Synthesis of 9H-carbazole-9-carbothioic methacrylic thioanhydride, electropolymerization, characterization and supercapacitor applications

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Polymer Bulletin ISSN 0170-0839Volume 71Number 6 Polym. Bull. (2014) 71:1557-1573DOI 10.1007/s00289-014-1141-2

Synthesis of 9H-carbazole-9-carbothioic methacrylic thioanhydride,electropolymerization, characterizationand supercapacitor applications

Murat Ates, Nesimi Uludag & FatihArican

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ORI GIN AL PA PER

Synthesis of 9H-carbazole-9-carbothioic methacrylicthioanhydride, electropolymerization, characterizationand supercapacitor applications

Murat Ates • Nesimi Uludag • Fatih Arican

Received: 20 August 2013 / Revised: 27 March 2014 / Accepted: 31 March 2014 /

Published online: 10 April 2014

� Springer-Verlag Berlin Heidelberg 2014

Abstract A novel organic molecule of 9H-carbazole-9-carbothioic methacrylic

thioanhydride (CzCS2metac) was synthesized by incorporating CS2 and methacry-

late groups into the carbazole monomer structure. CzCS2metac was characterized by

FTIR, 1H-NMR and 13C-NMR spectroscopy. CzCS2metac was electropolymerized

in 0.1 M tetraethylammonium tetrafluoroborate (TEABF4)/acetonitrile (CH3CN) on

glassy carbon electrode (GCE). The characterization of the electrocoated

P(CzCS2metac)/CFME thin film was studied by various techniques, such as cyclic

voltammetry, scanning electron microscopy–energy-dispersive X-ray analysis and

electrochemical impedance spectroscopy. The specific capacitance (Csp) of

P(CzCS2metac)/MWCNT/GCE in the scan rate of 20 mV s-1 (Csp = 38.48 F g-1

from area formula, Csp = 38.52 F g-1 from charge formula) was increased *15.66

and *15.64 times in area and charge formulas compared to P(CzCS2metac)/GCE

(Csp = 2.46 F g-1 from area and charge formulas). The same results were also

obtained from Nyquist graphs. The specific capacitance value of composite film

(Csp = 1.09 9 10-3 F) is *15.66 times higher than the polymer film

(Csp = 6.92 9 10-5 F). The composite film may be used as supercapacitor elec-

trode material in energy storage devices.

Keywords Carbazole functionalized methacrylate � Scanning electron

microscopy � Capacitance � Multi-walled carbon nanotube

M. Ates (&) � N. Uludag � F. Arican

Department of Chemistry, Faculty of Arts and Sciences, Namik Kemal University,

Degirmenalti Campus, 59030 Tekirdag, Turkey

e-mail: [email protected]

URL: http://mates-en.nku.edu.tr; http://www.atespolymer.org

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DOI 10.1007/s00289-014-1141-2

Author's personal copy

Introduction

Polymers and copolymers obtained with carbazole and methacrylates, acrylates, and

dimethacrylates have a wide variety of applications in dentistry, optical eyewear,

fiber optics, holography, and microelectronics [1]. Functional p-conjugated systems

of novel synthesized organic molecules are associated with new behaviors of

polymers or composite materials such as electric, electronic, optic, and mechanistic

properties afforded by covalently attached functional groups [2–4]. In previous

papers, carbazole derivatives have been studied electrochemically such as poly(N-

hydroxymethyl carbazole) [5], poly(9-(4-vinylbenzyl)-9H-carbazole) [6], poly(N-

alkyl-3,6-carbazoles) [7], 9-benzyl-9H-carbazole [8], poly(9-tosyl-9H-carbazole)

[9], poly(N-vinylcarbazole) [10], and poly(ThCzHa) [11]. Carbazole derivatives are

good electron donors, which mean they can be used electron transfer to electron

acceptor groups. So, polycarbazole and its substituents are used in many electronic

applications, energy storage capability [12] and photoelectronic applications [13,

14]. The synthesis of multi-walled carbon nanotube/polymer/GCE composites is a

promising approach to the effective incorporation of multi-walled carbon nanotube

