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conductive polymer nano composite for super capacitor applications
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Electrochemical study of perlite-barium ferrite/ conductive polymer nano composite for super capacitor applications Mohammad Sadeghinia a, Javad Shabani Shayeh b,*, Fataneh Fatemi b, Moones Rahmandoust b, Ali Ehsani c, Mehran Rezaei d a
Department of Chemistry, Faculty of Science, University of Tehran, Tehran, Iran Protein Research Center, Shahid Beheshti University G.C., Tehran, Iran c Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran d School of Chemical, Petroleum and Gas Engineering, Iran University of Science and Technology (IUST), Tehran, Iran b
highlights
graphical abstract
Developing a simple and facile process for synthesis of PANI/ BaFe12O19. Preparing a novel and efficient nanocomposite
for
electro-
chemical capacitors. Enhancing
specific
capacitance
and stability through incorporation of BaFe12O19.
article info
abstract
Article history:
Polyaniline/perlite-barium ferrite nanoparticles (PANI/PBF-NPs) composite electrodes were
Received 8 May 2019
studied in here for super capacitor applications. The PBF-NPs synthesized using hydro-
Received in revised form
thermal technique and then the composite electrode was fabricated electrochemically by
18 July 2019
cyclic voltammetry (CV) technique. Transmission electron microscopy (TEM), Scanning
Accepted 10 September 2019
electron microscopy (SEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller nitrogen
Available online xxx
adsorption/desorption (BET) and fast Fourier transform infrared spectroscopy (FTIR) were employed to study the morphological and structural properties of the prepared electrodes.
Keywords:
Furthermore, various electrochemical techniques were used such as CV, Galvano static
Nanocomposite
charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) to investigate
Perlite
their electrochemical performance as well. SEM graphs show uniform distribution of 60-
Supercapacitor
nm PBF-NPs in the PANI filaments. The specific capacitance of PANI and composite elec-
Conductive polymers
trodes was obtained to be 225 and 330 F/g, respectively. In addition, inclusion of PBF-NPs in
Electrosynthesis
the structure of PANI electrode had significantly increased the conductivity of composite
Metal oxide
* Corresponding author. E-mail address: [email protected] (J.S. Shayeh). https://doi.org/10.1016/j.ijhydene.2019.09.085 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved. Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
2
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electrodes. Continuous charge-discharge cycles test illustrated the good capability of this nano composite material for use as a charge storage device. © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction Super capacitors, also known as electrochemical capacitors (ECs), have attracted much attention due to their high-power and long life-cycle characteristics, which can fill the gap between conventional capacitors and batteries [1]. To investigate the performance and charge storage mechanism of ECs, one must be focuse on the nature of materials used in the structure of ECs and their capacitance mechanism [2e4]. In terms of material, ECs can be divided into three major classifications of active materials, including metal oxides, carbon materials and conductive polymers. Metal oxides, such as MnO2, RuO2, NiO2, etc., store the electrical charge thorough the charge transfer reaction in the oxidation states of metal atoms [5]. In the other category of active materials, i.e. the conjugated polymers such as polyaniline, polypyrrole and poly thiophene derivatives, the mechanism of charge storage is also similar to metal oxides in that by oxidation of polymer chains the counter ions form solution miggreat to polymer structure and therfore the electrical charge stored [4,6], where as in carbon materials such as graphene, as the final classification, the specific capacitance of composite electrodes is increased by increasing the surface of the electrode through storage the charge by their electrical double layer [5,16,17]. Chemical stability, higher specific capacitance, ease of synthesis and economic concerns are the reasons to choose polyaniline (PANI) as an active material of ECs [7e9]. However, the weakness of using conductive polymers for ECs is their poor life-cycle, due to the accumulation of stress on the polymer through insertion and de-insertion of solution ions over the electrode/electrolyte interface that combination of these materials together is one the methods to solve these problems [10,11]. The combination of nano materials with conductive polymers, on the other hand, is expected to increase the stability and specific capacitance of composite electrodes [12,13]. Nano materials can also boost the connection of polymer filaments together and improve their mechanical stability. They can participate in the charge transfer process, increasing the specific capacitance of the composite electrode as well [14,15]. Many papers reported the application of metal oxide nano materials in the structure of PANI and that increasing the capacitance and stability of composite electrodes are some significant features of employing these nano materials [18e20]. Bimetallic compounds nowadays attract much attention, due to their unique electrochemical behavior. The combination of two or more transition metal oxides can increase the electronic conductivity of complex oxide compounds [21]. There are two methods for the synthesis of PANI. The first method is chemical synthesis, where PANI is synthesized by
adding an initiator to the solution containing the monomer; and the second is the electrochemical method, which has the ability to control the mass of polymer and its thickness. Furthermore, the magnitude of nano materials that must be used to produce composite electrodes is very low [22]. In this work, we studied the super capacitive performance of poly aniline/perlite-barium ferrite (BaFe12O1) nanoparticle (PANI/ PBF-NP) electrodes in acidic media. For this purpose, PBF-NPs were synthesized using the hydrothermal method and later composite electrodes were produced using the electrochemical technique.
