The present work has studied electrochemical and optical properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film electrodes drop-casted from commercial PEDOT:PSS aqueous dispersion with preliminary addition and without addition of LiClO4 electrolyte (further denoted as PEDOT:PSS/LiClO4 and PEDOT:PSS). Cyclic voltammetry measurements showed the significant increase in capacitance of PEDOT:PSS/LiClO4 film electrodes in comparison to PEDOT:PSS. Furthermore, the improved charge transport in PEDOT:PSS/LiClO4 films was demonstrated by electrochemical impedance spectra. In situ spectroelectrochemical measurements revealed that preliminary addition of LiClO4 into PEDOT:PSS aqueous dispersion allows to increase amount of free charge carriers (polaron and bipolaron states) in the resulting film during electrochemical oxidation in LiClO4 propylene carbonate solution. This increase was attributed to ion-induced charge screening between positively charged PEDOT and negatively charged PSS in polyelectrolyte structure, which was supported by structural investigations of both types of film electrodes by using FTIR, SEM, and XPS measurements. Charge screening results from a more open structure that allows conformational relaxation of PEDOT molecules during charge transport, which leads to partial separation of oppositely charged PSS and PEDOT molecules and facilitating the increase of electrochemical activity.
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.
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 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.
In the current work, the effect of aniline concentration on the polymerization process and supercapacitive behavior of graphene oxide/multiwalled carbon nanotubes/polyaniline (GMP) nanocomposites were studied. Based on the obtained results, GMP nanocomposite with 0.5 M aniline (GMP5) was selected as the optimum concentration in terms of high current density and high specific capacitance. Nafion-based ionic polymer-free metal composite (IPFMC) supercapacitor was fabricated for the GMP5 nanocomposite. Solid-state symmetric supercapacitor was made after spraying of GMP5 in. on both sides of Nafion membrane. The electrochemical properties were investigated by cyclic voltammetry (CV), galvanostatic charge–discharge (CD), and electrochemical impedance spectroscopy (EIS) techniques in 0.5 M Na2SO4.The specific capacitance of 383.25 F g?1 (326 mF cm?2) and 527.5 F g?1 (42 mF cm?2) was obtained for the GMP5 in solid-state supercapacitor and three-electrode cell at a scan rate of 10 mV s?1, respectively. The maximum energy and power densities of 53.64 and 1777.4 W kg?1 were obtained for the IPFMC-based supercapacitor.
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.
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.
The influence of the atmosphere composition (CO, Ar, air), in which wet synthesis of Pt/C electrocatalyst was carried out, on the structural and morphological characteristics, and electrochemical behavior of electrocatalysts have been studied. For comparison, commercial Pt/C electrocatalysts with the same platinum loading were also studied. It has been shown that the adsorption of CO molecules on the surface of the growing platinum nuclei leads to the decrease in the average size of the nanoparticles and the narrowing of the size distribution in the Pt/C. Homemade electrocatalysts, with the values of electrochemically active surface area being from 94 to 139 m2 g?1 (Pt), prove to be in no way inferior to their commercial counterparts in oxygen reduction reaction mass activity. Durability of the homemade Pt/C samples in accelerated stress tests exceeds durability of the commercial ones.
The preparation of molybdenum-modified hematite electrodes by means of chemical bath deposition and their photoelectrochemical behavior toward water oxidation are reported in this work. The addition of a molybdenum precursor to the bath solution for hematite deposition induces a remarkable change of morphology in the resulting film from (110)-oriented nanorods to polyhedral nanoparticles. Despite the resulting loss of order, by controlling the Mo/Fe molar ratio in the bath solution, a significant improvement of the water oxidation photocurrent is achieved compared to nanorod pristine hematite electrodes. Such a (photo)electrochemical enhancement is mainly explained by an effective surface state passivation in Mo-modified hematite films. FE-SEM, TEM, XRD, and XPS were employed for electrode structural and morphological characterization.
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.
