石墨负极在Et4NBF4+LiPF6/EC+PC+DMC电解液中的电化学行为

在PC+EC+DMC复合溶剂体系中, 研究了Et4NBF4(四氟硼酸四乙基铵)与LiPF6组成的复合盐电解质对石墨负极材料界面性质的影响. 用循环伏安和恒电流充放电测试方法研究了电解液与石墨负极的相容性, 通过傅里叶变换红外光谱(FTIR)对固体电解质中间相膜(SEI)的成分变化进行了研究. 结果表明, 电解液中的Et4NBF4参与了SEI膜的形成; 当Et4NBF4浓度为0.2 和0.5 mol·L-1时, 电池首次充放电不可逆容量损失明显减少, 循环效率分别上升到76.0%和81.6%. Et4NBF4/LiPF6复合盐电解质改善了PC基电解质与石墨负极的相容性.     

石墨负极电化学扫描循环过程的EIS、Raman光谱和XRD研究

运用电化学阻抗谱(EIS)、Raman光谱和XRD研究了石墨负极在1 mol/L LiPF6-EC∶DEC∶DMC电解液中的电化学循环扫描过程. EIS研究结果表明, 在电化学循环扫描4~10周范围内, SEI膜(固体电解质相界面膜)电阻随循环扫描周数增加近似线性增长, 但石墨负极/电解液界面总阻抗由于电荷传递电阻的降低而减小. Raman光谱研究结果表明, 在经历电化学循环扫描后, 活性材料表层发生粉化和无定形化, 石墨化程度降低; 但XRD研究结果显示, 石墨材料的本体结构没有发生变化, 仍然保持着完整的石墨层状结构.     

V_2O_5/C电化学电容器有机电解液的性能研究

以偏钒酸铵为反应原料,采用液相沉淀法制备出不定型V2O5电极材料.以V2O5为正极,石墨为负极,分别选用1.0 mol/L LiClO4/EC+DMC、1.0 mol/L LiPF6/EC+DEC+DMC、1.6 mol/L Et4NBF4/AN 3种有机电解液组成不对称电化学电容器,恒流充放电、循环伏安和交流阻抗等测试该模拟电容器,如以1.0 mol/LLiClO4/EC+DMC作电解液则具有良好的循环性能和较小的阻抗,且在500 mA/g电流密度下比能量达到8.4Wh/kg,充放电效率达98%.     

二氟二草酸硼酸锂对LiFePO4/石墨电池高温性能的影响

研究了二氟二草酸硼酸锂(LiODFB)作为锂盐加入到碳酸丙烯酯(PC)+碳酸乙烯酯(EC)+碳酸甲乙酯(EMC)(质量比为1:1:3)混合溶剂中对LiFePO4/石墨电池高温(60 ℃)循环性能的影响. 用线性扫描伏安法(LSV)测试了电解液的电化学窗口. 通过等离子发射光谱(ICP)和能量散射光谱(EDS)对LiFePO4材料高温条件下在不同电解液中的稳定性进行了研究; 并用扫描电镜(SEM)和电化学交流阻抗谱(EIS)分析了石墨负极表面的固体电解液相界面(SEI)膜的热稳定性. 结果表明: 一方面LiODFB基电解液能抑制LiFePO4材料在高温条件下Fe(II)的溶解, 防止溶解的Fe(II)在石墨上还原, 有效地降低电池阻抗; 另一方面, 在LiODFB基电解液中形成的石墨负极表面SEI膜具有更好的热稳定性, 能显著提高LiFePO4/石墨电池的高温循环性能.     

