Vacuum 178 (2020) 109453

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Vacuum
journal homepage: http://www.elsevier.com/locate/vacuum

Fabrication of NiO–ZnO-modified g-C3N4 hierarchical composites for

high-performance supercapacitors
Xiaoyan Chen, Xinzhen Wang *, Fengjun Liu, Xiaojie Song, Hongzhi Cui
School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao, Shandong, 266590, People’s Republic of China

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, NiO and ZnO co-modified g-C3N4 (NiO–ZnO@g-C3N4) hierarchical nanocomposite was synthesized
g-C3N4 using a simple hydrothermal method and used as a high-performance supercapacitor electrode. NiO–ZnO@g-
NiO C3N4 consisted of NiO nanoparticles, ZnO nanoparticles, and g-C3N4 nanosheets, in which the g-C3N4 nanosheets
ZnO
served as the matrix for the attachment of NiO and ZnO nanoparticles. Electrochemical tests showed that
Modification
Supercapacitor
NiO–ZnO@g-C3N4 displayed an improved electrochemical performance compared with pure NiO. The specific
capacitance of NiO–ZnO@g-C3N4 was 726.7 F g 1 at a current density of 0.5 A g 1, which was about 2.1 times
higher than that of pure NiO (346.2 F g 1). The capacitance remained at 78% after 1000 cycles at 5 A g 1,
demonstrating the good cycle performance of NiO–ZnO@g-C3N4. Moreover, the energy density of NiO–ZnO@g-
C3N4 reached 7.91 Wh kg 1 at a power density of 160 W kg 1. The enhanced performance of the NiO–ZnO@g-
C3N4 hierarchical nanocomposite was attributed to its unique structure and composition.

1. Introduction
Supercapacitors (SCs) have attracted increasing attention due to
their high energy and power densities, long cycle life, high charge/
discharge rates, and environmental friendliness [1–3]. Supercapacitors
can be divided into two categories according to their energy storage
mechanism [4,5]. The first category is electric double-layer capacitors
(EDLCs), which store charge by the adsorption/desorption of ions in an
electric double-layer formed at the electrolyte/electrode interface [6].
The other type is pseudocapacitors (PCs), which store energy via a rapid
surface redox reaction [7]. Compared with the former, pseudocapacitors
have drawn much attention due to their higher specific capacitances [8].
The main materials used for supercapacitor electrodes include carbon
materials [9,10], conducting polymers [11,12], transition metal-based
oxides [13,14], hydroxides [15,16], phosphides [17,18], and sulfides
[19,20]. Among these, transition metal-based oxides are attractive due
to their high redox activities, better theoretical capacitive performance,
as well as low cost [21–23]. NiO is commonly used for supercapacitor
electrodes due to its ultra-high theoretical specific capacitance (2583 F
g 1) [24]. However, the real specific capacitance value of NiO electrodes
greatly depends on their morphology, surface area, and pore properties,
which influence its practical use in supercapacitors [25].
In order to improve the electrochemical properties of NiO, many
NiO-based nanocomposites have been designed and fabricated for high-
performance supercapacitors. In previous reports, Wu et al. [26] re­
ported that hollow double-shelled NiO nanospheres was successfully
prepared by the calcination of Ni-based MOF precursor at 400 � C, which
exhibited a good charge storage with specific capacitance of 473 F g 1 at
current density of 0.5 A g 1. Liu et al. [27] synthesized the N-doped
carbon hollow spheres grown with NiO nanosheet (NiO/NCHS) hierar­
chical pore structure via facile chemical bath deposition followed by
calcination, exhibiting a high specific capacitance of 585 F g 1 at 1 A
g 1. Chen et al. [28] reported that NiO@MnO2 core/shell nano­
composites were fabricated by a two-step method, which indicates that
the composite exhibits a specific capacitance of 266.7 F g 1 at 0.5 A g 1
and excellent cycling stability. These previous results showed that
combining NiO and other advantageous materials can significantly in­
creases the capacitance of the resulting composite.
In recent years, carbon based composites have been considered as a
good support material for the research of electrode materials for
supercapacitors [29–32]. Herein, the graphitic carbonitride (g-C3N4) we
choose is a two-dimensional (2D) layered material that has been widely
applied in various areas such as photocatalysis [33,34], electrocatalysis
[35,36], sensing [37,38], and energy storage [39,40]. g-C3N4 is favored
as a supercapacitor due to its high specific surface area, high nitrogen
content, stable structure, low interfacial impedance, and simple