Experimental Materials All the chemical materials used in this study were purchased from Merck Chemical Company in analytical grade and were used without further purification. Double distilled water was used throughout the experiments. Aniline was doubly distilled and the resulting colorless liquid was kept in the dark at 5 C.
Apparatus Electrochemical experiments were carried out by an Auto Lab General Purpose System PGSTAT 30 (Eco-chime, Netherlands). A conventional three electrode cell holding a glassy carbon electrode, with the area of 0.03 cm2 was used as the working electrode, platinum wire and an Ag/AgCl (Argental, 3M KCl) were used as counter and reference electrode, respectively. The electrochemical impedance spectroscopy (EIS) experiments were conducted in the frequency range between 100 kHz and 15 mHz with perturbation amplitude of 5 mV to provide Nyquist curves. Morphological investigations of the polymeric films were carried out using Scanning electron microscopy (SEM) (Philips XL 30). X-ray diffraction (XRD) patterns were obtained from an X-ray diffractometer (PANalytical X’Pert-Pro) with a Cu-Ka mono-chromatized radiation source and Ni filter. The Fourier transform infrared (FTIR) spectra were recorded on Nicolet 6700 with the sweeping range of 500e4500 cm1 wavenumber. Brunauer-Emmett-Teller N2 adsorption/desorption test was performed by (BELSORP MINI II, Japan) to study the porosity and pore size distribution of the electrodes.
Synthesis of BaFe12O19 nanoparticles 2.35143 g of Ba(NO3)2 and 43.6 g of Fe(NO3)3$9H2O were dissolved in deionized water to make 1M nitrate solution and were warmed to complete solvation. Then, the nitrate
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
international journal of hydrogen energy xxx (xxxx) xxx
3
Fig. 1 e TEM graphs of PBF-NPs. solution was pumped to the reaction vessel containing 100 ml of deionized water and was co-precipitated via a 1M NaOH solution at pH ¼ 12 in 60 C. The precipitate was aged for 5 h at the same temperature, 60 C. It was then dried at 80 C and calcined at 900 C for 3 h.
Preparation of working electrodes The PANI/PBF-NPs composite was electro-polymerized on the surface of glassy carbon electrodes. The electropolymerization process was conducted by 10 cyclic voltammograms at the sweep rate of 10 mV/s, in a solution of 0.03M monomer in H2SO4 1M, 0.2 wt% of PBF-NPs and 0.005M of sodium dodecyl sulfate (SDS) that was dispersed in solution by sonication. PANI electrodes were synthesized in same solution in the absence of PBF-NPs and SDS. The mass of PANI electrodes were approximated assuming a current efficiency
of 100% for the electro-polymerization process, using Faraday’s law [6,23].
Results and discussion TEM graphs of PBF nano particles presented in Fig. 1. It can be found that PBF nano particles synthesized in hexagonal form with average size of 40 nm. This average size can be change after combination with PANI due to agglomeration of PBF nano particles in polymer matrix as presented in SEM graphs of PANI and PANI/PBF-NPs composite electrodes that PANI filaments are entangled together to form a three-dimensional network, with porosities suitable for the insertion/deinsertion of counter ions. Furthermore, polymeric electrodes are good platforms for NPs in that NPs can be dispersed on the surface of electrodes to increase their activity. The size of the
Fig. 2 e SEM graphs of (a and b) PANI and (c and d) PANI/PBF-NPs electrodes. Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 3 e (a) XRD patterns of PBF-NPs, PANI and the PANI/PBF-NPs composite electrodes, (b) FTIR spectra of electrodes.
