in the square is the reference.) The corre-
sponding obtained materials of each report are shown as follows: Ref.15: Stoichiometric Cu2S; Ref.26: CuS/Graphene composites; Ref.27: CuS nanowires/rGO nanocomposites;
Ref.36: Hollow CuS@MoS2 microcubes; Ref.45: CuS nanorods; Ref.51: CuS nanowire bundles; Ref.54: CuS nanorods; Ref.63: CuS nanospheres; Ref.66: CuS hollow spheres; Ref.67:
CuS hierarchical superstructures; Ref.81: Cu2S/carbon composites; Ref.82: Tunable core-shell single-walled carbon nanotube-Cu2S networked nanocomposites; Ref.92: Meso-
structured Cu2S/C composites; Ref.94: CuS@Cu; Ref.96: Hierarchical CuS/graphene architectures; Ref.108: Cobalt-doped CuS/carbon nanosheets; Ref.119: CuS@Sisal fiber carbon
composites; Ref.130: Bamboo-like Cu2-xS@C nanorods; Ref.132: CuS@Cu-BTC composites; Ref.136: CuS/3D intertwined CNTs; Ref.149: CuxS nanowire-in-carbon composites; Ref.150:
Stoichiometric Cu2S; Ref.153: Cu2S; Ref.154: CuS nanowires; Ref.160: CuS.

[81]. In comparison with amorphous carbon, carbon materials with
nanostructures can exhibit better electrical conductivity and sta-
bility. Qin et al. [119] synthesized CuS@Sisal fiber carbon (CuS@SFC)
composite, which includes CuS nanoparticles (size: ~200 to
500 nm) dispersed homogeneously on SFC surfaces. The CuS@SFC
composite can exhibit the initial discharge capacity of 903 mA h/g
at 0.05 A/g, which is better than that of SFC (523 mA h/g). As the
extensional carbon materials, 2D GO and rGO nanosheets are also
used widely because of the good conductivity, strong elasticity, and
strong electrochemical activity [120e123]. Feng et al. [27] obtained
CuSNWs/rGO (CuS nanowires/rGO) through wrapping CuS nano-
wires on the rGO nanosheets (Fig. 8f). The reports have shown that
synergistic effect between CuS and rGO can improve the lithium
storage properties [124]. The initial discharge/charge capacity of
prepared electrode is 908/630 mA h/g (Fig. 8g), which can be
attributed to the solid electrolyte interface (SEI) film on the rGO
surface during the electrolyte decomposition [102]. By comparing
with different electrode materials, the capacity of CuSNWs/rGO
maintains at 620 mA h/g after 100 cycles, which is higher than
those of CuS nanowires electrodes (400 mA h/g; Fig. 8h).
4.1.1.2. Improved cycling performance. When tested as the electrode
of LIBs, CuxS, as one of the conversion reactionebased materials,
often put up with the severe pulverization problem during elec-
trochemical reaction, resulting in the loss of active materials and
rapid capacity decay. To solve these problems, numerous plans such
as constructing nanostructures to reduce the size of materials
[125,126], complexing with carbon matrix materials to improve
electric conductivity, and relieving the volume expansion
[120,127e129] have been reported.
More detailly, reducing the dimension of materials can guar-
antee the short transport pathway of Liþ to obtain enhanced rate
capacity and can also properly accommodate the volume change
during (de)lithium reaction [133,134]. In addition, among various
carbon materials coating, amorphous carbon coating is the simplest
way to complex with carbon matrix [118,120]. Wang et al. [130]
12
prepared Cu2-xS@C nanorods (Fig. 9a) through carbon coating and
calcination on the CuS nanorod precursors (Fig. 9b), and the com-
posite exhibits admirable cycling performance. The electrode ex-
hibits a discharge capacity of 309 mA h/g at 0.337 A/g after 300
cycles and still possesses capacity of more than 270 mA h/g after
600 cycles, which correspond to capacity retentions are 75.8% and
66.2%, respectively. Comparing the cycling performance of Cu2-xS
and Cu2-xS@C electrodes, it can be found that Cu2-xS@C exhibits
superior performance obviously (Fig. 9c), which can be ascribed to
carbon layers improve the interfacial properties of Cu2-xS and the
bamboo-like structures provide space to accommodate the volume
expansion. Although the cycling performance has been improved,
the electrode still suffers from the serious capacity fading in the
first several cycles. On the one hand, nanoparticles will gather and
affect the performance of the battery. On the other hand, the
conductive frameworks provided by carbon matrix are not strong
enough to maintain during re-oxidation reaction of Li2S [135].
Introducing 3D interior conducting network has been proved to
further improve the electrochemical performance of CuxS. Wang
et al. [136] obtained CuS nanospheres interconnected by the CNTs,
which showed excellent cycling performance (a discharge capacity
of more than 400 mA h/g at 0.4 A/g after 450 cycles). Although the
morphology of the electrode is destroyed and turns into nano-
particles after the first cycle, the homogenously distributed CNTs
can still provide effective electron transport conductive network for
the active material and maintain stability. In addition to the two
common strategies, doping of heteroatoms can also improve the
cycling performance to some extent. For example, N-doped
carbonaceous materials show strong chemisorption for poly-
sulfides, which can improve the cycling performance, and S-doping
could enhance conductivity owing to its more effective reduction as
well as stronger electron donor ability. Ding et al. [131] obtained
CuS nanoparticle/N,S co-doped rGO hybrids, with small size
(Fig. 9d) as the anode of LIBs. The average reversible capacities of
CuS@N/S-G-C6 ranged from 522.4 mA h/g at 0.1 C to 403.6 mA h/g
at 5 C (1 C ¼ 560 mA h/g; Fig. 9e), and the electrode shows the rate
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Fig. 8. (a) SEM and (b) TEM of CuS@MoS2 microcubes; (c) Voltage-capacity profiles for the 1st, 2nd, and 200th cycle at 0.5 A/g; (d) Schematic synthesis route for ultrathin 2D Co-
Cu2S@C composites; (e) Chargeedischarge curves of 2D Co-Cu2S@C at 0.5 A/g; (f) TEM image of CuSNW/rGO; (g) chargeedischarge curves for the CuSNWs/rGO nanocomposites
electrode at a rate of 0.5 C between 0.02 and 3.00 V; (h) Cycling performance of the CuSNWs/rGO nanocomposites electrode and CuS nanowires electrode at 4 C. (aec) Reproduced
with permission [36]. Copyright 2017, Elsevier Ltd. (dee) Reproduced with permission [108]. Copyright 2020, Elsevier Inc. (feh) Reproduced with permission [27]. Copyright 2015,
American Chemical Society.

capacity of 530 mA h/g at 2 A/g after 1,000 cycles (Fig. 9f). The
conductive networks built by rGO, which show the advantages of
the excellent conductivity as well as flexibility of rGO nanosheets,
could not only effectively reduce the volume changes in continuous
(de)lithiation process but also guarantee the high, efficient, fast,
and short transport of electrons and Liþ.
4.1.1.3. Improved rate capability. The rate capability of LIBs is
mainly depended on the transport rate of ions. Hence, materials
with hierarchical pores or micro/medium/macropores provide a
great quantity of channels for the transport of Liþ, which usually
show higher rate capacity [137,138]. Recently, MOFs have been
widely used as precursors because of the high porosity and large
specific surface area to synthesize some derivatives (metal oxides
and MSs), which retain their special morphology and thus exhibit
excellent rate capacity [139e142]. Wang et al. [132] prepared MOF-
derived CuS@Cu-BTC (BTC ¼ 1,3,5-benzenetricarboxylate) com-
posites (Fig. 9g) as anode for LIBs. Hence, the CuS nanorods, with
20e100 nm length and 10 nm diameter, are arranged on the surface
of octahedrons MOF structure, which is conducive to electrolyte
penetration into the electrode and shortens the diffusion path of
Liþ. The electrode retains 480 mA h/g at 1 A/g, and it can attain an
average capacity of 800 mA h/g when the current return to 0.1 A/
13
g (Fig. 9h). The great electrochemical performance could be
ascribed to the special component of CuS (x wt%)@Cu-BTC: CuS acts
as active materials to improve conductivity, and Cu-BTC provides
the pores and improves chemical stability. Nowadays, conductive
polymers electrode materials have received considerable attention
for their excellent conductivity and electrochemical performance.
Compounding with conductive materials is another method to
improve the rate capacity except for nanostructure design. Gra-
phene possesses high electrical conductivity, superior thermal
conductivity, and high chemical stability and can be used to
enhance electrochemical performance [143e145]. Iqbal et al. [26]
synthesized 2D GR/PANI/CuS NC (polyaniline anchored CuS/Gra-
phene nanoactive composite; Fig. 9i), which GR and PANI grow on
the CuS NPs surfaces successfully. With the introduction of GR and
PANI, the as-prepared material exhibits good rate capacity, around
600 mA h/g at 2 A/g, and even at the high rate of 5 A/g, the com-
posite can remain about 374 mA h/g (Fig. 9j).
4.1.2. LIB cathode
4.1.2.1. Increased capacity. Because of the phenomenon of degra-
dation, volume expansion, and aggregation of electrode materials
during (de)lithiation reaction, LIBs suffer from low specific capacity
[146]. To improve the performance of LIBs, a large number of
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Fig. 9. (a) Synthetic scheme of bamboo-like Cu2-xS@C nanorods; (b) SEM images of CuS, (c) cycling performances of both materials at 1 C and 2 C; (d) The microstructure of CuS@N/
S-G-Cn; (e) rate performance of CuS@N/S-G-C6 from 0.1 C to 5 C; (f) Cycling performance of CuS@N/S-G-C6 at 2 A/g; (g) SEM images of CuS (70 wt %)@Cu-BTC; (h) rate capabilities
impedance spectrum of CuS (70 wt %)@Cu-BTC; (i) HRTEM of GR/PANI/CuS NC; (j) rate performance from 0.1 A/g to 5 A/g in the voltage range of 0.01e3.0 V. (aec) Reproduced with
permission [130]. Copyright 2017, Elsevier Ltd. (def) Reproduced with permission [131]. Copyright 2019, Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim. (g, h) Reproduced with
permission [132]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (i, j) Reproduced with permission [26]. Copyright 2017, Elsevier Inc.

studies have been carried out on the synthesis of nano- and
microstructure CuxS. Up till now, nanorods, nanowires [106,147],
NFs, nanoflakes, nanocages, flower-like, and hollow spheres of
copper sulfides [66,72,148] have been successfully fabricated and
tested as the cathode materials in LIBs. Hence, the reaction mech-
anism of CuxS (x ¼ 1, 2) used as negative electrode material in LIB is
shown as follows:
2Liþ þ 2CuS þ 2e
/ Li2S þ Cu2S
2Liþ þ Cu2S þ 2e
/ Li2S þ 2Cu
Zhao et al. [66] prepared CuS with hollow spheres and porous
spheres by changing the ratio of solvent simply. The hollow
structure exhibits higher capacity, which may be ascribed to the
fact that the hollow sphere structure can adapt to the volume
change during the charge/discharge reaction, providing more re-
action sites on the surface as well as reducing the transport length
of Liþ. As a result of the special shape-dependent properties and
high capacity, 3D inorganic nanostructures made up of 0D, 1D, and
2D nanomaterials have been proved to exhibit higher capacity. In
2013, Li et al. [63] prepared monodispersed CuS nanospheres
assembled of nanoplates, and the electrode showed an initial
discharge capacity of 628 mA h/g. Two years later, Hosseinpour
et al. [67] prepared tubular ball-like (Fig. 10a) and dandelion-like
(Fig. 10b) CuS consisting of small semispherical nanoparticles
(size: 30e40 nm) and compared their electrochemical properties.
As Fig. 10c and d show, the initial discharge capacity of the ball-
like/dandelion-like morphology is about 390/500 mA h/g at
0.56 A/g. Therefore, by using hierarchical superstructures with
specific morphology (such as dandelion-like structure) to
optimize the conversion reaction at the nanoscale, high energy
density and low-cost LIBs can be obtained.
Carbon materials are appropriate materials to compound with
CuxS because of their electronic conductivity, and they can further
improve the performance of cathode materials. Because of the large
surface area, crystallinity, and inherent modularity of MOFs,
nanostructured MSs can be formed by calcining MOF materials as
sacrificial precursors in inert atmosphere and in the presence of
(1) sulfur. Based on the theory, Foley et al. [149] prepared CuxS
nanowire-in-carbon (CuxS/C) composites (CuS/C-350, Cu1.8S/C-500,
(2) and Cu2S/C-650) by changing temperature, and CuS/C-350 shows a
higher capacity and locates at a higher voltage (2.25 V; Fig. 10e and
f). In another study [150], the stoichiometric Cu2S of monoclinic
crystal structure coated on CFP (a carbon fiber paper) displayed
excellent initial discharge capacity of 532 mA h/g at 0.337 mA h/g
(Fig. 10h). The improved capacity can be attributed to the good
connection of carbon fibers, as well as their conductive property
and appropriate pore channels, which create an effective electronic
pathway for the connection of electrolyte and active materials.
Meng et al. [82] prepared tunable core-shell SWCNTs-Cu2S nano-
materials (Fig. 10i and j) through ALD, and the composites exhibited
a capacity of 270 mA h/g after 300 cycles without any obvious ca-
pacity loss. Through comparing different materials including
SWCNTs, n-Cu2S (nanoscale Cu2S with ~15 nm), m-Cu2S (commer-
cial micro-sized Cu2S), SWCNT-m-Cu2S, as well as SWCNT-n-Cu2S
composites, the results show that SWCNT-n-Cu2S have a better
capacity performance (Fig. 10k,l), which may be ascribed to the
close connection between the SWCNTs and Cu2S and the quick
ionic/electronic conducting pathways provided by nanoscale ALD
Cu2S coatings. Foamed copper/copper foil has the advantages of
good conductivity and convenient operation. Therefore, the direct
14
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Fig. 10. TEM images of (a) CuS ball-like, (b) Dandelion-like; (c) First two charge/discharge cycles at 0.56A/g of (c) ball-like structures (d) dandelion-like structures; SEM images of (e)
HKUST-1 and (f) CuxS/C-500; (g) Initial discharge/charge curves at 250 mA/g; (h) Chargeedischarge curves of stoichiometric Cu2S coated on a CFP of 1.0e3.0 V at 0.1 C. Inset: SEM
image of powders; (i) SEM images of the pristine SWCNTs; (j) TEM images of the 100-ALD cycle SWCNT-n-Cu2S; dischargeecharge characteristics of the first three cycles of 100 mA/
g from 0.01 to 3.00 V. (k) m-Cu2S (l) 200-ALD cycle SWCNT-n-Cu2S. (aed) Reproduced with permission [67]. Copyright 2015, Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim. (eeg)
Reproduced with permission [149]. Copyright 2018, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (h) Reproduced with permission [150]. Copyright 2016, Elsevier Ltd. (iel)
Reproduced with permission [82]. Copyright 2015, Elsevier B.V.

