High oxygen-reduction activity of silk-derived activated carbon

Activated carbon prepared from silk fibroin, which is free of metal elements, showed a high catalytic activity for the oxygen-reduction reaction (ORR). The activated carbon had a very high onset potential of E_onset = 0.83 V (vs. RHE) in oxygen-saturated 0.5 M H₂SO₄ at 60 °C. The ORR on the activated carbon proceeded by a four-electron process in the high-electrode-potential region; this gradually decreased to a 3.5-electron reaction below about 0.6 V (vs. RHE). Only about 1% of nitrogen atoms (mostly quaternary) remained in the activated carbon by heat-treatment at up to 1200 °C are responsible for the high catalytic activity. The open circuit voltage of a polymer electrolyte fuel cell using the activated carbon as the cathode and a platinum/carbon black anode under pure oxygen and hydrogen gases, respectively, both at one atmosphere, was 0.96 V at 27 °C.     

Study on electrochemical performance of activated carbon in aqueous Li2SO4, Na2SO4 and K2SO4 electrolytes

The electrochemical performances of activated carbon (AC) in 0.5 mol/l Li₂SO₄, Na₂SO₄ and K₂SO₄ aqueous electrolytes were investigated. The cyclic voltammetric results at different scan rates show that the rate behaviors of AC in the three electrolytes improve in the order of Li₂SO₄ < Na₂SO₄ < K₂SO₄. This improvement can be mainly ascribed to the following two reasons: (1) the decreasing equivalent series resistance in the order of Li₂SO₄ > Na₂SO₄ > K₂SO₄, which is the main factor influencing the maximum output power, and (2) the increasing migration speed of hydrated ions in the bulk electrolyte and in the inner pores of AC electrode in the order of Li⁺ < Na⁺ < K⁺. Their cycling behaviors do not show any differences in capacitive fading. The above results provide valuable information to explore new hybrid supercapacitors.     

Na4Mn9O18 as a positive electrode material for an aqueous electrolyte sodium-ion energy storage device

Here we demonstrate Na₄Mn₉O₁₈ as a sodium intercalation positive electrode material for an aqueous electrolyte energy storage device. A simple solid-state synthesis route was used to produce this material, which was then tested electrochemically in a 1 M Na₂SO₄ electrolyte against an activated carbon counter electrode using cyclic voltammetry and galvanostatic cycling. Optimized Na₄Mn₉O₁₈ was documented as having a specific capacity of 45 mAh/g through a voltage range of 0.5 V, or an equivalent specific capacitance of over 300 F/g. With the proper negative:positive electrode mass ratio, energy storage cells capable of being charged to at least 1.7 V without significant water electrolysis are documented. Cycling data and rate studies indicate promising performance for this unexplored low-cost positive electrode material.     

Nanoporous carbon electrode from waste coffee beans for high performance supercapacitors

Activated carbon was produced from waste coffee grounds by treatment with ZnCl₂. Supercapacitor electrodes prepared from this coffee grounds carbon exhibited energy densities up to 20 Wh kg⁻¹ in 1 M H₂SO₄, and excellent stability at high charge–discharge rates. In a two-electrode cell a specific capacitance as high as 368 F g⁻¹ was observed, with rectangular cyclic voltammetry curves and stable performance over 10,000 cycles at a cell potential of 1.2 V and current load of 5 A g⁻¹. The good electrochemical performance of the coffee grounds carbon was attributed to a well developed porosity, with a distribution of micropores and mesopores 2–4 nm wide, and the presence of electrochemically active quinone oxygen groups and nitrogen functional groups. This work highlights the potential to utilize waste biomass to produce electrode materials for cost-effective energy storage systems.     

Li2SO4-polyacrylamide polymer electrolytes for 2.0 V solid symmetric supercapacitors

A neutral polymer electrolyte comprised of lithium sulfate (Li₂SO₄) and polyacrylamide (PAM) was developed. The Li₂SO₄-PAM electrolyte film shows an ionic conductivity up to 10 mS cm^− 1 in 45%RH conditions. Solid double layer capacitors were demonstrated using CNT-graphite electrodes and Li₂SO₄-PAM solid electrolytes. The voltage window of the solid cell was about 2.0 V, identical to that of a Li₂SO₄ liquid cell used as baseline. The demonstrated voltage window is significantly larger than that reported for proton- or hydroxyl-conducting electrolytes, suggesting that the Li₂SO₄-PAM electrolyte is a promising system for high energy density supercapacitors. The solid device also demonstrated excellent rate capability (up to 5 V s^− 1) and good cycle life (beyond 10,000 charge/discharge cycles).     

