Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Modeling Electrochemical Reaction”

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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Exploring non-adiabaticity to CO reduction reaction through ab initio molecular dynamics simulation

Non-adiabatic chemical reaction refers to the electronic excitation during reactions. This effect cannot be modeled by the ground-state Born-Oppenheimer molecular dynamics (BO-MD), where the electronic structure is at the ground state for every step of ions' movement. Although the non-adiabatic effect has been explored extensively in gas phase reactions, its role in electrochemical reactions, such as water splitting and CO 2 reduction, in electrolyte has been rarely explored. On the other hand, electrochemical reactions usually involve electron transport; thus, a non-adiabatic process can naturally play a significant role. In this work, using one-step CO 2 reduction as an example, we investigated the role of the non-adiabatic effect in the reaction. The reaction barriers were computed by adiabatic BO-MD and non-adiabatic real-time time dependent density functional theory (rt-TDDFT). We found that by including the non-adiabatic effect, rt-TDDFT could increase the reaction barrier up to 6% compared to the BO-MD calculated barrier when the solvent model is used to represent water. Simulations were carried out using explicit water molecules around the reaction site under different overpotentials, and similar non-adiabatic effects were found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Intrinsic chemical reactivity of solid-electrolyte interphase components in silicon–lithium alloy anode batteries probed by FTIR spectroscopy

Herein we report the solid reaction products from the chemical reaction of aprotic battery electrolyte and three purported components of the Si-based anode SEI : SiO 2 nanoparticles (NPs), lithium silicate (Li x SiO y ) powders, and Si NPs. We use FTIR and classical molecular dynamics/density functional perturbation theory to assess the solid products remaining with these model materials after exposure to electrolyte. The absence of electrochemical bias provides a view of the chemical speciation resulting from early-stage chemical reactivity during battery assembly as well as under open circuit storage conditions. We believe these species represent the initial stages of SEI growth and predict they likely drive subsequent chemical and electrochemical reactions by controlling molecular interactons at the Si active material interface. We find that nominally equivalent materials react differently even before any electrochemistry is performed (e.g., acidic SiO 2 dissolves whereas alkaline SiO 2 is relatively robust), and derive new understanding of the chemical species that could and could not form stable SEI components in Si-based anodes. These results can be used to inform how to passivate Si anode surfaces and potentially generate an artificially engineered SEI that would be stable and enable next-generation battery anodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

BEAST DB: Grand-Canonical Database of Electrocatalyst Properties

We present BEAST DB, an open-source database comprised of ab initio electrochemical data computed using grand-canonical density functional theory in implicit solvent at consistent calculation parameters. The database contains over 20,000 surface calculations and covers a broad set of heterogeneous catalyst materials and electrochemical reactions. Calculations were performed at self-consistent fixed potential as well as constant charge to facilitate comparisons to the computational hydrogen electrode. This article presents common use cases of the database to rationalize trends in catalyst activity, screen catalyst material spaces, understand elementary mechanistic steps, analyze the electronic structure, and train machine learning models to predict higher fidelity properties. Users can interact graphically with the database by querying for individual calculations to gain a granular understanding of reaction steps or by querying for an entire reaction pathway on a given material using an interactive reaction pathway tool. BEAST DB will be periodically updated, with planned future updates to include advanced electronic structure data, surface speciation studies, and greater reaction coverage.

database↗
DOE OSTI2020

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↗
DOE OSTI2023

Plating and Stripping of Lithium Metal Stabilized by a Block Copolymer Electrolyte: Local Current Density Measurement and Modeling

