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Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors
In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film was prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance, due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as-prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder-free electrode effectively reduces electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provides a high specific surface area to improve electron transport, enhancing rapid ion transport and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/micro-size electronic devices.
Thermal conversion in air of rare-earth fluorides to rare-earth oxyfluorides and rare-earth oxides
Phase transformations of seven different rare-earth fluorides (i.e., REF3) where RE = La, Ce, Pr, Nd, Tm, Yb, Lu at temperatures ranging from 400–1400°C in air were investigated with X-ray diffraction. All of the REF3 compounds first transformed to oxyfluorides and then to oxides, with the exception of CeF3, which transformed directly to an oxide. This study focuses on the phase transitions of REF3 to REOx by simple heat-treatment processes in air and shows plausibility to remove RE elements from fluoride salt streams from molten salt reactors through fluoride-to-oxyfluoride or fluoride-to-oxide conversion mechanisms, which will result in precipitation. This could be used to remove fission product poisons from molten salt reactor waste streams. A waste form option for the resulting REOx products is lanthanide aluminoborosilicate (LABS) glass. To demonstrate this NdF3 was converted to Nd2O3 and immobilized in a LABS glass.
Luminescence and Scintillation in the Niobium Doped Oxyfluoride Rb4Ge5O9F6:Nb
A new niobium-doped inorganic scintillating oxyfluoride, Rb4Ge5O9F6:Nb, was synthesized in single crystal form by high-temperature flux growth. The host structure, Rb4Ge5O9F6, crystallizes in the orthorhombic space group Pbcn with lattice parameters a = 6.98430(10) Å, b = 11.7265(2) Å, and c = 19.2732(3) Å, consisting of germanium oxyfluoride layers made up of Ge3O9 units connected by GeO3F3 octahedra. In its pure form, Rb4Ge5O9F6 shows neither luminescence nor scintillation but when doped with niobium, Rb4Ge5O9F6:Nb exhibits bright blue luminescence and scintillation. The isostructural doped structure, Rb4Ge5O9F6:Nb, crystallizes in the orthorhombic space group Pbcn with lattice parameters a = 6.9960(3) Å, b = 11.7464(6) Å, and c = 19.3341(9) Å. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements suggest that the niobium is located in an octahedral coordination environment. Optical measurements inform us that the niobium dopant acts as the activator. The synthesis, structure, and optical properties are reported, including radioluminescence (RL) measurements under X-ray irradiation.
Pentanary cesium titanyl/titanate silicate oxyfluorides: Syntheses and structures
Not provided.
Understanding the role of crystallographic shear on the electrochemical behavior of niobium oxyfluorides
Abstract not provided
Thermal Analysis, Compressibility, and Decomposition of Synthetic Bastnäsite-(La) to Lanthanum Oxyfluoride
Abstract not provided
A{sub 5}RE{sub 4}X[TO{sub 4}]{sub 4} crystal growth: Fluoride flux synthesis of Na{sub 5}Ln{sub 4}F[GeO{sub 4}]{sub 4} (Ln=Pr, Nd), the first quaternary germanate oxyfluorides
Crystals of Na{sub 5}Pr{sub 4}F[GeO{sub 4}]{sub 4} and Na{sub 5}Nd{sub 4}F[GeO{sub 4}]{sub 4} were synthesized using a eutectic sodium fluoride, sodium chloride flux. Both compounds crystallize in the tetragonal space group I-4 with lattice parameters of a=12.1173(4) Å and c=5.6795(2) Å (Pr) and of a=12.0642(17) Å and c=5.6674(11) Å (Nd). The structure of the reported compounds is three-dimensional with face and corner sharing lanthanide polyhedra which edge and corner share with isolated germanium tetrahedra. These novel compositions represent the first example of quaternary germanium containing oxyfluorides. - Graphical abstract: Structural image of the first examples of quaternary germanate oxyfluorides. Display Omitted - Highlights: • Molten flux growth of crystals of two lanthanide germanate oxyfluorides. • Expansion of the A{sub 5}RE{sub 4}X[TO{sub 4}]{sub 4} family into germanate oxyfluorides. • Synthesis of Na{sub 5}Nd{sub 4}F[GeO{sub 4}]{sub 4} and Na{sub 5}Pr{sub 4}F[GeO{sub 4}]{sub 4}.
