Electrolyte Solution Research Articles

Molecular dynamics simulations and FTIR Spectroscopy investigations on the hydration, transport, and dielectric properties of the NaF(aq) system at various concentrations

Sodium fluoride has many applications in various fields, such as dentistry, geochemistry, and rechargeable battery technology. Indeed, the determination of the hydration structures, dynamics, and dielectric properties of the NaF electrolyte in aqueous solutions is a crucial element in order to optimize its performance and predict its intervention mechanisms in industrial processes. In this study, we used the molecular dynamics approach to study the NaF(aq) binary system at different concentrations ranging from 0.1 to 1.0 mol.kg−1 using the OPLS-AA force field combined with the extended simple point load water model (SPC/E). Thus, the ions were represented as charged Lennard-Jones particles. The radial distribution functions (RDF) have been calculated to analyze the hydration shell structures of different ion pairs. The microstructures, self-diffusion coefficient, and dielectric constant were determined by molecular dynamics at various concentrations. Moreover, our FTIR spectroscopy data confirm the results obtained from molecular simulations.

Nickel-molybdenum bimetallic sulfide decorated biomass derived carbon support for high performance asymmetric supercapacitor application

Biomass - derived carbon electrode material with a porous structure is widely used in supercapacitor applications, which can improve electron transfer and shorter ion diffusion pathways. In this work, the garlic peel biomass carbon (GPBC), NiMo3S4(NMS) and garlic peel biomass carbon decorated with NiMo3S4 (GPBC/NMS) composite were prepared through a in situ two-step hydrothermal method. The synthesized materials were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM), energy dispersive x-ray spectroscopy (EDS), Transmission electron microscopy techniques (TEM), Raman spectroscopy and Brunauer-Emmett-Teller (BET) techniques were used to analyze the structure, morphology and specific surface areas and X-ray photoelectron spectroscopy (XPS). The prepared bimetallic metal sulfide on a biomass - derived carbon namely the GPBC/NMS composite is used in supercapacitor application. The GPBC/NMS composite electrode exhibits good cycle performance with high specific capacity of 304C/g at current density of 1 A/g in a 3 M KOH electrolyte solution. The electrochemical performance of the GPBC/NMS//GPBC asymmetric supercapacitor device produces an excellent energy density 45.5 Wh kg−1 at a power density of 1125 W kg−1 in the 1.6 V operating potential window. The GPBC/NMS//GPBC also exhibits 93 % retention of its initial capacitance after the 10,000 GCD cycle performance. The above results demonstrate a new way of developing high performance electrode materials for energy storage applications.

Enhanced hydrogen storage performance of zinc and magnesium cobaltite nanocomposites

Renewable and sustainable energies are vital for the near future. Hydrogen, as a clean energy carrier, is a potential candidate for supplying energy in the foreseeable future. Nowadays, hydrogen storage technology has become a significant issue in the energy sector. In this study, ZnCo2O4/ZnO and MgCo2O4/MgO nanocomposites have been synthesized using the sol-gel method with stearic acid as a complexing agent. Different analyses were studied to examine the crystal structure, morphology, and physical properties of the as-prepared samples, including X-ray diffraction (XRD), Fourier transforms infrared (FT-IR), field emission scanning electron microscopy (FESEM), diffuse reflectance spectroscopy (DRS), and vibrating sample magnetometer (VSM). Various methods have been utilized for hydrogen storage technology. In a pioneering approach, the electrochemical hydrogen storage of samples was compared by the chronopotentiometry technique in KOH (4 M) electrolyte solution. The results reveal that ZnCo2O4/ZnO and MgCo2O4/MgO nanocomposites exhibit excellent discharge capacities of 4240 and 3529 mAh/g, respectively, after 11 cycles.

