Transport Properties Of Electrolyte Solutions Research Articles

Ionic Conduction and Speciation in LiPF6 and LiBF4 Dimethyl Sulfoxide Electrolytes: Comparison with Propylene Carbonate Electrolytes

Innovative Li-ion battery technology requires a fundamental understanding of the intricate ion–ion and ion–solvent interactions that govern the ion transport properties of electrolyte solutions. This study investigates the ion conduction and solution structure of 0.1–3.0 M LiPF6 and LiBF4 dimethyl sulfoxide (DMSO) solutions using Raman, dielectric relaxation, and pulsed-field gradient nuclear magnetic resonance spectroscopies for a comparison with a previous work on propylene carbonate (PC) solutions. Notably, LiBF4–DMSO displays higher ion conductivity than LiPF6–DMSO, whereas LiBF4–PC exhibits lower conductivity than LiPF6–PC. This different conductivity trend is rationalized by the interplay between solution viscosity and the degree of salt dissociation. In DMSO solution, viscosity governs the ion conductivity as salts readily dissociate into free ions and solvent-shared ion pairs owing to the high donor number of DMSO solvent. In contrast, the number of charge carriers determines the conductivity in PC solution, where charge-neutral contact ion pairs are dominant due to the low donicity of PC. Moreover, the conductivity of the DMSO solutions obeys the Nernst–Einstein (NE) theory, whereas that of LiBF4–PC deviates from the NE theory. This study underscores the crucial role of the microscopic solution structure in determining the ionic conduction of electrolyte solutions.

How does the solvent composition influence the transport properties of electrolyte solutions? LiPF6 and LiFSA in EC and DMC binary solvent.

In this study, we experimentally measured the viscosity, η, and ionic conductivity, σ, of the electrolyte solutions of 1 mol kg-1 of LiPF6 or LiFSA dissolved in the binary mixture solvent of EC and DMC in a temperature range of 288 ≤ T/K ≤ 328 by varying the EC content from 0 to 60 vol%, which translates into the molar fraction of EC of 0 ≤ xEC ≤ 0.7. The diffusion coefficient, D, of each species, Li+, PF6-, FSA-, EC and DMC, was determined by pulse gradient spin-echo NMR. The state of molecules around Li+ was examined using the Raman spectra of the solvents and anions; the quantitative analysis suggests that EC is about twice as much preferred as DMC in the solvation shell at low xEC, while the EC-preference decreases with an increase in xEC. The classical Stokes-Einstein relation still quantitatively holds when evaluating the hydrodynamic radius, rSt, of transporting entities from D and η, in that (i) rSt,EC and rSt,DMC without the solute do not significantly differ from those in the solution; (ii) rSt,Li roughly coincides with the size estimated from the solvation number determined by Raman spectroscopy, which implies that rSt,Li reflects the solvation shell size; and (iii) rSt,anion is close to the static size, suggesting that anions are little solvated. The increase in xEC results in a decrease in rSt for all species, among which anions are most influenced, which is consistent with the view that the highly Li+-solvating EC, with its better dielectric shielding effect than DMC, liberates the anions from Li+, whereby enhancing the anion transfer that positively contributes to the ionic conductivity until the viscosity prevails at high xEC.

How Does the Solvent Composition Influence the Transport Properties of Electrolyte Solutions?

