Metal phthalocyanine-based conjugated microporous polymer/carbon nanotube composites as flexible electrodes for supercapacitors

Article abstract of DOI:10.1016/j.dyepig.2021.109299

Conjugated microporous polymers with active functional groups have attracted more and more attentions in energy conversion systems. However, their low electrical conductivity results in low capacitance, thus limiting their practical application. Herein, conjugated microporous polymer with triphenylamine aldehyde linked to metal phthalocyanines (MNC) is synthesized and then compounded with high-conductivity carbon nanotubes (CNTs) (denoted as CoNCCs) by vacuum filtration. Moreover, CoNCCs exhibit flexibility, which could be served as a self-standing and binder-free flexible electrode of supercapacitors. As a result, the optimized CoNCCs as the flexible electrode show high specific capacitance of 213.4 F g^?1 at 0.5 A g^?1. In addition, the higher capacity retention rate 85.3% can be retained after 1750 cycles at 20 A g^?1. The good electrochemical properties can be attributed to the synergistic effect and strong dual-phase interaction between MNC and CNTs. This work opens the way to develop high-performance and low environmental footprint organic electrode materials for SCs.

Full text of DOI:10.1016/j.dyepig.2021.109299

Dyes and Pigments 190 (2021) 109299
Contents lists available at ScienceDirect
Dyes and Pigments
journal homepage: http://www.elsevier.com/locate/dyepig
Metal phthalocyanine-based conjugated microporous polymer/carbon
nanotube composites as flexible electrodes for supercapacitors
,b,
Lan Meia, Xu Cuia, Juncheng Weia, Qian Duana *, Yanhui Lia
a School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun, 130022, China
b Engineering Research Center of Optoelectronic Functional Materials, Ministry of Education, Changchun, 130022, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Conjugated microporous polymers with active functional groups have attracted more and more attentions in
energy conversion systems. However, their low electrical conductivity results in low capacitance, thus limiting
their practical application. Herein, conjugated microporous polymer with triphenylamine aldehyde linked to
metal phthalocyanines (MNC) is synthesized and then compounded with high-conductivity carbon nanotubes
(CNTs) (denoted as CoNCCs) by vacuum filtration. Moreover, CoNCCs exhibit flexibility, which could be served
as a self-standing and binder-free flexible electrode of supercapacitors. As a result, the optimized CoNCCs as the
flexible electrode show high specific capacitance of 213.4 F gꢀ 1 at 0.5 A gꢀ 1. In addition, the higher capacity
retention rate 85.3% can be retained after 1750 cycles at 20 A gꢀ 1. The good electrochemical properties can be
attributed to the synergistic effect and strong dual-phase interaction between MNC and CNTs. This work opens
the way to develop high-performance and low environmental footprint organic electrode materials for SCs.
Metal phthalocyanine
Conjugated microporous polymer
Carbon nanotubes
Supercapacitors
Flexible electrode
1. Introduction
solve this problem [12,13].
Organic electrode materials have aroused widespread attentions in
The energy crises and consumption of resources concerning the
environment have aroused our crisis consciousness and requirement for
the development of effective and renewable energy storage technology
[1–3]. Electrochemical energy storage equipment has played an
extremely important role in solving energy shortages [4]. Super-
capacitors (SCs) with high rate performance, excellent cycle stability,
high power density and environment-friendly properties are considered
as promising energy storage devices [5–7]. SCs include two categories:
pseudocapacitors and electrochemical double-layer capacitors (EDLCs).
Considering that the working mechanisms, the pseudocapacitors store
electrical energy through the reversible redox reaction of electrode
materials. By contrast, the EDLCs store electrical energy through rapid
and reversible adsorption and desorption of the electrolytic ions at the
electrode/electrolyte interface [8,9]. No matter which type of SCs, the
influence of the electrode materials on its electrochemical performance
is crucial [10,11]. In recent years, inorganic electrode materials have
been extensively widely used in SCs, but most of them have a few de-
fects, for instance the resource shortage and environmental contami-
nation during the mining process. Thus, efforts have been made to
develop cheaper and more environment-friendly electrode materials to
view of their advantages of environmental friendliness, low energy
consumption and high redox activity [14–16]. As a type of important
organic electrode material, conjugated microporous polymers (CMPs)
have been widely used in SCs due to their abundant pore structure and
structural tenability [17–19]. Generally, CMPs are composed of some
specific structure unit and linking group, in which the specific structure
unit with redox activity could endow them with high electrochemical
performance. In this context, phthalocyanines peculiarly metal-
lophthalocyanines (MPcs), a type of 18-electron coplanar aromatic
macrocycles could be used as the vital functional π-conjugated structural
units [20–22]. MPcs and their derivant are known to be excellent
organic semiconductors with potential applications in many fields
[23–26]. Thus, CMPs based on MPcs are considered as a type of fasci-
nating electrode materials for energy conversion systems [27–30].
Whereas, the inherent low electrical conductivity of CMPs results in low
capacitance. To improve the conductivity of CMPs, combining
low-conductivity CMPs with high-conductivity carbon materials,
including graphene and carbon nanotubes (CNTs), is an effective strat-
egy [31–33]. Among them, CNTs have aroused great scientific attention
in view of their unique flexible, mechanical, electronic and structural
* Corresponding author. School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun, 130022, China.
