A series of PANI-CNTs/TiO2 nanotubes/Ti electrodes were fabricated via pulse current co-electrodeposition of polyaniline and functionalized carbon nanotubes onto TiO2 nanotubes/Ti electrodes. FT-IR spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy were applied in order to characterize the modified TiO2 nanotubes/Ti electrodes. The morphology studies showed that the PANI-CNTs/TiO2 nanotubes/Ti nanocomposite electrode has many interlaced PANI-CNTs nanorods on the surface of TiO2 nanotubes. The electrochemical measurements of the modified electrodes confirmed that the CNTs in the composite can significantly improve the capacitive behavior as well which have been compared with that of PANI/TiO2 nanotubes/Ti electrodes. The modified electrode exhibited much higher specific capacitance (190 mF cm?2 with 90% retention after 1000 cycles) compared to the PANI/TiO2 nanotubes/Ti (70 mF cm?2 with 77% retention after 1000 cycles) at a current density of 0.85 mA cm?2, indicating its great potential for supercapacitor applications.
Hierarchical CuO nanosheets were synthesized through a facile, eco-friendly reflux deposition approach for supercapacitor electrode material for energy storage. The resultant CuO nanosheets were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption isotherm techniques. The supercapacitor behavior of CuO nanosheets was investigated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy in novel 0.1 M aqueous 1-(1′-methyl-2′-oxo-propyl)-3-dimethylimidazolium chloride [MOPMIM][Cl] ionic liquid as an electrolyte. The result demonstrate that CuO nanosheets exhibit specific capacitance of 180 F g?1 at 10 mV s?1 scan rate which is the highest value in ionic liquid electrolyte and 87% specific capacitance retention after 5000th cycle. The electrochemical performance proves CuO nanosheets as electrode with ionic liquid electrolyte for developing green chemistry approach in supercapacitor.
Graphical abstract As-synthesized, CuO nanosheets demonstrate excellent supercapacitor electrode performance with high specific capacitance of 180 F g?1 at 10 mV s?1 scan rate and 87% specific capacitance retention in 0.1 M aqueous [MOPMIM][Cl] IL electrolyte
Tin (Sn) has been considered as an attractive anode material for sodium-ion batteries (SIBs) due to its high theoretical capacity (847 mAh g?1). Nevertheless, its low conductivity and large volume change during cycling essentially prevent the possibility of high capacity and long-term cycle for SIBs. In this work, Sn nanoparticles are well embedded into the highly ordered mesoporous carbon (CMK-3) matrix (Sn@CMK-3) using a facile sonochemical method combined with heat treatment. The resultant Sn@CMK-3 nanohybrid electrode delivers an initial charge capacity of 412 mAh g?1 at 100 mA g?1. A reversible capacity of 337 mAh g?1 is obtained after 200 cycles, indicating the good cycle stability of the nanohybrid structure. The electrode also shows a potential rate capability, which maintains a capacity of 228 mAh g?1 at 1000 mA g?1. When the current density returns to 50 mA g?1, the capacity goes back to 381 mAh g?1, with a capacity retention of 86.9%. The enhanced sodium storage performance of Sn@CMK-3 nanohybrid can be related to the synergistic effect between CMK-3 and Sn.
Graphical abstract Sn@CMK-3 nanohybrid with Sn nanoparticles uniformly distributed into the highly ordered mesoporous carbon matrix exhibited good cycling performance and rate capability.
