Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “electrochemical process”

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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Feasibility Study to Dissolve Additively Manufactured Inconel 718 Support Structures

Additive manufacture (AM) component design face constrains due to support structure removal. Interior passages or delicate geometries require supports yet cannot be removed without compromising the design or complicating post-processing. A process was developed to dissolve metal AM supports where a sensitizing agent is applied post-build. During stress relief the sensitizing agent diffuses into the surface and alters the chemical composition of the top 100 to 200 μm. During an electrochemical dissolution process the sensitized region is susceptible to corrosion/dissolution and the etching reaction self-terminates once the sensitized region is dissolved. Support thickness varies from 80 to 200 μm, resulting in total dissolution or sufficiently weakened to facilitate removal. The objective of this project was to demonstrate a support structure dissolution process for IN718 components built using AM and to characterize the impact on mechanical properties, microstructure, and surface finish.

Omar R Mireles↗
DOE OSTI2022

Temporal and spatial tuning of optical constants in praseodymium doped ceria by electrochemical means

Abstract Temporal and spatial tuning of the refractive index of optical thin films is desired for flat optics applications. The redistribution of mobile ions in mixed ionic-electronic conductors (MIEC) has been demonstrated to serve as a viable means for achieving optical tuning down to the nanoscale. Here we studied the dynamic range of the optical tuning achievable in the refractive index, in the MIEC oxide – Pr x Ce 1− x O 2− δ (PCO), for x = 0.1, 0.2 and 0.4, at 500 °C, by in-situ spectrophotometry. Significant increases in the modulation of both the imaginary and real optical constants in the visible and the adjacent spectra were obtained for increased doping levels. Device employing an electrochemical titration method was implemented to modulate the oxygen concentration, and thereby the optical transmission of PCO. Incorporation of a patterned top electrode allowed for the demonstration of spatial control of PCO thin film properties by in-situ video imaging of the optical switching process. The electrochemically induced optical state is shown to remain non-volatile upon quenching the device to room temperature under applied bias.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Improved methods for separation of Cobalt, Manganese, Nickel, Lithium from Waste Lithium-ion Battery Scrap

Improved methods for separation of Cobalt, Manganese, Nickel, Lithium from Waste Lithium-ion Battery Scrap Mark L. Strauss1, John Klaehn1 Luis Diaz Aldana1, Tedd Lister1 Idaho National Laboratory1, Biological and Chemical Processing Department, Idaho Falls, Idaho 83415 ABSTRACT The current methods for the separation of Co, Mn, Ni, Li require that the leach solution have a pH between 2-4 in order to use many Cyanex cationic exchange products. Using a unique buffer solution for the reagent combined with the leachate of innovative electrochemical leaching process for lithium batteries demonstrates the separation is possible without a large of pH modification as other commercial hydrometallugical separation process. This research demonstrates a process that is more environmentally sustainable because the reagent consumption may be less. The corresponding McCable-Thiele diagrams and number of theoretical stages were determined to achieve a 80-90% purity of cobalt, manganese, nickel and lithium.

