Membrane capacitive deionization

Membrane capacitive deionization (MCDI) is an ion-removal process based on applying an electrical potential difference across an aqueous solution which flows in between oppositely placed porous electrodes, in front of which ion-exchange membranes are positioned. Due to the applied potential, ions are adsorbed in the electrodes and a product stream with a reduced salt concentration is obtained. Including the membranes in the process has two advantages: first, they block co-ions from leaving the electrodes, thereby increasing the salt removal efficiency of the process, and second, when during ion release a reversed voltage is used, counterions can be more fully flushed from the electrode region, thereby increasing the driving force for ion removal in the next cycle. Here we present pilot-plant experimental data for salt removal in MCDI as function of inlet ionic strength and flow rate. In the subsequent stage of ion release the flow rate is temporarily reduced to zero and the voltage sign reversed. This “stop-flow” operation mode results in a small and concentrated product stream. We present a theoretical process model for MCDI which describes the time-dependent electric current and effluent ion concentration, both during the deionization stage and during the subsequent stage of ion release. The process model describes the MCDI cell as a number of stirred volumes placed in-series, and includes the transport resistance of the ion-exchange membrane and of the stagnant diffusion layer in front of the membrane. Ion storage in the electrodes is described according to the equilibrium Gouy–Chapman–Stern model for the electrostatic double layer.     

Membrane potential of a bipolar membrane: the effect of concentration perturbation of the intermediate phase around a certain value

A new model of a sandwich-type bipolar membrane potential was constructed by assuming the potential behavior of a bipolar membrane as a combination of each layer potential between two different states, i.e. the different concentrations of the bulk solution. Hence, we introduced the coion exclusion parameter that is derived from the Donnan equilibrium as a combinatorial function, which combined all the potential equations involved in our system. We assumed that the existence of the intermediate phase due to its volume would allow the Donnan equilibrium to play an important role, i.e. the vanishing of the coion exclusion effect of the membrane layer facing the bulk solution phase in high concentration. Sandwich-type bipolar membranes, which consist of a cation- (K-501) and an anion-exchange layer (A-501) were used in this study. A series of concentration perturbations of the intermediate phase was performed to examine the membrane potential behavior of the bipolar membrane experimentally. The experimental results showed a good agreement with the theoretical results, which led to the conclusion that explained the contribution of the intermediate phase to the membrane potential behavior through its volume and electrochemical properties.     

Tailoring A Poly(ether sulfone) Bipolar Membrane: Osmotic-Energy Generator with High Power Density

Osmotic energy, obtained through different concentrations of salt solutions, is recognized as a form of a sustainable energy source. In the past years, membranes derived from asymmetric aromatic compounds have attracted attention because of their low cost and high performance in osmotic energy conversion. The membrane formation process, charging state, functional groups, membrane thickness, and the ion-exchange capacity of the membrane could affect the power generation performance. Among asymmetric membranes, a bipolar membrane could largely promote the ion transport. Here, two polymers with the same poly(ether sulfone) main chain but opposite charges were synthesized to prepare bipolar membranes by a nonsolvent-induced phase separation (NIPS) and spin-coating (SC) method. The maximum power density of the bipolar membrane reaches about 6.2 W m⁻² under a 50-fold salinity gradient, and this result can serve as a reference for the design of bipolar membranes for osmotic energy conversion systems.     

Ion Transport in a Three-Layered Ion-Exchange Membrane: A Mathematical Model

An ion transport model is considered. The model is based on the Nernst–Planck equations, the elements of nonequilibrium thermodynamics, the principle of local equilibrium, and the concept of a virtual solution. The model is applied to an ion-exchange membrane with two diffusion layers for the cases of electrotransport of two and three types of ions. To determine transfer coefficients L ^* _j in the Nernst–Planck equations, two approaches are used. In the phenomenological approach, L ^* _j are found from experimental data on the electroconductivity and transport numbers. In the modeling approach, values of L ^* _j are sought for from a model of a microheterogeneous membrane. The obtained boundary-value problem is solved using a numerical method of parallel shooting developed earlier, which perfectly fits specific features of the problem formulation (utilizing the Nernst–Planck equations in all the three layers and the concept of a virtual solution).     

