On the magnetic properties of Lithium Vanadium Bronzes LixV2O5

Magnetic susceptibility of V₂O₅ and of the α-, ?-, δ- and γ-Li_xV₂O₅ bronzes prepared either at high or at room temperature has been measured between liquid helium and ambient temperature. The results are representative of the localized character of the V⁴⁺ ion d-electron and, for high enough x-values, of the existence of antiferromagnetic interactions in a low dimensional system. The intrachain exchange integral J has been determined using the Bonner/Fischer model for Heisenberg chains with S = 1/2 spin. It is larger for the γ- than for the δ-phase. This result as well as the occurrence of long range ordering below T_N ≈ 130 K in the γ-phase may be ascribed to ordering of V⁴⁺ and V⁵⁺ ions in the former bronze and to the random distribution of V⁴⁺ ions in the latter one.     

锂离子电池纳米结构正极材料LiV3O8的制备及性能

采用水热合成方法,在不同水热合成温度下制备了具有纳米结构的锂离子电池正极材料LiV3O8。并利用X射线衍射、透射电镜、恒流充放电、循环伏安以及电化学交流阻抗等测试手段对其结构、形貌和性能做了研究。结果表明,不同的水热合成温度影响到产物的结构、形貌和性能。随着水热温度的升高,粒子的直径随之增大,而形貌和尺寸的均一性则有所降低。电化学测试结果表明水热180℃得到产物的比容量较高,具有良好的电化学可逆性,而且随着水热温度的升高,材料的电荷转移电阻依次减小,有利于锂离子的嵌入与脱出,比容量也随之增加。可见材料的结构中存在一定的非晶缺陷,以及粒子具有一定范围内的尺寸分布,对材料的电化学性能有改善作用。     

锂电池正极材料LiV3O8制备及电化学性能影响因素

采用溶胶-凝胶法制备锂离子电池正极材料LiV3O8,研究了LiOH溶液的浓度对LiV3O8的结构、粒径、电导率和电化学性能的影响。实验发现,LiV3O8衍射峰的强度、粒径与电导率可以通过改变LiOH溶液浓度来控制。测试了LiV3O8材料的结构、粒径分布和电化学性能。结果表明,随着LiOH溶液浓度的增加,样品的结晶度降低,晶粒的择优取向(100)晶面的衍射峰强度明显减弱;当LiOH溶液浓度为0.030 mol/L时,可以得到较为理想的粒径分布和较高的电导率为9.06×10-2s/cm;LiV3O8材料的容量及循环性能均与LiOH溶液浓度有关,选择0.030 mol/L的LiOH溶液时,样品的比容量最大为310 mA.h/g;循环15次后,容量衰减最少为4%。     

铜掺杂五氧化二钒的制备及电化学性质

采用沉淀法于300 和600 ℃制备了结晶状的Cu0.04V2O5材料. 扫描电镜显示, 300 ℃时制备的样品具有多孔特征, 而600 ℃时制备的样品具有很高的结晶度. X射线研究表明, 少量铜掺杂不会改变V2O5的正交晶体结构. 红外光谱研究表明, 300 ℃时制备的Cu0.04V2O5样品含有少量水. 热失重分析确定了样品中所含水分是以吸附水的形式存在, 1 mol材料分子吸附水的摩尔数约为0.18 mol. 铜掺杂显著改善了V2O5的结构稳定性, 进而提高了材料的充放电循环性能. 于600 ℃制备的样品在C/5.6倍率下具有160 mAh·g-1的可逆比容量, 但提高放电倍率明显降低了材料的循环性能. 于300 ℃制备的样品在C/5.6倍率时的循环性能不如600 ℃样品, 但该材料在C/1.9倍率时仍具有100 mAh·g-1左右的可逆比容量. 两种材料在电化学性能上的差异与材料的微结构有关. 低温样品在较高放电倍率时良好的循环性能得益于其多孔的微结构, 而高温样品由于其较高的结晶度而表现出优异的低倍率充放电性能.     

Studies on polymorphic modifications of copper phthalocyanine

Four α-, β-, γ- and ε-polymorphic forms of copper phthalocyanine are synthesized. They are characterized and their properties are compared based on the IR spectral measurements in the finger print region, magnetic susceptibility measurements, ESR study, powder X-ray diffraction and electrical conductivity studies. The data support the existence of all the four polymorphic forms. All the forms are having the monoclinic structure with different crystal lattice constants. The electrical conductivity study in air from 25°C to 200°C for all the four polymorphic modifications are done and their differences may be accounted for difference in interplanar spacing, molecular orientations, intermolecular interactions and mobilities of the charge carriers.     

