Investigation of the sodium storage mechanism of iron fluoride hydrate cathodes using X-ray absorption spectroscopy and mossbauer spectroscopy

Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_(3)·0.5H_(2)O)electrode for sodium-ion batteries(SIBs).The electrode material is prepared by employing an ionic liquid 1-butyl-3-methylimidazolium-tetrafluoroborate,which serves as a reaction medium and precursor for F^(-)ions.The crystal structure of FeF_(3)·0.5H_(2)O is observed as pyrochlore type with large open 3-D tunnels and a unit cell volume of 1129A^(3).The morphology of FeF_(3)·0.5H_(2)O is spherical shape with a mesoporous structure.The microstructure analysis reveals primary particle size of around 10 nm.The FeF_(3)·0.5H_(2)O cathode exhibits stable discharge capacities of 158,210,and 284 mA h g^(-1) in three different potential ranges of 1.5-4.5,1.2-4.5,and 1.0-4.5 V,respectively at 0.05 C rate.The specific capacities remained stable in over 50 cycles in all three potential ranges,while the rate capability was best in the potential range of 1.5-4.5 V.The electrochemical sodium storage mechanism is studied using X-ray absorption spectroscopy,indicating higher conversion at a more discharged state.Ex-situ M?ssbauer spectroscopy strengthens the results for reversible reduction/oxidation of Fe.These results will be favorable to establish high-performance cathode materials with selective voltage window for SIBs.

Mössbauer Spectroscopic Characterization of Fe Occupation of Columns in the Nb28O70 Structure

In search of an experimental route to produce linear arrays of spins without the use of nanotechnological tools, we have doped Nb28O70 with small amounts of transition metal oxides (TM;in this case Fe2O3) or rare-earth oxides3, and investigated the location of the alien metal (Fe in this case) in the structure. Previous AC magnetic susceptibility measurements at low temperatures have been consistent with the formation of arrays of TM magnetic moments along the widely spaced columns parallel to the crystallographic b-axis in the Nb28O70 structure. To obtain further details about the TM distribution, the previous investigation has been extended now to include a room-temperature Mössbauer spectroscopic analysis of the Fe-doped material. The data are consistent with the presence of low-spin Fe3+ ions in both octahedral and tetrahedral coordinations of oxygens, and confirm (as suggested in the previous work) that Fe also interchanges positions with Nb ions located at tetrahedrally coordinated sites in the columns of the structure.

Mössbauer Spectroscopic Characterization of Fe Occupation of Columns in the Nb28O70 Structure

In search of an experimental route to produce linear arrays of spins without the use of nanotechnological tools, we have doped Nb28O70 with small amounts of transition metal oxides (TM;in this case Fe2O3) or rare-earth oxides3, and investigated the location of the alien metal (Fe in this case) in the structure. Previous AC magnetic susceptibility measurements at low temperatures have been consistent with the formation of arrays of TM magnetic moments along the widely spaced columns parallel to the crystallographic b-axis in the Nb28O70 structure. To obtain further details about the TM distribution, the previous investigation has been extended now to include a room-temperature Mössbauer spectroscopic analysis of the Fe-doped material. The data are consistent with the presence of low-spin Fe3+ ions in both octahedral and tetrahedral coordinations of oxygens, and confirm (as suggested in the previous work) that Fe also interchanges positions with Nb ions located at tetrahedrally coordinated sites in the columns of the structure.

Mssbauer studies on the shape effect of Fe_(84.94)Si_(9.68)Al_(5.38) particles on their microwave permeability

Ball milling for long time （such as 10, 20, and 30 h） can transform Fe84.94Si9,68A15.38 alloy powders with irregular shapes into flakes. X-ray diffraction （XRD） and M6ssbauer measurements have proven that the unmilled particles and the flakes obtained by milling for 10 h have the same D03-type superlattice structure. The flakes obtained by milling for 20 h and 30 h have the same disorder a-Fe（Si, A1） structure. There are more than 6 absorption peaks in the transmis- sion MSssbauer spectra （TMSs） for the particles with D03-type superlattice structure, which can be fitted with 5 sextets representing 5 different Fe-site environments. However, only 6 TMS absorption peaks have been found for particles with a disorder a-Fe（Si, A1） structure, which can be fitted with the distributions of M6ssbauer parameters （Bhf, isomer shift）. The TMS results show that the flaky particles have a stronger tendency to possess the planar magnetic anisotropy. As the result, the flakes have larger microwave permeability values than particles with irregular shapes. The conversion electron M6ssbauer spectra （CEMSs） also show the significantly different Fe-sites environments between the alloy surface and the inside.