NPs inserted in the structure of PANI electrodes was calculated to be about 60 nm (Fig. 2). To verify the structure and composition of composite electrodes, FTIR, XRD and N2 adsorption/desorption isotherm analyses were used. Fig. 3(a) presents the XRD pattern of PANI, PBF and composite electrode. As can be seen, XRD pattern of PBF shows sharp peaks at angle 0f 30.36, 32.32, 34.17, 37.13, 40.34, 55.18, 56, 64 that ascribed to (110), (107), (114), (203), (205), (217), (201) and (220), respectively. These diffraction planes attributed to hexagonal form of BPF (JCPDS#84-757). As illustrated, the PANI electrode has an amorphous structure, which alerts by the insertion of PBF nanoparticles in the polymer network and the formation of composite electrodes, leading to appearance of distinct diffraction peaks of PBF-NPs in it. Fig. 3(b) displays the FTIR spectra taken in the wavenumber range of 400e4000 cm1. As can be seen, in the FTIR spectra of PANI, the absorption peaks which appear at 1290 and 1560 cm1 correspond to leucoemeraldine and pernigraniline components, respectively. Furthermore, peak bands at 1120 and 813-503 cm1 ascribes the in-plane bending benzene rings and out-of-plane deformation of CeH benzene rings, respectively. In the FTIR spectra of PBF nanoparticles, the bands seen at 420 and 600 cm1 correspond to the stretching vibration of the ferrite materials and the broad peak at 3480 cm1 ascribed to OeH stretching of H2O [24]. FTIR spectra of composite electrodes shows the characteristic bands of PANI as well as PBF-NPs that confirm the successful formation of PANI/PBF-NPs composite electrode. To determine the surface area of the samples, BrunauerEmmett-Teller N2 adsorption/desorption analysis was performed (Fig. 4). As provided in detail in Table 1, three samples exhibit typical IV isotherms with H3-type in that the magnitude of meso porous in PBF-NPs (7.6 m2/g) is lower than both the PANI and composite electrodes, as to be 40.3 and 28.5 m2/g,
respectively. As results show, the combination of PBF-NPs with PANI caused a decrease in the surface area of composite electrodes, due to covering of the surface of PANI filaments with nanoparticles. This phenomenon results in an increase in the diameter of composite filaments compared to the PANI ones and furthermore, the pore-volume of composite electrodes decreases owing to the insertion of nanoparticles in the structure of PANI electrodes. Cyclic voltammetry (CV) curves for electro polymerization of PANI and PANI/PBF-NPs electrodes after 10 cycles are presented in Fig. 5(a). As it can be seen, each curve has three redox peaks, where the first redox peak is related to the formation of free radicals in the PANI chain (0.3, 0.1 V), the second one is due to the oxidation and reduction of intermediates that were produced in the electro polymerization process (0.5, 0.4 V), and finally the third redox peak is because of the oxidation of PANI. CVs of polymeric PANI and composite PANI/PBF-NPs electrodes in acidic media show that the composite electrodes have higher specific capacitance (C), compared to PANI ones (Fig. 5(b)). As can it be seen in both curves, there are two redox peaks, appeared between 0.4 and 0.6 V, that are related to the transition of PANI from the emeraldine to pernigraniline form. The combination of PBFNPs with PANI causes an increase in the C of composite electrodes. Furthermore, both electrodes show the ideal capacitive performance, implying that the PBF-NPs have improved the super capacitive performance of PANI electrodes. The C of electrodes can be calculated according to the CV curves, based on the following equation: C¼
I mv
(1)
where I is the current, m is the mass of the active materials and v is the scan rate. The specific capacitance for PANI and
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Table 1 e N2 adsorption/desorption analysis data for PBFNPs, PANI and PANI/PBF-NPs electrodes. Sample
Properties Mean pore Total pore Surface area diameter (nm) volume (cm3/g) (m2/g)
PBF-NPs PANI PANI/PBF-NPs
7.6 40.3 28.5
67.59 30.77 35.22
0.1292 0.3104 0.2516
presented in Fig. 5(c), CV curves of composite electrodes show an ideal capacitive performance at high scan rates, while saving its rectangular shape. By increasing the scan rate, deviation from rectangularity gets obvious that are attributed to the electrolyte and electrode resistances. At high scan rates, however, the deeper active sites in composite electrodes do not have enough time to react with counter ions of the solution. The variation of specific capacitance as a function of scan rate for both electrodes shows a decreasing pattern, due to the inaccessibility of deeper active sites at high sweep rates (Fig. 5(d)). Galvano static charge-discharge (GCD) curves, as one of the other most important electrochemical analysis techniques, were used to illustrate the super capacitive performance of the active materials. Fig. 5(e) presents the GCD curves of PANI and PANI/PBF-NPs electrodes in 1M H2SO4 media at a constant current density of 4.5 A/g. As one can see, both curves have a triangular shape that shows their ideal super capacitive behavior. The capacitance equation of electrodes can also be evaluated as provided in equation (2), using GCD curves, as. I C¼ DE Dt :m
Fig. 4 e Nitrogen adsorption/desorption isotherms, and desorption pore size distribution profiles (insets) of (a) PBF nanoparticles, (b) PANI and (c) composite electrode.
PANI/PBF-NPs electrodes were obtained to be 225 and 330 F/g, respectively. One of the most important parameters of an electrode super capacitor is its kinetics through various sweep rates. As
(2)
where DE is the slope of the discharge curve, after the voltage Dt drop at the beginning of each discharge, known as the equivalent series resistance (ESR) phenomenon; I is the current and m is the mass of the composite electrodes. Using this equation, the specific capacitance for PANI and PANI/PBF-NPs were calculated as 158 and 310 F/g, respectively. Finally, to study the performance of composite electrodes at various kinetics, GCD curves of composite PANI/ PBF-NPs electrodes were studied in 1M H2SO4 media at various current densities (Fig. 5(f)). The GCD curves show that composite electrodes have good super capacitive performance, with capability of storing electrical charge. As presented, by increasing the current, the length of the charge-discharge process, and therefore, the C of composite electrodes decreased. The highest obtained C was achieved at current density of 0.9 A/g. At low current densities, all of the active sites in a composite electrode have enough time to react with counter ions and contribute to the charge storage process. Based on the obtained results, the insertion of PBF-NPs in the structure of PANI filaments has two benefits. The first one is the increase of the specific capacitance of composite electrodes compared to polymeric PANI ones, implied by the required time for discharging the electrodes. This benefit can
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 5 e CV curves for the (a) synthesis of PANI and PANI/PBF-NPs electrodes, (b) PANI and PANI/PBF-NPs electrodes in 1M H2SO4 (scan rate: 25 mV/s), (c) PANI/PBF-NPs composite electrode at various scan rates in 1M H2SO4 media; (d) C of PANI and PANI/PBF-NPs electrodes, as a function of scan rate; GCD curves of (e) PANI and PANI/PBF-NPs electrodes in 1M H2SO4 (current density: 4.5 A/g); and (f) PANI/PBF-NPs composite electrodes at various current densities.
