Applied Surface Science 572 (2022) 151373

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Applied Surface Science

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

Full Length Article

Composite material CCO/Co-Ni-Mn LDH made from sacrifice template

CCO/ ZIF-67 for high-performance supercapacitor
Chen Hao *, Xiaokun Wang , Xingli Wu , Yaning Guo , Linli Zhu , Xiaohong Wang *
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013, China

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

Keywords: Herein, composite material cotton carbon/Co-Ni-Mn LDH (CCO/CNM) combining the cotton carbon and the
Cotton carbon metal organic framework (ZIF-67) material is successfully prepared depending on solvothermal method and
LDH calcination. Simultaneously, the impact of load upon the sacrifice template CCO/ZIF-67 and electrochemical
MOF
performance of CCO/CNM are further studied, and find that the optimized CCO/Co-Ni-Mn LDH-2 (CCO/CNM-2)
Supercapacitor
composite electrode exhibits excellent electrochemical properties. In the case of a current density of 1 A g− 1, the
Composite material
high specific capacitance of CCO/CNM-2 electrode materials can be calculated as 2995.56F g− 1. In addition,
when the current density is set to 10 A g− 1, the capacitance value can still maintain 91.8% of the initial
capacitance after experiencing 5000 cycles of charging and discharging. Moreover, the assembled CCO/CNM-2//
activated carbon (AC) asymmetric supercapacitor shows a superior energy density of 104.98Wh kg− 1 at power
density of 800 kW kg− 1, and 79.3% of the capacitance retention rate at current density of 10 A g− 1 after 10,000
charge–discharge cycles. Finally, three light emitting diodes (LEDs) are successfully lit by connecting with two
CCO/CNM-2//AC asymmetric supercapacitor.

1. Introduction ligands through covalent bonds or ion-covalent bonds.[11–13] Due to

the different coordination modes of the two involved in the assembly, its
In recent years, with the development of the country, the rapid structure presents diversity. MOF is a kind of crystalline multi-pore
growth of the economy and the explosive generation of all kinds of material with high porosity, large specific surface area, structural di­
portable electronic devices, the global energy is being consumed at an versity and adjustability, so it has a very promising application in the
alarming rate. At the same time, the serious problem between energy field of supercapacitors.[14–16] As one of the MOFs materials, ZIF-67
and environmental pollution is also subtly changing people’s under­ not only has the characteristics of ordinary MOFs, but also has high
standing of safe, green and renewable energy storage. With the devel­ thermal stability, high chemical stability, and good absorption and
opment of science and technology, many electronic devices tend to be desorption performance. At the same time, it also has the advantages of
small, portable and integrated. Therefore, people’s requirements for adjustable morphology and pore size, structure and function diversity,
power supply and energy storage unit performance are constantly flexibility of the skeleton structure, large specific surface area and pore
improved.[1–5] As an important part of electronic devices, super­ volume, etc.[17–19] Therefore, if the advantages of ZIF-67 can be used
capacitors store energy through the electrochemical reaction compared in the electrode material of the supercapacitor, it will greatly improve
with conventional batteries.[6,7] Supercapacitors have been widely the contact between the electrolyte and the electrode material, and
studied for their excellent electrochemical properties such as fast further improve the electrochemical performance of the supercapacitor.
charging and discharging speed, high power density and good cycling Layered bimetallic hydroxides (LDH), also known as hydrotalcite
stability. In addition, the electrode material is not only the most basic like compounds, are cationic two-dimensional metallic hydroxides in
part of the supercapacitors, but also plays a key role in its electro­ which the anions act as intercalations.[20,21] Their chemical equations
chemical performance.[8–10] could be written as [M1-x2+Mx3+(OH)2]Ax/nn–⋅mH2O, where M2+ rep­
Metallic organic framework (MOF) is a kind of mixed porous mate­ resents bivalent metal cations (Co2+、Ni2+、Mn2+、Fe2+ and so on),
rial obtained by connecting metal ions or metal clusters with organic M3+ represents the trivalent metal cation (like Fe3+、Al3+、Mn3+、

* Corresponding authors.
E-mail addresses: chhao@ujs.edu.cn (C. Hao), xhwang@ujs.edu.cn (X. Wang).

https://doi.org/10.1016/j.apsusc.2021.151373
Received 3 July 2021; Received in revised form 13 September 2021; Accepted 20 September 2021
Available online 23 September 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
C. Hao et al. Applied Surface Science 572 (2022) 151373

