Relaxation time and conductivity of comb‐like gel polymer electrolytes

Using the copolymer of acrylonitrile (AN), methyl methacrylate (MMA), and poly(ethylene glycol) methyl ether methacrylate as a backbone and poly(ethylene glycol) methyl ether (PEGME) with 1100 molecular weight as side chains, comb‐like gel polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the gel copolymer electrolytes possess two glass transitions: α‐transition and β‐transition. Based on the time–temperature equivalence principle, a master curve was constructed by selecting T_α as reference temperature. By reference to T₀ = 50°C, the relation between log τ_c and c was found to be linear. The master curves are displaced progressively to higher frequencies as the content of plasticizer is increased. The relation between log τ_p and the content of plasticizer is also linear. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 576–584, 2007     

蒸发工段电解液预热工艺改造总结

针对蒸发工段电解液预热效果不理想，从工艺、设备两方面入手，对电解液预热工艺进行了改造，并对经济效益进行了分析。     

Ameliorating effect of silica addition in the anode-catalyst layer of the membrane electrode assemblies for polymer electrolyte fuel cells

Incorporation of silica particles through a sol-gel process into the anode-catalyst layer with a sol-gel modified Nafion-silica composite membrane renders easy retention of back-diffused water from the cathode to anode through the composite membrane electrolyte, increases the catalyst-layer wettability and improves the performance of the Polymer Electrolyte Fuel Cell (PEFC) while operating under relative humidity (RH) values ranging between 18% and 100% with gaseous hydrogen and oxygen reactants at atmospheric pressure. A peak power density of 300 mW cm⁻² is achieved at a load current-density value of 1200 mA cm⁻² for the PEFC employing a sol-gel modified Nafion-silica composite membrane and operating at 18% RH. Under similar operating conditions, the PEFC with a Membrane Electrode Assembly (MEA) comprising Nafion-silica composite membrane with silica in the anode-catalyst layer delivers a peak power density of 375 mW cm⁻². By comparison, the PEFC employing commercial Nafion membrane fails to deliver satisfactory performance at 18% RH due to the limited availability of water at its anode, acerbated electro-osmotic drag of water from anode to cathode and insufficient water back diffusion from cathode to anode causing the MEA to dehydrate.     

Prediction of carbon dioxide gas hydrate formation conditions in aqueous electrolyte solutions

A methodology for predicting the incipient equilibrium conditions for carbon dioxide gas hydrates in the presence of electrolytes such as NaCl, KCl and CaCl₂ is presented. The method utilizes the statistical thermodynamics model of van der Waals and Platteeuw (1959) to describe the solid hydrate phase. Three different models were examined for the representation of the liquid phase: Chen and Evans (1986), Zuo and Guo (1991), and Aasberg-Petersen et al. (1991). It was found that the model of Zuo and Guo (1991) gave the best results for predicting incipient CO₂ gas hydrate conditions in aqueous single salt solutions. The model was then extended for prediction of CO₂ gas hydrates in mixed salts solutions. The predictions agree very well with experimental data.     

Proton conducting acid-base mixed materials under water-free condition

In recent years, a lot of attentions have been paid for a development of water-free polymer electrolyte membranes fuel cells (PEMFC) at intermediate temperatures (above 100 °C) because of many technological advantages of higher temperature operation. However, the proton conductivity of conventional polymer membranes under water-free condition is usually very low and the polymeric membranes are not stable at higher temperatures. So, the development of non-hydrous proton conducting membrane under water-free condition has been a state of the art issue in the advanced PEMFC technology. In this study, non-hydrous protonic conducting material was prepared by the mixing of acidic surfactant of mono-dodecylphosphate (MDP) and organic base of benzimidazole (BnIm). The proton conductivity and thermal stability of MDP-BnIm mixed material increased with the mixing ratio of BnIm. Maximum proton conductivity of MDP-BnIm mixed material (BnIm mixing ratio of 200 wt.%. vs. MDP) was found to be 1×10⁻³ S cm⁻¹ at 150 °C under water-free condition.     

Solid polymer electrolytes. XI. Preparation,characterization and ionic conductivity of new plasticized polymer electrolytes based on chemical‐covalent polyether–siloxane hybrids

