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Effect of the Nature of Both Cation and Anion Substitution on the Structural Symmetry of Li‐Rich 3 d ‐Metal Chalcogenide Electrodes

Abstract Li‐rich layered chalcogenides have recently led to better understanding of the anionic redox process and its associated high capacity while providing ways to overcome its practical limitations of voltage fade and irreversibility. This study reports on the feasibility of triggering anionic activity in Li 2 TiS 3 , through anionic substitution (Se for S) or cationic substitution (Fe for Ti). Herein, the chalcogenide chemical space is further explored to prepare mono‐substituted Li 1.7 Ti 0.85 Mn 0.45 Ch 3 (Ch = S/Se) and doubly substituted cationic and anionic phases (Li 1.7 Ti 0.85 Fe 0.45 S 3‐z Se z ) which crystallize either in the O3‐ or O1‐type structures depending upon substituents. All series show a bell‐shape capacity variation as function of the transition metal (TM) substitution degree with values up to 240 mAh g −1 . For specific compositions, a structural O3 to O1 phase transition is observed upon Li removal, which is not reversible upon Li re‐insertion due to kinetic limitations and negatively affects long‐term cycling performance. Density functional theory (DFT) calculations confirm the O3/O1 relative stability along the different series and point subtle electronic differences in the TM‐doping, rationalizing the structural and electrochemical behaviors of these phases upon cycling. These findings provide further insights into the link between structural and electronic stability, which is of key importance for designing chalcogenide‐based anionic redox compounds.

Chemistry

2005 NASA Seal/Secondary Air System Workshop

The 2005 NASA Seal/Secondary Air System workshop covered the following topics: (i) Overview of NASA’s new Exploration Initiative program aimed at exploring the Moon, Mars, and beyond; (ii) Overview of the NASA-sponsored Propulsion 21 Project; (iii) Overview of NASA Glenn’s seal project aimed at developing advanced seals for NASA’s turbomachinery, space, and reentry vehicle needs; (iv) Reviews of NASA prime contractor, vendor, and university advanced sealing concepts including tip clearance control, test results, experimental facilities, and numerical predictions; and (v) Reviews of material development programs relevant to advanced seals development. Turbine engine studies have shown that reducing high-pressure turbine (HPT) blade tip clearances will reduce fuel burn, lower emissions, retain exhaust gas temperature margin, and increase range. Several organizations presented development efforts aimed at developing faster clearance control systems and associated technology to meet future engine needs. The workshop also covered several programs NASA is funding to develop technologies for the Exploration Initiative and advanced reusable space vehicle technologies. NASA plans on developing an advanced docking and berthing system that would permit any vehicle to dock to any on-orbit station or vehicle. Seal technical challenges (including space environments, temperature variation, and seal-on-seal operation) as well as plans to develop the necessary “androgynous” seal technologies were reviewed. Researchers also reviewed tests completed for the shuttle main landing gear door seals.

Hypersonic

Ultrasonic Washer–Dryer System for Space Habitats: Design Upgrades and Parabolic Flight Readiness

Clothing makes up nearly 25% of all non-food supplies sent to the International Space Station (ISS). To support sustainable human missions in deep space, NASA’s Life Support and Habitation Systems Focus Area looks to advance technologies to support and improve logistics. Our team is creating a compact ultrasonic clothing washer/dryer system that bypasses traditional limitations and is suitable for space. Thermal drying uses a lot of energy to evaporate water, while our ultrasonic drying method offers a quicker, more efficient alternative. It uses piezoelectric transducers to vibrate textiles at the micron scale, mechanically removing water as cold mist rather than evaporating it. This speeds up drying and reduces energy use, no matter the fabric makeup. This paper details recent upgrades to a full-scale ultrasonic washer–dryer system, readying it for parabolic flight testing. Improvements include an enhanced human–machine interface, better packaging, and optimized performance and control. We also present extensive pre-flight ground tests conducted to ensure reliability and identify potential risks. Collaborating with P&G, we report preliminary cleaning tests using various detergents. These results lay a crucial foundation for the laundry system designed specifically for space. By cutting clothing-related payload and waste by over 97%, this technology supports long-term human exploration missions on the ISS, the Moon, Mars, and beyond.

