A theory and a simulation capability for the growth of a solid electrolyte interphase layer at anode particles in lithium ion batteries

A major mechanism for electrochemical aging of Li-ion batteries is the formation of a solid electrolyte interphase (SEI) layer, which results in an impedance rise at the anode and also leads to capacity fade. The formation of an SEI layer consumes Li-ions and competes with the desired Li intercalation. Often, the cyclic volume changes – or “breathing” – of an anode particle during Li-ion intercalation and deintercalation can cause the SEI layer to delaminate from the surface of the particle, which causes new SEI to be formed on the newly exposed particle surface and this accelerates capacity fade. We have formulated a continuum theory for the formation and growth of an SEI layer, and the theory has been numerically implemented in a finite-element program. This simulation capability for SEI growth is coupled with our earlier published chemomechanical simulation capability for intercalation of Li-ions in electrode particles. Using this new combined capability we have simulated the formation and growth of an SEI layer during cyclic lithiation and delithiation of an anode particle and predicted the evolution of the growth stresses in the SEI layer. The evolution of the stress state at the SEI–particle interface for spheroidal-shaped particles is studied, and this gives us a good indicator for the propensity of potential delamination of the SEI layer from the anode particle

Diffusion–deformation theory for amorphous silicon anodes: The role of plastic deformation on electrochemical performance

Amorphous silicon (a-Si) is a promising material for anodes in Li-ion batteries due to its increased capacity relative to the current generation of graphite-based anode materials. However, the intercalation of lithium into a-Si induces very large elastic–plastic deformations, including volume changes of approximately 300%. We have formulated and numerically implemented a fully-coupled diffusion–deformation theory, which accounts for transient diffusion of lithium and accompanying large elastic–plastic deformations. The material parameters in the theory have been calibrated to experiments of galvanostatic cycling of a half-cell composed of an a-Si thin-film anode deposited on a quartz substrate, which have been reported in the literature. We show that our calibrated theory satisfactorily reproduces the mechanical response of such an anode — as measured by the changes in curvature of the substrate, as well as the electrochemical response — as measured by the voltage versus state-of-charge (SOC) response. We have applied our numerical simulation capability to model galvanostatic charging of hollow a-Si nanotubes whose exterior walls have been oxidized to prevent outward expansion; such anodes have been recently experimentally-realized in the literature. We show that the results from our numerical simulations are in good agreement with the experimentally-measured voltage versus SOC behavior at various charging rates (C-rates). Through our simulations, we have identified two major effects of plasticity on the electrochemical performance of a-Si anodes: • First, for a given voltage cut-off, plasticity enables lithiation of the anode to a higher SOC. This is because plastic flow reduces the stresses generated in the material, and thus reduces the potential required to lithiate the material. • Second, plastic deformation accounts for a significant percentage of the energy dissipated during the cycling of the anode at low C-rates. Hence, plasticity can have either (a) a beneficial effect, that is, a higher SOC for a given voltage cut-off; or (b) a detrimental effect, that is significant energy dissipation at low C-rates.National Science Foundation (U.S.) Division of Civil, Mechanical and Manufacturing Innovation (Award CMMI-1063626

Interplay of phase boundary anisotropy and electro-autocatalytic surface reactions on the lithium intercalation dynamics in LiX_XFePO4_4 platelet-like nanoparticles

Experiments on single crystal Li$_X$FePO$_4$ (LFP) nanoparticles indicate rich nonequilibrium phase behavior, such as suppression of phase separation at high lithiation rates, striped patterns of coherent phase boundaries, nucleation by binarysolid surface wetting and intercalation waves. These observations have been successfully predicted (prior to the experiments) by 1D depth-averaged phase-field models, which neglect any subsurface phase separation. In this paper, using an electro-chemo-mechanical phase-field model, we investigate the coherent non-equilibrium subsurface phase morphologies that develop in the $ab$- plane of platelet-like single-crystal platelet-like Li$_X$FePO$_4$ nanoparticles. Finite element simulations are performed for 2D plane-stress conditions in the $ab$- plane, and validated by 3D simulations, showing similar results. We show that the anisotropy of the interfacial tension tensor, coupled with electroautocatalytic surface intercalation reactions, plays a crucial role in determining the subsurface phase morphology. With isotropic interfacial tension, subsurface phase separation is observed, independent of the reaction kinetics, but for strong anisotropy, phase separation is controlled by surface reactions, as assumed in 1D models. Moreover, the driven intercalation reaction suppresses phase separation during lithiation, while enhancing it during delithiation, by electro-autocatalysis, in quantitative agreement with {\it in operando} imaging experiments in single-crystalline nanoparticles, given measured reaction rate constants

