Journal of Alloys and Compounds 885 (2021) 161080

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Ag nanoparticles decorated CuS sub-micron flowers with enhanced

energy storage performance for hybrid supercapacitors ]]
]]]]]]
]]

⁎
Congmei Yue a, Hougui Li a, Hongwei Shi b, Aifeng Liu a, , Zengcai Guo a, Jingbo Mu a,
⁎
Xiaoliang Zhang a, Xiaoyan Liu a, Hongwei Che a,
a
College of Materials Science and Engineering, Technology Innovation Center of Modified Plastics of Hebei Province, Hebei University of Engineering, Handan
056038, PR China
b
China Water Investment Co., LTD., Beijing 100053, PR China

a r t i cl e i nfo a bstr ac t

Article history: In this reported work, Ag nanoparticles (NPs) decorated CuS sub-micron flowers are synthesized using a
Received 1 May 2021 facile, solvothermal reaction coupled with a silver mirror reaction. The experimental results and theoretical
Received in revised form 30 June 2021 calculations reveal that decorating the CuS with Ag NPs increases its intrinsic electrical conductivity and
Accepted 5 July 2021
generates an electric field at the interface between Ag and CuS. These effects promote the efficient utili­
Available online 7 July 2021
zation of active materials and accelerate the interface charge transfer and electrochemical reaction kinetics.
Consequently, the maximum specific capacity of the prepared CuS@Ag electrodes is found to be as high as
Keywords:
Copper sulfide 702 C g−1 at 2 A g−1, which is about 5 times greater than the pure CuS electrode. In addition, the capacity
Silver nanoparticles value is 400 C g−1 at 20 A g−1 and it exhibits 93% retention of the initial capacity after 5000 cycles at 10 A g−1.
Solvothermal reaction Moreover, a hybrid supercapacitor (HSC) device is assembled employing the CuS@Ag electrode as the po­
Hybrid supercapacitor sitive electrode, which delivers an energy density of 51.1 Wh kg−1 at a power density of 798 W kg−1. These
Energy storage property results demonstrate the promising potential of the fabricated CuS@Ag composites for further application in
HSCs.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction than the corresponding metal oxides/hydroxides [15–17]. Among

Over the past two decades years, considerable effort has been
expended in the development of hybrid supercapacitors (HSCs) that
combine the merits of supercapacitors and rechargeable batteries for
the promising applications in electronic devices, electrical vehicles,
and other systems [1–3]. Various metal oxide nanoparticles (NPs)
and nanocomposites have been used as SCs and achieved higher
activity [4–12]. Nevertheless, their practical application continues to
be limited by the undesirable energy storage properties of battery-
type electrodes, which includes low practical specific capacity, rate
capability, and cyclic stability [13,14]. Therefore, optimizing the en­
ergy storage properties of these battery-type electrodes is greatly
desired to promote the commercial development of HSCs.
Transition metal sulfides have attracted significant interest as
one type of promising battery-type electrode material for HSCs due
to their high theoretical capacity and lower electrical conductivity
⁎
Corresponding authors.
E-mail addresses: liuaifeng@hebeu.edu.cn (A. Liu),
hongweiche@hebeu.edu.cn (H. Che).
these, CuS has gained much attention as suitable battery-type
electrode materials due to its natural abundance, low cost, and en­
vironmental friendliness, especially its high electrochemical activity
and large theoretical specific capacity [18–21]. Therefore, many in­
vestigations have focused on constructing various CuS micro-/na­
nostructures as prospective candidate electrodes for HSCs, including
nanospheres [22], nanosheets [23], nanocages [24], microspheres
[25], and microflowers [26]. However, the energy storage properties
of these reported micro-/nanostructured CuS electrodes proved to be
less favorable than expected due to their relatively low electrical
conductivity. In this regard, combining CuS with other highly con­
ductive materials to produce a composite with higher electrical
conductivity has been considered to be a promising strategy for
improving the energy storage property of CuS.