Ultrasonic

Physics-Based Modeling and Simulation of Emerging Battery Technologies for Aerospace

Recently there is a growing interest in the aviation sector to reduce air and noise pollution. Electrochemical energy storage devices such as batteries coupled with a distributed electric propulsion system can reduce noise concerns as well as emissions and allow the concept of Urban Air Mobility to come to fruition. The battery performance needs to improve considerably compared from current state-of-art Li-ion battery (about 200Wh/Kg) to realize all-electric passenger jet for short flights (up to 690 miles). NASA is exploring lithium-oxygen battery chemistry to power hybrid (battery powered electrical system) and all-electric aircraft for short distance and long-distance flights. Li-O2 is one of the advanced Li-ion technologies that promise to provide specific energy of more than 750Wh/Kg. For this presentation, we present our work on improving power density of Li-O2 batteries through the use of multiphysics simulations. Next, a path is outlined to port these model to simulate performance for a new battery chemistry for space application, Li-CO2. Li-CO2 uses carbon dioxide as the active material instead of oxygen. Although this technology is in its early development, the offers two benefits: it can be used as a CO2 scrubber, as oxygen is one of the by-products on charging, and as a backup or a standalone battery for various Mars or Venus missions, where the carbon dioxide content in the atmosphere is high and need battery to operate at higher temperatures.

Mehta, Mohit

Nuclear–Electronic Orbital General Rate Theory: Predicting Hydrogen Kinetic Isotope Effects in the Deep Tunneling Regime

Hydrogen transfer is a critical component of many chemical and biological processes. The ratio of rate constants for hydrogen and deuterium transfer defines the H/D kinetic isotope effect (KIE), which is a powerful tool for elucidating hydrogen transfer mechanisms. Interpretation of experimental H/D KIEs relies on accurate and affordable computational methods. However, due to their light mass, hydrogen and deuterium can undergo tunneling, which is challenging to describe in multidimensional molecular systems. Herein, we introduce the nuclear–electronic orbital general rate theory (NEO-GRT), which enables the efficient prediction of H/D KIEs based on full-dimensional molecular quantum chemistry calculations. The NEO-GRT approach describes the hydrogen transfer rate constant with a general expression that spans the vibrationally adiabatic and nonadiabatic hydrogen tunneling regimes. The input quantities are computed using NEO density functional theory, which treats the transferring hydrogen or deuterium nucleus quantum mechanically on the same level as the electrons. We investigate two intramolecular proton transfer reactions in organic molecules at temperatures down to 50 K to evaluate the performance of NEO-GRT by comparison to transition state theory and ring-polymer instanton theory. The KIEs computed with NEO-GRT agree with those calculated using ring-polymer instanton theory for the full-dimensional molecular systems at the same level of electronic structure theory. This agreement indicates that NEO-GRT captures the deep hydrogen tunneling effects, in contrast to transition state theory, which neglects such effects. Given its relatively low computational cost, NEO-GRT is a promising approach for predicting H/D KIEs in large organic and organometallic systems.

Hydrogen

Revealing the Roles of CuF 2 /NiF 2 Incorporation in the Electrochemical Performance of FeF 3 Cathodes in Solid‐State Batteries

Mixed metal fluorides have been considered as a promising candidate to lower the voltage hysteresis of conversion-type iron fluoride cathodes, but their cycling stability is limited due to transition metal dissolution and interphase growth in liquid electrolyte batteries. Here, we study the role of incorporating CuF 2 and NiF 2 in the electrochemical performance of FeF 3 cathode in halide-based solid-state batteries to test whether we can transfer the kinetic benefit of low voltage hysteresis to solid-state batteries while using solid electrolyte to eliminate transition metal dissolution and stabilize the interphase. Synchrotron X-ray absorption spectroscopy results indicated the redox reactions are attributed to Cu 0 /Cu + and Fe 0 /Fe 2+ in 25CuF 2 -75FeF 3 and Ni 0 /Ni 2+ and Fe 0 /Fe 3+ in 10NiF 2 -90FeF 3 . While no apparent improvement in electrode kinetics can be observed, the incorporation of CuF 2 and NiF 2 can largely improve the cycling stability of FeF 3 cathodes. In conclusion, the results demonstrate the advantages of using solid-state concept to improve the cycling stability of conversion-type cathodes.

