Chemical Engineering Journal 458 (2023) 141434

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

A novel COF/MXene film electrode with fast redox kinetics for

high-performance flexible supercapacitor
Ning An a, *, Zhen Guo a, Chao Guo a, Maoqing Wei a, Daming Sun a, Yuanyuan He b, Wenli Li a,
Lei Zhou a, Zhongai Hu b, Xiuyan Dong a, *
a
College of Chemistry and Chemical Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China
b
Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry
and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

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

Keywords: Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymer due to their well-
Supeicapacitor defined channels, highly accessible surface areas and tunable active sites, showing great application potential
COFs in the field of energy storage. However, their low inherent conductivity and poor accessibility (difficult to
Mxene
dissolve or melt) have largely limited their electrochemical performances and practical applications. Here, a
Electrostatic self-assembly
cation-driven self-assembly process was used to prepare flexible carbonyl containing COF/MXene composite film
Flexible electrode
Electrochemical kinetics electrode (CMFs). The uniform intercalation of porous COFs in layered MXene was realized by electrostatic
attraction between negatively charged 2D MXene nanosheets and the protonated DAAQ-COFs. Porous COFs
tightly contact with MXene and effectively alleviate the self-restacking of MXene nanosheets. In addition, under
the synergistic effect, the ordered one-dimensional pore structure of COFs and excellent intrinsic conductivity of
MXene can greatly enhances the electron transfer and ion migration rates and further improves the reaction
kinetics for flexible composite electrodes. In the three-electrode system, the integrated CMFs film electrode
delivers excellent electrochemical performances (the capacitance of 390 F g− 1 at 0.5 A/g), excellent kinetic
energy storage characteristics (capacitive contribution can be up to 96.7 % at 50 mV/s) and superb mechanical
strength (repeated bending 100 times). By assembling into all-solid-state flexible supercapacitor, CMFs//CCMP
asymmetric supercapacitors (ASC) achieves the maximum energy density of 27.5 Wh kg− 1 (at a power density of
350 W kg− 1), maximum power density of 7000 W kg− 1 (at an energy density of 19.7 Wh kg− 1) and the ultrahigh
capacitance retention of 88.9 % after 20,000 charging-discharging long cycles, suggesting great potentials for the
applications in future flexible and wearable devices.

1. Introduction developing novel electrode materials with high performance is of vital

importance. In addition, flexible supercapacitor electrode materials also
The increasing demand for portable and flexible electronics such as need to be constructed more supple and robust mechanical strength[6].
roll-up displays, bendable transistors, electronic papers, and wearable Therefore, the systematic development of conductive, porous and redox-
sensing devices have inspired the development of flexible energy storage active flexible electrode materials plays an important and positive role
devices. Among various energy storage devices, supercapacitors, known in the construction of high-performance flexible supercapacitors[7].
for ultrafast charge–discharge ability and long cycling life, are viewed as Covalent organic frameworks (COFs) are a class of crystalline porous
an ideal power source for next-generation electronics[1–4]. Unfortu­ materials comprised of periodic organic building blocks held together by
nately, the traditional supercapacitor has a rigid bulky or planar struc­ covalent bonds. COFs showcase unique physicochemical features, and
ture and there is little possibility of achieving future applications[5]. To thus featuring huge potentials for the construction of promising super­
transcend the limitations, various of supercapacitors with more func­ capacitors devices[8–13]. First of all, various redox-active moieties can
tions and novel features have been designed to extend their applications. be accurately anchored to specific sites on the skeleton with the pre­
To obtain higher energy densities and energy conversion efficiency, designed environment and the density of active sites can be facilely

* Corresponding authors.
E-mail addresses: [email protected] (N. An), [email protected] (X. Dong).

https://doi.org/10.1016/j.cej.2023.141434
Received 3 August 2022; Received in revised form 29 October 2022; Accepted 10 January 2023
Available online 13 January 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
N. An et al. Chemical Engineering Journal 458 (2023) 141434

