Das erste Titanat mit „Stuffed Pyrgoms”︁: RbNa3Li12[TiO4]4 = RbNa3Li8{Li[TiO4]}4

The First Titanate with ?Stuffed Pyrgoms”?: RbNa₃Li₁₂[TiO₄]₄ = RbNa₃Li₈{Li[TiO₄]}₄ By heating a well grounded mixture of the binary oxides Rb₂O, Na₂O, Li₂O, and TiO₂ [Rb:Na:Li:Ti = 1.1:3.1:12.5:4.0; 780°C, 41 d] we obtained RbNa₃Li₈{Li[TiO₄]}₄ as colourless platelike crystals. This first titanate with ?stuffed pyrgoms”? is isostructural with RbNa₃Li₈{Li[SiO₄]}₄, CsKNa₂Li₈{Li[SiO₄]}₄ and CsKNaLi₉{Li[SiO₄]}₄ [2]. The compound crystallizes tetragonal I4/m with a = 1 125.8(1) pm and c = 652.4(1) pm (Guinier-Simon-Data, Z = 2). The structure was determined by four-cyrcle-data (Siemens AED2, MoK) and leds to the residual values R = 3.7% and R_w = 3.1% (additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Raddii (MEFIR) and the Charge Distribution in Solids (CHARDI) are calculated and discussed.     

Phosphinophosphiniden-Phosphorane tBu2P?P = P(R)tBu2 aus Li(THF)2[η2-(tBu2P)2P] und Alkylhalogeniden

The Phosphinophosphinidene-phosphoranes ^tBu₂P? P = P(R)^tBu₂ from Li(THF)₂[η²-(^tBu₂P)₂P] and Alkyl Halides We report the formation of ^tBu₂P? P = P(R)^tBu₂ a and (^tBu₂)₂PR b (with R = Me, Et, ⁿPr, ⁱPr, ⁿBu, PhCH₂, H₂C = CH? CH₂ and CF₃) reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 2 with MeCl, MeI, EtCl, EtBr, ⁿPrCl, ⁿPrBr, ⁱPrCl, ⁿBuBr, PhCH₂Cl, H₂C = CH? CH₂Cl or CF₃Br. In THF solutions the ylidic compounds a predominate, whereas in pentane the corresponding triphosphanes b are preferrably formed. With ClCH₂? CH = CH₂ only b is produced; CF₃Br however yields both ^tBu₂P? P = P(Br)^tBu₂ and ^tBu₂P? P = P(CF₃)^tBu₂, but no b . The ratio of a:b is influenced by the reaction temperature, too. The compounds ^tBu₂P? P = P(Et)^tBu₂ 4a and (^tBu₂P)₂PEt 4 b , e. g., are produced in a ratio of 4:3 at ?70°C in THF, and 1:1 at 20°C; whereas 1:1 is obtained at ?70°C in pentane, and 1:2 at 20°C. Neither ^tBuCl nor H₂C = CHCl react with 2 . The compounds a decompose thermally or under UV irradiation forming ^tBu₂PR and the cyclophosphanes (^tBu₂P)_nP_n.     

R?ntgenspektrometrische Bestimmung von Eisen-55 in Luftstaub- und Niederschlagsproben

Zusammenfassung Eisen-55 wurde in Neuherberg bei München seit März 1970 in monatlich gesammelten Luftstaubproben und seit Januar 1971 in Monatsniederschlagsproben bestimmt. Nach dem Veraschen der Proben wurde Eisen durch Extraktion' mit Di-iso-propyläther abgetrennt. Zur weiteren Entfernung störender Radionuklide des Fallouts wurde eine Ionenaustauschertrennung angeschlossen. Nach der elektrolytischen Abscheidung des Eisens auf Kupferplättchen wurden die Röntgenspektren mit einem Proportionalzähler sowie einem Si(Li)-Detektor aufgenommen.Die mittlere spezifische Luftaktivität betrug in Neuherberg 1,0 fCi/m³ im Jahr 1970 (ab März), 1,2 fCi/m³ im Jahr 1971 und 0,36 fCi/m³ im Jahr 1972. Die dem Boden durch den Niederschlag zugeführte Aktivität wurde zu 697 pCi/m² · Jahr für 1971 und 178 pCi/m² · Jahr für 1972 bestimmt.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen.     

