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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Understanding the effect of salt concentrations on fast charging performance of Li-ion cells

Here, different lithium salt (lithium bis(fluorosulfonyl) imide (LiFSI)/LiPF 6 9/1 mol ratio) concentrations in carbonate electrolyte were studied on the fast charging performance of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)/graphite pouch cells. The cells with electrolyte concentration from 0.75 M to 1.50 M showed similar fast charging capabilities. Further increase of the concentration to 1.75 M and 2.00 M decreased the attainable capacity in fast charging. In the long-term cycling test, the capacity retention after 200 fast charging cycles increased with the increase of salt concentration in electrolyte. Cells with 1.5 M electrolyte showed the best overall performance in fast charging capacity and long-term cycling. Li platings were observed in the cells with 0.75 M, 1.00 M and 1.25 M electrolyte. It was improved with greatly reduced Li plating area in 1.50 M, and no Li plating at all in 1.75 M and 2.00 M electrolyte. Post-mortem analysis such as neutron powder diffraction (NPD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the electrode after cycling. It suggests that electrolyte concentration needs to be optimized for a given cell configuration with specific electrode and loading.

25 ENERGY STORAGE↗
DOE OSTI2022

Diatom influence on the production characteristics of hydrate-bearing sediments: Examples from Ulleung Basin, offshore South Korea

The Ulleung Basin Gas Hydrate field expeditions in 2007 (UBGH1) and 2010 (UBGH2) sought to assess the Basin's gas hydrate resource potential. Coring operations in both expeditions recovered evidence of gas hydrate, primarily as fracture-filling (or vein type) morphologies in mainly silt-sized, fine-grained sediment, but also as pore-occupying hydrate in the coarser-grained layers of interbedded sand and fine-grained systems. A commonality across many of these occurrences is the presence of diatoms in the fine-grained sediment. Here we tested fine-grained sediment (median grain size <12.5 μm) associated with hydrate occurrences at four UBGH2 sites (UBGH2-2-2, UBGH2-3, UBGH2-6 and UBGH2-11) to investigate potential impacts of diatoms on efforts to extract methane from hydrate, or to tap hydrocarbon reservoirs beneath hydrate-bearing sediment. Two key considerations are: the extent to which diatoms control sediment mechanical properties, and the extent to which pore-water freshening, which occurs as gas hydrate breaks down during resource extraction, alters the diatom control on sediment mechanical properties. We conducted experiments to measure sediment index properties, sedimentation behavior and compressibility to address these considerations. We relied on scanning electron microscope (SEM) imagery and X-ray powder diffraction (XRD) to characterize the sediment mineralogy. Our high-level findings are that at the ~20–45% (by volume) diatom concentrations observed at these UBGH2 sites, sediment compressibility increases with diatom content, but diatoms only appear to increase porosity and permeability at the highest diatom concentration (~45%). Our measurements suggest in situ compression indices of 0.35–0.55 and permeabilities on the order of 0.01milliDarcies (1 × 10 -17 m 2 ) can be anticipated at these sites. Importantly, these properties are not expected to vary significantly upon pore water freshening that accompanies gas hydrate dissociation during production.

58 GEOSCIENCES↗
DOE OSTI2020

XRD and SEM/EDS characterization of two quaternary fuel alloys (U-2.5Mo-2.5Ti-5.0Zr and U-1.5Mo-1.5Ti-7.0Zr in wt. %) for fast reactors

The current study focuses on characterization of two potential fuel alloys for sodium-cooled fast reactors: U-2.5Mo-2.5Ti-5.0Zr (U-MT5Z) and U-1.5Mo-1.5Ti-7.0Zr (U-MT7Z) in wt. %. As-cast alloys and annealed (600°C, 500h) alloys are studied by X-ray powder diffraction (XRD) for their bulk structures, and scanning electron microscopy / energy dispersive X-Ray spectroscopy (SEM/EDS) for their microstructures and phase constituents. For as-cast alloys, the XRD results show that U-MT5Z mainly contains γ, while U-MT7Z alloy contains a. In both alloys, there are three phases indicated by EDS, a U-rich phase, secondary phase, and Zr-rich phase. Further, the elemental compositions varied in different phases and in different alloys. After annealing, both alloys exhibit the structures of α-U and U 2 Ti according to XRD. The EDS results suggest there are five phases found in both alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Novel white light-emitting CdSe:Mn 2+ synthesized by photo-assisted chemical bath deposition

