Dynamic properties of aqueous electrolyte solutions from non-polarisable,polarisable, and scaled-charge models

We investigated the dynamic properties of alkali halide solutions (NaCl, NaF, NaBr, NaI, LiCl, and KCl) using molecular dynamics simulations and several non-polarisable, polarisable, and scaled-charge models. The concentration dependence of shear viscosity was obtained with low statistical uncertainties to allow for calculation of the viscosity Jones-Dole B-coefficients. No prior values are available for the B-coefficients from molecular simulations of fully atomistic models for electrolyte solutions. In addition, we obtained diffusion coefficients with rigorous finite-size corrections to access ion mobilities; these provide insights on single ion hydration behaviour. We find that all models studied, even polarisable and scaled-charge models, quantitatively over-predict water structuring but qualitatively follow the experimentally determined Hofmeister series. All ion models considered are kosmotropes based on their calculated B-coefficient and diffusion coefficients, even for ions experimentally found to be chaotropes. These observations indicate that the water-ion interactions in these models are not adequately represented; additional interactions such as charge transfer must be incorporated in future models in order to better represent electrolyte solution properties.     

About Some Structural Differences of Certain Inorganic Salt Solutions in Natural and Heavy Water

Based on viscosity measurements of seven electrolyte soultions (KCl, K Br, KI, LiCl, Na₂CO₃, Li₂SO₄, and MnSO₄) in heavy water and the viscosity data of four electrolyte solutions (KCl, KBr, Kl, and Na₂CO₃) in ordinary water the activation energies of viscosity have been determined from the Pantchenkov equation. The dtermination were made at 25°, 35°, 45°, 60°, 75°, and 90°, at various concentrations up to near saturation. The activation energies of viscosity for pure heavy and ordinary water have been determined, too. The results allowed conclusions on the various influences of the investigated salts on the structure of heavy and ordinary water solutions.     

Conductivity studies on PEO:NaClO3 electrolyte system with different plasticizers

A new ion conducting solid polymer electrolyte thin film based on Polyethylene oxide (PEO) with NaClO₃ salt is prepared by solution-casting method. The solvation of salt with PEO has been confirmed by X-ray diffraction and IR spectral studies. Plasticizer effects were studied in PEO:NaClO₃ system by using low molecular weight polyethylene glycol (PEG), dimethyl formamide (DMF) and propylene carbonate(PC). AC conductivity in the temperature range (308–378 K) was measured to evaluate the conductivity of the polymer electrolytes. From the conductivity data, it was found that the conductivity value of pure PEO increases 10²–10⁴ order of magnitude with the addition of salts as well as plasticizers. From the transference number experiments, it was confirmed that the charge transport in these electrolyte is mainly due to the ions (t_ion≈0.94). Finally, the conductivity value of all PEO: NaClO₃ systems were compared.     

Molecular dynamics simulations of carbon dioxide hydrate growth in electrolyte solutions of NaCl and MgCl2

Molecular dynamics simulations are performed to study the growth of carbon dioxide (CO₂) hydrate in electrolyte solutions of NaCl and MgCl₂. The kinetic behaviour of the hydrate growth is examined in terms of cage content, density profile, and mobility of ions and water molecules, and how these properties are influenced by added NaCl and MgCl₂. Our simulation results show that both NaCl and MgCl₂ inhibit the CO₂ hydrate growth. With a same mole concentration or ion density, MgCl₂ exhibits stronger inhibition on the growth of CO₂ hydrate than NaCl does. The growth rate of the CO₂ hydrate in NaCl and MgCl₂ solutions decreases slightly with increasing pressure. During the simulations, the Na⁺, Mg²⁺, and Cl^? ions are mostly excluded by the growing interface front. We find that these ions decrease the mobility of their surrounding water molecules, and thus reduce the opportunity for these water molecules to form cage-like clusters toward hydrate formation. We also note that during the growth processes, several 5¹²6³ cages appear at the hydrate/solution interface, although they are finally transformed to tetrakaidecahedral (5¹²6²) cages. Structural defects consisting of one water molecule trapped in a cage with its hydrogen atoms being attracted by two Cl^? ions have also been observed.     

X‐ray Raman spectroscopy of lithium‐ion battery electrolyte solutions in a flow cell

The effects of varying LiPF₆ salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium‐ion battery electrolyte solvents (ethylene carbonate–dimethyl carbonate and propylene carbonate) have been investigated. X‐ray Raman scattering spectroscopy (a non‐resonant inelastic X‐ray scattering method) was utilized together with a closed‐circle flow cell. Carbon and oxygen K‐edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li⁺ ion concentration in the solvent manifests itself as a blue‐shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K‐edge results agree with previous soft X‐ray absorption studies on LiBF₄ salt concentration in propylene carbonate, carbon K‐edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.     

