Nonequilibrium Thermodynamics of Porous Electrodes

We reformulate and extend porous electrode theory for non-ideal active materials, including those capable of phase transformations. Using principles of non-equilibrium thermodynamics, we relate the cell voltage, ionic fluxes, and Faradaic charge-transfer kinetics to the variational electrochemical potentials of ions and electrons. The Butler-Volmer exchange current is consistently expressed in terms of the activities of the reduced, oxidized and transition states, and the activation overpotential is defined relative to the local Nernst potential. We also apply mathematical bounds on effective diffusivity to estimate porosity and tortuosity corrections. The theory is illustrated for a Li-ion battery with active solid particles described by a Cahn-Hilliard phase-field model. Depending on the applied current and porous electrode properties, the dynamics can be limited by electrolyte transport, solid diffusion and phase separation, or intercalation kinetics. In phase-separating porous electrodes, the model predicts narrow reaction fronts, mosaic instabilities and voltage fluctuations at low current, consistent with recent experiments, which could not be described by existing porous electrode models

Phase Transformation Dynamics in Porous Battery Electrodes

Porous electrodes composed of multiphase active materials are widely used in Li-ion batteries, but their dynamics are poorly understood. Two-phase models are largely empirical, and no models exist for three or more phases. Using a modified porous electrode theory based on non-equilibrium thermodynamics, we show that experimental phase behavior can be accurately predicted from free energy models, without artificially placing phase boundaries or fitting the open circuit voltage. First, we simulate lithium intercalation in porous iron phosphate, a popular two-phase cathode, and show that the zero-current voltage gap, sloping voltage plateau and under-estimated exchange currents all result from size-dependent nucleation and mosaic instability. Next, we simulate porous graphite, the standard anode with three stable phases, and reproduce experimentally observed fronts of color-changing phase transformations. These results provide a framework for physics-based design and control for electrochemical systems with complex thermodynamics

Particle-Level Modeling of the Charge-Discharge Behavior of Nanoparticulate Phase-Separating Li-Ion Battery Electrodes

In nanoparticulate phase-separating electrodes, phase separation inside the particles can be hindered during their charge/discharge cycles even when a thermodynamic driving force for phase separation exists. In such cases, particles may (de)lithiate discretely in a process referred to as mosaic instability. This instability could be the key to elucidating the complex charge/discharge dynamics in nanoparticulate phase-separating electrodes. In this paper, the dynamics of the mosaic instability is studied using Smoothed Boundary Method simulations at the particle level, where the concentration and electrostatic potential fields are spatially resolved around individual particles. Two sets of configurations consisting of spherical particles with an identical radius are employed to study the instability in detail. The effect of an activity-dependent exchange current density on the mosaic instability, which leads to asymmetric charge/discharge, is also studied. While we show that our model reproduces the results of a porous-electrode model for the simple setup studied here, it is a powerful framework with the capability to predict the detailed dynamics in three-dimensional complex electrodes and provides further insights into the complex dynamics that result from the coupling of electrochemistry, thermodynamics, and transport kinetics

Linear programming can help identify practical solutions to improve the nutritional quality of food aid.

OBJECTIVES: To assess the nutritional quality of food aid delivered by food banks in France and to identify practical modifications to improve it. DESIGN: National-level data were collected for all food aid distributed by French food banks in 2004, and its nutrient content per 2000 kcal was estimated and compared with French recommendations for adults. Starting with the actual donation and allowing new foods into the food aid donation, linear programming was used to identify the minimum changes required in the actual donation to achieve the French recommendations. RESULTS: French food-bank-delivered food aid does not achieve the French recommendations for dietary fibre, ascorbic acid, vitamin D, folate, magnesium, docosahexaenoic acid, alpha-linolenic acid and the percentage of energy from saturated fatty acids. Linear programming analysis showed that these recommendations are achievable if more fruits, vegetables, legumes and fish were collected and less cheese, refined cereals and foods rich in fat, sugar and/or salt. In addition, new foods not previously collected are needed, particularly nuts, wholemeal bread and rapeseed oil. These changes increased the total edible weight (42%) and economic value (55%) of the food aid donation, with one-third of its edible weight coming from fruits and vegetables, one-third from staples, one-quarter from dairy products and approximately a tenth from meat/fish/eggs. CONCLUSIONS: Important changes in the types and amounts of food collected will improve the nutritional quality of food-bank-delivered food aid in France. Such changes are recommended to improve the diets of deprived French populations