* Corresponding author.
E-mail address: xzwang@sdust.edu.cn (X. Wang).

https://doi.org/10.1016/j.vacuum.2020.109453
Received 13 December 2019; Received in revised form 6 May 2020; Accepted 7 May 2020
Available online 15 May 2020
0042-207X/© 2020 Elsevier Ltd. All rights reserved.
X. Chen et al.
Fig. 1. Schematic diagram illustrating the fabrication of NiO–ZnO@g-
C3N4 composites.
preparation. For example, Vattikuti et al. [41] used a one-step recom­
bination self-assembly method to synthesize C/CuO@g-C3N4 composites
as supercapacitor electrodes with a specific capacitance of 247 F g 1 at
1 A g 1. Wu et al. [42] synthesized Fe3O4 nanorod/g-C3N4 composites
using a hydrothermal method and confirmed that synergistic effect be­
tween Fe3O4 nanorods and g-C3N4 was the reason for their improved
capacitance. NiCo2O4@g-C3N4(C) was synthesized by growing NiCo2O4
on g-C3N4, which resulted in a high specific capacitance of 325.7 F g 1 at
the current density of 1 A g 1 [43]. Kavil et al. demonstrated that the
MnO2– SnO2 @ g-C3N4 was an efficient electrode material for super­
capacitors [44]. The above discussion indicates that g-C3N4 is a good
matrix for the adhesion of metal oxides and provides abundant active
sites for chemical reactions. Furthermore, ZnO was a common semi­
conductor material. It was an alternate material for supercapacitors
owing to its high energy density, high efficiency and low coast, which
can replace high-cost transition metal oxide electrodes [45,46]. To the
best of our knowledge, there has been no report on the use of NiO–ZnO
co-modified with g-C3N4 (NiO–ZnO@g-C3N4) for supercapacitors.
Therefore, we tried to improve the electrochemical performance of NiO
by the surface modification of ZnO and increasing of specific surface
using g-C3N4 matrix.
In this work, a NiO–ZnO@g-C3N4 hierarchical nanocomposite was
prepared by a facile chemical precipitation method using g-C3N4 as the
matrix. The electrochemical performance of as-prepared NiO–ZnO@g-
C3N4 was examined by cyclic voltammetry and alternating current
impedance. Compared with pure NiO, the NiO–ZnO@g-C3N4 composites
displayed higher capacity. The improved electrochemical properties of
NiO–ZnO@g-C3N4 composites were attributed to its unique hierarchical
structure and composition. The NiO–ZnO@g-C3N4 hierarchical structure
has the potential for use as an electrode material for advanced
supercapacitors.
2. Experimental
2.1. Materials
Nickel(II) nitrate hexahydrate (Ni(NO3)2⋅6H2O), hexamethylenetet­
ramine (HMTA) and sulfuric acid (98%) were obtained from Chengdu
Cologne Chemicals Co., Ltd. Acetoxyzinc dihydrate (C4H6O4Zn⋅2H2O)
was purchased from Sinopharm Chemical Reagent Co., Ltd. Melamine
was purchased from Tianjin Dingsheng Chemical Co., Ltd. Ethanol
(99.7%) and nitric acid (65–68%) were purchased from Yantai Yuan­
dong Chemical Co., Ltd. and Shanghai Titan Scientific Co., Ltd.,
respectively. All chemical reagents used in this study were analytical
grade and used as received without further purification. All aqueous
solutions were prepared with deionized water.
2
Vacuum 178 (2020) 109453
2.2. Preparation of g-C3N4
g-C3N4 nanosheets were prepared using melamine as the precursor.
Melamine (3 g) was annealed in a tube furnace at 550 � C for 5 h with a
heating rate of 2 � C min 1 under N2 atmosphere to obtain g-C3N4. Then,
the obtained bulk g-C3N4 was added to a mixed solution of sulfuric acid
