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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.

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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

A temperature-induced hysteretic behavior of resistivity and magnetoresistance of electrodeposited bismuth microbridges for X-ray transition-edge sensor absorbers

This study investigates the temperature-induced hysteretic behavior of resistivity and magnetoresistance in electrodeposited bismuth films, with a focus on their application as absorbers in transition-edge sensors (TESs) for X-ray detection. Through a series of resistivity versus temperature measurements from room temperature to a few Kelvin, we explore the change in the conductive behavior of bismuth electrodeposited on various substrates. Our findings show for the first time both hysteretic and irreversible changes in resistivity as a function of temperature. Further, magnetoresistance measurements reveal notable variations in resistance behavior under different magnetic fields, highlighting the impact of magnetic fields on these films’ electronic transport properties, with an indication of potential weak anti-localization effects at the lowest temperatures. This study not only provides a deeper understanding of bismuth’s conductivity characteristics at low temperatures but also sheds light on the practical implications for developing more effective TESs for synchrotron X-ray facilities.

42 ENGINEERING↗
DOE OSTI2016

Laser annealing of electrodeposited CuInSe 2 semiconductor precursors: experiment and modeling

Laser annealing can reduce the annealing time required to form Cu(In,Ga)(S,Se) 2 (CIGSe) thin films for use in thin film photovoltaics to a single second timescale, if not faster. In this work, we use microstructural characterization coupled with modeling of the optical and thermal properties to understand the laser annealing of three types of electrodeposited precursor stacks for the CIGSe parent compound CuInSe 2 . The precursor films are: stacked elemental layers Cu/In/Se, stacked binary selenides In 2 Se 3 /Cu 2– x Se, and a single layer of coelectrodeposited Cu–In–Se. Conceptually, these stacks are ordered in terms of decreasing stored chemical and interfacial potential free energy, consideration of which predicts that the formation of large grained CuInSe 2 from the stacked elemental layers would be the most exothermic and thus most rapid process. However we find that microstructural details of the electrodeposited films such as void fraction present in the stacked binary selenides dramatically alter the heat and mass flow. Additionally, modeling of the optical absorption within the elemental stacked precursor suggests extremely localized heating at the In/Se interface resulting in significant Se loss. Despite its lower chemical potential energy, the coelectrodeposited CuInSe 2 precursor's more uniform optical absorption of near-bandgap light coupled with its compact, low void fraction microstructure of nano-sized grains results in the most optimal recrystallization and compositional homogenization via interdiffusion. Furthermore this annealed layer formed a working device with a short circuit current density of 23 mA cm –2 . As a result, this combined modeling and experimental investigation underscores the need to consider practical micro- and nanostructure-dependent properties as well as the optical absorption and not simply thermodynamics when designing accelerated two step deposition and annealing processes for compound semiconductors.

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

Regulating the growth of aluminum electrodeposits: towards anode-free Al batteries

The high earth abundance and large specific capacity of aluminum on either a volume (8040 mA h cm -3 ) or mass (2980 mA h g -1 ) basis continues to drive interest in electrochemical cells that utilize metallic Al as the anode. At practical anode capacities, uneven and non-planar deposition of Al during battery recharge combined with the high Young's modulus (EAl = 70 Ga) of the metal limits the electrode lifetime in all known electrolytes. Here we study the effect of a thin, textured coating composed of two-dimensional gold nanosheets with strong diffraction from (111) facets and low lattice mismatch for Al, as a substrate for regulating the Al electrodeposit morphology. We report that these coatings are not only effective in preventing Al deposition in non-planar morphologies, but have a large beneficial effect on the reversibility of Al electrodes. In Al plating/stripping studies, the textured Au coatings sustain stable cell operations for 500 cycles or more with a high coulombic efficiency of over 99%. Full cell Al batteries composed of the Au nanosheets as the anode substrate and graphene as the cathode are reported to exhibit capacity retention of 80% after 1000 charge–discharge cycles, and 74% at the 2000th cycle, exceeding the lifetimes (~200 cycles) of comparable Al batteries in which a standard stainless steel material is used as the anode substrate. Our results demonstrate that through rational design of the substrate for Al deposition, both the electrodeposit morphology and cycle life of Al-based batteries can be markedly improved.

