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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

The Source Permeator System and Tritium Transport in the TEX PbLi Loop

In this work, permeation is investigated for the introduction of hydrogen isotopes into PbLi for the Tritium Extraction eXperiment (TEX). TEX is a forced-convection PbLi loop under construction at Idaho National Laboratory (INL) that will test the vacuum permeator (VP) method of tritium extraction from PbLi. The source permeator (SP) delivers atomic hydrogen (H, D, and T) from a gas-phase reservoir into the PbLi via a permeable dense metal membrane. A modular and a fixed source permeator system are presented. In the modular design, PbLi flows through the inside of a tubular membrane and gas-phase hydrogen is introduced on the outside of the membrane. Atomic hydrogen permeates radially inward through the membrane into the PbLi. In the fixed design, PbLi flows into an expansion chamber with closed-ended tubular membranes inserted. Gas-phase hydrogen is introduced on the inside of the closed-ended membranes and atomic hydrogen permeates radially outward into the flowing PbLi. Hydrogen-transport models based on steady-state mass transport through PbLi and permeation through the metal membrane were developed to assess the operation of the source permeator relative to experimental variables and to allow understanding of uncertain parameter effects, such as PbLi hydrogen-transport properties and the effective hydrogen permeability of the vacuum permeator. This modeling effort considers iron as the source permeator material and vanadium as the vacuum permeator material.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Surface effects on deuterium permeation through vanadium membranes

Dense vanadium-based membranes offer high permeability and perfect selectivity to hydrogen isotopes, maintain favorable neutronic properties, and are compatible with liquid metals such as PbLi. These properties make vanadium membranes a promising fusion fuel cycle technology for processes such as tritium extraction from PbLi and exhaust processing. Surface contamination has a deleterious effect on the gas-phase hydrogen permeation through vanadium, and the reported permeabilities range from 10 -14 to 10 -7 mol m -1 s -1 Pa -0.5 . Thin dense films of palladium applied to clean vanadium surfaces enable a consistently high hydrogen permeability. In this study, uncoated vanadium resulted in deuterium permeabilities ranging from 2.8 × 10 -11 to 6.4 × 10 -9 mol m -1 s -1 Pa -0.5 at 300 °C–700 °C, respectively. Post-test analysis revealed a VO x surface layer and VC x subsurface layer formed on the feed side, while the as-received surface oxide dissolved leaving a submonolayer oxide on the permeate surface. Furthermore, the Pd-coated V resulted in a maximum deuterium permeability of 2.1 × 10 -7 m -1 s -1 Pa -0.5 at 375 °C upon activation of the Pd surface by oxidation and reduction. The deuterium permeation declined upon heating to 500 °C due to intermetallic diffusion between the Pd and V. The Mo 2 C-coated V resulted in deuterium permeabilities ranging from 2.7 × 10 -10 to 1.8 × 10-9 at 500 °C–700 °C, respectively, and a post-test analysis found the carbon in the Mo 2 C layer had dissolved into the V near the interface.

13 HYDRO ENERGY↗
DOE OSTI2021

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries

Abstract Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g −1 vs. <0.03 mAh g −1 ) at −40 °C under reduced pressure of the electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2022

Nafion Inhibits Polysulfide Crossover in Hybrid Nonaqueous Redox Flow Batteries

Here, we report on the effectiveness of sodium-exchanged Nafion membranes for inhibiting polysulfide crossover during redox flow battery operation. The solubility of polysulfides allows them to be used as a high-capacity catholyte for nonaqueous redox flow batteries (NARFB). The NARFB cathode capacity is controlled by the total tank catholyte volume and polysulfide concentration and, as such, is independent of polysulfide adsorption sites on carbon fibers or nanotubes as found within traditional Na or Li–S batteries. However, one of the major barriers to the realization of polysulfide NARFBs is associated with developing a robust membrane that has minimal polysulfide crossover under the operating conditions. We found that sodium-exchanged Nafion membrane separators effectively inhibit polysulfide crossover within a Na–sulfur NARFB. These membranes significantly improve both capacity retention (70%) and Coulombic efficiencies (99%) after 50 cycles. Commercial porous membranes showed a large crossover as detected by UV–vis spectroscopy and resulted in low capacity retention (20%) and Coulombic efficiency (74%) after 45 cycles. Electrochemical impedance spectroscopy (EIS) measurements highlighted the trade-off between innate reactivity and ionic conduction of the membranes. The results show that dense, single ion conducting Nafion enables a long cycle life; however, it reacts with Na metal to form a resistive passivation layer and increases the cell resistance. On the contrary, the open pore structure of Celgard allows for higher current charge/discharge, and its chemical nature is compatible with Na; however, it has a high degree of polysulfide crossover.