More recently, reports have emerged of the synthesis of Ag NPs
for its application in the biomedical and electrochemical fields
[27–30]. In particular, Ag NPs modified electrode materials have
been reported to demonstrate improved energy storage property
thanks to the highest electrical conductivity of Ag (6.3 × 107 S m−1)
[31–36]. For example, Yu et al. reported the synthesis of Ag NPs
decorated Ni0.67Co0.33S with forest-like nanostructures as a battery-

https://doi.org/10.1016/j.jallcom.2021.161080
0925-8388/© 2021 Elsevier B.V. All rights reserved.
C. Yue, H. Li, H. Shi et al.
type electrode for HSCs, which exhibited a capacity value of
864.9 μAh cm−2 at 2 mA cm−2, which was greater than the pure
Ni0.67Co0.33S electrode (864.9 μAh cm−2) [33]. Xie et al. fabricated the
Ag NPs decorated CuO nanowire arrays grown on Cu foam, which
exhibited a two-fold higher specific capacity of 1481 mC cm−2 at
2 mA cm−2 than the pure CuO nanowire arrays [34]. Similarly, Ryu
et al. prepared Ag NPs decorated Ag3VO4 stacked nanosheets, that
delivered a two-fold higher capacity than the pure Ag3VO4 electrode
[35]. However, to the best of our knowledge, there have been very
few reports of the combination of Ag NPs with micro/nanostructured
CuS for use as HSC electrodes.
In this reported work, we detail the fabrication of CuS@Ag elec­
trodes by decorating the surface of CuS sub-micron flowers with Ag
NPs and examined the energy storage properties of this material in
HSCs electrodes. As shown in Fig. 1a, the CuS sub-micron flowers
were initially synthesized using a facile hydrothermal sulfurization
reaction. Ag NPs were subsequently decorated on the surface of CuS
sub-micron flowers using a silver mirror reaction at room tem­
perature. The resulting improved electrical conductivity of the
CuS@Ag electrodes produced improved energy storage properties
when compared to the pure CuS electrode. In addition, a two-elec­
trode HSC device was fabricated using the synthesized CuS@Ag-2 as
the positive electrode and nitrogen-doped carbon nanotubes (N-
CNTs) as the negative electrode, also exhibited high energy and
power densities along with good cyclic durability.
Fig. 1. (a) Schematic illustration of the synthesis of the CuS@Ag composites; SEM images of the CuS (b, c) and CuS@Ag-2 (d, e).
2
Journal of Alloys and Compounds 885 (2021) 161080
2. Experimental
2.1. Preparation of CuS sub-micron flowers
The CuS sub-micron flowers were prepared as follows. Typically,
0.41 g of CuCl2·2H2O (2.4 mmol) and 0.18 g of CH3CSNH2 (2.4 mmol)
were dissolved into 30 ml of deionized water. This solution was then
placed into a 50 ml Teflon-lined autoclave and maintained at 160 °C
for 1 h. The CuS sub-micron flowers were obtained after washed
with deionized water and ethanol several times and dried at 80 °C in
vacuum overnight.
2.2. Preparation of the CuS@Ag composites
Ag NPs were decorated onto the surface of CuS sub-micron
flowers using a silver mirror reaction [36]. In brief, 50 mg of CuS sub-
micron flowers powder was dispersed in 30 ml of a AgNO3
(0.02–0.08 M) and glucose (0.01–0.04 M) aqueous solution (molar
ratio of Ag+ to glucose = 2) under ultrasonication for 30 min at room
temperature, and then aged for 6 h. The resultant CuS@Ag compo­
sites were obtained using this method and denoted as CuS@Ag-1,
CuS@Ag-2, and CuS@Ag-3, respectively based on the corresponding
AgNO3 concentrations of in the silver mirror reaction solution: 0.02,
0.04, and 0.08 M.
