Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ELECTRODE”

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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Electrochemical Stiffness Changes in Lithium Manganese Oxide Electrodes

In situ strain and stress measurements are performed on composite electrodes to monitor potential‐dependent stiffness changes in lithium manganese oxide (LiMn 2 O 4 ). Lithium insertion and removal results in asynchronous strain and stress generation in the electrode. Electrochemical stiffness changes are calculated by combining coordinated stress and strain measurements. The electrode experiences dramatic changes in electrochemical stiffness due to potential‐dependent Li + ion intercalation mechanisms. The development of stress in the early stages of delithiation (at ≈3.95 V) due to a kinetic barrier at the electrode surface gives rise to stiffness changes in the electrode. Strain generation due to phase transformations reduces stiffness in the electrode at 4.17 V during delithiation and at 4.11 V during lithiation. During lithiation, stress generation due to Coulombic repulsions between occupied and incoming Li + ions leads to stiffening of the electrode at 3.96 V. The electrode also experiences greater changes in stiffness during delithiation compared to lithiation. These changes in electrochemical stiffness provide insight into the interplay between mechanical and electrochemical properties which control electrode response to lithiation and delithiation.

Çapraz, Ömer Özgür↗
DOE OSTI2018

Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In Situ Electrochemical Process

Although the rechargeable lithium-oxygen (Li-O2) batteries have extremely high theoretical specific energy, the practical application of these batteries is still limited by the instability of their carbon-based air-electrode, Li metal anode, and electrolytes towards reduced oxygen species. Here we demonstrate a simple one-step in-situ electrochemical pre-charging strategy to generate thin protective films on both carbon nanotubes (CNTs) air-electrode and Li metal anode simultaneously under an inert atmosphere. Li-O2 cells after such pre-treatment demonstrate significantly extended cycle life of 110 and 180 cycles under the capacity-limited protocol of 1000 mAh g-1 and 500 mAh g-1, respectively, which is far more than those without pre-treatment. The thin-films formed from decomposition of electrolyte during in-situ electrochemical pre-charging process in an inert environment can protect both CNTs air-electrode and Li metal anode prior to conventional Li-O2 discharge/charge cycling where reactive reduced oxygen species are formed. This work provides a new approach for protections of carbon-based air-electrode and Li metal anode in practical Li-O2 batteries, and may also be applied to other battery systems.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

Structural Dynamics and Evolution of Bismuth Electrodes during Electrochemical Reduction of CO 2 in Imidazolium-Based Ionic Liquid Solutions

Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near -1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than -1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM]+-based electrolytes, including the reduction of bismuth oxide to bismuth metal and changes in roughness and near-surface viscosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Carbon Nanotube Web with Carboxylated Polythiophene “Assist” for High-Performance Battery Electrodes

In this paper, a carbon nanotube (CNT) web electrode comprising magnetite spheres and few-walled carbon nanotubes (FWNTs) linked by the carboxylated conjugated polymer, poly[3-(potassium-4-butanoate) thiophene] (PPBT), was designed to demonstrate benefits derived from the rational consideration of electron/ion transport coupled with the surface chemistry of the electrode materials components. To maximize transport properties, the approach introduces monodispersed spherical Fe 3 O 4 (sFe 3 O 4 ) for uniform Li + diffusion and a FWNT web electrode frame that affords characteristics of long-ranged electronic pathways and porous networks. The sFe 3 O 4 particles were used as a model high-capacity energy active material, owing to their well-defined chemistry with surface hydroxyl (-OH) functionalities that provide for facile detection of molecular interactions. PPBT, having a π-conjugated backbone and alkyl side chains substituted with carboxylate moieties, interacted with the FWNT π-electron-rich and hydroxylated sFe 3 O 4 surfaces, which enabled the formation of effective electrical bridges between the respective components, contributing to efficient electron transport and electrode stability. To further induce interactions between PPBT and the metal hydroxide surface, polyethylene glycol was coated onto the sFe 3 O 4 particles, allowing for facile materials dispersion and connectivity. Additionally, the introduction of carbon particles into the web electrode minimized sFe 3 O 4 aggregation and afforded more porous FWNT networks. Finally, as a consequence, the design of composite electrodes with rigorous consideration of specific molecular interactions induced by the surface chemistries favorably influenced electrochemical kinetics and electrode resistance, which afforded high-performance electrodes for battery applications.

