Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Electrochemical interfaces”

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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

In situ electrochemical scanning/transmission electron microscopy of electrode–electrolyte interfaces

Insights into the dynamics of electrochemical processes are critically needed to improve our fundamental understanding of electron, charge, and mass transfer mechanisms and reaction kinetics that influence a broad range of applications, from the functionality of electrical energy-storage and conversion devices (e.g., batteries, fuel cells, and supercapacitors), to materials degradation issues (e.g., corrosion and oxidation), and materials synthesis (e.g., electrodeposition). To unravel these processes, in situ electrochemical scanning/transmission electron microscopy (ec-S/TEM) was developed to permit detailed site-specific characterization of evolving electrochemical processes that occur at electrode–electrolyte interfaces in their native electrolyte environment, in real time and at high-spatial resolution. This approach utilizes “closed-form” microfabricated electrochemical cells that couple the capability for quantitative electrochemical measurements with high spatial and temporal resolution imaging, spectroscopy, and diffraction. Here, we review the state-of-the-art instrumentation for in situ ec-S/TEM and how this approach has resulted in new observations of electrochemical processes.

25 ENERGY STORAGE↗
DOE OSTI2026

Pattern-enhanced Resonant Soft X-ray Scattering for Operando monitoring of electrochemical solid-liquid interfaces

Unveiling interfaces at sub-nanometer scales is essential for advancing the understanding of complex chemical transformations. However, characterizing solid-liquid interfaces with high dimensional sensitivity and temporal resolution remains challenging, due to their dynamic nature and inaccessibility by conventional probes. Here we present an approach, Pattern-enhanced Resonant Soft X-ray Scattering, to overcome the challenges. Rooted in a “sample-as-optics” philosophy, this technique utilizes precisely engineered line-grating nanopatterns to modulate near-field X-ray illumination, coherently enhancing scattering signals from the line-gratings. We implement the method using Ni line-grating nanopatterns in electrochemical water oxidation. The periodic nanostructures serve as diffractive optical elements to reveal the Ni oxidation gradients and structural dynamics at the electrode-electrolyte interfaces. Finite-element simulations corroborate the observed trends by modeling variations in compositions and structures during electrocatalysis. Through integrating advanced sample design with coherent wave nature of soft X-rays, our approach opens accessible pathways to operando exploring chemical evolution and sub-nanometer dimensional variations simultaneously in electrochemical systems. This non-destructive method is efficient and element-specific, making it valuable for probing chemical and dimensional dynamics with appropriate modeling.

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

Electrochemical Imaging of Precisely‐Defined Redox and Reactive Interfaces

Abstract Understanding the diverse electrochemical reactions occurring at electrode‐electrolyte interfaces (EEIs) is a critical challenge to developing more efficient energy conversion and storage technologies. Establishing a predictive molecular‐level understanding of solid electrolyte interphases (SEIs) is challenging due to the presence of multiple intertwined chemical and electrochemical processes occurring at battery electrodes. Similarly, chemical conversions in reactive electrochemical systems are often influenced by the heterogeneous distribution of active sites, surface defects, and catalyst particle sizes. In this mini review, we highlight an emerging field of interfacial science that isolates the impact of specific chemical species by preparing precisely‐defined EEIs and visualizing the reactivity of their individual components using single‐entity characterization techniques. We highlight the broad applicability and versatility of these methods, along with current state‐of‐the‐art instrumentation and future opportunities for these approaches to address key scientific challenges related to batteries, chemical separations, and fuel cells. We establish that controlled preparation of well‐defined electrodes combined with single entity characterization will be crucial to filling key knowledge gaps and advancing the theories used to describe and predict chemical and physical processes occurring at EEIs and accelerating new materials discovery for energy applications.

