Prussian Blue Anchored on Reduced Graphene Oxide Substrate Achieving High Voltage in Symmetric Supercapacitor.

In this work, iron hexacyanoferrate (FeHCF-Prussian blue) particles have been grown onto a reduced graphene oxide substrate through a pulsed electrodeposition process. Thus, the prepared FeHCF electrode exhibits a specific volumetric capacitance of 88 F cm-3 (specific areal capacitance of 26.6 mF cm-2) and high cycling stability with a capacitance retention of 93.7% over 10,000 galvanostatic charge-discharge cycles in a 1 M KCl electrolyte. Furthermore, two identical FeHCF electrodes were paired up in order to construct a symmetrical supercapacitor, which delivers a wide potential window of 2 V in a 1 M KCl electrolyte and demonstrates a large energy density of 27.5 mWh cm-3 at a high power density of 330 W cm-3.

Exploring morphological variation in bismuth ferrite nanostructures by pulsed laser deposition: synthesis, structural and electrochemical properties.

Structural and electrochemical properties of bismuth ferrite nanostructures produced by pulsed laser deposition with various morphologies are reported. The nanostructures are also explored as electrode materials for high-performance supercapacitors. Scanning electron microscopy images revealed that various bismuth ferrite morphologies were produced by varying the background pressure (10-6, 0.01, 0.10, 0.25, 0.50, 1.0, 2.0 and 4.0 Torr) in the deposition chamber and submitting them to a thermal treatment after deposition at 500◦C. The as-deposited bismuth ferrite nanostructures range from very compact thin-film (10-6, 0.01, 0.10 Torr), to clustered nanoparticles (0.25, 0.50, 1.0 Torr), to very dispersed arrangement of nanoparticles (2.0 and 4.0 Torr). The electrochemical characteristic of the electrodes was investigated through cyclic voltammetry process. The increase in the specific surface area of the nanostructures as background pressure in the chamber increases does not lead to an increase in interfacial capacitance. This is likely due to the wakening of electrical contact between nanoparticles with increasing porosity of the nanostructures. The thermal treatment increased the contact between nanoparticles, which caused an increase in the interfacial capacitance of the nanostructure deposited under high background pressure in the chamber.

Gel Biopolymer Electrolytes Based on Saline Water and Seaweed to Support the Large-Scale Production of Sustainable Supercapacitors.

Climate change and the demand for clean energy have challenged scientists worldwide to produce/store more energy to reduce carbon emissions. This work proposes a conductive gel biopolymer electrolyte to support the sustainable development of high-power aqueous supercapacitors. The gel uses saline water and seaweed as sustainable resources. Herein, a biopolymer agar-agar, extracted from red algae, is modified to increase gel viscosity up to 17-fold. This occurs due to alkaline treatment and an increase in the concentration of the agar-agar biopolymer, resulting in a strengthened gel with cohesive superfibres. The thermal degradation and agar modification mechanisms are explored. The electrolyte is applied to manufacture sustainable and flexible supercapacitors with satisfactory energy density (0.764 Wh kg-1 ) and power density (230 W kg-1 ). As an electrolyte, the aqueous gel promotes a long device cycle life (3500 cycles) for 1 A g-1 , showing good transport properties and low cost of acquisition and enabling the supercapacitor to be manufactured outside a glove box. These features decrease the cost of production and favor scale-up. To this end, this work provides eco-friendly electrolytes for the next generation of flexible energy storage devices.

Functional Materials Made by Combining Hydrogels (Cross-Linked Polyacrylamides) and Conducting Polymers (Polyanilines)-A Critical Review.

Hydrogels made of cross-linked polyacrlyamides (cPAM) and conducting materials made of polyanilines (PANIs) are both the most widely used materials in each category. This is due to their accessible monomers, easy synthesis and excellent properties. Therefore, the combination of these materials produces composites which show enhanced properties and also synergy between the cPAM properties (e.g., elasticity) and those of PANIs (e.g., conductivity). The most common way to produce the composites is to form the gel by radical polymerization (usually by redox initiators) then incorporate the PANIs into the network by oxidative polymerization of anilines. It is often claimed that the product is a semi-interpenetrated network (s-IPN) made of linear PANIs penetrating the cPAM network. However, there is evidence that the nanopores of the hydrogel become filled with PANIs nanoparticles, producing a composite. On the other hand, swelling the cPAM in true solutions of PANIs macromolecules renders s-IPN with different properties. Technological applications of the composites have been developed, such as photothermal (PTA)/electromechanical actuators, supercapacitors, movement/pressure sensors, etc. PTA devices rely on the absorption of electromagnetic radiation (light, microwaves, radiofrequency) by PANIs, which heats up the composite, triggering the phase transition of a thermosensitive cPAM. Therefore, the synergy of properties of both polymers is beneficial.

