Ca10Ge16B6O51 and Cd12Ge17B8O58: two types of new 3D frameworks based on BO4 tetrahedra and 1D [Ge4O12]n chains

Two new acentric borogermanates, Ca(10)Ge(16)B(6)O(51) (Pba2) and Cd(12)Ge(17)B(8)O(58) (P4), have been successfully synthesized by high-temperature solid-state reactions of CaCO(3) (or CdCO(3)), GeO(2), and H(3)BO(3). Both structures display the same one-dimensional (1D) [Ge(4)O(12)](n) chains composed of GeO(4) tetrahedra and GeO(6) octahedra. In Ca(10)Ge(16)B(6)O(51), neighboring 1D [Ge(4)O(12)](n) chains are condensed into a two-dimensional (2D) [Ge(4)O(10.75)](n) layer via corner sharing, and such layers are further interconnected by "isolated" BO(4) tetrahedra and B(2)O(7) dimers into a three-dimensional (3D) framework, forming 1D tunnels of 5-, 6-, and 7-MRs along the c axis that are occupied by Ca(2+) cations. In Cd(12)Ge(17)B(8)O(58), neighboring 1D [Ge(4)O(12)](n) chains are interconnected into a [Ge(4)O(10.5)](n) open framework via corner sharing with large pores filled by big [Ge(B(2)O(7))(4)](28-) clusters, leading to formation of three types of 1D tunnels of 5-, 6-, and 7-membered rings (MRs) along the c axis which are occupied by the Cd(2+) cations. Both compounds are transparent in the range of 0.3-6.67 μm and exhibit very weak SHG responses.     

New second-order NLO materials based on polymeric borate clusters and GeO4 tetrahedra: a combined experimental and theoretical study

Three novel rubidium borogermanates with three types of noncentrosymmetric structures, namely, RbGeB(3)O(7), Rb(2)GeB(4)O(9), and Rb(4)Ge(3)B(6)O(17), have been synthesized by high-temperature solid-state reactions in platinum crucibles. The structure of RbGeB(3)O(7) features a three-dimensional (3D) anionic framework composed of cyclic B(3)O(7) groups corner-sharing GeO(4) tetrahedra. The structure of Rb(2)GeB(4)O(9) shows a 3D anionic framework based on B(4)O(9) clusters connected by GeO(4) tetrahedra via corner sharing. The structure of Rb(4)Ge(3)B(6)O(17) is a novel 3D anionic framework composed of cyclic B(3)O(8) groups, Ge(2)O(7) dimers, and GeO(4) tetrahedra that are interconnected via corner sharing. Second harmonic generation (SHG) measurements indicate that RbGeB(3)O(7), Rb(2)GeB(4)O(9), and Rb(4)Ge(3)B(6)O(17) display moderate SHG responses that are approximately 1.3, 2.0, and 1.3 × KH(2)PO(4) (KDP), respectively, which are slightly smaller than those from theoretical calculations (about 3.7, 2.8, and 2.4 × KDP, respectively).     

Ba3[Ge2B7O16(OH)2](OH)(H2O) and Ba3Ge2B6O16: novel alkaline-earth borogermanates based on two types of polymeric borate units and GeO4 tetrahedra

Two new barium borogermanates with two types of novel structures, namely, Ba(3)[Ge(2)B(7)O(16)(OH)(2)](OH)(H(2)O) and Ba(3)Ge(2)B(6)O(16), have been synthesized by hydrothermal or high-temperature solid-state reactions. They represent the first examples of alkaline-earth borogermanates. Ba(3)[Ge(2)B(7)O(16)(OH)(2)](OH)(H(2)O) crystallized in a polar space group Cc. Its structure features a novel three-dimensional anionic framework composed of [B(7)O(16)(OH)(2)](13-) polyanions that are bridged by Ge atoms with one-dimensional (1D) 10-membered-ring (MR) tunnels along the b axis. The Ba(II) cations, hydroxide ions, and water molecules are located at the above tunnels. Ba(3)Ge(2)B(6)O(16) crystallizes in centrosymmetric space group P1. Its structure exhibits a thick layer composed of circular B(6)O(16) units connected by GeO(4) tetrahedra via corner sharing, forming 1D 4- and 6-MR tunnels along the c axis. Ba1 ions reside in the tunnels of the 6-MRs, whereas Ba2 ions are located at the interlayer space. Both compounds feature new types of topological structures. Second-harmonic-generation (SHG) measurements indicate that Ba(3)[Ge(2)B(7)O(16)(OH)(2)](OH)(H(2)O) displays a weak SHG response of about 0.3 times that of KH(2)PO(4). Optical, thermal stability, and ferroelectric properties as well as theoretical calculations have also been performed.     