Nowadays, white light-emitting materials have attracted extensive research due to their potential applications in lighting devices and displaying images. Several semiconductor nanoparticles have been explored to achieve efficient white light emission. In this work, we report on novel white light-emitting CdSe:Mn 2+ thin films synthesized by photo-assisted chemical bath deposition. The effect of varying the Mn 2+ ion concentrations on the thin film structure, morphology, and optical properties was investigated. X-ray powder diffraction results indicated that all the films annealed at 250 degrees C possessed a cubic structure, with crystallite sizes in the range of 1-130 nm. Scanning electron microscopy demonstrated spherical nanoparticles with no significant changes with varying Mn 2+ doping concentrations. Energy dispersive X-ray spectroscopy confirmed the presence of the anticipated elements. The atomic force microscope revealed that the surface roughness has decreased with an increase in Mn 2+ ion concentrations but decreased for 0.7 %Mn 2+ . The UV-Vis absorption spectra showed absorption edges around 600-650 nm. Photoluminescence emission spectra excited at 3.8 eV (325 nm) showed emission bands at around 1.75 eV (709 nm), and 1.88 eV (659 nm), which were attributed to the band-to-band emission, and 4 T 1 ( 4 G)-> 6 A 1 ( 6 S) transitions of Mn 2+ ions, respectively, while emission bands at 2.35 eV (528 nm), and prominent at 3.17 eV (391 nm) were due to the glass substrate. The temperature-dependent luminescence showed a decrease in relative emission intensity with the increase in the operating temperature. The chromaticity colour coordinates showed white light-emitting thin films. These present findings open a new door to developing white light using CdSe thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

An investigation of the phase behaviors for quaternary U-Nb/Mo-Ti-Zr metallic fuel alloys

We report quaternary fuel alloys containing U, Nb/Mo, Ti, and Zr are proposed as fuel candidates for sodium-cooled fast reactors (SFRs). In this work, two Nb-bearing alloys, i.e., U-NT5Z (U-2.5Nb-2.5Ti-5.0Zr in wt%) and U-NT7Z (U-1.5Nb-1.5Ti-7.0Zr in wt%), and two Mo-bearing alloys, i.e., U-MT5Z (U-2.5Mo-2.5Ti-5.0Zr in wt%) and U-MT7Z (U-1.5Mo-1.5Ti-7.0Zr in wt%) were characterized and compared. The characterization techniques were differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS). DSC was performed to obtain the transition behaviors, and XRD and SEM/EDS were applied for phase identification. The results were combined to obtain the solid-state phase transitions between 500 °C and 850 °C for the alloys. It is found that the Nb-bearing alloys comprise similar phase transition behaviors as the Mo-bearing alloys. The phase transitions in U-NT5Z are a →γ at 608 °C and U 2 Ti → γ at 627 °C, which are ~40 °C higher than that of U-MT5Z. The phase transition in U-NT7Z is a → γ at 645 °C, and is 23 °C higher than that of U-MT7Z.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Identifying point defects and ordering in the high-entropy layered oxide Li 1.5 MO 3-δ (M=Mn, Al, Fe, Co, Ni) for energy storage applications

High-entropy layered oxides (HELOs) represent a very promising class of next-generation battery cathodes, combining the well-studied properties of layered cathode materials such as LiCoO 2 with the chemical tunability and stability of high-entropy materials. HELO materials often form particles with complex defects and domain structures, complicating accurate characterization of structure and cation mixing. Understanding disorder and order in HELO materials is necessary for understanding their performance and utility as cathodes. Here we demonstrate the characterization of the HELO Li 1.5 MO 3-δ (M = Mn, Al, Fe, Co, Ni), wherein X-ray powder diffraction, transmission electron microscopy imaging, and electron diffraction patterns are analyzed to reveal the presence of ordering in the HELO, with imaging and diffraction simulation employed to compare experimental results to atomic modeling. Finally, without rigorous characterization at the atomic scale, important features such as defect ordering can be easily overlooked and therefore remain unconsidered when interpreting experimental results.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Anion and cation co-doping of Na 4 SnS 4 as sodium superionic conductors

