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At least 721 records · Page 40

High-Energy-Density Capacitors

Capacitors capable of storing energy at high densities are being developed for use in pulse-power circuits in such diverse systems as defibrillators, particle- beam accelerators, microwave sources, and weapons. Like typical previously developed energy-storage capacitors, these capacitors are made from pairs of metal/solid-dielectric laminated sheets that are wound and pressed into compact shapes to fit into cans, which are then filled with dielectric fluids. Indeed, these capacitors can be fabricated largely by conventional fabrication techniques. The main features that distinguish these capacitors from previously developed ones are improvements in (1) the selection of laminate materials, (2) the fabrication of the laminated sheets from these materials, and (3) the selection of dielectric fluids. In simplest terms, a high-performance laminated sheet of the type used in these capacitors is made by casting a dielectric polymer onto a sheet of aluminized kraft paper. The dielectric polymer is a siloxane polymer that has been modified with polar pendant groups to increase its permittivity and dielectric strength. Potentially, this polymer is capable of withstanding an energy density of 7.5 J/cm3, which is four times that of the previous state-of-the-art-capacitor dielectric film material. However, the full potential of this polymer cannot be realized at present because (1) at thicknesses needed for optimum performance (.8.0 m), the mechanical strength of a film of this polymer is insufficient for incorporation into a wound capacitor and (2) at greater thickness, the achievable energy density decreases because of a logarithmic decrease in dielectric strength with increasing thickness. The aluminized kraft paper provides the mechanical strength needed for processing of the laminate and fabrication of the capacitor, and the aluminum film serves as an electrode layer. Because part of the thickness of the dielectric is not occupied by the modified siloxane polymer, the achievable energy density must be somewhat less than the maximum value. The laminate is produced by a continuous film-casting process, using the machinery depicted schematically in the figure. The designs of the process and machinery are dictated partly by the fact that during the processing step prior to casting the polymer, the aluminized kraft paper becomes wet with water. Because the polymer resin to be cast is hydrophobic, the paper must be dried to make it possible to coat the paper uniformly, leaving no pinholes. Accordingly, an infrared heater is placed next to the paper feed roll to dry the paper prior to casting.

Slenes, Kirk↗

Diagnostic for Plasma Enhanced Chemical Vapor Deposition and Etch Systems

In order to meet NASA's requirements for the rapid development and validation of future generation electronic devices as well as associated materials and processes, enabling technologies ion the processing of semiconductor materials arising from understanding etch chemistries are being developed through a research collaboration between Stanford University and NASA-Ames Research Center, Although a great deal of laboratory-scale research has been performed on many of materials processing plasmas, little is known about the gas-phase and surface chemical reactions that are critical in many etch and deposition processes, and how these reactions are influenced by the variation in operating conditions. In addition, many plasma-based processes suffer from stability and reliability problems leading to a compromise in performance and a potentially increased cost for the semiconductor manufacturing industry. Such a lack of understanding has hindered the development of process models that can aid in the scaling and improvement of plasma etch and deposition systems. The research described involves the study of plasmas used in semiconductor processes. An inductively coupled plasma (ICP) source in place of the standard upper electrode assembly of the Gaseous Electronics Conference (GEC) radio-frequency (RF) Reference Cell is used to investigate the discharge characteristics and chemistries. This ICP source generates plasmas with higher electron densities (approximately 10(exp 12)/cu cm) and lower operating pressures (approximately 7 mTorr) than obtainable with the original parallel-plate version of the GEC Cell. This expanded operating regime is more relevant to new generations of industrial plasma systems being used by the microelectronics industry. The motivation for this study is to develop an understanding of the physical phenomena involved in plasma processing and to measure much needed fundamental parameters, such as gas-phase and surface reaction rates. species concentration, temperature, ion energy distribution, and electron number density. A wide variety of diagnostic techniques are under development through this consortium grant to measure these parameters. including molecular beam mass spectrometry (MBMS). Fourier transform infrared (FTIR) spectroscopy, broadband ultraviolet (UV) absorption spectroscopy, a compensated Langmuir probe. Additional diagnostics. Such as microwave interferometry and microwave absorption for measurements of plasma density and radical concentrations are also planned.

