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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 271 records · Page 15

Thin Film Electrodes with an Integral Current Collection Grid for Use with Solid Electrolytes

Thin film, high performance electrodes which can operate in high temperature environments are necessary for many devices which use a solid electrolyte. Electrodes of rhodium-tungsten alloy have been deposited on solid electrolyte using photolytic chemical vapor deposition (PCVD). A technique for depositing electrodes and current collection grids simultaneously has been developed using the prenucleation characteristics of PCVD. This technique makes it possible to fabricate electrodes which allow vapor transport through the thin (<1 (micro)m) portions of the electrode while integral thick grid lines improve the electronic conductivity of the electrode, thus improving overall performance.

thin film electrodes solid electrolyte vapor depos↗

Surface analysis insight note: X‐ray photoelectron spectroscopy analysis of battery electrodes—Challenges with nickel–manganese–cobalt and Li examples using an Al Kα x‐ray source

X‐ray photoelectron spectroscopy (XPS) has become a highly important tool for the analysis of battery materials and components. However, both anecdotal and detailed analysis of selected parts of the literature indicate that many reports of XPS on battery electrodes have significant analysis or data flaws. In this paper, we highlight several of the common challenges that analysts face when using XPS for battery materials, pointing to recent literature that addresses many of the critical issues associated with sample preparation as well as data collection and analysis. A common error for battery materials (and other materials) involves ignoring peak overlaps and interferences. Specifically, when a “minor” peak associated with a component in relatively high concentration overlaps or contributes to the primary peak (or one recommended for quantitative analysis) from a different element in the material. Overlap issues apply to many battery electrodes composed of many elements with complex photoelectron peak structures, as well as those involving peaks with seemingly simpler spectral envelopes such as Li and F. Examples of issues associated with battery systems are highlighted by a discussion of challenges associated with XPS analysis of Li and nickel–manganese–cobalt (NMC) electrodes in battery systems. Lithium analysis has challenges associated with the preparation and an often‐unrecognized peak overlap with F. In our laboratory and in the literature, NMC electrodes are often examined and new XPS users do not always recognize interference of the Auger signal from F KLL (in or on the electrode) with Ni 2p photoelectron spectrum when generated with Al Kα X‐rays. The use of simulated spectra involving both F and NiO demonstrates the extent of F Auger contributions to the Ni 2p signal strength as a function of the F/Ni atom ratio in the material and suggests spectra information that can be used to identify how significant effects will be on the resultant spectra. Our analysis demonstrates that in many cases overlap issues are significant for real electrode materials.

25 ENERGY STORAGE↗

Designing Low Tortuosity Electrodes through Pattern Optimization for Fast-Charging

The development of fast-charging technologies is crucial for expediting the progress and promotion of electric vehicles. In addition to innovative material exploration, reduction in the tortuosity of electrodes is a favored strategy to enhance the fast-charging capability of lithium-ion batteries by optimizing the ion-transfer kinetics. To realize the industrialization of low-tortuosity electrodes, a facile, cost-effective, highly controlled, and high-output continuous additive manufacturing roll-to-roll screen printing technology is proposed to render customized vertical channels within electrodes. Extremely precise vertical channels are fabricated by applying the as-developed inks, using LiNi 0.6 Mn 0.2 Co 0.2 O 2 as the cathode material. Additionally, the relationship between the electrochemical properties and architecture of the channels, including the pattern, channel diameter, and edge distance between channels, is revealed. The optimized screen-printed electrode exhibited a seven-fold higher charge capacity (72 mAh g -1 ) at a current rate of 6 C and superior stability compared with that of the conventional bar-coated electrode (10 mAh g -1 , 6 C) at a mass loading of 10 mg cm -2 . Finally, this roll-to-roll additive manufacturing can potentially be applied to various active materials printing to reduce electrode tortuosity and enable fast charging in battery manufacturing.

42 ENGINEERING↗

Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes

We report electrospun materials have been gaining great interest in the energy sector. Their tunability and robustness make them highly attractive, particularly for proton-exchange membrane fuel cell (PEMFC) electrodes. Conventional PEMFC electrodes, prepared by either spraying, painting, or slot-die coating, have not yet met the needs of large-scale PEMFC use. Electrospinning of fibrous materials has already shown great promise as an alternative methodology for electrode fabrication. Electrospinning has been used in fuel cell electrodes through two primary means: (1) segmented carbon or inorganic fibers to serve as precious metal catalyst support, and (2) high aspect ratio polymer/particle fibers to serve directly as the electrode. The use of electrospun fibrous electrodes has led to improved PEMFC durability and increased power output at low catalyst loadings, both of which are of paramount importance to large-scale commercialization of PEMFC electric vehicles.

