Li2ZrO3材料吸收CO2性能的进一步研究

用不同结构的ZrO₂合成了一系列在高温下吸收CO₂的Li₂ZrO₃材料，并详细的研究了反应物质的物理和化学性质对生成物吸收CO₂性能的影响。采用SEM、XRD以及TG分析法分别进行了材料结构及其吸收CO₂性能的表征，并使用XPS法测定了材料表面的元素组成。实验结果表明，使用不同结构的ZrO₂合成的Li₂ZrO₃，其吸收CO₂的性能明显的不同。用ZrO₂(t)(四方)合成的Li₂ZrO₃吸收CO₂的速度快，在500 ℃下，20% CO₂（80%空气）的气氛中保持3h，其吸收量可达25（±0.6）%（wt），而以ZrO₂(m)(单斜)为原料制备的Li₂ZrO₃在上述吸收条件下重量仅增加9（±0.6）%（wt）。此外，实验结果还表明化学元素的掺杂对用ZrO₂(m)合成的Li₂ZrO₃的CO₂吸收速度及吸收容量影响较大。     

正极材料LiNi0.5Mn1.5O4的合成及性能

采用低温固相法制备镍锰复合草酸盐，煅烧后生成的镍锰复合氧化物与Li₃CO₃混合，在空气中于700 ℃反应12 h，得到LiNi_0.5Mn_1.5O₄。通过XRD，SEM和恒电流充放电测试对样品进行了表征。XRD结果表明：复合草酸盐经390 ℃煅烧3 h，生成了多相氧化物；合成的LiNi_0.5Mn_1.5O₄为纯相，具有立方尖晶石结构。电化学测试结果表明，合成的样品在室温和高温(55 ℃)下，具有较好的电化学性能；大电流充放电时，具有良好的循环性能。     

不同温度下合成的LiCoO2的晶体结构

研究了用Li₂CO₃和Co₃O₄固相合成锂离子电池正极材料钴酸锂(LiCoO₂)过程中，LiCoO₂的晶体结构随合成温度的变化。利用X射线衍射、扫描和透射电子显微技术等各种分析测试方法，对750～900 ℃范围内合成的LiCoO₂的形貌、晶体结构以及电化学性能进行了表征。实验证实，随着合成温度的增加，合成的LiCoO₂颗粒的形貌没有明显变化，但颗粒尺寸会增加；电子衍射结果表明，合成温度为800 ℃时可以合成Li、Co原子各自分层的六方晶体结构的LiCoO₂，随着合成温度的升高LiCoO₂中Li、Co原子层之间可能发生部分混合，合成温度为900 ℃时LiCoO₂为立方岩盐型晶体结构；800 ℃合成的LiCoO₂的充放电循环性能较好。     

xLi2MnO3-(1-x)LiNi0.7Co0.3O2的低温燃烧合成及电化学性能研究

采用低温燃烧法合成了锂离子电池正极材料xLi₂MnO₃-(1-x)LiNi_0.7Co_0.3O₂,对合成产物的结构、形貌和电化学性能进行了系统的研究, 通过单因素试验对合成条件和材料的组成进行了优化。结果表明:采用低温燃烧法合成的富锂层状正极材料具有α-NaFeO₂型层状结构、球状形貌和良好的电化学性能;其最佳合成条件为:回火温度850℃, 回火时间20 h;Li₂MnO₃的最佳配比为x=0.7.在此条件下合成的0.7Li₂MnO₃-0.3LiNi_0.7Co_0.3O₂,最高放电比容量达到263.1 mAh·g^-1,并具有良好的循环性能和倍率性能。     

Li3V2(PO4)3的溶胶-凝胶合成及其性能研究

以LiOH·H₂O(LiF、Li₂CO₃、LiCH₃COO·2H₂O)、NH₄VO₃、H₃PO₄和柠檬酸为原料,采用Sol-gel法合成锂离子电池正极材料Li₃V₂(PO₄)₃。优化了锂源、溶胶的pH值、预烧条件、煅烧温度等合成条件,并采用XRD、SEM、恒电流充放电及循环伏安试验等方法,研究了所合成的Li₃V₂(PO₄)₃的结构形貌和电化学性能。结果表明,以LiOH·H₂O为锂源,溶胶的pH值等于3,于氩气氢气(体积比9∶1)混合气中300 ℃预烧 4 h,并在氩气氢气(体积比9∶1)混合气中600 ℃煅烧8 h合成的Li₃V₂(PO₄)₃正极材料为标准的单斜结构,具有较高的放电比容量和较好的循环稳定性,0.1C和1C倍率下首次放电比容量分别为130 mAh·g^-1和129 mAh·g^-1;1C倍率下循环40次后,容量仍为127 mAh·g^-1,容量保持率为98.4%;随后又进行10C倍率放电,10次循环后容量为105 mAh·g^-1,容量保有率达98.1%。循环伏安测试表明,该正极材料具有较好的电化学可逆性。     

高温下锆酸锂吸收二氧化碳的研究

Li₂ZrO₃ to be used as a CO₂ absorbent at 450℃ to 710℃ is synthesized. The results indicate that the loading capacity of Li₂ZrO₃ for CO₂ is slightly improved than that reported previously. The absorption capacity attain to about 25(±0.6)%(wt)at 500℃ kept 3h in an atmosphere containing 20% CO₂ (balanced by air). Moreover， the temperature of synthesis is lower than the temperature reported in the literature， and also the time of synthesis is shorter.     

