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1.
We have successfully synthesized a polycrystalline sample of tetragonal garnet-related Li-ion conductor Li7La3Hf2O12 by solid state reaction. The crystal structure is analyzed by the Rietveld method using neutron powder diffraction data. The structure analysis identifies that tetragonal Li7La3Hf2O12 has the garnet-related type structure with a space group of I41/acd (no. 142). The lattice constants are a=13.106(2) Å and c=12.630(2) Å with a cell ratio of c/a=0.9637. The crystal structure of tetragonal Li7La3Hf2O12 has the garnet-type framework structure composed of dodecahedral La(1)O8, La(2)O8 and octahedral HfO6. Li atoms occupy three types of crystallographic site in the interstices of this framework structure, where Li(1) atom is located at the tetrahedral 8a site, and Li(2) and Li(3) atoms are located at the distorted octahedral 16f and 32g sites, respectively. These Li sites are filled with the Li atom. The present tetragonal Li7La3Hf2O12 sample exhibits bulk Li-ion conductivity of σb=9.85×10−7 S cm−1 and grain-boundary Li-ion conductivity of σgb=4.45×10−7 S cm−1 at 300 K. The activation energy is estimated to be Ea=0.53 eV in the temperature range of 300-580 K.  相似文献   

2.
The crystal structure of metastable Li2Si3O7 was determined from single crystal X-ray diffraction data. The orthorhombic crystals were found to adopt space group Pmca with unit cell parameters of , and . The content of the cell is Z=4. The obtained structural model was refined to a R-value of 0.035. The structure exhibits silicate sheets, which can be classified as [Si6O14] using the silicate nomenclature of Liebau. The layers are build up from zweier single chains running parallel to c. Raman spectra are presented and compared with other silicates. Furthermore, the structure is discussed versus Na2Si3O7.  相似文献   

3.
The crystal structures of Ca2Ln3Sb3O14 (Ln=La, Pr, Nd and Y) and Ca2Sb2O7 at room temperature were refined by the Rietveld method using combined X-ray and neutron powder diffraction data. Ca2Sb2O7 adopts the weberite structure having the space group Imma. The structures of Ca2Ln3Sb3O14 are, however, neither the orthorhombic nor the tetragonal chiolite as has been suggested previously. They crystallize in the monoclinic space group I2/m11 belonging to a hitherto unknown type of deformation of the parent (orthorhombic) weberite structure.  相似文献   

4.
The crystal structure of Ca5Te3O14 at room temperature was studied by the Rietveld method using combined X-ray and neutron powder diffraction data. The compound crystallizes in the space group Cmca with the lattice parameters a=10.4268(2) Å, b=10.3908(2) Å and c=10.4702(2) Å. The structure of Ca5Te3O14 is chiolite-like and consists of a framework of corner-linked TeO6 octahedral layers in which a linear TeO2 group of every fourth octahedron is substituted by a Ca atom. This type of structure was previously observed in BaSr4U3O14. The relationship between the chiolite-like structure and the fluorite structure is discussed.  相似文献   

5.
The garnets Li3Nd3W2O12 and Li5La3Sb2O12 have been prepared by heating the component oxides and hydroxides in air at temperatures up to 950 °C. Neutron powder diffraction has been used to examine the lithium distribution in these phases. Both compounds crystallise in the space group with lattice parameters a=12.46869(9) Å (Li3Nd3W2O12) and a=12.8518(3) Å (Li5La3Sb2O12). Li3Nd3W2O12 contains lithium on a filled, tetrahedrally coordinated 24d site that is occupied in the conventional garnet structure. Li5La3Sb2O12 contains partial occupation of lithium over two crystallographic sites. The conventional tetrahedrally coordinated 24d site is 79.3(8)% occupied. The remaining lithium is found in oxide octahedra which are linked via a shared face to the tetrahedron. This lithium shows positional disorder and is split over two positions within the octahedron and occupies 43.6(4)% of the octahedra. Comparison of these compounds with related d0 and d10 phases shows that replacement of a d0 cation with d10 cation of the same charge leads to an increase in the lattice parameter due to polarisation effects.  相似文献   

