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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 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

Low potassium enhances sodium uptake in red-beet under moderate saline conditions

Due to the discrepancy in metabolic sodium (Na) requirements between plants and animals, cycling of Na between humans and plants is limited and critical to the proper functioning of bio-regenerative life support systems, being considered for long-term human habitats in space (e.g., Martian bases). This study was conducted to determine the effects of limited potassium (K) on growth, Na uptake, photosynthesis, ionic partitioning, and water relations of red-beet (Beta vulgaris L. ssp. vulgaris) under moderate Na-saline conditions. Two cultivars, Klein Bol, and Ruby Queen were grown for 42 days in a growth chamber using a re-circulating nutrient film technique where the supplied K levels were 5.0, 1.25, 0.25, and 0.10 mM in a modified half-strength Hoagland solution salinized with 50 mM NaCl. Reducing K levels from 5.0 to 0.10 mM quadrupled the Na uptake, and lamina Na levels reached -20 g kg-1 dwt. Lamina K levels decreased from -60 g kg-1 dwt at 5.0 mM K to -4.0 g kg-1 dwt at 0.10 mM K. Ruby Queen and Klein Bol responded differently to these changes in Na and K status. Klein Bol showed a linear decline in dry matter production with a decrease in available K, whereas for cv. Ruby Queen, growth was stimulated at 1.25 mM K and relatively insensitive to a further decreases of K down to 0.10 mM. Leaf glycinebetaine levels showed no significant response to the changing K treatments. Leaf relative water content and osmotic potential were significantly higher for both cultivars at low-K treatments. Leaf chlorophyll levels were significantly decreased at low-K treatments, but leaf photosynthetic rates showed no significant difference. No substantial changes were observed in the total cation concentration of plant tissues despite major shifts in the relative Na and K uptake at various K levels. Sodium accounted for 90% of the total cation uptake at the low K levels, and thus Na was likely replacing K in osmotic functions without negatively affecting the plant water status, or growth. Our results also suggest that cv. Ruby Queen can tolerate a much higher Na tissue concentration than cv. Klein Bol before there is any growth reduction. Grant numbers: 12180.

NASA Center KSC↗
DOE OSTI2021

Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode

Ionic liquid (IL) additives to both traditional and advanced oxygen reduction reaction (ORR) electrocatalysts have yielded remarkable improvements in catalyst performance and durability. However, incorporating ILs or IL-modified catalysts into the electrodes of a proton exchange membrane fuel cell (PEMFC) membrane electrode assembly (MEA) has proven to be challenging. Sulfonated poly(ionic liquid) block copolymers (S-PILBCP) present an opportunity to incorporate IL functionality directly into the ionomer, orthogonal to protonic conductivity. Here, we use a rotating disc electrode (RDE) to characterize the interface between a S-PILBCP and Pt catalyst in comparison to Nafion. Catalyst thin films prepared with S-PILBCP show an 80% improvement in the ORR activity over those containing Nafion. Thin films of S-PILBCP also show a significantly reduced degree of poisoning sulfonate adsorption on a Pt(111) surface in comparison to Nafion. Furthermore, these half-cell results provide useful insights that help to highlight the source of the impact of the S-PILBCP on PEMFC MEA performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Ionothermal Synthesis of Carbon/TiO 2 Nanocomposite for Supercapacitors

A facile in-situ ionothermal strategy is designed to synthesize carbon/oxide composites with nanoporous structure. Ionic liquids play key roles in this ionothermal method as the solvents, porous structure directing templates and carbon sources. Here, the interaction between ionic liquids and oxides greatly improves the carbon yield of ionic liquids from nearly 0 to 18 wt.%. With the synergistic effects of the high electrical conductivity of the nitrogen-rich carbon species and the Ti 3+ self-doping enhanced electrical conductivity of TiO 2 , C/TiO 2 -4 composite exhibits better electrochemical performance than C/SiO 2 and C/Nb 2 O 5 do as a supercapacitor electrode material, delivering a high specific capacitance of 152.4 F g -1 at 5 mV s -1 with good capacitance retentions of 84.7%, 72.2% and 46.0% at 30, 100 and 500 mV s -1 , respectively.