Cappelli, Mark A.↗

Activating magnetite ores for aqueous ironmaking at high current densities

Low-temperature electrochemical cells reducing iron oxides to metal in alkaline electrolytes can support fully electrified steelmaking processes. Previous studies on these cells have primarily focused on high-surface-area hematite, Fe 2 O 3 , reactants whereas attempts to reduce suspensions of magnetite, Fe 3 O 4 —one of the two feedstocks for existing ironmaking reactors—have generally been limited to low rates of reaction (<30 mA cm −2 ). Here, in this study, we control the crystalline domain size of Fe 2 O 3 and Fe 3 O 4 particles in 10 M NaOH electrolytes to study how the nanoscale morphology of oxides controls the rate of electrochemical ironmaking. Rotating-ring disk electrode measurements of Fe 2+ , in situ Raman spectroscopy of the electrode surface, and ex situ electron microscopy were consistent with a hypothesized passivation process at Fe 3 O 4 surfaces that may prevent the continuous formation of soluble intermediates. Sufficiently small (<100 nm diameter) oxide particles yielded Fe partial current densities >160 mA cm −2 , a fivefold increase relative to previously reported rates for Fe 3 O 4 suspensions and comparable to active Fe 2 O 3 . Electron microscopy revealed that electrodeposited films were composed of micron-scale crystalline Fe domains with a porous film of Fe 3 O 4 nanoparticles and supports a model where Fe is grown primarily from soluble Fe 2+ intermediates. Based on these insights, inactive blast-furnace-grade iron-oxides were transformed into high surface area nanoparticles (1.6 to 229.2 m 2 g −1 ) via reprecipitation, leading to a ninefold enhancement in faradaic efficiency and an Fe partial current density of 120 mA cm −2 . When integrated with chlor-iron cells producing reagents for reprecipitation, this approach could lead to a cost-competitive process for electrochemical ironmaking from industrially relevant feedstocks.

TEM↗

Processing of Superconductor-Normal-Superconductor Josephson Edge Junctions

The electrical behavior of epitaxial superconductor-normal-superconductor (SNS) Josephson edge junctions is strongly affected by processing conditions. Ex-situ processes, utilizing photoresist and polyimide/photoresist mask layers, are employed for ion milling edges for junctions with Yttrium-Barium-Copper-Oxide (YBCO) electrodes and primarily Co-doped YBCO interlayers.

photoresist polyimide process interlayer materials↗

Mesocrystallizing Nanograins for Enhanced Li + Storage

Morphology and crystallinity of electrode materials have a major effect on their charge carrier storage properties when applied in rechargeable batteries. While nanosizing electrode particles (with larger surface area) and maintaining electrode integrity are both good for performance enhancement, they seem to contradict each other and can be hardly well-balanced. Herein, we designed electrode particles consisting of numerous nanograins with uniform crystalline orientation to guarantee both high surface area and high structural integrity, allowing the significant improvement of Li + storage kinetics and performance. Applying this “mesocrystallizing” strategy to a NiCo 2 O 4 -based anode, resulting in various degrees of pseudocapacitance response, the long-term cyclability and rate performance of this material have been largely enhanced. Impressively, the mesocrystalline NiCo 2 O 4 electrode exhibits a high reversible capacity of 1403 mAh g -1 after 200 cycles at 1.6 A g -1 (a rate of 1.8 C). The growth mechanism of mesocrystalline materials with different morphologies is identified to be a topotactic strctural transition process featuring a gradual edge-to-core corrasion process. This work presents an important synthetic clue to balance the morpholgy and crystallinity of battery electrode materials for their perforamnce optimization and is expected to inspire future structural design for battery materials beyond the one prototyped here.