6.
Li2CoTi3O8 has an ordered Li2BB′3O8 spinel structure, space group P4332, at room temperature with 3:1 ordering of Ti and Li on the octahedral sites, and Li, Co disordered over the tetrahedral site. Rietveld refinement of variable temperature neutron powder diffraction data has shown an order-disorder phase transition in Li2CoTi3O8 which commences at ∼500 °C with Li and Co mixing on the tetrahedral and 4-fold octahedral sites and is complete at a first order structural discontinuity at ∼915 °C. The fraction of Ti on the 12-fold octahedral site exhibits a small decrease with increasing temperature, which may suggest that the disordering involves all three cations. Above 930 °C, the structure, space group Fdm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site, although Co still exhibits a preference for tetrahedral coordination. A labelling scheme for ordered and partially ordered 3:1 spinels is devised which focuses on the occupancy of the Li,B cations.  相似文献   

7.
Garnet-structure related metal oxides with the nominal chemical composition of Li5La3Nb2O12, In-substituted Li5.5La3Nb1.75In0.25O12 and K-substituted Li5.5La2.75K0.25Nb2O12 were prepared by solid-state reactions at 900, 950, and 1000 °C using appropriate amounts of corresponding metal oxides, nitrates and carbonates. The powder XRD data reveal that the In- and K-doped compounds are isostructural with the parent compound Li5La3Nb2O12. The variation in the cubic lattice parameter was found to change with the size of the dopant ions, for example, substitution of larger In3+(rCN6: 0.79 Å) for smaller Nb5+ (rCN6: 0.64 Å) shows an increase in the lattice parameter from 12.8005(9) to 12.826(1) Å at 1000 °C. Samples prepared at higher temperatures (950, 1000 °C) show mainly bulk lithium ion conductivity in contrast to those synthesized at lower temperatures (900 °C). The activation energies for the ionic conductivities are comparable for all samples. Partial substitution of K+ for La3+ and In3+ for Nb5+ in Li5La3Nb2O12 exhibits slightly higher ionic conductivity than that of the parent compound over the investigated temperature regime 25-300 °C. Among the compounds investigated, the In-substituted Li5.5La3Nb1.75In0.25O12 exhibits the highest bulk lithium ion conductivity of 1.8×10−4 S/cm at 50 °C with an activation energy of 0.51 eV. The diffusivity (“component diffusion coefficient”) obtained from the AC conductivity and powder XRD data falls in the range 10−10-10−7 cm2/s over the temperature regime 50-200 °C, which is extraordinarily high and comparable with liquids. Substitution of Al, Co, and Ni for Nb in Li5La3Nb2O12 was found to be unsuccessful under the investigated conditions.  相似文献   

8.
The single crystals of caesium magnesium titanium (IV) tri-oxo-tetrakis-diphosphate bis-monophosphate, Cs3.70Mg0.60Ti2.78(TiO)3(P2O7)4(PO4)2, crystallize in sp. gr. P-1 (No. 2) with cell parameters a=6.3245(4), b=9.5470(4), c=15.1892(9) Å, α=72.760(4), β=85.689(5), γ=73.717(4), z=1. The titled compound possesses a three-dimensional tunnel structure built by the corner-sharing of distorted [TiO6] octahedra, [Ti2O11] bioctahedra, [PO4] monophosphate and [P2O7] pyrophosphate groups. The Cs+ cations are located in the tunnels. The partial substitution of Ti positions with Mg atoms is observed. The negative charge of the framework is balanced by Cs cations and Mg atoms leading to pronounced concurrency and orientation disorder in the [P2O7] groups, which coordinate both.  相似文献   

9.
The crystal structures, synthesis and physical properties of ruthenium hollandites ALi2Ru6O12 (A=Na, K) with a new pseudo-hexagonal structure type are described. Analogous to tetragonal hollandites, the framework is made of MO6 octahedra in double chains that share corner oxygens with each other to create interstitial tunnels. The tunnels are either hexagonal or triangular in cross-section. Magnetic susceptibilities, low temperature specific heat, and electrical resistivities are reported. The data indicate that these materials are normal, low density of states metals. This new structure type can be extended from A=Group I to A=Group II ions with the synthesis of CaLi2Ru6O12 and SrLi2Ru6O12.  相似文献   

