Synthesis and phase transition of Li-Mn-O spinels with high Li/Mn ratio by thermo-decomposition of LiMnC2O4(Ac)

LiMnC₂O₄(Ac) precursor in which Li⁺ and Mn²⁺ were amalgamated in one molecule was prepared by solid-state reaction at room-temperature using manganese acetate, lithium hydroxide and oxalic acid as raw materials. By thermo-decomposition of LiMnC₂O₄(Ac) at various temperatures, a series of Li_1+y[Mn_2−xLi_x]_16dO₄ spinels were prepared with Li₂MnO₃ as impurities. The structure and phase transition of these spinels were investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. Results revealed that the Li-Mn-O spinels with high Li/Mn ratio were unstable at high temperature, and the phase transition was associated with the transfer of Li⁺ from octahedral 16c sites to 16d sites. With the sintering temperature increasing from 450 to 850 °C, the phase structure varied from lithiated-spinel Li₂Mn₂O₄ to Li₄Mn₅O₁₂-like to LiMn₂O₄-like and finally to rock-salt LiMnO₂-like. A way of determining x with average oxidation state of Mn and the content of Li₂MnO₃ was also demonstrated.     

Apparent Molar Volume, Heat Capacity, and Conductance of Lithium Bis(trifluoromethylsulfone)imide in Glymes and Other Aprotic Solvents

Lithium bis(trifluoromethylsulfone)imide (LiTFSI) is a promising electrolyte for high-energy lithium batteries due to its high solubility in most solvents and electrochemical stability. To characterize this electrolyte in solution, its conductance and apparent molar volume and heat capacity were measured over a wide range of concentration in glymes, tetraethylsulfamide (TESA), acetonitrile, -butyrolactone, and propylene carbonate at 25°C and were compared with those of LiClO₄ in the same solvents. The glymes or n(ethylene glycol) dimethyl ethers (nEGDME), which have the chemical structure CH₃–O–(CH₂–CH₂–O) _n –CH₃ for n = 1 to 4, are particularly interesting since they are electrochemically stable, have a good redox window, and are analogs of the polyethylene oxides used in polymer-electrolyte batteries. TESA is a good plasticizer for polymer-electrolyte batteries. Whenever required, the following properties of the pure solvents were measured: compressibilities, expansibilities, temperature and pressure dependences of the dielectric constant, acceptor number, and donor number. These data were used in particular to calculate the limiting Debye-Hückel parameters for volumes and heat capacities. The infinite dilution properties of LiTFSI are quite similar to those of other lithium salts. At low concentrations, LiTFSI is strongly associated in the glymes and moderately associated in TESA. At intermediate concentrations, the thermodynamic data suggests that a stable solvate of LiTFSI in EGDME exists in the solution state. At high concentrations, the thermodynamic properties of the two lithium salts approach those of the molten salts. These salts have a reasonably high specific conductivity in most of the solvents. This suggests that the conductance of ions at high concentration in solvents of low dielectric constant is due to a charge transfer process rather than to the migration of free ions.     

Polygermoxanes suitable for biochemical purposes: II Linear trigermoxanes (high-viscosity oils)

Linear trigermoxanes, R¹ RGeOGe(R³)₂OGeRR¹, a new series of organogermanium compounds, were synthesized by reaction of a lithium organogermanolate with a suitable organogermanium dihalide. With alkyl or phenyl substituents, these trigermoxanes are structurally unstable viscous oils, due to redistribution reactions. When R³ substituents are bulky groups, such as mesityl, trigermoxanes are thermally and structurally stable oils; depending on the R¹ and R² substituents their viscosities lie in the range 240 to more than 1500 cPo (mPa s) at 20°C. When both terminal germanium atoms are substituted with two mesityl groups, trigermoxanes are stable glassy solids.     