Identifying ILI Cases from Chief Complaints: Comparing the Accuracy of Keyword and Support Vector Machine Methods

We compared the accuracy of two methods of identifying ILI cases from chief complaints. We found that a support vector machine method was more accurate than a keyword method

A Deep Photometric Look at Two of Andromeda's Dwarf Spheroidals: X and XVII

We use deep wide-field photometry from the Large Binocular Camera to study the stellar and structural properties of the recently discovered Andromeda X and Andromeda XVII (And X and And XVII) dwarf galaxies. Using the mean apparent magnitude of the horizontal branch (HB), we derive distances of 621 +- 20 kpc to And X and 734+- 23 kpc to And XVII, closer by >60 kpc than the previous estimates which were based on red giant branch (RGB) observations. Thus our results warrant against the use of the RGB tip method for determining distances to systems with sparsely populated RGBs, and show how crucial HB observations are in obtaining accurate distances in systems such as these. We find that And X is a relatively faint (MV = -7.36), highly elongated (e = 0.48) system at a distance of 174 +- 62 kpc from Andromeda. And XVII is brighter (MV = -8.61) with an M31-centric distance of 73 kpc which makes it one of the closest satellites to Andromeda. Both galaxies are metal-poor: we derive =-2.2 for And X, while And XVII shows = -2.0, consistent with the relation of higher luminosity dwarfs being more metal- rich. Additionally, both galaxies show considerable intrinsic spreads in metallicity (0.2 and 0.3 dex for And X and And XVII respectively), consistent with multiple stellar populations.Comment: 8 pages, 6 figure

A corpus-based method for controlling guitar feedback

The use of feedback created by electric guitars and amplifiers is problematic in musical settings. For example, it is difficult for a performer to accurately obtain specific pitch and loudness qualities. This is due to the complex relationship between these quantities and other variables such as the string being fretted and the positions and orientations of the guitar and amplifier. This research investigates corpus-based methods for controlling the level and pitch of the feedback produced by a guitar and amplifier. A guitar-amplifier feedback system was built in which the feedback is manipulated using (i) a simple automatic gain control system, and (ii) a band-pass filter placed in the signal path. A corpus of sounds was created by recording the sound produced for various combinations of the parameters controlling these two components. Each sound in the corpus was analysed so that the control parameter values required to obtain particular sound qualities can be recalled in the manner of concatenative sound synthesis. As a demonstration, a recorded musical target phrase is recreated on the feedback system

Developing essential professional skills: a framework for teaching and learning about feedback.

BACKGROUND: The ability to give and receive feedback effectively is a key skill for doctors, aids learning between all levels of the medical hierarchy, and provides a basis for reflective practice and life-long learning. How best to teach this skill? DISCUSSION: We suggest that a single "teaching the skill of feedback" session provides superficial and ineffective learning in a medical culture that often uses feedback skills poorly or discourages feedback. Our experience suggests that both the skill and the underlying attitude informing its application must be addressed, and is best done so longitudinally and reiteratively using different forms of feedback delivery. These feedback learning opportunities include written and oral, peer to peer and cross-hierarchy, public and private, thereby addressing different cognitive processes and attitudinal difficulties. SUMMARY: We conclude by asking whether it is possible to build a consensus approach to a framework for teaching and learning feedback skills?RIGHTS : This article is licensed under the BioMed Central licence at http://www.biomedcentral.com/about/license which is similar to the 'Creative Commons Attribution Licence'. In brief you may : copy, distribute, and display the work; make derivative works; or make commercial use of the work - under the following conditions: the original author must be given credit; for any reuse or distribution, it must be made clear to others what the license terms of this work are