Here, plating and stripping of lithium protrusions in lithium metal symmetric cells containing a solid block copolymer electrolyte was studied as a function of time in 3D using time-resolved X-ray tomography. These measurements enabled determination of the spatial variation in current densities at the plating and stripping electrodes. The initial interelectrode distance was 27 μm. Correlation functions were calculated to reveal the relationships between current densities at the two electrodes and local electrolyte thickness. Current densities at opposing electrode locations during protrusion growth is uncorrelated until the local interelectrode distance decreases to less than 6 μm, just before the cell shorts. Mass balance was used to determine the area from which lithium ions that form a protrusion were stripped. Computational modeling of the plating and stripping process reveals the interplay between electrochemical and mechanical driving forces and their effect on nonuniform current distribution. Model predictions were compared with experiments without resorting to any adjustable parameters. The computed correlation functions were in qualitative agreement with experiments. Finally, the model was used to calculate contour plots of electrochemical potential within the electrolyte, shedding light on how geometry, salt concentration, interelectrode distance, and mechanical stress influence local rates of electrochemical reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Minimum conditions for accurate modeling of urea production via co-electrolysis

Co-electrolysis of carbon oxides and nitrogen oxides promise to simultaneously help restore the balance of the C and N cycles while producing valuable chemicals such as urea. However, co-electrolysis processes are still largely inefficient and numerous knowledge voids persist. Here, we provide a solid thermodynamic basis for modelling urea production via co-electrolysis. First, we determine the energetics of aqueous urea produced under electrochemical conditions based on experimental data, which enables an accurate assessment of equilibrium potentials and overpotentials. Next, we use density functional theory (DFT) calculations to model various co-electrolysis reactions producing urea. The calculated reaction free energies deviate significantly from experimental values for well-known GGA, meta-GGA and hybrid functionals. These deviations stem from errors in the DFT-calculated energies of molecular reactants and products. In particular, the error for urea is approximately -0.25 ± 0.10 eV. Finally, we show that all these errors introduce large inconsistencies in the calculated free-energy diagrams of urea production via co-electrolysis, such that gas-phase corrections are strongly advised.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ni coarsening under humid atmosphere in the electrode of solid oxide cells: A combined study of density-functional theory and phase-field modeling

Ni coarsening in solid oxide cell (SOC) electrodes is known to be significantly faster under a humid atmosphere. The underlying mechanisms, though, have not been fully understood. In this work, we examine the surface diffusion of Ni(OH) x by a combination of density-functional theory and phase-field modeling. Here, density-functional theory is used to evaluate the adsorption and diffusion of the Ni(OH) x species on Ni (111) surface, and the results are used to obtain the effective surface diffusivity of Ni versus steam and hydrogen gas partial pressures. This diffusivity is used as an input for a phase-field model to investigate the Ni coarsening in SOC electrodes. It is found that Ni(OH) x formed through chemical reaction cannot accelerate coarsening unless an extremely high steam to hydrogen ratio is reached. However, if Ni(OH) x is formed through electrochemical reactions near triple phase boundaries (TPBs), surface diffusion of Ni(OH) x may cause faster Ni coarsening in fuel cell mode under a large overpotential. Specifically, surface diffusion of Ni(OH) may be comparable to or faster than that of Ni under an overpotential that is large but still possible under fuel cell operating conditions.

25 ENERGY STORAGE↗
DOE OSTI2022

A Critical Review of Radiolysis Issues in Water-Cooled Fission and Fusion Reactors: Part I, Assessment of Radiolysis Models

A critical review is presented on modeling of the radiolysis of the coolant water in nuclear power reactors with emphasis on ITER. The review is presented in two parts: In Part I, we assess previous work in terms of compliance with important chemical principles and conclude that no model proposed to date is completely satisfactory, in this regard. Thus, some reactions that have been proposed in various radiolysis models are not elementary in nature and can be decomposed into two or more elementary reactions, some of which are already included in the models. These reactions must be removed in formulating a viable model. Furthermore, elementary reactions between species of like charge are also commonly included, but they can be discounted upon the basis of Coulombic repulsion under the prevailing conditions (T < 350 °C) and must also be removed. Likewise, it is concluded that the current state of knowledge with respect to radiolytic yields (i.e., G-values) is also unsatisfactory. More work is required to ensure that the yields used in radiolysis models are truly “primary” yields corresponding to a time scale of nanoseconds or less. This is necessary to ensure that the impact of the reactions that occur outside of the spurs (ionizing particle tracks in the medium) are not counted twice. In Part II, the authors review the use of the radiolysis models coupled with electrochemical models to predict the water chemistry, corrosion potential, crack growth rate in Type 304 SS, and accumulated damage in the coolant circuits of boiling water reactors, pressurized water reactors, and the test fusion reactor, ITER. Based on experience with fission reactors, the emphasis should be placed on the control of the electrochemical corrosion potential because it is the parameter that best describes the state of corrosion in coolant circuits.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

