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At least 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Electrochemical Behavior of Cerium at an Indium Tin-Doped Oxide Electrode in Acidic Media

The redox behavior and speciation of cerium at mesoporous thin films composed of nanoparticles of indium tin-doped oxide (nITO) electrodes were characterized in pH 4.8, 0.1 M acetate buffer and both 0.1 and 1 M HNO 3 using electrochemical techniques and X-ray photoelectron spectroscopy. Anodic deposition of ceria species from Ce(III) to the nITO electrode was achieved under all solvent conditions via spontaneous condensation of electrochemically generated ceric hydroxide species. In 1 M nitric acid, the rate of CeO 2 dissolution is on the same order as CeO 2 deposition, resulting in negligible amounts of CeO 2 electrodeposited at the nITO surface. The cathodic stripping of CeO 2 from the nITO substrate deposited in 0.1 M nitric acid or pH 4.8 acetate buffer follows a 2-step process where Ce(IV)-oxide is initially reduced to an unstable Ce(III)-oxide species that rapidly undergoes acid catalyzed dissolution to yield soluble Ce(III) (aq) . These findings provide a foundation for the pH and anodic potential controlled deposition of CeO 2 thin films to ITO substrates, which can aid in the development of materials composed of ceria. As a result, they can also be used to infer likely analogous actinide redox behavior and speciation at these electrodes.

Cerium↗
DOE OSTI2020

Si Microwire-Array Photocathodes Decorated with Cu Allow CO 2 Reduction with Minimal Parasitic Absorption of Sunlight

High loadings of Cu were integrated on the light-facing side of Si microwire arrays used under simulated sunlight for the photoelectrochemical reduction of CO 2 (aq) to hydrocarbons in 0.10 M KHCO 3 (aq). Radial-junction n + p-Si microwire arrays decorated with Cu exhibited absolute photocurrent densities comparable to an uncovered Si surface. Moreover, with respect to a Cu foil electrode, the positive shift in the onset potential for hydrocarbon formation at n + p-Si/Cu microwire arrays was equal to or greater than the photovoltage of the semiconductor alone. Selective electrodeposition of Cu on the tips and sidewalls of Si microwires was responsible for the minimal parasitic reflection and absorption exhibited by the catalyst, such that light-limited, absolute current densities >25 mA·cm –2 were sustained for 48 h under simulated sunlight. Photoelectrodes prepared from semiconductors with low diode quality factors and electrocatalysts with large Tafel slopes are shown to benefit from increased microstructured surface area. Si microwire arrays are thus suitable for photoelectrochemical reactions requiring high loadings of metallic and reflective electrocatalysts.

25 ENERGY STORAGE↗
DOE OSTI2022

High-Performance InZn Alloy Anodes toward Practical Aqueous Zinc Batteries

Aqueous Zn batteries have high safety, low-cost and potential of delivering comparable energy density to alkali-ion batteries. However, its practical application is largely hampered by the limited cycle life associated with Zn anodes under conditions of high depth of discharge and high plating current densities. In this work, we report on electrodeposited indium-zinc alloy anodes that have well-dispersed zinc-domains surrounding indium domains that form a porous structure after dealloying which greatly improves tolerance to Zn dendrite formation. The InZn anodes exhibit low polarization of ~5 to 25 mV and demonstrate 700 cycles at a current density of ~10 mA cm -2 with a capacity of 5 mAh cm-2 capacity (45% depth-of-discharge). Full cells with an InZn anode, dibenzo[b,i]thianthrene-5,7,12,14-tetraone (DTT) cathode, in 2M ZnSO 4 deliver a capacity of ~ 110 mAh g -1 and good stability over 40 cycles. Finally, the work reveals a rational design of Zn-based anodes towards practical battery applications and opens the curtain for future development of aqueous Zn batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Surface Composition Impacts Selectivity of ZnTe Photocathodes in Photoelectrochemical CO 2 Reduction Reaction

Light-driven reduction of CO 2 into chemicals using a photoelectrochemical (PEC) approach is considered as a promising way to meet the carbon neutral target. The very top surface of the photoelectrode and semiconductor/electrolyte interface plays a pivotal role in defining the performance for PEC CO 2 reduction. However, such impact remains poorly understood. Here, we report an electrodeposition-annealing route for tailoring surface composition of ZnTe photocathodes. Our work demonstrates that a Zn-rich surface on the ZnTe photocathode is essential to impact the CO 2 reduction activity and selectivity. In particular, the Zn-rich surface not only facilitated the interfacial charge carrier transfer, but also acted as electrocatalyst for boosting carbon product selectivity and suppressing the hydrogen evolution reaction. This work provides a new avenue to optimize the photocathode, as well as improvement of the CO 2 RR performance.