(MWCNT) into the industrial devices [15, 16]. Electrochemical capacitors have

been investigated to perform energy storage systems capable of providing electricity

with high power density and/or pulse power [17]. In literature, copper chloride-

doped polypyrrole multi-walled carbon nanotube nanocomposites were investigated

by an in situ oxidative polymerization method [18]. Liu et al. [19] have studied the

Ag/polypyrrole composites with different surfactants via interface polymerization

method. Polyaniline nanofibers (PANI-NFs) were fabricated by electro spinning

method for supercapacitors by Chaudhari et al. [20]. Kalra et al. have reported a

facile method for obtaining extremely high surface area and uniformly porous

carbon nanofibers for supercapacitors [21].

In this paper, we present studies of a novel synthesis of CzCS2metac, and its

characterization by FTIR, 1H-NMR, and 13C-NMR spectroscopy. The functional

carbazole was electrodeposited in TEABF4/CH3CN on GCE. The polymer film was

characterized by CV, SEM–EDX, and EIS. P(CzCS2metac)/MWCNT/GCE was

studied for the capacitance values in three different ways (area, charge formulas and

Nyquist plots).

Experimental

Materials

Carbazole (Cz, [99 %), tetraethylammonium tetrafluoroborate (TEABF4), acetone

(99.7 %, Purex PA), silica gel (60 F254) were obtained from Merck. Acetonitrile

(CH3CN), hydrochloric acid, and ethyl acetate were from Carlo Erba. Dimethyl-

sulfoxide (DMSO), methacroyl chloride ([97 %), and carbon disulfide (CS2),

sodium dodecylsulphate (SDS) were obtained from Sigma-Aldrich. High-strength

(HS) carbon fibers C320000A (CA) (Sigri Carbon, Meitingen, Germany) containing

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320.000 single filaments in a roving were used as working electrodes. All chemicals

were high-grade reagents and were used as received.

Instrumentation

1H-NMR spectra were recorded on a Varian Gemini 400 spectrometer, operating at

400 MHz. Spectra were registered in CDCl3 using the solvent as internal standard at

400 MHz for 1H-NMR at room temperature. Chemical shifts are expressed in terms

of parts per million (d) and the coupling constants are given in Hz. IR spectra were

recorded using Mattson 1000 FTIR spectrometer as KBr pellets. Melting points

were determined in a capillary tube on Electro thermal IA 9000 apparatus.

Reactions were monitored by thin-layer chromatography (silica gel 60 F254).

Purification of solvents was performed according to standard methods.

Electrocoated polymers were analyzed by scanning electron microscopy (SEM)

and energy-dispersive X-ray analysis (EDX) using a Carl Zeiss Leo 1430 VP.

Average values of the increase in thickness were obtained from SEM images taking

into account the diameter of the uncoated CFME.

Cyclic voltammetry was performed using a PARSTAT 2273 and IVIUM-

VERTEX potentiostat/galvanostat (software, powersuit and Faraday cage, BASI

Cell Stand C3) in a three-electrode electrochemical cell employing glassy carbon

(GCE, diameter &3 mm) as the working electrode, platinum disc electrode as the

counter electrode, and Ag/AgCl (3.5 M) as the reference electrode.

Electrochemical impedance spectroscopy

The electrochemical impedance spectroscopy (EIS) measurements were taken at

room temperature (24 ± 1 �C) using a conventional three-electrode cell configu-

ration. EIS measurements were conducted in monomer-free electrolyte solution with

perturbation amplitude 10 mV over a frequency range of 10 mHz to 100 kHz with

PARSTAT 2273 and IVIUM-VERTEX (software; powersuit).

Electrosynthesis procedure

Electropolymerization process was achieved by cyclic voltammetric (CV) method at

a scan rate of 100 mV s-1. Electropolymerization experiments were done in 0.1 M

TEABF4/CH3CN containing in the initial molar concentrations of [CzCS2me-

tac]0 = 5 mM in the potential ranges from 0.00 to 1.800 mV at room temperature.

