Simply Prepared Magnesium Vanadium Oxides as Cathode Materials for Rechargeable Aqueous Magnesium Ion Batteries.

Vanadium-oxide-based materials exist with various vanadium oxidation states having rich chemistry and ability to form layered structures. These properties make them suitable for different applications, including energy conversion and storage. Magnesium vanadium oxide materials obtained using simple preparation route were studied as potential cathodes for rechargeable aqueous magnesium ion batteries. Structural characterization of the synthesized materials was performed using XRD and vibrational spectroscopy techniques (FTIR and Raman spectroscopy). Electrochemical behavior of the materials, observed by cyclic voltammetry, was further explained by BVS calculations. Sluggish Mg2+ ion kinetics in MgV2O6 was shown as a result of poor electronic and ionic wiring. Complex redox behavior of the studied materials is dependent on phase composition and metal ion inserted/deinserted into/from the material. Among the studied magnesium vanadium oxides, the multiphase oxide systems exhibited better Mg2+ insertion/deinsertion performances than the single-phase ones. Carbon addition was found to be an effective dual strategy for enhancing the charge storage behavior of MgV2O6.

Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage.

The capacitance and operating voltage of supercapacitors as well as their energy density have been increased by development of different materials and electrolytes. In this paper, two strategies, for the first time, were used to improve energy density: Mn3O4- and N-dual doped carbon electrode and aqueous mixture of multivalent ions as electrolyte. Mn3O4- and N-dual doped carbon was prepared by a novel and cost-effective procedure using deep eutectic solvent. XRD, XPS, and FTIR confirmed presence of Mn3O4 and nitrogen, while SEM and EDS elemental mapping showed micrometer-sized nanosheets with uniform distribution of C, O, N, and Mn atoms. Charge storage behavior of carbon was tested in aqueous multivalent-based electrolytes and their mixture (Ca2+-Al3+). Regarding both specific capacitance and workable voltage, the Ca2+-Al3+ mixed electrolyte was found as the best optimal solution. The calcium addition to the Al-electrolyte allows the higher operating voltage than in the case of individual Al(NO3)3 electrolyte while the addition of Al3+ ion in the Ca(NO3)2 electrolyte improves the multivalent-ion charge storage ability of carbon. As a result, the specific energy density of two-electrode Mn3O4@N-doped carbon//Al(NO3)2+Ca(NO3)2//Mn3O4@N-doped carbon supercapacitor (34 Wh kg-1 at 0.1 A g-1) overpasses the reported values obtained for Mn-based carbon supercapacitors using conventional aqueous electrolytes.

The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte.

Layered VOPO4·2H2O is synthesized by the sonochemical method. An X-ray powder diffraction is used to examine the crystal structure, while scanning electron microscopy is used to reveal the morphology of the powder. The crystal structure refinement is performed in the P4/nmmZ space group. The electrochemical intercalation of several cations (Na+, Mg2+, Ca2+, and Al3+) in saturated nitrate aqueous solutions is investigated. The most notable reversible activity is found for the cycling in aluminium nitrate aqueous solution in the voltage range from -0.1 to 0.8 V vs. SCE. During the preparation of the electrode, it is observed that the structure is prone to changes that have not been recorded in the literature so far. Namely, the use of conventional binder PVDF in NMP solution deteriorates the structure and lowers the powder's crystallinity, while the use of Nafion solution causes the rearrangement of the atoms in a new crystal form that can be described in the monoclinic P21/c space group. Consequently, these structural changes affect electrochemical performances. The observed differences in electrochemical performances are a result of structural rearrangements.

Carbon-Supported Mo2C for Oxygen Reduction Reaction Electrocatalysis.

Molybdenum carbide (Mo2C)-based electrocatalysts were prepared using two different carbon supports, commercial carbon nanotubes (CNTs) and synthesised carbon xerogel (CXG), to be studied from the point of view of both capacitive and electrocatalytic properties. Cation type (K+ or Na+) in the alkaline electrolyte solution did not affect the rate of formation of the electrical double layer at a low scan rate of 10 mV s-1. Conversely, the different mobility of these cations through the electrolyte was found to be crucial for the rate of double-layer formation at higher scan rates. Molybdenum carbide supported on carbon xerogel (Mo2C/CXG) showed ca. 3 times higher double-layer capacity amounting to 75 mF cm-2 compared to molybdenum carbide supported on carbon nanotubes (Mo2C/CNT) with a value of 23 mF cm-2 due to having more than double the surface area size. The electrocatalytic properties of carbon-supported molybdenum carbides for the oxygen reduction reaction in alkaline media were evaluated using linear scan voltammetry with a rotating disk electrode. The studied materials demonstrated good electrocatalytic performance with Mo2C/CXG delivering higher current densities at more positive onset and half-wave potential. The number of electrons exchanged during oxygen reduction reaction (ORR) was calculated to be 3, suggesting a combination of four- and two-electron mechanism.

Molybdenum Carbide Nanoparticles on Carbon Nanotubes and Carbon Xerogel: Low-Cost Cathodes for Hydrogen Production by Alkaline Water Electrolysis.

Low-cost molybdenum carbide (Mo2 C) nanoparticles supported on carbon nanotubes (CNTs) and on carbon xerogel (CXG) were prepared and their activity for the hydrogen evolution reaction (HER) was evaluated in 8 m KOH aqueous electrolyte at 25-85 °C. Measurements of the HER by linear scan voltammetry allowed us to determine Tafel slopes of 71 and 74 mV dec(-1) at 25 °C for Mo2 C/CNT and Mo2 C/CXG, respectively. Stability tests were also performed, which showed the steady performance of the two electrocatalysts. Moreover, the HER kinetics at Mo2 C/CNT was enhanced significantly after the long-term stability tests. The specific activity of both materials was high, and a higher stability was obtained for the activated Mo2 C/CNT (40 A g(-1) at -0.40 V vs. the reversible hydrogen electrode).