controlled. The judicious installations of redox moieties on COFs pro­ was purchased from Aladdin Industrial Corporation. Ti3AlC2 was pur­
vides great opportunities for improving the storage capacity of COFs. chased from Ningbo jin lei nano Mstar Technology Co. ltd and. LiF and
Secondly, well-defined open channels of COFs provide high surface area Polyvinyl Alcohol were purchased from J&K-Chemical Co., ltd. Beijing,
and regularly porous structure with large pore volume[14,15]. It facil­ China. N, N-Dimethylformamide (DMF) and dioxane was purchased
itates adsorption of electrolyte ions and enable fast transport of elec­ from Tianjin Damao Chemical Reagent (Tianjin, China). All the exper­
trolyte ions, and thus increase the rate capability of the electrodes. iments were carried out using deionized (DI) water and analytical
Thirdly, the redox process of organic active groups only involves the reagents.
reversible transformation of chemical bonds, and it is not easy to lead to
structural collapse and intermediate dissolution in the reaction process. 2.2. Synthesis of DAAQ-COFs materials
Hence the rigid framework structures can be maintained under harsh
conditions and exhibit superior electrochemical stability in various 1,3,5-triformylphloroglucinol (Tp, 10 mg, 0.048 mmol) was mixed
electrolytes. However, the inherent low conductivity of traditional COFs with 2,6-diaminoanthraquinone (DAAQ, 17 mg, 0.071 mmol) in a
impedes charge transfer in the frame, thus limiting their electrochemical mortar-pestle. After the mixture was uniformly grinded for 3 min, few
performance[16]. In addition, COFs are generally produced in the form drops of 3 M Ac (OH) (~5–10 μL) was added. Continue to grind the
of insoluble and unprocessable microcrystalline powders, which pre­ mixture until the powder turns orange. Collect the above orange solids
vents them from being solution- or melt-processed like conventional and put them into the glass pressure tube (18 cm of length, 25 mL). Add
polymers[14]. More importantly, COFs tend to exhibit rigid nano­ the mesitylene/dioxane = 1/1 (v/v) solution (3 mL) and of 3 M Ac(OH)
structures. The development of freestanding COFs films by self-assembly (0.6 mL) to the pressure tube. The tube was sealed off and then heated at
[17], interfacial polymerization[18] and templating methods[19] 120 ◦ C for 72 h. The red precipitate was collected by filtration and rinsed
generally exhibits weak mechanical properties, greatly limiting their with N, N-dimethylformylamide (DMF), tetrahydrofuran (THF) and
application in flexible devices[20,21]. ethanol in turn. The powders were collected and dried at 60 ◦ C for 24 h.
Transition metal carbides, nitrides, and carbonitrides, also known as
MXenes, is an emerging family of 2D layered structures, particularly 2.3. Synthesis of monolayer Ti3C2Tx MXene solution and Ti3C2Tx MXene
suitable as promising platforms or building blocks for fabricating films film
with designed microstructures[22,23]. More concretely, (i) The metallic
conductivity endow MXenes the ability to serve as the superexcellent 0.8 g of LiF was added to 10 mL of 9 M HCl aqueous solution, fol­
substrates of active materials (Si, polymers, metal oxides/sulfides, etc.) lowed by slow addition of 0.5 g of Ti3AlC2 in ice bath. After stirred at
due to the rapid kinetics of electron transfer[24–29]; (ii) The surface of 35 ◦ C for 24 h, the resultant mixture was centrifuged and washed with
MXenes obtained by etching of MAX phase has negative charge and deionized water until pH value of supernatant reached 7. The precipitate
excellent hydrophilicity, which can be readily dispersed in water and was added to 100 mL of deionized water and was sonicated in ice bath
organic solvents and processed into MXene films by filtration and layer for 1 h, followed by centrifugation at 3,500 r.p.m for 1 h, the resultant
by layer assembly[5]; (iii) Compared to traditional bulk electrode ma­ dark supernatant was collected to obtain the solution of Monolayer
terials, MXene films fabricated in well-designed strategies show excel­ Ti3C2Tx MXene. The Ti3C2Tx MXene film is formed by filtering 15 mL of
lent mechanical properties and can be used directly after their monolayer Ti3C2Tx MXene solution through cellulose membrane with a
fabrication without sacrificing electroconductibility[30]. All of these pore size of 0.22 μm, and the Ti3C2Tx MXene film is freeze-dried in a
features make them preferable to flexible and wearable electronics vacuum drying machine.
[31,32]. Therefore, we anticipate that combining the uniform pore
channels of 2D COFs with the high conductivity of MXene in a promising 2.4. Synthesis of CMFs film
material is an effective way to achieve high performance COFs-based
flexible energy storage device. AQ-COFs/Ti3C2Tx nanocomposites were prepared by electrostatic
Here, we selected anthraquinone-based COFs (DAAQ-COFs) as active self-assembly. AQ-COFs of different masses were added to 0.03 M
material and layered Ti3C2Tx MXene as flexible conductive substrate to aqueous hydrochloric acid solution, and sonicated for 0.5 h to obtain
construct DAAQ-COFs/MXene flexible film electrode (CMFs). CMFs was protonated DAAQ-COFs suspension. Measure 10 mL (15 mg) of the
prepared by cationic driven electrostatic self-assembly method, which monolayer MXene dispersion and slowly drop it into the DAAQ-COFs
overcomes the technical difficulty of processing powder COFs. Besides, aqueous dispersion, stir for 2 h to complete the electrostatic self-
the resultant CMFs film efficiently alleviates the self-restacking of assembly, and then dry it under vacuum for 12 h to obtain an easily
MXene. Benefits from abundant pore structure and 3D conductive peelable CMFs composite membrane.
network, the electrode achieves rapid mass transfer and efficient utili­
zation of active sites. Electrochemical tests show that the specific 2.5. Synthesis of positive CCMP
capacitance of the flexible electrode is up to 390F g− 1 at 0.5 A/g (almost
12 times that of pure COFs). Compared with 1 A/g, the capacitance Conjugated microporous polymer aerogel sheets (CMP) and KOH (1/
retention rate at 10 A/g is as high as 81.3 %, indicating the fast elec­ 4, mass ratio) were added to the aqueous ethanol solution. After
trochemical kinetic characteristics. The flexible film has good mechan­ standing for 24 h, it was taken out, dried under vacuum at 70 ◦ C for 24 h,
ical properties and can be directly used as electrode for all-solid flexible and then quenched at 700 ◦ C for 2 h under an argon atmosphere. The
supercapacitor without conducting additives or binders. The super­ products were treated in 2.0 M HCl, acetone, water, and ethanol,
capacitor achieves a high energy density of 27.5 Wh kg− 1 at a power respectively, to remove excess KOH and impurities. The obtained sample
density of 350 W kg− 1, and excellent cycle stability of 88.9 % after was dried at 70 ◦ C for 24 h and named as conjugated microporous
20,000 cycles, indicating its great application potential. polymer carbon aerogel (CCMP).