25 ENERGY STORAGE↗
DOE OSTI2018

Relaxation of asymmetric crystallographic tilt: In situ x-ray diffraction studies of epitaxial electrodeposition of bismuth on GaAs (110)

High quality, epitaxial thin-films are key components of almost all modern electronic devices. During deposition, lattice mismatch between the substrate and the film generates elastic strain. The strain energy grows with film thickness until a defect is generated that relieves the strain. The strain relaxation mechanism is critical in epitaxial electrodeposition. Here, we study how a metal (bismuth) film growing via electrodeposition on a semiconductor substrate [GaAs(110)] relaxes the lattice mismatch-induced strain. Using in situ synchrotron-based X-ray techniques, we monitor the crystallographic orientation and grain size of the growing film during electrochemical deposition. We (1) confirm that a single crystallographic orientation of the film, with ($01\bar{1}8$) as the oriented plane, can be selected by controlling the overpotential, η, and (2) find that, after a threshold thickness is reached, the tilt angle varies monotonically with film thickness. Our data are consistent with the film relaxing the strain by forming low-energy, asymmetric tilt boundaries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The early-stage growth and reversibility of Li electrodeposition in Br-rich electrolytes

Significance Spatial variations in chemical composition and transport properties of the material phases (interphases) formed on reactive metals in liquid electrolytes are thought to be responsible for the propensity of metal battery electrodes to electrodeposit in irregular, nonplanar morphologies. Equilibrium theoretical calculations using joint density functional analysis in vacuum and generic liquid media indicate that in-plane transport at such interphases is enhanced substantially if LiX (X = Br > Cl > F) species predominate. This study employs optical visualization experiments and nucleation theory to experimentally investigate nucleation and early-stage growth dynamics of metallic lithium in electrolytes enriched with LiBr. It is shown that the Li-Br–rich interphases formed profoundly alter the morphology of Li electrodeposits by enhancing Li-ion surface diffusion.

25 ENERGY STORAGE↗
DOE OSTI2017

Role of anisotropy in determining stability of electrodeposition at solid-solid interfaces

Here, we investigate the stability of electrodeposition at solid-solid interfaces for materials exhibiting an anisotropic mechanical response. The stability of electrodeposition or resistance to the formation of dendrites is studied within a linear stability analysis. The deformation and stress equations are solved using the Stroh formalism and faithfully recover the boundary conditions at the interface. The stability parameter is used to quantify the stability of different solid-solid interfaces incorporating the full anisotropy of the elastic tensor of the two materials. Our results show a high degree of variability in the stability parameter depending on the crystallographic orientation of the solids in contact, and point to opportunities for exploiting this effect in developing Li metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2016

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2 O 3 using XPS.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions

Ion transport–driven instabilities in electrodeposition of metals that lead to morphological instabilities and dendrites are receiving renewed attention because mitigation strategies are needed for improving rechargeability and safety of lithium batteries. The growth rate of these morphological instabilities can be slowed by immobilizing a fraction of anions within the electrolyte to reduce the electric field at the metal electrode. We analyze the role of elastic deformation of the solid electrolyte with immobilized anions and present theory combining the roles of separator elasticity and modified transport to evaluate the factors affecting the stability of planar deposition over a wide range of current densities. Lastly, we find that stable electrodeposition can be easily achieved even at relatively high current densities in electrolytes/separators with moderate polymer-like mechanical moduli, provided a small fraction of anions are immobilized in the separator.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spontaneous and field-induced crystallographic reorientation of metal electrodeposits at battery anodes

The propensity of metal anodes of contemporary interest (e.g., Li, Al, Na, and Zn) to form non-planar, dendritic morphologies during battery charging is a fundamental barrier to achievement of full reversibility. We experimentally investigate the origins of dendritic electrodeposition of Zn, Cu, and Li in a three-electrode electrochemical cell bounded at one end by a rotating disc electrode. We find that the classical picture of ion depletion–induced growth of dendrites is valid in dilute electrolytes but is essentially irrelevant in the concentrated (≥1 M) electrolytes typically used in rechargeable batteries. Using Zn as an example, we find that ion depletion at the mass transport limit may be overcome by spontaneous reorientation of Zn crystallites from orientations parallel to the electrode surface to dominantly homeotropic orientations, which appear to facilitate contact with cations outside the depletion layer. This chemotaxis-like process causes obvious texturing and increases the porosity of metal electrodeposits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Flow Injection Electrochemical Quartz Crystal Microbalance with ICP-OES Detection: Recovery of Silver by Electrodeposition with Redox Replacement in a Flow Cell