锂离子电池负极材料Cu2O的制备及电化学性能

采用多元醇法,以丙三醇、氢氧化钠、硫酸铜为原料,在油浴中共热制备Cu2O．通过X射线衍射分析（XRD）和电化学测试对材料进行了表征．结果表明,丙三醇能够将Cu^2＋还原为Cu^＋．并且,采用该方法制备出的Cu2O材料作为锂电池负极材料,具备较好的循环性能．     

高电导率LiAl0.3Co0.7-xMgxO2的制备与表征

用柠檬酸配位聚合法合成了LiAl0.3Co0.7-xMgxO2(x=0.01～0.13)粉体,并进行了X射线衍射(XRD)和透射电子显微镜(TEM)的表征.结果发现晶粒粒径都小于1μm,且在x≤0.11的范围内,材料的XRD谱峰形锐利,表明800℃下材料有良好的结晶性,通过对几组衍射峰的标定,确定材料保持了六方层状α-NaFeO2结构,这种结构在充放电过程中为锂离子提供了良好通道.     

有机胺柱类钙钛矿型钽酸盐的制备与表征

采用分步交换法，合成了新型的正丙胺、正丁胺柱层状类钙钛矿型钽酸盐C3H7NH3-Sr2Ta3O10与C4H9NH3-Sr2Ta7O10，采用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)对该类化合物的结构与形貌进行了表征，并测定了其比表面积。     

Studies on phthalocyanine sheet polymers

Cobalt, nickel and copper phthalocyanine sheet polymers are synthesized by heating their respective metal (II) phthalocyanine tetracarboxylic acids at 400 °C in nitrogen atmosphere. These polymers are characterized using UV-Visible spectra, IR spectra, magnetic susceptibility, X-ray powder diffraction and thermogravimetric analysis. Electrical conductivity studies are carried out using two-probe technique in the temperature range 25-200 °C for each polymer. These polymeric materials showed room temperature electrical conductivity 10-1000 times higher values compared to earlier reported values for this type of sheet polymers.     

锂离子电池正极材料LiMn2O4的制备及其电化学性能的研究

锂离子电池具有比能量高、质量轻、体积小、电压高、安全性好和无记忆效应等特点,而正极材料是其研究的重点.采用溶胶-凝胶法合成了锂离子电池的正极材料,结果表明,其初始容量高,循环性能理想,并且整个合成过程也较为简单,合成的温度相对较低,样品的颗粒比较均匀.     

Crystal Structure and Properties of Some Filled and Unfilled Skutterudites: GdFe4P12, SmFe4P12, NdFe4As12, Eu0.54Co4Sb12, Fe0.5Ni0.5P3, CoP3, and NiP3

The new cubic compound Fe_0.5Ni_0.5P₃ (a = 775.29(5) pm) as well as the known compounds CoP₃ and NiP₃ were synthesized from the elemental components using tin as a flux. Their skutterudite (CoAs₃) type structures were refined from single‐crystal X‐ray data. The new compound GdFe₄P₁₂ was prepared by reaction of an alloy Gd_1/3Fe_2/3 with phosphorus in a tin flux. Its cubic “filled” skutterudite (LaFe₄P₁₂ type) structure was refined from single‐crystal X‐ray data: a = 779.49(4) pm, R = 0.019 for 304 structure factors and 11 variable parameters. SmFe₄P₁₂ shows Van Vleck paramagnetism while GdFe₄P₁₂ is a soft ferromagnet with a Curie temperature of T_C = 22(5) K. Both are metallic conductors. The new isotypic polyarsenide NdFe₄As₁₂ (a = 830.9(1) pm) was obtained by reacting NdAs₂ with iron and arsenic in the presence of a NaCl/KCl flux. The new isotypic polyantimonide Eu_0.54(1)Co₄Sb₁₂ (a = 909.41(8) pm) was prepared by reaction of EuSb₂ with cobalt and antimony. Its structure was refined from single‐crystal X‐ray data to a residual of 0.024 (137 F values, 12 variables). A comparison of the Fe–P and P–P bond lengths in the compounds AFe₄P₁₂, where the A atoms (A = Ce, Eu, Gd, Th) have differing valencies, suggests that the Fermi level cuts through Fe–P bonding and P–P antibonding bands.     