36 MATERIALS SCIENCE↗

Modification of lithium electrodeposition behavior by variation of electrode distance

Developing a better understanding and control over the lithium electrodeposition behavior will assist with the commercial application of lithium metal anodes for rechargeable batteries. Despite intensive research over the past decade, our understanding of the deposition of lithium is limited. Here a new observation on the effect of distance between the working electrode and the counter electrode for electrochemical lithium deposition behavior is reported. From this fundamental investigation of distance, the high lithium ion concentration regions formed by release of lithium ions from the counter electrode modify the lithium deposition behavior on the working electrode, resulting in the generation of non-uniform lithium dendrites with a thick diversely composed surface film. Alternatively, increasing the distance between the electrodes results in the deposition of a spherical lithium morphology with a thin LiF rich surface film. Here, this fundamental study provides a deeper understanding of correlation between lithium deposition behavior and electrode separation and provides insight to inhibit lithium dendrite formation.

25 ENERGY STORAGE↗

Mechanistic insights into structural parameters maximizing energy storage density in Si mesoporous electrodes for Li-ion batteries

Mesoporous Si electrodes have an interesting set of structural parameters, which, when carefully optimized, can lead to ultrahigh energy density Si electrodes for Li-ion batteries. We present here in this paper details of a systematic research leading to the discovery of an “ideal” structure of mesoporous Si electrode, which results in exceptional cracking/damage resistance, while simultaneously having very high specific (>2000 mAh g-1) and total (>1.5 mAh cm-2) capacities for large number of cycles. The electrodes near the “ideal” value of the characteristic structural parameter (the ratio of Si wall thickness to pore diameter) are free from first-cycle capacity degradation, and are efficient in accommodating the volume changes during lithiation by uniformly filling up the porous space between Si walls. Interestingly, these electrodes are also found to be structurally damage-resistant, surviving through many lithiation-delithiation cycles. Using charge-discharge cycling and electron microscopy we show that ideal structure is the key for achieving ultrahigh energy storage density in Si mesoporous electrodes for Li-ion batteries.

25 ENERGY STORAGE↗

Long carbon fibers boost performance of dry processed Li-ion battery electrodes

Dry processing (DP) is an advanced manufacturing technique for lithium-ion battery (LIB) electrodes. Unlike conventional wet-process-based manufacturing that involves dissolving polyvinylidene fluoride (PVDF) binder in n-methyl-2-pyrrolidone (NMP) solvent for slurry-casting, DP involves fibrillation of polymer binders. This method offers environmental and cost benefits by eliminating the need for expensive and environmentally hazardous organic solvents. However, DP-produced electrode films often lack mechanical stability due to the absence of a current collector substrate during electrode material layer fabrication. This reduced mechanical instability results in difficulty during fabricating of thin electrodes (≈5 mAh/cm 2 ). To address this issue, long (>8 mm) carbon fiber (CF) has been incorporated to reinforce the mechanical strength of the electrode films. In conclusion, the study demonstrates that the inclusion of long carbon fiber boosts the mechanical, electrical, thermal, and electrochemical performance of DP electrodes.

25 ENERGY STORAGE↗

Electrode roughness dependent electrodeposition of sodium at the nanoscale

Na metal is an attractive anode material for rechargeable Na ion batteries, however, the dendritic growth of Na can cause serious safety issues. Along with modifications of solid-electrolyte interphase (SEI), engineering the electrode has been reported to be effective in suppressing Na dendritic growth, likely by reducing localized current density accumulation. However, fundamental understanding of Na growth at the nanoscale is still limited. Here, we report an in-situ study of Na electrodeposition in electrochemical liquid cells with the electrodes in different surface roughness, e.g., flat or sharp curvature. Real time observation using transmission electron microscopy (TEM) reveals the Na electrodeposition with remarkable details. Relatively large Na grains (in the micrometer scale) are achieved on the flat electrode surface. The local SEI thickness variations impact the growth rate, thus the morphology of individual grains. In contrast, small Na grains (in tens of nanometers) grow explosively on the electrode at the point with sharp curvature. The newly formed Na grains preferentially deposit at the base of existing grains close to the electrode. Further studies using continuum-based computational modeling suggest that the growth mode of an alkali metal (e.g. Na) is strongly influenced by the transport properties of SEI. Our direct observation of Na deposition in combination with the theoretical modeling provides insights for comprehensive understanding of electrode roughness and SEI effects on Na electrochemical deposition.