Effect of ethanolamine as a steel corrosion inhibitor in realkalization of carbonated concrete

ABSTRACT This paper assessed the electromigration behavior of ethanolamine and its efficiency as a corrosion inhibitor of rebar during the realkalization. Cylindrical concrete specimen (diameter 45 mm, height 20 mm) with steel rebar (6 mm in diameter, 35 mm in length) were artificially carbonated and corroded in an accelerated manner with impressed anodic current. The specimens were realkalized in the electrolyte solution containing ethanolamine, while the steel rebars were connected to the cathodic current (200 mA·h, 1 A/m2). After 25 days of monitoring the repair process, experimental data revealed notable changes in electrochemical parameters. The corrosion potential increased from −627 mV to −236 mV, signifying a reduction in corrosion activity. The cathodic exchange current density decreased from 4.9 μA/cm2 to 2.3 μA/cm2, showing a decrease in the corrosion rate. Also, the pH value of the solution dropped to a comparatively lower level, the ethanolamine and potassium ion concentrations decreased from 22 to 30.54 g/L to 3.22 and 10.23 g/L, respectively. Moreover, nitrogen detection on the steel surface and varied levels of ethanolamine concentration at different depths in the concrete were also measured, both indicating a clear migration of inhibitor to the steel surface to form a passive film.

Tetraethylammonium Perfluorobutanesulfonate as an Alternative Salt for Electric Double Layer Capacitors

The utilization of tetraethylammonium perfluorobutane sulfonate as a promising alternative salt for electrolyte solutions in electrochemical double layer capacitors is introduced in this study. A thorough analysis of the physical and electrochemical characteristics of tetraethylammonium perfluorobutane sulfonate was conducted, including the assessment of its ionic conductivity, viscosity, and thermal behavior, using a 1 M solution in acetonitrile. Comparative assessments were made between the performance of this novel electrolyte and two well‐studied electrolytes: 1 m tetraethylammonium tetrafluoroborate and 1 m tetraethylammonium bis(trifluoromethanesulfonyl)imide in acetonitrile, focusing on electrochemical performance and long‐term stability. Furthermore, an investigation into the impact of tetraethylammonium perfluorobutane sulfonate on the anodic dissolution of aluminum current collectors was conducted. The results highlight the potential of tetraethylammonium perfluorobutane sulfonate as an effective replacement for bis(trifluoromethanesulfonyl)imide‐based electrolytes.

Fluoride Ions Post-Treatment Regulates Interfacial Charge Separation and Transport to Promote Solar Water Splitting of Bismuth Vanadate.

Herein, we propose a simple and effective fluoride (F-) ions post-treatment method to improve the solar water splitting performance of BVO. The surface modification of BVO with functional F- ions not only facilitates the transfer and separation efficiency of carriers at the electrode/electrolyte interface but also promotes the adsorption and activation of water, resulting in a photocurrent of 3.2 mA/cm2 at a bias voltage of 1.2 VRHE. Furthermore, the transfer and separation of carriers in the bulk and on the surface are further regulated by the oxygen vacancies induced by F- ions, thereby enhancing the PEC water splitting performance of BVO. Notably, the experimental findings demonstrate that the inclusion of F- ions in the KBi electrolyte enhances the photo-charging process of BVO. Specifically, at a bias voltage of 0.6 VRHE, the BVO-0.12F sample exhibits a stable photocurrent of 1.2 mA/cm2, which is twice as high as that of the initial BVO sample. Remarkably, our study unveils that the addition of F- ions into the KBi electrolyte solution plays a pivotal role in facilitating the separation of charge carriers and promoting interfacial charge transport. Consequently, this further leads to a substantial enhancement in the solar water splitting performance for BVO-0.12F photoanode.

Spatially Confined Radical Addition Reaction for Electrochemical Synthesis of Carboxylated Graphene and its Applications in Water Desalination and Splitting.

Due to the chemical stability of graphene, synthesis of carboxylated graphene still remains challenging during the electrochemical exfoliation of graphite. In this work, a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets for the electrochemical synthesis of highly stable carboxylated graphene is reported. Here, formate anions act as both intercalation ions and co-reactant acid for the confinement of electro-generated carboxylic radical (●COOH) in the sub-nanometer scaled interlayers, which facilitates the radical addition reaction on graphene sheets. The controllable carboxylation of graphene is realized by tuning the concentration of formate anions in the electrolyte solution. The high crystallinity of the obtained product indicates the occurrence of spatially confined ●COOH addition reaction between the sub-nanometer interlayers of expanded graphite. In addition, the carboxylated graphene have been used for water desalination and hydrogen/oxygen reduction reaction. Therefore, this work provides a new method for the in situ preparation of functionalized graphene through the electrolysis and its applications in water desalination and hydrogen/oxygen reduction reactions.