Anharmonicity and fragility in lithium borate glasses

Since the physical properties of lithium borate glasses xLi₂O-(1-x)B₂O₃ (0<x< 0.28) vary over a wide range with the composition, this binary system is particularly suitable for studying the relationship between vibrational anharmonicity and fragility. The density, the linear expansion coefficient, the longitudinal and transverse ultrasonic velocities and their respective temperature coefficients of the velocities are measured, from which the vibrational anharmonicity in lithium borate glasses is evaluated with the help of the Grüneisen parameter at the Debye cut-off frequency and the Anderson-Grüneisen parameter: these two parameters plotted vs. composition have the same characteristics with minima at x≈0.08. The fragility is evaluated from the temperature width of the glass transition; the fragility also shows a minimum at x≈0.08. The presence of minima at x≈0.08 is ascribable to the fact that the crosslinking density between six-membered rings in the glass reaches a maximum at this composition. We show that the anharmonic parameters strongly correlate with the fragility metrics. This revised version was published online in August 2006 with corrections to the Cover Date.     

添加剂对SiO电性能的影响及其机理分析

SiO_x/CoO and SiO/Li₂CO₃ composite materials were prepared by mechanical ball-milling. The structures of the obtained materials were characterized by X-ray diffraction (XRD). And scanning electron microscopes (SEM) of three samples after 20 cycles were also given. In addition， the electrochemical performances of three materials with galvanostatic charge-discharge cycling were investigated. The results show that the composite samples have larger initial reversible capacities and better cycle performance than pure SiO. Also，a schematic diagram showing the buffer effects of Li₂CO₃ addition and the mechanism of improving electrochemical performance by adding Li₂CO₃ are suggested.     

Phase transformations during electrochemical incorporation of lithium in intermetallic compounds of aluminum

Comparative study of the regularities of the reaction and specific features of phase formation during electrochemical incorporation of lithium from propylene carbonate solutions in intermetallic aluminum-based compounds (CuAl₂, Mg₂Al₃, and NiAl) and pure metals (Al, Cu, Mg, and Ni) was performed. The initial stage of the process was shown to be dissolution of lithium in the solid phase limited by diffusion for all studied substrates. Trace amounts of lithium-containing by-products, were detected in NiAl, Ni, and Cu samples. The subsequent change in the limiting stage is related to the beginning of formation of a new phase: metallic lithium (on Mg₂Al₃, NiAl, Mg, Ni, and Cu) or LiAl (on Al and CuAl₂ cathodes). In the latter case, the solid-phase substitution occurs, which is formally described by the equation: CuAl₂+2Li⁺+2e→2LiAl+Cu. Thus, the specific features of phase formation on the CuAl₂ electrode correspond to the highest (among three intermetallides studied) concentration of Al atoms in the crystal lattice of the compound. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 1525–1530, August, 1998.     

Molecular mechanics (MM3) calculations on lithium amide compounds

The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations.     

Installation of carbon chain onto 2-cyclohexene-1,4-diol monoacetate

Alkylation of cyclohexenyl monoacetate 1 with R₂Cu(CN)(MgCl)₂ or RMgBr/CuCN (cat.) in Et₂O produced trans 1,2-isomers 4, while arylation and alkenylation of 1 was accomplished with lithium borates 5 and a nickel cat. to afford trans 1,4-isomers 3 selectively. Furthermore, several transformations of the products were carried out to demonstrate synthetic advantages of the present reactions.     

锂离子电池锡氧化物基负极材料的湿化学合成与电化学性质

采用新兴的湿化学方法合成了锡氧化物基粉末材料。用X-射线衍射、扫描电镜和电化学方法对材料的微观结构、形貌和电化学性能进行了详细的研究。结果表明，经400 ℃热处理4 h的锡氧化物基材料的颗粒大小均匀，平均粒径约为200 nm。这种材料的可逆充电容量超过570 mAh·g^-1，30次循环后平均每次循环的容量衰减只有0.15%。良好的电化学性能表明锡氧化物基材料有望作为新一代锂离子电池的负极材料。     

锂离子蓄电池正极材料LiFePO4研究进展

锂离子电池正极材料正在向着高比能量、长寿命、低成本、环境友好的方向发展,而具有橄榄石结构的LiFePO_4正极材料以其结构稳定、成本低、无污染等优点成为21世纪最理想的绿色电源,但自身也存在缺点。综述了锂离子电池正极材料LiFePO_4的研究进展。系统地阐述了LiFePO_4的晶体结构特征及性能、多种合成方法以及掺杂多种导电材料和控制晶体生长制备纳米粉体对材料性能的影响。对该材料的应用前景进行了展望,并提出了下一步可能的研究趋势。