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At least 91 records · Page 5

Intrinsic chemical reactivity of solid-electrolyte interphase components in silicon–lithium alloy anode batteries probed by FTIR spectroscopy

Herein we report the solid reaction products from the chemical reaction of aprotic battery electrolyte and three purported components of the Si-based anode SEI : SiO 2 nanoparticles (NPs), lithium silicate (Li x SiO y ) powders, and Si NPs. We use FTIR and classical molecular dynamics/density functional perturbation theory to assess the solid products remaining with these model materials after exposure to electrolyte. The absence of electrochemical bias provides a view of the chemical speciation resulting from early-stage chemical reactivity during battery assembly as well as under open circuit storage conditions. We believe these species represent the initial stages of SEI growth and predict they likely drive subsequent chemical and electrochemical reactions by controlling molecular interactons at the Si active material interface. We find that nominally equivalent materials react differently even before any electrochemistry is performed (e.g., acidic SiO 2 dissolves whereas alkaline SiO 2 is relatively robust), and derive new understanding of the chemical species that could and could not form stable SEI components in Si-based anodes. These results can be used to inform how to passivate Si anode surfaces and potentially generate an artificially engineered SEI that would be stable and enable next-generation battery anodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enabling Extreme Fast-Charging: Challenges at the Cathode and Mitigation Strategies

We report charging lithium-ion batteries (LiBs) in 10 to 15 min via extreme fast-charging (XFC) is important for the widespread adoption of electric vehicles (EVs). Lately, the battery research community has focused on identifying XFC bottlenecks and determining novel design solutions. Like other LiB components, cathodes can present XFC bottlenecks, especially when considering long-term battery life. Therefore, it is necessary to develop a comprehensive understanding of how XFC conditions degrade LiB cathodes. The present article reviews relevant cathode-focused studies and summarizes the current understanding regarding cathode performance and aging issues under XFC conditions. Dominant aging modes and mechanisms are identified at different length-scales with electrochemical correlations for LiNi x Mn y Co z O 2 (NMC)-based cathodes. A range of electrochemical techniques and models provide key insights into cathode performance and life issues. A suite of multimodal and multiscale microscopy and X-ray techniques is surveyed to quantify chemical, structural, and crystallographic NMC-cathode degradation. Cathode cycle-life is scaled to equivalent EV miles to illustrate how cathode degradation translates to real-world scenarios and quantifies cathode-related bottlenecks that hinder XFC adoption. Finally, the article discusses several cathode cycle-life aging mitigation strategies with example case studies and identifies remaining challenges.

25 ENERGY STORAGE↗

Command of active and responsive elastomers by topological defects and patterns

The project resulted in the development of stimuli-responsive elastomer coatings formed by photopolymerized liquid crystal molecules. The molecular orientation of the liquid crystal elastomers is coupled to rubber-like elasticity. The project developed an approach to produce complex patterns of molecular orientation in elastomers by employing photopatterning technique based on plasmonic metamasks that convert unpolarized incoming light into a transmitted light beam with spatially-varying linear polarization. The polarization-modulated light beam aligns the film of azodye molecules, which serves as the substrate for liquid crystal elastomer coating. The alignment of the azodye molecules follows the polarization pattern with a phase shift of the alignment direction by 90 degrees. The azodye substrate imposes orientation of molecules in the adjacent liquid crystal layer which is preserved after the monomers are polymerized into a liquid crystal elastomer. By using differently aligned substrates one could produce various patterns of molecular orientation in the elastomer, which dictate the mechanical properties of the elastomers and their response to external stimuli such as temperature, humidity, and ultraviolet irradiation. In particular, the predesigned molecular orientation produces deterministically defined topography response of the liquid crystal coatings, in which their free surface changes from flat to either locally elevated or locally compressed, depending on whether the pre-inscribed molecular orientation is predesigned with a splay or bend deformation. The research established that the mechanism of this deterministic relation between the dynamic topography and pre-inscribed molecular orientation is rooted in the change of the tensorial order parameter that characterizes the degree of orientational order, and in the contraction/expansion of polymer molecules in response to the order parameter changes. In particular, lowering the order causes contraction of polymer globules. The work demonstrated that the dynamic topography of elastomer coatings with three-dimensional pattern of orientational order includes up and down motion of the material (along the normal to the coating) and also shifts in lateral directions. We demonstrate that the deterministic relationship between the orientational patterns and variations of coatings’ profile is caused by forces that are mathematically equivalent to active forces in the system of “pullers” or “pushers” in active matter, demonstrating universality of the out-of-equilibrium behavior. The project resulted in theoretical models that predictively describe the dynamic response of coatings. The topography of liquid crystal elastomers is sensitive to stimuli such as temperature, ultraviolet irradiation, and humidity. The applicability of the patterned approach to produce dynamic coatings was expanded from nematic elastomers to their smectic counterparts. The project combined a battery of imaging techniques to unveil the dynamic properties of the coatings, ranging from the state-of-the-art dynamic holographic microscopy to fluorescent confocal polarizing microscopy and polscope microscopy. The research uncovered potential applications of dynamic elastomer coatings, such as control placement of colloidal particles, engineering of living tissues with alignment patterns of cells that follow the orientational order of elastomer coatings. The approach developed in the project can be used to design programmable dynamic coatings with functionalities that mimic biological tissues such as skin.