The metallogenic environment of the Dounan manganese deposit,Southeast Yunnan, China: evidence from geochemistry and Mössbauer spectroscopic

The Dounan manganese deposit is a typical large-scale marine sedimentary manganese deposit of the Middle Triassic in China. The metallogenic environment and change process directly dictate the migration, enrichment, and precipitation of Mn. To better understand its metallogenetic environment, a detailed study was undertaken involving field observation, mineralogical and geochemical and M?ssbauer spectroscopic analyses. The major findings are as follows:(1) Lithofacies paleogeography, sedimentary structural characteristics, and geochemical indexes indicate that the deposits were formed in an epicontinental marine sedimentary basin environment of normal salinity;(2) there were three ore phases including Mn oxides, Mn carbonates, and mixed Mn ores. The ore minerals found were braunite, manganite, Ca-rhodochrosite, manganocalcite, and kutnahorite. Petrographic and mineralogical information indicates that the metallogenic environment was a weakly alkaline and weakly oxidized to weakly reduced environment, and the mineralization occurred near the redox interface;(3) the V/(V + Ni)ratios, δCe and Fe^(2+)/Fe^(3+) found in profiles of Baigu and Gake ore sections show that the redox conditions of the ore-forming environment were continuously changing; and(4) three Fe species, α-Fe_2O_3, para-Fe^(3+), and para-Fe^(2+),were found in hematite and clay mineral samples using M?ssbauer spectrum analysis. The presence and distribution of these Fe species indicate that the deposit was formed in a typical sedimentary environment during the mineralization process. In summary, our study showed that redox was a key factor controlling the mineralization of the Dounan manganese deposit. Our results have led us to the conclusion that transgression and regression caused fluctuations in sea level, which in turn caused the change of the redox environment. M?ssbauer spectroscopy is an effective tool for studying the redox conditions of the paleoenvironment in which sedimentary manganese deposits were formed.

Mssbauer spectra of MnFe_(2-2x)Al_(2x)O_4(0≤x≤0.4) ferrites

The effect of non-magnetic Al3+ ion doping on the magnetic properties of MnFe2-2xAl2xO4(0≤x≤0.4) spinel ferrites was studied using Mssbauer spectroscopy measurements at room temperature.From the Mssbauer study,it is observed that the resolved hyperfine sextets are due to the distribution of Fe ions on the two sublattices of the spinel ferrites.The value of the isomer shift obtained from the fitting of the Mssbauer spectra indicates that Fe ions are in +3 state.A paramagnetic doublet is observed at degree of inversion x=0.4,superimposed on the hyperfine sextets,indicating that the super-exchange interaction A-B decreases due to the dilution of sublattice by Al3+ ions.The hyperfine magnetic field decreases at both interstitial sites of tetrahedral(A) and octahedral(B) with the increase in Al concentration.

Theoretical Review of Mossbauer Effect,Hyperfine Interactions Parameters and the Valence Fluctuations in Eu Systems

In this paper, an overview of the theory of Mössbauer effect is covered, and the main hyperfine interactions parameters which affect the shape of the resultant Mössbauer spectrum are explained and illustrated as well. In principle, Mössbauer effect applies to any and all nuclides, but in practice, certain ideal properties are desirable;that is, the conditions for recoil-free emission and absorption of gamma rays must be optimized. Therefore, briefly discussed in this review, one of the most commonly used for practical and fundamental studies the 151Eu Mössbauer isotope. Also, the intermediate valence phenomena and their theoretical treatments are briefly discussed.

X-Ray and Mössbauer Study of Magnetic Black Sand from Mayotte Island

Natural magnetic black sands are known from several sites often located in areas of volcanic origin. Their elemental and mineral composition provides information on the geology of their territory and depends on several factors occurred during their formation. A sample of black sand was collected on the seashore of the island of Mayotte in the Indian Ocean and its magnetic part was investigated by means of energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), and MÖssbauer spectroscopy at room temperature. The mineral composition is dominantly magnetite, in good agreement with samples collected in other sites of volcanic origin. Contrary to pure magnetite, a relevant fraction of Ti was detected by EDS. The 16% Ti and 1% Mn content increase the magnetite lattice parameter to 8.4312 (25) Å. The broadening of XRD lines pointed towards a significant degree of disorder. This was confirmed by MÖssbauer spectroscopy and is attributed to the presence of Ti replacing Fe in the magnetite lattice. The presence of Ti modifies the local magnetic field on the Fe sites, leading to a broader and more complex MÖssbauer transmission spectrum with respect to the one of pure magnetite. To study the effect of temperature, samples were heated for 12 hours to 600°C and 800°C in argon and to 1000°C in air. Annealing in argon did not improve the crystallinity while annealing in air caused a complete decomposition of magnetite into hematite and pseudobrookite.