A new hybrid polymer electrolyte system based on chemical‐covalent polyether and siloxane phases is designed and prepared via the sol–gel approach and epoxide crosslinking. FT‐IR, ¹³C solid‐state NMR, and thermal analysis (differential scanning calorimetry (DSC) and TGA) are used to characterize the structure of these hybrids. These hybrid films are immersed into the liquid electrolyte (1M LiClO₄/propylene carbonate) to form plasticized polymer electrolytes. The effects of hybrid composition, liquid electrolyte content, and temperature on the ionic conductivity of hybrid electrolytes are investigated and discussed. DSC traces demonstrate the presence of two second‐order transitions for all the samples and show a significant change in the thermal events with the amount of absorbed LiClO₄/PC content. TGA results indicate these hybrid networks with excellent thermal stability. The EDS‐0.5 sample with a 75 wt % liquid electrolyte exhibits the ionic conductivity of 5.3 × 10^?3 S cm^?1 at 95°C and 1.4 × 10^?3 S cm^?1 at 15°C, in which the film shows homogenous and good mechanical strength as well as good chemical stability. In the plot of ionic conductivity and composition for these hybrids containing 45 wt % liquid electrolyte, the conductivity shows a maximum value corresponding to the sample with the weight ratio of GPTMS/PEGDE of 0.1. These obtained results are correlated and used to interpret the ion conduction behavior within the hybrid networks. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1000–1007, 2006     

Polymer electrolytes from PEO and novel quaternary ammonium iodides for dye-sensitized solar cells

Polymer electrolytes were prepared by blending high molecular weight poly(ethylene oxide) (PEO) and a series of novel quaternary ammonium iodides, the polysiloxanes with oligo(oxyethylene) side chains and quaternary ammonium groups. X-ray diffraction (XRD) measurements ensured relatively low crystallinity when the quaternary ammonium iodides were incorporated into the PEO host. The ionic conductivity of these complexes was improved with the addition of plasticizers. The improvement in the ionic conductivity was determined by the polarity, viscosity and amounts of plasticizers. A plasticized electrolyte containing the novel quaternary ammonium iodide was successfully used in fabricating a quasi-solid-state dye-sensitized solar cell for the first time. The fill factor and energy conversion efficiency of the cell were calculated to be 0.68 and 1.39%, respectively.     

Gel polymer electrolyte based on poly(acrylonitrile-co-styrene) and a novel organic iodide salt for quasi-solid state dye-sensitized solar cell

A gel polymer electrolyte based on poly(acrylonitrile-co-styrene) as polymer matrix and N-methyl pyridine iodide salt as I⁻ source was prepared. Controlling the concentration of polymer matrix of poly(acrylonitrile-co-styrene) at 17.5 wt.%, mixing the binary organic solvents mixture ethylene carbonate and propylene carbonate with 6:4 (w/w), and the concentration of N-methyl pyridine iodide and iodine with 0.5 and 0.05 M, respectively, the gel polymer electrolyte attains the maximum ionic conductivity (at 30 °C) of 4.63 mS cm⁻¹. Based on the gel polymer electrolyte, a quasi-solid state dye-sensitized solar cell was fabricated and its overall energy conversion efficiency of light-to-electricity of 3.10% was achieved under irradiation of 100 mW cm⁻².     

AMPS对PEO/PMMA固态聚合物电解质电导率的影响

针对固态聚合物电解质室温电导率较低的问题,采用刮膜法制备了PEO/PMMA/LiClO_4/AM PS共混聚合物电解质,考察了2-丙烯酰胺-2-甲基丙磺酸(AM PS)的端基磺酸基团对电解质性能的影响.结果表明,添加AMPS后,红外图谱中出现了由C—O的拉伸振动和SO_3~(2-)的络合作用所引起的尖峰.PMMA与PEO共混后,大大降低了PEO的结晶度,且添加AMPS后,电解质形成了完全均相体系.AMPS的添加使得电解质的电导率明显提升了两个数量级.当AMPS的质量分数为1.3%时,电解质的室温电导率达到最大值.添加同样含有端基磺酸基团的液晶离聚物(LCI)后,电解质的电导率无明显提升,因而可以选择磺酸基团质量比更高的AMPS作为添加剂.     

Electrolyte composition and removal mechanism of Cu electrochemical mechanical polishing

The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization （ECMP） at different pH values including 5-methyl-1H-benzotriazole （TTA）, hydroxyethylidenediphosphoric acid （HEDP）, and tribasic ammonium citrate （TAC） were investigated by electrochemical techniques, X-ray photoelectron spectrometer （XPS） analysis, nano-scratch tests, AFM measurements, and polishing of Cu-coated blanket wafers. The experimental results show that the planarization efficiency and the surface quality after ECMP obtained in alkali-based solutions are superior to that in acidic-based solutions, especially at pH=8. The optimal electrolyte compositions （mass fraction） are 6% HEDP, 0.3% TTA and 3% TAC at pH=8. The main factor affecting the thickness of the oxide layer formed during ECMP process is the applied potential. The soft layer formation is a major mechanism for electrochemical enhanced mechanical abrasion. The surface topography evolution before and after electrochemical polishing （ECP） illustrates the mechanism of mechanical abrasion accelerating electrochemical dissolution, that is, the residual stress caused by the mechanical wear enhances the electrochemical dissolution rate. This understanding is beneficial for optimization of ECMP processes.