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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Non-contact electrochemical evaluation of biofilms

Abstract Here, we demonstrate a non-contact technique for electrochemical evaluation of biofilms on surfaces in relation to corrosion. Electrochemical impedance spectrometry was employed, incorporating flat patterned electrodes positioned over the surfaces of aluminum and glass with and without biofilms. Signal communication from the working electrode to the counter electrode followed electric field lines passing tangentially through the biofilms. Electrochemical impedance parameters that were evaluated included complex impedance, phase angle, imaginary (out of phase) conductivity and Cole–Cole plots with a corresponding equivalent circuit. Changes in the impedance properties due to the presence of biofilms were monitored and correlated through microbiological, chemical and electrochemical assays. Impedance parameters associated with microbial activity correlated with biofilms on aluminum and glass surfaces. This technical approach provides impedance information about the biofilm without the signal traveling through the underlying conductive media or disrupting the biofilm. In this way, biological contributions to surface fouling can be evaluated with minimal contribution from the inorganic surface under the biofilm. In addition, this technique can be used to monitor biofilms on electrochemically inert surfaces as well as electrically conductive surfaces. Graphic abstract

Turick, Charles E. (ORCID:0000000307815846)↗

Lithium-Ion Batteries with Safer Current Collectors

The US Department of Energy’s Oak Ridge National Laboratory and Soteria Battery Innovation Group collaborated to develop a metallized polymer film as a current collector for lithium-ion batteries and design slit patterns for electrodes to improve battery safety. The metallized polymer film serves as a fuse that will break under high temperature resulting from a short circuit. Consequently, the short circuit will be broken and the heat generated from the short circuit will be alleviated to avoid thermal runaway. The electrodes with slit patterns are expected to be broken into small segments upon mechanical impact, which can isolate the damaged electrodes from the rest. Thus, the heat generation associated with the mechanical impact will be reduced, along with the likelihood of thermal runaway. This effort aimed to improve lithium-ion battery safety by replacing traditional metal foils with metallized polymer films as current collector and introducing slit patterns to battery electrodes. The metallized polymer films were polyethylene terephthalate with a thin metal (aluminum for cathodes and copper for anodes) coating on both sides. Slit patterns with various geometries and dimensions were designed via simulation. Temperature distribution on cells with electrodes with and without slit patterns was also simulated via nemerical modeling. Electrodes on traditional metal foils and metallized polymer films were coated via a pilot-scale slot-die coater at the US Department of Energy Battery Manufacturing Facility at Oak Ridge National Laboratory. The electrodes were calendered to 35% porosity and punched out with and without slit patterns. Pouch cells were assembed with the electrodes inside a dry room for electrochemical and safety testing. Electrodes coated on metallized polymer films exhibited comparable electrochemical performance to their counterparts coated on traditional metal foils. They also showed improved safety in nail penetration and indentation tests.

25 ENERGY STORAGE↗

Melamine modification of fuel cell electrodes

A method for forming a melamine-modified electrode that includes providing a metal based electrode and patterning a surface of the metal-based electrode by contacting the electrode with a melamine solution to form a patterned metal-based electrode. The patterned metal-based electrode includes metal sites blocked with melamine molecules and metal sites which are not blocked such that the metal-based electrode selectively adsorbs O2 instead of at least one of sulfate, phosphate, or sulphonate. A range of 20% to 40% of the metal sites are blocked with melamine molecules.

Strmcnik, Dusan↗

Controlled Nucleation and Stabilization of Ferroelectric Domain Wall Patterns in Epitaxial (110) Bismuth Ferrite Heterostructures

