An evaluation of the capacitive behavior of supercapacitors as a function of the radius of cations using simulations with a constant potential method.

We report on the atomistic molecular dynamics, applying the constant potential method to determine the structural and electrostatic interactions at the electrode-electrolyte interface of electrochemical supercapacitors as a function of the cation radius (Cs+, Rb+, K+, Na+, Li+). We find that the electrical double layer is susceptible to the size, hydration layer volume, and cations' mobility and analyzed them. Besides, the transient potential shows an increase in magnitude and length as a function of the monocation size, i.e., Cs+ > Rb+ > K+ > Na+ > Li+. On the other hand, the charge distribution along the electrode surface is less uniform for large monocations. Nonetheless, the difference is not observed as a function of the radius of the cation for the integral capacitance. Our results are comparable to studies that employed the fixed charge method for treating such systems.

Exploring doped or vacancy-modified graphene-based electrodes for applications in asymmetric supercapacitors.

We report here density functional theory calculations and molecular dynamics atomistic simulations to determine the total capacitance of graphene-modified supercapacitors. The contributions of quantum capacitance to the total capacitance for boron-, sulfur-, and fluorine-doped graphene electrodes, as well as vacancy-modified electrodes, were examined. All the doped electrodes presented significant variations in quantum capacitance (ranging from 0 to ∼200 µF cm-2) due to changes in the electronic structure of pristine graphene. The graphene-modified supercapacitors show any appreciable effect on double-layer capacitance being virtually the same for all the devices investigated. The total differential capacitance was found to be limited by the quantum capacitance, and for all the systems, it is lower than the quantum capacitance over the entire voltage window. We found that the total capacitance can be optimized by considering an adequate modification to each electrode in the supercapacitor. In addition, we found that an asymmetric supercapacitor assembled with different doped electrodes, i.e. an F doped negative electrode and an N doped positive electrode, is the best choice for a supercapacitor since this combination results in better capacitance over the entire potential window.

How to Measure and Calculate Equivalent Series Resistance of Electric Double-Layer Capacitors.

Electric double-layer capacitors (EDLCs) are energy storage devices that have attracted attention from the scientific community due to their high specific power storage capabilities. The standard method for determining the maximum power (Pmax) of these devices uses the relation Pmax = U2/4RESR, where U stands for the cell voltage and RESR for the equivalent series resistance. Despite the relevance of RESR, one can observe a lack of consensus in the literature regarding the determination of this parameter from the galvanostatic charge-discharge findings. In addition, a literature survey revealed that roughly half of the scientific papers have calculated the RESR values using the electrochemical impedance spectroscopy (EIS) technique, while the other half used the galvanostatic charge discharge (GCD) method. RESR values extracted from EIS at high frequencies (>10 kHz) do not depend on the particular equivalent circuit model. However, the conventional GCD method better resembles the real situation of the device operation, and thus its use is of paramount importance for practical purposes. In the latter case, the voltage drop (ΔU) verified at the charge-discharge transition for a given applied current (I) is used in conjunction with Ohm's law to obtain the RESR (e.g., RESR = ΔU/ΔI). However, several papers have caused a great confusion in the literature considering only applied current (I). In order to shed light on this important subject, we report in this work a rational analysis regarding the GCD method in order to prove that to obtain reliable RESR values the voltage drop must be normalized by a factor of two (e.g., RESR = ΔU/2I).

Bioactivity behaviour of nano-hydroxyapatite/freestanding aligned carbon nanotube oxide composite.

Bioactive and low cytotoxic three dimensional nano-hydroxyapatite (nHAp) and aligned carbon nanotube oxide (a-CNTO) composite has been investigated. First, freestanding aligned carbon nanotubes porous scaffold was prepared by large-scale thermal chemical vapour deposition and functionalized by oxygen plasma treatment, forming a-CNTO. The a-CNTO was covered with plate-like nHAp crystals prepared by in situ electrodeposition techniques, forming nHAp/a-CNTO composite. After that nHAp/a-CNTO composite was immersed in simulated body fluid for composite consolidation. This novel nanobiomaterial promotes mesenchymal stem cell adhesion with the active formation of membrane projections, cell monolayer formation and high cell viability.

Differential pulse adsorptive stripping voltammetric determination of nanomolar levels of atorvastatin calcium in pharmaceutical and biological samples using a vertically aligned carbon nanotube/graphene oxide electrode.

