聚醚砜-聚乙烯吡咯烷酮高温聚合物电解质膜及燃料电池堆性能研究

基于磷酸掺杂聚苯并咪唑膜（PA/PBI）的高温聚合物电解质膜燃料电池具有高的输出功率和优异的稳定性,然而PBI膜昂贵的价格和复杂的制备工艺限制了高温聚合物电解质膜燃料电池的商业化应用。本研究以成本低和制备工艺简单的聚醚砜-聚乙烯吡咯烷酮（PES-PVP）膜的商业化应用为目标,小规模制备了幅宽为40 cm的PES-PVP复合膜,证实了流延法放大制备PES-PVP复合膜的可行性。PES-PVP膜中每个PVP重复单元的吸附量达4.9个磷酸（PA）分子,且在180℃的质子电导率达85 mS·cm^-1。此外,尺寸为165 cm²的PA/PES-PVP高温膜电极在150℃的输出功率达0.19 W·cm^-2@0.6 V,与同尺寸的商业化PA/PBI高温膜电极的输出功率相当,并在近3000 h的寿命测试中展示出良好的稳定性。最后,将PA/PES-PVP高温膜电极（单片有效面积200 cm²）组装高温膜燃料电池短堆,其中基于3片膜电极的短堆展现出良好的电堆启停稳定性;基于20片膜电极电堆的峰值功率达1.15 kW。以上结果表明所制备的PA/PES-PVP是一种性能优良、价格便宜的高温聚合物电解质膜材料,并且基于该膜材料组装的高温聚合物电解质膜电池和电堆性能优异。本研究工作为高温聚合物电解质膜燃料电池关键材料和电堆的国产化提供了研究基础。     

进气流场结构对电气设备用PEMFC电池性能的影响

质子交换膜燃料电池的流场结构对其内部流体的运动（包括流体的传递和反应速度）有直接影响，这个问题也是当前的研究热点。本文主要对不同流场结构下燃料电池的性能进行研究，本文所用燃料电池阴极氧化剂分别采用空气和氧气，通过对不同进气流场结构下电池的性能进行测试得到流场结构对气体的流动速度、电流密度和气体浓度的影响。通过对不同结构的电池进行相关实验得到以下结论：当流场结构不同时，所得电池的性能也各不相同，当所通入的氧气浓度越高，所得燃料电池的活化损失越小，所得电池的性能越好。     

阳极和阴极流场组合对直接甲醇燃料电池性能的影响

采用蛇形、平行和交指流场分别作为阳极和阴极流场,考察了其对直接甲醇燃料电池(DMFC)性能的影响。结果表明,对于阳极流场,蛇形流场因其更易于排除CO₂气泡而性能最好,而平行和交指流场中则出现了CO₂气泡堵塞流道的现象,影响了甲醇的传输,性能较差。对于阴极流场,平行流场下半部分流道出现了"水淹"现象,影响了氧气的传输,性能较差。蛇形和交指流场均能顺利排除水滴,性能比平行流场的好;交指流场能保证氧气的充足供应,高电流密度时比蛇形流场的电池性能好。蛇形流场作为阳极流场以及交指流场作为阴极流场将是电池性能较好的流场组合形式之一。     

基于电-化-热耦合关系NH3-SOFC数值模拟

为探究高温工作状态下的电池内部运行情况，对固体氧化物燃料电池(SOFC)电化学性能及传热传质分布情况进行有效分析，利用COMSOL Multiphysics软件，结合电池内气体扩散、浓物质传递、热量传递和电极中二次电流密度构建多物理场模型，研究了NH₃-SOFC中的传热传质、化学和电化学反应特性。结果表明：燃料为氨气时，提高电池工作温度有利于提高电池输出功率，当1 073.2 K工作温度继续提高时，最大功率和电流密度增长速度降低；NH₃-SOFC与H₂-SOFC输出性能相近。进一步探究了温度和反应物进气摩尔分数对NH₃-SOFC性能影响。发现入口氨气摩尔分数自0.7提升至1时，电池性能得到明显提高；而氧气摩尔分数高于0.2时，其对电池性能影响较小，空气可作为电池阴极气体使用。     

