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At least 1,243 records · Page 69

Multi-fidelity electrochemical modeling of thermally activated battery cells

Thermally activated batteries undergo a series of coupled physical changes during activation that influence battery performance. These processes include energetic material burning, heat transfer, electrolyte phase change, capillary-driven two-phase porous flow, ion transport, electrochemical reactions, and electrical transport. Several of these processes are strongly coupled and have a significant effect on battery performance, but others have minimal impact or may be suitably represented by reduced-order models. Additionally, assessing the relative importance of these phenomena must be based on comparisons to a high-fidelity model including all known processes. In this work, we first present and demonstrate a high-fidelity, multi-physics model of electrochemical performance. This novel multi-physics model enables predictions of how competing physical processes affect battery performance and provides unique insights into the difficult-to-measure processes that happen during battery activation. We introduce four categories of model fidelity that include different physical simplifications, assumptions, and reduced-order models to decouple or remove costly elements of the simulation. Using this approach, we show an order-of-magnitude reduction in computational cost while preserving all design-relevant quantities of interest within 5 percent. The validity of this approach and these model reductions is demonstrated by comparison between results from the full fidelity model and the different reduced models.

25 ENERGY STORAGE↗

In-situ electrochemical optical techniques in the investigation of lithium interfacial phenomena with a liquid and a solid-state electrolyte

An in-situ electrochemical optical diagnosis is the key to the investigation of electrode interface during a redox reaction. Because the morphology changes particularly, dendrite formation, dendrite shapes, solid electrolyte interface formation and gas generation can be revealed visually. The challenge of ensuring uniform current density on a flat Li anode in a liquid electrolyte was addressed and uniform Li plating was demonstrated. The dendrite shape change under different reduction current density was discussed. Here the Li dendrite shape change and the performance of Li anodes with a surface lamination of graphite and red phosphate were used as examples to demonstrate the capability of the in-situ optical cell. An in-situ electrochemical optical cell used in the investigation of the increasingly popular solid-state Li batteries has its own challenges. Due to the untransparent nature of a solid-state electrolyte, an optical investigation on a solid-state electrolyte Li battery needs to be done by exposing the cross-section of the cell. In addition, it is very difficult to assemble an optical cell with a brittle and fragile solid-state electrolyte in a glove box. A set of formation and transfer dies, and an optical cell were introduced. The Li dendrite growth at the interface can be observed in a solid-state Li cell.

25 ENERGY STORAGE↗

High performance porous Si anode enabled by an organic-solvent assisted etching process

Silicon (Si) is a promising anode for the next generation of lithium-ion batteries, but its large volume changes (~300 %) during cycling hindered its practical applications. One method to improve its stability is to etch micron sized Si/SiO 2 particles to form porous Si (p-Si) and accommodate volume changes internally. However, the conventional HF etching method generates excess gas/heat and is difficult to scale up. Herein, we developed an organic-solvent-assisted HF etching process (O-HF) using a mixture of benzene and saturated HF aqueous solution. The organic solvent can be preferentially absorbed on the surface of Si/SiO 2 powder so etching rate of SiO 2 can be controlled to avoid rapid gas/heat generation. This method can also prevent over-etching of Si by minimizing direct contact/react between water and newly exposed Si. Si||NMC622 cells using carbon coated p-Si particles prepared by optimized O-HF etching process demonstrate a capacity retention of 82.0 % after 500 cycles, which is much better than those prepared by conventional HF etching (73.7 %). The thickness of Si anode increases only ~10 % during the initial lithiation, which is comparable with those of graphite anode. In conclusion, the O-HF etching strategy developed in this work can also be applied to the etching of a broad range of materials.