Ferroelectric domain walls, topological entities separating domains of uniform polarization, are promising candidates as active elements for nanoscale memories. In such applications, controlled nucleation and stabilization of domain walls are critical. In this work, using in situ transmission electron microscopy and phase-field simulations, a controlled nucleation of vertically oriented 109° domain walls in (110)-oriented BiFeO 3 (BFO) thin films is reported. In the switching experiment, reversed domains that are nucleated preferentially at the nanoscale edges of the “crest and sag” pattern-like electrode under external bias subsequently grow into a stable stripe configuration. In addition, when triangular pockets (with an in-plane polarization component) are present, these domain walls are pinned to form stable flux-closure domains. Phase field simulations show that i) field enhancement at the edges of the electrode causes site-specific domain nucleation, and ii) the local electrostatics at the domain walls drives the formation of flux closure domains, thus stabilizing the striped pattern, irrespective of the initial configuration. The results demonstrate how flux closure pinning can be exploited in conjunction with electrode patterning and substrate orientation to achieve a desired topological defect configuration. These insights constitute critical advancements in exploiting domain walls in next generation ferroelectronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Does one need to polish electrodes in an eight pattern? Automation provides the answer

Automation of electrochemical measurements can accelerate the discovery of new electroactive materials. One of the hurdles to automated electrochemical measurement is the pretreatment of electrodes because mechanical polishing is usually conducted manually. Here we investigate the automation of electrochemical measurements using a robotic arm. We demonstrate automated mechanical polishing using a station with a moving polishing pad and evaluate the effect of different polishing patterns. Our automatic method improved the corroded electrodes, and we found the effect of pattern was not significant, which diverges from the current common belief amongst practitioners that a figure eight pattern is best for pretreatment. This research is a step toward automating electrochemistry experiments without human intervention.

Yoshikawa, Naruki [University of Toronto, ON (Cana↗

Modelling and Experimental Validation of Improved Performance of Lithium-Ion Batteries Having Thick Electrodes with Laser-Ablated Micro-Structures

For widespread adoption of electric vehicles, lithium-ion batteries (LiBs) need to achieve energy densities of >275 Wh/kg, cost less than $100/Wh, and charge to more than 80% capacity within 15 minutes. Increasing the battery electrode thicknesses is one way to increase cell energy densities while also saving on cell manufacturing cost by increasing the ratio of electrode active material to inactive material within each cell. However, increased electrode loading is often accompanied by decreased Li+-ion diffusion across the full thick electrodes. This leads to significant cell polarization that prevents full capacity utilization and accelerates cell degradation, especially at fast charging/discharging rates. The introduction of secondary pore networks in thick battery electrodes alleviates some of the trade-offs between energy and power performance. These microstructures provide low tortuosity pathways for facile Li+-ion diffusion deep into the thick electrodes, diminishing detrimental concentration gradients within the cell. Ultrafast-pulsed laser ablation is a promising method to introduce micro pores or channels in thick battery electrodes as it allows for precise control of pattern geometries, results in minimal damage to the electrode and can be introduced into existing roll-to-roll electrode manufacturing lines. Herein, the limitations of thick planer electrodes and the advanced predictive models to identify optimal electrode patterns for improved cycling performance will be presented. The impact of electrode laser patterning to create secondary pore networks also will be discussed. Materials characterization techniques (SEM-EDS, XRD) were used to explore the affect ultrafast laser ablation had on the electrode materials’ morphology and structure. The improvements in the patterned electrodes’ electrochemical cycling performances and degrees of wetting will be compared to a pristine baseline case. Finally, the discrepancies between experimentally obtained data and model predictions will be explained.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗

Manufacturing Water‐Based Low‐Tortuosity Electrodes for Fast‐Charge through Pattern Integrated Stamping

Achieving high energy density and fast charging of lithium‐ion batteries can accelerate the promotion of electric vehicles. However, the increased mass loading causes poor charge transfer, impedes the electrochemical reaction kinetics, and limits the battery charging rate. Herein, this work demonstrated a novel pattern integrated stamping process for creating channels in the electrode, which benefits ion transport and increases the rate performance of the electrode. Meanwhile, the pressure applied during the stamping process improved the contact between electrode and current collector and also enhanced the mechanical stability of the electrode. Compared to the conventional bar‐coated electrode with the same thickness of 155 μm (delivered a discharge capacity of 16 mAh g −1 at the rate of 3 C), the stamped low‐tortuosity LiFePO 4 electrode delivered 101 mAh g −1 capacity. Additionally, water was employed as a solvent in this study. Owing to its eco‐friendliness, high scalability, and minimal waste generation, this novel stamping technique inspire a new method for the industrial‐level efficient roll to roll fabrication of fast‐charge electrodes.