We developed a new on-line hyphenated flow injection analysis technique (FI-EQCM-ICP-OES) that allows electrochemical deposition and stripping with mass detection and elemental analysis. This technique was used to study a new system for electrochemical recovery of silver from a 0.5 mM Ag + /5 mM Cu 2+ /0.5 M H 2 SO 4 solution by pulsed electrodeposition with redox replacement (EDRR) in a small flow cell. The metal ions in a 500 μ l sample are injected into the sulfuric acid carrier stream and deposited onto an electrochemical quartz crystal microbalance (EQCM) electrode housed in a 50 μ l flow cell. The deposits are subsequently stripped off electrochemically in the same cell and analyzed downstream in an ICP-OES. The stripped metal layer was found to be composed of Ag with no detectable Cu for a redox replacement time of 10 s, and 91 wt.% Ag–9 wt.% Cu for a redox replacement time of 5 s. Microscopy measurements demonstrated that the electrode was covered with silver particles, some of which contain Cu in the case of the 5 s replacement time. This technique allowed the study of mass changes on the electrode during electrodeposition and open circuit times in each EDRR cycle in flowing solutions.

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

Facile Electrodeposition and Aging to Generate 3-Dimensional α-MnO 2 Battery Cathodes

Conventional tape casting forms 2-dimensional (2D) electrodes containing active material, conductive additive, and binder with restricted ion access as electrodes increase in thickness. To improve the transport properties, 3D architectures were developed using electrodeposition to ensure contact between the active material with the substrate, and provide enhanced electrolyte access. This paper investigates electrodeposition of cryptomelane ( α -MnO 2 ) as a model cathode material to efficiently accommodate (de)lithation and increase areal capacity vs conventional 2D coatings. Electodeposited samples on titantium (Ti) foil substrates were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) and show a linear increase of the average oxidation of Mn (3.5–3.8) and active mass loading (1.27–9.9 mg) with deposition and aging times (0–120 min). The initial deposition is amorphous and forms the crystalline material during the elevated temperature aging step. The active material, α -MnO 2 , was also deposited on C-cloth and these cathodes at deposition times of 3, 6, and 9 min deliver 9, 36, and 69% higher areal capacities, respectively, at 0.2 mA cm −2 compared to conventional 2D electrodes with a mass loading equal to the 3 min sample. These results demonstrate the benefit of α -MnO 2 within a porous architecture providing enhanced transport properties.

Electrochemistry↗
DOE OSTI2023

Predictive Modeling of Electrodeposition in a Single Pore Flow-Through Electrode: From Electronucleation to Coating Thickness Uniformity

The emergence of advanced manufacturing methods capable of producing porous three-dimensional structures has expanded the design space for next-generation functional components. The ability to fabricate ordered 3D foams for use in electrocatalysis reactors has increased the need for controlled deposition of catalytic metals onto porous support materials, such as carbon. However, there is a lack of clear design guidelines for electrodeposition onto 3D substrates, due to the geometric complexity and multi-scale nature of the problem. Furthermore, electro-nucleation phenomena are often overlooked in macro-scale models of current distribution during deposition. Here, a graphite flow-through electrode (FTE) is used as a model system for copper deposition within a single pore. Potential distributions and electro-nucleation phenomena are coupled in a continuum level model by incorporating nucleation size and density as a function of overpotential, determined experimentally using in situ atomic force microscopy (AFM). The model predictions are validated by measuring the coating uniformity in the pore using micro-computed X-ray tomography (μCT). A scaling analysis comprising dimensionless parameters such as the Wagner number is presented. The simplified scaling relationship framework can guide the electrodeposition process and electrode design to optimize plating of porous substrates under fluid flow conditions.

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

High-Resolution Nanoprinting Approach through Self-Driven Electrodeposition

A novel high-resolution nanoprinting method through self-driven electrodeposition is proposed and certain aspects are confirmed with known copper electrochemistry through multiphysics modeling. A series of simulations are conducted involving a nanopipette filled with concentrated CuSO 4 solution introduced close to the working electrode (WE) in the cell of diluted CuSO 4 electrolyte, where Cu 2+ ions diffuse from nanopipette to the electrode and form a limited region with more concentrated cations compared to the rest of the cell. Meanwhile, this process leads to a more positive equilibrium potential of copper redox reaction and thereby local negative surface overpotential on WE. The negative surface overpotential drives the Cu 2+ electrodeposition in the form of a nano-protrusion on the target location.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

High Resolution Aerosol Jet Printed Components with Electrodeposition-Enhanced Conductance