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↗
DOE OSTI2024

From Fundamental Interfacial Reaction Kinetics to Macroscopic Current–Voltage Characteristics: Case Study of Solid Acid Fuel Cell Limitations and Possibilities

The unique properties of solid acid electrolytes, in particular CsH 2 PO 4 , are in many ways ideal for fuel cell operation. However, the technology is constrained by high cathode overpotentials. Here a simplified cathode geometry is employed to obtain the fundamental electrochemical parameters (exchange current density and charge transfer coefficient) describing the oxygen reduction reaction (ORR) at the CsH 2 PO 4 -Pt-gas interface. The parameters are incorporated into a 1D model of the voltage–current characteristics of realistic SAFC cathodes, which reproduced the measured polarization behavior of such cathodes without recourse to fitting adjustable parameters. Following this validation, the model is utilized to evaluate the impact of changes to cathode properties, microstructure, and operating conditions. Of these, the charge transfer coefficient, measured to have a value of ≈0.6 for ORR on Pt in the SAFC cathode environment, is found to have the greatest impact on power output. Nevertheless, even without material modifications, a combination of microstructural and operational modifications are identified with projected performance metrics meeting Department of Energy targets (0.8 V at 300 mA cm –2 , and peak power density of 1 W cm –2 ), albeit at high Pt loadings. However, the analysis indicates that truly meaningful advances will likely necessitate the discovery of alternative ORR catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Predictive Models and Novel Accelerated Tests for the Reliability of Cell Metallization in Photovoltaic Modules (Final Report)

Studies of metallization corrosion m photovoltaics have mainly been limited to comparisons of modules placed in accelerated chambers to fielded modules [1]. Damp Heat accelerated tests and phenomenological equations [2] are used to assess metallization corrosion without understanding the effect of UV light and temperature and humidity cycles on encapsulant adhesion degradation. The roles of encapsulant in-and out-diffusions of moisture and encapsulant impurities are important. Furthermore, few photovoltaic metallization corrosion studies included the role of bias and leakage currents, which are crucial in the electrochemical reaction of metallization. Leakage currents can highly accelerate the corrosion mechanism and are important to include in the studies of corrosion. In our research plan, we will address the following gaps in the PV community's understanding of metallization corrosion: (1) metallization corrosion with bias, humidity, and impurities in the encapsulant or metallization; (2) humidity diffusion through fresh and degraded encapsulants; and (3) comparison of model predictions with outdoor field modules and SunPower's extensive data for its back-contact and front-contact fleets [2] along with NREL's store of >20 year old modules. Our goal is to build models and accelerated tests to predict long term degradation of metallization corrosion of photovoltaic modules in the field. Our studies will include metals used in c-Si solar cells (Cu, Ag, and Al) and commonly used encapsulants (EV A (ethylene vinyl acetate), TPO (thermoplastic olefin), and silicone).