Li4Ti5O12/(Ag+C)电极材料的固相合成及电化学性能

以Li₂CO₃,TiO₂为原料,葡萄糖为碳源,采用固相煅烧工艺合成了亚微米级的Li₄Ti₅O₁₂/C复合负极材料。并将之与AgNO₃复合,采用固相方法制备出了Ag表面修饰的Li₄Ti₅O₁₂/(Ag+C)复合材料。采用XRD、SEM和TEM测试方法对材料的微结构进行了表征。结果表明,C的存在对Ag单质在Li₄Ti₅O₁₂/C颗粒表面的大量形成起到了积极的促进作用,从而很大程度地提高了Li₄Ti₅O₁₂/C的电导率,因此有效地改善了其电化学性能。在1C倍率下,Li₄Ti₅O₁₂/(Ag+C)复合材料的首次放电容量达到了164 mAh·g^-1。     

三维尖晶石Li4Ti5O12纳米丝网状电极的构置与电化学性能

首次采用电纺丝技术结合高温退火成功地构置了含尖晶石Li₄Ti₅O₁₂的纳米纤维丝三维(3D)网状结构，并测量了三维电池的充放电性能。X射线衍射谱(XRD)、扫描电子显微镜(SEM)和电池循环性能测试等方法表征纤维丝3D结构和电化学性能。研究结果表明了Li₄Ti₅O₁₂纳米丝的零应变特性、构建的3D阵列的结构稳定性和在大电流密度下较好的充放电性能。显示了Li₄Ti₅O₁₂可作为3D电池的电极材料。     

Na 掺杂对硅酸锂吸收CO2性能的影响

通过高温固相反应法, 在添加不同比例Na2CO3的条件下, 合成出一系列可在高温500～750 ℃之间直接吸收CO2的硅酸锂材料. 利用扫描电子显微镜、X射线粉末衍射仪分别观察和评价了合成材料的表面形貌与结构特征, 用热重分析仪测量了硅酸锂材料的CO2吸收性能. 实验结果表明, 通过适量Na元素的掺杂, 能够提高硅酸锂材料吸收CO2的性能, 当Na2CO3的添加量x=0.02时, 合成的硅酸锂材料在CO2气氛下, 于700 ℃恒温保持约15 min即可达到吸收平衡, 材料的吸收量为(46±0.6)%(w), 与未经掺杂的材料相比, 吸收容量有所提高. 此外, 气氛中CO2的浓度对材料吸收CO2的速率有较大影响.     

低温固相反应合成Li3V2(PO4)3正极材料及其性能

利用V₂O₅·nH₂O湿凝胶，LiOH·H₂O，NH₄H₂PO₄和C等作原料，通过低温固相还原反应在550 ℃焙烧12 h制备出Li₃V₂(PO₄)₃正极材料。采用XRD，SEM和电化学测试对Li₃V₂(PO₄)₃样品性能进行研究。XRD研究表明本法所合成的Li₃V₂(PO₄)₃同传统的高温固相反应法所合成的Li₃V₂(PO₄)₃一样同属于单斜晶系结构。SEM测试表明所合成的样品平均粒径大小约为0.5 μm且粒径分布较窄。电化学测试表明以0.2 C的倍率放电时，样品的首次放电容量为130 mAh·g^-1，室温下循环30次后其比容量为124 mAh·g^-1。     

Investigation of phase equilibria in the systems K2SO4Sc2(SO4)3, Rb2SO4Sc2(SO4)3 and Cs2SO4Sc2(SO4)3

Phase diagrams of the systems K₂SO₄Sc₂(SO₄)₃, Rb₂SO ₄Sc₂(SO₄)₃ and Cs₂SO₄ Sc₂(SO₄)₃ have been investigated by X-ray diffraction phase analysis and differential thermal analysis techniques. A salient feature of all the systems is the formation of M₃Sc(SO₄)₃, which melt incongruently, and MSc(SO₄)₂, which on heating decompose in the solid state.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.     

Phenol methylation over CrPO4 and CrPO4?AlPO4 catalysts

The vapor-phase catalytic alkylation of phenol with methanol and dimethyl carbonate on a series of differently prepared CrPO₄ (Cr/P=1) and CrPO₄-AlPO₄ (CrAIP) catalysts, has been studied at different temperatures (473–673 K). The reaction is first order in phenol, giving a mixture of O- and C-alkylated products (C-alkylation taking place preferentially at theortho-position). Moreover, dimethyl carbonate is a better methylating agent than methanol.     

