Effects of Nanoparticle Geometry and Size Distribution on Diffusion Impedance of Battery Electrodes

The short diffusion lengths in insertion battery nanoparticles render the capacitive behavior of bounded diffusion, which is rarely observable with conventional larger particles, now accessible to impedance measurements. Coupled with improved geometrical characterization, this presents an opportunity to measure solid diffusion more accurately than the traditional approach of fitting Warburg circuit elements, by properly taking into account the particle geometry and size distribution. We revisit bounded diffusion impedance models and incorporate them into an overall impedance model for different electrode configurations. The theoretical models are then applied to experimental data of a silicon nanowire electrode to show the effects of including the actual nanowire geometry and radius distribution in interpreting the impedance data. From these results, we show that it is essential to account for the particle shape and size distribution to correctly interpret impedance data for battery electrodes. Conversely, it is also possible to solve the inverse problem and use the theoretical "impedance image" to infer the nanoparticle shape and/or size distribution, in some cases, more accurately than by direct image analysis. This capability could be useful, for example, in detecting battery degradation in situ by simple electrical measurements, without the need for any imaging.Comment: 30 page

Induced-charge Electrokinetic Phenomena: Theory and Microfluidic Applications

We give a general, physical description of ``induced-charge electro-osmosis'' (ICEO), the nonlinear electrokinetic slip at a polarizable surface, in the context of some new techniques for microfluidic pumping and mixing. ICEO generalizes ``AC electro-osmosis'' at micro-electrode arrays to various dielectric and conducting structures in weak DC or AC electric fields. The basic effect produces micro-vortices to enhance mixing in microfluidic devices, while various broken symmetries -- controlled potential, irregular shape, non-uniform surface properties, and field gradients -- can be exploited to produce streaming flows. Although we emphasize the qualitative picture of ICEO, we also briefly describe the mathematical theory (for thin double layers and weak fields) and apply it to a metal cylinder with a dielectric coating in a suddenly applied DC field.Comment: 4 pages, 4 figs; revsion with more refs, one new fig, and more emphasis on microfluidic

Induced-Charge Electro-Osmosis

We describe the general phenomenon of `induced-charge electro-osmosis' (ICEO) -- the nonlinear electro-osmotic slip that occurs when an applied field acts on the ionic charge it {\sl induces} around a polarizable surface. Motivated by a simple physical picture, we calculate ICEO flows around conducting cylinders in steady (DC), oscillatory (AC), and suddenly-applied electric fields. This picture, and these systems, represent perhaps the clearest example of nonlinear electrokinetic phenomena. We complement and verify this physically-motivated approach using a matched asymptotic expansion to the electrokinetic equations in the thin double-layer and low potential limits. ICEO slip velocities vary like $u_s \propto E_0^2 L$, where $E_0$ is the field strength and $L$ is a geometric length scale, and are set up on a time scale $\tau_c = \lambda_D L/D$, where $\lambda_D$ is the screening length and $D$ is the ionic diffusion constant. We propose and analyze ICEO microfluidic pumps and mixers that operate without moving parts under low applied potentials. Similar flows around metallic colloids with fixed total charge have been described in the Russian literature (largely unnoticed in the West). ICEO flows around conductors with fixed potential, on the other hand, have no colloidal analog and offer further possibilities for microfluidic applications.Comment: 36 pages, 8 figures, to appear in J. Fluid Mec

Front dynamics during diffusion-limited corrosion of ramified electrodeposits

Experiments on the diffusion-limited corrosion of porous copper clusters in thin gap cells containing cupric chloride are reported. By carefully comparing corrosion front velocities and concentration profiles obtained by phase-shift interferometry with theoretical predictions, it is demonstrated that this process is well-described by a one-dimensional mean-field model for the generic reaction A + B (static) -> C (inert) with only diffusing reactant (cupric chloride) and one static reactant (copper) reacting to produce an inert product (cuprous chloride). The interpretation of the experiments is aided by a mathematical analysis of the model equations which allows the reaction-order and the transference number of the diffusing species to be inferred. Physical arguments are given to explain the surprising relevance of the one-dimensional mean-field model in spite of the complex (fractal) structure of the copper clusters.Comment: 26 pages, 10 figures, submitted to J. Phys. Chem. B, high quality eps figures available at http://www-math.mit.edu/~bazant/paper