growth of Cu2S on foamed copper or copper foil is a facile approach
to prepare Cu2S materials with enhanced capacity. For instance, Ni
et al. [71] obtained Cu2S film with possible hollow structure grown
on Cu foil, when served as electrode, the initial discharge/charge
capacity is about 0.74/0.40 mA h/cm2.
4.1.2.2. Improved cycling performance. The poor cycling perfor-
mance of LIBs is principally resulted from the great volume change
as well as side reaction of CuxS during the electrochemical test.
Nanostructure CuxS can alleviate the volume change because of
the small size and the multihole structure. Moreover, the elec-
trolyte even the foil which electrode coated can make a difference
to the electrochemical performance. Kalimuldina et al. [15] syn-
thesized stoichiometric Cu2S consisting of spherical particles
(Fig. 11a) with a geometric average diameter of 0.45 mm and re-
ported the electrochemical performance of Cu2S with different
foil. Analyzing from Fig. 11b and c, the corrosion of Al foil by Cu can
be ascribed to the gradual capacity fading in discharge process as
well as the large scattering in charge process during the battery
reaction. On the contrary, the Cu2S electrode coated on a copper
foil current collector exhibits steady cycling performance at 30 C.
In addition, the stability, conductivity, and non-toxic of electrolyte
have certain influence on the performance of electrode materials,
so the selection of electrolyte is also important. Reports have
shown that Li2S produced during the cell reaction can keep
reversibly active in ether-based electrolytes such as a mixed so-
lution of dimethoxyethane and 1,3-dioxolane, so the performance
could be improved in ether-based electrolyte [151,152]. However,
Shi et al. [153] measured the cyclability of commercial Cu2S in
different carbonate-based electrolytes such as linear carbonates
(DMC: dimethyl carbonate, EMC: ethyl methyl carbonate) and
cyclic carbonates (PC: propylene carbonate, VC: vinylene
15
carbonate, FEC: fluoroethylene carbonate, and EC: ethylene car-
bonate), The results show that the cyclic carbonate-based elec-
trolytes are more unstable because of the fact that the cyclic
carbonate molecules can easily obtain electrons through electro-
philic reaction and have higher energy, resulting in poor cycling
performance (Fig. 11d).
4.1.2.3. Improved rate capability. The rate capability is mainly
depended on the electroconductivity and the nanostructures of the
electrode materials. The main way to improve the rate performance
of CuxS is to composite them with metal [68,155], carbon
[92,96,155e157], and other conductive materials. Tang et al. [94]
synthesized 3D porous CuS@Cu composite through the vulcaniza-
tion of copper foam (Fig. 11e), and the electrode can exhibit
discharge capacity of 414 mA h/g after 300 cycles at 2 A/g (Fig. 11f).
The improvement of the rate capacity can be ascribed to the
numerous nanosized holes on the interconnected nanoflake.
Moreover, Cheng et al. [68] also prepared CuS monolith materials
with hybrid networks, which are composed of microporous net-
works made up of CuS sheets/particles on 3D microporous mono-
lith Cu film. The rate capacity of this obtained material is 83.9%
capacity of initial capacity after 70 cycles at rates of 0.1 Ce1 C
(1 C ¼ 560 mA/g), which indicates the hybrid network structure can
improve the conductivity of the electrode as well as strengthen the
contact between electrolyte and electrode (Fig. 10g).
Carbon materials have the advantages of good conductivity,
numerous structures, and excellent stability so that have been
widely used. Han et al. [92] used Cu2S/tubular mesoporous car-
bon composite in which Cu2S nanoparticles are highly dispersed
throughout carbon. The reversible capacity can maintain at
225 mA h/g at 3.37 A/g, which benefits from the conductive Cu2S
nanoparticles. Moreover, the confinement effect of the carbon
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Fig. 11. (a) SEM image of stoichiometric Cu2S powders. Cycling performance of stoichiometric Cu2S electrode (b) coated on an Al foil current collector (c) at a current rate of 1 C; (d)
Cycling performance of the Cu2S electrode in different electrolytes, inset SEM images of commercial Cu2S powder; (e) SEM images of Cu foam; (f) Capacity retention at various
specific currents; (g) Rate capability at various current rates, inset: SEM image of Cu foam; (h) TEM image of CuS; (i) TEM image of CuS/graphene composite; (j) Rate performances of
bare CuS and CuS/graphene composite electrodes; (k) Rate capability and Coulombic efficiency of the CuxS (4:1)/rGO and CuxS (2:1)/rGO from 1.00 to 3.00 V. Inset: SEM of CuxS (4:1)
a-c) Reproduced with permission [15]. Copyright 2016, Elsevier B.V. (d) Reproduced with permission [153]. Copyright 2015, Elsevier Ltd. (e and f) Reproduced with permission [94].
Copyright 2017, Elsevier B.V. (g) Reproduced with permission [68]. Copyright 2016, Elsevier B.V. (hej) Reproduced with permission [96]. Copyright 2017, Elsevier B.V. (k) Reproduced
with permission [157]. Copyright 2016, Elsevier B.V.

matrix can release Cu2þ to immobilize the dissolved polysulfide
ions and avoid the sulfur from dissolving. As typical forms of
carbon materials, GO and rGO have stable structure and superior
property so that enhance the mechanical stability and effectively
alleviate the volume changes upon cycling [158,159]. Ding et al.
[96] prepared CuS/graphene composites, which the CuS was
uniform microparticles composed of well-arranged nanosheets
and CuS were coated on wrinkled graphene layers. By comparing
the rate capacity of CuS and CuS/graphene composites (Fig. 11h
and i), the results show that the later electrode exceeds the pure
CuS electrode 96 mA h/g at 1 A/g (Fig. 11j). For another, Zhang
et al. [157] obtained CuxS/rGO nanocomposites, which non-stoi-
chiometric CuxS microspheres wrapped with rGO through sul-
furation of as-prepared Cu/rGO. In the study, reporters change
the ratio of Cu and S and obtain CuxS (2:1)/rGO and CuxS (4:1)/
rGO, and the results exhibit that CuxS (2:1)/rGO have a higher
rate capacity, which may mean that stoichiometry CuS have
better performance (Fig. 11k). In fact, appropriate nanostructures
can improve the rate capacity of CuS to some extent. For instance,
Wang et al. [160] obtained CuS 3D network structure cathodes,
which composed of plenty of nanoflakes and exhibit reversible
capacity of 376 mA h/g over 100 cycles at 2 C (1 C ¼ 560 mA/g),
which can be ascribed to the conductive 3D network and pro-
duction of mixed ion electron.
4.2. Lithium-sulfur batteries
LSBs have become a promising candidate for next-generation
energy storage device because of the low cost, rich abundance of
S, high theoretical energy density, and specific capacity
(~2,500 W h/kg and 1,675 mA h/g, respectively) [161]. However,
typical LSBs consisting of the S cathode, metallic Li anode,
separator, and electrolyte are still faced with many shortcomings,
which hinder the practical applications [162,163]. For the S cathode,
there are several problems: the low conductivity of S and its
discharge products (Li2S), dissolution of lithium polysulfides (Li2Sx,
4  x  8) followed by seriously shuttle effects, and the severe
volume change of the S electrode on lithiation, which result in
poorer utilization of S, self-discharging, lower Coulombic efficiency,
and weaker cycle stability [164e170].
To overcome the previously mentioned problems, various
methods have been reported, such as the combination of sulfur
with a variety of conductive materials [171], optimization of the
organic electrolyte [172], as well as integration of multifunctional
separators or interlayers [173]. Meanwhile, exploring appropriate
electrode materials, which have excellent conductivity and good
stability, and new electrolyte is the effective method [174e176].
CuxS materials have been proved as the promising materials
because of the low Li/Liþ lithiation voltages, the strong chemical
interaction with sulfur-containing species, and excellent conduc-
tivity. Moreover, the electrode can exhibit superior performance
through nanostructure designing and compounding with other
materials (see Table 7). The novel structure (porous, core shell,
nanotubes, yolk shell, and hollow structures) can offer numerous
active adsorption sites to fix S particles and polysulfide to further
keep the stability. Introduction of conductive materials such as
metal oxides/sulfides, carbon materials, as well as conductive
polymers on cathode can improve the electroconductivity, provide
more active cites, avoid polysulfides dissolution, and reduce the
interface resistance [170,177].
It is demonstrated that the electrochemical performance of
composites depends on the dispersion of S, and CuxS materials can
act as S carrier for LSBs because of the excellent conductivity, which
can provide strong chemical adsorptions with polysulfides and c

16
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Table 7
The electrochemical performance of CuxS and its composites in LSBs.

Material Electrode Initial discharge capacity Current density Cycling performance Rate capacity Ref.

CuS/S Cathode 1,100 mA h/g ~0.03 A/g 750 mA h/g after 200 cycles ~400 mA h/g at 0.15 A/g [178]
S@CuS@CNT Cathode 1,019 mA h/g ~0.17 A/g 878.9 mA h/g after 100 cycles 513.1 mA h/g at ~3.35 A/g [99]
CuS/graphene Separator 1,302 mA h/g ~0.67 A/g 760 mA h/g after 100 cycles 568 mA h/g at ~ 1 A/g [179]
CuS-n/CA Cathode 1,318 mA h/g ~0.67 A/g 1,073 mA h/g after 100 cycles 908 mA h/g at ~0.67 A/g [49]
CuxS/S Cathode 782.4 mA h/g 0.08 A/g 580.2 mA h/g after 50 cycles e [180]
CuxS/S Cathode 971.1 mA h/g ~0.03 A/g e e [181]
CuxS@NC/SeF Cathode 1,432 mA h/g ~0.03 A/g 1,169 mA h/g after 120 cycles 729 mA h/g at ~ 1.3 A/g [182]

prohibit the shuttle process [47,169,183]. For instance, He et al.
[180] obtained trifunctional CuxS, which includes highly dispersed
Cu2S and CuS as S carrier. In addition, CuxS shows excellent
chemical interactions, which can firmly surround S to prevent the
polysulfides dissolution, reduce the irreversible deposition and
aggregation of insoluble reduction products on the electrode sur-
face, and improve the stability and cycle life of the electrode. In fact,
layer-structured materials could enhance the stability of electrode
as well as the adsorption of S, which can improve the cycle per-
formance of LSBs [184e186]. Long et al. [178] synthesized 3D
multilayered and porous CuS scaffold derived from an MOF as S
host for LSBs. By using CuBDC MOFs (Fig. 12a), the porous and
structurally robust 3D structure can be obtained (Fig. 12b), which
results in the good performance. The results show that the elec-
trode exhibits initial capacity of 1,097 mA h/g, and it can still
maintain 750 mA h/g after 200 cycles (Fig. 12c). Moreover, after 500
cycles, the composite can show charge/discharge capacity of 575/
560 mA h/g. While the pure S electrode decayed rapidly after 135
cycles (Fig. 12d). The good performance is benefit from the porous
structure, which can provide frame for volume change during
charge and discharge. Carbon materials can greatly improve the
encapsulation performance of polysulfides, but their physical con-
straints are weak. Compounding carbon materials with transition
MSs is an advisable method to enhance the electrochemical

Fig. 12. SEM images of the (a) CuBDC/MOFs; (b) CuS/S; (c) Galvanostatic dischargeedischarge curves of CuS/S, (d) Cycling capacities of the CuS/S and pure S at a rate of 0.2 C, and
the columbic efficiency of CuS/S; (e) HMSEM images of S@CuS@CNT; (f) Cycling performance and Coulombic efficiency of the S@CuS@CNT composite electrode; (g)
Chargeedischarge curves in the first three cycles at 0.1 C; (h) Rate capability behavior of the S@CuS@CNT composite electrodes at different current densities; (i) TEM images of
CuxS@NC/S-F composite; (j) SEM images of Cu@NC-F; (k) Chargeedischarge voltage profiles in the first three cycles at 0.1 C of CuxS@NC/S-F; (l) Cycling performance and Coulombic
efficiency of the CuxS@NC/S-F composite electrode at 0.1 C; (m) Schematic for the formation of CuS-n/CA-S and the electrochemical process during lithium insertion and extraction;
(n) FE-SEM images of CuS-4/CA; (o) Chargeedischarge profiles of the CuS-4/CA-S cathode at 1 C; (q) The synthetic process of CuS and CuS/graphene composite; (p) Cycling
performances and columbic efficiency at 0.2 C; (r) Discharge/charge voltage profiles of Li/S batteries with CuS/graphene-coated separator. (aed) Reproduced with permission [178].
Copyright 2020, Elsevier Ltd. (eeh) Reproduced with permission [99]. Copyright 2016, Springer. (iel) Reproduced with permission [182]. Copyright 2018, WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim. (mep) Reproduced with permission [49]. Copyright 2016, The Royal Society of Chemistry. (q, r) Reproduced with permission [179]. Copyright 2018, Elsevier
B.V.

17
Y. Shi, B. Yang, X. Guo et al.
performance of LSBs. For instance, Hou et al. [99] prepared
S@CuS@CNT (Fig. 12e) for LSBs, and the electrode shows superior
performance: Coulombic efficiency was close to 100%, and the ca-
pacity was kept above 500 mA h/g with progressive cycling up to
more than 100 cycles (Fig. 12f). In the complex, CNTs was acted as
the support of active substance growth and provided network,
which can be ascribed to the enhancement of performance: initial
discharge capacity of more than 1,400 mA h/g as well as rate ca-
pacity of 513.1 mA h/g at 2 C. When the current density was tuned
back to 0.1 C, the capacity can still recover to 1,012 mA h/g
(Fig. 12g), which shows the well cycling performance. In fact, car-
bon network was used widely owing to the well conductivity and
the anchoring to polysulfides. Yu et al. [182] obtained CuxS@NC/S-F
composite (CuxS, N co-doped hierarchically porous graphitic carbon
network; Fig. 12i) through the sulfuration of Cu@NC-F network
(Fig. 12j); when used as electrode for LSBs, the electrode exhibits
excellent electrochemical performance. The electrode assembled
by the composite shows initial capacity of up to 1,432 mA h/g
(Fig. 12k); after 120 cycles, it still can retain a discharge capacity of
1,169 mA h/g with a Coulombic efficiency of nearly 100% (Fig. 12l).
The superior capacity and cycle performance can be ascribed to the
doping of heteroatom and unique 3D networks providing by carbon
network, which provide plentiful space for volume expansion and
effective adsorption of polysulfide. Li et al. [49] synthesized CuS-n/
CA-S (CA: carbon aerogel) composites (Fig. 12m,n), which provide
initial capacity of 1,038 mA h/g and retains 798 mA h/g after 100
cycles (Fig. 12o). Moreover, the electrode can retain stabilized ca-
pacity of 840 mA h/g after 500 cycles (Fig. 12p) and show good
cycling performance, which can be ascribed to the framework
formed by CuS QDs, and carbon aerogels facilitate tight adhesion of
S and provide active sites for immobilizing polysulfides.
Except for the S carrier, multifunctional separators and in-
terlayers have attracted extensive attention all over the world
because of their low cost, high yield, and integrated structure of
adsorption function layer and barrier layer [187]. At present,
multifunctional separators mainly include polymer-modified
multifunctional separator, carbon-modified multifunctional sepa-
rator, as well as oxide-modified multifunctional separator. More-
over, CuxS materials and their compound can be used as separator
for LSBs to reduce the shuttle effect because of the strong adsorp-
tion of MSs with S [188]. For instance, Li et al. [179] obtained flower-
like CuS/graphene-coated composites owning a special nanosheet
thickness of around 27e42 nm (Fig. 12q). As can be seen in Fig. 12r,
the cell demonstrates an enhanced initial capacity (more than
1,200 mA h/g), reversible capacity of 1,017 mA h/g at 0.2 C and a
rate capability of 568 mA h/g at 3 C, indicating that the CuS/gra-
phene coating layer can shorten the electron-ion diffusion pathway
and further promote the electrochemical reaction. Meanwhile, the
introduction of CuS/graphene-coated separator can effectively
reduce the dissolution of lithium polysulfide and improve the
integrity of sulfur cathode, which is beneficial to the cycle perfor-
mance. In fact, CuxS materials are promising additives for LSBs for
the reason that they can increase the electrical conductivity of the
sulfur cathode, enhance the power capability of battery, and help to
improve the overall cell-discharge capacity [47,189]. Moreover, as
Sun reported [189], the S:CuS hybrid electrodes (the CuS work as
addictive) exhibit better rate performance while the poor cycling
performance. The results may cause by the conductive CuS addic-
tive can enhance the utilization of the sulfur cathode but soon
dissolute with the reaction.
4.3. Sodium-ion batteries
SIBs have become one of the potential candidates for energy
storage owing to excellent theoretical specific energy density
18
Materials Today Chemistry 23 (2022) 100675
(760 Wh/kg), long cycling life, as well as low material expense.
Despite that the nanoscale reaction pathways are remarkably
different from LIBs, Na/CuxS electrochemical batteries are first
revealed to display outstanding cycling performance (capacity
decay over 400 cycles is negligible), which closely resembles the Li
case [69,107,190,191]. However, there are still some challenges,
which limit the development of SIBs. First, the large atomic weight
and the low standard electrochemical potential of Na may cause
explosion, corrosion, and power consumption. Second, Na metal
tends to deposit in dendritic form and undergoes great volume
change during cycling. Third, the high reactivity may cause degra-
dation of the electrolyte and breaking and reforming of the SEI,
which may result in poor cycling performance [192e194]. More-
over, searching suitable Na-host materials is a challenge because of
larger ionic radius of Naþ. The main strategy to improve the per-
formance of SIBs is to search attractive materials as anode/cathode
and appropriate electrolytes [195e197]. Recently, the anode ma-
terials for SIBs have been developed to a great degree, and various
materials have been reported, including carbon-based, titanium-
based, alloy-based materials, and conversion reactionebased ma-
terials, such as metal oxides/sulfides/selenides [195,198]. CuxS can
be one of the possible candidates for SIBs’ anode materials owing to
excellent theoretical capacity as well as lower material cost. In
addition, nanostructure designing and compounding with other
materials can provide more enhanced performance, for the reason
that hollow structure can accommodate the volume change during
sodiation/desodiation, and provide more surface area and well-
defined cavities at the same time, which can improve the stability
of SIBs [199,200].
For the large radius of Naþ, it is necessary to explore suitable
host materials to adapt the Naþ during the reaction. Hence, syn-
thesizing materials that have hollow/porous structures and large
surface area has been exemplified as an effective strategy to
enhance the electrochemical performance (see Table 8) [204e207].
What is more, the reaction mechanism of Cu2S as negative elec-
trode material in sodium-ion electrolysis can be seen as follows:
Cu2S þ xNaþ þxe
/ NaxCu2S (1a)
NaxCu2S þ (2-x)Naþ þ (2-x)e
/ 2Cu þ Na2S (2a)
Wang et al. [208] prepared Cu2S hollow spheres (Fig. 13a), and
the hollow structure can shorten the diffusion pathway and
accommodate volume variation of Naþ, which result in high-rate
capacity of 319 mA h/g at 4 A/g (Fig. 13b) as well as long-term
cycling stability of 343 mA h/g at 2 A/g after 1,000 cycles
(Fig. 13c). Different from Wang’s work, Li et al. [42] synthesized
micron-sized CuS flakes (Fig. 13d) as anode and used DME-based
electrolyte. During sodiation and desodiation, the structure of CuS
flakes turns to porous integrity structure after 100 cycles and keeps
the structure even after 1,000 cycles, which results in an enhanced
cycling performance of 88.2% of capacity retention after 5,000 cy-
cles at 5 A/g (Fig. 13f). Moreover, the porous structure can provide
transmission pathway and porosity for Naþ and electrolyte, which
make the electrode exhibit high-rate capacity of 337 mA h/g at
20 A/g (Fig. 13e). Besides Cu2S, CuS can also become a promising
material applied in SIBs through nanostructuring. Gu et al. [209]
synthesized hexagonal CuS nanosheets and microspheres made up
of numerous flakes and compared the electrochemical difference.
The nanosheets are less compact, and the size of pores is smaller
than microspheres, which results in larger specific area, enhanced
BET pore size distribution, and better electrochemical performance.
Based on the nanosheets, some 3D structures have been synthe-
sized. An et al. [210] fabricate CuS microflower composed of
nanosheets (Fig. 13g), and the electrode exhibits superior cycling
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Table 8
The electrochemical performance of CuxS and its composites in SIBs.

