Microelectrode study of pore size, ion size, and solvent effects on the charge/discharge behavior of microporous carbons for electrical double-layer capacitors

The capacitive behavior of TiC-derived carbon powders in two different electrolytes, NEt4BF4 in acetonitrile AN and NEt4BF4 in propylene carbonate PC, was studied using the cavity microelectrode CME technique. Comparisons of the cyclic voltammograms recorded at 10–1000 mV/s enabled correlation between adsorbed ion sizes and pore sizes, which is important for understanding the electrochemical capacitive behavior of carbon electrodes for electrical double-layer capacitor applications. The CME technique also allows a fast selection of carbon electrodes with matching pore sizes different sizes are needed for the negative and positive electrodes for the respective electrolyte system. Comparison of electrochemical capacitive behavior of the same salt, NEt4BF4, in different solvents, PC and AN, has shown that different pore sizes are required for different solvents, because only partial desolvation of ions occurs during the double-layer charging. Squeezing partially solvated ions into subnanometer pores, which are close to the desolvated ion size, may lead to distortion of the shape of cyclic voltammograms

Improved breeding and seed production of climbing perch (<em>Anabas testudineus</em>) in controlled tanks and cage systems

The climbing perch (Anabas testudineus) is a valuable fish species with significant potential for aquaculture. However, a low survival rate was observed at its early development stages, requiring an optimized protocol for sustainable aquaculture production. This paper presents an improved breeding and seed production technology for climbing perch. Mature climbing perch were induced to spawn using salmon gonadotropin-releasing hormone analog (sGnRHa) at a dose of 30 µg/kg-1 body weight of the breeder. The female broodfish spawn 9–10 hours after hormone injection. Developmental stages were defined based on the morphological features of the embryos from the first cleavage to the hatching stage. The first cleavage began at approximately 18–20 minutes after fertilization. Newly hatched larvae were observed within 18–20 h at 30°C, having an average larval size of 0.389±0.042 mm (total length). Successful breeding entails a selection of suitable algal species, an optimal aquaculture environment, regular feeding rates, consistent monitoring of larval development, and effective management of water quality. Survival rates from the larval stage to fry were achieved at 84.69% and 77.60%, respectively, while the survival rate to the fingerlings stage was 72.51%. Therefore, by implementing an optimized protocol, aquaculture practitioners can maximize the production potential of climbing perch while ensuring sustainable cultivation practices. The findings from this research contribute to the advancement of climbing perch aquaculture by providing valuable insights for the successful cultivation and increased economic profitability of A. testudineus species in hatchery productions

Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon

Electrochemical capacitors, also called supercapacitors, store energy in two closely spaced layers with opposing charges, and are used to power hybrid electric vehicles, portable electronic equipment and other devices¹. By offering fast charging and discharging rates, and the ability to sustain millions of ²⁻⁵, electrochemical capacitors bridge the gap between batteries, which offer high energy densities but are slow, and conventional electrolytic capacitors, which are fast but have low energy densities. Here, we demonstrate microsupercapacitors with powers per volume that are comparable to electrolytic capacitors, capacitances that are four orders of magnitude higher, and energies per volume that are an order of magnitude higher. We also measured discharge rates of up to 200 V s⁻¹, which is three orders of magnitude higher than conventional supercapacitors. The microsupercapacitors are produced by the electrophoretic deposition of a several micrometre-thick layer of nanostructured carbon onions⁶‚⁷ with diameters of 6-7 nm. Integration of these nanoparticles in a microdevice with a high surface-to-volume ratio, without the use of organic binders and polymer separators, improves performance because of the ease with which ions can access the active material. Increasing the energy density and discharge rates of supercapacitors will enable them to compete with batteries and conventional electrolytic capacitors in a number of applications

Modification of Al Current Collector/Active Material Interface for Power Improvement of Electrochemical Capacitor Electrodes

This paper presents results about carbon nanofibers (CNFs) synthesis and their use as surface treatments for Al current collector for carbon electrochemical capacitors in organic electrolyte. CNFs have been successfully synthesized on a pretreated Al substrate; the pretreatment of Al consists of an etching followed by a carbonaceous sol-gel deposit. Performances of cells assembled with pretreated Al and pretreated Al coated by CNFs have been compared by using galvanostatic cycling measurements. Internal resistances as low as 0.4 Omega cm2 are obtained for cells using CNF-treated Al. The increase of the surface contact and interface conductivity between the Al and the active material are responsible for this internal resistance decrease. The capacitance obtained for the two cells is the same (95 F g–1 of activated carbon). Performances [both equivalent series resistance (ESR) and capacitance] are stable over 10 000 cycles, proving the great efficiency of surface treatments

Oncogenic driver mutations predict outcome in a cohort of head and neck squamous cell carcinoma (HNSCC) patients within a clinical trial