HF etching↗

An Accelerated Testing and Analysis Framework for Qualification of Battery Materials Part I: A Case Study with LFP Cathodes

The growing demand for batteries used within automotive, aviation, and grid applications has exacerbated the need to supplement critical battery material feedstocks, such as those for anode and cathode active materials. New or supplementary material sources, however, universally comprise unique properties that can affect the lifetime and performance of resultant batteries. Even minor differences between new sources and established supplies can delay qualification, making it difficult for new suppliers to commercialize and resulting in a less resilient supply chain. Accordingly, the influence of composition, microstructure, and morphology on electrochemical performance should be characterized quickly and accurately to accelerate commercialization of new sources. This work introduces a tiered framework to assess new material viability and understand the influence of physicochemical properties on battery performance. The Tier 1 testing described here is rapid and low-effort to recognize materials with fundamental flaws and potentially disqualify them. Later testing would require more effort but provide higher-fidelity information with a goal of application-based validation. A case study examining commercial sources of LiFePO4 (LFP) is presented, using Tier 1 of the protocol to identify rapid electrochemical and physicochemical signals that correlate with performance and provide early go/no-go decisions for LFP materials without requiring long-term cycling.

25 ENERGY STORAGE↗

Cloud-based implementation of white-box model predictive control for a GEOTABS office building: A field test demonstration

Model predictive control (MPC) has been proven in simulations and pilot case studies to be a superior control strategy for large buildings. MPC can utilize the weather and occupancy schedule forecasts, together with the system model, to predict the future thermal behavior of the building and minimize the overall energy use and maximize thermal comfort. However, these advantages come with the cost of increased modeling effort, computational demands, communication infrastructure, and commissioning efforts. Thus a typical approach is to, often rapidly, simplify the building modeling and MPC optimization problem while paying a price of not reaching the full performance potential. It has been shown that by employing accurate physics-based models, MPC performance can be notably increased closer to its theoretical performance bound. However, implementation of such high-fidelity MPC in real buildings remains a challenge, resulting in a lack of successful field test studies. This work presents the methodology and field test demonstration of a computationally efficient implementation of the white-box MPC in an office building in Belgium. The detailed model of the building is based on first-principle physical equations. The deployment and supervision of MPC operation in a practical setting are supported by an automated cloud-based communication infrastructure. The motivating factor behind the cloud-based architecture is its compatibility with a commercially appealing control as a service concept. The building is equipped with a ground source heat pump (GSHP) and thermally activated building structures (TABS), where the combination of both is also known as GEOTABS. From a control perspective, GEOTABS buildings are particularly challenging systems due to large scale, complex heating, ventilation and air conditioning (HVAC) system, and slow dynamics with time delays. On the other hand, there is an increased potential for energy savings due to the high thermal mass, which acts as thermal storage. The MPC operation is demonstrated during the challenging transient seasons (switching between heating and cooling), and its performance is compared to a traditional rule-based controller (RBC). We provide a proof of concept of real MPC operation for the most difficult seasons with notable GSHP energy use savings equal to 53.5% and thermal comfort improvement by 36.9%. Other MPC applications found in the literature describe tests for only cooling or only heating, and up to now only for a black-box or a grey-box approach.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

A variance deconvolution estimator for efficient uncertainty quantification in Monte Carlo radiation transport applications

Monte Carlo simulations are at the heart of many high-fidelity simulations and analyses for radiation transport systems. As is the case with any complex computational model, it is important to propagate sources of input uncertainty and characterize how they affect model output. Unfortunately, uncertainty quantification (UQ) is made difficult by the stochastic variability that Monte Carlo transport solvers introduce. The standard method to avoid corrupting the UQ statistics with the transport solver noise is to increase the number of particle histories, resulting in very high computational costs. In this contribution, we propose and analyze a sampling estimator based on the law of total variance to compute UQ variance even in the presence of residual noise from Monte Carlo transport calculations. Here, we rigorously derive the statistical properties of the new variance estimator, compare its performance to that of the standard method, and demonstrate its use on neutral particle transport model problems involving both attenuation and scattering physics. We illustrate, both analytically and numerically, the estimator’s statistical performance as a function of available computational budget and the distribution of that budget between UQ samples and particle histories. We show analytically and corroborate numerically that the new estimator is unbiased, unlike the standard approach, and is more accurate and precise than the standard estimator for the same computational budget.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

An improved specimen preparation method for marine shallow gas-bearing sand sediments and its validations