Synthesis and Characterization of Gadolinium Oxide-Hematite Magnetic Ceramic Nanostructures

Mixed-oxide nanostructures of the type xGd2O3-(1-x)α-Fe2O3 (x=0.1, 0.3, 0.5 and 0.7) were synthesized by mechanochemical activation for ball milling times of 0, 2, 4, 8 and 12 hours. The systems were subsequently analyzed by Mӧssbauer spectroscopy, X-ray powder diffraction (XRPD), magnetic measurements and optical diffuse reflectance spectroscopy. The magnetic hyperfine field was studied as function of ball milling time for all sextets involved and found to be consistent with the formation of a limited solid solution in the systems investigated. The end-product was the gadolinium perovskite, represented by a doublet whose abundance was derived as function of the milling time. The XRPD patterns recorded for the equimolar composition were dominated by the diffraction peaks of GdFeO3 after 12 hours of milling. The hysteresis loops were recorded at 300 and 5 K in an applied magnetic field of 5 T and were interpreted as a superposition of paramagnetic behavior of gadolinium oxide and weak ferromagnetic behavior of hematite and gadolinium perovskite. The Morin transition of hematite was inferred from zero-field-cooling-field-cooling (ZFC-FC) curves measured with a magnetic field of 200 Oe in the 5-300 K temperature range and was found to depend on the ball milling time. Optical diffuse reflectance spectra showed that the compounds were semiconductors with an optical band gap of 2.1 eV.

Structural and Magnetic Studies of Ga-doped Yttrium Iron Garnet

Ga-doped Yttrium Iron Garnet (Y_(3)Ga_(x)Fe_(5-x)O_(12),Ga:YIG) was prepared by solid state reaction method and sintering at 1 300 ℃.Rietveld analysis of X-ray diffraction patterns indicated that all samples crystallized in a single cubic structure (space group Ia-3d) with decreasing lattice constant as Ga concentration increased.SEM surface micrograph images of YIG samples showed highly compacted grains with small reduction in the grain size with increasing Ga concentration.Raman spectroscopy measurements confirmed the replacement of Fe^(3+) ions by Ga^(3+) ions in the garnet structure was revealed by the observed blue shifts in Raman spectra.The saturation magnetization decreased from 28.2 to 4.98 emu g^(-1) with increasing x from 0.0 to 1.0 due to the preferential substitution of Ga^(3+) ions for Fe^(3+) ions at tetrahedral sites.Room temperature Mössbauer spectra for the samples revealed a reduction of the hyperfine field values for octahedral and tetrahedral sites,and the development of additional components with increasing Ga concentration.Analysis of the magnetic data and Mössbauer spectra confirmed that spin canting in the substituted garnets plays an important role in explaining the observed reduction of the saturation magnetization as x increased.

Effect of Si on austenite stabilization,martensite morphology,and magnetic properties in Fe-26%Ni-x%Si alloys

The effect of Si on the austenite stabilization, martensite morphology, and magnetic properties in Fe-26%Ni-x%Si （x=3.5, 5, and 6） alloys have been studied by means of transmission electron microscopy （TEM） and M？ssbauer spectroscopy techniques. TEM observations reveal that the martensite morphology is closely dependent on the Si content. The volume fraction changes of martensite and austenite phases, the hyperfine magnetic field, and isomer shift values have been determined by Mssbauer spectroscopy. The M？ssbauer study reveals that the hyperfine magnetic field, the isomer shift values and the volume fraction of martensite decrease with increasing Si content.