Hierarchical Biobased Macroporous/Mesoporous Carbon: Fabrication, Characterization and Electrochemical/Ion Exchange Properties.

With the goal of improving the mechanical properties of porous hierarchical carbon, cellulosic fiber fabric was incorporated into the resorcinol/formaldehyde (RF) precursor resins. The composites were carbonized in an inert atmosphere, and the carbonization process was monitored by TGA/MS. The mechanical properties, evaluated by nanoindentation, show an increase in the elastic modulus due to the reinforcing effect of the carbonized fiber fabric. It was found that the adsorption of the RF resin precursor onto the fabric stabilizes its porosity (micro and mesopores) during drying while incorporating macropores. The textural properties are evaluated by N2 adsorption isotherm, which shows a surface area (BET) of 558 m2g-1. The electrochemical properties of the porous carbon are evaluated by cyclic voltammetry (CV), chronocoulometry (CC), and electrochemical impedance spectroscopy (EIS). Specific capacitances (in 1 M H2SO4) of up to 182 Fg-1 (CV) and 160 Fg-1 (EIS) are measured. The potential-driven ion exchange was evaluated using Probe Bean Deflection techniques. It is observed that ions (protons) are expulsed upon oxidation in acid media by the oxidation of hydroquinone moieties present on the carbon surface. In neutral media, when the potential is varied from values negative to positive of the potential of zero charge, cation release, followed by anion insertion, is found.

MXene/Ferrite Magnetic Nanocomposites for Electrochemical Supercapacitor Applications.

MXene has been identified as a new emerging material for various applications including energy storage, electronics, and bio-related due to its wider physicochemical characteristics. Further the formation of hybrid composites of MXene with other materials makes them interesting to utilize in multifunctional applications. The selection of magnetic nanomaterials for the formation of nanocomposite with MXene would be interesting for the utilization of magnetic characteristics along with MXene. However, the selection of the magnetic nanomaterials is important, as the magnetic characteristics of the ferrites vary with the stoichiometric composition of metal ions, particle shape and size. The selection of the electrolyte is also important for electrochemical energy storage applications, as the electrolyte could influence the electrochemical performance. Further, the external magnetic field also could influence the electrochemical performance. This review briefly discusses the synthesis method of MXene, and ferrite magnetic nanoparticles and their composite formation. We also discussed the recent progress made on the MXene/ferrite nanocomposite for potential applications in electrochemical supercapacitor applications. The possibility of magnetic field-assisted supercapacitor applications with electrolyte and electrode materials are discussed.

Biomimetic Synthesis of PANI/Graphitic Oxidized Carbon Nitride for Supercapacitor Applications.

Polyaniline (PANI) composites have gained momentum as supercapacitive materials due to their high energy density and power density. However, some drawbacks in their performance remain, such as the low stability after hundreds of charge-discharge cycles and limitations in the synthesis scalability. Herein, we report for the first time PANI-Graphitic oxidized carbon nitride composites as potential supercapacitor material. The biomimetic polymerization of aniline assisted by hematin, supported by phosphorous and oxygen-modified carbon nitrides (g-POCN and g-OCN, respectively), achieved up to 89% yield. The obtained PAI/g-POCN and PANI/g-OCN show enhanced electrochemical properties, such as conductivity of up to 0.0375 S/cm, specific capacitances (Cs) of up to 294 F/g (at high current densities, 5 A/g) and a stable operation after 500 charge-discharge cycles (at 3 A/g). In contrast, the biomimetic synthesis of Free PANI, assisted by stabilized hematin in cosolvents, exhibited lower performance properties (65%). Due to their structural differences, the electrochemical properties of Free PANI (conductivity of 0.0045 S/cm and Cs of up to 82 F/g at 5 A/g) were lower than those of nanostructured PANI/g-POCN and g-OCN supports, which provide stability and improve the properties of biomimetically synthesized PANI. This work reveals the biomimetic synthesis of PANI, assisted by hematin supported by modified carbon nitrides, as a promising strategy to produce nanostructured supercapacitors with high performance.