36 MATERIALS SCIENCE↗

Adoption of Plug-in Electric Vehicles: Local Fuel Use and Greenhouse Gas Emissions Reductions Across the U.S.

The dependence on gasoline-powered light-duty automobiles has made U.S. households vulnerable to the burden of fuel costs. Tailpipe emissions from these vehicles constitute 58% of greenhouse gas (GHG) emissions in the U.S., which are damaging to the environment (EPA, 2023). The adoption of plug-in electric vehicles (PEVs) has been shown to effectively reduce fuel costs and GHG emissions. However, local effects on these benefits are not well understood by American consumers, potentially limiting adoption and therefore the realization of PEV benefits at scale (MacInnis & Krosnick, 2020; EY Americas, 2023). To fill this research gap, this study estimates the fuel cost savings and GHG emission reductions at the state and ZIP code levels by considering local fuel prices, vehicle class preference, average vehicle model year, fuel efficiencies, and driving intensities. The study's findings reveal that the adoption of PEVs can yield substantial benefits in terms of fuel cost savings and GHG emission reductions nationwide. Specifically, driving a battery electric vehicle (BEV) is estimated to result in annual savings of up to $\$2,200$, while driving a plug-in hybrid electric vehicle (PHEV) can lead to savings up to $\$1,500$, when compared to an internal combustion engine vehicle (ICEV) of equivalent size. Moreover, using population-weighted averages by ZIP code, BEVs and PHEVs show the potential to save 400 and 200 grams of carbon dioxide equivalent per mile, respectively, compared to a representative ICEV of the same class. The magnitude of fuel cost savings and emissions reduction vary by region due to various factors. Generally, regions with high gasoline prices, low electricity prices, preferences for larger vehicles, and high driving intensities tend to see relatively large fuel savings. The emissions reductions are more pronounced in areas with clean grids where consumer preferences lie with large vehicles. This regional variability underscores the importance of considering local contextual factors when assessing the potential benefits of PEV adoption. In more than 99% of U.S. ZIP codes, PEVs result in overall savings in fuel use (and subsequent costs) and GHG emissions. While not a central focus of this analysis, reductions in GHG tailpipe emissions from PEV adoption would also come with reductions in criteria pollutant emissions, contributing to improved local air quality depending on the PEV penetration, population density, and electricity generation infrastructure in the locality.

33 ADVANCED PROPULSION SYSTEMS↗

Home charging for all: Techno-economic and life cycle assessment of multi-unit dwelling electric vehicle charging hubs

