Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “electrode processing”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 739 records · Page 41

Topology Optimization of 3D Flow Fields for Flow Batteries

We report as power generated from renewables becomes more readily available, the need for power-efficient energy storage devices, such as redox flow batteries, becomes critical for successful integration of renewables into the electrical grid. An important aspect of a redox flow battery is the planar flow field, which is usually composed of two-dimensional channels etched into a backing plate. As reactant-laden electrolyte flows into the flow battery, the channels in the flow field distribute the fluid throughout the reactive porous electrode. We utilize topology optimization to design flow fields with full three-dimensional geometry variation, i.e., 3D flow fields. Specifically, we focus on vanadium redox flow batteries and use the optimization algorithm to generate 3D flow fields evolved from standard interdigitated flow fields by minimizing the electrical and flow pressure power losses. To understand how these 3D designs improve performance, we analyze the polarization of the reactant concentration and exchange current within the electrode to highlight how the designed flow fields mitigate the presence of electrode dead zones. While interdigitated flow fields can be heuristically engineered to yield high performance by tuning channel and land dimensions, such a process can be laborious; this work provides a framework for automating that design process.

25 ENERGY STORAGE↗

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↗

Characterizing Dynamic Structure in Battery Electrodes by Time-Resolved Cryo-TEM

In recent years, cryogenic transmission electron microscopy (cryo-TEM) has enabled high-resolution characterization of sensitive battery materials by minimizing electron beam-induced artifacts and damage. Success of this technique relies on the preparation of thin, rapidly frozen samples, generally by disassembling batteries under inert atmosphere, transferring materials of interest to a TEM grid, and finally plunge freezing into a cryogen. In material degradation studies, this extensive time between electrochemical cycling and cryo-TEM characterization leaves room for structural relaxation, diffusion, and other dynamic processes that make it difficult to precisely correlate the imaged structure with the native structure that evolves during battery cycling or aging. Here, we present a method to integrate battery cycling with fast preparation of electrode samples for cryo-TEM. This enables higher fidelity between the structures characterized and the electrochemical state of interest, which we use to study deformation in silicon nanoparticle anodes for lithium-ion batteries.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗

High-Temperature Reference Electrode for Chloride Salts

The unique properties of molten salts enable their use in a wide range of applications, including metal electrodeposition, electrorefining, and as electrolytes in high-temperature batteries. Moreover, molten salts will be used as a coolant in molten salt reactors and as working media in pyrorocessing for nuclear energy applications. As a result, predicting the behavior and properties of the elements involved in the technological processes that employ molten salts is important. The activity of chloride ions in chloride molten salts has a large influence on the behavior of the salts in these applications and one of the key components in measuring the chloride activity is a stable reference electrode. This project aims to develop a reliable and convenient method for measuring chloride ion activity over a wide range of temperatures and salt compositions in chloride salt mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically decorated gold nanoparticles on CVD graphene ChemFET sensor for the highly sensitive detection of As(III)

Here, in this paper, we report a novel reusable receptor-free chemically sensitive field-effect transistor (ChemFET) sensor for the sensitive detection of As(III) using electrochemical doping of Au nanoparticles (AuNPs)-chemical vapour deposition (CVD) graphene (Gr) sensing film (AuNPs-Gr). The sensor consists of a single-gap gold electrode and a single layer of CVD graphene as a conducting/sensing channel decorated with a thin layer of electrochemically deposited AuNPs to catalyze the electroreduction of As(III) ions onto the sensing channel. A new detection strategy was proposed by measuring the resistance change rate of the AuNPs-Gr sensing channel modified between the source electrode and drain electrode, wherein the resistance change was caused by the electrochemical doping of As(0). The results indicated that the electrochemical doping of As(0) onto the sensing channel led to an increase in resistance through the doping interaction among As(0), AuNPs and graphene, enabling the proposed sensor to have an extraordinary detection performance with a high sensitivity. Moreover, the proposed sensor can be recycled by removing the As(0) deposited on the sensing film with the aid of a simple electrochemical oxidization process. Additionally, the mechanism of the sensing strategy based on the electrochemical n-doping of As(0) into the AuNPs-Gr sensing film was investigated using a top liquid gate electrode. The As(III) concentration detected by the AuNPs-Gr ChemFET sensor was as low as 0.001 μg/L, demonstrating that such sensors with a compatible sensing strategy can be used to detect As(III) with high sensitivity, easy fabrication, fast response and can be recycled.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A stable atmospheric-pressure plasma for extreme-temperature synthesis