36 MATERIALS SCIENCE↗
NASA NTRS2000

Determination of anionic surfactants during wastewater recycling process by ion pair chromatography with suppressed conductivity detection

A direct approach utilizing ion pairing reversed-phase chromatography coupled with suppressed conductivity detection was developed to monitor biodegradation of anionic surfactants during wastewater recycling through hydroponic plant growth systems and fixed-film bioreactors. Samples of hydroponic nutrient solution and bioreactor effluent with high concentrations (up to 120 mS electrical conductance) of inorganic ions can be analyzed without pretreatment or interference. The presence of non-ionic surfactants did not significantly affect the analysis. Dynamic linear ranges for tested surfactants [Igepon TC-42, ammonium lauryl sulfate, sodium laureth sulfate and sodium alkyl (C10-C16) ether sulfate] were 2 to approximately 500, 1 to approximately 500, 2.5 to approximately 550 and 3.0 to approximately 630 microg/ml, respectively.

NASA Program Advanced Human Support Technology↗
DOE OSTI2025

Atomistic Mechanisms of the Crystallographic Orientation‐Dependent Cu 1.8 S Conductive Channel Formation in Cu 2 S‐Based Memristors

Achieving multiple types of resistive switching in a single material with controlled ionic motion is a key challenge in neuromorphic computing, traditionally addressed by combining materials with distinct switching behaviors. Here, Cu 2-x S is identified as a promising candidate to overcome this limitation due to its hierarchical phase transitions. Using in situ biasing experiments, reversible and non-reversible phase transitions (and resistive switching) are demonstrated in γ-Cu 2 S by controlling the compliance current. The formation of parallel high-digenite Cu 1.8 S channels, orientated along the γ-Cu 2 S [201] crystallographic direction, drives the nonvolatile resistive switching. These channels emerge via an intermediate δ-Cu 2 S phase and are stabilized at room temperature by residual strains, alongside β-Cu 2 S phase. In conclusion, the work clarifies the complex, electrically triggered phase transformations in γ-Cu 2 S, and highlights the potential of Cu 2-x S as a versatile material for neuromorphic computing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

HTO and selenate diffusion through compacted Na-, Na–Ca-, and Ca-montmorillonite

Radionuclide transport in smectite clay barrier systems used for nuclear waste disposal is controlled by diffusion, with adsorption significantly retarding transport rates. While a relatively minor component of spent nuclear fuel, 79 Se is a major driver of the safety case for spent fuel disposal due to its long half-life (3.3×10 5 yr) and its low adsorption to clay (K D < 10 L/kg), thus a thorough understanding of Se diffusion through clay is critical for understanding the long-term safety of spent fuel disposal systems. Through-diffusion experiments with tritiated water (HTO, conservative tracer) and Se(VI) were conducted with a well-characterized, purified montmorillonite source clay (SWy-2) under a constant ionic strength (0.1 M) and three different electrolyte compositions: Na + , Ca 2+ , and a Na + -Ca 2+ mixture at pH 6.5 in order to probe the effects of electrolyte composition and interlayer cation composition on clay microstructure, Se(VI) aqueous speciation, and ultimately diffusion. Further, the results were modeled using a reactive transport modeling approach to determine values of porosity (ε), D e (effective diffusion coefficient), and K D (distribution coefficient for adsorption). HTO diffusive flux was higher in Ca-montmorillonite (D e =1.68×10 -10 m 2 s -1 ) compared to Na-montmorillonite (De=7.83×10 -11 m 2 s -1 ). This increase in flux is likely due to a greater degree of clay layer stacking in the presence of Ca 2+ compared to Na + , which leads to larger inter-particle pores. Overall, the Se(VI) flux was much lower than the HTO flux due to anion exclusion, with Se(VI) flux following the order Ca (D e = 1.03×10 -11 m 2 s -1 ) > Na–Ca (D e = 2.12×10 -12 m 2 s -1 ) > Na (D e = 1.28×10 -12 m 2 s -1 ). These differences in Se(VI) flux are due to a combination of factors, including (1) larger accessible porosity in Ca-montmorillonite due to clay layer stacking and smaller electrostatic effects compared to Na-montmorillonite, (2) larger accessible porosity for neutral-charge CaSeO4 species which makes up 32% of aqueous Se(VI) in the pure Ca system, and (3) possibly higher Se(VI) adsorption for Ca-montmorillonite. Through a combination of experimental and modeling work, this study highlights the compounding effects that electrolyte and counterion compositions can have on radionuclide transport through clay. Diffusion models that neglect these effects are not transferable from laboratory experimental conditions to in situ repository conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Adapting confocal Raman microscopy for in situ studies of redox transformations at electrode-electrolyte interfaces