14 SOLAR ENERGY↗
DOE OSTI2023

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

36 MATERIALS SCIENCE↗
DOE OSTI2020

Active Learning Accelerated Discovery of Stable Iridium Oxide Polymorphs for the Oxygen Evolution Reaction

The discovery of high-performing and stable materials for sustainable energy applications is a pressing goal in catalysis and materials science. Understanding the relationship between a material’s structure and functionality is an important step in the process, such that viable polymorphs for a given chemical composition need to be identified. Machine-learning-based surrogate models have the potential to accelerate the search for polymorphs that target specific applications. Herein, we report a readily generalizable active-learning (AL) accelerated algorithm for identification of electrochemically stable iridium oxide polymorphs of IrO 2 and IrO 3 . The search is coupled to a subsequent analysis of the electrochemical stability of the discovered structures for the acidic oxygen evolution reaction (OER). Structural candidates are generated by identifying all 956 structurally unique AB2 and AB3 prototypes in existing materials databases (more than 38000). Next, using an active learning approach, we find 196 IrO 2 polymorphs within the thermodynamic amorphous synthesizability limit and reaffirm the global stability of the rutile structure. We find 75 synthesizable IrO 3 polymorphs and report a previously unknown FeF 3 -type structure as the most stable, termed α-IrO 3 . To test the algorithms performance, we compare to a random search of the candidate space and report at least a 2-fold increase in the rate of discovery. Additionally, the AL approach can acquire the most stable polymorphs of IrO 2 and IrO 3 with fewer than 30 density functional theory optimizations. Analysis of the structural properties of the discovered polymorphs reveals that octahedral local coordination environments are preferred for nearly all low-energy structures. Subsequent Pourbaix Ir–H 2 O analysis shows that α-IrO3 is the globally stable solid phase under acidic OER conditions and supersedes the stability of rutile IrO 2 . Calculation of theoretical OER surface activities reveal ideal weaker binding of the OER intermediates on α-IrO 3 than on any other considered iridium oxide. We emphasize that the proposed AL algorithm can be easily generalized to search for any binary metal oxide structure with a defined stoichiometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

On the origin of multihole oxygen evolution in haematite photoanodes

The oxygen evolution reaction (OER) plays a crucial role in (photo)electrochemical devices that use renewable energy to produce synthetic fuels. Recent measurements on semiconducting oxides have found a power law dependence of the OER rate on surface hole density, suggesting a multihole mechanism. In this study, using transient photocurrent measurements, density functional theory simulations and microkinetic modelling, we have uncovered the origin of this behaviour in haematite. We show here that the OER rate has a third-order dependence on the surface hole density. We propose a mechanism wherein the reaction proceeds by accumulating oxidizing equivalents through a sequence of one-electron oxidations of surface hydroxy groups. The key O–O bond formation step occurs by the dissociative chemisorption of a hydroxide ion involving three oxyl sites. At variance with the case of metallic oxides, the activation energy of this step is weakly dependent on the surface hole coverage, leading to the observed power law.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electrolyte Organization Leads to Potential-Dependence in Thermochemical Catalysis of Nonpolar Reactions

Electrochemical polarization is now known to play a key role in thermochemical catalysis at solid–liquid interfaces. However, existing frameworks cannot account for why even nonpolar, nonfaradaic reactions are sensitive to interfacial polarization. In order to uncover the molecular basis of this phenomenon, we herein study the potential-dependent reaction kinetics of ethylene and trans-2-butene hydrogenation at Pt–liquid interfaces. Measurements were performed in aqueous and ortho-difluorobenzene (o-DFB) solutions, spontaneously polarizing the Pt–liquid interfaces by, respectively, varying the pH or dissolving distinct metallocene redox buffers into solution. Here, we find that at comparable mechanistic regimes, the rates of both ethylene and trans-2-butene hydrogenation are maximized near the same electrochemical potential, E. Moreover, the potential-dependence, defined as $\frac{∂ln 𝑟}{∂𝐸}$, of trans-2-butene hydrogenation is approximately 2.2× greater than that of ethylene hydrogenation across the full potential range studied. These observations are all consistent with a model in which polarization of the Pt surface away from the local potential of zero free charge (E PZFC ) induces electrostatic organization of the polar solvent and charged ions near the interface, which impedes olefin adsorption and surface reaction because these surface reactions induce electrolyte displacement. Accordingly, interfacial polarization alters the free energy landscape and thus the rate of nonpolar heterogeneous catalysis by controlling the degree of electrostatic organization of polar and charged spectators at the interface, which do not in general need to be specifically chemisorbed onto the surface but could simply be close enough to the surface to be perturbed by the olefin adsorption. These results point toward electrochemical design handles, namely, the electrolyte, catalyst potential, and local E PZFC of the catalyst, with which to tune interfacial catalysis of thermochemical organic transformations.

