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At least 181 records · Page 10

Conduction mechanism of single-crystal alumina

The fully guarded three-terminal technique was used to perform conductivity measurements on single-crystal alumina at temperatures of 400-1300 C. The conductivity was also determined as a function of time at various temperatures and applied fields. Further, the fractions of the current carried by Al and O ions (ionic transference numbers) were determined from long-term transference experiments in the temperature range 1100-1300 C. A mathematical model of the conduction mechanism is proposed, and model predictions are compared with experimental results.

Will, Fritz G.↗

A high-performance hydroxide exchange membrane enabled by Cu 2+ -crosslinked chitosan

We report ion exchange membranes are widely used to selectively transport ions in various electrochemical devices. Hydroxide exchange membranes (HEMs) are promising to couple with lower cost platinum-free electrocatalysts used in alkaline conditions, but are not stable enough in strong alkaline solutions. Herein, we present a Cu 2+ -crosslinked chitosan (chitosan-Cu) material as a stable and high-performance HEM. The Cu 2+ ions are coordinated with the amino and hydroxyl groups of chitosan to crosslink the chitosan chains, forming hexagonal nanochannels (similar to 1nm in diameter) that can accommodate water diffusion and facilitate fast ion transport, with a high hydroxide conductivity of 67 ms cm -1 at room temperature. The Cu 2+ coordination also enhances the mechanical strength of the membrane, reduces its permeability and, most importantly, improves its stability in alkaline solution (only 5% conductivity loss at 80 degrees C after 1,000 h). These advantages make chitosan-Cu an outstanding HEM, which we demonstrate in a direct methanol fuel cell that exhibits a high power density of 305 mWcm -2 . The design principle of the chitosan-Cu HEM, in which ion transport channels are generated in the polymer through metal-crosslinking of polar functional groups, could inspire the synthesis of many ion exchange membranes for ion transport, ion sieving, ion filtration and more.

36 MATERIALS SCIENCE↗

Ion energetics in the Venus nightside ionosphere

Consideration is given to the energetics of the ion gas flowing across the terminator into the Venus nightside ionosphere. Expressions are derived for the transport time of the ion gas (through 1 radian in solar zenith angle), the heat transfer time from the hot electron gas to the ions of an amount equal to the ion thermal energy), and the time required for vertical heat conduction to remove the internal energy of the ion column above a reference altitude, and it is shown that the time constant for transport is an order of magnitude smaller than the electron heat transfer time and comparable to the conduction time, and thus the ion gas is not a vertical conductive steady state. The conversion of bulk flow ion kinetic energy into heat is suggested as the mechanism responsible for the maintenance of the nightside ion temperatures at their observed values. It is thus concluded that the flow of the ion gas is quasi-adiabatic, and that steady-state, vertical, one dimensional energy balance models must be used with caution in the Venus ionosphere.

Knudsen, W. C.↗

Multiscale operando X-ray investigations provide insights into electro-chemo-mechanical behavior of lithium intercalation cathodes

The electrochemical performance and cycle life of lithium-ion batteries (LIBs) depend on the electrochemical, chemical, and mechanical behavior of electrodes and electrolytes. Despite extensive studies conducted previously, challenges exist to decouple these behaviors, capture the evolution of electro-chemo-mechanical behavior in realistic conditions, and correlate atomic-scale stress evolution to micro-scale bulk mechanical degradation. Here, we report multiscale operando techniques to investigate polydisperse battery electrodes by integrating volume-averaged quantitative synchrotron X-ray scattering with high-resolution transmission X-ray microscopy (TXM). The former provides us information spanning a wide spatial range, from Angstrom-level atomic structures to micrometer-level particle scales, while the latter provides time-resolved 2D images of the particles during cycling. The complementarity of the two operando techniques is demonstrated by an over-lithiation test of LiCoO 2 electrodes, where particles crack and eventually pulverize. Additionally, the techniques are applied to study LiCoO 2 cycling stability from 3.0 V to 4.5 V. Operando X-ray scattering result shows nanometer-scale features keep forming in LiCoO 2 electrodes during cycling, resulting in an increased projected area observed by the TXM experiment. The formation of such features is inhibited by a polymer coating on the electrode, leading to vastly improved cycling stability. The polymer coating alleviates LiCoO 2 surface deterioration, reduces side product generation, and inhibits LiCoO 2 particles volume expansion during the cycling test. These operando multimodal X-ray techniques presented herein thus offer a novel, multiscale diagnostic modality for studying existing and emerging battery materials, aiding the development of next-generation LIBs.

