Electrospun polyaniline nanofibers web electrodes for supercapacitors

Polyaniline nanofibers (PANI‐NFs) web are fabricated by electrospinning and used as electrode materials for supercapacitors. Field‐emission scanning electron microscope micrographs reveal nanofibers web were made up of high aspect ratio (>50) nanofibers of length ～30 μm and average diameter ～200 nm. Their electrochemical performance in aqueous (1M H₂SO₄ and Na₂SO₄) and organic (1M LiClO₄ in propylene carbonate) electrolytes is compared with PANI powder prepared by in situ chemical oxidative polymerization of aniline. The electrochemical properties of PANI‐NFs web and PANI powder are studied using cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. PANI‐NFs web show higher specific capacitance (～267 F g^?1) than chemically synthesized PANI powder (～208 F g^?1) in 1M H₂SO₄. Further, PANI‐NFs web demonstrated very stable and superior performance than its counterpart due to interconnected fibrous morphology facilitating the faster Faradic reaction toward electrolyte and delivered specific capacitance ～230 F g^?1 at 1000th cycle. Capacitance retention of PANI‐NFs web (86%) is higher than that observed for PANI powder (48%) indicating the feasibility of electro spun PANI‐NFs web as superior electrode materials for supercapacitors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrospun carbon nanofiber web electrode: Supercapacitor behavior in various electrolytes

Carbon nanofibers (CNFs) draw great interest due to their noticeable mechanical, electrochemical, and physical properties. In this study, polyacrylonitrile‐based CNFs are obtained via electrospinning technique. Thermal oxidation and low temperature (950 °C) carbonization are applied to the electrospun web in order to achieve CNF. Through the process, Fourier transform infrared‐attenuated total reflectance spectroscopy and Raman spectroscopic results are investigated. The electrochemical properties of the self‐standing CNF webs are examined with electrochemical impedance spectroscopy and cyclic voltammetry. In addition, various electrolyte solutions are studied to investigate the capacitive behavior of CNF webs. Electrolyte type variation has a significant effect on the capacitance results and high capacitance values are achieved in aqueous solution. According to the differing electrolyte types, specific capacitance values (C_sp) are recorded between 204 and 149 F g^?1 where maximum specific capacitance is obtained in 0.5 M H₂SO₄ as 204 F g^?1. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45723.     

Role of dual dopants in highly ordered crystalline polyaniline nanospheres: Electrode materials in supercapacitors

Aniline is oxidized by ammonium persulfate oxidant with a weak organic acid, 1,3‐(6,7)‐napthalene trisulfonic acid (NTSA), via an aqueous polymerization pathway to polyaniline (PANI) salt. The effects of the sodium lauryl sulfate surfactant, mineral acid [sulfuric acid (H₂SO₄)], and a combination of surfactant with mineral acid in the aniline polymerization reaction are also carried. These salts were designated as PANI–NTSA–dodecyl hydrogen sulfate (DHS), PANI–NTSA–H₂SO₄, and PANI–NTSA–DHS–H₂SO₄, respectively. Interestingly, PANI–NTSA–DHS showed a highly ordered crystalline sample with a nanosphere morphology. These PANIs were used as electrode materials in supercapacitor applications. Among the four salts, the PANI–NTSA–DHS–H₂SO₄ material showed higher values of specific capacitance (520 F/g), energy (26 W h/kg), and power densities (200 W/kg) at 0.3 A/g. Moreover, 77% of the original capacitance was retained after 2000 galvanostatic charge–discharge cycles with a Coulombic efficiency of 98–100%. PANI–NTSA–DHS–H₂SO₄ was obtained in excellent yield with an excellent conductivity (6.8 S/cm) and a thermal stability up to 235°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42510.     