An environmentally friendly cell using polypyrrole-air regenerative cathode and zinc as anode is investigated in the 3% sodium chloride solution. The cell can operate in different charge and discharge mode. Polypyrrole can be reoxidized (doped) with chloride anions either by using dissolved oxygen or by an external power supply, e.g., small photovoltaic cell. In that way, after discharge, capacity retaining can be achieved by using seawater as the electrolyte. During low discharge rate, the delicate balance between solid state diffusion-controlled dedoping and chemical oxidation of polypyrrole produced by hydrogen peroxide is achieved, generating stable voltage plateau. The cell is proposed to operate as a power supply for different sensor devices in two modes. In the low discharge mode (10–20 mA g?1), it can be used for data acquisition, and at the fast discharge mode (up to 2 A g?1) for collecting data transmission.
Graphical abstract Charge-discharge curves for different curent densities of Zn|3.5% NaCl(aq)|PPy. Inset: Continuous discharge of the cell under external load of 1 kΩ and constant air supply, during 1-h discharge and 1-h reoxidation charge
An electrochemical chiral sensor was designed based on graphene (GR) as a catalyst for signal enhancement. Hydrocortisone has been immobilized as a chiral selector on GR to discriminate electrochemical signals of mandelic acid (MA) enantiomers. A two-step electrodeposition strategy was used to fabricate hydrocortisone-loaded overoxidized polypyrrole film (HC-OPPy) on graphene-modified glassy carbon electrode, which was successfully utilized as a working electrode for direct monitoring of MA enantiomers based on an inhibitory sensing mechanism. The stepwise modification of the surface was confirmed by cyclic voltammetry, impedance spectroscopy, and scanning electron microscopy. Because of the different interactions of enantiomers with the chiral electroactive platform, voltammetric signals with different intensities were observed for S-MA and R-MA at 1.36 and 1.40 V (vs. Ag/AgCl), respectively. The introduced design for the chiral sensor, with exploiting the chemometrics tools such as partial least squares, principle component regression, and genetic algorithm, was able to discriminate highly overlapping signals of MA enantiomers in their mixtures. The hydrocortisone-based sensor showed a linear response towards MA enantiomers within a concentration range of 1.0–25 mM with a detection limit of 0.25 mM (S/N = 3). The sensor not only extends the enantioselective sensing of MA enantiomers but also stimulates new opportunities for investigating stereo-selective behavior of hydrocortisone. The recognition mechanism was also investigated using docking analysis and DFT calculations.
Free-standing and flexible NiMoO4 nanorods/reduced graphene oxide (rGO) membrane with a 3D hierarchical structure was successfully synthesized by a general approach including vacuum filtration followed by thermal reduction. NiMoO4 nanorods with about 50–100 nm diameter were embedded homogenously into the 3D rGO sheets and assembled with rGO to form a membrane about 10 μm in thickness. The NiMoO4/rGO membrane could be directly evaluated as anode materials for lithium-ion batteries (LIBs) without using binder. The 3D layer stacked graphene hierarchical architecture can not only offers a continuous conducting framework for efficient diffusion and transport of ion/electron but also accommodates the large volume expansion of NiMoO4 nanorod changes during cycling. Moreover, our results show that the NiMoO4/rGO membrane exhibited excellent electrochemical performance with a high reversible capacity of 945 mAh g?1 at a current density of 0.25 A g?1 as anode materials in LIBs.
Galvanic exchange involving dissolution of iron and the simultaneous growth of platinum onto 316 L stainless steel was investigated for specimens manufactured by 3D-printing, and the behavior was compared to conventional stainless steel. Novel phenomena associated with the 3D-printed steel, but not conventional steel, reacting in three distinct phases were observed: first, with low platinum loading, a bright etching pattern linked to the laser-manufacturing process is revealed at the steel surface; second, a nanostructured pore pattern with platinum nano-deposits forms; and third, a darker platinum film coating of typically 500-nm thickness forms and then peels off the steel surface with further platinum growth underneath. Unlike the conventional steel (and mainly due to residual porosity), 3D-printed steel supports well-adhered platinum films for potential application in electrocatalysis, as demonstrated for alkaline methanol oxidation.
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.
