Effects of the nanostructured SiO2 coating on the performance of LiNi0.5Mn1.5O4 cathode materials for high-voltage Li-ion batteries

LiNi_0.5Mn_1.5O₄ spinels coated with various amounts of fumed silica have been synthesized and investigated as cathode materials for high-voltage lithium-ion batteries at the elevated temperature (55 °C). The morphology and structure of the coated LiNi_0.5Mn_1.5O₄ samples were characterized by XRD, TEM and EDX. It was found that the surfaces of the coated LiNi_0.5Mn_1.5O₄ samples are covered with a porous, amorphous, nanostructured SiO₂ layer. The results of electrochemical experiments showed that the SiO₂-coated LiNi_0.5Mn_1.5O₄ samples display obviously improved capacity retention rate, and the improvement effect enhances with the increase of SiO₂ content. The XPS results revealed that the surfaces of the SiO₂-coated LiNi_0.5Mn_1.5O₄ cathode materials have relatively low content of LiF, and this is mainly responsible for their improved electrochemical cycling stability.     

Silica Nanoboxes as New Nano-structured Materials: Their Secondary Synthesis from Alumina-Rich Zeolites

Novel silica nanoboxes were prepared by controlled dealumination of Na-X and Ca-A type zeolites using ammonium hexafluorosilicate (AHFS). The silica-richer the parent zeolite, the smaller the average pore size produced and the narrower the pore size distribution obtained. This was due to the specific reactivity of the extracting agent with the zeolite framework aluminum atoms. High temperature calcination of the dealuminated X-zeolite (ammonium form) resulted in mesoporous materials exhibiting an ink-bottle shape, a quite high surface area (330 m²/g, no micropores), an average pore diameter of 4.5 nm with a quite narrow pore size distribution (± 1.0 nm) and finally, a pore opening diameter of 3.9 nm. The latter was determined by using the nitrogen sorption isotherms (BET technique) and related pore volume data. The sorption behavior also suggested the interconnecting character of the newly created nanoboxes. The periodicity of these nanoboxes throughout the mesoporous material was clearly shown by X-ray powder diffraction at very small angles. These materials, herein called monomodal nanoboxes because of the absence of micropores in the structure, were also thermally stable. Incorporation of orthosilicate into the obtained silica nanoboxes, in accordance with the recently developed technique for pore size engineering in zeolites, led to materials with smaller pore openings but having almost the same textural properties. Solid superacidic materials were prepared by incorporating a liquid superacid (triflic acid or trifluoromethanesulfonic acid) into the silica nanoboxes using the wet impregnation technique. The maximum triflic acid loading which did not significantly affect the mesoporous framework of the materials was 24 wt%. As a reference, the maximum loading of less acidic sulfuric acid was slightly lower. All this showed the high chemical stability of the silica nanoboxes for supporting very acidic species. Temperature-programmed desorption using a combined DTA/TGA system allowed the identification of the bound phases and some liquid phase of the loaded triflic acid.     

沉淀法白炭黑化学指标与胶料物理性能的关系

分析了沉淀法白炭黑BET，CTAB，Ssears比表面，DBP吸油值，平均粒径与粒径分布对胶料物理性能的影响。得出结论：满足轮胎综合力学性能的沉淀法白炭黑应为低BET比表面积，低BET与CTAB比，高BET与Ssears比，适中的DBP吸油值，中值粒径小且易崩解的产品。     

Mode of oleic acid adsorption on rice hull ash cristobalite

Fourier transform infrared spectroscopy was used to investigate the adsorption of oleic acid (OA) onto dry rice hull ash (RHA) silica. Adsorption partially occurred by surface hydrogen bonding of the carboxylic acid. There was also formation of carboxylate ions by reaction of OA with residual potassium oxide. These ions were strongly bound by the ash. Isopropanol inhibited OA adsorption by H-bonding and encouraged desorption of H-bonded OA, but without itself being significantly bound. RHA with 40% moisture also adsorbed a small amount of OA by H-bonding and reacted with OA to form and adsorb carboxylate ions.     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

Cesium salt of a heteropolyacid in nanotubular channels and on the external surface of SBA-15 crystals: preparation and performance as acidic catalysts