Synthesis of UV-11 MOF and Its Characterization by Cyclic Voltammetry.

In this work a Metal-Organic Framework (MOF) was prepared using a solvothermal method, taking as precursors 1. 2-di-(4-pyridyl)-ethylene, 1.2.4.5-benzenetetracarboxylic acid and Co(No3)2-6H2O. This MOF was called UV-11 and was evaluated using microscopic, spectroscopic and electrochemical techniques. According to the obtained results, the melting point of the compound is located in a higher interval than its precursors. Stereoscopic microscopy analysis shows the presence of pink crystals in the form of needles. MEB technique displays a laminar morphology as well as crystals with approximate sizes (36 mm wide and 150 mm long). EDS analysis corroborated the presence of precursor elements such as cobalt, carbon and oxygen. Furthermore, the XRD technique shows the cobalt-related phases in the sample, which is cobalt bis (pyridine-6-carboxylic-2-carboxylate). A modified carbon paste electrode was prepared using MOF UV-11 and by cyclic voltammetry electrochemical technique, semi-reversible redox processes are identified, as well as thermodynamic and kinetic parameters were obtained with the Laviron equation, and electrochemical performance properties from the cyclic voltammetry experimental data.

Graphene Oxide-Polypyrrole Coating for Functional Ceramics.

Ceramic substrates were metallized with a Ni-Mo-P electroless coating and further modified with a polypyrrole (PPy) coating by the electrodeposition method. The properties of the polypyrrole coating were studied with the addition of a graphene oxide (GO) nanomaterial prior to the electrodeposition and its reduction degree. Fourier Transform Infrared Spectroscopy, Field-Emission Scanning Electron Microscopy, Raman spectroscopy and cyclic voltammetry were employed to characterize the properties of the coatings. The results indicated the successful synthesis of conductive electrodes by the proposed approach. The electrodeposition of PPy and its charge storage properties are improved by chemically reduced GO. The surface capacitive contribution to the total stored charge was found to be dominant and increased 2-3 fold with the reduction of GO. The chemically reduced GO-modified PPy exhibits the highest capacitance of 660 F g-1 at 2 mV s-1, and shows a good cyclability of 94% after 500 charge/discharge cycles. The enclosed results indicate the use of an NiMoP electroless coating, and modification with a carbon nanomaterial and conducting polymer is a viable approach for achieving functional ceramics.

Room temperature and aqueous synthesis of bimetallic ZIF derived CoNi layered double hydroxides and their applications in asymmetric supercapacitors.

Single imidazolate framework-67 (ZIF-67) is commonly used as a template to prepare layered double hydroxides (LDHs) with specific morphology to improve the performance of materials. Herein, the Co2+ ion in ZIF-67 is partially substituted by Ni2+ to obtain the dodecahedron bimetallic imidazolate framework (CoNi-ZIF). Subsequently, using bimetallic CoNi-ZIF as the sacrificial template, CoNi-LDH hierarchical hollow cage structures with wrinkled nanosheet arrays are synthesized at room temperature and in aqueous solution by an inexpensive and environment friendly surfactant-free approach. The optimized etched CoNi-LDH4 has a maximum specific capacitance of 1877 F g-1 at a current density of 1 A g-1, and cycling stability of 99.89% after 5000 cycles, which is significantly better than that of ZIF-67 derived CoNi-LDH67 (1357 F g-1 at 1 A g-1, cycling stability of 73.35%). The asymmetric supercapacitor with CoNi-LDH4 as a cathode and activated carbon (AC) as anode has an energy density of 49.3 Wh kg-1 at 750 W kg-1 power output and stable cycling performance (capacity retention of 92.13% after 5000 cycles). This study shows the prospect of bimetallic CoNi-ZIF derived LDHs nanostructures prepared at room temperature and in aqueous solution to improve the performance and stability of supercapacitors.

Electric double layer formation and storing energy processes on graphene-based supercapacitors from electrical and thermodynamic perspectives.

Atomistic molecular dynamics simulations were used to investigate the processes of electrical double layer formation and electrolyte confinement in graphene-based supercapacitors. For both processes, free energy calculations were used to analyze the thermodynamics involved in the electrolyte confinement and its re-arrangement in a double layer on the electrode surface. The value of the free energy of the formation of the double electric layer was related to the energy required to charge the supercapacitor, i.e., the energy density stored, and compared with values obtained using Poisson's electrostatic formalism, which is the conventionally employed approach. Both analyzes were consistent with each other, presenting compatible values for the stored energy.