The Influence of Addition of Inorganic Carbonates on the Relative Volatility Factor of Light and Heavy Water at Temperatures Close to the Isotope Effect Inversion Temperature

The influence of Na₂, CO₃, K₂CO₃, and Li₂CO₃ addition on the relative volatility factor α of light and heavy water ai temperatures close to the isotope effect inversion temperature has been investigated. The measurements for Na₂CO₃ and K₂CO₃ solutions have been made in the temperature range. 100–330 °C at various salt concentrations. In the case of Li₂CO₃ temperature range and concentration was limited by the solubility of this salt. The factor α was determined by analysis of gas and liquid phases at equilibrium. Data on pure waters obtained by other investigators are listed for comparison. The temperature dependence of factor α for salt solutions and pure waters is presented in the form of equations derived from experimental data.     

Fuel quality and operational issues for polymer electrolyte membrane (PEM) fuel cells

Polymer electrolyte membrane (PEM) fuel cells are susceptible to degradation due to the catalyst poisoning caused by CO present in the fuel above certain limits. Although the amount of CO in the fuel may be within the permissible limit, the fuel composition (% CO₂, CH₄, CO and H₂O) and the operating conditions of the cell (level of gas humidification, cell temperature and pressure) can be such that the equilibrium CO content inside the cell may exceed the permissible limit leading to a degradation of the fuel cell performance. In this study, 50 cm² active area PEM fuel cells were operated at 55–60 °C for periods up to 250 hours to study the effect of methane, carbon dioxide and water in the hydrogen fuel mix on the cell performance (stability of voltage and power output). Furthermore, the stability of fuel cells was also studied during operation of cells in a cyclic dead end / flow through configuration, both with and without the presence of carbon dioxide in the hydrogen stream. The presence of methane up to 10% in the hydrogen stream showed a negligible degradation in the cell performance. The presence of carbon dioxide in the hydrogen stream even at 1–2% level was found to degrade the cell performance. However, this degradation was found to disappear by bleeding only about 0.2% oxygen into the fuel stream.     

Effect of sodium salt addition upon electrochemical behavior of natural graphite

Despite the reported enhanced electrochemical behavior of graphite anodes due to the addition of NaClO₄ salts in to the electrolytes used in lithium battery applications, a detailed investigation upon the effect of addition of NaPF₆ salt in an electrolyte containing 1 M LiPF₆ in 1:1 V/V EC:DEC has resulted in inferior electrochemical behavior of graphite, i.e., quite contrast to the reported behavior of improved effects of addition of NaClO₄ into 1 M LiClO₄ solution, the addition of 0.22 mol dm⁻³ NaPF₆ salt has been found to reduce the capacities of lithium-ion cells containing 1 M LiPF₆ in 1:1 V/V EC:DEC. Towards this study, cells fabricated with and without the addition of 0.22 mol dm⁻³ NaPF₆ in 1 M LiPF₆ (1:1 V/V EC:DEC) were subjected to a systematic charging at a constant C/10 rate and discharging of cells at four different rates, viz., C/5, C/2 and C rates at the end of every 5 cycles. The observed results of the charge-discharge studies up to 15 cycles are discussed in this preliminary communication.     

Synthesis and studies of new plasticized PVP: NaClO3 electrolyte system for battery applications

A new thin film sodium ion conducting plasticized polymer electrolyte based on poly(vinyl pyrrolidone) (PVP) complexed with NaClO₃ salt systems was prepared by the solution-cast method. The interaction of NaClO₃ salt with PVP was confirmed by Infrared (IR) study. Charge transport of these polymer electrolytes is due to ions, which was confirmed by Wagner’s polarization method. From the conductivity measurements, the highest conductivity value 6.71×10⁻⁵ S/cm was observed for the composition PVP:PEG:NaClO₃(30:60:10) at room temperature 35 °C. The redox behaviour and good reversibility of the plasiticized electrolytes are confirmed by electrochemical techniques. Electrochemical cell studies of these polymer electrolytes were analyzed from their discharge characteristics. The open-circuit voltage (OCV) and short-circuit current (SCC) were found to in the range of 2.52 V to 2.36 V and 760 μA to 1040 μA, respectively.     

Preparation and characterization of (PVP + NaClO4) electrolytes for battery applications

A sodium ion-conducting polymer electrolyte based on polyvinyl pyrrolidone (PVP) complexed with NaClO₄ was prepared using the solution-cast technique. The cathode film of V₂O₅ xerogel modified with polyvinyl pyrrolidone was prepared using the sol-gel method. Investigations were conducted using X-ray diffractometry (XRD), Fourier transformation infrared (FT-IR) spectroscopy. The ionic conductivity and transference number measurements were performed to characterize the polymer electrolyte for battery applications. The transference number data indicated that the conducting species in these electrolytes are the anions. Using the electrolyte, electrochemical cells with a configuration Na/(PVP + NaClO₄)/V₂O₅ modified by (PVP) were fabricated and their discharge profiles studied.