Cr3+、Ga3+ and so on), An- is the interlaminar N-valent anion (like Cl-、 allowed to stand for 12 h. After that, the samples were washed again to
OH–、NO3–、SO42-、organic anion and so on), x represents any value neutral, centrifuged, collected and vacuum dried at 80 ℃ for 24 h. The
between 0.2 and 0.33, and m represents the number of crystalline water black powder was named CCO.
molecules.[22–24] The positive charge is generated by replacing M2+
ions with M3+ ions in the main layer of hydroxide and can be balanced 2.3. Synthesis of CCO/ZIF-67
by anions located in the LDH interlayer space. The advantages of LDH as
an energy-storing electrode material are generally as follows: (1) LDH The CCO/ZIF-67 is synthesized mainly by solvothermal method.
with layered structure and grown as 2D nanocrystals has a large specific Firstly, 15 mg of CCO and 291 mg of cobalt nitrate hexahydrate were
surface area, a large number of active sites and a short diffusion dis­ added to 25 mL of methanol, and the resulting mixed solution was
tance, which is conducive to the rapid transfer of ions from the elec­ sonicated for one hour. At the same time, 328 mg of dimethyl imidazole
trolyte to the surface of the active material; (2) The adjustable metal was weighed and dissolved in 25 mL of methanol. The above two so­
cation composition in the LDH host layer greatly improves the capaci­ lutions were mixed and stirred for 30 min, and aged for 24 h at room
tance properties of multiple reducing states, such as Ni2+, Co2+ and temperature after the completion of the stirring. Finally, after cleaning
Mn2+; (3) LDH exhibits excellent anion exchange performance because the samples collected by centrifugation, they are dried, and the dried
the layer spacing can be adjusted by the insertion of various inorganic samples were named CCO/ZIF-67.
and organic anions.[25–27] A large number of studies related to LDH
have been reported and proved that it has good pseudocapacitance ac­ 2.4. Synthesis of CCO/Co-Ni-Mn LDH
tivity. For example, Wang et al. using ZIF-67-derived strategy on Ni
foam obtained a binder-free organic domestic wastes-derived carbons As above, CCO/Co-Ni-Mn LDH is also synthetized by solvothermal
(OCS) decorated NiCo-LDH nanocages with a specific capacitance of method. Firstly, 40 mg of CCO/ZIF-67 was added to 15 mL of ethanol
1784F g− 1 at a current density of 1 A g− 1. [28] However, the LDH of solution and sonicated for 10 min. Meanwhile, 50 mg of nickel nitrate
most electrode materials, especially nickel based LDH, exhibits poor hexahydrate and 62.5 mg of manganese nitrate hexahydrate were
electrical conductivity and cyclic stability in alkaline electrolytes, which weighed and dissolved in 15 mL of ethanol. The above two solutions
limits their application in energy storage. Therefore, in order to solve were mixed and stirred for 5 min, and then the solution was directly
this problem, the preparation of nanostructures with controlled transferred to a 50 mL reactor and reacted at 80 ℃ for 6 h. After the
morphology to increase the specific surface area of LDH is one of the reaction, the precipitate was collected by centrifugation and vacuum
strategies. For example, the exfoliated/layered LDH is prepared into a dried at 65 ℃ for 12 h, and is named CCO/Co-Ni-Mn LDH-2, which is
single brucite nanosheet, nanowire and nanorods with core shells and abbreviated as CCO/CNM-2. When the mass of CCO/ZIF-67, Ni
porous structures. Another method is to form composites with enhanced (NO3)2⋅6H2O and Mn(NO3)2⋅6H2O is 40 mg, 40 mg and 49.2 mg,
electrical conductivity and mechanical stability by combining LDH with respectively, the sample is named CCO/CNM-1. When the mass of CCO/
various conductive substrates, such as graphene and carbon nanotubes. ZIF-67, Ni(NO3)2⋅6H2O and Mn(NO3)2⋅6H2O is 40 mg, 60 mg and 62.5
[29,30] In addition, biomass carbon materials are often used in high mg, respectively, the complex is named CCO/CNM-3.
performance energy storage systems due to their rate and cycling ability,
improved capacity and excellent physical and chemical properties. It 2.5. Materials characterization
also has high surface volume, relatively thin diffusion distances, struc­
tural flexibility, thermal and chemical stability, rich surface functional The X-ray diffraction (XRD) data were studied on a Bruker D8
groups, wide electrochemical windows, and open pore systems that ADVANCE X-ray diffractometer via the radiation of Cu Kα (λ = 1.5406
improve ion transfer kinetics. Å). In details, the test parameters are as follows: 2θ with the range 10 to
In this work, the precursors CCO/ZIF-67 and CCO/CNM were pre­ 80, the voltage with 40 kV, the current with 30 mA and the scanning rate
pared by a simple solvothermal method. Among them, CCO is mainly with 7◦ min− 1. Fourier transformed infraredspectra (FTIR) was charac­
synthesized by calcination, which provides deposition sites for ZIF-67 terized by Nicolet Nexus 470 spectrometer. In order to know more about
and increases the specific surface area of the composite. CCO/CNM-2 the morphology, scanning electron microscope (SEM, JSM-7800) and
composite exhibits high specific capacitance (2995.56F g− 1 at 1 A high resolution transmission electron microscope (HRTEM, Jeol, JEM-
g− 1) and outstanding cycle stability (91.8% after 5000 cycles). In 2100HR) were put into use. SEM (JSM-7800) with the function of
addition, The assembled CCO/CNM-2//AC ASC device possesses high Energy-Dispersive X-ray spectroscopy was also utilized to know the
energy density (104.98Wh kg− 1) and superior retention rate (79.3% composition and to achieve mapping images. N2 adsorption–desorption
after 10,000 cycles). Therefore, CCO/CNM-2 electrode materials may isotherm data were acquired on a Tristar-3000. The surface areas of
have great application prospects in energy storage. samples were tested by means of the Brunauer-Emmett-Teller (BET). The
pore-size distribution was informed from the adsorption branches. The
2. Experiment section X-ray photoelectron spectrometer (XPS, Versa Probe PHI5000) also
played the role in understanding the samples.
2.1. Material and reagents
2.6. Electrochemical measurements
All chemicals were of analytical grade and put into employ without
purification. In this article, the three-electrode electrochemical test method
(electrolyte solution : 2 M KOH, counter electrode : Pt foil, reference
2.2. Synthesis of CCO electrode : saturated calomel electrode, and working electrode: the
prepared composite material) was adopted to figure out electrochemical
The CCO was synthesized mainly by calcination. Firstly, 2 g cotton properties. We chose to perform all electrochemical tests on the elec­
was soaked in 7 M potassium hydroxide solution, sonicated for half an trochemical workstation (CHI 660C) made in China. The most important
hour, and then taken out and allowed to stand for 24 h. Then the pro­ part was our working electrode, which was made of the composite
cessed cotton was filtered and dried. The dried cotton was calcined: first material, carbon black and polytetrafluoroethylene in a weight ratio of
calcining at 400 ℃ for half an hour, and then increasing the temperature 8: 1: 1, and the composite material was fabricated from our research
to 800 ℃ for one hour. After calcination, the sample was taken out and team. Next, clean nickel foam was immersed in the mixture solution and
cooled to room temperature. Finally, the cleaned sample was immersed removed to an oven at 60 ℃ for 12 h. Finally, a pressure of 10Mpa was
in a 5 M nitric acid solution, stirred magnetically for 1 h and then applied to the nickel foam with the sample, and the working electrode

