Spatial distribution of reaction products in direct ethanol fuel cell

The electro-catalytic oxidation of ethanol in a direct-type polymer electrolyte membrane fuel cell is known to be more complex than that of methanol. We used both solution and solid-state nuclear magnetic resonance (NMR) methods for the first time to successfully identify and quantify the reaction intermediates and the fuel itself which were distributed differently over fuel pathways and the polymer membrane (PEM) in the direct ethanol fuel cell (DEFC). The diverse chemical species present in the exhaust were identified by high-resolution solution NMR, while the nature and amounts of the species in the PEM of the DEFC were analyzed by solid-state NMR. The relative amount of reaction intermediates of ethanol detected in the PEM was an order of magnitude higher than that observed in the exhaust, which might be of critical importance in understanding and developing DEFC systems.     

羟基磷灰石在磺化聚醚苯并咪唑薄膜表面的生长

以聚[2,2′-(对氧基联苯)-5,5′-苯并咪唑](OPBI)及其磺化产物磺化聚[2,2′-(对氧基联苯)-5,5′-苯并咪唑](SOPBI)薄膜作为基体, 采用交替沉积和模拟体液(SBF)浸泡相结合的方法快速在薄膜表面沉积羟基磷灰石层. 采用选区电子衍射(SAED)和衰减全反射傅里叶变换红外光谱(ATR-FTIR)对羟基磷灰石(HA)的晶体结构进行了分析. 用扫描电子显微镜(SEM)对整个沉积过程中羟基磷灰石的形态变化进行了跟踪. 实验结果表明, SOPBI薄膜诱导HA沉积的速率明显快于OPBI薄膜. SOPBI的磺酸基团不但提供了固定Ca²⁺的负电表面, 而且还有助于咪唑基团对Ca²⁺的固定. 而缺失磺酸基团的OPBI在不同pH值的交替沉积溶液中的电离形式阻碍了咪唑基团对Ca²⁺和HPO₄^2-的作用, 且未能在SBF浸泡过程中得到改善.     

Non-Fluorinated Polymer Composite Proton Exchange Membranes for Fuel Cell Applications – A Review

The critical component of a proton exchange membrane fuel cell (PEMFC) system is the proton exchange membrane (PEM). Perfluorosulfonic acid membranes such as Nafion are currently used for PEMFCs in industry, despite suffering from reduced proton conductivity due to dehydration at higher temperatures. However, operating at temperatures below 100 °C leads to cathode flooding, catalyst poisoning by CO, and complex system design with higher cost. Research has concentrated on the membrane material and on preparation methods to achieve high proton conductivity, thermal, mechanical and chemical stability, low fuel crossover and lower cost at high temperatures. Non-fluorinated polymers are a promising alternative. However, improving the efficiency at higher temperatures has necessitated modifications and the inclusion of inorganic materials in a polymer matrix to form a composite membrane can be an approach to reach the target performance, while still reducing costs. This review focuses on recent research in composite PEMs based on non-fluorinated polymers. Various inorganic fillers incorporated in the PEM structure are reviewed in terms of their properties and the effect on PEM fuel cell performance. The most reliable polymers and fillers with potential for high temperature proton exchange membranes (HTPEMs) are also discussed.     

Highly branched polyethylene used as sorbents for oil-spill cleanup and separation

Highly branched polyethylene (HBPE) was developed into practical application as highly efficient sorbent material for oil-spill cleanup and oil/water separation. To obtain large-scale production of HBPE, a thermal stable Ni(II)-α-diimine catalyst for ethylene polymerization in our previous work has been employed to prepare the polyolefin material in a 10-liter polymerization reactor with a high activity (>10⁶ g_PE/mol_[Ni] h). The structure, molecular weight and distribution, thermal and mechanical properties were systematically characterized by NMR, ATR-FTIR, GPC, DSC, DMA, and TGA, respectively. Through simple but feasible cross-linking process, the HBPE-based oil-absorption materials with contact angles up to 111.5° were directly applied into absorption test using various oil and pure hydrocarbons. Reusability and recovery of the absorption materials and oil or solvents were probed by drying or using the distillation method. Oil/water separation was made to determine the hydrophobic and oleophilic nature of this material. Flory-Rehner polymer swelling theory is employed to study the structure–property relationship via determining the network structure including cross-linking density ρ_c and average molecular weight M_c between two cross-links. The mixture of sorbent material after absorbing oil was regarded as crude oil component to simulate oil refinery process by thermogravimetric analysis, providing an alternative approach for oil-collection.     

Prediction of the energy of mechanical failure for elastomers filled with solid particles

Prediction (solution of direct problem) of the mechanical characteristics, including the energy of failure under extension, was considered for 3D-cross-linked elastomeric binders, filled with solid particles of polyfractional composition, in relation to the basic structural parameters of the composite material. It was shown that the use of lightly cross-linked highly silica-filled elastomeric binders with the optimal three-fraction composition represents a promising option for development of a frost-resistant waterproofing rolled material intended as a coating for road asphalt.     