E-mail address: duanqian88@hotmail.com (Q. Duan).
https://doi.org/10.1016/j.dyepig.2021.109299
Received 10 January 2021; Received in revised form 4 March 2021; Accepted 10 March 2021
Available online 23 March 2021
0143-7208/© 2021 Elsevier Ltd. All rights reserved.

L. Mei et al.
Dyes and Pigments 190 (2021) 109299
properties. Some studies have shown that the introduction of CNTs can
improve the activity resulted from the large surface area and excellent
electronic properties [34–36]. Therefore, it is important to construct
flexible and integrated electrode based on CMPs and CNTs for SCs.
Herein, we prepared the composite film composed of CMP with tri-
phenylamine aldehyde linked to metal phthalocyanines (M = Co and Fe)
and high-conductivity CNTs by using the microwave method as well as
the vacuum filtration strategy, which are the binder-free and free-
1285, 1180, 824, 714, 649, 571; Anal. calcd (%) for C39H27NO3: C,
84.00; H, 4.88; N, 2.51; O, 8.61. Found: C, 83.85; H, 4.96; N, 2.44; O,
8.78.
2.1.4. Synthesis of MNC (M = Co, Fe)
Specifically, CoPc(NH2)4 (0.06 mmol, 30 mg) and NBC (0.08 mmol,
45 mg) were dissolved in N, N-dimethylacetamide (DMAc) by using the
easy microwave heating method to synthesize CoNC. The mixture was
filled in a microwave tube (5 mL), which was vacuumized and sealed in
a glovebox. The microwave-assisted device was used by Biotage Ini-
tiator+ Microwave System, in which the microwave was heated at
200 ◦C for 1.5 h using the power of the microwave irradiation was 90 W.
The as-obtained sample was filtrated, washed with DMAc, THF and
standing flexible electrode of SCs. Profiting by the strong π-π interac-
tion and synergistic effect between MNC and CNTs, the optimized
CoNCCs show high specific capacitance of 213.4 F gꢀ 1 at 0.5 A gꢀ 1 and
good capacity retention of 85.3% after 1750 cycles at 20 A gꢀ 1. This
work opens up the way to construct high-performance flexible SCs by
reasonable recombination of MNC with highly conductive CNTs.
◦
ethanol and finally dried at 50 C overnight. And FeNC was prepared
using the similar procedures by replacing CoPc(NH2)4 with FePc(NH2)4.
The isolated yields of CoNC and FeNC were 69% and 73%, respectively.
2. Experimental details
2.1. Synthesis of samples
2.2. Instruments and parameters
2.1.1. Synthesis of tetra-nitro metallophthalocyanine (MPc(NO2)4, M =
Co, Fe)
Microwave-assisted device was used by Biotage Initiator+ Micro-
wave System and the power of the microwave irradiation was 90 W.
Ultraviolet–visible (UV–vis) spectra were procured in DMF at room
temperature with a Shimadzu UV-2600 spectrophotometer. 1H NMR
spectra (liquid state) were recorded in Chloroform-d (CDCl3) on AV-400
NMR spectrometer (Bruker), using TMS as an internal standard. X-ray
photoelectron spectroscopy (XPS) analysis conducted with ESCALAB
Typically, the tetra-nitro metallophthalocyanine (MPc(NO2)4) was
synthesized by solid phase reaction [37], which was reacted with
4-nitrophthalonitrile (3.8 g, 0.02 mol), CoCl2⋅6H2O (1.2 g, 0.005 mol),
urea (9.6 g, 0.16 mol) and an appropriate amount of ammonium
molybdate in a 250 mL round bottom flask at 160 ◦C under reflux for 5 h.
Then, the product was stirred magnetically with hydrochloric acid (HCl)
solution (0.2 L, 1 mol Lꢀ 1) and sodium hydroxide (NaOH) solution (0.2
MK II X-ray instrument using an Al Kα source was used to analyze the
composition of the materials. Matrix-assisted laser desorption ionization
time-of-flight mass (MALDI-TOF MS) spectra were recorded on Bruker
Autoflex III. Element analysis was obtained on an Elementar vario EL
cube instrument. Fluorescence spectra were measured on a PerkinElmer
LS-55 Fluorescence Spectrometer using appropriate filters. Specific
surface areas were calculated using the Brunauer-Emmett-Teller (BET)
model via Quantachrome NOVA2200e nitrogen adsorption apparatus.
Fourier transform infrared spectra (FTIR) measurements performed on a
PerkinElmer Frontier spectrometer using KBr pellets technique with the
scanning from 400 to 4000 cmꢀ 1. The microstructures of the samples
were studied by scanning electron microscopy (SEM Hitachi S-4800).
Mechanical stress-strain measurements were obtained by microcom-
puter controlled single-arm electronic universal testing machine (WDW-
01T). All the electrochemical measurements were performed on CS350
Electrochemical Workstation (Wuhan CorrTest Instruments Co., Ltd.).