Ubiquitous electric vehicle adoption can drastically reduce greenhouse gas emissions (GHG) but will require equitable home charging infrastructure for all residences. Unlike single-family homes, Multi-Unit Dwellings (MUD) currently lack market share and access to nearby charging infrastructure partly due to expensive capital costs for reluctant residential property-owners. Further, this work evaluates the levelized cost of charging (LCOC) for Battery Electric Vehicles (BEVs) at MUD community charging hubs through a techno-economic analysis (TEA) that leverages real-world charging data and costs. Three different MUD charging types are investigated for a baseline and optimistic case: 1.9-kW Level 1 (L1), 6.6-kW Level 2 (L2), and 50-kW Direct Current Fast Charging (DCFC) stations under three different ownership models: resident, utility, and private company. Results demonstrate L1 and L2 chargers to be less expensive than the gasoline equivalent across the United States. Further, utility and private company ownership models, which avoid initial costs for residential property owners, result in a large LCOC premium for L1 and moderate LCOC premium for L2 relative to the resident ownership model. In contrast, DCFC is shown to be expensive for baseline scenarios but economical for optimistic scenarios especially under private company ownership. This work also performs a cradle to grave (C2G) life cycle assessment (LCA) of an average passenger BEV and gasoline conventional vehicle (CV) using yearly (grid mix & vehicle parameters), hourly (grid mix), and state-level (grid mix) resolution. Results show BEVs to have lower GHG emissions (-86% to-10%) than gasoline CVs in the contiguous U.S. Next, the system boundary of the TEA is extended to the total cost of ownership (TCO) of BEVs. The TCO is then coupled with the C2G GHG emissions to calculate the cost of GHG emissions reduction. Ultimately, the cost of GHG emissions reduction from MUD BEVs relative to gasoline CVs is shown to be negative for every scenario except baseline DCFC, meaning MUD BEV charging infrastructure can be a cost-effective endeavor to reduce GHG emissions.

33 ADVANCED PROPULSION SYSTEMS↗

Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation

The development of non-uniform reaction current distribution within porous electrodes is a ubiquitous phenomenon during battery charging/discharging and frequently controls the rate performance of battery cells. Reaction inhomogeneity in porous electrodes is usually attributed to the kinetic limitation of mass transport within the electrolyte and/or solid electrode phase. In this work, however, we reveal that it is also strongly influenced by the intrinsic thermodynamic behavior of electrode materials, specifically the dependence of the equilibrium potential on the state of charge: the electrode reaction becomes increasingly non-uniform when the slope of the equilibrium potential curve is reduced. We employ numerical simulations and equivalent circuit model to elucidate such a correlation and show that the degree of reaction inhomogeneity and the resultant discharge capacity can be predicted by a dimensionless reaction uniformity number. For electrode materials that have equilibrium potentials insensitive to the state of charge and exhibit significant reaction non-uniformity, we demonstrate several approaches to spatially homogenizing the reaction current inside porous electrodes, including matching the electronic and ionic resistances, introducing graded electronic conductivity and reducing the surface reaction kinetics.

25 ENERGY STORAGE↗

A Simulation Framework for Battery Cell Impact Safety Modeling Using LS-DYNA

The development process of electrified vehicles can benefit significantly from computer-aided engineering tools that predict themultiphysics response of batteries during abusive events. A coupled structural, electrical, electrochemical, and thermal model framework has been developed within the commercially available LS-DYNA software. The finite element model leverages a three-dimensional mesh structure that fully resolves the unit cell components. The mechanical solver predicts the distributed stress and strain response with failure thresholds leading to the onset of an internal short circuit. In this implementation, an arbitrary compressive strain criterion is applied locally to each unit cell. A spatially distributed equivalent circuit model provides an empirical representation of the electrochemical responsewith minimal computational complexity.The thermalmodel provides state information to index the electrical model parameters, while simultaneously accepting irreversible and reversible sources of heat generation. The spatially distributed models of the electrical and thermal dynamics allow for the localization of current density and corresponding temperature response. The ability to predict the distributed thermal response of the cell as its stored energy is completely discharged through the short circuit enables an engineering safety assessment. A parametric analysis of an exemplary model is used to demonstrate the simulation capabilities.

25 ENERGY STORAGE↗

Opportunities for low-carbon generation and storage technologies to decarbonise the future power system

Alternatives to cope with the challenges of high shares of renewable electricity in power systems have been addressed from different approaches, such as energy storage and low-carbon technologies. However, no model has previously considered integrating these technologies under stability requirements and different climate conditions. In this study, we include this approach to analyse the role of new technologies to decarbonise the power system. The Spanish power system is modelled to provide insights for future applications in other regions. After including storage and low-carbon technologies (currently available and under development), batteries and hydrogen fuel cells have low penetration, and the derived emission reduction is negligible in all scenarios. Compressed air storage would have a limited role in the short term, but its performance improves in the long term. Flexible generation technologies based on hydrogen turbines and long-duration storage would allow the greatest decarbonisation, providing stability and covering up to 11-14 % of demand in the short and long term. The hydrogen storage requirement is equivalent to 18 days of average demand (well below the theoretical storage potential in the region). When these solutions are considered, decarbonising the electricity system (achieving Paris targets) is possible without a significant increase in system costs (< 114 euro/MWh).