(C4N3H15)[(BO2)2(GeO2)4]: the first organically templated 3D borogermanate showing 1D 12-rings, large channels, and a novel zeolite-type framework topology constructed from Ge8O24 and B2O7 cluster units

The first organically templated 3D borogermanate with a novel zeolite-type topology, (C4N3H15)[(BO2)2(GeO2)4] FJ-17, has been solvothermally synthesized and characterized by IR spectroscopy, powder X-ray diffraction (PXRD), TGA, and single-crystal X-ray diffraction. The compound crystallized in the monoclinic space group P2(1)/c with a = 6.967(1) A, b = 10.500(1) A, c = 20.501(1) A, beta = 90.500(3) degrees , V = 1499.68(8) A3, and Z = 4. The framework topology of this compound is the previously unknown topology with the vertex symbols 3.4.3.9.3.8(2) (vertex 1), 3.8.3.4.6(2).9(2) (vertex 2), 3.8(2).4.6(2).6(2).8 (vertex 3), 4.8.4.8.8(3).12 (vertex 4), 4.8.4.8.8(2).12 (vertex 5), and 3.8.4.6(2).6.8(2) (vertex 6). The structure is constructed from Ge8O24 and B2O7 clusters. The Ge8O24 cluster contains eight GeO4 tetrahedra that share vertices; the B2O7 unit is composed of two BO4 tetrahedra sharing a vertex. The cyclic Ge8O24 clusters connect to each other through vertices to form a 2D layer with 8,12-nets. The adjacent layers are further linked by the dimeric B2O7 cluster units, resulting in a 3D framework with 12- and 8-ring channels along the a and b axes, respectively. In addition, there is a unique B2GeO9 3-ring in the structure.     

K2[Ge(B4O9)].2H2O: a unique 3D alternating linkage mode of a B4O9 cluster and GeO4 unit in borogermanate with two pairs of interweaving double helical channels

The first noncentrosymmetric potassium templated borogermanate, K(2)[Ge(B(4)O(9))].2H(2)O, has been solvothermally synthesized and characterized by IR, SEM, powder X-ray diffraction (PXRD), TGA, energy dispersive spectroscopy (EDS), single crystal X-ray diffraction, and second harmonic generation (SHG) activity, respectively. This compound crystallized in the monoclinic space group Cc with a = 6.793(1) A, b = 12.0699(3) A, c = 11.895(3) A, beta = 91.156(4) degrees, V = 975.1(4) A(3), and Z = 4. Interestingly, the structure possesses a unique 3D alternating linkage mode of B(4)O(9) clusters and GeO(4) units and contains two pairs of interweaving double helical channels with a 10-membered ring. In one, the right- and left-handed helices couple each other, and in the other, the left- and right-handed helices couple together. The compound exhibits distinct nonlinear optical (NLO) properties because it lacks a symmetric center. Furthermore, the framework of the title compound not only displays high thermal stability but also can be recoverable to a large degree during a dehydration-hydration cycle.     

GeO2 natrolite-type infinite four and eight R-containing layers in a 2D pure-Ge framework: Ge3O5(OH)4[C2N2H10

A new two-dimensional framework germanate, Ge3O5(OH)4[C2N2H10] (denoted ICMM-8), with a 3:9 Ge:O ratio has been synthesized, using a mixture of pyridine, water, and ethanol as the solvent and 1,4-diazabicyclo[2.2.2]octane and ethylenediamine as the structure-directing agents, under solvothermal conditions. The structure was determined by single-crystal X-ray diffraction. In this new compound, the GeO2 natrolite-type infinite four and eight R-containing layers appears for the first time in a pure GeO2 framework. The total 2D structure is built up from SBU-6, four tetrahedra, and two octahedra. The hydroxyl groups occupy four positions of each octahedral germanium atom. The compound is characterized by IR spectra and TGA-DTA. Crystal data: Ge3O5(OH)4[C2N2H10], monoclinic space group P2(1)/c; a = 11.3570(9) Angstroms, b = 8.8819(7) Angstroms, c = 9.9200(8) Angstroms, beta = 90.710(1), V = 1000.6(1) Angstroms(3), Z = 4, R(1) = 0.044 (I > 2(I)), and wR(2) = 0.1051 (all data).     