Materials Electrolyte Initial charge/discharge capacity Cycling performance Rate capacity Ref.

PNL-CuS 1M NaSO3CF3-DME 550/560 mA h/g at 0.1 A/g Without obvious fading at 5 A/g 317 mA h/g at 20 A/g [201]
CuS-RGO 1M NaSO3CF3eNaFS/DMG ~600/570 mA h/g at 0.1 A/g 345 mA h/g after 450 cycles at 1 A/g 350 mA h/g at 1 A/g [103]
Cu9S5@NC e ~390/410 mA h/g at 0.3 A/g ~250 mA h/g after 4,000 cycles at 0.3 A/g 237 mA h/g at 5 A/g [199]
CuS@CoS2 e ~700/750 mA h/g at 0.1 A/g ~380 mA h/g after 500 cycles at 0.1 A/g ~310 mA h/g at 5 A/g [202]
CuS DME ~600/650 mA h/g at 0.1 A/g 517 mA h/g after 2,000 cycles at 5 A/g 268 mA h/g at 100 A/g [203]
Cu2S 1M NaPF6-DME 370/420 mA h/g at 0.1A cm
2 ~280 mA h/g after 5,000 cycles at 5 A/g 337 mA h/g at 20 A/g [42]
CuS 1M NaClO4-TEGDME 400/410 mA h/g at 0.05 A/g 162 mA h/g after 200 cycles at 0.05 A/g 90 mA h/g at 1.6 A/g [64]
GO/CuS Ether-based solutions 482.4/639.0 mA h/g at 0.05 C 228.7 mA h/g after 100 cycles at 0.05 C 96.8 mA h/g at 6 C [69]
CuS-CTAB 1M NaSO3CF3-DEGDME ~650/670 mA h/g at 0.1 A/g 312.5 mA h/g after 1,000 cycles at 10 A/g 172.2 mA h/g at 20 A/g [191]

Fig. 13. (a) TEM images of Cu2S hollow spheres; (b) Rate performance of Cu2S hollow spheres at 2 A/g; (c) Cycling performance of Cu2S hollow spheres at 2 A/g; (d) SEM images of
products obtained under electrolysis voltage of 1.0 V; (e) Rate capability at different densities; (f) Long-term cyclic properties at 5 A/g; (g) Illustration of the preparation process for
the different structure copper sulfide samples; (h) Cycle performance of the S48 electrode at 5 A/g; (i) Rate performances of S24, S36, and S48 electrodes. (aec) Reproduced with
permission [208]. Copyright 2020, Elsevier B.V. (def) Reproduced with permission [42]. Copyright 2018, American Chemical Society. (gei) Reproduced with permission [210].
Copyright 2018, the Partner Organisations.

performance of almost no capacity decay at a current density of 5 A/
g after 5,000 cycles. The 3D flower-like structure could provide
more Naþ diffusion paths and more interspace to tolerate volume
change in the charge and discharger process because of large sur-
face and small-sized pore, which result in the enhanced perfor-
mance: the initial charge/discharge capacity of ~490/164 mA h/g at
2 A/g (Fig. 13h and i). Similarly, Yu et al. [201] synthesized PNL-CuS
(pine-needle-like CuS) self-assembled from hollow nanotubes, and
the hierarchical architecture results in long-term cycle stability of
1,000 cycles without obvious fading at 5 A/g. Besides the electrode
materials, the option of electrolyte can have great influence on the
performance [211,212]. Li et al. [64] prepared CuS microspheres and
used triethylene glycol dimethyl ether (TEGDME) as the electrolyte.
In carbonate-based electrolyte (mixture solvent of EC and DEC), the
capacity declines quickly after several cycles, whereas in TEGDME
electrolyte, the discharge capacity can retain 162 mA h/g even after
200 cycles. This is because sodium polysulfide generated by elec-
trochemistry will react with carbonate-based electrolyte, resulting
in sustainable consumption of electrolyte.
The large volume change in the process of CuxS sodiation brings
about a new reaction pathway, which does not lead to the accel-
erated capacity decay as is commonly believed in the case of SIB.
Boebinger et al. [213] found that although the atomic radius of Na
are larger than Li, and the volume changes of SIB is larger than LIBs
during reaction, the capacity decay is not speeded up, but they do
induce the reaction to continue via a different pathway. These re-
sults suggest that other large-volume-change electrode materials
may also be engineered for long cycle life in next-generation SIBs.
By compounding other materials with CuxS, the compound can
show a better electrochemical performance. Among various ma-
terials, carbon materials attract much attention for the superior
chemical stability, excellent electrical conductivity, and various

19
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

structures. Moreover, carbon materials can limit the expansion of
CuxS, which can improve the performance. For example, Kim et al.
[55] have prepared CuS nanodisks (CuS-NDs) with acid-treated
SWCNTs (a-SWCNTs; nanohybrids) and used as the anode mate-
rials in SIBs. The nanohybs exhibited high-rate capabilities, stable
cycling performances, and an excellent reversible capacity of
~610 mA h/g, which can remain 75% of the original capacity. What is
more, the Coulombic efficiencies of all cycles are close to 100%,
except in the first 10 cycles. It was demonstrated that CuS-NDs can
store Naþ stably during a conversion reaction for long-term cycling
(CuS þ 2 M 4 M2S þ Cu [M: Li, Na, and K]), reversibly forming
much smaller Cu and Na2S nanoparticles. By providing a con-
ducting pathway for the CuS-NDs, the a-SWCNTs played a very
important role in the stability of the nanohybrids despite the large
volume changes after cycling for more than 500 cycles. RGO is an
ideal material to compound with CuxS for the high specific surface
area and excellent stability. Li et al. [103] prepared CuS-RGO com-
posites, and the anode has enhanced performance with ether-
based electrolyte. The obtained composites were prepared using
the precursor with 0, 100, 200, and 400 mg GO and labeled as CuS,
CuS-RGO-1, CuS-RGO-2, as well as CuS-RGO-3 (Fig. 14a). From the
FESEM images, CuS-RGO composites show similar morphologies,
and CuS nanoparticles are transformed into nanosheets as well as
partially immobilized on the RGO surface. The RGO nanosheets act
as a buffer layer, which can slow down the volume change in the
reaction, and the small-sized nanosheets CuS can easily enter the
electrolyte and shorten the diffusion path of sodium ions. Mean-
while, at the same time, the polarization voltage of ester-based and
ether-based electrolyte is different: NaFS/DGM has smaller voltage
polarization than NaClO4/FEP (Fig. 14b). Among various samples,
CuS-RGO-2 exhibits a superior cycling performance of 345.7 mA h/g
after 450 cycles and indicates that CuS-RGO-2 exhibits the excellent
structure stability in the repeated sodiationedesodiation process
(Fig. 14c).
Metal oxides can be used to improve the performance of CuxS.
Fang et al. [202] synthesize CuS@CoS2 double-shelled nanoboxes

Fig. 14. (a) FESEM images of (I) CuS, (II) CuS-RGO-1, (III) CuS-RGO-2, and (Ⅳ) CuS-RGO-3; (b) Chargeedischarge curves of CuS-RGO-2 electrode at 0.1 A/g in NaClO4/FEP, 0.4e2.6 V
and NaFS/DGM, 0.4e2.6 V; (c) Cycling performance of CuS-RGO-2 at 1 A/g; (d) Schematic illustration of the synthetic process of CuS@CoS2 DSNBs; (e) FESEM images of the (I) Cu2O
nanocubes, (II) Core-shell Cu2O@Co(OH)2 nanocubes, (III) Cu2O@CuS@Co(OH)2 nanocubes, (Ⅳ) CuS@Co(OH)2 nanoboxes, (Ⅴ) CuS@CoS2 DSNBs; (f) Cycling performance of the
CuS@CoS2 DSNBs, CuS-CoS2 DSNBs, CoS2 SSNBs, and CuS SSNBs at a current density of 0.5 A/g, and the corresponding Coulombic efficiency of the CuS@CoS2 DSNBs. (aec)
Reproduced with permission [103]. Copyright 2017, American Chemical Society. (def) Reproduced with permission [202]. Copyright 2019, Wiley-VCH.

20
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Table 9
The electrochemical performance of CuxS and its composites in MIBs.

Material Initial charge/discharge capacity Cycling performance Rate capacity Ref.

CuS ~90/275 mA h/g at 0.05 A/g ~120 mA h/g after 350 cycles at 0.05 A/g ~90 mA h/g at 1 A/g [214]
CuS ~200/430 mA h/g at 0.1 A/g 50 mA h/g after 200 cycles at 1 A/g 50 mA h/g at 1 A/g [217]
CuS ~270/310 mA h/g at 0.1 A/g 250 mA h/g after 500 cycles at 0.1 A/g 125 mA h/g at 0.4 A/g [218]
CuS ~200/370 mA h/g at 0.1 A/g 150 mA h/g after 40 cycles at 0.1 A/g e [219]
CuS ~260/360 mA h/g at 0.05 A/g e e [220]
CuS-CTAB ~460/440 mA h/g at 0.1 A/g 125 mA h/g after 1,000 cycles at 0.56 A/g 100 mA h/g at 1 A/g [221]

(DSNBs), and the materials have enhanced properties when
assembled as anode for SIBs. Fig. 14d exhibits the synthetic process
and intermediate products, and Fig. 14e shows the corresponding
FESEM image. The as-prepared CuS@CoS2 DSNBs have a structure of
hierarchical CoS2 nanosheet-on-CuS nanobox, and the hollow
structure can accommodate mechanical strain and keep stability
during (de)sodiation processes, which ascribe to the superior
cycling performance. Of note, 79% of the initial capacity is retained
after 500 cycles at a current density of 0.5 A/g (Fig. 14f). Moreover,
the electrode shows excellent capacity, even at a large current
density of 5 A/g, the CuS@CoS2 DSNBs can also deliver a capacity of
304 mA h/g, and the high capacitive contribution can be ascribed to
the nanosheet-on-nanobox structure with a large surface.
4.4. Magnesium-ion batteries
MIBs are applied widely as safe, low-cost system for the high
charge density, theoretical capacities (3,833 mA h/cm3/2,205 mA h/
g) and lower reduction potential (
2.37 V vs. SHE). Compared with
lithium anode, magnesium anode is safer because it does not
generate dendrites during electrochemical deposition/dissolution
process. However, magnesium anodes are also faced with many
problems: (1) As a result of the high charge density and strong
polarization ability of Mg2þ, Mg anodes usually have the problem of
slow solid-state diffusion; (2) The appropriate active sites of Mg2þ
intercalation in the lattice are relatively insufficient, resulting in
low specific capacity [214]. Exploring novel and effective materials
as cathode is of great significance to improve the electrochemical
performance of MIBs. CuxS could be used as the cathode materials
for MIBs as a result of the high mobility of Cu2þ, which can be
conducive to the conversion reaction between CuxS and Mg2þ and
improve the reversibility of the reaction. CuxS with core-shell,
hollow, yolk shell, and other nanostructures can provide more
space for active cites and more area to diffusion, so that enhanced
rate capability as well as cycle stability could be obtained [215,216].
Moreover, conductive materials (carbon, metal oxides, mental
sulfides, etc.) can be compounded with CuxS to improve the elec-
troconductivity and performance (see Table 9).
CuxS materials with a small size can be effective materials for
MIBs. Blanc et al. [222] compared four sulfide cathode materials
include layered TiS2, CuS, spinel Ti2S4, and CuCo2S4 and concluded
nanodimensional crystallites are critical to activate or improve
electrochemistry of cathode. Wu et al. [214] obtained CuS nano-
particles (Fig. 15a and b) with size smaller than 100 nm as cathode
material. The cell exhibited a reversible capacity of around 90 mA h/
g at 1 A/g, and the Coulombic efficiency can retain around 100%
during the cycling (Fig. 15c), which ascribe to the remarkable
electronic conductivity as well as the small particle size of CuS. For
the reason of solid-state Mg2þ diffusion, MIBs may possess a poor
cycle performance. Constructing porous or hollow structures can
offer more void space for active sites and large contact area for
electrolyte-electrode. Shen et al. [217] synthesized three hollow

