静电自组装聚电解质/有机染料插层蒙脱土光致变色纳米复合膜

从构筑静电自组装聚电解质／有机染料插层蒙脱土光致变色纳米复合膜所必需 的基本纳米构件--有机染料插层蒙脱土光致变色纳米复合物的设计出发，制备了具有光致 变色功能的蒙脱土／阳离子偶氮染料（GTL）均插层纳米复合物现，插人蒙脱土层 间的GTL热稳定性大幅度提高．由于GTL在纳米受限空间的超分子有序结构共轭，使 偶氮基发生了高达91 nm的显著红移．使用该插层纳米复合物构件与阳离子聚电解 质（PDAC）通过静电自组装得到了生长均匀、排列规整有序的光致变色聚电解质／ 阳离子偶氮染料插层蒙脱土纳米复合膜.     

Surface structure and electrochemical characteristics of natural graphite fluorinated by ClF3

Natural graphite samples with average particle sizes of 5, 10 and 15 μm (NG5 μm, NG10 μm and NG15 μm, respectively) were fluorinated by ClF₃ (3 × 10⁴ Pa) at 200 and 300 °C for 2 min. X-ray photoelectron spectra of surface-fluorinated samples showed that surface fluorine concentration increased with increase in the particle size of graphite and reaction temperature. Small amounts of chlorine were also detected in all the fluorinated samples. Raman spectra of original and surface-fluorinated samples indicated that the surface disordering was increased for NG10 μm and NG15 μm. Surface areas were decreased by the fluorination for NG5 μm and NG10 μm but unchanged for NG15 μm. The mesopores with diameter of 1.5-2 nm increased while those of 2-3 nm decreased for all the samples. First coulombic efficiencies for NG10 μm and NG15 μm were highly increased by surface fluorination in 1 mol/dm³ LiClO₄-EC/DEC/PC (EC: ethylene carbonate, DEC: diethyl carbonate, PC: propylene carbonate) solution.     

Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O

¹⁹F and ³¹P NMR spectroscopy were used to study the kinetics of the hydrolysis of LiPF₆ in the homogenous solvent system propylene carbonate (PC)—dimethyl carbonate (DMC)—H₂O. It was found that the main products of the hydrolysis are HF, LiPO₂F₂ and Li₂PO₃F. The content of POF₃ and PF₅ was negligibly low. We set up a hypothesis that the main factor determining the rate of the process is the so-called ‘secondary’ catalytic effect, caused by solvated H⁺ ions.     

Possible Mechanisms of Intercalation

Recent knowledge of the kinetics and intercalation mechanisms are summarized and accompanied by examples of intercalation reactions of water and ethanol into anhydrous vanadyl phosphate and redox intercalation of alkali metal cations into vanadyl phosphate dihydrate. Three possible mechanisms of intercalation are presented which are based on: (i) a concept of exfoliation of layers; (ii) the formation of stages and randomly stacked layers; (iii) co-existence of intercalated and non-intercalated parts of crystals of the host separated by an advancing phase boundary. The corresponding kinetic curves are ascribed to mechanisms (ii) and (iii).     

Novel composite anode materials for lithium ion batteries with low sensitivity towards humidity

Graphitic anode materials for lithium ion batteries processed under high humidity conditions show severe performance losses. The sensitivity of these materials towards humidity can be significantly reduced by adsorbing metal ions like silver or copper ions, with subsequent heat treatment of these composites. Results of X-ray photoelectron spectroscopy, high-resolution electron microscopy, thermogravimetry, and differential thermal analysis indicate that the deposited metals exist in metallic and carbide, M_xC (M=Cu or Ag), forms. They remove or cover (i.e. deactivate) active hydrophilic sites at the surface of the graphite. These composites absorb less water during processing. The electrochemical performance, including reversible capacity, coulombic efficiency in the first cycle, and cycling behavior, is markedly improved. This approach provides a potentially powerful method to manufacture lithium ion batteries under less demanding conditions.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

Palladium-catalyzed reactions for the synthesis of chlorins and 5,10-porphodimethenes

The palladium-catalyzed reaction of RLi with various 5,10,15,20-tetrasubstituted porphyrins offers a convenient synthetic route to chlorins and porphodimethenes (calixphyrins). The reactions utilized various Pd catalysts and CuI and yielded either 2,3-substituted chlorins or 5,10-disubstituted porphodimethenes in yields ranging from 20-40%. The reaction of octaethylporphyrin with t-BuLi in the presence of a Pd-catalyst generated the corresponding 5,10-porphodimethene in 72% yield.     

The electronic structure of small lithium clusters

Ab initio molecular orbital calculations using the STO-6G and STO6-21G basis sets have been performed for the cluster series Li _n ⁺ , Li _n , and Li _n ^– (wheren=2–7). Thirty-two optimized structures are discussed and reported, many of which (especially for the anionic structures) have not yet been considered. The calculations suggest that for all three species the optimum geometries are planar. Of the two levels of theories that were investigated, STO-6G//STO-6G and STO6-21G//STO-6G, the latter hybrid theory was found to be less reliable. In particular, for the anionic structures these calculations should provide a platform from which more sophisticated, i.e., configuration interaction, geometry optimization can be performed.     

Novel Gel—like Process for Synthesizing Submicron LiaNi0.8Co0.2O2 Powders Used in Lithium Ion Batteries

A novel gel-like process has been developed for synthesizing LiaNi0.8Co0.2O2 powders,using citric acid as a chelating agent. This process improves the homogeneity of constituent cation and enhances their reactivity in the obtained precursor. The results of electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. Its initial capacity reached 181.6 mAh/g and reversible efficiency at the first cycle is about 88.6%.     

A DFT study of lithium battery materials: application to the β-VOXO4 systems (X=P, As, S)

VOXO₄ systems have been considered as potential lithium battery electrodes. They mainly present two distinct structural types: the tetragonal “α” type with a two-dimensional framework, and the three-dimensional orthorhombic “β”. DFT calculations were performed on this latter system for several β-Li_xVOXO₄ compounds (x=0, 1; X=P, As, S). They allowed to propose structural models for VOAsO₄ and LiVOSO₄, not fully crystallographically well described yet. Based on an experimental model of two-phase processes, these calculations led also to a good simulation of electrochemical potential values. A density of states analysis put in evidence the “inductive effect” and the role played by (XO₄)ⁿ⁻ groups inside the host frameworks on these potentials.