The electrolyte solutions used in lithium ion batteries have been optimized based on the empirical knowledge and concept. Yet the ion transport phenomena in the electrolyte solution, which composed of mixed solvent with salt concentration of about 1 mol kg−1, are complicated and significantly different from those in dilute solutions. In the present study, the characteristics of the electrolyte solutions are reanalyzed by using physical and spectroscopic data for the electrolyte solutions, which were obtained from our experiment, and by referring to recent theoretical studies 1,2) and the experimentally determined diffusion coefficient in previous studies 3,4).We experimentally measured the viscosity η and ionic conductivity σ of the electrolyte solutions of 1 mol kg−1 of LiPF6 and lithium bis(fluorosulfonyl)imide (LiFSA) dissolved in the binary mixture solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) in the temperature range of 288 ≤ T/K ≤ 328 with varying the EC content from 0 to 60 vol.%, which translates into the molar fraction of EC in 0 ≤ x EC ≤ 0.6 and the solute to solvent ratio constant (total ca. 11 solvent molecules are present per solute in the system). The diffusion coefficients D of each species, Li+, PF6, FSA−, EC and DMC, were determined by pulse gradient spin echo NMR. The state of molecules around Li+ was examined by the Raman spectra of the solvents and anions.With the increase in x EC, DMC solvating Li+ is replaced by EC, resulting in the increase in the total number of solvents around Li+. Reanalysis of Raman spectra based on Borodin's calculations 2) reassessed the solvation numbers and confirmed that the preferential coordination of EC to Li+, but the extent of the preference was not as strong as previously conceived. The addition of EC, more viscous fluid than DMC, into the system leads to the increase in η, which should be responsible for the monotonous decrease in D of all the species with x EC. On the other hand, σ initially increases until marking the maximum at x EC = ~0.3. The opposite trend between D and σ, i.e., dD/dx EC < 0 while dσ/dx EC > 0, at low x EC suggests that the Nernst-Einstein relation does not hold as it ignores the inter-ionic correlations. The analysis of the Stokes radii r St based on η and D obtained in the present study implies that the increase in x EC results in the decrease in r St for all the species, among which the anions are most influenced. Although only an equivocal picture on the cation-anion correlation, such as the ion pair formation, was obtained from the Raman spectroscopy, the present study is consistent with the view that the highly Li+-solvating EC, with its higher dielectric shielding effect than DMC, liberates the anions from the attraction from Li+, enhancing the cation-anion anti-correlation, which positively contributes to the ionic conductivity until the viscosity prevails at high x EC. The Einstein-Stokes formula and van der Waals radius are certainly "classical" concepts; nonetheless, if properly formulated, they can be consistent with the solvation number obtained from Raman spectra not only qualitatively but also semi-quantitatively. References Borodin, G. V. Zhuang, P. N. Ross and K. Xu, Phys. Chem. C, 117, 7433 – 7444 (2013).Borodin, M. Olguin, P. Ganesh, P. R. C. Kent, J. L. Allen and W. A. Henderson, Chem. Chem. Phys., 18, 164 – 175 (2016).Hayamizu, Y. Aihara, S. Arai, C. Garcia-Martinez, J. Phys. Chem. B, 103, 519 – 524 (1999).Hayamizu, J. Chem. Eng. Data, 57, 2012 – 2017 (2012). Figure 1

Insights into the Transport Properties of Electrolyte Solutions in a Hierarchical Carbon Electrode by Molecular Dynamics Simulations

We report here the transport properties obtained through molecular dynamics simulations of a 1.5 M dimethyl sulfoxide (DMSO) lithium hexafluorophosphate (LiPF6) electrolyte solution confined in a n...

Polarizable Molecular Dynamics and Experiments of 1,2-Dimethoxyethane Electrolytes with Lithium and Sodium Salts: Structure and Transport Properties