Investigation of the GeO2-1,6-diaminohexane-water-pyridine-HF phase diagram leading to the discovery of two novel layered germanates with extra-large rings

The systematic exploration of the phase diagram of the GeO(2)-1,6-diaminohexane-water-pyridine-HF system has allowed the identification of specific roles of the HF, H(2)O contents, and HF/H(2)O ratio in the formation of Ge(7)X(19) (Ge(7)), Ge(9)X(25-26) (Ge(9)), and Ge(10)X(28) (Ge(10)) clusters (X = O, OH, F). This work has led to the discovery of two novel structures with extra-large 18-membered rings accommodating 1,6-diaminohexane (DAH): SU-63, |1.5H(2)DAH|[Ge(7)O(14)X(3)]·2H(2)O, a layered germanate constructed from Ge(7) clusters with the Kagome? topology, and SU-64, |11H(2)DAH|[Ge(9)O(18)X(4)][Ge(7)O(14)X(3)](6)·16H(2)O, a germanate built of two-dimensional slabs containing both Ge(7) and Ge(9) clusters (X = OH or F). We also put SU-64 in context with previously reported cluster germanate compounds with related topologies by means of a simple crystal deconstruction study.     

New members in the Ni(n+1)(QO3)nX2 family: unusual 3D network based on Ni4ClO3 cubane-like clusters in Ni7(TeO3)6Cl2

Three new members in the family of nickel(II) tellurium(IV)/selenium(IV) oxyhalides generally formulated as Ni(n+1)(QO3)nX2 (Q = Te, X = Cl, n = 6, 10; Q = Se, X = Br, n = 4) have been synthesized by solid-state reactions of NiX2, QO2, and NiO (or Ni2O3) at high temperature. The structure of Ni7(TeO3)6Cl2 features a novel 3D network based on Ni4ClO3 cubane-like clusters with Te atoms located at the cavities of the network. Ni4ClO3 clusters are interconnected into a hexagonal layer through additional O...O edges. The neighboring two layers are further interconnected, via sharing of common Ni(II) atoms, into a novel 3D network. The 3D open framework of Ni5(SeO3)4Br2 is built from 2D nickel(II) oxybromide layers bridged by Se and additional Ni atoms. The structure of Ni11(TeO3)10Cl2 features a condensed 3D network based on NiO5Cl, NiO6, and NiO5 polyhedra interconnected via corner and edge sharing, as well as O-Te-O bridges. The results of magnetic property measurements indicate that all three compounds display antiferromagnetic interactions between nickel(II) centers.     

NH4[BGe3O8]: a new borogermanate framework made of infinite-chain building blocks

A new microporous borogermanate NH4[BGe3O8] has been synthesized by a molten boric acid flux method with "reagent" quantities of water in which GeO2, ethylenediamine, H2O, and H3BO3 (5:8:14:25) were heated together at 513 K for 4 days. The structure consists of {Ge6O18}n chains, further linked together via BO4 tetrahedra, forming a three-dimensional open framework with intersecting channel systems including one-dimensional 10-membered-ring (MR) channels. Interestingly, the infinite chains {Ge6O18}n as building blocks, built of alternating 4- and 6-MRs made of vertex-sharing GeO4 tetrahedra, construct the borogermanate framework. It is noteworthy that the high viscosity of the reactive medium and the quantity of water play important roles in the formation of the compound.     

Small gas-phase dianions of Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-)

We have searched for new species of small oxygen-containing gas-phase dianions produced in a secondary ion mass spectrometer by Cs+ ion bombardment of solid samples with simultaneous exposure of their surfaces to O2 gas. The targets were a pure zinc metal foil, a copper-contaminated zinc-based coin, two silicon-germanium samples (Si(1-x)Ge(x)(with x= 6.5% or 27%)) and a piece of titanium metal. The novel dianions Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-) have been observed at half-integer m/z values in the negative ion mass spectra. The heptamer dianions Zn3O(4)(2-) and Ti2O(5)(2-) have been unambiguously identified by their isotopic abundances. Their flight times through the mass spectrometer are approximately 20 micros and approximately 17 micros, respectively. The geometrical structures of the two heptamer dianions Ti2O(5)(2-), and Zn3O(4)(2-) are investigated using ab initio methods, and the identified isomers are compared to those of the novel Ge2O(5)(2-) and the known Si2O(5)(2-) and Be3O(4)(2-) dianions.     