Membrane potential across reverse osmosis membranes under pressure gradient

Membrane potential measurement has been widely used for the characterization of ionic membranes such as ion-exchange membranes without solvent permeability. However, there have been few studies on membrane potentials across pressure-driven processes such as reverse osmosis (RO) membranes with solvent permeability. In the present study, the membrane potential across RO membranes in NaCl and MgCl2 under the pressure gradient, DeltaP=0-0.3 MPa, was measured. The experimental results were analyzed by the theoretical model based on the Donnan equilibrium and the extended Nernst-Planck flux equation considering the pressure effect. The theoretical values agreed well with the experimental ones. This indicates that membrane potential is useful for characterizing the effective charge density of the active layer of RO membranes under pressure gradient.     

Kinetic Parameters of Ion-Exchange Membrane in Amino Acid Solutions

Kinetic parameters of amino acid cations in an MK-40 ion-exchange membrane are calculated from the conductivity data. A theoretical quantum-chemical analysis of experimental activation energies for conduction suggests a mechanism of elementary act of transport of amino acid cations in the membrane.     

A simple currentless method of determination of ion fluxes to and within electroactive ion-exchange membranes

A simple protocol applicable for the determination of ion fluxes from a solution to an ion-exchange membrane and within it was proposed. Advantages of this method include the application of a simple typical potentiometric set-up, as the method uses open circuit potential measurements; thus, the membrane state is not biased by external polarization. The proposed approach is based on the analysis of potential vs. time dependences in the course of building up or disappearance of a diffusion layer in a solution, controlled by solution stirring. Using equations describing diffusion processes, both ion fluxes from a solution to a membrane and within the membrane can be calculated. Experimental studies were carried out on examples of electrodes coated by two different kinds of membranes: (i) poly(vinyl chloride)-based silver-selective membrane and (ii) polypyrrole film doped by poly(4-styrenesulfonate) ions, in solutions of silver ions. The results obtained for non-saturated silver-selective membranes highlight the role of membrane thickness and conditioning time as well as confirm the role of diffusion in the membrane as a rate-determining step. For polypyrrole layers, the ion flux results from silver deposition in the surface part of a conducting polymer film, and the flux value was found consistent with silver deposition rate determined earlier.     

荷电膜的膜电位研究进展

膜电位的测定是表征荷电膜的传递现象的重要参数之一。本文简要介绍了膜电位理论基础,包括T. M. S.理论和不可逆热力学理论。分别阐述了关于离子交换膜、双极膜、两性膜以及复合膜的膜电位的最新进展,并提出今后的发展方向。     

Effect of the Interface Component on Current-voltage Curves of a Composite Bipolar Membrane for Water and Methanol Solutions

The current-voltage curves of a composite bipolar membrane (CBM) were experimentally measured by varying the interface component between cation- and anion-exchange membranes for water and methanol solutions. In each solution system, 0.05 mol/l LiCl was used as the electrolyte. The interface component was varied by pasting the polymers or installing the thin membranes in the intermediate region of the CBM. The measured results show that the functional groups of the polymers and thin membranes enhanced the water and methanol splitting effect. This phenomenon can be explained by the protonation-deprotonation reactions occurring between these functional groups and the water or methanol molecules in the intermediate region of the CBM. The effect of transition metal compounds existing in the intermediate region of the CBM was also experimentally examined in this study. It was found that the effect of transition metal compounds on water or methanol splitting was not obvious. Copyright 1999 Academic Press.     

Experimental and theoretical investigations of steady and transient states in systems of ion exchange bipolar membranes

The electrochemical characteristics of one commercial bipolar ion exchange membrane and of two home-made bipolar membranes are investigated over a range of current densities up to 2 kA m⁻². Studies are performed using galvano-potentiometry (i/V) and impedance spectrometry methods. The temperature dependence of i/V curves enables the determination of the activation energies related to the overall electrochemical process of H⁺ and OH⁻ production by water dissociation at the membrane junction. The physical analysis of the experimental data is made on the basis of a neutral layer model for the membrane junction. The theoretical treatment leads first to establish a thermodynamic framework insuring the validity of the criteria used in the interpretation of the results in terms of the model. Application of current electrochemical kinetic concepts at steady state involves the idea that, in the presence of an efficient catalyst, a quasi-reversible state of the water dissociation reaction may be achieved at the junction. A theoretical approach is developed for treating the data obtained with transient measurements in absence of co-ion transport. This study reveals the intrinsic roles played in the overall process of respectively: (a) the H⁺ and OH⁻ ion transport; (b) the electrical double layers at the membrane junction boundaries; and (c) the chemical mechanism of water dissociation.     