be related to the contribution of PBF-NPs to the charge transfer reaction of the composite electrode. The second benefit is the decrease of the electrical resistance of the composite electrodes, as compared to PANI electrodes, which is resulted from the I·R drop of GCD curves at the beginning of the discharge process, known as the ESR phenomenon. The stability of electrodes through the continuous GCD process is one of the other most important parameters in the study of the performance of super capacitors. Fig. 6(a) presents the last 16 cycles of the continuous GCD of composite PANI/PBF-NPs electrodes. As illustrated, capacitive
performance of the PANI/PBF-NPs electrode shows, the nano composite can be effectively used as an active super capacitor material, after over 1000 cycles. The EIS was used to study the electrochemical nature of all electrodes [25e28]. Fig. 6(b), presents the Nyquist curves of PANI and PANI/PBF-NPs electrodes in 1M H2SO4 solution, obtained by EIS technique. As can be seen, both curves have a semi-circle shape in the high-frequency range that is followed by a straight line in low frequencies. The intercept of the Nyquist plots is related to the ESR, arisen from the contributions of electronic and ionic resistances.
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 6 e (a) Continuous charge-discharge curves of composite electrodes at a current density of 9 A/g, and (b) Nyquist diagrams of PANI and PANI PBF-NPs in 1M H2SO4 solution (Inset: equivalent circuit for Nyquist diagrams).
The semi-circle at the high-frequency range, on the other hand, is caused by the combination of faradic reaction (Rct) and double layer capacitance (Cdl) at the electrode/electrolyte interface. The straight line at the low-frequency range, with the slope of 45 , called Warburg resistance, (ZW), is a result of the frequency dependence of ion diffusion/transport in the electrolyte to the electrode surface. As the diameter of the semi-circles implies, the magnitude of Rct for composite electrode is lower than that of the polymeric one, which shows the higher conductivity of composite PANI/PBF-NP electrodes. Table 2, presents the fitted values of model parameters of electrodes. As shown, by combination of PBF nano particles with PANI, the magnitude of Rct in composite electrode decreased that emphasize to increase the conductivity of composite electrode. Furthermore, increasing the values of capacitance elements in composite electrode are another advantage of using PBF nano particles in the structure of PANI electrode. The low-frequency capacitance (Clf) of each electrode was determined from the slope of a plot of the imaginary component of impedance (Z”) at low frequency versus the inverse of frequency (f), using equation (3).
Table 2 e Fitted values of model parameters. Fitting parameter
PANI
PANI/PBF
R1(ohm) R2(ohm) Q2(mF) N2 Q1(mF) N1
21.4 121 0.465 0.81 0.114 0.83
26.5 61 0.672 0.89 0.702 0.91
Clf ¼
1 m:2pfZ}
(3)
The specific capacitance for PANI and PANI/PBF-NPs composite electrodes that calculated using electrochemical techniques are compared in Table 3. As can be seen, all results are in agreement with each other and combination of PBF nano particles and PANI caused to increase the specific capacitance of composite electrode.
Conclusion In this work, the super capacitive behavior of PANI/PBF-NPs was studied. FTIR and SEM analysis show that PBF-NPs were well embedded between the PANI filaments and caused a decrease in the surface area of composite electrodes, due to covering of the surface of PANI filaments with nanoparticles. This phenomenon results in an increase in the pore-diameter of composite filaments and a decrease of its pore-volume. Through formation of the PANI/PBF-NP nano composite, not only the capability of electrical charge storage was significantly improved, but also the electro-conductivity of composite electrodes was remarkably enhanced. The increase of the specific capacitance of composite electrodes compared to polymeric PANI ones, can be related to the contribution of PBF-NPs to the charge transfer reaction of the composite electrode. The second benefit, i.e. the decrease of the electrical resistance of the composite electrodes and enhancement of the current, on the other hand, is resulted from the I·R drop of GCD curves at the beginning of the discharge process, known as the ESR phenomenon.