25 ENERGY STORAGE↗
DOE OSTI2023

High temperature steam separation membrane

Ceramic proton-conducting oxide membranes are described herein, which are useful for separating steam from organic chemicals under process conditions. The membranes have a layered structure, with a dense film of the perovskite over a porous composite substrate comprising the perovskite material and a metallic material (e.g., Ni, Cu, or Pt). The perovskite comprises an ABO 3 -type structure, where “A” is Ba and “B” is a specified combination of Ce, Zr, and Y. The perovskite ceramic materials described herein have an empirical formula of Ba(Ce x Zr 1-x-n Y n )O 3-δ , wherein 0<x<0.8 (e.g., 0.1≤x≤0.7 or 0.2≤x≤0.5); and 0.05≤n≤0.2; and δ=n/2. In some embodiments n is about 0.2. In some other embodiments 0.6≤x≤0.8; and n is about 0.2, such as Ba(Ce 0.7 Zr 0.1 Y 0.2 )O 3-δ , also referred to herein as BCZY712.

Lee, Tae H.↗
DOE OSTI2023

Hierarchically Porous Carbons with Highly Curved Surfaces for Hosting Single Metal FeN 4 Sites as Outstanding Oxygen Reduction Catalysts

Iron–nitrogen–carbon (Fe₋N₋C) materials have emerged as a promising alternative to platinum-group metals for catalyzing the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells. However, their low intrinsic activity and stability are major impediments. Herein, an Fe₋N–C electrocatalyst with dense FeN 4 sites on hierarchically porous carbons with highly curved surfaces (denoted as FeN 4 - hc C) is reported. The FeN 4 - hc C catalyst displays exceptional ORR activity in acidic media, with a high half-wave potential of 0.85 V (versus reversible hydrogen electrode) in 0.5 m H 2 SO 4 . When integrated into a membrane electrode assembly, the corresponding cathode displays a high maximum peak power density of 0.592 W cm -2 and demonstrates operating durability over 30 000 cycles under harsh H 2 /air conditions, outperforming previously reported Fe–N₋C electrocatalysts. These experimental and theoretical studies suggest that the curved carbon support fine-tunes the local coordination environment, lowers the energies of the Fe d-band centers, and inhibits the adsorption of oxygenated species, which can enhance the ORR activity and stability. This work provides new insight into the carbon nanostructure–activity correlation for ORR catalysis. It also offers a new approach to designing advanced single-metal-site catalysts for energy-conversion applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

A Non Rigid Reusable Surface Insulation Concept for the Space Shuttle Thermal Protection System

A reusable thermal protection system concept was developed for the space shuttle that utilizes a flexible, woven ceramic mat insulation beneath an aerodynamic skin and moisture barrier consisting of either a dense ceramic coating or a super alloy metallic foil. The resulting heat shield material has unique structural characteristics. The shear modulus of the woven mat is very low such that bending and membrane loads introduced into the underlying structural panel remain isolated from the surface skin.

Alexander, J. G.↗
DOE OSTI2021

Catalyst-containing oxygen transport membrane

A method is described of producing a catalyst-containing composite oxygen ion membrane and a catalyst-containing composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln 1−x A x ) w Cr 1−y B y O 3−δ and a doped zirconia. Adding certain catalyst metals into the fuel oxidation layer not only enhances the initial oxygen flux, but also reduces the degradation rate of the oxygen flux over long-term operation. One of the possible reasons for the improved flux and stability is that the addition of the catalyst metal reduces the chemical reaction between the (Ln 1−x A x ) w Cr 1−y B y O 3−δ and the zirconia phases during membrane fabrication and operation, as indicated by the X-ray diffraction results.