25 ENERGY STORAGE↗

Structural insights into GABA A receptor potentiation by Quaalude

Methaqualone, a quinazolinone marketed commercially as Quaalude, is a central nervous system depressant that was used clinically as a sedative-hypnotic, then became a notorious recreational drug in the 1960s-80s. Due to its high abuse potential, medical use of methaqualone was eventually prohibited, yet it persists as a globally abused substance. Methaqualone principally targets GABA A receptors, which are the major inhibitory neurotransmitter-gated ion channels in the brain. The restricted status and limited accessibility of methaqualone have contributed to its pharmacology being understudied. Here, we use cryo-EM to localize the GABA A receptor binding sites of methaqualone and its more potent derivative, PPTQ, to the same intersubunit transmembrane sites targeted by the general anesthetics propofol and etomidate. Both methaqualone and PPTQ insert more deeply into subunit interfaces than the previously-characterized modulators. Binding of quinazolinones to this site results in widening of the extracellular half of the ion-conducting pore, following a trend among positive allosteric modulators in destabilizing the hydrophobic activation gate in the pore as a mechanism for receptor potentiation. These insights shed light on the underexplored pharmacology of quinazolinones and further elucidate the molecular mechanisms of allosteric GABA A receptor modulation through transmembrane binding sites.

59 BASIC BIOLOGICAL SCIENCES↗

Argyrodite-type advanced lithium conductors and transport mechanisms beyond paddle-wheel effect

Abstract Development of next-generation solid-state Li-ion batteries requires not only electrolytes with high room-temperature (RT) ionic conductivities but also a fundamental understanding of the ionic transport in solids. In spite of considerable work, only a few lithium conductors are known with the highest RT ionic conductivities ~ 0.01 S/cm and the lowest activation energies ~0.2 eV. New design strategy and novel ionic conduction mechanism are needed to expand the pool of high-performance lithium conductors as well as achieve even higher RT ionic conductivities. Here, we theoretically show that lithium conductors with RT ionic conductivity over 0.1 S/cm and low activation energies ~ 0.1 eV can be achieved by incorporating cluster-dynamics into an argyrodite structure. The extraordinary superionic metrics are supported by conduction mechanism characterized as a relay between local and long-range ionic diffusions, as well as correlational dynamics beyond the paddle-wheel effect.

25 ENERGY STORAGE↗

Transport of penetrants in polymeric materials

Transport phenomena of chemical species in polymers underpin many applications. This mini-review discusses several key transport scenarios in polymer gels, melts and crosslinked polymer networks. Transport mechanisms of a wide variety of penetrant and polymer chemistries are discussed via activated hopping theory and cover across the rubbery, intermediate/deeply supercooled and glassy states of polymers. Moreover, we also discuss the ionic conductivity in polymer electrolytes, emphasizing the relationship between ion diffusion and the segmental relaxation of polymers and highlighting current challenges in the community. Finally, potential research directions are suggested concerning how external fields, such as mechanical force fields, active matter and self-propelling particles, affect the particle transport in polymers. This mini-review offers a general overview of motivations for studying penetrant transports in polymers and diverse mechanisms involved.

