Evaluation of structural and electrochemical properties of the MnSb–Li system as anode for Li-ion batteries

The electrochemical reaction mechanisms between lithium and cystalline MnSb are investigated by X-ray diffraction, ¹²¹Sb Mössbauer spectroscopy, and X-ray absorption spectroscopy (XAS). The analysis of the experimental data at different depths of the electrochemical discharge process reveals a complex reaction mechanism comprising two steps. The main reaction of the first step corresponds to the dispersion of lithium in the MnSb matrix with formation of the intermediate compound LiMnSb. The second step corresponds to a Li–Sb alloying process with formation of Li₃Sb.     

Iron-57 Mössbauer spectroscopy study of phases in the CaZrTi2−2x Nb x Fe x O7 zirconolite system

Materials of composition CaZrTi_2?2x Nb _x Fe _x O₇ with the fluorite-related zirconolite structure have been prepared. The ⁵⁷Fe Mössbauer spectra show that iron is initially located in the five co-ordinate cation sites. As the iron content increases the iron enters the octahedral sites until, at a composition CaZrTi_0.4Nb_0.8Fe_0.8O₇, ca. 50% of the iron is five co-ordinate and the remainder is located in the octahedral sites.     

Debye temperature and magnetic ordering in K x Ba1−x Fe2S3

⁵⁷Fe Mössbauer measurements are reported for the series K _x Ba_1?x Fe₂S₃, x ≤ 0.3, at temperatures between 4.2 K ≤ T ≤ 294 K. A decrease of the Debye temperature from 435 to 405 K with x, indicates a weakening of the stiffness of the Fe sublattice. The ordering temperatures, taken from the appearance of magnetic hyperfine splitting in the spectra, are approximately 40 K lower for x ≥ 0.1. The values of the centre shift and the small temperature dependence of the quadrupole splitting strongly supports that similar to the border compound BaFe₂S₃ also the K containing samples should be characterised as mixed valence compounds.     

57Fe Mössbauer spectroscopy on the cyclic spin-cluster Fe6(tea)6(CH3OH)6

We present ⁵⁷Fe Mössbauer spectroscopy experiments on the cyclic spin-cluster Fe₆(tea)₆(CH₃OH)₆ (tea = triethanolaminato(-3)). In former studies, the spin cluster has been treated as a homogenous, quasi-one-dimensional spin S=5/2 Heisenberg antiferromagnet. Our experiments reveal spectra, which consists of two different quadrupolar doublets. In consequence, there are two different Fe sites among the hexanuclear iron spin-cluster.     

Backscattering Mössbauer spectroscopy of Martian dust

We report on the determination of the mineralogy of the atmospherically suspended Martian dust particles using backscattering ⁵⁷Fe Mössbauer spectroscopy on dust accumulated onto the magnets onboard the Mars Exploration Rovers. The spectra can be interpreted in terms of minerals of igneous origin, and shows only limited, if any, amounts of secondary minerals that may have formed in the presence of liquid water. These findings suggest that the dust has formed in a dry environment over long time in the history of the planet.     

Identification of substitutional and interstitial Fe in 6H-SiC

Iron impurities on interstitial (Fe_i) and substitutional sites (Fe_S) in SiC have been detected by ⁵⁷Fe emission Mössbauer spectroscopy following implantation of radioactive ⁵⁷Mn⁺ parent ions. At temperatures <900 K two Fe_i species are found, assigned to quasi-tetrahedral interstitial sites surrounded by, respectively, four C (Fe_i,C) or Si atoms (Fe_i,Si). Above 900 K, the Fe_i,Si site is proposed to “transform” into the Fe_i,C site by a single Fe_i jump during the lifetime of the Mössbauer state (T _1/2?=?100 ns). Fe_i,C and substitutional Fe_S sites are stable up to >1,070 K.     

Creation of ferromagnetic properties of V–Fe and Zr–Fe alloys by hydrogen absorption

The results of investigations of V_1?y Fe _y H _x and Zr_1?y Fe _y H _x alloys by ⁵⁷Fe Mössbauer spectroscopy are presented and discussed in view of hydrogen ability to create ferromagnetic properties of the alloy. The results indicate two different possibilities of hydrogen influence on the hyperfine magnetic field. Hydrogen absorption causes the ferromagnetic behaviour of the alloys at significant lower iron concentration compared to the concentration of magnetic transition in binary alloys. The main reason for such behaviour is the anisotropic lattice expansion in hydrogenated V–Fe and Zr–Fe alloys as well as the decomposition of paramagnetic Zr-rich intermetallic compounds in the aftermath of the strong electron affinity of hydrogen for zirconium. These trends give rise to growth of magnetic clusters of Fe atoms so strong that they can participate in the overall magnetic properties of the system under investigation.     