The structure and transport properties of electrolyte solutions of 1,2-dimethoxyethane (DME) having salts of Li+ with bis(trifluoromethanesulfonyl)imide ([TFSI]-) or Na+ with [TFSI]- are investigated with polarizable molecular dynamics and experiments. Polarizable force fields for Li+ and Na+ with DME and [TFSI]- were developed based on quantum chemistry calculations, ab initio molecular dynamics simulations, and thermodynamic liquid-state properties. Simulation results for density, viscosity, self-diffusion coefficient, and conductivity of the electrolytes all agree well with the trends and magnitudes of available experimental data for a wide range of salt concentrations. As the concentration of salt increases, the electrolytes become more viscous and molecular species become less mobile. Ionic conductivity does not change monotonically with salt concentration and exhibits a maximum between 0.5 and 1.0 M for both Li[TFSI] and Na[TFSI] electrolytes. Comparatively, both cations are solvated by 5-6 DME or [TFSI]- oxygen atoms and exhibit similar diffusivities and conductivities. The solvation shell of Na+ is found to be more weakly bound and to have a lower binding residence time than that of Li+. The transport of Li+ therefore is more vehicular, through the motion of the solvation shell, while the transport of Na+ is based more on exchange, through the replacement of solvating species. The atomistic insight provided by this work can be used as the basis for future rational design of improved electrolyte solvents for lithium-oxygen, sodium-oxygen, and lithium-sulfur batteries.

A Critical Evaluation of the Advanced Electrolyte Model

A fast and accurate method to obtain transport properties of electrolyte solutions for Li-ion batteries is of great interest for both screening potential electrolyte candidates and for use in physics-based models of Li-ion cells. The Advanced Electrolyte Model (AEM) considers various molecular-scale interactions in a chemical physics framework to calculate these electrolyte transport properties in a computationally inexpensive manner. Should these calculations match experiment well, the AEM would be an ideal tool for the rapid determination of transport properties for various electrolyte systems. This paper aims to evaluate the accuracy of the AEM against experimental viscosity and conductivity data for electrolytes of interest in lithium batteries. Recent measurements, as well as previous measurements of now-obsolete electrolyte systems, are compared to corresponding calculations from the AEM. The availability of accurate laboratory data has allowed for improved accuracy of the AEM theory, molecular parameters and related predictions of properties, in particular for certain systems with low concentrations of ethylene carbonate (i.e. low permittivity electrolytes), as well as systems containing the salt Li triflate or the solvent sulfolane. The model now provides accurate calculations for the transport properties of most of the different systems considered here.

In Situ NMR Imaging of Ion Transport in Li-Ion Batteries

The operation of battery management systems requires that the transient conditions experienced by a battery in electrified vehicle applications can be accurately described through battery modeling. Reliable data on the transport properties of electrolyte solutions, as functions of both salt concentration and temperature, are a prerequisite for such a task. The accurate characterization of the transport parameters is a complex problem, because the values of ionic diffusion coefficients in an electrolyte solution depend strongly on the salt concentration. At the same time, the salt concentration inside a battery is neither stationary nor homogeneous, during battery operation at high charge/discharge rates. It is, rather, a function of current density, time and distance from the electrodes. Recently, MRI was used for in operando characterization of materials used in Li-ion batteries. The main advantage of MRI over commonly used methods, such as NMR and electrochemical techniques, is its ability to provide spatially resolved details regarding the chemical and dynamic features of solution species. Therefore, such data enable a more accurate representation of the processes occurring in an electrolyte solution under an applied electrical potential, instead of values averaged over the entire volume of a sample cell. Using in situ MRI, we have unambiguously mapped the large concentration polarization experienced by an electrolyte solutions during battery operation.1 The concentration gradient created in the electrolyte solution of the cell under galvanostatic conditions will increase until a steady-state (time invariant) condition is achieved, when the diffusion flux compensates for the migration flux of the ions. Our results confirm that the concentration gradient developed under such conditions is proportional to the applied current (Fig. 1b) as described by the diffusion-migration equation (Eqn. 1), where i is the current density and F is the Faraday constant.2 We have shown previously that, while the degree of ion pairing is quite high (up to 67%) in electrolyte solutions under normal operating conditions, it is almost constant during a steady-state NMR gradient measurements (with salt concentrations varying from 0.8 to 1.2 M).3 Therefore, one can use averaged diffusion coefficients of charged and neutral species measured by pulsed field gradient NMR (PFG-NMR) in Eqn. 1. Also the total salt concentration, obtained directly by MRI should be used, instead of concentration of free ions.2 The inverse modeling of evolution of salt concentration profiles measured by in situ MRI under applied electric current also supported this conclusion.4 Therefore, by combining the PFG-NMR and the in situ MRI techniques into one experiment, one can simultaneously determine the distribution of salt concentration and the salt diffusivity in the electrolyte solution during a galvanostatic experiment (Fig. 2). It can be readily seen that the diffusion coefficient has a significant dependence on the salt concentration, with the values of D measured at opposite ends of the cell varying by more than 60%. Such changes obviously must be taken into account in order to provide an accurate description of mass-transport. The Li+ transference number (t+ ) can then be obtained by means of Eqn.(1). A slight decrease in t+ with concentration was observed, which can be explained by an increase in ion association. However, with the exception of data point at the lowest concentration, all of values of the Li+ transference numbers thus obtained fall within the experimental error and t += 0.31 ± 0.03. The formed concentration gradient affects not only the mass transport in electrolyte solution, but also the electrode lithiation. The electrolyte depletion prevents the active material in the solid from being lithiated in regions where electrolyte has been depleted. Furthermore, when the electrolyte concentration approaches zero, its conductivity drops, significantly hampering the process. The current tends to flow into the particles nearest the separator until they are completely lithiated, causing the intercalation reaction to occur preferentially at the front of the electrode. Implementation of pure phase-encoding MRI methods allows us to visualize non-uniform lithiation of the graphite electrode during cycling of Li-ion cell (Fig. 1c), leading to the next level of battery performance characterization.