L, 1 mol Lꢀ 1) at 90 C for 1 h. Finally, the product was filtered and
◦
washed repeatedly with deionized water to neutral and then dried in a
vacuum drying oven to give a dark green solid in 78% isolated yield. IR
(KBr, cmꢀ 1): 1521, 1339, 1140, 1093, 846, 760, 726; MALDI-TOF-MS
m/z: calc. for C32H12N12O8Co [M-H] +: 751.0; found 751.2; Anal.
calcd (%) for C32H12N12O8Co: C, 51.15; H, 1.61; N, 22.37; O, 17.03.
Found: C, 51.47; H, 1.52; N, 22.62; O, 16.87.
2.1.2. Synthesis of tetra-amino metallophthalocyanines (MPc(NH2)4, M =
Co, Fe)
The cobalt tetra-amino-phthalocyanines (CoPc(NH2)4) was synthe-
sized from CoPc(NO2)4 [38,39]. Concretely, the CoPc(NO2)4 (1.5 g,
0.002 mol) and Na2S⋅9H2O (5.8 g, 0.074 mol) were dissolved in N,
N-dimethylformamide (DMF,30 mL) and then reacted at 60 ◦C for 1 h.
Subsequently, the deionized water (500 mL) was added into the above
solution and the cyan CoPc(NH2)4 was obtained by centrifugation and
washed with water to neutral and then dried under vacuum. The FePc
(NH2)4 was synthesized by the same procedure only replacing
CoCl2⋅6H2O using FeCl2⋅4H2O. The isolated yields of the CoPc(NH2)4
and FePc(NH2)4 were 56% and 72%, respectively. IR (KBr, cmꢀ 1): 3344,
3221, 1609, 1496, 1345, 1092, 830, 747, 655; MALDI-TOF-MS m/z:
calc. for C32H20N12Co [M-H] +: 631.1; found 631.3; Anal. calcd (%) for
C32H20N12Co: C, 60.86; H, 3.19; N, 26.62. Found: C, 61.15; H, 3.32; N,
26.34.
2.3. Preparation of the electrodes
2.3.1. Preparation of the flexible MNCCs (M = Co, Fe) films
Firstly, MNC and CNTs with the appropriate amount were separately
added into N-methylpyrrolidone (NMP) under the action of ultrasound.
Next, the above two suspensions were mixed and further stirred for 12 h
under the action of ultrasound. Then, the polyvinylidene fluoride
microporous membrane (0.22 μm) was used to vacuum filtrate the ho-
mogeneous suspensions. As last, the as-obtained flexible films were
dried at 50 ◦C overnight under vacuum. For comparison, various MNCCs
with different proportion by weight of MNC and MWCNT (1:1, 1:2, 1:3
and 1:5) were synthesized (named as MNCCs-x, x = 1, 2, 3 and 5). The
pure CNT film was synthesized using the similar way without the
addition of MNC.
2.1.3. Synthesis of 4′,4’’,4′′′-nitrilotris(([1,1′-biphenyl]-4-carbaldehyde))
(NBC)
Tris(4-iodophenyl)amine (0.16 mmol) and 4-formylphenylboronic
acid (0.48 mmol) were dissolved in 10 mL of tetrahydrofuran (THF)
[40,41] and then K2CO3 aqueous solution (5.0 mL, 2.0 mol Lꢀ 1) and bis
(triphenylphosphine)palladium(II) dichloride (30 mg) was added in
sequence under nitrogen atmosphere. After the mixture was refluxed for
12 h, the obtained solution was extracted twice with dichloromethane
(3 × 100 mL). The residue was chromatographed on a silica gel column
to get yellow solid with 72% yield. 1H NMR (400 MHz, CDCl3): δ (ppm)
10.05 (s, 3H, –CHO), 7.96 (d, J = 8.0 Hz, 6H, Ar–H), 7.77 (d, J = 8.0 Hz,
6H, Ar–H), 7.62 (d, J = 8.0 Hz, 6H, Ar–H), 7.29 (d, J = 8.0 Hz, 6H,
Ar–H); IR (KBr, cmꢀ 1): 3032, 2830, 2732, 1701, 1590, 1525, 1499,
2.3.2. Preparation of CoNC electrode
Since the CoNC powder cannot be directly fabricated for the super-
capacitor electrode, the electrode was prepared by the following
method: the as-prepared active materials CoNC, acetylene black and
poly(vinylidene fluoride) (PVDF) binder were first mixed in NMP with
8:1:1 wt%. Then, the slurry was coated on a titanium form (1.0 cm × 2.0
cm), which was vacuum dried at 70 ◦C for 12 h.
2

L. Mei et al.
Dyes and Pigments 190 (2021) 109299
2.4. Electrochemical measurements
process. Therefore, flexible electrodes show great advantages in bend-
ability, ductility and long cycle life.
The electrochemical properties of the as-prepared sample were
tested on a three-electrode system. And 1 M H2SO4 solution was used as
electrolytes, a platinum foil as the counter electrode, an Ag/AgCl elec-
trode (saturated KCl solution) as the reference electrode and the CoNC
electrode or the CoNCCs flexible electrode was used as a working elec-
trode. The electrochemical test of the CoNCCs flexible electrode and the
CoNC electrodes were carried out with potentials ranging from ꢀ 0.15 to
1.45 V. The cyclic voltammetry (CV) curves were performed using
different sweep speeds from 5 to 200 mV sꢀ 1 and the galvanostatic
charge-discharge (GCD) measurements were tested at different current
densities. The specific capacitance was calculated according to the re-
ported literature [42].
