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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 361 records · Page 20

Selective ion transport through hydrated micropores in polymer membranes

Abstract Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis 1 , redox flow batteries 2 , fuel cells 3 and electrolysers 4,5 . Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state 6 , they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate their hydration capacity and pore swelling. Modulation of the hydrated micropore size (less than two nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoring approach provides a promising avenue to membranes with precisely controlled ionic and molecular transport functions.

Science & Technology - Other Topics↗

Nanoscale Li, Na, and K ion-conducting polyphosphazenes by atomic layer deposition

A key trailblazer in the development of thin-film solid-state electrolytes has been lithium phosphorous oxynitride (LiPON), the success of which has led to recent progress in thin-film ion conductors. Here we compare the structural, electrochemical, and processing parameters between previously published LiPON and NaPON ALD processes with a novel ALD process for the K analogue potassium phosphorous oxynitride (KPON). In each ALD process, alkali tert-butoxides and diethylphosphoramidate are used as precursors. To understand the ALD surface reactions, this work proposes a reaction mechanism determined by in-operando mass spectrometry for the LiPON process as key to understanding the characteristics of the APON (A = Li, Na, K) family. As expected, NaPON and LiPON share similar reaction mechanisms as their structures are strikingly similar. KPON, however, exhibits similar ALD process parameters but the resulting film composition is quite different, showing little nitrogen incorporation and more closely resembling a phosphate glass. Due to the profound difference in structure, KPON likely undergoes an entirely different reaction mechanism. Furthermore, this paper presents a comprehensive summary of ALD ion conducting APON films as well as a perspective that highlights the versatility of ALD chemistries as a tool for the development of novel thin film ion-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application-driven synthesis and characterization of hexagonal boron nitride deposited on metals and carbon nanotubes

Hexagonal boron nitride (h-BN) is unique among two-dimensional materials, with a large band gap (~6 eV) and high in-plane thermal conductivity (>400 W m -1 K -1 ), second only to diamond among electrical insulators. Many studies to date have relied on exfoliated h-BN, however, for large-scale applications the material must be synthesized by methods such as chemical vapor deposition (CVD). Here, we first investigate single-layer h-BN synthesized by CVD on single crystal platinum (Pt), comparing these films with h-BN deposited on more commonly used polycrystalline Pt and Cu. The h-BN film grown on single crystal Pt has the lowest surface roughness and best spatial homogeneity, and our electrochemical transfer process allows the Pt to be reused with no measurable degradation. Additionally, we also demonstrate direct capping of carbon nanotubes (CNTs) with as-grown h-BN, but we find that the direct growth partly degrades the CNT electrical conductivity. On the other hand, we show that transferred monolayer h-BN can serve as an ultrathin barrier which protects MoS2 from damage at high temperatures and discuss other applications that take advantage of the conformal h-BN deposition.

2D materials↗

Refinement of Salt Dissolution Inhibitor Requirements (Final Report)

