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- ItemOvercoming the shortcomings of the Nernst-Planck model(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2012) Dreyer, Wolfgang; Guhlke, Clemens; Müller, RüdigerThis is a study on electrolytes that takes a thermodynamically consistent coupling between mechanics and diffusion into account. It removes some inherent deficiencies of the popular Nernst-Planck model. A boundary problem for equilibrium processes is used to illustrate the new features of our model.
- ItemAnalysis of improved Nernst-Planck-Poisson models of compressible isothermal electrolytes. Part II: Approximation and a priori estimates(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2017) Dreyer, Wolfgang; Druet, Pierre-Étienne; Gajewski, Paul; Guhlke, ClemensWe consider an improved NernstPlanckPoisson model first proposed by Dreyer et al. in 2013 for compressible isothermal electrolytes in non equilibrium. The model takes into account the elastic deformation of the medium that induces an inherent coupling of mass and momentum transport. The model consists of convectiondiffusionreaction equations for the constituents of the mixture, of the Navier-Stokes equation for the barycentric velocity, and of the Poisson equation for the electrical potential. Due to the principle of mass conservation, crossdiffusion phenomena must occur and the mobility matrix (Onsager matrix) has a kernel. In this paper, which continues the investigation of [DDGG17a], we derive for thermodynamically consistent approximation schemes the natural uniform estimates associated with the dissipations. Our results essentially improve our former study [DDGG16], in particular the a priori estimates concerning the relative chemical potentials.
- ItemA new perspective on the electron transfer: Recovering the Butler-Volmer equation in non-equilibrium thermodynamics(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2015) Dreyer, Wolfgang; Guhlke, Clemens; Müller, RüdigerUnderstanding and correct mathematical description of electron transfer reaction is a central question in electrochemistry. Typically the electron transfer reactions are described by the Butler-Volmer equation which has its origin in kinetic theories. The Butler-Volmer equation relates interfacial reaction rates to bulk quantities like the electrostatic potential and electrolyte concentrations. Since in the classical form, the validity of the Butler-Volmer equation is limited to some simple electrochemical systems, many attempts have been made to generalize the Butler-Volmer equation. Based on non-equilibrium thermodynamics we have recently derived a reduced model for the electrode-electrolyte interface. This reduced model includes surface reactions and adsorption but does not resolve the charge layer at the interface. Instead it is locally electroneutral and consistently incorporates all features of the double layer into a set of interface conditions. In the context of this reduced model we are able to derive a general Butler-Volmer equation. We discuss the application of the new Butler-Volmer equations to different scenarios like electron transfer reactions at metal electrodes, the intercalation process in lithium-iron-phosphate electrodes and adsorption processes. We illustrate the theory by an example of electroplating.
- ItemAnalysis of improved Nernst-Planck-Poisson models of compressible isothermal electrolytes. Part I: Derivation of the model and survey of the results(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2017) Dreyer, Wolfgang; Druet, Pierre-Étienne; Gajewski, Paul; Guhlke, ClemensWe consider an improved NernstPlanckPoisson model first proposed by Dreyer et al. in 2013 for compressible isothermal electrolytes in non equilibrium. The model takes into account the elastic deformation of the medium that induces an inherent coupling of mass and momentum transport. The model consists of convectiondiffusionreaction equations for the constituents of the mixture, of the Navier-Stokes equation for the barycentric velocity, and of the Poisson equation for the electrical potential. Due to the principle of mass conservation, crossdiffusion phenomena must occur and the mobility matrix (Onsager matrix) has a kernel. In this paper we establish the existence of a globalintime weak solution for the full model, allowing for a general structure of the mobility tensor and for chemical reactions with highly non linear rates in the bulk and on the active boundary. We characterise the singular states of the system, showing that the chemical species can vanish only globally in space, and that this phenomenon must be concentrated in a compact set of measure zero in time. With respect to our former study [DDGG16], we also essentially improve the a priori estimates, in particular concerning the relative chemical potentials.
- ItemA mixture theory of electrolytes containing solvation effects(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2013) Dreyer, Wolfgang; Guhlke, Clemens; Landstorfer, ManuelIn this work we present a new mixture theory of a liquid solvent containing completely dissociated ions to study the space charge layer of electrolytes in contact with some inert metal. We incorporate solvation shell effects (i) in our derivation of the mixing entropy and (ii) in the pressure model. Chemical potentials of ions and solvent molecules in the incompressible limit are then derived from a free energy function. For the thermodynamic equilibrium the coupled equation system of mass and momentum balance, the incompressibility constraint and the Poisson equation are summarized. With that we study the space charge layer of the electrolytic solution for an applied half cell potential and compare our results to historic and recent interpretations of the double layer in liquid electrolytes. The novelties of the new model are: (i) coupling of momentum- and mass-balance equations, (ii) calculation of entropic contributions due to solvated ions and (iii) the potential and pressure dependence of the free charge density in equilibrium.