High‐temperature oxidation of aniline to highly ordered polyaniline–sulfate salt with a nanofiber morphology and its use as electrode materials in symmetric supercapacitors

In this study, for the first time, aniline was oxidized by ammonium persulfate (APS) at higher temperatures without any protic acid, and APS acted as an oxidizing agent and a protonating agent. During the oxidation of aniline by APS, sulfuric acid formation occurred, and the sulfuric acid was incorporated into polyaniline (PANI) as a dopant. PANI–sulfate samples were characterized by IR spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. In this methodology, a highly ordered PANI–sulfate salt (H₂SO₄) with a nanofiber morphology was synthesized. Interestingly, a PANI base was also obtained with a highly ordered structure with an agglomerated netlike nanofiber morphology. PANI–H₂SO₄ was used as an electrode material in a symmetric supercapacitor cell. Electrochemical characterization, including cyclic voltammetry (CV), charge–discharge (CD), and impedance analysis, was carried out on the supercapacitor cells. In this study, the maximum specific capacitance obtained was found to be 273 F/g at 1 mV/s. Scan rate from cyclic voltammetry and 103 F/g at 1 mA discharge current from CD measurement. Impedance measurement was carried out at 0.6 V, and it showed a specific capacitance of 73.2 F/g. The value of the specific capacitance and energy and power densities for the PANI–H₂SO₄ system were calculated from CD studies at a 5‐mA discharge rate and were found to be 43 F/g, 9.3 W h/kg, and 500 W/kg, respectively, with 98–100% coulombic efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of dopant and oxidant on the electrochemical properties of polyaniline/graphite nanoplate composites

Optimizing the synthesis parameters of polyaniline/graphite nanoplate (PANI/GNP) composite is essential to the final electrochemical performance. Herein, the electrochemical properties of PANI/GNP composites, prepared by in situ chemical polymerization using varying amounts of different oxidants, with or without the addition of 4‐dodecylbenzenesulfonic acid (DBSA) as dopant, were investigated. Cyclic voltammetric results suggested that a stoichiometric amount of the oxidant iron chloride (FeCl₃) was beneficial to the electrochemical properties of the composites. The use of ammonium persulfate (APS) instead of FeCl₃ as oxidant largely increased the actual PANI content, conductivity and specific capacitance of the PANI/GNP composites. The dopant DBSA increased the conductivity of the PANI/GNP composites but did not show a positive effect on the electrochemical behavior. The cyclic voltammograms of the PANI/GNP composites indicated that the pseudocapacitance of PANI contributes more than the electrical double‐layer capacitance of GNP to the capacitance of the composites, while the presence of GNP plays an essential role in the rate capability of the composites. In this study, PANI/GNP (1:1) composite synthesized with an APS to aniline molar ratio of 1 showed a balanced combination of high specific capacitance (180.5 F g^?1 at 20 mV s^?1) and good rate capability (78% retention at 100 mV s^?1). © 2018 Society of Chemical Industry     

Improved electrochemical performances of polyaniline by graphitized mesoporus carbon: Hybrid electrode for supercapacitor

In this work, graphitized mesoporus carbon (GMC) was used to increase the specific capacitance and cycle stability of polyaniline (PANI). Hybrid material of polyaniline‐graphitized mesoporus carbon (GMCP) was prepared by in situ chemical polymerization of aniline in presence of sulphuric acid using ammonium persulfate oxidant with various amounts of GMC. Formation of hybrid sample was confirmed from X‐ray diffraction, and the composite sample was stable up to 250°C. Morphology, crystalline nature, and electrochemical performance of GMCP were compared with that of its individual components, GMC and PANI. GMC showed particle morphology and PANI showed nanofiber morphology. GMCP2 composite showed nanofibrous form of PANI grown on GMC (spherical form) along with PANI nanofibers. Higher crystallinity was obtained for GMCP than that of PANI. Cycling stability of GMCP2 was carried up to 12,000 cycles at 1200 W kg^?1 and the retention capacitance was 66% of its original capacitance of 243 F g^?1. With the same power density, GMC showed less capacitance value of 53 F g^?1 with 92% retention and PANI showed capacitance of 187 F g^?1 and it underwent 1500 cycles only. Higher supercapacitor performance was obtained for GMCP composite compared to that of its components, PANI and GMC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42540.     

Preparation and capacitance performance of polyaniline/titanium nitride nanotube hybrid

A polyaniline/titanium nitride (PANI/TiN) nanotube hybrid was prepared and used for an electrochemical supercapacitor application. Firstly, the well-aligned TiN nanotube array was prepared by anodization of titanium foil and subsequent nitridation through ammonia annealing. Then, PANI was deposited into TiN nanotube through the electrochemical polymerization process. The obtained PANI/TiN nanotube hybrid had an ordered porous structure. A high specific capacitance of 1,066 F g^?1 was obtained at the charge–discharge current density of 1 A g^?1 when only the mass of PANI was considered. The specific capacitance can even achieve 864 F g^?1 at 10 A g^?1 and still keep 93 % of the initial capacity after 200 cycles. An aqueous supercapacitor, consisting of two symmetric PANI/TiN nanotube hybrid electrodes and 1.0 M H₂SO₄ electrolyte solution, showed the specific capacitance of 194.8 F g^?1, energy density of 9.74 Wh kg^?1, and power density of 0.3 kW kg^?1.     