The Cs-salt of heteropolyacid with stoichiometry Cs_2.5H_0.5PW₁₂O₄₀ (CsHPW) was deposited selectively at the external surface of the SBA-15 silica microcrystals, inside its mesoporous channels and simultaneously at both location modes. The structure, texture and performance of these CsHPW/SBA-15 composites were compared with that of a reference bulk salt of the same composition. Location of CsHPW salt on the external surface of SBA-15 microcrystals leads to disintegration of its agglomerates increasing acidity of the catalytic phase. A novel preparation strategy consisting of grafting the basic Cs-species at the internal pores surface of SBA-15 stabilized the CsHPW phase inside the channels in form of 5–8 nm nanocrystals at 30–70 wt.% loadings. The catalytic tests demonstrated that insertion of the CsHPW catalytic phase inside the nanotubular channels of SBA-15 in combination with location of an additional amount of this phase at the external surface of SBA-15 microcrystals allows to increase the specific activity of this phase in MTBE synthesis, propionylation of anisole and alkylation of catechol with t-butanol by a factor of 1.5–3. This level of specific activity in combination with high total loading of catalytic phase >60 wt.% permit to get composite catalytic materials with catalytic activity higher by a factor of 1.2–1.5 with respect to the bulk CsHPW catalyst and stabilizing the catalytic phase against colloidization in polar media.     

Characterization and Sintering Behavior of Alkoxide-Derived Aluminosilicate Powders

Submicrometer SiO₂-Al₂O₃ powders with compositions of 46.5 to 76.6 wt% Al₂O₃ were prepared by hydrolysis of mixed alkoxides. Phase change, mullite composition, and particle size of powders with heating were analyzed by DTA, XRD, IR, BET, and TEM. As-produced amorphous powders partially transformed to mullite and Al-Si spinel at around 980°C. The compositions of mullite produced at 1400° and 1550°C were richer in Al₂O₃ than the compositions of stable mullite solid solutions predicted from the phase diagram of the SiO₂-Al₂O₃ system. Particle size decreased with increasing Al₂O₃ content. The sintered densities depended upon the amount of SiO₂-rich glassy phase formed during sintering and the green density expressed as a function of particle size.     

Effect of filler network on dynamic viscoelastic properties of uncured polymethylvinylsiloxanes filled with silica and carbon black

Dynamic properties of polymethylvinylsiloxane (PMVS) filled with filler‐blends composed of carbon black (CB) and silica (SiO₂) were investigated using an advanced rheometric expansion system. A variety of weight fraction of CB to SiO₂ were 0/100, 10/90, 30/70, 50/50, 70/30, 90/10, and 100/0, and a bifunctional organsilane, bis(3‐triethoxysilylpropyl)tetrasurfane, was used to facilitate the filler dispersion. The results reveal that the incorporation of CB/SiO₂ filler‐blends into PMVS result in a reduced Payne effect. This effect reaches a minimum when the ratio of CB/SiO₂ approaches 1, and then it began to rebound with the ratio increase. Meanwhile, a characteristic Newtonian viscosity plateau appearing in low frequencies also significantly decreases, depending on the amount of CB or SiO₂ added. On the basis of a simplified Fowke model, we ascribe this phenomenon to the deteriorated filler network, which is predominantly induced by the totally different surface activity between CB and SiO₂. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3477–3482, 2006     

Silica to Silicon: Key Carbothermic Reactions and Kinetics

The primary carbothermic reactions for the reduction of silica to produce silicon were defined and the reaction kinetics were determined. Most possible reactions between silicon oxide and carbon or carbon compounds were studied by a series of thermogravimetric analyses at temperatures up to 2000°C. Four key sequential reactions occur with SiC and SiO as intermediate reactants; two reactions involve SiO₂ and two involve SiO. Reaction rate versus temperature, activation energy, and preexponential factors were determined for each of six reactions involving SiO₂ or SiO. These kinetic studies show that SiO, when combined with either carbon or Sic, reacts in the gaseous state, and the sublimation of SiO is not the rate-limiting reaction for forming silicon.     

掺氟石英玻璃的研究

利用溶胶-凝胶法,以氟化铵(NH_4F)作掺氟源,使氟离子参与水解和聚合反应,经过热处理制成掺氟石英玻璃。在烧结时通入氟里昂(CCl_2F_2)进一步提高玻璃中氟重量含量直至2.50%。研究得出石英玻璃中氟含量与折射率、密度呈线性关系。氟有利于凝胶玻璃成块。用Raman和红外光谱研究掺氟石英玻璃结构,提出了氟进入玻璃网络的结构模型,并认为氟在玻璃中的存在状态为[SiO_3F]。