For purpose of determine the chemical components of samples, FT-IR
tests are performed (Fig. 3a). The FT-IR spectrum of CoPc(NO2)4 dis-
plays vibrational absorption peaks of phthalocyanine skeleton at 1140,
1093, 760 and 726 cmꢀ 1, which proves the formation of phthalocyanine
macrocycles. The in-plane and out-plane vibrational absorption peaks of
–NO2 appear at 1521 and 1339 cmꢀ 1, respectively. There is no charac-
teristic absorption peak of C≡N appeared at about 2200 cmꢀ 1, indi-
cating the synthesis of CoPc(NO2)4 [39]. The FT-IR spectrum of CoPc
(NH2)4 displays the N–H stretching peaks at 3344 and 3221 cmꢀ 1 from
the amino groups. And the phthalocyanine macrocycle shows the
characteristic and vibration peaks at 1092 and 747 cmꢀ 1, respectively.
The bending vibration absorption peak of N–H in –NH2 appears at 1609
cmꢀ 1, while the characteristic absorption peak of –NO2 disappears,
suggesting the completely reduction from CoPc(NO2)4 to CoPc(NH2)4.
Absorption band of NBC at 1701 cmꢀ 1 is related with the stretching
vibration of the carbonyl part of the aldehyde. FT-IR spectrum of CoNC
3. Results and discussion
The CoPc(NO2)4 is synthesized by a typical solid-state method. And
CoPc(NH2)4 is reduced from CoPc(NO2)4 with Na2S⋅9H2O (Fig. S1). To
confirm the successful synthesis of CoPc(NO2)4 and CoPc(NH2)4, UV–Vis
absorption spectroscopy is carried out (Fig. S2). CoPc(NO2)4 shows two
characteristic absorption bands of the B and Q bands. The Q-band is a
double peak and appears at 615 nm and 661 nm, respectively. The
shoulder peak around 615 nm is the weak vibrational absorption peak of
the CoPc(NO2)4 dimer. CoPc(NH2)4 exhibits the double peaks of the Q-
band appear at 648 nm and 706 nm, respectively. The shoulder peak
around 648 nm is the weak vibrational absorption peak of the CoPc
(NH2)4 dimer. Obviously, the Q band of CoPc(NH2)4 occurs the red shift
resulted from the molecule conjugation effect [38]. In addition, the
synthesis of CoPc(NO2)4 and CoPc(NH2)4 has been confirmed by Mass
spectra (Fig. S3). And NBC is synthesized by tris(4-iodophenyl)amine
and 4-formylphenylboronic acid (Fig. S4). 1H NMR spectroscopy is
used to demonstrate the successful synthesis of the obtained NBC
(Fig. S5). Then the MNC is synthesized by the polycondensation reaction
between CoPc(NH2)4 and NBC (Fig. 1), which is performed using the fast
microwave heating way. Finally, the vacuum filtration way is used to
prepare the flexible MNCCs films (Fig. 2). Interestingly, vacuum filtra-
tion method is a simple, safe, low-cost and mass produced. In addition,
the easy vacuum filtration method is able to provide the films as the
flexible electrodes. The flexible electrodes can be made into an inte-
grated electrode by avoiding the use of binder in the preparation
shows peaks of residual –NH2 groups within the scope of 3000–3500
cmꢀ 1 [43], indicating some retained edge linkages. Moreover, the C
N
–
–
stretching vibration contributed to the imine bond appear at 1609 cmꢀ 1
[40,41]. At the meantime, the carbonyl part of CoNC is observably
weakened, reflecting that CoNC is successfully synthesized. The fluo-
rescence emission properties of the CoPc(NO2)4、CoPc(NH2)4 and CoNC
polymers are investigated by fluorescence spectra in DMF (Fig. S6).
Under excitation wavelength of 530 nm, CoPc(NO2)4, CoPc(NH2)4 and
CoNC show the maximum emission spectral band at 637, 627 and 627
nm, indicating their fluorescence properties. To determine the oxidation
state of Co, XPS measurement is tested. The high-resolution Co 2p XPS
spectra of CoPc(NO2)4 show two pairs of 2p3/2/2p1/2 doublets of Co2+
(796/780.2 eV) (Fig. S7). The specific surface area and porous structure
of the CoNC are tested by nitrogen adsorption/desorption measure-
ments. The Brunauer-Emmett-Teller (BET) surface area of CoNC is
14.727 m2 gꢀ 1 (Fig. S8). The pore size distribution of CoNC tested by
BJH method (inset of Fig. S8) shows that the pore diameter is mainly
distributed from 2 to 10 nm. Subsequently, the morphology of the
sample is characterized using scanning electron microscope (SEM). The
SEM image of CoNCCs shows that the granular CoNC is diffused on the
surface of CNTs (Fig. S9a). In addition, the relevant energy dispersive
X-ray spectroscopy (EDS) images confirm existence of Co, N and C
Fig. 1. Schematic synthetic process for the synthesis of MNC (M = Co, Fe).