25 ENERGY STORAGE↗

17.2% Efficient CdSexTe1−x solar cell with (InxGa1−x)2O3 emitter on lightweight and flexible glass

High-efficiency, lightweight, and flexible solar cells are sought for a variety of applications particularly when high power density and flexible form factors are desired. Development of solar cells on flexible substrates may also offer production advantages in roll-to-roll or sheet-to-sheet processes. Here, we report device efficiencies of 17.2% and 14.6%, under AM1.5G and AM0 irradiances, respectively, for a flexible, lightweight, CdTe-based solar cell. To advance the efficiency relative to the highest previously reported AM1.5G value of 16.4%, we used an indium gallium oxide (IGO) emitter layer on a cadmium stannate (CTO) transparent conductor, which was deposited on 100-μm thick Corning® Willow® Glass. A sputtered CdSe layer was employed to incorporate Se into a CdTe absorber that was deposited by close-space sublimation, and CuSCN was used as a hole transport layer between the CdTe and the back metal electrode. The IGO and CTO layers remained intact during the high temperature film processing as seen in cross-sectional imaging and elemental mapping. This device configuration offers great promise for building-integrated photovoltaics, space applications, and higher rate manufacturing.

Physics↗

Unraveling the hysteretic behavior at double cations-double halides perovskite - electrode interfaces

Despite over a decade of research on metal halide perovskites (MHPs) in the context of photovoltaic applications, understanding the nature of electronic and ionic processes associated with current-voltage (I-V) hysteretic behavior has been limited. Here, we explore the hysteretic behavior in (FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 perovskite devices with lateral Cr electrodes by applying first order reversal curve (FORC) bias waveform in I-V, Kelvin probe force microscopy (KPFM) measurements, and in-situ chemical imaging by time-resolved time-of-flight secondary ion mass spectrometry (tr-ToF-SIMS). In dark, we reveal pronounced hysteretic behaviors of charge dynamics in the off-field by probing time-dependent current and contact potential difference (CPD). Under illumination, transient and hysteretic behaviors are significantly reduced. The tr-ToF-SIMS results reveal that the hysteretic behaviors are strongly associated with accumulation of Br- ions at the interfaces. In addition, the low mobility MA + ions result in transient behavior and contribute to the hysteretic phenomena. It was shown that Pb 2+ ions can be reduced at the interfaces due to electrochemical reactions with the electrode in the presence of charge injection and photogenerated charges. Furthermore, these hysteretic behaviors associated with charge dynamics, ion migration, and interfacial electrochemical reaction are critical to further improve the performance and stability of MHPs photovoltaics and optoelectronics.

42 ENGINEERING↗

Distinct Melt Infusion Architectures of Antiperovskite Solid Electrolytes

Antiperovskite solid electrolytes are an emerging class of lithium‐ion conductors distinguished by their unusually low melting points, enabling scalable, low‐temperature processing routes not accessible to most solid electrolytes. In this work, we synthesize phase‐pure chloride (Cl), bromide (Br), and mixed halide (ClBr) variants of antiperovskites and investigate their ionic conductivities in both powder and hot‐pressed forms. Hot pressing significantly enhances conductivity across all compositions, while energy‐dispersive X‐ray spectroscopy (EDS) of the mixed halide system reveals halide surface migration during densification. We further investigate the melt‐infiltration behavior of these electrolytes into substrates relevant to solid‐state battery architectures, including Al and Cu current collectors, conventional NMC and LFP cathodes, and a foamed NMC cathode with a highly porous architecture. The foamed cathode enables deep and uniform electrolyte penetration, highlighting the role of electrode architecture in facilitating melt infiltration. Across all substrates, electrolyte halide chemistry strongly influences wetting behavior, penetration depth, and resulting microstructural morphology. Together, these results establish clear processing–structure relationships for melt‐infiltrated antiperovskite solid electrolytes and demonstrate how electrolyte chemistry and electrode architecture govern interfacial morphology during integration, providing practical guidelines for processing and structural design in solid‐state battery systems.

antiperovskite↗

Electrowetting‐Mediated Transport to Produce Electrochemical Transistor Action in Nanopore Electrode Arrays

