Impact of Thermally Reducing Temperature on Graphene Oxide Thin Films and Microsupercapacitor Performance.

In this work, a thermally reduced graphene oxide (TRGO) thin film on microscopic glass was prepared using spray coating and atmospheric pressure chemical vapour deposition. The structure of TRGO was analysed using X-ray diffraction (XRD) spectroscopy, scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible spectroscopy (UV-Vis) suggesting a decrease in oxygen functional groups (OFGs), leading to the restacking, change in colour, and transparency of the graphene sheets. Raman spectrum deconvolution detailed the film's parameters, such as the crystallite size, degree of defect, degree of amorphousness, and type of defect. The electrochemical performance of the microsupercapacitor (µ-SC) showed a rectangular cyclic voltammetry shape, which was maintained at a high scan rate, revealing phenomenal electric double-layer capacitor (EDLC) behaviour. The power law and Trasatti's analysis indicated that low-temperature TRGO µ-SC is dominated by diffusion-controlled behaviour, while higher temperature TRGO µ-SC is dominated by surface-controlled behaviour.

Novel Thermally Reduced Graphene Oxide Microsupercapacitor Fabricated via Mask-Free AxiDraw Direct Writing.

We demonstrate a simple method to fabricate all solid state, thermally reduced graphene oxide (TRGO) microsupercapacitors (µ-SCs) prepared using the atmospheric pressure chemical vapor deposition (APCVD) and a mask-free axiDraw sketching apparatus. The Fourier transform infrared spectroscopy (FTIR) shows the extermination of oxygen functional groups as the reducing temperature (RT) increases, while the Raman shows the presence of the defect and graphitic peaks. The electrochemical performance of the µ-SCs showed cyclic voltammetry (CV) potential window of 0-0.8 V at various scan rates of 5-1000 mVs-1 with a rectangular shape, depicting characteristics of electric double layer capacitor (EDLC) behavior. The µ-SC with 14 cm-2 (number of digits per unit area) showed a 46% increment in capacitance from that of 6 cm-2, which is also higher than the µ-SCs with 22 and 26 cm-2. The TRGO-500 exhibits volumetric energy and power density of 14.61 mW h cm-3 and 142.67 mW cm-3, respectively. The electrochemical impedance spectroscopy (EIS) showed the decrease in the equivalent series resistance (ESR) as a function of RT due to reduction of the resistive functional groups present in the sample. Bode plot showed a phase angel of -85° for the TRGO-500 µ-SC device. The electrochemical performance of the µ-SC devices can be tuned by varying the RT, number of digits per unity area, and connection configuration (parallel or series).

Enhanced Electrochemical Behavior of Peanut-Shell Activated Carbon/Molybdenum Oxide/Molybdenum Carbide Ternary Composites.

Biomass-waste activated carbon/molybdenum oxide/molybdenum carbide ternary composites are prepared using a facile in-situ pyrolysis process in argon ambient with varying mass ratios of ammonium molybdate tetrahydrate to porous peanut shell activated carbon (PAC). The formation of MoO2 and Mo2C nanostructures embedded in the porous carbon framework is confirmed by extensive structural characterization and elemental mapping analysis. The best composite when used as electrodes in a symmetric supercapacitor (PAC/MoO2/Mo2C-1//PAC/MoO2/Mo2C-1) exhibited a good cell capacitance of 115 F g-1 with an associated high specific energy of 51.8 W h kg-1, as well as a specific power of 0.9 kW kg-1 at a cell voltage of 1.8 V at 1 A g-1. Increasing the specific current to 20 A g-1 still showcased a device capable of delivering up to 30 W h kg-1 specific energy and 18 kW kg-1 of specific power. Additionally, with a great cycling stability, a 99.8% coulombic efficiency and capacitance retention of ~83% were recorded for over 25,000 galvanostatic charge-discharge cycles at 10 A g-1. The voltage holding test after a 160 h floating time resulted in increase of the specific capacitance from 74.7 to 90 F g-1 at 10 A g-1 for this storage device. The remarkable electrochemical performance is based on the synergistic effect of metal oxide/metal carbide (MoO2/Mo2C) with the interconnected porous carbon. The PAC/MoO2/Mo2C ternary composites highlight promising Mo-based electrode materials suitable for high-performance energy storage. Explicitly, this work also demonstrates a simple and sustainable approach to enhance the electrochemical performance of porous carbon materials.