MnO has a high theoretical capacity, moderate discharge plateau, and low polarization when it is used as the anode material in lithium battery. However, the issues that limit its application are its poor conductivity and large volume changes, which can easily result in the collapse of electrode structure during long-term cycling. In the present work, a carbon-coated MnO/graphene 3D-network anode material is synthesized by an electrostatic adsorption of dispersed precipitates precipitation method. The MnO nanoparticles coated by carbon are uniformly distributed on the surface of graphene nanosheets and form a 3D sandwich-like nanostructure. A carbon layer is coated on the surface of MnO nanoparticles, which slows down the volume expansion in the process of lithium intercalation. The graphene nanosheets are cross-linked through carbons in this 3D nanostructure, which provides mechanical support and effective electron conduction pathways during the charge-discharge. The electrochemical tests indicate that the prepared 3D carbon-coated MnO/graphene electrode exhibits an excellent rate capacity of 1247.3 and 713.2 mAh g?1 at 100 and 1000 mA g?1, respectively. The capacity is 792.2 mAh g?1 after long cycle at a current density of 1000 mA g?1. The specific capacity is higher than that of MnO-based composite lithium anode materials currently reported. The superior rate and cycling performances are attributed to the unique 3D-network structure, which provides an effectively conductive network, buffers volume expansion, and prevents falling and aggregation of MnO in the charge and discharge process of the electrode materials. The 3D-structured carbon-coated MnO/graphene anode material will have an excellent application prospect.
This paper reports the voltammetric determination of 17β-estradiol in urine and buttermilk samples using a simple detector based on a carbon paste electrode (CPE) modified with copper(II) oxide (CuO). The CuO was obtained by the Pechini method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive (EDS), Fourier transform infrared (FTIR), and Raman spectroscopies. Cyclic voltammetry (CV) and square-wave voltammetry (SWV) demonstrated that the CuO-modified carbon paste electrode (CuO/CPE detector) displayed much higher electrocatalytic activity in the 17β-estradiol oxidation reaction than the CPE without modification, exhibiting a low detection limit of 21.0 nmol L?1 with a wide linear range from 60.0 to 800.0 nmol L?1 (R = 0.998). Satisfactory results were obtained for the determination of 17β-estradiol in human urine and buttermilk samples. The proposed electrochemical detector offers high repeatability, stability, fast response, low cost, and potential for practical application in the quantification of this hormone.
A porous, hollow, microspherical composite of Li2MnO3 and LiMn1/3Co1/3Ni1/3O2 (composition: Li1.2Mn0.53Ni0.13Co0.13O2) was prepared using hollow MnO2 as the sacrificial template. The resulting composite was found to be mesoporous; its pores were about 20 nm in diameter. It also delivered a reversible discharge capacity value of 220 mAh g?1 at a specific current of 25 mA g?1 with excellent cycling stability and a high rate capability. A discharge capacity of 100 mAh g?1 was obtained for this composite at a specific current of 1000 mA g?1. The high rate capability of this hollow microspherical composite can be attributed to its porous nature.
A biodegradable composite polymer membrane is fabricated by synthesizing polyvinylpyrrolidone (PVP) on the matrix of lignin, and then the corresponding gel polymer electrolyte (LP-GPE) is further prepared by absorbing the liquid electrolyte. The morphology, mechanical property, and thermal stability of the composite lignin-PVP membrane and the electrochemical properties of LP-GPE are investigated. The results of the investigation present that the mechanical property of the membrane is remarkable improved (670%) and the composite membrane exhibits a better thermal security. For electrochemical properties, a high ionic conductivity of 2.52 × 10?3 S cm?1 at room temperature, excellent lithium-ion transference number of 0.56, and outstanding electrochemical stability of LP-GPE are confirmed. Moreover, the C-rate performance and capacity retention based on Li/LP-GPE/LiFePO4 cell are superior to that of the commercial Celgard 2730 cell. Consequently, all these results demonstrate that LP-GPE can be applied as a novel electrolyte for lithium ion battery with high-performance, low-cost, and environment-friendly properties.