10.
The complex perovskite BiMn7O12 occurs with two polymorphic structures, cubic and monoclinic. Currently their crystal structures are investigated with high-resolution synchrotron powder X-ray diffraction at room temperature. Rietveld analysis reveals unusual behavior for, respectively, the oxygen and bismuth atoms in the monoclinic and cubic phases. Bond valence calculations indicate that all the Mn atoms in both the phases are in trivalent state. Possible roles of the 6s2 lone-pair electrons of Bi3+ in BiMn7O12 are discussed in comparison with the LaMn7O12 phase that is isomorphic to monoclinic BiMn7O12. Multiple roles of the lone-pair electrons are revealed, causing (i) A-site cation deficiency, (ii) octahedral tilting, (iii) A-site cation displacement, and (iv) Mn3+ Jahn-Teller (JT) distortion. Relationships between the monoclinic and cubic phases are discussed with emphasis on the MnO2 and MnO6 local structural aspects. All Mn atoms in the monoclinic polymorph have distorted coordination consistent with JT-active Mn(III) high spin, whereas for the cubic polymorph, the B-site Mn atoms show regular octahedral coordination.  相似文献   

11.
New compounds CaY2Ge3O10 and CaY2Ge4O12 were prepared by heating mixtures of CaCO3, Y2O3 and GeO2 at 1200 °C. CaY2Ge3O10 is stable at 1300 °C, while CaY2Ge4O12 decomposes into a melt and CaY2Ge3O10 at approximately 1250 °C. We obtained single crystals of CaY2Ge3O10 by cooling a sample with an initial composition of Ca:Y:Ge=1:2:8 from 1300 °C with a rate of −6 °C/h. The crystal structure of CaY2Ge3O10 was determined by single crystal X-ray diffraction. CaY2Ge3O10 crystallizes in the monoclinic space group P21/c with a=6.0906(8), b=6.8329(8), and β=109.140(3)°, Z=4, and R1=0.029 for I>2σ(I). In the structure of CaY2Ge3O10, Ca and Y atoms are situated disorderly in three 7-fold coordination sites between isolated germanate groups of triple GeO4 tetrahedra, Ge3O10. The structural formula of CaY2Ge3O10 is expressed as (Ca0.45Y0.55)(Ca0.46Y0.54)(Ca0.09Y0.91)Ge3O10. The crystal structure of CaY2Ge4O12 was analyzed by the Rietveld method for the X-ray powder diffraction pattern. CaY2Ge4O12 is isotypic with SrNa2P4O12, crystallizing in the orthorhombic space group P4/nbm, a=9.99282(6), , Z=2, Rwp=0.092, Rp=0.067. CaY2Ge4O12 contains four-membered GeO4-tetrahedra rings, Ge4O12. Eight-fold coordinated square-anitiprism sites and 6-fold octahedral sites between the layers of the Ge4O12 rings are occupied by Y atom and Ca/Y atoms, respectively The structural formula is Y(Ca0.5Y0.5)2Ge4O12.  相似文献   

12.
A new cesium uranyl niobate, Cs9[(UO2)8O4(NbO5)(Nb2O8)2] or Cs9U8Nb5O41 has been synthesized by high-temperature solid-state reaction, using a mixture of U3O8, Cs2CO3 and Nb2O5. Single crystals were obtained by incongruent melting of a starting mixture with metallic ratio=Cs/U/Nb=1/1/1. The crystal structure of the title compound was determined from single crystal X-ray diffraction data, and solved in the monoclinic system with the following crystallographic data: a=16.729(2) Å, b=14.933(2) Å, c=20.155(2) Å β=110.59(1)°, P21/c space group and Z=4. The crystal structure was refined to agreement factors R1=0.049 and wR2=0.089, calculated for 4660 unique observed reflections with I?2σ(I), collected on a BRUKER AXS diffractometer with MoKα radiation and a CCD detector.In this structure the UO7 uranyl pentagonal bipyramids are connected by sharing edges and corners to form a uranyl layer corresponding to a new anion-sheet topology, and creating triangular, rectangular and square vacant sites. The two last sites are occupied by Nb2O8 entities and NbO5 square pyramids, respectively, to form infinite uranyl niobate sheets stacking along the [010] direction. The Nb2O8 entities result from two edge-shared NbO5 square pyramids. The Cs+ cations are localized between layers and ensured the cohesion of the structure.The cesium cation mobility between the uranyl niobate sheets was studied by electrical measurements. The conductivity obeys the Arrhenius law in all the studied temperature domains. The observed low conductivity values with high activation energy may be explained by the strong connection of the Cs+ cations to the infinite uranyl niobate layers and by the high density of these cations in the interlayer space without vacant site.Infrared spectroscopy investigated at room temperature in the frequency range 400-4000 cm−1, showed some characteristic bands of uranyl ion and niobium polyhedra.  相似文献   