Tuning the Nanoporous Structure of Carbons Derived from the Composite of Cross-Linked Polymers for Charge Storage Applications.

Controlling the porosity of carbon-based electrodes is key toward performance improvement of charge storage devices, e.g., supercapacitors, which deliver high power via fast charge/discharge of ions at the electrical double layer (EDL). Here, eco-friendly preparation of carbons with adaptable nanopores from polymers obtained via microwave-assisted cross-linking of poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) is reported. The polymeric hydrogels possess porous and foam-like structures, giving excellent control of porosity at the precursor level, which are then subjected to activation at high temperatures of 700-900 °C to prepare carbons with a surface area of 1846 m2 g-1 and uniform distribution of micro-, meso-, and macropores. Then, graphene as an additive to hydrogel precursor improves the surface characteristics and elaborates porous texture, giving composite materials with a surface area of 3107 m2 g-1. These carbons show an interconnected porous structure and bimodal pore size distribution suitable for facile ionic transport. When implemented in symmetric supercapacitor configuration with aqueous 5 mol L-1 NaNO3 electrolyte, a capacitance of 163 F g-1 (per average mass of one electrode) and stable evolution of capacitance, coulombic, and energy efficiency during 10 000 galvanostatic charge/discharge up to 1.6 V at 1.0 A g-1 have been achieved.

Ex-situ nitrogen-doped porous carbons as electrode materials for high performance supercapacitor.

Nitrogen (N) doping of porous carbon materials is an effective strategy for enhancing the electrochemical performance of electrode materials. Herein, we report on ex-situ (post) nitrogen-doped porous carbons prepared using a biomass waste, peanut shell (PS) as a carbon source and melamine as the nitrogen source. The synthesis method involved a two-step mechanism, initial chemical activation of the PS using KOH and post N-doping of the activated carbon. The effect of the activating agent/precursor ratio and the ex-situ N-doping on the structural, textural, electrochemical properties of the porous carbons was studied. The ex-situ N-doped porous carbon with an optimum amount of KOH to PS exhibited the best capacitance performance with a specific surface area (SSA) of 1442 m2 g-1 and an enriched nitrogen content (3.2 at %). The fabricated symmetric device exhibited a 251.2 F g-1 specific capacitance per electrode at a gravimetric current of 1 A g-1 in aqueous electrolyte (2.5 M KNO3) at a wide cell voltage of 2.0 V. A specific energy of 35 Wh kg-1 with a corresponding specific power of 1 kW kg-1 at 1 A g-1 was delivered with the device still retaining up to 22 Wh kg-1 and a 20 kW kg-1 specific power even at 20 A g-1. Moreover, long term device stability was exhibited with an 83.2% capacity retention over 20 000 charge/discharge cycles and also a good rate capability after 180 h of floating at 5 A g-1. This great performance of the symmetric supercapacitor can be correlated to the surface porosity and post nitrogen-doping effect which increased the electrochemically-active sites resulting in a remarkable charge storage capability.

Bullet-like microstructured nickel ammonium phosphate/graphene foam composite as positive electrode for asymmetric supercapacitors.

