Generalized staircase model of electrochemical impedance of pores in supercapacitor electrodes

Представлена новая обобщенная лестничная модель электрохимического импеданса для пористых материалов электродов в устройствах хранения энергии. Дано краткое описание существующих моделей межфазного импеданса и их ограничений. Новая модель основана на общепринятой “лестничной” модели импеданса цилиндрических пор. Однако новая модель учитывает сложную пористую структуру электродных материалов. В частности, модель описывает импеданс электродов с иерархической пористой разветвленной структурой, в которой широкие поры разветвляются в более узкие. Новая модель позволяет вычислить импеданс межфазной границы электрод/электролит в присутствии как нефарадеевских, так и фарадеевских процессов. Модель успешно опробована для пор с простой геометрией, для которых существуют точные решения. Изучено влияние структурных параметров модельных пористых электродов на их характеристики работы в суперконденсаторах. Проанализировано влияние диаметра пор, величины расширения начал пор и разветвления пор. Сформулированы критерии направленного дизайна электродных материалов для суперконденсаторов A new generalized staircase model of the electrochemical impedance is presented for porous electrode materials in energy storage devices. A brief overview on existing models of interfacial impedance and their limitations is given. The new model is based on the conventional staircase model of the impedance in cylindrical pores. However, the new model takes into account the complex porous structure of electrode materials. In particular, the impedance of hierarchical branching porous electrodes is described, i.e. the wide pores branching into the narrower pores. The new model allows to evaluate the impedance of the electrode/electrolyte interface in the presence of both non-faradaic and faradaic processes. The model is validated using the available exact solutions and experimental data for simple pore geometries. The influence of the parameters of structure of model porous electrodes on their performance in supercapacitors is studied. In particular, the influence of the diameter of the pores, width of pore openings, branching of pores is analyzed. The guideline for focused design of electrode materials of supercapacitors is outlined

Polymer Brush in a Nanopore: Effects of Solvent Strength and Macromolecular Architecture Studied by Self-Consistent Field and Scaling Theory

To study conformational transition occuring upon inferior solvent strength in a brush formed by linear or dendritically branched macromolecules tethered to the inner surface of cylindrical or planar (slit-like) pore, a self-consistent field analytical approach is employed. Variations in the internal brush structure as a function of variable solvent strength and pore radius, and the onset of formation of a hollow channel in the pore center are analysed. The predictions of analytical theory are supported and complemented by numerical modelling by a self-consistent field Scheutjens–Fleer method. Scaling arguments are used to study microphase segregation under poor solvent conditions leading to formation of a laterally and longitudinally patterned structure in planar and cylindrical pores, respectively, and the effects of confinement on "octopus-like" clusters in the pores of different geometries.

Polyelectrolyte Functionalisation of Track Etched Membranes: Towards Charge-Tuneable Adsorber Materials

Porous adsorber membranes are promising materials for the removal of charged pollutants, such as heavy metal ions or organic dyes as model substances for pharmaceuticals from water. Here, we present the surface grafting of polyethylene terephthalate (PET) track-etched membranes having well defined cylindrical pores of 0.2 or 1 µm diameter with two polyelectrolytes, poly(2-acrylamido glycolic acid) (PAGA) and poly(N-acetyl dehydroalanine) (PNADha). The polyelectrolyte functionalised membranes were characterised by changes in wettability and hydraulic permeability in response to the external stimuli pH and the presence of Cu2+ ions. The response of the membranes proved to be consistent with functionalisation inside the pores, and the change of grafted polyelectrolyte macro-conformation was due to the reversible protonation or binding of Cu2+ ions. Moreover, the adsorption of the model dye methylene blue was studied and quantified. PAGA-grafted membranes showed an adsorption behavior following the Langmuir model for methylene blue.

CYLINDRICAL CONFINEMENT OF SOLUTIONS CONTAINING SEMIFLEXIBLE MACROMOLECULES: SURFACE-INDUCED NEMATIC ORDER VERSUS PHASE SEPARATION

Solutions of semiflexible polymers confined in cylindrical pores with repulsive walls are studied by Molecular Dynamics simulations for a wide range of polymer concentrations. Both the case where both lengths...

Intermolecular channels direct crystal orientation in mineralized collagen

The mineralized collagen fibril is the basic building block of bone, and is commonly pictured as a parallel array of ultrathin carbonated hydroxyapatite (HAp) platelets distributed throughout the collagen. This orientation is often attributed to an epitaxial relationship between the HAp and collagen molecules inside 2D voids within the fibril. Although recent studies have questioned this model, the structural relationship between the collagen matrix and HAp, and the mechanisms by which collagen directs mineralization remain unclear. Here, we use XRD to reveal that the voids in the collagen are in fact cylindrical pores with diameters of ~2 nm, while electron microscopy shows that the HAp crystals in bone are only uniaxially oriented with respect to the collagen. From in vitro mineralization studies with HAp, CaCO3 and γ-FeOOH we conclude that confinement within these pores, together with the anisotropic growth of HAp, dictates the orientation of HAp crystals within the collagen fibril.

Intermolecular Channels Direct Crystal Orientation in Mineralized Collagen

ABSTRACTThe mineralized collagen fibril is the basic building block of bone, commonly pictured as a parallel array of ultrathin carbonated hydroxyapatite (HAp) platelets distributed throughout the collagen. This orientation is often attributed to an epitaxial relationship between the HAp and collagen molecules inside 2D voids within the fibril. Although recent studies have questioned this model, the structural relationship between the collagen matrix and HAp, and the mechanisms by which collagen directs mineralization remain unclear. Here, we use XRD to reveal that the voids in the collagen are in fact cylindrical pores with diameters of ∼2 nm, while electron microscopy shows that the HAp crystals in bone are only uniaxially oriented with respect to the collagen. From in vitro mineralization studies with HAp, CaCO3 and γ-FeOOH we conclude that confinement within these pores, together with the anisotropic growth of HAp, dictates the orientation of HAp crystals within the collagen fibril.