C. Yue, H. Li, H. Shi et al.
2.3. Materials characterization
The crystal phase and surface information of the various samples
were determined using X-ray diffractometer (XRD, Rigaku Smartlab)
with a Cu Kα radiation (λ = 1.54 Å) and X-ray photoelectron spec­
troscopy (XPS, Kratos Amicus spectrometer). The morphologies and
microstructures were investigated by field emission scanning elec­
tron microscopy (FESEM, Hitachi SU8200) and transmission electron
microscopy (TEM, FEI Tecnai F20) operated at 200 kV.
2.4. Electrochemical measurements
Cyclic voltammetry (CV), galvanostatic charge–discharge (GCD),
and electrochemical impedance spectroscopy (EIS) tests were con­
ducted on the sample materials using an electrochemical test cell
(CHI 660E, China) with a saturated calomel electrode (SCE) as the
reference electrode, Pt wire as the counter electrode, and CuS@Ag on
Ni foam as the working electrode in a 6 M KOH aqueous solution. The
fabrication of the working electrode and two-electrode HSC device
are described in Supporting Information.
3. Results and discussion
Fig. 1(b, c) show the SEM images of the prepared pure CuS and
CuS@Ag-2. As shown, the pure CuS exhibited a flower-like mor­
phology with an average size of 400 nm (Fig. 1b). Close observation
of this material revealed that these sub-micron flowers were com­
posed of interconnected nanosheets through both edge-to-surface
and edge-to-edge link (Fig. 1c), generating numerous open spaces
between adjacent nanosheets and thus assisting in the full contact
with the electrolyte ions. After decorating the CuS with Ag NPs, the
CuS@Ag-2 still retained its flower-like morphology with a large
number of irregular Ag NPs with sizes of 50–100 nm distributed on
the surface of the CuS flowers (Fig. 1d, e). The Ag NPs decoration
effectively increased the electrical conductivity of the CuS sub-mi­
cron flowers, resulting in the improved electrochemical perfor­
mance.
The SEM images of the CuS@Ag-1 and CuS@Ag-3 are also pre­
sented in Fig. S1. The CuS@Ag-1 that was prepared using a silver
mirror reaction with a lower 0.02 M AgNO3 concentration and when
compared to the CuS@Ag-2, a small amount of Ag NPs can be ob­
served on the surface of CuS sub-micron flowers (Fig. S1a, b). The
sizes of these Ag NPs ranged from 20 to 50 nm. As the AgNO3 con­
centration in the silver mirror reaction solution was further in­
creased to 0.08 M, the resulting CuS sub-micron flowers were
densely wrapped with aggregated Ag NPs with particle sizes ranging
of 150–300 nm in the CuS@Ag-3 (Fig. S1c, d). Based on these SEM
observations, it appeared that the amount and size of decorated Ag
NPs gradually increased as the AgNO3 concentration was increased
in the silver mirror reaction solution. It was noted that the dec­
orating CuS sub-micron flowers with Ag NPs with larger particle
sizes on the surface of may detract from the full exposure of the CuS
active component to the electrolyte, which would decrease the
electrochemical properties of the composite.
The TEM images of the CuS@Ag-2 are displayed in Fig. 2(a–c), and
these further confirm the successful decorating of Ag NPs on the
surface of CuS sub-micron flowers. The average particle size of Ag
NPs was 63 nm (inset in Fig. 2b). These results are consistent with
the SEM observations. The high-resolution TEM images reveal lattice
fringes in the experimental product with d-spacings of 0.24 and
0.19 nm (insets in Fig. 2c), respectively, which corresponded to cubic
Ag (111) and CuS (110) crystal planes [36,37]. The TEM elemental
mapping images in Fig. 2d reveal that the Ag was uniformly dis­
tributed in the Ag NPs, while Cu and S were homogeneously present
throughout the entire CuS nanosheets. This confirmed that Ag NPs
3
Journal of Alloys and Compounds 885 (2021) 161080
were anchored on the surface of CuS nanosheets. The TEM-EDS
spectrum in Fig. 2e shows that the CuS@Ag-2 consisted of Ag, Co,
and S, and the atomic ratio of S to Cu was 0.97, which approaches the
stoichiometric value of CuS. Moreover, the ratio of Cu to Ag was
determined to be 1: 0.26 (Table S1), and the content of Ag in the
CuS@Ag-2 was calculated to be 22.68 wt%. The contents of Ag in the
CuS@Ag-1 and CuS@Ag-3 are also provided in Table S1.