Fig. 15. SEM images of (a) CuS-I and (b) CuS-II; (c) Cycle performance of CuS-I electrode in Mg cells at 50 mA/g; (d) Schematic illustration for the fabrication process of hollow CuS
nanocubes; (e) TEM images of CuS-I; (f) Cycle performance of CuS-I electrode at 1 A/g; (g) The SEM image; (h) The TEM image of as-synthesized CuS; (i) Charge/discharge curves of
CuS cathode with Mg(ClO4)2/AN as electrolyte at 50 mA/g; (j) SEM image; (k) TEM image of CuS-CTAB-2, (l) GCD curves of CuS-CTAB-2 at different current densities; (m) Cycle
performance and Coulombic efficiency of CuS-CTAB-2 at 560 mA/g. (aec) Reproduced with permission [214]. Copyright 2018, Royal Society of Chemistry. (def) Reproduced with
permission [217]. Copyright 2018, Royal Society of Chemistry. (gei) Reproduced with permission [220]. Copyright 2019, Elsevier Inc. (jem) Reproduced with permission [221].
Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

21
Y. Shi, B. Yang, X. Guo et al. Materials Today Chemistry 23 (2022) 100675

Fig. 16. (a) SEM image of CuS/Cu2O/Cu nanowires; FESEM image of (b) Cu2S, (c) PANI, and (d) cross-sectional image of Cu-P; (e) Atomic structure of CuS/NiS2 INs with interfaces; (f)
Discharge voltage curve and the corresponding power density with CuS/NiS2 INs; (g) Schematic illustration of the locations of S vacancies in CuS/NiS2 Ins; (h) TEM (the top part) and
HAADF-STEM images (the bottom part) of CuS/NiS2 Ins; (i) Galvanostatic dischargeecharge cycling curves at 25 mA/cm2 of the Zn-air batteries with CuS/NiS2 INs as the catalyst; (j)
Schematic illustration of the solvothermal process for the formation of CuS; (k, l) FE-SEM images of the as-prepared 3D hierarchical nanostructured CuS microspheres at different
magnification; (m) Cycle performance with Coulombic efficiency at a current density of 20 mA/g. (a) Reproduced with permission [224]. Copyright 2019, Elsevier B.V. (bed)
Reproduced with permission [226]. Copyright 2017, The Electrochemical Society. (eei) Reproduced with permission [35]. Copyright 2017, WILEY-VCH. (j and k) Reproduced with
permission [29]. Copyright 2016, American Chemical Society.