A novel vertically aligned carbon nanotube/graphene oxide (VACNT-GO) electrode is proposed, and its ability to determine atorvastatin calcium (ATOR) in pharmaceutical and biological samples by differential pulse adsorptive stripping voltammetry (DPAdSV) is evaluated. VACNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method and then treated with oxygen plasma to produce the VACNT-GO electrode. The oxygen plasma treatment exfoliates the carbon nanotube tips exposing graphene foils and inserting oxygen functional groups, these effects improved the VACNT wettability (super-hydrophobic) which is crucial for its electrochemical application. The electrochemical behaviour of ATOR on the VACNT-GO electrode was studied by cyclic voltammetry, which showed that it underwent an irreversible oxidation process at a potential of +1.08 V in pHcond 2.0 (0.2 mol L(-1) buffer phosphate solution). By applying DPAdSV under optimized experimental conditions the analytical curve was found to be linear in the ATOR concentration range of 90 to 3.81 × 10(3) nmol L(-1) with a limit of detection of 9.4 nmol L(-1). The proposed DPAdSV method was successfully applied in the determination of ATOR in pharmaceutical and biological samples, and the results were in close agreement with those obtained by a comparative spectrophotometric method at a confidence level of 95%.

Absence of mutagenic and recombinagenic activity of multi-walled carbon nanotubes in the Drosophila wing-spot test and Allium cepa test.

In order to assess the safety of the carbon nanotubes to human health and the environment, we investigated the potential toxicity and ability of multi-walled carbon nanotubes (NT), to induce DNA damage by employing the Allium cepa genotoxicity/mutagenicity test and the Somatic Mutation and Recombination Test (SMART) in the fruitfly, Drosophila melanogaster. The results demonstrated that NT did not significantly induce genotoxic or mutagenic effects in the Allium cepa test. All concentrations evaluated in the SMART assay showed survival rates higher than 90percent, indicating the absence of chronic toxicity for NT. Furthermore, the various treatments showed no significant increase in the NT mutation and recombination frequencies in mwh/flr(3) genotype compared to respective negative controls, demonstrating the absence of DNA damage caused by NT.

Electrochemical Behavior of Symmetric Electrical Double-Layer Capacitors and Pseudocapacitors and Identification of Transport Anomalies in the Interconnected Ionic and Electronic Phases Using the Impedance Technique.

A double-channel transmission line impedance model was applied to the study of supercapacitors to investigate the charge transport characteristics in the ionic and electronic conductors forming the electrode/solution interface. The macro homogeneous description of two closely mixed phases (Paasch-Micka-Gersdorf model) was applied to study the influence of disordered materials on the charge transport anomalies during the interfacial charge-discharge process. Different ex situ techniques were used to characterize the electrode materials used in electrical double-layer (EDLC) and pseudocapacitor (PC) devices. Two time constants in the impedance model were adequate to represent the charge transport in the different phases. The interfacial impedance considering frequency dispersion and blocked charge transfer conditions adequately described the charge storage at the interface. Deviations from the normal (Fickian) transport involving the ionic and electronic charge carriers were identified by the dispersive parameters (e.g., n and s exponents) used in the impedance model. The ionic and electronic transports were affected when the carbon-based electrical double-layer capacitor was converted into a composite with strong pseudocapacitive characteristics after the decoration process using NiO. The overall capacitance increased from 2.62 F g-1 to 536 F g-1 after the decoration. For the first time, the charge transport anomalies were unequivocally identified in porous materials used in supercapacitors with the impedance technique.

New Insights on the Sodium Water-in-Salt Electrolyte and Carbon Electrode Interface from Electrochemistry and Operando Raman Studies.

Comprehensive electrochemical and operando Raman studies are performed to investigate the electrochemical stability window (ESW) of supercapacitors filled with normal (salt-in-water) and highly concentrated (water-in-salt, WiSE) electrolytes. Impedance and chronoamperometric experiments are employed and combined with cyclic voltammetry to correctly define the ESW for a WiSE-based device. The total absence of water-splitting resulted in phase angles close to -90° in the impedance data. It is verified that a 17 m NaClO4 electrolyte avoids the water-splitting up to 1.8 V. Furthermore, Raman studies under dynamic and static polarization conditions corroborate the existence of a solvent blocking interface (SBI), which inhibits the occurrence of water-splitting. Also, the reversible nature of the charge-storage process is assessed as a function of the applied voltage. At extreme polarization, the SBI structure is disrupted, thus allowing the occurrence of water-splitting and anionic (ClO4-) intercalation between the graphene sheets.