Plasmas can generate ultra-high-temperature reactive environments that can be used for the synthesis and processing of a wide range of materials. However, the limited volume, instability and non-uniformity of plasmas have made it challenging to scalably manufacture bulk, high-temperature materials. Here we present a plasma set-up consisting of a pair of carbon-fibre-tip-enhanced electrodes that enable the generation of a uniform, ultra-high temperature and stable plasma (up to 8,000 K) at atmospheric pressure using a combination of vertically oriented long and short carbon fibres. The long carbon fibres initiate the plasma by micro-spark discharge at a low breakdown voltage, whereas the short carbon fibres coalesce the discharge into a volumetric and stable ultra-high-temperature plasma. As a proof of concept, we used this process to synthesize various extreme materials in seconds, including ultra-high-temperature ceramics (for example, hafnium carbonitride) and refractory metal alloys. Moreover, the carbon-fibre electrodes are highly flexible and can be shaped for various syntheses. In conclusion, this simple and practical plasma technology may help overcome the challenges in high-temperature synthesis and enable large-scale electrified plasma manufacturing powered by renewable electricity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Development and Characterization of Electrodes for Surface-Specific Attenuated Total Reflection Two-Dimensional Infrared Spectroelectrochemistry

Electrochemical interfaces still have remaining mysteries surrounding the interfacial region of the electrical double layer, despite being prevalent throughout the energy and water remediation industries. The electrical double layer is where many important dynamic processes such as catalysis and electron transfer occur. The goal of this work is to study the electrical double layer with two-dimensional infrared (2D IR) spectroscopy to experimentally access the details of the structural dynamics of this complex environment. However, there are several experimental challenges to applying 2D IR spectroscopy to this application, such as assuring the surface specificity of the spectrum, optimizing the signal strength while minimizing spectral distortions from dispersion and Fano line shapes, and selecting electrode materials that are both sufficiently IR compatible and conductive. Here we will discuss various considerations when designing 2D IR experiments of electrode interfaces utilizing several substrates and experimental configurations and demonstrate a robust method for 2D IR experiments of electrode interfaces under applied potential that combines nonconducting Si ATR wafers with conductive ITO and thin nanostructured films of plasmonically active Au functionalized with 3-mercapto-2-butanone (MCB). We show that layered electrodes on thin Si ATR wafers with MCB are sensitive to applied potential and that the distortions in the linear and 2D IR spectra are heavily dependent on the morphology of the Au surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrical Resistivity Tomography data from 2016 to 2018 at the Lower Montane site in the East River Watershed, Colorado

This dataset contains time-lapse Electrical Resistivity Tomography (ERT) data along a transect located on the northeast-facing hillslope at the lower montane site (Pumphouse site) in the upper East River Watershed. The monitoring dataset covers the period from November 2, 2016, to August 6, 2018. In addition, the archive also contains a baseline dataset from October 9, 2016. The ERT transect consisted of 128 electrodes with an electrode spacing of 1.25 m. The acquisition system was located in the middle of the transect, about 50 m on one side, and included an MPT (Multi-Phase Technologies) ERT system, a mini computer, and batteries with solar panels. Acquisition occurred daily under normal circumstances. The first 16 electrodes (from the upper end of the transect) could not be used after the cable was damaged during the 2017–2018 winter. Also, due to multiple failures in the power system, the temporal resolution of the data is much lower in 2018 compared to 2016 and 2017. The data have been processed and used in Dafflon et al., 2023, and the baseline dataset was used in Falco et al., 2019 (see reference list). This archive contains the measurements (ER.zip containing csv files) for each of the 326 acquisition times and a filtered version where only electrodes 17 to 128 are included (ERT_sm.zip containing csv files). The archive also contains the baseline dataset and two acquisitions with full reciprocals (ERT_RB.zip containing csv files), as well as all the raw MPT files (ERT_raw_MTP.zip). The geometry (electrode position and elevation) is provided in Universal Transverse Mercator (UTM) 13N Geoid2012AB in the file named ERT_Location.csv. The archive contains 1 *.csv data files, four *.zip files, and three metadata *.csv files. This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

54 ENVIRONMENTAL SCIENCES↗

Imaging the Phase Transformation in Single Particles of Lithium Titanate Anode for Lithium-ion Batteries