25 ENERGY STORAGE↗

Surface restructuring of a perovskite-type air electrode for reversible protonic ceramic electrochemical cells

Reversible protonic ceramic electrochemical cells (R-PCECs) are ideally suited for efficient energy storage and conversion; however, one of the limiting factors to high performance is the poor stability and insufficient electrocatalytic activity for oxygen reduction and evolution of the air electrode exposed to the high concentration of steam. Here we report our findings in enhancing the electrochemical activity and durability of a perovskite-type air electrode, Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O 3-δ (BCFN), via a water-promoted surface restructuring process. Under properly-controlled operating conditions, the BCFN electrode is naturally restructured to an Nb-rich BCFN electrode covered with Nb-deficient BCFN nanoparticles. When used as the air electrode for a fuel-electrode-supported R-PCEC, good performances are demonstrated at 650 °C, achieving a peak power density of 1.70 W cm –2 in the fuel cell mode and a current density of 2.8 A cm –2 at 1.3 V in the electrolysis mode while maintaining reasonable Faradaic efficiencies and promising durability.

30 DIRECT ENERGY CONVERSION↗

Thermal processing to modulate surface chemistry and bulk charge distribution in nickel-rich layered lithium positive electrodes

The broader application of nickel-rich layered oxides as positive electrode materials for lithium-ion batteries has been hindered by their high manufacturing cost and inferior cycling stability. Thermal processing, which is integral to electrode materials manufacturing and fundamental in materials science, has not been fully utilized to design advanced positive electrode materials. Herein, we demonstrate the capability of using quenching heat treatment to regulate Li distribution and modulate electronic structure near particle surface. The resulting materials exhibit less parasitic reactions with the electrolyte and an improved charge distribution homogeneity in secondary particles, leading to more stable cycling performance at high voltages (4.5 V vs Li/Li + ). Our synchrotron X-ray analyses reveal the underlying interplay between surface structure and bulk charge distribution in positive electrode materials particles. While strategies used to stabilize positive electrode materials through compositional control, surface modification, and electrolyte engineering have become mature, thermal processing can be advantageous to further improve positive electrode materials manufacturing.

36 MATERIALS SCIENCE↗

Effect of crystallite geometries on electrochemical performance of porous intercalation electrodes by multiscale operando investigation

Lithium-ion batteries are yet to realize their full promise because of challenges in the design and construction of electrode architectures that allow for their entire interior volumes to be reversibly accessible for ion storage. Electrodes constructed from the same material and with the same specifications, which differ only in terms of dimensions and geometries of the constituent particles, can show surprising differences in polarization, stress accumulation and capacity fade. Here, using operando synchrotron X-ray diffraction and energy dispersive X-ray diffraction (EDXRD), we probe the mechanistic origins of the remarkable particle geometry-dependent modification of lithiation-induced phase transformations in V2O5 as a model phase-transforming cathode. A pronounced modulation of phase coexistence regimes is observed as a function of particle geometry. Specifically, a metastable phase is stabilized for nanometre-sized spherical V2O5 particles, to circumvent the formation of large misfit strains. Spatially resolved EDXRD measurements demonstrate that particle geometries strongly modify the tortuosity of the porous cathode architecture. Greater ion-transport limitations in electrode architectures comprising micrometre-sized platelets result in considerable lithiation heterogeneities across the thickness of the electrode. These insights establish particle geometry-dependent modification of metastable phase regimes and electrode tortuosity as key design principles for realizing the promise of intercalation cathodes. Designing electrode architectures for Li-ion batteries that can be reversibly accessible for ion storage can be challenging. Using operando techniques the mechanistic origin of lithiation-induced phase transformations in a V2O5 model cathode is now clarified.

Luo, Yuting↗

Electrode material–ionic liquid coupling for electrochemical energy storage

The development of new electrolyte and electrode designs and compositions has led to advances in electrochemical energy-storage (EES) devices over the past decade. However, focusing on either the electrode or electrolyte separately is insufficient for developing safer and more efficient EES devices in various working environments, as the energy-storage ability is determined by the ion arrangement and charge and/or electron transfer at the electrode–electrolyte interface. Here, we assess the fundamental physicochemical and electrochemical properties at the electrode–electrolyte interfaces in Li-ion batteries and supercapacitors using safe and electrochemically stable ionic-liquid electrolytes. Key reactions and interactions at the electrode–electrolyte interface, as well as geometric constraints and temperature effects, are highlighted. Building on the fundamental understanding of interfacial processes, we suggest potential strategies for designing stable and efficient ionic-liquid-based EES devices with emerging electrode materials.