Preparation of CFMEs

The electrodes were prepared using a 3 cm length of the CFME (diameter *7 lm)

attached to copper wire with a Teflon tape. The aim is to characterize the modified

film electrode by SEM–EDX and FTIR-ATR analysis. Only 1.0 cm of the carbon

fiber was dipped into the solution to keep the electrode area constant (*0.022 cm2).

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Polymerization procedure with carbon nanotube

Carbon nanotube (CNT) (15 mg) was dispersed in supporting electrolyte of sodium

dodecyl sulphate (SDS) solution (5 mL, 0.1 M) for 45 min [22]. The electrode was

produced by modifying the literature [23] procedure. CNT (5 lL) was applied on to

a glassy carbon (GC) electrode surface and dried initially in air and then by blowing

nitrogen. CzCS2metac was electrosynthesized by chronoamperometric method in

0.1 M tetraethyl ammonium tetrafluoroborate (TEABF4)/acetonitrile (CH3CN)

solution at a constant potential of 1.2 V at the polymerization time of 100 s. Then,

nafion solution (5 lL, 5 %) was dropped onto the surface of the electrode. CNT–

polymer ratio was calculated using the following formula; CNT % ratio = MCNT/

MPoly 9 100.

The polymer mass was calculated using the following formula: Qdep 9 MMon/

Z 9 F

Where F: Faraday constant (96485), Z = 2 (for our polymer), Qdep: deposition

charge, Mmon: monomer mass.

Calculation of specific capacitance with cyclic voltammetry

Cyclic voltammograms and electrochemical impedance spectroscopy data for initial

monomer concentration of [CzCS2metac]0 = 5 mM in total solution of 5 mL of

H2SO4 (0.5 M) were measured and specific capacitance calculated using two

different formulas.

1. Specific capacitance (Sc)

Sc ¼ DQ=M � DV

Where DQ voltammetric charge integrated from cyclic voltammogram (C); DV

potential range (V), M mass of the electrode material on the electrode surface (g),

calculated using the following formula:

M ¼ MCNT þ MPolym

2.

Sc ¼Z

I � dV=S� m� DV

Where $(I 9 dV) area integrated from CV, S scan rate (mVs-1), DV potential

range and m mass of the electrode material on the electrode surface (g).

EIS was measured in 0.5 M H2SO4 in monomer-free solution at different scan

rates of 25, 50, 100, 250 mV s-1 for polymers, coated with MWCNT for 100, 200,

300, 400 s.

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Results and discussion

Synthesis procedure of 9H-carbazole-9-carbothioic methacrylic thioanhydride

A suspension of NaOH (30 mmol) in dimethylsulfoxide (150 mmol) was prepared

in a beaker. Afterwards, carbazole (29.9 mmol) was added under vigorous stirring

for 2 h at room temperature. Carbon disulfide (30 mmol) was added dropwise into

this mixture, and the resultant reddish solution was obtained for *4 h at room

temperature, followed by adding slowly methacroyl chloride (30 mmol) in DMSO.

The final mixture was stirred for a night. The resultant reaction mixture was poured

into a large amount of water and yellow solid was obtained by filtration. The crude

product was purified by silica gel chromatography and crystallized from ethyl

acetate. The resultant mass was obtained as 4.2 g, yield of 74 %, melting point of

180 �C and molecular weight of 311.05 g mol-1 as shown in Fig. 1.

As a basic for the synthetic approaches 9H-carbazole-9-carbothioic methacrylic

thioanhydride was synthesized from carbazole by the methods given in the

literatures [24, 25]. The obtained spectral of dithiocarbamates were identical to

those of the produced in this literatures. 9H-carbazole-9-carbothioic methacrylic

thioanhydride was determined by FTIR, 1NMR, and 13C-NMR. Synthesis mech-

anism of 9H-carbazole-9-carbothioic methacrylic thioanhydride was given in Fig. 2.

