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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 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

LiMo 8 O 10 : Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

Here, polycrystalline LiMo 8 O 10 was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I4 1 md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7 Li/ 6 Li solid-state NMR. The crystal structure features infinite chains of Mo 4 O 5 (i.e., Mo 2 Mo 4/2 O 6/2 O 6/3 ) as a repeat unit containing edge-sharing Mo 6 octahedra with strong Mo–Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L 3 edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo 8 O 10 is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott’s variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ 1.8 /ρ 300 = 435. LiMo 8 O 10 shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Li 2 GeS 3 : Lithium Ionic Conductor with an Unprecedented Structural Type

Lithium-ion batteries (LIBs) are widely used in electric vehicles, mobile electronic devices, and large-scale stationary energy storage systems. However, their liquid electrolytes present significant safety concerns due to their inherent flammability. To address this, the focus has shifted toward all-solid-state batteries (ASSBs) utilizing inorganic solid electrolytes that promise enhanced safety. In this work, we report the discovery of a new crystal structural type of Li-ion conductor, Li 2 GeS 3 , with a unique structure, synthesized by a solid-state reaction from Li 2 S and GeS 2 . It was first reported in 2000 with an orthorhombic unit cell, but its detailed crystal structure remains veiled. Here, we have unveiled its structure for the first time, employing an ab initio structure determination technique from powder X-ray and time-of-flight neutron diffraction data. The compound has an unprecedented crystal structural type with a hexagonal $P6_1$ symmetry and a unit cell of α = 6.79364(4) Å and c = 17.90724(14) Å. Its structure is comprised of a distorted hexagonal close-packed arrangement of sulfur anions with three asymmetric metal atoms: Li1, Li2, and Ge are in tetrahedral cavities surrounded by sulfur atoms. The ionic conductivity of Li 2 GeS 3 was measured to be 1.63 × 10 –8 S cm –1 at 303 K and 2.45 × 10 –7 S cm –1 at 383 K. Bond valence energy landscape calculations revealed three-dimensional lithium diffusion pathways within the structure. This novel crystal structure in Li 2 GeS 3 holds the potential for developing high-performance ionic conductors through suitable chemical substitution and offers valuable insights into designing new ionic conductors for ASSBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Retention of a Paramagnetic Ground State at Low Temperatures in a Family of Structurally Related U IV Phosphates

A new uranium fluoride phosphate, UFPO4, was synthesized via a mild hydrothermal route and characterized optically, thermally, and magnetically. Two thermal transformation products, U 2 O(PO 4 ) 2 and U IV U VI O 2 (PO 4 ) 2 , were discovered to be structurally related, and were subsequently synthesized for bulk property measurements. All three materials failed to follow Curie–Weiss behavior at low temperatures, attributed to the nearly ubiquitous singlet ground state of U(IV), transitioning into a Curie–Weiss paramagnetic regime at high temperatures. Neutron diffraction experiments were performed on UFPO 4 and U IV U VI O 2 (PO 4 ) 2 in order to characterize this unusual magnetic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Single Crystals of Cubic Rare-Earth Pyrochlore Germanates: RE 2 Ge 2 O 7 (RE = Yb and Lu) Grown by a High-Temperature Hydrothermal Technique

Here, large single crystals of Yb 2 Ge 2 O 7 in the cubic Fd $\bar{3}$ m space group, are synthesized and characterized from a high-temperature hydrothermal method (650°C/200 MPa in 1 M KF). The cubic phase displays spin frustration and possibly nonclassical quantum-spin behavior at low temperature. Furthermore, this is the first report of single crystals of this important phase of size and quality suitable for single-crystal neutron diffraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Na 2 Mn 3 Se 4 : Strongly Frustrated Antiferromagnetic Semiconductor with Complex Magnetic Structure

A new ternary selenide, Na 2 Mn 3 Se 4 , was prepared by a stoichiometric reaction between Na 2 Se 4 and metallic Mn at 923 K. Crystal structure determination revealed a new structure type, built of alternating layers of Na + ions and [Mn 3 Se 4 ] 2– anionic slabs. Band structure calculations indicate that Na 2 Mn 3 Se 4 is an indirect band gap semiconductor with E g = 1.59 eV, although a direct band gap is only marginally larger, at 1.64 eV. The material shows antiferromagnetic (AFM) ordering at 27 K, while the Weiss constant of ~–400 K suggests much stronger nearest-neighbor AFM exchange between the Mn sites. This discrepancy is attributed to the strong spin frustration caused by a triangulated arrangement of the Mn sites in the [Mn 3 Se 4 ] 2– layer. In conclusion, the magnetic frustration leads to the stabilization of a complex AFM ordered structure with non-collinear arrangement of the Mn magnetic moments, as established from neutron diffraction data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation

