Li2I(OH): Eine Verbindung mit eindimensional unendlich kantenverknüpften [Li4/2(OH)]+-Pyramiden

Li₂I(OH): A Compound with Onedimensional Infinite Edge Sharing [Li_4/2(OH)⁺] Pyramids The pseudobinary system LiOH/LiI was investigated by X-ray methods. Two compounds, Li₂I(OH) and Li₅I(OH)₄ exist. The structure of Li₂I(OH) was solved by single-crystal data. For Li₅I(OH)₄ lattice constants and space group symmetry are given: Li₂I(OH): Pnma, Z = 4, a = 10.339(4) Å, b = 5.567(1) Å, c = 6.643(2) Å, Z(F_o) mit (F_o)² ≧ 3σ(F_o)² = 439, Z (parameter) = 23, R/R_w = 0.030/0.040 Li₅I(OH)₄: Pmmn or P2₁mn(= Pmn2₁), Z = 2, a = 10.42 Å, b = 5.30 Å, c = 5.81 Å Li₂I(OH) crystallizes in a new type of structure. The motif of a distorted hexagonal close-packed arrangement of iodide ions is penetrated by chains of [Li_4/2(OH)⁺].     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Die Kristallstrukturen der Hydroxyhalogenide Li4(OH)3Br und Li4(OH)3I

The Crystal Structures of the Lithium Hydroxide Halides Li₄(OH)₃Br and Li₄(OH)₃I Using single crystal analysis and powder diffraction data the crystal structures of the lithium hydroxide halides Li₄(OH)₃Br and Li₄(OH)₃I were solved and refined. Li₄(OH)₃Br crystallises in the space group P2₁/m and is isotypic with the lighter homologue Li₄(OH)₃Cl. (Rietveld‐refinement; T = 293 K; a = 545, 41(1); b = 758, 13(1); c = 650, 20(1) pm; β = 93, 82(1)°; Z = 2; 300 unique reflections; R_p = 0, 106; R_wp = 0, 109; R_exp = 0, 081). Li₄(OH)₃I crystallises in the space group Pmmn in a variant of the LiOH structure in which 1/4 of the hydroxide anions are replaced by iodide anions. (Single crystal analysis; T = 100 K; a = 1029, 5(4); b = 525, 9(2); c = 573, 2(2) pm; Z = 2; 392 unique reflections; R₁ = 0, 0642).     

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.     

碳包覆Li3V2(PO4)3正极材料在LiPF6电解液中的表面/界面行为

利用碳热还原法成功制备了碳包覆Li3V2(PO4)3正极材料。X射线衍射研究表明材料具有纯相单斜结构。高分辨透射电子显微镜观察到材料表面存在5～10 nm的包覆碳层。碳包覆Li3V2(PO4)3材料在3.0～4.3 V电压区间内可提供120 mA.h/g(C/4倍率)、115 mA.h/g(1C倍率)和110 mA.h/g(2C倍率)的可逆容量,并且在循环300次后容量保持率超过97%,显示出良好的应用前景。该材料在充放电循环初期经历了不可逆容量损失。高分辨透射电子显微镜研究表明,该不可逆容量损失来源于材料表面生成的固体电解质中间相(SEI膜),红外光谱分析表明,SEI膜的成份主要包括ROCO2Li和RCO2Li等有机物,以及Li2CO3、LixPFy和LixPOyFz等无机物。表面SEI膜经历初期电化学循环后趋于稳定,从而保证碳包覆Li3V2(PO4)3正极材料优良的电化学性能。     

Verfeinerung der Kristallstruktur von Kupfer(II)-hydroxichlorid,Cu(OH)Cl

The crystal structure of Cu(OH)Cl [a=5.555 (2) Å,b=6.671 (4) Å,c=6.127 (2) Å, =114.88 (3)°, space group P2_I/a,Z=4] was refined for 810 observed reflections with sin /0.80 Å^–1 toR=0.035. Crystals were synthesized under hydrothermal conditions. The copper atom is planar four coordinated by three oxygen atoms and one chlorine atom; two further chlorine atoms complete its coordination. The copper polyhedra share edges to build up sheets, which are connected by hydrogen bonds to the chlorine atoms of adjacent sheets.