42 ENGINEERING↗
DOE OSTI2022

An Improved Pathway to Ethylene Glycol via CO 2

This report describes our efforts to develop a partial electrochemical oxidation process to produce formaldehyde selectively from methanol. The effort examined numerous potential anode materials in pursuit of 70% Faradaic efficiency for conversion of methanol to formaldehyde. Among the various electrode materials tested herein both Pt and PtRu were identified as the most promising catalysts in this process as the Faradaic efficiency obtained in these cases are 40% and >70% respectively. Several other 3d transition metals, Pt group metals and their alloys were also studied in which the Faradaic efficiency was obtained within 5-30%. In case of Pt and PtRu bulk metal electrode shows higher selectivity to formaldehyde compared to their nanostructured materials. Based on the literature, nanostructured Pt and PtRu are considered as active catalysts for methanol fuel cells, thus, lower selectivity to formaldehyde with nano Pt and PtRu in our case was attributed to their preferential oxidation of methanol to CO 2 . Severe catalyst deactivation was noted when 0.5 (M) sulfuric acid was used as the electrolyte irrespective of catalyst formulation. On the other hand, much higher activity and selectivity for formaldehyde was noted when alkaline electrolyte was employed during oxidation. Considering selective electrochemical oxidation of methanol to formaldehyde is an area which is underexplored as of today, our findings about catalyst formulation and process condition is noteworthy in this direction. Both bulk metal electrodes of Pt and PtRu may be cost prohibitive and thus present challenges to the scale up this technology. Therefore, we recognize that additional efforts are needed to develop catalysts with high activities and Faradaic efficiencies similar to bulk electrodes for the electrooxidation of methanol to formaldehyde.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Mitigating Cyclable Li‐Ion Inventory Loss in Full Cells with Mn‐Rich Disordered Rocksalt Cathodes

Lithium (Li)- and manganese (Mn)-rich disordered rock salt (DRX) materials are promising cathode materials for next-generation Li-ion batteries. Although these cathode materials are Li-ions rich in their pristine state, their incorporation into full cells results in challenges with maintaining Li-ion inventory during cycling. Herein, the degradation mechanisms of DRX materials in different DRX||Graphite full cells are reported. It is found that DRX electrodes contain Li impurities, primarily due to the environmental sensitivity of mechanochemically synthesized DRX materials during sample transfer and storage. In addition, the structural instability of DRX triggers Mn dissolution. Dissolved Mn ions react with exposed Li x C y compounds and induce electrolyte decomposition on the anode, further depleting Li-ion inventory. Control experiments involving the pre-addition of Mn 2+ provide clear evidence of the impact of Mn dissolution on Li-ion inventory. The electrochemical activation process can stabilize DRX, alleviate Mn dissolution and thus mitigate the loss of Li-ion inventory. These mechanistic insights inform the development of chemical pre-lithiation and electrolyte additive strategies to collectively passivate interfaces, mitigate the effects of trace dissolved Mn ions, and preserve Li-ion inventory. Ultimately, the DRX||Graphite full cell achieves highly reversible electrochemical reactions with a high capacity retention. This study fills a research gap in DRX-based full cells and provides insights into degradation mechanisms and optimization strategies for their practical use.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A Perspective into Operando Methods for Probing Catalytic Interfaces

Rational design of electrocatalysts for (photo)electrochemical (PEC) processes like hydrogen and oxygen evolution and CO2 reduction reactions is aided by the recent improvements in capabilities of operando measurements, where morphology, composition, and/or function are probed during active catalysis. Through operando microscopy and spectroscopy, structure, catalytic microenvironment, oxidation state, adsorbates, and products can be measured to gain a better understanding of catalyst behavior and suggest possible improvements. Visualizing evolving catalyst morphologies, surface compositions, and electrochemical behavior also helps address many fundamental research questions for a better understanding of catalytic mechanisms. Correlating morphology with chemical identity or functional behavior using a variety of innovative microscopy methods is particularly promising for guiding development of next generation catalysts, and there are also many recent examples of using AI and robotics tools to innovate and speed development. In this Perspective, advances made over the past few years in operando imaging of catalysts relevant to solar fuels will be explored, followed by an outlook on technological developments in instrumentation, sample design, and computational power that may be applied to this field.

Catalysts↗
DOE OSTI2020

Uncovering phase transformation, morphological evolution, and nanoscale color heterogeneity in tungsten oxide electrochromic materials