固体氧化物燃料电池氧化钇稳定氧化锆电解质的等离子喷涂制备及性能

金属支撑型固体氧化物燃料电池极具应用前景,但缺少高性价比制备技术。采用高效率、低成本大气等离子喷涂（APS）在金属基体上制备了氧化钇稳定氧化锆（YSZ）电解质,研究加热基体条件下沉积粒子形貌与涂层结构间的联系,并评估电解质的力学性能和电池性能。结果表明：加热后的基体上,YSZ沉积粒子铺展充分,片层内存在微裂纹,导致结构中除未结合区域外还存在垂直裂纹,涂层孔隙率为7.16%,YSZ纳米压痕硬度和弹性模量分别为（13.0±1.0） GPa和（188.5±2.6） GPa。受电解质不致密的影响,APS沉积的YSZ单电池最高开路电压为0.97 V,致密度还需进一步提高,但电池输出性能可观,900℃峰功率密度为850 mW/cm²。随着设备迭代优化或结合后处理工艺,APS有望实现致密YSZ电解质的大规模低成本制备。     

熔融碳酸盐燃料电池堆开发及其性能试验

针对大面积熔融碳酸盐燃料电池及其大功率电堆本体开发过程中关键材料的制备以及匹配特性难题，开发了大面积熔融碳酸盐燃料电池隔膜和电极的制备方法，提出了10 kW级熔融碳酸盐燃料电池堆的组装与测试运行方法。组装并运行了120节、每节电池有效面积为0.2 m²的10 kW级MCFC电堆，恒电压放电测试中，最大输出功率达16.51 kW,电流密度大于95 mA/cm²。通过多次试验研究与分析，获得了一种有效的在线评价MCFC电解质隔膜焙烧效果的方法，使熔融碳酸盐燃料电池本体中隔膜、电极以及熔盐电解质三者形成良好的匹配，对提高MCFC电池堆组装成功率与长周期的运行寿命具有重要指导意义。电池堆本体开发及性能测试方法，将为后续更大功率的熔融碳酸盐燃料电池发电系统的开发提供有效的理论与试验指导，对推动MCFC的商业化示范推广等具有重要的意义。     

高温质子交换膜燃料电池用离子液体聚合物电解质的研究进展

综述了近十几年来高温质子交换膜燃料电池用离子液体聚合物电解质的研究进展及其在高温质子交换膜燃料电池中的应用进展,指出了此类电解质目前存在的亟待解决的两个问题：咪唑类离子液体毒化Pt基催化剂和复合膜中离子液体的长期稳定性。最后对高温质子交换膜燃料电池用离子液体聚合物电解质的发展前景作了展望,即开发与Pt基催化剂相容的离子液体聚合物电解质以及预防复合膜内离子液体的流失,即提高高温质子交换膜燃料电池的性能及长期稳定性,最终提高高温燃料电池的寿命。     

重整甲醇高温聚合物电解质膜燃料电池研究进展与展望

甲醇作为一种安全便捷的液态储氢燃料,具有高含氢量以及高体积能量密度,可经重整为富氢气后与燃料电池系统集成为重整甲醇高温聚合物电解质膜燃料电池,从而高效地将甲醇和氧气的化学能转变为电能。本文针对重整甲醇高温聚合物电解质膜燃料电池的不同类型（外置重整型和内置重整型）,分别对其系统集成的实现与发展进行了总结,并介绍了其现阶段在军用和民用方面的应用情况,同时指出了技术研究与应用存在的瓶颈,并对未来的研究方向进行了展望。未来提升重整甲醇高温聚合物电解质膜燃料电池性能的努力在于开发低温工作的高效甲醇重整催化剂,以及高温稳定运行的聚合物电解质膜和非贵金属材料等燃料电池关键材料。     

复合阳极Ni-Fe/Ce0.9Gd0.1O1.95在阴极支撑单电池的性能及其表征

为了提高固体氧化物燃料电池在中温条件下的电性能,探索了一种双金属阳极的阴极支撑单电池。单电池以La_0.6Sr_0.4CoO₃（LSC）-Ce_0.9Gd_0.1O_1.95（GDC）为阴极支撑体,旋涂了甘氨酸-硝酸盐法制备的La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ（LSGM）电解质及Sm_0.2Ce_0.8O_1.9（SDC）缓冲层,涂覆了由硬模板法和浸渍法结合制备的Ni-Fe/GDC双金属阳极。对制备材料进行了XRD和微观形貌分析,单电池电化学测试在800 ℃和750 ℃下,以氢气为燃料的最大功率密度达0.73 W/cm²和0.64 W/cm²,以甲烷为燃料时达0.41 W/cm²和0.40 W/cm²。测试后的SEM表明,阳极具有多孔的微观结构,金属颗粒均匀包覆蠕虫状GDC,保证了单电池具有较高的发电性能。     