Polyaniline/MnO2 composite with high performance as supercapacitor electrode via pulse electrodeposition

A method of pulse electrodeposition was proposed to synthesize polyaniline (PANI)/MnO₂ composite in aniline, H₂SO₄, and MnSO₄ aqueous solution. The PANI/MnO₂ composite has rod‐like structure and MnO₂ particles are distributed on PANI uniformly. To evaluate the performance of the as‐prepared materials as supercapacitor electrodes, cyclic voltammetry, galvanostatic charge–discharge measurements, and electrochemical impedance spectroscopy were performed. The PANI/MnO₂ composite shows a higher specific capacitance (810 F g⁻¹) than pure PANI (662 F g⁻¹) at a current density of 0.5 A g⁻¹. The cycle life of the composite was also excellent. After 1,000 cycles, it maintained 86.3% of its initial capacitance. POLYM. COMPOS., 36:113–120, 2015. © 2014 Society of Plastics Engineers     

Preparation and electrochemical properties of poly‐2,5‐dihydroxyaniline/activated carbon composite electrode in organic electrolyte

Poly‐2,5‐dimethoxyaniline coating has been fabricated on active carbon (AC) substrates by cyclic voltammetry (CV) in organic system. The resulted coating is hydrolyzed to produce poly‐2,5‐dihydroxyaniline (PDHA) to enhance the capacitance of the composite electrode. Scanning electron microscope, Fourier transform infrared spectroscopy, X‐ray diffraction, Raman spectra, CV, electrochemical impedance spectroscopy, and galvanostatic charge/discharge test are used to investigate the properties of these electrodes. In organic electrolyte, due to the introduced hydroquinone units, high value of capacitance up to 975 F g^?1 of the PDHA/AC has been obtained at a current density of 0.37 A g^?1 at a potential window of 0–1.5 V. An asymmetric capacitor has been assembled with the PDHA/AC positive and pure AC negative electrodes, which is able to obtain a specific energy as high as 178 Whkg^?1 in the potential range of 0–2.0 V at a current density of 0.93 A g^?1. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High performance electrospun PVdF‐HFP/SiO2 nanocomposite membrane electrolyte for Li‐ion capacitors

Electrospun poly[(vinylidene fluoride)‐co ‐hexafluoropropylene]/silica (PVdF‐HFP/SiO₂) nanocomposite polymer membranes (esCPMs) were prepared by incorporating different weight percentages of SiO₂ nanoparticles onto electrospun PVdF‐HFP by electrospinning technique. The surface morphology of electrospun PVdF‐HFP nanocomposite membranes was characterized by scanning electron microscopy. The effect of SiO₂ nanoparticles incorporation onto electrospun PVdF‐HFP polymer membranes (esPMs) has been studied by XRD, DSC, TGA, and tensile analysis. The electrospun PVdF‐HFP/SiO₂ based nanocomposite membrane electrolytes (esCPMEs) were prepared by soaking the corresponding esCPMs into 1 M LiPF₆ in EC:DMC (1:1 vol/vol %). The ionic conductivity of the esCPMEs was studied by AC‐impedance studies and it was found that the incorporation of SiO₂ nanoparticles into PVdF‐HFP membrane has improved the ionic conductivity from 1.320 × 10^?3 S cm^?1 to 2.259 × 10^?3 S cm^?1. The electrochemical stability of the esCPME was studied by linear sweep voltammetry studies and it was found to be 2.87 V. Finally, a prototype LiCo_0.2Mn_1.8O₄//C Li‐ion capacitor (LIC) cell was fabricated with esCPME, which delivered a discharge capacitance of 128 F g^?1 at the current density of 1 A g^?1 and retained 86% of its discharge capacitance even after 10,000 cycles. These results demonstrated that the esCPMEs could be used as promising polymer membrane electrolyte for LICs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45177.     