Controlling the electrochemical interfacial processes that govern the durability of electrochromic devices represents a key challenge in developing sustainable and cost-effective smart windows. Here, we revisit the classical tungsten trioxide (WO 3 ) materials as a platform to uncover the previously unknown interrelationship between phase transformation, morphological evolution, and nanoscale color heterogeneity in these materials. Through synchrotron/electron spectroscopic and imaging analyses, we report that the WO 3 –electrolyte interface is influenced by the tungsten dissolution and redeposition during the electrochemical cycling. The tungsten redeposition provokes the in situ crystal growth, which ultimately leads to the phase transformation from the semicrystalline WO 3 to a nanoflake-shaped, proton-trapped tungsten trioxide dihydrate (H x WO 3 · 2 H 2 O). The multidimensional quantification of the electronic structure reveals that the tungsten reduction caused by the proton trapping is heterogeneous at the nanometric scale and is responsible for the nanoscale color heterogeneity. The interplay between phase transformation, morphological evolution, and nanoscale color heterogeneity results in degraded optical modulation, switching kinetics, coulombic efficiency, and bleached-state transparency. Our results highlight that the high interfacial reactivity near the electrode surface may be the underlying mechanism for undesired bulk structural changes of electrochromic materials, and calls for fundamental studies in probing and controlling the electrode–electrolyte interfacial processes in electrochromic devices.

36 MATERIALS SCIENCE↗
NASA NTRS2007

Process for derivatizing carbon nanotubes with diazonium species

The invention incorporates new processes for the chemical modification of carbon nanotubes. Such processes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications and sensor devices. The methods of derivatization include electrochemical induced reactions thermally induced reactions (via in-situ generation of diazonium compounds or pre-formed diazonium compounds), and photochemically induced reactions. The derivatization causes significant changes in the spectroscopic properties of the nanotubes. The estimated degree of functionality is ca. 1 out of every 20 to 30 carbons in a nanotube bearing a functionality moiety. Such electrochemical reduction processes can be adapted to apply site-selective chemical functionalization of nanotubes. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes ##STR00001##.

Tour, James M.↗
DOE OSTI2025

Cold-Sprayed NMC622 Composite as a Cathode for Lithium-Ion Batteries

The growing demand for high-energy, low-cost lithium-ion batteries (LIBs) to power electric vehicles (EVs) necessitates advances in both materials and manufacturing processes. Conventional cathode fabrication methods, such as slurry casting and drying, are energy-intensive and pose challenges for scalability and environmental compliance. In this study, we propose cold-spray (CS) deposition as a solvent-free approach for fabricating LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) composite cathodes. Powder blends of NMC622, poly(vinylidene fluoride) (PVDF), and carbon black (CB) are directly deposited onto stainless steel and Inconel substrates under varied gas temperatures, pressures (and thus velocities), and standoff distances. The effects of temperature on the deposit morphology, coating density, and volume are systematically investigated. Computational fluid dynamics simulations reveal that increasing the gas temperature enhances the particle velocity, narrows the spray angle, and reduces the mass concentration radially at the nozzle outlet. CS deposition results in a dense cathode microstructure, accompanied by fracture in polycrystalline NMC622 particles. X-ray diffraction analysis further verifies that there are no phase changes during the deposition process. The electrochemical performance of the cold-sprayed cathodes reveals an initial capacity of approximately 96 mAh g –1 for single-crystal NMC622 and 167 mAh g –1 for polycrystalline NMC622. While these values are modest compared to state-of-the-art slurry-cast cathodes, which typically exhibit 180–200 mAh g –1 under optimized conditions. The results demonstrate a competitive performance given the solvent-free nature of the CS process and compare favorably with tape-cast samples made from identical feedstock. In conclusion, he CS process enables the formation of dense, binder-integrated cathode coatings without the need for solvent processing, offering a promising pathway for scalable, energy-efficient dry electrode manufacturing of next-generation LIBs.