Hydrothermal synthesis and structural characterization of a new organically templated germanate,Ge(10)O(21)(OH).N(4)C(6)H(21)

A new open-framework germanium oxide Ge(10)O(21)(OH).N(4)C(6)H(21) has been hydrothermally synthesized at 180 degrees C for 6 days by using the tris(2-aminoethyl)amine (tren) molecule as a structure-directing agent. This compound was characterized by means of single-crystal X-ray diffraction and FTIR. It crystallizes in the noncentric monoclinic system Cm (a = 14.0495(2) A, b = 12.8058(3) A, c = 9.2637(2) A, beta = 128.406(1) degrees, Z = 4). Its three-dimensional framework is built up from GeO(4) and GeO(3)(OH) tetrahedra connected by vertexes to GeO(5) trigonal bipyramids and GeO(6) octahedra. A pseudo-cubic building unit ("4-3" subunit) consists of four GeO(4) tetrahedra, two GeO(5) trigonal bipyramids, and one GeO(6) octahedron (Ge(7)). In the "4-3" block, the GeO(5) trigonal bipyramids share a common edge. This Ge(7) entity is linked to three tetrahedral units GeO(3)X (X = O, OH), and this forms an original decameric building unit Ge(10)O(21)(OH) which is new in the germanates crystal chemistry. It results in a relatively dense open framework composed of pear-shape cavities (7(8)6(2)5(2)4(4)3(2)) encapsulating the triprotonated tren molecule. The inorganic network contains small pores delimited by 7-ring channels running along [001].     

Li2O-Al2O3-GeO2-P2Os微晶玻璃的微观结构和离子电导率

采用传统熔体冷却法制备了Li3-xAl2-xGex(PO4)3(x=1.1～1.9)体系玻璃,并通过热处理工艺获得了高电导率的微晶玻璃.通过XRD、TEM和交流阻抗等测试方法,研究了该系微晶玻璃的物相组成、微观形貌和锂离子电导率.结果表明:该系统微晶玻璃析出导电主晶相为LiGe2(PO4)3,杂质相为AlPO4和GeO2.当x=1.5时,由于导电主晶相LiGe2(PO4)3晶粒充分长大、分布均匀,所制备微晶玻璃的室温锂离子电导率最高(5.72×10-4 S·cm-1),可以满足全固态锂离子电池对电解质高室温电导率的要求.     

Surface dependence of CO2 adsorption on Zn2GeO4

An understanding of the interaction between Zn(2)GeO(4) and the CO(2) molecule is vital for developing its role in the photocatalytic reduction of CO(2). In this study, we present the structure and energetics of CO(2) adsorbed onto the stoichiometric perfectly and the oxygen vacancy defect of Zn(2)GeO(4) (010) and (001) surfaces using density functional theory slab calculations. The major finding is that the surface structure of the Zn(2)GeO(4) is important for CO(2) adsorption and activation, i.e., the interaction of CO(2) with Zn(2)GeO(4) surfaces is structure-dependent. The ability of CO(2) adsorption on (001) is higher than that of CO(2) adsorption on (010). For the (010) surface, the active sites O(2c)···Ge(3c) and Ge(3c)-O(3c) interact with the CO(2) molecule leading to a bidentate carbonate species. The presence of Ge(3c)-O(2c)···Ge(3c) bonds on the (001) surface strengthens the interaction of CO(2) with the (001) surface, and results in a bridged carbonate-like species. Furthermore, a comparison of the calculated adsorption energies of CO(2) adsorption on perfect and defective Zn(2)GeO(4) (010) and (001) surfaces shows that CO(2) has the strongest adsorption near a surface oxygen vacancy site, with an adsorption energy -1.05 to -2.17 eV, stronger than adsorption of CO(2) on perfect Zn(2)GeO(4) surfaces (E(ads) = -0.91 to -1.12 eV) or adsorption of CO(2) on a surface oxygen defect site (E(ads) = -0.24 to -0.95 eV). Additionally, for the defective Zn(2)GeO(4) surfaces, the oxygen vacancies are the active sites. CO(2) that adsorbs directly at the Vo site can be dissociated into CO and O and the Vo defect can be healed by the oxygen atom released during the dissociation process. On further analysis of the dissociative adsorption mechanism of CO(2) on the surface oxygen defect site, we concluded that dissociative adsorption of CO(2) favors the stepwise dissociation mechanism and the dissociation process can be described as CO(2) + Vo → CO(2)(δ-)/Vo → CO(adsorbed) + O(surface). This result has an important implication for understanding the photoreduction of CO(2) by using Zn(2)GeO(4) nanoribbons.     