Sodium vanadium nitridophosphate Na3V(PO3)3N as a high-voltage positive electrode material for Na-ion and Li-ion batteries

We report the preparation and electrochemical properties of Na₃V(PO₃)₃N made by ammonolysis. Na₃V(PO₃)₃N is reversibly oxidized to Na₂V(PO₃)₃N at high voltage (4.0 V vs. Na⁺/Na⁰ and 4.1 V vs. Li⁺/Li⁰) with an unusually small difference in the insertion/extraction voltage between both alkali metal reference electrodes. In both cases, the voltage hysteresis is extremely small (~ 0.035 V vs. sodium and ~ 0.065 V vs. lithium), which suggests facile migration of alkali cations within the structure. Further oxidation to NaV(PO₃)₃N is predicted to occur beyond the voltage stability window of the electrolytes.     

Thermodynamic evaluation and optimization of the (NaNO3 + KNO3 + Na2SO4 + K2SO4) system

A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases of the (NaNO₃ + KNO₃ + Na₂SO₄ + K₂SO₄) ternary reciprocal system, and optimised model parameters have been found. The model parameters obtained for the four binary common-ion subsystems (i.e. (NaNO₃ + Na₂SO₄), (KNO₃ + K₂SO₄), (NaNO₃ + KNO₃) and (Na₂SO₄ + K₂SO₄)) are used to predict thermodynamic properties and phase equilibria for the entire system. The Modified Quasichemical Model in the Quadruplet Approximation for short-range ordering was used for the molten salt phase, and the Compound Energy Formalism was used for the various solid solutions.     

Nano-structured Li3V2(PO4)3/carbon composite for high-rate lithium-ion batteries

Nano-structured Li₃V₂(PO₄)₃/carbon composite (Li₃V₂(PO₄)₃/C) has been successfully prepared by incorporating the precursor solution into a highly mesoporous carbon with an expanded pore structure. X-ray diffraction analysis, scanning electron microscopy, and transmission electron microscopy were used to characterize the structure of the composites. Li₃V₂(PO₄)₃ had particle sizes of < 50 nm and was well dispersed in the carbon matrix. When cycled within a voltage range of 3 to 4.3 V, a Li₃V₂(PO₄)₃/C composite delivered a reversible capacity of 122 mA h g^? 1 at a 1C rate and maintained a specific discharge capacity of 83 mA h g^? 1 at a 32C rate. These results demonstrate that cathodes made from a nano-structured Li₃V₂(PO₄)₃ and mesoporous carbon composite material have great potential for use in high-power Li-ion batteries.     

Ternary non-noble metal chalcogenide (W–Co–Se) as electrocatalyst for oxygen reduction reaction

In this study, a catalyst based on a novel ternary non-noble metal chalcogenide, W–Co–Se, was synthesized for the oxygen reduction reaction (ORR) in acidic medium. The non-noble metal chalcogenide catalyst was electrochemically stable in the potential range of 0.05–0.8 V versus NHE in 0.5 M H₂SO₄ aqueous solution. This catalyst demonstrated significant catalytic activity towards the ORR, showing the ORR onset potential at 0.755 V versus NHE in 0.5 M H₂SO₄ at 25 °C. Such high activity might be attributed to the electronic structure of non-noble metals modified by chalcogen.     

Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7: High potential and high capacity electrode material for sodium-ion batteries

Na₄Co_2.4Mn_0.3Ni_0.3(PO₄)₂P₂O₇ has been evaluated as a positive electrode for sodium-ion batteries. The novel material has two redox couples around 4.2 V and 4.6 V and can deliver the high capacity of ca. 103 mAh g^− 1 at the high current density of 850 mA g^− 1 (5 C). X-ray absorption spectroscopy (XAS) results show that the redox reactions of Co, Mn and Ni ions proceed simultaneously in the charge process and it is indicated the novel material provide high mixed potential by the redox reactions of Co, Mn and Ni ions. These findings suggest that the derivatives of Na₄Co₃(PO₄)₂P₂O₇ should be employed as high potential and high capacity electrode materials.     