- ItemExistence of weak solutions for improved Nernst-Planck-Poisson models of compressible reacting electrolytes(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2016) Dreyer, Wolfgang; Druet, Pierre-Étienne; Gajewski, Paul; Guhlke, ClemensWe consider an improved Nernst-Planck-Poisson model for compressible electrolytes first proposed by Dreyer et al. in 2013. The model takes into account the elastic deformation of the medium. In particular, large pressure contributions near electrochemical interfaces induce an inherent coupling of mass and momentum transport. The model consists of convection-diffusion-reaction equations for the constituents of the mixture, of the Navier-Stokes equation for the barycentric velocity and the Poisson equation for the electrical potential. Cross-diffusion phenomena occur due to the principle of mass conservation. Moreover, the diffusion matrix (mobility matrix) has a zero eigenvalue, meaning that the system is degenerate parabolic. In this paper we establish the existence of a global-in-time weak solution for the full model, allowing for cross-diffusion and an arbitrary number of chemical reactions in the bulk and on the active boundary.
- ItemThe impact of solvation and dissociation on the transport parameters of liquid electrolytes: Continuum modeling and numerical study(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2018) Dreyer, Wolfgang; Guhlke, Clemens; Müller, RüdigerElectro-thermodynamics provides a consistent framework to derive continuum models for electrochemical systems. For the application to a specific experimental system, the general model must be equipped with two additional ingredients: a free energy model to calculate the chemical potentials and a kinetic model for the kinetic coefficients. Suitable free energy models for liquid electrolytes incorporating ion-solvent interaction, finite ion sizes and solvation already exist and have been validated against experimental measurements. In this work, we focus on the modeling of the mobility coefficients based on MaxwellStefan setting and incorporate them into the general electro-thermodynamic framework. Moreover, we discuss the impact of model parameter on conductivity, transference numbers and salt diffusion coefficient. In particular, the focus is set on the solvation of ions and incomplete dissociation of a non-dilute electrolyte.
- ItemHysteresis and phase transition in many-particle storage systems(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2010) Dreyer, Wolfgang; Guhlke, Clemens; Herrmann, MichaelWe study the behavior of systems consisting of ensembles of interconnected storage particles. Our examples concern the storage of lithium in many-particle electrodes of rechargeable lithium-ion batteries and the storage of air in a system of interconnected rubber balloons. We are particularly interested in those storage systems whose constituents exhibit non-monotone material behavior leading to transitions between two coexisting phases and to hysteresis. In the current study we consider the case that the time to approach equilibrium of a single storage particle is much smaller than the time for full charging of the ensemble. In this regime the evolution of the probability to find a particle of the ensemble in a certain state, may be described by a nonlocal conservation law of Fokker-Planck type. Two constant parameter control whether the ensemble transits the 2-phase region along a Maxwell line or along a hysteresis path or if the ensemble shows the same non-monotone behavior as its constituents.
- ItemHysteresis in the context of hydrogen storage and lithium-ion batteries(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2009) Dreyer, Wolfgang; Guhlke, Clemens; Huth, RobertThe processes of reversible storage of hydrogen in a metal by loading and unloading and of charging and discharging of lithium-ion batteries have many things in common. The both processes are accompanied by a phase transition and loading and unloading run along different paths, so that hysteretic behavior is observed. For hydrogen storage we consider a fine powder of magnesium (Mg) particles and lithium storage is studied for iron phosphate (FePO_4) particles forming the cathode of a lithium-ion battery. The mathematical models that are established in citeDGJ08 and citeDGH09a, describe phase transitions and hysteresis exclusively in a single particle and on that basis they can predict the observed hysteretic plots with almost horizontal plateaus. Interestingly the models predict that the coexistence of a 2-phase system in an individual particle disappears, if its size is below a critical value. However, measurements reveal that this is qualitatively not reflected by the mentioned hysteretic plots of loading and unloading. In other words: The behavior of a storage system consisting of many particles is qualitatively independent of the fact whether the individual particles itself develop a 2-phase system or if they remain in a single phase state. This apparent paradoxical observation will be resolved in this article. It will be shown that if each of the individual particles homogeneously distributes the supplied matter, nevertheless the many particle ensemble exhibits phase transition and hysteresis, because one of the two phases is realized in some part of the particles while the remaining part is in the other phase.
- ItemRational modeling of electrochemical double-layers and derivation of Butler-Volmer equations(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2013) Dreyer, Wolfgang; Guhlke, Clemens; Müller, RüdigerWe derive the boundary conditions for the contact between an electrolyte and a solid electrode. At first we revisit the thermodynamic consistent complete model that resolves the actual electrodeelectrolyte interface and its adjacent boundary layers. The width of these layers is controlled by the Debye length that is typically very small, leading to strongly different length scales in the system. We apply the method of asymptotic analysis to derive a simpler reduced model that does not resolve the boundary layers but instead incorporates the electrochemical properties of the layers into a set of new boundary conditions. This approach fully determines the relation of bulk quantities to the boundary conditions of the reduced model. In particular, the Butler-Volmer equations for electrochemical reactions, which are still under discussion in the literature, are rational consequences of our approach. For illustration and to compare with the literature, we consider a simple generic reaction.