In situ synchrotron X-ray studies on copper-nickel 5 V Mn oxide spinel cathodes for Li-ion batteries

Partial substitution of Mn in lithium manganese oxide spinel materials by Cu and Ni greatly affects the electrochemistry and the cycle life characteristics of the cathode. Substitution with either metal or a combination of both metals in the spinel lattice structure reduces the 3.9-4.2 V potential plateaus associated with the conversion of Mn³⁺ to Mn⁴⁺. Higher potential plateau associated with oxidation of the substituted transition elements is also observed. These substituents also significantly alter the onset of Jahn-Teller distortions in the 3 V potential plateau. Synchrotron based in situ X-ray absorption (XAS) was used to determine the exact nature of the oxidation state changes in order to explain the overall observed capacities at different potential plateaus. The studies on LiCu_0.5Mn_1.5O₄ show single phase behavior in the 4-5 V potential region with a good cycle life. Lower cycle life characteristic observed in cycling LiNi_0.5Mn_1.5O₄ and LiNi_0.25Cu_0.25Mn_1.5O₄ versus Li metal are ascribed to coexistence of several phases in this potential region. However, LiCu_0.5Mn_1.5O₄ shows onset of Jahn-Teller distortions in the 3 V potential plateau, in contrast to LiNi_0.5Mn_1.5O₄ and LiNi_0.25Cu_0.25Mn_1.5O₄ cathode materials.     

阴离子表面活性剂与阳离子表面活性剂的相互作用(Ⅲ)——高浓度区溶液性质

综述了阴/阳离子表面活性剂混合溶液在浓度比较高时出现的双水相和囊泡现象,并对这种双水相形成条件和囊泡的稳定性进行了比较详细的讨论。阴/阳离子表面活性剂混合溶液中的双水相现象只能在两个非常狭窄的区域形成,可能由不同浓度的胶束溶液、胶束溶液与液晶相或囊泡等组成。在一定的条件下,比较稳定的囊泡可以自发或经过超声处理形成。     

电致孔经皮给药：表面活性剂对孔道存在时间和药物传输的影响

Electroporation creates aqueous pathways by short high-voltage pulses resulting in a transient perme- abilization of stratum corneum and an increase in the transdermal delivery rate.However the aqueous pathways will reseal after pulsing,which leads to the rapid drop of transdermal flux.In the present study,the surfactants were added to the donor solution to hinder the shrinkage and resealing of the electropore,and to prolong the lifetime of the aqueous pathways with the consideration that the surfactants could reduce the surface energy of the electropore. These effects of surfactants were demonstrated by the dynamic electrical resistance of the skin and the fluorescent imaging of the local transport regions.Piroxicam（PIX）was transported percutaneously in the presence of surfactants in vitro.Owing to the longer lifetime of aqueous pathways,together with the promotion of PIX availability at the barrier exterior and the improvement in the partition of PIX into the aqueous pathways,the presence of surfactants led to a remarkable increase in the transdermal delivery rate during electroporation and a significant growth of the accumulative transdermal amount of PIX.     

Electrochemical properties of carbon-coated CaWO4 versus Li

Carbon-coated CaWO₄ nano-crystalline phases have been synthesized by ambient temperature solution precipitation method, characterized by X-ray diffraction, SEM and thermogravimetry and their electrochemical properties were studied versus Li metal. Galvanostatic cycling at a current of 60 mA/g in the voltage range 0.005-3.0 V on the 5 wt.% C-coated CaWO₄ gave a reversible capacity of 230 ± 5 mAh/g corresponding to 2.5 mol of Li, which is almost stable from 20 to 50 cycles. Under the same conditions, the 10 wt.% C-coated CaWO₄ showed a capacity of 355 ± 5 mAh/g (3.8 mol of Li) during the initial cycles, but the capacity degraded at a rate of 1.6 mAh/g per cycle in the range 5-100 cycles. A good operating voltage range was found to be 0.005-3.0 V with average discharge and charge potentials being 0.6 and 1.3 V, respectively. Coulombic efficiency in all cases was 96-98%. Cyclic voltammograms compliment the galvanostatic results. Impedance spectral data on the 10 wt.% C-coated CaWO₄ at different voltages during the first and 20th discharge-charge cycle have been interpreted in terms of the variations in the bulk and charge-transfer resistances of the composite electrode. A reaction mechanism involving the formation/decomposition of the oxide bronze, ‘Li_xWO_y’ has been proposed to explain the electrochemical cycling.     