Determination of formal potential of NADH/NAD+ redox couple and catalytic oxidation of NADH using poly(phenosafranin)-modified carbon electrodes

The electrochemical regeneration of NADH/NAD⁺ redox couple has been studied using poly(phenosafranin) (PPS)-modified carbon electrodes to evaluate the formal potential and catalytic rate constant for the oxidation of NADH. The PPS-modified electrodes were prepared by electropolymerization of phenosafranin onto different carbon substrates (glassy carbon (GC) and basal-plane pyrolytic graphite (BPPG)) in different electrolytic solutions. The formal potential was estimated to be ? 0.365 ± 0.002 V vs. SHE at pH 7.0. As for the bare carbon electrodes, the oxidation of NADH at the BPPG electrode was found to be enhanced compared with the GC electrode. For the PPS-modified electrodes, it was found that the electrocatalysis of PPS-modified electrodes for the oxidation of NADH largely depends on the carbon substrate and electrolyte solution employed for their preparation, i.e., the PPS-modified BPPG electrode prepared in 0.2 M NaClO₄/acetonitrile solution exhibits an excellent and persistent electrocatalytic property toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 740 and 670 mV compared with those at the bare GC electrode and the PPS-modified GC electrode prepared in 0.2 M H₂SO₄ solution, respectively. A quantitative analysis of the electrocatalytic reaction based on rotating disk voltammetry gave the electrocatalytic reaction rate constants of the order of 10³–10⁴ M^?1 s^? 1 depending on the preparation conditions of the PPS-modified electrodes.     

V2O5·0.6H2O nanoribbons as cathode material for asymmetric supercapacitor in K2SO4 solution

V₂O₅·0.6H₂O nanoribbons were prepared and their electrochemical behaviors in K₂SO₄ aqueous solution were investigated. Results show for the first time that K⁺ ions could intercalate/deintercalate reversibly in the V₂O₅·0.6H₂O lattice. An asymmetric supercapacitor activated carbon/0.5 mol/l K₂SO₄/V₂O₅·0.6H₂O was successfully assembled, which could be cycled reversibly in the voltage region of 0–1.8 V. This supercapacitor presents an energy density of 29.0 Wh/kg based on the total mass of the active electrode materials, a very good rate behavior with energy density of 20.3 Wh/kg at power density of 2 kW/kg, and also a rather good cycling performance.     

Enhanced supercapacitive behaviors of birnessite

The birnessite type manganese dioxide electrode was prepared by the electrochemical stimulation as we recently described. It showed 190 F g⁻¹ in a Na₂SO₄ aqueous solution between −0.1 and 0.9 V versus Ag/AgCl at 1 A g⁻¹. The specific capacitance of birnessite was decreased by the manganese dissolution when the reduction and oxidation were repeated. By adding small amounts of Na₂HPO₄ or NaHCO₃ into the electrolyte, the capacitance increased to 200–230 F g⁻¹ and the manganese dissolution was successfully suppressed. Thanks to the additives, the birnessite demonstrated the much improved cycleability over >1800 cycles.     

Nitrogen enriched mesoporous carbon spheres obtained by a facile method and its application for electrochemical capacitor

A kind of mesoporous carbon spheres (MCS) containing in-frame incorporated nitrogen has been prepared by a facile polymerization-induced colloid aggregation method. As the electrode material for electric double layer capacitor (EDLC) in 5 mol/L H₂SO₄, the MCS products present excellent specific capacitance as 211 F/g much larger than that of the most popularly applied activated carbon at a high discharge current density of 1 A/g. Its specific capacitance can still remain 200 F/g at 20 A/g. The superior electrochemical performance of MCS is associated with the following characteristics: high specific surface area (∼1330 m²/g) contributed mainly by the mesopores, uniform pore size as large as 29 nm and moderate content of nitrogen (10 wt%), which are the requirements for ideal supercapacitors.     