CuS nanocubes (Fig. 15d and e), which can exhibit a reversible ca-
pacity of 200 mA h/g at 0.1 A/g, a rate capability of 50 mA h/g at 1 A/
g, and a cycling performance of shown as 50 mA h/g after 200 cycles
at 1 A/g (Fig. 15f). The outstanding electrochemical performance
can be attributed to the hollow and cube morphology, which can
provide surface for the diffusion of solid-state Mg2þ. Similarly, Ma
et al. [218] prepared erythrocyte-like CuS cathode, and the as-
prepared electrode exhibits improved performance with a stabi-
lized capacity of 250 mA h/g without the activation process and
superior cycling stability over 500 cycles. Moreover, Ren et al. [219]
prepared CuS porous nanocages (CSePNCs) and exhibits an excel-
lent reversible capacity as 228 mA h/g when worked as electrode
for MIBs. In fact, the kinds of electrolyte can show great influence
on the performance of MIBs. For instance, Xiong et al. [220] pre-
pared CuS composed of nanospheres with diameter of
300e800 nm (Fig. 15g and h) when assembled as cathode for MIBs
and use Mg(ClO4)2/AN as electrolyte. The result shows that the
initial chargeedischarge capacity with Mg(ClO4)2/AN electrolyte is
260/350 mA h/g at 0.05 A h/g, which is much higher than the ca-
pacity with APC/THF electrolyte. Through compounding with other
materials, CuxS can also exhibit enhanced performance for MIBs.
Among various materials, carbon materials are used widely for the
22
excellent performance. In addition, Shen et al. [221] synthesized
CuS-CTAB as cathode for MIBs. As the results show, the CuS has
structures of microrods and microspheres, and CuS-CTAB has the
structure of microflower of 2e4 mm, which consist of microsheets
of about 10 nm (Fig. 15j and k). The electrode can exhibit capacity of
450 mA h/g at 0.1 A/g, even at a high current density of 1 A/g, it still
shows a capacity of 90 mA h/g (Fig. 15l). The as-prepared CuS-CTAB
cathode has excellent cycle performance at 560 mA/g over 1,000
cycles (Fig. 15m).
4.5. Solar cells
Photovoltaic technology has been prosperous for decades and is
considered to be one of the best ways to meet energy demand,
which including perovskite solar cells (PSCs), quantum
dotesensitized solar cells (QDSCs), CdTe solar cells, and dye-
sensitized solar cells. Developing novel structures of various ma-
terials to enhance the capacity and stability of solar cells is a
common project. As a typical p-type semiconductor, CuxS has a high
mobility and has used for solar cells widely. For instance, Hu et al.
[223] prepared CuS nanostructures incorporated with low-
temperature carbon layers for hole conductor-free PSCs to
Y. Shi, B. Yang, X. Guo et al.
improve the hole mobility. Compared with the pure C-based PSCs,
the maximum power conversion efficiency (PCE) of hybrid carbon-
based PSCs was improved (11.2759% with a VOC of 0.9767 V and JSC
of 18.26 mA/cm2). Moreover, Wang et al. [224] synthesized CuS/
Cu2O/Cu nanowire (Fig. 16a) photocathode for the photocatalytic
fuel cell, with a corresponding CdS/ZnS/TiO2 photoanode. In addi-
tion, CNT can be used to synthesize hybrid materials to improve the
electrochemical performance. Zhang et al. [225] prepared CuS
nanoparticles grown on the multiwall carbon nanotubes (MWCNT)
branches in 3D porous system and used the materials as counter
electrode (CE) for QDSCs. The results show that 100% CuS/MWCNTs
CE exhibits the highest electrocatalytic activity, the PCE of QDSCs,
and superior photovoltaic stability. The excellent performance can
be ascribed to that MWCNTs serve as framework to support CuS
nanoparticles in advantage of their individual characteristics.
Conducting polymer can be compounded with CuxS to modify the
structure and improve the performance of solar cells. Vijayakumar
et al. [226] synthesized Cu2S-Polyaniline (Cu-P) CE through the
electropolymerization of polyaniline (PANI) on an FTO/Cu2S film
(FTO: fluorine-doped tin oxide). The close connection between
Cu2S and PANI on the FTO and Cu2S nanosheets can be found
through Fig. 16 bed, which could be owing to the strong interaction
between the metal particles and electronegative nitrogen of PANI.
Hence, the QDSSC with the FTO/Cu-P CE shows an enhanced energy
conversion efficiency (4.12%) than those with Pt (1.85%), Cu2S
(3.71%), PANI (0.77%), and PANI-Cu2S (P-Cu) (1.01%) CEs.
4.6. Others
Except for the previously mentioned applications, CuxS have
been used widely for other electrochemical applications. For
instance, Yan et al. [227] obtained rGO/CuS nanoflakes hybrids
assembled non-enzymatic electrochemical sensor for selective
detection as well as highly sensitive of glucose. The non-enzymatic
glucose sensor exhibited a lower detection limit, great reproduc-
ibility, and long-term storage stability because the composite can
effectively accelerate electron transport and extend catalytic active
sites. Except for LIBs, LSBs, SIBs, MIBs, CuxS materials have been
explored for new kinds of batteries. For example, An et al. [35]
prepared CuS/NiS2 INs (interface nanocrystals; Fig. 16e) owning
plentiful vacancy defects as boost oxygen catalysis for Zn-air bat-
tery. Liquid Zn-air battery with the CuS/NiS2 INs as air electrode
shows an enhanced peak power density (172.4 mW/cm2; Fig. 16f),
an excellent specific capacity (775 mA h/gZn) as well as long cycling
life (up to 83 h). From Fig. 16g and h, anomalous edges as well as
rough surfaces of CuS/NiS2 INs can be found, which indicate strong
lattice disorder exists. The disordered atoms could accelerate the
formation of more and more active sites and improve the proper-
ties of the materials by reducing the surface energy. Fig. 16i shows
the long cycle life of Zn-air battery: a low charging voltage
(Echarging) of 1.92 V as well as a discharging voltage (Edischarging) of
1.35 V, along with a small voltage gap of 0.57 V and a high round-
trip efficiency of 70%. Even after 500 continuous cycles, the voltage
fading can be neglected. Moreover, Wang et al. reported
outstanding performance aluminum-ion battery with CuS micro-
sphere (Fig. 16j-l) cathode, and the electrode exhibits reversible
specific capacity of about 90 mA h/g at 20 mA/g [29]. Thanks to the
uniform nanoflakes as well as special crystalline structure, the as-
obtained CuS further promotes electron and ion transfer in the
discharge and charge reactions. The discharge/charge capacity after
the 100th cycle is both around 90 mA h/g, which means that the
Coulombic efficiency is close to 100% (Fig. 16m). Moreover, potas-
sium-ion battery (PIB) is a promising energy storage technology
with low price as well as excellent energy density of potassium. Jia
et al. [228] prepared CuS@GO (CuS nanosheet fixed on graphene
23
Materials Today Chemistry 23 (2022) 100675
oxide). GO can significantly increase the active site of electrode
material and effectively alleviate the polymerization of CuS during
the cycling process. What is more, CuxS materials can be used for
PIBs, and Cao et al. prepared core shell structure CuS-C@Nb2O5-C
NFs electrode for PIBs, which show superior Coulombic efficiency
and cycling stability. The remarkable performance could be profited
from the shell layer, which protects the CuS nanoplates from im-
mediate contact with the electrolyte [229e231].
5. Conclusions and outlook
With the increasing demand for energy, energy shortage and
serious environmental pollution caused by fossil fuel combustion
have become the most concerned problems in the 21st century. It is
urgent to explore clean, sustainable, low-cost energy and efficient
energy storage devices, such as batteries (LIBs, LSBs, SIBs, and so
on), supercapacitors, and so on. Among the rechargeable batteries,
LIBs have dominated the portable electronic device market since
the 1990s, owing to attractive electrochemical performance (long-
term cycling life and excellent specific energy and high operating
voltage). Due to the similar reaction mechanism with LIBs and
unrestricted sodium availability, SIBs have been considered as one
of the most promising alternatives to LIBs. However, because of the
larger ion radius of sodium ions (0.3 Å larger than lithium), the
reversible sodium/sodium removal reaction is hindered, and the
requirements for the material structures are higher. Therefore,
numerous studies have demonstrated that the electrochemical
performance mainly depends on the electrode materials, which
means that exploring suitable materials is a major strategy to meet
effective energy storage device. In recent years, as a new type of
electrode material of batteries, transition-metal chalcogenides,
especially sulfides, which can be synthesized in different physical
and chemical routes, are widely studied because of their excellent
chemical and physical properties. Hence, CuxS is one such transition
MS that it shows lower price, natural abundance, environmental
friendliness, and excellent specific capacity. For example, Cu2S, as
the anode of LIBs, shows a flat lithium insertion/extraction voltage
platform at room temperature of about 1.70 V (relative to lithium/
lithium ion), which is higher than the voltage of the graphite anode,
and enhanced volume capacity in comparison with the common
graphite carbon anode. In this review, the synthesis strategies and
related morphologies of CuxS and its composites have been dis-
cussed first. Then, CuxS and its composites served as high-
performance electrode materials in batteries, such as LIBs, LSBs,
SIBs, MIBs, and so on, were comprehensively investigated.
The future directions of CuxS materials for batteries can be as
follows: (1) For pure CuxS materials, CuxS materials with different
morphologies and structures can be synthesized by nanostructure
design, such as nanorods, nanosheets, nanobelts, nanoflowers,
nanospheres, and so on; (2) For CuxS composites, the electrode
materials prepared by introducing other materials and substrate
growth method mostly show improved electrical conductivity and
mechanical properties. Generally, the selection of composites
should follow three main principles: (1) good conductivity; (2)
proper size and mechanical strength structure, which can fix the
active substances to solve the problem of volume expansion during
chargeedischarge cycle; (3) physical adsorption or chemical
interaction between composites is the way to avoid shuttle in the
cycle process. Hence, CuxS materials grown on substrates usually
have ordered array nanostructures, with an enhanced cyclability
and rate capability; (3) As for the synthesis method, the method of
preparing CuxS materials should be as simple, environmentally
friendly, efficient, and controllable as possible apart from the as-
sembly process of electrodes. For the CuxS composite on the sub-
strate, composite template-assisted electrodeposition and
Y. Shi, B. Yang, X. Guo et al.
template-free method are the necessary conditions to obtain the
above ideal nanostructures and electrochemical properties. It is
anticipated that CuxS, and its related materials will have wide ap-
plications for electrodes in the future.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (U1904215 and 21875207), Natural Science
Foundation of Jiangsu Province (BK20200044), and Changjiang
scholars program of the Ministry of Education (Q2018270). The
authors also acknowledge the Priority Academic Program Devel-
opment of Jiangsu Higher Education Institutions.
References
[1] B. Dunn, H. Kamath, J. Tarascon, Electrical energy storage for the grid: a
battery of choices, Science 334 (2011) 928e935.
[2] Q. Li, Y.X. Xu, S.S. Zheng, X.T. Guo, H.G. Xue, H. Pang, Recent progress in some
amorphous materials for supercapacitors, Small 14 (2018) 1800426.
[3] L.D. Lin, K. Qin, Q.H. Zhang, L. Gu, L.M. Suo, Y.S. Hu, H. Li, X.J. Huang, L.Q. Li-
Rich, Li2[Ni0.8Co0.1Mn0.1]O2 for anode-free lithium metal batteries, Angew.
Chem. Int. Ed. 60 (2021) 8289e8296.
[4] J. Li, H.X. Zhao, X.H. Chen, H.M. Jia, Z. Zheng, In situ fabricate Cu2S thin film
with hierarchical petal-like nanostructures, Mater. Res. Bull. 48 (2013)
2940e2943.
[5] S.Y. Zheng, F. Yi, Z.P. Li, Y. Zhu, Y.J. Xu, C. Luo, J.H. Yang, C.S. Wang, Copper-
stabilized sulfur-microporous carbon cathodes for Li-S batteries, Adv. Funct.
Mater. 24 (2014) 4156e4163.
[6] Q.Y. Gao, X.Q. Wang, Z.Y. Shi, Z.R. Ye, W.C. Wang, N. Zhang, Z.L. Hong, M.J. Zhi,
Synthesis of porous NiCo2S4 aerogel for supercapacitor electrode and oxygen
evolution reaction electrocatalyst, Chem. Eng. J. 331 (2018) 185e193.
[7] J.J. Wang, S. Lin, N. Tian, T.Y. Ma, Y.H. Zhang, H.W. Huang, Nanostructured
metal sulfides: classification, modification strategy, and solar-driven CO2
reduction application, Adv. Funct. Mater. 31 (2021) 2008008.
[8] X.H. Xia, C.R. Zhu, J.S. Luo, Z.Y. Zeng, C. Guan, C.F. Ng, H. Zhang, H.J. Fan,
Synthesis of free-standing metal sulfide nanoarrays via anion exchange re-
action and their electrochemical energy storage application, Small 10 (2014)
766e773.
[9] Q.F. Zhang, L.L. Wang, J. Wang, X.Z. Yu, J.M. Ge, H. Zhang, B.G. Lu, Semi-
metallic vanadium molybdenum sulfide for high-performance battery elec-
trodes, J. Mater. Chem. A. 6 (2018) 9411e9419.
[10] R. Rameshbabu, P. Ravi, M. Sathish, Cauliflower-like CuS/ZnS nano-
composites decorated g-C3N4 nanosheets as noble metal-free photocatalyst
for superior photocatalytic water splitting, Chem. Eng. J. 360 (2019)
1277e1286.
[11] S. Chandrasekaran, L. Yao, L. Deng, C. Bowen, Y. Zhang, S. Chen, Z. Lin, F. Peng,
P. Zhang, Recent advances in metal sulfides: from controlled fabrication to
electrocatalytic, photocatalytic and photoelectrochemical water splitting and
beyond, Chem. Soc. Rev. 48 (2019) 4178e4280.
[12] J. Jiang, Y.Y. Li, J.P. Liu, X.T. Huang, C.Z. Yuan, X.W. Lou, Recent advances in
metal oxide-based electrode architecture design for electrochemical energy
storage, Adv. Mater. 24 (2012) 5166e5180.
[13] P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.M. Tarascon, Nano-sized
transition-metal oxides as negative-electrode materials for lithium-ion bat-
teries, Nature 407 (2000) 496e499.
[14] J. Chmiola, P.L.T. Celine Largeot, P. Simon, Y. Gogotsi, Monolithic carbide-
derived carbon films for micro-supercapacitors, Science 328 (2010)
480e483.
[15] G. Kalimuldina, I. Taniguchi, Synthesis and electrochemical characterization
of stoichiometric Cu2S as cathode material with high rate capability for
rechargeable lithium batteries, J. Power Sources 331 (2016) 258e266.
[16] Y.W. Chen, J.M. Li, Z.W. Lei, Y.K. Huo, L.L. Yang, S.Y. Zeng, H.H. Ding, Y. Qin,
Y.L. Jie, F.Y. Huang, Q. Li, J.F. Zhu, R.G. Cao, G.Q. Zhang, S.H. Jiao, D.S. Xu,
Hollow CuS nanoboxes as Li-free cathode for high-rate and long-life lithium
metal batteries, Adv. Energy Mater. 10 (2020) 1903401.
[17] X. Yang, J.J. Mao, H. Niu, Q. Wang, K. Zhu, K. Ye, G.L. Wang, D.X. Cao, J. Yan,
NiS2/MoS2 mixed phases with abundant active edge sites induced by sulfi-
dation and graphene introduction towards high-rate supercapacitors, Chem.
Eng. J. 406 (2021) 126713.
[18] B. Liu, Y.M. Li, Y.S. Wu, S.T. Xing, Enhanced degradation of ofloxacin
by persulfate activation with Mn doped CuO: synergetic effect
24
Materials Today Chemistry 23 (2022) 100675
between adsorption and non-radical activation, Chem. Eng. J. 417 (2021)
127972.
[19] A.E. Reddy, T. Anitha, C.V.V.M. Gopi, S. Srinivasa Rao, C.V. Thulasi-Varma,