Biomass-derived carbon (BMC) materials have attracted much attention due to their high performance and properties of abundant source. Herein, biomass carbon sheets (BMCS) from wheat straws had been successfully synthesized via a facile high temperature carbonization and expansion processes. The morphology of BMCS keeps the natural honeycomb-like shape of the cross section and the hollow tubular array structure of the vertical section with rich pores, which provides low-resistant ion channels to support fast diffusion. The (002) crystal plane reveals that the intercalation distance of carbon sheets is 0.383 nm larger than that graphite (0.335 nm), which benefits the larger sodium ion de/intercalation. By comparing different carbonization temperatures, wheat straws carbonized at 1200 °C (BMCS-1200) with well graphite microcrystallites show more excellent sodium ion storage performance than that of 900 °C (BMC-900). BMCS-1200 shows a stable reversible capacity of 221 mAh g?1 after 200 cycles at 0.05 A g?1, while BMC-900 is 162 mAh g?1 after 100 cycles. And it also exhibits better rate capability (220, 109 mAh g?1) than that of BMC-900 (125, 77 mAh g?1) at 0.2 and 1 A g?1, respectively. Finally, it delivers 89 mAh g?1 stable capacity after 1400 cycles at 1 A g?1 to prove its excellent long-term cycling stability.
Graphical abstract High temperature carbon sheets with well graphite microcrystallites synthesized from wheat straw forexcellent sodium ion storage performance
The three-dimensional porous Li3V2(PO4)3/nitrogen-doped reduced graphene oxide (LVP/N-RGO) composite was prepared by a facile one-pot hydrothermal method and evaluated as cathode material for lithium-ion batteries. It is clearly seen that the novel porous structure of the as-prepared LVP/N-RGO significantly facilitates electron transfer and lithium-ion diffusion, as well as markedly restrains the agglomeration of Li3V2(PO4)3 (LVP) nanoparticles. The introduction of N atom also has positive influence on the conductivity of RGO, which improves the kinetics of electrochemical reaction during the charge and discharge cycles. It can be found that the resultant LVP/N-RGO composite exhibits superior rate properties (92 mA h g?1 at 30 C) and outstanding cycle performance (122 mA h g?1 after 300 cycles at 5 C), indicating that nitrogen-doped RGO could be used to improve the electrochemical properties of LVP cathodes for high-power lithium-ion battery application.
Graphical abstract The three-dimensional porous Li3V2(PO4)3/nitrogen-doped reduced graphene oxide composite with significantly accelerating electron transfer and lithium-ion diffusion exhibits superior rate property and outstanding cycle performance.
This paper reports a simple methodology for the synthesis of a polyaniline/titanium oxide/graphene hybrid (Pani/TiO2/GN) using a simple methodology, and their application as a supercapacitor electrode material for energy storage. The Pani/TiO2/GN hybrid was prepared by a simple approach by simultaneous generation of Pani and TiO2 in situ from aniline and titanium iso-propoxide, respectively, in the presence of GN under ice bath conditions. The incorporation of GN improved the electrical conductivity of Pani and helped to decrease the charge transfer resistance, whereas TiO2 generation by an in situ method increased the surface area considerably and enhanced the capacitance of the Pani/TiO2/GN hybrid. TEM showed that Pani and TiO2 were well incorporated and coated on the GN successfully. The shift of the peaks in the FTIR spectrum and XRD pattern of the Pani/TiO2/GN hybrid compared to their pure counterparts suggested that TiO2 and Pani had been perfectly coated on the GN, and there was a strong interaction among Pani, GN, and TiO2 particles. The electrochemical performance of the as-prepared Pani/TiO2/GN hybrid electrode showed a high specific capacitance of 403.2 F g?1 at a current density of 2 A g?1 and excellent cycling stability for up to 1000 cycles. This suggested that the effective incorporation of GN and TiO2 into Pani and the high surface area could simultaneously increase the electrochemical capacitance and cyclic stability of the Pani/TiO2/GN hybrid, leading to superior electrochemical performance.
Graphical abstract The electrochemical performance of as-prepared Pani/TiO2/GN hybrid electrode showed a high specific capacitance of 403.2 F g?-1 at a current density of 2 A g?-1 and excellent cycling stability for up to 1000 cycles. This suggested that the effective incorporation of GN and TiO2 into Pani and the high surface area could simultaneously increase the electrochemical capacitance and cycle stability of the Pani/TiO2/GN hybrid, leading to superior electrochemical performance.