Abstract Understanding water behavior in confined volumes is important in applications ranging from water purification to healthcare devices. Especially relevant are wetting and dewetting phenomena which can be switched by external stimuli, such as light and electric fields. Here, these behaviors are exploited for electrochemical processing by voltage‐directed ion transport in nanochannels contained within nanopore arrays in which each nanopore presents three electrodes. The top and middle electrodes (TE and ME) are in direct contact with the nanopore volume, but the bottom electrode (BE) is buried beneath a 70 nm silicon nitride (SiN x ) insulating layer. Electrochemical transistor operation is realized when small, defect‐mediated channels are opened in the SiN x . These defect channels exhibit voltage‐driven wetting that mediates the mass transport of redox species to/from the BE. When BE is held at a potential maintaining the defect channels in the wetted state, setting the potential of ME at either positive or negative overpotential results in strong electrochemical rectification with rectification factors up to 440. By directing the voltage‐induced electrowetting of defect channels, these three‐electrode nanopore structures can achieve precise gating and ion/molecule separation, and, as such, may be useful for applications such as water purification and drug delivery.

Kwon, Seung‐Ryong↗

Oligoether-Functionalized PEDOT: Combining an EDOT Backbone with Polar Side Chains for Solution Processability and High Electrical Conductivity

Conjugated polymers functionalized with oligoether (OE)-based side chains are a key class of materials for various organic electronic applications, including transparent electrodes, thermoelectrics, electrochromic displays, and electrochemical transistors. Herein, we report a highly soluble OE-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) homopolymer, prepared by direct (hetero)arylation polymerization, which allows solution processing to yield films with comparable redox properties to oxidatively polymerized PEDOT. This polymer, PEDOT(OE3), when optimally oxidatively doped, reaches among the highest electrical conductivities of any OE-functionalized polymer and is comparable to more synthetically complex OE-functionalized polymers. X-ray scattering and spectroscopy were utilized to rationalize the transport properties resulting from varying the doping level. Comparison of PEDOT(OE3) to a series of OE-functionalized dioxythiophenes with varying amounts of 3,4-ethylenedioxythiophene units allows for a deeper understanding of structure–property relationships through charge-transport models. Ultimately, PEDOT(OE3) is shown to be a material with exceptional charge-transport properties and is promising for various applications.

36 MATERIALS SCIENCE↗

Operando characterization and regulation of metal dissolution and redeposition dynamics near battery electrode surface

Mn dissolution has been a longstanding, ubiquitous issue that negatively impacts the performance of Mn-based battery materials. Mn dissolution involves complex chemical and structural transformations at the electrode-electrolyte interface. The continuously evolving electrodeelectrolyte interface has posed great challenges for characterizing the dynamic interfacial process and quantitatively establishing the correlation with battery performance. In this study, we visualize and quantify the temporally and spatially resolved Mn dissolution/redeposition (D/R) dynamics of electrochemically operating Mn-containing cathodes. The particle-level and electrode-level analyses reveal that the D/R dynamics is associated with distinct interfacial degradation mechanisms at different states of charge. Our results statistically differentiate the contributions of surface reconstruction and Jahn-Teller distortion to the Mn dissolution at different operating voltages. Introducing sulfonated polymers (Nafion) into composite electrodes can modulate the D/R dynamics through trapping the dissolved Mn species and rapidly establishing the local Mn D/R equilibrium. This work represents an inaugural effort to pinpoint the chemical and structural transformations responsible for Mn dissolution via an operando synchrotron study and develops an effective method to regulate Mn interfacial dynamics for improving battery performance.

