Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium‐ion cells using LiPF₆ (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li₂CO₃ up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd.     

Cyclic Voltammograms of Ferrocene on Multi‐Walled Carbon Nanotubes (MWCNTs)‐Modified Edge Plane Pyrolytic Graphite (EPPG) Electrode in Room Temperature Ionic Liquids (RTILs) of 1‐Ethyl‐3‐Methylimidazolium Tetrafluoroborate (EMIBF4)

In this work, the electrochemical behavior of ferrocene (Fc) was investigated by cyclic voltammetry (CV) in room temperature ionic liquids (RTILs) of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄) on glass carbon (GC), edge plane pyrolytic graphite (EPPG) and multi‐walled carbon nanotube (MWCNTs)‐modified EPPG electrodes, respectively. The results demonstrated that on GC electrode, pairs of well‐defined reversible peaks were observed, while for the electrode of EPPG, the peak potential separation (ΔE_p) is obviously larger than the theoretical value of 59 mV, hinting that the electrode of EPPG is distinguished from the commonly used electrode, consistent with the previous proposition that EPPG has many “defects”. To obtain an improved electrochemical response, multi‐walled carbon nanotubes (MWCNTs) were modified on the electrode of EPPG; the increased peak current and promoted peak potential separation not only proved the existence of “defects” in MWCNTs, but also supported that “creating active points” on an electrode is the main contribution of MWCNTs. Initiating the electrochemical research of Fc on the MWCNTs‐modified EPPG electrode in RTILs and verifying the presence of “defects” on both EPPG and MWCNTs using cyclic voltammograms (CVs) of Fc obtained in RTILs of EMIBF₄, is the main contribution of this preliminary work.     

碳纤维中的单层石墨物相及其对力学性能的影响

依据碳纤维中各种物相的X射线衍射特性, 确认PAN基碳纤维中除了乱层石墨微晶外, 还存在大量的单层六元环C原子层面物相, 建立起两种非完整结晶物相的定量分析方法. 实验结果表明, 随着退火温度由1350 ℃上升到2400 ℃, Tx-3高强型碳纤维中的单层石墨含量由59.6%下降到34.8%, 乱层石墨含量由40.4%上升为65.2%. 与此同时, 碳纤维的拉伸强度则由3.65 GPa下降到2.05 GPa, 而延伸率也由1.04%下降到0.58%. 并对PAN基碳纤维中单层石墨对其力学性能的影响也进行了初步的探讨.     

反胶束模板制备聚甲基丙烯酸甲酯/无机纳米粒子/石墨纳米复合材料及其表征

以甲基丙烯酸甲酯(MMA)和三氯甲烷(CHCl₃)为油相制备反胶束微乳液, 依靠表面活性剂十六烷基三甲基溴化铵(CTAB)自组装形成的“微反应器”作为模板成功地制备了PMMA/Eu(OH)₃/EG和PMMA/Ni(OH)₂/EG纳米复合材料. 并用红外光谱(IR)、扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)和差热-热重(TG-DTA)对该复合材料进行了表征和分析. 研究结果表明, 反胶束法可以有效地应用于有机-无机纳米复合材料的制备.     

Effects of EG and MoSi2 on thermal degradation of intumescent coating

An intumescent flame retardant coating was prepared with resin, solvent and flame retardant system composed of ammonium polyphosphate-APP, pentaerythritol-PER and melamine-MEL. The modifiers such as molybdenum disilicide (MoSi₂) and expandable graphite (EG) were used to improve the performances of the APP-PER-MEL coating. The effects of EG, MoSi₂ and MoSi₂/EG on the fireproofing time and char formation of the coating were investigated by using heat insulation test, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electric microscope (SEM). The results showed that by adding modifiers, the fireproofing time was prolonged and char formation rate was evidently enhanced. The largest improvement was achieved with 9 wt.% MoSi₂/5 wt.% EG, XPS analysis indicated that the performance of anti-oxidation of the coating was improved by adding EG and MoSi₂, and SEM images showed that a good synergistic effect was obtained through a ceramic-like layer produced by MoSi₂ covered on the surface of “open-cellular” structural char.     

元素在石墨炉内石墨探针表面上的原子化机理研究 ⅩⅢ.钼的原子化机理

本文应用x-射线衍射(XRD)、X-射线光电子能谱(XPS)、俄歇电子能谱(AES)、扫描电子显微技术(SEM)研究了钼酸铵在石墨炉内石墨探针表面上的原子化机理。实验结果表明,在温度<1350K时,钼酸铵经历MoO_3和Mo_4O_(11)中间产物转变为MoO_2(s)。在更高温度下,MoO_2(s)首先还原为Mo_2C,而后进一步转变为MoC(s)。MoC再分解为Mo(s)。钼的原子化起源于Mo的升华。     

A new dodecylsulfate-selective supported liquid membrane electrode based on its N-cetylpyridinium ion-pair