Batteries↗
DOE OSTI2024

Tuning Local Atomic Structures in MoS 2 Based Catalysts for Electrochemical Nitrate Reduction

In recent years, there has been a substantial surge in the investigation of transition-metal dichalcogenides such as MoS 2 as a promising electrochemical catalyst. Inspired by denitrification enzymes such as nitrate reductase and nitrite reductase, the electrochemical nitrate reduction catalyzed by MoS 2 with varying local atomic structures is reported. Further, it is demonstrated that the hydrothermally synthesized MoS 2 containing sulfur vacancies behaves as promising catalysts for electrochemical denitrification. With copper doping at less than 9% atomic ratio, the selectivity of denitrification to dinitrogen in the products can be effectively improved. X-ray absorption characterizations suggest that two sulfur vacancies are associated with one copper dopant in the MoS 2 skeleton. DFT calculation confirms that copper dopants replace three adjacent Mo atoms to form a trigonal defect-enriched region, introducing an exposed Mo reaction center that coordinates with Cu atom to increase N 2 selectivity. Apart from the higher activity and selectivity, the Cu-doped MoS 2 also demonstrates remarkably improved tolerance toward oxygen poisoning at high oxygen concentration. Finally, Cu-doped MoS 2 based catalysts exhibit very low specific energy consumption during the electrochemical denitrification process, paving the way for potential scale-up operations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Chemo‐Mechanics Interplay Dictates Interface Instability and Asymmetry in Plating and Stripping of Sodium Metal Electrodes

Abstract The development of practical sodium (Na) metal batteries is hindered by key challenges including dendrite growth, dead metal formation, and unstable solid electrolyte interphase (SEI) growth. A fundamental understanding of the chemo‐mechanical interactions at the Na/SEI interface is critical for designing stable Na metal electrodes. In this work, the coupled electrochemical‐mechanical processes governing the morphological evolution and stability of Na metal during plating and stripping are investigated. The heterogeneous nature of transport and morphological interactions at the Na/SEI interface is revealed to result in nonuniform mechanical overpotentials and reaction fronts, eventually leading to Na filaments or pits. The spatio‐temporal evolution of stress heterogeneities during Na plating and stripping is shown to be asymmetric, manifesting in varying morphological nonuniformities and instability modes. The crucial role of external pressure in modulating the electrochemical‐transport interactions, the mechanical response of Na, and the localized reaction currents and stresses at the Na/SEI interface is demonstrated. At different external pressure conditions, the correlation between transport heterogeneities in the SEI and the onset and propagation of interface instability has been delineated. This work highlights the need for synergistic tailoring of external pressure and SEI heterogeneity toward achieving stable electrodeposition and dissolution in Na metal electrodes.

Singla, Aditya [School of Mechanical Engineering P↗
DOE OSTI2023

Reduced metal nanocatalysts for selective electrochemical hydrogenation of biomass-derived 5-(hydroxymethyl)furfural to 2,5-bis(hydroxymethyl)furan in ambient conditions

Selective electrochemical hydrogenation (ECH) of biomass-derived unsaturated organic molecules has enormous potential for sustainable chemical production. However, an efficient catalyst is essential to perform an ECH reaction consisting of superior product selectivity and a higher conversion rate. Here, we examined the ECH performance of reduced metal nanostructures, i.e., reduced Ag (rAg) and reduced copper (rCu) prepared via electrochemical or thermal oxidation and electrochemical reduction process, respectively. Surface morphological analysis suggests the formation of nanocoral and entangled nanowire structure formation for rAg and rCu catalysts. rCu exhibits a slight enhancement in ECH reaction performance in comparison to the pristine Cu. However, the rAg exhibits more than two times higher ECH performance without compromising the selectivity for 5-(HydroxyMethyl) Furfural (HMF) to 2,5-bis(HydroxyMethyl)-Furan (BHMF) formation in comparison to the Ag film. Moreover, a similar ECH current density was recorded at a reduced working potential of 220 mV for rAg. This high performance of rAg is attributed to the formation of new catalytically active sites during the Ag oxidation and reduction processes. This study demonstrates that rAg can potentially be used for the ECH process with minimum energy consumption and a higher production rate.

