Safety assessment of scenarios triggered by accidental seawater immersion of lithium batteries in innovative naval applications

The request of lithium-ion batteries in naval applications features an increasing trend due to the need of high performance energy storage devices. Beside the hazard of runaway when the battery is crushed or overcharged, the naval environment poses additional safety issues due to the possible immersion with seawater of the battery room following accidental flooding. In such a case, seawater electrolysis may generate hydrogen and chlorine, thus giving rise to an explosive and toxic mixture in a confined environment. In this study, a quantitative safety assessment of the possible accidental scenarios induced by seawater electrolysis in battery rooms is performed. The analysis is based on i) the deterministic evaluation of the hazardous gases development according to a three-dimensional physically-based electrochemical model and ii) the discussion of possible prevention and mitigation measures. The dynamics of gas release and the time required to produce an explosive atmosphere are evaluated as a function of the level of seawater for a reference case study. The outcomes of the study support the safety assessment of accidental scenarios induced by seawater electrolysis in naval applications and provide indications on the effectiveness of hazard reduction measures. More specifically, the study reveals that a proper electric insulation of the surface of battery terminals represents a sensible mitigation strategy to reduce the severity of explosions in addition to the ventilation of the battery room

Physically-based deconvolution of impedance spectra for LSCF-based SOFC

A physically-based model for the interpretation of the impedance spectra of an anode-supported LSCF/GDC/YSZ/Ni:YSZ solid oxide fuel cell is presented in this work. The model locally describes transport and reaction phenomena within the cell components through mass conservation equations. The microstructural properties of the electrodes are predicted through numerical three-dimensional reconstruction of the microstructure, with input parameters obtained from the analysis of SEM pictures of each layer. Simulations show that the model reproduces impedance spectra obtained in different operating conditions with the same set of fitting parameters, comprising material-specific kinetic constants and electrochemical capacitances, which fairly agree with independent literature data and a previous analysis of the spectra through DRT. The model allows for the deconvolution and quantification of the characteristic resistance and frequency of the different physical processes that build up the impedance of the cell. In particular, 7 processes are identified: charge-transfer reactions between LSCF/GDC, GDC/YSZ and Ni/YSZ interfaces appear in the high-frequency range, the medium-frequency feature is due the oxygen reduction reaction and the gas diffusion in the anode, while the low-frequency arc is mainly due to the gas conversion in the anodic channel. An additional low frequency contribution (< 1Hz), not considered in the model, is observed and tentatively attributed to the adsorption of oxygen onto the LSCF surface. Simulation results suggest that more efforts must be dedicated to characterize and improve the oxygen transfer at the LSCF/GDC and GDC/YSZ interfaces. The study shows that a quantitative interpretation of impedance spectra is possible with a reduced number of fitting parameters when a physically-based approach is adopted, making the model an attractive tool for diagnostic purposes

Heterogeneous electrocatalysis in porous cathodes of solid oxide fuel cells

A general physics-based model is developed for heterogeneous electrocatalysis in porous electrodes and used to predict and interpret the impedance of solid oxide fuel cells. This model describes the coupled processes of oxygen gas dissociative adsorption and surface diffusion of the oxygen intermediate to the triple phase boundary, where charge transfer occurs. The model accurately captures the Gerischer-like frequency dependence and the oxygen partial pressure dependence of the impedance of symmetric cathode cells. Digital image analysis of the microstructure of the cathode functional layer in four different cells directly confirms the predicted connection between geometrical properties and the impedance response. As in classical catalysis, the electrocatalytic activity is controlled by an effective Thiele modulus, which is the ratio of the surface diffusion length (mean distance from an adsorption site to the triple phase boundary) to the surface boundary layer length (square root of surface diffusivity divided by the adsorption rate constant). The Thiele modulus must be larger than one in order to maintain high surface coverage of reaction intermediates, but care must be taken in order to guarantee a sufficient triple phase boundary density. The model also predicts the Sabatier volcano plot with the maximum catalytic activity corresponding to the proper equilibrium surface fraction of adsorbed oxygen adatoms. These results provide basic principles and simple analytical tools to optimize porous microstructures for efficient electrocatalysis

An Electrically Conductive Oleogel Paste for Edible Electronics

Edible electronics will facilitate point-of-care testing through safe devices digested/degraded in the body/environment after performing a specific function. This technology, to thrive, requires a library of materials that are the basic building blocks for eatable platforms. Edible electrical conductors fabricated with green methods and at a large scale and composed of food derivatives, ingestible in large amounts without risk for human health are needed. Here, conductive pastes made with materials with a high tolerable upper intake limit (≥mg kg−1 body weight per day) are proposed. Conductive oleogel composites, made with biodegradable and food-grade materials like natural waxes, oils, and activated carbon conductive fillers, are presented. The proposed pastes are compatible with manufacturing processes such as direct ink writing and thus are suitable for an industrial scale-up. These conductors are built without using solvents and with tunable electromechanical features and adhesion depending on the composition. They have antibacterial and hydrophobic properties so that they can be used in contact with food preventing contamination and preserving its organoleptic properties. As a proof-of-principle application, the edible conductive pastes are demonstrated to be effective edible contacts for food impedance analysis, to be integrated, for example, in smart fruit labels for ripening monitoring

Multi-length scale microstructural design of lithium-ion battery electrodes for improved discharge rate performance