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

Hydrogen Evolution with Minimal Parasitic Light Absorption by Dense Co–P Catalyst Films on Structured p-Si Photocathodes

Planar and three-dimensionally structured p-Si devices, consisting of an electrodeposited Co–P catalyst on arrays of Si microwires or Si micropyramids, were used as photocathodes for solar-driven hydrogen evolution in 0.50 M H 2 SO 4 (aq) to assess the effects of electrode structuring on parasitic absorption by the catalyst. Without the use of an emitter layer, p-Si/Co–P microwire arrays produced a photocurrent density of -10 mA cm –2 at potentials that were 130 mV more positive than those of optimized planar p-Si/Co–P devices. Champion p-Si/Co–P microwire array devices exhibited ideal regenerative cell solar-to-hydrogen efficiencies of >2.5% and were primarily limited by the photovoltage of the p-Si/Co–P junction. Therefore, the vertical sidewalls of the Si microwire photoelectrodes minimized effects due to parasitic absorption at high loadings of catalyst for device structures with or without emitters.

14 SOLAR ENERGY↗
DOE OSTI2022

Evaluating the Physisorption and Chemisorption of Iodine on Bismuth-Functionalized Carbon Foams

Bismuth-containing carbon materials have been shown to be highly promising sorbents for the capture of radioiodine. However, there is still a need to understand the effects of carbon and bismuth on the iodine sorption mechanism. In this study, we show the relationship between the physical and chemical sorption of iodine under different bismuth loading conditions. Here, highly porous and non-friable conductive carbon foams were prepared and bismuth was electrodeposited to provide strong iodine binding sites. For pure carbon foams, equal ratios of physisorbed and chemisorbed iodine-carbon phases were detected before desorption. As the concentration of bismuth increased, the chemisorption between bismuth and iodine dominated the total capture mechanism and physisorption was almost completely eliminated. Additionally, chemisorption of iodine depended upon the size and specific surface area of the bismuth particles present within the framework of the foam.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Durian-Inspired Design of Bismuth–Antimony Alloy Arrays for Robust Sodium Storage

Sodium-ion batteries have attracted widespread attention for cost-effective and large-scale electric energy storage. However, their practical deployment has been largely retarded by the lack of choice of efficient anode materials featuring large capacity and electrochemical stability and robustness. Herein, we report a durian-inspired design and template-free fabrication of a robust sodium anode based on triangular pyramid arrays of Bi 0.75 Sb 0.25 alloy electrodeposited on Cu substrates. The Bi 0.75 Sb 0.25 arrays exhibit an appreciable electrochemical robustness for sodium storage, sustaining a reversible capability 335 mAh g –1 at a high rate of 2.5 A g –1 and 87% of the initial capacity over 2000 cycles. We further demonstrate the applicability of the Bi 0.75 Sb 0.25 array anode in sodium full cells by pairing it with a Na 3 V 2 (PO 4 ) 3 /C cathode. This full cell achieves a high specific energy of 203 Wh kg –1 (based on both active electrodes). Such an enhanced performance is attributed to the thorny-durian-like architecture and bimetallic alloy composition. In conclusion, the pyramid tip induces ion enrichment for rapid charge-transfer reaction, while the alloy design reduces the electrode volume swelling for stable Na cycling.

25 ENERGY STORAGE↗
DOE OSTI2017

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61 Co 0.12 Mn 0.27 O 2 , over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtually atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.

25 ENERGY STORAGE↗
DOE OSTI2025

Geobacter sulfurreducens Immobilized Boron-Doped Diamond Electrodes for Uranium(VI) in Water Electrochemical Bioremediation

The proliferation of nuclear science and technology has resulted in an increase in nuclear waste containing uranium, posing significant risks to both human and environmental health. This study proposes the use of Geobacter sulfurreducens (G. sulfurreducens) modified boron-doped diamond electrodes to facilitate the reduction and removal of uranium(VI) from aqueous media. The bioremediation process involves electrochemically immobilizing the bacteria on a boron-doped diamond electrode (BDD). The immobilization process requires applying reduction potentials ranging from −0.40 to −0.70 V (vs Ag/AgCl (3 M NaCl)), with −0.60 V identified as the optimal potential for effective bacterial modification. The uranium source is provided by a 2.0 mM uranyl acetate solution in G. sulfurreducens growth medium. Scanning electron microscopy (SEM) reveals a highly uniform layer of uranium on the electrode surface. Energy-dispersive X-ray fluorescence spectroscopy (EDS) and cyclic voltammetry (CV) studies confirm the presence of uranium in the system. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) successfully elucidate the reduction process of U(VI) to predominantly U(IV) using a bacteria-electrode coupled system. Additionally, a comparison is made with the electrochemical removal of uranyl ions using the electrodeposition method on unmodified BDD. Results demonstrate the presence of three uranium oxide species (UO 2 , UO 3 , and U 3 O 8 ) on the BDD electrode after experimentation, in contrast to the G. sulfurreducens/BDD assembly, which achieves the predominant reduction of UO 2 2+ to UO 2 with a small quantity of UO 3 as the final species. This study highlights the efficient electrochemical removal of uranyl ions from aqueous media at the G. sulfurreducens/BDD interface through chronoamperometry, presenting a promising approach for remediating sites contaminated with radioactive materials. The findings contribute to the exploration of sustainable alternatives for managing nuclear waste, emphasizing the potential of this electrochemical bioremediation strategy.