Instabilities of shallow gas-charged seabed are potential geological hazards in ocean engineering. In practice, the conventional field sampling techniques failed to obtain undisturbed gas-bearing sediments from the seabed for laboratory mechanical testing because of sensitive gas exsolution and escape from sediments. However, preparation of representative remoulded gas-charged specimens is a challenging issue, because it is rather difficult to quantitatively control the gas content and obtain uniform distribution of gas bubbles within the specimen. Given the above problems, this work proposes a reliable approach to reconstitute the high-saturation specimen of gas-charged sediments in the laboratory by an improved multifunction integrated triaxial apparatus (MITA). This apparatus is developed based on an advanced stress path triaxial system by introducing a temperature-controlled system and a wave-monitoring system. The temperature-controlled system is used to accurately mimic the in situ environments of sediments in the seabed. The wave-monitoring system is utilized to identify exsolution point of free gas and examine the disturbance of gas to specimens during gas exsolution. The detailed procedure of gassy specimen preparation is introduced. Then, the quality of prepared specimens using our improved apparatus is validated by the high-resolution micro-X-ray computed tomography (μCT) scanning test, from which bubble occurrence and size distribution within the gassy sand specimen can be obtained; and preliminary mechanical tests on gassy sand specimens with various initial saturation degrees are performed. The proposed specimen preparation procedure succeeds in proving the postulated occurrence state of gas bubbles in coarse-grained sediments and accurately controlling the gas content.

58 GEOSCIENCES↗

Generating synthetic signaling networks for in silico modeling studies

Predictive models of signaling pathways have proven to be difficult to develop. Reasons include the uncertainty in the number of species, the complexity in species’ interactions, and the sparseness and uncertainty in experimental data. Traditional approaches to developing mechanistic models rely on collecting experimental data and fitting a single model to that data. This approach works for simple systems but has proven unreliable for complex systems such as biological signaling networks. For example, uncertainty and sparseness of the data often result in overfitted models that have little predictive value beyond recapitulating the experimental data itself. Thus, there is a need to develop new approaches to create predictive mechanistic models of complex systems. However, to determine the effectiveness of any new algorithm, a baseline model is needed to test its performance. To meet this need, we developed a method for generating artificial synthetic networks that are reasonably realistic and thus can be treated as ground truth models. These synthetic models can then be used to generate synthetic data for developing and testing algorithms designed to recover the underlying network topology and associated parameters. Here, we describe a simple approach for generating synthetic signaling networks that can be used for this purpose.

42 ENGINEERING↗

Rapid grain refinement and compositional homogenization in a cast binary Cu50Ni alloy achieved by friction stir processing

Friction stir processing (FSP) has been increasingly adopted for joining and processing materials in automotive, aerospace and industrial construction. During FSP a dynamic competition between high-speed shear deformation and deformation-induced heating brings about a complex competition between multiple dynamic microstructural evolution mechanisms making it difficult to predict the microstructural evolution pathway. Hence, improved understanding of microstructural evolution mechanisms during FSP can be beneficial for continued growth in the adoption of FSP for demanding applications of future. Towards this goal, this study uses a model binary Cu – 50 at.% Ni alloy to clarify the effect of single and double pass FSP on the microstructural evolution of a coarse grained and compositionally heterogeneous cast microstructure. High energy synchrotron X-ray diffraction, electron backscatter diffraction, and nanoindentation are used to clarify the microstructural evolution due to FSP. The process of compositional homogenization of as-cast segregations is studied by energy dispersive spectroscopy and atom probe tomography. Our results show that a single fast FSP pass at 30 mm.s -1 produces a 100 µm deep layer of submicrometric and hall-petch hardened CuNi grains. The initial cast compositional heterogeneities in a micrometric scale is rapidly transformed to nano-sized domains, mainly confined at grain boundaries. Double pass FSP increases the penetration depth of the processed layer and leads to a 2.9 times grain growth relative to single pass FSP. Grain fragmentation, discontinuous dynamic recrystallization, grain growth, and twinning mechanisms are discussed. In conclusion, these results highlight the value of FSP for ultrafast grain refinement and compositional homogenization of cast alloys.