Na based all-solid-state batteries are one of the most promising candidates for large-scale electrochemical energy storage owing to their low cost and outstanding safety properties. The key enabler of this technology is solid electrolyte with sufficiently high ionic conductivity at room temperature. In this work, the design, synthesis, characterization and testing of a series of novel fast Na-ion conductors, Na 4-x-y Sn 1-x A x S 4-y X y with aliovalent cation (P 5+ /Sb 5+ ) and anion substitutions (Cl - /Br - ) of the parent compound Na 4 SnS 4 are reported. The doped samples crystalize in a new phase with space group I4 1 /acd and show ionic conductivities that are one to four orders of magnitude higher than that of undoped Na 4 SnS 4 . R. t. conductivity of 0.64 mS cm -1 is achieved in Na 3.7 Sn 0.8 Sb 0.2 S 3.9 Cl 0.1 with a low activation energy of 0.26 eV. Furthermore, Rietveld refinement against high resolution synchrotron X-ray powder diffraction data reveals that the distribution of the doping ions and the resulted Na vacancies are underlying cause of the enhanced conductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The surface triple-coupling on single crystalline cathode for lithium ion batteries

Single crystalline (SC) cathode materials, which are less susceptible to micro/nano-cracks formation and offer better structure stability compared to the polycrystalline counterpart, have attained great attention. However, the parasitic side reactions at the cathode-electrolyte interface induces the loss of active species, which consequently leads to continual degradation of the electrochemical performances. Herein, a triple coupling of concentration-gradient Na+, F- co-doping and surface NaF coating are exploited for the first time on SC LiNi 0.5C o 0.2 Mn 0.3 O 2 cathode by the hydrolysis of NaPF 6 . This process regulates the external structure of materials by constructing a “sandwich” configuration from surface to bulk: rock salt - mixing zone - layered phase. The detailed interface transformation mechanism is revealed by Neutron powder diffraction (NPD), spherical aberration corrected high-resolution scanning transmission electron microscopy (HR-STEM), electron energy loss spectroscopy (EELS), and Ar+ sputtering assisted X-ray photoelectron spectroscopy (XPS). The synergistic effects endow the SC cathode with outstanding capacity retentions: 91.3% at 25 °C and 85% at 45 °C, after 500 cycles at 5 C between 3.0 and 4.5 V. In addition, a high full-cell reversible capacity of 168.9 mAh g -1 with a capacity retention of 92.4% is achieved after 300 cycles at 1 C. Multiple characterizations further indicate that these superior results are mainly ascribed to the overall structure integrity of SC material, the thin cathode electrolyte interface, high content of lithium fluoride, and the low solubility of transition metal ions. This work opens a new avenue to construct a benign interface towards high-performance lithium ion batteries.

lithium ion batteries↗
DOE OSTI2023

Mechanisms of phosphate removal by Micron-Scale Zero-Valent iron

Extensive studies have been carried out on phosphate removal by zero valent iron (ZVI). Different mechanisms of phosphate removal by ZVI such as phosphate adsorption and precipitation of ferric phosphate and vivianite (Fe 3 (PO 4 ) 2 ·8H 2 O) have been reported. In this study, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray powder diffraction (XRD), and X-ray absorption near edge spectroscopy (XANES) were used to elucidate the mechanisms of phosphate removal by micron-scale zero-valent (mZVI). Time-series ATR-FTIR analysis revealed that phosphate was removed by ZVI in two steps: a) adsorption of phosphate in the first 3 days, and b) slow conversion of the adsorbed phosphate into the precipitated form in 6 days. XRD and XANES analysis determined that iron oxides, ferric ion, and ZVI with oxide layer inhibited the formation of vivianite, resulting in the formation of phosphate precipitates, such as H 2 Fe(II)P 2 O 7 . The results suggested that phosphate is removed by ZVI mainly through precipitation under aerobic conditions. In conclusion, the knowledge gained in this study improves the fundamental understanding of the phosphate removal processes via ZVI.