At Savannah River Site (SRS), High-Level Waste is stored in below-grade carbon steel tanks. This waste in part consists of sludge, salt cake, and/or supernate. Preparation of this waste for future processing involves dissolution of the salt cake layer. The salt dissolution process can create conditions that leave the carbon steel tanks susceptible to localized corrosion. The salt to be dissolved contains high concentrations of nitrate, that once released, create an environment that may be conducive to pitting corrosion and/or stress corrosion cracking (SCC) of carbon steel. The salt dissolution process also liberates interstitial liquid trapped between the salt crystals. This liquid is initially high in nitrite and hydroxide concentration. High pH and greater ratios of nitrite to nitrate act as inhibitors to minimize corrosion of carbon steel in high nitrate environments. However, as dissolution proceeds, the concentration of nitrate will increase, while the hydroxide and nitrite concentration of the interstitial liquid will deplete and become insufficient to prevent the onset of corrosion attack. Tank blending and addition of inhibitors are used to ensure adequate concentrations of hydroxide and nitrite. However, this is not desirable during salt dissolution as it can reduce process efficiency and increase the amount of waste that needs processing. It has been proposed that these corrosion control limits be revisited to evaluate the corrosion susceptibility of carbon steel in environments that more closely resemble current operating conditions at SRS. An experimental matrix was designed to evaluate the use of the pitting factor for supernate chemistries characteristic to SRS, particularly during the salt dissolution process. Two electrochemical methods were identified to determine the susceptibility of A537 and A285 low-carbon steels to pitting corrosion with this chemistry envelope at temperatures up to 75 °C. The predominant electrochemical test method was Cyclic Potentiodynamic Polarization (CPP) studies. Through CPP, the pitting factor was used, based on Hanford Site corrosion studies, to accurately identify pitting susceptibility within the compositional range studied with some conservatism. Additionally, sulfate was determined to have no statistically significant influence, at concentrations up to 0.6 M, on pitting behavior in more concentrated solutions where other aggressive species govern pitting susceptibility. Where CPP was inconclusive, Modified ASTM G192 was successfully used to evaluate pitting susceptibility conditions and allowed for a pass/fail result to be determined. In all cases, the pitting factor was determined to be applicable to the simulants tested, with this metric accurately predicting incidences in which pitting occurred. Based upon the findings in this work, a pitting factor of 1.2 is being proposed to build in a safety factor and remain consistent with the Hanford Site approach. Additionally, a minimum pH limit of 12 is proposed to ensure carbon steel passivity and localized corrosion the primary degradation mechanism. Susceptibility to SCC was evaluated using a reduced matrix of tests at 75 °C. No failures due SCC were observed at open circuit. In addition, tests polarized anodically by 200 mV only resulted in failures for trials with pitting factors less than 0.86. However, a test with a passing condition based upon the pitting factor metric (pitting factor = 1.40) did exhibit a failure with an applied potential of +300 mV vs. OCP. This result is contrary to the prediction based upon the pitting factor, however, a polarization of 300 mV, or even 200 mV, from open circuit is substantial. The relationship between these testing parameters and service environment/conditions and the desired level of conservatism in the metric should be further evaluated in the determination of the significance of this result. While the pitting factor accurately predicted susceptibility to SCC at temperatures up to 75 °C and with positive overpotentials up to 200 mV, the relatively small sample matrix and failure of a passing pitting factor with a 300 mV polarization resulted in an inconclusive determination of whether the pitting factor may be used for predicting susceptibility to SCC at temperatures between 50 °C and 75 °C. As such, additional testing is recommended to evaluate the validity of the pitting factor for SCC susceptibility prediction at temperatures between 50 °C and 75 °C.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Techno-Economic Analysis of a Thermally Integrated Solid Oxide Fuel Cell and Compressed Air Energy Storage Hybrid System

Natural-gas-fueled solid oxide fuel cell (SOFC) systems have the potential for high-efficiency conversion of carbon to power due to the underlying electrochemical conversion process while readily facilitating carbon capture through the separation of the fuel and oxidant sources. Compressed air energy storage (CAES) technology can potentially store significant quantities of energy for later use with a high round-trip efficiency and lower cost when compared with state-of-the-art battery technology. The base load generation capability of SOFC can be coupled with CAES technology to provide a potentially flexible, low-carbon solution to meet the fluctuating electricity demands imposed by the increasing share of intermittent variable renewable energy (VRE) production. SOFC and CAES can be hybridized through thermal integration to maximize power output during periods of high electrical demand and then store power when either demand is low or renewable generation reduces power prices. The techno-economics of a low-carbon hybrid SOFC and CAES system was developed and investigated in the present study. The proposed hybrid system was found to be cost-competitive with other power-generating base-load facilities when power availability was considered. The hybrid system shows increased resilience to changes in a high VRE grid market scenario.

25 ENERGY STORAGE↗

Development of uniform and predictable battery materials for nickel-cadmium aerospace cells

Battery materials and manufacturing methods were analyzed with the aim of developing uniform and predictable battery plates for nickel cadmium aerospace cells. A study is presented for the high temperature electrochemical impregnation process for the preparation of nickel cadmium battery plates. This comparative study is set up as a factorially designed experiment to examine both manufacturing and operational variables and any interaction that might exist between them. The manufacturing variables in the factorial design include plaque preparative method, plaque porosity and thickness, impregnation method, and loading, The operational variables are type of duty cycle, charge and discharge rate, extent of overcharge, and depth of discharge.

Source record↗

Moisture-temperature degradation in module encapsulants: The general problem of moisture in photovoltaic encapsulants

A general research approach was outlined toward understanding water-module interactions and the influence of temperature involving the need to: quantify module performance loss versus level of accumulated degradation, establish the dependence of the degradation reaction rate on module moisture and temperature levels, and determine module moisture and temperature levels in field environments. These elements were illustrated with examples drawn from studies of the now relatively well understood module electrochemical degradation process. Research data presented include temperature and humidity-dependent equilibrium leakage current values for multiparameter module material and design configurations. The contributions of surface, volume, and interfacial conductivities was demonstrated. Research directions were suggested to more fully understand the contributions to overall module conductivity of surface, volume, and interfacial conductivities over ranges of temperature and relative humidity characteristic of field environments.

