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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Sodium-halogen secondary cell

An intermediate temperature sodium-halogen secondary cell that includes a negative electrode compartment housing a negative, molten sodium-based electrode and a positive electrode compartment housing a current collector disposed in a highly conductive molten positive electrolyte. A sodium halide (NaX) positive electrode is disposed in a molten positive electrolyte comprising one or more AlX3 salts, wherein X may be the same or different halogen selected from Cl, Br, and I, wherein the ratio of NaX to AlX3 is greater than or equal to one. A sodium ion conductive solid electrolyte membrane separates the molten sodium negative electrode from the molten positive electrolyte. The secondary cell operates at a temperature in the range from about 80° C. to 210° C.

Bhavaraju, Sai↗
DOE OSTI2023

Rational Selection of Sodium Layered Oxides for High Performance Na-Ion Batteries: P2 vs O3 vs P2-O3 Intergrowths

Sodium ion batteries (NIBs) are gaining importance as an energy storage technology complementary to the Li-ion batteries. In this regard, sodium-based layered oxides are recognized as one of the most suitable positive electrode candidate for NIBs, but vast variety of their chemical compositions and crystal structures complicates the selection of the best material. To shed light on different figures of merit that control the selection of layered oxide material for NIB applications, we compare here a P2, P2-O3 intergrowth and two O3 sodium layered oxides composed of the same transition metals (Ni, Mn, Ti and Zn) but in differing stoichiometries. The results show that the new P2-type Na 0.67 Ni 0.3 Zn 0.03 Mn 0.52 Ti 0.15 O 2 phase reported here combines most of the advantages, such as stability towards moisture, reduced surface reactivity, better thermal stability and high rate capability, which are essential for commercialization, except for a limited capacity (∼125 mAh g −1 ) compared to the O3 NaNi 0.45 Zn 0.05 Mn 0.4 Ti 0.1 O 2 phase (∼180 mAh g −1 ), reported by our group previously. Altogether, this work enlarges the family of attractive Na-based positive electrodes and teaches us that we should not solely be obsessed with the capacity of a material to decide of its applicability.

Electrochemistry↗
DOE OSTI2026

Porin-Inspired Ionomers with sub-nm Gated Ion Channels for High Ion Conductivity and Selectivity (Final Project Report (2026))

The physiological functions of living systems heavily rely on biological ion channels, whose malfunction can lead to disease. These channels enable selective and regulated transport of water, ions, or small molecules across membranes. Analogously, ionomers used in energy conversion and storage technologies govern ion transport within membrane separators and catalyst binder layers. This DOE Office of Science Early CAREER project aimed to achieve molecular-level control over ionic conductivity and ion permselectivity by translating the functionalities of biological, gated ion channels into a novel class of ion-conducting polymers (ionomers) incorporating macrocyclic calix[4]arene-based repeat units. The overarching goal was to establish fundamental design principles and elucidate proton conduction mechanisms through strategic design of macrocyclic calix[4]arene-containing ionomers, with close relevance to energy conversion and storage devices, including proton exchange membrane fuel cells (PEMFCs). The project leveraged sub-nm-sized macrocyclic pores to facilitate exceptionally fast ion transport (beneficial to addressing sluggish ORR kinetics of PEMFC electrodes) and achieve functionalities of ionic diodes under applied electrochemical fields, beneficial for selective transport/separation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Laser ablation for structuring Li-ion electrodes for fast charging and its impact on material properties, rate capability, Li plating, and wetting

Laser ablation is a scalable technique for decreasing the effective tortuosity of electrodes by selectively removing material with high precision. Applied to ≈ 110 um thick electrode coatings, this work focuses on understanding the impact of laser ablation on electrode material properties at the beginning of life and synergistic impacts of ablated channels on cell performance throughout their cycle life. Post laser ablation, local changes in chemistry, crystallography, and morphology of the laser-impacted electrode regions are investigated. It is shown that femtosecond pulsed laser ablation can achieve high-rate material removal with minor material damage locally at the interface of the impacted zones. The capacity achieved during a 6C (10 min) constant-current constant-voltage charge to 4.2 V improved from 1 mAh cm -2 for the non-ablated electrodes to almost 2 mAh cm -2 for the ablated electrodes. This benefit is attributed to a synergistic effect of enhanced wetting and decreased electrode tortuosity. The benefit was maintained for over 120 cycles, and upon disassembly decreased Li-plating on the graphite anode was observed. Finally, multi-physics modeling in conjunction with wetting analyses showed that laser ablating either one of the electrodes led to substantial improvements in wetting and rate capability, indicating that substantial performance benefits can be achieved by ablating only the graphite anode as apposed to both electrodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries

Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture, the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures. The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured, benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW), a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. Furthermore, while the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs, including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.