13.
Bi2O3-MoO3 system shows a large panoply of phases depending on Bi/Mo ratio, among them, the low temperature phases of the homologous series Bi2(n+2)MonO6(n+1) with n=3, 4, 5 and 6. They exhibit, alike most of the phases of this system, strong fluorite sub-network. Nevertheless, a multitechnique approach has been followed in order to solve the crystal structure of the n=3 member, i.e. Bi10Mo3O24. From ab initio indexing X-ray powder pattern cell parameters were derived. It belongs to the monoclinic system, space group C2, with cell parameters: a=23.7282(2) Å, b=5.64906(6) Å, c=8.68173(9) Å, β=95.8668(7)° with Z=2. The matrix relating this cell with the fluorite one is 4 0 1/0 1 0/ 0  and a cationic localization was derived. HRTEM allowed the cationic Bi and Mo order to be modified and specified, as well as to build up a full structural ab initio model on the basis of crystal chemistry considerations. Simultaneous Rietveld refinement of multipattern X-ray and neutron powder diffraction data taking advantage of the neutron scattering length for O location have been performed. The goodness of the model was ascertained by low reliability factors, weighted Rb=4.97% and Rf=3.21%. This complex Bi10Mo3O24 structure, with 5Bi, 2Mo and 13O in different crystallographic positions of the asymmetric unit, shows good agreement between observed and calculated patterns within the data resolution. Moreover, the determination of this structure sets the basis for the crystallographic characterization of the complete family Bi2(n+2)MonO6(n+1), whose guidelines are also evidenced in this paper.  相似文献   

14.
Single crystals of NaCoO2 have been successfully synthesized for the first time by a flux method at 1323 K. A single-crystal X-ray diffraction study confirmed the trigonal space group and the lattice parameters , . The crystal structure has been refined to the conventional values R=1.9% and wR=2.1% for 309 independent observed reflections. The electron density distribution of NaCoO2 has been studied by the maximum entropy method (MEM) using single-crystal X-ray diffraction data obtained at 298 K. From the results of the MEM analysis, the strong covalent bonding was clearly observed between Co and O atoms, while no bonding was observed around Na atoms. We also calculated the electron density of NaCoO2 by first principles calculations. The electron density obtained experimentally is in good agreement with the theoretical one.  相似文献   

15.
The crystal structures of Ba2LnSbO6 (Ln=La, Pr, Nd and Sm) at room temperature have been investigated by profile analysis of the Rietveld method using either combined X-ray and neutron powder diffraction data or X-ray powder diffraction data. It has been shown that the structure of Ba2LnSbO6 with Ln =La, Pr and Nd are neither monoclinic nor cubic as were previously reported. They are rhombohedral with the space group . The distortion from cubic symmetry is due to the rotation of the LnO6/SbO6 octahedra about the primitive cubic [111]p-axis. On the other hand, the structure of Ba2SmSbO6 is found to be cubic. All compounds contain an ordered arrangement of LnO6 and SbO6 octahedra.  相似文献   

16.
Single crystals of iron(II) pyroborate, Fe2B2O5, were prepared at 1000–1050 °C under an argon atmosphere. The crystals were transparent, yellowish in color and needle-like or columnar. The crystal structure of Fe2B2O5 was analyzed by single-crystal X-ray diffraction. Refined triclinic unit cell parameters were a=3.2388(2), b=6.1684(5), c=9.3866(8) Å, α=104.613(3)°, β=90.799(2)° and γ=91.731(2)°. The final reliability factors of refinement were R1=0.020 and wR2=0.059 [I > 2σ(I)]. Transmittance over 50% in the visible light region from 500 to 750 nm was observed for a single crystal of Fe2B2O5 with a thickness of about 0.3 mm. The light absorption edge estimated from a diffuse reflectance spectrum was at around 350 nm (3.6 eV). Magnetic susceptibility was measured for single crystals at 4–300 K. Fe2B2O5 showed antiferromagnetic behavior below the Néel temperature, TN≈70 K, and the Weiss temperature was TW=36 K. The effective magnetic moment of Fe was 5.3μB.  相似文献   