(12 ml), nitric acid (12 ml), and deionized water (30 ml) under stirring.
After stirring for 12 h, a black precipitate was obtained through
centrifugation and was successively washed with ethanol and deionized
water 5 times. Finally, g-C3N4 nanosheets were prepared after drying the
precipitate at 60 � C in a drying oven for 24 h.
2.3. Preparation of NiO–ZnO @ g-C3N4
NiO–ZnO@g-C3N4 hierarchical nanocomposite was prepared by a
facile hydrothermal method combined with calcination as shown in
Fig. 1 g-C3N4 nanosheets (35 mg) was dispersed in 60 ml of a deionized
water and ethanol solution (Vwater: Vethanol ¼ 2:1). After ultrasonication
for 30 min, 1.5 mmol Ni(NO3)2⋅6H2O, 1.5 mmol C4H6O4Zn⋅2H2O, and 6
mmol HMTA were added to the above solution and stirred until dis­
solved. Then, the mixture was transferred to a Teflon-lined stainless-
steel autoclave (100 ml). After being heated for 4 h at 90 � C, the products
were centrifuged and washed several times by deionized water and
ethanol, and then dried 12 h at 60 � C. Finally, NiO–ZnO@g-C3N4 was
obtained after calcining at 300 � C for 2 h with a heating rate of 2 � C
min 1 in air. For comparison, NiO, ZnO, NiO–ZnO, NiO@g-C3N4, and
ZnO@g-C3N4 were prepared via the same method.
2.4. Characterizations
The crystal structures of synthesized samples were analyzed using X-
ray diffraction (XRD) in the 2θ range of 10� -100� at a scan of 4� min 1
using monochromatic Cu Kα radiation (λ ¼ 0.154 nm, V ¼ 40 kV, I ¼ 50
mA, Rigaku D/Max2500PC, Japan). The surface characteristics of sam­
ples were examined by a high-resolution field emission scanning elec­
tron microscope (FESEM, FEI Nova Nanosem 450, USA) equipped with
energy-dispersive X-ray spectroscopy (EDS). High-resolution trans­
mission electron microscopy (HRTEM, JEOL JEM 2100F) and field-
emission scanning electron microscopy (HITACHI-4800) were used to
characterize the morphology and inner structure of samples. The
chemical states of elements in the samples were evaluated using X-ray
photoelectron spectrometry (XPS, Thermo ESCALAB 250XL, USA). The
specific surface areas of samples were characterized by N2 adsorption-
desorption (JW-BK 122W, JWGB, China) at 77 K. The molar ratio of g-
C3N4, NiO, and ZnO was confirmed with an Inductively Coupled Plasma
Optical Emission Spectrometer (ICP-OES, Agilent 725, Australia).
2.5. Electrochemical measurements
Electrodes were prepared by mixing the active material, conductive
carbon black, and polyvinylidene fluoride (PVDF) in a weight ratio of
7:2:1 using N-methyl-2-pyrrolidinone (1 ml) and ethanol (0.1 ml) as the
dispersant. After stirring for 3 h, the mixed slurry was deposited on Ni
foam (with a size of 1 cm � 1 cm), in which the Ni foam was previously
washed with ethanol for 10 min and dried at 80 � C for 12 h in vacuum.
Electrodes were obtained by pressing the Ni-coated foam with active
materials under a pressure of 10 MPa. The electrochemical properties
were measured using a three-electrode system, in which Hg/HgO, Pt,
and the electrodes coated with the active material were used as the
reference, counter, and working electrodes, respectively. Cyclic vol­
tammetry (CV) curves were obtained over a voltage range of 0–0.65 V
scan rates of 5, 10, 15, 20, 25, 50, and 100 mV s 1. The galvanostatic
charge-discharge (GCD) curves were recorded over a voltage range of
0–0.45 V at scan rates of 0.5, 1, 2, 5, 10, and 20 A g 1. Electrochemical
