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。     

1～5 kW高温聚合物电解质膜燃料电池堆的理论模拟与组装测试

以大尺寸单电池(有效工作面积为165 cm²)和多片单电池组装而成的电堆为研究对象，通过数值模拟和实验测试相结合的方法探究了单电池数量对高温聚合物电解质膜燃料电池堆输出性能、单池一致性和热管理的影响。模拟结果显示，当电堆的单池数量从10片增加至60片时，平均单池电压从0.6414 V略微降低至0.6404 V，且单池之间电压极差从1.8 mV增加至6.5 mV；单池间的平均工作温度从431.01 K升高至433.90 K，且每单池自身工作温度的极差从6.95 K增加至10.22 K。表明随着电堆单池数量的增加，电堆的平均单池电压呈轻微下降趋势，且单池间电压极差变大，单池电压一致性有所下降，单池间的温差变大，其单池自身的均温一致性也有所降低，电堆热管理难度增加。在模拟结果的指导下分别组装了30、60和120片单池的高温膜燃料电池堆，在氢/空干气、33 A的恒流放电条件下，测得30、60和120片单池电堆的平均单池电压分别为0.6566、0.6548和0.6552 V，单池极差从24 mV增加到59 mV，与模拟结果显示出良好的一致性，验证了模拟结果的有效性。在氢/空...     

PEMFC用Pt纳米线阴极催化剂的制备及在电堆中的应用

采用无模板法制备了用于质子交换膜燃料电池（PEMFC）的碳载铂纳米线（Pt NWs/C）阴极催化剂,使用透射电镜（TEM）和X射线衍射图谱技术（XRD）对催化剂的微观结构和形貌进行了表征。研究结果表明,制备的铂催化剂具有纳米线的结构,平均截面直径为（4.0±0.2）nm,线长为15～25 nm。利用循环伏安（CV）法和线性伏安扫描法（LSV）表征催化剂的电化学活性和氧还原反应（ORR）特性,结果表明制备的Pt NWs/C催化剂电化学特性良好。利用Pt NWs/C和Pt/C作为阴极催化剂制备膜电极（MEA）,并进行测试,最大功率密度分别为705.6 mW·cm^-2和674.4 mW·cm^-2。然后以Pt NWs/C和Pt/C为阴极催化剂组装了18片和20片的电堆,并进行性能测试,电堆的最大功率密度分别为409.2 mW·cm^-2和702.7 mW·cm^-2,单电池电压差异系数（C_v）分别为16.1%和4.36%,这表明Pt NWs/C作为阴极催化剂在放大后的膜电极组件（MEA）里表现出较好的催化活性,但与商业催化剂相比其性能与均一性还有待提高。该研究可为Pt NWs/C催化剂放大制备提供依据,同时可为后续的基于Pt NWs/C的电堆的耐久性测试和车载应用奠定基础。     

应用于大尺寸平板型固体燃料电池电堆的Al2O3-SiO2-CaO基密封材料软化特性及其验证

设计研制了Al₂O₃-SiO₂-CaO基密封材料,对其高温晶化与软化、热性能、界面黏结特性开展了原位观察,并进行了电堆实际应用验证。结果表明:在不高于1 100℃时该密封材料均为非晶态,850℃开始软化,900~1 000℃出现球化。热重分析表明密封材料在0~960℃的质量损失较小,约为0.06%;密封材料与连接板、电池界面黏结紧密,利于固体氧化物燃料电池(SOFC)电堆密封应用。采用研制的密封材料组装了2个5单元SOFC短堆,分别进行了热循环与稳定性研究。结果表明:2个5单元电堆的开路电压达到6.0 V,平均开路电压1.2 V,电堆1热循环前后在35 A(0.56 A/cm²)条件下输出功率为运行无衰减,电堆2在27 A(电流密度0.43 A/cm²)进行恒流放电,运行300 h较为稳定。     