Characterisation of 9H-carbazole-9-carbothioic methacrylic thioanhydride

FTIR spectrum of 9H-carbazole-9-carbothioic methacrylic thioanhydride is given in

Fig. 3. The characteristic peaks of FTIR spectrum was given in the following: FTIR

analysis (potassium bromide): v 3,401 cm-1 (aromatic C–H), 1,604 cm-1 (aromatic

C=O), 1,495 cm-1 (aromatic C=C), 1,445 cm-1 (aromatic C=C), 1,330 cm-1

(C=S), 750 cm-1 (C–S) [26].1H-NMR spectrums of 9H-carbazole-9-carbothioic methacrylic thioanhydride are

given in Fig. 4a. The characteristic peaks were given in the following: 1H-NMR

(deuteriochloroform) spectrum: d 7.21–7.45 (m, 4H, aromatic C–H), 7.48–7.64 (m,

Fig. 1 Molecular structure of9H-carbazole-9-carbothioicmethacrylic thioanhydride

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2H, aromatic C–H), 8.02–8.05 (d, 2H, aromatic C–H). 9H-carbazole-9-carbothioic

methacrylic thioanhydride was determined by NMR experiments and FTIR

spectroscopy.13C-NMR spectrums of 9H-carbazole-9-carbothioic methacrylic thioanhydride

are shown in Fig. 4b. The important peaks were given in the following: 13C-NMR

(deuteriochloform): d140.10; 139.76; 126.79; 126.30; 125.90; 123.69; 123.33;

120.62; 120.45; 115.35; 110.59; 109.32; 77.37; 77.25, 77.03; 76.73; 16.48.

Analytically calculated for C17H13NOS2 (311.05 g mol-1): C (65.55); H (4.20);

N (4.50). Found: C (65.58.04); H (417); N (4.46).

Electropolymerization of monomer

The cyclic voltammogram of CzCS2metac monomer which was electrocoated on

GCE recorded in 0.1 M TEABF4/CH3CN is shown in Fig. 5. In our previous paper

[27], carbazole was electropolymerized on CFME at the anodic peak potential of

0.94 V and the cathodic peak potential at 0.88 V in 0.1 M TEABF4/CH3CN. In our

novel synthesized monomer was electrochemically polymerized on the anodic peak

potential at 0.99 V and the cathodic peak potential at 0.83 V. The anodic and

Fig. 2 Synthesis mechanism of 2-(3,6-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-9H-carbazole-9-yl)ethyl methacrylate

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cathodic peak potentials shift to the higher potential values for CzCS2metac due to

the functional groups of carbon disulfide (CS2) and methacroyl groups into the

carbazole structure. And the oxidation peak potentials of monomer also shifts to

higher value from *1.30 to *1.47 V from carbazole monomer to CzCS2metac

monomer, respectively. In our previous study of 2-(9H-carbazole-9-yl) ethyl

methacrylate, which is absent of CS2 group in the carbazole structure, has the anodic

peak potential at Epa = 0.87 V and the cathodic peak potential at Epc = 0.79 V in

the initial monomer concentration of 1 mM in 0.1 M NaClO4/CH3CN. The most

reversible polymer (DE = 0.09 V, Epa = 0.79 V, and Epc = 0.70 V) and total

charge of polymer growth (Q = 52.74 mC) were obtained in the initial monomer

concentration of 5 mM.

Effect of scan rate in monomer-free solution

The electrocoated film was inserted into monomer-free electrolyte solution and its

redox behavior was investigated in detail. One oxidation peak potential was

observed at 1.47 V by increasing the applied potential (Fig. 6a). The anodic process

is associated with one cathodic peak at 0.25 V. The scan rate dependence of the

electroactive film current density was investigated only on the reversible system.

The peak current density (ip) for a reversible voltammogram at 25 �C is given by

Randless–Sevcik equation: ip = (2.69 9 105) 9 A9D1/2 9 C0 9 t1/2 where t is

the scan rate, A is the electrode area, D is the diffusion coefficient of electroactive

species and C0 is the concentration of electroactive species in the solution. Current

density is proportional to t1/2 in the range of square root of scan rate, which

indicates a diffusion-limited redox process [28]. Peak current density was

determined to be proportional with t1/2 in the range of square root of scan rates

Fig. 3 FTIR spectrum of 9H-carbazole-9-carbothioic methacrylic thioanhydride

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from 5 to 22.36 mV s-1 (Regression fit (RAn) = 0.99937, and RCat = -0.99354)

where diffusion control applies [29].