新型锂盐LiBC2O4F2在EC＋DMC溶剂中的电化学行为

采用差热-热重(TG-DTA)、恒电流充放电和交流阻抗(EIS)分析了二氟草酸硼酸锂(LiODFB)的热稳定性,研究了LiODFB/碳酸乙烯酯(EC)+碳酸二甲酯(DMC)电解液的电化学性能及界而特征.实验结果表明,LiODFB不仅具有更高的热稳定性,而且在EC+DMC溶剂中具有较好的电化学性能.与使用LiPF6/EC+DMC的电解液相比,锂离子电池应用LiODFB基电解液在55℃的高温具有更好的容量保持能力;以0.5C、1C(1C=250 mA·g-1)倍率循环放电,两种电池间的倍率性能差别较小;LiODFB能够在1.5 V(vs Li/Li+)左右在石墨电极表面还原形成一个优异稳定的保护性固体电解质相界面膜(SEI膜);交流阻抗表明,使用LiODFB基电解液的锂离子电池仅具有稍微增加的界面阻抗.因此LiODFB是一种非常有希望替代LiPF6用作锂离子电池的新盐.     

温度对石墨电极性能的影响

运用电化学阻抗谱(EIS)并结合循环伏安法(CV)研究了石墨电极25和60 ℃时在1 mol·L-1 LiPF6-EC(碳酸乙烯酯):DEC(碳酸二乙酯):DMC(碳酸二甲酯)电解液中, 以及60 ℃时在1 mol·L-1 LiPF6-EC:DEC:DMC+5%VC(碳酸亚乙烯酯)电解液中的首次阴极极化过程. 发现高温下(60 ℃)石墨电极在1 mol·L-1 LiPF6-EC:DEC:DMC电解液中可逆循环容量衰减的主要原因在于其表面无法形成稳定的固体电解质相界面(SEI)膜. 实验结果显示, VC添加剂能够增进高温下石墨电极表面SEI膜的稳定性, 进而改进石墨电极的循环性能.     

微晶碳电活化过程中离子尺寸效应研究

以石油焦基微晶碳作为电极材料,并由N2吸附,X射线衍射(XRD)表征其孔结构和微晶结构.研究了4种电解液Et4NBF4/PC(四乙基铵四氟硼酸盐/碳酸丙烯酯)、Et4NBF4/AN(四乙基铵四氟硼酸盐/乙腈)、Bu4NBF4/PC(四丁基铵四氟硼酸盐/碳酸丙烯酯)和Bu4NBF4/AN(四丁基铵四氟硼酸盐/乙腈)的微晶碳电容器特性.结果表明:电解质离子与溶剂AN的溶剂化半径较小,容易嵌入类石墨微晶碳层,其于AN的电活化电位比在PC中的低,致使电活化程度更深,材料的表面利用率更高,电容量较大.电解质阳离子(Et4N+,Bu4N+)大小对电活化影响不大.电活化使材料类石墨微晶层间距(d002)变大,离子尺寸越大,层间距增加越明显.     

电解液组成对中间相石墨微球电化学性能的影响

以2800℃热处理的煤焦油沥青基中间相石墨微球为锂离子二次电池负极材料,考察了中间相石墨微球在不同组成的电解质溶液中的电化学嵌脱锂性能.确定了试样在不同电解液中电极表面生成的SEI膜的化学组成和相对含量,剖析了共溶剂对SEI膜形成反应、膜组成和织构的影响.结果表明,在不同共溶剂的EC基电解液中,电极界面SEI膜形成的电位虽然不同,但SEI膜的化学组成基本相同,负极界面SEI膜的织构是决定电解液与电极材料相容性的关键.     

新型锂盐LiBC2O4F2在EC+DMC溶剂中的电化学行为

采用差热-热重(TG-DTA)、恒电流充放电和交流阻抗(EIS)分析了二氟草酸硼酸锂(LiODFB)的热稳定性, 研究了LiODFB/碳酸乙烯酯(EC)+碳酸二甲酯(DMC)电解液的电化学性能及界面特征. 实验结果表明, LiODFB不仅具有更高的热稳定性, 而且在EC+DMC溶剂中具有较好的电化学性能. 与使用LiPF6/EC+DMC的电解液相比, 锂离子电池应用LiODFB基电解液在55 ℃的高温具有更好的容量保持能力; 以0.5C、1C(1C=250 mA·g-1)倍率循环放电, 两种电池间的倍率性能差别较小; LiODFB能够在1.5 V(vs Li/Li+)左右在石墨电极表面还原形成一个优异稳定的保护性固体电解质相界面膜(SEI膜); 交流阻抗表明, 使用LiODFB基电解液的锂离子电池仅具有稍微增加的界面阻抗. 因此LiODFB是一种非常有希望替代LiPF6用作锂离子电池的新盐.     