Crucial Roles of Ethyl Methyl Carbonate in Lithium-Ion and Dual-Ion Batteries: A Review.

The essential role of electrolyte solutions in traditional electrochemical energy storage devices is crucial to enhancing their performance. Consequently, a wide array of electrolyte mixtures along with diverse electrodes have been extensively explored across different models of secondary batteries. Fascinatingly, the role of ethyl methyl carbonate (EMC) as a key cosolvent in the electrolyte mixture of commercial lithium-ion batteries with a graphite anode is garnering growing attention in alternative rechargeable dual-ion batteries utilizing graphite cathodes. In this context, the advancement and function of EMC as a solvent in electrolyte mixtures for lithium-ion and dual-ion batteries were extensively and thoroughly examined in this analysis, encompassing the genesis, synthesis process, and diverse characteristics for the practical uses of these batteries. Here, the review aims to guide readers in understanding EMC's function and impact as a cosolvent in electrolyte mixtures for both major secondary lithium-ion and dual-ion batteries, considering their distinct physicochemical characteristics.

Streaming Potential and Associated Electrokinetic Effects through a Channel Filled with Electrolyte Solution Surrounded by a Layer of Immiscible and Dielectric Liquid.

The present article deals with the streaming potential-mediated pressure-driven flow across a channel in which the electrolyte solution is surrounded by a layer of cell membrane. Such a membrane of a biological cell may be modeled as an immiscible and dielectric liquid, which may bear free lipid molecules or charged surfactants. The presence of such additional charged molecules may lead to formation of liquid-liquid interfacial charge. In addition, the dielectric gradient-mediated ion partitioning effect further plays an important role in two-phase electrokinetic motion. We aim to study the generation of streaming potential and electrokinetic conversion efficiency as well as associated electroviscous effect for the undertaken problem. The mathematical model is based on the Poisson-Boltzmann equation for electrostatic potential and the Stokes equation for fluid flow, and the problem is studied considering suitable interfacial conditions for the flow variables along the liquid-liquid interface. The explicit analytical results for velocity and streaming field, electrokinetic energy conversion efficiency, and the parameter indicating the electroviscous effect are derived under the Donnan limit and within the Debye-Hückel electrostatic framework. We further numerically calculated the aforementioned intrinsic electrokinetic parameter associated with the problem undertaken for a wide range of pertinent parameters. The results are illustrated to indicate the impact of pertinent parameters on the generation of the streaming potential and associated electrokinetic effects.

Bouguer–Lambert–Beer Law of Absorption: Spectrophotometry in Electrolyte Solutions

Bouguer–Lambert–Beer Law of Absorption: Spectrophotometry in Electrolyte Solutions

Methyl Acetate Boosts the Low-Temperature Performance of Li4Ti5O12/Graphite Dual-Ion Batteries.

Methyl acetate (MA) is a suitable solvent for low-temperature electrolyte solutions, but its poor stability against lithium metal is a big problem. Herein, a simple and cheap solution of LiPF6 dissolved in MA was successfully employed for Li4Ti5O12/graphite dual-ion batteries (DIBs). This cell has a long cycle life with 93.1% capacity retention after 1000 cycles. Moreover, it has superior performance at low temperatures (-40 °C) compared to other reported DIBs. The storage behavior of PF6- solvated by MA in graphite cathode has been investigated in detail by in situ X-ray diffraction (XRD) in combination with electrochemical dilatometry (ECD).