We present that the ability to probe the structure of a salt solution at the atomic scale is fundamentally important for our understanding of many chemical reactions and their mechanisms. The capability of neutron diffraction to “see” hydrogen (or deuterium) and other light isotopes is exceptional for resolving the structural complexity around the dissolved solutes in aqueous electrolytes. We have made measurements using oxygen isotopes on aqueous nitrate to reveal a small hydrogen-bonded water coordination number (3.9 ± 1.2) around a nitrate oxyanion. This is compared to estimates made using the existing method of nitrogen isotope substitution and those of computational simulations (>5–6 water molecules). The low water coordination number, combined with a comparison to classical molecular dynamics simulations, suggests that ion-pair formation is significant. Finally, this insight demonstrates the utility of experimental diffraction data for benchmarking atomistic computer simulations, enabling the development of more accurate intermolecular potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

First Observation of Low-Temperature Magnetic Transition in CuAgSe

In this Article, the temperature-dependent magnetic properties of CuAgSe pellet sintered from surfactant-free CuAgSe nanoparticles synthesized by a wet chemistry method were investigated in the temperature range of 4–300 K. A magnetic transition between diamagnetism and weak ferromagnetism is observed at around 60–70 K. The results from magnetic measurements under different machines/magnetic fields, room-temperature X-ray photoelectron spectroscopy, and temperature-dependent nuclear magnetic resonance all demonstrate that this magnetic transition is an intrinsic property rather than an effect of impurities. Combining these results with temperature-dependent neutron diffraction, the origin of the weak ferromagnetism is ascribed to a structural crossover-induced canted antiferromagnetism and possible deviation of Cu valence. In conclusion, the transition is strongly dependent on the sintering temperature and pressure, which could induce the structural phase transition.

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

Correction to Unveiling the Role of Al 2 O 3 in Preventing Surface Reconstruction During High-Voltage Cycling of Lithium-Ion Batteries

A correction to this article was necessary to replace the original Figure 2 with the actual data in the revised Figure 2 shown here. An error was made while preparing the graphs from the neutron diffraction analysis software, and panel a was accidentally inserted into the panel b–d spots, such that all four panels were replicates. Since the original analysis of the data collected was made correctly, the conclusions and key points related to this section and the whole article remain unchanged. The revised goodness factors are slightly different because the refinements were repeated with small changes to the refinement conditions. The corresponding author has obtained approval from all coauthors in the article prior the submission of the Correction. The authors apologize for any inconveniences caused.

25 ENERGY STORAGE↗
DOE OSTI2021

Li 0.625 Al 0.125 H 0.25 Cl 0.75 O 0.25 Superionic Conductor with Disordered Rock-Salt Structure

Solid-state Li-ion conductors are of broad interest in electrochemical energy storage, especially in solid-state Li batteries that serve as a promising alternative for the next-generation safe and high-energy-density batteries. Exploring solid-state superionic conductors is significant for the development of solid-state Li batteries with high performance. Herein, we report a disordered rock-salt (A 1 B 1 )-structured solid electrolyte (Li 0.625 Al 0.125 H 0.25 )(Cl 0.75 O 0.25 ) (abbr. LAHCO) that was synthesized using Li 2 OHCl and LiAlCl 4 as precursors. Neutron diffraction reveals that Li, Al, and H atoms occupy the A sites and O and Cl atoms occupy the B sites in the A 1 B 1 structure for pure LAHCO. The LAHCO compound with excess LiAlCl 4 shows the highest Li + ionic conductivity of ~10 –4 S cm –1 at room temperature due to the disordering induced by configurational entropy as well as the entropy of mixing. Moreover, LAHCO–LiAlCl 4 solid electrolyte exhibits a stable polarization voltage under a current density of 5–50 μA cm –2 in Li symmetric cells. Furthermore, this work not only explicates the importance of Li-ion conductors with a rock-salt structure but also contributes toward the development of solid-state Li-ion conductors for broad applications.

