Electrosynthesis and capacitive performance of polyaniline–polypyrrole composite

The composite of polyaniline and polypyrrole (PPY‐PANI) was prepared by two‐step electrochemical polymerization method. Techniques of scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal gravity analysis (TG/DTG) measurements were used to characterize the morphology and structure of the composite. The electrochemical properties of the composite were investigated by cyclic voltammetry (CV), galvanostatic charge‐discharge, and electrochemical impedance spectroscopy (EIS). The results indicated that the polyaniline–polypyrrole composite showed better electrochemical capacitive performance than polypyrrole (PPY) and polyaniline (PANI). The specific capacitance of the composite electrode was 523 F/g at a current of 6 mA/cm² in 0.5 M H₂SO₄ electrolyte. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

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     

Electrochemical fabrication of polyaniline/MnO2/graphite felt as free‐standing,flexible electrode for supercapacitors

Polyaniline/MnO₂/graphite felt (PMGF) composite, which can be used as a novel free‐standing, flexible electrode for supercapacitors, was fabricated via a facile electrochemical method. Polyaniline/graphite felt (PANI/GF) electrode was prepared by electropolymerization of PANI onto the GF. Subsequently, manganese dioxide (MnO₂) was electrodeposited on the surface of the PANI/GF electrode to prepare PMGF electrode. The microstructure and morphology of the as‐prepared samples were characterized by Fourier transform infrared spectra, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. Specific surface area was examined using N₂ adsorption/desorption test. Cyclic voltammogram, chronopotentiometry techniques and electrochemical impedance spectroscopy were introduced to investigate the electrochemical performance of the composites. The PMGF electrode exhibited specific capacitance as high as about 630 F g⁻¹ at the current density of 0.5 A g⁻¹, which is much higher than that of PANI/MnO₂ composites reported previously. The high specific capacitance of PMGF may be attributed to the fact that the porous GF is a good conductive matrix for the dispersion of PANI/MnO₂ and it can facilitate easy access of electrolytes to the electrode, which results in enhancement of the electrochemical performance of the composite. Moreover, the specific capacitance of PMGF is much larger than that of MnO₂/GF (MGF), which may be ascribed to the participant of PANI, which contributes additional pseudocapacitance and electron transport path. POLYM. COMPOS., 34:819–824, 2013. © 2013 Society of Plastics Engineers     

Influences of graphene oxide support on the electrochemical performances of graphene oxide-MnO2 nanocomposites

MnO₂ supported on graphene oxide (GO) made from different graphite materials has been synthesized and further investigated as electrode materials for supercapacitors. The structure and morphology of MnO₂-GO nanocomposites are characterized by X-ray diffraction, X-ray photoemission spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and Nitrogen adsorption-desorption. As demonstrated, the GO fabricated from commercial expanded graphite (denoted as GO(1)) possesses more functional groups and larger interplane gap compared to the GO from commercial graphite powder (denoted as GO(2)). The surface area and functionalities of GO have significant effects on the morphology and electrochemical activity of MnO₂, which lead to the fact that the loading amount of MnO₂ on GO(1) is much higher than that on GO(2). Elemental analysis performed via inductively coupled plasma optical emission spectroscopy confirmed higher amounts of MnO₂ loading on GO(1). As the electrode of supercapacitor, MnO₂-GO(1) nanocomposites show larger capacitance (307.7 F g^-1) and better electrochemical activity than MnO₂-GO(2) possibly due to the high loading, good uniformity, and homogeneous distribution of MnO₂ on GO(1) support.     

MnO2 with controlled phase for use in supercapacitors

Nanostructured MnO₂ has been synthesized using a simple and rapid microwave‐assisted hydrothermal (MHT) technique through the decomposition of KMnO₄ in a hydrochloric acid solution. The effects of hydrothermal temperature and ramp rate were examined and discussed. It was found that a lower temperature (140°C) favors the formation of cauliflower‐like δ‐MnO₂ particles while a higher temperature (160°C, 180°C, or 200°C) favors the formation of α‐MnO₂ nanorods. The dimensions of the obtained MnO₂ nanorods were affected by the ramp rate. The cauliflower‐like δ‐MnO₂ particles have higher specific surface areas than the α‐MnO₂ nanorods. Supercapacitors having the obtained MnO₂ as the electrodes were evaluated using cyclic voltammetry and electrochemical impedance spectroscopy in a 1 mol·L^?1 Na₂SO₄ solution within a potential window of ?0.1‐0.9 V. The cauliflower‐like δ‐MnO₂ electrodes give higher capacitance, up to 202 F/g, than the nanorods α‐MnO₂ electrodes, at most 61 F/g.     