Table 3 e Specific capacitance magnitudes of samples calculated by electrochemical techniques. Electrochemical technique electrode PANI PANI/PBF-NPs
Cyclic Voltammetry (F/g)
Galvano static charge disgharge (F/g)
Impedance spectroscopy (F/g)
225 330
158 310
180 250
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
Available online at www.sciencedirect.com
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Electrochemical study of perlite-barium ferrite/ conductive polymer nano composite for super capacitor applications Mohammad Sadeghinia a, Javad Shabani Shayeh b,*, Fataneh Fatemi b, Moones Rahmandoust b, Ali Ehsani c, Mehran Rezaei d a
Department of Chemistry, Faculty of Science, University of Tehran, Tehran, Iran Protein Research Center, Shahid Beheshti University G.C., Tehran, Iran c Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran d School of Chemical, Petroleum and Gas Engineering, Iran University of Science and Technology (IUST), Tehran, Iran b
highlights
graphical abstract
Developing a simple and facile process for synthesis of PANI/ BaFe12O19. Preparing a novel and efficient nanocomposite
for
electro-
chemical capacitors. Enhancing
specific
capacitance
and stability through incorporation of BaFe12O19.
article info
abstract
Article history:
Polyaniline/perlite-barium ferrite nanoparticles (PANI/PBF-NPs) composite electrodes were
Received 8 May 2019
studied in here for super capacitor applications. The PBF-NPs synthesized using hydro-
Received in revised form
thermal technique and then the composite electrode was fabricated electrochemically by
18 July 2019
cyclic voltammetry (CV) technique. Transmission electron microscopy (TEM), Scanning
Accepted 10 September 2019
electron microscopy (SEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller nitrogen
Available online xxx
adsorption/desorption (BET) and fast Fourier transform infrared spectroscopy (FTIR) were employed to study the morphological and structural properties of the prepared electrodes.
Keywords:
Furthermore, various electrochemical techniques were used such as CV, Galvano static
Nanocomposite
charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) to investigate
Perlite
their electrochemical performance as well. SEM graphs show uniform distribution of 60-
Supercapacitor
nm PBF-NPs in the PANI filaments. The specific capacitance of PANI and composite elec-
Conductive polymers
trodes was obtained to be 225 and 330 F/g, respectively. In addition, inclusion of PBF-NPs in
Electrosynthesis
the structure of PANI electrode had significantly increased the conductivity of composite
Metal oxide
* Corresponding author. E-mail address: [email protected] (J.S. Shayeh). https://doi.org/10.1016/j.ijhydene.2019.09.085 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved. Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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electrodes. Continuous charge-discharge cycles test illustrated the good capability of this nano composite material for use as a charge storage device. © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction Super capacitors, also known as electrochemical capacitors (ECs), have attracted much attention due to their high-power and long life-cycle characteristics, which can fill the gap between conventional capacitors and batteries [1]. To investigate the performance and charge storage mechanism of ECs, one must be focuse on the nature of materials used in the structure of ECs and their capacitance mechanism [2e4]. In terms of material, ECs can be divided into three major classifications of active materials, including metal oxides, carbon materials and conductive polymers. Metal oxides, such as MnO2, RuO2, NiO2, etc., store the electrical charge thorough the charge transfer reaction in the oxidation states of metal atoms [5]. In the other category of active materials, i.e. the conjugated polymers such as polyaniline, polypyrrole and poly thiophene derivatives, the mechanism of charge storage is also similar to metal oxides in that by oxidation of polymer chains the counter ions form solution miggreat to polymer structure and therfore the electrical charge stored [4,6], where as in carbon materials such as graphene, as the final classification, the specific capacitance of composite electrodes is increased by increasing the surface of the electrode through storage the charge by their electrical double layer [5,16,17]. Chemical stability, higher specific capacitance, ease of synthesis and economic concerns are the reasons to choose polyaniline (PANI) as an active material of ECs [7e9]. However, the weakness of using conductive polymers for ECs is their poor life-cycle, due to the accumulation of stress on the polymer through insertion and de-insertion of solution ions over the electrode/electrolyte interface that combination of these materials together is one the methods to solve these problems [10,11]. The combination of nano materials with conductive polymers, on the other hand, is expected to increase the stability and specific capacitance of composite electrodes [12,13]. Nano materials can also boost the connection of polymer filaments together and improve their mechanical stability. They can participate in the charge transfer process, increasing the specific capacitance of the composite electrode as well [14,15]. Many papers reported the application of metal oxide nano materials in the structure of PANI and that increasing the capacitance and stability of composite electrodes are some significant features of employing these nano materials [18e20]. Bimetallic compounds nowadays attract much attention, due to their unique electrochemical behavior. The combination of two or more transition metal oxides can increase the electronic conductivity of complex oxide compounds [21]. There are two methods for the synthesis of PANI. The first method is chemical synthesis, where PANI is synthesized by
adding an initiator to the solution containing the monomer; and the second is the electrochemical method, which has the ability to control the mass of polymer and its thickness. Furthermore, the magnitude of nano materials that must be used to produce composite electrodes is very low [22]. In this work, we studied the super capacitive performance of poly aniline/perlite-barium ferrite (BaFe12O1) nanoparticle (PANI/ PBF-NP) electrodes in acidic media. For this purpose, PBF-NPs were synthesized using the hydrothermal method and later composite electrodes were produced using the electrochemical technique.