impedance spectroscopy (EIS) was performed over a frequency range of
10 2 - 105 Hz. A 6 M KOH solution was used as the electrolyte.
X. Chen et al.
Fig. 2. XRD patterns of NiO–ZnO@g-C3N4.
3. Result and discussions
3.1. Characterization of NiO–ZnO @ g-C3N4 composite
The crystal and phase structures of NiO–ZnO@g-C3N4 were
confirmed by XRD. As shown in Fig. 2, the peaks located at 27.9� , 37.5� ,
and 69.6� corresponded to the (100), (200), and (211) crystal faces of g-
C3N4 ((JCPDS No. 50–1512)). The peaks at 2θ values of 37.2� , 43.3� ,
62.9� , 75.4� , 79.5� , and 95.1� were indexed to the (101), (012), (110),
(113), (006), and (024) planes of NiO (JCPDS No. 44–1159). The peaks
at 2θ values of 31.8� , 34.4� , 36.3� , 47.5� , 56.6� , 62.9� , 67.9� , 69.1� ,
89.6� , and 98.1� were matched to the (100), (002), (101), (102), (110),
(103), (112), (201), (203), and (114) planes of ZnO (JCPDS No.
36–1451). No other diffraction peaks were observed, indicating the high
purity of NiO–ZnO@g-C3N4. After adding g-C3N4, the diffraction peaks
Fig. 3. SEM images of pure NiO (a), and NiO–ZnO@g-C3N4 (b,c).
Fig. 4. TEM image and HRTEM image (a, b), and the EDS elemental mapping (c) of as prepared NiO–ZnO@g-C3N4 composite.
3
Vacuum 178 (2020) 109453
of NiO–ZnO showed no major changes, indicating that g-C3N4 did not
affect the crystal structure of NiO–ZnO (Fig. S1). The XRD pattern of
NiO–ZnO@g-C3N4 revealed that the as-prepared composites were
consist of NiO, ZnO, and g-C3N4.
The morphology of as-prepared samples was observed by SEM as
shown in Fig. 3. The as-prepared pure NiO has nanoparticles
morphology (Fig. 3a). The two-dimensional structure of g-C3N4 (Fig. S2)
provides a large number of nucleation sites for the growth of NiO–ZnO
materials. After the modification of NiO and ZnO, NiO–ZnO@g-C3N4
composites curled and formed a cluster structure (Fig. 3b and c). The
SEM images of ZnO, NiO–ZnO, NiO@g-C3N4, and ZnO@g-C3N4 are also
provided for comparison (Fig. S2). Compared to pure NiO, the as-
prepared NiO–ZnO@g-C3N4 composites have a hierarchical
morphology with loose structure, which is helpful to increase the spe­
cific surface area and enhance their electrochemical properties.
To further confirm the microstructures and composition of as-
prepared NiO–ZnO@g-C3N4, TEM and HRTEM were used to analyze
the samples (Fig. 4). The black and white contrast in the low-
magnification TEM image reveals that the NiO–ZnO@g-C3N4 compos­
ite consisted of nanosheets and nanoparticles (Fig. 4a), which agrees
with the SEM results. The lattice fringe spacings of 0.21 nm and 0.26 nm
correspond to NiO (200) and ZnO (002), respectively [47,48]. In addi­
tion, the interface between g-C3N4 and NiO–ZnO can be clearly observed
[49], and no lattice fringes appeared in the HRTEM images of g-C3N4
nanosheets due to its low crystallinity (Fig. 4b). EDS elemental maps
(Fig. 4c) confirmed that NiO–ZnO@g-C3N4 consisted of C, N, Ni, Zn, and
O. The molar ratio of g-C3N4, NiO, and ZnO was 1:4:4, determining by
ICP analysis. The XRD, SEM, and TEM results confirmed that the
NiO–ZnO@g-C3N4 hierarchical structures were prepared successfully.
XPS analysis was carried out to further investigate the surface
chemical states and chemical bonding states of each element of
NiO–ZnO@g-C3N4 as shown in Fig. 5. The excitation source was micro-
focused Al K-Alpha (hv ¼ 1486.6 eV) and a monochromator was used,
X. Chen et al. Vacuum 178 (2020) 109453