alpha- and beta-A2Hg3M2S8 (A = K,Rb; M = Ge,Sn): polar quaternary chalcogenides with strong nonlinear optical response

The closely related phases alpha- and beta-A(2)Hg(3)M(2)S(8) (A = K, Rb; M = Ge, Sn) have been discovered using the alkali polychalcogenide flux method and are described in detail. They present new structure types with a polar noncentrosymmetric crystallographic motif and strong nonlinear second-harmonic generation (SHG) properties. The alpha-allotropic form crystallizes in the orthorhombic space group Aba2 with a = 19.082(2) A, b = 9.551(1) A, c = 8.2871(8) A for the K(2)Hg(3)Ge(2)S(8) analogue, and a = 19.563(2) A, b = 9.853(1) A, c = 8.467(1) A for the K(2)Hg(3)Sn(2)S(8) analogue. The beta-form crystallizes in the monoclinic space group C2 with a = 9.5948(7) A, b = 8.3608(6) A, c = 9.6638(7) A, beta = 94.637 degrees for the K(2)Hg(3)Ge(2)S(8) analogue. The thermal stability and optical and spectroscopic properties of these compounds are reported along with detailed solubility and crystal growth studies of the alpha-Kappa(2)Hg(3)Ge(2)S(8) in K(2)S(8) flux. These materials are wide gap semiconductors with band gaps at approximately 2.40 and approximately 2.64 eV for the Sn and Ge analogues, respectively. Below the band gap the materials exhibit a very wide transmission range to electromagnetic radiation up to approximately 14 microm. alpha-K(2)Hg(3)Ge(2)S(8) shows anisotropic thermal expansion coefficients. SHG measurements, performed with a direct phase-matched method, showed very high nonlinear coefficient d(eff) for beta-K(2)Hg(3)Ge(2)S(8) approaching 20 pm/V. Crystals of K(2)Hg(3)Ge(2)S(8) are robust to air exposure and have a high laser-damage threshold.     

K3[Tb(x)Eu(1-x)Ge3O8(OH)2] (x = 1, 0.88, 0.67, 0): 2D-layered lanthanide germanates with tunable photoluminescent properties

A family of novel 2D-layered lanthanide germanates K(3)[Tb(x)Eu(1-x)Ge(3)O(8)(OH)(2)] (x = 1, 0.88, 0.67, 0; denoted as TbGeO-JU-87, Tb(0.88)Eu(0.12)GeO-JU-87, Tb(0.67)Eu(0.33)GeO-JU-87, and EuGeO-JU-87) were synthesized under mild hydrothermal conditions in a concentrated gel system. They are isostructural, as confirmed by the powder X-ray diffraction analysis. The single-crystal X-ray diffraction analysis of EuGeO-JU-87 reveals that it is a 2D-layered [EuGe(3)O(8)(OH)(2)](n)(3n-) anionic framework, which is built up from GeO(4)H/GeO(4) tetrahedra and EuO(6) octahedra by sharing vertex O atoms. Charge neutrality is achieved by K(+) ions located in the free void space. Interestingly, photoluminescence studies show that Tb(0.88)Eu(0.12)GeO-JU-87 and Tb(0.67)Eu(0.33)GeO-JU-87 exhibit a high Tb(3+)-to-Eu(3+) energy-transfer efficiency and the Tb(x)Eu(1-x)GeO-JU-87 system displays tunable photoluminescent properties.     