A supported liquid and a poly(vinyl chloride) (PVC)-based membrane selective for dodecylsulfate (DS⁻) ion are described. The active element is a membrane containing a dissolved ion association complex of DS⁻ with cetylpyridinium (CP⁺) cation. The supported liquid membrane electrode (acetophenone as solvent) showed a Nernstian response towards the DS⁻ anion over the concentration range of sodium dodecylsulfate (SDS) from 8.3×10⁻³ to 1.0×10⁻⁶ mol dm⁻³ at 25 °C. The proposed electrode also showed a super-Nernstian potential response (108±2 mV decade⁻¹) at low concentrations (1.0×10⁻⁹ to 1.0×10⁻⁶ mol dm⁻³). Moreover, this electrode showed good selectivity and precision (R.S.D.?2.0%), and was usable within the pH range 4.0-6.8. The proposed electrode revealed a lower limit of detection of 6.3×10⁻⁷ mol dm⁻³ and improved selectivity in comparison with the some previously reported DS⁻ ion selective electrodes. The isothermal temperature coefficient of this electrode amounted to −0.001 V °C⁻¹. The liquid membrane electrode may find application in the direct determination of SDS by the standard addition method at pH 5.0, and in the physicochemical studies of surfactant solutions.     

Determination of trace metals in industrial boron carbide by solid sampling optical emission spectrometry. Optimization of DC arc excitation (current, atmosphere and chemical modifier)

Graphite arc emission spectrometry has become possible as a result of the invention of novel types of optical spectrometers with Echelle-optics and semiconductor array detectors, and by the application of electronically controlled, high current arc generators. An optimization of the excitation parameters to boron carbide analysis is reported here, measuring background corrected line intensities that were integrated for the time of total evaporation of 5 mg boron carbide sample with or without added chemical modifiers. The following set of experimental conditions were compared with respect of analytical sensitivity and precision: (A) no modifier, Ar + O₂ (20%), 16 A; (B) sample + graphite powder (1 + 1), Ar + O₂ (20%), 16 A; (C) sample + CaF₂ (1 + 1), Ar, 25 A; (D) sample + CaF₂ + graphite powder (1 + 1 + 1), Ar, 25 A. The graphite powder modifier resulted in improved precision in general, and the CaF₂ was effective as a plasma ionization buffer and fluorinating agent. The best compromise was found under conditions B, when oxygen was present in the discharge atmosphere. This is likely due to the stepwise conversion of the boron carbide matrix to the more volatile boron oxide. Under conditions B, detection limits in the ranges of 0.3–9 μg g⁻¹ for Al, Ca, Cr, Cu, Fe, Mg, Mn and Si and that of 18–38 μg g⁻¹ for Ti, W, and Zr were attained. Average RSDs of 10.2 and 9.7% were found, respectively, without and with internal referencing to boron.     

Electrochemical Synthesis of Co-intercalation Compounds in the Graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>3</Subscript>PO<Subscript>4</Subscript>System

Anodic oxidation of highly oriented pyrolytic graphite in an electrolyte containing concentrated sulfuric and anhydrous phosphoric acids is studied for the first time. The synthesis was carried out under galvanostatic conditions at a current I = 0.5 mA and an elevated temperature (t = 80°C). Intercalation compounds of graphite (ICG) are shown to form at all concentration ratios of H₂SO₄ and H³PO⁴ acids. The intercalation compound of step I forms in solutions containing more than 80 wt % H₂SO₄, a mixture of compounds of intercalation steps I and II forms in 60% H²SO⁴, intercalation step II is realized in the sulfuric acid concentration range from 10 to 40%, and a mixture of compounds of intercalation steps III and II is formed in 5% H₂SO₄ solutions. The threshold concentration of H₂SO₄ intercalation is ∼2%. With the decrease in active intercalate (H₂SO₄) concentration, the charging curves are gradually smoothed, the intercalation step number increases, and the potentials of ICG formation also increase. As the sulfuric acid concentration in the electrolyte changes from 96 to 40 wt %, the filled-layer thickness d _i in ICG monotonously increases from 0.803 to 0.820 nm, which apparently is associated with the greater size of phosphoric acid molecules. With further increase in H₃PO₄ concentration in solution, d _i remains unchanged. According to the results of chemical analysis, both acids are simultaneously incorporated into the graphite interplanar spacing and their ratio in ICG is determined by the electrolyte composition.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 651–655.Original Russian Text Copyright © 2005 by Leshin, Sorokina, Avdeev.     

The electrochemistry and determination of Ligustrazine hydrochloride

Ligustrazine is one of the active ingredients contained in Ligusticum chuanxiong Hort. (Umbelliferae), which is widely used in traditional Chinese medicine for the treatment of cardiovascular problems. In this work, the electrochemistry of Ligustrazine hydrochloride (LZC) and its determination are investigated. The detection limit is estimated to be 8.0×10^–8 M, with three linear ranges from 1.0×10^–6 to 1.0×10^–4 M, 1.0×10^–4 to 5.0×10^–4 M, and 6.5×10^–4 to 1.6×10^–3 M. The method has been proved to be highly sensitive, selective, and stable, and has been successfully applied to determining LZC in LZC injections.