Lu, Zigui↗
DOE OSTI2021

Promoting Atomically Dispersed MnN 4 Sites via Sulfur Doping for Oxygen Reduction: Unveiling Intrinsic Activity and Degradation in Fuel Cells

Carbon supported and nitrogen coordinated single Mn site catalysts (Mn-N-C) catalysts are the most desirable platinum group metal (PGM)-free cathode catalysts for proton exchange membrane fuel cells (PEMFCs) due to their insignificant Fenton reactions (vs. Fe), earth abundances (vs. Co) and encouraging activity and stability. However, current Mn-N-C catalysts suffer from high over-potential due to low intrinsic activity and less dense MnN 4 sites. Herein, we present sulfur-doped Mn-N-C catalyst (Mn-N-C-S) synthesized through an effective adsorption-pyrolysis process. Using electron microscopy and X-ray absorption spectroscopy (XAS) techniques, we verify the uniform dispersion of MnN 4 sites and confirm the effect of S doping on the Mn-N coordination. The Mn-N-C-S catalyst exhibits a favorable oxygen reduction reaction (ORR) activity in acidic media relative to the S-free Mn-N-C catalyst. The corresponding membrane electrode assembly (MEA) generated a remarkable performance with a peak power density of 500 mW cm -2 under a realistic H 2 /air environment. The constant voltage tests of fuel cells confirm the much-enhanced stability of the Mn-N-C-S catalyst compared to the Fe-N-C and Fe-N-C-S catalysts. The electron microscopy and Fourier transform XAS analysis provide insights into catalyst degradation associated with Mn oxidation and agglomeration. The theoretical calculation elucidates that the promoted ORR activity is mainly attributed to the spatial effect stemmed from the repulsive interaction between the ORR intermediates and adjacent S do-pants.

25 ENERGY STORAGE↗
DOE OSTI2024

Permeation Properties of Disordered Metal-Organic Framework Membranes Made by Vapor Phase Ligand Treatment

Zeolitic imidazolate frameworks (ZIFs) are nanoporous molecular sieves offering exciting opportunities for membrane- and adsorption-based gas separations. The Tsapatsis group developed an all-vapor-phase ligand induced permselectivation (LIPS) method for the fabrication of ZIF nanocomposite membranes. The LIPS method consists of a combination of atomic layer deposition of a dense oxide inside the mesopores of a porous support followed by transformation of the dense oxide deposit to nanoporous ZIF by exposure to sublimated vapors of an imidazolate ligand. It enables the formation of thin nanocomposite films consisting of ZIF deposited inside pores with diameters smaller than 10 nm. Vapor-phase conversion of the impermeable ZnO to ZIF increases flux of certain gases more than others. Vapor phase linker/ligand treatment (VPLT) can further modify the properties of LIPS and other membranes. The combination of LIPS with VPLT provides an all-vapor methodology for making and modifying ZIF membranes with the ability to control the ZIF deposit composition and the level of confinement in a variety of mesoporous supports. The propylene/propane separation performance of LIPS/VPLT ZIF membranes confined (entirely or partially) inside mesopores is remarkably superior to that of most conventional ZIF membranes consisting of unconfined (deposited on the external surface of porous supports) polycrystalline films. The accomplishments of this award are: (i) understanding of the LIPS process using mathematical models of atomic layer deposition (ALD), (ii) development of surface modification methods (vapor, e-beam, plasma, and X-ray treatments) to tune permeation properties, (iii) microstructural control of ZIF-8 films using ALD (support modification, direct ALD, and by use of in situ permeability monitoring), (iv) molecular simulations, and (v) thin film characterization and adsorption measurements using spectroscopy.

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

Frontiers of Ionic Liquids in Carbon Dioxide Separation and Valorization

Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO 2 -containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. Here, this Review explores IL-derived systems for CO 2 -related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO 2 sorption, focusing on the correlation between IL-CO 2 interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO 2 separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO 2 capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.

Qiu, Liqi [Univ. of Tennessee, Knoxville, TN (Unit↗
DOE OSTI2022

A Bilayer Electrolyte Design to Enable High-Areal-Capacity Composite Cathodes in Polymer Electrolytes Based Solid-State Lithium Metal Batteries