25 ENERGY STORAGE

Technology Assessment and Modelling of Three Terminal Tandem Solar Cells for In-Space Utilization

NASA seeks a sustained human presence on the lunar surface. High-efficiency and resilient energy systems are critical to supporting habitats, scientific outposts, and lunar surface operations. Photovoltaics have long been the backbone of space power systems, transitioning from silicon solar cells to multi-junction III-V solar cells, which now dominate state-of-the-art (SOA) technology. Multi-junction cells achieve high efficiency by layering semiconductors, each absorbing a specific portion of the solar spectrum. However, efficiency gains are increasingly constrained by device physics and manufacturing complexity. Additionally, higher-order junctions pose challenges for accurate modelling and performance characterization due to difficulties in replicating the AM0 spectrum.

solar cells

Expanding Space with Inflatable Softgoods: Roadmap for In-Space Manufacturing of Resilient Space Structures

Overview of inflatable softgoods and their emerging role in enabling large, resilient space habitats and infrastructure. It highlights the advantages of inflatable systems, such as exceptional packing efficiency and scalable habitable volume, while also addressing challenges related to outfitting, complex material behavior, structural design, manufacturing precision, and testing limitations. Core architectural elements of crewed inflatable habitats are described, along with shell layer composition, structural interfaces, and examples of conceptual habitat configurations for transit, lunar, and surface applications. The presentation concludes by outlining key technology shortfalls, including structural health monitoring, ultra‑high‑strength materials, lifetime performance, and integration strategies, emphasizing the need for continued development to support future in‑space manufacturing and exploration missions.

Habitat

Reduced salen in a monomeric Fe complex

We report the first monomeric formally M I transition metal salen complex without ion pairing. A combination of spectroscopy, crystallography, and computations indicates that reduction of an Fe II salen complex gives substantial reduced ligand character. We also present a computational method for accurately predicting 57 Fe Mössbauer parameters of Fe salen complexes.

Feldman, Dana M. [Yale University, New Haven, CT (

Early Progress Toward the Feasibility of the Centrifugal Nuclear Thermal Rocket

The Centrifugal Nuclear Thermal Rocket (CNTR) is a Nuclear Thermal Propulsion (NTP) concept designed to heat propellant directly by the reactor fuel. The primary difference between the CNTR concept and traditional NTP systems is that rather than using traditional solid fuel elements, the CNTR uses liquid fuel with the liquid contained in rotating cylinders by centrifugal force. If the concept can be successfully realized, the CNTR would have a high specific impulse (~1800 seconds) at high thrust, which may enable (i) viable near-term human Mars exploration by reducing round-trip times to 420 days and (ii) direct injection orbits for scientific missions to the Solar System outer planets and potentially Kuiper Belt objects. The CNTR could also use storable propellants such as ammonia, methane, or hydrazine at an Isp of ~900 seconds, enabling long-term in-space storage of a dormant system. Significant engineering challenges must be addressed to establish the technical viability of the CNTR. Research is presently underway to determine resolutions for these engineering challenges. In particular, research has begun on the analytical modeling and simulation of the two-phase heat transfer between the liquid metallic uranium fuel and the gaseous propellant. A paper was presented at the 2021 IAC which described these challenges and the study plan to address them. This paper describes the analytical and experimental progress to date toward resolving these challenges and establishing the engineering feasibility of the CNTR technology.

Nuclear Thermal Propulsion

Three Dimensionally Woven Mid-Density Carbon Phenolic (3MDCP) is a Novel Single Piece Ablative TPS for Extreme Entry Environments

Three Dimensionally Woven Mid-Density Carbon Phenolic (3MDCP) is robust, single piece, carbon phenolic ablative thermal protection system under development at NASA Ames Research Center initially for the Mars Sample Return Earth Entry System (MSR EES). The MSR EES requirements drove the need for TPS with no seams, capable of surviving the highest entry conditions for any NASA Earth return capsule with heat fluxes >2000 W/cm2 and pressures >1.5 atmospheres. To produce 3MDCP required development of new weaving infrastructure to enable weaving of preforms large enough to form into a single piece heatshield. It required development of forming techniques to transform a flat woven panel into a sphere cone shape and enhanced infusion processes to support larger scale infusion of resin into the formed preforms. A rigorous performance testing campaign was conducted to develop and validate the materials thermal response model used to determine the required material thickness and to demonstrate the material can survive the extreme entry conditions. The end of the development effort (end of FY26) will result in a TPS at Technical Readiness Level (TRL) 6 and Manufacturing Readiness Level (MRL) 6+ for the MSR EES mission and a mature system ready to support other missions. This poster will provide a snapshot of where 3MDCP is in its development phase.