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

Electrochemical Imaging of Precisely‐Defined Redox and Reactive Interfaces

Abstract Understanding the diverse electrochemical reactions occurring at electrode‐electrolyte interfaces (EEIs) is a critical challenge to developing more efficient energy conversion and storage technologies. Establishing a predictive molecular‐level understanding of solid electrolyte interphases (SEIs) is challenging due to the presence of multiple intertwined chemical and electrochemical processes occurring at battery electrodes. Similarly, chemical conversions in reactive electrochemical systems are often influenced by the heterogeneous distribution of active sites, surface defects, and catalyst particle sizes. In this mini review, we highlight an emerging field of interfacial science that isolates the impact of specific chemical species by preparing precisely‐defined EEIs and visualizing the reactivity of their individual components using single‐entity characterization techniques. We highlight the broad applicability and versatility of these methods, along with current state‐of‐the‐art instrumentation and future opportunities for these approaches to address key scientific challenges related to batteries, chemical separations, and fuel cells. We establish that controlled preparation of well‐defined electrodes combined with single entity characterization will be crucial to filling key knowledge gaps and advancing the theories used to describe and predict chemical and physical processes occurring at EEIs and accelerating new materials discovery for energy applications.

Edgecomb, Joseph↗
DOE OSTI2024

Scalable Enrichment of 48 Ca at the Solid/liquid Interface by Chemical and Electrochemical Methods

This award targets to develop methods to enrich 48 Ca, which is a critical isotope for synthesizing superheavy elements and testing the standard model through neutrinoless double beta decay. The team first tested chemical exchange-based separation between solids and liquids, which is based on the free energy change due to the different vibrational frequencies caused by Ca isotopes in a material. However, the separation factor (alpha), which is defined as the ratio of 40 Ca/ 48 Ca ratios in the two phases, only reach ~1.01. The team then developed liquid centrifugation-based isotope separation, where a Ca salt aqueous solution is centrifuged at a speed of ~60 kRPM, and 48 Ca is enriched at the bottom of a centrifuge tube due to its larger mass. A high α of ~1.2-1.4 is achieved for 40 Ca/ 48 Ca at 40 °C. This method is further approved to be generic for any isotope that can be dissolved in a liquid solution or form liquid chemicals near room temperature. The experimental results also align well with modeling prediction. The team further develop a model to evaluate isotope separation in countercurrent liquid centrifugation. The team found that the countercurrent configuration can also enhance isotope separation in liquids, similar with gas centrifugation, which boost separation for isotopes which are difficult to be gasified near room temperature.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2023

Lithium crystallization at solid interfaces

Understanding the electrochemical deposition of metal anodes is critical for high-energy rechargeable batteries, among which solid-state lithium metal batteries have attracted extensive interest. A long-standing open question is how electrochemically deposited lithium-ions at the interfaces with the solid-electrolytes crystalize into lithium metal. Here, using large-scale molecular dynamics simulations, we study and reveal the atomistic pathways and energy barriers of lithium crystallization at the solid interfaces. In contrast to the conventional understanding, lithium crystallization takes multi-step pathways mediated by interfacial lithium atoms with disordered and random-closed-packed configurations as intermediate steps, which give rise to the energy barrier of crystallization. This understanding of multi-step crystallization pathways extends the applicability of Ostwald’s step rule to interfacial atom states, and enables a rational strategy for lower-barrier crystallization by promoting favorable interfacial atom states as intermediate steps through interfacial engineering. Our findings open rationally guided avenues of interfacial engineering for facilitating the crystallization in metal electrodes for solid-state batteries and can be generally applicable for fast crystal growth.

25 ENERGY STORAGE↗
DOE OSTI2023

Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface

Rational construction of the electrode–solution interface where electrochemical processes occur is of paramount importance in electrochemistry. Efforts to gain better control and understanding of the interface have been hindered by lack of probing methods. Here, in this study, we show that the hydrogen evolution and oxidation reactions (HER/HOR) catalysed by platinum in base can be promoted by introduction of N-methylimidazoles at the platinum–water interface. In situ spectroscopic characterization together with simulations indicate that the N-methylimidazoles facilitate diffusion of hydroxides across the interface by holding the second layer of water close to platinum surfaces, thereby promoting the HER/HOR. We thus propose that the HER/HOR kinetics of platinum in acid and base is governed by diffusion of protons and hydroxides, respectively, through the hydrogen-bond network of interfacial water by the Grotthuss mechanism. Moreover, we demonstrate a 40% performance improvement of an anion exchange membrane electrolyser by adding 1,2-dimethylimidazole into the alkali fed into its platinum cathode.