Preparation,Structure and Magnetic Properties of Lithium Substituted NiO by Molten Salt Method

A typical Li⁺ substituted NiO compound, Li_0.29Ni_0.71O, was synthesized by molten nitrate method. The effects of Li⁺ substitution on the structure and magnetic properties of NiO were investigated. X-Ray diffraction(XRD), scanning electron microscope(SEM) and high-resolution transmission electron microscope(HRTEM) analyses confirm the cubic structure of Li_0.29Ni_0.71O, with a primary particle size of 150 nm. Analysis of the Ni X-ray photoelectron spectroscopy(XPS) shows the transformation from Ni²⁺ to Ni³⁺ induced by Li⁺ substitution. Two magnetic transitions were observed at 225 and 55 K which were assigned to the ferrimagnetic ordering and spin glass transition, respectively. The different magnetic behavior with respect to that of NiO was attributed to the break of superexchange interaction Ni²⁺-O-Ni²⁺ and the formation of different spin clusters after non-magnetic Li⁺ doping.     

用于锂离子电池的凝胶聚合物电解质的制备与性能

以丙烯腈(AN)、丙烯酸甲酯(MA)和衣康酸锂(IALi)为自由基共聚反应的主要单体, 采用溶液聚合方法, 合成轻度交联的P(AN-MA-IALi)聚合物电解质膜.通过FTIR, DSC和SEM等测试方法对共聚物的结构进行了表征, 利用交流阻抗等电化学方法对该膜的导电性能进行了研究.实验结果表明, 所制备的交联聚合物的室温电导率达到10-5~10-4 S/cm, 当IALi的质量分数为3%时, 所制备的聚合物电解质膜的电导率最大可达到1.89×10-4 S/cm.     

Crystal Structure and Magnetic Properties of a Vanadium (IV) Pyrophosphate: Rb2V3P4O17

The crystal structure of Rb₂V₃P₄O₁₇ has been determined from single-crystal X-ray diffraction data. Rb₂V₃P₄O₁₇ crystallizes in the orthorhombic space group Pnma (No. 62) with a = 17.502(7), b = 7.292(2), c = 11.399(6) ų, V = 1455(1) ų, Z=4, R=0.0295, R_W = 0.0320 for 1129 unique reflections with I > 2.5 σ(I). The structure contains intersecting tunnels where the Rb⁺ cations are located. The framework can be described as consisting of V²O₁₀ units formed from one VO₅ square pyramid and one VO₆ octahedron sharing a corner, and infinite chains of corner-shared VO₆ octahedra, which are linked in three dimensions by pyrophosphate groups. The structural formula is Rb₂(VO)₃(P₂O₇)₂. A single-phase product can be obtained by heating appropriate amounts of Rb₄V₂O₇, VO₂, V, and P₂O₅ in an evacuated fused silica tube at 950°C. Powder magnetic susceptibility data confirm the presence of V⁴⁺ (d¹) ions without magnetic ordering down to 3 K.     

二次锂电池正极材料Li_xNi_（0．3）Co_（0．7）O_2的XPS与XRD

结果表明，ＬｉｘＮｉ０．３Ｃｏ０．７Ｏ２具有六方晶系Ｒ３－ｍ空间群结构。当Ｘ＝１，０．３１５时，其晶胞参数分别为ａ＝２．８２６ｎｍ，ｃ＝１４．１３０ｎｍ和ａ＝０．２８０８ｎｍ，ｃ＝１．４２５３ｎｍ；ＭＯ６（Ｍ＝Ｎｉ，Ｃｏ）八面体中Ｍ－Ｏ平均距离分别为０．１９４１ｎｍ和０．１９３３ｎｍ。ＸＰＳ分析结果表明ＬＩｘＮｉ０．３ＣＯ０．７Ｏ２表面存在Ｌｉ２Ｏ，同时探讨了其中过渡金属离子的３ｄ电子结构变化。     

纳米Cr2O3的制备、表征及催化性能

首次采用溶胶-凝胶法与共沸蒸馏法耦合技术制备了纳米Cr2O3粉体，并运用BET、TEM、XRD、FT-IR、XPS及H2-TPR对其进行表征，同时采用CO2氧化乙烷脱氢制乙烯反应作为探针反应，考察了纳米Cr2O3的催化性能。首次发现纳米ErgO3的FT-IR谱出现了蓝移现象，并且630cm^-1附近的伸缩振动峰强度增强。初步探讨了纳米氧化物的IR蓝移和红移的原因，指出晶型是影响纳米氧化物红外光谱特征的重要因素。实验结果表明纳米Cr2O3上乙烷和CO2转化率均明显高于常规Cr2O3催化剂；在700℃下，乙烷转化率高达77．1％，而乙烯产率达到了58．98％。     