36 MATERIALS SCIENCE↗

Experimental investigation of the dependence of void nucleation and growth on initial microstructure in high-purity titanium under tension

An experimental investigation of failure mechanisms in relation to the initial microstructure in high-purity titanium samples is presented. The initial microstructure of the specimens was measured in 3D using diffraction-contrast tomography (DCT). Ex-situ X-ray computed tomography (XCT) was used to visualize voids in specimens at various levels of deformation attained by interrupted tensile testing. Electron backscatter diffraction (EBSD) mapping was used to characterize the deformed microstructures per specimen. The investigation showed that the location of failures was unrelated to the formation of the first voids, but rather the nucleation and growth of cracks were from heavily deformed surface regions. The areas surrounding the failure-causing cracks had the highest propensity for void development of any area in the specimen. This facilitated crack propagation through the specimen via “linking up”. The failure of the specimens by microvoid coalescence was bolstered by “dimpled” fracture surfaces. Paint composed of gallium embedded in rubber was used to track the displacement of points along the loading direction of the specimens, to relate the location of failure to the material's initial microstructure. However, the correlation proved difficult, due to complex microstructural evolution involving voids, grain fragmentations, and profuse twinning. Nevertheless, it was shown that necking occurred near the largest grain in the gauge section of the specimens. This is likely caused by the decrease in strength of larger grains, causing strain to concentrate in their vicinity. Here, a comprehensive picture of the failure processes in high-purity titanium under axial loading is presented and discussed in the paper.

36 MATERIALS SCIENCE↗

Monitoring and flaw detection during wire-based directed energy deposition using in-situ acoustic sensing and wavelet graph signal analysis

The goal of this work is to detect flaw formation in the wire-based directed energy deposition (W-DED) process using in-situ sensor data. The W-DED studied in this work is analogous to metal inert gas electric arc welding. The adoption of W-DED in industry is limited because the process is susceptible to stochastic and environmental disturbances that cause instabilities in the electric arc, eventually leading to flaw formation, such as porosity and suboptimal geometric integrity. Moreover, due to the large size of W-DED parts, it is difficult to detect flaws post-process using non-destructive techniques, such as X-ray computed tomography. Accordingly, the objective of this work is to detect flaw formation in W-DED parts using data acquired from an acoustic (sound) sensor installed near the electric arc. To realize this objective, we develop and apply a novel wavelet integrated graph theory approach. The approach extracts a single feature called graph Laplacian Fiedler number from the noise-contaminated acoustic sensor data, which is subsequently tracked in a statistical control chart. Using this approach, the onset of various types of flaws are detected with a false alarm rate less-than 2%. This work demonstrates the potential of using advanced data analytics for in-situ monitoring of W-DED.

42 ENGINEERING↗

Clarifying the formation of equiaxed grains and microstructural refinement in the additive manufacturing of Ti-Cu

Controlling microstructural evolution in metallic additive manufacturing (AM) is difficult, especially in producing refined as-built grains instead of coarse, directional grains. Traditional solutions involve adding inoculants to AM feedstocks, but titanium (Ti) alloys cannot employ this approach without producing detrimental secondary phases. Ti-Cu (Ti-copper) alloys offer a solution through constitutional supercooling and/or solid state thermal cycling under AM conditions. This work analyzes a compositionally graded directed energy deposition (DED) Ti-Cu build, single-melt laser tracks, and dilatometric heat treatments to evaluate if, when, and by what mechanism(s) microstructural refinement occurs. Refinement by inoculation of unmelted powder particles was also considered. Constitutional supercooling produced no net microstructural refinement as any equiaxed dendrites which form are remelted with new deposition. This finding agreed with solidification modeling of powder bed fusion-laser beam (PBF-LB) and DED builds. Solid state thermal cycling refined microstructures only during ex-situ dilatometric heat treatments, suggesting build parameter optimization is needed to achieve refinement in-situ. Accidental heterogeneous nucleation on unmelted Ti powder, originating from the different thermophysical properties of Ti and Cu, provided the most significant microstructural refinement. This work systematically assesses the microstructural refinement mechanisms of Ti-Cu in AM builds and offers insights into microstructural control in eutectoid alloys.