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

Direct and Sensitive Electrochemical Evaluation of Pramipexole Using Graphitic Carbon Nitride (gCN) Sensor

Pramipexole (PMXL) belongs to the benzothiazole class of aromatic compounds and is used in treating Parkinson’s disease; however, overdosage leads to some abnormal effects that could trigger severe side effects. Therefore, it demands a sensitive analytical tool for trace level detection. In this work, we successfully developed an electrochemical sensor for the trace level detection of PMXL, using the voltammetric method. For the analysis, graphitic carbon nitride (gCN) was opted and synthesized by using a high-temperature thermal condensation method. The synthesized nanoparticles were employed for surface characterization, using transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic force microscopy (AFM) techniques. The electrochemical characterization of the material was evaluated by using the electrochemical impedance spectroscopy (EIS) technique to evaluate the solution–electrode interface property. The cyclic voltammetry (CV) behavior of PMXL displayed an anodic peak in the forward scan, indicating that PMXL underwent electrooxidation, and an enhanced detection peak with lower detection potential was achieved for gCN-modified carbon paste electrode (gCN·CPE). The influence of different parameters on the electrochemical behavior was analyzed, revealing the diffusion governing the electrode process with an equal number of hydronium ions and electron involvement. For the fabricated gCN·CPE, good linearity range was noticed from 0.05 to 500 µM, and a lower detection limit (L D ) of 0.012 µM was achieved for the selected concentration range (0.5 to 30 µM). Selectivity of the electrode in PMXL detection was investigated by conducting an interference study, while the tablet sample analysis demonstrates the sensitive and real-time application of the electrode. The good recovery values for the analysis illustrate the efficiency of the electrode for PMXL analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Water-coupled monovalent and divalent ion transport in polyviologen networks

Redox-active polymers (RAPs) are of interest as environmentally friendly and earth-abundant energy storage materials. Polyviologens are promising RAPs, but they tend to dissolve during operation. Further, the two-electron redox reaction for polyviologens in various electrolytes is not always reversible, highlighting the need for a deeper understanding of the redox mechanism. Here, the energy storage mechanism for a cross-linked viologen (PTPM) is demonstrated using electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D), comparing NaCl and Na2SO4 aqueous electrolytes. E-QCMD reveals that the ion-electron transport mechanism is strongly dependent on the valency of the anion. More sudden and dramatic changes in the electrode's mass were observed for the divalent sulfate ion as compared to the smooth mass transitions associated with the monovalent chloride ion. Meanwhile, there was marked hysteresis in the mass transfer profile for NaCl, but little hysteresis for Na2SO4. Our results demonstrate that electrolyte design, and specifically ion valency, will have a large impact on the nature of mass transport in polymer-based electrodes. This work enables electrolyte selection for the next generation polymer batteries with improved performance.

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

Polymer-iron oxide hybrid films for controlling electrokinetic properties

Electrokinetic phenomena at polymer-water interfaces are central to technologies for water purification, ion separations, and energy conversion, yet the ability to systematically control polymer surface charge and associated electrokinetic processes remains limited. Here, we demonstrate a simple liquid-phase infiltration (LPI) method to synthesize polymer–metal oxide hybrid films with controllable interfacial properties. Hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) brushes grafted to silicon substrates were infiltrated with iron nitrate from ethanolic solution, followed by low-temperature thermal treatment to convert the infiltrated precursor into iron oxide. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis confirmed oxide incorporation and hybrid film formation without polymer degradation. Electrokinetic measurements reveal that the hybrid films acquire the electrokinetic properties of the infiltrated oxide, with concentration-dependent streaming potentials and surface conductivities closely matching those of pure iron oxide films. These results establish metal oxide infiltration as a scalable and low-cost strategy for controlling interfacial charge in polymer surfaces. The approach introduces new materials and design parameters for tailoring ion selectivity, transport, and energy conversion, with broad implications for the development of advanced membranes, electrokinetic harvesting devices, and polymer-supported oxide electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Electrochemically-assisted removal of cadmium ions by redox active Cu-based metal-organic framework