In Situ NMR Imaging: A Tool for Characterizing Ion Transport Properties in Li-Ion Battery Electrolyte Solutions

The operation of battery management systems requires that the transient conditions experienced by a battery cell in electrified vehicle applications can be accurately described through battery modeling [1]. Reliable data on the transport properties of electrolyte solutions, as functions of both salt concentration and temperature, are a prerequisite for accurate electrochemical modeling. Complicating the acquisition of such reliable data is the fact that Li-ion battery (LIB) electrolyte solutions can experience large concentration polarizations during battery operation, due to fairly low values of the Li+ cation transference number (t+ ) and the salt diffusivity (D), particularly during battery operation at high charge/discharge rates or at low temperatures. While modern computerized instrumentation makes specific conductivity and viscosity measurements routine, this is not the case for diffusivity and transference number measurements. In order to determine the latter two transport properties, we apply the in situ magnetic resonance imaging (MRI) technique [2] for the in-operando visualisation of the steady-state ion concentration in LIB electrolytes during the application of a constant current. Our results confirm that the concentration gradient developed is proportional to the applied current (Fig. 1) as described by the diffusion-migration equation under steady-state conditions (Eqn. 1), where i is the current density and F is the Faraday constant. Taking into account that ∂c/∂x is the salt concentration gradient obtained from imaging, the task of determining t +(c) and D(c) is reduced to measuring of the concentration dependence of the diffusivity D(c). We showed previously that salt diffusivity can be accurately determined as the harmonic mean of the cation and anion diffusion coefficients as measured by pulsed-field gradient NMR (PFG NMR) [3]. By combining the PFG NMR and MRI techniques into one experiment, we can determine the salt concentration and the salt diffusivity of the electrolyte during the application of a constant current (Fig. 2). It can be readily seen that the diffusion coefficient has a significant dependence on the salt concentration, with the values of D measured at opposite ends of the cell varying by more than 60%. This conclusion is in good agreement with our previous results obtained by in situ, slice-selective NMR diffusion measurements [4]. On the other hand the lithium transference number varies less with salt concentration [3]. From the experimentally derived D and concentration profiles one obtains t+ = 0.31 ± 0.03, by using Eqn. (1).