36 MATERIALS SCIENCE↗

Additive manufacturing of metal matrix composites

Although Metal matrix composites (MMCs) are superior to most sought-after metallic alloys, their challenging fabricability has limited their widespread use in bulk-form applications. Among the many advanced fabrication techniques, Additive Manufacturing (AM), owing to its unique capabilities to produce near-net shapes, has drawn significant traction in the past two decades, especially for materials that are difficult to process using traditional methods. However, unlike pure metal/alloy systems, MMCs are highly sensitive to the processing conditions prevailing in AM techniques due to factors such as the high melting point of reinforcement particles and the potential for in-situ reactions. Therefore, it may be a while before metal matrix composites are commercially produced via AM. This review will discuss the current state-of-the-art design, fabricability, and performance of various additively manufactured MMCs. A particular focus will be on microstructural evolution and microstructure-property relationships. The most employed AM techniques, such as directed energy deposition, powder bed fusion, binder jetting, sheet lamination, and solid-state friction stir processing, are fundamentally different in terms of thermo-kinetics, forming the perspective for this review. A detailed comparison of microstructural evolution and process parameter optimization, including feedstock preparation methods and the role of machine learning and modeling among the different AM processes, is also presented. Finally, a critical evaluation of emerging AM technologies for MMCs is also provided, highlighting their potential advantages and challenges.

36 - MATERIALS SCIENCE↗

Dynamic and Programmable Cellular-Scale Granules Enable Tissue-like Materials

Living tissues are an integrated, multiscale architecture consisting of dense cellular ensembles and extracellular matrices (ECMs). The cells and ECMs cooperate to enable specialized mechanical properties and dynamic responsiveness. However, the mechanical properties of living tissues are difficult to replicate. A particular challenge is identification of a cell-like synthetic component, which is tightly integrated with its matrix and also responsive to external stimuli. Here, we demonstrate that cellular-scale hydrated starch granules, an underexplored component in materials science, can turn conventional hydrogels into tissue-like materials when composites are formed. By using several synchrotron-based X-ray techniques, we reveal the mechanically induced organization and training dynamics of the starch granules in the hydrogel matrix. These dynamic behaviors enable multiple tissue-like properties such as programmability, anisotropy, strain-stiffening, mechanochemistry, and self-healability.

36 MATERIALS SCIENCE↗

Critical roles of pores and moisture in sustainable nanocellulose-based super-thermal insulators

In a recent report in Matter, Bergström and co-workers describe a novel thermal transport behavior that subverts this assumption of porous materials. In their work, the authors describe a nanocellulose-based foam that features ultrahigh porosity (> 99.6%) and aligned µm-scale pores (10–100 µm) whose radial thermal conductivity (i.e., perpendicular to the pore alignment) is close to that of free air in the dry state. Furthermore, the radial thermal conductivity of the cellulose-based foam can be reduced to ~14 mW/(m·K) when the relative humidity is ~35%. Super-thermal insulators, which demonstrate a thermal conductivity below that of stationary air (~ 25 mW/(m·K), 20 ºC, 1.0 atm), are needed to minimize heat loss in various applications (e.g., buildings, thermal energy storage tanks, cold chain packaging, etc.) to mitigate the energy crisis and reduce carbon emissions. Introducing pores into a material is a facile and effective way to achieve low thermal conductivity as pores can suppress thermal transport through solids by reducing the cross-sectional area and increasing the tortuosity of the heat transfer pathway. In porous structures there are two kinds of pores: open and closed. While increased porosity can reduce heat conduction through solids with an open porous structure, the improved gas conduction creates a competing effect that simultaneously elevates the heat transfer. Therefore, the thermal conductivity of a material with µm-scale open pores is usually larger than that of stationary air. Reducing the pore size to less than the mean free path of air (~ 70 nm, 20 ºC, 1.0 atm) can effectively reduce gas conduction, enabling the material to achieve a thermal conductivity below that of stationary air. However, high cost of the nanosized raw materials and time-consuming fabrication processes limit the large-scale applications of nanoporous thermal insulators. Meanwhile, closed pores can block heat transport only through the continuous gas phase. As a result, the thermal conductivity of a closed porous structure can theoretically be much smaller than that of stationary air if the solid conduction can also be suppressed by (1) lowering the solid content of the material, (2) reducing the thermal conductivity of the building blocks of the material, and/or (3) increasing interfacial thermal resistance between neighboring building blocks. Most processes used to generate porous structures (e.g., supercritical drying, freeze drying) involve a solvent that escapes the material. Therefore, it is difficult to create pores and isolate them simultaneously, preventing the fabrication of super-thermal insulators with closed pores.