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

Crystal structure of calcium L-5-methyltetrahydrofolate trihydrate type I, C 20 H 23 N 7 O 6 Ca(H 2 O) 3

The crystal structure of L-5-methyltetrahydrofolate calcium trihydrate has been solved and refined using synchrotron X-ray powder diffraction data and optimized using density functional techniques. Calcium levomefolate trihydrate crystallizes in space group P2 1 2 1 2 1 (#19) with a = 7.1706(6), b = 6.5371(5), c = 53.8357(41) Å, V = 2523.58(26) Å 3 , and Z = 4. The structure is characterized by alternating hydrophobic and hydrophilic layers along the c-axis. The Ca cations are 7-coordinate, and share edges to form chains along the b-axis. Each of the water molecules acts as a donor in two hydrogen bonds. The coordinated water molecule makes two strong intermolecular O–H∙∙∙O hydrogen bonds to carboxyl and carbonyl groups. The two zeolitic water molecules form weaker hydrogen bonds, to carbonyl O atoms, ring N atoms, and aromatic C atoms. Several N–H∙∙∙O/N hydrogen bonds, as well as C–H∙∙∙O hydrogen bonds, also contribute to the lattice energy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Adsorption of Ar into zeolite Al-MFI (NH 4 )

The crystal structure of anhydrous Al-MFI (NH 4 ) containing adsorbed Ar has been determined and refined using synchrotron X-ray powder diffraction data taken at 90 K, and optimized using density functional theory techniques. Six highly occupied Ar sites almost completely fill the pore volume of the zeolite. Changing the gas flow from Ar to He at 90 K decreases the Ar occupancies of all six sites, but two decrease more than the others. Warming the sample from 90 to 295 K in Ar flow results in further decreases in site occupancies, but five of the original six sites persist.

Materials Science↗
DOE OSTI2022

Carboxylic Group Rotation and Lattice Expansion in a Co 2 (Pyrazine-2,3-Dicarboxylate) 2 (4,4'-Bipyridine) Porous Coordination Polymer Induced by CO 2 Adsorption at Ambient Temperature

Here, a Co 2 (pzdc) 2 (bpy)(H 2 O) m (pzdc: pyrazine-2,3dicarboxylate; bpy: 4,4'-bipyridine) porous coordination polymer (PCP) was studied for CO 2 uptake and concomitant structural changes at ambient temperature. Extended structural characterization included evaluation of lattice parameter changes upon CO 2 adsorption and in situ synchrotron X-ray powder diffraction data. The PCP effective pore size increased by ~2% with gas uptake over the pressure range of 1-50 atm, allowing the adsorption capacity to double. Furthermore, the hysteretic behaviors seen during CO 2 adsorption at moderate pressures are commensurate with the structural changes from synchrotron data. The adsorption and hysteresis occur with rotation of the linking carboxylate groups, and yet only minor changes in unit cell volume (ΔV ≈ 6 Å 3 ) are observed. This contrasts the findings for [Cu 2 (pzdc) 2 (bpy)] n , where a combination of pillar bpy rotations and significant lattice expansion (ΔV ≈ 68 Å(3)) takes place upon hysteretic adsorption of CO 2 . In situ high-temperature X-ray diffraction revealed that the Co(II)-based material has good thermal stability up to ca. 200° C. Finally, the CO 2 uptake also appears to be at a physisorption level, with adsorbent-adsorbate interactions that are ca. 30% stronger than what has been reported for CO 2 adsorption onto [Cu 2 (pzdc) 2 (bpy)] n .

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

Enumeration as a Tool for Structure Solution: A Materials Genomic Approach to Solving the Cation-Ordered Structure of Na 3 V 2 (PO 4 ) 2 F 3

While powder diffraction methods are routinely utilized to optimize structural models for compounds whose crystal structures are known, the determination of unknown structures is far more challenging. When the unknown structure is large, structure solution can become a virtually intractable problem using standard structure solution methodologies, especially when the space group cannot be unambiguously resolved. One such system is the promising Na-ion battery cathode material Na 3 V 2 (PO 4 ) 2 F 3 whose high temperature and room temperature structures were previously solved, but whose more complex low-temperature structure could not be determined. Here, a novel materials genomic approach is demonstrated for the solution of the unknown 100 K structure of Na 3 V 2 (PO 4 ) 2 F 3 in which enumeration methods are first used to generate a large number (~3,000) of trial structures based on plausible orderings of Na ions and then automated Rietveld refinements are carried out to optimize each of these trial structures. Based on both the analysis of the ensemble of optimized trial structures and the density functional theory energy minimization of selected trial structures, the 100 K structure of Na 3 V 2 (PO 4 ) 2 F 3 is best described as belonging to the space group A2 1 am with unit cell dimensions of a = 9.01928(4), b = 27.1379(1), c = 10.73307(5). The 100 K unit cell has a large volume of 2627.07(2) Å 3 with Z = 12 and 33 independent crystallographic sites (9 Na, 3 V, 3 P, 12 O, and 6 F) that is 3x and 6x larger than the room- and high-temperature polymorphs of this phase, respectively. Finally, the novel methods described here will be generally applicable for the solution of the complex cation-ordered structures that commonly occur for battery materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Further Investigations of Racemic and Chiral Molecular Sieves of the STW Topology