activated hopping↗

Defect-driven anomalous transport in fast-ion conducting solid electrolytes

We report solid-state ionic conduction is a key enabler of electrochemical energy storage and conversion. The mechanistic connections between material processing, defect chemistry, transport dynamics, and practical performance are of considerable importance, but remain incomplete. Here, inspired by studies of fluids and biophysical systems, we re-examine anomalous diffusion in the iconic two-dimensional fast-ion conductors, the β- and β"-aluminas. Using large-scale simulations, we reproduce the frequency dependence of alternating-current ionic conductivity data. We show how the distribution of charge-compensating defects, modulated by processing, drives static and dynamic disorder, which lead to persistent sub-diffusive ion transport at macroscopic timescales. We deconvolute the effects of repulsions between mobile ions, the attraction between the mobile ions and charge-compensating defects, and geometric crowding on ionic conductivity. Our quantitative framework based on these model solid electrolytes connects their atomistic defect chemistry to macroscopic performance with minimal assumptions and enables mechanism-driven 'atoms-to-device' optimization of fast-ion conductors.

25 ENERGY STORAGE↗

Thermal effects mediating the flow induced by laser-induced optical breakdown

Here, a short focused laser pulse can generate a hot plasma, which expands then contracts and can eject a hot jet, the speed and direction of which is sensitive to the details of the plasma kernel. The coupling of thermal and chemical nonequilibrium plasma mechanisms with this hydrodynamic development is assessed with detailed simulations of a two-temperature, three-species plasma model. Time scales for electron recombination, thermal relaxation, and diffusion are compared to that of the plasma expansion to anticipate conditions in which these mechanisms might affect the vorticity generation that leads to the ultimate flow pattern. The effect of these mechanisms are analyzed through comparison with corresponding inert-gas and equilibrium models. Thermal-nonequilibrium effects are found to be weak due to rapid relaxation of the heavy-particle and electronic temperatures. In contrast, chemical equilibration occurs at a rate comparable to the expansion and thereby enhance both it and subsequent hydrodynamic mechanisms as the energy stored in ion formation during the preceding breakdown is released by electron recombination. Thermal conduction, enhanced by high-temperature free electrons, weakens the ejection.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA Tech Briefs, April 2007

Topics include: Wearable Environmental and Physiological Sensing Unit; Broadband Phase Retrieval for Image-Based Wavefront Sensing; Filter Function for Wavefront Sensing Over a Field of View; Iterative-Transform Phase Retrieval Using Adaptive Diversity; Wavefront Sensing With Switched Lenses for Defocus Diversity; Smooth Phase Interpolated Keying; Maintaining Stability During a Conducted-Ripple EMC Test; Photodiode Preamplifier for Laser Ranging With Weak Signals; Advanced High-Definition Video Cameras; Circuit for Full Charging of Series Lithium-Ion Cells; Analog Nonvolatile Computer Memory Circuits; JavaGenes Molecular Evolution; World Wind 3D Earth Viewing; Lithium Dinitramide as an Additive in Lithium Power Cells; Accounting for Uncertainties in Strengths of SiC MEMS Parts; Ion-Conducting Organic/Inorganic Polymers; MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells; Counterrotating-Shoulder Mechanism for Friction Stir Welding; Strain Gauges Indicate Differential-CTE-Induced Failures; Antibodies Against Three Forms of Urokinase; Understanding and Counteracting Fatigue in Flight Crews; Active Correction of Aberrations of Low-Quality Telescope Optics; Dual-Beam Atom Laser Driven by Spinor Dynamics; Rugged, Tunable Extended-Cavity Diode Laser; Balloon for Long-Duration, High-Altitude Flight at Venus; and Wide-Temperature-Range Integrated Operational Amplifier.