Study on the Optimization of the Preparation Process of ZM5 Magnesium Alloy Micro-Arc Oxidation Hard Ceramic Coatings and Coatings Properties

Hard ceramic coatings were successfully prepared on the surface of ZM5 magnesium alloy by micro-arc oxidation (MAO) technology in silicate and aluminate electrolytes, respectively. The optimization of hard ceramic coatings prepared in these electrolyte systems was investigated through an orthogonal experimental design. The microstructure, elemental composition, phase composition, and tribological properties of the coatings were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and tribological testing equipment. The results show that the growth of the hard ceramic coatings is significantly influenced by the different electrolyte systems. Coatings prepared from both systems have shown good wear resistance, with the aluminate electrolyte system being superior to the silicate system in performance. The optimized formulation for the silicate electrolyte solution has been determined to be sodium silicate at 8 g/L, sodium dihydrogen phosphate at 0.2 g/L, sodium tetraborate at 2 g/L, and potassium hydroxide at 1 g/L. The optimized formulation for the aluminate electrolyte solution consists of sodium aluminate at 5 g/L, sodium fluoride at 3 g/L, sodium citrate at 3 g/L, and sodium hydroxide at 0.5 g/L.

Modulation of polyaniline memristive device switching voltage by nucleotide-free analogue of vitamin B12.

Memristive devices offer essential properties to become a part of the next-generation computing systems based on neuromorphic principles. Organic memristive devices exhibit a unique set of properties which makes them an indispensable choice for specific applications, such as interfacing with biological systems. While the switching rate of organic devices can be easily adjusted over a wide range through various methods, controlling the switching potential is often more challenging, as this parameter is intricately tied to the materials used. Given the limited options in the selection conductive polymers and the complexity of polymer chemical engineering, the most straightforward and accessible approach to modulate switching potentials is by introducing specific molecules into the electrolyte solution. In our study, we show polyaniline-based device switching potential control by adding nucleotide-free analogue of vitamin B12, aquacyanocobinamide, to the electrolyte solution. The employed concentrations of this molecule, ranging from 0.2 to 2 mM, enabled organic memristive devices to achieve switching potential decrease for up to 100 mV, thus providing a way to control device properties. This effect is attributed to strong aromatic interactions between polyaniline phenyl groups and corrin macrocycle of the aquacyanocobinamide molecule, which was supported by ultraviolet-visible spectra analysis.

Application of on-line sample preconcentration by large-volume dual preconcentration by isotachophoresis and stacking (LDIS) on straight-channel microchips.

In this study, large-volume dual preconcentration by isotachophoresis and stacking (LDIS) which is an on-line sample preconcentration technique coupling large-volume sample stacking with an electroosmotic flow pump (LVSEP) with transient isotachophoresis (tITP) was applied to microchip electrophoresis (MCE) for improving both detection sensitivities and peak shapes. To realize LDIS in MCE, we investigated experimental procedures for injecting a short plug of a leading electrolyte (LE) solution into a straight microchannel without any sophisticated injector apparatus. We found that a short LE plug could be injected into a sample-filled straight-channel only by making the liquid level of the LE solution in an outlet reservoir higher than that in an inlet one. By applying a reversed-polarity voltage to the microchip, anionic analytes injected throughout the microchannel were first enriched by LVSEP, followed by tITP. Through the second preconcentration effect by tITP in LDIS, sensitivity enhancement factor (SEF) and asymmetry factor for a standard dye were improved from 878 and 0.62 to 1330 and 1.14, respectively, relative to those in conventional LVSEP. It should be noted that more viscous running buffer containing sieving polymers could be employed to the LDIS analysis, which was effective for improving the SEF and the separation efficiencies, especially for bio-polymeric compounds. Finally, LDIS was applied to the oligosaccharide and protein analyses in MCE, resulting in the SEFs of 1410 and ca. 50 for maltotriose and bovine milk casein, respectively.

Nano-Sheets of CsNiVF6 Pyrochlore Electrocatalyst for Enhanced Urea Oxidation and Hydrogen Green Production Reactions