Confocal Raman microscopy was applied to quantify redox species present within the diffusion layer adjacent to an electrode surface under potentiostatic control. A glass microscope coverslip with a thin indium tin oxide (ITO) coating served as both the working electrode and optical window for a microscope-stage mountable spectroelectrochemical cell. A high numerical aperture objective mounted in an inverted microscope frame just below the stage brought excitation radiation through the coverslip window and to a tight focus a few micrometers above the ITO film surface. Species diffusing into the confocal probe volume defined by the excitation beam focus and the collected light region were detected, identified and quantified based on their Raman scattering frequencies and intensities. Here, in measurements that interrogated the interconversion of ferrocyanide and ferricyanide ions as a function of applied voltage, least-squares regression analysis of spectral datasets predicted the formal potential and relative surface concentrations of the ions in good agreement with the expected Nernstian response. Preliminary studies of methyl viologen reduction at an ITO film/Nafion membrane interface were conducted and show the possibility for estimation of mass transport coefficients of redox species within ionic polymer materials.

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

Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi 0.5 Mn 1.5 O 4 Cathode Films

The high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi x Mn y Co z O 2 (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF 6 decomposition and subsequent Mn 2+ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn 3+ sites on the LNMO particle surface that can disproportionate into Mn 2+ (dissolved) and Mn 4+ (s) . During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF 2 ) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF 2 decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enriching Cations Using Electric Field Gradients Generated by Bipolar Electrodes in the Absence of Buffer

We discuss that ionic current gradients and corresponding electric field gradients formed at bipolar electrodes are useful for enriching cations up to ~350-fold at specific locations in microfluidic devices. The enrichment mechanism is determined by collecting current data, measuring solution conductivity, and by performing pH indicator experiments. These data reveal the dynamic nature of the enrichment mechanism. Specifically, they show the complex relationship between the ionic current gradients formed at the bipolar electrode and the extent of cation enrichment. Finally, we demonstrate cation enrichment is possible in buffer-free solutions containing up to 50.0 mM KCl. This finding is significant because it broadens the range of solutions in which membrane-free, electrochemical separations using bipolar electrodes can be performed.

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

Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–Ce Z+ as a Model System

Perfluorosulfonic acids (PFSAs) are commonly used as solid polymer electrolyte membranes (PEMs) in electrochemical energy devices, where they are vulnerable to attack by radical species during operation. A popular strategy to combat this problem is to introduce radical scavengers like cerium (Ce) ions that neutralize these species before they attack the PFSA. Such cation doping creates a multi-ion system, in which understanding the mechanisms of cation solvation and transport becomes important for the effective design and utilization of PFSA–cation systems. Ce ions also provide a representative model system for multication-exchanged ionomers in electrochemical systems. In this study, hydration and conductivity measurements, along with X-ray fluorescence and scattering, are employed to elucidate how Ce ion exchange alters PFSA’s ionic solvation, as well as nano- and mesoscale morphologies, which ultimately control its ion transport properties. A molecular transport model is used to deconvolute the impact of Ce ions on the local solvation structure of water in the membrane from mesoscale changes of the transport pathways. The combined experimental and theoretical analysis reveals a nonlinear decrease in conductivity driven by cation solvation at the molecular level and morphological changes at longer length scales. Migration–diffusion coupling, its nonlinear dependence on ion exchange and hydration, and its overall implications for ionomer performance are also discussed. Finally, these findings have the potential to be translated into other mixed cation–ionomer systems for a wide range of energy and environmental devices.