Unique microstructured nickel ammonium phosphate Ni(NH4)2(PO3)4·4H2O and Ni(NH4)2(PO3)4·4H2O/GF composite were successfully synthesized through the hydrothermal method with different graphene foam (GF) mass loading of 30, 60 and 90 mg as a positive electrode for asymmetric supercapacitors. The crystal structure, vibrational mode, texture and morphology of the samples were studied with X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis and scanning electron microscopy (SEM). The prepared materials were tested in both 3-and 2-electrode measurements using 6 M KOH electrolyte. The composite material Ni(NH4)2(PO3)4·4H2O/60 mg exhibited a remarkable gravimetric capacity of 52 mA h g-1, higher than the 34 mA h g-1 obtained for the Ni(NH4)2(PO3)4·4H2O pristine sample, both at 0.5 A g-1. For the fabrication of the asymmetric device, activated carbon from pepper seed (ppAC) was used as a negative electrode while Ni(NH4)2(PO3)4·4H2O/60 mg GF was adopted as the positive electrode. The Ni(NH4)2(PO3)4·4H2O/60 mg GF//ppAC asymmetric device delivered a specific energy of 52 Wh kg-1 with an equivalent specific power of 861 W kg-1 at 1.0 A g-1 within a potential range of 0.0-1.5 V. Moreover, the asymmetric device displayed a capacity retention of about 76% for over 10 000 cycles at a high specific current of 10.0 A g-1.

Onion-derived activated carbons with enhanced surface area for improved hydrogen storage and electrochemical energy application.

High surface area activated carbons (ACs) were prepared from a hydrochar derived from waste onion peels. The resulting ACs had a unique graphene-like nanosheet morphology. The presence of N (0.7%) and O content (8.1%) in the OPAC-800 °C was indicative of in situ incorporation of nitrogen groups from the onion peels. The specific surface area and pore volume of the best OPAC sample was found to be 3150 m2 g-1 and 1.64 cm3 g-1, respectively. The hydrogen uptake of all the OPAC samples was established to be above 3 wt% (at 77 K and 1 bar) with the highest being 3.67 wt% (800 °C). Additionally, the OPAC-800 °C achieved a specific capacitance of 169 F g-1 at a specific current of 0.5 A g-1 and retained a capacitance of 149 F g-1 at 5 A g-1 in a three electrode system using 3 M KNO3. A symmetric supercapacitor based on the OPAC-800 °C//OPAC-800 °C electrode provided a capacitance of 158 F g-1 at 0.5 A g-1. The maximum specific energy and power was found to be 14 W h kg-1 and 400 W kg-1, respectively. Moreover, the device exhibited a high coulombic efficiency of 99.85% at 5 A g-1 after 10 000 cycles. The results suggested that the high surface area graphene-like carbon nanostructures are excellent materials for enhanced hydrogen storage and supercapacitor applications.

Nitridation Temperature Effect on Carbon Vanadium Oxynitrides for a Symmetric Supercapacitor.

In this work, porous carbon-vanadium oxynitride (C-V2NO) nanostructures were obtained at different nitridation temperature of 700, 800 and 900 °C using a thermal decomposition process. The X-ray diffraction (XRD) pattern of all the nanomaterials showed a C-V2NO single-phase cubic structure. The C-V2NO obtained at 700 °C had a low surface area (91.6 m2 g-1), a moderate degree of graphitization, and a broader pore size distribution. The C-V2NO obtained at 800 °C displayed an interconnected network with higher surface area (121.6 m2 g-1) and a narrower pore size distribution. In contrast, at 900 °C, the C-V2NO displayed a disintegrated network and a decrease in the surface area (113 m2 g-1). All the synthesized C-V2NO yielded mesoporous oxynitride nanostructures which were evaluated in three-electrode configuration using 6 M KOH aqueous electrolyte as a function of temperature. The C-V2NO@800 °C electrode gave the highest electrochemical performance as compared to its counterparts due to its superior properties. These results indicate that the nitridation temperature not only influences the morphology, structure and surface area of the C-V2NO but also their electrochemical performance. Additionally, a symmetric device fabricated from the C-V2NO@800 °C displayed specific energy and power of 38 W h kg-1 and 764 W kg-1, respectively, at 1 A g-1 in a wide operating voltage of 1.8 V. In terms of stability, it achieved 84.7% as capacity retention up to 10,000 cycles which was confirmed through the floating/aging measurement for up to 100 h at 10 A g-1. This symmetric capacitor is promising for practical applications due to the rapid and easy preparation of the carbon-vanadium oxynitride materials.

Deciphering the Structural, Textural, and Electrochemical Properties of Activated BN-Doped Spherical Carbons.