Cd2Ge7O16中Tb的长余辉发光特性

本文研究了Cd₂Ge₇O₁₆∶Tb³⁺材料的发光及其长余辉性质。指出Tb³⁺的发光是该离子的 ⁵D₃- ⁷D_J、 ⁵D₄- ⁷D_J两种跃迁产生的；随着掺杂浓度的增加 ⁵D₄- ⁷D_J跃迁增强，发光颜色由蓝变绿。并把该材料的长余辉性质归结为基质结构中有电子陷阱和空穴陷阱。提出余辉机理模型。     

Syntheses, crystal structures and SHG properties of a series of polar alkali-metal molybdenum(VI) selenites based on strandberg-type [Mo5O15(SeO3)2]4- polyanion

Four new quaternary molybdenum selenites, namely, HRb(3)(Mo(5)O(15))(SeO(3))(2)(H(2)O)(2)1, α-Rb(4)Mo(5)O(15)(SeO(3))(2)(H(2)O)(2)2, β-Rb(4)Mo(5)O(15)(SeO(3))(2)(H(2)O)(2)3 and K(4)Mo(5)O(15)(SeO(3))(2)(H(2)O)(2)4 were synthesized by hydrothermal reactions. All of the four compounds feature a zero-dimensional (0D) [(Mo(5)O(15))(SeO(3))(2)](4-) anionic unit composed of a five-member MoO(6) octahedral ring capped by two SeO(3)(2-) trigonal pyramids, with the Rb(+)/K(+) or/and H(+) cations and water molecules acting as spacers and keeping charge balance. Although these compounds exhibit similar chemical formula, their structures are slightly different. HRb(3)(Mo(5)O(15))(SeO(3))(2)(H(2)O)(2)1 crystallizes in a polar space group (Pca2(1)). α-Rb(4)Mo(5)O(15)(SeO(3))(2)(H(2)O)(2)2 crystallizes in a centrosymmetric (CS) space group (P2(1)/n) whereas β-Rb(4)Mo(5)O(15)(SeO(3))(2)(H(2)O)(2)3 and K(4)Mo(5)O(15)(SeO(3))(2)(H(2)O)(2)4 are isomorphous, crystallize in a chiral space group (C2). The chiral structures of 3 and 4 contain two similar polyanions of [Mo(5)O(15)(SeO(3))(2)](4-) with opposite handedness. Second-harmonic-generation (SHG) measurements indicate that 1, 3 and 4 are all SHG-active. Compound 1 displays a weak SHG response of about 20% of that of KDP (KH(2)PO(4)) and is phase-matchable whereas the SHG responses of 3 and 4 are very weak (less than 5% of that of KDP). Thermal analyses and optical property measurements have also been performed.     

Se2(B2O7): a new type of second-order NLO material

Exploration on the compounds in the selenite-borate system led to the discovery of a new second-order NLO material, Se2B2O7, with a SHG efficiency of about 2.2 times that of KDP (KH2PO4). Its structure features a 3D network with helical tunnels, and it is transparent in the UV and visible region. The compound is a wide band gap semiconductor.     

3-D germanate constructed with Ge7 cluster layers and nickel-ethanolamine linkage

A Ge(7) germanate, [Ni(H(2)O)(μ-C(2)H(6)NO)(2)Ge(7)O(14)(C(2)H(7)NO)]·C(2)H(5)OH (1), was prepared by the solvothermal method using ethanolamine (C(2)H(7)NO) as solvent, ligand, and structure-directing agent. Compound 1 shows an unusual GeO framework fused with transition metal complex. The 2-D layers of Ge(7) clusters are linked by a [Ni(H(2)O)(μ-C(2)H(6)NO)(2)] moiety, forming a 3-D architecture. The preparation and structure of 1 are discussed in comparison with the Ge(9) germanates decorated with metal ethylenediamine complexes. The hydroxyl group of the ethanolamine plays an important role in formation of the 3-D structure, in which the ligand ethanolamine is coordinated directly onto the Ge cluster by the hydroxyl group. It is a new type of germanates incorporated with a TM complex bridge. The proton on the flexible amine side can be exchanged by alkali metal ions.     

Li2O-Al2O3-GeO2-P2O5微晶玻璃的微观结构和离子电导率

采用传统熔体冷却法制备了Li3-xAl2-xGex(PO4)3(x=1.1~1.9)体系玻璃,并通过热处理工艺获得了高电导率的微晶玻璃。通过XRD、TEM和交流阻抗等测试方法,研究了该系微晶玻璃的物相组成、微观形貌和锂离子电导率。结果表明:该系统微晶玻璃析出导电主晶相为LiGe2(PO4)3,杂质相为AlPO4和GeO2。当x=1.5时,由于导电主晶相LiGe2(PO4)3晶粒充分长大、分布均匀,所制备微晶玻璃的室温锂离子电导率最高(5.72×10-4 S.cm-1),可以满足全固态锂离子电池对电解质高室温电导率的要求。