锂-氧气电池用泡桐木衍生三维自支撑Co、N、S共掺杂多孔炭

正极是锂-氧气（Li-O₂）电池的电化学反应场所，其直接决定了电池性能。本研究采用泡桐木为原材料，在NaCl/CoCl₂混合熔融盐介质中，以三聚氰胺和硫脲为氮源和硫源，一步热解炭化制备出Co、N、S共掺杂的三维自支撑多孔炭材料（wd-NSC），并直接用作Li-O₂电池正极。利用X射线衍射、扫描电镜、透射电镜、氮气吸脱附、拉曼光谱、X射线光电子能谱等对所获三维自支撑多孔炭材料的形貌、晶体结构与化学成分进行了表征。研究结果表明，Co、N、S共掺杂的三维自支撑多孔炭材料表现出高比容量（在0.05mA/cm²的电流密度下，放电比容量可达12.83mA·h/cm²）和出色的循环稳定性（在电流密度为0.1mA/cm²和限定容量为0.5mA·h/cm²下，循环寿命可达125次），优异的电池性能可归因于三维分级多孔结构及Co、N、S共掺杂的协同作用。     

Influence of bio-inspired flow channel designs on the performance of a PEM fuel cell

Performance of the proton exchange membrane fuel cell(PEMFC) is appreciably affected by the channel geometry. The branching structure of a plant leaf and human lung is an efficient network to distribute the nutrients in the respective systems. The same nutrient transport system can be mimicked in the flow channel design of a PEMFC, to aid even reactant distribution and better water management. In this work, the effect of bio-inspired flow field designs such as lung and leaf channel design bipolar plates, on the performance of a PEMFC was examined experimentally at various operating conditions. A PEMFC of 49 cm~2 area, with a Nafion 212 membrane with a 40% catalyst loading of 0.4 mg·cm-2 on the anode side and also 0.6 mg·cm~(-2) on the cathode side is assembled by incorporating the bio-inspired channel bipolar plate, and was tested on a programmable fuel-cell test station.The impact of the working parameters like reactants' relative humidity(RH), back pressure and fuel cell temperature on the performance of the fuel cell was examined; the operating pressure remains constant at 0.1 MPa. It was observed that the best performance was attained at a back pressure of 0.3 MPa, 75 °C operating temperature and 100% RH. The three flow channels were also compared at different operating pressures ranging from 0.1 MPa to 0.3 MPa, and the other parameters such as operating temperature, RH and back pressure were set as 75 °C,100% and 0.3 MPa. The experimental outcomes of the PEMFC with bio-inspired channels were compared with the experimental results of a conventional triple serpentine flow field. It was observed that among the different flow channel designs considered, the leaf channel design gives the best output in terms of power density. Further,the experimental results of the leaf channel design were compared with those of the interdigitated leaf channel design. The PEMFC with the interdigitated leaf channel design was found to generate 6.72% more power density than the non-interdigitated leaf channel design. The fuel cell with interdigitated leaf channel design generated5.58% more net power density than the fuel cell with non-interdigitated leaf channel design after considering the parasitic losses.     

直接液流燃料电池的制备、活化及性能

采用热压方法制备阳极半膜电极（AHME）用于直接液流氧化还原燃料电池（DLRFC）单体中,研究了热压过程的条件参数对AHME性能的影响。为了使组装后的DLRFC达到最佳性能,采用高温水、恒电流放电以及变电流放电3种方式对其进行活化,研究了恒电流活化过程中活化条件对DLRFC电化学性能的影响。结果表明,最适宜热压条件是120 ℃,以200 kg/cm²的热压压力保压120 s左右。对于DLRFC单体而言,采用放电活化的方式优于高温水活化。恒电流活化方式中的最适宜活化时间、活化温度和活化电流密度分别是3 h、60 ℃和20 mA/cm²。     