Cauliflower-like poly(3,4-ethylenedioxythipohene)/nanocrystalline cellulose/manganese oxide ternary nanocomposite for supercapacitor

A cauliflower-like ternary nanocomposite of poly(3,4-ethylenedioxythipohene)/nanocrystalline cellulose/manganese oxide (PEDOT/NCC/MnO₂) was synthesized using one-step electropolymerization technique. The effect of manganese (Mn) concentration on the supercapacitive performance was investigated. The structural and morphology studies were conducted using field emission scanning electron microscope, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray diffraction. The morphology of ternary nanocomposite at an optimized concentration of Mn resembles the cauliflower-like structure. The two-electrode electrochemical analysis of a ternary nanocomposite PEDOT/NCC/MnO₂ exhibited a higher specific capacitance of 144.69 F/g at 25 mV/s in 1.0 M potassium chloride compared to PEDOT/NCC(63.57 F/g). PEDOT/NCC/MnO₂ ternary nanocomposite was able to deliver a specific power of 494.9 W/kg and 10.3 Wh/kg of specific energy at 1 A g⁻¹ and retained 83% of initial capacitance after 2,000 cycles. These promising results from the incorporation of Mn displayed great prospective in developing PEDOT/NCC/MnO₂ as an electrode material for supercapacitor.     

Flexible electrodes based on polypyrrole/manganese dioxide/polypropylene fibrous membrane composite for supercapacitor

The composites of polypyrrole/manganese dioxide/polypropylene fibrous films (PPy/MnO₂/PPF) have been prepared in situ through chemical oxidation polymerization by using the mixture of FeCl₃·6H₂O and MnO₂ adsorbed on PPF as oxidant in the atmosphere of pyrrole vapor at room temperature. The morphologies and structures of the composites are investigated by using scanning electron microscope and X-ray diffraction spectroscopy. The properties of the capacitor cells assembled by the composites of PPy/MnO₂/PPF are evaluated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy methods. The results reveal that the morphologies, conductivities and capacitance performance of the composites are influenced strongly by the content of MnO₂ in the solution of oxidant. The capacitors assembled by PPy/MnO₂/PPF exhibit the property of quick charge/discharge, and the highest specific capacitance of about 110 F g⁻¹ is obtained when the PPy/MnO₂ content in the composite is about 17.4%.     

Manganese dioxide/cobalt tungstate/ nitrogen-doped carbon nano-onions nanocomposite as new supercapacitor electrode

Application of the electrochemical supercapacitors is one way to store energy, which has widely attracted scientists worldwide. In this regard, in the present work, a triple-segment nanocomposite of manganese dioxide, cobalt tungstate, and nitrogen-doped carbon nano onions (MnO₂/CoWO₄/NCNO) was prepared based on a facile chemical method. The synthesized nanomaterials were analyzed by X-ray diffraction, infrared, as well as scanning electron microscopy. The supercapacitive properties of the synthesized nanomaterials were checked using electrochemical impedance spectroscopy, galvanostatic charge-discharge and voltammetry methods. The value of specific capacitor for the prepared electrodes containing MnO₂, CoWO₄, NCNO, MnO₂/CoWO₄, and MnO₂/CoWO₄/NCNO in an alkaline electrolyte (KOH: 6 M) at a current density of 2 A/g have obtained as 209, 97, 170, 413, and 536 F/g, respectively (Three-electrode system). Also, the retained stability of the MnO₂/CoWO₄/NCNO electrode after 3000 consecutive charges and discharges was 96%. The supercapacitive behavior and excellent capacitance of the MnO₂/CoWO₄/NCNO electrode was due to the synergistic effects of MnO₂, CoWO₄, and NCNO. A two-electrode symmetric supercapacitor assembled device is fabricated and exhibits a high specific capacitance of 1036 F/g at 2 A/g. It shows that the MnO₂/CoWO₄/NCNO composite provides potential applications in energy storage.     

Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors

A ternary composite of CNT/polypyrrole/hydrous MnO₂ is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ binary composites estimated by CV technique in 1.0 M Na₂SO₄ electrolyte are 281, 150 and 35 F g⁻¹ at 20 mV s⁻¹ and 209, 75 and 7 F g⁻¹ at 200 mV s⁻¹, respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s⁻¹. The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g⁻¹ at a current loading of 1.0 mA cm⁻² during initial cycling, which decreased drastically to a value of 35 F g⁻¹ at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials.     

