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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Tuning Catalyst Activation and Utilization Via Controlled Electrode Patterning for Low-Loading and High-Efficiency Water Electrolyzers

An anode electrode concept of thin catalyst-coated liquid/gas diffusion layers (CCLGDLs), by integrating Ir catalysts with Ti thin tunable LGDLs with facile electroplating in proton exchange membrane electrolyzer cells (PEMECs), is proposed. The CCLGDL design with only 0.08 mg Ir cm -2 can achieve comparative cell performances to the conventional commercial electrode design, saving ~97% Ir catalyst and augmenting a catalyst utilization to ~24 times. CCLGDLs with regulated patterns enable insight into how pattern morphology impacts reaction kinetics and catalyst utilization in PEMECs. A specially designed two-sided transparent reaction-visible cell assists the in situ visualization of the PEM/electrode reaction interface for the first time. Oxygen gas is observed accumulating at the reaction interface, limiting the active area and increasing the cell impedances. In this work, it is demonstrated that mass transport in PEMECs can be modified by tuning CCLGDL patterns, thus improving the catalyst activation and utilization. The CCLGDL concept promises a future electrode design strategy with a simplified fabrication process and enhanced catalyst utilization. Furthermore, the CCLGDL concept also shows great potential in being a powerful tool for in situ reaction interface research in PEMECs and other energy conversion devices with solid polymer electrolytes.

08 HYDROGEN↗
DOE OSTI2023

Mathematical Framework Underlying the In Situ Electrochemical Diagnosis of Adsorbed Intermediates Formed during Redox Reactions at Electrode Surfaces

Previously, we have presented an electrochemical technique wherein an electroactive tracer species is employed to probe the rate-limiting factors governing redox reactions at an electrode surface. In this technique, the electrode is first held potentiostatically to facilitate a redox process (step 1), and then the potential is released to open circuit conditions (step 2) so as to monitor the time-dependent re-equilibration of the electrode potential in the presence of the tracer. The time-dependent potential response in step 2 has been shown to contain information about diffusion—limited or desorption—limited steps, enabling in situ probing of the electrochemistry at the electrode surface during step 1. In the present contribution, a theoretical model governing the transient response in step 2 is developed for two limiting cases: diffusion—limited and desorption—limited recovery of the electrode potential. Mathematical modeling shows that, during re-equilibration, the step 2 potential transient corresponding to a case where step 1 involves surface adsorbed species which undergo desorption in step 2 exhibits a much longer time constant than that when re-equilibration occurs under diffusion limitations. The mathematical framework presented herein provides a sound fundamental basis for applying the aforementioned technique to studying adsorption-desorption processes during electrochemistry. Also, technique limitations are presented in light of the modeling findings.

25 ENERGY STORAGE↗
DOE OSTI2024

Elucidating the Link Between Alkali Metal Ions and Reaction-Transport Mechanisms in Cathode Electrodes for Alkali-ion Batteries

Our long-term goal is to improve the reliability of electrode materials and their ability to transport and store various metal ions for electrochemical energy storage applications. The main objective of this work was to investigate the intrinsic relationship between the role of alkali metal ions and electrochemically driven mechanical stability and kinetic properties of battery materials. The overall question was “What is the role of alkali metal ions on the electrochemical and mechanical behavior of cathode electrodes? Our guiding hypothesis was that intercalation of larger alkali metal ions (Na and K) inevitably alters the coupled transport-reaction processes during battery operation in organic electrolytes, leading to more intensive chemo-mechanical instabilities in cathode electrodes, resulting in rapid capacity fade. To validate the hypothesis, we experimentally characterized the reaction-transport processes and governing forces driving the instability of electrode materials in different alkali metal-ion environments. The project had three main tasks. The first one was to investigate intercalation-induced strains and associated stress generation, and their impact on structural deformations in composite cathode electrodes. The second task focused on identifying potential-dependent dynamic changes in the electrode-electrolyte interface in alkali metal ion batteries. The last task was focused on determining how larger alkali metal ions with slower diffusivity affect the transport-mechanics coupling at faster scan rates, compared to smaller ions with faster diffusivity in electrodes. We shortly provided the outcome of each task in the accomplishment section. This project produced 10 peer-reviewed publications (9 research papers and one review manuscript) and supported two Ph.D. students, who graduated from Oklahoma State University.