3

L. Mei et al.
Dyes and Pigments 190 (2021) 109299
Fig. 2. Schematic preparation process for MNCCs (M = Co, Fe).
elements in CoNCCs-3 (Figs. S9b–d). In addition, the dynamic me-
chanical analysis method is used to study the mechanical properties of
the CoNCCs-3 film. The stress-strain curves exhibit that the obtained
CoNCCs-3 film has good mechanical strength and fracture strain. The
tensile strength of pure CNTs is 0.227 MPa with ~2.423% strain. And
the tensile strength of CoNCCs-3 film is 1.5 MPa with ~2.17% strain
(Fig. 3b). The Young’s moduli of CoNCCs-3 and pure CNTs are calcu-
lated to be 0.067 and 0.017 GPa, respectively, which shows that
CoNCCs-3 has excellent mechanical properties. Moreover, pure CNTs
films have large elongation at break due to weak interfacial interactions
peaks and larger CV integrated area, proposing the heightened specific
capacitance. Furthermore, the best ratios between CoNC and CNTs are
studied (Fig. 4b). Obviously, the integrated CV region of CoNCCs-3 is
enlarged, reflecting the higher charge storage capacity. In addition, the
CV curves of different MNCCs-3 (M = Co and Fe) are compared (Fig. 4c).
CoNCCs-3 shows CV curves with typical pseudo-capacitance features
and increased integrated CV area, indicating that CoNCCs-3 has great
charge storage capabilities. In addition, the samples are further analysed
for GCD measurements at 1 A gꢀ 1. CoNCCs-3 exhibits long charging and
discharging times, indicating a high specific capacitance. On the basis of
GCD curves, the relevant specific capacitance could be computed. For
CoNC, CNTs and CoNCCs-3, the specific capacitance is 55, 49 and 195.3
F gꢀ 1, respectively (Fig. 4d). And for CoNCCs-1, CoNCCs-2, CoNCCs-3
and CoNCCs-5, the specific capacitance is 52, 100, 195.3, and 97.5 F
between CNTs. After the introduction of CoNC, π-π coupling crosslinking
occurs between CoNC and CNTs, and the relative slip between CNTs is
limited, resulting in lower elongation at break. At the same time, the
stress transfer efficiency is significantly improved, which increased the
tensile strength and modulus [44]. Therefore, CoNCCs-3 has important
application prospects in the field of flexible energy storage [45]. Besides,
the self-supporting films could show the flexible and integrated char-
acteristics (Fig. 3c).
gꢀ 1 (Fig. 4e). Equally, specific capacitance of FeNCCs-3 is 99 F gꢀ 1
Obviously, CoNCCs-3 also shows a high specific capacitance (Fig. 4f).
.
Moreover, CoNCCs-3 shows the performance of both pseudo-
capacitance and EDLC capacitance (Fig. 5a). Thus, the electrochemical
capacitance is higher than CoNC and CNTs. With increase of scan rate
the area of CV curve increases. At a high scan rate of 200 mV sꢀ 1, a pair
of obvious reversible redox peaks are still displayed, which shows the
good charge storage characteristics. For purpose of further confirm
excellent electrochemical properties of CoNCCs-3, CV curves of all the
samples are listed at different scan rates from 5 to 200 mV sꢀ 1. Pure
CoNC shows a CV curve with pseudo-capacitance characteristics
The electrochemical properties of the samples are performed by
using 1 M H2SO4 as electrolyte in a three-electrode system. All the
samples show different CV curves at the scan rate of 50 mV sꢀ 1. By
comparison, pure CNTs show the differences with CoNC and CoNCCs-3
(Fig. 4a). The pure CNTs show the typical electric double layer capacitor
(EDLC) behavior. And CoNC exhibits the pseudocapacitance character-
istics. Moreover, CoNCCs-3-based electrodes show a typical pair of redox
4

L. Mei et al.
Dyes and Pigments 190 (2021) 109299
Fig. 3. (a) FT-IR spectra, (b) mechanical stress-strain curve, (c) digital photographs of flexible MNCCs (M = Co, Fe) electrode.
Fig. 4. Comparisons of the CV curves of (a) CNTs, CoNC and CoNCCs-3, (b) CoNCCs, (c) MNCCs-3 (M = Co, Fe) at a scan rate of 50 mV sꢀ 1. Comparisons of the GCD
curves of (d) CNTs, CoNC and CoNCCs-3, (e) CoNCCs, (f) MNCCs-3 (M = Co, Fe) at 1 A gꢀ 1
.
5

L. Mei et al.
Dyes and Pigments 190 (2021) 109299
Fig. 5. (a) CV curves of CoNCCs-3 at different scan rates, (b) GCD curves of CoNCCs-3 obtained at different current densities, (c) specific capacitances of CoNCCs-3 at
different current densities, (d) cycling performance and coulombic efficiency of CoNCCs-3 at 20 A gꢀ 1
.