Large single crystals of pure-silica STW-type molecular sieves are prepared using 1,2,3,4,5-pentamethylimidazolium (12345PMI) and 2-ethyl-1,3,4-trimethylimidazolium (2E134TMI) as organic structure-directing agents (OSDAs) and α-amino acid additives. The effects of the amount and type of amino acid on the crystallization of pure-silica STW materials are investigated. Room-temperature single-crystal X-ray diffractometry shows that 12345PMI better fits the STW cage than 2E134TMI and is fully consistent with computed simulations. The synthesis of an enantioenriched R-STW-type molecular sieve having a Si/Ge ratio of 2.2 is achieved using a chiral, dicationic OSDA that contains two stereocenters. Furthermore, the conformation of the chiral OSDA in the chiral framework has been obtained from a Rietveld refinement using synchrotron powder diffraction data and is the first structure refinement of an enantioenriched, inorganic molecular sieve prepared from a pure, asymmetric OSDA.

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

Local Distortions and Metal–Semiconductor–Metal Transition in Quasi-One-Dimensional Nanowire Compounds AV 3 Q 3 O δ (A = K, Rb, Cs and Q = Se, Te)

Metal cluster compounds have garnered renewed interest in the search for novel superconductors and topological semimetals owing to structural instabilities of metal-cluster geometries and broken symmetries. Here we synthesized needle-like crystals of the V-cluster-based quasi-one-dimensional (Q1D) materials AV 3 Q 3 O δ (A = K, Rb, Cs, Q= Se, Te) which can also be viewed as being composed of parallel nanowires. We examine how changes in their average and local structure control their electronic properties. All compounds crystallize in the TIFe 3 Te 3 -type structure (P6 3 /m space group) with infinite (V 3 )Q 3 ) - double-walled columnar chains separated by A + cations. Our single-crystal and synchrotron powder diffraction studies indicate oxygen atoms partially occupy the center site of the V 6 octahedral metal cluster cages in KV 3 Te 3 O 0.33 , RbV 3 Te 3 O 0.32 , and CsV 3 Te 3 O 0.35 , whereas KV 3 Se 3 is structurally oxygen-free. Our synchrotron X-ray pair distribution function (PDF) analyses indicate that the oxygen-free V 6 cluster octahedra in KV 3 Se 3 are highly distorted perpendicular to the chain direction even at room temperature, reducing the symmetry of the average structure from hexagonal P6 3 /m to monoclinic P2 1 /m. Our theoretical calculation supports this P2 1 /m distortion and suggests the structure further distorts to P2 1 or P2 1 /c at lower temperatures. In contrast, the oxygen-centered V-cluster in KV 3 Te 3 O 0.33 exhibits a V-3-triangle-trimerization along the chain direction. This feature is discernible from the local PDF and is consistent with lattice dynamical calculations based on density functional theory. Resistivity measurements indicate that KV 3 Se 3 exhibits metallic behavior, whereas a dramatic metal-semiconductor-metal transition emerges in KV 3 Te 3 O 6.33 , RbV 3 Te 3 O 0.32 , and CsV 3 Te 3 O 0.35 because of oxygen disorder and changes in local structure captured from our electronic structure analyses of the Fermi surface. Our investigation of the AV 3 Q 3 O 6 family demonstrates the importance of understanding local changes in structure driven by electronic instabilities, which can guide the search for new quantum materials in other low-dimensional cluster-compound materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The Impact of Structural Distortions on the Magnetism of Double Perovskites Containing 5d 1 Transition-Metal Ions