Charge-storage mechanism of highly defective NiO nanostructures on carbon nanofibers in electrochemical supercapacitors.

An electrode composed of highly defective nickel oxide (NiO) nanostructures supported on carbon nanofibers (CNFs) and immersed in an Li+-based aqueous electrolyte is studied using Raman spectroscopy under dynamic polarization conditions to address the charge-storage phenomenon. By this operando technique, the formation of Li2SO4·H2O during the discharge process is verified. At the same time, we observed the phase transformation of NiO to NiOOH. The Ni(OH)2/NiOOH redox couple is responsible for the pseudocapacitive behavior with intercalation of cationic species in the different Ni structures. A 'substitutive solid-state redox reaction' is proposed to represent the amphoteric nature of the oxide, resulting in proton intercalation, while the insertion of Li+ occurs to a less extent. The electrode material exhibits outstanding stability with 98% coulombic efficiency after 10 000 charge-discharge cycles. The excellent electrode properties can be ascribed to a synergism between CNFs and NiO, where the carbon nanostructures ensured rapid electron transport from the hydrated nickel nanoparticles. The NiO@CNF composite material is a promising candidate for future applications in aqueous-based supercapacitors. DFT simulation elucidates that compressive stress and Ni-site displacement lead to a decrease up-to 3.5-fold on the electron density map located onto the Ni-atom, which promotes NiO/Ni(OH)2/NiOOH transition.

A rational experimental approach to identify correctly the working voltage window of aqueous-based supercapacitors.

It is common to find in the literature different values for the working voltage window (WVW) range for aqueous-based supercapacitors. In many cases, even with the best intentions of the widening the operating voltage window, the measured current using the cyclic voltammetry (CV) technique includes a significant contribution from the irreversible Faradaic reactions involved in the water-splitting process, masked by fast scan rates. Sometimes even using low scan rates is hard to determine precisely the correct WVW of the aqueous-based electrochemical capacitor. In this sense, we discuss here the best practices to determine the WVW for capacitive current in an absence of water splitting using complementary techniques such as CV, chronoamperometry (CA), and the electrochemical impedance spectroscopy (EIS). To accomplish this end, we prepare and present a model system composed of multiwalled carbon nanotubes buckypaper electrodes housed in the symmetric coin cell and soaked with an aqueous-based electrolyte. The system electrochemical characteristics are carefully evaluated during the progressive enlargement of the cell voltage window. The presence of residual Faradaic current is verified in the transients from the CA study, as well as the impedance changes revealed by EIS as a function of the applied voltage, is discussed. We verify that an apparent voltage window of 2.0 V determined using the CV technique is drastically decreased to 1.2 V after a close inspection of the CA findings used to discriminate the presence of a parasitic Faradaic process. Some orientations are presented to instigate the establishment in the literature of some good scientific practices concerned with the reliable characterization of supercapacitors.

Multi-walled carbon nanotubes/graphene oxide hybrid and nanohydroxyapatite composite: A novel coating to prevent dentin erosion.

To date is emergent the development of novel coatings to protect erosion, especially to preventive dentistry and restorative dentistry. Here, for the first time we report the effectiveness of multi-walled carbon nanotube/graphene oxide hybrid carbon-base material (MWCNTO-GO) combined with nanohydroxyapatite (nHAp) as a protective coating for dentin erosion. Fourier transform Raman spectroscopy (FT-Raman), scanning electron (SEM), and transmission electron (TEM) microscopy were used to investigated the coatings and the effect of acidulated phosphate fluoride gel (APF) treatment on bovine teeth root dentin before and after erosion. The electrochemical corrosion performance of the coating was evaluated. Raman spectra identified that: (i) the phosphate (ν1PO43-) content of dentin was not significantly affected by the treatments and (ii) the carbonate (ν1CO32-) content in dentin increased when nHAp was used. However, the nHAp/MWCNTO-GO composite exposited lower levels of organic matrix (CH bonds) after erosion compared to other treatments. Interesting, SEM micrographs identified that the nHAp/MWCNTO-GO formed layers after erosive cycling when associate with APF treatment, indicating a possible chemical bond among them. Treatments of root dentin with nHAp, MWCNTO-GO, APF_MWCNTO-GO, and APF_nHAp/MWCNTO-GO increased the carbonate content, carbonate/phosphate ratio, and organic matrix band area after erosion. The potentiodynamic polarization curves and Nyquist plot showed that nHAp, MWCNT-GO and nHAp/MWCNT-GO composites acted as protective agents against corrosion process. Clearly, the nHAp/MWCNTO-GO composite was stable after erosive cycling and a thin and acid-resistant film was formed when associated to APF treatment.