钙钛矿阳极固体氧化物燃料电池在CO–CO2燃料下的性能和稳定性

以原位析出纳米Co–Fe颗粒的La_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3–δ(LSCFN)钙钛矿为阳极,考察了直接使用CO–CO₂燃料时的阳极结构演变、单电池电化学性能和稳定性。结果表明:在CO燃料中,ABO₃钙钛矿结构LSCFN转变为A₂BO₄层状钙钛矿结构;在CO中引入少量CO₂后,LSCFN则以单钙钛矿结构为主,并有效抑制了碳沉积。单电池在CO燃料下的最大功率密度可达0.6 W/cm²(850℃),并在n(CO):n(CO₂)=5:1(摩尔比)燃料下运行超过100 h。     

Water flooding and pressure drop characteristics in flow channels of proton exchange membrane fuel cells

Water flooding of the flow channels is one of the critical issues to the design and operation of proton exchange membrane fuel cells (PEMFCs). The liquid water and total pressure drop characteristics both in the anode and cathode parallel flow channels of an operating PEMFC were experimentally studied. The gas/liquid two-phase flow both in the anode and cathode flow channels was observed, and the total pressure drop between the inlet and outlet of the flow field was measured. The effects of cell temperature, current density and operating time on the total pressure drop were investigated. The results indicated that the total pressure drop in the flow channels mainly depends on the resistance of the liquid water in the flow channels to the gas flow, and the different flow patterns distinguish the total pressure drops in the flow field. Clogging by water columns result in a higher pressure drop in the flow channels. The total pressure drop measurement can be considered as an in situ diagnoses method to characterize the degree of the flow channels flooding. The liquid water in the cathode flow channels was much more than that in the anode flow channels. The pressure drop in the cathode flow channels was higher than that in the anode flow channels. During the fuel cell operation, the cell performance decreased gradually and the pressure drop both in the anode and the cathode flow channels increased. The rate of flooding at the cathode side reached 49.56% under experimental conditions after 78 min of operation. However, it was zero at the anode side.     

空气源电化学连续分离制氧(Ⅰ):单池性能优化

随着工业化进程高速发展,尤其受近期“雾霾”的影响,大气环境质量越来越受重视。空气中氧气补给是提高空气质量的关键方法之一。相对于传统制氧技术(如空气物理分离法、化学法以及水电解法等),空气源电化学连续分离制纯氧技术具有空气源分离制纯氧、能量效率高、连续运行、环境友好、安静、易规模放大等特点,可实现室内外场合应用。该技术的关键部件是质子交换膜燃料电池和固体聚合物电解质电解池(简称燃料电池和电解池)。分别考察了其单池操作条件对性能的影响,如燃料电池的操作温度、相对湿度、气体利用率和压强,以及电解池的供水方式、循环水流速、操作温度等。测试了燃料电池单池极化曲线、电化学交流阻抗谱,并计算了膜电导率和活化能。对极化曲线进行拟合得出塔菲尔(Tafel)斜率、氧还原反应交换电流密度i₀以及传质影响参数m、n等基本动力学参数。结果表明,氢空燃料电池单池最优化条件为:常压条件下,操作温度为60℃,峰值功率密度可达0.42 W·cm^-2,膜面电阻为77 mΩ·cm²,膜电导率为41.4 mS·cm^-1。Tafel斜率受温度影响较小,在120 mV·dec^-1左右,但受相对湿度影响较大。相对湿度对单池性能影响显著。电解池单池最优化操作条件为:操作温度对性能影响较大且最佳为65℃,膜面电阻为1.08 Ω·cm²,膜电导率为11.7 mS·cm^-1。循环水流速对性能影响较小。供水方式的优劣次序为两极供水≈阳极供水>阴极供水。在上述实验条件下,燃料电池中Nafion^®211膜和电解池中Nafion^®115膜的活化能计算值分别为3.75和4.61 kJ·mol^-1。基于燃料电池和电解池的单池电化学性能优化,研究结果可为后续的制氧机系统中电池堆的实施提供实验依据。     

High-loading Pt-alloy catalysts for boosted oxygen reduction reaction performance