LiBOB基电解液成膜性及其循环性能

通过循环伏安(CV)、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和傅立叶变换红外(FTIR)光谱研究了双乙二酸硼酸锂(LiBOB)基电解液在石墨表面的成膜性及其在常温(25 ℃)和高温(70 ℃)下对石墨循环性能的影响. 结果表明, LiBOB基电解液的成膜电位在1.7 V, 其中BOB-离子还原形成的草酸盐是固体电解质相界面(SEI)膜的有效成分之一. 电化学阻抗谱显示, 膜阻抗在循环过程中呈现减小趋势, 这有利于提高循环稳定性. 在常温和高温条件下, 石墨在该电解液体系中均表现出优于其在LiPF6基电解液体系中的循环性能.     

Variationen modulo 4–4+, 4+3–3+4–, 4–5+, 5–4+4–5+4–4+ bei Seltenerdcarbidhalogeniden

The new compounds Pr₈(C₂)₄Cl₅ (1), Pr₁₄(C₂)₇Cl₉ (2), Pr₂₂(C₂)₁₁Cl₁₄ (3), Ce₂(C₂)Cl (4), La₂(C₂)Br (5), Ce₂(C₂)Br (6), Pr₂(C₂)Br (7), Ce₁₈(C₂)₉Cl₁₁ (8), and Ce₂₆(C₂)₁₃Cl₁₆ (9) were prepared by heating mixtures of LnX₃, Ln and carbon or in an alternatively way LnX₃, and “Ln₂C_3–x” in appropriate amounts for several days between 750 and 1200 °C. The crystal structures were investigated by X‐ray powder analysis (5–7) and/or single crystal diffraction (1–4, 8, 9). Pr₈(C₂)₄Cl₅ crystallizes in space group P2₁/c with the lattice parameters a = 7.6169(12), b = 16.689(2), c = 6.7688(2) Å, β = 103.94(1) °, Pr₁₄(C₂)₇Cl₉ in Pc with a = 7.6134(15), b = 29.432(6), c = 6.7705(14) Å, β = 104.00(3) °, Pr₂₂(C₂)₁₁Cl₁₄ in P2₁/c with a = 7.612(2), b = 46.127(9), c = 6.761(1) Å, β = 103.92(3) °, Ce₂(C₂)₂Cl in C2/c with a = 14.573(3), b = 4.129(1), c = 6.696(1) Å, β = 101.37(3) °, La₂(C₂)₂Br in C2/c with a = 15.313(5), b = 4.193(2), c = 6.842(2) Å, β = 100.53(3) °, Ce₂(C₂)₂Br in C2/c with a = 15.120(3), b = 4.179(1), c = 6.743(2) Å, β = 101.09(3) °, Pr₂(C₂)₂Br in C2/c with a = 15.054(5), b = 4.139(1), c = 6.713(3) Å, β = 101.08(3) °, Ce₁₈(C₂)₉Cl₁₁ in P$\bar{1}$ with a = 6.7705(14), b = 7.6573(15), c = 18.980(4) Å,α = 88.90(3) °, β = 80.32(3) °, γ = 76.09(3) °, and Ce₂₆(C₂)₁₃Cl₁₆ in P2₁/c with a = 7.6644(15), b = 54.249(11), c = 6.7956(14) Å, β = 103.98(3) ° The crystal structures are composed of Ln octahedra centered by C₂ dumbbells. Such Ln₆(C₂)‐octahedra are condensed into chains which are joined into undulated sheets. In compounds 1–4 three and four up and down inclined ribbons alternate (4₊4_–, 4₊3_–3₊4_–, 4₊4_–3₊4_–4₊3_–), in compounds 8 and 9 four and five (4₊5_–, 5₊4_–4₊5_–4₊4_–), and in compounds 4–7 one, one ribbons (1₊1_–) are present. The Ln‐(C₂)‐Ln layers are separated by monolayers of X atoms.     