An electrochemically-assisted wastewater treatment using Faradaic materials offers a promising technique for the selective removal of hazardous substances. Here, we demonstrate the reversible capture and release of cadmium ions in aqueous solutions, using a redox-active metal-organic framework (MOF) electrode. As-synthesized copper-based MOF (Cu-MOF-74; copper 2,5-dihydroxyterephthalate) is a highly attractive candidate for Faradaic electrosorption due to its large surface area, water stability, and redox-active metal nodes. Our work demonstrates the reversible capture and release of Cd 2+ ions assisted by the electrochemical redox reaction of Cu 2+ /Cu + within the MOF structure. Combined material characterization and electrosorption tests were carried out to determine the operational conditions for maximizing adsorption capacity, energy efficiency, and material stability, thus leading to excellent electrosorption (>100 mg g -1 ) and regeneration efficiency (>90%). This study demonstrates the feasibility of leveraging MOFs containing redox-active metal nodes for the selective separation of toxic cations, and paves the way for promising future applications of these 3-D porous structures for wastewater treatment and environmental remediation.

42 ENGINEERING↗
DOE OSTI2020

Structure and Stability of the Ionic Liquid Clusters [EMIM]n[BF4]n+1- (n = 1 – 9): Implications for Electrochemical Separations

Precise functionalization of electrodes with size-selected ionic liquid (IL) clusters may improve the application of ILs in electrochemical separations. Herein, we report our combined experimental and theoretical investigation of the IL clusters [EMIM]????[BF4]????+1- (n = 1 – 9) and demonstrate their selectivity and efficiency towards targeted adsorption of molecules from solution. The structures and energies of the IL clusters, predicted with global optimization, agree with and help interpret the ion abundances and stabilities measured by high mass resolution electrospray ionization mass spectrometry and collision induced dissociation experiments. The [EMIM][BF4]2- cluster, which was identified as the most stable IL cluster, was selectively soft landed onto a working electrode. Electrochemical impedance spectroscopy revealed a lower charge transfer resistance on the soft-landed electrode containing [EMIM] [BF_4 ]_2^- compared to an electrode prepared by drop casting of IL solution, which contains the full range of IL clusters. Our findings indicate that specific IL clusters may be used to increase the efficiency of electrochemical separations by lowering the overpotentials involved.

Zhang, Jun↗
DOE OSTI2024

Impact of Electrolyte Additives on the Lifetime of High Voltage NMC Lithium-Ion Pouch Cells

This work involves improving the lifetime of lithium-ion cells during high voltage cycling using electrolyte additives. Three generations of electrolyte additives were investigated and screened in NMC442/graphite pouch cells using a 24 h voltage-hold protocol at 40 degrees C to accelerate oxidative reactions occurring at 4.4 V. Once promising additives and combinations were identified, they were then tested in cobalt-free NMC640/graphite cells for long-term cycling to upper cutoff voltages of 4.3, 4.4, and 4.5 V at temperatures of 20, 40, and 55 degrees C. Degradation mechanisms were probed using dV/dQ analysis, micro-X-ray fluorescence spectroscopy, and electrochemical impedance spectroscopy. The primary failure mode of cells held at high voltages is due to increase in cell impedance, which is correlated to the dissolution of transition metals, specifically manganese, originating from the positive electrode. We believe this dissolution is presumably due to the formation of a high impedance rock salt surface layer on the NMC positive electrode particles. Such deleterious outcomes can be limited by selecting an appropriate electrolyte additive package. It is hoped that this paper can provide a starting point for developing NMC Li-ion cells that can operate to voltages as high as 4.4 V and still display long lifetimes.