36 MATERIALS SCIENCE↗
NASA NTRS2011

Variable Emittance Electrochromics Using Ionic Electrolytes and Low Solar Absorptance Coatings

One of the last remaining technical hurdles with variable emittance devices or skins based on conducting polymer electrochromics is the high solar absorptance of their top surfaces. This high solar absorptance causes overheating of the skin when facing the Sun in space. Existing technologies such as mechanical louvers or loop heat pipes are virtually inapplicable to micro (< 20 kg) and nano (< 5 kg) spacecraft. Novel coatings lower the solar absorption to Alpha(s) of between 0.30 and 0.46. Coupled with the emittance properties of the variable emittance skins, this lowers the surface temperature of the skins facing the Sun to between 30 and 60 C, which is much lower than previous results of 100 C, and is well within acceptable satellite operations ranges. The performance of this technology is better than that of current new technologies such as microelectromechanical systems (MEMS), electrostatics, and electrophoretics, especially in applications involving micro and nano spacecraft. The coatings are deposited inside a high vacuum, layering multiple coatings onto the top surfaces of variable emittance skins. They are completely transparent in the entire relevant infrared region (about 2 to 45 microns), but highly reflective in the visible-NIR (near infrared) region of relevance to solar absorptance.

Chandrasekhar, Prasanna↗
DOE OSTI2021

Alkaline anion exchange membranes derived from diphenylethylene and co-monomer feedstock

The anion exchange membranes exhibit enhanced chemical stability and ion conductivity when compared with traditional styrene-based alkaline anion exchange membranes. A copolymer backbone is polymerized from a reaction medium that includes a diphenylalkylene and an alkadiene. The copolymer includes a plurality of pendant phenyl groups. The diphenyl groups on the polymer backbone are functionalized with one or more haloalkylated precursor substrates. The terminal halide from the precursor substrate can then be substituted with a desired ionic group. The diphenylethylene-based alkaline anion exchange membranes lack the .alpha.-hydrogens sharing tertiary carbons with phenyl groups from polystyrene or styrene-based precursor polymers, resulting in higher chemical stability. The ionic groups are also apart from each other by about 3 to 6 carbons in the polymer backbone, enhancing ion conductivity. These membrane are advantageous for use in fuel cells, electrolyzers employing hydrogen, ion separations, etc.

Lee, Sangwoo↗
DOE OSTI2024

Alkaline anion exchange membranes derived from diphenylethylene and co-monomer feedstock

The anion exchange membranes exhibit enhanced chemical stability and ion conductivity when compared with traditional styrene-based alkaline anion exchange membranes. A copolymer backbone is polymerized from a reaction medium that includes a diphenylalkylene and an alkadiene. The copolymer includes a plurality of pendant phenyl groups. The diphenyl groups on the polymer backbone are functionalized with one or more haloalkylated precursor substrates. The terminal halide from the precursor substrate can then be substituted with a desired ionic group. The diphenylethylene-based alkaline anion exchange membranes lack the α-hydrogens sharing tertiary carbons with phenyl groups from polystyrene or styrene-based precursor polymers, resulting in higher chemical stability. The ionic groups are also apart from each other by about 3 to 6 carbons in the polymer backbone, enhancing ion conductivity. These membrane are advantageous for use in fuel cells, electrolyzers employing hydrogen, ion separations, etc.