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.     

Controllable preparation and heavy‐metal‐ion adsorption of lignosulfonate‐polypyrrole composite nanosorbent

Lignosulfonate‐polypyrrole (LS‐PPY) composite nanospheres were prepared facilely via an in situ polymerization of pyrrole monomers in the presence of lignosulfonate as a dispersant and ammonium persulfate as an oxidant. The LS‐PPY composite was characterized with Fourier Transform infrared spectroscopy (FTIR), thermogravimetric analysis, wide‐angle X‐ray diffraction (XRD), scanning electron microscopy (SEM), field‐emission SEM, and transmission electron microscopy. Uniform LS‐PPY solid composite nanospheres with an average diameter of 154 nm were obtained. The LS‐PPY composite nanospheres were applied to adsorption of Ag(I) and Pb(II) ions from aqueous solutions. Maximum adsorption capacities of Ag(I) and Pb(II) were up to 759.3 mg g⁻¹ and 207.5 mg g⁻¹, respectively. Furthermore, the silver ions can be reduced to metallic silver nanowires through a redox reaction between the LS‐PPY composite nanospheres and the silver ions. A productive no‐template route to fabrication of LS‐PPY composite nanospheres with controllable size and heavy‐metal‐ion adsorption ability was achieved. POLYM. COMPOS., 36:1546–1556, 2015. © 2014 Society of Plastics Engineers     

The additive-free electrode based on the layered MnO2 nanoflowers/reduced,graphene oxide film for high performance supercapacitor

The MnO₂ nanoflowers/reduced graphene oxide composite is coated on a nickel foam substrate (denoted as MnO₂ NF/RGO @ Ni foam) via the layer by layer (LBL) self-assembly technology without any polymer additive, following the soft chemical reduction. The layered MnO₂ NF/RGO composite is uniformly anchored on the Ni foam skeleton to form the 3D porous framework, and the interlayers have access to lots of ions channels to improve the electron transfer and diffusion. This special construction of 3D porous structure is beneficial to the enhancement of electrochemical property. The specific capacitance is up to 246 F g⁻¹ under the current density of 0.5 A g⁻¹. After 1000 cycles, it can retain about 93%, exhibiting excellent cycle stability. The electrochemical impedance spectroscopy measurements confirm that MnO₂ NF/RGO @ Ni foam electrode has lower R_ESR and R_CT values when compared to MnO₂ @ Ni foam and RGO @ Ni foam. This study opens a new door to the preparation of composite electrodes for high performance supercapacitor.     

Enhanced corrosion protection coatings prepared from soluble electronically conductive polypyrrole‐clay nanocomposite materials

A series of electronically conductive nanocomposite materials that consisted of soluble polypyrrole (PPY) and layered montmorillonite (MMT) clay platelets were prepared by effectively dispersing the inorganic nanolayers of MMT clay in organic PPY matrix via an in situ oxidative polymerization with dodecylbenzene sulfonic acid (DBSA) as dopant. Organic pyrrole monomers were first intercalated into the interlayer regions of organophilic clay hosts and followed by a one‐step oxidative polymerization. The as‐synthesized electronically conductive polypyrrole–clay nanocomposite (PCN) materials were then characterized by Fourier transformation infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD), and transmission electron microscopy (TEM). PCNs in the form of coatings with low clay loading (e.g., 1.0 wt %) on cold‐rolled steel (CRS) were found to exhibit much better in corrosion protection over those of pristine PPY based on a series of electrochemical measurements including corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Effects of the material composition on the thermal stability, optical properties, and electrical conductivity of pristine PPY along with PCN materials, in the form of fine powder, powder‐pressed pellet, and solution, were also studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), UV‐visible absorption spectra, and four‐point probe technique, respectively. The viscosity of PPY existed in PCN materials and pristine PPY were determined by viscometric analysis with m‐cresol as solvent. The heterogeneous nucleating effect of MMT clay platelets in PPY matrix was studied by wide‐angle powder XRD. The corresponding morphological images of the nucleating behavior of clay platelets in PPY matrix were investigated by scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3264–3272, 2003     

Bifunctional ternary manganese oxide/vanadium oxide/reduced graphene oxide as electrochromic asymmetric supercapacitor