In this study, the effect of K2CO3 activation on the structural, textural, and electrochemical properties of carbon spheres (CSs) and boron and nitrogen co-doped carbon spheres (BN-CSs) was evaluated. Activation of the CSs and BN-CSs by K2CO3 resulted in increased specific surface areas and ID/IG ratios. From the X-ray photoelectron spectroscopy (XPS) results, the BN-CSs comprised of 64% pyridinic-N, 24% pyrrolic-N and 7% graphitic-N whereas the activated BN-CSs had 19% pyridinic-N, 40% pyrrolic-N and 22% graphitic-N displaying the effect of activation on the type of N configurations in BN-CSs. A possible BN-co-doping and activation mechanism for the BN-CSs is proposed. Electrochemical analysis of the electrode materials revealed that BN doping, carbon morphology, structure, and porosity played a crucial role in enhancing the capacitive behavior of the CSs. As a proof of concept, a symmetric device comprising the activated BN-CSs displayed a specific power of 800 W kg-1 at a specific current of 1 A g-1 within an operating cell potential of 1.6 V in a 3 M KNO3 electrolyte. The study illustrated for the first time the role of K2CO3 activation in influencing the physical and surface properties of template-free activated BN-CSs as potential electrode materials for energy storage systems.

Malathion-filled trilayer polyolefin film for malaria vector control.

The emergence of pyrethroid resistance in mosquitoes is complicating malaria elimination efforts in Africa and alternative insecticides have to be considered for indoor residual spray. Unfortunately, the high volatility of WHO-approved organophosphate alternatives, e.g. malathion, translates into an early loss of residual efficacy. This laboratory study explored the concept of trilayer films as potential wall or ceiling linings. In the proposed design, the fugitive liquid insecticide is trapped in an inner core layer. The two sheath layers act as low-permeability membranes controlling the release of the insecticide. The concept was explored using poly(ethylene-co-vinyl acetate) (EVA) and low density polyethylene (LDPE) as core and sheath polymers respectively. The polarity of the EVA polymer matrix allowed incorporation of substantial quantities (up to 30 wt%) of malathion. The low polarity of the LDPE provided the necessary barrier properties and, in addition, allowed film blowing to be conducted at relatively low processing temperatures. Trilayer films containing about 6 wt% malathion were prepared on a film blowing line. Scanning electron microscopy confirmed the trilayer film structure. Confocal Raman microscopy studies revealed a malathion concentration gradient across the thickness of the polyethylene layers. Mass loss measurements and FTIR spectroscopy studies showed that the malathion release followed first-order kinetics. Bioassays, on samples aged at 22 °C, indicated that the residual efficacy against mosquitoes can be maintained for up to about six months. This suggests that trilayer films impregnated with organophosphates, may have potential as alternative mosquito control interventions in pyrethroid resistant settings.

Electrochemical analysis of Na-Ni bimetallic phosphate electrodes for supercapacitor applications.

Bimetallic sodium-nickel phosphate/graphene foam composite (NaNi4(PO4)3/GF) was successfully synthesized using a direct and simple precipitation method. The hierarchically structured composite material was observed to have demonstrated a synergistic effect between the conductive metallic cations and the graphene foam that made up the composite. The graphene served as a base-material for the growth of NaNi4(PO4)3 particles, resulting in highly conductive composite material as compared to the pristine material. The NaNi4(PO4)3/GF composite electrode measured in a 3-electrode system achieved a maximum specific capacity of 63.3 mA h g-1 at a specific current of 1 A g-1 in a wide potential range of 0.0-1.0 V using 2 M NaNO3 aqueous electrolyte. A designed and fabricated hybrid NaNi4(PO4)3/GF//AC device based on NaNi4(PO4)3/GF as positive electrode and activated carbon (AC) selected as a negative electrode could operate well in an extended cell potential of 2.0 V. As an assessment, the hybrid NaNi4(PO4)3/GF//AC device showed the highest energy and power densities of 19.5 W h kg-1 and 570 W kg-1, respectively at a specific current of 0.5 A g-1. The fabricated device could retain an 89% of its initial capacity with a coulombic efficiency of about 94% over 5000 cycling test, which suggests the material's potential for energy storage devices applications.