08 HYDROGEN↗

Creating a Lunar EVA Work Envelope

A work envelope has been defined for weightless Extravehicular Activity (EVA) based on the Space Shuttle Extravehicular Mobility Unit (EMU), but there is no equivalent for planetary operations. The weightless work envelope is essential for planning all EVA tasks because it determines the location of removable parts, making sure they are within reach and visibility of the suited crew member. In addition, using the envelope positions the structural hard points for foot restraints that allow placing both hands on the job and provides a load path for reacting forces. EVA operations are always constrained by time. Tasks are carefully planned to ensure the crew has enough breathing oxygen, cooling water, and battery power. Planning first involves computers using a virtual work envelope to model tasks, next suited crew members in a simulated environment refine the tasks. For weightless operations, this process is well developed, but planetary EVA is different and no work envelope has been defined. The primary difference between weightless and planetary work envelopes is gravity. It influences anthropometry, horizontal and vertical mobility, and reaction load paths and introduces effort into doing "overhead" work. Additionally, the use of spacesuits other than the EMU, and their impacts on range of motion, must be taken into account. This paper presents the analysis leading to a concept for a planetary EVA work envelope with emphasis on lunar operations. There is some urgency in creating this concept because NASA has begun building and testing development hardware for the lunar surface, including rovers, habitats and cargo off-loading equipment. Just as with microgravity operations, a lunar EVA work envelope is needed to guide designers in the formative stages of the program with the objective of avoiding difficult and costly rework.

Griffin, Brand N.↗

How reliable is distribution of relaxation times (DRT) analysis? A dual regression-classification perspective on DRT estimation, interpretation, and accuracy

The distribution of relaxation times (DRT) has gained increasing attention and adoption in recent years as a versatile method for analyzing electrochemical impedance spectroscopy (EIS) data obtained from complex devices like fuel cells, electrolyzers, and batteries. The DRT deconvolutes the impedance without a priori specification of a generative model, which is especially useful for interpretation and model selection when the governing principles of the system under study are not fully understood. However, DRT estimation is an ill-posed inversion problem that must be addressed with a subjective choice of regularization and tuning, which leaves substantial risk of misleading interpretations of EIS data. In this work, we suggest a new classification view of the DRT inversion to clarify DRT estimation and interpretation. We introduce a dual regression-classification framework that unifies the classification and regression views of the DRT inversion with wide-reaching implications for DRT analysis. The dual framework is employed to demonstrate a new kind of DRT inversion algorithm and develop novel evaluation metrics that capture previously ignored aspects of DRT accuracy. These approaches are applied to both synthetic data and experimental spectra collected from a protonic ceramic fuel cell and a lithium-ion battery to illustrate their broad utility. The dual inversion algorithm shows promising performance for accurate DRT estimation and autonomous model identification, while the dual evaluation approach produces metrics that meaningfully assess the strengths and risks of DRT algorithms. Here this work provides valuable insight for both practical application of the DRT to experimental data and further development of EIS analysis methods.

36 MATERIALS SCIENCE↗

Computational study of Li 3 BO 3 and Li 3 BN 2 II: Stability analysis of pure phases and of model interfaces with Li anodes

Both Li 3 BO 3 and Li 3 BN 2 materials have promising properties for use in all solid-state batteries and other technologies dependent on electrolytes with significant ionic conductivity. As the second of a two-part study, the structural properties of Li 3 BO 3 and three reported phases of Li 3 BN 2 are investigated using first-principles modeling techniques. For alpha- Li 3 BN 2 , the tetragonal P4 2 / mnm structure reported in the literature is found to be unstable as evidenced by imaginary phonon modes near the M point of its Brillouin zone. Our simulations within the harmonic approximation suggest that the real α phase has the orthorhombic space group symmetry Pmmn formed with twice as many formula units and tiny adjustments of the equivalent lattice parameters and fractional coordinates. Extending the analysis of the Pmmn α- Li 3 BN 2 structure to the quasiharmonic approximation improves the agreement between the room-temperature x-ray pattern reported in the literature and the corresponding simulation results. In anticipation of the use of the monoclinic phases of Li 3 BO 3 and Li 3 BN 2 in Li ion conducting applications, chemical stability is investigated in terms of free-energy differences of possible decomposition and Li reaction processes, finding encouraging results. As further investigations of Li 3 BO 3 and β- Li 3 BN 2 as electrolyte or coating materials, particularly for use with Li metal anodes, idealized electrolyte/Li interfaces were investigated in terms of their geometric, energetic, and electronic properties. The results find the electrolyte/Li interfaces to be quite favorable, perhaps comparable to the pioneering LiPON/Li system.