There is a growing need for the electrode with high mass loading of active materials, where both high energy and high power densities are required, in current and near-future applications of supercapacitor. Here, an ultrathin Co3S4 nanosheet decorated electrode (denoted as Co3S4/NF) with mass loading of 6 mg cm?2 is successfully fabricated by using highly dispersive Co3O4 nanowires on Ni foam (NF) as template. The nanosheets contained lots of about 3～5 nm micropores benefiting for the electrochemical reaction and assembled into a three-dimensional, honeycomb-like network with 0.5～1 μm mesopore structure for promoting specific surface area of electrode. The improved electrochemical performance was achieved, including an excellent cycliability of 10,000 cycles at 10 A g?1 and large specific capacitances of 2415 and 1152 F g?1 at 1 and 20 A g?1, respectively. Impressively, the asymmetric supercapacitor assembled with the activated carbon (AC) and Co3S4/NF electrode exhibits a high energy density of 79 Wh kg?1 at a power density of 151 W kg?1, a high power density of 3000 W kg?1 at energy density of 30 Wh kg?1 and 73 % retention of the initial capacitance after 10,000 charge-discharge cycles at 2 A g?1. More importantly, the formation process of the ultrathin Co3S4 nanosheets upon reaction time is investigated, which is benefited from the gradual infiltration of sulfide ions and the template function of ultrafine Co3O4 nanowires in the anion-exchange reaction.
Graphical abstract The ultrathin 2D Co3S4 nanosheets fabricated on 3D Ni foam and the formation process of the ultrathin Co3S4 nanosheets upon reaction times has been investigated. At the same time, the Co3S4/NF electrode displays an outstanding specific capacitance of 2420 F g?1 at 1 A g?1 with high mass loading of 6 mg cm?2.
In this work, Bi3.64Mo0.36O6.55 nanoparticles (NPs) were successfully prepared by a facile hydrothermal method and utilized in pseudocapacitor for the first time. Within a redox potential range from ?1.0 to 0 V vs. Hg/HgO in a 1 M aqueous KOH solution by cyclic voltammetry (CV), chronopotentiometry (CP) and AC impendence, the specific capacitance could reach 998 F g?1 at 1 A g?1, which is possibly ascribed to the higher Bi content of Bi3.64Mo0.36O6.55 NPs. Furthermore, the Bi3.64Mo0.36O6.55 NP electrode exhibited good cycle stability maintaining over 85 % after 5000 cycles. These results demonstrated Bi3.64Mo0.36O6.55 NPs might be a promising electrode material for pseudocapacitor.
Graphical abstract The fabrication of uniform Bi3.64Mo0.36O6.55 nanoparticles with a diameter of 100 nm were succefully reported by a facial hydrothermal method, which exhibits a extraordinary electronic performance with 998 F g-1 at 1 A g-1 and cycling stability
A novel polyhedral oligomeric silsesquioxane (POSS) composite polyacrylonitrile (PAN)-based porous structure gel polymer electrolyte (GPE) is prepared by phase inversion method. The POSS additive filler is firstly obtained in the dehydration condensation reaction of vinyltrimethoxysilane (VTMS) and 3-methacryloxypropyltrimethoxysilane (MPTMS). The composition and structure of synthetic POSS and the prepared POSS composite PAN-based GPEs are investigated. It is found that compared with pure PAN-based GPE, the POSS composite PAN-based GPE with 8 wt.% POSS presents the homogeneous pore distribution and abundant electrolyte uptake (540.4 wt.%), which endows GPE-8% with the excellent comprehensive performances: the highest ionic conductivity of 2.62?×?10?3 S cm?1 at room temperature, the higher lithium ion transference number of 0.38, the good compatibility with lithium anode, and the higher electrochemical stability window of 5.7 V (vs. Li/Li+). At 0.2 C, the GPE-8%-based lithium ion battery produces a satisfactory discharge capacity of 140 mAh g?1.
