Ionic Mass Transfer at Point Electrodes Located at Cathode Support Plate in an Electrorefining Cell in Presence of Rectangular Turbulent Promoters

Current density plays a major role in deciding the plant size, current efficiency, and energy consumption in electrorefining cells. In general, operating current density will be 40% of the limiting current density. Forced circulation of the electrolyte in the presence of promoters improves the mass transfer coefficient. In the present study, rectangular turbulence promoters are fitted at the bottom side of the cell to improve the mass transfer coefficient at the cathode support plate. The limiting current density technique is used to measure the mass transfer coefficient. The variables covered in the present study are the effects of flow rate, promoter height, and spacing among the promoters. The electrolyte consists of copper sulfate and sulphuric acid. At a regulated flow rate, the electrolyte is pumped from the recirculation tank to the cell through an intermediate overhead tank. The limiting current density increased with an increasing flow rate in the presence of promoters, and thus the overall mass transfer coefficient on the cathode support plate also improved. With an increase in the flow rate of the electrolyte from 6.67 × 10−6 to 153.33 m3/s, limiting current density increased from 356.8 to 488.8 A/m2 for spacing of 0.30 m, with a promoter height of 0.01 m. However, it is noteworthy that when the promoter height is increased from 0.01 to 0.07 m, the overall mass transfer coefficient is found to increase up to 60%, but with the further increase in the promoter height to 0.30 m the mass transfer coefficient starts to decrease. Therefore, the optimized cell parameters are established in this work. The current sustainable concept of employing rectangular turbulence promoters will bring benefits to any precious metal refining or electrowinning tank house electrolytes.

Interplay between Mechanical and Electrochemical Properties of Block Copolymer Electrolytes and its Effect on Stability against Lithium Metal Electrodes

We have studied the cycle life of two polyhedral oligomeric silsesquioxane-b-poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (POSS-PEO-POSS) block copolymer electrolytes differing primarily in molecular weights and composition using lithium/polymer/lithium symmetric cells. The higher molecular weight electrolyte, labeled H, has a higher storage modulus, Gel. However, the volume fraction of the conducting phase in the low molecular weight electrolyte, labeled L, is higher and this leads to a four-fold increase in limiting current density, iL. Measurement of ionic conductivity provides insight into the reason for the observed differences in limiting current density. The average lifetime of symmetric cells with electrolyte L was slightly higher than that of cells with electrolyte H. The combined effect of mechanical and electrochemical properties of electrolytes on the stability of lithium electrodeposition was quantified by examining two dimensionless parameters, i/iL and Gel/GLi, introduced in the theory developed by Barai and Srinivasan [Phys. Chem. Chem. Phys., 19, 20493–20505 (2017)]. This theory predicts the regime of stable lithium electrodeposition as a function of these two parameters. Despite large differences in Gel and iL between the two electrolytes, we show that similar cell lifetimes are consistent with the theoretical predictions of unstable lithium electrodeposition without resorting to any adjustable parameters.

Effect of Temperature on Diluate Water in Batch Electrodialysis Reversal

A high percentage of the agricultural wells in the state of Sonora are overexploited, thus generating a significant degree of saline intrusion and abandonment by nearby communities. In this paper, the effect of temperature on the final concentration of diluted water was evaluated with variations in voltage and input concentration in a batch electrodialysis reversal (EDR) process in order to find the optimal operating conditions, with an emphasis on reducing the energy consumption and cost of desalinated water. Thirty-six samples were prepared: eighteen samples of 2000 mg/L total dissolved solids (TDS) and eighteen samples of 5000 mg/L TDS; brackish well water of 639 mg/L TDS and synthetic salt were mixed to obtain these concentrations. Three different temperatures (25, 30, and 35 °C) and two different voltages (10 and 20 V) were tested for each sample after evaluating the limiting current density. The best salt removal occurred in the 20 V sets, with 18.34% higher removal for the 2000 mg/L TDS experiments and 25.05% for the 5000 mg/L experiments (average between the 25 to 35 °C tests). The temperature positively affected the EDR, especially in the experiments at 10 V, where increasing by 10 °C increased the efficiency by 10.83% and 24.69% for 2000 and 5000 mg/L TDS, respectively. The energy consumption was lower with increasing temperature (35 °C), as it decreased by 1.405% and 1.613% for the 2000 and 5000 mg/L TDS concentrations, respectively (average between the 10 and 20 V tests), thus decreasing the cost per m3 of water.