SEM–EDX analysis of P(CzCS2metac)

The morphological features of the electrocoated carbon fiber microelectrodes were

performed with different initial monomer concentrations of [CzCS2metac]0 = 1 mM

Fig. 4 a 1H-NMR (CDCl3; 400 MHz) b 13C-NMR spectrums of 9H-carbazole-9-carbothioic methacrylicthioanhydride

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Fig. 5 Electrogrowth of 9H-carbazole-9-carbothioicmethacrylic thioanhydride,[CzCS2metac]0 = 5 mM(Qa = 37.46 mC); 8 cycles,scan rate 100 mV s-1, 0.1 MTEABF4/CH3CN

Fig. 6 a Current density vs. potential graph obtained from monomer-free solution, b scan ratedependence of poly(CzCS2metac), c plots of anodic and cathodic peak current density vs. the square rootof scan rate dependence of poly(CzCS2metac), [CzCS2metac]0 = 5 mM. All measurements are taken inmonomer-free solution in 0.1 M TEABF4/CH3CN. Scan rates were given from 25 to 1,000 mV s-1

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(Fig. 7a), [CzCS2metac]0 = 3 mM (Fig. 7b), [CzCS2metac]0 = 5 mM (Fig. 7c), and

[CzCS2metac]0 = 10 mM (Fig. 7d), via SEM. The fibers were attached on copper

plate by use of a double-sided carbon tape. The morphology of CF itself exhibits

smooth surface with a surface curvature and the morphology of the polymer films is

clearly dependent on the initial monomer concentration, indicating that electron

transfer to electrode at a scan rate of 100 mVs-1 in 0.1 M TEABF4/CH3CN which can

be used to control surface morphology. The high-resolution images obtained by SEM

analysis of the electrocoated CFMEs show that the electropolymerization of

conductive polymers with different initial monomer concentrations produces

different-sized grainy orientations [30]. Poly(CzCS2metac) is given in Fig. 7a–d.

Energy-dispersive X-ray (EDX) images indicated the formation of the homopol-

ymer (Fig. 8a–d). EDX data from point analysis experiments for different initial

monomer concentrations of [CzCS2metac]0 = 1 mM (Fig. 8a), [CzCS2me-

tac]0 = 3 mM (Fig. 8b), [CzCS2metac]0 = 5 mM (Fig. 8c), and [CzCS2me-

tac]0 = 10 mM (Fig. 8d) were performed in 0.1 M TEABF4/CH3CN on CFME.

The results show that CS2 and methacylic groups were successfully included into the

polymer structure. This was evidenced by the existence of sulfur in the highest

amount of weight percent of 2.51 %, [CzCs2metac]0 = 5 mM, compared to initial

monomer concentrations of [CzCS2metac]0 = 3 mM (2.04 %) and [CzCS2me-

tac]0 = 10 mM (1.38 %). The presence of the peaks, belonging to oxygen and

Fig. 7 SEM image of poly(CzCS2metac)/CFME, 0.1 M TEABF4/CH3CN, a [CzCS2metac]0 = 1 mM,b [CzCS2metac]0 = 3 mM, c [CzCS2metac]0 = 5 mM, d [CzCS2metac]0 = 10 mM, potential range0–1,8 V, 30 cycle, scan rate 100 mV s-1

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carbon and nitrogen indicates the polymer formation. The existence of fluorine

element for [CzCS2metac]0 = 1 mM inclusion of dopant anion (BF4-) of the

supporting electrolyte into the polymer during electro-growth process.

Electrochemical impedance spectroscopic study

CzCS2metac was electropolymerized by chronoamperometric method at polymer-

ization time (100 s) in 0.1 M TEABF4/CH3CN at a constant potential of 1.2 V. The

highest specific capacitances (Csp = 38.48 F g-1 from area formula and

Csp = 38.52 F g-1 from charge formula) were obtained for P(CzCS2metac)/

MWCNT/GCE in the initial monomer concentration of 5 mM at the polymerization

time of 100 s. The Csp are very higher values compared to without MWCNT in the

composite material, such as Csp = 2.46 F g-1, obtained from area and charge

formulas.