36 MATERIALS SCIENCE↗

Magnetic molecules lose identity when connected to different combinations of magnetic metal electrodes in MTJ-based molecular spintronics devices (MTJMSD)

Abstract Understanding the magnetic molecules’ interaction with different combinations of metal electrodes is vital to advancing the molecular spintronics field. This paper describes experimental and theoretical understanding showing how paramagnetic single-molecule magnet (SMM) catalyzes long-range effects on metal electrodes and, in that process, loses its basic magnetic properties. For the first time, our Monte Carlo simulations, verified for consistency with regards to experimental studies, discuss the properties of the whole device and a generic paramagnetic molecule analog (GPMA) connected to the combinations of ferromagnet-ferromagnet, ferromagnet-paramagnet, and ferromagnet-antiferromagnet metal electrodes. We studied the magnetic moment vs. magnetic field of GPMA exchange coupled between two metal electrodes along the exposed side edge of cross junction-shaped magnetic tunnel junction (MTJ). We also studied GPMA-metal electrode interfaces’ magnetic moment vs. magnetic field response. We have also found that the MTJ dimension impacted the molecule response. This study suggests that SMM spin at the MTJ exposed sides offers a unique and high-yield method of connecting molecules to virtually endless magnetic and nonmagnetic electrodes and observing unprecedented phenomena in the molecular spintronics field.

42 ENGINEERING↗

An alternative electrode design for accurate spectral induced polarization measurements in variably saturated porous media

SUMMARY Applications of spectral induced polarization (SIP) require electrodes that maintain hydrologic contact with surrounding soils to capture small electrical responses, often observed as phase shifts in milliradians. For unsaturated soils, electrodes must overcome increased electrical contact impedance due to reduced pore fluid. Traditional designs use a ceramic membrane electrode (CME) with a water reservoir and metal conductor, requiring periodic maintenance to retain electrolytic solution. For field applications where maintenance is impractical, alternative designs are needed. This study evaluated a new electrode design (silica flour electrode, SFE) alongside a CME. SFEs use packed silica flour to store water via capillary forces against a metal conductor. This study examined both designs in three variably saturated soils at soil suctions up to 700 mbar and soil water contents below 1 percent, with SIP measurements across 0.01 to 10 000 Hz frequencies. SFEs match CMEs at high frequencies and perform better at lower frequencies, without requiring ongoing maintenance, making them ideal for field use. In water-only experiments, CMEs produced errors and high noise below 1.5 Hz, whereas SFEs were more accurate. However, CMEs performed better above 300 Hz. In fine sand, SFEs performed better due to the relatively lower contact impedance as compared to CMEs. Both electrode types performed comparably in silty sand and silt loam soils, although CMEs required ongoing maintenance, suggesting potential for long-term reliability issues.

58 GEOSCIENCES↗

A Low-Cost Iron-Based Current Collector for Alkaline Battery Electrodes

The use of three-dimensional porous nickel foam as the current collector of the nickel hydroxide electrode adds significantly to the cost of the nickel-based alkaline rechargeable batteries. Although iron is considerably less expensive than nickel, iron corrodes at the operating potential of the nickel hydroxide electrode. We have found that a 70–100 nm thick thermal coating of cobalt ferrite spinel protects the iron from corrosion. Such a coated iron substrate was found to be stable against corrosion even when polarized anodically at 10 mA cm -2 in 30% potassium hydroxide electrolyte for 1000 h. While the thermal coating of cobalt ferrite protected iron against corrosion, incorporation of lithium ions into the coating was found to enhance the electrical conductivity of the coating. XPS and EXAFS studies confirmed that the enhanced conductivity resulted from an increase in the population of Co 3+ in the ferrite spinel lattice. An inexpensive iron (steel) substrate protected by such a coating when used as a nickel hydroxide battery electrode exhibited a specific capacity of 0.25 Ah g -1 at C/5 discharge rate, comparable to a nickel hydroxide electrode based on a relatively expensive nickel foam substrate. The steel-based electrode also exhibited no noticeable degradation over 150 cycles at C/2 rate. This demonstration of a robust and economical steel substrate presents a unique opportunity for reducing the cost of the nickel hydroxide battery electrode in alkaline batteries