17.
The crystal structure of the promising optical materials Ln2M2+Ge4O12, where Ln=rare-earth element or Y; M=Ca, Mn, Zn and their solid solutions has been studied in detail. The tendency of rare-earth elements to occupy six- or eight-coordinated sites upon iso- and heterovalent substitution has been studied for the Y2−xErxCaGe4O12 (x=0-2), Y2−2xCexCa1+xGe4O12 (x=0-1), Y2Ca1−xMnxGe4O12 (x=0-1) and Y2−xPrxMnGe4O12 (x=0-0.5) solid solutions. A complex heterovalent state of Eu and Mn in Eu2MnGe4O12 has been found.  相似文献   

18.
Single crystals of the LiCoO2-LiAlO2 solid solution compounds LiAl0.32Co0.68O2 and LiAl0.71Co0.29O2 were synthesized by a flux method using alumina crucibles. A single-crystal X-ray diffraction study confirmed the trigonal space group and the lattice parameters a=2.8056(11) Å, c=14.1079(15) Å, and c/a=5.028 for LiAl0.32Co0.68O2, and a=2.8023(7) Å, c=14.184(4) Å, and c/a=5.061 for LiAl0.71Co0.29O2. The crystal structures have been refined to the conventional values R=3.2% and wR=2.4% for LiAl0.32Co0.68O2, and R=3.6% and wR=3.5% for LiAl0.71Co0.29O2. The evidence of the location of Al atoms in the pseudotetragonal coordination (6c site), reported previously in LiAl0.2Co0.8O2, could not be observed in the present electron density distribution maps in both LiAl0.32Co0.68O2 and LiAl0.71Co0.29O2. The octahedral distortion analysis indicated that the Al-substitution strongly affected the distortion of the LiO6 octahedron in this solid-solution compound system, but hardly affected that of the (Al.Co)O6 octahedron.  相似文献   

19.
A new bismuth tellurium oxychloride was obtained by reaction of BiOCl and TeO2 in air. According to energy dispersive X-ray spectroscopy and neutron powder diffraction refinement the composition of the substance was determined as Bi0.87Te2O4.9Cl0.87. The new compound crystallizes in the trigonal system space group R 3¯ (#148), Z=6, a=4.10793(4), c=31.1273(4) Å, χ2=3.20, wRp=0.0369. Bi0.87Te2O4.9Cl0.87 has a new type of layered structure constructed by Bi-Te-O layers separated by chloride ions. The Te atoms in Bi0.87Te2O4.9Cl0.87 show an unusual umbrella-like environment. A comparison with known related structures has been made.  相似文献   

20.
Two types of strontium-, barium- and europium-containing germanides have been synthesized using high temperature reactions and characterized by single-crystal X-ray diffraction. All reported compounds also contain mixed-occupied Li and In atoms, resulting in quaternary phases with narrow homogeneity ranges. The first type comprises EuLi0.91(1)In0.09Ge2, SrLi0.95(1)In0.05Ge2 and BaLi0.99(1)In0.01Ge2, which crystallize in the orthorhombic space group Pnma (BaLi0.9Mg0.1Si2 structure type, Pearson code oP16). The lattice parameters are a=7.129(4)-7.405(4) Å; b=4.426(3)-4.638(2) Å; and c=11.462(7)-11.872(6) Å. The second type includes Eu2Li1.36(1)In0.64Ge3 and Sr2Li1.45(1)In0.55Ge3, which adopt the orthorhombic space group Cmcm (Ce2Li2Ge3 structure type, Pearson code oC28) with lattice parameters a=4.534(2)-4.618(2) Å; b=19.347(8)-19.685(9) Å; and c=7.164(3)-7.260(3) Å. The polyanionic sub-structures in both cases feature one-dimensional Ge chains with alternating Ge-Ge bonds in cis- and trans-conformation. Theoretical studies using the tight-binding linear muffin-tin orbital (LMTO) method provide the rationale for optimizing the overall bonding by diminishing the π-p delocalization along the Ge chains, accounting for the experimentally confirmed substitution of Li forIn.  相似文献   

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