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At least 307 records · Page 17

Solid State Laser Technology Development for Atmospheric Sensing Applications

NASA atmospheric scientists are currently planning active remote sensing missions that will enable global monitoring of atmospheric ozone, water vapor, aerosols and clouds as well as global wind velocity. The measurements of these elements and parameters are important because of the effects they have on climate change, atmospheric chemistry and dynamics, atmospheric transport and, in general, the health of the planet. NASA will make use of Differential Absorption Lidar (DIAL) and backscatter lidar techniques for active remote sensing of molecular constituents and atmospheric phenomena from advanced high-altitude aircraft and space platforms. This paper provides an overview of NASA Langley Research Center's (LaRC's) development of advanced solid state lasers, harmonic generators, and wave mixing techniques aimed at providing the broad range of wavelengths necessary to meet measurement goals of NASA's Earth Science Enterprise.

Barnes, James C.↗

Towards a high-performance garnet-based solid-state Li metal battery: A perspective on recent advances

Garnet-based solid-state Li metal batteries have been widely considered one of the most promising next-generation energy storage systems. However, the performance of these batteries is plagued by various limitations caused by the solid-state electrolyte (SSE). The poor wetting of lithium on the garnet surface diminishes the contact between the anode and electrolyte, leading to extremely high anode interfacial resistance. Similarly, the point-to-point contact between the cathode and electrolyte leads to high impedance on the cathode side. Moreover, although the SSE serves a firm barrier separating the anode and cathode, lithium dendrites can still grow through, causing a short circuit. Lastly, the solid/solid interface cannot be well maintained under cycling at high current density and capacity. Recently, remarkable progress has been achieved in garnet electrolyte to resolve these problems towards the aim of a high-performance solid-state Li metal battery. In this perspective, we highlight various recent advances in the field of garnet-based solid-state battery, including improving the anode/electrolyte interface, lithium dendrite detection, reducing cathode impedance, and electrolyte architecture design.

25 ENERGY STORAGE↗

Current limitations of solid-state NMR in carbohydrate and cell wall research

High-resolution investigation of cell wall materials has emerged as an important application of biomolecular solid-state NMR (ssNMR). Multidimensional correlation experiments have become a standard method for obtaining sufficient spectral resolution to determine the polymorphic structure of carbohydrates and address biochemical questions regarding the supramolecular organization of cell walls. Here, using plant cellulose and matrix polysaccharides as examples, we will review how the multifaceted complexity of polysaccharide structure is impeding the resonance assignment process and assess the available biochemical and spectroscopic approaches that could circumvent this barrier. We will emphasize the ineffectiveness of the current methods in reconciling the ever-growing dataset and deriving structural information. We will evaluate the protocols for achieving efficient and homogeneous hyperpolarization across the cell wall material using magic-angle spinning dynamic nuclear polarization (MAS-DNP). Critical questions regarding the line-broadening effects of cell wall molecules at cryogenic temperature and by paramagnetic biradicals will be considered. Finally, the MAS-DNP method will be placed into a broader context with other structural characterization techniques, such as cryo-electron microscopy, to advance ssNMR research in carbohydrate and cell wall biomaterials.

09 BIOMASS FUELS↗

Design Considerations for Practical Li-S Battery Components for Electric Aviaiton

The development of high-energy, high-safety, and high-power batteries beyond electric automobile requirements is vital for future electric aviation applications. The transition to non-volatile solid-state electrolytes (SSE) promises many advantages over traditional flammable liquid electrolytes, and may also be an enabling technology for next generation chemistries. However, significant manufacturing challenges must be overcome before the adoption of such technology. Electrolytes developed in this study were produced as sulfide-polymer composites with densified thicknesses between 20-30 microns using a tape-casting technique and elastomer binder [1]. The composites were determined to retain reasonable ionic conductivity with improved flexibility and scalability critical for practical manufacturing of such cells. Films were produced 10-15 times thinner than comparable bulk powder electrolytes and within the range of commercial polyolefin separators (25 micron) used in commercial liquid containing lithium-ion cells. Composite conductivities were maintained above 0.2mS/cm, which holds promise for future electric aviation applications. Processing techniques are investigated to further improve electrochemical performance.

battery↗

Solid-state Laser Development for the in Situ Spectroscopic Europa Explorer Instrument