2. Experimental section 2.6. Synthesis of polyvinyl alcohol (PVA) gel electrolyte

2.1. Materials Add 2 g of polyvinyl alcohol to 20 mL of 1 M H2SO4 aqueous solution,

heat and stir to 90 ◦ C until it is completely dissolved, keep stirring for 20
Sulfuric acid (98 %, H2SO4), 2, 6 Diaminoanthraquinone (97 %, min, and then put it into a glass container and cool to room temperature.
DAAQ) were obtained from Alfa Aesar Chemicals Co. ltd., Shanghai, The 1 M H2SO4-PVA hydrogel electrolyte was obtained by placing it in
China. 1,3,5-triformylphloroglucinol (Tp) and 1,3,5-Trimethylbenzene the refrigerator for three cycles of freezing and thawing.

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 1. (a) Schematic of CMFs preparation. (b) Calculated the differential charge density of the interface between DAAQ-COFs and Ti3C2Tx, the turquoise and yellow
regions indicate depletion and accumulation of electrons, respectively. (c) Density of state of DAAQ-COFs/Ti3C2Tx heterostructure, Ti3C2Tx and DAAQ-COFs. (d)
Planar-averaged electrostatic potential.

2.7. Analysis and characterization electrolyte. A series of electrochemical measuring techniques including
cyclic voltammogram (CV) and galvanostatic charge–discharge (GCD),
The morphologies of products were observed by using a field- which were performed on a CHI 660E electrochemical workstation
emission scanning electron microscope (FESEM; ULTRA plus, Ger­ (Shanghai CH Instruments, China). Both MXene and CMFs were tested
many) and Transmission electron microscopy (FEI Tecna G2 F20). directly using thin films. In order to facilitate the test, the film was
UV–vis-NIR spectra were recorded in transmission geometry using a UV- mechanically pressed on the carbon paper, and the electrode was
3600 Plus spectrometer equipped with a 150 mm In GaAs integrating clamped with a platinum electrode clip for testing. The reference elec­
sphere. The absolute fluorescence quantum yields were measured on trode, auxiliary electrode and electrolyte were all unchanged. The
HITACHI F-7100 by using an integrating sphere. The crystallinity of the flexible supercapacitor was assembled with CMFs as the negative elec­
samples was tested on X-ray diffraction (D/Max-2400, Japan) at the Cu trode and C-CMP as the positive electrode, 1 M H2SO4-PVA hydrogel as
Kα radiation (λ = 0.15418 nm) in the 2θ range of 0◦ -70◦ . The surface the electrolyte, and sealed with polyvinyl chloride tape. Electrochemical
chemical states were characterized by the X-ray photoelectron spec­ impedance spectroscopy (EIS) measurements in the frequency range of
troscopy (XPS) using a Physical Electronics PHI 5000 Versa Probe 0.01 Hz to 100 kHz with an AC voltage amplitude of 5 mV were con­
spectrometer equipped with a monochromatic Al Kα source. The ducted on an electrochemical workstation (CHI660E).
chemical structures of the samples were recorded on a Fourier transform
infrared spectra (FT-IR, VERTEX 70, Germany Bruker) with KBr pellets 2.9. DFT calculations
in the wavelength range of 4000–400 cm-1. Zeta potential was measured
using a Malvern Zetasizer Nano ZS ZEN 3600 (Malvern Instruments, The calculation was performed using the CASTEP software pack-age
USA). Nitrogen adsorption–desorption isotherms were measured on a based on Density Functional Theory (DFT) in Material Studio software.
Micromeritics ASAP 2020 gas adsorption analyzer at 77 K. The The CASTEP software package required that the computing system must
Brunauer-Emmett-Teller (BET) method was utilized to calculate the be periodic. Perdew-Burke-Ernzerh (PBE) of unctional and generalized
specific surface areas and pore volume, the NLDFT method was applied gradient approximation (GGA) were used. An ultra-soft pseudo-poten­
for the estimation of pore size distribution. tial method is used to simulate electron–ion interactions. The Grimme
method based on DFT-D was used as the interlayer van der Waals force
2.8. Electrochemical characterizations correction. After receiving the calculation model and calculation con­
ditions, the truncation energy was set to 400 eV, and the k point of the
In three-electrode system, the glassy carbon electrode (d = 5 mm) Brillouin zone divided by the Gamma method was set to 1 * 1 * 1 to meet
was used as current collector, the working electrode was prepared as the geometric relationship of the reciprocal space.
follow: 4 mg of as-prepared sample and 0.7 mg acetylene black were
dispersed in 0.4 mL of 0.25 wt% Nafion after milling sufficiently. Then 6 3. Results and discussion
μL above suspension was dropped onto the current collector by using of
the pipet gun, and then dried under room temperature. The carbon rod Fig. 1a illustrates the fabrication of the CMFs with good mechanical
and saturated calomel electrode were used as counter electrode and properties prepared by cation-induced electrostatic self-assembly pro­
reference electrode, respectively, and the 1.0 M H2SO4 was used as cess. Firstly, the flower-like DAAQ-COFs were synthesized by a Schiff-

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 2. (a) Digital photograph of DAAQ-COFs pure Ti3C2Tx dispersion and DAAQ-COFs/Ti3C2Tx mixture (mass ratio 1:1). (b) DAAQ-COFs protonated Zeta potential
of pure Ti3C2Tx dispersion and DAAQ-COFs/Ti3C2Tx mixture (mass ratio 1:1). (c) Digital photographs of pure Ti3C2Tx film and CMFs. (d, e) Flexible demonstration of
CMFs films (bendable, foldable and tailorable).