Lithium uptake and release in lithium titanate (LTO) anode materials during a discharge and charge cycle is one of the fundamental processes of a Lithium-ion battery (LIB), still not fully understood at the microscopic level.During discharge cycle, LTO undergoes a phase transformation between Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 states within a cubic crystal lattice. To reveal the details of the microscopic mechanism,it is necessary to track the sequence of phase transformation sat different discharge/charge states under operating conditions.Here we use in-situ Bragg Coherent Diffraction Imaging (BCDI) and in-situ X-ray diffraction (XRD) experiments to examine the lithium insertion-induced materials phase transformation within a single LTO particle anda bulk battery analogue,respectively. BCDI analysis from (111) Bragg peak, shows the two-phase transformation manifesting as a distinct image phase modulation within a single LTO nanoparticle occurring in the middle of the discharge region then subsiding towards the end of the discharge cycle. We observe the biggest phase variation at the two-phase stage,indicating the formation of phase domains of 200 nm in size during the discharge process. Additionally, we also observe a lattice contraction of >0.2% in a single LTO nanoparticle at the (400) Bragg peak measurement, larger than that in the corresponding bulk material. Our observation of this phase transformation at a single particle level has implications for the understanding of the microscopic/mesoscale picture of the phase transformation in anode and cathode LIBs materials.

25 ENERGY STORAGE↗

Electrochemically Grown Ultrathin Platinum Nanosheet Electrodes with Ultralow Loadings for Energy-Saving and Industrial-Level Hydrogen Evolution

Nanostructured catalyst-integrated electrodes with remarkably reduced catalyst loadings, high catalyst utilization and facile fabrication are urgently needed to enable cost-effective, green hydrogen production via proton exchange membrane electrolyzer cells (PEMECs). Herein, benefitting from a thin seeding layer, bottom-up grown ultrathin Pt nanosheets (Pt-NSs) were first deposited on thin Ti substrates for PEMECs via a fast, template- and surfactant-free electrochemical growth process at room temperature, showing highly uniform Pt surface coverage with ultralow loadings and vertically well-aligned nanosheet morphologies. Combined with an anode-only Nafion 117 catalyst-coated membrane (CCM), the Pt-NS electrode with an ultralow loading of 0.015 mg Pt cm -2 demonstrates superior cell performance to the commercial CCM (3.0 mg Pt cm -2 ), achieving 99.5% catalyst savings and more than 237-fold higher catalyst utilization. The remarkable performance with high catalyst utilization is mainly due to the vertically well-aligned ultrathin nanosheets with good surface coverage exposing abundant active sites for the electrochemical reaction. Overall, this study not only paves a new way for optimizing the catalyst uniformity and surface coverage with ultralow loadings but also provides new insights into nanostructured electrode design and facile fabrication for highly efficient and low-cost PEMECs and other energy storage/conversion devices.

42 ENGINEERING↗

Process model for multilayer slide coating of polymer electrolyte membrane fuel cells

Slide coating is a precision method suitable for depositing multiple liquid-film layers simultaneously. Originally developed in the photographic film industry, it has been deployed for manufacturing of other products that benefit from multilayer coatings. One emerging application is the manufacture of polymer electrolyte membrane fuel cells (PEMFCs), which are used to produce electricity through electrochemical reactions of hydrogen and oxygen gas. The membrane-electrode assembly (MEA), in which key electrochemical reactions occur, consists of three layers that are typically deposited separately in serial fashion and then laminated together to form the three-layer MEA, i.e., three sequential steps of coat and dry. Adapting the process to simultaneous, multilayer slide coating of all three layers will save equipment cost and space while minimizing possible exposure to contaminants during transition between the steps. We are developing a three-layer slide coating model to aid the manufacturing process design of PEMFC. The model accounts for rheology of each layer, which typically exhibit shear thinning behavior. Model predictions are used to investigate simultaneous coatability of catalyst inks and to determine the best layer-by-layer ink selection.