Experimental Materials All the chemical materials used in this study were purchased from Merck Chemical Company in analytical grade and were used without further purification. Double distilled water was used throughout the experiments. Aniline was doubly distilled and the resulting colorless liquid was kept in the dark at 5 C.
Apparatus Electrochemical experiments were carried out by an Auto Lab General Purpose System PGSTAT 30 (Eco-chime, Netherlands). A conventional three electrode cell holding a glassy carbon electrode, with the area of 0.03 cm2 was used as the working electrode, platinum wire and an Ag/AgCl (Argental, 3M KCl) were used as counter and reference electrode, respectively. The electrochemical impedance spectroscopy (EIS) experiments were conducted in the frequency range between 100 kHz and 15 mHz with perturbation amplitude of 5 mV to provide Nyquist curves. Morphological investigations of the polymeric films were carried out using Scanning electron microscopy (SEM) (Philips XL 30). X-ray diffraction (XRD) patterns were obtained from an X-ray diffractometer (PANalytical X’Pert-Pro) with a Cu-Ka mono-chromatized radiation source and Ni filter. The Fourier transform infrared (FTIR) spectra were recorded on Nicolet 6700 with the sweeping range of 500e4500 cm1 wavenumber. Brunauer-Emmett-Teller N2 adsorption/desorption test was performed by (BELSORP MINI II, Japan) to study the porosity and pore size distribution of the electrodes.
Synthesis of BaFe12O19 nanoparticles 2.35143 g of Ba(NO3)2 and 43.6 g of Fe(NO3)3$9H2O were dissolved in deionized water to make 1M nitrate solution and were warmed to complete solvation. Then, the nitrate
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 1 e TEM graphs of PBF-NPs. solution was pumped to the reaction vessel containing 100 ml of deionized water and was co-precipitated via a 1M NaOH solution at pH ¼ 12 in 60 C. The precipitate was aged for 5 h at the same temperature, 60 C. It was then dried at 80 C and calcined at 900 C for 3 h.
Preparation of working electrodes The PANI/PBF-NPs composite was electro-polymerized on the surface of glassy carbon electrodes. The electropolymerization process was conducted by 10 cyclic voltammograms at the sweep rate of 10 mV/s, in a solution of 0.03M monomer in H2SO4 1M, 0.2 wt% of PBF-NPs and 0.005M of sodium dodecyl sulfate (SDS) that was dispersed in solution by sonication. PANI electrodes were synthesized in same solution in the absence of PBF-NPs and SDS. The mass of PANI electrodes were approximated assuming a current efficiency
of 100% for the electro-polymerization process, using Faraday’s law [6,23].
Results and discussion TEM graphs of PBF nano particles presented in Fig. 1. It can be found that PBF nano particles synthesized in hexagonal form with average size of 40 nm. This average size can be change after combination with PANI due to agglomeration of PBF nano particles in polymer matrix as presented in SEM graphs of PANI and PANI/PBF-NPs composite electrodes that PANI filaments are entangled together to form a three-dimensional network, with porosities suitable for the insertion/deinsertion of counter ions. Furthermore, polymeric electrodes are good platforms for NPs in that NPs can be dispersed on the surface of electrodes to increase their activity. The size of the
Fig. 2 e SEM graphs of (a and b) PANI and (c and d) PANI/PBF-NPs electrodes. Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 3 e (a) XRD patterns of PBF-NPs, PANI and the PANI/PBF-NPs composite electrodes, (b) FTIR spectra of electrodes.