base condensation reaction between 2, 6-diaminoanthraquinone effectively prevent the self-restacking of MXene nanosheets. In the
(DAAQ) and 1, 3, 5-trihydroxybenzaldehyde (TFP) molecule according composites not only the beneficial properties of the single component
to our previous work report (Fig. S1) [33,34]. The prepared DAAQ-COFs are retained, but due to the presence of MXene, they often show
were dispersed in hydrochloric acid (HCl) solution to induce protonation enhanced electrical conductivity and mechanical properties.
of the –NH- group on the skeleton, so that the pore surface of COFs was Our design concept was verified by the first-principles density
filled with positive charges (H+). Then Ti3C2Tx MXene nanosheets were functional theory (DFT) calculation at first. Fig. 1b shows the differential
produced from Ti3AlC2 by selectively etching the metallic Al-Ti bonds charge density of the DAAQ-COFs/ Ti3C2Tx heterostructure, where
with LiF/HCl. Owing to the existence of surface functional groups (e.g., DAAQ-COFs is located above the phase boundaries and Ti3C2Tx is
-O, –OH, and -F), the as-exfoliated Ti3C2Tx nanosheet is highly nega­ located below the phase boundaries, which clearly shows the electron
tively charged[32]. Finally, strong interactions are established between accumulation (yellow sphere) and depletion (green sphere) between
MXene and protonated COFs through electrostatic attraction and the MXene and COFs. Obviously, the uneven charge distribution in DAAQ-
flexible freestanding composite films CMFs were obtained through COFs/Ti3C2Tx structure disturbs the charge balance at the interface of
vacuum-assisted filtration. The heterostructure is more stable and can the model. The electron transfer from the Ti3C2Tx to DAAQ-COFs side,

Fig. 3. (a, b) Top view SEM images of the CMFs. (c, d) Cross-sectional SEM images of the CMFs. (e, d) TEM images of CMFs. (g) Elemental mapping of C, N, O, Ti, and
F of CMFs.

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 4. (a) FT-IR spectra of DAAQ, TFP and DAAQ-COFs. (b) FT-IR spectra of DAAQ-COFs, Ti3C2Tx and CMFs. (c) XPS survey spectra and (d) high-resolution Ti 2p
XPS for CMFs and Ti3C2Tx.

confirming that the existence of intense interfacial interaction in the electrostatic self-assembly between MXene and COFs. Notably, the close
heterostructure. Besides, the density of states (DOS) for DAAQ-COFs/ contact between MXene flakes and COFs constructs an effective mass
Ti3C2Tx heterostructure and DAAQ-COFs, Ti3C2Tx with single- transfer channel between MXene layers and slows down the self-stacking
component were calculated and analyzed as shown in Fig. 1c. It is of MXene nanosheets. Compared with pure MXene film, the surface of
visible that the DOS intensity of DAAQ-COFs/Ti3C2Tx heterostructure is obtained CMFs is slightly rougher (Fig. 2c). It can be clearly seen from
increased near Fermi energy, illustrating the promotion of electron Fig. 2d and 2e that the obtained CMFs film can be easily wound on a
conductivity. Ultimately, for the planar averaged electrostatic potential glass rod and folded or cut at will. It shows its good mechanical prop­
of DAAQ-COFs/Ti3C2Tx heterostructure (Fig. 1d), the averaged elec­ erties and durability, as well as its great potential in flexible device
trostatic potential of DAAQ-COFs (-11.38 eV) is higher than that of applications.
Ti3C2Tx (-20.58 eV). It reveals the migration of electrons from Ti3C2Tx to The morphologies and microstructures of DAAQ-COFs, monolayer
DAAQ-COFs section because of the strong electrostatic field between MXene, multilayer MXene and CMFs composite films were characterized
heterogeneous structures. Consequently, the surface of DAAQ-COFs will by scanning electron microscopy (SEM). As shown in Fig. S2, the pre­
gather electrons while Ti3C2Tx will lack electrons, which can cause the pared DAAQ-COFs showed uniform flower-like morphology, and each
redistribution of interfacial charges[35]. These results theoretically COFs nanoflower is composed of many radial nanorods “petals” about
demonstrate that the presence of MXene plays a pivotal role in tuning 150 nm in diameter and 3–4 μm in length. Fig. S3 shows exfoliated few
the charge distribution. layers of MXene obtained by direct freeze-drying of MXene dispersion. It
Zeta potentials of MXene nanosheets and DAAQ-COFs nanoflakes reveals a loose thin sheet morphology with an average lateral dimension
were measured to imply an electrostatic self–assembly mechanism. The of several microns, indicating few layers of MXene were fabricated. After
enamine bonds of DAAQ-COFs in the protonated state absorb a large the vacuum filtration, the cross-sectional SEM image of the MXene
amount of H+, the pore wall and the entire surface of COFs were covered shows a well-aligned, layered structure (Fig. S3b). After introducing of
with positive charges (Zeta potential: +22.4 mV)[36]. Owing to the flower-like COFs, the surface folds of the composite film become more
hydrophilicity and electrostatic repulsion between neighboring nano­ tridimensional compared with pure MXene film (Fig. S3 and Fig. 3a, b).
sheets, the MXene colloidal solution is very stable in water (Fig. 2a, right By means of high-magnification SEM, the evenly distributed flowers
vial). Because of the surface functional groups, the as-prepared MXene is appear to be tightly packed with MXene nanosheets (Fig. 3c, d). The
negatively charged with a Zeta potential of − 39.5 mV. When positively TEM image shows the general state of the CMFs, lattice fringe with a
charged COFs was added into the negatively charged MXene solution, spacing of 0.35 nm corresponding to the (0 0 1) plane of the DAAQ-COFs
the flower-like COFs were rapidly wrapped by the MXene nanosheets (Fig. 3e, f). The CMFs section diagram further demonstrates the ad­
under electrostatic attraction. After several minutes, large agglomerates vantages of composite structure. The COFs flower is evenly wrapped and
appeared and settled down to the bottom of the container to form pre­ embedded in the MXene frames, forming a 3D conductive network and
cipitates leaving a clear supernatant (Fig. 2a, middle vial), indicating also alleviating the aggregation and self-stacking between adjacent