(Fig. S10a). Pure CNTs show a CV curve with almost rectangular EDLC
behavior (Fig. S10b). And FeNCCs-3 also shows a CV curve with pseudo-
capacitance characteristics (Fig. S10c). In addition to CoNCCs-3, CV
curves of all the samples with different ratios between CoNC and CNTs
(from 5 to 200 mV sꢀ 1) are also studied (Figs. S11a–c). It can be noticed
that CV curves exhibit typical pseudocapacitance characteristics. In
addition, GCD curves of all the samples are performed at different cur-
rent densities. CoNCCs-3 shows a larger plateau (Fig. 5b), which is
similar to pure CoNC and FeNCCs-3, but different from pure CNTs
(Fig. S12). The results are compliance with the CV curve. The relevant
specific capacitance can be computed on the basis of GCD curves.
CoNCCs-3 shows specific capacitances of 213.4, 195.3, 79.8, 63.3, 53.9,
49.5 and 45.4 F gꢀ 1 at the current densities of 0.5, 1, 2, 3, 5, 10 and 20 A
gꢀ 1, respectively (Fig. 5c). By comparison, pure CoNC exhibits specific
synergistic effect of the capacitance contribution and good electrical
conductivity CNTs.
4. Conclusions
We show an effective strategy to construct the composite film
composed of CMP with triphenylamine aldehyde linked to metal
phthalocyanines (M = Co and Fe) and high-conductivity CNTs by
combining the microwave method and the vacuum filtration strategy.
Interetingly, the composite film shows fascinating flexible features as
binder-free and free-standing electrode for SCs. The highly active CoNC
with metallic characteristics can be composited with highly conductive
CNTs through the π-π interaction between them without any covalent
bonds. Thanks to the synergistic effect between the high pseudocapa-
citance of CoNC and the great conductivity of CNTs, flexible electrode of
CoNCCs has a high specific capacitance of 213.4 F gꢀ 1 at 0.5 A gꢀ 1 and
capacitances of 55, 18, 11, 7.6 and 6.9 F gꢀ 1 at 1, 2, 3, 5 and 10 A gꢀ 1
,
respectively (Fig. S12a). The pure CNTs show the specific capacitance of
49, 47.5, 41.3, 36.9 and 32.2 F gꢀ 1 at 1, 2, 3, 5 and 10 A gꢀ 1, respectively
(Fig. S12b). In addition, FeNCCs-3 shows specific capacitances of 99, 60,
50.5, 42.5 and 35.7 F gꢀ 1 at 1, 2, 3, 5 and 10 A gꢀ 1, respectively
(Fig. S12c). Except as CoNCCs-3, the GCD curves of samples with
different ratios of CoNC and CNTs are also studied (Fig. S13). It can be
found that all GCD curves correspond to the corresponding CV curves.
CoNCCs-1 shows the specific capacitances of 52, 30, 24.7, 20.3 and 16.7
F gꢀ 1 at 1, 2, 3, 5 and 10 A gꢀ 1 (Fig. S13a). CoNCCs-2 shows the specific
capacitance of 100, 55, 44, 36 and 33 F gꢀ 1 at 1, 2, 3, 5 and 10 A gꢀ 1
(Fig. S13b). And CoNCCs-5 shows specific capacitance of 97.5, 69.5, 62,
51 and 41 F gꢀ 1 at 1, 2, 3, 5 and 10 A gꢀ 1, respectively (Fig. S13c).
Obviously, the optimal ratio and synergy of CoNC and CNTs make the
composite material with a higher specific capacitance. Moreover,
CoNCCs-3 shows good cycle stability with high specific capacitance
retention rate of 85.3% after 1750 cycles even at the higher current
density of 20 A gꢀ 1 (Fig. 5d). Overall, the good electrochemical per-
formance is resulted from the high pseudo-capacitance of CoNC and the
the good capacity retention rate of 85.3% after 1750 cycles at 20 A gꢀ 1
.
The synergy and powerful functions of the conjugated microporous
polymer connected with metal phthalocyanine and triphenylamine
aldehyde (MNC) and highly conductive CNTs offer the probability of
developing higher performance supercapacitors.
Credit authorship contribution statement
Lan Mei: Investigation, Data curation, Writing- Original draft.
Xu Cui: Formal analysis, Conceptualization.Juncheng Wei: Inves-
tigation. Qian Duan: Funding acquisition,Project administration,
Writing- Reviewing and Editing.Yanhui Li: Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
6

L. Mei et al.
Dyes and Pigments 190 (2021) 109299
[21] Mu JB, Shao CL, Guo ZC, Zhang MY, Zhang ZY, Zhang P, et al. Solvothermal
synthesis and electrochemical properties of 3D flower-like iron phthalocyanine
hierarchical nanostructure. Nanoscale 2011;3:5126–31.
the work reported in this paper
Acknowledgments
[22] Lekitima JN, Ozoemena KI, Jafta CJ, Kobayashi N, Song Y, Tong D, et al. High-
performance aqueous asymmetric electrochemical capacitors based on graphene
oxide/cobalt (II)-tetrapyrazinoporphyrazine hybrids. J Mater Chem A 2013;1:
2821–6.
The authors are grateful for financial support from Jilin Science &
Technology Department (20190303069SF, 20150520025JH and
20180520166JH).
[23] Nombona N, Nyokong T. The synthesis, cyclic voltammetry and
spectroelectrochemical studies of Co(II) phthalocyanines tetra-substituted at the
and β positions with phenylthio groups. Dyes Pigments 2009;80(1):130–5.