Ablator

Planetary and Deep Space Requirements for Photovoltaic Solar Arrays

In the past 25 years, the majority of interplanetary spacecraft have been powered by nuclear sources. However, as the emphasis on smaller, low cost missions gains momentum, more deep space missions now being planned have baselined photovoltaic solar arrays due to the low power requirements (usually significantly less than 100 W) needed for engineering and science payloads. This will present challenges to the solar array builders, inasmuch as planetary requirements usually differ from earth orbital requirements. In addition, these requirements often differ greatly, depending on the specific mission; for example, inner planets vs. outer planets, orbiters vs. flybys, spacecraft vs. landers, and so on. Also, the likelihood of electric propulsion missions will influence the requirements placed on solar array developers. This paper will discuss representative requirements for a range of planetary and deep space science missions now in the planning stages. We have divided the requirements into three categories: Inner planets and the sun; outer planets (greater than 3 AU); and Mars, cometary, and asteroid landers and probes. Requirements for Mercury and Ganymede landers will be covered in the Inner and Outer Planets sections with their respective orbiters. We will also discuss special requirements associated with solar electric propulsion (SEP). New technology developments will be needed to meet the demanding environments presented by these future applications as many of the technologies envisioned have not yet been demonstrated. In addition, new technologies that will be needed reside not only in the photovoltaic solar array, but also in other spacecraft systems that are key to operating the spacecraft reliably with the photovoltaics.

C P Bankston

Spray Forming of NiTi and NiTiPd Shape-Memory Alloys

In the work to be presented, vacuum plasma spray forming has been used as a process to deposit and consolidate prealloyed NiTi and NiTiPd powders into near net shape actuators. Testing showed that excellent shape memory behavior could be developed in the deposited materials and the investigation proved that VPS forming could be a means to directly form a wide range of shape memory alloy components. The results of DSC characterization and actual actuation test results will be presented demonstrating the behavior of a Nitinol 55 alloy and a higher transition temperature NiTiPd alloy in the form of torque tube actuators that could be used in aircraft and aerospace controls.

Aero-Surface Controls

Astrophysical science with a spaceborne photometric telescope

The FRESIP Project (FRequency of Earth-Sized Inner Planets) is currently under study at NASA Ames Research Center. The goal of FRESIP is the measurement of the frequency of Earth-sized extra-solar planets in inner orbits via the photometric signature of a transit event. This will be accomplished with a spaceborne telescope/photometer capable of photometric precision of two parts in 100,000 at a magnitude of m(sub v) = 12.5. To achieve the maximum scientific value from the FRESIP mission, an astrophysical science workshop was held at the SETI Institute in Mountain View, California, November 11-12, 1993. Workshop participants were invited as experts in their field of astrophysical research and discussed the astrophysical science that can be achieved within the context of the FRESIP mission.

Granados, Arno F.

Performance of a Regenerative Fuel Cell System for the Lunar Surface

Regenerative fuel cells (RFCs) are an attractive energy storage solution for lunar missions as a technology capable of providing a higher specific energy (i.e., W∙h/kg) than state-of-the-art packaged Li-ion battery systems. An RFC consists of the (1 & 2) electrochemical stacks (chemical to electrical energy conversion to supply electricity to an external load, i.e. the fuel cell reaction, and electrical to chemical energy conversion of supplied electrical power to dissociate water into hydrogen and oxygen gases, i.e. water electrolysis), (3) fluidic conditioning, (4) reactant storage, (5) avionics, (6) power management and distribution (PMAD), and (7) thermal management. NASA’s Glenn Research Center has designed, assembled, and tested a breadboard RFC sys-tem capable of operating autonomously for multiple simulated lunar day/night cycles in a laboratory environment. The system is comprised of a non-flow through proton exchange membrane (PEM) fuel cell stack and a liquid-anode feed PEM electrolyzer (EZ) stack designed to electrochemically compress the reactants at balanced pressures up to 12.4 MPa (1800 psia). The fluidic conditioning, avionics, PMAD, and thermal management sub-systems are largely comprised of commercial-off-the-shelf components for this system-level development effort. The hardware is controlled by a CubeSat space processor running an operational program based on core flight architecture that can control the RFC hardware autonomously through a state machine with fault monitoring. The testing results highlighted here were completed with the system in an open-loop configuration such that reactants generated through water electrolysis were vented while gas cylinders supplied fuel cell operation. The breadboard operated autonomously, but there were five unplanned transitions to a safe state that required a manual restart after reviewing the data, determining a root cause, and implementing a solution. Four of the transitions were caused by the thermal management subsystem and the fifth was caused by a water management control issue in the EZ sub-system. The RFC system operated for over 550 hours with the final cycle being slightly abbreviated due to reasons unrelated to system performance.