25 ENERGY STORAGE↗
DOE OSTI2019

Novel Ordered Rocksalt-Type Lithium-Rich Li 2 Ru 1–x Ni x O 3-δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential

In this work, a series of ordered rocksalt (OR) type Li-rich Li 2 Ru 1–x Ni x O 3-δ (LRN x O, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN 0.4 O, an ~350 mV decrease of the oxygen oxidation potential compared with Li 2 RuO 3 (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. Additionally, the role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN 0.4 O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Kinetically Controlled Linker Binding in Rare Earth-2,5-Dihydroxyterepthalic Acid Metal–Organic Frameworks and Its Predicted Effects on Acid Gas Adsorption

In the pursuit of highly stable and selective metal–organic frameworks (MOFs) for the adsorption of caustic acid gas species, an entire series of rare earth MOFs have been explored. Each of the MOFs in this series (RE-DOBDC; RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; DOBDC = 2,5-dihydroxyterepthalic acid) was synthesized in the tetragonal space group I4/m. Crystallized MOF samples, specifically Eu-DOBDC, were seen to have a combination of monodentate and bidentate binding when synthesized under typical reaction conditions, resulting in a contortion of the structure. However, extended crystallization times determined that this binding is kinetically controlled and that the monodentate binding option was crystallographically eliminated by extended reaction times at higher temperatures. Furthermore, this series allows for the direct study of the effect of the metal center on the structure of the of the MOF; herein, the lanthanide metal ionic radii contraction across the periodic table results in a reduction of the MOF pore size and lattice parameters. Scanning electron microscopy–energy-dispersive spectroscopy was used to investigate the stages of crystal growth for these RE-DOBDC MOFs. All MOFs, except Er-DOBDC had a minimum of two stages of growth. These analogues were demonstrated by analysis of neutron diffraction (PND) to exhibit a cooperative rotational distortion of the secondary building unit, resulting in two crystallographically distinct linker sublattices. Computational modeling efforts were used to show distinct differences on acid gas (NO 2 and SO 2 ) binding energies for RE-DOBDC MOFs when comparing the monodentate/bidentate combined linker with the bidentate-only linker crystal structures.

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

Understanding the Reactivity and Decomposition of a Highly Active Iron Pincer Catalyst for Hydrogenation and Dehydrogenation Reactions

The iron pincer complex ( iPr PNP)Fe(H)(CO) (1, iPr PNP – = N(CH 2 CH 2 PiPr 2 ) 2 - ) is an active (pre)catalyst for many hydrogenation and dehydrogenation reactions. This is in part because 1 can reversibly add H 2 across the iron-amide bond to form ( iPr PN H P)Fe(H) 2 (CO) (2, iPr PN H P = HN(CH 2 CH 2 P i Pr 2 ) 2 ). However, rapid decomposition limits the catalytic performance of 1 and related complexes. We explored the pathways through which catalytic intermediates related to 1 and 2 undergo decomposition. This involved characterizing the unstable and previously unobserved complexes [( iPr PN H P)Fe(H)(CO)(L)] + (5-L; L = THF or N 2 ) and [( iPr PN H P)Fe(H)(H 2 )(CO)] + (8), which are proposed as intermediates when 1 and 2 are used as catalysts. Compound 8 was synthesized through the reaction of ( iPr PN H P)Fe(H)(CO)(PF 6 ) (6) with H 2 , and the solid-state structure was established using both X-ray and neutron diffraction. As part of our studies on understanding the reactivity of 5-L, we determined the thermodynamic hydricity of 2, which is valuable for predicting its reactivity as a hydride donor. Further, it is shown that species such as 5-L decompose to the same inactive species observed in catalysis using 1 and 2, and theoretical calculations suggest that this likely occurs via a bimolecular pathway. To provide support for this hypothesis, we isolated the dimeric species [{( iPr PN H P)Fe(H)(CO)} 2 {μ-CN}] + (11) and [{( iPr PN H P)Fe(H)(CO)} 2 {μ-OC(H)O}] + (12), which show that catalytic intermediates ligated by iPr PN H P can form dimeric species. Our results provide general strategies for improving catalysis using 1 and 2, and we used this information to rationally increase the performance of 1 in formic acid dehydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Hyperconjugation Promotes Catalysis in a Pyridoxal 5'-Phosphate-Dependent Enzyme

Pyridoxal 5'-phosphate (PLP)-dependent enzymes facilitate reaction specificity by aligning the scissile σ-bond of the PLP-substrate covalent complex perpendicular to the ring of the cofactor. Current models propose that this alignment causes a destabilization of the ground state. To test this hypothesis, quantum chemical calculations, utilizing our recent neutron diffraction models of aspartate aminotransferase, were performed. The calculations reveal that the scissile σ-bond orbital overlaps significantly with the π* orbital of the Schiff base. Here, this σ → π* hyperconjugation interaction stabilizes the ground state of the external aldimine and substantially contributes to transition-state stabilization by withdrawing electron density from the Cα-H σ bond into the π system of PLP, enhancing the rate of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Li 3– x Zr x (Ho/Lu) 1– x Cl 6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