     

Li2CrO4 · 2H2O: Ungewöhnliche Wasserstoffbrückenbindung und Koordination der O-Liganden des Anions CrO42−

Li₂CrO₄ · 2H₂O: Unusual Hydrogen Bridge Bonding and Coordination for Oxygen of the Anions CrO₄^2? The crystal structure of Li₂CrO₄ · 2H₂O was solved including the positions of hydrogen by X-ray methods. Li₂CrO₄ · 2H₂O: P2₁2₁2₁, Z = 4, a = 5.503(1) Å, b = 7.733(2) Å, c = 11.987(2) Å, Z(F_o) with (F_o)² ? 3σ(F_o)² = 2284, Z (parameter) = 99, R/R_w = 0.025/0.029 LiCrO₄ · 2H₂O contains a locally bordered hydrogen bridge bonding system between water molecules as donors and two O of CrO₄^2? as acceptors. This system connects anions in the direction [010]. It is noticeable that oxygen ligands of the anion CrO₄^2? have strongly differing coordination.     

Ti4+离子掺杂对Li3V2(PO4)3晶体结构与性能的影响

采用溶胶凝胶/碳热还原法合成了锂离子电池正极材料Li3V2(PO4)3及其掺Ti化合物Li3-2x(V1-xTix)2-(PO4)3. 电化学测试结果表明, 经Ti4+离子掺杂后材料的充放电性能及循环性能明显提高. 与纯相Li3V2(PO4)3在3.58、3.67和4.08 V出现三个平台相比, 掺杂后材料的前两个平台发生简并且平台趋于模糊的倾斜状态. 这种趋势随掺杂量的增大而增强. 差热分析(DTA)表明掺杂生成了稳定的酌相产物. 采用X射线衍射和Rietveld方法表征了化合物的晶体结构, 结果表明, 三个不同位置Li的不完全占据导致晶体中产生阳离子空穴, 使材料在常温下的离子电导率提高了3个数量级. 锂离子混排提高了样品的电导率和充放电比容量.     

Fast and Efficient Reductive Amination of Aldehydes by NaBH4/B(OH)3 and NaBH4/Al(OH)3

Reductive amination a variety of aldehydes and anilines to their corresponding secondary amines were carried out with NaBH₄/B(OH)₃ and NaBH₄/Al(OH)₃ as new reducing systems in CH₃CN at room temperature in high to excellent yields of products (90‐96%).     

Li3Fe2(PO4)3/C正极材料的电化学性能及其反应机理研究

采用溶胶凝胶及高能球磨制得Li₃Fe₂(PO₄)₃/C材料,利用多种物理及其电化学技术观察材料形貌,表征材料结构及电化学性能,用电化学原位XAFS等初步研究Li₃Fe₂(PO₄)₃/C超理论容量电化学反应机理. 结果显示,Li₃Fe₂(PO₄)₃/C的结构为单斜晶系,空间群P21/n. 2.0 ~ 4.0 V电位区间,10 mAh·g^-1电流密度,Li₃Fe₂(PO₄)₃/C电极的首周期放电比容量为129 mAh·g^-1,达到其理论容量. 若电位区间拓宽至2.0 ~ 4.95 V,其首周期放电比容量高达165 mAh·g^-1,超出理论的“额外”容量30%. 电化学原位XAFS测试未观察到明显的Fe³⁺/Fe⁴⁺氧化还原对参与电化学反应,初步推测“额外”容量可能来自于该复合材料的高浓度表面缺陷.     

Tl4Pd3Cl10 – eine Verbindung mit neuartiger [(PdCl2Cl2/2)4]4–‐Baugruppe

Tl₄Pd₃Cl₁₀ – A Compound with a New [(PdCl₂Cl_2/2)₄]^4– Group Single crystals of Tl₄Pd₃Cl₁₀ can be obtained by hydrothermal synthesis. They show tetragonal symmetry with lattice parameters a = 15.956(1) Å and c = 14.146(1) Å, Z = 8 and space group I42d (No. 122). The atomic arrangement of Tl₄Pd₃Cl₁₀ is explored by X‐ray crystal structure analysis. Tl₄Pd₃Cl₁₀ is the first example of a new structural type with a hitherto not isolated tetramer [(PdCl₂Cl_2/2)₄]^4– group.     