Preparation,Crystal Structure,and Physical Properties of the Rare-Earth Metal Palladium Silicides LnPdSi (Ln = La,Ce, Pr) and the a-ThSi2 Type Compounds LaPd0.787(2)Si1.213(2) and CePd0.758(5)Si1.242(5)

Darstellung, Kristallstruktur und physikalische Eigenschaften der Seltenerdmetall-Palladium-Silicide LnPdSi (Ln = La, Ce, Pr) und die Verbindungen LaPd_0,787(2)Si_1,213(2) und CePd_0,758(5)Si_1,242(5) mit a-ThSi₂-Struktur Die äquiatomaren Seltenerdmetall-Palladium-Silicide LnPdSi (Ln = La, Ce, Pr) kristallisieren mit einem neuen monoklinen Strukturtyp, welcher aus Einkristall-Röntgen-Diffraktometerdaten von PrPdSi bestimmt worden ist: P2₁/c, a = 1079,1(5) pm, b = 584,1(2) pm, c = 786,7(2) pm, β = 92,00(2)°, Z = 8. Die Palladium- und Siliciumatome bilden ein dreidimensional-unendliches Netzwerk, in dem die Palladiumatome drei Siliciumnachbarn haben, während ein Teil der Siliciumatome vier Palladium- und der andere Teil ein Silicium- und zwei Palladiumnachbarn hat. Die Abstände Pd–Si (zwischen 242,8 und 255,3 pm) und Si–Si (233,0 pm) sind ähnlich wie die entsprechender Zweielektronen-Bindungen. Die Praseodymatome haben zwölf Silicium- und Palladiumnachbarn. Ein Pr–Pr-Abstand ist überraschend kurz mit 347,5 pm. LaPdSi ist ein metallischer Leiter und Pauli-paramagnetisch, während CePdSi und PrPdSi Curie-Weiss-Verhalten zeigen mit magnetischen Momenten, wie sie für Ce⁺³ und Pr⁺³ erwartet werden und ferro- oder ferrimagnetischer Ordnung unterhalb von 7 K. Die Verbindungen LaPd_0,787(2)Si_1,213(2) und CePd_0,758(5)Si_1,242(5) kristallisieren mit α-ThSi₂-Struktur. Ihre Zusammensetzung wurde durch Strukturverfeinerungen aus Einkristall-Diffraktometerdaten bestimmt.     

0/1/2维混合纳米形貌V2 O5的制备与储锂性能

以P123为结构导向剂,采用溶胶-凝胶法结合冷冻干燥技术制备了0/1/2维混合纳米形貌的正交相V₂O₅电极活性材料.利用XRD和SEM表征了样品的结构和形貌,通过循环伏安法、恒流充放电和交流阻抗谱测试研究了样品的储锂性能.结果显示,这种0/1/2维混合纳米形貌V₂O₅具有较高的储锂容量、优异的电化学循环稳定性和出色的大倍率充放电性能,在1 A/g电流密度下循环500次后放电比容量稳定在117.5 mA·h/g,容量保持率为94.4%,在5 A/g大电流密度下,其放电比容量仍保持在88.2 mA·h/g,性能明显优于未添加P123制备的2D片状V₂O₅材料.     

钒酸盐化合物NaV_2O_5的水热合成及电化学性质

应用水热合成法制备NaV2O5晶体,XRD、SEM、拉曼光谱和XPS分析测试及电化学表明,该材料属正交晶系,空间群为Pmmn,呈纯相的棒状结构,长度约有20μm,宽度大约200 nm.该材料的V离子均价为+4.5价.首次放电容量达到120 mAh/g,放电平台为2.0 V.经过20个循环,容量保持率98 mAh/g,表现了良好的循环性能.     

新型电荷转移复合物(BEDT-TTF)4·H2O·Fe(C2O3)3·C6H5NO2的合成、结构与物理性质

导电性的电荷转移复合物（盐）由于其特殊的物理性质和潜在的应用前景，近年来得到广泛研究［１，２］．导电电荷转移复合物主要包括基于Ｍ（ｄｍｉｔ）２（ｄｍｉｔ＝１，３－二硫－２－硫酮－４，５－二硫醇盐）阴离子自由基［３～５］和ＢＥＤＴ－ＴＴＦ（乙二硫撑四硫...