The Characterization of FeZSM-5 by 57Fe Mössbauer Spectroscopy: Sensitivity Towards Nitrogen

Hyperfine Interactions - Mössbauer spectra were recorded at 4.2 K of an FeZSM-5 zeolite that has been treated with nitrogen at 623 K. Changes in the sample environment clearly show the...     

Experimental observation of vibrations produced by pulsed laser beam in MgO:57Fe

We report the first observation of a laser-produced vibration with the aid of Mössbauer techniques. Thin platelets of MgO single crystals were doped by diffusion of ⁵⁷Fe atoms. The illumination of the MgO:⁵⁷Fe sample with a pulsed Nd:YAG laser produced a significant broadening of the Mössbauer spectrum. In order to find out what caused these changes, we performed a series of time-domain experiments, in which the Mössbauer spectra were collected only during a 2.5 μs gate interval. This gate interval was swept from 5 μs to 190 μs over the time interval between the two laser pulses. After laser irradiation, the position of the Mössbauer line was found to be changing in time as a decaying oscillations of well-defined frequency, which can be due to the vibration of the sample induced by the laser pulse.     

NMR and Mössbauer Study of Al2O3–Eu2O3

Alumina–europia mixed oxides with 5 and 10 wt.% Eu₂O₃ were studied by Mössbauer spectroscopy, ²⁷Al MAS-NMR and X-ray diffraction (XRD). The samples were prepared by the sol–gel technique. The XRD patterns for the calcined samples show a broad peak around 2θ = 30° which is assigned to the Eu₂O₃; after treatment with hydrogen at 1073 K no reduction to Eu⁺² or Eu⁰ was observed. The NMR spectra show three peaks, which are assigned to the octahedral, pentahedral and tetrahedral aluminum sites; the intensity of each peak depends on the concentration of europium ions. The Mössbauer spectra of the calcined samples show a single peak near zero velocity which is attributed to the Eu⁺³; after H₂ treatment at 1073 K similar spectra were obtained, suggesting Eu⁺³ is not reducibly at this temperature.     

Moessbauer study and magnetic properties of electrochemical material LiFePO4

Magnetic properties and crystal symmetry of electrochemical material LiFePO4 have been investigated by Moessbauer spectroscopy and magnetization measurement. Magnetization reveals the antiferromagnetic nature of LiFePO4. Temperature dependence of inverse susceptibility and that of hyperfine field confirm that there is an antiferromagnetic-paraxaagnetic transition at about 50K.     

Study on charge transfer interaction and valence state of layered perovskite-type mixed valence complex [NH3(CH2) n NH3]2[(AuII2)(AuIIII4)(I3)2] (n = 7, 8), by means of 197Au Mössbauer spectroscopy

Cs₂[Au^I X ₂][Au^III X ₄](X = Cl, Br, and I) is well known for the three-dimensional perovskite-type gold mixed valence system. Recently, layered perovskite-type gold mixed valence complexes, [NH₃(CH₂) _n NH₃]₂[(Au^II₂)(Au^IIII₄)(I₃)₂] (n = 7 and 8), have been synthesized. We have investigated the relationship between the structural dimensionality and the Au^I–Au^III charge transfer interaction for Cs₂[Au^II₂][Au^IIII₄] and [NH₃(CH₂) _n NH₃]₂[(Au^II₂)(Au^IIII₄)(I₃)₂] (n = 7 and 8) by means of ¹⁹⁷Au Mössbauer spectroscopy.     

Antiferromagnetism in double-layered perowskitic oxides SrLa2Fe2O7 and BaLa2Fe2O7

Il Nuovo Cimento D - Two double-layered perowskitic compounds have been investigated by XRD analysis and Mössbauer spectroscopy. The experimental data allow the conclusion that magnetization...     

Reactions of 57Mn implanted into solid oxygen

The in-beam Mössbauer spectroscopy using a short-lived ⁵⁷Mn (T _1/2=1.5 min) beam was carried out to study the production of the exotic chemical species of ⁵⁷Fe atoms arising from ⁵⁷Mn implanted into solid oxygen. The obtained spectra can be analyzed by four components of doublets at least, which are assigned to be novel Fe species of FeO, Fe(O₂), (O₂)FeO₂, and Fe(O₂)₂, on the basis of ab initio molecular orbital calculations.     

237Np and 57Fe Mössbauer study of NpFeGa5

⁵⁷Fe and ²³⁷Np Mössbauer ōmeasurements have been performed for NpFeGa₅, which is one of the so-called neptunium 1-1-5 compounds. The ⁵⁷Fe Mössbauer spectra below T _N = 118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the ⁵⁷Fe nucleus is determined to be 1.98 ± 0.05 T at 10 K. From the ²³⁷Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the ²³⁷Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μ_B using the Np atomic magnetic moment of 0.86 μ_B determined by the neutron diffraction study.     