The phase structure and elemental valence state information of
the prepared pure CuS and CuS@Ag-2 were obtained using XRD and
XPS analysis. As shown in Fig. 3a, the XRD pattern of pure CuS shows
the typical diffraction peaks at 2θ = 27.7°, 29.3°, 31.8°, 47.9°, 52.7°and
59.3°, which matched with the hexagonal CuS covellite phase (JCPDS
06-0464) [38,39]. The crystallite size of CuS was calculated to be
16.1 nm using the Scherrer equation. As for the XRD patterns of the
CuS@Ag-2 (Fig. 3a), apart from those peaks related to the CuS phase,
four new diffraction peaks appeared at 2θ = 38.3°, 44.3°, 64.3°, and
77.4°, corresponding to the cubic metallic Ag (JCPDS 89-3722) [36]
The calculated crystallite size of Ag was 28.4 nm. Fig. 3b shows the
XPS full survey spectrum of the CuS@Ag-2, which exhibits the peaks
of Cu 2p, S 2p, and Ag 3d. This result was consistent with the TEM-
EDS spectrum for this material. Fig. 3c shows the high-resolution Cu
2p spectrum, where two distinct peaks are present at 932.6 eV (Cu
2p3/2) and 952.4 eV (Cu 2p1/2) which suggest the existence of Cu2+ in
CuS [40,41]. The high-resolution S 2p spectrum is presented in
Fig. 3d, which reveals the features of S2- in CuS based on the two
main peaks at 161.8 eV (S 2p3/2) and 162.7 eV (S 2p1/2) [40,41]. For
the high-resolution Ag 3d spectrum (Fig. 3e), the two main peaks at
368.2 eV (Ag 3d5/2) and 374.3 eV (Ag 3d3/2) generate a spin orbital
separation of about 6 eV, which confirms the metallic Ag0 in Ag NPs
[42,43]. These XRD and XPS results further confirmed the successful
preparation of the CuS@Ag composites.
To assess the potential applications of the prepared CuS@Ag as
the HSC electrodes, the electrochemical behavior of these electrodes
were determined using a three-electrode test cell. First, CV curves of
the pure CuS and CuS@Ag electrodes were obtained at the same scan
rate of 5 mV s−1. Typical redox peaks appear in all the CV curves
(Fig. 4a), indicating battery-type electrochemical behavior in these
electrodes [19,37,38]. The possible Faradaic electrode reaction may
be described as follows [18,37,38]:
CuS + OH- ↔ CuSOH + e- (1)
It was noted that the peak currents and enclosed areas of the
CuS@Ag electrodes were significantly larger than those of the pure
CuS electrode, suggesting that the decoration of Ag NPs had en­
hanced the energy storage property. Moreover, the CuS@Ag-2 elec­
trode developed the highest current during the potential scan. The
GCD curves of different electrodes were also compared at the same
current density of 2 A g−1 (Fig. 4b), in which the CuS@Ag electrodes
exhibited a longer discharge time than the pure CuS electrode. In
addition, the CuS@Ag-2 electrode exhibited the longest discharge
time. Therefore, the CV and GCD results suggested that the decora­
tion of Ag NPs exhibited enhanced energy storage.