Aerosol Jet Printing (AJP) is one technique of additive manufacturing used in the printing of electronics components. AJP enables the patterning of features at the ~10 μm–100 μm scale based on hardware and print parameters. Additionally, optimization of print conditions enables the printing of high-resolution features with linewidths approaching 10 μm. The aerosol jet printing of electronic parts can be limited by the conductivities which are achievable by Ag nanoparticle inks (typically 15%–25% of bulk Ag). For certain electronics applications, the increased conductivity produces unacceptable loses during operation and methods are needed to increase the conductance of the devices without sacrificing resolution. Here, we report on the AJP of inductor spirals conductor traces of linewidth 50 μm separated by 55 μm gaps. The conductivity of these features is enhanced by electrodeposition of Cu onto the Ag, resulting in a decrease in resistance of 35–45x. Impedance measurements demonstrate that the addition of Cu by electrodeposition to a 27-turn spiral inductor resulted in an inductance of 3.6 μH. Finally, we demonstrate the use of a lift-off process to produce free-standing, flexible, conductive films using AJP.

36 MATERIALS SCIENCE↗
DOE OSTI2019

On our Limited Understanding of Electrodeposition

The energy density of electrodeposition reactions makes them attractive for energy storage. Although its scientific inquiries nearly date back to the inception of electrochemistry, its behavior at microscopic dimensions (relevant to battery application) is mysteriously uncontrollable. We examine experimental reports of singular spatiotemporal evolutions with a hope to identify universality in deposition patterns. We conclude that a macroscopic mass transport instability cannot account for various growth morphologies and alludes to poorly understood materials interplay at smaller scales. We summarize representative characteristics of electrodeposition to encourage mechanistic investigations.

25 ENERGY STORAGE↗
DOE OSTI2017

Morphological stability during electrodeposition

The uniform electrodeposition of certain materials, such as Li metal, remains elusive because the mechanisms controlling growth instability are not fully understood. To determine the conditions that lead to either stable or unstable deposition, we develop a phase-field model for the growth of multiple deposits in a binary electrolyte and examine the behavior as the kinetic parameters are varied. We find that the second Damköhler number, defined as the ratio between the reaction and the mass transfer fluxes, is an indicator of deposition instability. Our results suggest that controlling reaction kinetics and initial roughness are essential in achieving stable electrodeposition.

Enrique, Raúl A.↗
DOE OSTI2019

Electrodeposition of Nanostructured Copper on Gas Diffusion Layers as Electrocatalysts for Carbon Dioxide Reduction

The aim of the summer project was to immobilize copper nanostructures on gas diffusion layers to serve as electrocatalysts for the electrochemical reduction of CO 2 . Gas diffusion layers are typically bilayer structures consisting of a macro-porous backing material (carbon fiber paper) and a microporous, carbon-based layer (MPL). Classically, the copper catalysts are loaded on the microporous layer. Furthermore, the GDL is intrinsically hydrophobic due to polytetrafluoroethylene (PTFE)in its chemical composition, with the MPL having a more hydrophobic character due to its higher PTFE content. While beneficial for rendering the MPL impervious to electrolytes during actual CO 2 reduction, the hydrophobicity precludes sufficient wetting of the MPL layer, preventing conformal, uniformly distributed and strongly adhered deposits. A two electrode electrodeposition system was used to facilitate copper deposition. An implication of this system is the inability to ascertain or accurately modulate the cathodic over-potential. Hence, galvanostatic (current control) procedures are utilized for all deposition. To improve the wetting behavior of the MPL, the surface is subjected to surface pretreatment protocols prior to electrodeposition. In addition, as morphology of deposits play a role in their efficacy as catalysts in terms of selectivity and conversion, we systematically investigate the effects of different galvanostatic deposition procedures on copper morphology.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Engineered Reliability via Intrinsic Thermomechanical Stability of an Electrodeposited Au-Pt Nanocrystalline Alloy

This research objective of this EELDRD study was to learn to electrodeposit Pt Au alloys with independently controlled composition and grain size. What was accomplished was the capability to electrodeposit PtAu alloys with controlled composition and a nanocrysolline grain size. Nanocrystalline metals as a class and, specifically, the Pt 0.9 Au 0.1 alloy developed in 2015-17 via sputtering at Sandia National Labs have clear advantages in strength, wear resistance, and fatigue tolerance over commercially-available structural alloys. With this capability befitting coating of complex components and implementable at existing vendors, we can upgrade the electrical contact component reliability of selected Labs systems.

36 MATERIALS SCIENCE↗