A bifunctional ternary manganese oxide/vanadium oxide/reduced graphene oxide (MnO₂/V₂O₅/rGO) was developed for asymmetric electrochromic supercapacitor (EC-SC) application. The elemental mapping revealed uniformly distributed MnO₂, V₂O₅ and rGO, depicting homogenous synthesis of the hybrid composite. The phase composition, vibration modes and valance state of the ternary composite were analyzed via X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis, respectively. Interestingly, the as-prepared MnO₂/V₂O₅/rGO composite disclosed tremendous C_sp of 1403.5 F/g, which was higher compared to MnO₂/V₂O₅ (801.1 F/g), V₂O₅ (613.1 F/g), MnO₂ (126.7 F/g) and rGO (60.7 F/g). MnO₂/V₂O₅/rGO that appeared in dark green switched its visual color to orange at the charged state, confirming the electrochromic property. The bifunctional manganese oxide/vanadium oxide/reduced graphene oxide//copper-based metal-organic framework/reduced graphene oxide (MnO₂/V₂O₅/rGO//MrGO) asymmetrical EC-SC device revealed outstanding cycling stability (90.3% charge retention over 5000 cycles), tremendous specific capacitance (652.7 F/g) and maximum specific energy (60.4 Wh/kg). MnO₂/V₂O₅/rGO//MrGO asymmetrical EC-SC device demonstrated reversible color changes from dark green to orange at the discharged and charged states, respectively. The significantly great electrochromic and supercapacitive performance revealed that MnO₂/V₂O₅/rGO//MrGO is an outstanding electroactive candidate for the next generation of electrochromic supercapacitors.     

Preparation and modification of polythiophene–organic montmorillonite composite

Polythiophene‐organic montmorillonite (PTP‐OMMT) composites were prepared via Fe³⁺‐H₂O₂ catalytic oxidation system at room temperature in water (medium) within the presence of sodium dodecyl benzene sulfonate. The PTP‐OMMT composite made from 2 g/ml solution of OMMT/TP with reacting for 12 h shown the highest conductivity (3.44 × 10⁻⁵ S/cm). The prepared PTP‐OMMT was modified with aniline (ANI) and pyrrole (PY) under Fe³⁺‐H₂O₂ and ammonium persulfate (APS) oxidation systems. The conductivity of PANI‐(PTP‐OMMT) and PPY‐(PTP‐OMMT) reached the range from 10⁻² S/cm to 10⁻¹ S/cm, showing a growth of 10³ to 10⁴ times. Fourier transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) revealed that thiophene enter into OMMT to form intercalation compounding, which undamaged after ANI and PY modification. Thermogravimetric analysis (TGA) comfirmed the improved thermostability of PTP‐OMMT and the decreased thermostability of modified materials. Scanning electron microscopy (SEM) indicated that modified materials under Fe³⁺‐H₂O₂ oxidation system presented regular spherical structures. POLYM. COMPOS., 37:2503–2510, 2016. © 2015 Society of Plastics Engineers     

Reduced graphene oxide anchored with δ-MnO2 nanoscrolls as anode materials for enhanced Li-ion storage

We developed a one-pot in situ synthesis procedure to form nanocomposite of reduced graphene oxide (RGO) sheets anchored with 1D δ-MnO₂ nanoscrolls for Li-ion batteries. The as-prepared products were characterized by X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). The electrochemical performance of the δ-MnO₂ nanoscrolls/RGO composite was measured by galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy. The results show that the δ-MnO₂ nanoscrolls/RGO composite displays superior Li-ion battery performance with large reversible capacity and high rate capability. The first discharge and charge capacities are 1520 and 810 mAh g⁻¹, respectively. After 50 cycles, the reversible discharge capacity is still maintained at 528 mAh g⁻¹ at the current density of 100 mAh g⁻¹. The excellent electrochemical performance is attributed to the unique nanostructure of the δ-MnO₂ nanoscrolls/RGO composite, the high capacity of MnO₂ and superior electrical conductivity of RGO.     