mCMC-PEG/mCS-PEG双极膜的制备与表征

以Fe3+改性羧甲基纤维素(mCMC)和聚乙二醇(PEG)共混为阳膜;以戊二醛改性壳聚糖(mCS)和聚乙二醇共混为阴膜,制备了mCMC-PEG/mCS-PEG双极膜.以FTIR测定了膜红外光谱,以扫描电镜观察了膜表面和界面层的形态,以TG进行膜的热重分析.测定了mCMC-PEG和mCS-PEG不同比例共混膜的含水率、离子交换容量、溶胀度,及mCMC-PEG/mCS-PEG双极膜的电性能.研究结果表明,在双极膜材料中引入亲水性的聚乙二醇后,因分子间的相容性增大,故而提高了双极膜的离子交换容量,并减小了膜的溶胀性.当CMC∶PEG质量比等于10∶1和CS∶PEG质量比等于2∶1时所制得的双极膜具有良好的电化学性能,在酸碱溶液中机械强度高、溶胀小.     

Characterization of ion-exchange membrane materials: properties vs structure

This review focuses on the preparation, structure and applications of ion-exchange membranes formed from various materials and exhibiting various functions (electrodialytic, perfluorinated sulphocation-exchange and novel laboratory-tested membranes). A number of experimental techniques for measuring electrotransport properties as well as the general procedure for membrane testing are also described. The review emphasizes the relationships between membrane structures, physical and chemical properties and mechanisms of electrochemical processes that occur in charged membrane materials. The water content in membranes is considered to be a key factor in the ion and water transfer and in polarization processes in electromembrane systems. We suggest the theoretical approach, which makes it possible to model and characterize the electrochemical properties of heterogeneous membranes using several transport-structural parameters. These parameters are extracted from the experimental dependences of specific electroconductivity and diffusion permeability on concentration. The review covers the most significant experimental and theoretical research on ion-exchange membranes that have been carried out in the Membrane Materials Laboratory of the Kuban State University. These results have been discussed at the conferences "Membrane Electrochemistry", Krasnodar, Russia for many years and were published mainly in Russian scientific sources.     

Effect of ion-exchange nanofiber fabrics on water splitting in bipolar membrane

In the present study, the effect of ion-exchange fiber fabric made by electrospray deposition (ESD) on water splitting in a composite bipolar membrane (CBM) was investigated. Cation- and anion-exchange fiber (CEF and AEF) fabrics, which were composed of very thin fibers, were prepared by ESD and postdeposition chemical modification and then used as the intermediate layer of a CBM. The current-voltage characteristics under reverse bias conditions showed that the AEF fabrics enhanced water splitting. The water dissociation is accelerated by the AEF fabric, which contains both tertiary pyridyl groups and quaternary pyridinium groups and has a high specific surface area. On the other hand, the CEF fabric, which contains sulfonic acid groups and has an insufficient specific surface area, reduced water splitting. These results indicate that fiber fabric with catalytic activity and a high surface area obtained by ESD can improve the performance of a CBM.     

Membrane distillation: theory and experiments

A theoretical approach is presented that describes membrane distillation processes due to the simultaneous action (in a proactive or in a counteractive way) of temperature and concentration differences through porous hydrophobic membranes. The model developed emphasizes the importance of the boundary layers, shows the existence of a coupling term between the two thermodynamic forces acting on the system, and permits the definition and characterization of the so-called steady states. In order to check the model, two membranes have been studied in different experimental conditions. The influence of some relevant parameters, such as solution concentration, stirring rate, mean temperature and temperature difference has been considered and the theoretical predictions of the model have been applied to the obtained results. The accordance may be considered good.     