NPs inserted in the structure of PANI electrodes was calculated to be about 60 nm (Fig. 2). To verify the structure and composition of composite electrodes, FTIR, XRD and N2 adsorption/desorption isotherm analyses were used. Fig. 3(a) presents the XRD pattern of PANI, PBF and composite electrode. As can be seen, XRD pattern of PBF shows sharp peaks at angle 0f 30.36, 32.32, 34.17, 37.13, 40.34, 55.18, 56, 64 that ascribed to (110), (107), (114), (203), (205), (217), (201) and (220), respectively. These diffraction planes attributed to hexagonal form of BPF (JCPDS#84-757). As illustrated, the PANI electrode has an amorphous structure, which alerts by the insertion of PBF nanoparticles in the polymer network and the formation of composite electrodes, leading to appearance of distinct diffraction peaks of PBF-NPs in it. Fig. 3(b) displays the FTIR spectra taken in the wavenumber range of 400e4000 cm1. As can be seen, in the FTIR spectra of PANI, the absorption peaks which appear at 1290 and 1560 cm1 correspond to leucoemeraldine and pernigraniline components, respectively. Furthermore, peak bands at 1120 and 813-503 cm1 ascribes the in-plane bending benzene rings and out-of-plane deformation of CeH benzene rings, respectively. In the FTIR spectra of PBF nanoparticles, the bands seen at 420 and 600 cm1 correspond to the stretching vibration of the ferrite materials and the broad peak at 3480 cm1 ascribed to OeH stretching of H2O [24]. FTIR spectra of composite electrodes shows the characteristic bands of PANI as well as PBF-NPs that confirm the successful formation of PANI/PBF-NPs composite electrode. To determine the surface area of the samples, BrunauerEmmett-Teller N2 adsorption/desorption analysis was performed (Fig. 4). As provided in detail in Table 1, three samples exhibit typical IV isotherms with H3-type in that the magnitude of meso porous in PBF-NPs (7.6 m2/g) is lower than both the PANI and composite electrodes, as to be 40.3 and 28.5 m2/g,
respectively. As results show, the combination of PBF-NPs with PANI caused a decrease in the surface area of composite electrodes, due to covering of the surface of PANI filaments with nanoparticles. This phenomenon results in an increase in the diameter of composite filaments compared to the PANI ones and furthermore, the pore-volume of composite electrodes decreases owing to the insertion of nanoparticles in the structure of PANI electrodes. Cyclic voltammetry (CV) curves for electro polymerization of PANI and PANI/PBF-NPs electrodes after 10 cycles are presented in Fig. 5(a). As it can be seen, each curve has three redox peaks, where the first redox peak is related to the formation of free radicals in the PANI chain (0.3, 0.1 V), the second one is due to the oxidation and reduction of intermediates that were produced in the electro polymerization process (0.5, 0.4 V), and finally the third redox peak is because of the oxidation of PANI. CVs of polymeric PANI and composite PANI/PBF-NPs electrodes in acidic media show that the composite electrodes have higher specific capacitance (C), compared to PANI ones (Fig. 5(b)). As can it be seen in both curves, there are two redox peaks, appeared between 0.4 and 0.6 V, that are related to the transition of PANI from the emeraldine to pernigraniline form. The combination of PBFNPs with PANI causes an increase in the C of composite electrodes. Furthermore, both electrodes show the ideal capacitive performance, implying that the PBF-NPs have improved the super capacitive performance of PANI electrodes. The C of electrodes can be calculated according to the CV curves, based on the following equation: C¼
I mv
(1)
where I is the current, m is the mass of the active materials and v is the scan rate. The specific capacitance for PANI and
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Table 1 e N2 adsorption/desorption analysis data for PBFNPs, PANI and PANI/PBF-NPs electrodes. Sample
Properties Mean pore Total pore Surface area diameter (nm) volume (cm3/g) (m2/g)
PBF-NPs PANI PANI/PBF-NPs
7.6 40.3 28.5
67.59 30.77 35.22
0.1292 0.3104 0.2516
presented in Fig. 5(c), CV curves of composite electrodes show an ideal capacitive performance at high scan rates, while saving its rectangular shape. By increasing the scan rate, deviation from rectangularity gets obvious that are attributed to the electrolyte and electrode resistances. At high scan rates, however, the deeper active sites in composite electrodes do not have enough time to react with counter ions of the solution. The variation of specific capacitance as a function of scan rate for both electrodes shows a decreasing pattern, due to the inaccessibility of deeper active sites at high sweep rates (Fig. 5(d)). Galvano static charge-discharge (GCD) curves, as one of the other most important electrochemical analysis techniques, were used to illustrate the super capacitive performance of the active materials. Fig. 5(e) presents the GCD curves of PANI and PANI/PBF-NPs electrodes in 1M H2SO4 media at a constant current density of 4.5 A/g. As one can see, both curves have a triangular shape that shows their ideal super capacitive behavior. The capacitance equation of electrodes can also be evaluated as provided in equation (2), using GCD curves, as. I C¼ DE Dt :m
Fig. 4 e Nitrogen adsorption/desorption isotherms, and desorption pore size distribution profiles (insets) of (a) PBF nanoparticles, (b) PANI and (c) composite electrode.
PANI/PBF-NPs electrodes were obtained to be 225 and 330 F/g, respectively. One of the most important parameters of an electrode super capacitor is its kinetics through various sweep rates. As
(2)
where DE is the slope of the discharge curve, after the voltage Dt drop at the beginning of each discharge, known as the equivalent series resistance (ESR) phenomenon; I is the current and m is the mass of the composite electrodes. Using this equation, the specific capacitance for PANI and PANI/PBF-NPs were calculated as 158 and 310 F/g, respectively. Finally, to study the performance of composite electrodes at various kinetics, GCD curves of composite PANI/ PBF-NPs electrodes were studied in 1M H2SO4 media at various current densities (Fig. 5(f)). The GCD curves show that composite electrodes have good super capacitive performance, with capability of storing electrical charge. As presented, by increasing the current, the length of the charge-discharge process, and therefore, the C of composite electrodes decreased. The highest obtained C was achieved at current density of 0.9 A/g. At low current densities, all of the active sites in a composite electrode have enough time to react with counter ions and contribute to the charge storage process. Based on the obtained results, the insertion of PBF-NPs in the structure of PANI filaments has two benefits. The first one is the increase of the specific capacitance of composite electrodes compared to polymeric PANI ones, implied by the required time for discharging the electrodes. This benefit can
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 5 e CV curves for the (a) synthesis of PANI and PANI/PBF-NPs electrodes, (b) PANI and PANI/PBF-NPs electrodes in 1M H2SO4 (scan rate: 25 mV/s), (c) PANI/PBF-NPs composite electrode at various scan rates in 1M H2SO4 media; (d) C of PANI and PANI/PBF-NPs electrodes, as a function of scan rate; GCD curves of (e) PANI and PANI/PBF-NPs electrodes in 1M H2SO4 (current density: 4.5 A/g); and (f) PANI/PBF-NPs composite electrodes at various current densities.