D. Punnoose, H.J. Kim, Fabrication of a snail shell-like structured MnO2@
CoNiO2 composite electrode for high performance supercapacitors, RSC Adv.
7 (2017) 12301e12308.
[20] Y.L. Ding, Peter Kopold, Kersten Hahn, Peter A. van Aken, Joachim Maier,
Y. Yu, A lamellar hybrid assembled from metal disulfide nanowall arrays
anchored on a carbon layer: in situ hybridization and improved sodium
storage, Adv. Mater. 28 (2016) 7774e7782.
[21] Y. Zhong, X.H. Xia, F. Shi, J.Y. Zhan, J.P. Tu, H.J. Fan, Transition metal carbides
and nitrides in energy storage and conversion, Adv. Sci. 3 (2015) 1500286.
[22] M. Li, Y. Wang, H. Yang, P.K. Chu, Hierarchical CoMoO4@Co3O4 nano-
composites on an ordered macro-porous electrode plate as a multi-
dimensional electrode in high-performance supercapacitors, J. Mater.
Chem. A. 5 (2017) 17312e17324.
[23] M.X. Liu, Y. Liu, B.B. Gu, X.B. Wei, G.X. Xu, X.M. Wang, Mark T. Swihart,
Yong Ken-Tye, Recent advances in copper sulphide-based nano-
heterostructures, Chem. Soc. Rev. 48 (2019) 4950e4965.
[24] J.F. Mao, Q. Shu, Y.Q. Wen, H.Y. Yuan, D. Xiao, Choi, facile fabrication of
porous CuS nanotubes using well-aligned [Cu(tu)]Cl$1/2H2O nanowire pre-
cursors as self-sacrificial templates, choi, Cryst. Growth Des. 9 (2009)
2546e2548.
[25] J. Joo, T. Kim, J. Lee, S. Il Choi, K. Lee, Morphology-controlled metal sulfides
and phosphides for electrochemical water splitting, Adv. Mater. 31 (2019)
1806682.
[26] S. Iqbal, A. Bahadur, A. Saeed, K.B. Zhou, M. Shoaib, M. Waqas, Electro-
chemical performance of 2D polyaniline anchored CuS/Graphene nano-
active composite as anode material for lithium-ion battery, J. Colloid Inter-
face Sci. 502 (2017) 16e23.
[27] C.H. Feng, L. Zhang, M.H. Yang, X.Y. Song, H. Zhao, Z. Jia, K.N. Sun, G. Liu,
One-pot synthesis of copper sulfide nanowires/reduced graphene oxide
nanocomposites with excellent lithium-storage properties as anode ma-
terials for lithium-ion batteries, ACS Appl. Mater. Interfaces 7 (2015)
15726e15734.
[28] D.H. Li, D.J. Yang, X.F. Yang, Y. Wang, Z.Q. Guo, Y.Z. Xia, S.L. Sun, S.J. Guo,
Double-helix structure in carrageenan-metal hydrogels: a general approach
to porous metal sulfides/carbon aerogels with excellent sodium-ion storage,
Angew. Chem. Int. Ed. 55 (2016) 15925e15928.
[29] S. Wang, S.Q. Jiao, J.X. Wang, H.S. Chen, D.H. Tian, H.P. Lei, D.N. Fang, High-
performance aluminum-ion battery with CuS@C microsphere composite
cathode, ACS Nano 11 (2017) 469e477.
[30] W.J. Dong, J.J. Xu, C. Wang, Y. Lu, X.Y. Liu, X. Wang, XiT. Yuan, Z. Wang,
T.Q. Lin, M.L. Sui, I.W. Chen, F.Q. Huang, A robust and conductive black tin
oxide nanostructure makes efficient lithium-ion batteries possible, Adv.
Mater. 29 (2017) 1700136.
[31] G.M. Zhou, L. Li, C.Q. Ma, S.G. Wang, Y. Shi, Nikhil Koratkar, W.C. Ren, F. Li,
H.M. Cheng, A graphene foam electrode with high sulfur loading for flexible
and high energy Li-S batteries, Nanomater. Energy 11 (2015) 356e365.
[32] L.G. Beka, X. Li, X. Wang, C. Han, W. Liu, Reduced graphene oxide/CoS2
porous nanoparticle hybrid electrode material for supercapacitor applica-
tion, RSC Adv. 9 (2019) 26637e26645.
[33] X. Xiao, L. Zou, H. Pang, Q. Xu, Synthesis of micro/nanoscaled metal-organic
frameworks and their direct electrochemical applications, Chem. Soc. Rev. 49
(2020) 301e331.
[34] C.W. Shi, K.A. Owusu, X.M. Xu, T. Zhu, G.B. Zhang, W. Yang, L.Q. Mai, 1D
carbon-based nanocomposites for electrochemical energy storage, Small 15
(2019) 1902348.
[35] L. An, Y.X. Li, M.C. Luo, J. Yin, Y.Q. Zhao, C.L. Xu, F.Y. Cheng, Y. Yang, P.X. Xi,
S.J. Guo, Atomic-level coupled interfaces and lattice distortion on CuS/NiS2
nanocrystals boost oxygen catalysis for flexible Zn-air batteries, Adv. Funct.
Mater. 27 (2017) 1703779.
[36] H. Zhou, Z.L. Lv, H. Liu, M.F. Liang, B.H. Liu, H. Guo, Self-assembled hierar-
chical hollow CuS@MoS2 microcubes with superior lithium storage, Elec-
trochim. Acta 250 (2017) 376e383.
[37] B.A. Taleatu, E.A.A. Arbab, E. Omotoso, G.T. Mola, Synthesis and micro-
structural studies of annealed Cu2O/CuxS bilayer as transparent electrode
material for photovoltaic and energy storage devices, J. Microsc. 256 (2014)
61e71.
[38] P. Roy, S.K. Srivastava, Nanostructured copper sulfides: synthesis, properties
and applications, CrystEngComm 17 (2015) 7801e7815.
[39] Y. Liu, Y. Li, H. Kang, T. Jin, L. Jiao, Design, synthesis, and energy-related
applications of metal sulfides, Mater. Horiz. 3 (2016) 402e421.
[40] Q. Xu, B. Huang, Y. F Zhao, Y.F. Yan, R. Noufi, S.H. W, Crystal and electronic
structures of CuxS solar cell absorbers, Appl. Phys. Lett. 6 (2016), 061906.
[41] M. Mousavi-Kamazani, Z. Zarghami, M. Salavati-Niasari, Facile and novel
chemical synthesis, characterization, and formation mechanism of copper
sulfide (Cu2S, Cu2S/CuS, CuS) nanostructures for increasing the efficiency of
solar cells, J. Phys. Chem. C 120 (2016) 2096e2108.
[42] H. Li, K. Wang, S. Cheng, K. Jiang, Controllable electrochemical synthesis of
copper sulfides as sodium-ion battery anodes with superior rate capability
and ultralong cycle life, ACS Appl. Mater. Interfaces 7 (2018) 8016.
[43] S. Gorai, D. Ganguli, S. Chaudhuri, Synthesis of 1D Cu2S with tailored
morphology via single and mixed ionic surfactant templates, Mater. Chem.
Phys. 88 (2004) 383e387.
Y. Shi, B. Yang, X. Guo et al.
[44] P. Leidinger, R. Popescu, D. Gerthsen, H. Lünsdorf, C. Feldmann, Nanoscale
copper sulfide hollow spheres with phase-engineered composition: covellite
(CuS), digenite (Cu1.8S), chalcocite (Cu2S), Nanoscale 3 (2011) 2544e2551.
[45] X. Li, X.Y. He, C.M. Shi, B. Liu, Y.Y. Zhang, S.Q. Wu, Z.Z. Zhu, J.B. Zhao, Syn-
thesis of one-dimensional copper sulfide nanorods as high-performance
anode in lithium ion batteries, ChemSusChem 7 (2014) 3328e3333.
[46] W.Y. Wu, S. Chakrabortty, C.K.L. Chang, A. Guchhait, M. Lin, Y. Chan, Pro-
moting 2D growth in colloidal transition metal sulfide semiconductor
nanostructures via halide ions, Chem. Mater. 26 (2014) 6120e6126.
[47] L. Jia, T.P. Wu, J. Lu, L. Ma, W.T. Zhu, X.P. Qiu, Polysulfides capture-copper
additive for long cycle life lithium sulfur batteries, ACS Appl. Mater. In-
terfaces 8 (2016) 30248e30255.
[48] K. Krishnamoorthy, G.K. Veerasubramani, S. Radhakrishnan, S.J. Kim, Prep-
aration of copper sulfide nanoparticles by sonochemical method and study
on their electrochemical properties, J. Nanosci. Nanotechnol. 15 (2015)
4409e4413.
[49] X.L. Li, K. Hu, R.W. Tang, K. Zhao, Y.S. Ding, CuS quantum dot modified carbon
aerogel as an immobilizer for lithium polysulfides for high-performance
lithium-sulfur batteries, RSC Adv. 6 (2016) 71319e71327.
[50] M. Kumar, A. Chandra, In situ production of CuS particles in polymer elec-
trolyte matrix for mixed ionþ electron conduction, Ionics 16 (2010)
849e853.
[51] C.H. Feng, L. Zhang, Z.H. Wang, X.Y. Song, K.N. Sun, F. Wu, G. Liu, Synthesis of
copper sulfide nanowire bundles in a mixed solvent as a cathode material for
lithium-ion batteries, J. Power Sources 269 (2014) 550e555.
[52] G.Y. Chen, Z.Y. Wei, B. Jin, X.B. Zhong, H. Wang, W.X. Zhang, J.C. Liang,
Q. Jiang, Hydrothermal synthesis of copper sulfide with novel hierarchical
structures and its application in lithium-ion batteries, Appl. Surf. Sci. 277
(2013) 268e271.
[53] L. Qian, X.Q. Tian, L. Yang, J.F. Mao, H.Y. Yuan, D. Xiao, High specific capaci-
tance of CuS nanotubes in redox active polysulfide electrolyte, RSC Adv. 3
(2013) 1703e1708.
[54] M. Zhou, N. Peng, Z. Liu, Y. Xi, H. He, Y. Xia, Z. Liu, S. Okada, Synthesis of sub-
10 nm copper sulphide rods as high-performance anode for long-cycle life
Li-ion batteries, J. Power Sources 306 (2016) 408e412.
[55] N.R. Kim, J. Choi, H.J. Yoon, M.E. Lee, S.U. Son, H.J. Jin, Y.S. Yun, Conversion
reaction of copper sulfide based nanohybrids for sodium-ion batteries, ACS
Sustain. Chem. Eng. 5 (2017) 9802e9808.
[56] Y. Chen, C. Davoisne, J.-M. Tarascon, C. Gue ry, Growth of single-crystal
copper sulfide thin films via electrodeposition in ionic liquid media for
lithium ion batteries, J. Mater. Chem. 22 (2012) 5295e5299.
[57] H. Mazor, D. Golodnitsky, L. Burstein, E. Peled, High power copper sulfide
cathodes for thin-film microbatteries, Electrochem. Solid State Lett. 12
(2009) A232.
[58] K. He, Z. Yao, S. Hwang, N. Li, K. Sun, H. Gan, Y. Du, H. Zhang, C. Wolverton,
D. Su, Kinetically-driven phase transformation during lithiation in copper
sulfide nanoflakes, Nano Lett. 17 (2017) 5726e5733.
[59] Y. Du, Z. Yin, J. Zhu, X. Huang, X.J. Wu, Z. Zeng, Q. Yan, H. Zhang, A general
method for the large-scale synthesis of uniform ultrathin metal sulphide
nanocrystals, Nat. Commun. 3 (2012) 1177.
[60] Y. Han, Y. Wang, W. Gao, Y. Wang, L. Jiao, H. Yuan, S. Liu, Synthesis of novel
CuS with hierarchical structures and its application in lithium-ion batteries,
Powder Technol. 212 (2011) 64e68.
[61] Y.L. Auyoong, P.L. Yap, X. Huang, S.B. Abd Hamid, Optimization of reaction
parameters in hydrothermal synthesis: a strategy towards the formation of
CuS hexagonal plates, Chem. Cent. J. 7 (2013) 67.
[62] M. Nagarathinam, K. Saravanan, W.L. Leong, P. Balaya, J.J. Vittal, Hollow
nanospheres and flowers of cus from self-assembled Cu(II) coordination
polymer and hydrogen-bonded complexes of N-(2-Hydroxybenzyl)-L-serine,
Cryst. Growth Des. 9 (2009) 4461e4470.
[63] Q.W. Li, Y. Xue, Y.C. Zhu, Y.T. Qian, Facile synthesis and application of CuS
nanospheres in aqueous and organic lithium ion batteries, J. Nanosci.
Nanotechnol. 13 (2013) 1265e1269.
[64] H. Li, Y.H. Wang, J.L. Jiang, Y.Y. Zhang, Y.Y. Peng, J.B. Zhao, CuS microspheres
as high-performance anode material for Na-ion batteries, Electrochim. Acta
247 (2017) 851e859.
[65] B. Shi, W. Liu, K. Zhu, J.Y. Xie, Synthesis of flower-like copper sulfides mi-
crospheres as electrode materials for sodium secondary batteries, Chem.
Phys. Lett. 677 (2017) 70e74.
[66] L. Zhao, F.Q. Tao, Z. Quan, X.L. Zhou, Y.H. Yuan, J.C. Hu, Bubble template
synthesis of copper sulfide hollow spheres and their applications in lithium
ion battery, Mater. Lett. 68 (2012) 28e31.
[67] Z. Hosseinpour, A. Scarpellini, S. Najafishirtari, S. Marras, M. Colombo,
A. Alemi, M. De Volder, C. George, V. Lesnyak, Morphology-dependent
electrochemical properties of CuS hierarchical superstructures, Chem-
PhysChem 16 (2015) 3418e3424.
[68] J.J. Cheng, Y. Pan, J.T. Zhu, Z.Z. Li, J.N. Pan, Z.S. Ma, Hybrid network CuS
monolith cathode materials synthesized via facile in situ melt-diffusion for
Li-ion batteries, J. Power Sources 257 (2014) 192e197.
[69] W. Liu, B. Shi, Y. Wang, Y. Li, H.J. Pei, R. Guo, X.W. Hou, K. Zhu, J.J. Xie,
A flexible, binder-free graphene oxide/copper sulfides film for high-
performance sodium ion batteries, Chemistry 3 (2018) 5608e5613.
[70] S. Xiao, X.P. Li, W.W. Sun, B.Q. Guan, Y. Wang, General and facile synthesis of
metal sulfide nanostructures: in situ microwave synthesis and application as
binder-free cathode for Li-ion batteries, Chem. Eng. J. 306 (2016) 251e259.
25
Materials Today Chemistry 23 (2022) 100675
[71] S.B. Ni, T. Li, X.L. Yang, Fabrication of Cu2S on Cu film electrode and its
application in lithium ion battery, Thin Solid Films 520 (2012) 6705e6708.
[72] S.B. Ni, X.H. Lv, T. Li, X.L. Yang, Fabrication of Cu2S cathode for Li-ion battery
via a low temperature dry thermal sulfuration method, Mater. Chem. Phys.
143 (2013) 349e354.
[73] C.H. Lai, K.W. Huang, J.H. Cheng, C.Y. Lee, B.J. Hwang, L.J. Chen, Direct growth
of high-rate capability and high capacity copper sulfide nanowire array
cathodes for lithium-ion batteries, J. Mater. Chem. 20 (2010) 6638e6645.
[74] B. Zhang, S. Hao, J. Wu, X. Li, Y. Huang, Evidence of a nanosized copper anodic
reaction in an anaerobic sulfide aqueous solution, RSC Adv. 6 (2016)
19937e19943.
[75] H.J. Yoo, A.P. Tiwari, J. Lee, D. Kim, J.H. Park, Cylindrical nanostructured MoS2
directly grown on CNT composites for lithium-ion batteries, Nanoscale 8
(2015) 3404e3409.
[76] S.R. Kadam, D.J. Late, R.P. Panmand, M.V. Kulkarni, B.B. Kale, Nanostructured
2D MoS2 honeycomb and hierarchical 3D CdMoS4 marigold nanoflowers for
hydrogen production under solar light, J. Mater. Chem. 3 (2015)
21233e21243.
[77] Y.M. Chen, X.Y. Yu, Z. Li, U. Paik, X. Wen, Lou, Hierarchical MoS2 tubular
structures internally wired by carbon nanotubes as a highly stable anode
material for lithium-ion batteries, Sci. Adv. 2 (2016) e1600021.
[78] W. Chen, H. Chen, H. Zhu, Q. Gao, J. Luo, Y. Wang, S. Zhang, K. Zhang, C. Wang,
Y. Xiong, Y. Wu, X. Zheng, Solvothermal synthesis of ternary Cu2MoS4
nanosheets : structural characterization at the atomic level, Small 22 (2014)
4367e4644.
[79] S.R. Kadam, R.S. Kalubarme, S.P. Deshmukh, R.P. Panmand, U.V. Kawade,
M.V. Kulkarni, S.S. Deo, S.W. Gosavi, B.B. Kale, Facilitated lithium storage in
hierarchical microsphere of Cu2S-MoS2 ultrathin nanosheets, Chemistry 3
(2018) 11020e11026.
[80] W. Wang, Y. Yang, Y. NuLi, J. Zhou, J. Yang, J. Wang, Metal Organic Frame-
work (MOF)-Derived carbon-encapsulated cuprous sulfide cathode based on
displacement reaction for Hybrid Mg2þ/Liþ batteries, J. Power Sources 445
(2020) 227325.
[81] Y. Liu, B. Jin, Y.F. Zhu, X.Z. Ma, X.Y. Lang, Synthesis of Cu2S/carbon composites
with improved lithium storage performance, Int. J. Hydrogen Energy 40
(2015) 670e674.
[82] X. Meng, S.C. Riha, J.A. Libera, Q. Wu, H.H. Wang, A.B.F. Martinson, J.W. Elam,
Tunable core-shell single-walled carbon nanotube-Cu2S networked nano-
composites as high-performance cathodes for lithium-ion batteries, J. Power
Sources 280 (2015) 621e629.
[83] Y. Wang, J. Zeng, Y. Peng, J. Li, Y. Zhang, H. Li, J. Zhao, Ultrafast one-pot air
atmospheric solution combustion approach to fabricate mesoporous metal
sulfide/carbon composites with enhanced lithium storage properties, ACS
Appl. Energy Mater. 1 (2018) 6190e6197.
[84] X. Zhang, L. Duan, X. Zhang, X. Li, W. Lü, Preparation of Cu2S@rGO hybrid
composites as anode materials for enhanced electrochemical properties of
lithium ion battery, J. Alloys Compd. 816 (2019) 152539.
[85] M. Li, X.Y. Li, Z.Z. Li, Y.H. Wu, Retraction of “hierarchical nanosheet-built
CoNi2S4 nanotubes coupled with carbon-encapsulated carbon nanotubes@
Fe2O3 composites toward high-performance aqueous hybrid supercapacitor
devices, ACS Appl. Mater. Interfaces 11 (2019) 29476.
[86] H.Y. Phin, Y.T. Ong, J.C. Sin, Effect of carbon nanotubes loading on the pho-
tocatalytic activity of zinc oxide/carbon nanotubes photocatalyst synthesized
via a modified sol-gel method, J. Environ. Chem. Eng. 27 (2020) 103222.
[87] R.X. Zhang, S.Q. Cheng, N. Li, W.T. Ke, N, S-codoped graphene loaded Ni-Co
bimetal sulfides for enhanced oxygen evolution activity, Appl. Surf. Sci.
503 (2020) 144146.
[88] X.M. Luo, J.F. Huang, Q. Xi, L.Y. Cao, J.Y. Li, K. Kajiyoshi, A general synthesis of
transition metal sulfide and nitrogen/sulfur co-doped three-dimensional
graphene composite for high performance sodium storage, Solid State Ionics
356 (2020) 115438.
[89] Y. Liu, X.M. Xu, Z.P. Shao, S.P. Jiang, Metal-organic frameworks derived
porous carbon, metal oxides and metal sulfides-based compounds for
supercapacitors application, Energy Storage Mater. 26 (2020) 1e22.
[90] M. Du, Q. Li, Y. Zhao, C.S. Liu, H. Pang, A review of electrochemical energy