AC impedance spectra of bipolar membranes: an experimental study

A bipolar membrane (BM) is composed of one cation and one anion ion-exchange layers joined together in series. In order to obtain the AC electrical impedance of a BM, a small sinusoidal current perturbation was superimposed to the DC current, and the resulting frequency-dependent impedance spectra were recorded under different conditions of electrical polarisation and temperature for five BMs. The experimental spectra were measured in three current ranges: below the limiting current region, at the onset of the overlimiting region and in the electric field enhanced water dissociation region. This allows for a better understanding of the contributions of the salt and water ions to the measured impedance spectra. Measurements of the impedance of the forward biased membrane were also carried out. Although the experimental impedance spectra appear to be in qualitative agreement with previous theoretical models incorporating the effect of the electric field enhanced water dissociation, a quantitative analysis of the results is not still possible due to the high number of parameters involved.     

A Study of Concentration Polarization on Ion Exchange Membrane Electrodialysis

The concentration polarization phenomena in ion exchange membrane electrodialysis have been studied with single exchange membrane cell. The limiting current densities of Asahi ion-permselective membranes CK-1 and CK-2, Selemion ion-exchange membranes CMV, AMV, DMV and ASV have been measured with Ag-AgCl reversible electrode in various electrolyte solutions under 25°C and constant flow rate. In sodium chloride solution, the cation exchange membrane is easier to occur concentration polarization than the anion exchange membrane. The limiting current density increases as the concentration of solution increases for the same kind of ion exchange membrane. The experimental limiting current densities of Selemion CMV and AMV in NaCl, KCl, MgCl₂, CaCl₂, BaCl₂, Na₂SO₄, NaOH and HCl aqueous solutions are measured. The results show that the limiting current density increases as the ion mobility and diffusivity increase, and is affected by the transference number of ion. For the mixture of electrolyte solution, there are linear relationship between limiting current density and equivalent fraction of electrolytes.     

Modeling Transport Asymmetry in Bilayered Ion-Exchange Membranes Interacting with Surface-Active Organic Substances

A model is suggested for the electrical mass transfer in bilayered ion-exchange membranes, which accounts for the layers' structure. The concentration polarization in a bilayered system is analyzed and the extreme concentration variations at the boundary between layers with different selectivities are determined. It is shown that the current characteristics and the diffusion penetrability can go asymmetric following a change in the orientation of a bilayered membrane with respect to the ion flow. The asymmetry of an integral diffusion penetrability coefficient is determined quantitatively for ion-exchange membranes modified with surface-active organic substances. It is shown that the proposed approach is adequate for describing transport phenomena in anisotropic membranes with stable layer characteristics.     

An electrical impedance spectroscopic (EIS) study on transport characteristics of ion-exchange membrane systems

This study aimed at investigating ion-exchange membrane systems using impedance spectroscopy. Nyquist plots showed that the impedance obtained in this study described the ion-exchange membrane system well, as consisting of (i) an ion-exchange membrane immersed in solution, (ii) electrical double layers at the membrane surface, and (iii) diffusion boundary layers arising from the interface between the ion-exchange membrane and the electrolyte solutions. Taking into account the physical and electrochemical understanding of the ion-exchange membrane system, an equivalent circuit was suggested to quantitatively analyze each component of the ion-exchange membrane system. To confirm the reliability of the proposed equivalent circuit, the resistance and capacitance were estimated from the impedance data and the values were compared with other experimental results (e.g., I-V curves). The comparison showed good agreement and validated the equivalent circuit. Moreover, the impedance measurements made it possible to confirm the electroconvective effects in the over LCD region.     

Membrane potential across low-water-content charged membranes: Effect of ion pairing

In the present paper, we systematically examined the ion-pairing effect in low-water-content charged membranes. Cation- and anion-exchange membranes with various water contents and homogeneous fixed-charge distribution were prepared by radical copolymerization and then characterized by membrane potential measurements. The experimental results were analyzed by our recently developed theoretical model (Yamamoto, R.; Matsumoto, H.; Tanioka, A. J. Phys. Chem. B 2003, 107, 10615), which is based on the Donnan equilibrium, the Nernst-Planck equation for ion flux, and the Fuoss formalism for ion-pair formation between the fixed-charge group and the counterion in the membrane. The theoretical predictions agreed well with the experimental results for both cation- and anion-exchange membranes. This supported the belief that the ion-pairing effect was substantial in a low-water-content membrane system. Our theoretical analysis also showed the following results: (i) the dielectric constant in the membrane, epsilon(r), was smaller than the value in bulk water, (ii) the center-to-center distance of the ion pair, a, was independent of the water content of the membranes, and (iii) the charge effectiveness of all membranes, Q, was small (<0.35).