25 ENERGY STORAGE↗

Enabling fast-charging of lithium-ion batteries through printed electrodes

It has been well recognized that introducing secondary porous networks (SPNs) into the electrodes can effectively improve the electrochemical performance of lithium-ion batteries (LIBs), especially under fast-charging operations. However, the process complexity and high cost limit the commercial success of advanced electrodes with SPNs. To address this issue, we developed a facile screen-printing process to produce structured graphite electrodes with SPNs. The experimental results demonstrated that, by tuning the diameter and center-to-center (C2C) distance of emulsion dots on the stencil screen, the pore diameters and C2C pore distances of SPNs in screenprinted electrodes can be precisely controlled in the range of 100 mu m to 1 mm and 100 mu m to 3 mm respectively. In addition, the SPNs with hexagonal and square-shape pore alignments have also been imprinted onto the electrode coatings through adjusting the patterns of screen stencils. Used as anodes, the printed graphite electrodes demonstrated significantly reduced overpotential and voltage fluctuation under fast-charging operations from 2C to 6C. Coupled with LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathodes, the full cells with printed graphite anodes exhibited an unprecedently stable performance with almost no capacity decay up to 170 cycles when charged to 80 % SOC at 2C. Observations from electron microscopy showed plated lithium undetectable at the surface of printed graphite electrodes after numerous cycles. The electrochemical analysis on the voltage evolution during the cell rest period indicated the significantly delayed onset of lithium plating in the presence of printed graphite electrodes. In conclusion, all these results suggest that the significantly improved cell performance is associated with the shortened Li-ion diffusion distance, reduced polarization and suppressed Li plating in the printed electrodes with patterned SPNs.

25 ENERGY STORAGE↗

Laser ablation of high-loading Li-ion battery electrodes improves accessible capacity and cycle life for Behind-the-Meter Storage

Adoption of Behind-the-Meter Storage (BTMS) requires design of batteries that enable high safety, long cycle life, and low cost at the system level. Pairing Li 4 Ti 5 O 12 (LTO) with LiMn 2 O 4 (LMO) achieves targets related to safety and cycle life, but these materials' low energy densities contribute to higher cost at the system scale. Increasing electrode loading is a simple approach to improve energy density, but comes with a trade-off in electrode utilization due to long, tortuous Li + diffusion pathways. Here, laser ablation is used to microstructure (pattern) high-loading electrodes to enhance electrode performance through improved Li + diffusion pathways. Four cell types, comprising combinations of standard or patterned anode and cathode, were prepared to evaluate the effects of laser ablation at each electrode. A rate test shows that patterning electrodes enhances active material utilization at ≳1C rates. Patterning the cathode yields the most benefit, as cells with a patterned cathode demonstrate a ~20% higher accessible capacity than those without at 1.4C. Additionally, 1C capacity retention of cells with patterned cathode (91% through 3000 cycles) is significantly improved over cells with only the anode patterned (64%) and non-patterned electrodes (50%). Characterization of post-mortem cells before and after refreshing their electrolyte suggests that 1C capacity retention is improved by mitigation of electrode "dry-out". We hypothesize that the microstructure acts as a reservoir of additional electrolyte, or a path for gas to escape, so that active material remains wetted throughout long-term cycling, and/or the microstructure may reduce localized, gas-forming overpotentials in the high-loading electrode.

25 ENERGY STORAGE↗

One–Step Fabrication of Nanocrystalline Nanonetwork SnO 2 Gas Sensors by Integrated Multilaser Processing