The in Situ Spectroscopic Europa Explorer (iSEE) instrument is an ultra-compact laser-enabled Raman spectrometer instrument that meets the top-level science requirements for multiple future planetary in situ missions to explore the surface and atmospheric chemistry of planetary bodies across the Solar System. Enceladus, Europa, the Moon, Mars, and Venus are some of the primary targets for future NASA missions to search for extraterrestrial life and potentially habitable environments beyond Earth, further our understanding of the timing and formation of the Solar System and identify potentially viable economic resources such as water and/or valuable metal assets. We report on the advancement and space flight qualification of a compact, robust, solid-state laser operating at 515 nm that serves as the excitation source for the iSEE investigation. The iSEE instrument is being developed under a NASA Maturation of Instruments for Solar System Exploration (MatISSE) program. The iSEE laser is a diode pumped 1030 nm Yb:YAG microchip laser with a second harmonic generator to achieve an output wavelength of 515 nm and coupled to a multi-mode fiber for delivery to the Raman spectrometer probe. The fundamental 1030 nm laser operates at a pulse repetition frequency (PRF) of 1-10 kHz with pulse energy of 95 μJ and ~800 ps pulse width. A 15 mm long Type II KTP crystal is used for second harmonic generation from 1030 nm to 515 nm. The residual fundamental 1030 nm is separated from the 515 nm beam using a pair of dichroic filters. A focusing lens couples the 515 nm beam to the optical fiber to produce an output laser pulse energy of 20 μJ. A custom vacuum fiber feedthrough assembly was designed with two 105 μm core fibers, and two 200 μm core fibers. One fiber is needed for coupling the laser to the iSEE instrument, and the additionally fibers provide redundancy and design flexibility. The laser enclosure is pressurized with >1 atm of clean dry air. The laser has been designed to minimize the size, weight, and power (SWaP) for a lander instrument with minimal resources. The laser will go through environmental testing including vibration and thermal vacuum testing for space flight qualification. Here we discuss the design, trade studies, performance, and environmental qualificationtesting of the iSEE laser.

Solid state laser, Raman spectrometer, visible las↗

Solid-State Laser Development for the in Situ Spectroscopic Europa Explorer Instrument

The in Situ Spectroscopic Europa Explorer (iSEE) instrument is an ultra-compact laser-enabled Raman spectrometer instrument that meets the top-level science requirements for multiple future planetary in situ missions to explore the surface and atmospheric chemistry of planetary bodies across the Solar System. Enceladus, Europa, the Moon, Mars, and Venus are some of the primary targets for future NASA missions to search for extraterrestrial life and potentially habitable environments beyond Earth, further our understanding of the timing and formation of the Solar System, and identify potentially viable economic resources such as water and/or valuable metal assets. We report on the advancement and space flight qualification of a compact, robust, solid-state laser operating at 515 nm that serves as the excitation source for the iSEE investigation.

Solid state laser, Raman spectrometer, visible las↗

Advances in solid-state NMR for the studies of mesoporous solids: fast magic spinning and dynamic nuclear polarization

Here, this review provides an up-to-date account of the development of two solid-state (SS)NMR methods for enhancing resolution and sensitivity, fast magic angle spinning (MAS) and dynamic nuclear polarization (DNP), and the resulting progress in surface science. We demonstrate the high resolution and efficiency that can be achieved by using two-dimensional homo- and heteronuclear correlation experiments with small rotors capable of MAS at rates exceeding 100 kHz. DNP has offered significant enhancements in signal sensitivity and allowed access to nuclei and experiments that are beyond the limits of conventional SSNMR. The continuing progress in fast MAS and DNP methodologies in recent years generated an unprecedented shift in SSNMR’s capabilities in the studies of surface and interface regions of solids, especially mesoporous supports and catalysts. We give numerous examples of recent applications and discuss the prospects for further improvements of both methods.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Determination of the chemical shift tensor anisotropy and asymmetry of strongly dipolar coupled protons under fast MAS

Orientationally-dependent interactions such as dipolar coupling, quadrupolar coupling, and chemical shift anisotropy (CSA) contain a wealth of spatial information that can be used to elucidate molecular conformations and dynamics. To determine the sign of the chemical shift tensor anisotropy parameter (δ aniso ), both the |m| = 1 and |m| = 2 components of the CSA need to be symmetry allowed, while the recoupling of the |m| = 1 term is accompanied with the reintroduction of homonuclear dipolar coupling components. Therefore, previously suggested sequences which solely recouple the |m| = 2 term cannot determine the sign a 1 H's δ aniso in a densely-coupled network. Here, we demonstrate the CSA recoupling of strongly dipolar coupled 1 H spins using the $Cn^1_n (90_{0}360_{180}540_{0}360_{180}90_{0})$ sequence. This pulse scheme recouples both the |m| = 1 and |m| = 2 CSA terms but the scaling factors for the homonuclear dipolar coupling terms are zeroed. Consequently, the sequence is sensitive to the sign of δ aniso but is not influenced by homonuclear dipolar interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Plasticizer Content and Ceramic Addition on Electrochemical Properties of Cross-Linked Polymer Electrolyte