Mon, G. R.↗

New secondary batteries utilizing electronically conductive polymer cathodes

The objectives are to optimize the transport rates in electronically conductive polypyrrole films by controlling the morphology of the film and to assess the utility of these films as cathodes in a lithium/polypyrrole secondary battery. During this research period, a better understanding was gained of the fundamental electrochemical switching processes within the polypyrrole film. Three publications were submitted based on the work completed.

Martin, Charles R.↗

Electrodeposited Zinc-Nickel as an Alternative to Cadmium Plating for Aerospace Application

Corrosion evaluation studies were conducted on 4130 alloy steel samples coated with electrodeposited zinc-nickel and samples coated with electrodeposited cadmium. The zinc nickel was deposited by the selection electrochemical metallizing process. These coated samples were exposed to a 5-percent salt fog environment at 35 plus or minus 2 C for a period ranging from 96 to 240 hours. An evaluation of the effect of dichromate coatings on the performance of each plating was conducted. The protection afforded by platings with a dichromate seal was compared to platings without the seal. During the later stages of testing, deposit adhesion and the potential for hydrogen entrapment were also evaluated.

Mcmillan, V. C.↗

Electron microscopy study of the iron meteorite Santa Catharina

A characterization of the microstructural features of Santa Catharina (SC) from the millimeter to submicron scale is presented. The same specimen was examined using an optical microscope, a scanning electron microscope, an electron probe microanalyzer, and an analytical electron microscope. Findings include the fact that SC metal nodules may have different bulk Ni values, leading to different microstructures upon cooling; that SC USNM 6293 is the less corroded sample, as tetrataenite exists as less than 10 nm ordered domains throughout the entire fcc matrix (it is noted that this structure is the same as that of the Twin City meteorite and identical to clear taenite II in the retained taenite regions of the octahedrites); that SC USNM 3043 has a more complicated microstructure due to corrosion; and that the low Ni phase of the cloudy zone was selectively corroded in some areas and formed the dark regions, indicating that the SC meteorite corrosion process was electrochemical in nature and may involve Cl-containing akaganeite.

Zhang, J.↗

Stirling Space Engine Program: Final Report - Volume 1

The objective of this program was to develop the technology necessary for operating Stirling power converters in a space environment and to demonstrate this technology in full-scale engine tests. Hardware development focused on the Component Test Power Converter (CTPC), a single cylinder, 12.5-kWe engine. Design parameters for the CTPC were 150 bar operating pressure, 70 Hz frequency, and hot-and cold-end temperatures of 1050 K and 525 K, respectively. The CTPC was also designed for integration with an annular sodium heat pipe at the hot end, which incorporated a unique "Starfish" heater head that eliminated highly stressed brazed or weld joints exposed to liquid metal and used a shaped-tubed electrochemical milling process to achieve precise positional tolerances. Selection of materials that could withstand high operating temperatures with long life were another focus. Significant progress was made in the heater head (Udimet 700 and Inconel 718 and a sodium-filled heat pipe); the alternator (polyimide-coated wire with polyimide adhesive between turns and a polyimide-impregnated fiberglass overwrap and samarium cobalt magnets); and the hydrostatic gas bearings (carbon graphite and aluminum oxide for wear couple surfaces). Tests on the CTPC were performed in three phases: cold end testing (525 K), engine testing with slot radiant heaters, and integrated heat pipe engine system testing. Each test phase was successful, with the integrated engine system demonstrating a power level of 12.5 kWe and an overall efficiency of 22 percent in its maiden test. A 1500-hour endurance test was then successfully completed. These results indicate the significant achievements made by this program that demonstrate the viability of Stirling engine technology for space applications.