Capacitive performance of polyaniline/manganese dioxide nanofiber microsphere

This work has obtained polyaniline/manganese dioxide (PANI/MnO₂) nanofibers microsphere by interfacial chemical synthesis with 4‐amino‐thiophenol (4‐ATP) as the structure‐directing agent on the Au substrate. The cyclic voltammograms, galvanostatic charge–discharge, and electrochemical impedance spectroscopy were used to determine their capacitive performance. Powder X‐ray diffraction, thermogravimetry and differential scanning calorimetry, Fourier transformed infrared spectroscopy, Brunauer–Emmett–Teller surface area measurements, and scanning electron microscope were performed for physical and chemical characterization. The effect of 4‐ATP and acids on the capacitive performance of PANI/MnO₂ nanofibers microsphere was elucidated. The as‐prepared PANI/MnO₂ was nanofiber about 30 nm diameters, and they further self‐assembled into sphere. Its specific capacitance is up to 765 F g^?1 at 1.0 mA cm^?2 in 1.0M Na₂SO₄ solution. And it shows a high stability with a capacitance fade of only 14.9% after 400 charge–discharge cycles. The symmetric capacitor of PANI/MnO₂ (PM10+)/PANI/MnO₂ (PM10?) is assembled in 1.0M Na₂SO₄ solution, and its capacitive performance is compared with that of PANI (+)/PANI (?) and MnO₂ (+)/MnO₂ (?). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40575.     

In situ doping of PANI nanocomposites by gold nanoparticles for high‐performance electrochemical energy storage

Polyaniline (PANI) in situ doped with gold nanoparticles (Au/PANI) is synthesized by oxidative polymerization as electrode material for supercapacitor. The morphologies and structure of the obtained products are characterized by transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy; and electrochemical behaviors were measured by electrochemical workstation. The results show that the nanocomposites of Au/PANI are fabricated with gold nanoparticles (nano‐Au) dispersed well in PANI bulk; and specific capacitance (SC) and rate ability of Au/PANI are improved compared to the pristine PANI due to the introduction of nano‐Au. With nano‐Au content increasing, SC first increase and then decrease and the maximum SC of Au/PANI nanocomposite is up to 462 F g^?1 with the nano‐Au content of 1.64 wt %. Finally, both asymmetric and symmetric supercapacitor devices are assembled, exhibiting high energy densities of 8.95 and 4.17 Wh kg^?1, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45309.     

High capacitance properties of polyaniline by electrochemical deposition on a porous carbon substrate

Electrochemical deposition of polyaniline (PANI) is carried out on a porous carbon substrate for supercapacitor studies. The effect of substrate is studied by comparing the results obtained using platinum, stainless steel and porous carbon substrates. PANI deposited at 100 mV s⁻¹ sweep rate by potentiodynamic technique on porous carbon substrate is found to possess superior capacitance properties. Experimental variables, namely, concentrations of aniline monomer and H₂SO₄ supporting electrolyte are varied and arrived at the optimum concentrations to obtain a maximum capacitance of PANI. Low concentrations of both aniline and H₂SO₄, which produce PANI at low rates, are desirable. The PANI deposits prepared under these conditions possess network morphology of nanofibrils. Capacitance values as high as 1600 F g⁻¹ are obtained and PANI coated carbon electrodes facilitate charge-discharge current densities as high as 45 mA cm⁻² (19.8 A g⁻¹). Electrodes are found to be fairly stable over a long cycle-life, although there is some capacitance loss during the initial stages of cycling.     

Influence of the reaction temperature on polyaniline morphology and evaluation of their performance as supercapacitor electrode

The polyaniline (PANI) nanostructures of tubular, spherical, and granules morphologies were synthesized by chemical oxidation approach in different reaction temperatures and used as the active electrode materials of symmetric redox supercapacitors. X‐ray diffraction and scanning electron microscopy techniques are employed for characterization of these PANIs. With the initial and reaction temperature increase, the morphology of PANI turned from block to spherical and tubular. Electrochemical properties of these PANI electrodes are studied by cyclic voltammetry (CV), agalvanostatic charge–discharge test, and electrochemical impedance spectroscopy (EIS) in 1M H₂SO₄ aqueous solution. The highest electrochemical properties are obtained on the PANI with tubular morphology. The initial specific capacitance of tubular, spherical, and granules PANI are about 300, 300, and 290 F g^?1 at a constant current of 5 mA. Meanwhile, the retention of the tubular PANI capacitance after 500 charge–discharge cycles was 75%, whereas the spherical and granules PANI was only 35% and 57%. The results indicate that tubular PANI electrodes have potential applications as high‐performance supercapacitors electrode materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3753–3758, 2013     