Intense 2.7 μm mid-infrared emission of Er{sup 3+} in oxyfluoride glass ceramic containing NaYF{sub 4} nanocrystals
Highlights: • Transparent oxyfluoride glass-ceramics containing NaYF{sub 4}:Er{sup 3+} nanocrystals have been prepared. • Intense 2.7 μm emission of the glass-ceramics has been demonstrated. • Prolonged decay lifetimes of Er{sup 3+}:{sup 4}I{sub 11/2} and {sup 4}I{sub 13/2} levels have been achieved. - Abstract: Transparent oxyfluoride glass ceramics containing NaYF{sub 4}:Er{sup 3+} nanocrystals have been prepared by melt quenching and subsequent thermal treatment. X-ray diffraction and high-resolution transmission electron microscopy analysis confirmed the precipitation of NaYF{sub 4} nanocrystals in glass. Energy dispersive spectrometer results evidenced the preferential concentration of Er{sup 3+} ions in nanocrystals. Mid-infrared, upconversion, and near-infrared emissions were measured upon excitation with 980 nm laser diode and the luminescence mechanisms were discussed. Intense 2.7 μm emission originating from the Er{sup 3+}:{sup 4}I{sub 11/2} → {sup 4}I{sub 13/2} transition was achieved due to the incorporation of Er{sup 3+} ions into the precipitated low phonon energy fluoride nanocrystals. The results indicate that oxyfluoride glass ceramic containing NaYF{sub 4}:Er{sup 3+} nanocrystals is a promising candidate material for 2.7 μm laser.
Strain-Induced Anion-Site Occupancy in Perovskite Oxyfluoride Films
Anion ordering is a promising route to engineer physical properties in functional heteroanionic materials. A central challenge in the study of anion-ordered compounds lies in developing robust synthetic strategies to control anion occupation and in understanding the resultant implications for electronic structure. Here, we show that epitaxial strain induces preferential occupation of F and O on the anion sites in perovskite oxyfluorides SrMn O2.5-δ F γ films grown on different substrates. Under compressive strain, F tends to occupy the apical-like sites, which was revealed by F and O K-edge linearly polarized x-ray absorption spectroscopy and density functional theory calculations, resulting in an enhanced c-axis expansion. Under tensile strain, F tends to occupy the equatorial-like sites, enabling the longer Mn-F bonds to lie within the plane. The oxyfluoride films exhibit a significant orbital polarization of the 3d electrons, distinct F-site dependence to their valence band density of states, and an enhanced resistivity when F occupies the apical-like anion site compared to the equatorial-like site. By demonstrating a general strategy for inducing preferential anion-site occupancy in oxyfluoride perovskites, this work lays the foundation for future materials design and synthesis efforts that leverage this greater degree of atomic control to realize new polar or quasi-two-dimensional materials.
Structural and Chemical Evolution of Highly Fluorinated Li‐Rich Disordered Rocksalt Oxyfluorides as a Function of Temperature
Abstract Li‐rich disordered rocksalt (DRS) oxyfluorides have emerged as promising high‐energy cathode materials for lithium‐ion batteries. While a high level of fluorination in DRS materials offers performance advantages, it can only be achieved via mechanochemical synthesis, which poses challenges of reproducibility and scalability. The definition of relationships between fluorination and structural stability is required to devise alternative methods that overcome these challenges. In this study, the thermal evolution of three highly fluorinated phases, Li 2 TMO 2 F (TM = Mn, Co, and Ni), is investigated in an inert atmosphere. Diffraction and spectroscopic techniques are utilized to examine their electronic and chemical states up until conditions of decomposition. The analysis reveals that the materials phase‐separate above 400 °C, at most. It is also observed that heat‐treated DRS materials exhibit intricate changes in the local coordination of the metals, including their spin, and ordering compared to the pristine states. The changes upon annealing are accompanied by a modulation of the voltage profile, including reduced hysteresis, when used as electrodes. These results provide an in‐depth understanding of the fundamental crystal chemistry of DRS oxyfluorides in view of their promising role as the next generation of Li‐ion cathodes.