36 MATERIALS SCIENCE↗
DOE OSTI2026

An immersed interface method for microstructure-scale electrochemical battery models: numerical formulation and performance portable implementation

We present the numerical formulation, verification, and performance portable implementation of an immersed interface method for microstructure scale electrochemical modeling of batteries. The innovation in this approach is the resolution of chemical species and electrostatic potential discontinuities at active interfaces without the use of interface conforming unstructured grids. A unified formulation on Cartesian grids for all domains (electrodes and electrolyte) is used with interfacial flux conditions applied using volume fraction or “color” function gradients. We have developed one dimensional and two dimensional test cases with analytic solutions for electrochemical modeling using which we verified the consistency and accuracy of our scheme. Our solver is also validated against solutions from a macroscale model and an unstructured multi-subdomain solver for a full lithium ion cell. We then demonstrated the utility of our solver on an image-based complex battery electrode microstructure at high charging rate. Our technique also exhibits good scalability on distributed memory architectures using central processing units (CPU), with problem sizes up to 1.8 billion degrees of freedom and with 5400 ranks. Initial performance studies of our open-source performance portable solver showed about 70 times speed up using a graphics processing unit (GPU) compared to single compute core for a problem with 4 million cells.

25 ENERGY STORAGE↗
DOE OSTI2022

A Hybrid Quantum–Classical Study of Ion Adsorption at the Copper Electrode

Here, we present a set of computational studies that surveys the molecular structure and thermodynamics of simple ions at the electrode–electrolyte interface. A hybrid quantum–classical approach is used to obtain free energy profiles and solvent structure as a function of the ion’s position relative to the electrochemical liquid/solid interface and system potential. Model systems consist of a copper electrode and single halide or alkali metal ion in contact with an implicit solvent and reveal new insights into the interplay of forces that drive or resist ion absorption at the electrode/ electrolyte interface. We also expand on subtleties of absorption site preference and describe the complex relationship between the energetic barrier to absorption and the ion–electrode binding energy as a function of electrode potential.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Oxygen-Plasma-Induced Hetero-Interface NiFe2O4/NiMoO4 Catalyst for Enhanced Electrochemical Oxygen Evolution

The electrolysis of water to produce hydrogen is an effective method for solving the rapid consumption of fossil fuel resources and the problem of global warming. The key to its success is to design an oxygen evolution reaction (OER) electrocatalyst with efficient conversion and reliable stability. Interface engineering is one of the most effective approaches for adjusting local electronic configurations. Adding other metal elements is also an effective way to enrich active sites and improve catalytic activity. Herein, high-valence iron in a heterogeneous interface of NiFe 2 O 4 /NiMoO 4 composite was obtained through oxygen plasma to achieve excellent electrocatalytic activity and stability. In particular, 270 mV of overpotential is required to reach a current density of 50 mA cm -2 , and the overpotential required to reach 500 mA cm -2 is only 309 mV. The electron transfer effect for high-valence iron was determined by X-ray photoelectron spectroscopy (XPS). The fast and irreversible reconstruction and the true active species in the catalytic process were identified by in situ Raman, ex situ XPS, and ex situ transmission electron microscopy (TEM) measurements. This work provides a feasible design guideline to modify electronic structures, promote a metal to an active oxidation state, and thus develop an electrocatalyst with enhanced OER performance.

36 MATERIALS SCIENCE↗
DOE OSTI2022

High-Energy Solid-State Lithium Batteries with Organic Cathode Materials (Final Report)

Organic materials made from abundant elements via low-energy processes are emerging as sustainable and low-cost alternatives to transition metal oxides as the electrode materials for high- energy batteries in the wake of supply chain and environmental issues associated with critical materials during the transition to clean energy. Organic insertion materials (OIMs) offer material- level energy comparable to transition metal oxides, but they have durability difficulties owing to dissolving in common liquid electrolytes. Combining ceramic-based solid electrolytes with organic electrode materials is one intriguing solution. The goal of this project is to design and synthesize high-energy OIMs, to understand the chemical dynamics and mechanical properties at the OIM-sulfide interface during electrochemical cycling, and to develop methods for constructing the optimum cathode microstructure, which will lead to improved electrochemical performance. The project team has accomplished the following over the last four years: (a) demonstrating that the mechanical softness of organic electrode materials is uniquely beneficial in suppressing crack formation at the electrode-electrolyte interface during cell operation; (b) understanding the interaction between cathode microstructure and the mechanical properties of individual components; and (c) establishing predictive control of cathode microstructure by tuning the mechanical properties of solid electrolytes and OIMs; (d) determining the chemical combability of sulfide electrolyte with high-energy OIMs and finally (f) laying out a road map toward a specific energy of 500 Wh kg -1 for solid-state lithium batteries. 14 publications resulted from this project.