234 diagnostic formalin-fixed paraffin-embedded (FFPE) blocks from homogeneously treated patients with locally advanced head and neck squamous cell carcinoma (HNSCC) within a multicentre phase III clinical trial were characterised. The mutational spectrum was examined by next generation sequencing in the 26 most frequent oncogenic drivers in cancer and correlated with treatment response and survival. Human papillomavirus (HPV) status was measured by p16INK4a immunohistochemistry in oropharyngeal tumours. Clinicopathological features and response to treatment were measured and compared with the sequencing results. The results indicated TP53 as the most mutated gene in locally advanced HNSCC. HPV-positive oropharyngeal tumours were less mutated than HPV-negative tumours in TP53 (p < 0.01). Mutational and HPV status influences patient survival, being mutated or HPV-negative tumours associated with poor overall survival (p < 0.05). No association was found between mutations and clinicopathological features. This study confirmed and expanded previously published genomic characterization data in HNSCC. Survival analysis showed that non-mutated HNSCC tumours associated with better prognosis and lack of mutations can be identified as an important biomarker in HNSCC. Frequent alterations in PI3K pathway in HPV-positive HNSCC could define a promising pathway for pharmacological intervention in this group of tumours

Capacitive energy storage from -50 to 100 °C using an ionic liquid electrolyte

Relying on redox reactions, most batteries are limited in their ability to operate at very low or very high temperatures. While performance of electrochemical capacitors is less dependent on the temperature, present-day devices still cannot cover the entire range needed for automotive and electronics applications under a variety of environmental conditions. We show that the right combination of the exohedral nanostructured carbon (nanotubes and onions) electrode and a eutectic mixture of ionic liquids can dramatically extend the temperature range of electrical energy storage, thus defying the conventional wisdom that ionic liquids can only be used as electrolytes above room temperature. We demonstrate electrical double layer capacitors able to operate from -50 to 100 °C over a wide voltage window (up to 3.7 V) and at very high charge/discharge rates of up to 20 V/s

Ultrahigh-rate supercapacitors based on eletrochemically reduced graphene oxide for ac line-filtering

The recent boom in multifunction portable electronic equipments requires the development of compact and miniaturized electronic circuits with high efficiencies, low costs and long lasting time. For the operation of most line-powered electronics, alternating current (ac) line-filters are used to attenuate the leftover ac ripples on direct current (dc) voltage busses. Today, aluminum electrolytic capacitors (AECs) are widely applied for this purpose. However, they are usually the largest components in electronic circuits. Replacing AECs by more compact capacitors will have an immense impact on future electronic devices. Here, we report a double-layer capacitor based on three-dimensional (3D) interpenetrating graphene electrodes fabricated by electrochemical reduction of graphene oxide (ErGO-DLC). At 120-hertz, the ErGO-DLC exhibited a phase angle of −84 degrees, a specific capacitance of 283 microfaradays per centimeter square and a resistor-capacitor (RC) time constant of 1.35 milliseconds, making it capable of replacing AECs for the application of 120-hertz filtering

In Situ NMR Spectroscopy of Supercapacitors: Insight into the Charge Storage Mechanism

Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance(NMR) methodologies to study changes at the electrode−electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations

High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications

All battery technologies are known to suffer from kinetic problems linked to the solid-state diffusion of Li in intercalation electrodes, the conductivity of the electrolyte in some cases and the quality of interfaces. For Li-ion technology the latter effect is especially acute when conversion rather than intercalation electrodes are used. Nano-architectured electrodes are usually suggested to enhance kinetics, although their realization is cumbersome. To tackle this issue for the conversion electrode material Fe3O4, we have used a two-step electrode design consisting of the electrochemically assisted template growth of Cu nanorods onto a current collector followed by electrochemical plating of Fe3O4. Using such electrodes, we demonstrate a factor of six improvement in power density over planar electrodes while maintaining the same total discharge time. The capacity at the 8C rate was 80% of the total capacity and was sustained over 100 cycles. The origin of the large hysteresis between charge and discharge, intrinsic to conversion reactions, is discussed and approaches to reduce it are proposed. We hope that such findings will help pave the way for the use of conversion reaction electrodes in future-generation Li-ion batteries

Vertically aligned ZnO nanorod core-polypyrrole conducting polymer sheath and nanotube arrays for electrochemical supercapacitor energy storage

Nanocomposite electrodes having three-dimensional (3-D) nanoscale architecture comprising of vertically aligned ZnO nanorod array core-polypyrrole (PPy) conducting polymer sheath and the vertical PPy nanotube arrays have been investigated for supercapacitor energy storage. The electrodes in the ZnO nanorod core-PPy sheath structure are formed by preferential nucleation and deposition of PPy layer over hydrothermally synthesized vertical ZnO nanorod array by controlled pulsed current electropolymerization of pyrrole monomer under surfactant action. The vertical PPy nanotube arrays of different tube diameter are created by selective etching of the ZnO nanorod core in ammonia solution for different periods. Cyclic voltammetry studies show high areal-specific capacitance approximately 240 mF.cm(-2) for open pore and approximately 180 mF.cm(-2) for narrow 30-to-36-nm diameter PPy nanotube arrays attributed to intensive faradic processes arising from enhanced access of electrolyte ions through nanotube interior and exterior. Impedance spectroscopy studies show that capacitive response extends over larger frequency domain in electrodes with PPy nanotube structure. Simulation of Nyquist plots by electrical equivalent circuit modeling establishes that 3-D nanostructure is better represented by constant phase element which accounts for the inhomogeneous electrochemical redox processes. Charge-discharge studies at different current densities establish that kinetics of the redox process in PPy nanotube electrode is due to the limitation on electron transport rather than the diffusive process of electrolyte ions. The PPy nanotube electrodes show deep discharge capability with high coulomb efficiency and long-term charge-discharge cyclic studies show nondegrading performance of the specific areal capacitance tested for 5,000 cycles