be related to the contribution of PBF-NPs to the charge transfer reaction of the composite electrode. The second benefit is the decrease of the electrical resistance of the composite electrodes, as compared to PANI electrodes, which is resulted from the I·R drop of GCD curves at the beginning of the discharge process, known as the ESR phenomenon. The stability of electrodes through the continuous GCD process is one of the other most important parameters in the study of the performance of super capacitors. Fig. 6(a) presents the last 16 cycles of the continuous GCD of composite PANI/PBF-NPs electrodes. As illustrated, capacitive
performance of the PANI/PBF-NPs electrode shows, the nano composite can be effectively used as an active super capacitor material, after over 1000 cycles. The EIS was used to study the electrochemical nature of all electrodes [25e28]. Fig. 6(b), presents the Nyquist curves of PANI and PANI/PBF-NPs electrodes in 1M H2SO4 solution, obtained by EIS technique. As can be seen, both curves have a semi-circle shape in the high-frequency range that is followed by a straight line in low frequencies. The intercept of the Nyquist plots is related to the ESR, arisen from the contributions of electronic and ionic resistances.
Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085
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Fig. 6 e (a) Continuous charge-discharge curves of composite electrodes at a current density of 9 A/g, and (b) Nyquist diagrams of PANI and PANI PBF-NPs in 1M H2SO4 solution (Inset: equivalent circuit for Nyquist diagrams).
The semi-circle at the high-frequency range, on the other hand, is caused by the combination of faradic reaction (Rct) and double layer capacitance (Cdl) at the electrode/electrolyte interface. The straight line at the low-frequency range, with the slope of 45 , called Warburg resistance, (ZW), is a result of the frequency dependence of ion diffusion/transport in the electrolyte to the electrode surface. As the diameter of the semi-circles implies, the magnitude of Rct for composite electrode is lower than that of the polymeric one, which shows the higher conductivity of composite PANI/PBF-NP electrodes. Table 2, presents the fitted values of model parameters of electrodes. As shown, by combination of PBF nano particles with PANI, the magnitude of Rct in composite electrode decreased that emphasize to increase the conductivity of composite electrode. Furthermore, increasing the values of capacitance elements in composite electrode are another advantage of using PBF nano particles in the structure of PANI electrode. The low-frequency capacitance (Clf) of each electrode was determined from the slope of a plot of the imaginary component of impedance (Z”) at low frequency versus the inverse of frequency (f), using equation (3).
Table 2 e Fitted values of model parameters. Fitting parameter
PANI
PANI/PBF
R1(ohm) R2(ohm) Q2(mF) N2 Q1(mF) N1
21.4 121 0.465 0.81 0.114 0.83
26.5 61 0.672 0.89 0.702 0.91
Clf ¼
1 m:2pfZ}
(3)
The specific capacitance for PANI and PANI/PBF-NPs composite electrodes that calculated using electrochemical techniques are compared in Table 3. As can be seen, all results are in agreement with each other and combination of PBF nano particles and PANI caused to increase the specific capacitance of composite electrode.
Conclusion In this work, the super capacitive behavior of PANI/PBF-NPs was studied. FTIR and SEM analysis show that PBF-NPs were well embedded between the PANI filaments and caused a decrease in the surface area of composite electrodes, due to covering of the surface of PANI filaments with nanoparticles. This phenomenon results in an increase in the pore-diameter of composite filaments and a decrease of its pore-volume. Through formation of the PANI/PBF-NP nano composite, not only the capability of electrical charge storage was significantly improved, but also the electro-conductivity of composite electrodes was remarkably enhanced. The increase of the specific capacitance of composite electrodes compared to polymeric PANI ones, can be related to the contribution of PBF-NPs to the charge transfer reaction of the composite electrode. The second benefit, i.e. the decrease of the electrical resistance of the composite electrodes and enhancement of the current, on the other hand, is resulted from the I·R drop of GCD curves at the beginning of the discharge process, known as the ESR phenomenon.
Table 3 e Specific capacitance magnitudes of samples calculated by electrochemical techniques. Electrochemical technique electrode PANI PANI/PBF-NPs
Cyclic Voltammetry (F/g)
Galvano static charge disgharge (F/g)
Impedance spectroscopy (F/g)
225 330
158 310
180 250
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Please cite this article as: Sadeghinia M et al., Electrochemical study of perlite-barium ferrite/conductive polymer nano composite for super capacitor applications, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.09.085