An integrated multilaser process is developed to fabricate nanocrystalline nanonetwork SnO 2 gas sensors in one integrated procedure, which combines electrodes fabrication, nanomaterials deposition, and postannealing. Interdigit electrodes are fabricated on an Au-coated fused silica substrate using a picosecond (ps) laser, which ablates the Au coating from the back of the substrate to pattern the electrodes. A novel transmitted Ps laser deposition (TPLD) process is designed to deposit SnO 2 nanonetwork on the interdigit electrodes with precise deposition area control under a close target-to-substrate distance. The obtained SnO 2 nanonetwork is in situ postannealed by a CO 2 laser to improve the crystallinity, while the nano morphology and grain size keep intact. To investigate the morphology and formation process of the nanonetwork, the microstructure of the laser-deposited SnO 2 layer is characterized. As a result, the crystallization control of CO 2 laser annealing is investigated through analyzing the Raman spectrum, X-ray diffraction (XRD) patterns, and lattice structures of the samples. By exposed to H 2 atmosphere, the fabricated gas sensor is demonstrated for H 2 monitoring.

08 HYDROGEN↗

Topology optimization for the design of porous electrodes

Porous electrodes are an integral part of many electrochemical devices since they have high porosity to maximize electrochemical transport and high surface area to maximize activity. Traditional porous electrode materials are typically homogeneous, stochastic collections of small-scale particles and offer few opportunities to engineer higher performance. Fortunately, recent breakthroughs in advanced and additive manufacturing are yielding new methods to structure and pattern porous electrodes across length scales. These architected electrodes are emerging as a promising new technology to continue to drive improvement; however, it is still unclear which structures to employ and few tools are available to guide their design. Here we address this gap by applying topology optimization to the design of porous electrodes. We demonstrate our framework on two applications: a porous electrode driving a steady Faradaic reaction and a transiently operated electrode in a supercapacitor. We present computationally designed electrodes that minimize energy losses in a half-cell. For low-conductivity materials, the optimization algorithm creates electrode designs with a hierarchy of length scales. Further, the designed electrodes are found to outperform undesigned, homogeneous electrodes. Finally, we present three-dimensional porous electrode designs. We thus establish a topology optimization framework for designing porous electrodes.

25 ENERGY STORAGE↗

Patterned anodes with sub-millimeter spatial resolution for large-area MCP-based photodetector systems

Micro-channel-plate-based photo-detectors are unique in being capable of covering very large areas such as those required in elementary particle and nuclear physics, while providing sub-millimeter space resolution, time resolutions of less than 10 picoseconds for charged particles, and time resolutions of 30 psec–50 psec for single photons. In such systems the electronic channel count is a major cost driver. Incorporating a capacitively-coupled anode allows the use of external pickup electrodes with patterns of individual channels optimized for occupancy, rate, and time/space resolution. The signal pickup antenna can be economically implemented as a printed circuit card with a 2-dimensional array of pads for high-occupancy/high-rate applications such as in particle colliders and medical imaging, or a 1-dimensional array of strips for a lower channel count in low-occupancy/low-rate applications such as large neutrino detectors. In this paper we present pad patterns that enhance signal-sharing between pads to lower the channel count per unit area in large-area systems by factors up to 4, while maintaining spatial resolutions of approximately 100 to 200 μ m for charged particles and 400 to 1000 μ m for single photons. Patterns that use multiple signal layers in the signal-pickup board can lower the channel count even further, moving the scaling behavior in the number of pads versus total area from quadratic to linear.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Strain-Based Chemiresistive Polymer-Coated Graphene Vapor Sensors

Suspended chemiresistive graphene sensors have been fabricated using well-established nanofabrication techniques to generate sensors that are highly sensitive to pyridine and with excellent discrimination between polar and nonpolar analytes. When coated with a polymer surface layer and suspended on 3-D patterned glass electrodes, a hybrid combination of polymer and graphene yields chemiresistive vapor sensors. Expansion and contraction of the polymer layer produces strain on the suspended graphene (Gr). Hence, when organic vapors permeate into the polymer layer, the high gauge factor of the graphene induces substantial electrical resistive changes as folds and creases are induced in the graphene. The hybrid suspended polymer/Gr sensor exhibits substantial responses to polar organic vapors, especially pyridine, while also exhibiting reversibility and increased discrimination between polar and nonpolar analytes compared to previous approaches. This sensor design also allows for potential tunability in the types of polymers used for the reactive surface layer, allowing for use in a variety of potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular beam epitaxy of the magnetic Kagome metal FeSn on LaAlO 3 (111)