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 5. (a) XRD patterns of Ti3AlC2 and Ti3C2Tx. (b) XRD patterns of DAAQ-COFs, Ti3C2Tx and CMFs. (c) N2 adsorption/desorption curves and (d) pore size dis­
tribution of DAAQ-COFs and CMFs.

nanosheets. More importantly, the solid and flexible internal structure correspond to Ti-C, C-Ti-F-(OH), C-Ti-O and Ti-O bonds, respectively
provide the full penetration of electrolyte and greatly enhance the (Fig. 4d)[38], suggesting the structural integrity of Ti3C2 nanosheets in
electrochemical accessibility of redox active sites[37]. Fig. 3g and CMFs.
Fig. S4 shows EDS mapping rendered by the energy spectrum probe in In the powder X-ray diffraction (XRD) pattern of Ti3C2Tx (Fig. 5a),
the SEM equipment, where the Ti element corresponds to the flaky the disappearance of typical diffraction peaks (2θ = 39.1◦ ) for Ti3AlC2
Ti3C2Tx MXene and N is derived from the nitrogen in DAAQ-COFs. reveals the removal of the aluminum layer from Ti3AlC2, and it dis­
Moreover, the homogeneous distribution of C, N, O, Ti and F elements played a typically intense (0 0 2) diffraction peak at 2θ = 6.8◦ corre­
proves the indicative of homogeneous loading of DAAQ-COFs on the sponding to the interlayer stacking[39]. As shown in Fig. 5b, the
surface of Ti3C2Tx MXene. synthesized DAAQ-COFs powder showed good crystallinity. DAAQ-
FT-IR spectra were performed to analyze the structure and chemical COFs has a dominant diffraction peak at 3.2◦ as well as smaller peaks
composition of the samples (Fig. 4a and 4b). In the DAAQ monomer at 5.7◦ , 6.8◦ and a broad peak at 26.8◦ (2θ). These peaks correspond to
curve, the absorption peaks located at 1658 and 1627 cm− 1 correspond the (1 0 0), (1 1 0), (2 0 0) in-plane reflections as well as the (0 0 1)
to the stretching vibration of C–
– O bond, and the peaks near 3423 and stacking reflection. According to the Bragg equation, the interlayer π-π
3332 cm− 1 correspond to the stretching vibration of –NH2. Typically, stacking distance between COF layers along the (0 0 1) plane is 3.4 Å.
the characteristic absorption peaks at 1658 and 1627 cm− 1 of the DAAQ The XRD pattern of DAAQ-COFs, in agreement with previous studies,
correspond to the asymmetric and symmetric stretching vibrations of indicates an AA stacking manner where COF layers are stacked layer by
C–– O bonds. Compared with its monomer, the FT-IR spectra of DAAQ- layer with an orderly arrangement of pores. Two peaks of CMFs heter­
COFs powder show the disappearance of N–H stretches and the emer­ ostructure at 3.4◦ and 7.1◦ correspond to the (1 0 0) diffraction of DAAQ-
gence C–N at 1253 cm− 1. In addition, the carbonyl peak C– – O stretch COFs and (0 0 2) diffraction of Ti3C2Tx[40], respectively. Notably, all of
found in the TFP monomer at 1652 cm− 1 shifts to 1618 cm− 1, consistent two typical diffraction peaks are slightly shift to a higher 2θ angle in the
with the C–– O of the β-ketoenamine linkage. These results confirmed the CMFs heterostructure. It may be caused by H+ electrostatic attraction
successful construction of DAAQ-COFs by employing DAAQ and TFP as between the MXene sheet and the extended π-conjugated COFs skeleton,
building blocks. With regards to CMFs film, the strong characteristic which also reinforces the heterogeneous structure.
peaks at 1486 cm− 1 and 1176 cm− 1 are attributed to the –OH and C–O The permanent porosity of the samples was examined by N2
stretching vibrations of pristine MXene, showing that the chemical adsorption/desorption at 77 K. As shown in Fig. 5c, both pristine DAAQ-
groups remain. Meanwhile, the strong characteristic peaks of the C– –O COFs and CMFs exhibits the typical I-type isotherms with a sharp in­
and C–N stretching vibrations of DAAQ-COFs can be observed. The FT- crease at a low relative pressure of P/P0 < 0.1, which is characteristic for
IR spectrum of CMFs was slightly changed upon the electrostatic microporous materials. Pore size distribution analysis from the adsorp­
adsorption of DAAQ-COFs onto the MXene (e. g. the symmetric stretch of tion isotherms indicated that the DAAQ-COFs contain micropores with
C–– C of DAAQ-COFs mostly disappeared and the C–N stretching band is diameters of ~1.2 and 2.0 nm (Fig. 5d). The Brunauer-Emmett-Teller
broadened). X-ray photoelectron spectroscopy (XPS) survey spectrum of (BET) surface area and pore volume of DAAQ-COFs were 926.6 m2
CMFs shows typical N 1s peaks derived from DAAQ-COFs (Fig. 4c). High- g− 1 and 0.647 cm3 g− 1, respectively, which showed rich and regular
resolution Ti 2p XPS spectra of both Mxene and CMFs show the identical pore structure of COFs. However, pure MXene exhibits a typically low
binding energy peaks at 453.6, 454.6, 455.7 and 457.9 eV, which specific surface area (only 5 m2 g− 1) owing to its strong stacking effect.