25 ENERGY STORAGE↗

Production-Ready CsPbBr3 Module Fabrication

The purpose of this SBIR was to work on evaluation, development, and testing of CsPbBr3 semiconductors for use in commercial gamma-ray detection. The overarching goal was to demonstrate the capability to fabricate functional detectors through resources available to H3D, Inc in pursuit of an alternative to CdZnTe for room-temperature semiconductor detectors. Throughout the project, CdZnTe crystals from Redlen were used as a control group to demonstrate whether the fabrication processes could produce reasonable results. The CdZnTe crystals were diced into roughly 6 mm x 6 mm x 4.5 mm pieces and electrodes were evaporated onto planar faces. In one case, pixels were patterned through a laser ablation method; in the other, a rudimentary pixel shadow-mask was fabricated, and the pixels were generated in the evaporation process. A 16 mm x 16 mm x 14 mm CsPbBr3 crystal was diced into four smaller crystals. These CsPbBr3 had electrodes applied in a similar way to the CdZnTe samples with a rudimentary mask used for pixels on the cathode. Tested CdZnTe pieces were found to generally function with reasonable, low-energy performance. CsPbBr3 crystals were found to be non-functional under forward bias with a large dark-current. A separate attempt, using reverse bias in a non-H3D, Inc test system, observed a dark current similar to previous observations, and some active pixels but no waveforms were observed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Origin of layered perovskite device efficiencies revealed by multidimensional time-of-flight spectroscopy

Mixtures of layered perovskite quantum wells with different sizes form prototypical light-harvesting antenna structures in solution-processed films. Gradients in the bandgaps and energy levels are established by concentrating the smallest and largest quantum wells near opposing electrodes in photovoltaic devices. Whereas short-range energy and charge carrier funneling behaviors have been observed in layered perovskites, our recent work suggests that such light-harvesting processes do not assist long-range charge transport due to carrier trapping at interfaces between quantum wells and interstitial organic spacer molecules. Here, we apply a two-pulse time-of-flight technique to a family of layered perovskite systems to explore the effects that interstitial organic molecules have on charge carrier dynamics. In these experiments, the first laser pulse initiates carrier drift within the active layer of a photovoltaic device, whereas the second pulse probes the transient concentrations of photoexcited carriers as they approach the electrodes. The instantaneous drift velocities determined with this method suggest that the rates of trap-induced carrier deceleration increase with the concentrations of organic spacer cations. Overall, our experimental results and model calculations suggest that the layered perovskite device efficiencies primarily reflect the dynamics of carrier trapping at interfaces between quantum wells and interstitial organic phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas Evolution in Water Electrolysis

Gas bubbles generated by the hydrogen evolution reaction and oxygen evolution reaction during water electrolysis influence the energy conversion efficiency of hydrogen production. Here we survey what is known about the interaction of gas bubbles and electrode surfaces and the influence of gas evolution on practicable devices used for water electrolysis. Here, we survey the physical processes occurring during the life cycle of a bubble, summarize techniques used to characterize gas evolution phenomena in-situ and in practical device environments, and discuss ways that electrodes can be tailored to facilitate gas removal at high current densities. Lastly, we summarize efforts to model the behavior of individual gas bubbles and multiphase flows produced at gas evolving electrodes. We conclude our review with a short summary of outstanding questions which could be answered by future efforts to characterize gas evolution in electrochemical device environments or by improved simulations of multiphase flows.

Bubbles↗

Nitroxide Radical Polymer–Solvent Interactions and Solubility Parameter Determination

Redox-active polymers such as macromolecular nitroxide radicals have been studied as electrode materials for organic batteries and electronics. Polymer–solvent interactions are essential to processing and device performance, but macromolecular nitroxide radical–solvent interactions are currently not well described. In this work, the Hildebrand and Hansen solubility parameters of poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), oxidized PTMA (PTMA + ), and PTMA’s precursor (PTMPM) are determined using both experimental and group contribution methods for the first time. This work indicates that the hydrogen-bonding Hansen solubility parameter (δ h ) and the solubility sphere radii (R) provide the best prediction of the macromolecular radical’s interaction with solvents. From these solubility parameters, the group contribution values for the nitroxide and oxoammonium cation were then calculated. It is shown that this information allows for the prediction of polymer–solvent interactions for other nitroxide-based macromolecular radicals. Lastly, the discovered solubility parameters are used to predict PTMA electrode formulations for batteries that outperform controls.

36 MATERIALS SCIENCE↗