25 ENERGY STORAGE↗
DOE OSTI2023

Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces

Proton transfer is critically important to many electrocatalytic reactions, and directed proton delivery could open new avenues for the design of electrocatalysts. However, although this approach has been successful in molecular electrocatalysis, proton transfer has not received the same attention in heterogeneous electrocatalyst design. Here, in this work, we report that a metal oxide proton relay can be built within heterogeneous electrocatalyst architectures and improves the kinetics of electrochemical hydrogen evolution and oxidation reactions. The volcano-type relationship between activity enhancement and pK a of amine additives confirms this improvement; we observe maximum rate enhancement when the pK a of a proton relay matches the pH of the electrolyte solution. Density-functional-theory-based reactivity studies reveal a decreased proton transfer energy barrier with a metal oxide proton relay. These findings demonstrate the possibility of controlling the proton delivery and enhancing the reaction kinetics by tuning the chemical properties and structures at heterogeneous interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Nano-engineered Multiwall Carbon Nanotube-copper Composite Thermal Interface Material for Efficient Heat Conduction

Efforts in integrated circuit (IC) packaging technologies have recently been focused on management of increasing heat density associated with high frequency and high density circuit designs. While current flip-chip package designs can accommodate relatively high amounts of heat density, new materials need to be developed to manage thermal effects of next-generation integrated circuits. Multiwall carbon nanotubes (MWNT) have been shown to significantly enhance thermal conduction in the axial direction and thus can be considered to be a candidate for future thermal interface materials by facilitating efficient thermal transport. This work focuses on fabrication and characterization of a robust MWNT-copper composite material as an element in IC package designs. We show that using vertically aligned MWNT arrays reduces interfacial thermal resistance by increasing conduction surface area, and furthermore, the embedded copper acts as a lateral heat spreader to efficiently disperse heat, a necessary function for packaging materials. In addition, we demonstrate reusability of the material, and the absence of residue on the contacting material, both novel features of the MWNT-copper composite that are not found in most state-of-the-art thermal interface materials. Electrochemical methods such as metal deposition and etch are discussed for the creation of the MWNT-Cu composite, detailing issues and observations with using such methods. We show that precise engineering of the composite surface affects the ability of this material to act as an efficient thermal interface material. A thermal contact resistance measurement has been designed to obtain a value of thermal contact resistance for a variety of different thermal contact materials.

Ngo, Quoc↗
DOE OSTI2025

Electrosynthesis of high purity ethylene using high-index facet Cu 2 O nanocrystals electrocatalyst

Electrochemical CO 2 reduction reaction (eCO2RR) to multi-carbon (C 2+ ) products with copper-based catalysts is often limited by poor selectivity. This challenge arises from the concurrent formation of various intermediates, dictated by the atomic arrangement and electronic properties of surface atoms. In this study, we found that copper (I) oxide (Cu 2 O) nanocrystals with 50 facets (50F-NC), predominantly featuring (211) facets that offers high density of under-coordinated sites, demonstrate superior ethylene (C 2 H 4 ) selectivity of 92% ± 2 with an overall current density of 212 mA/cm 2 at -650 mV vs RHE. Furthermore, after one month of storage in a 1 M KOH electrolyte, this catalyst demonstrated a C 2 H 4 Faradaic efficiency of 87% highlighting its stabile structure under strong alkaline environments. Here, operando electrochemical Raman spectroscopy revealed enhanced CO* intermediate coverage on the 50F-NC catalyst, correlating with improved C-C coupling. SEM, TEM, and XPS analyses, along with DFT calculations, suggested that Cu sites on the (211) facet of 50F-NC and those at the Cu/Cu 2 O interface formed in-situ due to the surface reconstruction during the reaction, are likely active sites for effective C-C coupling and sustained high-rate C 2 H 4 production.