Fig. 5. XPS spectra of NiO–ZnO@g-C3N4 composite: (a) survey spectrum, (b) C 1s, (c) N 1s, (d) Ni 2p, (e) Zn 2p, (f) O 1s.

operated at a power of 150 W. The spectra were acquired in parallel
mode and used Ag 3d5/2 (FWHM ¼ 0.5 eV) as the scanning parameter.
The size of the analyzed sample area was 50 � 20 mm. The NiO–ZnO@g-
C3N4 sample was not sputter-cleaned before the XPS analysis in order to
avoid the bespattering effects of the Ar ion radiation. All XPS spectra
referenced to the binding energy of the C1s adventitious carbon peak
from the surface contamination layer at 284.8 eV. All XPS spectra
referenced to the binding energy of the C1s adventitious carbon peak
from the surface contamination layer at 284.8 eV [50]. Fig. 5a repre­
sents the survey spectra and indicates that C, N, Ni, Zn, and O elements
are all detected without any other impurities. The C 1s spectra (Fig. 5b)
is divided into three peaks, the binding energy at 284.7 eV is ascribed to
the sp2 hybridized C– – C bond in the graphite carbon [51]. For g-C3N4,
the peak at 288.1 eV is assigned to the sp2 hybridized carbon bounding
to nitrogen in the C–N–C coordination, and the other peak at 285.7 eV is
corresponded to the C–N bond [52–54]. The N 1s spectrum (Fig. 5c) can
be divided into three peaks at 398.6, 399.9, and 404.6 eV, which are
corresponded to the C– – N–C and N-(C)3 groups, and charging effects
and surface contaminations, respectively [55–57]. As shown in Fig. 5d,
two spin-orbit doublets located at around 853.7 and 872.7 eV are
allotted to the Ni 2p3/2 and Ni 2p1/2, suggesting the Ni2þ in the pre­
pared NiO [58–60]. Moreover, two satellite peaks located at the binding