Synthesis and structure of a new layered oxyfluoride Sr{sub 2}ScO{sub 3}F with photocatalytic property
Highlights: • A new oxyfluoride compound Sr{sub 2}ScO{sub 3}F was prepared by a solid state route. • The structure of this compound was determined by GSAS program based on XRD data. • The photocatalytic property was investigated under UV irradiation. - Abstract: A new Ruddlesden–Popper type scandium oxyfluoride, Sr{sub 2}ScO{sub 3}F, was synthesized by a conventional solid state reaction route. The detailed structure of Sr{sub 2}ScO{sub 3}F was investigated using X-ray diffraction (XRD) and selected area electron diffraction (SAED). The disorder distribution pattern of fluorine anions was determined by the {sup 19}F nuclear magnetic resonance (NMR) spectrum. The compound crystallizes in a K{sub 2}NiF{sub 4}-type tetragonal structure (space group I4/mmm) with O/F anions disordered over the apical sites of the perovskite-type Sc(O,F){sub 6} octahedron layers interleaved with strontium cations. Ultraviolet–visible (UV–vis) diffuse reflection spectrum of the prepared Sr{sub 2}ScO{sub 3}F indicates that it has an absorption in the UV–vis region. The photocatalytic activity of Sr{sub 2}ScO{sub 3}F was further investigated, showing an effective photodegradation of Rhodamine-B (RB) within 2 h under UV light irradiation.
Synthesizing High-Capacity Oxyfluoride Conversion Anodes by Direct Fluorination of Molybdenum Dioxide (MoO 2 )
High-capacity metal oxide conversion anodes for lithium-ion batteries (LIBs) are primarily limited by their poor reversibility and cycling stability. In this study, a promising approach has been developed to improve the electrochemical performance of a MoO 2 anode by direct fluorination of the prelithiated MoO 2 . The fluorinated anode contains a mixture of crystalline MoO 2 and amorphous molybdenum oxyfluoride phases, as determined from a suite of characterization methods including X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, and scanning transmission electron microscopy. Electrochemical measurements indicate that fluorination facilitates the conversion reaction kinetics, which leads to increased capacity, higher coulombic efficiency, and better cycling stability as compared to the nonfluorinated samples. Overall, these results suggest that fluorination after prelithiation not only favors formation of the oxyfluoride phase but also improves the lithium-ion diffusivity and reversibility of the conversion reaction, making it an attractive approach to address the problems of conversion electrodes. These findings provide a new route to design high-capacity negative electrodes for LIBs.
Activity of Metal-Fluorine States upon Delithiation of Disordered Rocksalt Oxyfluorides
The capacity of transition-metal oxides as Li-ion battery cathodes is limited by instabilities that arise when high states of charge are achieved. Oxyfluorides with a disordered rocksalt structure have emerged as attractive alternatives, but the role of F in their electrochemical function, particularly when cationic redox produces high formal oxidation states, remains to be ascertained. Here, using X-ray absorption spectroscopy, we confirm the existence of Mn-F covalent interactions in Li 2 MnO 2 F and Li 2 Mn 2/3 Nb 1/3 O 2 F. New unoccupied states evolve from hybrid 3d-2p states of both Mn-F and Mn-O bonds when the phases are delithiated, particularly in the presence of Mn(IV). The results challenge the assumption of F as anion whose covalent states with the metal are tapped at very high potentials, providing instead a nuanced picture of redox compensation in oxyfluorides. They suggest the existence of unique knobs of design of battery cathodes by manipulating the covalent interactions between transition metals and two different anions.
Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs 11 [(UO 2 ) 12 (PO 4 ) 3 O 13 ] and the Layered Uranyl Oxyfluoride-Phosphate Rb 11 [(UO 2 ) 12 (PO 4 ) 3 O 12 F 2 ] Prepared by Flux Crystal Growth
We report single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs 11 [(UO 2 ) 12 (PO 4 ) 3 O 13 ] ( 1 ) and Rb 11 [UO 2 ) 12 (PO 4 ) 3 O 12 F 2 ] ( 2 ) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U 3 O 8 , while Cs 4.4 K 0.6 [(UO 2 ) 6 O 4 F(PO 4 ) 4 (UO 2 )] ( 3 ) and Rb 4.4 K 0.6 [(UO 2 ) 6 O 4 F(PO 4 ) 4 (UO 2 )] ( 4 ) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2 - 4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase ( 1 ) and in contrast an oxyfluoride phase for the Rb containing phase ( 2 ). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the UO 2 2 + uranyl group.