Three dimensional vanadium pentoxide/graphene foam composite as positive electrode for high performance asymmetric electrochemical supercapacitor.

The electrochemical performance of hydrothermal synthesized three dimensional (3D) orthorhombic vanadium pentoxide (V2O5) nanosheets and vanadium pentoxide/graphene foam (V2O5/GF) composites at different mass loading of GF were successfully studied. The optimized V2O5/GF-150 mg composite provided a high specific capacity of 73 mA h g-1, which was much higher than that the pristine V2O5 (60 mA h g-1) nanosheets at a specific current of 1 A g-1. A hybrid capacitor was also fabricated by adopting a carbon-based negative electrode obtained from the pyrolysis of an iron-PANI polymer (C-Fe/PANI) mixture and the 3D V2O5/GF-150 mg composite as the positive electrode in 6 M KOH electrolyte. The hybrid device of V2O5/GF-150 mg//C-Fe/PANI demonstrated a high energy density of 39 W h kg-1 with a corresponding high power density of 947 W kg-1 at a specific current of 1 A g-1 in an operating voltage window of 0.0-1.6 V. The hybrid device also exhibited an excellent cycling stability with 74% capacity retention recorded for up to 10,000 constant charging-discharge cycles and an excellent ageing test at a specific current of 10 A g-1.

Preparation of carbon nanofibers/tubes using waste tyres pyrolysis oil and coal fly ash derived catalyst.

In this study, two waste materials namely; coal fly ash (CFA) and waste tyres pyrolysis oil, were successfuly utilized in the synthesis of carbon nanofibers/tubes (CNF/Ts). In addition, Fe-rich CFA magnetic fraction (Mag-CFA) and ethylene gas were also used for comparison purposes. The carbons obtained from CFA were found to be anchored on the surface of the cenosphere and consisted of both CNTs and CNFs, whereas those obtained from Mag-CFA consisted of only multi-walled carbon nanotubes (MWCNTs). The study further showed that the type of carbon precursor and support material played an important role in determining the nanocarbon growth mechanism. The findings from this research have demonstrated that it is possible to utilize waste tyres pyrolysis oil vapor as a substitute for some expensive commercial carbonaceous gases.

Utilization of waste tyres pyrolysis oil vapour in the synthesis of Zeolite Templated Carbons (ZTCs) for hydrogen storage application.

In this study, we investigated the potential for use of waste tyre pyrolysis oil vapour as a carbon precursor in the synthesis of zeolite templated carbons (ZTC). With Zeolite 13X as the template, the ZTCs were synthesised using two methods namely: 1-step process which involved the carbonization of gaseous carbon precursor in the zeolite template (in this case, ethylene and pyrolysis oil vapour) and the 2-step synthesis method involved the impregnation of zeolite pores with furfural alcohol prior to carbonization of the gaseous carbon precursor. The replication of the zeolite 13X structural ordering was successful using both methods. The 2-step synthesized ZTCs were found to possess the highest specific surface area (3341 m2 g-1) and also had the highest H2 storage capacity (2.5 wt.%). The study therefore confirmed an additional novel strategy for value-addition of waste tyre pyrolysis by-products.

Hydrothermal synthesis of manganese phosphate/graphene foam composite for electrochemical supercapacitor applications.

Manganese phosphate (Mn3(PO4)2 hexagonal micro-rods and (Mn3(PO4)2 with different graphene foam (GF) mass loading up to 150mg were prepared by facile hydrothermal method. The characterization of the as-prepared samples proved the successful synthesis of Mn3(PO4)2 hexagonal micro-rods and Mn3(PO4)2/GF composites. It was observed that the specific capacitance of Mn3(PO4)2/GF composites with different GF mass loading increases with mass loading up to 100mg, and then decreases with increasing mass loading up to 150mg. The specific capacitance of Mn3(PO4)2/100mg GF electrode was calculated to be 270Fg-1 as compared to 41Fg-1 of the pristine sample at a current density of 0.5Ag-1 in a three-electrode cell configuration using 6M KOH. Furthermore, the electrochemical performance of the Mn3(PO4)2/100mg GF electrode was evaluated in a two-electrode asymmetric cell device where Mn3(PO4)2/100mg GF electrode was used as a positive electrode and activated carbon (AC) from coconut shell as a negative electrode. AC//Mn3(PO4)2/100mg GF asymmetric cell device was tested within the potential window of 0.0-1.4V, and showed excellent cycling stability with 96% capacitance retention over 10,000 galvanostatic charge-discharge cycles at a current density of 2Ag-1.