具有Cl…Cl作用的一维链状有机锡化合物四(2，4-二氯苄基)锡的合成、表征和晶体结构

The tetra(2, 4-dichlorobenzyl)tin was synthesized and characterized by elementary analysis, IR and ¹H NMR. The crystal and molecular structure were determined by X-ray single crystal diffraction. The crystal of the title compound belongs to triclinic, space group P1 with a=1.089 7(3) nm, b=1.050 33(4) nm, c=1.858 5(4) nm, α=96.822(4)°, β=94.477(4)°, γ=94.636(3)°, V=3.001 3(12) nm³, Z=4, D_c=1.679 Mg·m^-3, μ(Mo Kα)=1.582 mm^-1, S=1.005, F(000)=1 496, R₁=0.040 7, wR₂=0.076 3. In compound, the tin atom has a distorted tetrahedral coordination configuration. The molecules are packed in one-dimensional chain polymer through a weak interaction between the chlorine atoms from adjacent molecules, respectively. CCDC: 286106.     

Synthese,Eigenschaften und Struktur von oktamerem Titanimidchlorid [Ti(NSiMe3)Cl2]8

Synthesis, Properties, and Structure of Octameric Titanium Imide Chloride [Ti(NSiMe₃)Cl₂]₈ The reaction of TiCl₄ with N(SiMe₃)₃ in sealed glas-tubes yields the titanium imide chloride [Ti(NSiMe₃)Cl₂]₈ ( 1 ). It crystallizes in the space group C2/c with a = 2 704.5(4), b = 1 303.9(1), c = 2 205.4(2) pm, β = 112.78(1)°, Z = 4. In 1 six Ti atoms are linked together by chloro and trimethylsilylimido bridges to form a ring structure. Two TiCl₂-groups are bound in addition to the ring by two imido bridges. Upon annealing at 250°C 1 transformes to the isomeric polymer [Ti(NSiMe₃)Cl₂]_n. Above 250°C 1 decomposes under separation of Me₃SiCl affording TiNCl.     

流变相法制备海藻酸基碳包覆Li3V2(PO4)3材料的电化学性能

Li₃V₂(PO₄)₃/C (LVP/C) cathode materials were successfully prepared by a rheological phase method using alginic acid as the carbon source. The X-ray diffraction (XRD) patterns demonstrate that all the samples contain pure LVP with the same monoclinic structure. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show that LVP/C materials have a uniform particle size. The LVP/C sample with 10% (w) alginic acid shows the best cycling stability. It delivers a discharge capacity of 117.5 mAh·g^-1 (3.0-4.3 V), which can be maintained at 116.5 mAh·g^-1 after 50 cycles at a rate of 0.1C. Its capacity retentions of 99.1% (3.0-4.3 V) and 76.8% (3.0-4.8 V) after 50 cycles are prominently higher than those of pristine Li₃V₂(PO₄)₃, which are 89.7% (3.0-4.3 V) and 62.39% (3.0-4.8 V). These outstanding electrochemical performances are mainly attributed to the alginic acid-based carbon coating, which can increase the electronic conductivity of materials and buffer the mechanical damage of the active materials during the Li ion insertion/extraction process, thus improving the electrochemical performance of the LVP/C samples.     

Preparation and crystal structure of Li6Zr2O7 and Li6Hf2O7

Li₆Zr₂O₇ was obtained by annealing an intimate mixture of LiOH · H₂O and freshly prepared ZrO₂ in a stream of argon. It is monoclinic: C2/c, a = 1 044.5(1), b = 598.9(1), c = 1 020.0(1) pm, β = 100.26(1)°, Z = 4, R = 0.016 for 1 218 F values and 55 variables. The structure is closely related to that of NaCl with an ordered distribution of the metal atoms on the sodium sites while the oxygen atoms occupy seven eighths of the chlorine positions. Li has square pyramidal, Zr octahedral oxygen coordination. The corresponding Hf compound is isotypic: a = 1 040.2(1), b = 596,2(1), c = 1 015.0(1) pm, β = 100.36(1)°. ⁷Li nuclear magnetic resonance spectra of this compound give no indication for a high mobility of the Li⁺ ions.     