Self-Assembled and One-Step Synthesis of Interconnected 3D Network of Fe3O4/Reduced Graphene Oxide Nanosheets Hybrid for High-Performance Supercapacitor Electrode.

In the present work, we have synthesized three-dimensional (3D) reduced graphene oxide nanosheets (rGO NSs) containing iron oxide nanoparticles (Fe3O4 NPs) hybrids (3D Fe3O4/rGO) by one-pot microwave approach. Structural and morphological studies reveal that the as-synthesized Fe3O4/rGO hybrids were composed of faceted Fe3O4 NPs induced into the interconnected network of rGO NSs. The morphologies and structures of the 3D hybrids have been characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectrometer (XPS). The electrochemical studies were analyzed by cyclic voltammetry, galvanostatic charge/discharge measurements, and electrochemical impedance spectroscopy, which demonstrate superior electrochemical performance as supercapacitors electrode application. The specific capacitances of 3D hybrid materials was 455 F g-1 at the scan rate of 8 mV s-1, which is superior to that of bare Fe3O4 NPs. Additionally, the 3D hybrid shows good cycling stability with a retention ratio of 91.4 after starting from ∼190 cycles up to 9600 cycles. These attractive results suggest that this 3D Fe3O4/rGO hybrid shows better performance as an electrode material for high-performance supercapacitors.

Self-Assembled Hierarchical Formation of Conjugated 3D Cobalt Oxide Nanobead-CNT-Graphene Nanostructure Using Microwaves for High-Performance Supercapacitor Electrode.

Here we report the electrochemical performance of a interesting three-dimensional (3D) structures comprised of zero-dimensional (0D) cobalt oxide nanobeads, one-dimensional (1D) carbon nanotubes and two-dimensional (2D) graphene, stacked hierarchically. We have synthesized 3D self-assembled hierarchical nanostructure comprised of cobalt oxide nanobeads (Co-nb), carbon nanotubes (CNTs), and graphene nanosheets (GNSs) for high-performance supercapacitor electrode application. This 3D self-assembled hierarchical nanostructure Co3O4 nanobeads-CNTs-GNSs (3D:Co-nb@CG) is grown at a large scale (gram) through simple, facile, and ultrafast microwave irradiation (MWI). In 3D:Co-nb@CG nanostructure, Co3O4 nanobeads are attached to the CNT surfaces grown on GNSs. Our ultrafast, one-step approach not only renders simultaneous growth of cobalt oxide and CNTs on graphene nanosheets but also institutes the intrinsic dispersion of carbon nanotubes and cobalt oxide within a highly conductive scaffold. The 3D:Co-nb@CG electrode shows better electrochemical performance with a maximum specific capacitance of 600 F/g at the charge/discharge current density of 0.7A/g in KOH electrolyte, which is 1.56 times higher than that of Co3O4-decorated graphene (Co-np@G) nanostructure. This electrode also shows a long cyclic life, excellent rate capability, and high specific capacitance. It also shows high stability after few cycles (550 cycles) and exhibits high capacitance retention behavior. It was observed that the supercapacitor retained 94.5% of its initial capacitance even after 5000 cycles, indicating its excellent cyclic stability. The synergistic effect of the 3D:Co-nb@CG appears to contribute to the enhanced electrochemical performances.

Lithium recovery from brine using a λ-MnO2/activated carbon hybrid supercapacitor system.

Lithium is one of the most important elements in various fields including energy storage, medicine manufacturing and the glass industry, and demands for lithium are constantly increasing these days. The lime soda evaporation process using brine lake water is the major extraction method for lithium, but this process is not only inefficient and time-consuming but also causes a few environmental problems. Electrochemical recovery processes of lithium ions have been proposed recently, but the better idea for the silver negative electrodes used in these systems is required to reduce its cost or increase long term stability. Here, we report an electrochemical lithium recovery method based on a λ-MnO2/activated carbon hybrid supercapacitor system. In this system, lithium ions and counter anions are effectively captured at each electrode with low energy consumption in a salt solution containing various cationic species or simulated Salar de Atacama brine lake water in Chile. Furthermore, we designed this system as a flow process for practical applications. By experimental analyses, we confirmed that this system has high selectivity and long-term stability, with its performance being retained even after repetitive captures and releases of lithium ions.