To improve performance of membrane electrode assembly (MEA) at large current density region, efficient mass transfer at the cathode is desired, for which a feasible strategy is to lower catalyst layer thickness by constructing high loading Pt-alloy catalysts on carbon. But the high loading may induce unwanted particle aggregation. In this work, H-PtNi/C with 33% (mass) Pt loading on carbon and monodisperse distribution of 3.55?nm PtNi nanoparticles, was prepared by a bimodal-pore route. In electrocatalytic oxygen reduction reaction (ORR), H-PtNi/C displays an activity inferior to the low Pt loading catalyst L-PtNi/C (13.3% (mass)) in the half-cell. While in H₂-O₂ MEA, H-PtNi/C delivers the peak power density of 1.51?W·cm^?2 and the mass transfer limiting current density of 4.4?A·cm^?2, being 21% and 16% higher than those of L-PtNi/C (1.25?W·cm^?2, 3.8?A·cm^?2) respectively, which can be ascribed to enhanced mass transfer brought by the thinner catalyst layer in the former. In addition, the same method can be used to prepare PtFe alloy catalyst with a high-Pt loading of 36% (mass). This work may lead to a range of catalyst materials for the large current density applications, such as fuel cell vehicles.     

Combinatorial investigation of Pt–Ru–M as anode electrocatalyst for direct methanol fuel cell

The addition of Au/TiO₂ and zeolites as active components to PtRu/C electrode in DMFC was investigated by using combinatorial high-throughput-screening test. Addition of Au/TiO₂ to PtRu/C electrode, especially in the ratio of PtRu/C: Au/TiO₂ 9:1, 8:2, 7:3, were effective to improve the performance of direct methanol fuel cell. The electrochemical properties of the prepared electrodes were compared using cyclic voltammetry, impedance spectroscopy and a single cell performance test of a direct methanol fuel cell (DMFC). The adsorbed CO on Pt might be easily oxidized on the surface of Au/TiO₂ by interaction between PtRu/C and Au/TiO₂. The addition of the solid acid proton conducting materials (ZSM-5) on PtRu/C anode leads to the high temperature operation. The cell performance was maintained over the cell temperature 120 °C (maximum current density was 200 mA/cm² at 160 °C) by the addition of ZSM-5 as proton conducting materials.     

表面修饰对镧锶钴铁阴极材料电化学性能的影响

通过柠檬酸-EDTA络合法制备固体氧化物燃料电池阴极材料La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(LSCF)粉体。以Sm_0.2Ce_0.8O_1.9(SDC)为电解质,制备了LSCF/SDC/LSCF对称电极。采用浸渍法在LSCF/SDC/LSCF两侧浸渍La(NO₃)₃、Ni(NO₃)₂、Fe(NO₃)₃混合溶液,850℃烧结后得到表面修饰后的阴极材料。研究了浸渍烧结后表面修饰阴极材料的物相结构特征、电化学交流阻抗、电化学催化活性及单电池输出性能。结果表明:通过浸渍法在LSCF阴极表面形成了与LSCF结构相似的La_0.62Sr_0.38Ni_0.03Co_0.19Fe_0.78O_3-δ(LSNCF)固溶体,在表面产生的纳米颗粒提升了阴极材料对O2的吸附解离能力,并表现出较低的极化阻抗,在800℃时LSNCF阴极材料的极化面电阻为0.083Ω·cm²,在800℃连续工作7 200 min后,LSNCF阴极材料对称电池极化阻抗为0.117Ω·cm²。以Ni-SDC为阳极,SDC为电解质,LSNCF为阴极组装阳极支撑单电池,在750℃时最大功率密度为693 m W/cm²。     

Reinforcement of proton-exchange membrane fuel cell performance through a novel flow field design with auxiliary channels and a hole array

A novel flow field was designed by deploying auxiliary channels inside the partially hollow ribs and drilling a series of arrayed holes on the auxiliary channels. This novel design rationally utilizes the ribs of the current collector and improves the volumetric efficiency of the parallel channels, leading to improved cell performance and homogeneity of current distribution. A three-dimensional, two-phase flow model was developed to analyze the influence of a variety of parameters on the oxygen and water saturation profiles, cell performance, and current uniformity. It was found that the combination of auxiliary channels and hole array provides an extra pathway for reactant transport and water removal. A reasonable optimization of the flow field geometry, for example, the hole size, the area ratio of arrayed holes and auxiliary channels, nonuniform distribution of arrayed holes, could further improve the cell performance and current uniformity at an extremely low pressure drop.