2,5- bis(hydroxymethyl)furan (BHMF)↗
DOE OSTI2024

Unraveling the Structure and Composition of Li 4 Mn 2 O 4.5 (Li 2 O·Li 0.667 Mn 1.333 O 2 ) Electrodes for Lithium Batteries Using a High-Temperature Synthesis Approach

This paper addresses the debate about the composition and structure of a lithium-rich manganese oxide electrode with a fully disordered rock salt component, Li 4 Mn 2 O 5 (or Li 2 O·2LiMnO 2 ), first reported by Freire et al. in 2016; it is typically prepared by a high-energy ball milling procedure. It has now been demonstrated that, when prepared at 800°C, the formula of this compound is Li 4 Mn 2 O 4.5 , alternatively Li 2 O·Li 0.667 Mn 1.333 O 2 , or close thereto. The cubic, disordered Li 0.667 Mn 1.333 O 2 (or Li 0.333 Mn 0.667 O) rock salt component, in which the manganese ions adopt an average oxidation state of 2.5+, transforms to a clearly-defined spinel configuration during electrochemical cycling. The electrochemical activation process that occurs during the initial charge reaction includes the oxidation of the manganese ions by oxygen released by the Li 2 O component between 4.5 and 4.6 V. In complete contrast, nickel- and nickel-cobalt-substituted electrodes, such as Li 2 O·2LiMn 0.5 Ni 0.5 O 2 (Li 4 MnNiO 5 ) and Li 2 O·2LiMn 0.475 Ni 0.475 Co 0.050 O 2 (Li 4 Mn 0.95 Ni 0.95 Co 0.10 O 5 ), in which the manganese ions adopt a tetravalent state, have completely disordered rock salt components that are electrochemically inactive.

25 ENERGY STORAGE↗
DOE OSTI2023

Electrochemically Grown Ultrathin Platinum Nanosheet Electrodes with Ultralow Loadings for Energy-Saving and Industrial-Level Hydrogen Evolution

Nanostructured catalyst-integrated electrodes with remarkably reduced catalyst loadings, high catalyst utilization and facile fabrication are urgently needed to enable cost-effective, green hydrogen production via proton exchange membrane electrolyzer cells (PEMECs). Herein, benefitting from a thin seeding layer, bottom-up grown ultrathin Pt nanosheets (Pt-NSs) were first deposited on thin Ti substrates for PEMECs via a fast, template- and surfactant-free electrochemical growth process at room temperature, showing highly uniform Pt surface coverage with ultralow loadings and vertically well-aligned nanosheet morphologies. Combined with an anode-only Nafion 117 catalyst-coated membrane (CCM), the Pt-NS electrode with an ultralow loading of 0.015 mg Pt cm -2 demonstrates superior cell performance to the commercial CCM (3.0 mg Pt cm -2 ), achieving 99.5% catalyst savings and more than 237-fold higher catalyst utilization. The remarkable performance with high catalyst utilization is mainly due to the vertically well-aligned ultrathin nanosheets with good surface coverage exposing abundant active sites for the electrochemical reaction. Overall, this study not only paves a new way for optimizing the catalyst uniformity and surface coverage with ultralow loadings but also provides new insights into nanostructured electrode design and facile fabrication for highly efficient and low-cost PEMECs and other energy storage/conversion devices.

42 ENGINEERING↗
NASA NTRS1975

Research and development of an electrochemical biocide reactor

An alternate disinfecting process to chemical agents, heat, or radiation in an aqueous media has been studied. The process is called an electrochemical biocide and employs cyclic, low-level voltages at chemically inert electrodes to pass alternating current through water and, in the process, to destroy microorganisms. The paper describes experimental hardware, methodology, and results with a tracer microorganism (Escherichia coli). The results presented show the effects on microorganism kill of operating parameters, including current density (15 to 55 mA/sq cm (14 to 51 ASF)), waveform of applied electrical signal (square, triangular, sine), frequency of applied electrical signal (0.5 to 1.5 Hz), process water flow rate (100 to 600 cc/min (1.6 to 9.5 gph)), and reactor resident time (0 to 4 min). Comparisons are made between the disinfecting property of the electrochemical biocide and chlorine, bromine, and iodine.

See, G. G.↗