25 ENERGY STORAGE↗
NASA NTRS2004

Direct Electrolytic Deposition of Mats of Mn(x)O(y) Nanowires

Mats of free-standing manganese oxide (MnxOy) nanowires have been fabricated as experimental electrode materials for rechargeable electrochemical power cells and capacitors. Because they are free-standing, the wires in these mats are electrochemically accessible. The advantage of the mat-of-nanowires configuration, relative to other configurations of electrode materials, arises from the combination of narrowness and high areal number density of the wires. This combination offers both high surface areas for contact with electrolytes and short paths for diffusion of ions into and out of the electrodes, thereby making it possible to charge and discharge at rates higher than would otherwise be possible and, consequently, to achieve greater power densities. The nanowires are fabricated in an electrolytic process in which there is no need for an electrode binder material. Moreover, there is no need to incorporate an electrically conductive additive into the electrode material; the only electrically conductive material that must be added is a thin substrate contact film at the anchored ends of the nanowires. Hence, the mass fraction of active electrode material is close to 100 percent, as compared with about 85 percent in conventional electrodes made from a slurry of active electrode material, binder, and conductive additive pressed onto a metal foil. The locations and sizes of the nanowires are defined by holes in templates in the form of commercially available porous alumina membranes. In experiments to demonstrate the present process, alumina membranes of various pore sizes and degrees of porosity were used. First, a film of Au was sputtered onto one side of each membrane. The membranes were then attached, variously, to carbon tape or a gold substrate by use of silver or carbon paste. Once thus attached, the membranes were immersed in a plating solution comprising 0.01 M MnSO4 + 0.03 M (NH4)2SO4. The pH of the solution was kept constant at 8 by addition of H2SO4 or NH4OH as needed. Mn(x)O(y) nanowires were potentiostatically electrodeposited in the pores in the alumina templates. Depending on the anodic deposition potentials, Mn(x)O(y) was deposited in various oxidation states [divalent (Mn3O4), trivalent (Mn2O3), or tetravalent (MnO2)]. The Mn(x)O(y) wires were made free-standing (see figure) by dissolving the alumina templates, variously, in KOH or NaOH at a concentration of 20 volume percent.

Myung, Nosang↗
DOE OSTI2021

Parametric analysis of anodic degradation mechanisms for fast charging lithium batteries with graphite anode

In this work, we report the impact of the temperature-driven synergistically-coupled anodic degradation mechanisms on the electrochemical performance of lithium batteries with graphite anode over multiple cycles. Temperature dependence of electrochemical reactions and damage mechanisms, such as solid electrolyte interface (SEI) growth, lithium plating/stripping, dead lithium storage/dissolution, and film cracking are incorporated into the degradation model. Results of a parametric analysis are presented, evaluating the effects of charging rates (1–6 C), operating temperatures (-15 – 45°C) and electrode design parameters, on the relative performance fade in the lithium-ion battery. Thermo-electrochemical process maps are developed to provide insights into the relationship between electrode performance and failure mechanisms. The simulation results predict a severe capacity loss due to lithium plating at low temperatures, which is further aggravated at high charging rates. A common strategy for mitigating lithium plating, through charging at high temperatures, also results in rapid capacity loss due to accelerated SEI formation. Simulation results are used to identify the combination of operating conditions and electrode design parameters that improve the electrochemical performance of the battery. These results demonstrate an opportunity to design safe and high-performance lithium-ion batteries, guided by anodic degradation models.

Battery design↗
NASA NTRS1977

A model for particle confinement in a toroidal plasma subject to strong radial electric fields

A toroidal plasma is confined and heated by the simultaneous application of strong d.c. magnetic fields and electric fields. Strong radial electric fields (about 1 kilovolt per centimeter) are imposed by biasing the plasma with up to 12 negative electrode rings which surround its minor circumference. The plasma containment is consistent with a balance of two processes: a radial infusion of ions in those sectors not containing electrode rings, resulting from the radially inward electric fields; and ion losses to the electrode rings, each of which acts as a sink and draws ions out the plasma in the manner of a Langmuir probe in the ion saturation regime. The highest density on axis which has been observed so far in this steady-state plasma is 6.2 x 10 to the 12th power particles per cubic centimeter, for which the particle containment time is 2.5 milliseconds. The deuterium ion kinetic temperature for these conditions was in the range of 360 to 520 eV.

Roth, J. R.↗
NASA NTRS1977

A model for particle confinement in a toroidal plasma subject to strong radial electric fields

The approach adopted in the NASA Lewis Bumpy Torus experiment is to confine and heat a toroidal plasma by the simultaneous application of strong dc magnetic fields and electric fields. Strong radial electric fields (about 1 kV/cm) are imposed by biasing the plasma with up to 12 negative electrode rings which surround its minor circumference. The plasma containment is consistent with a balance of two processes: a radial infusion of ions in those sectors not containing electrode rings, resulting from the radially inward electric fields; and ion losses to the electrode rings, each of which acts as a sink and draws ions out the plasma in the manner of a Langmuir probe in the ion saturation regime. The highest density on axis which has been observed so far in this steady-state plasma is 6.2 trillion particles per cu cm, for which the particle containment time is 2.5 msec. The deuterium ion kinetic temperature for these conditions was in the range of 360 to 520 eV.