Cyclic voltammetric (CV) measurements of the composite electrode, i.e.,

P(CzCS2metac)/MWCNT, were conducted in H2SO4 (0.5 M) solution at various

scan rates of 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 mVs1 (Fig. 9).

The specific capacitances were obtained from the area (Table 1) and charge

formulas of CV (Table 2), which indicated that the highest Csp obtained from area

formula was 38.52 F g-1 for P(CzCS2metac)/MWCNT/GCE at a scan rate of 20

Fig. 8 EDX point analysis of poly(CzCS2metac)/CFME, 0.1 M TEABF4/CH3CN,a [CzCS2metac]0 = 1 mM, b [CzCS2metac]0 = 3 mM, c [CzCS2Metac]0 = 5 mM,d [CzCS2metac]0 = 10 mM, potential range 0–1.8 V, 30 cycle, scan rate 100 mV s-1

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mV s-1. It means that Csp was increased *15.66 and *15.64 times in area and

charge formulas compared to P(CzCS2metac)/GCE.

All electrodes show a slight deviation from the capacitive line (y-axis), indicating

fast charge transfer at GCE/polymer/MWCNT and GCE/polymer/MWCNT/solution

interfaces, as well as fast charge transport in the polymer bulk. The increase in

steepness in Nyquist plot is as given in Fig. 10. The lowest frequency (f) and the

highest Zim (Z00) values are placed in the formula of: Csp = 1/2p 9 f9Z00 for specific

capacitance calculations. Nyquist plot for P(CzCS2metac)/MWCNT/GCE indicates

the highest capacitive behavior at the frequency of 0.01 Hz in the initial monomer

concentration of [CzCS2metac]0 = 5 mM as Csp = 1.09 9 10-3 F. The specific

capacitance for P(CzCS2metac)/GCE was obtained as Csp = 6.92 9 10-5 F.

Composite materials Csp are 15.66 times higher than the Csp value of polymer.

Fig. 9 Cyclic voltammograms of a P(CzCS2metac)/GCE, ([CzCS2metac]0 = 5 mM, 1.2 V, 100 s)b P(CzCS2metac)/MWCNT/GCE, in H2SO4 solution (0.5 M) at a scan rate of 5, 10, 20, 30, 40, 50, 60, 70,80, 90 and 100 mVs-1

Table 1 Specific capacitances obtained by chronoamperometric method from area formula for

P(CzCS2metac)/MWCNT/GCE. ([CzCS2metac]0 = 5 mM, 1.2 V, 100 s)

Scan rates/mV s-1 Csp/F g-1 from area formula

P(CzCS2metac)/GCE P(CzCS2metac)/MWCNT/GCE

5 3.41 32.46

10 2.91 36.45

20 2.46 38.48

30 2.28 37.88

40 2.11 36.94

50 2.02 35.43

60 1.87 36.12

70 1.78 31.01

80 1.76 27.23

90 1.21 26.66

100 1.59 25.12

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A value of double-layer capacitance (Cdl) can be calculated from Bode-

magnitude plot, where by extrapolating the linear section to value x = 1

(logx = 0), employing the relationship IZI = 1/Cdl as given in Fig. 11. Cdl value

for P(CzCS2metac)/GCE is obtained as 3.44 9 10-4 F. However, Cdl value for

P(CzCS2metac)/MWCNT/GCE was obtained as 3.83 9 10-3 F. Double-layer

capacitance value of composite material is *11.13 times higher than polymer/

GCE. Double-layer capacitances of poly[2-(9H-carbazole-9-yl) ethyl methacrylate

(Cdl = 15 lF cm-2) in the initial monomer concentration of 5 mM, for poly(9-

Table 2 Specific capacitances obtained by chronoamperometric method from charge (Q) formula for

P(CzCS2metac)/MWCNT/GCE. ([CzCS2metac]0 = 5 mM, 1.2 V, 100 s)