Localized Electroconvection at Ion-Exchange Membranes with Heterogeneous Surface Charge

Operating electrochemical membrane processes beyond the limiting current density bears the potential to decrease the investment cost of desalination plants significantly. However, while there are strategies for successfully reducing energy demand by shortening the plateau region, their influence on the formation of electroconvection is still unknown. This study demonstrates control over the electroconvective vortices' rotational direction and position using a surface patterning method. We compare the development of electroconvection at two membranes modified with patterns of different surface charges. We analyze the electroconvective vortex field's build-up, the vortices' rotational direction, and structural stability in the steady-state. Finally, we showcase the control possibilities by enforcing a specific structure along an asymmetric letter pattern. Such tailor-made patterns have the potential to diminish the plateau region's energy loss completely. Furthermore, the scale-up of these membranes to industrial processes will allow the economic operation in the overlimiting regime, significantly increasing their space-time yield.

Flow field designs developed by comprehensive CFD model decrease system costs of vanadium redox-flow batteries

Different flow field designs are known for vanadium redox-flow batteries (VFB). The best possible design to fulfil a variety of target parameters depends on the boundary conditions. Starting from an exemplary interdigitated flow field design, its channel and land dimensions are varied to investigate the impact on pressure drop, channel volume, flow uniformity and limiting current density. To find a desirable compromise between these several partly contrary requirements, the total costs of the VFB system are evaluated in dependence of the flow field’s dimensions. The total costs are composed of the electrolyte, production and component costs. For those, the production technique (injection moulding or milling), the pump and nominal power density as well as depth of discharge are determined. Finally, flow field designs are achieved, which lead to significantly reduced costs. The presented method is applicable for the design process of other flow fields and types of flow batteries. Graphical abstract

Low concentrated green NaClO: influence of cathode material on kinetic regularities of electrolysis

Kinetic regularities of cathode processes during electrolysis of low concentrated NaCl solutions have been investigated in this work. It was shown that the reduction of hypochlorite ion on platinum in the concentration range up to 0.015 M is limited by the diffusion stage as evidenced by linear dependence of the reciprocal limiting current density versus reciprocal square root of the electrode rotation rate. The diffusion coefficient of ClO– ions to the Pt-RDE surface was calculated from the Koutecki-Levich equation and it was 6.610–6 cm2 s–1. It was stated that the cathode material has a significant effect on the overvoltage of hypochlorite ion reduction. For example, on platinum, the beginning of the current increase corresponding to the reduction of ClO– is observed at +0.3 V, whereas it is –0.25 V on steel and nickel and –0.8 V on titanium. The preparation of a platinum electrode, which affects the texture and condition of the surface, also affects the reduction potential of the hypochlorite ion. Thus, the current increase is observed at +0.1 V on a molded and machined Pt-RDE, while the growth of the current is observed at +0.3 V on a flat Pt electrode etched in aqua regia. The potentials of the beginning of hydrogen evolution are practically indistinguishable. It was shown that the electrolysis of NaCl solutions in an undivided cell should be performed at the maximum possible cathode current densities in order to minimize sodium hypochlorite losses due to its reduction at the cathode and reduce the rate of chlorate accumulation.

Layer-by-Layer Coating of MK-40 Heterogeneous Membrane with Polyelectrolytes Creates Samples with Low Electrical Resistance and Weak Generation of H+ and OH− Ions

Ion exchange membranes covered with layers of polyelectrolytes of alternating charges are characterized by very high monovalent selectivity. This allows the use of such membranes for electrodialytic fractionation of multicomponent solutions. However, the very existence of the boundary at which differently charged layers come in contact can hinder a membrane’s effectiveness by limiting its ion permeability, raising levels of H+ and OH− ions (thus shifting the pH) and increasing the electrical resistance of the membrane, which leads to increased energy consumption. To test how these properties would be changed, we created cheap layer-by-layer-modified membranes based on the heterogeneous MK-40 membrane, on which we adsorbed layers of polyallylamine and sulfonated polystyrene. We created samples with 3, 4, and 5 layers of polyelectrolytes and characterized them. We showed that the application of layers did not decrease the efficiency of the membrane, since the electrical resistance of the modified samples, which increased after application of the first oppositely charged layer, declined with the application of the following layers and became comparable to that of the substrate, while their limiting current density was higher and the shift of pH of treated solution was low in magnitude and comparable with that of the substrate membrane.