旋转磁场对质子交换膜燃料电池工作性能的影响

外加磁场可以提高PEM（Proton Exchange Membrane,质子交换膜）燃料电池的工作性能,本文通过在PEM燃料电池表面分别附加正方形梯度磁场、同极性组合圆柱形磁场以及异极性组合圆柱形磁场,分析旋转磁场、静态磁场以及未加磁场3种磁场环境下燃料电池的输出功率密度变化. 研究发现,外部磁场的分布规律不同,磁场的变动对燃料电池的影响也不相同,尤其是异极性组合磁场,旋转的磁场使燃料电池的最大功率密度提高了21.27%,明显高于加载静态磁场时提高的11.70%. 旋转磁场产生的效果与磁场旋转速度有关,提高转速有利于增强磁场对燃料电池工作性能的影响,当转速为30 r·min^-1时影响最大,随着转速进一步提高,影响效果逐渐变差。     

Direct PEM fuel cell using "organic chemical hydrides" with zero-CO2 emission and low-crossover

A series of "organic chemical hydrides" such as cyclohexane, methylcyclohexane, cyclohexene, 2-propanol, and cyclohexanol were applied to the direct PEM fuel cell. High performances of the PEM fuel cell were achieved by using cyclohexane (OCV = 920 mV, PD(max) = 15 mW cm(-2)) and 2-propanol (OCV = 790 mV, PD(max) = 78 mW cm(-2)) as fuels without CO(2) emissions. The rates of fuel crossover for cyclohexane, 2-propanol, and methanol were estimated, and the rates of fuel permeation of cyclohexane and 2-propanol were lower than that of methanol. Water electrolysis and electro-reductive hydrogenation of acetone mediated by PEM were carried out and formation of 2-propanol in cathode side was observed. This system is the first example of a "rechargeable" direct fuel cell.     

Influence of polyfurfuryl alcohol (PFA) loading on the properties of Nafion composite membranes

Composite membranes based on Nafion (N115) loaded with furfuryl alcohol (FA) were prepared by in situ acid-catalyzed polymerization technique, with the aim to improve the ionic conductivity of Nafion membranes. The functionalization, thermal stability, electrical properties and mechanical strength of N115-PFA composites was analyzed by means of Fourier transform infrared (FT-IR) attenuated total reflection (ATR) spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), electrical impedance spectroscopy, dynamic vapor sorption (DVS) and dynamic mechanical analyser (DMA). The FA loading in the resultant composites had a positive correlation with the water uptake (W_u), water vapor uptake (W_vu), ionic conductivity and thermo-mechanical stability. At low polyfurfuryl alcohol (PFA) loading, these membranes displayed higher W_u and improved ionic and electrical properties. Further, the thermo-mechanical stability also gradually increased with the PFA loading. All the composites showed a well-defined glass transition temperature in DMA, which shifted to higher temperature with repeated PFA loading. Overall, the results indicate that the developed composite membrane are promising for low temperature polymer electrolyte membrane (PEM) fuel cells.     

侧链磺化聚芳醚质子交换膜的研究进展

燃料电池是以氢气、甲醇等作为燃料的一种新型能量转化装置,其中质子交换膜燃料电池（Proton Exchange Membrane Fuel Cell, PEMFC）凭借其能量功率高、启动速度快和使用寿命长等优点已经在移动电源、潜艇和电动汽车等领域得到了广泛应用。质子交换膜（Proton Exchange Membrane, PEM）对PEMFC的性能影响最大,高效的PEMFC需要PEM具有高的质子电导率、良好的热稳定性和机械性能、低燃料渗透率以及优异的物理化学稳定性等。目前市面上多数使用的均是具有优异质子电导率的Nafion系列膜,但其存在制备困难、成本昂贵、质子电导率严重依赖湿度等缺点,在一定程度上限制了其发展。为了让PEM有更多的选择,科学家一直专注于使用新材料替代Nafion膜。近年来,科学家们模拟Nafion结构,通过合成各种侧链含磺酸基团的聚芳醚结构,使得亲水基团磺酸基和疏水基团之间形成微相分离结构,从而获得了一系列具有优异综合性能的PEM。本文将重点对侧链烷基磺化型、侧链磺化嵌段型、侧链局部密集磺化型、侧链磺化交联型和侧链磺化复合型这几种常见策略的合成方法及性能进行了综述,最后展望了侧链磺化聚芳醚在PEM领域的优势及发展前景。     

Zero-CO2 emission and low-crossover 'rechargeable' PEM fuel cells using cyclohexane as an organic hydrogen reservoir

High performance (open circuit voltage = 920 mV, maximum power density = 14-15 mW cm(-2)) of the PEM fuel cell was achieved by using cyclohexane as a fuel with zero-CO2 emission and lower-crossover through PEM than with a methanol-based fuel cell.     