连续浊点法快速测定含盐水溶液的固液平衡

建立一套连续浊点法快速测定含盐水溶液固液平衡的实验方法和装置，不同温度下二元和三元体系的实验值与文献值比较，表明该方法所测数据是可靠的。在此基础上测定了２９８．１５～３２３．１５Ｋ下三元体系ＮＨ４ＣｌＫＣｌＨ２Ｏ的固液平衡数据，并同作者开发的电解质溶液相平衡软件包ＰＨＥＥＳ的预测值作了比较，得到了较为满意的结果     

反式-1,4-聚异戊二烯的氯化改性

采用水相悬浮法，在常压下对反式-1，4-聚异戊二烯（TPI）进行氯化改性。研究了温度、时间、粒径等对氯化反式-1，4-聚异戊二烯（CTPI）氯含量的影响。得到适宜的反应条件是：采用两阶段升温的方法，控制一定的通氯量，第一阶段，反应温度为35℃，反应时间为2～3h；第二阶段．反应温度为50～55℃，反应时间为1～6h，可获得氯质量分数在50％以内的CTPI，产品为可溶解的白色疏松颗粒。     

Electroplating synthesis and electrochemical properties of macroporous Sn-Cu alloy electrode for lithium-ion batteries

Macroporous material of Sn-Cu alloy of different pore sizes designated as anode in lithium-ion batteries were fabricated through colloidal crystal template method. The structure and electrochemical properties of the macroporous Sn-Cu alloy electrodes were examined by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and galvanostatic cycling. The results demonstrated that the electrodes of macroporous Sn-Cu alloy with pore size respectively of 180 and 500 nm can deliver reversible capacity of 350 and 270 mAh g⁻¹ up to 70th cycles of charge/discharge. The cycle performance of the macroporous Sn-Cu alloy of 180 nm in pore size is better than that of the macroporous Sn-Cu alloy with 500-nm-diameter pores. It has revealed that the porous structure of the macroporous Sn-Cu alloy material is of importance to strengthen mechanically the electrode and to reduce significantly the effect of volume expansion during cycling.     

Synthesis and electrochemical characterization of a new Se-doped spinel material for lithium secondary batteries

A new Se-doped spinel material, LiAl_0.18Se_0.02Mn_1.8O₄ powder with a phase-pure polycrystalline was synthesized by a sol–gel method. The material in the 3 V region (2.4 3.5 V) and both the 3 and 4 V region (2.4 4.4 V) initially deliver a discharge capacity of 81 and 178 mA h g^–1 which increase with cycling to reach 110 and 204 after 50 cycles, respectively. The material shows excellent cycleability in the 4 V region (3.0 4.4 V) with almost no capacity loss. The structural integrity of the Se-doped spinel was characterized by charge–discharge cycling tests and X-;ray diffraction.     

Binder effect on cycling performance of silicon/carbon composite anodes for lithium ion batteries

The cycling performance of a silicon/carbon composite anode has been significantly enhanced by using acrylic adhesive and modified acrylic adhesive as binder to fabricate the electrodes for lithium ion batteries. The capacity retentions of Si/C composite electrodes bound by acrylic adhesive and modified acrylic adhesive are 79% and 90% after 50 cycles, respectively. These two binders are electrochemically stable in the organic electrolyte in the working window. They also show larger adhesion strength between the coating and the Cu current collector as well as smaller solvent absorption in the electrolyte solvent than polyvinylidene fluoride (PVDF). Furthermore, sodium carboxyl methyl cellulose (CMC) plays an important role on improving the properties of acrylic adhesive, which increases the adhesive strength of acrylic adhesive and improves the activation of the electrodes.     

Development of high‐definition aqueous polyvinylpyrrolidone photoresists for cathode ray tubes

Aqueous photoresists that are capable of higher resolutions than are currently employed by the cathode ray tube (CRT) industry were developed by combining photoactivators, which activate at shorter UV wavelengths with polyvinylpyrrolidone (PVP). Two photoactivators were synthesized: 4,4′‐diazido‐2,2′‐biphenyl disodium disulfonate (DABP), which has a maximum absorbance at 264 nm, and 4,4′‐diazido‐2,2′‐biphenylethane disodium disulfonate (DABPE), which has a maximum absorbance at 258 nm. The PVP/DABP and PVP/DABPE photoresists successfully imaged a pattern with resolution as small as 4.4 μm with photoactivator concentrations greater than 20% of the PVP concentration. Addition of silane and emulgen greatly improved the performance of the photoresists with more uniform coatings of thicknesses of up to 1.4 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1637–1644, 2006