36 MATERIALS SCIENCE↗

Piezoelectric Charging and Wireless Communication

Modern medicine is undergoing a revolution in the application of new sensor capabilities for aiding in diagnosis of specific conditions and monitoring a variety of informative vital signs. In the past, many of the measurements were limited by what could be accomplished externally. A shift toward in-vivo monitoring for both diagnostic and therapeutic sensing and actuation [1] has created a need for low power electronics, high energy density batteries and methods to successfully power devices embedded in the body. For a review of the field and sensing capabilities see [2]. Recent studies suggest that charging with ultrasound is more efficient at longer transmission distance (> 10cm) than inductive charging [3]. In this manuscript, we discuss the modeling and experimentation that we have accomplished and demonstrate in ultrasonic charging of sensors having the form and fit of in-vivo sensors. The task goal has been to use piezoelectric transducers for wireless communication and powering of sensors internal to the human body with a goal to transmit power levels of 100 W a receiver with receiving area of 3x3 mm2 over a distance of 16 cm equivalent to human body interior. The results suggest that we can transmit power levels that exceed this baseline requirement.

Jackson, Shannon↗

Stress and Strain in Silicon Electrode Models

While the high capacity of silicon makes it an attractive negative electrode for Li-ion batteries, the associated large volume change results in fracture and capacity fade. Composite electrodes incorporating silicon have additional complexity, as active material is attached to surrounding material which must likewise experience significant volume change. In this paper, a finite-deformation model is used to explore, for the first time, mechanical interactions between a silicon particle undergoing lithium insertion, and attached binder material. Simulations employ an axisymmetric model system in which solutions vary in two spatial directions and shear stresses develop at interfaces between materials. The mechanical response of the amorphous active material is dependent on lithium concentration, and an equation of state incorporating reported volume expansion data is used. Simulations explore the influence of active material size and binder stiffness, and suggest delamination as an additional mode of material damage. Computed strain energies and von Mises equivalent stresses are in physically-relevant ranges, comparable to reported yield stresses and adhesion energies, and predicted trends are largely consistent with reported experimental results. It is hoped that insights from this work will support the design of more robust silicon composite electrodes.

36 MATERIALS SCIENCE↗

Nanostructure-Driven Ion Transport in PCBM-Based Polymer Electrolytes

Nanostructure-Driven Ion Transport in PCBM-Based Polymer ElectrolytesChe-Nan Sun1, Thomas A. Zawodzinski1,2, Fei Ren3, Jong Kahk Keum1 and Jihua Chen1, (1)Oak Ridge National Laboratory, (2)The University of Tennessee, (3)Temple University Polyethylene oxide or PEO is an extensively-examined candidate for solid polymer electrolyte materials of lithium ion batteries, and its composite electrolytes has promising ion conductivities.[1-3] Oxide nanoparticles with sizes of 5-10 nm are often introduced into these polymer-based composite electrolytes in order to suppress their room-temperature crystallite formation.1-9 The size, geometry and surface functionality of the added particles were known to largely affect the structure and performance of the blended electrolytes.5,10 In this study, we examined a functionalized-fullerene-based composite electrolytes, providing details in their self-assembled nanostructures, modulus, hardness, as well as temperature-dependent ion-conducting behaviors. To the best of our knowledge, no fullerene-based, lithium conducting, composite electrolyte has been reported previously. Herein we used a bench-mark fullerene derivative, phenyl-C61-butyric acid methyl ester (PCBM) as a model fullerene compound and performed impedance spectroscopy, equivalent circuit modeling, nanoscale elemental mapping (in transmission electron microscope), wide-angle X-ray diffraction, as well as nanoindentation to shed light on a 6-fold enhancement in low temperature (less than 50oC) ion conductivity of PEO - lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-PCBM electrolytes, along with the underlying changes in nanomorphology , mechanical properties, and crystal structures. Based on a previous density functional theory (DFT) calculation, 11 the interaction energies Ei among PEO polymers is estimated to be 2.58 kcal mol-1 per monomer, the Ei between PCBM and PEO is 3.50 kcal mol-1 per monomer (PCBM is taken as 1 repeat unit), and the Ei among PCBMs themselves is 6.01 kcal mol-1 per monomer. This explains that at very low PCBM weight percentage, without sufficient PCBM-PCBM contacts, it is more energetically favorable for fullerenes to disperse into PEO matrix. However, with higher PCBM concentration, the fullerenes will efficiently pack with each other into domains with gradually increased dimensions. Quantification of PCBM domains is performed by line scan analysis of energy filtered TEM (EFTEM) images. Upon the addition of PCBM, the average domain sizes gradually increase from 3.4±1 nm ( 0% PCBM), to 4.6±1 nm (10% PCBM) and 4.9±2 nm (20% PCBM), and finally to 7.5±5 nm (40% PCBM ). (A precise determination of PCBM domain dimension is not possible when the domain size is less than 3 nm, due to the lack of EFTEM contrast in these samples). We attribute the observed ion conductivity improvement to those nanomorphological variation in PCBM-PEO-LiTFSi systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Quantifying policy gaps for achieving the net-zero GHG emissions target in the U.S. light-duty vehicle market through electrification