Bacteria↗
DOE OSTI2019

Electrochemical Deposition of Conformal Semiconductor Layers in Nanoporous Oxides for Sensitized Photoelectrodes

Nanoporous photoelectrodes with photoactive semiconductors have been investigated for various energy applications such as solar cells and photoelectrochemical cells, but the deposition of the semiconducting materials on the nanoporous electrodes has been very challenging due to pore clogging or complete pore filling. Here, we propose a band alignment model that explains the morphology of the electrochemically deposited semiconductor layer on the semiconducting nanoporous oxide electrode. Briefly, the coating material with a conduction band edge higher (i.e., more negative) than that of the electrode material forms a conformal coating, which maintains the initial nanoporous structure. As a result, a conformal CdSe layer can be electrodeposited onto TiO 2 nanotubes, which can be used as a photoelectrode of a sensitized solar cell. The electron dynamics studies revealed that the CdSe-sensitized TiO 2 nanotube electrode exhibited faster charge transport and slower charge recombination than its dye-sensitized counterpart, which has been ascribed to the passivation of surface traps and the physically blocked back-electron transfer by the CdSe layer as well as the higher conduction band of CdSe.

36 MATERIALS SCIENCE↗
DOE OSTI2019

A Hybrid Catalyst-Bonded Membrane Device for Electrochemical Carbon Monoxide Reduction at Different Relative Humidities

A hybrid catalyst-bonded membrane device using gaseous reactants for a carbon monoxide reduction (COR) reaction in the cathode chamber, an aqueous electrolyte for an oxygen evolution reaction (OER) in the anode chamber, and an anion exchange membrane (AEM) for product separation as modeled, constructed, and tested. The Cu electrocatalyst was electrodeposited onto gas diffusion layers (GDLs) and was directly bonded to AEM by mechanical pressing in the hybrid device. The impacts of relative humidity at the cathode inlet on the selectivity and activity of COR were investigated by computational modeling and experimental methods. At a relative humidity of 30%, the Cu-based catalyst in the hybrid device exhibited a total operating current density of 87 mA cm -2 with a -2.0 V vs Ag/AgCl reference electrode, a Faradaic efficiency (FE) for C 2 H 4 generation of 32.6%, and an FE for a liquid-based carbon product of 42.6%. Significant improvements in the partial current densities for COR were observed in relation to planar electrodes or flooded gas diffusion electrodes (GDEs). Finally in addition, a custom test bed was constructed to characterize the oxidation states of the Cu catalysts in real time along with product analysis though the backside of the GDLs via operando X-ray absorption (XAS) measurements.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Three-Dimensionally Mesostructured Fe 2 O 3 Electrodes with Good Rate Performance and Reduced Voltage Hysteresis

Ni scaffolded mesostructured 3D Fe 2 O 3 electrodes were fabricated by colloidal templating and pulsed electrodeposition. The scaffold provided short pathways for both lithium ions and electrons in the active phase, enabling fast kinetics and thus a high power density. The scaffold also resulted in a reduced voltage hysteresis. The electrode showed a reversible capacity of ~1000 mA h g -1 at 0.2 A g -1 (~0.2 C) for about 20 cycles, and at a current density of 20 A g -1 (~20 C) the deliverable capacity was about 450 mA h g -1 . The room temperature voltage hysteresis at 0.1 A g -1 (~0.1 C) was 0.62 V, which is significantly smaller than that normally reported in the literature. And it could be further reduced to 0.42 V when cycling at 45 ºC. Potentiostatic electrochemical impedance spectroscopy (PEIS) studies indicated the small voltage hysteresis may be due to a reduction in the Li 2 O/Fe interfacial area in the electrode during cycling relative to convention-al conversion systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Cation-Tethered Flowable Polymeric Interface for Enabling Stable Deposition of Metallic Lithium

A fundamental challenge, shared across many energy storage devices, is the complexity of electrochemistry at the electrode–electrolyte interfaces that impacts the Coulombic efficiency, operational rate capability, and lifetime. Specifically, in energy-dense lithium metal batteries, the charging/discharging process results in structural heterogeneities of the metal anode, leading to battery failure by short-circuit and capacity fade. In this work, we take advantage of organic cations with lower reduction potential than lithium to build an electrically responsive polymer interface that not only adapts to morphological perturbations during electrodeposition and stripping but also modulates the lithium ion migration pathways to eliminate surface roughening. As a result, we find that this concept can enable prolonging the long-term cycling of a high-voltage lithium metal battery by at least twofold compared to bare lithium metal.

25 ENERGY STORAGE↗
DOE OSTI2017

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η of -η < 100 mV at a current density of -10 mA cm -2 in 0.500 M H 2 SO 4 (aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H 2 SO 4 (aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Lastly, operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

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

Gold-supported cerium-doped NiO x catalysts for water oxidation

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x –Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highly active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x –Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

36 MATERIALS SCIENCE↗