Electrocatalytic Performance of MnMoO4-rGO Nano-Electrocatalyst for Methanol and Ethanol Oxidation.

Today, finding low-cost electro-catalysts for methanol and ethanol oxidation with high performance and stability is one of the new research topics. A nanocatalyst based on metal oxides in the form of MnMoO4 was synthesized by a hydrothermal method for methanol (MOR) and ethanol (EOR) oxidation reactions. Adding reduced graphene oxide (rGO) to the catalyst structure improved the electrocatalytic activity of MnMoO4 for the oxidation processes. The crystal structure and morphology of the MnMoO4 and MnMoO4-rGO nanocatalysts were investigated by physical analyses such as scanning electron microscopy and X-ray diffraction. Their abilities for MOR and EOR processes in an alkaline medium were evaluated by performing electrochemical tests such as cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. MnMoO4-rGO showed oxidation current densities of 60.59 and 25.39 mA/cm2 and peak potentials of 0.62 and 0.67 V in MOR and EOR processes (at a scan rate of 40 mV/s), respectively. Moreover, stabilities of 91.7% in MOR and 88.6% in EOR processes were obtained from the chronoamperometry analysis within 6 h. All these features make MnMoO4-rGO a promising electrochemical catalyst for the oxidation of alcohols.

Hydrogen-Assisted Thermal Treatment of Electrode Materials for Electrochemical Double-Layer Capacitors.

The capacitance of electrode materials used in electrochemical double-layer capacitors (EDLCs) is currently limited by several factors, including inaccessible isolated micropores in high-surface area carbons, the finite density of states resulting in a quantum capacitance in series to Helmholtz double-layer capacitance, and the presence of surface impurities, such as functional groups and adsorbed species. To unlock the full potential of EDLC active materials and corresponding electrodes, several post-production treatments are commonly proposed to improve their capacitance and, thus, the energy density of the corresponding devices. In this work, we report a systematic study of the effect of a prototypical treatment, namely H2-assisted thermal treatment, on the chemical, structural, and thermal properties of activated carbon and corresponding electrodes. By combining multiple characterization techniques, we clarify the actual origins of the improvement of the performance (e.g., > +35% energy density for the investigated power densities in the 0.5-45 kW kg-1 range) of the EDLCs based on treated electrodes compared to the case based on the pristine electrodes. Contrary to previous works supporting a questionable graphitization of the activated carbon at temperatures <1000 °C, we found that a "surface graphitization" of the activated carbon, detected by spectroscopic analysis, is mainly associated with the desorption of surface contaminants. The elimination of surface impurities, including adsorbed species, improves the surface capacitance of the activated carbon (CsurfAC) by +37.1 and +36.3% at specific currents of 1 and 10 A g-1, respectively. Despite the presence of slight densification of the activated carbon upon the thermal treatment, the latter still improves the cell gravimetric capacitance normalized on the mass of the activated carbon only (CgAC), e.g., + 28% at 1 A g-1. Besides, our holistic approach identifies the change in the active material and binder contents as a concomitant cause of the increase of cell gravimetric capacitance (Cg), accounting for the mass of all of the electrode materials measured for treated electrodes compared to pristine ones. Overall, this study provides new insights into the relationship between the modifications of the electrode materials induced by H2-assisted thermal treatments and the performance of the resulting EDLCs.

Coexistence of Redox-Active Metal and Ligand Sites in Copper-based 2D Conjugated Metal-Organic Frameworks for Battery-Supercapacitor hybrid systems.

Two-dimensional (2D) conjugated metal-organic frameworks (c-MOFs) are promising materials for supercapacitor (SC) electrodes due to their high electrochemically accessible surface area coupled with superior electrical conductivity compared to traditional MOFs. Here, porous and non-porous HHB-Cu (HHB=hexahydroxybenzene), derived through surfactant-assisted synthesis, are studied as representative 2D c-MOF models, showing different reversible redox reactions with Na+ and Li+ in aqueous and organic electrolytes, respectively. We deployed these redox activities to design negative electrodes for hybrid SCs (HSCs), combining the battery-like property of HHB-Cu as negative electrode and the high capacitance and robust cyclic stability of activated carbon (AC) as positive electrode. In organic electrolyte, porous HHB-Cu-based HSC achieves a maximum cell specific capacity (Cs) of 22.1 mAhg-1 at 0.1 Ag-1, specific energy (Es) of 15.55 Whkg-1 at specific power (Ps) of 70.49 Wkg-1, and 77% cyclic stability after 3000 gravimetric charge-discharge (GCD) cycles at 1 Ag-1 (calculated on the mass of both electrode materials). In the aqueous electrolyte, porous HHB-Cu-based HSC displays a Cs of 13.9 mAhg-1 at 0.1 Ag-1, Es of 6.13 Whkg-1 at 44.05 Wkg-1, and 72.3% Cs retention after 3000 GCD cycles. The non-porous sample shows lower Es performance but better rate capability compared to the porous one.