Source record↗

Insight into the deformation features and capacity loss mechanisms of lithium-ion pouch cells under spherical indentation conditions

Mechanical deformation under extreme conditions is one of the important reasons for the failure of lithium-ion batteries in automotive application. However, the deformation features and component failure of lithium-ion cells to external loading has never been a design consideration. Here, in this study, we conduct spherical indentation tests on a dozen of lithium-ion cells with different capacities under different control mode conditions to investigate their deformation features and capacity loss mechanisms. The experimental results show that, under mechanical deformation conditions, internal faults of cells occur in stages, and energy accumulation and sudden release are two key processes of cell's mechanical failure. The cells' state of charge is the main factor affecting their thermal runaway behaviors. In addition, a finite element model is developed to simulate the deformation features and the failure mechanism of key components of lithium-ion pouch cells; the 3D x-ray computed tomography is employed to demonstrate its internal configuration. With this model, the force-strain response, the deformation features as well as the size of the failure area of lithium-ion cells under spherical indentation conditions are accurately predicted. In 3D x-ray computed tomography images, unique mud cracks in cooper current collector are observed, and the influence mechanisms of the isolated fragments on the cell capacities are revealed. These results may provide useful information for the mechanical structure design of the components of lithium-ion pouch cells.

25 ENERGY STORAGE↗

Mechanically Robust Bismuth-Embedded Carbon Microspheres for Ultrafast Charging and Ultrastable Sodium-Ion Batteries

Advancements in the development of fast-charging and long-lasting microstructured alloying anodes with high volumetric capacities are essential for enhancing the operational efficiency of sodium-ion batteries (SIBs). These anodes, however, face challenges such as declined cyclability and rate capability, primarily due to mechanical degradation reduced by significant volumetric changes (over 252%) and slow kinetics of sodium-ion storage. Herein, we introduce a novel anode design featuring densely packed bismuth (Bi) embedded within highly conductive carbon microspheres to overcome the aforementioned challenges. Remarkably, the high loading Bi anode within carbon microspheres with a high tap density of 2.59 g cm -3 possesses significant mechanical strength exceeding 590 MPa and limits volume swelling of only 10.9% post-sodiation. This anode demonstrates a high volumetric capacity (908.3 mAh cm -3 ), ultrafast chargeability (200 A g -1 , full charge/discharge in just 5.5 s), and outstanding cyclability over 12,000 cycles and maintains exceptional cycling stability even at -30 °C. The full cell paired with a Na 3 V 2 (PO 4 ) 3 cathode retains over 80% capacity after 600 cycles at 36 C, demonstrating a remarkable rate capability of 126 C (full charge/discharge in 28.6 s). Our comprehensive experimental evaluations and chemo-mechanical simulations shed light on the mechanisms underpinning the anode's superior performance. In conclusion, this development marks a significant advancement in the design of durable and fast-charging anodes for high-performance SIBs.

25 ENERGY STORAGE↗

A two-electron transfer mechanism of the Zn-doped δ-MnO 2 cathode toward aqueous Zn-ion batteries with ultrahigh capacity

Neutral aqueous zinc-ion batteries (ZIBs) have attracted considerable attention due to their safe and green features. As one typical cathode, birnessite MnO 2 (δ-MnO 2 ) suffers from low conductivity and structural instability, and its energy storage mechanism is still not well established yet. Herein, we developed a Zn-doped δ-MnO 2 material via a facile and effective microwave-assisted method for the cathode in aqueous ZIBs. By incorporating Zn to modify the microstructure and promote reaction kinetics, the Zn-doped δ-MnO 2 electrode demonstrates significantly enhanced electrochemical performance with an ultrahigh reversible capacity of 455 mA h g –1 and excellent specific energy of 628 W h kg –1 . In addition, the successive insertion of H + and Zn 2+ and deep two-electron transfer routes are revealed systematically by ex situ experiments. In this study, the two-electron transfer route (Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ ) mechanism of Zn-doped δ-MnO 2 electrodes explains the exceedingly high capacity and opens new opportunities to develop high-energy aqueous ZIBs.