Supercapacitive properties of composite electrodes consisting of polyaniline, carbon nanotube, and RuO2

Three types of composite supercapacitor electrodes were prepared; electroactive polyaniline (PANI), PANI/multi-walled carbon nanotube (CNT), and PANI/CNT/RuO₂. Specifically, the PANI and PANI/CNT were prepared by polymerization, and PANI/CNT/RuO₂ was prepared by electrochemical deposition of RuO₂ on the PANI/CNT matrix. Cyclic voltammetry between −0.2 and 0.8 V (vs. Ag/AgCl) at various scan rates was performed to investigate the supercapacitive properties in an electrolyte solution of 1.0 M H₂SO₄. The PANI/CNT/RuO₂ electrode showed the highest specific capacitance at all scan rates (e.g., 441 and 392 F g⁻¹ at 100 and 1,000 mV s⁻¹, respectively). In contrast, the PANI/CNT electrode demonstrated the best capacitance retention (66%) after 10⁴ cycles. Additional analysis including morphology and complex impedance spectroscopy suggested that with small loading of RuO₂, an increase in capacitance was observed, but dissolution and/or detachment of RuO₂ species from the electrode might occur during cycling to reduce the cycle performance.     

Novel chemically synthesized polyaniline electrodes containing a fluoroboric acid dopant for supercapacitors

The performance of chemically synthesized dual‐acid‐doped polyaniline (PANI) electrode material was investigated for supercapacitors for the first time. Three different grades of PANI‐containing fluoroboric acid (HBF₄) as one of the dopants were prepared by a chemical polymerization method. PANI–dodecylhydrogen sulfate–HBF₄ salt was synthesized by an emulsion polymerization pathway. A PANI–HBF₄–sodium tetrafluoroborate composite and PANI–HBF₄ salt were prepared from different modifications of dopants by a dedoping–redoping process. Capacitative behaviors of the three grades of PANI electrode materials were investigated. Among the three different grades of PANI, PANI–HBF₄ electrode showed the best performance in terms of conductivity (2.3 × 10^?1 S/cm), specific capacitance of the supercapacitor (140 F/g), specific energy (9.6 W h/kg), and specific power (58.8 W/kg). An increase in the capacitance of PANI–HBF₄ was achieved, which identified the significant contribution of the dedoping–redoping processes in the PANI system for supercapacitors. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A redox‐mediator‐doped gel polymer electrolyte applied in quasi‐solid‐state supercapacitors

Methylene blue (MB) redox mediator was introduced into polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend host to prepare a gel polymer electrolyte (PVA‐PVP‐H₂SO₄‐MB) for a quasi‐solid‐state supercapacitor. The electrochemical properties of the supercapacitor with the prepared gel polymer electrolyte were evaluated by cyclic voltammetry, galvanostatic charge–discharge, electrochemical impedance spectroscopy, and self‐discharge measurements. With the addition of MB mediator, the ionic conductivity of gel polymer electrolyte increased by 56% up to 36.3 mS·cm^?1, and the series resistance reduced, because of the more efficient ionic conduction and higher charge transfer rate, respectively. The electrode specific capacitance of the supercapacitor with PVA‐PVP‐H₂SO₄‐MB electrolyte is 328 F·g^?1, increasing by 164% compared to that of MB‐undoped system at the same current density of 1 A·g^?1. Meanwhile, the energy density of the supercapacitor increases from 3.2 to 10.3 Wh·kg^?1. The quasi‐solid‐state supercapacitor showed excellent cyclability over 2000 charge/discharge cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39784.     