Low-temperature absorption spectra of the MoO2−4 ion in Cs2SO4 and of the ReO−4 ion in RbClO4 and in (C2H5)4NClO4

Absorption spectra of single crystals of Cs₂SO₄ doped with MoO^2?₄ and of RbClO₄ and (C₂H₅)₄HClO₄ doped with ReO^?₄ have been measured at the liquid-helium temperature. All spectra show two band systems with pronounced vibrational structures. In T_d symmetry they must correspond to ¹T₂ - ¹A₁ charge-transfer electornic transitions. It is likely that in the two band systems there are more than two electronic transitions.     

Zur struktur von CaPdF4, CdPdF4, HgPdF4 und HpPdF2

Single crystals of CaPdF₄ (purple) and CdPdF₄ (dark blue) have been obtained by heating CaF₂ (CdF₂) with PdF₂ at 820°C (900°C) for ca. 20–30 d in sealed Pd (Pt) tubes. CaPdF₄ crystallizes tetragonal (KBrF₄-Type) with a = 5.52₁, c = 10.57₀ Å (space group I4/mcm ? D^18_4h, No. 140) Z = 4, 283 unique reflexions, R = 0.083; R_w = 0.079, CdPdF₄ cubic (CaF₂-variant) with a = 5.40₃ Å (space group Pa3 ? T^6_h, No. 205) Z = 4, 165 unique reflexions, R = 0.047, R_w = 0.032. The high pressure modification of PdF₂, obtained by heating PdF₂ in closed Pt-tubes under a pressure of ≈ 60 kbar and ‘HgPdF₄’, both black, a = 5.32₇ Å and a = 5.43 Å are isotypic. CaPdF₄ is diamagnetic, CdPdF₄ and HPPdF₂ are antiferromegnetic.     

A new three-dimensional cobalt phosphate: Co5(OH2)4(HPO4)2(PO4)2

A three-dimensional (3D) cobalt phosphate: Co₅(OH₂)₄(HPO₄)₂(PO₄)₂ (1), has been synthesized by hydrothermal reaction and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic techniques. The title compound is a template free cobalt phosphate. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO₆ and PO₄ polyhedra. The magnetic susceptibility measurements indicated that the title compound obeys Curie-Weiss behavior down to a temperature of 17 K at which an antiferromagnetic phase transition occurs.     

DSC investigation of the thermal behaviour of (NH4)2SO4, NH4HSO4 and NH4NH2SO3

Gaseous products evolved from (NH₄)₂SO₄, NH₄HSO₄ and NH₄NH₂SO₃ during successive heating and cooling cycles were flushed with inert gas into analyzer Dräger tubes hooked tightly to the terminal port of the DSC cell base. This simple procedure allowed the starting temperature of the decomposition to be determined and the amount of the individual gases in the mixture to be identified and even estimated. NH₄NH₂SO₃ at 523 K in humid air produced HNH₂SO₃ initially and, on further cycling, (NH₄)₂SO₄ and NH₄HSO₄ also appeared. The ΔH_f values for NH₄HSO₄ were (kJ mole^?1): in an airtight sample holder 12.67, in a dry argon atmosphere 11.93, and in a static air atmosphere 10.92. Endothermic peaks for (NH₄)₂SO₄ and 498 and 411 K represented the incongruent melting point and the polymorphic transition of (NH₄)₂SO₄·NH₄HSO₄. After the first heating in air to 530 K, (NH₄)₂SO₄ and NH₄HSO₄ exhibited closely similar cyclic DSC curves. The endothermic peaks at about 393–420 K may be assigned to different combinations of (NH₄)₂SO₄ and NH₄HSO₄.     

Structures of SO4 and Na2SO4

Full structure determinations of SO₄ and molecular Na₂SO₄ have been made using an atom superposition and electron delocalization molecular orbital theory. A C₁ structure in the form of a planar bent SO₂ + O₂ adduct is favored for SO₄. In Na₂SO₄, xxx edges of tetrahedral SO₄^2?.     

Vibrational Spectra of the Cyclic SN-Compounds S4N4, S4N4H4 and S3N3Cl3

The IR and Raman spectra of solid and dissolved S₄N₄, S₄N₄H₄, S₄N₄D₄ and S₃N₃Cl₃ have been recorded and are assigned according to D_2d, C_4v and C_3v symmetry respectively. In the solid state, many forbidden bands and splittings of degenerate vibrations are observed because of the symmetry lowering in the crystals. Due to the different size and shape of the rings and to strong coupling of the normal modes there is no clear correlation between the SN ring stretching vibrations and the strength of the SN bonds, except for the one of the E modes. However, the stretching force constant show the trend expected from changes in interatomic distances.     

Thermal behaviour of (NH4)3VO2F4 and Na(NH4)2VO2F4

The thermal behaviour of (NH₄)₃VO₂F₄ and Na(NH₄)₂VO₂F₄ was investigated using TG, DTA and DSC techniques. The occurrence of a first order phase transition with the onset of decomposition in both the compounds is confirmed. The temperature, energetics and hysteresis of the transition are obtained. A possible path for the thermal degradation is given for both the compounds, and the residues are identified.