[24] Colson JW, Woll AR, Mukherjee A, Levendorf MP, Spitler EL, Shields VB,
Spencer MG, Park J, Dichtel WR. Oriented 2D covalent organic framework thin
films on single-layer graphene. Science 2011;332:228.
α
Appendix A. Supplementary data
[25] Spitler EL, Dichtel WR. Lewis acid-catalysed formation of two-dimensional
phthalocyanine covalent organic frameworks. Nat Chem 2010;2:672–7.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.dyepig.2021.109299.
[26] Mackintosh HJ, Budd PM, McKeown NB. Catalysis by microporous phthalocyanine
and porphyrin network polymers. J Mater Chem 2008;18:573–8.
[27] Spitler EL, Colson JW, Uribe-Romo FJ, Woll AR, Giovino MR, Saldivar A,
Dichtel WR. Lattice expansion of highly oriented 2D phthalocyanine covalent
organic framework films. Angew Chem Int Ed 2012;51:2623–7.
References
[1] Miller JR, Simon P. Electrochemical capacitors for energy management. Science
2008;321:651–2.
[28] Kang X, Han X, Yuan C, Cheng C, Liu Y, Cui Y. Reticular synthesis of tbo topology
covalent organic frameworks. J Am Chem Soc 2020;142:16346–56.
[29] Agboola BO, Ozoemena KI. Synergistic enhancement of supercapacitance upon
integration of nickel (II) octa [(3,5-biscarboxylate)-phenoxy] phthalocyanine with
SWCNT-phenylamine. J Power Sources 2010;195:3841–8.
[2] Li L, Lu F, Xue R, Ma BL, Li Q, Wu N, Liu H, Yao WQ, Guo H, Yang W. Ultrastable
triazine-based covalent organic framework with an interlayer hydrogen bonding
for supercapacitor applications. ACS Appl Mater Interfaces 2019;11:26355–63.
[3] Najib S, Erdem E. Current progress achieved in novel materials for supercapacitor
electrodes: mini review. Nanoscale Adv 2019;1:2817–27.
[30] Gao J, Cheng C, Zhou X, Li Y, Xu X, Du X, et al. Synthesis of size controllable cu-
phthalocyanine nanofibers by simple solvent diffusion method and their
electrochemical properties. J Colloid Interface Sci 2010;342:225–8.
[31] Nguyen HL, Gropp C, Ma YH, Zhu CH, Yagh OM. 3D covalent organic frameworks
selectively crystallized through conformational design. J Am Chem Soc 2020;142:
20335–9.
[4] Wang F, Wu X, Yuan X, Liu Z, Zhang Y, Fu L, Zhu Y, Zhou Q, Wu Y, Huang W. Latest
advances in supercapacitors: from new electrode materials to novel device designs.
Chem Soc Rev 2017;46:6816–54.
[5] Khattak AM, Sin H, Ghazi ZA, He X, Liang B, Khan NA, Alanagh HR, Iqbal A, Li LS,
Tang ZT. Controllable fabrication of redox-active conjugated microporous polymer
on reduced graphene oxide for high performance faradaic energy storage. J Mater
Chem A 2018;6:18827–32.
[32] Wu ZS, Zheng YJ, Zheng SH, Wang S, Sun CL, Parvez K, Ikeda T, Bao XH, Mullen K,
Feng XL. Stacked-layer heterostructure films of 2D thiophene nanosheets and
graphene for high-rate all-solid-state pseudocapacitors with enhanced volumetric
capacitance. Adv Mater 2017;29:1602960.
´
[6] Beguin F, Presser V, Balducci A, Frackowiak E. Carbons and electrolytes for
advanced supercapacitors. Adv Mater 2014;26:2219–51.
[7] Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater 2008;7:
845–54.
[33] Zhuang X, Zhang F, Wu D, Feng X. Graphene coupled schiff-base porous polymers:
towards nitrogen-enriched porous carbon nanosheets with ultrahigh
electrochemical capacity. Adv Mater 2014;26:3081–6.
[8] Manjunatha N, Imadadulla M, Lokesh KS, Reddy KR. Synthesis and
electropolymerization of tetra-[β-(2-benzimidazole)] and tetra-[β-(2-(1-(4-
aminophenyl))benzimidazole)] embedded cobalt phthalocyanine and their
supercapacitance behaviour. Dyes Pigments 2018;153:213–24.
[9] Wang YG, Song YF, Xia YY. Electrochemical capacitors: mechanism, materials,
systems, characterization and applications. Chem Soc Rev 2016;45:5925–50.
[10] Han Y, Zhang Q, Hu NT, Zhang X, Mai YY, Liu JQ, Hua XL, Wei H. Core-shell
nanostructure of single-wall carbon nanotubes and covalent organic frameworks
for supercapacitors. Chin Chem Lett 2017;28:2269–73.
[34] Wan Y, Liang Q, Cong TT, Wang XY, Tao YY, Sun MY, Li ZY, Xu S. Novel catalyst of
zinc tetraamino-phthalocyanine supported by multi-walled carbon nanotubes with
enhanced visible-light photocatalytic activity. RSC Adv 2015;5:66286–93.