The paper reports the effect of SiO2 nano-filler on structural, thermal, and ion transport properties of polymer electrolyte system comprising polyvinyl alcohol (PVA) and 1-butyl-3-methylimidazolium hydrogen sulfate [C4C1Im][HSO4] ionic liquid. The addition of SiO2 nano-filler results into enhancement in amorphicity and thermal stability and lowering of glass transition temperature of the membranes. A detailed investigation of possible interactions among the constituents PVA, [C4C1Im][HSO4] and SiO2, and cation–anion and anion–anion pairs of [C4C1Im][HSO4] in the polymer electrolyte and their dissociation due to SiO2 filler has been carried out in the membranes using Fourier transform infra-red (FTIR) and Raman spectroscopy. The membranes show maximum room temperature ionic conductivity as 9.9?×?10?3 S cm?1 for 6 wt.% of the nano-filler which is about four times higher than the membrane without nano-filler and an order higher than pure [C4C1Im][HSO4]. With temperature, the ionic conductivity shows VTF behavior in the temperature range 40–120 °C. On the basis of FTIR and ion transport results, a model for ion transport in the membranes is proposed.
The authors describe an immunoassay for the determination of carcinoembryonic antigen (CEA) tumor markers by depositing a polydopamine-Pb(II) nanocomposite on the surface of a glassy carbon electrode. The nanocomposite acts as a redox system that displays a large specific surface and provides a strong current signal at ?0.464 V (vs. Ag/AgCl). After the deposition of PDA-Pb2+ on glassy carbon electrode, the electrode was additionally coated with a chitosan-gold nanocomposite. The immunoassay platform was obtained by immobilization of antibodies against carcinoembryonic antigens by using glutaraldehyde and blocking with bovine albumin. Owing to its large surface, good electrical conductivity and powerful current response, the immunoassay has a wide linear range that extends from 1 fg·mL?1 to 100 ng·mL?1, with a detection limit as low as 0.26 fg·mL?1. The results obtained with this immunoassay when determining CEAs in human serum were found to be consistent with those obtained by ELISAs.
Graphical abstract Schematic of an ultrasensitive electrochemical immunosensor for the carcinoembryonic antigen. It is based on a glassy carbon electrode modified with a polydopamine-Pb(II) nanocomposite acting as a signal-inherent substrate.
Aluminum-doped ZnO thin films with pebble-like structures have been successfully deposited on glass substrates by successive ionic layer adsorption reaction method. The effect of percentage composition of the aluminum dopant on the flower-like clusters of the ZnO nanostructures on the structure, morphology, and optical properties was investigated. The ZnO thin films which were crystallized in hexagonal wurtzite structures with crystallite sizes of 44, 51, 56, and 43 nm for the intrinsic and 1, 3, and 5% Al-doped ZnO thin films, respectively. Preferred orientation of crystallites is in all cases in [001] direction perpendicular to the sample surface The Raman spectroscopy revealed decrease in the intensity of the ZnO characteristic peak due to the substitution of the Zn2+ atoms by the Al3+ and attributed to potential fluctuations of the alloy disorder. The introduction of the Al3+ dopant significantly increased the optical band gap.
The activated carbon was modified by the wet method with a solution of ammonium persulfate at room temperature with different times. Kinetics studies showed that the modification took place mostly during the first 60 min of the process. The physicochemical properties of the obtained carbon were evaluated by thermogravimetric studies, Raman and FTIR spectroscopy, elementary and BET analyses. Furthermore, the fabricated material was applied in symmetric capacitors operated on the three aqueous electrolytes (1 M H2SO4, 6 M KOH and 1 M Na2SO4). Mild conditions of the modification process are optimal to obtain electroactive groups on the carbon surface, which make this material useful in a supercapacitor application. In our studies, we noticed that this type of functional groups mainly appears on the surface of the activated carbon, in the first oxidation stage. With prolonged oxidation, they may transform into undesirable groups. The results show that this kind of modification improves the capacity of all the tested supercapacitors. It was connected mainly with an increase of the carbon material’s wettability and in the case of capacitor operated in acid and base electrolytes due to a redox reaction of oxygen functional groups.