To better understand the electrochemical behavior of the
CuS@Ag-2 electrode, the CV curves were measured at different scan
rates of 5–50 mV s−1 (Fig. 4c). It was found that as the scan rates
were increased, the anodic peaks shifted to higher potentials, while
the cathodic peaks shifted to lower potentials, which was attributed
to the polarization of electrode [44,45]. Similar results were also
found for the CuS@Ag-1 and the CuS@Ag-3 electrodes as well as
the pure CuS electrode based on their corresponding CV curves
(Fig. S2a–c). It was noted that all the CV curves almost did not
substantially change in shape at the higher scan rates, suggesting
high electrochemical activity [37,46]. To study the charge storage
behavior of the CuS@Ag-2 electrode, plots from the anodic/cathodic
C. Yue, H. Li, H. Shi et al.
Fig. 2. TEM images (a–c), elemental mapping images (d), and TEM-EDS pattern (e) of the CuS@Ag-2. The insets in (b) and (c) show the particle size distribution of Ag NPs and
high-resolution TEM images of CuS and Ag, respectively.
peak current (ip) vs. the square root of scan rate (v1/2) are presented
in Fig. S3a. A typical linear relation is exhibited between ip vs. v1/2,
indicating diffusion-controlled charge storage in the CuS@Ag-2
electrode [1,47]. In order to verify this conclusion, the b-value was
calculated using the following formula [1,47]:
logip = a + blogv
where a is an adjustable parameter. The b-values were calculated to
be 0.6 and 0.57, respectively, according to the linear logip vs. logʋ
plots for anodic and cathodic peaks (Fig. S3b). Both b-values were
close to 0.5, indicating a diffusion-controlled process at the CuS@Ag-
Journal of Alloys and Compounds 885 (2021) 161080
2 electrode. Furthermore, the diffusion-controlled contribution in
this electrode can be quantified using the following equation [1,47]:
i = k1v + k2v1/2 (3)
1/2
where k1v and k1v stand for the capacitive and diffusion-con­
trolled contributions, respectively. Fig. 4d shows a capacitive con­
(2)
tribution of 12% for the CuS@Ag-2 electrode at 5 mV s−1, and the
diffusion contribution counterpart was 88%. The diffusion con­
tribution value began to decrease and remained as high as 70%
(Fig. 4e) as the scan rate was greater than 5 mV s−1 and further in­
creased to 50 mV s−1. This result confirmed that a diffusion-
4
C. Yue, H. Li, H. Shi et al.
Fig. 3. (a) XRD patterns of the CuS and CuS@Ag-2; XPS survey spectrum (b), high-resolution Cu 2p (c), S 2p (d), and Ag 3d (e) XPS spectra of the CuS@Ag-2.
controlled process was prevalent for the charge storage of the
CuS@Ag-2 electrode.
Fig. 4f shows the nonlinear GCD curves of the CuS@Ag-2 elec­
trode measured at current densities ranging from 2 to 20 A g−1, all of
which exhibited an obvious voltage plateaus. This was typical bat­
tery-type Faradaic redox behavior [19,37,38]. Similarly, the GCD
curve of the CuS@Ag-1, CuS@Ag-3, and pure CuS electrodes also
exhibited battery-type characteristics (Fig. S4a–c). These results are
consistent with the CV test results. Based on these GCD results, the
specific capacity values of the CuS@Ag-1, CuS@Ag-2, and CuS@Ag-3
electrodes were calculated to be 229, 702, and 442 C g−1 at 2 A g−1,
respectively (Fig. 4g). Whereas, the pure CuS electrode demonstrated
a low specific capacity of 138 C g−1 at 2 A g−1. Even at 20 A g−1, the
CuS@Ag-1, CuS@Ag-2, and CuS@Ag-3 electrodes delivered specific
capacities of as high as 118, 400, and 226 C g−1, respectively, with the
corresponding capacity retention of 52%, 57%, and 51% compared
with the capacity values at 2 A g−1. By contrast, a low specific ca­
pacity of only 62 C g−1 as well as a capacity retention of 45% was
exhibited by the pure CuS electrode at the same 20 A g−1. Notably,
these capacity values of the CuS@Ag-2 electrode are also comparable
to the of previously reported copper sulfide-based electrodes for
5
Journal of Alloys and Compounds 885 (2021) 161080
HSCs (Table S2 in Supporting Information). Moreover, the capacity
values of the CuS@Ag electrodes initially increased and then de­
creased with the increase of the AgNO3 concentration in the silver
mirror reaction solution. These results suggested that the charge
storage properties of the CuS@Ag electrodes could be optimized by
adjusting the distribution of Ag NPs on the surface of CuS sub-mi­
cron flowers.