Colouration efficiency measurements in electrochromic polymers: The importance of charge density

A poly(3,4-ethylenedioxythiopene) (PEDOT)/polyaniline (PANI) electrochromic device (ECD) was fabricated for the purpose of examining colouration efficiency (CE) as a function of charge density ingress/egress. CE is typically measured in cm²/C with the aim being to produce as large an optical density change as possible with the least amount of charge being consumed. Results indicate that CE is not constant but is highly dependent on charge density insertion and the switching voltage. At a switching voltage of 1.9 V the maximum CE_max was 1186 cm²/C, recorded at 60% of the full optical switch where as the CE_95% was 302 cm²/C at 95% of the full optical switch. Furthermore, CE_max varied depending on the switching voltage from a high of 2212 cm²/C at a switching voltage of 1.2 V, 1528 cm²/C at 1.6 V and down to 1186 cm²/C at 1.9 V. The results highlight the fact that the current practice of quoting CE as a single-valued number may not reveal enough detail about the performance of ECDs and polymers.     

Electrochemical behaviors of nicotine and its interaction with DNA

The studies of the interaction between nicotine and DNA on the solid electrode were proposed for the first time. The electrochemical behaviors of nicotine and its interaction with DNA were explored by differential pulse voltammetry (DPV) at the DNA modified glassy carbon electrode (DNA/GCE). In 0.05 M Na₂C₂O₄ (pH 4.24), nicotine at DNA/GCE showed an irreversible reductive behavior in the range of ?1.6 to ?1.1 V. The presence of DNA led to the decrease in the peak current of nicotine and the negative shift in the potential, indicating that nicotine could interact with DNA by electrostatic mode. The binding ratio between nicotine and DNA was calculated to be 2:1 and the binding constant was 8.31(±0.36) × 10². The interaction between nicotine and DNA could be further verified by UV–vis spectroscopy.     

Highly mesoporous and high surface area carbon: A high capacitance electrode material for EDLCs with various electrolytes

Activated carbon fibers (ACFs) with high surface area and highly mesoporous structure for electrochemical double layer capacitors (EDLCs) have been prepared from polyacrylonitrile fibers by NaOH activation. Their unique microstructural features enable the ACFs to present outstanding high specific capacitance in aqueous, non-aqueous and novel ionic liquid electrolytes, i.e. 371 F g⁻¹ in 6 mol L⁻¹ KOH, 213 F g⁻¹ in 1 mol L⁻¹ LiClO₄/PC and 188 F g⁻¹ in ionic liquid composed of lithium bis(trifluoromethane sulfonyl)imide (LiN(SO₂CF₃)₂, LiTFSI) and 2-oxazolidinone (C₃H₅NO₂, OZO), suggesting that the ACF is a promising electrode material for high performance EDLCs.     

Ordered mesoporous silicon carbide-derived carbon for high-power supercapacitors

Micro/mesoporous carbon was prepared by chlorination of ordered mesoporous silicon carbide derived from magnesio-thermal reduction of templated carbon-silica precursors. These materials were then used as active materials for electrochemical capacitors and characterized in 1.5 M NEt₄BF₄/AN. The electrodes showed outstanding rate capability (90% of capacity retention at 1 V/s and time constant of 1 s) with high specific areal capacitance (0.5 F/cm² of electrode), that makes such hierarchical porous carbons promising for high power and energy density supercapacitors.     

A high-voltage asymmetric electrical double-layer capacitors using propylene carbonate

The upper limit of the double-layer potential window for the propylene carbonate/carbon black interface is effectively extended from 0.1 to 1 V (vs. Ag/AgNO₃), compared with activated carbon. Commercial carbon black with low defects and activated carbon are respectively employed as positive and negative electrode materials to construct an advanced asymmetric supercapacitor with cell voltage reaching 3 V in propylene carbonate. This asymmetric supercapacitor of the double-layer type with a cell voltage of 3 V is very stable in 10,000-cycle charge-discharge tests.     

Cloud-point measurement for (sulphate salts + polyethylene glycol 15000 + water) systems by the particle counting method

The phase separation of (water + salt + polyethylene glycol 15000) systems was studied by cloud-point measurements using the particle counting method. The effect of three kinds of sulphate salt (Na₂SO₄, K₂SO₄, (NH₄)₂SO₄) concentration, polyethylene glycol 15000 concentration, mass ratio of polymer to salt on the cloud-point temperature of these systems have been investigated. The results obtained indicate that the cloud-point temperatures decrease linearly with increase in polyethylene glycol concentrations for different salts. Also, the cloud points decrease with an increase in mass ratio of salt to polymer.