Roth, J. R.↗
NASA NTRSDate not supplied

Layered Electrode Architectures Enabled by Holey Graphene Hosts

Battery electrodes are typically prepared using a slurry-based method, where high boiling point organic solvents are typically used with a polymer binder to disperse active electrode materials and conductive carbon additives followed by casting into current collector sheets. In this process, the use of organic solvents are environmentally hazardous, energy intensive, and time-consuming, while polymeric binders add weight and can undergo parasitic reactions during battery cycling. Here we discuss the use of a unique conductive carbon nanomaterial, namely holey graphene, as a multifunctional host that can be processed via a facile, solvent-free, binder-free, cold pressing method to prepare electrodes with unique architectures. This approach can accommodate a broad range of battery chemistries, such as lithium oxygen/carbon dioxide (Li-O2/CO2), lithium sulfur/selenium (Li-S/Se), and various lithium ion chemistries. The successful use of dry, cold compression allows the convenient modification of electrode mass loading with unique architectures containing active materials randomly mixed or layered with single or multiple layers of one or more active materials. In the conventional slurry-based electrode fabrication method, it is difficult, if not impossible, to achieve such layered architectures. In particular, the layered electrode architectures from the dry, cold press approach are easy to fabricate without significantly sacrificing device performance, and are amenable to continuous roll-to-roll dry processing. In addition, these architectures offer unprecedented perspectives on the battery material loading vs. utilization efficiency, as well as enabling unique characterization opportunities to advance mechanistic understanding of various battery chemistries. Potential applications of this unique electrode fabrication approach for solid-state batteries will also be discussed.

holey graphene, batteries, electrode architecture,↗
DOE OSTI2023

Modeling Electrochemical and Rheological Characteristics of Suspension-Based Electrodes for Redox Flow Cells

Flowable suspension-based electrodes (FSEs) have gained attention in recent years, as the integration of solid materials into electrochemical flow cells can offer improved performance and flexible operation. However, under conditions that engender favorable electrochemical properties (e.g., high particle loading, high conductivity, high surface area), FSEs can exhibit non-Newtonian characteristics that impose large pumping losses and flow-dependent transport rates. These multifaceted trade-offs motivate the use of models to broadly explore scaling relationships and better understand design rules for electrochemical devices. To this end, we present a one-dimensional model, integrating porous electrode theory with FSE rheology as well as flow-dependent electron and mass transport under pressure-driven flow. We study FSE behavior as a function of material properties and operating conditions, identifying key dimensionless groups that describe the underlying physical processes. We assess flow cell performance by quantifying electrode polarization and relative pumping losses, establishing generalized property-performance relationships for FSEs. Importantly, we expound relevant operating regimes—based on a subset of dimensionless groups—that inform practical operating envelopes, ultimately helping to guide FSE and cell engineering for electrochemical systems.

25 ENERGY STORAGE↗
DOE OSTI2023

Carbon Coating Influence on the Formation of Percolating Electrode Networks for Silicon Anodes

Previous studies have demonstrated that chemical vapor deposition carbon coating on silicon (Si@C) can enhance the electrochemical performance of lithium-ion batteries with Si-based anodes. However, the underlying mechanisms contributing to this improvement have not been fully explored. Here, we address this knowledge gap by applying a suite of characterization methods to evaluate Si@C anodes prepared by reducing acetylene on ball-milled Si particles. Raman mapping measurements show that the C coating (<5 nm thick) enables a homogeneous Si and carbon distribution during the slurry casting process, thereby promoting Si utilization during cycling. The coating’s microstructure and morphology were evaluated using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy, and neutron reflectivity experiments. Electrochemical impedance spectroscopy measurements upon cycling indicate that carbon coating also reduces the overall resistance as benchmarked against bare Si anodes. Galvanostatic cycling in half-cell studies revealed higher initial Coulombic efficiency and specific capacities with increasing carbon coating time. However, solid electrolyte interphase (SEI) investigations using XPS showed that the coated and uncoated samples have very similar characteristics, suggesting that the SEI may only play a minor role in enhancing the performance of Si@C. Full-cell evaluation of the Si electrodes was consistent with half-cell results relating to performance and SEI properties, further supporting the conclusion that electronic and ionic percolation, enabled by effective electrode manufacturing, are the dominant factors contributing to the favorable performance of Si@C.