Tin-doped spinel-related oxides of composition M3O4 (M = Mn, Fe, Co)

Tin-doped compounds of spinel-related M₃O₄ (M = Fe, Mn, Co) have been studied by ¹¹⁹Sn and ⁵⁷Fe Mössbauer spectroscopy in the temperature range of 20–600 K. The ¹¹⁹Sn Mössbauer spectra recorded down to 20 K from the non-iron-containing compounds of Co₃O₄ and Mn₃O₄ contained only doublets showing no transfer of magnetic properties from cobalt or manganese to the dopant tin ions. In contrast, the tin-doped-(FeCo)₃O₄ and (FeMn)₃O₄ gave ¹¹⁹Sn and ⁵⁷Fe Mössbauer spectra, which showed magnetic hyperfine interactions. The Curie temperature has been estimated for the former sample.     

119Sn Mössbauer study of nickel–tin anodes for rechargeable lithium-ion batteries

¹¹⁹Sn Mössbauer spectrometry has been carried out on Ni–Sn alloys (Ni₃Sn LT, Ni₃Sn₂ LT and Ni₃Sn₄) and combined with ab initio calculations. Lithium insertion/extraction mechanisms of the most interesting compound (Ni₃Sn₄) have been studied from ¹¹⁹Sn Mössbauer measurements. The first discharge shows a plateau close to 0.0 V, which can be attributed to the formation of the Li₇Sn₂ alloy.     

Iron-based nanocrystalline alloys investigated by 57Fe Mössbauer spectrometry

Soft magnetic nanocrystalline alloys have attracted great fundamental interest in recent years due to their two-phase structural and magnetic behaviour. We review first the reliability of the fitting procedures of spectra obtained by ⁵⁷Fe Mössbauer spectrometry which is a very efficient tool to investigate such materials. Then, we report the common features which characterise the temperature dependence of Mössbauer spectra; the hyperfine field temperature dependence of both the crystalline grains and the intergranular phase is discussed for different crystalline fractions in order to model the magnetic behaviour of the nanocrystalline alloys.     

Volume and surface oxidation of basalt

Natural, Fe²⁺-rich basalt glass (quenched lava) was heat treated as glass pieces and glass powder in air, in 6.0 Ar and in a 9×10^?6 mbar vacuum below temperatures of significant crystallization to access volume and surface oxidation by ⁵⁷Fe Mössbauer spectroscopy. While no oxidation occurs upon heating in vacuum, the amount of Fe³⁺ formed in powder (surface oxidation) is about 10 times higher than in pieces (volume oxidation), and surface oxidation is of the same order in air and Ar. This effect is assigned to chemisorption of water or CO₂. Crystalline basalt, investigated by wet chemistry, includes five glass pieces treated above T of crystallization in air and in 6.0 Ar, and three lava samples of increasing depth up to 9 cm of lava lobes. The high Fe₂O₃ of all these crystalline samples is explained as a stabilization of Fe³⁺ due to the change of the local electronic environment in the course of crystallization; volume oxidation therefore appears to be independent on the environmental atmosphere.     

Characterisation of the reduction properties of La0.5Sr0.5Fe0.5Co0.5O3

We report here on the characterisation by temperature programmed reduction, ⁵⁷Fe Mössbauer spectroscopy and X-ray absorption spectroscopy of the phases resulting from treatment of the perovskite-related material La_0.5Sr_0.5Fe_0.5Co_0.5O₃ in a flowing 90% hydrogen/10% nitrogen atmosphere. The results show that treatment of La_0.5Sr_0.5Fe_0.5Co_0.5O₃ (which contains approximately 50% Fe⁴⁺ and 50% Fe³⁺) in the flowing 90% hydrogen/10% nitrogen atmosphere at 600°C does not result in the reduction of any of the constituent elements of the material and that the perovskite structure is still retained. The Mössbauer spectrum recorded following heating in the gaseous reducing environment at 1,000°C shows the presence of metallic iron, an Fe³⁺-containing phase with parameters compatible with the presence of SrLaFeO₄ which has a K₂NiF₄-type structure, and a paramagnetic Fe³⁺ phase. The X-ray absorption spectroscopy results show the presence of metallic cobalt. The Mössbauer spectrum recorded following heating at 1,200°C continues to show the Fe³⁺-containing components plus a larger contribution from metallic iron. The X-ray absorption spectroscopy results show the presence of metallic cobalt, SrLaFeO₄, La₂O₃ and SrO.