Sulfonated NbS2-based proton-exchange membranes for vanadium redox flow batteries.

In this work, novel proton-exchange membranes (PEMs) based on sulfonated poly(ether ether ketone) (SPEEK) and two-dimensional (2D) sulfonated niobium disulphide (S-NbS2) nanoflakes are synthesized by a solution-casting method and used in vanadium redox flow batteries (VRFBs). The NbS2 nanoflakes are produced by liquid-phase exfoliation of their bulk counterpart and chemically functionalized with terminal sulfonate groups to improve dimensional and chemical stabilities, proton conductivity (σ) and fuel barrier properties of the as-produced membranes. The addition of S-NbS2 nanoflakes to SPEEK decreases the vanadium ion permeability from 5.42 × 10-7 to 2.34 × 10-7 cm2 min-1. Meanwhile, it increases the membrane σ and selectivity up to 94.35 mS cm-2 and 40.32 × 104 S min cm-3, respectively. The cell assembled with the optimized membrane incorporating 2.5 wt% of S-NbS2 nanoflakes (SPEEK:2.5% S-NbS2) exhibits high efficiency metrics, i.e., coulombic efficiency between 98.7 and 99.0%, voltage efficiency between 90.2 and 73.2% and energy efficiency between 89.3 and 72.8% within the current density range of 100-300 mA cm-2, delivering a maximum power density of 0.83 W cm-2 at a current density of 870 mA cm-2. The SPEEK:2.5% S-NbS2 membrane-based VRFBs show a stable behavior over 200 cycles at 200 mA cm-2. This study opens up an effective avenue for the production of advanced SPEEK-based membranes for VRFBs.

Functionalized Metallic 2D Transition Metal Dichalcogenide-Based Solid-State Electrolyte for Flexible All-Solid-State Supercapacitors.

Highly efficient and durable flexible solid-state supercapacitors (FSSSCs) are emerging as low-cost devices for portable and wearable electronics due to the elimination of leakage of toxic/corrosive liquid electrolytes and their capability to withstand elevated mechanical stresses. Nevertheless, the spread of FSSSCs requires the development of durable and highly conductive solid-state electrolytes, whose electrochemical characteristics must be competitive with those of traditional liquid electrolytes. Here, we propose an innovative composite solid-state electrolyte prepared by incorporating metallic two-dimensional group-5 transition metal dichalcogenides, namely, liquid-phase exfoliated functionalized niobium disulfide (f-NbS2) nanoflakes, into a sulfonated poly(ether ether ketone) (SPEEK) polymeric matrix. The terminal sulfonate groups in f-NbS2 nanoflakes interact with the sulfonic acid groups of SPEEK by forming a robust hydrogen bonding network. Consequently, the composite solid-state electrolyte is mechanically/dimensionally stable even at a degree of sulfonation of SPEEK as high as 70.2%. At this degree of sulfonation, the mechanical strength is 38.3 MPa, and thanks to an efficient proton transport through the Grotthuss mechanism, the proton conductivity is as high as 94.4 mS cm-1 at room temperature. To elucidate the importance of the interaction between the electrode materials (including active materials and binders) and the solid-state electrolyte, solid-state supercapacitors were produced using SPEEK and poly(vinylidene fluoride) as proton conducting and nonconducting binders, respectively. The use of our solid-state electrolyte in combination with proton-conducting SPEEK binder and carbonaceous electrode materials (mixture of activated carbon, single/few-layer graphene, and carbon black) results in a solid-state supercapacitor with a specific capacitance of 116 F g-1 at 0.02 A g-1, optimal rate capability (76 F g-1 at 10 A g-1), and electrochemical stability during galvanostatic charge/discharge cycling and folding/bending stresses.

3D printed silicon-few layer graphene anode for advanced Li-ion batteries.