25 ENERGY STORAGE↗
DOE OSTI2025

A Diffuse-Interface Model for Predicting the Evolution of Metallic Negative Electrodes and Interfacial Voids in Solid-State Batteries with Homogeneous and Polycrystalline Solid Electrolyte Separators

Here, this paper presents a novel diffuse-interface electrochemical model that simultaneously simulates the evolution of the metallic negative electrode and interfacial voids during the stripping and plating processes in solid-state batteries. The utility and validity of this model are demonstrated for the first time on a cell with a sodium (Na) negative electrode and a Na-β″-alumina ceramic solid electrolyte (SE) separator. Three examples are simulated. First, stripping and plating with a perfect electrode/electrolyte interface; second, stripping and plating with a single interfacial void at the electrode/electrolyte interface; third, stripping with multiple interfacial voids. Both homogeneous and polycrystalline SEs with low and high-conductivity grain boundaries (GBs) are considered for all three examples. Heterogeneous GB conductivity marginally impacts the thickness of the Na electrode in cases with a perfect electrode/electrolyte interface. Moreover, it results in local changes to void growth due to the interactions between the void edge and the GBs. The void growth rate is a linear function of the flux of Na atoms at the void edge, which in turn depends on the applied current density. We also show that the void coalescence rate increases with applied current density and can be marginally influenced by GB conductivity.

batteries↗
NASA NTRS2006

Nano-interconnection for microelectronics and polymers with benzo-triazole

Benzo-Triazole (BTA) is considered as an important bridging material that can connect an organic polymer to the metal electrode on silicon wafers as a part of the microelectronics fabrication technology. We report a detailed process of surface induced 3-D polymerization of BTA on the Cu electrode material which was measured with the Ultraviolet Photoemission Spectroscopy (UPS), X-ray Photoemission Spectroscopy (XPS), and Scanning Tunneling Microscope (STM). The electric utilization of shield and chain polymerization of BTA on Cu surface is contemplated in this study.

Park, Yeonjoon↗
DOE OSTI2023

In Situ Ion‐Exchange Metathesis Induced Conformal LiF Surface Films on Cathode (NMC811) as a Cathode Electrolyte Interphase

High-capacity cathodes (LiNi 0.8 Mn 0.1 Co 0.1 O 2 , NMC811) are promising for vehicle electrification because of their high gravimetric energy density. However, their electrochemical performance still relies upon the stability of the cathode electrolyte interphase (CEI). A highly reactive cathode interface leads to parasitic side reactions with electrolytes, resulting in accelerated capacity fading. Well-developed LiF and LiF-like inorganic compounds are believed to be good CEI components for stabilizing such reactive electrode interfaces. However, it is challenging to form an optimal surface sub-nanolayer of LiF on the cathode surfaces because of the complexity of the electrochemical reaction during battery cycling. Herein, the formation of a conformal LiF layer on the NMC811 electrode surface via an in situ ion-exchange metathesis process is reported, demonstrating a promising electrochemical performance because of a LiF-stabilized CEI. In situ generated LiF-coated NMC811 electrodes exhibit ≈97% capacity retention up to 100 cycles at a 0.3 C rate with average coulombic efficiency of ≈99.9% and ≈80% capacity retention up to 200 cycles at a 1 C rate with average coulombic efficiency of >99.6%. This finding may pave the way for reengineering the CEI to enhance the electrochemical performances and cycling stability of the high-capacity cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Multielectrode sensor for concentration and depth measurements in molten salt

A multi electrode sensor that provides in-situ, real time measurements for molten salts and other process fluids such as real-time concentration and salt level measurements for nuclear systems such as molten salt reactors, nuclear reprocessing facilities utilizing molten salts and concentrated solar power systems. The sensor has multiple electrodes with unique lengths which are connected to a potentiostat. Measurements are taken when the electrodes are immersed in the process fluid.

Hoyt, Nathaniel C.↗
DOE OSTI2025

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE↗
NASA NTRS1994

Laser-Induced Fluorescence Helps Diagnose Plasma Processes

Technique developed to provide in situ monitoring of rates of ion sputter erosion of accelerator electrodes in ion thrusters also used for ground-based applications to monitor, calibrate, and otherwise diagnose plasma processes in fabrication of electronic and optical devices. Involves use of laser-induced-fluorescence measurements, which provide information on rates of ion etching, inferred rates of sputter deposition, and concentrations of contaminants.

Beattie, J. R.↗