25 ENERGY STORAGE↗

Thermal Control and Enhancement of Heat Transport Capacity of Two-Phase Loops With Electrohydrodynamic Conduction Pumping

There are three kinds of electrohydrodynamics (EHD) pumping based on Coulomb force: induction pumping, ion-drag pumping, and pure conduction pumping. EHD induction pumping relies on the generation of induced charges. This charge induction in the presence of an electric field takes place due to a non-uniformity in the electrical conductivity of the fluid which can be caused by a non-uniform temperature distribution and/or an inhomogeneity of the fluid (e.g. a two-phase fluid). Therefore, induction pumping cannot be utilized in an isothermal homogeneous liquid. In order to generate Coulomb force, a space charge must be generated. There are two main mechanisms for generating a space charge in an isothermal liquid. The first one is associated with the ion injection at a metal/liquid interface and the related pumping is referred to as ion-drag pumping. Ion-drag pumping is not desirable because it can deteriorate the electrical properties of the working fluid. The second space charge generation mechanism is associated with the heterocharge layers of finite thickness in the vicinity of the electrodes. Heterocharge layers result from dissociation of the neutral electrolytic species and recombination of the generated ions. This type of pumping is referred to as pure conduction pumping. This project investigates the EHD pumping through pure conduction phenomenon. Very limited work has been conducted in this field and the majority of the published papers in this area have mistakenly assumed that the electrostriction force was responsible for the net flow generated in an isothermal liquid. The main motivation behind this study is to investigate an EHD conduction pump for a two-phase loop to be operated in the microgravity environment. The pump is installed in the liquid return passage (isothermal liquid) from the condenser section to the evaporator section. Unique high voltage and ground electrodes have been designed that generate sufficient pressure heads with very low electric power requirements making the EHD conduction pumping attractive to applications such as two-phase systems (e.g. capillary pumped loops and heat pipes). Currently, the EHD conduction pump performance is being tested on a two-phase loop under various operating conditions in the laboratory environment. The simple non-mechanical and lightweight design of the EHD pump combined with the rapid control of performance by varying the applied electric field, low power consumption, and reliability offer significant advantages over other pumping mechanisms; particularly in reduced gravity applications.

Seyed-Yagoobi, J.↗

Isolating p- and n-Doped Fingers With Intrinsic Poly-Si in Passivated Interdigitated Back Contact Silicon Solar Cells

Polycrystalline silicon on silicon oxide (poly-Si/SiO x ) passivating contacts enable ultra high efficiency interdigitated back contact silicon solar cells. To prevent shunt between n- and p-type doped fingers, an insulating region is required between them. We evaluate the use of intrinsic poly Si for this isolation region. Interdigitated fingers were formed by plasma deposition of doped hydrogenated amorphous silicon through mechanically aligned shadow masks, on top of a full-area intrinsic amorphous silicon layer. High temperature annealing then crystallized the a-Si:H to poly Si and drove in the dopants. Two mechanisms were identified which cause contamination of the intrinsic poly Si gap during processing. During deposition of doped fingers, we show using secondary ion mass spectrometry and conductivity measurements that the intrinsic gap becomes contaminated by doped a-Si:H tails several nanometers thick to concentrations of ~10 20 cm -3 . Another source of contamination occurs during high-temperature annealing, where dopants desorb from doped regions and readsorb onto intrinsic a Si:H. Both pathways reduce the resistivity of the intrinsic gap from ~10 5 Ω·cm to ~10 -1 Ω·cm. We show that plasma etching of the a-Si:H surface before crystallizing with a capping layer can eliminate the contamination of the intrinsic poly-Si, maintaining a resistivity of ~10 5 Ω·cm. Lastly, this demonstrates masked plasma deposition as a dopant patterning method for Si solar cells.