A Finite Element Implementation of a Coupled Diffusion-Deformation Theory for Elastomeric Gels

The theory of Chester and Anand (2011) for fluid diffusion and large deformations of elastomeric gels is implemented as a user-defined element (UEL) subroutine in the commercial finite element software package ABAQUS. A specialized form of the constitutive equations and the governing partial differential equations of the theory are summarized, and the numerical implementation is described in detail. To demonstrate the robustness of the numerical implementation a few illustrative numerical simulation examples for axisymmetric, plane strain, and three-dimensional geometries are shown. For educational purposes, and also to facilitate the numerical implementation of other coupled multiphysics theories, the source code for the UEL is provided as an online supplement to this paper.National Science Foundation (U.S.) (NSF CMMI-1063626

Three-dimensional multifractal analysis of trabecular bone under clinical computed tomography

Purpose: An adequate understanding of bone structural properties is critical for predicting fragility conditions caused by diseases such as osteoporosis, and in gauging the success of fracture prevention treatments. In this work we aim to develop multiresolution image analysis techniques to extrapolate high-resolution images predictive power to images taken in clinical conditions. Methods: We performed multifractal analysis (MFA) on a set of 17 ex vivo human vertebrae clinical CT scans. The vertebræ failure loads (FFailure) were experimentally measured. We combined bone mineral density (BMD) with different multifractal dimensions, and BMD with multiresolution statistics (e.g., skewness, kurtosis) of MFA curves, to obtain linear models to predict FFailure. Furthermore we obtained short- and long-term precisions from simulated in vivo scans, using a clinical CT scanner. Ground-truth data - high-resolution images - were obtained with a High-Resolution Peripheral Quantitative Computed Tomography (HRpQCT) scanner. Results: At the same level of detail, BMD combined with traditional multifractal descriptors (Lipschitz-Hölder exponents), and BMD with monofractal features showed similar prediction powers in predicting FFailure (87%, adj. R2). However, at different levels of details, the prediction power of BMD with multifractal features raises to 92% (adj. R2) of FFailure. Our main finding is that a simpler but slightly less accurate model, combining BMD and the skewness of the resulting multifractal curves, predicts 90% (adj. R2) of FFailure. Conclusions: Compared to monofractal and standard bone measures, multifractal analysis captured key insights in the conditions leading to FFailure. Instead of raw multifractal descriptors, the statistics of multifractal curves can be used in several other contexts, facilitating further research.Fil: Baravalle, Rodrigo Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Centro Internacional Franco Argentino de Ciencias de la Información y de Sistemas. Universidad Nacional de Rosario. Centro Internacional Franco Argentino de Ciencias de la Información y de Sistemas; ArgentinaFil: Thomsen, Felix Sebastian Leo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Sur; ArgentinaFil: Delrieux, Claudio Augusto. Universidad Nacional del Sur; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Lu, Yongtao. Dalian University of Technology; ChinaFil: Gómez, Juan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Centro Internacional Franco Argentino de Ciencias de la Información y de Sistemas. Universidad Nacional de Rosario. Centro Internacional Franco Argentino de Ciencias de la Información y de Sistemas; ArgentinaFil: Stošić, Borko. Universidade Federal Rural Pernambuco; BrasilFil: Stošić, Tatijana. Universidade Federal Rural Pernambuco; Brasi

A MILP approach for designing robust variable-length codes based on exact free distance computation

International audienceThis paper addresses the design of joint source-channel variable-length codes with maximal free distance for given codeword lengths. While previous design methods are mainly based on bounds on the free distance of the code, the proposed algorithm exploits an exact characterization of the free distance. The code optimization is cast in the framework of mixed-integer linear programming and allows to tackle practical alphabet sizes in reasonable computing time

LCA Study on Sheep Milk Production in Sardinian Farms at Different Input Levels

This paper illustrates a Life Cycle Assessment (LCA) study carried out with the purposes of comparing the environmental impacts of sheep milk production from three different dairy farms in Sardinia, Italy, characterized by different production systems

GLUT1 expression patterns in different Hodgkin lymphoma subtypes and progressively transformed germinal centers