25 ENERGY STORAGE↗
DOE OSTI2015

Materials for suspension (semi-solid) electrodes for energy and water technologies

Suspension or semi-solid electrodes have recently gained increased attention for large-scale applications such as grid energy storage, capacitive water deionization, and wastewater treatment. A suspension electrode is a multiphase material system comprised of an active (charge storing) material suspended in ionic solution (electrolyte). Gravimetrically, the electrolyte is the majority component and aids in physical transport of the active material. This principle enables, for the first time, scalability of electrochemical energy storage devices (supercapacitors and batteries) previously limited to small and medium scale applications. This critical review describes the ongoing material challenges encompassing suspension-based systems. The research described here combines classical aspects of electrochemistry, colloidal science, material science, fluid mechanics, and rheology to describe ion and charge percolation, adsorption of ions, and redox charge storage processes in suspension electrodes. This review summarizes the growing inventory of material systems, methods and practices used to characterize suspension electrodes, and describes universal material system properties (rheological, electrical, and electrochemical) that are pivotal in the design of high performing systems. A discussion of the primary challenges and future research directions is included.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

An apparatus for studying electrical breakdown in liquid helium at 0.4 K and testing electrode materials for the neutron electric dipole moment experiment at the Spallation Neutron Source

In this study, we have constructed an apparatus to study DC electrical breakdown in liquid helium at temperatures as low as 0.4 K and at pressures between the saturated vapor pressure and ~600 Torr. The apparatus can house a set of electrodes that are 12 cm in diameter with a gap of 1–2 cm between them, and a potential up to ±50 kV can be applied to each electrode. Initial results demonstrated that it is possible to apply fields exceeding 100 kV/cm in a 1 cm gap between two electropolished stainless steel electrodes 12 cm in diameter for a wide range of pressures at 0.4 K. We also measured the current between two electrodes. Our initial results, I < 1 pA at 45 kV, correspond to a lower bound on the effective volume resistivity of liquid helium of ρ V > 5 × 10 18 Ω cm. This lower bound is 5 times larger than the bound previously measured. Finally, we report the design, construction, and operational experience of the apparatus, as well as initial results

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Novel Ionomers and electrode structures for improved PEMFC electrode performance at low PGM loadings (Final Report)

In this project, the objective is to develop new ORR electrocatalysts on optimized supports which can exceed all of the Department of Energy (DOE) 2020 targets listed in DE-FOA-0001412 directly relevant to the subtopic. This project’s approach is to develop novel, electrode-specific ionomers, and integrate them with state-of-the-art NSTF electrocatalyst powder to develop a cathode electrode achieving >= 044 A/mg PGM mass activity, <=30% mass activity loss during metal cycling, and <=0.125 g PGM /kW performance under DOE testing protocols. Ionomer O 2 permeability and proton conductivity will be increased by up to 1.5X over the baseline 3M800 perfluorosulfonate (PFSA) ionomer to enhance cathode electrode performance. Integration of cathode NSTF powder into an ionomer-containing electrode will increase the surface enhancement factor (SEF) to >=40 cm 2 PGM /cm 2 GEO allowing NSTF containing cathodes to exceed DOE MEA robustness targets. This report summarizes this project’s progress towards meeting the stated objectives and includes a summary of significant findings, conclusions, and developments over the entire project period from Oct. 1 st 2016 – Jan. 31 st 2020. This work has overcome key operation robustness issues with classic NSTF electrodes, identified pathways to improved dispersed and dispersed NSTF cathode performance, developed novel ionomers with high bulk conductivity and oxygen permeability, demonstrated exceptional support-independent electrode activity, and significantly increased metal and support stability through ionomer development. At this point, Tufts, MTU and all 5 FCPAD national labs have been involved, and contributed to, the improvements, learning and achievements of this work. Over the course of this project, more than 50 grams of dispersed NSTF powder in 15 different configurations have been generated, paving the way for scaleup within 3M. These whiskers have been processed in multiple ways, including acid leaching, powder-annealed, and sonicated by various means. For Task 2, 27 different types of ionomers were tested, 19 of which were made for the first time during the course of this project. 377 electrode inks with both NSTF and metal-on-carbon catalysts with I/C ratios from 0.2 to 1.2 were generated and mostly coated on a 3M pilot manufacturing line resulting in more than 700 different electrode types.