Electrochemical performance of porous diamond-like carbon electrodes for sensing hormones, neurotransmitters, and endocrine disruptors.

Porous diamond-like carbon (DLC) electrodes have been prepared, and their electrochemical performance was explored. For electrode preparation, a thin DLC film was deposited onto a densely packed forest of highly porous, vertically aligned multiwalled carbon nanotubes (VACNT). DLC deposition caused the tips of the carbon nanotubes to clump together to form a microstructured surface with an enlarged surface area. DLC:VACNT electrodes show fast charge transfer, which is promising for several electrochemical applications, including electroanalysis. DLC:VACNT electrodes were applied to the determination of targeted molecules such as dopamine (DA) and epinephrine (EP), which are neurotransmitters/hormones, and acetaminophen (AC), an endocrine disruptor. Using simple and low-cost techniques, such as cyclic voltammetry, analytical curves in the concentration range from 10 to 100 µmol L(-1) were obtained and excellent analytical parameters achieved, including high analytical sensitivity, good response stability, and low limits of detection of 2.9, 4.5, and 2.3 µmol L(-1) for DA, EP, and AC, respectively.

Fast preparation of free-standing nanohydroxyapatite-vertically aligned carbon nanotube scaffolds.

We present a simple, low cost, and fast method to produce free-standing nanohydroxyapatite/carbon-based scaffolds. We electrodeposited nanohydroxyapatite onto vertically aligned carbon nanotube flakes and reticulated vitreous carbon bars. We prepared a highly crystalline and homogeneous thin film without any post-thermal treatment, and our results evidence that we can control the nanohydroxyapatite crystal formation according to the substrate employed. Immersion tests using simulated body fluid showed that these new nanobiomaterials had in vitro bioactivity. The free-standing nanohydroxyapatite/carbon-based scaffolds have been shown to be a suitable surface for mesenchymal stem cell adhesion with active formation of membrane projections and cell monolayer formation.

Fast preparation of nano-hydroxyapatite/superhydrophilic reduced graphene oxide composites for bioactive applications.

A method for the direct electrodeposition of globular nano-hydroxyapatite (nHAp) onto reduced graphene oxide (RGO) is presented and a model for the specific growth preference is discussed. Results show that the carboxyl (carboxylic acid)/carboxylate functional groups attached directly to the RGO after oxygen plasma treatment were essential to accelerate the OH- formation and the deposition of globular nHAp crystals. High resolution scanning electron microscopy, energy dispersive X-ray and X-ray diffraction showed that homogeneous, highly crystalline, stoichiometric nHAp crystals, with preferential growth in the (002) plane direction, were formed without any thermal treatment. The nHAp/RGO composites were shown to be an appropriate surface for mesenchymal stem cell adhesion with active formation of membrane projections.

Effect of ultrasound irradiation on the production of nHAp/MWCNT nanocomposites.

Large amounts of nanohydroxyapatite (nHAp)-multiwall carbon nanotube (MWCNT) nanocomposites are produced by two different aqueous precipitation methods. The ultrasonic irradiation (UI) and slow-drip addition under continuous magnetic stirring (DMS) methods were used to investigate the precipitation of nHAp acicular crystals. Calcium-nitrate, diammonium hydrogen phosphate, and ammonium hydroxide were used as precursor reagents. Superhydrophilic MWCNT were also employed. XPS analysis evidences that the functionalized MWCNTs are composed of 18 to 20 at.% of oxygen and that this property influences the nHAp formation. The high surface area of the MWCNT decreases the mean free path of ions, favoring the nHAp formation assisted by UI. The crystallinity was evaluated using the Scherrer equation. Semi-qualitative energy dispersive spectroscopy (EDS) analysis showed that the main components of HAp powders were calcium and phosphorus in the ratio Ca/P around of 1.67. Bioactivity properties of the nHAp/MWCNT-UI nanocomposites could be evaluated after 14 days soaking in simulated body fluid medium. Scanning electron microscopy, EDS, Fourier transform infrared attenuated total reflection spectroscopy, and X-ray diffraction techniques proved that the apatites formed on the surface and to points that the nHAp/MWCNT-UI have potential biological applications.