Electrode stability during cycling is another important factor for
evaluating the energy storage properties of electrode materials,
which was determined by repeated charging–discharging of the
electrodes. As shown in Fig. 4h, the CuS@Ag-1, CuS@Ag-2 and
CuS@Ag-3 electrodes exhibited initial capacity retention of 86%, 93%,
and 90%, over 5000 cycles at 10 A g−1, all of which were higher than
the pure CuS electrode (81%) over the same cycle life. Moreover, the
SEM image of the CuS@Ag-2 electrode after cycling showed that it
retained the Ag NPs on the CuS sub-micron flowers after 5000 cy­
cles, implying the good electrode stability (Fig. S5).
EIS measurements were performed to ascertain the electronic
conductivity of these electrodes and their electrolyte diffusion ki­
netics. The corresponding Nyquist plots are presented in Fig. 4i. As
shown, the pure CuS electrode exhibited an internal resistance (Rs)
C. Yue, H. Li, H. Shi et al.
Fig. 4. (a) CV curves of different electrodes at 5 mV s−1; (b) GCD curves of different electrodes at 2 A g−1; (c) CV curves of the CuS@Ag-2 electrode at 5–50 mV s−1; (d) Capacitive and
diffusion-controlled contributions to charge storage for the CuS@Ag-2 electrode at 5 mV s−1; (e) Capacitive and diffusion-controlled contribution ratios of the CuS@Ag-2 electrode
at different scan rates; (f) GCD curves of the CuS@Ag-2 electrode at 2–20 A g−1; Rate capabilities (g), cyclic lifetime (h) over 5000 cycles at 10 A g−1, and Nyquist plots (i) of different
electrodes.
of 2.69 Ω. By contrast, the CuS@Ag electrodes exhibited lower Rs
values of 2.59 Ω for CuS@Ag-1, 2.16 Ω for CuS@Ag-2, and 2.02 Ω for
CuS@Ag-3, indicating that the electrical conductivity of composite
electrodes gradually increased with the addition of more conductive
Ag NPs. Meanwhile, the charge transfer resistance (Rct) values for
the CuS@Ag-1, CuS@Ag-2, and CuS@Ag-3 electrodes were 0.90, 0.63,
and 0.59 Ω, respectively. These Rct values were smaller than those
for the pure CuS electrode (1.27 Ω). The lower Rct values of the
CuS@Ag electrodes implied the presence of a faster Faradic redox
reaction at the electrode/electrolyte interface. Moreover, in a low-
frequency region of the Nyquist plots, the CuS@Ag electrodes ex­
hibited vertical lines that were more intense than the pure CuS
electrode, suggesting improved electrolyte diffusion through the
composite electrodes. Similar results were also reported for rGO/Ag/
Ni3S2 [42] and Ti3C2Tx/Ag [48] electrodes that exhibited lower dif­
fusion resistance after decoration with Ag NPs. Note that the
CuS@Ag-3 electrode showed a less inclined straight line compared to
the CuS@Ag-2 electrode, suggesting a greater diffusion resistance.
These results strongly suggest that the higher loading of Ag NPs were
not conductive to electrolyte diffusion through the composite elec­
trode. These EIS results indicated that the decoration of Ag NPs on
CuS flowers effectively increased the charge transport and ion dif­
fusion kinetics through the composite electrodes, which produced
the improved electrochemical charge storage in the composite
electrodes.
6
Journal of Alloys and Compounds 885 (2021) 161080
To further elucidate how the decoration with Ag NPs improves
the electrochemical properties of the composite electrodes, density
functional theory (DFT) calculations were conducted and the com­
putational details are provided in Supporting Information. To de­
termine the effect of the decoration of Ag NPs on the electronic
structure of CuS, the density of states (DOS) of the pure CuS and
CuS@Ag materials were calculated and are presented in Fig. 5a. As
can be seen, these two DOS curves continuously cross the Fermi
energy level and no band gaps are present, suggesting a metallic
state for the pure CuS and CuS@Ag. The metallic nature of CuS has
also been reported in the literature [49,50]. It is noted that the
CuS@Ag had a significantly enhanced DOS around Fermi energy level
compared to the pure CuS, meaning a higher carrier concentration
and higher electrical conductivity after decorating with Ag NPs [51].