Isotopic replacement in ionic systems: the 4He2+ + 3He-->3He 4He+ + 4He reaction

Full quantum dynamics calculations have been carried out for the ionic reaction (4)He(2) (+)+(3)He and state-to-state reactive probabilities have been obtained using both time-dependent and time-independent approaches. An accurate ab initio potential-energy surface has been employed for the present quantum dynamics and the two sets of results are shown to be in agreement with each other. The results for zero total angular momentum suggest a marked presence of atom exchange (isotopic replacement) reaction with probabilities as high as 60%. The reaction probabilities are only weakly dependent on the initial vibrational state of the reactants, while they are slightly more sensitive to the degree of rotational excitation. A brief discussion of the results for selected higher total angular momentum values is also presented, while the l-shifting approximation [S. K. Gray et al., Phys. Chem. Chem. Phys. 1, 1141 (1999)] has been used to provide estimates of the total reaction rates for the title process. Such rates are found to be large enough to possibly become experimentally accessible.     

超价化合物NLin+4和OLin+4电子结构和性质

以6-3lG·基组利用HF、MP2和DFT方法优化了超价化合物NLin+4和OLn+4的几何构型.研究结果表明,MP2和DFT法计算出的OLi4分子解离出Li和Li2的反应能与已有的实验值吻合.对于NLi4分子,得到其解离出Li和Li2的反应能分别为191.78和515.37 kJ/mol(MP2值).并预测了OLin+4和NLin+4分子的基振动频率.     

4+1 and 4+2 coordinated complexes of magnesium phthalocyanine with dioxane

Two complexes of magnesium phthalocyanine with dioxane were obtained. They co-crystallise in the centrosymmetric space group of the triclinic system. One of them is biaxially ligated (4+2) complex MgPc(dioxane)₂ and the other is bridged μ-dioxane(MgPc)₂. The interaction of the bridged dioxane molecule with two MgPc molecules is stronger than the interaction of two dioxane molecules axially ligated to the metal center of MgPc on the both sides of the Pc-plane. The strength of the MgO bond in these complexes correlates with their thermal stability. Owing to the Mg?O interaction of the bridged dioxane molecule with two MgPc units and formation of the μ-dioxane(MgPc)₂ complex, the Mg atom is significantly displaced (0.357(3) Å) from the plane defined by four isoindole N atoms of Pc. This interaction causes a distortion of planar Pc(2-) macrocycle to the saucer-shape form. In biaxially ligated MgPc(dioxane)₂ molecule the Pc(2-) macroring exhibits the planar form. Due to the steric hindrance of the axial ligand, the crystals exhibit better solubility than the parent MgPc, since the structure is less stabilized by π-π interactions between the aromatic Pc(2-) macrorings than in the structure of MgPc. Ligation of MgPc by dioxane does not change the colouring properties compared with the MgPc pigment. The calculated 3D molecular electrostatic potential maps are helpful for understanding the organisation and arrangement of molecules in the crystal.     

Adsorption of Zr4+, Hf4+, Rf4+ and Po4+ diketonate complexes on hydrophobized glass surface

Studies of the complexes of the title ions with and diketonate ligands were performed with the aim of verifying the influence of relativistic effects upon the coordination number of rutherfordium. Since the diketonate complexes are volatile, we developed a new solid-liquid extraction system based on the adsorption of neutral complexes on hydrophobized glass surfaces. This system was applied to the studies of complexation of the short-lived isotopes Zr⁴⁺, Hf⁴⁺, Po⁴⁺ and Rf⁴⁺. The procedure including collection of radioactivity, adsorption of complexes and preparation of the -source, took roughly 50–60 seconds to complete. The obtained results show that studies of adsorption on hydrophobized glass surface may provide important experimental data on the formation of chelate complexes with short-lived radionuclides.