Thermodynamic Analysis of Deoxidation of Titanium Through the Formation of Rare-Earth Oxyfluorides
In this work, the possibility of the direct removal of oxygen species from metallic Ti through the formation of rare-earth oxyfluorides has been investigated from a thermodynamic viewpoint. The deoxidation limit of β-Ti using rare-earth metals (M: Y, La, Ce, and Nd) as deoxidants was evaluated. It was found that Ti metal with an oxygen concentration of 200 mass ppm or less could be theoretically obtained under the M/MOF/MF{sub 3} equilibrium at 1300 K (1027 °C), which suggested a possibility of reducing the oxygen content in Ti below 500 mass ppm utilizing a fluoride-based molten salt. Furthermore, a new deoxidation process, in which oxygen was removed in the form of MOF compounds using Mg deoxidant, was discussed as well. The obtained results revealed that the oxygen content in β-Ti could be theoretically reduced to a level below 1000 mass ppm using a MF{sub 3}-containing molten salt equilibrated with Mg. Rare-earth metals and their alloys are usually produced by the electrolysis in a fluoride-based molten salt; hence, the modern industrial electrolysis techniques can be potentially utilized for deoxidizing Ti scrap.
Gamma ray irradiation-induced variations in structure and optical properties of cerium/titanium-doped oxyfluoride transparent glass-ceramics
Highlights: • CeO{sub 2} favors CaF{sub 2} crystallization while TiO{sub 2} suppresses CaF{sub 2} crystallization. • Doping TiO{sub 2} helps reduce intrinsic coloring caused by CeO{sub 2}. • Doping CeO{sub 2} and/or TiO{sub 2} improves defects saturation over irradiation does. • Doping CeO{sub 2} allows lower radiation induced absorption coefficient than co-doping CeO{sub 2}/TiO{sub 2}. - Abstract: CeO{sub 2}/TiO{sub 2}-doped oxyfluoride transparent glass ceramics with a composition of 45SiO{sub 2}–20Al{sub 2}O{sub 3}–10CaO–25CaF{sub 2} were synthesized and irradiated by gamma ray. The effects of CeO{sub 2}/TiO{sub 2} on the structure and optical properties of the samples before and after irradiation were investigated. Doping with CeO{sub 2} causes network depolymerization and conversion of [AlO{sub 6}] to [AlO{sub 4}], enlarging the percolation region and promoting CaF{sub 2} crystallization. Co-doping with CeO{sub 2}/TiO{sub 2} helps reduce the intrinsic coloring of transparent glass ceramics containing only CeO{sub 2}, and the addition of TiO{sub 2} enhances network interconnectivity, suppressing CaF{sub 2} crystallization. Doping with CeO{sub 2} and/or TiO{sub 2} improves the structural stability of transparent glass ceramics upon irradiation and maintains the optical band gap and Urbach energy constant due to the defect saturation over the irradiation dose. Doping solely with CeO{sub 2} allows for a lower radiation-induced absorption coefficient than co-doping CeO{sub 2}/TiO{sub 2} because of the enhanced crystallization induced by CeO{sub 2} and balanceable light absorption of polyvalent cerium ions.
Synthesis and structural characterization of the vividly colored first row transition metal-containing oxyfluoride antiperovskites Sr3-xMnxMO4F and Sr3-xMnxMO4-αF1-δ (M = Al, Ga)
Highlights: • Substitution of Mn{sup 2+} demonstrates Sr{sub 3-x}A{sub x}MO{sub 4}F can tolerate divalent first row transition metals. • The colors of these materials vary from green to purple depending on anion stoichiometry. • Intense colors are likely due to small amounts of Mn{sup 3+} on the tetrahedral Al site. • Structural data is consistent with preferential occupation of eight-coordinate Sr(2) site by Mn{sup 2+}. • Large off-center displacements are observed on the underbonded ten-coordinate Sr(1) site. - Abstract: Incorporation of dopant amounts of the divalent transition metal cation Mn{sup 2+} into the oxyfluoride material Sr{sub 3-x}Mn{sub x}MO{sub 4}F (M = Al, Ga; 0 ≤ x ≤ 0.1) yields green powders which vary in hue depending on the identity of M. Treatment of these phases with post-synthesis annealing under reducing conditions produces anion deficient phases according to Sr{sub 3-x}Mn{sub x}MO{sub 4-α}F{sub 1-δ} displaying vivid purple coloration. Intense colors are likely due to small amounts of Mn{sup 3+} on the tetrahedral M site. Full structural characterization based upon powder X-ray diffraction (PXRD), neutron powder diffraction (NPD), and thermogravimetric analysis (TGA) data are presented herein, demonstrating that the Sr{sub 3-x}A{sub x}MO{sub 4}F (A = Ca, Sr, Ba; M = Al, Ga) anti-perovskite structure can readily accommodate first row transition metals.