High performance asymmetric supercapacitor based on molybdenum disulphide/graphene foam and activated carbon from expanded graphite.

Molybdenum disulphide which has a graphene-like single layer structure has excellent mechanical and electrical properties and unique morphology, which might be used with graphene foam as composite in supercapacitor applications. In this work, Molybdenum disulphide (MoS2)/graphene foam (GF) composites with different graphene foam loading were synthesized by the hydrothermal process to improve on specific capacitance of the composites. Asymmetric supercapacitor device was fabricated using the best performing MoS2/GF composite and activated carbon derived from expanded graphite (AEG) as positive and negative electrodes, respectively, in 6M KOH electrolyte. The asymmetric MoS2/GF//AEG device exhibited a maximum specific capacitance of 59Fg-1 at a current density of 1Ag-1 with maximum energy and power densities of 16Whkg-1 and 758Wkg-1, respectively. The supercapacitor also exhibited a good cyclic stability with 95% capacitance retention over 2000 constant charge-discharge cycles. The results obtained demonstrate the potential of MoS2/GF//AEG as a promising material for electrochemical energy storage application.

High electrochemical performance of hybrid cobalt oxyhydroxide/nickel foam graphene.

In this study, we report the in-situ hydrothermal synthesis of mesoporous nanosheets of cobalt oxyhydroxide (CoOOH) on nickel foam graphene (Ni-FG) substrate, obtained via atmospheric pressure chemical vapour deposition (AP-CVD). The produced composite were closely interlinked with Ni-FG, which enhances the synergistic effect between graphene and the metal hydroxide, CoOOH. It is motivating that the synthesized CoOOH on the Ni-FG substrate showed a homogenous coating of well-ordered intersected nanosheets with porous structure. The electrochemical properties of the material as electrode showed a maximum specific capacity of 199mAhg-1 with a capacity retention of 98% after 1000 cycling in a three electrode measurements.

Microwave-assisted synthesis of high-voltage nanostructured LiMn1.5Ni0.5O4 spinel: tuning the Mn3+ content and electrochemical performance.

The LiMn1.5Ni0.5O4 spinel is an important lithium ion battery cathode material that has continued to receive major research attention because of its high operating voltage (∼4.8 V). This study interrogates the impact of microwave irradiation on the Mn(3+) concentration and electrochemistry of the LiMn1.5Ni0.5O4 spinel. It is shown that microwave is capable of tuning the Mn(3+) content of the spinel for enhanced electrochemical performance (high capacity, high capacity retention, excellent rate capability, and fast Li(+) insertion/extraction kinetics). This finding promises to revolutionize the application of microwave irradiation for improved performance of the LiMn1.5Ni0.5O4 spinel, especially in high rate applications.

Large anomalous Hall effect in a silicon-based magnetic semiconductor.

Magnetic semiconductors are attracting great interest because of their potential use for spintronics, a new technology that merges electronics with the manipulation of conduction electron spins. (GaMn)As and (GaMn)N have recently emerged as the most popular materials for this new technology, and although their Curie temperatures are rising towards room temperature, these materials can only be fabricated in thin-film form, are heavily defective, and are not obviously compatible with Si. We show here that it is productive to consider transition metal monosilicides as potential alternatives. In particular, we report the discovery that the bulk metallic magnets derived from doping the narrow-gap insulator FeSi with Co share the very high anomalous Hall conductance of (GaMn)As, while displaying Curie temperatures as high as 53 K. Our work opens up a new arena for spintronics, involving a bulk material based only on transition metals and Si, which displays large magnetic-field effects on its electrical properties.