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 6. (a) CV and (b) GCD of DAAQ-COFs, Ti3C2Tx and CMFs with different COFs and Ti3C2Tx mass ratios. (c) CV diagram of CMFs at different scanning speeds. (d)
GCD maps of CMFs. (e) EIS diagrams of different materials. (f) Cyclic stability and coulomb efficiency of CMFs measured at 5 A/g for 30,000 cycles.

As for the CMFs heterostructure, the isotherm has a sharp increase in further achieve efficient energy storage.
adsorption capacity at lower relative pressures (P/P0 < 0.1) and a hys­ The electrochemical performances of all electrode materials were
teresis loop at higher relative pressures (0.3 < P/P0 < 0.9), which estimated by employing three-electrode configuration in the range of
attributed to the coexistence of micropores and mesopores. According to − 0.5 to 0.2 V. The CV curves of DAAQ-COFs electrode in Fig. 6a shows a
the calculation, the specific surface area of CMFs heterostructures is pair of well-defined redox peaks, which are attributable to a reversible
significantly increased to 148.1 m2 g− 1. The corresponding concentrated transition between quinone carbonyl group (C– – O) and phenolic hy­
pore size distribution matches well with the channels of DAAQ-COFs. It droxyl group (C-OH). However, there is very weak current response can
is noteworthy that the average pore size of the heterostructure (3.1 nm) be observed in the DAAQ-COFs CV curve. This is because the low con­
is higher than that of the pure DAAQ-COFs (2.8 nm). It derived from the ductivity seriously hinders the charge transfer in the organic framework
3D structure formed by flower-like COFs embedded between the MXene and limits the release of energy storage performance. MXene is catego­
nanosheets, which was consistent with the SEM cross-section results. In rized as a negative potential intercalation pseudocapacitance material in
this regard, the introduction of COFs not only provides abundant H2SO4 medium[41]. The CV curves of Ti3C2Tx electrode at different scan
nanochannels, but also acts as an expansion layer by suppressing MXene rates all showed a pair of wide redox peaks (Fig. S5a). This is due to
restacking to construct a hierarchical porous scaffold. Abundant pore electron transfer and protonation of oxygen-containing functional
channels and the increase of specific surface area is conducive to the groups resulting in changes in the oxidation state of titanium. In
active site of CMFs fully in contact with electrolyte, which is expected to Fig. S5b, all curves of the constant-current charge–discharge curves of