质子交换膜燃料电池及电池组模型分析

本文对现有质子交换膜燃料电池以及电池组模型进行比较分析,认为数学模型的建立,可以增加对燃料电池及电池组内部的传递现象和反应机理的认识,同时可以预测电池以及电池组的性能,并且对优化电池结构参数具有指导意义.模型分析包括了现阶段质子交换膜燃料电池单电池模型和电池组模型的基本类别,它们是单电池CFD数值模拟模型、单电池以及电池组性能模拟模型、燃料电池组气体分配模型、系统模型和非稳态模型.比较了几种模型的建模方式及不同模型的应用范围和各自的优缺点.     

Polymers for electrochemical devices

Polymeric materials are already present in electrochemical storage devices such as batteries and PEM fuel cells. The polymer is an electro-active material in lithium polymer batteries. Several network based polymer electrolytes provide thermal, mechanical and redox stabilities, while insuring a high conductivity level. Linear unsaturated polyether precursors may be obtained either by step-growth polymerization from oligomeric polyethers, or by ring-opening polymerization from oxirane mixtures. Some prototype performances, performed on a 10 Wh lithium polymer cell, are presented and discussed.     

Durability investigation of graphene-supported Pt nanocatalysts for PEM fuel cells

We report graphene nanosheets as a durable alternative support material for Pt nanoparticle catalysts for oxygen reduction in proton exchange membrane (PEM) fuel cells and compared them to XC-72. The materials were characterized by X-ray diffraction and transmission electron microscopy. Electrochemical surface oxidation of XC-72 and graphene, and of Pt/XC-72 and Pt/graphene has been compared following treatments for up to 120 h. The electrochemical performance of the specimens was evaluated by cyclic voltammetry and linear sweep voltammetry at different surface oxidation time intervals. Electrochemical measurements indicate that the graphene exihibits greatly enhanced electrochemical durability. It is suggested that graphene nanosheet is a promising, low-cost, and durable electrocatalyst support for oxygen reduction in the PEM fuel cell.     

Development of a lateral PEM fuel cell

A novel lateral PEM fuel cell was developed. The anodes and cathodes are situated nearby each other on a polymer electrolyte membrane. The transport of the protons takes place in a lateral way in the membrane. All manufacturing steps of the lateral PEM fuel cell were designed to meet the requirements of mass production. The base plate being the central part was made by means of polymer micro injection moulding.     

Photopatterned nanoporosity in polyelectrolyte multilayer films

We report on spatial control of nanoporosity in polyelectrolyte multilayer (PEM) films using photopatterning and its effects on film optical and adsorption properties. Multilayers assembled from poly(acrylic acid-ran-vinylbenzyl acrylate) (PAArVBA), a photo-cross-linking polymer, and poly(allylamine hydrochloric acid) (PAH) were patterned using ultraviolet light followed by immersion in low pH and then neutral pH solutions to induce nanoporosity in unexposed regions. Model charged small molecules rhodamine B, fluorescein, and propidium iodide and the model protein albumin exhibit increased adsorption to nanoporous regions of patterned PEM films as shown by fluorescence microscopy and radiolabeling experiments. Films assembled with alternating stacks of PAH/poly(sodium-4-styrene sulfonate) (SPS), which do not become nanoporous, and stacks of PAH/PAArVBA were patterned to create nanoporous capillary channels. Interdigitated channels demonstrated simultaneous, separate wicking of dimethyl sulfoxide-solvated fluorescein and rhodamine B. In addition, these heterostack structures exhibited patternable Bragg reflectivity of greater than 25% due to refractive index differences between the nanoporous and nonporous stacks. Finally, the PEM assembly process coupled with photo-cross-linking was used to create films with two separate stacked reflective patterns with a doubling in reflectivity where patterns overlapped. The combined adsorptive and reflective properties of these films hold promise for applications in diagnostic arrays and therapeutics delivery.     

In situ ATR-FTIR and SFM Studies on the Influence of Adsorption time on Deposition and Nanostructure of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers

Summary: The deposition and the nanostructure of polyelectrolyte multilayers (PEM) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAC) was studied in dependence of the adsorption time (t_ADS) of the individual steps. PEM were reproducibly deposited applying up to z = 20 adsorption steps at the fixed pH combination of 10/4 and polyelectrolyte concentration c_PEL = 0.005 M in a flow cell using an automated valve system. in situ ATR-FTIR spectroscopy and SFM were used for quantitative determination of deposited amount and thickness, respectively. A linear relation between PEL band integrals and thickness of thin PEM films was found. Varying t_ADS from 0.5 to 5 min in each of the adsorption steps resulted in a steep rise of the deposited PEM amount. For t_ADS > 5 min the deposition did only marginally increase. Evidence for the release of outermost located PEI upon PAC immersion (even step) and of outermost PAC upon PEI immersion (odd step) was obtained. SFM images on consecutively deposited PEM-6 showed a slight increase in structure size and roughness for increasing t_ADS. These studies help to prepare polyelectrolyte based films with controlled thickness for the interaction with biofluids in the biomedical and food field.     