Novel mesoporous MnO2 for high-rate electrochemical capacitive energy storage

MnO₂ with novel mesoporous structure has been firstly synthesized via a simple in situ reduction process by using different carbon materials as sacrificed template and reducing agent. The morphology and microstructure of as-synthesized mesoporous MnO₂ were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), nitrogen adsorption and desorption experiments. The results demonstrate that porous MnO₂ prepared using mesoporous carbon as template has very large specific surface area and uniform pore-size distribution. The electrochemical measurements showed that novel porous MnO₂ have higher capacity (221 F g⁻¹) with excellent rate and higher capacity retention as electrochemical capacitors (ECs) electrode materials, which may be attributed to the unique nanostrcture of porous MnO_2. These all imply that MnO₂ with novel mesoporous structure has been attractive for practical and large-scale applications in mobile equipment.     

Nanocomposites of manganese oxides and carbon nanotubes for aqueous supercapacitor stacks

Symmetrical supercapacitors and their serially connected two-cell stacks via a bipolar electrode were constructed with nanocomposites of manganese oxides and carbon nanotubes (MnO_x/CNTs) as the electrode materials. Nanocomposites with different contents of MnO_x were synthesised through the redox reaction between KMnO₄ and CNTs in aqueous solutions. The nanocomposites were characterised by scanning and transmission electron microscopy, BET nitrogen adsorption and X-ray diffraction before being examined in a three-electrode cell with a novel trenched graphite disc electrode by electrochemical means, including cyclic voltammetry, galvanostatic charging-discharging, and electrochemical impedance spectroscopy. The nanocomposites demonstrated capacitive behaviour in the potential range of 0-0.85 V (vs Ag/AgCl) in aqueous KCl electrolytes with less than 9% capacitance decrease after 9000 charging-discharging cycles. Symmetrical supercapacitors of identical positive and negative MnO_x/CNTs electrodes showed capacitive performance in good agreement with the individual electrodes (e.g. 0.90 V, 0.53 F, 1.3 cm²). The bipolarly connected two-cell stacks of the symmetrical cells exhibited characteristics in accordance with expectation, including a doubled stack voltage and reduced internal resistance per cell.     

Fourier transform infrared study of polypyrrole–poly(vinyl alcohol) conducting polymer composite films: Evidence of film formation and characterization

The electrochemical preparation of polypyrrole (PPY)–poly(vinyl alcohol) (PVA) conducting polymer composite films on an indium–tin oxide glass electrode from an aqueous solution containing a pyrrole monomer, a p‐toluene sulfonate electrolyte, and a PVA insulating polymer is reported. The prepared PPY–PVA composite films were characterized by Fourier Transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and conductivity measurements. The FTIR study showed that the composite of PPY and PVA formed through bond formation between PVA and the p‐toluene sulfonate dopant anion. The conductivity data of PPY–PVA showed that with increasing PVA concentration in the pyrrole solution, the conductivity of the prepared PPY–PVA film increased up to a certain level due to an increase in conjugation length, and later, it decreased with further increases in the PVA concentration in the solution due to a decrease in conjugation length. This was supported by the FTIR band intensity I₁₅₆₀/I₁₄₈₀. The TGA results show that the PPY–PVA polymer composite film was thermally more stable than the PPY film. A shielding effectiveness of 45.6 dB was exhibited by the PPY–PVA composite film in the microwave frequency range. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4107–4113, 2006     

Coaxial carbon nanofibers/MnO2 nanocomposites as freestanding electrodes for high-performance electrochemical capacitors

Carbon nanofibers (CNFs)/MnO₂ nanocomposites were prepared as freestanding electrodes using in situ redox deposition and electrospinning. The electrospun CNFs substrates with porosity and interconnectivity enabled the uniform incorporation of birnessite-type MnO₂ deposits on each fiber, thus showing unique and conformal coaxial nanostructure. CNFs not only provided considerable specific surface area for high mass loading of MnO₂ but also offered reliable electrical conductivity to ensure the full utilization of MnO₂ coatings. The effect of MnO₂ loading on the electrochemical performances was investigated by cyclic voltammetry (CV), impedance measurements and Galvonostatic charging/discharging technique. The results showed that an ultrathin MnO₂ deposits were indispensable to achieve better electrochemical performance. The maximum specific capacitance (based on pristine MnO₂) attained to 557 F/g at a current density of 1 A/g in 0.1 M Na₂SO₄ electrolyte when the mass loading reached 0.33 mg/cm². This freestanding electrode also exhibited good rate capability (power density of 13.5 kW/kg and energy density of 20.9 Wh/kg at 30 A/g) and long-term cycling stability (retaining 94% of its initial capacitance after 1500 cycles). These characteristics suggested that such freestanding CNFs/MnO₂ nanocomposites are promising for high-performance supercapacitors.