Kerrigan Cain

Performance of a Regenerative Fuel Cell System for the Lunar Surface

Regenerative fuel cells (RFCs) are an attractive energy storage solution for lunar missions as a technology capable of providing a higher specific energy (i.e., W∙h/kg) than state-of-the-art packaged Li-ion battery systems. An RFC consists of the (1 & 2) electrochemical stacks (chemical to electrical energy conversion to supply electricity to an external load, i.e. the fuel cell reaction, and electrical to chemical energy conversion of supplied electrical power to dissociate water into hydrogen and oxygen gases, i.e. water electrolysis), (3) fluidic conditioning, (4) reactant storage, (5) avionics, (6) power management and distribution (PMAD), and (7) thermal management. NASA’s Glenn Research Center has designed, assembled, and tested a breadboard RFC sys-tem capable of operating autonomously for multiple simulated lunar day/night cycles in a laboratory environment. The system is comprised of a non-flow through proton exchange membrane (PEM) fuel cell stack and a liquid-anode feed PEM electrolyzer (EZ) stack designed to electrochemically compress the reactants at balanced pressures up to 12.4 MPa (1800 psia). The fluidic conditioning, avionics, PMAD, and thermal management sub-systems are largely comprised of commercial-off-the-shelf components for this system-level development effort. The hardware is controlled by a CubeSat space processor running an operational program based on core flight architecture that can control the RFC hardware autonomously through a state machine with fault monitoring. The testing results highlighted here were completed with the system in an open-loop configuration such that reactants generated through water electrolysis were vented while gas cylinders supplied fuel cell operation. The breadboard operated autonomously, but there were five unplanned transitions to a safe state that required a manual restart after reviewing the data, determining a root cause, and implementing a solution. Four of the transitions were caused by the thermal management subsystem and the fifth was caused by a water management control issue in the EZ sub-system. The RFC system operated for over 550 hours with the final cycle being slightly abbreviated due to reasons unrelated to system performance.

Kerrigan Cain

Thermally-Choked Combustor Technology

A program is underway to demonstrate the practical feasibility of thermally-choked combustor technology with particular emphasis on rocket propulsion applications. Rather than induce subsonic to supersonic flow transition in a geometric throat, the goal is to create a thermal throat by adding combustion heat in a diverging nozzle. Such a device would have certain advantages over conventional flow accelerators assuming that the pressure loss due to heat addition does not severely curtail propulsive efficiency. As an aid to evaluation, a generalized one-dimensional compressible flow analysis tool was constructed. Simplified calculations indicate that the process is fluid dynamically and thermodynamically feasible. Experimental work is also being carried out in an attempt to develop, assuming an array of practical issues are surmountable, a practical bench-scale demonstrator using high flame speed H2/O2 combustibles.

William H. Knuth

Method of tuning physical properties of thermosets

Polymerization-induced phase separation enables fine control over thermoset network morphologies, yielding heterogeneous structures with domain sizes tunable over 1-100 nm. However, the controlled chain-growth polymerization techniques exclusively employed to regulate morphology at these length scales are unsuitable for most thermoset materials typically formed through step-growth mechanisms. By employing binary mixtures in place of the classic constituents of phase-separating thermosets—resin, curing agent, and secondary polymer—facile tunability over morphology can be achieved through a single compositional parameter. Indeed, this method yields morphologies spanning nano-scale to macro-scale, controlled by the relative reactivities and thermodynamic compatibility of the network components. Due to the connection between chain dynamics and microstructure in these materials, the tunable morphology enables exquisite control over glass transition and other physical and mechanical properties.

Jones, Brad Howard