In this study, a novel modified glassy carbon electrode with copper polydopamine complex/multiwalled carbon nanotubes (GCE/Cu2+@PDA-MWCNTs) was fabricated and used for voltammetric determination of ascorbic acid (AA), dopamine (DA), acetaminophen (AC), nitrite (Nit), and xanthine (XN). Different techniques such as field emission electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, and electrochemical impedance spectroscopy were performed for characterization of the GCE/Cu2+@PDA-MWCNTs. Different electrochemical methods such as cyclic voltammetry, electrochemical impedance spectroscopy and differential pulse voltammetry (DPV) methods were employed to study the behavior of AA, DA, AC, Nit, and XN on this proposed modified electrode. The proposed modified electrode displays intense and indelible electrooxidation response for simultaneous determination of AA, DA, AC, Nit, and XN to five well-separated peaks in the potential range from 0.1 to 1.1 V using CV and DPV methods in phosphate buffer solution with pH 2.0. Under the optimum conditions, the calibration curves were liner up to 175, 125, 75, 150, and 115 μM with detection limits of 0.82, 0.45, 0.87, 0.92, and 0.67 μM for AA, DA, AC, Nit, and XN, respectively. This sensor was used to successfully determine these compounds in human urine and serum samples.
Hydrothermally synthesized Co3O4 microspheres were anchored to graphite oxide (GO) and thermally reduced graphene oxide (rGO) composites at different cobalt weight percentages (1, 10, and 100 wt%). The composite materials served as the active materials in bulk electrodes for two-electrode cell electrochemical capacitors (ECCs). GO/Co3O4–1 exhibited a high energy density of 35 W kg?1 with a specific capacitance (Csp) of 196 F g?1 at a maximum charge density of 1 A g?1. rGO/Co3O4-100 presented high specific power output values of up to 23.41 kW h kg?1 with linear energy density behavior for the charge densities applied between 0.03 and 1 A g?1. The composite materials showed Coulombic efficiencies of 96 and 93 % for GO/Co3O4–1 and rGO/Co3O4–100 respectively. The enhancement of capacitive performance is attributed to the oxygenated groups in the GO ECC and the specific area in the rGO ECC. These results offer an interesting insight into the type of carbonaceous support used for graphene derivative electrode materials in ECCs together with Co3O4 loading to improve capacitance performance in terms of specific energy density and specific power.
We obtained Tannin-4-azobenzoic acid (azo dye) by the conventional method of diazotization and coupling of aromatic amines. The properties of the azo dye were characterized via ultraviolet-visible (UV–vis), infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy. Nanocrystalline titanium dioxide (TiO2) thin films were deposited by hydrothermal method onto fluorine-doped tin (IV) oxide (FTO)-coated glass substrate at 353 K for 4 h. The as-deposited and annealed films were characterized for structural, morphological, optical, thickness, and wettability properties. The synthesized metal free azo dye was used to sensitize the prepared TiO2 thin film with thickness of 26 μm. The photoelectrochemical (PEC) performance of TiO2 sensitized with the azo dye was evaluated in polyiodide (0.1 M KI + 0.01 M I2 + 0.1 M KCl) electrolyte at 40 mW cm?2 illumination intensity. The cell yielded a short circuit current of 2.82 mA, open circuit voltage of 314.3 mV, a fill factor of 0.30, and a photovoltaic conversion efficiency value of 0.64%.
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.
Nanoporous gold (NPG) prepared via chemical de-alloying has been recently shown to dramatically improve the reversibility and kinetics of Li-O2 batteries, but high cost makes its use as practical electrode material difficult. Recently developed electrochemical routines for synthesis of very thin NPG layers (<100 nm) on various low-cost substrates could potentially provide a feasible economic alternative. In this work, NPG on both gold and glassy carbon (GC) substrates was successfully synthesized via electrochemical de-alloying method and tested as cathode material in Li-O2 batteries. The results show that electrochemically synthesized NPG cathode cycles repeatedly with LiFePO4 anode. The voltage hysteresis is also significantly reduced when NPG is used in comparison with plain GC. Along with these results, challenges that need to be addressed for future implementation of NPG cathode in practical Li-O2 batteries are also discussed.