To gain insight into the interaction between Ag and CuS, the
differential charge density of the pure CuS and CuS@Ag composite
were calculated and the results are shown in Fig. S6. As can be seen,
the pure CuS exhibited a strong charge accumulation that was ob­
served at the S atom side because of the higher electronegativity of S
compared to the Cu atom. After decorating the CuS with Ag NPs, the
charge density surrounding S atoms appeared to significantly de­
crease. This was also found in the calculated Mulliken charge value
of S (Fig. 5b), which varied from −0.5 to −0.3. Meanwhile, the Mul­
liken charge value of Cu changed from 0.3 to 0.2. So, the total Mul­
liken charge value of Cu and S changed from −0.2 to −0.1, meaning an
C. Yue, H. Li, H. Shi et al.
Fig. 5. (a) Partial and total densities of states of the pure CuS and CuS@Ag-2; (b) Calculated Mulliken charge values of the S and Cu atoms for the CuS and CuS/Ag heterostructure;
(c) Illustration of the charge distribution and electron transfer mechanism at the CuS/Ag interface during the discharging process; (d) Illustration of the diffusion and adsorption of
electrolyte within the CuS@Ag electrode.
electron transfer from CuS to Ag. Consequently, a positive charge
region was located at the CuS side, while a negative charge region
appeared at the Ag side. Accordingly, an intrinsic electric field
spontaneously built at the interface between CuS and Ag (Fig. 5c).
Due to the existence of electric field, the incoming electrons during
the discharge process can be accelerated, as a result of the faster
electron transfer from Ag to CuS which enhanced the electrode re­
action kinetics (Fig. 5c). Furthermore, as shown in Fig. 5d, the surface
of CuS nanosheets was positively charged, which favors the easier
adsorption of negatively charged OH−ions and promotes their fast
diffusion within the entire CuS microstructures. Therefore, the above
DFT calculation results not only accounted for the improved elec­
trical conductivity but also revealed the electronic interaction nature
at the interface between CuS and Ag.
Based on these results, the enhanced energy storage properties
for the CuS@Ag electrodes can be attributed to the following factors:
First, the prepared CuS sub-micron flowers are composed of inter­
twined nanosheets, which enabled rich electroactive sites, short ion
diffusion pathways, and buffering spaces. Second, the decoration of
Ag NPs on CuS flowers not only enhances the electrical conductivity
of the composite electrodes but also promotes the electrolyte dif­
fusion through the composite electrodes. Third, the generated elec­
tric field at the CuS/Ag interface can accelerate the charge transfer
between CuS and Ag, which enables fast electrode reaction kinetics.
All these advantageous factors work together to improve the charge
storage properties of the CuS@Ag electrodes.