The development of a safe electrolyte is the key to improving energy density for next generation lithium batteries. In this work, UV-crosslinked poly(ethylene oxide) (PEO) -based polymer and composite electrolytes are systematically investigated on their ionic conductivity, mechanical and electrochemical properties. The polymer electrolytes are plasticized with non-flammable linear short-chain PEO. In the composite electrolytes, a doped lithium aluminum titanium phosphate (LATP) ceramic, LICGC™, is used as the ceramic filler. It is found that the addition of the plasticizer leads to a tradeoff between ion transport and mechanical properties. In contrast, the addition of ceramic fillers improves both the ionic conductivity and mechanical properties. The sample with 20 wt% of LICGC™ shows a conductivity of ~0.6 mS cm –1 at 50 °C. This sample also demonstrates much longer cycle life than the neat polymer electrolyte in Li platting/stripping test with a capacity of 1 mAh cm –2 . Further, a full cell made with this composite electrolyte against Li metal anode and high voltage LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode shows 94% capacity retention after 30 cycles, compared to 58% capacity retention with the neat polymer electrolyte. These results demonstrate that a hybrid of polymer/ceramic/non-flammable plasticizer is a promising path to high energy density, high voltage lithium batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Temperature Proton-Conducting Ceramics Developed

High-temperature protonic conductors (HTPC) are needed for hydrogen separation, hydrogen sensors, fuel cells, and hydrogen production from fossil fuels. The HTPC materials for hydrogen separation at high temperatures are foreseen to be metal oxides with the perovskite structure A(sup 2+)B(sup 4+)C(sup 2-, sub 3) and with the trivalent cation (M(sup 3+)) substitution at the B(sup 4+)-site to introduce oxygen vacancies. The high affinity for hydrogen ions (H(sup +)) is advantageous for protonic transport, but it increases the reactivity toward water (H2O) and carbon dioxide (CO2), which can lead to premature membrane failure. In addition, there are considerable technological challenges related to the processing of HTPC materials. The high melting point and multi-cation chemistry of HTPC materials creates difficulties in in achieving high-density, single-phase membranes by solid-state sintering. The presence of secondary phases and grain-boundary interfaces are detrimental to the protonic conduction and environmental stability of polycrystalline HTPC materials.

Sayir, Ali↗

AstroBiology Explorer Mission Concepts (ABE/ASPIRE)

The AstroBiology Explorer (ABE) and the Astrobiology Space InfraRed Explorer (ASPIRE) Mission Concepts are two missions designed to address the questions (1) Where do we come from? and (2) Are we alone? as outlined in NASA s Origins Program using infrared spectroscopy to explore the identity, abundance, and distribution of molecules of astrobiological importance throughout the Universe. The ABE mission s observational program is focused on six tasks to: (1) Investigate the evolution of ice and organics in dense clouds and star formation regions, and the young stellar/planetary systems that form in them; (2) Measure the evolution of complex organic molecules in stellar outflows; (3) Study the organic composition of a wide variety of solar system objects including asteroids, comets, and the planets and their satellites; (4) Identify organic compounds in the diffuse interstellar medium and determine their distribution , abundance, and change with environment; (5) Detect and identify organic compounds in other galaxies and determine their dependence on galactic type; and (6) Measure deuterium enrichments in interstellar organics and use them as tracers of chemical processes. The ASPIRE mission s observational program expands upon ABE's core mission and adds tasks that (7) Address the role of silicates in interstellar organic chemistry; and (8) Use different resolution spectra to assess the relative roles and abundances of gas- and solid-state materials. ABE (ASPIRE) achieves these goals using a highly sensitive, cryogenically-cooled telescope in an Earth drift-away heliocentric orbit, armed with a suite of infrared spectrometers that cover the 2.5-20(40) micron spectral region at moderate spectral resolution (R>2000). ASPIRE's spectrometer complement also includes a high-resolution (R>25,000) module over the 4-8 micron spectral region. Both missions target lists are chosen to observe a statistically significant sample of a large number of objects of varied types in support of the tasks outline above. The ABE and ASPIRE mission lifetimes are designed to be 14 months and 3 years, respectively, both with significant cryogen and propellant lifetime margins to support an extended observing campaign. The ABE/ASPIRE mission concepts and their supporting Science Teams are led by Principal Investigator Dr. Scott Sandford of NASA s Ames Research Center, with industry partner Ball Aerospace Technologies Ltd., and managed by Jet Propulsion Laboratory. The ABE/ASPIRE Science Operations will be carried out at NASA s Ames Research Center, and the ABE/ASPIRE database will be archived at Caltech/IPAC.