Nonanatrium-bis(hexahydroxoaluminat)-trihydroxid-hexahydrat (Na9[Al(OH)6]2(OH)3 · 6H2O) – Kristallstruktur,NMR-Spektroskopie und thermisches Verhalten

Nonasodium Bis(hexahydroxoaluminate) Trihydroxide Hexahydrate (Na₉[Al(OH)₆]₂(OH)₃ · 6H₂O) – Crystal Structure, NMR Spectroscopy and Thermal Behaviour The crystal structure of the nonasodium bis(hexahydroxoaluminate) trihydroxide hexahydrate Na₉[Al(OH)₆]₂(OH)₃ · 6H₂O (4.5 Na₂O Al₂O₃ · 13.5 H₂O) (up to now described as 3 Na₂O · Al₂O₃ · 6H₂O, 4Na₂O · Al₂O₃ · 13 H₂O and [3 Na₂O · Al₂O₃ · 6H₂O] [xNaOH · yH₂O], respectively) was solved. The X-ray single crystal diffraction analysis (triclinic, space group P1 , a = 8.694(1) Å, b = 11.344(2) Å, c = 11.636(3) Å, α = 74.29(2)°, β = 87.43(2)°, γ = 70.66(2)°, Z = 2) results in a structure, consisting of monomeric [Al(OH)₆]^3? aluminate anions, which are connected by NaO₆ octahedra groups. Furthermore the structure contains both, two hydroxide anions only surrounded by water of crystallization and OH groups of [Al(OH)₆]^3? aluminate anions and a hydroxide anion involved in three NaO₆ coordination octahedra directly and moreover connected with a water molecule by hydrogen bonding. The results of ²⁷Al and ²³Na-MAS-NMR investigations, the thermal behaviour of the compound and possible relations between the crystal structure and the conditions of coordination in the corresponding sodium aluminate solution are discussed as well.     

[Li(12-Krone-4)]Cl: Kristallstruktur und IR-Spektrum

[Li(12-Crown-4)]Cl: Crystal Structure and I.R. Spectrum Colourless single crystals of [Li(12-crown-4)]Cl were obtained from acetonitrile solutions of LiCl in the presence of 12-crown-4. They were characterized by i. r. spectroscopy as well as by an X-ray structure determination. Space group P4/n, Z = 2, 1 080 observed unique reflections, R = 0.034. Lattice dimensions at ?50°C; a = 837.8(5), c = 752.0(2) pm. [Li(12-crown-4)]Cl forms ion pairs with tetragonal symmetry and bond lengths Li? O of 212.8 pm and Li? Cl of 229.0 pm.     

Conducting Graphene Decorated Li3V2(PO4)3/C for Lithium‐Ion Battery Cathode with Superior Rate Capability and Cycling Stability

In this study, core‐shell structured Li₃V₂(PO₄)₃/C wrapped in graphene nanosheets has been successfully prepared. The reduction of graphene oxide and the synthesis of Li₃V₂(PO₄)₃/C are carried out simultaneously using a chemical route followed by a solid‐state reaction. The effects of conducting graphene are studied by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra and electrochemical measurements. The results reveal that the graphene sheets not only form a compact and uniform coating layer throughout the Li₃V₂(PO₄)₃/C, but also stretch out and cross‐link into a conducting network around the Li₃V₂(PO₄)₃/C particles. Thus, the graphene decorated Li₃V₂(PO₄)₃/C electrode exhibits superior high‐rate capability and long‐cycle stability. It delivers a reversible discharge capacity of 178.2 mAh·g^?1 after 60 cycles at a current density of 0.1 C, and the rate performances of 176, 169.3, 156.1 and 135.7 mAh·g^?1 at 1, 2, 5 and 10 C, respectively. The superior electrochemical properties make the graphene decorated Li₃V₂(PO₄)₃/C composite a promising cathode material for high‐performance lithium‐ion battery.