Azam, Saad↗
DOE OSTI2025

Assessing the coating implications of slurry formulations in NCMA and LFMP blend cathodes for lithium-ion batteries

This paper investigates the implications of slurry formulations and electrode processing on the performance of lithium-ion battery (LIB) cathodes, focusing on Nickel Cobalt Manganese Aluminum (NCMA) and Lithium Ferro Manganese Phosphate (LFMP) blends. Through a comprehensive examination of electrode processing steps, from material selection to coating application, we elucidate the critical role of processing parameters in shaping electrode morphology and electrochemical behavior. Rheological studies reveal the influence of slurry composition on viscosity and flow behavior, highlighting the importance of achieving optimal rheological properties for uniform coating deposition. Electrochemical characterization, including cyclic voltammetry and rate capability tests, unveils the electrochemical behavior of NCMA, LFMP, and their blend, showcasing the synergistic effects of material blending on battery performance. In conclusion, our findings underscore the intricate relationship between slurry formulation, electrode processing, and LIB performance, offering valuable insights for the design and optimization of high-performance electrode materials for next-generation batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

High energy density secondary lithium batteries

A lithium ion battery includes a positive electrode comprising carbon fibers, a binder composition with conductive carbon, and a lithium rich composition. The lithium rich composition comprises at least one selected from the group consisting of Li 1+x (My Mz II Mw III )O 2 where x+y+z+w = 1, and where M, M II and M III are interchangeably manganese, nickel and cobalt, and LiM* 2-x M x * II O 4 , where M* and M* II are manganese and nickel, respectively, with x = 0.5. A negative electrode comprises carbon fibers having bound thereto silicon nanoparticles, and a mesophase pitch derived carbon binder between the silicon nanoparticles and the carbon fibers. An electrolyte is interposed between the positive electrode and the negative electrode. Methods of making positive and negative electrodes are also disclosed.

Nanda, Jagjit↗
DOE OSTI2024

Oxide-Encapsulated Ruthenium Oxide Catalysts for Selective Oxygen Evolution in Unbuffered pH-Neutral Seawater

Direct seawater electrolysis is a promising approach to producing green hydrogen in water-scarce environments using renewable energy. However, the undesirable chlorine evolution reaction and hypochlorite evolution reaction compete with the desired oxygen evolution reaction (OER) at the anode electrocatalyst. This issue is most pronounced in unbuffered pH-neutral solutions due to local acidification resulting from the OER. To overcome this challenge, this study provides a comprehensive evaluation of the use of silicon oxide (SiO x ) and titanium oxide (TiO x ) nanoscale overlayers coated on metallic ruthenium (Ru) and ruthenium oxide (RuO x ) thin film electrodes and their ability to block chloride ions from reaching active sites during operation in an unbuffered 0.6 M NaCl electrolyte. Using a combination of (electro)analytical techniques, encapsulated RuO x anodes are shown to effectively suppress Cl - transport to buried catalyst active sites while allowing for the desired OER to occur, leading to increases in OER faradaic efficiency at moderate overpotentials. Evidence for the ability of SiO x overlayers to block Cl - ions from reaching the active buried interface was obtained by monitoring the ν(O-H) stretching mode of OH adsorbates using in situ Raman spectroscopy. Here, this study also reports trade-offs between the activity, selectivity, and stability of bare and encapsulated Ru and RuO x electrocatalysts, finding that the magnitude of these trade-offs strongly depends on the complex interplay between electrode architecture, material properties, and catalytic performance, especially in unbuffered pH-neutral seawater.

58 GEOSCIENCES↗
DOE OSTI2023

Selective heterogeneous capture and release of actinides using carborane-functionalized electrodes

Here we report the heterogenization of molecular, electrochemically switchable ortho-substituted carboranes ( PO Cb, PO Cb-Pyr) for selective metal capture. Films of PO Cb and PO Cb-Pyr on glassy carbon and carbon fiber (CF) electrodes demonstrated heterogeneous electrochemical behaviour that was enhanced by the inclusion of single-walled carbon nanotubes (CNTs). Galvanostatically charged CF|CNT| PO Cb and CF|CNT| PO Cb-Pyr electrodes selectively captured and released actinides (Th 4+ , UO 2 2+ ) from mixed solutions containing alkali (Cs + ), lanthanide (Nd 3+ , Sm 3+ ) and actinide (Th 4+ , UO 2 2+ ) metal ions.