Scan rates/mV s-1 Csp/F g-1 from Q formula

P(CzCS2metac)/GCE P(CzCS2metac)/MWCNT/GCE

5 3.42 32.49

10 2.91 36.45

20 2.46 38.52

30 2.28 37.90

40 2.11 36.60

50 2.01 35.47

60 1.86 32.53

70 1.78 31.00

80 1.77 27.20

90 1.21 26.68

100 1.59 25.12

Fig. 10 Nyquist plots of P(CzCS2metac)/GCE, ([CzCS2metac]0 = 5 mM, 1.2 V, 100 s) andP(CzCS2metac)/MWCNT/GCE in 0.5 M H2SO4. Amplitude of 10 mV, frequency range 10 mHz–100 kHz

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tosyl-9H-carbazole) (Cdl = 11 lF cm-2) in the initial monomer concentration of

10 mM, for poly(9-vinylbenzyl)-9H-carbazole) (Cdl = 108 lF cm-2) in the initial

monomer concentration of 10 mM and for poly(9-benzyl-9H-carbazole)

(Cdl = 21.14 lF cm-2) in the initial monomer concentration of 3 mM were

obtained in our previous work.

The phase angle is plotted versus the logarithm of the angular frequency. The

phase angle is higher for composite material compared to polymer film toward

lower impedances especially at 10 mHz. The maximum phase angle for

P(CzCS2metac)/MWCNT/GCE was obtained as h = *70� at the frequency of

0.01 Hz. However, the maximum phase angle for P(CzCS2metac)/GCE was

obtained as h = *55� at the same frequency as given in Fig. 12.

Stability test study of P(CzCS2metac)

As it is well-known, the stability is a significant consideration for the practical

application of a capacitor. Stability measurements for P(CzCS2metac)/MWCNT/

GCE were performed at a scan rate of 100 mVs-1 over 500 cycles. Long-term

stability of the capacitor was also tested by CV, and the result of the specific

capacitance was found to still at *68.82 %, the initial capacitance (Fig. 13),

P(CzCS2metac)/MWCNT/GCE. The composite film of P(CzCS2metac)/MWCNT/

GCE is suitable for the capacitor applications as it had high stability for practical

applications. In literature, there is a 20 % decrease in specific capacitance for

various conducting polymers [31, 32]. The results show that P(CzCS2metac)/

MWCNT/GCE was decreased only in 31.18 % in specific capacitance value.

Fig. 11 Bode-magnitude plots of P(CzCS2metac)/GCE, ([CzCS2metac]0 = 5 mM, 1.2 V, 100 s) andP(CzCS2metac)/MWCNT/GCE in 0.5 M H2SO4. Amplitude of 10 mV, frequency range 10 mHz–100 kHz

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Conclusion

In this study, CzCS2metac was first chemically synthesized to obtain a new

composite material. CzCS2metac was characterized by FTIR, 1H-NMR, and 13C-

NMR spectroscopy. Monomer was electrodeposited together with MWCNT on

GCE to form composite material. Polymer or composite/GCE was characterized via

CV, SEM–EDX, and EIS analysis. P(CzCS2metac)/MWCNT/GCE in the scan rate

of 20 mV s-1 increased the specific capacitance values of *15.66, *15.64 and

*15.66 times in area, charge formulas and from Nyquist plot, respectively.

P(CzCS2metac)/MWCNT/GCE is the good performance electrode material for

supercapacitor applications.

Author contributions The manuscript was written through the contributions of

all authors. All authors have given approval to the final version of the manuscript.

Fig. 12 Bode-phase plots of of P(CzCS2metac)/GCE, ([CzCS2metac]0 = 5 mM, 1.2 V, 100 s) andP(CzCS2metac)/MWCNT/GCE in 0.5 M H2SO4. Amplitude of 10 mV, frequency range 10 mHz–100 kHz

Fig. 13 Stability test results ofP(CzCS2metac)/MWCNT/GCE,scan rate 100 mVs-1. 500 cycleswas performed for stability test.Csp was calculated and plottedon the graph at every 10 cycle

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Acknowledgments This work supported by The Scientific & Technological Council of Turkey

(TUBITAK)-TBAG-110T791 Project.

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Documents

Synthesis of 9H-carbazole-9-carbothioic methacrylic thioanhydride, electropolymerization, characterization and supercapacitor applications