Background: Increased glycolytic activity is a hallmark of cancer, allowing staging and restaging with 18F-fluorodeoxyglucose-positron-emission-tomography (PET). Since interim-PET is an important prognostic tool in Hodgkin lymphoma (HL), the aim of this study was to investigate the expression of proteins involved in the regulation of glucose metabolism in the different HL subtypes and their impact on clinical outcome. Methods: Lymph node biopsies from 54 HL cases and reactive lymphoid tissue were stained for glucose transporter 1 (GLUT1), lactate dehydrogenase A (LDHA) and lactate exporter proteins MCT1 and MCT4. In a second series, samples from additional 153 HL cases with available clinical data were stained for GLUT1 and LDHA. Results: Membrane bound GLUT1 expression was frequently observed in the tumor cells of HL (49% of all cases) but showed a broad variety between the different Hodgkin lymphoma subtypes: Nodular sclerosing HL subtype displayed a membrane bound GLUT1 expression in the Hodgkin-and Reed-Sternberg cells in 56% of the cases. However, membrane bound GLUT1 expression was more rarely observed in tumor cells of lymphocyte rich classical HL subtype (30%) or nodular lymphocyte predominant HL subtype (15%). Interestingly, in both of these lymphocyte rich HL subtypes as well as in progressively transformed germinal centers, reactive B cells displayed strong expression of GLUT1. LDHA, acting downstream of glycolysis, was also expressed in 44% of all cases. We evaluated the prognostic value of different GLUT1 and LDHA expression patterns; however, no significant differences in progression free or overall survival were found between patients exhibiting different GLUT1 or LDHA expression patterns. There was no correlation between GLUT1 expression in HRS cells and PET standard uptake values. Conclusions: In a large number of cases, HRS cells in classical HL express high levels of GLUT1 and LDHA indicating glycolytic activity in the tumor cells. Although interim-PET is an important prognostic tool, a predictive value of GLUT1 or LDHA staining of the primary diagnostic biopsy could not be demonstrated. However, we observed GLUT1 expression in progressively transformed germinal centers and hyperplastic follicles, explaining false positive results in PET. Therefore, PET findings suggestive of HL relapse should always be confirmed by histology

Sistema para obtener balances de carga e índices de productividad en la fundición de coladas de metal aplicado en el área de costos de producción

Pretende crear un modelo que permita manejar la variabilidad en la carga fría para los diferentes metales con respecto a su composición química; y de esta manera poder establecer escenarios que nos permitan analizar las consecuentes variabilidades en la productividad y en los costos. El acero es una aleación de hierro y carbono, cuyo proceso de producción básico se realiza en dos fases: Primero el mineral de hierro es reducido o fundido con coque y piedra caliza, produciendo hierro fundido que es moldeado como arrabio o conducido a la siguiente fase como hierro fundido. La segunda fase, la de acería, tiene por objetivo reducir el alto contenido de carbono que el coque introdujo al fundir el mineral y eliminar las impurezas tales como azufre y fósforo, al mismo tiempo que algunos elementos como manganeso, níquel, cromo o vanadio son añadidos en forma de ferro-aleaciones para producir el tipo de acero demandado. En nuestro caso particular no partimos del mineral hierro sino de la chatarra reciclada y es el área de acería, quién se encarga de convertir la chatarra en acero. Este proceso, se basa en la combinación de chatarra, ferroaleaciones, materiales auxiliares y material reutilizable; Con un previo análisis de balance de carga para todos los componentes implicados. En donde nuestro punto de partida, para el análisis de la variabilidad en los componentes implicados, será el material reutilizable (regresos). Debido a que su costo es cero y en consecuencia manejar su variabilidad nos permitirá establecer parámetros de productividadTrabajo de suficiencia profesiona

Nitinol-reinforced shape-memory polymers

Thesis (S.B.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2010.Cataloged from PDF version of thesis.Includes bibliographical references (p. 33).Reinforced shape-memory polymers have been developed from an acrylate based thermoset shape-memory polymer and nitinol wires. A rectangular shape-memory polymer measuring approximately 1 by 2 by 0.1 inches has a ten fold increase in actuation force under three-point bending when reinforced with two 0.02 inch diameter nitinol wires. A constitutive model for shape-memory polymers and nitinol has been used to predict with good correlation the actuation-versus-time and displacement-versustime behavior of the reinforced shape-memory polymer composites. It is possible then, using finite-element modeling, to design and manufacture reinforced shape-memory polymers tailored for use as thermally-activated actuators of specific force.by Claudio V. Di Leo.S.B