Cu nano particle↗
DOE OSTI2020

Combined Cr and S poisoning behaviors of La 1-x Sr x MnO 3±δ and La 1-x Sr x Co 1-y FeyO 3-δ cathodes in solid oxide fuel cells

Although the individual effects of airborne Cr and S contaminants on SOFC cathode performance degradation have been extensively studied, the combined effects of Cr and S contaminants remain largely unexplored. Under the real SOFC operating condition where the Cr and S species coexist, their effects may compete, affecting the poisoning behavior. Here, our investigation reveals that the combined Cr and S poisoning behavior of LSCF remains different from those of individual Cr and S poisonings, while the combined poisoning mechanism of LSM is equivalent to the sum of those of individual Cr and S effects. For LSCF electrode, gaseous Cr species are deposited mainly at the LSCF/GDC interface by electrochemical reduction, rather than forming SrCrO 4 on LSCF surfaces (as in the case of Cr-only poisoning), indicating no reaction between Cr vapors and SrO on the LSCF surface. Thermodynamic analysis demonstrates that the SrO on LSCF surface absorbs SO 2 (g) and thereby loses the Cr-gettering effect, allowing Cr vapors to flow through LSCF and to reach the LSCF/GDC interface where the Cr deposition occurs. Unlike LSCF, LSM electrode shows cumulative effects of Cr and S, as Cr accumulation occurs at the triple-phase boundary and S absorption takes place at localized Sr-rich regions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Interfacial properties in energy storage systems studied by soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering

Interfacial behaviors and properties play critical roles in determining key practical parameters of electrochemical energy storage systems, such as lithium-ion and sodium-ion batteries. Soft x-ray spectroscopy features shallow penetration depth and demonstrates inherent surface sensitivity to characterize the interfacial behavior with elemental and chemical sensitivities. Here, we present a brief survey of modern synchrotron-based soft x-ray spectroscopy of the interface in electrochemical energy storage systems. The technical focus includes core-level spectroscopy of conventional x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS). We show that while conventional techniques remain powerful for probing the chemical species on the surface, today’s material research studies have triggered much more demanding chemical sensitivity that could only be offered by advanced techniques such as RIXS. Another direction in the field is the rapid development of various in situ/operando characterizations of complex electrochemical systems. Notably, the solid-state battery systems provide unique advantages for future studies of both the surface/interface and the bulk properties under operando conditions. We conclude with perspectives on the bright future of studying electrochemical systems through these advanced soft x-ray spectroscopic techniques.

25 ENERGY STORAGE↗
DOE OSTI2022

Thermodynamic, Kinetic and Electrochemical Studies on Mixed Proton, Oxygen Ion and Electron (Hole) Conductors

The report contains a summary of work done during the period of performance September 1, 2015 through August 31, 2021. The principal objective of the work was to conduct thermodynamic, kinetic and electrochemical studies on mixed proton, oxygen ion and electron (hole) conductors. The project also involved studies on cation conductors such as Li + and Na + ion conductors of particular relevance to batteries. The work involved theory and experiments. Since any use of ionic conductors necessarily entails two electrodes, electrode reactions are central to the overall transport processes from one electrode, through the electrolyte, to the other electrode. The role of interfaces and electrochemical reactions is thus of central importance. Transport processes in fuel cells, electrolyzers, lithium batteries and sodium batteries were examined using linear non-equilibrium thermodynamics, which is based on the assumption of small departures from thermodynamic equilibrium. The main approach involved expressing transport processes using the Onsager equations which naturally include coupling of thermodynamic flows and thermodynamic forces. The basic tenet of linear nonequilibrium thermodynamics is the existence of local thermodynamic equilibrium which means that all thermodynamic functions are locally defined. Thus, chemical potentials of various species are defined locally as a function of position and also of time. The existence of local thermodynamic equilibrium has fundamental implications concerning transport of electronic species through a predominantly ionic conductor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