storage behaviors based on pristine metal-organic frameworks and their
composites, Coord. Chem. Rev. 416 (2020) 213341.
[91] F. Han, D. Li, W.C. Li, C. Lei, Q. Sun, A.H. Lu, Nanoengineered polypyrrole-
coated Fe2O3@C multifunctional composites with an improved cycle stabil-
ity as lithium-ion anodes, Adv. Funct. Mater. 23 (2013) 1692e1700.
[92] F. Han, W.C. Li, D. Li, A.H. Lu, In situ electrochemical generation of meso-
structured Cu2S/C composite for enhanced lithium storage: mechanism and
material properties, ChemElectroChem 1 (2014) 733e740.
[93] Y. Yang, G.H. Yu, J.J. Cha, H. Wu, M. Vosgueritchian, Y. Yao, Z.N. Bao, Y. Cui,
Improving the performance of lithium-sulfur batteries by conductive poly-
mer coating, ACS Nano 11 (2017) 9187e9193.
[94] J. Tang, S. Ni, Q. Chen, J. Zhang, X. Yang, CuS@Cu freestanding electrode via
electrochemical corrosion for high performance Li-ion batteries, Mater. Lett.
201 (2017) 13e17.
[95] K. Wang, C. Zhao, Z. Zhang, S. Min, X. Qian, A facile one-step route to syn-
thesize the three-layer nanostructure of CuS/RGO/Ni3S2 and its high elec-
trochemical performance, RSC Adv. 6 (2016) 16963e16971.
[96] C. Ding, D. Su, W. Ma, Y. Zhao, D. Yan, J. Li, H. Jin, Design of hierarchical CuS/
graphene architectures with enhanced lithium storage capability, Appl. Surf.
Sci. 403 (2017) 1e8.
Y. Shi, B. Yang, X. Guo et al.
[97] B. De, J. Balamurugan, N.H. Kim, J.H. Lee, Enhanced electrochemical and
photocatalytic performance of core-shell CuS@Carbon quantum Dots@
Carbon hollow nanospheres, ACS Appl. Mater. Interfaces 9 (2017)
2459e2468.
[98] H. Liu, W. Zhou, Y. Zhang, One-pot solvothermal synthesis of CuS-CNTs
hybrid as binder-free anode material for lithium ion batteries, Colloids
Interf. Sci. Commun. 15 (2016) 1e4.
[99] X. Hou, X. Liu, Y. Lu, J. Cheng, R. Luo, Q. Yu, X. Wei, H. Yan, X. Ji, J.K. Kim,
Y. Luo, Copper sulfide nanoneedles on CNT backbone composite electrodes
for high-performance supercapacitors and Li-S batteries, J. Solid State Elec-
trochem. 21 (2017) 349e359.
[100] H. Li, Y. Wang, J. Huang, Y. Zhang, J. Zhao, Microwave-assisted synthesis of
CuS/graphene composite for enhanced lithium storage properties, Electro-
chim. Acta 225 (2017) 443e451.
[101] Z. He, Y. Zhu, Z. Xing, Z. Wang, Cuprous sulfide/reduced graphene oxide
hybrid nanomaterials: solvothermal synthesis and enhanced electro-
chemical performance, J. Electron. Mater. 45 (2016) 285e290.
[102] Y. Ren, H. Wei, B. Yang, J. Wang, J. Ding, Double-sandwich-like CuS@reduced
graphene oxide as an anode in lithium ion batteries with enhanced elec-
trochemical performance, Electrochim. Acta 145 (2014) 193e200.
[103] J. Li, D. Yan, T. Lu, W. Qin, Y. Yao, L. Pan, Significantly improved sodium-ion
storage performance of cus nanosheets anchored into reduced graphene
oxide with ether-based electrolyte, ACS Appl. Mater. Interfaces 9 (2017)
2309e2316.
[104] J.F. Zhang, Y. Zhao, Y.G. Zhang, J.D. Li, M.-R. Babaa, N. Liu, Z. Bakenov, Syn-
thesis of microflower-like vacancy defective CuS/reduced graphene oxide
(rGO) composites for highly efficient lithium-ion batteries, Nanotechnology
31 (2020), 095405.
[105] X. Rui, H. Tan, Q. Yan, Nanostructured metal sulfides for energy storage,
Nanoscale 6 (2014) 9889e9924.
[106] L.J. Chen, Nanoscale copper and copper compounds for advanced device
applications, Metall. Mater. Trans. A Phys. Metall. Mater. Sci. 47 (2016)
5845e5851.
[107] Q. Chen, M. Ren, H. Xu, W. Liu, J. Hei, L. Su, L. Wang, Cu2S@ N,S dual-doped
carbon matrix hybrid as superior anode materials for lithium/sodium ion
batteries, ChemElectroChem 5 (2018) 2135e2141.
[108] H.L. Qing, R.R. Wang, Z.L. Chen, M.M. Li, L.L. Zhang, Y.-N. Zhou, R.B. Wu, In-
situ embedding cobalt-doped copper sulfide within ultrathin carbon nano-
sheets for superior lithium storage performance, J. Colloid Interface Sci. 566
(2020) 1e10.
[109] M. Yu, L.F. Hu, H.D. Liu, S.P. Yang, J.F. Ruan, H.T. Wu, P. Wang, Y. Song,
D.L. Sun, F. Fang, Cu0.33Co0.67S2 hexagonal sheets with 2D hierarchical
structures for high-rate and long-term lithium storage, ChemNanoMat 5
(2019) 531e538.
[110] Y. Gao, L. Kang, Y. Lian, W. Xin, R. Wang, J. Liang, L. Zhang, D. Wang, S. Xu, In-
situ sulfuration synthesis of N,S-doped carbon nanosheet encapsulated Fe-
doped Co9S8 as anodes for tunable lithium storage, Appl. Surf. Sci. 473
(2019) 673e680.
[111] S. Ni, X. Lv, T. Li, X. Yang, L. Zhang, Y. Ren, A novel electrochemical activation
effect induced morphology variation from massif-like CuxO to forest-like
Cu2O nanostructure and the excellent electrochemical performance as
anode for Li-ion battery, Electrochim. Acta 96 (2013) 253e260.
[112] M. Chhowalla, H.S. Shin, G. Eda, L. Li, K.P. Loh, H. Zhang, The chemistry of
two-dimensional layered transition metal dichalcogenide nanosheets, Nat.
Publ. Gr. 5 (2013) 263e275.
[113] Z.S. Wu, K. Parvez, A. Winter, H. Vieker, X. Liu, S. Han, A. Turchanin, X. Feng,
K. Müllen, Layer-by-layer assembled heteroatom-doped graphene films with
ultrahigh volumetric capacitance and rate capability for micro-super-
capacitors, Adv. Mater. 26 (2014) 4552e4558.
[114] L. Peng, Y. Zhu, D. Chen, R.S. Ruoff, G. Yu, Two-dimensional materials for
beyond-lithium-ion batteries, Adv. Energy Mater. 6 (2016) 1600025.
[115] L. Smith, B. Dunn, Opening the window for aqueous electrolytes, Science 350
(2015) 6263.
[116] A. Jain, B.J. Paul, S. Kim, V.K. Jain, J. Kim, A. Kumar, Two-dimensional porous
nanodisks of NiCo2O4 as anode material for highperformance rechargeable
lithium-ion battery, J. Alloys Compd. 772 (2019) 72e79.
[117] J. Liu, X.W. Liu, Two-dimensional nanoarchitectures for lithium storage, Adv.
Mater. 24 (2012) 4097e4111.
[118] H.J. Chen, X.D. Ma, P.K. Shen, NiCo2S4 nanocores in-situ encapsulated in
graphene sheets as anode materials for lithium-ion batteries, Chem. Eng. J.
364 (2019) 167e176.
[119] A. Qin, J. Ji, R. Du, N. Tian, L. Liao, K. Zhang, C. Wei, Hydrothermal synthesis
and electrochemical performance of CuS@Sisal fiber carbon composite
Lithium- ion battery anodes, Compos. Commun. 7 (2018) 47e50.
[120] T. Liu, L.M. Li, L.Y. Zhang, B. Cheng, W. You, J.G. Yu, 0D/2D (Fe0.5Ni0.5)S2/rGO
nanocomposite with enhanced supercapacitor and lithium ion battery per-
formance, J. Power Sources 426 (2019) 266e274.
[121] X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner, A. Velamakanni, I. Jung, E. Tutuc,
S.K. Banerjee, L. Colombo, R.S. Ruoff, Large-area synthesis of high-quality and
uniform graphene films on copper foils, Science 324 (2009) 1312e1314.
[122] M.Q. Zhao, Q. Zhang, J.Q. Huang, G.L. Tian, J.Q. Nie, H.J. Peng, F. Wei,
Unstacked double-layer templated graphene for high-rate lithium-sulphur
batteries, Nat. Commun. 5 (2014) 3410.
[123] V.R. Govindaraju, M. Sreeramareddygari, N.D. Hanumantharayudu,
S. Devaramani, R. Thippeswamy, W. Surareungchai, Solvothermal decoration
26
Materials Today Chemistry 23 (2022) 100675
of Cu3SnS4 on reduced graphene oxide for enhanced electrocatalytic
hydrogen evolution reaction, Environ. Prog. Sustain. Energy 40 (2021)
e13558.
[124] S. Han, L. Hu, Z. Liang, S. Wageh, A.A. AlGhamdi, Y. Chen, X. Fang, One-step
hydrothermal synthesis of 2D hexagonal nanoplates of a-Fe2O3/graphene
composites with enhanced photocatalytic activity, Adv. Funct. Mater. 24
(2014) 5719e5727.
[125] R. Sun, S. Liu, Q. Wei, J. Sheng, S. Zhu, Q. An, L. Mai, Mesoporous NiS2
nanospheres anode with pseudocapacitance for high-rate and long-life so-
dium-ion battery, Small 13 (2017) 1701744.
[126] J. Li, X. Lei, F. Qin, C. Zong, L. Liu, K. Zhang, MoSe2 nanosheets embedded in
mesoporous carbon as anode materials for sodium ion batteries, Ionics 25
(2019) 3143e3152.
[127] Z. Chen, R. Wu, H. Wang, Y. Jiang, L. Jin, Y. Guo, Y. Song, F. Fang, D. Sun,
Construction of hybrid hollow architectures by in-situ rooting ultrafine ZnS
nanorods within porous carbon polyhedra for enhanced lithium storage
properties, Chem. Eng. J. 326 (2017) 680e690.
[128] S. Wang, Y. Xing, C. Xiao, H. Xu, S. Zhang, A peapod-inspired MnO@C
core-shell design for lithium ion batteries, J. Power Sources 307 (2016)
11e16.
[129] D. Yuan, G. Huang, F. Zhang, D. Yin, L. Wang, Facile synthesis of CuS/rGO
composite with enhanced electrochemical lithium-storage properties
through microwave-assisted hydrothermal method, Electrochim. Acta 203
(2016) 238e245.
[130] Y. Wang, Y. Zhang, H. Li, Y. Peng, J. Li, J. Wang, B.J. Hwang, J. Zhao, Preparation
of one-dimensional bamboo-like Cu2-xS@C nanorods with enhanced lithium
storage properties, Electrochim. Acta 247 (2017) 271e280.
[131] X. Ding, S. Lei, C. Du, Z. Xie, J. Li, X. Huang, Small-sized CuS nanoparticles/N, S
Co-doped rGO composites as the anode materials for high-performance
lithium-ion batteries, Adv. Mater. Interf. 6 (2019) 1900038.
[132] P. Wang, M. Shen, H. Zhou, C. Meng, A. Yuan, MOF-derived CuS@Cu-BTC
composites as high-performance anodes for lithium-ion batteries, Small 15
(2019) 1903522.
[133] G. Chen, L. Yan, H. Luo, S. Guo, Nanoscale engineering of heterostructured
anode materials for boosting lithium-ion storage, Adv. Mater. 28 (2016)
7580e7602.
[134] J.Y. Wang, Y. Cui, D. Wang, Design of hollow nanostructures for energy
storage, conversion and production, Adv. Mater. 31 (2019) 1801993.
[135] Q. Xu, J.K. Sun, J.Y. Li, Y.X. Yin, Y.G. Guo, Scalable synthesis of spherical Si/C
granules with 3D conducting networks as ultrahigh loading anodes in
lithium-ion batteries, Energy Storage Mater. 12 (2018) 54e60.
[136] Y. Wang, Y. Zhang, H. Li, Y. Peng, J. Li, J. Wang, B.J. Hwang, J. Zhao, Realizing
high reversible capacity: 3D intertwined CNTs inherently conductive
network for CuS as an anode for lithium ion batteries, Chem. Eng. J. 332
(2018) 49e56.
[137] L. Wang, H. Liu, J. Zhao, X. Zhang, C. Zhang, G. Zhang, Q. Liu, H. Duan,
Enhancement of charge transport in porous carbon nanofiber networks via
ZIF-8-enabled welding for flexible supercapacitors, Chem. Eng. J. 382 (2020)
122979.
[138] K.C. Ho, L.Y. Lin, A review of electrode materials based on core-shell nano-
structures for electrochemical supercapacitors, J. Mater. Chem. A. 7 (2019)
3516e3530.
[139] W.M. Zhang, Z.W. Yue, Q.M. Wang, X.X. Zeng, C.C. Fu, Q. Li, X.T. Li, L.D. Fang,
L. Li, Carbon-encapsulated CoS2 nanoparticles anchored on N-doped carbon
nanofibers derived from ZIF-8/ZIF-67 as anode for sodium-ion batteries,
Chem. Eng. J. 380 (2020) 122548.
[140] R. Wu, X. Qian, K. Zhou, J. Wei, J. Lou, P.M. Ajayan, Porous spinel ZnxCo3- xO4
hollow polyhedra templated for high-rate lithium-ion batteries, ACS Nano 8
(2014) 6297e6303.
[141] X. Cao, B. Zheng, X. Rui, W. Shi, Q. Yan, H. Zhang, Metal oxide-coated three-
dimensional graphene prepared by the use of metal-organic frameworks as
precursors, Angew. Chem. 126 (2014) 1428e1433.
[142] H.Y. Xu, C.H. Wang, J.F. Zhang, J.Y. Zhang, L. Cao, B. Zhang, X. Ou, Rational
design of bimetal-organic framework-derived ZnSnS3 nanodots incorporated
into the nitrogen-doped graphene framework for advanced lithium storage,
ACS Sustain. Chem. Eng. 8 (2020) 4464e4473.
[143] C. Yang, L. Zhang, N. Hu, Z. Yang, H. Wei, Z.J. Xu, Y. Wang, Y. Zhang, Densely-
packed graphene/conducting polymer nanoparticle papers for high-
volumetric-performance flexible all-solid-state supercapacitors, Appl. Surf.
Sci. 379 (2016) 206e212.
[144] H. Qiu, X. Han, F. Qiu, J. Yang, Facile route to covalently-jointed graphene/
polyaniline composite and it's enhanced electrochemical performances for
supercapacitors, Appl. Surf. Sci. 376 (2016) 261e268.
[145] M. Naseri, L. Fotouhi, A. Ehsani, F. Babaei, Physicoelectrochemical properties
of facilely electrosynthesized reduced graphene oxide/p-type conductive
polymer nanocomposite film, New J. Chem. 40 (2016) 2565e2573.
[146] C. Shi, Q. Xia, X. Xue, Q. Liu, H.J. Liu, Synthesis of cobalt-based layered co-
ordination polymer nanosheets and their application in lithium-ion batteries
as anode materials, RSC Adv. 6 (2016) 4442e4447.
[147] L.D.L. Thi, N.V. Din, C.N. Dinh, N.T. Nguyen, T.D. Manh, V.T. Nguyen, D.V. Tac,
L.T. Hai, Three-dimensional heterostructures of Co@CuxS core-shell nano-
wire arrays as efficient bifunctional electrocatalysts for overall water split-
ting, Colloid. Surface. 611 (2021) 125779.
[148] X. Hou, Y. Zhang, Q. Dong, Y. Hong, Y. Liu, W. Wang, J. Shao, W. Si, X. Dong,
Metal organic framework derived core-shell structured Co9S8@N-C@MoS2
Y. Shi, B. Yang, X. Guo et al.
nanocubes for supercapacitor, ACS Appl. Energy Mater. 1 (2018)
3513e3520.
[149] S. Foley, H. Geaney, G. Bree, K. Stokes, S. Connolly, M.J. Zaworotko, K.M. Ryan,
Copper sulfide (CuxS) nanowire-in-carbon composites formed from direct
sulfurization of the metal-organic framework HKUST-1 and their use as Li-
ion battery cathodes, Adv. Funct. Mater. 28 (2018) 1800587.
[150] G. Kalimuldina, I. Taniguchi, High performance stoichiometric Cu2S cathode
on carbon fiber current collector for lithium batteries, Electrochim. Acta 224
(2017) 329e336.
[151] Y.Q. Zheng, Y.F. Yuan, M. Zhu, S.M. Yin, G.S. Cai, S.Y. Guo, Triple-layered
sandwich nanotube of carbon nanotube@TiO2 nanocrystalline@carbon with
superior lithium storage performance, Mater. Res. Bull. 133 (2021) 111076.
[152] Y. Fu, A. Manthiram, Electrochemical properties of Cu2S with ether-based
electrolyte in Li-ion batteries, Electrochim. Acta 109 (2013) 716e719.
[153] C. Shi, X. Li, X. He, J. Zhao, New insight into the interaction between
carbonate-based electrolyte and cuprous sulfide electrode material for
lithium ion batteries, Electrochim. Acta 174 (2015) 1079e1087.
[154] Z.F. Wang, X.M. Zhang, Y.G. Zhang, M. Li, C.l. Qin, Z. Bakenov, Chemical
dealloying synthesis of CuS nanowire-on-nanoplate network as anode ma-
terials for Li-ion batteries, Metals 8 (2018) 252.
[155] S.P. Mohanty, M. Nookala, Investigation of in situ grown and carbon-free
copper sulfide electrode for rechargeable lithium battery, J. Electroanal.
Chem. 794 (2017) 8e14.
[156] G. Kalimuldina, I. Taniguchi, Electrochemical properties of stoichiometric
CuS coated on carbon fiber paper and Cu foil current collectors as cathode
material for lithium batteries, J. Mater. Chem. A. 5 (2017) 6937e6946.
[157] Y. Zhang, K. Li, Y. Wang, J. Zeng, P. Ji, J. Zhao, Copper sulfide microspheres
wrapped with reduced graphene oxide for high-capacity lithium-ion stor-
age, Mater. Sci. Eng. B Solid-State Mater. Adv. Technol. 213 (2016) 57e62.
[158] C. Zhao, X. Luo, C. Chen, H. Wu, Sandwich electrode designed for high per-
formance lithium-ion battery, Nanoscale 8 (2016) 9511e9516.
[159] S. Jin, C. Wang, Synthesis and first investigation of excellent lithium storage
performances of Fe2GeO4/reduced graphene oxide nanocomposite, Nano-
mater. Energy 7 (2014) 63e71.
[160] Y. Wang, X. Zhang, P. Chen, H. Liao, S. Cheng, In situ preparation of CuS
cathode with unique stability and high rate performance for lithium ion
batteries, Electrochim. Acta 80 (2012) 264e268.
[161] L. Ji, M. Rao, H. Zheng, L. Zhang, Y. Li, W. Duan, J. Guo, E.J. Cairns, Y. Zhang,
Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur
cells, J. Am. Chem. Soc. 133 (2011) 18522e18525.
[162] I. Raguzin, S. Choudhury, F. Simon, M. Stamm, L. Ionov, Effect of current
collector on performance of Li-S batteries, Adv. Mater. Interf. 4 (2017)
1600811.
[163] L.T. Chen, X.T. Guo, W.J. Lu, M. Chen, Q. Li, H.G. Xue, H. Pang, Manganese