Structural reconstruction of Sn-based metal-organic frameworks for efficient electrochemical CO_(2) reduction to formate

MOF-based materials have been widely explored in electrochemical CO_(2)reduction reactions for the production of valuable chemicals.Understanding the reconstruction of those catalysts under working conditions is crucial for the identification of active sites and clarification of reaction mechanism.Herein,a series of six N coordinated Sn-based metal-organic frameworks(Sn-N6-MOFs)are newly developed for electrochemical CO_(2)reduction(CO_(2)RR).2%Sn-N6-MOF achieves the optimal catalytic performance with a formate Faradaic efficiency of~85%and a current density of 23 mA·cm^(-2) at-1.23 V vs.RHE.In-situ Raman results combined with ex-situ ^(119)Sn Mössbauer measurements reveal the structural reconstruction of Sn-N6-MOFs during CO_(2)RR,generating tin nanoclusters as the real active sites for CO_(2)electroreduction to HCOOH.

Effect of hydrogen plasma implantation on the micro-structure and magnetic properties of hcp-Co_(80)^(57)Fe_(4)Ir_(16)thin films

We present detailed investigations of structural and static/dynamic magnetic properties of hydrogenated hcp-Co_(80)^(57)Fe_(4)Ir_(16) soft magnetic thin films.Two different kinds of defects,i.e.,destructive and non-destructive,were demonstrated by controlling the negative bias voltage of the hydrogenation process.Our results show that the structure and magnetic properties of our sample can be tuned by the density of the induced defects.These results provide better understanding of the hydrogenation effect and thus can be used in the future for materials processing to meet the requirements of different devices.

Properties of Biogenic Magnetite Nanoparticles in the Radula of Chiton Acanthochiton rubrolineatus Lischke

The properties of biogenic magnetite（Fe 3 O 4 ）nanoparticles in chiton acanthochiton rubrolineatus lischke were characterized by selected electron diffractometry,high resolution transmission electron microscopy,Fourier transform infrared spectroscopy,M·ssbauer spectroscopy and magnetization measurements.Results showed that the magnetite nanoparticles presented crystalline appearance,exhibiting strong absorptions at 595,1 463,3 467 cm-1 and weak adsorptions at 1 697,1 113,1 048,848,445 cm-1 in FT-IR,two partially overlapping sextets in M·ssbauer spectrum,and the area ratio of the sextets was 1.08.Also,the particles exhibited ferromagnetic behavior,and had 82 A·m2/kg saturation magnetization,1.4·104 A/m coercive force and 4.0 A·m2/kg remnant magnetization,respectively.The investigation indicates that the biogenic magnetite nanoparticles mineralized in the chiton are impure in composition and non-stoichiometric.

2 GeV Electron Beam Irradiation Effects in Advanced Metallic Glasses

Six amorphous alloys (Alloy 1: Fe56Co24Nb4B13Si2Cu1, Alloy 2: Fe68.5Co5Nb3Cu1Si15.5B7, Alloy 3: Fe75.3Ni0.8Cr0.9Si8.7B14.3, Alloy 4: Fe56Co24Cr10Nb4B3Si1Cu2, Alloy 5: Fe72.9Nb3Cu1Si16.2B6.9, Alloy 6: Fe83.3Si8.6Nb5.5B1.4Cu1.2) were selected in terms of their composition and magnetostriction constants and uniformly irradiated in a high radiation environment in Hall A of the Thomas Jefferson National Accelerator Facility. The 2 GeV electron beam irradiation-induced effects were characterized by Mӧssbauer spectroscopy. The microstructural changes were related to the evolution of the hyperfine magnetic field distributions and isomer shifts. In particular, the occurrence of stress centers in the amorphous materials was evidenced.

Influence of cerium ions on structure-dependent magnetic properties of Ba-Sr M-type hexaferrite nanocrystals

The present study is a systematic effort to investigate the structure-sensitive magnetic parameters of Ce^(3+) substituted Ba-Sr hexaferrite nanocrystals chemically formulated as Ba_(0.5)Sr_(0.5)Ce_(x)Fe_(12-x)O_(19) where x=0.0-0.2 with Δx=0.05.The hexaferrite powders were prepared using the sol-gel self-ignition route and structurally characterized by means of powder X-ray diffraction and Fourier transform infrared spectroscopy.The creation of the M-type hexaferrite phase within the synthesized samples was revealed from the Rietveld refinement of the X-ray diffractograms.The occurrence of a secondary phase of CeO_(2) was revealed within the hexaferrites for the substitution,x> 0.The refined X-ray diffraction data were utilized to compute the lattice parameters,X-ray density,and lattice parameter ratio.The crystal structure plotted from the refined XRD data reveals the occupancy of the ions at different lattice sites.The XPS data of the hexaferrite were analyzed to confirm the oxidation states of the constituent elements.The nanocrystalline nature of the hexaferrites was revealed from the crystallite sizes calculated using Scherer's formula.The analysis of FTIR spectra confirms that only a fraction of Ce^(3+)accommodated in the lattice and the remaining Ce content reside in the form of the CeO_(2) phase.The morphology of the hexaferrites was analyzed from the FESEM profiles of the ferrite samples.The magnetic behavior study was performed by analyzing the Curie temperature,hysteresis loops,and hyperfine interactions by means of susceptibility,V.S.M,and Mossbauer spectroscopy,respectively.The hexaferrites with increasing coercivity,decreasing saturation magnetization,and decreasing Curie temperature are reported in the study.The substituted Ce^(3+)ions inhibit the grain growth and create lattice imperfections giving rise to hexaferrites with tuned magnetic parameters suitable for different applications.