Lee, Sangwoo↗
DOE OSTI2022

Oxygen vacancy-rich amorphous FeNi hydroxide nanoclusters as an efficient electrocatalyst for water oxidation

Here, a one-pot strategy is presented to directly synthesize amorphous Fe x Ni y hydroxide nanoclusters (denoted as ANC-Fe x Ni y , <2 nm) with oxygen vacancies induced by ionic liquids. The ANC-Fe x Ni y catalyst presents abundant catalytic sites and high intrinsic conductivity. As such, the optimized ANC-Fe 1 Ni 2 exhibits high activity in oxygen evolution reaction (OER) with a Tafel slope of 39 mV dec –1 and an overpotential of 266 mV at 10 mA cm –2 . Notably, the optimized ANC-Fe 1 Ni 2 shows an extraordinarily large mass activity of 3028 A g FeNi –1 at the overpotential of 300 mV, which is ~24-fold of commercial RuO 2 catalyst. The superior activity of these Fe x Ni y hydroxide nanoclusters is ascribed to (i) the amorphous and distorted structure with abundant oxygen vacancies, and (ii) enhanced active site density by downsizing the ANC-Fe x Ni y clusters. This strategy provides a novel route for enhancing OER electrocatalytic performance and highly encouraging for the future application of amorphous metal hydroxides in catalysis.

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

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration Using Copolymer Grain Encapsulation

Thermal stability of organic–inorganic hybrid perovskites (OIHPs) remains as one of the critical challenges against the stable operation of perovskite solar cells (PSCs) in direct sunlight with elevated temperatures. Here, we show that the addition of a polystyrene-co-polyacrylonitrile (SAN) copolymer can significantly enhance thermal stability of OIHPs and improve the stability of the corresponding PSCs by suppressing the migration of organic cations in OHIP. The methylammonium lead iodide (MAPI) with SAN incorporated within the perovskite layer featured a superior thermal stability compared to pure MAPI without SAN, only displaying an average of 5–15% decrease in PCE even after continuous thermal aging for 24 h at 100 °C. The secondary ion mass spectrometry revealed that the thermal degradation of the pure MAPI was largely associated with MA+ out-migration. Conducting atomic force microscopy analysis further indicated that the incorporated SAN led to a suppression of ionic currents present at the grain boundaries of the perovskite film, which was understood by high immiscibility between SAN and MA+ components as confirmed by the experimentally estimated Flory–Huggins parameter between them. This study newly identifies a potential of using polymer grain encapsulation for enhancing thermal stability of OIHPs and their solar cell performance by suppressing the out-diffusion of cationic organic components.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Proton switching molecular magnetoelectricity

Abstract The convergence of proton conduction and multiferroics is generating a compelling opportunity to achieve strong magnetoelectric coupling and magneto-ionics, offering a versatile platform to realize molecular magnetoelectrics. Here we describe machine learning coupled with additive manufacturing to accelerate the design strategy for hydrogen-bonded multiferroic macromolecules accompanied by strong proton dependence of magnetic properties. The proton switching magnetoelectricity occurs in three-dimensional molecular heterogeneous solids. It consists of a molecular magnet network as proton reservoir to modulate ferroelectric polarization, while molecular ferroelectrics charging proton transfer to reversibly manipulate magnetism. The magnetoelectric coupling induces a reversible 29% magnetization control at ferroelectric phase transition with a broad thermal hysteresis width of 160 K (192 K to 352 K), while a room-temperature reversible magnetic modulation is realized at a low electric field stimulus of 1 kV cm −1 . The findings of electrostatic proton transfer provide a pathway of proton mediated magnetization control in hierarchical molecular multiferroics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Bipolar ionomer membrane

Provided are membranes useful for electrochemical or fuel cells. A membrane may be formed of or include a sulfonated polymer whereby the sulfonated polymer is covalently or ionically associated with a multi-nitrogen containing heterocyclic molecule. The resulting membranes possess excellent ion conductivity and selectivity.

Treger, Jack↗