Fig. 6. (a) CV and (b) GCD curves of NiO–ZnO@g-C3N4; (c) specific capacitance and (d) cycling performance of NiO and NiO–ZnO@g-C3N4

4
X. Chen et al. Vacuum 178 (2020) 109453

Table 1 mass of the active material (g).

Comparison of the specific capacitance with other Ni-based electrodes. Fig. 6a shows the CV curves of as-prepared NiO–ZnO@g-C3N4 at test
Electrode Structure Specific Capacitance/(F Electrolyte Ref. scanning rates of 5, 10, 15, 20, 25, 50, and 100 mV s 1. Two current
g 1) peaks located near 2.5 V and 3.5 V were observed during the cathodic
NiO nanospheres 473 3 M KOH [70] and anodic process, suggesting NiO–ZnO@g-C3N4 possessed faradaic
NiO/MCNs 406 6 M KOH [71] pseudocapacitance. The complete actual response is as follows [68,69]:
NiO/Co3O4 405 6 M KOH [72]
PPyNF/NiOx 657 6 M KOH [73] NiO þ OH ↔ NiOOH þ e (3)
NiO/C 406 6 M KOH [74]
NiO/ZnO hollow 497 3 M KOH [75] ZnO þ K þ þ e ↔ ZnOK (4)
spheres
1 1
NiO–ZnO@g-C3N4 726.7 6 M KOH This As the scan rate increased from 5 mV s to 100 mV s , the current
work of NiO–ZnO@g-C3N4 also increased, demonstrating its high-speed
charge-discharge ability. In addition, the area under the CV curve of
NiO–ZnO@g-C3N4 (Fig. 6a) was larger than that of pure NiO, g-C3N4 and
energy of 860.9 and 879.0 eV further confirm the formation of NiO
NiO–ZnO (Fig. S3), indicating that NiO–ZnO@g-C3N4 had a higher
crystal phase [61]. The Zn 2p spectrum is fitted in two peaks as shown in
specific capacitance. Fig. 6b shows the GCD curves of NiO–ZnO@g-C3N4
Fig. 5e. The two strong peaks at 1021.4 and 1044.6 eV are ascribed to Zn
at current densities ranging from 0.5 A g 1 to 5 A g 1. Two well-defined
2p3/2 and Zn 2p1/2 of ZnO, indicating the presence of Zn with Zn2þ
plateaus were observed in the charge-discharge curves, which agree
chemical oxidation state in the sample [62,63]. As shown in Fig. 5f, the
with the CV curves. The specific capacitances of NiO–ZnO@g-C3N4 were
O 1s signal is divided into three peaks, including two strong peaks with
calculated to be 726.7, 702.2, 648.9, 555.6, and 466.7 F g 1 at current
binding energies of 529.2 eV and 530.9 eV, confirming the presence of
densities of 0.5, 1, 2, 5, and 10 A g 1, which are much higher than those
Ni–O and Zn–O bonds of NiO and ZnO, respectively [64]. The other peak
of pure NiO at identical current densities (346.2 F g 1, 327.3 F
at 531.9 eV indicates that the material contained many defect sites with
g 1,309.1 F g 1, and 272.1 F g 1) (Fig. 6c). In addition, the specific
low oxygen coordination [65]. The XPS analysis further confirmed the
capacitance of NiO–ZnO@g-C3N4 was also higher than that of
formation of NiO–ZnO@g-C3N4. It is worth noting that the binding en­
previously-reported NiO and NiO based materials. As shown in Table 1,
ergy of C1s may vary in the range of 1.44 eV due to all XPS spectra
the as-prepared NiO–ZnO@g-C3N4 displayed higher specific capacitance
referenced to the adventitious carbon peak from the surface contami­
(726.7 F g 1) than that of NiO nanospheres (473 F g 1), NiO/MCNs
nation layer at 284.8 eV, so it is necessary to choose a more reliable
composites (406 F g 1), NiO/Co3O4 (405 F g 1), PPyNF/NiOx (657 F
reference method to calibrate the peak position in XPS measurement
g 1), NiO/C (406 F g 1), and NiO/ZnO hollow spheres (497 F g 1). The
[66].
enhanced specific capacitance of NiO–ZnO@g-C3N4 may be attributed
to their unique layered structure and composition, which provide large
3.2. Electrochemical performance of NiO–ZnO@g-C3N4 composites
active surface area and good electrical conductivity for chemical
reaction.
The electrochemical properties of as-prepared NiO–ZnO@g-C3N4
The long-term work stability of as-prepared NiO–ZnO@g-C3N4 was
were tested via CV, GCD, and EIS methods using a three-electrode sys­
also investigated at a current density of 0.5 A g 1. As shown in Fig. 6d,
tem in a 6 M KOH aqueous electrolyte. The specific capacitance was
the capacitance of NiO–ZnO@g-C3N4 remained at about 78%, which
calculated from CV and GCD according to the following formula [67]:
was much higher than that of pure NiO (65%) demonstrating enhanced
Z �
cycling stability. In fact, the capacitance of NiO–ZnO@g-C3N4 decreased
CCV ¼ iðVÞdV 2ΔVvm (1)
slowly after working for 1000 cycles, which maybe ascribe to the
collapse of hierarchical structure. The electrochemistry test results
CGCD ¼ iΔt=ΔVm (2) confirmed that the NiO–ZnO@g-C3N4 composites displayed improved
electrochemistry performance compared to pure NiO including specific
where CCV and CGCD are the specific capacitance (F g 1) of the active capacity and work stability.
R
material electrode, iðVÞdV is the integrated area of the CV curve (m2), The Ragone plot for the power and energy densities of NiO–ZnO@g-
v is the scan rate (mV s 1), i is the constant current (A), Δt is the C3N4, NiO–ZnO, and g-C3N4 composites is shown in Fig. S4. The energy
discharge time (s), ΔV is the total voltage difference (V), and m is the density (E, Wh kg 1) and power density (P, W kg 1) can be calculated as
follows [76]:
�
E ¼ 1 7:2CV 2 (5)