25 ENERGY STORAGE↗

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Oxygen Evolution Electrode

Water electrolysis using an anion conductive, solid polymer electrolyte is an attractive method for point-of-use hydrogen production. Recent advances in catalysts and anion exchange membranes (AEM) have made alkaline devices increasingly competitive with their acidic counterparts. However, less attention has been paid to the anion conductive ionomers (ACI) used in the fabrication of electrodes for AEM electrolyzers. The ACI contributes to ion conduction between the catalyst and bulk electrolyte and serves as a binder for adhering the catalyst to the gas diffusion layer and AEM. Ionic conductivity, water uptake and ionomer swelling are critical properties for electrode performance. High ion exchange capacity (IEC) in the ionomer is desired for reduced electrode resistance, however, it can lead to excess water uptake (WU) and disruptive ACI swelling. In this study, a series of poly(norbornene)-based ionomers were synthesized, characterized and used to fabricate oxygen evolving anodes for low-temperature AEM water electrolysis. The IEC of the ionomers (0 to 4.73 meq g −1 ) was adjusted by controlling the ratio of ion conducting to non-ion conducting norbornene monomers in the ACI tetrablock copolymers. Low conductivity ionomers are shown to yield the best-performing oxygen evolution electrodes, in the absence of ACI polymer cross-linking because they do not experience excessive water swelling. Light cross-linking within the anode ACI was used as a means to independently lower WU of the ionomer without compromising ionic conductivity. This control over water swelling allows higher ionic conductivity within the ACI to be used in water-fed electrolyzer applications. Other methods of water management were compared including the use of hydrophobic additives and adjustment of the ionomer concentration in the electrode. As a result, it was shown that the cell performance greatly benefits from a highly conductive ionomer in the oxygen evolution reaction electrode if the WU is managed.

08 HYDROGEN↗

In Situ Reliability Investigation of All-Vanadium Redox Flow Batteries by a Stable Reference Electrode

Redox flow batteries (RFBs) have been studied over the past several decades as a promising candidate for stationary energy storage applications. It is therefore important to understand the reliability of RFBs and the mechanisms that cause degradation with time. Contributions from individual electrodes (cathode or anode) are difficult to separate especially for long-term cycle testing, due to the lack of a stable reference electrode. In our work, the reliability and degradation mechanisms of an all-vanadium RFB were investigated by a stable reference electrode based on the dynamic hydrogen electrode (DHE). With factor exploration and design optimization, the newly developed DHE reference electrode demonstrated high accuracy and long-term stability that enables in-situ monitoring of individual electrode signals (potentials and impedances) over hundreds of cycles in a vanadium RFB. This approach enables the full cell degradation to be separated and the degradation attributed to contributions from the cathode and anode. The cathode and anode were found to play quite different roles in the increase in overpotential of the vanadium RFB during long-term cycling. The anode reaction limited both the charge and discharge capacity over 100 cycles. In addition, the negative side also appeared to be the rate limiting factor throughout cycling as determined by EIS measurement. The cathode contributed to the performance degradation as cycling exceeded 50 cycles.

Huang, Qian↗

Electrophoretic Deposition of Platinum Nanoparticles using Ethanol-Water Mixtures Significantly Reduces Neural Electrode Impedance

We report platinum electrodes are critical components in many biomedical devices, an important example being implantable neural stimulation or recording electrodes. However, upon implantation, scar tissue forms around the electrode surface, causing unwanted deterioration of the electrical contact. We demonstrate that sub-monolayer coatings of platinum nanoparticles (PtNPs) applied to 3D neural electrodes by electrophoretic deposition (EPD) can enhance the electrode's active surface area and significantly lower its impedance. In this work we use ethanol-water mixtures as the EPD solvent, in contrast to our previous studies carried out in water. We show that EPD coating in 30 vol.% ethanol improves the device's electrochemical performance. Computational mesoscale multiparticle simulations were for the first time applied to PtNP-on-Pt EPD, revealing correlations between ethanol concentration, electrochemical properties, and coating homogeneity. Thereto, this optimum ethanol concentration (30 vol.%) balances two opposing trends: (i) the addition of ethanol reduces water splitting and gas bubble formation, which benefits surface coverage, and (ii) increased viscosity and reduced permittivity occur at high ethanol concentrations, which impair the coating quality and favoring clustering. A seven-fold increase in active surface area and significantly reduced in vitro impedance of the nano-modified neural stimulation electrode surfaces highlight the influence of ethanol-water mixtures in PtNP EPD.

36 MATERIALS SCIENCE↗