36 MATERIALS SCIENCE↗

Defect engineering of porous aromatic frameworks via end capping improves dioxane removal from water

Amorphous porous organic polymers show promise for energy-efficient adsorptive separations, but it is difficult to understand or improve their performance through intentional structural modification. Herein, we report the synthesis of porous aromatic frameworks (PAFs) with pore structures tailored by the incorporation of a monofunctionalized end-capping monomer that disrupts framework topology. Combining experimental characterization with molecular simulations, we show that this defect engineering strategy yields less densely crosslinked networks, which leads to pore collapse and the presence of unique adsorption sites. These defect-engineered PAFs exhibit enhanced removal of 1,4-dioxane, an important environmental pollutant, from water. Increasing the concentration of end-capping monomers produces PAFs with narrower pore size distributions and improved 1,4-dioxane uptake. These results illustrate that defect engineering can effectively modulate polymer connectivity and porosity for applications in selective adsorptive separations. In conclusion, this technique avoids post-synthetic treatments and presents another approach to tailor amorphous polymeric adsorbents.

36 MATERIALS SCIENCE↗

Making the most of your electrons: Challenges and opportunities in characterizing hybrid interfaces with STEM

Inspired by the unique architectures composed of hard and soft materials in natural and biological systems, synthetic hybrid structures and associated hard-soft interfaces have recently evoked significant interest. Soft matter is typically dominated by structural fluctuations even at room temperature, while hard matter is governed by rigid mechanical behavior. This dichotomy offers considerable opportunities to leverage the disparate properties offered by these components across a wide spectrum spanning from basic science to engineering insights with significant technological overtones. Such hybrid structures, which include polymer nanocomposites, DNA functionalized nanoparticle superlattices, and metal organic frameworks to name a few, have delivered promising insights into the technologically relevant applications such as catalysis, environmental remediation, optoelectronics, and medicine. The interfacial structure between the hard and soft phases demonstrates features across a variety of length scales and often strongly influence the functionality of hybrid systems. While scanning/transmission electron microscopy (S/TEM) has proven to be a valuable tool for acquiring intricate molecular and nanoscale details of these interfaces, the unusual nature of hybrid composites presents a suite of challenges that make assessing or establishing structure–property relationships especially difficult. There are additional considerations at all stages of sample analysis from preparing electron-transparent samples to obtaining sufficient contrast to resolve the interface between dissimilar materials given the dose sensitivity of soft materials. Here, we discuss each of these challenges and supplement a review of recent developments in the field with additional experimental investigations and simulations to present solutions for attaining a nano or molecular-level understanding of these interfaces. These solutions present a host of opportunities for investigating the role interfaces play in this unique class of functional materials.

36 MATERIALS SCIENCE↗

Discovery of Proteoforms Associated With Alzheimer's Disease Through Quantitative Top-Down Proteomics

The complex nature of Alzheimer's disease (AD) and its heterogenous clinical presentation has prompted numerous large-scale - omic analyses aimed at providing a global understanding of the pathophysiological processes involved. AD involves isoforms, proteolytic products, and posttranslationally modified proteins such as amyloid beta (Aβ) and microtubule-associated protein tau. Top-down proteomics directly measures these species and thus, offers a comprehensive view of pathologically relevant proteoforms that are difficult to analyze using traditional proteomic techniques. Here, we broadly explored associations between proteoforms and clinicopathological traits of AD by deploying a quantitative top-down proteomics approach across frontal cortex of 103 subjects selected from the ROS and MAP cohorts. The approach identified 1213 proteins and 11,782 proteoforms, of which 154 proteoforms had at least one significant association with a clinicopathological phenotype. One important finding included identifying Aβ C-terminal truncation state as the key property for differential association between amyloid plaques and cerebral amyloid angiopathy. Furthermore, various N-terminally truncated forms of Aβ had noticeably stronger association with amyloid plaques and global cognitive function. Additionally, we discovered six VGF neuropeptides that were positively associated with cognitive function independent of pathological burden. The database of brain cortex proteoforms provides a valuable context for functional characterization of the proteins involved in AD and other late-onset brain pathologies.

60 APPLIED LIFE SCIENCES↗