The U.S. light-duty vehicle (LDV) industry, a major greenhouse gas (GHG) emitting sector, is embracing decarbonization. Considering only electrification pathways, this study uses publicly-available tools – MA3T and VISION on vehicle market penetration, fleet accounting and life-cycle analysis to quantify the policy gaps for LDVs to achieve the net-zero GHG emissions target in nine vehicle penetration cases under two electricity mix scenarios, including the U.S. administration's decarbonization strategy – 100% clean electricity by 2035. The MA3T model is a multinomial discrete choice model for market share projection by vehicle technology, and the VISION is a vehicle stocks and GHG emissions projection model by using vehicle and travel characteristics. This study projects the impacts of technology and policy enforcement on shaping the dynamics and decarbonization of the LDV market. Additionally, achieving the expected improvement of battery technology and charging infrastructure is critical but can only reduce the 2050 GHG emissions to 48–54% of the 2020 level under the electricity renewable mix scenario. It is almost impossible to achieve a 100% battery electric vehicle stock by 2050 and the 2050 net-zero target in the LDV industry unless ban of internal combustion engine technology is implemented starting in 2035 and under the 2035 100% clean electricity scenario. These extreme conditions also sacrifice most from the consumer welfare perspective. A greater policy forcing intensity accelerates plug-in electric vehicle penetration, while with declining marginal effect and reduced consumer welfare. Among the investigated policy scenarios, the policy forcing intensity equivalent to a fuel tax of $1–2 per gasoline gallon reduces the most GHG emissions while keeping a positive consumer welfare.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Ion Transport in Concentrated Crosslinked Solid Polymer Electrolytes

Crosslinking polymers is a common approach to create mechanically stable solid materials such as polymer electrolytes for lithium batteries. In conventional liquid electrolytes, the solvent molecules move freely to accommodate the field-induced motion of ions. However, in crosslinked polymer electrolytes, the rearrangement of polymer segments is constrained by the deformation limits of the network. Herein, we develop a new transport model that accounts for both the formation of concentration gradients and the elasticity of the electrolyte. The elasticity is incorporated by adding an additional term related to the entropy of crosslinked strands to the electrochemical potential of the salt. The resulting Crosslink Model contains two adjustable parameters: $\mathcal{N}$, the average number of monomers in a strand, and λ crit , the maximum strain the network can sustain. These solid-like constraints produce singularities in the governing transport equations, fundamentally altering the concentration profiles. Plateaus in salt concentrations emerge near the electrodes, and network elasticity introduces a strain overpotential. When compared to a Baseline Model ($\mathcal{N}$ → ∞, equivalent to concentrated solution theory), which predicts steepest gradients near the electrodes, both models yield similar current–voltage relationships. Model predictions are compared to electrochemical data for a poly(ethylene oxide)-based crosslinked polymer electrolyte.