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Table 1 the electrode for long-term use, the specific capacitance of the CMFs
Comparison of electrochemical energy storage performances for COFs-based electrode was measured 30,000 times at a current density of 5 A/g to
electrodes in three-electrode system. characterize the cyclic stability of the electrode material. As shown in
Electrodes Electrolyte Potential Current C (F Ref. Fig. 6f, after 30,000 cycles, the capacitance retention of CMFs electrode
window Density (A g− 1) is 89.1 %, and coulomb efficiency remains above 99 % during the whole
g− 1) cycle, indicating its structural stability and good electrochemical
DAAQ-COFs/ 1 M H2SO4 − 0.5 to 1.0 361 This reversibility. In the process of circulation, the electrolyte continuously
Ti3C2Tx 0.2 V work wets the electrode surface and gradually penetrates through the COFs
DAAQ-TFP COF 1 M H2SO4 − 0.3 to 0.1 48 ± [42]
channels to the entire electrode surface, thus increasing the effective
0.3 V 10
MXene/RGO 1 M H2SO4 0–1.0 V 1.0 233 [43] contact area between the electrode and electrolyte ions, and further
COF@MXene- 1 M NaSO4 − 0.9 to 0.5 290 [44] improving the electrochemical performance of the electrode materials.
15 − 0.1 V We use qualitative and quantitative research methods to analyze and
COF/rGO 1 M H2SO4 0 to 1.0 V 1.0 321 [45] calculate the capacitance contribution. First, in order to better visually
COFBTA-DPPD- 2 M KOH 0–0.5 V 0.5 239.1 [46]
rGO
identify the dynamic behavior of the redox process, especially at low
scanning rates, the CV curve is expressed in terms of differential capacity
(ratio of charge to potential, dQ/dE) with respect to potential. As shown
Ti3C2Tx are nonlinear without obvious platform, and the specific in Fig. 7a, the differential capacity of the CMFs electrode only slightly
capacitance is 240F g− 1 at 1 A/g. Owing to the positive synergistic effect decreases with the increase of scanning rate, and slight deformation
of MXene and COFs, all CMFs electrode have two pairs of redox peaks at occurs at the position of the first pair of reduction peaks, while the
the same time and show higher charge storage capacity. With the in­ second pair of peak positions coincide completely, indicating that the
crease of COFs content, the integral area of CV curves increases first and redox reaction of the composite material is mainly controlled by the
then decreases. The capacitance values calculated from GCD curves of surface. However, MXene materials that rely on the Faradaic reaction
CMFs with different COFs and Ti3C2Tx mass ratios also reflect this result induced by ion intercalation suffer from slight diffusion control.
(Fig. 6b). The electron transfer rate and active site utilization of DAAQ- Secondly, Dunn’s method [47] was used to analyze the charge
COFs were significantly increased due to the “electron-ion highway” storage due to surface redox reaction and intercalation capacitance. The
formed by MXene and COFs. But excessive DAAQ-COFs with poor con­ relationship between their peak current (i) and scan rate (v) can be
ductivity will inevitably lead to “traffic jam”. It can be concluded that depicted through Equation (1):
DAAQ-COFs/Ti3C2Tx = 3:1 is the optimal sample, and the area of CV
curve is the largest. The specific capacitance value is 361F g− 1 at 1 A/g, i = avb (1)
which is almost 1.5 times that of pure MXene and 15 times that of the
where i is the current (A), ν is the potential sweep rate (V s− 1), and a and
DAAQ-COF electrode (Fig. S6), and the capacitance retention for the
b are variable parameters. Fig. 7b shows the functional relationship
DAAQ-COFs/Ti3C2Tx electrode is about 81.5 % at 10 A/g (Fig. S7). This
between log(i) and log(v) determined by CV curves at different sweep
specific capacity is better than most of the related reports presented in
speeds of CMFs. The b values of the anodic peak and the cathodic peak of
Table 1. When the scan rate was increased from 10 mV s− 1 to 100 mV
the redox reaction at − 0.15 V are 0.991 and 0.989, respectively, which
s− 1, the redox peak of CV curves of CMFs electrode remained highly
are very close to 1, indicating that the redox reaction has typical
symmetric without any deviation (Fig. 6c), which further proved its
capacitive behavior of rapid adsorption/desorption of surface ions and
excellent electrochemical reversibility and fast charge transfer process.
reversible redox reaction. In addition, the contributions of capacitance
It can be seen from Fig. 6d that the GCD curves under different current
and diffusion at different scanning rates to the total capacity are
densities are almost mirror images and the specific capacitance is 390F
calculated according to CV curves. Since the contribution of non-
g− 1 at 0.5 A/g. Due to the advantages of COFs channel structure in ion
capacitive current responsive processes is the largest at low sweep
transfer, the GCD curve hardly has deformation under high current
rate, the capacitance contribution at low sweep rate is of the most
density, showing good rate performance.
reference significance. According to the Dunn method, the ratios of the
Electrochemical impedance spectroscopy (EIS) was used to study the
surface-capacitive process (k1) and the diffusion-controlled process (k2)
conductivity and ion migration behavior of the samples during elec­
can be calculated according to the Equation (2) by plotting v1/2 versus i/
trochemical process. It is obvious that the Nyquist plots of all samples
v1/2.
consist of almost vertical straight lines in the low frequency region and
semicircle in the high frequency region (Fig. 6e). The sharp rise of the i(V) = k1 v + k2 v(1/2) (2)
imaginary part of the Nyquist diagram in the low frequency range in­ − 1
dicates that the mass transport resistance is low, which is attributed to As shown in Fig. 7c, at a low scanning rate of 5 mV s , capacitive
the significant improvement of ion migration efficiency brought by the charge storage (the shaded part) accounts for 89.9 % of the total charge
advantages of the well-arranged pore structure of COFs. There are storage, indicating that capacitive process is the most important part of
negligible semicircles in the high frequency region of the electrode, its capacitance contribution. According to the calculation results in
indicating that the overall charge transfer resistance of the Faraday re­ Fig. 7d, pseudocapacitance contribution at 10, 20, 30 and 50 mV s− 1 are
action occurring on the surface of the complex is low with the assistance 91.8 %, 93.6 %, 94.5 % and 96.7 %, respectively. Obviously, the
of the 3D MXene conducting network. This good conductivity ensures capacitance contribution increases with increasing scanning rate, which
rapid electrochemical reactions at the interface/reaction site between is consistent with surface-controlled rapid charge storage.
electrode and electrolyte. By expanding the Nyquist diagram in the high Trasatti’s methodis[48] often used to mathematically calculate the
frequency range (illustrated in Fig. 6e), it can be seen that the optimal contribution of capacitance and diffusion control processes to total
sample has the smallest and most competitive semicircular minimum charge storage. According to Trasatti’s theory, the total charge (CT)
equivalent series resistance (ESR). The small ESR represents the high stored in a capacitive electrode can be attributed to the sum of the
conductivity of the flexible electrode due to the three-dimensional charges stored on its surface-controlled capacitance (Csc) and charge
conductive network structure. After electrostatic self-assembly with storage associated with semi-infinite diffusion. Since the capacitive
DAAQ-COFs, the ESR of CMFs did not increase, indicating that the for­ charge storage process is almost always constant at any scanning rate, a
mation of the composite structure did not damage the original con­ Csc value corresponding to the surface-dominant process can be obtained
ductivity of MXene, and the interlayer electron transmission was at the infinite potential scanning rate (v), whereas the charge storage
promoted, resulting in smaller ESR. To further explore the potential of process from the diffusion-controlled redox process is highly dependent

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N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 7. Electrode reaction kinetics studies on CMFs electrode material. (a) Capacity vs potential curves at different scan rates. (b) Plot of log(i) vs log(v) of anodic
peaks and cathodic peaks. (c) Capacitive and diffusion-controlled contributions to charge storage at a scan rate of 5 mV s− 1. (d) Capacitive contribution at different
scan rates. (e) Plots of the gravimetric capacitance (C) against the reciprocal of the square root of scan rate (v− 0.5). (f) Plots of the reciprocal of gravimetric
capacitance (C− 1) against square root of scan rate (v0.5).