Determining the Transport Properties of Electrolyte Solutions By in-Situ NMR Imaging and Inverse Modeling

We used NMR imaging (MRI) combined with a data analysis by modeling of the inverse mass transport problem, to determine salt diffusion coefficients D+ and transference numbers t+ in electrolyte solutions of interest for Li-ion batteries. Sensitivity analyses have shown that accurate estimates of these parameters (as a function of concentration) are critical to the reliability of the predictions provided by models of porous electrodes. The inverse modeling (IM) solution was generated with an extension of the Planck-Nernst model for the transport of ionic species in electrolyte solutions. Concentration dependent diffusion coefficients and transference numbers were derived using concentration profiles obtained from in-situ 19F MRI measurements. Material properties were reconstructed with minimal assumptions, using methods of variational optimization to minimize the least-square deviation between experimental and simulated concentration values. Diffusion coefficients obtained by pulsed field gradient NMR (PFG NMR) fall within the 95% confidence bounds for the diffusion coefficient values obtained by the MRI+IM method. This demonstrates that PFG NMR determines chemical (Fickian) diffusion coefficients in concentrated electrolyte solutions and not self-diffusion coefficients. The MRI+IM method also yields the concentration dependence of the Li+transference number in agreement with trends obtained by electrochemical methods for similar systems and with predictions of theoretical models for concentrated electrolyte solutions, in marked contrast to the salt concentration dependence of transport numbers determined from PFG NMR data. Acknowledgements The authors acknowledge funding through the NSERC APC program and GM of Canada. Figure 1

A unifying mode-coupling theory for transport properties of electrolyte solutions. II. Results for equal-sized ions electrolytes

On the basis of a versatile mode-coupling theory (MCT) method developed in Paper I [C. Contreras Aburto and G. Nägele, J. Chem. Phys. 139, 134109 (2013)], we investigate the concentration dependence of conduction-diffusion linear transport properties for a symmetric binary electrolyte solution. The ions are treated in this method as charged Brownian spheres, and the solvent-mediated ion-ion hydrodynamic interactions are accounted for also in the ion atmosphere relaxation effect. By means of a simplified solution scheme, convenient semi-analytic MCT expressions are derived for the electrophoretic mobilities, and the molar conductivity, of an electrolyte mixture with equal-sized ions. These expressions reduce to the classical Debye-Falkenhagen-Onsager-Fuoss results in the limit of very low ion concentration. The MCT expressions are numerically evaluated for a binary electrolyte, and compared to experimental data and results by another theoretical method. Our analysis encloses, in addition, the electrolyte viscosity. To analyze the dynamic influence of the hydration shell, the significance of mixed slip-stick hydrodynamic surface boundary conditions, and the effect of solvent permeability are explored. For the stick boundary condition employed in the hydrodynamic diffusivity tensors, our theoretical results for the molar conductivity and viscosity of an aqueous 1:1 electrolyte are in good overall agreement with reported experimental data for aqueous NaCl solutions, for concentrations extending even up to two molar.

A unifying mode-coupling theory for transport properties of electrolyte solutions. I. General scheme and limiting laws

We develop a general method for calculating conduction-diffusion transport properties of strong electrolyte mixtures, including specific conductivities, steady-state electrophoretic mobilities, and self-diffusion coefficients. The ions are described as charged Brownian spheres, and the solvent-mediated hydrodynamic interactions (HIs) are also accounted for in the non-instantaneous ion atmosphere relaxation effect. A linear response expression relating long-time partial mobilities to associated dynamic structure factors is employed in our derivation of a general mode coupling theory (MCT) method for the conduction-diffusion properties. A simplified solution scheme for the MCT method is discussed. Analytic results are obtained for transport coefficients of pointlike ions which, for very low ion concentrations, reduce to the Deby-Falkenhagen-Onsager-Fuoss limiting law expressions. As an application, an unusual non-monotonic concentration dependence of the polyion electrophoretic mobility in a mixture of two binary electrolytes is discussed. In addition, leading-order extensions of the limiting law results are derived with HIs included. The present method complements a related MCT method by the authors for the electrolyte viscosity and shear relaxation function [C. Contreras-Aburto and G. Nägele, J. Phys.: Condens. Matter 24, 464108 (2012)], so that a unifying scheme for conduction-diffusion and viscoelastic properties is obtained. We present here the general framework of the method, illustrating its versatility for conditions where fully analytic results are obtainable. Numerical results for conduction-diffusion properties and the viscosity of concentrated electrolytes are presented in Paper II [C. Contreras Aburto and G. Nägele, J. Chem. Phys. 139, 134110 (2013)].