To further evaluate their practical application for the prepared
CuS@Ag electrodes, a CuS@Ag-2||N-CNTs HSC device was assembled
7
Journal of Alloys and Compounds 885 (2021) 161080
from the battery-type CuS@Ag-2 positive electrode and capacitor-
type N-CNTs (Fig. 6a). CV curves of the assembled HSC device were
produced by voltage scanning at 10 mV s−1 within different voltage
windows ranging from 1.0 V to 1.8 V (Fig. 6b), from which a voltage
of 1.6 V was determined for normal operation. Fig. 6c shows the CV
curves of the HSC device at different scan rates of 5–50 mV s−1
within 1.6 V, which combine the electrochemical behavior of bat­
tery-type CuS and capacitor-type N-CNTs. GCD curves of the HSC
device were measured at 1–20 A g−1, which exhibited nearly sym­
metric shapes (Fig. 6d). The specific capacities were calculated to be
230 (136) C g−1 at 1 (20) A g−1 (Fig. 6e). Furthermore, the HSC device
maintained its initial capacity retention and Coulombic efficiency
values of 94% and 98%, respectively after 5000 cycles at 10 A g−1
(Fig. 6f). Meanwhile, no obvious capacity loss was observed after 300
continuous cycles as the current density was increased from 1 A g−1
to 10 A g−1 and finally at 20 A g−1 and back to 1 A g−1 (Fig. S7). Fig. 6g
displays the Ragone plot of the HSC device, where a high energy
density of 51.1 Wh kg−1 was delivered at a power density of
798 W kg−1, and this remained at 30.2 Wh kg−1 even at a high power
density of 16.0 W kg−1. These energy density values are comparable
to those of other reported two-electrode HSC devices, including CoS-
CNTs||active carbon (AC) (22.1 Wh kg−1 at 183 W kg−1) [52], CuS@
carbon dot-graphene oxide hydrogel (CD-GOH)||reduced graphene
oxide (RGO) (28.0 Wh kg−1 at 700 W kg−1) [53], Ti3C2/CuS||Ti3C2
(15.2 Wh kg−1 at 750 W kg−1) [37], Ni3S4/CuS||AC (43.3 Wh kg−1 at
425 W kg−1) [54], Cu2Se/CuS||AC (42.7 Wh kg−1 at 381 W kg−1) [55],
CuS@carbon quantum dots (CQDs)||AC (44.2 Wh kg−1 at 398 W kg−1)
[56], and CuS/rGO||AC (16.7 Wh kg−1 at 681 W kg−1) [38]. In addition,
C. Yue, H. Li, H. Shi et al.
Fig. 6. (a) Schematic illustration of the HSC device with the battery-type and capacitor-type electrodes; (b) CV curves of the HSC device scanned at 10 mV s−1 within different
voltages; CV (c), GCD (d), and rate capabilities (e), cycling lifetime (f), and Ragone plot (g) of the HSC device. The inset in (g) shows a photograph of orange red LED indicators
lighted by two connected HSC devices.
two connected HSC devices were able to light 18 orange red light-
emitting diodes (inset in Fig. 6g). The above results are a further
indication of the great potential of the prepared CuS@Ag electrodes
for their application in energy storage devices.
4. Conclusions
In summary, Ag NPs decorated CuS sub-micron flowers were
successfully synthesized via a facile solvothermal reaction and
subsequent silver mirror reaction. These CuS@Ag materials were
used as HSC electrodes and demonstrated enhanced specific capa­
cities and cycling lifetimes compared to the pure CuS electrode. This
improved energy storage property was attributed to the decoration
of Ag NPs on CuS flowers, which increased the charge transport and
diffusion kinetics of the CuS active materials, but also accelerated
the electron transfer at the CuS/Ag interface through a generated
interfacial electric field. It was also found that the energy storage
property of the CuS@Ag electrodes can also be optimized by ad­
justing the distribution of Ag NPs on the surface of CuS sub-micron
flowers. Moreover, a two-electrode HSC device containing the
CuS@Ag electrode exhibited high energy and power densities. This
8
Journal of Alloys and Compounds 885 (2021) 161080
reported work may provide some insight into the design of metal
sulfide composite electrodes for their application in HSCs.
CRediT authorship contribution statement
Congmei Yue: Investigation. Hougui Li: Investigation. Hongwei
Shi: Formal analysis. Aifeng Liu: Conceptualization, Methodology,
and Writing – review & editing. Zengcai Guo: Formal analysis.
Jingbo Mu: Formal analysis. Xiaoliang Zhang: Formal analysis.
Xiaoyan Liu: Formal analysis. Hongwei Che: Investigation and
Writing – original draft.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by Natural Science Foundation of Hebei
Province (B2019402082), Science and Technology Project of Hebei
C. Yue, H. Li, H. Shi et al.
Education Department (QN2020214 and ZD2018213), and Scientific
Research Projects funded by Hebei Talent Project Training Funds
(A201803003).
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.jallcom.2021.161080.
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