2
C. Hao et al. Applied Surface Science 572 (2022) 151373

Fig. 1. Illustration of the fabrication process of CCO/CNM-2.

was finished completely. We needed to pick out the working electrode 2.7. Fabrication of the asymmetric supercapacitor
with 2 mg weight on Ni foam and used it for further testing. The specific
test content was as follows: cyclic voltammetry (CV), galvanostatic We selected the prepared working electrode (CCO/CNM-2) to be in
charge–discharge (GCD) and electrochemical impedance spectroscope charge of the positive electrode, the active carbon (AC) to hold the post
(EIS). Calculate the specific capacitance via testing and combining the of the negative electrode, and the PVA-KOH gel severed as semisolid
following formula (1):[31] electrolyte. In addition, the optimal active mass ratio between the pos­
itive electrodes and the negative electrode needs to follow the equation
IΔt
C= (1) (2):
mΔv
In the equation C (F⋅g− 1), Δt (s), I (A), ΔV (V) and m (g) represent the m+ c− ∆v−
= (2)
specific capacitance, the discharge time, the discharge current, the po­ m− c+ ∆v+
tential window and the mass of the electrode materials, severally.

Fig. 2. (a) XRD patterns of ZIF-67, CCO/ZIF-67. (b) XRD pattern of CNM-2, CCO/CNM-1, CCO/CNM-2 and CCO/CNM-3. (c) (d) SEM images of CCO. (e) (f) SEM
images of CCO/ZIF-67. (g) (h) SEM images of CCO/CNM-1. (i) (j) SEM images of CCO/CNM-2. (k) (l) SEM images of CCO/CNM-3.