Influence of Ion Properties on the Equilibrium and Transport Properties of Electrolyte Solutions

Strong electrolytes are described in the framework of the primitive model in which the solvent is regarded as a dielectric continuum, using the mean spherical approximation. The analytical solution of the equilibrium and transport properties is dependent on the ions' diameters and valencies. For hydrated or nonspherical ions, an effective diameter must be fitted. A sensitivity study of the osmotic coefficient and the transport coefficients is performed on theoretical 1-1, 2-1, and 3-1 electrolytes, up to a total ion concentration of 2 mol/L.

Self-diffusion coefficients of ions in primitive model electrolyte solutions by smart Brownian dynamics simulation

The structural properties and transport properties of electrolyte solutions are investigated by smart Brownian dynamics simulation based on the primitive model. To test the simulation program, the radial distribution functions of ions g+−(r) and g++(r) for KCl solution are calculated and compared with the results of previous simulations. And then, the effects of ions diameter and concentration on the structural properties and transport properties of electrolyte solution at 298K are extensively simulated. The results indicate that both the radial distribution function and the self-diffusion coefficient are more sensitive to the ion size than salt concentration. As the radius ratio of cation to anion increases, self-diffusion coefficients of both cation and anion become larger.

ChemInform Abstract: Beyond the Classical Transport Laws of Electrochemistry: New Microscopic Approach to Ionic Conductance and Viscosity

The concentration dependence of the transport properties (i.e., the conductivity and the viscosity) of an electrolyte solution has been a subject of lively debate for a very long time. The foundation for understanding the transport properties of electrolyte solutions was laid down by Debye, Huckel, Onsager, and Falkenhagen who derived several limiting laws valid at low ion concentration. These classical laws have been rederived several times, although their extension to concentrated solutions has proven to be very difficult. We discuss a new microscopic approach toward understanding the transport laws of electrochemistry. This new approach is based on the general ideas of the mode coupling theory. We show that the mode coupling theory approach is appropriate in the present case because concentration effects arise from collective variables (like charge density and current) which are treated correctly by the mode coupling theory. The new theory can describe the crossover from the low to high concentration seamlessly. Our study yields microscopic expressions of both conductivity and viscosity in terms of static and dynamic structure factors of the charge and number densities of the electrolyte solution. The celebrated expressions of Debye, Huckel, and Onsager for static conductance, of Debye and Falkenhagen for frequency dependent electrolyte friction, and of Falkenhagen for the viscosity follow exactly from the present microscopic theory in the limit of very low ion concentration. Recently derived microscopic expressions of Chandra, Wei, and Patey for the frequency dependent conductivity can also be derived from the present scheme. The present theory is a self-consistent theory. For conductance, the agreement of the present theory with experimental results is satisfactory even up to one molar concentration. For viscosity, the theory seems to give the right trend and suggests directions for further improvement to explain the myriad of unexplained behavior known for a long time.