Patel, Vivaan [University of California, Berkeley,↗

Insights into the crystal chemistry of Earth materials rendered by electron density distributions: Pauling's rules revisited

Pauling's first two rules are examined in terms of the accumulation of the electron density between bonded pairs of atoms for a relatively large number of oxide and silicate crystals and siloxane molecules. The distribution of the electron density shows that the radius of the oxygen atom is not fixed, but that it actually decreases systematically from ~1.40 Å to ~ 0.65 Å as the polarizing power and the electronegativity of the bonded metal atoms increase and the distribution of the O atom is progressively polarized and contracted along the bond vectors by the impact of the bonded interactions. The contractions result in an aspherical oxygen atom that displays as many different bonded “radii” as it has bonded interactions. The bonded radii for the metal atoms match the Shannon and Prewitt ionic radii for the more electropositive atoms like potassium and sodium, but they are systematically larger for the more electronegative atoms like aluminum, silicon and phosphorous. Pauling's first rule is based on the assumption that the radius of the oxide anion is fixed and that the radii of the cations are such that radius sum of the spherical oxide anion and a cation necessarily equals the separation between the cation-anion bonded pair with the coordination number of the cation being determined by the ratio of the radii of the cation and anion. In the case of the bonded radii, the sum of the bonded radii for the metal atoms and the oxide anion necessarily equals the bond lengths by virtue of the way that the bonded radii were determined in the partitioning of the electron density along the bond path into metal and O atom parts. But, the radius ratio for the O and M atoms is an unsatisfactory rule for determining the coordination number of the metal atom inasmuch as a bonded O atom is not, in general, spherical, and its size varies substantially along its bonded directions. But by counting the number of bond paths that radiate from a bonded atom, the coordination number of the atom is determined uniquely independent of the asphericity and sizes of the atom. A power law connection established between the bond lengths and bond strengths for crystals and molecules is mirrored by a comparable power law connection between bond length and the accumulation of the electron density between bonded pairs of atoms, a connection that is consistent with Pauling's electroneutrality postulate that the charges of the atoms in an oxide are negligibly small. The connection indicates that a one-to-one correspondence exists between the accumulation between a pair of bonded atoms and the Pauling bond strength for M-O bonded interaction for all atoms of the periodic table. The connection provides a common basis for understanding the success of the manifold applications that have been made with the bond valence theory model together with the modeling of crystal structures, chemical zoning, leaching and cation transport in batteries and the like. We believe that the wide spread applications of the model in mineralogy and material science owes much of its success to the direct connection between bond strength and the quantum mechanical observable, the electron density distribution. Comparable power law expressions established for the bonded interactions for both crystals and molecules support Pauling's assertion that his second rule has significance for molecules as well as for crystals. A simple expression is found that provides a one to one connection between the accumulation of the electron density between bonded M and O atoms and the Pauling bond strength for all M atoms of the periodic table with ~ 95 % of the variation of the bond strength being explained in terms of a linear dependence on the accumulated electron density. Compelling evidence is presented that supports the argument that the Si-O bonded interactions for tiny siloxane molecules and silicate crystals are chemically equivalent.

Environmental Molecular Sciences Laboratory↗

Vehicle Technologies Program Government Performance and Results Act (GPRA) Report for Fiscal Year 2012

The U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy has defined milestones for its Vehicle Technologies Program (VTP). This report provides estimates of the benefits that would accrue from achieving these milestones relative to a base case that represents a future in which there is no VTP-supported vehicle technology development. Improvements in the fuel economy and reductions in the cost of light- and heavy-duty vehicles were estimated by using Argonne National Laboratory's Autonomie powertrain simulation software and doing some additional analysis. Argonne also estimated the fraction of the fuel economy improvements that were attributable to VTP-supported development in four "subsystem" technology areas: batteries and electric drives, advanced combustion engines, fuels and lubricants, and materials (i.e., reducing vehicle mass, called "lightweighting"). Oak Ridge National Laboratory's MA 3 T (Market Acceptance of Advanced Automotive Technologies) tool was used to project the market penetration of light-duty vehicles, and TA Engineering's TRUCK tool was used to project the penetrations of medium- and heavy-duty trucks. Argonne's VISION transportation energy accounting model was used to estimate total fuel savings, reductions in primary energy consumption, and reductions in greenhouse gas emissions that would result from achieving VTP milestones. These projections indicate that by 2030, the on-road fuel economy of both light- and heavy-duty vehicles would improve by more than 20%, and that this positive impact would be accompanied by a reduction in oil consumption of nearly 2 million barrels per day and a reduction in greenhouse gas emissions of more than 300 million metric tons of CO 2 equivalent per year. These benefits would have a significant economic value in the U.S. transportation sector and reduce its dependency on oil and its vulnerability to oil price shocks.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