We report two new families of lithium metal chloride solid electrolytes Li 3–x Zr x (M) 1–x Cl 6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm –1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li 3 HoCl 6 , orthorhombic-I Li 3 LuCl 6 , and orthorhombic-II Li 2.4 Zr 0.6 (Ho/Lu) 0.4 Cl 6 . The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li 2.6 Zr 0.4 (Ho/Lu) 0.6 Cl 6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li + /Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li 0.7 Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3 mAh·cm –2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Comparative Analysis of Reactivity of Al and Ga Doped Garnet Solid State Electrolyte at the Interface with Li Metal

Lithium garnet (Li 7 La 3 Zr 2 O 12 , LLZO) based solid electrolytes are leading candidate materials for all-solid-state batteries with lithium metal anodes because of their high ionic conductivity, high mechanical toughness, and superior electrochemical stability. While doping LLZO with Al and Ga increases its ionic conductivity by stabilizing the cubic phase, the impact of dopants on its (electro)chemical stability at the interfaces with Li metal is critical. Here, our study of differences between Al- and Ga-doped LLZO when interfaced with lithium metal using X-ray photoelectron spectroscopy and density functional theory shows a higher propensity of Ga to move across LLZO interface with Li metal and form Ga-Li alloy. Additionally, neutron diffraction reveals loss of cubic phase resulting from the loss of dopant that explains electrochemical behavior differences between Ga- and Al-doped LLZO. Overall, our study reveals the key role of dopant chemistry in enabling stable solid electrolyte materials for all-solid-state batteries.

Klenk, Matthew↗
DOE OSTI2019

Elucidating the Limit of Li Insertion into the Spinel Li 4 Ti 5 O 12

Here in this work, we show that the well-known lithium-ion anode material, Li 4 Ti 5 O 12 , exhibits exceptionally high initial capacity of 310 mAh g –1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g –1 , far exceeding the “theoretical” capacity of 175 mAh g –1 when this anode is lithiated to the composition Li 7 Ti 5 O 12 . Neutron diffraction analyses identify that additional Li reversibly enters into the Li 7 Ti 5 O 12 to form Li 8 Ti 5 O 12 . density functional theory (DFT) calculations reveal the average potentials of the Li 4 Ti 5 O 12 to Li 7 Ti 5 O 12 step and the Li 7 Ti 5 O 12 to Li 8 Ti 5 O 12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li 4 Ti 5 O 12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li 4 Ti 5 O 12 , when lithiated to 0.01 V vs L

25 ENERGY STORAGE↗
DOE OSTI2019

An Ordered P2/P3 Composite Layered Oxide Cathode with Long Cycle Life in Sodium-Ion Batteries

Developing stable cathode materials represents a crucial step toward long-life sodium-ion batteries. P2-type layered oxides are important as cathodes for their reversibility, but their long-term performance in full cells remains a key challenge. Herein, we report Na 0.75 Co 0.125 Cu 0.125 Fe 0.125 Ni 0.125 Mn 0.5 O 2 with an intergrowth of ordered P2 and P3 phases, studied by neutron diffraction and Rietveld refinement. A stable electrochemical performance is achieved in Na half cells with 100% capacity retention at a rate of C/10 after 100 cycles (initial capacity of 90 mAh/g), 96% capacity retention at a rate of 1 C after 500 cycles (initial capacity of 70 mAh/g), and 85% capacity retention at a rate of 5 C after 1000 cycles (initial capacity of 55 mAh/g). Stable full cell performance is achieved with 84.2% capacity retention after 1000 cycles at a rate of 1 C. Synchrotron X-ray diffraction, spectroscopy, and imaging are applied to elucidate the relationship between chemical/structural evolution and battery performance. A reversible local and global structural evolution is observed during initial cycles. Meanwhile, the challenges with enabling prolonged cycling (beyond 1000 cycles) may be associated with Fe dissolution and formation of a copper oxide phase. This study implies that cathodes with complex chemical and structural formations may stabilize electrochemical performance and highlights the importance of decoupling the contribution of each transition metal to performance degradation.

25 ENERGY STORAGE↗
DOE OSTI2019

Integrating Density Functional Theory Calculations with Vibrational and Nuclear Magnetic Resonance Spectroscopy

This review focuses on the complementary nature of density functional theory calculations and spectroscopic studies related to cellulose and its interactions within plant cell walls (PCWs). The complexity, structural disorder, and nanoscale nature of PCWs make them difficult to analyze and understand, but advances in sum-frequency generation and nuclear magnetic resonance spectroscopies as well as in density functional theory have made it possible to elucidate structure not observable previously. Combined with other techniques such as wide-angle X-ray scattering and neutron diffraction, details of PCW components (e.g., cellulose, lignin, pectin) and their interactions with one another can be elucidated. Furthermore, these techniques provide new insight into biological and biochemical studies and provide a basis for creating improved models of the PCWs.

36 MATERIALS SCIENCE↗