Attractive forces in microporous carbon electrodes for capacitive deionization

The recently developed modified Donnan (mD) model provides a simple and useful description of the electrical double layer in microporous carbon electrodes, suitable for incorporation in porous electrode theory. By postulating an attractive excess chemical potential for each ion in the micropores that is inversely proportional to the total ion concentration, we show that experimental data for capacitive deionization (CDI) can be accurately predicted over a wide range of applied voltages and salt concentrations. Since the ion spacing and Bjerrum length are each comparable to the micropore size (few nm), we postulate that the attraction results from fluctuating bare Coulomb interactions between individual ions and the metallic pore surfaces (image forces) that are not captured by meanfield theories, such as the Poisson-Boltzmann-Stern model or its mathematical limit for overlapping double layers, the Donnan model. Using reasonable estimates of the micropore permittivity and mean size (and no other fitting parameters), we propose a simple theory that predicts the attractive chemical potential inferred from experiments. As additional evidence for attractive forces, we present data for salt adsorption in uncharged microporous carbons, also predicted by the theory.Comment: 19 page

Interfacial dynamics in transport-limited dissolution

Various model problems of ``transport-limited dissolution'' in two dimensions are analyzed using time-dependent conformal maps. For diffusion-limited dissolution (reverse Laplacian growth), several exact solutions are discussed for the smoothing of corrugated surfaces, including the continuous analogs of ``internal diffusion-limited aggregation'' and ``diffusion-limited erosion''. A class of non-Laplacian, transport-limited dissolution processes are also considered, which raise the general question of when and where a finite solid will disappear. In a case of dissolution by advection-diffusion, a tilted ellipse maintains its shape during collapse, as its center of mass drifts obliquely away from the background fluid flow, but other initial shapes have more complicated dynamics.Comment: 5 pages, 4 fig

Model B4 : multi-decade creep and shrinkage prediction of traditional and modern concretes

To improve the sustainability of concrete infrastructure, engineers face the challenge of incorporating new concrete materials while pushing the expected design life beyond 100 years. The time-dependent creep and shrinkage response of concrete governs the serviceability and durability in this multi-decade time frame. It has been shown that current prediction equations for creep and shrinkage underestimate material deformations observed in structures outside of a laboratory environment. A new prediction model for creep and shrinkage is presented that can overcome some of the shortcomings of the current equations. The model represents an extension and systematic recalibration of model B3, a 1995 RILEM Recommendation, which derives its functional form from the phenomena of diffusion, chemical hydration, moisture sorption, and the evolution of micro-stresses in the cement structure. The model is calibrated through a joint optimization of a new enlarged laboratory test database and a new database of bridge deflection records to overcome the bias towards short-term behavior. A framework for considering effects of aggregates, admixtures, additives, and higher temperatures is also incorporated

Size scaling of strength in thin film delamination

We investigate by numerical simulation the system size dependence of the shear delamination strength of thin elastic films. The films are connected to a rigid substrate by a disordered interface containing a pre-existing crack. The size dependence of the strength of this system is found to depend crucially on the crack shape. For circular cracks, we observe a crossover between a size-independent regime at large crack radii which is controlled by propagation of the pre-existing crack, and a size-dependent regime at small radii which is dominated by nucleation of new cracks in other locations. For cracks of finite width that span the system transversally, we observe for all values of the crack length a logarithmic system size dependence of the failure stress. The results are interpreted in terms of extreme value statistics.Comment: 10 pages, 4 figure

Diffusion-Limited Aggregation on Curved Surfaces

We develop a general theory of transport-limited aggregation phenomena occurring on curved surfaces, based on stochastic iterated conformal maps and conformal projections to the complex plane. To illustrate the theory, we use stereographic projections to simulate diffusion-limited-aggregation (DLA) on surfaces of constant Gaussian curvature, including the sphere ($K>0$) and pseudo-sphere ($K<0$), which approximate "bumps" and "saddles" in smooth surfaces, respectively. Although curvature affects the global morphology of the aggregates, the fractal dimension (in the curved metric) is remarkably insensitive to curvature, as long as the particle size is much smaller than the radius of curvature. We conjecture that all aggregates grown by conformally invariant transport on curved surfaces have the same fractal dimension as DLA in the plane. Our simulations suggest, however, that the multifractal dimensions increase from hyperbolic ($K0$) geometry, which we attribute to curvature-dependent screening of tip branching.Comment: 4 pages, 3 fig