High-areal-capacity cathodes are needed for energy-dense solid-state batteries. Here, we demonstrate a bilayer polymer electrolyte design for cycling 3–6 mAh/cm 2 NMC811 composite cathodes. In this work, the bilayer electrolyte comprises a cross-linked poly(ethylene oxide) (PEO)-based electrolyte layer and a linear-PEO-based electrolyte layer. The former provides dendritic resistance, and the latter provides a seamless interface with the cathode during cycling. Using a single layer of either membrane led to severe shorting or extremely low Coulombic efficiency (CE) in the first cycle. The general concept of a rigid dendrites-inhibiting electrolyte facing Li anode and a softer, cathode-integrated electrolyte that ensures contact with the cathodes during cycling may present a pattern for enabling high-energy-density cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

High‐Energy‐Density Chelated Chromium Flow Battery Electrolyte at Neutral pH

Abstract High‐concentration operation of redox flow batteries (RFBs) is essential for increasing their energy‐storage capacity, but non‐acidic electrolytes struggle to achieve the high concentrations of metal ions dissolved in acid, limiting the development of energy‐dense neutral pH electrolytes. We report neutral pH RFB operation of chromium 1,3‐propylenediaminetetraacetate (CrPDTA) at concentrations of 1.2 M at room temperature and 1.6 M at 40 °C, demonstrating 60% higher negolyte capacity, up to 42.9 Ah L −1 , than previously reported for non‐additive‐utilizing solutions of this promising material. With extended full cell cycling, we demonstrate the importance of buffer selection and pH when using the Fumasep E‐620(K) membrane. Finally, we expand the pH operation range of CrPDTA to pH 7, which when cycled at 100 mA cm −2 against a ferrocyanide posolyte demonstrated excellent coulombic efficiencies >99.7% and energy efficiencies >87%, while operating at almost 700 mV more negative than the thermodynamic hydrogen evolution window.

Chemistry↗
NASA NTRS2006

Evaluating Trichloroethylene Degradation Using Differing Nano- and Micro-Scale Iron Particles

Trichioroethylene, or TCE, is a central nervous system depressant and possible carcinogen, as well as a persistent groundwater pollutant. TCE exists in the aquifer either as free product in the form of a dense non-aqueous phase liquid (DNAPL) or as a dissolved-phase constituent. It is only slightly soluble in water, so dissolution of the contaminant is a long-term process and in-situ remediation is difficult. To remedy this, NASA and the University of Central Florida developed Emulsified Zero-Valent Iron, or EZVI. The emulsion droplet contains ZVI particles and water encapsulated by an oil/surfactant membrane, and effectively penetrates to degrade DNAPL-phase TCE. To maximize the efficiency of this process, several commercially available ZVIs of radically different particle sizes and morphologies both in emulsion and as neat (unemulsified) metal were evaluated for relative effectiveness at TCE degradation.

Berger, Cristina M.↗
DOE OSTI2025

Highly dense atomic Fe–Ni dual metal sites for efficient CO 2 to CO electrolyzers at industrial current densities

Carbon-supported, atomically dispersed, nitrogen-coordinated metal sites (e.g., Fe and Ni) are arguably the most promising catalysts for the electrochemical reduction of CO 2 to CO due to their unique catalytic properties and the use of earth-abundant elements. However, conventional single metal sites are constrained by their structural simplicity, causing either too weak or too strong absorption/desorption of multiple critical intermediates (e.g., *COOH and *CO). Current catalysts also suffer from ultra-low loadings (<1.0 wt%) of atomic metal active sites in catalysts, leading to inadequate performance for CO 2 -to-CO conversion. Here, we develop dual Ni/Fe metal site catalysts with significantly increased atomically dispersed metal loadings (up to 4.8 wt%). A gas-phase chemical vapor deposition (CVD) approach to introducing single Ni sites was integrated with Fe 2 O 3 /ZIF-8 precursors, followed by an optimal thermal activation. The optimized CVD-Ni/Fe–N–C catalyst exhibited remarkable electrocatalytic performance for the CO 2 reduction to CO in a continuous membrane-electrode-assembly electrolyzer, achieving a maximum CO faradaic efficiency (FE CO ) of 96% at a current density of 700 mA cm −2 in a near-neutral electrolyte. Furthermore, a desirable but challenging acidic flow-cell electrolyzer was designed using this dual metal site catalyst to improve CO 2 utilization, accomplishing a FE CO of up to 95% at a CO partial current density close to 600 mA cm −2 . Density functional theory (DFT) calculations suggest a synergetic effect between Fe–Ni pairs facilitating *COOH intermediate formation and *CO desorption simultaneously during CO 2 to CO conversion. This is key to breaking the linear scaling relationship of conventional single-metal site catalysts during the CO 2 reduction reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Synthesis and characteristics of porous ceramic tubes: a comparison of centrifugal casting and cold isostatic pressing methods