14 SOLAR ENERGY↗

Design of robust and versatile hydrocarbon-based single-ion-conducting polymer electrolytes

Hydrocarbon-based polymers offer several advantages, including lower environmental impacts, cost effectiveness, and the ability to finely tune properties. Here, we have developed trifluoromethanesulfonimide (TFSI)-functionalized poly(norbornene) (PNB) polymers utilizing a specifically designed oxa-Michael addition of a vinyl TFSI anion to an alcohol. Our results reveal that PNB-TFSI derivatives exhibit superior thermal stability and mechanical robustness compared with Nafion. The optimized PNB-TFSI-H-48 polymer (IEC 1.86 mmol/g) exhibits equivalent performance to Nafion as an anode ionomer in a proton exchange membrane fuel cell. Exchanging the counter ion to Li + enables PNB-TFSI to be used for Li-ion battery applications. Propylene carbonate plasticized PNB-TFSI derivatives achieve an Li-ion conductivity of over 10 −5 S/cm at 30°C. This Li polymer electrolyte exhibits excellent electrochemical stability (5 V vs. Li + /Li) and good cycling in a Li symmetric cell. These results highlight the potential and rational design of PNB-TFSI polymers for next-generation energy storage and conversion technologies.

08 HYDROGEN↗

Understanding why poly(acrylic acid) works: decarbonylation and cross-linking provide an ionically conductive passivation layer in silicon anodes

Poly(acrylic acid) (PAA) is commonly used as a binder for fabricating silicon (Si) anode active materials in lithium-ion batteries due to its useful properties including high polar solvent solubility, good rheology, and strong adhesive properties. However, the role and evolution of PAA during electrode fabrication, cycling, and calendar aging are not well understood. In this work, we reveal the evolution of PAA during electrode curing and relate its chemical change to the final electrode properties and performance. These studies are made possible using two types of in situ attenuated total reflectance-infrared Fourier transform (ATR-FTIR) spectroscopy: thermal ATR-FTIR to probe the cross-linking reaction, and ATR-FTIR spectroelectrochemistry of three-dimensional composite electrodes, a unique technique developed herein that probes the solvation dynamics of lithium ions at the silicon anode interface under electrochemical polarization. Specifically, we show that PAA undergoes a thermally-mediated, cross-linking decarbonylation reaction to form an ether-based network polymer. To show the importance of the polyether moieties, we synthesize partially esterified PAA analogues that do not undergo this cross-linking decarbonylation reaction and correlate the degree of cross-linking to half-cell performance metrics. Finally, we unveil the mechanism of the polyether binder performance through in situ ATR-FTIR spectroelectrochemistry and show that PAA acts as an interfacial material that conducts lithium-ions, limits solvent molecule access to the Si surface, and stabilizes the electrode against parasitic lithium inventory loss at high state of charge for an extended period of time.

25 ENERGY STORAGE↗

Effect of Negative Ions on the Conductivity of the Titan Atmosphere

In an earlier paper, Borucki et al (1987) calculated the electrical conductivity and electrical charge on aerosols in Titan's atmosphere due to the ionization by galactic cosmic rays and electron precipitation from Saturn's magnetosphere. The lower atmosphere was predicted to be substantially more conducting than the atmospheres of Earth and Venus because of the high concentration of free electrons. The prediction of a high conductivity is based on the lack of electrophillic species which form negative ions with low mobility and which reduce the number of free electrons. At that time, no molecular species capable of forming negative ions in concentrations sufficient to perturb the atmospheric conductivity were identified. Recently, E. Bakes and her colleagues have been investigating the formation of nitrogenous macromolecules using quantum mechanical methods. Their calculations indicate that the molecules will be highly electrophillic and are likely to be present in the atmosphere at mixing ratios of order 10(exp -7). This mixing ratio is sufficiently large that a substantial reduction in the conductivity is expected at altitudes below 100 km. Revision of the atmospheric model to accommodate the presence of negative ions and to increase the fidelity of the modeling will be described.

Borucki, W. J.↗