Materials with Kagome layers are expected to give rise to rich physics arising from band structures with topological properties, spin liquid behavior, and the formation of Skyrmions. Until now, most work on Kagome materials has been performed on bulk samples due to difficulties in thin film synthesis. Here, by using molecular beam epitaxy, layered Kagome-structured FeSn films are synthesized on the (111) oriented LaAlO3 substrate. Both in situ and ex situ characterizations indicate that these films are highly crystalline and c-axis oriented, with atomically smooth surfaces. The films grow as disconnected islands, with lateral dimensions on the micron meter scale. By patterning Pt electrodes using a focused electron beam, the longitudinal and transverse resistance of single islands have been measured in magnetic fields. Our work opens a pathway for exploring mesoscale transport properties in thin films of Kagome materials and related devices.

36 MATERIALS SCIENCE↗

Glove-based sensors for multimodal monitoring of natural sweat

Sweat sensors targeting exercise or chemically induced sweat have shown promise for noninvasive health monitoring. Natural thermoregulatory sweat is an attractive alternative as it can be accessed during routine and sedentary activity without impeding user lifestyles and potentially preserves correlations between sweat and blood biomarkers. We present simple glove-based sensors to accumulate natural sweat with minimal evaporation, capitalizing on high sweat gland densities to collect hundreds of microliters in just 30 min without active sweat stimulation. Sensing electrodes are patterned on nitrile gloves and finger cots for in situ detection of diverse biomarkers, including electrolytes and xenobiotics, and multiple gloves or cots are worn in sequence to track overarching analyte dynamics. Direct integration of sensors into gloves represents a simple and low-overhead scheme for natural sweat analysis, enabling sweat-based physiological monitoring to become practical and routine without requiring highly complex or miniaturized components for analyte collection and signal transduction.

42 ENGINEERING↗

Temporal and spatial tuning of optical constants in praseodymium doped ceria by electrochemical means

Abstract Temporal and spatial tuning of the refractive index of optical thin films is desired for flat optics applications. The redistribution of mobile ions in mixed ionic-electronic conductors (MIEC) has been demonstrated to serve as a viable means for achieving optical tuning down to the nanoscale. Here we studied the dynamic range of the optical tuning achievable in the refractive index, in the MIEC oxide – Pr x Ce 1− x O 2− δ (PCO), for x = 0.1, 0.2 and 0.4, at 500 °C, by in-situ spectrophotometry. Significant increases in the modulation of both the imaginary and real optical constants in the visible and the adjacent spectra were obtained for increased doping levels. Device employing an electrochemical titration method was implemented to modulate the oxygen concentration, and thereby the optical transmission of PCO. Incorporation of a patterned top electrode allowed for the demonstration of spatial control of PCO thin film properties by in-situ video imaging of the optical switching process. The electrochemically induced optical state is shown to remain non-volatile upon quenching the device to room temperature under applied bias.

36 MATERIALS SCIENCE↗

Science Driven Discovery of Nanoparticle Photocatalysts

Photocatalytic water splitting using suspensions of nanoparticle photocatalysts is a promising route to economically sustainable production of green hydrogen. The principal challenge is to develop photocatalysts with overall solar-to-hydrogen conversion efficiency that exceeds 10 percent. In this project we have developed a new platform for investigating candidate materials for photocatalytic water splitting. Our platform consists of patterned Au electrodes and a Ag/AgCl reference electrode on an insulating substrate onto which we disperse nanoparticle photocatalysts. We then cover the substrate with a thin layer of ionogel containing a protic ionic liquid that dissolves water from the ambient. Using this platform we have demonstrated photoelectrochemical activity mapping for single and small clusters of BiVO 4 nanoparticle photocatalysts and correlated these results to their Raman and photoluminescence spectra. The preliminary results suggest a strong correlation for low efficiency nanoparticles, followed by saturation for those with higher activities, indicating that interface reaction or electrolyte transport become the limiting factor. We anticipate that further application of this platform to investigation of candidate photocatalyst materials will provide useful insights into the mechanisms that limit their performance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