Sandford, Scott↗

A New Complex Borohydride LiAl(BH4)2Cl2

A new mixed alkali metal–aluminum borohydride LiAl(BH4)2Cl2 has been prepared via mechanochemical synthesis from the 2LiBH4–AlCl3 mixture. Structural characterization, performed using a combination of X-ray powder diffraction and solid-state NMR methods, indicates that the LiAl(BH4)2Cl2 phase adopts a unique 3D framework and crystallizes in an orthorhombic structure with the space group C2221, a = 11.6709(6) Å, b = 8.4718(4) Å, c = 7.5114(3) Å. The material shows excellent dehydrogenation characteristics, where hydrogen evolution starts at Tons = 70 °C, releasing approximately 2 wt.% of nearly pure (99.8 vol.%) hydrogen and a very small amount (~0.2 vol.%) of diborane. When compared to halide-free mixed alkali metal–aluminum borohydrides, the presence of Al‒Cl bonding in the LiAl(BH4)2Cl2 structure likely prevents the formation of Al(BH4)3 upon decomposition, thus suppressing the formation of diborane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Superatomic chemistry

Superatoms are atomic clusters with tailored size and composition that mimic the chemistry of atoms in the periodic table. However, unlike the atoms whose chemistry is governed by their valence electron orbitals, the chemistry of superatoms is governed by their highest occupied molecular orbitals. In addition, due to their large size and non-spherical geometry, superatoms can promote unusual reactions and serve as the building blocks of cluster assembled materials with properties very different from conventional materials. This perspective highlights the unique role of superatoms in chemical and material sciences by focusing on superhalogens, which not only possess electron affinities larger than those of halogens but also can be stable when multiply charged. We discuss how these unique features of superhalogens enable noble gas atoms like argon to form chemical bonds at room temperature and zinc to exhibit an oxidation state of +3. Here, the advantages of using superhalogens in the synthesis of water-resistant materials for solar cells, halogen-free electrolytes for solid-state batteries, and multiferroic materials are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The inorganic chemist's guide to actinide radiation chemistry: a review

This review aims to provide an overview of the current state of radiation chemistry with respect to the actinide elements, thorium through californium. Despite the inherent radioactivity of the actinides, only a few studies explore the effects of ionizing radiation on their redox chemistry and surrounding environment. This fundamental knowledge gap, coupled with the current renaissance in actinide-based technologies such as nuclear power, space exploration, and medicine, underscores the importance of research in this interdisciplinary area. This review will focus on the interactions between reactive species formed by radiolysis with actinides and their complexes, offering an inorganic chemist's perspective on research in radiation chemistry. In addition, a thorough discussion of our current understanding of radiation-induced changes in actinide speciation in both aqueous solution and the solid-state will be provided, focusing on changes in oxidation state distribution, complexation, and secondary coordination effects within inorganic materials. Finally, this review will discuss challenges and opportunities for inorganic chemists to explore this unique intersection of fields.

Actinides↗

Towards exact finite temperature electronic structure in solids and molecules (Final Technical Report)

This report describes the University of Iowa portion of a project that is now continuing at Michigan State University. We are developing novel methods, algorithms, and software to enable simulations of molecules and materials at high temperature. This is a key challenge in chemistry and materials science. By refining an approach called Density Matrix Quantum Monte Carlo (DMQMC), we developed faster and more accurate ways to conduct these simulations. These advances will help us understand how temperature affects the behavior of electrons, chemical bonds, and phase transitions in solids and molecules. These breakthroughs are especially important for applications where light and heat drive chemical reactions, superconductivity, and materials used in energy and sensing. In addition, this project involved the development of the open-source HANDE-QMC software package, supporting the broader community in benchmarking and developing finite-temperature electronic structure methods.

36 MATERIALS SCIENCE↗