[35] Pan X, Fan Z, Chen W, Ding Y, Luo H, Bao X. Enhanced ethanol production inside
carbon-nanotube reactors containing catalytic particles. Nat Mater 2007;6:507–11.
[36] Zhang HB, Dong X, Lin GD, Liang XL, Li HY. Carbon nanotube-promoted Co-Cu
catalyst for highly efficient synthesis of higher alcohols from syngas. ChemComm
2005:5094–6.
[37] Ding XS, Han BH. Metallophthalocyanine-based conjugated microporous polymers
as highly efficient photosensitizers for singlet oxygen generation. Angew Chem Int
Ed 2015;54:6536–9.
[11] Wang Y, Shi ZQ, Huang Y, Ma YF, Wang CY, Chen MM, Chen YS. Supercapacitor
devices based on graphene materials. J Phys Chem C 2009;113:13103–7.
[12] Son H, Yang MH, Mutyala AK, Chang DW, Park JS. Superior electrocatalytic
performance of polyisobutylene-substituted metallophthalocyanines supported on
single-walled carbon nanotubes for an oxygen reduction reaction. Dyes Pigments
2019;162:662–70.
[38] Li Q, Shao Q, Wu Q, Duan Q, Li YH, Wang HG. In situ anchoring of metal
nanoparticles in N-doped carbon framework derived from metallophthalocyanine-
based conjugated microporous polymers towards efficient oxygen reduction
reaction. Catal Sci Technol 2018;8:3572–9.
[13] Feng E, Ma GF, Peng H, Hua FT, Tang W, Lei Z, Tang W, Lei ZQ. Sponge integrated
highly compressible all-solid state supercapacitor with superior performance. New
J Chem 2017;41:13347–54.
[39] Mei L, Cui X, Duan Q, Li YH, Lv XL, Wang HG. Metal phthalocyanine-linked
conjugated microporous polymer hybridized with carbon nanotubes as a high-
performance flexible electrode for supercapacitors. Int J Hydrogen Energy 2020;
45:22950–8.
[14] Khalid M, Varela H. A general potentiodynamic approach for red phosphorus and
sulfur nanodot incorporation on reduced graphene oxide sheets: metal-free and
binder-free electrodes for supercapacitor and hydrogen evolution activities.
J Mater Chem A 2018;6:3141–50.
[40] Ding XS, Han BH. Copper phthalocyanine-based CMPs with various internal
structures and functionalities. ChemComm 2015;51:12783–6.
[41] Zhao YC, Wang T, Zhang LM, Cui Y, Han BH. Facile approach to preparing
microporous organic polymers through benzoin condensation. ACS Appl Mater
Interfaces 2012;4:6974–80.
[15] Cao JY, Zhao Y, Xu YF, Zhang Y, Zhang B, Peng HS. Sticky-note supercapacitors.
J Mater Chem A 2018;6:3355–60.
[16] Tabrizi AG, Arsalani N, Mohammadi A, Namazi H, Ghadimi LS, Ahadzadeh I. Facile
synthesis of a MnFe2O4/rGO nanocomposite for an ultra-stable symmetric
supercapacitor. New J Chem 2017;41:4974–84.
[42] Chidembo AT, Ozoemena KI, Agboola BO, Gupta V, Wildgoose GG, Compton RG.
Nickel (II) tetra-aminophthalocyanine modified MWCNTs as potential
nanocomposite materials for the development of supercapacitors. Energy Environ
Sci 2010;3:228–36.
[17] Zhang HH, Zhang YN, Gu C, Ma YG. Electropolymerized conjugated microporous
poly(zinc-porphyrin) films as potential electrode materials in supercapacitors. Adv
Energy Mater 2015;5:1402175.
[43] Schwab MG, Fassbender B, Spiess HW, Thomas A, Feng XL, Müllen K. Catalyst-free
preparation of melamine-based microporous polymer networks through schiff base
chemistry. J Am Chem Soc 2009;131:7216–7.
[18] Ahn H, Huang YC, Lin CW, Lee YH. Efficient defect healing of transition metal
dichalcogenides by metallophthalocyanine. ACS Appl Mater Interfaces 2018;10:
29145–52.
[44] Liang XM, Gao Y, Duan JL, Liu ZF, Fang SL, Baughman RH, Jiang L, Cheng QF.
Enhancing the strength, toughness, and electrical conductivity of twist-spun carbon
[19] Bıyıklıoglu Z, Çakır V, Koca A, Kantekin H. Synthesis, electrochemical, in-situ
spectroelectrochemical and in-situ electrocolorimetric characterization of non-
peripheral tetrasubstituted metal-free and metallophthalocyanines. Dyes Pigments
2011;89(1):49–55.
nanotube yarns by
π bridging. Carbon 2019;150:268–74.
[45] Amin K, Meng QH, Ahmad A, Cheng M, Zhang M, Mao LJ, Lu K, Wei ZX. A carbonyl
compound-based flexible cathode with superior rate performance and cyclic
stability for flexible lithium-ion batteries. Adv Mater 2018;30:1703868.
[20] Tang Q, Li L, Song Y, Liu Y, Li H, Xu W, Liu Y, Hu W, Zhu D. Photoswitches and
phototransistors from organic single-crystalline sub-micro/nanometer ribbons. Adv
Mater 2007;19:2624–8.
7