08 HYDROGEN↗
DOE OSTI2017

Ultrathin Co 3 O 4 Layers with Large Contact Area on Carbon Fibers as High-Performance Electrode for Flexible Zinc-Air Battery Integrated with Flexible Display

A facile and binder-free method is developed for the in situ and horizontal growth of ultrathin mesoporous Co 3 O 4 layers on the surface of carbon fibers in the carbon cloth (ultrathin Co 3 O 4 /CC) as high-performance air electrode for the flexible Zn-air battery. In particular, the ultrathin Co 3 O 4 layers have a maximum contact area on the conductive support, facilitating the rapid electron transport and preventing the aggregation of ultrathin layers. The ultrathin feature of Co 3 O 4 layers is characterized by the transmission electron microscopy, Raman spectra, and X-ray absorption fine structure spectroscopy. Benefiting from the high utilization degree of active materials and rapid charge transport, the mass activity for oxygen reduction and evolution reactions of the ultrathin Co 3 O 4 /CC electrode is more than 10 times higher than that of the carbon cloth loaded with commercial Co 3 O 4 nanoparticles. Compared to the commercial Co 3 O 4 /CC electrode, the flexible Zn-air battery using ultrathin Co 3 O 4 /CC electrode exhibits excellent rechargeable performance and high mechanical stability. Furthermore, the flexible Zn-air battery is integrated with a flexible display unit. The whole integrated device can operate without obvious performance degradation under serious deformation and even during the cutting process, which makes it highly promising for wearable and roll-up optoelectronics.

cobalt oxides↗
DOE OSTI2018

Electrode Edge Effects and the Failure Mechanism of Lithium-Metal Batteries

Lithium (Li) metal with very high specific capacity makes it one of the ideal anode for high energy batteries. However, Li dendrite growth and the formation of isolated (or “dead”) Li during repeated Li plating/stripping processes lead to its low Coulombic efficiency (CE). In this work, we discovered for the first time that part of Li CE loss can be attributed to the edge effect of the copper (Cu) substrate electrode in a conventional Li||Cu cell configuration. The “dead” Li formed on the edge of Cu substrate was systematically investigated through scanning electron microscopy, energy dispersive X-ray spectroscopy, and two-dimensional X-ray photoelectron spectroscopy. In order to minimize the Li loss at the edge of the Cu exposed to pressure-free space, modified Li||Cu cell configuration with a Cu electrode smaller than Li metal is preferred. It was clearly demonstrated that using an electrode configuration with minimal open space or “pressure-free space” across electrodes can reduce “dead” Li accumulated during cycling and increase Li CE. This phenomena was also verified in Li metal batteries (Li||LiNi1/3Mn1/3Co1/3O2) and should be considered in the design of practical Li metal batteries.

Lee, Hongkyung↗
DOE OSTI2016

Potassium-Based alpha-Manganese Dioxide Nanofiber BinderFree Self-Supporting Electrodes: A Design Strategy for High Energy Density Batteries

This work minimizes electrode passive components and moves toward bridging the gap between actual and theoretical battery gravimetric energy density. Binder-free self-supporting (BFSS) cathodes were prepared from redox-active, high aspect ratio, potassium α-MnO2 nanofibers (K-OMS-2), eliminating the binder and current collector. The electroactive and structural element, K-OMS-2, was prepared using a scalable, moderate temperature, aqueous synthesis. The BFFS electrode approach allows fabrication of thick, high energy density electrodes with low impedance, with up to 10 fold improvement in delivered specific energy relative to conventional cathodes. This could enable high capacity large form factor cell designs, as required for applications demanding high energy content. In principle, this approach suggests a widely applicable paradigm for the construction of other BFFS electrodes through the targeted synthesis of other transition metal oxides with high aspect, fibrous morphologies. Introduction

25 ENERGY STORAGE↗
DOE OSTI2014

Optimization of electrode characteristics for the Br-2/H-2 redox flow cell

The Br-2/H-2 redox flow cell shows promise as a high-power, low-cost energy storage device. The effect of various aspects of material selection, processing, and assembly of electrodes on the operation, performance, and efficiency of the system is determined. In particular, (+) electrode thickness, cell compression, hydrogen pressure, and (-) electrode architecture are investigated. Increasing hydrogen pressure and depositing the (-) catalyst layer on the membrane instead of on the carbon paper backing layers have a large positive impact on performance, enabling a limiting current density above 2 A cm(-2) and a peak power density of 1.4 W cm(-2). Maximum energy efficiency of 79 % is achieved. In addition, the root cause of limiting-current behavior in this system is elucidated, where it is found that Br- reversibly adsorbs at the Pt (-) electrode for potentials exceeding a critical value, and the extent of Br- coverage is potential-dependent. This phenomenon limits maximum cell current density and must be addressed in system modeling and design. These findings are expected to lower system cost and enable higher efficiency.