298.15K下Li2B4O7-H2O体系水蒸汽分压及渗透系数的等压测定和离子相互作用模型

在已有研究含硼体系的文献中仅考虑了硼酸根B4O7^-2或B(OH)4^-和H3BO3的存在，而对Li2B4O7-H2O体系具有多种硼物种聚合平衡体系的热力学性质的研究尚未见报道．本文用等压法研究了Li2B4O7-H2O体系于298．15K下浓度由稀到过饱和溶液的平衡气相蒸汽压及渗透系数．考虑了水溶液中多种硼物种的存在，以Pitzer方程为基础，建立了可描述该含硼体系的离子相互作用模型。     

Phase study of the system Li2Se-In2Se3

The binary system Li₂Se-In₂Se₃ was investigated in the range of 40 to 100 mol% In₂Se₃ by thermoanalytical and X-ray methods. The system is characterized by two eutectic points. Beside the two binary components and the known ternary compound LiInSe2 another ternary compound crystallizes in this binary system at 83.3 mol% In₂Se₃. This compound was identified as LiIn₅Se₈. In contrast to (Cu, Ag)^IB₅ ^IIIC₈ ^VI compounds such as CuIn₅S₈ [1] it does not crystallize in the spinel structure. LiIn₅Se₈ shows a stratified structure. The melting point was determined to be at 810°C. Starting from room temperature up to the melting point no phase transitions were observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium‐ion cells using LiPF₆ (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li₂CO₃ up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd.     

Über Perrhenate. 3 Zum Aufbau des Mesoperrhenates Na3[ReO5]

About Perrhenates. 3 On the Structure of the Mesoperrhenate Na₃[ReO₅] By tempering powder samples (prepared from mixtures of binary oxides: Na₂O₂/ReO₂ and Na₂O/ReO₃ respectively, Na : Re = 3 : 1, Ar and O₂ atmosphere respectively, 400–450°C, corundum boat) in a closed Ag cylinder (500–550°C, 10 d) yellow single crystals of Na₃ReO₅, sensitive to moisture, were grown. The compound crystallizes trigonal, space group P3₁, P3₂ respectively, with a = 5.544(1), c = 13.580(7) Å, Z = 3, d_rö. = 4.62 g/cm³. The crystal structure [4-circle diffractometer data, 1091 I₀(hkl), AgKα, R = 6.14, R_w = 6.08%] is characterized by “isolated” bipyramids ReO₅. Na⁺ ions are occupying all the tetrahedral (Na2, Na3) and octahedral (Na1) holes of the pseudocubic face centred (c/a = 2.441) Re part of the lattice; resulting in a Na₃Re kation framework corresponding to the Li₃Bi type of structure. Effective Coordination Numbers (ECoN), the Madelung Part of Lattice energy (MAPLE) and the charge distribution (CHARDI) are computed and discussed.     

Li2Br(NH2): Das erste ternäre Alkalimetallamidhalogenid

Li₂Br(NH₂): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH₂/LiBr was investigated by X-ray methods. The crystal structure of the compound Li₂Br(NH₂) was solved by single crystal data: Li₂Br(NH₂): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 348, Z (parameter) = 51, R/R_w = 0.019/0.021 Li₂Br(NH₂) crystallizes in a new type of structure. To one another isolated chains of [Li₂Li_4/2(NH₂)₂²⁺] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement.     

锂离子电池PMMA-VAc聚合物电解质的制备与性质研究

以甲基丙烯酸甲酯(MMA)和醋酸乙烯酯(VAc)为单体, 用乳液聚合法合成聚甲基丙烯酸甲酯-醋酸乙烯酯聚合物(PMMA-VAc), 并以此聚合物制备了新型聚烯烃膜支撑的聚合物膜及聚合物电解质. 用红外光谱(FTIR)、凝胶色谱(GPC)、差热和热重分析(DSC/TG)、扫描电镜(SEM)及电池充放电实验等方法研究了聚合物、聚合物膜和聚合物电解质的性质. 红外光谱结果表明, MMA与VAc通过各自的C＝C双键打开聚合成PMMA-VAc. PMMA-VAc易于分散在混合碳酸酯溶剂中并形成凝胶, 凝胶粘度随PMMA-VAc浓度的增加而增加, 当浓度为4%时成膜效果最佳. PMMA-VAc膜具有大量的微孔结构, 具有极强的吸液性能. PMMA-VAc膜具有良好的热稳定性: 在380 ℃范围内保持稳定. 聚烯烃膜支撑的PMMA-VAc膜室温下的离子电导率为1.85×10^－3 S•cm^－1, 用作为锂离子电池的聚合物电解质时, 电池具有良好的循环稳定性和倍率性能.