Dhar, Manmohan↗

Development of Thick-Film Thermoelectric Microcoolers Using Electrochemical Deposition

Advanced thermoelectric microdevices integrated into thermal management packages and low power, electrical source systems are of interest for a variety of space and terrestrial applications. By shrinking the size of the thermoelements, or legs, of these devices, it becomes possible to handle much higher heat fluxes, as well as operate at much lower currents and higher voltages that are more compatible with electronic components. The miniaturization of state-of-the-art thermoelectric module technology based on Bi2Te3 alloys is limited due to mechanical and manufacturing constraints for both leg dimensions (100-200 gm thick minimum) and the number of legs (100-200 legs maximum). We are investigating the development of novel microdevices combining high thermal conductivity substrate materials such as diamond, thin film metallization and patterning technology, and electrochemical deposition of thick thermoelectric films. It is anticipated that thermoelectric microcoolers with thousands of thermocouples and capable of pumping more than 200 W/sq cm over a 30 to 60 K temperature difference can be fabricated. In this paper, we report on our progress in developing an electrochemical deposition process for obtaining 10-50 microns thick films of Bi2Te3 and its solid solutions. Results presented here indicate that good quality n-type Bi2Te3, n-type Bi2Te(2.95)Se(0.05) and p-type Bi(0.5)Sb(1.5)Te3 thick films can be deposited by this technique. Some details about the fabrication of the miniature thermoelements are also described.

Fleurial, J.-P.↗

Formate as an Energy Source to Allow Sugar Fermentation with No Net CO2 Generation: Integration of Electrochemistry with Fermentation

This poster summarizes at a high-level the scope of various groups' work on Formate as an Energy Source to Allow Sugar Fermentation with No Net CO2 Generation: Integration of Electrochemistry with Fermentation. The goals of this research are to develop and demonstrate an integrated process that electrochemically generates formate from CO2 and use the formate as an energy source for the fermentation of sugars to fatty acid methyl esters (FAME) without net CO2 generation wherein formate provides reducing equivalents for sugar fermentation and a chemical looping reactor system takes advantage of intermittent low-cost electricity from wind and solar resources.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗

Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries

To understand the origins of failure and limited cycle life in lithium-ion batteries (LIBs), it is imperative to quantitatively link capacity-fading mechanisms to electrochemical and chemical processes. This is extremely challenging in real systems where capacity is lost during each cycle to both active material loss and solid electrolyte interphase (SEI) evolution, two indistinguishable contributions in traditional electrochemical measurements. Here, we have used a model system in combination with (1) precision measurements of the overall Coulombic efficiency via electrochemical experiments and (2) x-ray reflectivity measurements of the active material losses. The model system consisted of a 515 Å thick amorphous silicon (a-Si) thin film on silicon carbide in half-cell geometry using a carbonate electrolyte with LiPF6 salt. This approach allowed us to quantify the capacity lost during each cycle due to SEI evolution. Combined with electrochemical analysis, we identify SEI growth as the major contribution to capacity fading. Specifically, the continued SEI growth results in increasing overpotentials due to increased SEI resistance, and this leads to lower extent of lithiation when the cutoff voltage is reached during lithiation. Our results suggest that SEI grows more with increased time spent at low voltages where electrolyte decomposition is favored. Finally, we extracted a proportionality constant for SEI growth following a parabolic growth law. Our methodology allows for the quantitative determination of lithium-ion loss mechanisms in LIBs by separately tracking lithium ions within the active materials and the SEI and offers a powerful method of quantitatively understanding LIB loss mechanisms.

25 ENERGY STORAGE↗

Science of Scale-Up: Accelerating chemical manufacturing technology development workshop report

The Science of Scale-Up: Accelerating chemical manufacturing technology development workshop report outlines key insights and actionable recommendations for accelerating the scale-up of disruptive chemical manufacturing technologies. Convened in October 2024, the workshop brought together approximately fifty experts from academia, industry, national laboratories, and government agencies to address the barriers and solutions for maturing technologies from proof-of-concept to commercialization. The report identifies seven critical themes for enabling faster scale-up. These themes were explored through general discussions and breakout sessions focused on three specific chemical manufacturing technologies—electrochemical, thermochemical, and biological conversion processes. The findings emphasize the importance of interdisciplinary collaboration, robust funding mechanisms, and shared resources to overcome technical barriers and accelerate technology deployment. The report also highlights technology-specific challenges and opportunities, including the need for advanced materials, scalable manufacturing processes, and integrated testing environments. For electrochemical manufacturing processes, durability and material optimization are key priorities, while thermochemical processes require novel reactor designs and better supply chain integration. Biological conversion processes face hurdles in strain engineering, reactor design, and process integration. Across all technologies, the workshop emphasized the importance of leveraging computational tools, standardized protocols, and collaborative networks to address knowledge gaps and technical barriers. By acting on these insights, stakeholders can reduce the timeline for scaling up critical chemical manufacturing technologies, ensuring their timely impact on manufacturing competitiveness, and environmental sustainability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