P ¼ 3600E=Δt (6)

where C is the specific capacitance, V is the operating voltage, and Δt is

the discharging time. The energy density of as-prepared NiO–ZnO@g-
C3N4 composite electrodes was 7.91 Wh kg 1 at a power density of 160
W kg 1, which is much higher than that of NiO–ZnO (2.93 Wh kg 1) and
pure g-C3N4 (1.60 Wh kg 1) electrodes in at the same power density. As
the power density increased from 160 W kg 1 to 560 W kg 1, the energy
density of the as-prepared NiO–ZnO@g-C3N4 composite electrode
remained at 4.79 Wh kg 1, suggesting its excellent energy storage
performance.

3.3. Electrochemical mechanism of NiO–ZnO@g-C3N4 hierarchical

composites
Fig. 7. N2 adsorption-desorption isotherms and BJH pore size distribution
curves (inset) of NiO and NiO–ZnO@g-C3N4. From the above discussion, NiO–ZnO@g-C3N4 hierarchical

5
X. Chen et al.
Fig. 8. (a) EIS curves and enlarged (b) high-frequency curves of NiO and NiO–ZnO@g-C3N4 composites.
composite displayed advanced electrochemical performance compared
to pure NiO. In order to investigate the mechanism of the improved
electrochemical properties, the specific surface area and EIS of as-
prepared pure NiO and NiO–ZnO@g-C3N4 hierarchical composites
were carried out. First, the high specific surface area of NiO–ZnO@g-
C3N4 hierarchical composites was beneficial to their specific capacities.
The CV results revealed that the as-prepared NiO–ZnO@g-C3N4 com­
posites had Faradaic pesudocapacitance properties. The charge-
discharge realized through the redox reaction that occurred on the
surface of active materials. Therefore, the high specific capacity can be
obtained through enlarging the specific surface area of the active ma­
terials. The N2 adsorption-desorption isotherms of pure NiO and g-
C3N4@NiO–ZnO are given in Fig. 7.
The g-C3N4@NiO–ZnO sample exhibited a type IV physisorption
curve with an H3-type hysteresis loop, which is the characteristic feature
for mesoporous materials according to IUPAC. The BET surface area
calculated from the isotherm was 168.1 m2 g 1, which was much higher
than that of pure NiO (18.3 m2 g 1). The high BET surface area of
NiO–ZnO@g-C3N4 was attributed to the interlacing of the crimped
lamellar g-C3N4. In order to reveal the influence of specific surface area
on the electrochemistry properties of NiO–ZnO@g-C3N4, NiO and ZnO
nanoparticles co-modified g-C3N4 blocky structure was prepared for
comparison (blocky NiO–ZnO@g-C3N4) using the blocky g-C3N4 as
matrix. As shown in Fig. S5, the NiO–ZnO@g-C3N4 blocky structure has
morphology of agglomerate. The specific surface area of NiO–ZnO@g-
C3N4 blocky structure was 20.4 m2 g 1 (Fig. S6), which was much lower
than that of NiO–ZnO@g-C3N4 hierarchical structures (168.1 m2 g 1).
The specific capacities of the NiO–ZnO@g-C3N4 blocky structure were
418.1, 334.8, 280.6, 201.5, 104.2 F g 1 at the current densities of 0.5, 1,
2, 5, and 10 A g 1, which were much lower than those of as-prepared
NiO–ZnO@g-C3N4 hierarchical structures (Fig. S7). From the above
discussion, the NiO–ZnO@g-C3N4 hierarchical structures and blocky
structures have the same composition and different microstructure.
Therefore, the improved electrochemistry of NiO–ZnO@g-C3N4 hierar­
chical structures maybe ascribed to their high specific surface area. The
high surface area and pore volume possessed by NiO–ZnO@g-C3N4
composite can facilitate electrolyte transport and ion diffusion for
improving the electrochemical performance.
Second, the improved electronic conductivity of NiO–ZnO@g-C3N4
nanocomposites promoted the electron transfer and ion diffusion for
enhanced electrochemical performance. Fig. 8a shows the EIS results of
as-prepared pure NiO and NiO–ZnO@g-C3N4 composites with a fre­
quency range of 100 kHz to 0.1 Hz. The solution resistance (Rs) was
calculated from the real-axis intercept [77]. It is apparent from the inset
that NiO–ZnO@g-C3N4 has a lower solution resistance. The slope of the
45� portion of the intermediate frequency curve is called the Warburg
resistance (Zw) because of the dependence of the frequency of ions in the
electrolyte that diffuse/transmit to the electrode surface [78]. The slope
of NiO–ZnO@g-C3N4 is larger than that of pure NiO, indicating that it
has improved capacitive behavior. In addition, the radius of the Nyquist
6
Vacuum 178 (2020) 109453
semicircle indicates the charge transfer resistance (Rct) of the material
electrode. Fig. 8b indicates that the NiO–ZnO@g-C3N4 electrode has a
smaller radius than pure NiO in the high-frequency region, suggesting
high electron conductivity and rapid charge transfer [79]. The enhanced
electron conductivity of NiO–ZnO@g-C3N4 is ascribed to the surface
polarity and the lone pair electrons of g-C3N4 [39]. To sum up, the
NiO–ZnO@g-C3N4 composites have higher specific surface area and
better electronic conductivity than pure NiO, which increases active
sites of reaction and promotes the transformation of electrons, resulting
in improved electrochemistry properties.
4. Conclusions
NiO–ZnO@g-C3N4 layered structure was synthesized via a simple
hydrothermal/calcination method. Compared with pure NiO, NiO–Z­
nO@g-C3N4 composite material shows a higher specific capacitance,
better long-term cycle stability and higher energy density, which is due
to the large specific surface area and good conductivity by the
compositing with g-C3N4 and ZnO. This work proposes that the
improved electrochemical properties can be obtained using the hybrid
materials that consists of g-C3N4 and transition metal oxides.
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.
Acknowledgements
This work was supported by Distinguished Taishan Scholars in
Climbing Plan (No. tspd20161006), Shandong Provincial Natural Sci­
ence Foundation, (No. ZR2019MEM049), and the Natural Science
Foundation of China (No.51772176, 51971121).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.vacuum.2020.109453.
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