Tucker, MC↗
DOE OSTI2025

High tensile alloy of copper to mitigate current collector deformation in silicon electrodes for lithium-ion batteries

The volumetric changes of silicon electrodes, along with the strong adhesive properties of certain binders, can lead to plastic deformation of the current collector and create damage in the electrode coating. Here, in this study, we report a detailed study of silicon coatings on a high-tensile alloy (HTA) foil of copper with strength over twice that of conventional copper foils. The HTA current collectors with high mechanical strength can mitigate plastic deformation upon continuous cycling. At moderate areal capacities (2.5–3 mAh cm −2 ), conventional copper foils show significant wrinkling after only a few electrochemical cycles, whereas the HTA foils remain intact. We demonstrate viability of the HTA foils in large format xx6395 pouch cells, in which the HTA current collectors remain intact even at an areal capacity of 4.5 mAh cm −2 ; in contrast, wrinkles form in conventional copper current collectors increasing the likelihood of lithium plating. Computational studies show that stresses generated during cycling of silicon electrodes are very high in the current collector and at the current collector-coating interface, explaining the wrinkling of conventional Cu foils. Our studies highlight importance of current collector to solve the electrochemical and chemo-mechanical performance challenges associated with high-loading silicon electrodes.

Chemo-mechanical degradation↗
DOE OSTI2020

Enhancement of Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 fuel electrode performance by infiltration of Ce 0.8 Gd 0.2 O 2–δ nanoparticles

This paper addresses the use of Ce 0.8 Gd 0.2 O 2–δ (GDC) infiltration into the Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 (YSZ) fuel electrode of solid oxide cells (SOCs) for improving their electrochemical performance in fuel cell and electrolysis operation. Although doped ceria infiltration into Ni–YSZ has recently been shown to improve the electrode performance and stability, the mechanisms defining how GDC impacts electrochemical characteristics are not fully delineated. Furthermore, the electrochemical characteristics have not yet been determined over the full range of conditions normally encountered in fuel cell and electrolysis operation. Here we present a study of both symmetric and full cells aimed at understanding the electrochemical mechanisms of GDC-modified Ni–YSZ over a wide range of fuel compositions and temperatures. Single-step GDC infiltration at an appropriate loading substantially reduced the polarization resistance of Ni–YSZ electrodes in electrolyte-supported cells, as measured using electrochemical impedance spectroscopy (EIS) at various temperatures (600–800 °C) in a range of H 2 O–H 2 mixtures (3–90 vol% H 2 O). Fuel-electrode-supported cells had significant concentration polarization due to the thick Ni–YSZ supports. Here, a distribution of relaxation times approach is used to develop a physically-based electrochemical model; the results show that GDC reduces the reaction resistance associated with three-phase boundaries, but also appears to improve oxygen transport in the electrode. Increasing the H 2 O fraction in the H 2 –H 2 O fuel mixture reduced both the three-phase boundary resistance and the gas diffusion resistance for Ni–YSZ; with GDC infiltration, the electrode resistance showed less variation with fuel composition. GDC infiltration improved the performance of fuel-electrode-supported full cells, which yielded a maximum power density of 2.28 W cm –2 in fuel cell mode and an electrolysis current density at 1.3 V of 2.22 A cm –2 , both at 800°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Fabrication of Carbon-Platinum Interdigitated Array Electrodes and Their Application for Investigating Homogeneous Hydrogen Evolution Catalysis

Interdigitated array electrodes (IDAEs) with one carbon electrode and the other platinum electrode were constructed by electrodepositing platinum on one set of the carbon electrodes. Platinum deposition was confirmed by scanning electron microscope (SEM) and cyclic voltammetry. The width of the carbon and platinum digits is less than 2 μm and the gap between two adjacent digits is around 3 μm. The carbon-platinum IDAEs benefit from the characteristics of both carbon and platinum in that carbon can provide a wide nonreactive potential window while platinum is a good catalyst for hydrogen reactions making it useful to characterize the catalytic hydrogen production cycle of the molecular electrocatalyst [Ni(P Ph 2 N Ph 2 ) 2 (CH 3 CN)](BF 4 ) 2 (where P Ph 2 N Ph 2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane). With properly set potentials, the molecular electrocatalyst was reduced at the carbon digits to initiate a homogeneous H 2 production reaction while the platinum digits detect the H 2 by oxidation, providing direct evidence of its production rate from the catalytic cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