银在质子交换膜燃料电池空气阴极内促进氧传递研究

利用离子交换及随后的氢还原,将单质银负载在质子交换膜(Nafion)孔道内.TEM、XRD表征载银Nafion膜的结构,电化学极限电流法测定氧在载银Nafion膜内的扩散系数.结果表明,因银晶颗粒大于Nafion孔道直径,致使Nafion孔道有所扩张;氧在载银Nafion膜内的扩散系数是无银Nafion膜的4倍.据此,把银引入质子交换膜燃料电池空气阴极催化剂表面的Nafion薄层,则电池的性能在高电流密度下有明显的提高,显示了银对该电极内氧传递的促进作用.     

复合阳极共烧制备致密La0.7Ca0.3Cr0.97O3-δ连接体薄膜的研究

固体氧化物燃料电池(SOFC)陶瓷连接材料的低成本薄膜化制备是现在公认的技术难题。为了改善传统NiO/YSZ阳极与LaCrO3基连接材料的共烧匹配性能,将化学性质稳定的Y0.7Ca0.3Cr0.9Zn0.1O3-δ(YCCZ)连接材料创造性地引入到NiO/YSZ阳极中,制备NiO/YSZ/YCCZ(6∶4∶2,m/m/m)三相复合阳极,并进行烧结特性、微观结构、电导率、热膨胀系数等系列性能的对比测试,结果表明NiO/YSZ/YCCZ新型复合阳极具有优良的综合性能。以NiO/YSZ/YCCZ为支撑体,采用浆料浸渍法制备湿膜,1 400℃空气条件下共烧,成功制备致密La0.7Ca0.3Cr0.97O3-δ连接体薄膜。     

Preparation and characterization of polymer electrolyte membrane from chloroacetate chitosan/chitosan blended with epoxidized natural rubber

Chitosan-based membranes are among the most effective and efficient PEMs for fuel cells, however their low proton conductivity needs to be improved. In this study, chitosan, chloroacetate chitosan (CCS), chitosan blend with epoxidized natural rubber (ENR), and CCS with ENR blend based membranes were prepared by solution casting, crosslinked with NaOH and H₂SO₄, and investigated for physical, chemical, electrical and ionic properties. The functional groups were identified by ATR-FTIR spectroscopy and the peaks matched improved membrane properties. The surface roughness of the membranes was determined by AFM, and it increased with the amount of ENR. The electrical properties measured with an LCR meter showed that the CCS, CS and CS-B had the highest conductance, conductivity, capacitance and dielectric constant, while the CCS10/ENR8, CS10/ENR8 and CS15/ENR3 showed the highest resistance and resistivity. Furthermore, the CCS gave the lowest dissipation factor, which indicates its suitability for use in a PEM. In addition, the contact angle was relatively high for CS-B, CS and CCS.     

Water management improvement in PEM fuel cells via addition of PDMS or APTES polymers to the catalyst layer

Water management is one of the obstacles in the development and commercialization of proton exchange membrane fuel cells (PEMFCs). Sufficient humidification of the membrane directly affects the PEM fuel cell performance. Therefore, 2 different hydrophobic polymers, polydimethylsiloxane (PDMS) and (3-Aminopropyl) triethoxysilane (APTES), were tested at different percentages (5, 10, and 20 wt.%) in the catalyst layer. The solution was loaded onto the surface of a 25 BC gas diffusion layer (GDL) via the spraying method. The performance of the obtained fuel cells was compared with the performance of the commercial catalyst. Characterizations of each surface, including different amounts of PDMS and APTES, were performed via scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) analyses. Molecular bond characterization was examined via Fourier transform infrared spectroscopy (FTIR) analysis and surface hydrophobicity was measured via contact angle measurements. The performance of the fuel cells was evaluated at the PEM fuel cell test station and the 2 hydrophobic polymers were compared. Surfaces containing APTES were found to be more hydrophobic. Fuel cells with PDMS performed better when compared to those with APTES. Fuel cells with 5wt.% APTES with a current density of 321.31 mA/cm ² and power density of 0.191 W/cm ² , and 10wt.% PDMS with a current density of 344.52 mA/cm ² and power density of 0.205 W/cm ² were the best performing fuel cells at 0.6V.