Fast discharge capability of automotive batteries not only affects the acceleration and climbing performance of electric vehicles, but also the accessible driving range under complex driving cycles. Understanding the intricate physical and chemical processes across multiple length-scales is critical to assist the strategic design of electrodes for improved rate performance. Here, we correlate the discharge rate performance of Ni-rich LiNi1−x−yCoxMnyO2 (NMC) cathodes to the electrode architectures, ranging from the crystallographic orientations, surface morphology and cracks at single particle level, to the factors that affect the dominance of the solid and liquid-state transport (SST and LST) at electrode level. A random orientation of the primary particles is found to incur an increase of the SST resistance by a factor of 2.35 at 5C and a heterogeneous intra-particle lithiation. Internal cracks significantly restrict the accessibility to the active material. Double-layered particles are proved to be a more promising candidate than single-crystal particles. At electrode level, the SST-dominance depth is quantified for the first time to guide the microstructural tuning and rational operating windows are proposed for electrodes of various architectures. The reaction front is observed to shuttle across the electrode depth to mitigate the polarization, which can provide valuable insights into the battery management development. Finally, by comparing the performance of single crystal and polycrystalline NMC811 electrodes, it is suggested that electrode thickness and porosity are more critical in the former for enhanced discharge rate performance, in contrast to polycrystalline electrodes, in which a gradient particle fraction and size distribution are recommended

Study of ion responsive polymer brushes as smart coatings and physical gels models

The control of surface and interfacial properties has always played a critical role in the development of new materials. In the latest decades, polymer brushes have emerged as attractive nanostructures for their functional versatility, physico-mechanical properties and numerous fields of application. The extraordinary control over their features makes them not only a multipurpose platform for surface modification, but also a tool for modelling and studying interactions. This thesis focuses on designing a versatile model system to understand the physical, chemical and structural properties of gels used in the oral care industry, while also investigating the properties and potential applications of specific anionic polyelectrolyte brushes. Firstly, essential knowledge about both gels and polymer brushes is presented. Gels properties and fundamental theory are described along with state-of-the-art examples of applications. Next, polymer brushes are defined and discussed with emphasis on their stimuli responsiveness and their preparation strategies. The challenges in the fabrication of Carbopol® gels inspired by Haleon toothpaste formulations are evaluated and potential additives are investigated from a physico-chemical and structural point of view. In parallel, a study on poly(acylic acid) (PAA) and poly(3-sulfopropyl methacrylate) (PSPMA) brushes is conducted to investigate the role of copper catalyst residues and the ion responsiveness of the planar brushes under a variety of conditions. Alongside these studies, the potential antiviral properties of PSPMA brushes is also investigated and compared to other polymers through a collaboration with École Polytechnique Fédérale de Lausanne. Subsequently, the knowledge gained for planar substrates is applied to different types of silica particles, which are successfully coated with the polymer brushes and studied in colloidal suspensions. Finally, specific silica particles coated with PSPMA brushes are used to fabricate tunable physical gels, which constitute both a novel type of material and an adaptable model system to study gel formulations

A Particle-Based Model for Effective Properties in Infiltrated Solid Oxide Fuel Cell Electrodes

A modeling framework for the numerical reconstruction of the microstructure of infiltrated electrodes is presented in this study. A particle-based sedimentation algorithm is used to generate the backbone, while a novel packing algorithm is used to randomly infiltrate nanoparticles on the surface of backbone particles. The effective properties, such as the connected triple-phase boundary length, the effective conductivity, the effective diffusivity, are evaluated on the reconstructed electrodes by using geometric analysis, finite volume and random-walk methods, and reported in dimensionless form to provide generality to the results. A parametric study on the effect of the main model and operating parameters is performed. Simulations show that the critical loading (i.e., the percolation threshold) increases as the backbone porosity decreases and the nanoparticle diameter increases. Large triple-phase boundary length, specific surface area and good effective conductivity can be reached by infiltration, without detrimental effects on the effective transport properties in gas phase. Simulations reveal a significant sensitivity to the size and contact angle of infiltrated particles, suggesting that the preparation process of infiltrated electrodes should be properly tailored in order to obtain the optimized structures predicted by the model

Dusty-gas model with uniform pressure: A numerical study on the impact of a frequent inconsistent assumption in SOFC electrode modeling

One of the most popular models adopted to describe the gas transport in porous electrodes is the dusty-gas model (DGM). However, such a model is commonly applied under the assumption of uniform pressure, which is incompatible with the DGM formulation and does not allow fluxes to obey reaction stoichiometry. In such a case, the model fails to predict partial pressure profiles. In this study, the quantification of the error in the prediction of concentration overpotential, due the inconsistent assumption of uniform pressure, is obtained by simulating the gas transport in solid oxide fuel cell anodes in a broad range of conditions. Simulations show that an inconsistent use of the dusty-gas model may lead to relative errors in the prediction of concentration overpotential as large as 60%, especially in binary H2/H2O mixtures

A comparative study and an extended theory of percolation for random packings of rigid spheres

A new method for the prediction of coordination numbers in random packings of rigid spherical particles is presented, consisting of improvements of basic relationships of percolation theory for the determination of numbers of contacts, percolation thresholds and probability of connection in binary mixtures and their extension to multicomponent and polydisperse mixtures. The proposed model is critically compared with previous percolation theories, showing a satisfactory agreement with experimental data and computer simulations of random packings over a wide range of particle sizes and compositions for both binary and multicomponent/polydisperse mixtures. (C) 2011 Elsevier B.V. All rights reserved