Preparation and performance analysis of barium titanate incorporated in corn starch‐based polymer electrolytes for electric double layer capacitor application

Polymer electrolyte membranes composing of corn starch as host polymer, lithium perchlorate (LiClO₄) as salt, and barium titanate (BaTiO₃) as composite filler are prepared using solution casting technique. Ionic conductivity is enhanced on addition of BaTiO₃ by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolyte. The highest ionic conductivity of 1.28 × 10^?2 S cm^?1 is obtained for 10 wt % BaTiO₃ filler in corn starch‐LiClO₄ polymer electrolytes at 75°C. Glass transition temperature (T_g) of polymer electrolytes decreases as the amount of BaTiO₃ filler is increased, as observed in differential scanning calorimetry analysis. Scanning electron microscopy and thermogravimetric analysis are employed to characterize surface morphological and thermal properties of BaTiO₃‐based composite polymer electrolytes. The electrochemical properties of the electric double‐layer capacitor fabricating using the highest ionic conductivity polymer electrolytes is investigated using cyclic voltammetry and charge‐discharge analysis. The discharge capacitance obtained is 16.22 F g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43275.     

Aqueous,interfacial, and electrochemical polymerization pathways of aniline with thiophene: Nano size materials for supercapacitor

Aniline was mixed with thiophene and oxidized by ammonium persulfate in the presence of sulfuric acid via an aqueous polymerization pathway (PAT‐AP). Aqueous polymerization was also carried by sodium lauryl sulfate surfactant, and also by interfacial and electrochemical polymerization pathways. Polymers prepared were characterized by physical, spectral, and electrochemical methods. Nanofibers (30–60 nm diameter) was obtained in the case of aqueous polymerization pathway, whereas interfacial (40–60 nm) and electrochemical polymerization pathways show particulate (500–600 nm) morphology. Polymer samples were used as electrode materials in supercapacitor. Among the four different pathways, PAT‐AP nanofibers show higher capacitance of 614 F g^?1 at 1 mV s^?1. The values of specific capacitance, energy, and power densities of PAT‐AP were found to be 400 F g^?1, 20 W h kg^?1 and 1200 W kg^?1, respectively, at a current density of 2 A g^?1. The retention capacitance is 78% after completion of 1000 cycles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42013.     

Improved stability in P3HT:PCBM photovoltaics by incorporation of well‐designed polythiophene/graphene compositions

Morphological and photovoltaic stabilities of poly(3‐hexylthiophene) (P3HT):phenyl‐C₆₁‐butyric acid methyl ester (PC₇₁BM) solar cells were investigated in pristine and modified states. To this end, four types of patterned/assembled nanostructures, namely reduced graphene oxide (rGO)‐g‐poly(3‐dodecylthiophene)/P3HT patched‐like pattern, rGO–polythiophene/P3HT/PC₇₁BM nanofiber, rGO‐g‐P3HT/P3HT cake‐like pattern and supra(polyaniline (PANI)‐g‐rGO/P3HT), were designed on the basis of rGO and various conjugated polymers. Intermediately covered rGO nanosheets by P3HT crystals (supra(PANI‐g‐rGO/P3HT)) performed better than sparsely (patched‐like pattern) and fully (cake‐like pattern) covered ones in P3HT:PC₇₁BM solar cell systems. Supra(PANI‐g‐rGO/P3HT) nanohybrids largely phase‐separated in active layers (root mean square = 0.88 nm) and also led to the highest performance (power conversion efficiency of 5.74%). The photovoltaic characteristics demonstrated decreasing trends during air aging for all devices, but with distinct slopes. The steepest decreasing plots were obtained for the unmodified P3HT:PC₇₁BM devices (from 1.77% to 0.28%). The two supramolecules with the most ordered structures, that is, cake‐like pattern (10.12 mA cm^?2, 51%, 0.58 V, 2.2 × 10^?6 cm² V^?1 s^?1, 4.3 × 10^?5 cm² V^?1 s^?1, 0.69 nm and 2.99%) and supra(PANI‐g‐rGO/P3HT) (12.51 mA cm^?2, 57%, 0.63 V, 1.2 × 10^?5 cm² V^?1 s^?1, 3.4 × 10^?4 cm² V^?1 s^?1, 0.82 nm and 4.49%), strongly retained morphological and photovoltaic stabilities in P3HT:PC₇₁BM devices after 1 month of air aging. According to the morphological, optical, photovoltaic and electrochemical results, the supra(PANI‐g‐rGO/P3HT) nanohybrid was the best candidate for stabilizing P3HT:PC₇₁BM solar cells. © 2020 Society of Chemical Industry