Beyond the Classical Transport Laws of Electrochemistry: New Microscopic Approach to Ionic Conductance and Viscosity

The concentration dependence of the transport properties (i.e., the conductivity and the viscosity) of an electrolyte solution has been a subject of lively debate for a very long time. The foundation for understanding the transport properties of electrolyte solutions was laid down by Debye, Huckel, Onsager, and Falkenhagen who derived several limiting laws valid at low ion concentration. These classical laws have been rederived several times, although their extension to concentrated solutions has proven to be very difficult. We discuss a new microscopic approach toward understanding the transport laws of electrochemistry. This new approach is based on the general ideas of the mode coupling theory. We show that the mode coupling theory approach is appropriate in the present case because concentration effects arise from collective variables (like charge density and current) which are treated correctly by the mode coupling theory. The new theory can describe the crossover from the low to high concentration seamlessly. Our study yields microscopic expressions of both conductivity and viscosity in terms of static and dynamic structure factors of the charge and number densities of the electrolyte solution. The celebrated expressions of Debye, Huckel, and Onsager for static conductance, of Debye and Falkenhagen for frequency dependent electrolyte friction, and of Falkenhagen for the viscosity follow exactly from the present microscopic theory in the limit of very low ion concentration. Recently derived microscopic expressions of Chandra, Wei, and Patey for the frequency dependent conductivity can also be derived from the present scheme. The present theory is a self-consistent theory. For conductance, the agreement of the present theory with experimental results is satisfactory even up to one molar concentration. For viscosity, the theory seems to give the right trend and suggests directions for further improvement to explain the myriad of unexplained behavior known for a long time.

Inferences on dynamic water structure in aqueous solutions from diffusion measurements

The dynamic, hydrogen-bonded structure of water can be profoundly affected by addition of solutes as reflected by the resulting solute—solvent interactions. Measurements of diffusion coefficients for the solute species and for water are a useful probe for studying those interactions and changes in the dynamic water structure. The analysis of transport properties of electrolyte solutions is presently approached both theoretically and experimentally by the use of generalised transport coefficients such as Onsager phenomenological coefficients, velocity correlation coefficients or the closely related distinct diffusion coefficients of Friedman. However, two of these approaches generally use a solvent-fixed frame of reference and thereby exclude the information available from studying the diffusion of the solvent. The velocity correlation coefficient approach is used here to examine hydrogen-bonding effects in binary solution containing water as one component. We discuss also examples where intra-diffusion data for water in aqueous solutions give important insights into the dynamic structure of aqueous solutions.

Transport properties and their coupling with ion aggregate formation

Abstract

Data on transport properties of electrolyte solutions for applied research and technology

Abstract

ChemInform Abstract: Calculations of Ionic Contributions of Various Thermodynamic and Transport Properties of Electrolyte Solutions (46 Literaturangaben).

Chemischer InformationsdienstVolume 14, Issue 31 Reviews ChemInform Abstract: Calculations of Ionic Contributions of Various Thermodynamic and Transport Properties of Electrolyte Solutions (46 Literaturangaben). B. S. KRUMGALZ, B. S. KRUMGALZSearch for more papers by this author B. S. KRUMGALZ, B. S. KRUMGALZSearch for more papers by this author First published: August 2, 1983 https://doi.org/10.1002/chin.198331348AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume14, Issue31August 2, 1983 RelatedInformation

Electroanalytical Chemistry of Membranes

I. PERSPECTIVE ON THE ROLES OF MEMBRANE ELECTROCHEMISTRY AND ELECTROANALYTICAL CHEMISTRY The thrust of electrochemistry in the past 25 years has been the study of electrode processes at blocked and unblocked electrodes, primarily metal/electrolyte interfaces. The vast literature which has been contributed by both physical and analytical chemists comprises a topic now known as electrodics to distinguish it from the more classical topics – electrochemical thermodynamics (the study of equilibrium and transport properties of electrochemical cells) and ionics (the study of equilibrium and transport properties of electrolyte solutions) – which occupied a significant number of chemists during the first 50 years of this century. Analytical electrochemists have found their interests expanding as they turn from analytical methodology to fundamental and applied studies within electrodics. Many practical contributions have been made in new and improved battery systems, fuel cells, electrochemical synthesis, electroly...