25 ENERGY STORAGE↗

Toward practical issues: Identification and mitigation of the impurity effect in glyme solvents on the reversibility of Mg plating/stripping in Mg batteries

Reversible electrochemical magnesium plating/stripping processes are important for the development of high-energy-density Mg batteries based on Mg anodes. Ether glyme solutions such as monoglyme (G1), diglyme (G2), and triglyme (G3) with the MgTFSI 2 salt are one of the conventional and commonly used electrolytes that can obtain the reversible behavior of Mg electrodes. However, the electrolyte cathodic efficiency is argued to be limited due to the enormous parasitic reductive decomposition and passivation, which is governed by impurities. In this work, a systematic identification of the impurities in these systems and their effect on the Mg deposition–dissolution processes is reported. The mitigation methods generally used for eliminating impurities are evaluated, and their beneficial effects on the improved reactivity are also discussed. By comparing the performances, we proposed a necessary conditioning protocol that can be easy to handle and much safer toward the practical application of MgTFSI 2 /glyme electrolytes containing impurities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–Organic Framework Integrating Ionic Framework and Bimetallic Coupling Effect for Highly Efficient Oxygen Evolution Reaction

Metal–organic frameworks (MOFs) are recognized as promising electrocatalysts for the oxygen evolution reaction (OER) because of their permanent porosity and rich architectural diversity; however, ionic MOFs enabling fast ions exchange during OER are rarely explored. Here, an ionic MOF (Ni-btz) constructed with an azolate ligand is selected, and continuous 3D bimetallic MOF (NiFe-btz) films deriving from high-degree intergrowth of microsized MOFs particles are fabricated. The as-prepared NiFe-btz/NF-OH electrode exhibits excellent OER performance with a low overpotential of 239 mV at 10 mA cm –2 under alkaline condition. The OER charge transfer process and bimetallic coupling effect in ionic NiFe-btz are probed by density functional theory calculations and confirmed via X-ray photoelectron spectroscopy and in situ Raman measurements. The partial density of states of NiFe-btz indicates that the main contribution for electron density around the Fermi level is from Cl ions clarifying the profitable impact of ionic MOF framework. This work systematically demonstrates the relationship of electronic structure and OER activity in ionic, bimetallic MOFs and expands the scope of 3D MOF films for efficient OER.

36 MATERIALS SCIENCE↗

HRTEM Imaging and Mechanistic Insights Into Carbon Nanotube Nucleation and Growth on Fe Nanocatalysts in a Thermal Plasma

Thermal plasma decomposition of natural gas is a scalable pathway for the production of hydrogen alongside high-value carbon nanotubes (CNTs). Metals evaporate from an electrode and condense to form seed nanoparticles that nucleate and grow CNTs. However, the lack of mechanistic understanding of the CNT nucleation and growth processes in thermal plasma makes control over CNT diameter, chirality, length, and yield difficult. We debundled and separated CNTs from soots produced using iron (Fe) nanocatalysts, and distributed them on monolayer graphene for high-resolution transmission electron microscopy (HRTEM) imaging to gain mechanistic insights. Full graphene encapsulation was found for relatively small Fe nanoparticles that were molten at high temperatures. Zigzag single-wall or double-wall CNTs (SWCNTs or DWCNTs) appeared to have grown out directly from the graphene covering on the conical or cylindrical bodies of small molten Fe nanodroplets with high curvature. Also, SWCNTs likely grew out from H- or O-atom etched single-wall carbon nanocones observed on conical Fe nanoparticles. A SWCNT/DWCNT could also be generated from the cracked opening of the graphene covering on a face-centered cubic (FCC) Fe nanoparticle. A simple, plausible pathway is proposed for the growth of an open, H-passivated, zigzag SWCNT involving reaction of CH 2 and CH radicals at high temperatures.

Fe nanocatalysts↗

The effect of ink ball milling time on interparticle interactions and ink microstructure and their influence on crack formation in rod-coated catalyst layers

This work investigates the influence of ballmilling (sometimes also referred to as jar roller milling) time on cathode catalyst layer (CL) inks and electrode properties using formulations and coating methods relevant for industrial manufacturing. Four CL inks with the same composition were milled for 24, 48, 72, or 96 h. Rheological investigation of these inks showed a reduction of elastic moduli and steady-shear viscosity with continuous ink milling, which is correlated to a decrease in particle-particle interactions as well as formation of smaller agglomerates. Optical microscopy (OM) analysis of the fabricated electrodes revealed a trend in surface crack formation; formulations milled for 24 h contained the lowest average surface crack area percentages of 0.370% at heavy-duty loadings of ~0.300 mg Pt cm -2 , compared to 2.418% for the ink milled for 96 h. Further characterization of the CL through transmission electron microscopy (TEM) imaging showed a decrease in the mean agglomerate and pore size with milling time. Furthermore, these smaller electrode features were consistent with reduced fracture resistance and, hence, development of larger stresses during drying. Our results highlight the need to consider ink processing as an important component in defect-free CL manufacturing.