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

GaN vertical-channel junction field-effect transistors with regrown p-GaN by metal organic chemical vapor deposition (MOCVD)

Fabricating a vertical-channel junction field-effect transistor includes forming an unintentionally doped GaN layer on a bulk GaN layer by metalorganic chemical vapor deposition, forming a Cr/SiO 2 hard mask on the unintentionally doped GaN layer, patterning a fin by electron beam lithography, defining the Cr and SiO 2 hard masks by reactive ion etching, improving a regrowth surface with inductively coupled plasma etching, removing hard mask residuals, regrowing a p-GaN layer, selectively etching the p-GaN layer, forming gate electrodes by electron beam evaporation, and forming source and drain electrodes by electron beam evaporation. The resulting vertical-channel junction field-effect transistor includes a doped GaN layer, an unintentionally doped GaN layer on the doped GaN layer, and a p-GaN regrowth layer on the unintentionally doped GaN layer. Portions of the p-GaN regrowth layer are separated by a vertical channel of the unintentionally doped GaN layer.

Zhao, Yuji↗
DOE OSTI2024

Selective pseudocapacitive immobilization of REE elements on carbon based electrodes

Current extraction technologies for rare earth elements at ambient conditions are reagent and energy intensive, giving rise to significant quantities of secondary waste streams. Exploration of the removal of common cations from aqueous streams has been undertaken with carbon materials and have shown promising results. However, those promising materials have not been explored extensively for rare earth element capture from aqueous process streams. In this study, a carbon electrode was investigated for the adsorption and immobilization of REE elements from aqueous solutions. Cyclic voltammetry studies of the carbon electrode displayed a pseudocapacitive behavior where it was verified that cation adsorption is accompanied by an electron transfer process. Preliminary tests showed that a current density of 89.1 mA. g -1 , allowed for the pseudocapacitive adsorption (PSA) of Nd 3+ cation without the formation of rare earth hydroxides. Hence, the selective PSA of Nd 3+ was verified in an electrolyte solution with equimolar concentrations of Nd 3+ , Mg 2+ , Li + , Na + and K + , achieving separation factors of 8.6, 1.1, and 10.9 for Nd 3+ /Li + , Nd 3+ /Na + , and Nd 3+ /Mg 2+ , respectively. Analysis of the potential-time curves for the various cations suggests that storage of ions in the electrode involved pore-spacings rather than interlayer spacings and was corroborated by XRD analysis. Specific capacitance as high as >640 F.g -1 for Nd 3+ was also observed for the carbon electrode, with Faradaic efficiencies (FE) of > 20% for Nd 3+ and Mg 2+ , and > 9% for Na + . Furthermore, adsorption capacity of >125 mg g -1 after 4hrs of electrosorption was observed for Nd 3+ . In the presence of the Nd 3+ electrolyte, the electrode achieved increasing storage of Nd 3+ with >94% retention of Nd 3+ with a FE > 20% over 6 cycles between loading and releases in 1 M KCl solution. In conclusion, these preliminary results provide information and some guidance on the selective recovery of rare earth elements, such as Nd, in aqueous streams in the presence of competitive cations employing the use of carbon-based materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Data-driven design of electrolyte additives supporting high-performance 5 V LiNi 0.5 Mn 1.5 O 4 positive electrodes

LiNi 0.5 Mn 1.5 O 4 (LNMO) is a high-capacity spinel-structured material with an average lithiation/de-lithiation potential at ca. 4.6–4.7 V vs Li + /Li, far exceeding the stability limits of electrolytes. An efficient way to enable LNMO in lithium-ion batteries is to reformulate an electrolyte composition that stabilizes both graphitic (Gr) negative electrode with solid-electrolyte-interphase and LNMO with cathode-electrolyte-interphase. In this study, we select and test a diverse collection of 28 single and dual additives for the Gr||LNMO battery system. Subsequently, we train machine learning models on this dataset and employ the trained models to suggest 6 binary compositions out of 125, based on predicted final area-specific-impedance, impedance rise, and final specific-capacity. Such machine learning-generated new additives outperform the initial dataset. This finding not only underscores the efficacy of machine learning in identifying materials in a highly complicated application space but also showcases an accelerated material discovery workflow that directly integrates data-driven methods with battery testing experiments.

batteries↗