on the scanning rate. Thus, at sufficiently high scanning rates, more from the original linear slope, which may be due to factors such as
diffusion-controlled redox processes are excluded from charge storage. inaccessible pores and resistance deviation of the active material,
Trasatti’s theory can be described by the Equation (3) and (4): causing the influence of diffusion-controlled ion transfer to be too large
to be applicable. When v → 0, the qT is maximum because the time left
C = Csc + αv− 0.5
(3)
for participating in the electrochemical reaction is long enough for the
diffusion control process to fully contribute. Since C and v-0.5 increase
C− 1
= CT− 1 + αv0.5 (4)
linearly, it can be considered that C-1 and v-0.5 decrease linearly.
The v -0.5
versus specific capacitance diagram in Fig. 7e shows two Therefore, qT can be estimated by extrapolation of C-1 relative to v-0.5
regions with different slopes (k values) because charge storage is along the Y-axis in Fig. 7f. As shown in the figure, the specific capaci­
dominated by rapid ion adsorption/desorption when the scanning rate is tance value of capacitance contribution is 326 F g− 1, and the total
below 30 mV s− 1 (region 1). As v-0.5 approaches 0, the qo on the outer capacitance is 369 F g− 1. The calculated capacitance contribution rate is
surface can be estimated by linear extrapolation from region 1 to the Y- 88.3 %, which is consistent with the analysis result of Dunn method.
axis. When the scanning rate exceeds 30 mV s− 1 (region 2), it deviates Furthermore, the charge storage of the composites is a capacitive

9
N. An et al. Chemical Engineering Journal 458 (2023) 141434

Fig. 8. Electrochemical performances of the CMFs//CCMP. (a) Schematic representative of the ASC. (b) CV curves of the CMFs and CCMP electrodes at 50 mV s− 1 in
a three-electrode system. (c) CV curves at different potential windows at 50 mV s− 1. (d) CV curves of the ASC with different scan rates. (e) GCD curves of the ASC at
various current densities. (f) CV curves (scan rate: 10 mV s− 1) under different folding angles. (g) Ragone plot of the ASC. (h) Cycling stability test at 5 A/g for 20,000
cycles (inset is the digital photograph of LEDs and a watch powered by the ASC).

10
N. An et al. Chemical Engineering Journal 458 (2023) 141434

process controlled by the surface. These results further confirm the energy density of 27.5 Wh kg− 1 (at a power density of 350 W kg− 1) and
excellent rate performance and fast redox kinetics of properly designed maximum power density of 7000 W kg− 1 (at an energy density of 19.7
CMFs nanocomposites. Wh kg− 1). This study provides a new pathway for optimizing the
In view of the high flexibility, mechanical strength and conductivity structural design of COF-based materials, broadens the practical appli­
of CMFs, as well as excellent electrochemical performance, we assem­ cation range of COFs-based materials, and provides the possibility for
bled asymmetric supercapacitors (ASC) based on CMFs thin film application in the next generation of flexible electronic devices.
(negative electrode) and CCMP (conjugated microporous polymer car­
bon aerogel) aerogel sheet (positive electrode) to evaluate their per­
formance in flexible electrochemical supercapacitor device, as shown in Declaration of Competing Interest
Fig. 8a. Fig. S8 shows the CV curves and GCD curves of CCMP electrode.
Two titanium foil as collector, PVC material transparent insulation tape The authors declare that they have no known competing financial
as a protective case. A hydrogel prepared by dissolving polyvinyl alcohol interests or personal relationships that could have appeared to influence
(PVA) in an aqueous solution of 1 M H2SO4 is used as electrolyte. From the work reported in this paper.
the CV curves of the CMFs film and CCMP aerogel sheet electrodes in the
three-electrode test (Fig. 8b), it can be inferred that the operating Data availability
voltage window of CMFs//CCMP devices can reach ~1.4 V, and a good
charge capacity match can be seen from the integral area. CMFs is No data was used for the research described in the article.
directly used as the negative electrode, CCMP is directly used as the
positive electrode, without any conductive additives and binder. Fig. 8c Acknowledgements
shows the CV curves of ASC under different voltage windows at 50 mV
s− 1. As expected, no significant polarization of CV curves was observed The authors gratefully acknowledge the financial support offered by
even at 1.4 V, ensuring the accuracy of the operating cell voltage. A pair the National Natural Science Foundation of China (21905123), Lanzhou
of wide redox peaks can be observed in CV curves at different sweep Science and Technology Plan Project (2022-2-84) and Qingdao Post­
speeds in Fig. 8d, which is caused by the redox reaction of COFs quinone doctoral Funded Projects (QDBSH20220202107) and Gansu Key
carbonyl group and the intercalation pseudocapacitance of MXene. Research and Development Projects (22YF7GA147). This study was also
Fig. 8e GCD curve shows quasi-triangular curve in potential window supported by the Tian you Youth Talent Lift Program of Lanzhou Jiao­
0–1.4 V, and high Coulomb efficiency shows good reversibility of the tong University and the Young Scholars Science Foundation of Lanzhou
reaction. According to the calculation, the specific capacitance of the Jiaotong University (2020049).
device is 100 F g− 1 at the current density of 0.5 A/g, and 70 F g− 1 at the
current density of 10 A/g, and the capacitance retention rate is 70 %, Appendix A. Supplementary data
which shows good rate performance and proves the good matching of
the positive and negative load quality. In addition, the ASC developed in Supplementary data to this article can be found online at https://doi.
this study shows excellent flexibility. Bending (50, 100◦ ) or even folding org/10.1016/j.cej.2023.141434.
(150◦ ) the device has no influence on the CV curves (Fig. 8f). Ragone
diagram of energy/power density is drawn for comparison. As shown in References
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