30 DIRECT ENERGY CONVERSION↗

Thermally Driven Interfacial Degradation between Li 7 La 3 Zr 2 O 12 Electrolyte and LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode

Solid-state batteries offer higher energy density and enhanced safety compared to the present lithium-ion batteries using liquid electrolytes. A challenge to implement them is the high resistances, especially at the solid electrolyte interface with the cathode. Sintering at elevated temperature is needed in order to get good contact between the ceramic solid electrolyte and oxide cathodes and thus to reduce contact resistances. Many solid electrolyte and cathode materials react to form secondary phases. It is necessary to find out which phases arise as a result of interface sintering and evaluate their effect on electrochemical properties. Herein, we assessed the interfacial reactions between LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and Li 7 La 3 Zr 2 O 12 (LLZO) as a function of temperature in air. We prepared model systems by depositing thin-film NMC622 cathode layers on LLZO pellets. The thin-film cathode approach enabled us to use interface-sensitive techniques such as X-ray absorption spectroscopy in the near-edge as well as the extended regimes and identify the onset of detrimental reactions. We found that the Ni and Co chemical environments change already at moderate temperatures, on-setting from 500 °C and becoming especially prominent at 700 °C. By analyzing spectroscopy results along with X-ray diffraction, we identified Li 2 CO 3 , La 2 Zr 2 O 7 , and La(Ni,Co)O 3 as the secondary phases that formed at 700 °C. The interfacial resistance for Li transfer, measured by electrochemical impedance spectroscopy, increases significantly upon the onset and evolution of the detected interface chemistry. Our findings suggest that limiting the bonding temperature and avoiding CO 2 in the sintering environment can help to remedy the interfacial degradation.

36 MATERIALS SCIENCE↗

Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior

Transition metal dichalcogenide (TMD) nanoflake thin films are attractive electrode materials for photoelectrochemical (PEC) solar energy conversion and sensing applications, but their photocurrent quantum yields are generally lower than those of bulk TMD electrodes. The poor PEC performance has been primarily attributed to enhanced charge carrier recombination at exposed defect and edge sites introduced by the exfoliation process. Here, a single nanoflake PEC approach reveals how an alternative effect, doping heterogeneity, limits ensemble-level PEC performance. Photocurrent mapping and local photocurrent–potential (i–E) measurements of MoS 2 nanoflakes exfoliated from naturally occurring bulk crystals revealed the presence of n- and p-type domains within the same nanoflake. Interestingly, the n- and p-type domains in the natural MoS 2 nanoflakes were equally efficient for iodide oxidation and tri-iodide reduction (IQE values exceed 80%). At the single domain-level, the natural MoS 2 nanoflakes were nearly as efficient as nanoflakes exfoliated from synthetic n-type MoS 2 crystals. Single domain-level i–E measurements explain why natural MoS 2 nanoflakes exhibit an n-type to p-type photocurrent switching effect in ensemble-level measurements: the n- and p-type diode currents from individual domains oppose each other upon illuminating the entire nanoflake, resulting in zero photocurrent at the switching potential. Furthermore, the doping heterogeneity effect is likely due to nonideal stoichiometry, where p-type domains are S-rich according to XPS measurements. Although this doping heterogeneity effect limits photoanode or photocathode performance, these findings open the possibility to synthesize efficient TMD nanoflake photocatalysts with well-defined lateral p- and n-type domains for enhanced charge separation.

14 SOLAR ENERGY↗

Evaluation of a V 8 C 7 Anode for Oxygen Evolution in Alkaline Media: Unusual Morphological Behavior

Metallic vanadium carbide (V 8 C 7 ) with cubic symmetry is examined as an oxygen evolution reaction (OER) precatalyst in alkaline media. Herein, we used quasi in situ scanning electron microscopy and energy-dispersive X-ray spectrometry to investigate the structural transformation of the precatalyst V 8 C 7 microparticles during extended cyclic voltammetric (CV) OER testing. Interestingly, an anisotropic morphological transformation (from a distorted sphere to a cuboid) of V 8 C 7 was observed. Our theoretical and experimental results strongly suggest that this morphological change happens due to the selective self-oxidation and dissolution of the V 8 C 7 (110) and (111) surfaces and the subsequent exposure of the relatively stable (100), (010), and (001) surfaces. Lastly, these results also suggest that these stable facets are preferable for the OER, and a current density of 10 mA·cm –2 was delivered at an overpotential of 503 mV after the extended CV OER testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