Five double perovskites, each containing a transition-metal ion with a 5d 1 configuration, have been studied to better understand the surprising diversity of magnetic ground states seen in these isoelectronic compounds. Ba 2 ZnReO 6 adopts the cubic double perovskite structure and magnetically orders below 16 K, with a canted ferromagnetic structure and a saturated magnetization of ~0.24 μ B /Re. X-ray magnetic circular dichroism indicates a substantial orbital moment of approximately 0.4 μ B /Re that opposes the spin moment. The structures of Ba 2 NaOsO 6 (canted ferromagnet, T C = 7 K) and Ba 2 LiOsO 6 (antiferromagnet, T N = 8 K) are reinvestigated using time-of-flight neutron powder diffraction and found to crystallize with the cubic double perovskite structure. No evidence for a structural distortion can be found in either compound down to 10 K. Ba 2 CdReO 6 is also cubic at room temperature but undergoes a structural transition upon cooling below ~180 K to a tetragonal structure with I4/m symmetry that involves compression of the Re–O bonds that are parallel to the c-axis. Sr 2 LiOsO 6 shows a similar tetragonal distortion at room temperature and maintains that structure down to 10 K. Surprisingly, the Os-centered octahedron in Sr 2 LiOsO 6 is distorted in the opposite direction, exhibiting an elongation of the Os–O bonds along the c-axis. Differences in the distortions of the octahedra lead to different magnetic ground states, antiferromagnetic (T N = 4 K) for Ba 2 CdReO 6 and spin glass (T g = 30 K) for Sr 2 LiOsO 6 . Theoretical modeling shows that the varied magnetic behaviors of double perovskites containing 5d 1 ions are closely tied to crystallographic distortions. Furthermore, these distortions remove the degeneracy of the 5d t 2g orbitals, leading to changes in orbital occupation that ultimately determine which of the several competing magnetic ground states is favored.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Recovery of MOF-5 from Extreme High-Pressure Conditions Facilitated by a Modern Pressure Transmitting Medium

Here mechanisms underlying the mechanically induced amorphization of metal-organic frameworks (MOFs) are of current interest, and both high-pressure experimentation and molecular dynamics simulations have been used to reveal the fundamentals of load bearing, deformation, and pressure-induced amorphization (PIA) in these highly porous materials. Unfortunately, MOFs are typically highly susceptibility to amorphization, which limits the conditions under which they can be processed and used. However, their flexible structures can be stabilized to high pressures by incorporating guest species into the framework matrix. In this study, a large molecule pressure transmitting medium (DAPHNE 7575 ) is used as a structure-fortifying guest species to stabilize the prototypical MOF -5 to ultra-high pressures ( >9 GPa) and enable the recovery of crystalline material upon decompression. Structural changes associated with the penetration of the pressure transmitting medium on compression are examined using a combination of high pressure synchrotron powder diffraction and molecular dynamics simulations. This work enhances the understanding of PIA in MOFs while showcasing a potential route for the stabilization of MOFs to surprisingly high-pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Tuning Magnetic Symmetry and Properties in the Olivine Series Li 1–x Fe x Mn 1–x PO 4 through Selective Delithiation

In this work, we present the first in-depth study of the nuclear and magnetic structures of the fully lithiated LiFe x Mn 1–x PO 4 solid solutions as well as the partially delithiated Li 1– xFe x Mn 1–x PO 4 series using neutron powder diffraction. By using a weak oxidizing solution that only oxidizes Fe 2+ , we find that lithium can be removed from these olivines in a stepwise manner. Representational analysis was performed on the observed magnetic reflections and found that the lithiated solid solutions order in the magnetic space group Pnma', which is identical to triphylite (LiFePO 4 ). We report that, even when removing 20% of the lithium from the hcp lattice, the magnetic structure changes and multiple magnetic contributions are needed to fully encompass the observed magnetic order. We find that the partially delithiated x = 0.2 and 0.3 have a magnetic structure P2 1 '/n11, and when x surpasses 0.3, the magnetic structure changes to P2 1 2 1 2 1 . We give a detailed report on the effect of delithiation on magnetic order, bond distances/angles, and the super- and supersuperexchange interactions in the material. The symmetries of the magnetic order of these solid solutions are then discussed with regard to their potential as ferrotoroidic candidates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