高能球磨法制备的含铁TiO_2的穆斯堡尔谱研究(英文)

The structural evolution of Fe-doped TiO2 by high-energy ball milling was investigated by X-ray diffraction and Mǒssbauer spectroscopy, The results show that the original anatase-TiO2 transforms to srilankite-type and rutile-type during ball milling. Iron atoms are preferable to dissolve in rutile-TiO2 and there are two relative doublets appearing in Mǒssbauer spectra. A doublet is found in the condition of Fe atoms dissolved in srilankite TiO2 lattice. Mǒssbauer spectra show that the composition distribution is nonuniform in TiO2 during the mechanical alloying with Fe atoms rich at the interface or surface of TiO2 crystalline.

Magnetic moment distributions in a-Fe nanowire array

a-Fe nanowire array has been electrodeposited into anodic aluminum oxide template. The magnetic moment distributions, in the interior and near the extremities of a-Fe nanowire with 60 nm in diameter, have been studied by means of transmission M鰏sbauer spectroscopy (MS), conversion electron M鰏sbauer spectroscopy (CEMS) and micromagnetic simulation. Transmission M鰏sbauer spectrum (MS) shows that the magnetic moments, inside the a-Fe nanowire array, are well parallel to nanowire, while conversion electron M鰏sbauer spectrum (CEMS) reveals that the magnetic moments, near the extremities of nanowire, diverge from the long axis of wire, and the average diverging angle calculated by the intensity ratio of the 2,5 peaks is about 24.0°. Moreover, the magnetic moment distributions of different depths to the top of wire are counted using micromagnetic simulation, which indicates that, the interior magnetic moments are strictly parallel to nanowire, and the closer the magnetic moment to the top of wire, the larger the diverging angle. Magnetic measurement shows that this -Fe nanowire array represents a strong magnetic anisotropy.

Magnetocaloric effect of LaFe_(11.35)Co_(0.6)Si_(1.05) alloy

The aim of the present paper was to study the large magnetocaloric effect observed in LaFe_(11.35)Co_(0.6)Si_(1.05)alloy. X-ray diffraction(XRD) result reveals a coexistence of two crystalline phases: a dominant La(Fe,Si)_(13)-type and a minor a-Fe(Co,Si). It is confirmed by the Mössbauer spectroscopy and microstructural observations accompanied by an energy-dispersive spectroscopy(EDS) analysis. The value of the magnetic entropy changes(|S_(M)|) in the vicinity of the Curie temperature(TC= 268 K) was calculated using thermomagnetic Maxwell relation, and it equals to 21.4 J·kg^(-1)·K^(-1) under the change in an external magnetic field of μ_(0)ΔH = 3T. The investigation of magnetic phase transition was carried out using the Landau theory, an analysis of the field dependences of the magnetic entropy change and universal scaling curve, revealing the second order of phase transition in the studied material.

Magnetic glass-ceramics

We present the magnetic properties of magnetic glass ceramics obtained by crystallization of Fe containing borosilicate glass.Two types of nucleators have been used:Cr2O3 and P2O5.The role of the nucleators proved to be crucial in the size and morphology of the crystallites developed within glassy matrix as well in the magnetic response.The former stimulates the growth of regular single crystals uniformly dispersed within the matrix whereas the latter leads to the formation of grains made of tiny(30 nm),nanocrystals.The magnetic response depends on the amount of Fe ions left dispersed within glassy matrix as paramagnetic ions.Although P2O5 leads to the best structural magnetite,almost 42%of Fe ions are left dispersed in the matrix without magnetic interaction.In the case of Cr2O3,the paramagnetic Fe is decreased to 12%but structural deficiency in the occupancy of the Fe sites of magnetite is revealed by Mössbauer spectroscopy.