This study presents the successful synthesis of a cesium–nickel–vanadium fluoride (CsNiVF6) pyrochlore nano-sheet catalyst via solid-phase synthesis and its electrochemical performance in green hydrogen production through urea electrolysis in alkaline media. The physicochemical characterizations revealed that the CsNiVF6 exhibits a pyrochlore-type structure consisting of a disordered cubic corner-shared (Ni, V)F6 octahedra structure and nano-sheet morphology with a thickness ranging from 10 to 20 nm. Using the CsNiVF6 catalyst, the electrochemical analysis, conducted through cyclic voltammetry, demonstrates a current mass activity of ~1500 mA mg−1, recorded at 1.8 V vs. RHE, along with low-resistance (3.25 ohm) charge transfer and good long-term stability for 0.33 M urea oxidation in an alkaline solution. Moreover, the volumetric hydrogen production rate at the cathode (bare nickel foam) is increased from 12.25 to 39.15 µmol/min upon the addition of 0.33 M urea to a 1.0 KOH solution and at a bias potential of 2.0 V. The addition of urea to the electrolyte solution enhances hydrogen production at the cathode, especially at lower voltages, surpassing the volumes produced in pure 1.0 M KOH solution. This utilization of a CsNiVF6 pyrochlore nano-sheet catalyst and renewable urea as a feedstock contributes to the development of a green and sustainable hydrogen economy. Overall, this research underscores the potential use of CsNiVF6 as a cost-effective nickel-based pyrochlore electrocatalyst for advancing renewable and sustainable urea electrolysis processes toward green hydrogen production.

Multifunctional Supramolecular Hydrogel Modulated Heterojunction Interface Carrier Transport Engineering Facilitates Sensitive Photoelectrochemical Immunosensing.

Highly responsive interface of semiconductor nanophotoelectrochemical materials provides a broad development prospect for the identification of low-abundance cancer marker molecules. This work innovatively proposes an efficient blank WO3/SnIn4S8 heterojunction interface formed by self-assembly on the working electrode for interface regulation and photoregulation. Different from the traditional biomolecular layered interface, a hydrogel layer containing manganese dioxide with a wide light absorption range is formed at the interface after an accurate response to external immune recognition. The formation of the hydrogel layer hinders the effective contact between the heterojunction interface and the electrolyte solution, and manganese dioxide in the hydrogel layer forms a strong competition between the light source and the substrate photoelectric material. The process effectively improves the carrier recombination efficiency at the interface, reduces the interface reaction kinetics and photoelectric conversion efficiency, and thus provides strong support for target identification. Taking advantage of the process, the resulting biosensors are being explored for sensitive detection of human epidermal growth factor receptor 2, with a limit of detection as low as 0.037 pg/mL. Also, this study contributes to the advancement of photoelectrochemical biosensing technology and opens up new avenues for the development of sensitive and accurate analytical tools in the field of bioanalysis.

Defined Transfer of Colloidal Particles by Electrochemical Microcontact Printing

AbstractSoft lithography, in particular microcontact printing (µCP), represents a well‐established and widespread class of lithographic patterning techniques. It is based on a directed deposition of molecules or colloidal particles by a transfer process with a micro‐structured stamp. A critical aspect of µCP is the adhesion cascade that enables the directed transfer of the objects. Here, the interfacial properties of a µCP‐stamp are tuned electrochemically to modify the adhesion cascade. During the printing process, the µCP‐stamp is submerged in an electrolyte solution and acted as a working electrode whose surface properties depended on the externally applied potential, thus enabling in situ rapid switching of its adhesion properties. As a proof of principle, defined particle patterns are selectively removed from a monolayer of colloidal particles. The adhesion at the particle/solid interface and the transfer mechanisms are determined by using the colloidal probe technique based on atomic force microscopy (AFM). In this case, a single particle is brought into contact with an electrode with the same surface chemistry as the µCP‐stamp. Hence, it became possible to determine the electrochemical potential ranges suitable to establish an adhesion cascade.