monoxide-based materials for advanced batteries, Coord. Chem. Rev. 368
(2018) 13e34.
[164] F. Li, Q.H. Liu, J.W. Hu, Y.Z. Feng, P.B. He, J.M. Ma, Recent advances in cathode
materials for rechargeable lithium-sulfur batteries, Nanoscale 11 (2019)
15418e15439.
[165] Y. Hwa, J. Zhao, E.J. Cairns, Lithium sulfide (Li2S)/graphene oxide nano-
spheres with conformal carbon coating as a high-rate, long-life cathode for
Li/S cells, Nano Lett. 15 (2015) 3479e3486.
[166] J. He, A. Manthiram, A review on the status and challenges of electrocatalysts
in lithium-sulfur batteries, Energy Storage Mater. 20 (2019) 55e70.
[167] W. Ren, W. Ma, S. Zhang, B. Tang, Recent advances in shuttle effect inhibition
for lithium sulfur batteries, Energy Storage Mater. 23 (2019) 707e732.
[168] Z.Y. Wang, H.Z. Tao, Y.Z. Yue, Metal-organic-framework-based cathodes for
enhancing the electrochemical performances of batteries: a review, Chem-
ElectroChem 6 (2019) 5358e5374.
[169] Agostini Marco, Matic Aleksandar, Designing highly conductive functional
groups improving guestehost interactions in Li/S batteries, Small 16 (2020)
1905585.
[170] Q.Y. Guo, Z.J. Zheng, Rational design of binders for stable Li-S and Na-S
batteries, Adv. Funct. Mater. 30 (2020) 1907931.
[171] Z. Wu, W. Wang, Y. Wang, C. Chen, K. Li, G. Zhao, C. Sun, W. Chen, L. Ni,
G. Diao, Three-dimensional graphene hollow spheres with high sulfur
loading for high-performance lithium-sulfur batteries, Electrochim. Acta 224
(2017) 527.
[172] P.R. Li, L. Ma, T.P. Wu, H.L. Ye, J.H. Zhou, F.P. Zhao, N. Han, Y.Y. Wang, Y.L. Wu,
Y.G. Li, J. Lu, Chemical immobilization and conversion of active polysulfides
directly by copper current collector: a new approach to enabling stable
room-temperature Li-S and Na-S batteries, Adv. Energy Mater. 8 (2018)
1800624.
[173] H. Yao, K. Yan, W. Li, G. Zheng, D. Kong, Z.W. Seh, V.K. Narasimhan, Z. Liang,
Y. Cui, Improved lithium-sulfur batteries with a conductive coating on the
separator to prevent the accumulation of inactive S-related species at the
cathode-separator interface, Energy Environ. Sci. 7 (2014) 3381e3390.
[174] J.Y. Hwang, H.M. Kim, S.K. Lee, J.H. Lee, A. Abouimrane, M.A. Khaleel,
I. Belharouak, A. Manthiram, Y.K. Sun, Lithium-sulfur batteries: synergetic
effect of hollow TiO2-webbed carbon nanotubes and a dual functional
carbon-paper interlayer, Adv. Energy Mater. 6 (2016) 1501480.
[175] X. Yuan, L. Wu, X. He, K. Zeinu, L. Huang, X. Zhu, H. Hou, B. Liu, J. Hu, J. Yang,
Separator modified with N,S co-doped mesoporous carbon using egg shell as
template for high performance lithium-sulfur batteries, Chem. Eng. J. 320
(2017) 178.
27
Materials Today Chemistry 23 (2022) 100675
[176] W.B. Kong, L.J. Yan, Y.F. Luo, D.T. Wang, K.L. Jiang, Q.Q. Li, S.S. Fan, J.P. Wang,
Ultrathin MnO2/graphene oxide/carbon nanotube interlayer as efficient
polysulfide-trapping shield for high-performance Li-S batteries, Adv. Funct.
Mater. 27 (2017) 160663.
[177] X.Y. Deng, J.J. Li, L.Y. Ma, J.W. Sha, N.Q. Zhao, Three-dimensional porous
carbon materials and their composites as electrodes for electrochemical
energy storage systems, Mater. Chem. Front. 3 (2019) 2221e2245.
[178] J. Long, H. Zhang, J. Ren, J. Li, M. Zhu, T. Han, B. Sun, S. Zhu, H. Zhang, J. Liu,
A metal organic foam-derived multi-layered and porous copper sulfide
scaffold as sulfur host with multiple shields for preventing shuttle effect in
lithium-sulfur batteries, Electrochem. Commun. 365 (2020) 136853.
[179] H. Li, L. Sun, Y. Zhao, T. Tan, Y. Zhang, A novel CuS/graphene-coated separator
for suppressing the shuttle effect of lithium/sulfur batteries, Appl. Surf. Sci.
466 (2019) 13186.
[180] D. He, P. Xue, D. Song, J. Qu, C. Lai, Tri-functional copper sulfide as sulfur
carrier for high-performance lithium-sulfur batteries, J. Electrochem. Soc.
164 (2017) A1499eA1502.
[181] J.J. Cheng, L.F. Liu, S.W. Ou, Y. Ou, Q. Liu, H.J. Song, Y. Pan, Sulfur/CuxS hybrid
material for Li/S primary battery with improved discharge capacity, Mater.
Chem. Phys. 224 (2018) 384e388.
[182] Q. Yu, Y. Lu, R. Luo, X. Liu, K. Huo, J.K. Kim, J. He, Y. Luo, In situ formation of
copper-based hosts embedded within 3D N-doped hierarchically porous
carbon networks for ultralong cycle lithium-sulfur batteries, Adv. Funct.
Mater. 28 (2018) 1804520.
[183] P. Chen, Z. Wu, T. Guo, Y. Zhou, M.L. Liu, X.F. Xia, JiW. Sun, L.D. Lu,
X.P. Ouyang, X. Wang, Y.S. Fu, J.W. Zhu, Strong chemical interaction between
lithium polysulfides and flame-retardant polyphosphazene for
lithiumesulfur batteries with enhanced safety and electrochemical perfor-
mance, Adv. Mater. 33 (2021) 2007549.
[184] J.T. Zhang, Z. Li, Y. Chen, S.Y. Gao, X.W. Lou, Nickeleiron layered double
hydroxide hollow polyhedrons as a superior sulfur host for lithiumesulfur
batteries, Angew. Chem. Int. Ed. 57 (2018) 10944e10948.
[185] E. Cha, M.D. Patel, J. Park, J. Hwang, V. Prasad, K. Cho, W. Choi, 2D MoS2 as an
efficient protective layer for lithium metal anodes in high-performance Li-S
batteries, Nat. Nanotechnol. 13 (2018) 521.
[186] X. Liang, J. Yun, K. Xu, H. Xiang, Y. Wang, Y. Sun, Y. Yu, A multi-layered Ti3C2/
Li2S composite as cathode material for advanced lithium-sulfur batteries,
Energy Chem 39 (2019) 176e181.
[187] J.Q. Huang, Q. Zhang, F. Wei, Multi-functional separator/interlayer system for
high-stable lithium-sulfur batteries: progress and prospects, Energy Storage
Mater. 1 (2015) 127e145.
[188] M. Yan, W.P. Wang, Y.X. Yin, L.J. Wan, Y.G. Guo, Interfacial design for
lithiumesulfur batteries: from liquid to solid, EnergyChem 1 (2019) 100002.
[189] K. Sun, D. Su, Q. Zhang, D.C. Bock, A.C. Marschilok, K.J. Takeuchi,
E.S. Takeuchi, H. Gan, Interaction of CuS and sulfur in Li-S battery system,
J. Electrochem. Soc. 162 (2015) A2834eA2839.
[190] A.K. Wang, Y. Huang, Y. Zhu, M. Yu, Cubic Cu2O/Cu2S particles with a unique
truncated edge structure anchoring on reduced graphene oxide as an
enhanced anode material for sodium-ion batteries, ChemElectroChem 5
(2018) 630e636.
[191] Y.H. Xiao, D.C. Su, X.Z. Wang, S.D. Wu, L.M. Zhou, Y. Shi, CuS micro-
spheres with tunable interlayer space and micropore as a high-rate and
long-life anode for sodium-ion batteries, Adv. Energy Mater. 8 (2018)
1800930.
[192] Y. Zhang, P.X. Wang, Y.Y. Yin, X.Y. Zhang, L.S. Fan, N.Q. Zhang, K.N. Sun,
Heterostructured SnS-ZnS@C hollow nanoboxes embedded in graphene for
high performance lithium and sodium ion batteries, Chem. Eng. J. 356 (2019)
1042e1051.
[193] Q.M. Peng, X.B. Hu, T.B. Zeng, B. Shang, M.L. Mao, X. Jiao, G.C. Xi, FeSb2S4
anchored on amine-modified graphene towards high-performance anode
material for sodium ion batteries, Chem. Eng. J. 385 (2020) 123857.
[194] X.Q. Chang, Y.F. Ma, M. Yang, T. Xing, L.Y. Tang, T.T. Chen, Q.B. Guo, X.H. Zhu,
J.Z. Liu, H. Xia, In-situ solid-state growth of N, S codoped carbon nanotubes
encapsulating metal sulfides for high-efficient-stable sodium ion storage,
Energy Storage Mater. 23 (2019) 358e366.
[195] G.L. Xu, R. Amine, A. Abouimrane, H. Che, M. Dahbi, Z.F. Ma, I. Saadoune,
J. Alami, W.L. Mattis, F. Pan, Z. Chen, K. Amine, Challenges in developing
electrodes, electrolytes, and diagnostics tools to understand and advance
sodium-ion batteries, Adv. Energy Mater. 8 (2018) 1702403.
[196] Y.U. Park, D.H. Seo, H. Kim, J. Kim, S. Lee, B. Kim, K. Kang, A family of high-
performance cathode materials for na-ion batteries, Na3(VO1-xPO4)2 F1þ2x
(0  x  1): combined first-principles and experimental study, Adv. Funct.
Mater. 24 (2014) 4603e4614.
[197] I. Hasa, D. Buchholz, S. Passerini, B. Scrosati, J. Hassoun, High performance
Na0.5[Ni0.23Fe0.13Mn0.63]O2 cathode for sodium-ion batteries, Adv. Energy
Mater. 4 (2014) 1400083.
[198] W. Zhang, F. Zhang, F. Ming, H.N. Alshareef, Sodium-ion battery anodes:
status and future trends, EnergyChem 1 (2019) 100012.
[199] Y.J. Fang, X.Y. Yu, X.W. Lou, Bullet-like Cu9S5 hollow particles coated with
nitrogen-doped carbon for sodium-ion batteries, Angew. Chem. Int. Ed. 58
(2019) 7744e7748.
[200] L.J. Wu, J. Gao, Z.B. Qin, Y. Sun, R. Tian, Q. Zhang, Y. Gao, Deactivated-
desulfurizer-derived hollow copper sulfide as anode materials for advanced
sodium ion batteries, J. Power Sources 479 (2020) 228518.
Y. Shi, B. Yang, X. Guo et al.
[201] D.X. Yu, M.L. Li, T. Yu, C.Z. Wang, Y. Zeng, X.D. Hu, G. Chen, G.C. Yang, F. Du,
Nanotube-assembled pine-needle-like CuS as an effective energy booster for
sodium-ion storage, J. Mater. Chem. A. 7 (2019) 10619e10628.
[202] Y. Fang, B.Y. Guan, D. Luan, X.W. David Lou, Elegant synthesis of CuS@CoS2
double-shelled nanoboxes with enhanced sodium storage properties,
Angew. Chem. Int. Ed. 58 (2019) 7739e7743.
[203] H. Kim, M.K. Sadan, C. Kim, S.H. Choe, K.K. Cho, K.W. Kim, J.H. Ahn, H.J. Ahn,
Simple and scalable synthesis of CuS as an ultrafast and long-cycling anode
for sodium ion batteries, J. Mater. Chem. A. 7 (2019) 16239e16248.
[204] Q. Zhao, Y. Lu, J. Chen, Advanced organic electrode materials for rechargeable
sodium-ion batteries, Adv. Energy Mater. 7 (2017) 1601792.
[205] J.Y. Hwang, S.T. Myung, Y.K. Sun, Sodium-ion batteries: present and future,
Chem. Soc. Rev. 46 (2017) 3529e3614.
[206] J.X. Wang, X.J. Lyu, L.Y. Wang, S. Yu, W.X. Zhu, C. Han, X.Q. Cao, Preparation
and electrochemical performance of hierarchical CuS-rGO composite,
J. Alloys Compd. 694 (2017) 1067e1072.
[207] Y.H. Wang, B.H. Wu, X.Y. He, Y.Y. Zhang, H. Li, Y.Y. Peng, J. Wang, J.B. Zhao,
Synthesis of micro/nanostructured Co9S8 cubes and spheres as high perfor-
mance anodes for lithium ion batteries, Electrochim. Acta 230 (2017)
299e307.
[208] J.B. Wang, J. Okabe, K. Urita, I. Moriguchi, M.D. Wei, Cu2S hollow spheres as
an anode for high-rate sodium storage performance, J. Electroanal. Chem.
874 (2020) 114523.
[209] Y.R. Gu, T.T. Li, B.K. Guo, Y.T. Jiang, W.J. Wen, J.B. Wu, L.J. Zhao, Copper sulfide
nanostructures and their sodium storage properties, CrystEngComm 22
(2020) 7082e7089.
[210] C. An, Y. Ni, Z. Wang, X. Li, X. Liu, Facile fabrication of CuS microflower as a
highly durable sodium-ion battery anode, Inorg. Chem. Front. 5 (2018)
1045e1052.
[211] J. Zhang, D.W. Wang, W. Lv, L. Qin, S. Niu, S. Zhang, T. Cao, F. Kang, Q.H. Yang,
Ethers illume sodium-based battery chemistry: uniqueness, surprise, and
challenges, Adv. Energy Mater. 8 (2018) 1801361.
[212] Y. Zhu, L. Suo, T. Gao, X. Fan, F. Han, C. Wang, Ether-based electrolyte enabled
Na/FeS2 rechargeable batteries, Electrochem. Commun. 54 (2015) 18e22.
[213] M.G. Boebinger, M. Xu, X. Ma, H. Chen, R.R. Unocic, M.T. McDowell, Distinct
nanoscale reaction pathways in a sulfide material for sodium and lithium
batteries, J. Mater. Chem. A. 5 (2017) 11701e11709.
[214] M. Wu, Y. Zhang, T. Li, Z. Chen, S.A. Cao, F. Xu, Copper sulfide nanoparticles as
high-performance cathode materials for magnesium secondary batteries,
Nanoscale 10 (2018) 12526e12534.
[215] L. Jin, H. Pang, CoP@SiO2 nanoreactors: a core-shell structure for efficient
electrocatalytic oxygen evolution reaction, Chin. Chem. Lett. 31 (2020)
2300e2304.
[216] Q. Liu, X. Hong, X. You, X. Zhang, X. Zhao, X. Chen, M. Ye, X. Liu, Designing
heterostructured metal sulfide core-shell nanoneedle films as battery-type
electrodes for hybrid supercapacitors, Energy Storage Mater. 24 (2020)
541e549.
[217] J. Shen, Y. Zhang, D. Chen, X. Li, Z. Chen, S.A. Cao, T. Li, F. Xu, Hollow CuS
nanocube cathode for rechargeable Mg batteries: effect of the structure on
the performance, J. Mater. Chem. A. 7 (2019) 21410e21420.
[218] Y. Ma, K. Shuai, L. Zhou, J. Wang, Q. Wang, Effect of Mg2þand Mg2þ/
Liþelectrolytes on rechargeable magnesium batteries based on an
erythrocyte-like CuS cathode, Dalton Trans. 49 (2020) 15397e15403.
[219] W. Ren, F. Xiong, Y. Fan, Y. Xiong, Z. Jian, Hierarchical copper sulfide porous
nanocages for rechargeable multivalent-ion batteries, ACS Appl. Mater. In-
terfaces 12 (2020) 10471e10478.
[220] F. Xiong, Y. Fan, S. Tan, L. Zhou, Y. Xu, C. Pei, Q. An, L. Mai, Magnesium storage
performance and mechanism of CuS cathode, Nanomater. Energy 47 (2018)
210e216.
[221] Y.L. Shen, Y.J. Wang, Y.C. Miao, M. Yang, X.Y. Zhao, X.D. Shen, High-energy
interlayer-expanded copper sulfide cathode material in non-corrosive elec-
trolyte for rechargeable magnesium batteries, Adv. Mater. 32 (2020)
1905524.
28
Materials Today Chemistry 23 (2022) 100675
[222] L.E. Blanc, X. Sun, A. Shyamsunder, V. Duffort, L.F. Nazar, Direct nano-
synthesis methods notably benefit Mg-battery cathode performance, Small
4 (2020) 2000029.
[223] R. Hu, R. Zhang, Y. Ma, W. Liu, L. Chu, W. Mao, J. Zhang, Applied Surface
Science Enhanced hole transfer in hole-conductor-free perovskite solar cells
via incorporating CuS into carbon electrodes, Appl. Surf. Sci. 462 (2018)
840e846.
[224] H.N. Wang, X. Chen, R. Chen, X. Zhu, Q. Liao, D.D. Ye, B. Zhang, Y.X. Yu,
W. Zhang, J.W. Li, A ternary hybrid CuS/Cu2O/Cu nanowired photocathode
for photocatalytic fuel cell, J. Power Sources 435 (2019) 226766.
[225] Y. Zhang, D. Wang, Q. Wang, W. Zheng, One-step synthesized CuS and
MWCNTs composite as a highly efficient counter electrode for quantum dot
sensitized solar cells, Mater. Des. 160 (2018) 870e875.
[226] E. Vijayakumar, V.H.V. Quy, J. Kwon, J. Chae, J.H. Kim, S.H. Kang, H. Kim,
K.S. Ahn, Enhanced electrocatalytic activity of Cu2S-polyaniline hetero-
structure counter electrode for quantum dot-sensitized solar cells,
J. Electrochem. Soc. 164 (2017) F1211eF1215.
[227] X. Yan, Y. Gu, C. Li, B. Zheng, Y. Li, T. Zhang, Z. Zhang, M. Yang, A non-
enzymatic glucose sensor based on the CuS nanoflakes-reduced graphene
oxide nanocomposite, Anal. Meth. 10 (2018) 381e388.
[228] X.X. Jia, E. Zhang, X.Z. Yu, B.G. Lu, Facile synthesis of copper sulfide Nano-
sheet@Graphene oxide for the anode of potassium-ion batteries, Energy
Technol. 8 (2020) 1900987.
[229] K. Cao, R. Zheng, S. Wang, J. Shu, X. Liu, H. Liu, K.J. Huang, Q.S. Jing, L. Jiao,
Boosting coulombic efficiency of conversion-reaction anodes for potassium-
ion batteries via confinement effect, Adv. Funct. Mater. 30 (2020) 2007712.
[230] Y.Y. Liu, L. Xu, X.T. Guo, T.T. Lv, H. Pang, Vanadium sulfide based materials:
synthesis, energy storage and conversion, J. Mater. Chem. 8 (2020)
20781e20802.
[231] G.Q. Yuan, S.K. Yu, J. Jie, C. Wang, Qi Li, H. Pang, Cu/Cu2O nanostructures
derived from copper oxalate as high performance electrocatalyst for glucose
oxidation, Chin. Chem. Lett. 31 (2020) 1941e1945.
Yuxin Shi is now a student under Prof. Pang and Xu's
supervision, Yangzhou University of chemistry and
chemical engineering, in Jiangsu province in China. Her
research mainly focuses on the field of metal organic
frameworks and their applications.
Huan Pang received his Ph. D. degree from Nanjing Uni-
versity in 2011. He is now a university distinguished pro-
fessor at Yangzhou University and Young Changjiang
Scholars of the Ministry of Education, China. He is a senior
member of the China Chemical Association. He is the
managing editor of EnergyChem, the editorial board
member of FlatChem and Rare Metals, and the youth
editorial board member of e-Science, Advanced Fiber
Materials, Chinese Journal of Inorganic Chemistry, and
China Chemical Letters. He was recognized as a highly
cited researcher in Cross-Field by Clarivate Analytics in
2020.