The printing of three-dimensional (3D) porous electrodes for Li-ion batteries is considered a key driver for the design and realization of advanced energy storage systems. While different 3D printing techniques offer great potential to design and develop 3D architectures, several factors need to be addressed to print 3D electrodes, maintaining an optimal trade-off between electrochemical and mechanical performances. Herein, we report the first demonstration of 3D printed Si-based electrodes fabricated using a simple and cost-effective fused deposition modelling (FDM) method, and implemented as anodes in Li-ion batteries. To fulfil the printability requirement while maximizing the electrochemical performance, the composition of the FDM filament has been engineered using polylactic acid as the host polymeric matrix, a mixture of carbon black-doped polypyrrole and wet-jet milling exfoliated few-layer graphene flakes as conductive additives, and Si nanoparticles as the active material. The creation of a continuous conductive network and the control of the structural properties at the nanoscale enabled the design and realization of flexible 3D printed anodes, reaching a specific capacity up to ∼345 mA h g-1 at the current density of 20 mA g-1, together with a capacity retention of 96% after 350 cycles. The obtained results are promising for the fabrication of flexible polymeric-based 3D energy storage devices to meet the challenges ahead for the design of next-generation electronic devices.

Novel proton conducting core-shell PAMPS-PVBS@Fe2TiO5 nanoparticles as a reinforcement for SPEEK based membranes.

In this study, new nanocomposite membranes from sulfonated poly (ether ether ketone) (SPEEK) and proton-conducting Fe2TiO5 nanoparticles are prepared by the solution casting method. Sulfonated core-shell Fe2TiO5 nanoparticles are synthesized by redox polymerization. Therefore, 4-Vinyl benzene sulfonate (VBS) and 2-acrylamide-2-methyl-1-propane sulfonic acid (AMPS) are grafted on the surface of nanoparticles through radical polymerization. The different amounts of hybrid nanoparticles (PAMPS@Fe2TiO5 and PVBS@Fe2TiO5) are incorporated into the SPEEK matrix. The results show higher proton conductivity for all prepared nanocomposites than that of the SPEEK membrane. Embedding the sulfonated Fe2TiO5 nanoparticles into the SPEEK membrane improves proton conductivity by creating the new proton conducting sites. Besides, the nanocomposite membranes showed improved mechanical and dimensional stability in comparison with that of the SPEEK membrane. Also, the membranes including 2 wt% of PAMPS@Fe2TiO5 and PVBS@Fe2TiO5 nanoparticles indicate the maximum power density of 247 mW cm-2 and 226 mW cm-2 at 80 °C, respectively, which is higher than that of for the pristine membrane. Our prepared membranes have the potential for application in polymer electrolyte fuel cells.

Fabrication and performance evaluation of new nanocomposite membranes based on sulfonated poly(phthalazinone ether ketone) for PEM fuel cells.

The purpose of this work is to enhance the proton conductivity and fuel cell performance of sulfonated poly(phthalazinone ether ketone) (SPPEK) as a proton exchange membrane through the application of SrTiO3 perovskite nanoparticles. Nanocomposite membranes based on SPPEK and SrTiO3 perovskite nanoparticles were prepared via a casting method. The highest proton conductivity of nanocomposite membranes obtained was 120 mS cm-1 at 90 °C and 95% RH. These enhancements could be related to the hygroscopic structure of SrTiO3 perovskite nanoparticles and the formation of hydrogen bonds between nanoparticles and water molecules. The satisfactory power density, 0.41 W cm-2 at 0.5 V and 85 °C, of the nanocomposite membrane (5 wt% content of nanoparticles) confirms their potential for application in the PEM fuel cells.

Surface modification of Fe2TiO5 nanoparticles by silane coupling agent: Synthesis and application in proton exchange composite membranes.

Modifying surfaces of nanoparticles with silane coupling agent provides a simple method to alter their surface properties and improve their dispersibility in organic solvents and polymer matrix. Fe2TiO5 nanoparticles (IT) were modified with 3-aminopropyltriethoxysilane (APTES) as novel reinforcing filler for proton exchange membranes. The main operating parameters such as reaction time (R.T), APTES/IT and triethylamine (TEA)/IT ratios have been optimized for maximum grafting efficiency. The optimum conditions for R.T, APTES/IT and TEA/IT ratios were 6h, 4 and 0.3 respectively. It was observed that the APTES/IT and TEA/IT ratios were the most significant parameters affecting the grafting percentage. Modified nanoparticles were characterized using FT-IR, TGA, SEM, TEM and XRD techniques. Effects of modified nanoparticles in proton exchange membrane fuel cells (PEMFC) were evaluated. The resulting nanocomposite membranes exhibited higher proton conductivity in comparison with pristine SPPEK and SPPEK/IT membranes. This increase is attributed to connectivity of the water channels which creates more direct pathways for proton transport. Composite membrane with 3% AIT (6.46% grafting amount) showed 0.024 S cm(-1) proton conductivity at 25 °C and 149 mW cm(-2) power density (at 0.5V) at 80 °C which were about 243% and 51%, respectively higher than that of pure SPPEK.