adsorption↗
DOE OSTI2025

In-situ/operando study of Cu-based nanocatalysts for CO 2 electroreduction using electrochemical liquid cell TEM

The structure of a nanocatalyst during electrocatalytic reactions often deviates from its pristine structure due to intrinsic properties, or physical and chemical adsorption at the catalytic surfaces. Taking Cu-based catalysts for CO 2 electroreduction reactions (CO 2 RR) as an example, they often experience segregation, leaching, and alloying during reactions. With the recent breakthrough development of high-resolution polymer electrochemical liquid cells, in-situ electrochemical liquid cell transmission electron microscopy (EC-TEM) alongside other advanced microscopy techniques, has become a powerful platform for revealing electrocatalysts restructuring at the atomic level. Considering the complex reactions involving electrified solid-liquid interfaces and catalyst structural evolution with intermediates, systematic studies with multimodal approaches are crucial. In this article, we demonstrate a research protocol for the study of electrocatalysts structural evolution during reactions using the in-situ EC-TEM platform. Using Cu and CuAg nanowire catalysts for CO 2 RR as model systems, we describe the experimental procedures and findings. We highlight the platform’s crucial role in elucidating atomic-scale pathways of nanocatalyst restructuring and identifying catalytic active sites, as well as avoiding potential artifacts to ensure unbiased conclusions. Using the multimodal characterization toolbox, we provide the opportunity to correlate the structure of a working catalyst with its performance. Finally, we discuss advancements as well as the remaining gap in elucidating the structural-performance relationship of working catalysts. We expect this article will assist in establishing guidelines for future investigations of complex electrochemical reactions, such as CO 2 RR and other catalytic processes, using the in-situ EC-TEM platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elucidating a dissolution–deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO 2 batteries

Aqueous Zn/MnO 2 batteries with their environmental sustainability and competitive cost, are becoming a promising, safe alternative for grid-scale electrochemical energy storage. Here, presented as a promising design principle to deliver a higher theoretical capacity, this work offers fundamental understanding of the dissolution–deposition mechanism of Zn/β-MnO 2 . A multimodal synchrotron characterization approach including three operando X-ray techniques (powder diffraction, absorption spectroscopy, and fluorescence microscopy) is coupled with elementally resolved synchrotron X-ray nano-tomography. Together they provide a direct correlation between structural evolution, reaction chemistry, and 3D morphological changes. Operando synchrotron X-ray diffraction and spectroscopy show a crystalline-to-amorphous phase transition. Quantitative modeling of the operando data by Rietveld refinement for X-ray diffraction and multivariate curve resolution (MCR) for X-ray absorption spectroscopy are used in a complementary fashion to track the structural and chemical transitions of both the long-range (crystalline phases) and short-range (including amorphous phases) ordering upon cycling. Scanning X-ray microscopy and full-field nano-tomography visualizes the morphology of electrodes at different electrochemical states with elemental sensitivity to spatially resolve the formation of the Zn- and Mn-containing phases. Overall, this work critically indicates that for Zn/MnO 2 aqueous batteries, the reaction pathways involving Zn–Mn complex formation upon cycling become independent of the polymorphs of the initial electrode and sheds light on the interplay among structural, chemical, and morphological evolution for electrochemically driven phase transitions.

36 MATERIALS SCIENCE↗