We describe a chemical exfoliation method for the preparation of MoS2 nanosheets. The nanosheets were incorporated into poly(3,4-ethylenedioxythiophene) (PEDOT) by electrodeposition on a glassy carbon electrode (GCE) to form a nanocomposite. The modified GCE is shown to enable simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). Due to the synergistic effect of MoS2 and PEDOT, this electrode displays better properties in terms of electrocatalytic oxidation of AA, DA and UA than pure PEDOT, which is illustrated by cyclic voltammetry and differential pulse voltammetry (DPV). Under optimum conditions and at pH 7.4, the respective sensitivities and best working potentials are as follows: AA: 1.20 A?mM?1?m?2, 30 mV; DA: 36.40 A?mM?1?m?2, 210 mV; UA: 105.17 A?mM?1?m?2, 350 mV. The calculated detection limits for AA, DA and UA are 5.83 μM, 0.52 μM and 0.95 μM, respectively. The modified electrode was applied to the detection of the three species in human urine samples and gave satisfactory results.
Graphical abstract MoS2 nanosheets were prepared by a facile chemical exfoliation method. MoS2 and poly(3,4-ethylenedioxythiophene) nanocomposite modified glassy carbon electrodes were fabricated, which are shown to enable simultaneous determination of ascorbic acid, dopamine and uric acid with high sensitivity and selectivity.
In this paper, a facile immobilization of copper hexacyanoferrate nanoparticles (CuHCFNP) on a paraffin wax-impregnated graphite electrode (PIGE) was carried out using the room-temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) as an ionic binder. The characteristics of the CuHCFNP/EMIMBF4 gel-modified electrode were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques, and the modified electrode morphology was also characterized using field emission scanning electron microscopy (FESEM). The electrocatalytic behavior of butylated hydroxyl anisole (BHA) at the modified electrode has been investigated in 0.1 M KNO3 in static and dynamic conditions. Under the optimum conditions, the oxidation peak current was proportional to the BHA concentration in the range from 1.5 to 1000 μM with a detection limit of 0.5 μM (S/N = 3). The proposed method was applied to determine BHA content in real samples with satisfactory results.
The development of new techniques for rapid and continuous monitoring of urea in biomedical and clinical analysis is very important. Thus, conductive polymer-supported carbon nanotube as an effective electrochemical biosensing platform for direct detection of urea in blood samples was designed. For the assay optimization, several conductive polymers were synthesized and tested as electrode modifiers; among the tested polymers, poly-o-toluidine (PoT) showed the highest electrochemical signals. However, after the enzyme immobilization, direct bioelectrochemical signals were not obtained when the PoT was used alone. Due to the lower electrocatalytic feature of PoT, integration of carbon nanotube, to form a composite with the PoT, was exploited to enable the direct electron transfer. Successfully, using the hybrid, the catalytic activity of the immobilized urease enzyme was retained. Consequently, a sensitive and specific chronoamperometric signals were achieved after the bioassay optimization. Eventually, a standard calibration curve for urea determination was obtained. A linear range was found from 0.1 to 11 mM with the limit of detection of 0.03 mM. Successfully, several blood samples were analyzed and urea level was correlated with the reference analytical method.
Graphical abstract Scheme 1: Schematic representation of screen-printed electrode-modified urease biosensors. Three-layer functionalized surface (multi-walled carbon nanotube/poly(o-toluidine) nanocomposite, with glutaraldehyde (cross-linker and urease-immobilized enzyme), was designed for urea biosensors.