High-pressure intrusion of double salt aqueous solution in pure silica chabazite: searching for cation selectivity

Heterogeneous lyophobic systems (HLSs), i.e. systems composed of a nanoporous solid and a non-wetting liquid, have attracted much attention as promising candidates for innovative mechanical energy storage and dissipation devices. In this work, a new HLS based on a pure silica chabazite (Si-CHA) and a ternary electrolyte solution (KCl + CaCl2) is studied from porosimetric and crystallographic points of view. The combined approach of this study has been fundamental in unravelling the properties of the system. The porosimetric experiments allowed the determination of the energetic behaviour, while high-pressure in situ crystallographic analyses helped elucidate the mechanism of intrusion. The results are compared with those obtained for systems involving the same zeolite but intruded with solutions containing only single salts (CaCl2 or KCl). The porosimetric results of the three Si-CHA systems intruded by simple and complex electrolyte solutions (KCl 2 M, CaCl2 2 M and the mixture KCl 1 M + CaCl2 1 M) suggest that the intrusion pressure is mainly influenced by the nature of the cations. The CaCl2 2 M solution shows the highest intrusion pressure and KCl 2 M the lowest, whereas the mixture KCl 1 M + CaCl2 1 M is almost in the middle. These differences are probably related to the higher hydration enthalpy and Gibbs energy of Ca2+ compared with those of K+. It has been demonstrated that partial ion desolvation is needed to promote the penetration of the species, and a higher solvation energy requires higher pressure. The `intermediate' value of intrusion pressure shown by the complex electrolyte solution arises from the fact that, statistically, the second/third solvation cation shells can be assumed to be partially shared between K+ and Ca2+. The stronger interaction of Ca2+ with H2O molecules thus also influences the desolvation of K+, increasing the pressure needed to activate the process compared with the pure KCl 2 M solution. This is confirmed by the structural investigation, which shows that at the beginning of intrusion only K+, Cl− and H2O penetrate the pores, whereas the intrusion of Ca2+ requires higher pressure, in agreement with the hydration enthalpies of the two cations.

Development of a consistent geochemical model of the Mg(OH)2–MgCl2–H2O system from 25°C to 120°C

The formation of magnesium chloride-hydroxide salts (magnesium hydroxychlorides) has implications for many geochemical processes and technical applications. For this reason, a thermodynamic database for evaluating the Mg(OH)2–MgCl2–H2O ternary system from 0 °C–120 °C has been developed based on extensive experimental solubility data. Internally consistent sets of standard thermodynamic parameters (ΔGf°, ΔHf°, S°, and CP) were derived for several solid phases: 3 Mg(OH)2:MgCl2:8H2O, 9 Mg(OH)2:MgCl2:4H2O, 2 Mg(OH)2:MgCl2:4H2O, 2 Mg(OH)2:MgCl2: 2H2O(s), brucite (Mg(OH)2), bischofite (MgCl2:6H2O), and MgCl2:4H2O. First, estimated values for the thermodynamic parameters were derived using a component addition method. These parameters were combined with standard thermodynamic data for Mg2+(aq) consistent with CODATA (Cox et al., 1989) to generate temperature-dependent Gibbs energies for the dissolution reactions of the solid phases. These data, in combination with values for MgOH+(aq) updated to be consistent with Mg2+-CODATA, were used to compute equilibrium constants and incorporated into a Pitzer thermodynamic database for concentrated electrolyte solutions. Phase solubility diagrams were constructed as a function of temperature and magnesium chloride concentration for comparisons with available experimental data. To improve the fits to the experimental data, reaction equilibrium constants for the Mg-bearing mineral phases, the binary Pitzer parameters for the MgOH+ — Cl− interaction, and the temperature-dependent coefficients for those Pitzer parameters were constrained by experimental phase boundaries and to match phase solubilities. These parameter adjustments resulted in an updated set of standard thermodynamic data and associated temperature-dependent functions. The resulting database has direct applications to investigations of magnesia cement formation and leaching, chemical barrier interactions related to disposition of heat-generating nuclear waste, and evaluation of magnesium-rich salt and brine stabilities at elevated temperatures.

Resuscitation for injured patients requiring massive transfusion: A personal perspective.

The past century has seen many advances in the field of resuscitation. This is particularly true in the subset of patients who sustain major injuries causing hemorrhagic shock and require massive transfusion over 10 units of blood within the first 24 hours. Controversies on how best to resuscitate these patients include the role of fresh whole blood (WB), stored WB, fresh frozen plasma (FFP), platelets (PLTS), colloid solutions, balanced electrolytes solution, vasopressors and diuretics. This review summarizes the often-contradictory recommendations observed and studied by a single trauma surgeon working in a busy urban acute care center for 65 years.