Short porous ceramic tubes in small quantities are needed for membrane-related research and development efforts and can be synthesized by centrifugal casting (CC) or cold isostatic pressing (CIP) methods. Here, this work evaluates the characteristics of porous ceramic tubes prepared by both methods and provides a strategy for selecting the proper method for ceramic tube fabrication, depending on its application. Samarium-doped ceria (SDC) with an average crystallite size of 10 nm was synthesized by a citrate method and used to make porous SDC tubes by the CC and CIP methods under different conditions. Porous SDC tubes were prepared from an aqueous suspension of the SDC powder with polyvinyl alcohol (PVA) using a cylindrical metallic mold, centrifugated at 4000–6000 rpm, followed by sintering in 1200–1500 °C. SDC tubes were also made by the CIP method from the SDC powder placed inside a cylindrical rubber bag followed by isostatic compression at 1379 bar. The pore structure of the SDC tubes was characterized by helium permeation and liquid nitrogen Archimedes method. Due to high compression pressure giving a low porosity green tube, the CIP method with lower sintering temperature produces SDC tubes with much lower porosity and average pore size and similar tortuosity compared to the CC methods. The CIP method should be used to prepare low porosity or dense ceramic tubes, and the CC method should be used for preparing high-porosity ceramic tubes or tubes with pore gradient tube wall.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Developing Platinum-Group-Metal-Free Catalysts for Oxygen Reduction Reaction in Acid: Beyond the Single Metal Site

This project is to develop M (x) -N-C catalysts with dense multiple metal center (MMC) sites to meet the DOE 2025 activity target of 0.044 mA/cm 2 at 0.9 V IR-free ., as well as other goals such as durability. We have made important contributions to both catalyst development and fundamental understandings of the active sites in M-N-C catalysts in this project. We successfully made M (x) -N-C catalysts with some multiple metal center (MMC) sites by combining ionothermal carbonization with chemical vapor deposition (CVD). These catalysts, however, are not as active as the most active single-atom Fe-N-C catalysts made by the similar CVD process, owing likely to the low site density and the presence of inorganic Fe species such as iron carbides and nanoparticles. The most significant accomplishments we achieved in this project are: (1) we unraveled the formation pathway of Fe-N 4 sites during pyrolysis step-by-step and identified the trans-metalation mechanism, in collaboration with Deborah Myers and her colleagues at Argonne National Laboratory (ANL); (2) inspired by this finding, we pioneered the CVD synthesis of M-N-C catalysts (M = Mn, Fe, and Co), in which the Fe-N-C catalyst by CVD demonstrated an ORR activity of 33 mA/cm 2 at 0.9 V in H 2 -O 2 proton exchange membrane fuel cells (PEMFCs), very close to the ultimate goal of 35 mA/cm 2 of our project. This catalyst is the first Fe-N-C catalyst that contains only D1 sites without the D2 sites; whereas D1 and D2 sites have been always identified by Mossbauer in previous Fe-N-C catalysts. This finding helps to understand what the D1 and D2 sites are and their roles in catalyzing the ORR. (3) by improving the mass transport of the carbon matrix prior to the CVD process, the revised Fe-N-C catalyst made by CVD delivered a maximum power density of 0.53 W/cm 2 in H 2 -air PEMFCs. The improvement strategy was partly inspired by the computational modeling work by Adam Weber from LBNL, the Co-PI of this project, by developing, coding, and exercising a continuum level model of transport phenomena within a PGM-free catalyst layer. The model demonstrated that local resistances combined with limited site density of the PGM-free catalyst can result in limiting currents and poor polarization performance. The model also gave design guidance for impact of ECSA and overall catalyst-layer thickness. However, both Fe-N-C and Co-N-C catalysts developed by CVD showed poor durability in PEMFCS, in comparison with the traditional M-N-C catalysts synthesized via regular pyrolysis process. Consequently, we did not achieve the proposed durability targets. Despite so, we believe the FeNC-CVD catalysts with the poor durability and D1 sites only provides an excellent platform to understand the degradation mechanism of Fe-N-C in PEMFCs, the most important challenge in the development of M-N-C catalysts.

08 HYDROGEN↗