高温聚合物电解质膜燃料电池大尺寸(200cm2)多蛇形流场模拟与优化

以大尺寸（100mm×200mm, 200cm²）多蛇形流场为研究对象,通过数值模拟和实验的方法探究了阴极多蛇形流场的排布方式对高温聚合物电解质膜燃料电池输出性能的影响。相比于竖向排布多蛇形流场,基于横向排布的多蛇形流场的电池在进气量1.527L/min和电压0.6V时展示出了更高的平均输出电流密度222.78mA/cm²和更均匀的电流密度分布（均一指数为75.3%）。在此基础上,进一步对横向排布流场结构的气体通道数进行了优化。结果表明入口气体通道数的增加可以显著减少流场进出口的压降损失,但电池平均输出电流密度和均一指数也有所降低。其中,9通道横排多蛇形流场有较高的电池性能和较好的电流密度分布均匀性（相对于14通道）和较低的压降损失（相对于6通道）,对进一步提高高温聚合物电解质膜燃料电池的性能及稳定性和商业化应用具有指导意义。     

新型凝胶填充复合膜用于碱性水电解

采用多孔填充策略，以多孔聚苯硫醚(PPS)无纺布为基膜，以聚乙烯醇(PVA)凝胶作为填充物，制备出凝胶填充复合膜。通过简便的刮涂法，结合化学交联，制备出PVA填充PPS交联复合膜(PPS-PVA),该膜同时具有高离子传导率、阻气性、化学稳定性和机械稳定性。在80℃条件下，与Zirfon UTP-500商品膜相比，PPS-PVA复合膜具有低面电阻(150 mΩ·cm²)和低氢气渗透率[3.5×10^-8 mol·(cm^-2·s^-1·kPa^-1)]。在60℃、30%KOH溶液中进行碱稳定性测试，500 h后复合膜中PVA的质量仍能保持在初始值的88%左右，并且膜保持良好的机械强度。采用PPS-PVA复合膜在500 mA·cm^-2的电流密度下进行单池碱性水电解，需要电压为1.91 V,低于使用Zirfon UTP-500膜时需要的1.96 V。     

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。     

含氟聚芴醚二唑质子交换膜的性能

将十氟二唑和双酚芴作为聚合物单体制备了一种新型的偏氟聚芴醚二唑质子交换膜。通过加入4-羟基磺酸钠进攻十氟二唑邻位的C-F键引入官能基团探究了膜的制备方法。研究了膜的物理、电化学性能并组装了燃料电池单电池。实验结果表明:该膜具有较高的离子传导率、较强的机械性能及低的甲醇渗透率。30℃时,传导率为58 mS·cm^-1,70℃,传导率达到了137 mS·cm^-1。甲醇渗透率是Nafion^® 117膜的1/2,在100℃时,单电池的功率达到85 mW·cm^-2。     

磺化含酚酞侧基聚芳醚酮/氧化石墨烯复合质子交换膜的性能

采用共混制备了一系列磺化含酚酞侧基聚芳醚酮(SPEK-C)/氧化石墨烯(GO)复合质子交换膜,系统地研究了GO含量对复合膜性能的影响。结果表明,GO含量对膜的离子交换容量、稳定性、质子电导率和甲醇渗透率等有重要影响。复合膜质子电导率随GO含量增加而提高,GO含量为2%和5%的复合膜在80℃下质子电导率均在10^-1 S·cm^-1以上。80℃下,GO含量为5%的复合膜甲醇渗透率为6.69×10^-7 cm²·s^-1,低于同温度下复合前SPEK-C膜1个数量级。复合后膜的化学稳定性增强,离子交换容量和含水率均有提高,相对选择性明显增大,最高达SPEK-C的18.2倍。     

甲烷水蒸气重整与微管固体氧化物燃料电池电堆耦合性研究

目的：以甲烷水蒸气重整合成气为燃料，测试微管式固体氧化物燃料电池(MT-SOFC)电堆的电化学性能。方法：以活性氧化铝为载体，通过浸渍工艺制备出甲烷水蒸气重整催化剂，测试催化剂在不同反应温度、水碳比、体积空速下的反应活性。将甲烷水蒸气重整的合成气作为MT-SOFC电堆的燃料，测试电堆的发电性能。结果：在750℃，体积空速为550 h^-1时，甲烷转化率达99.5%。甲烷水蒸气重整耦合MT-SOFC电堆发电，其功率达43.5 W，功率密度达0.20 W/cm²。催化剂催化活性较高，电堆电化学性能平稳。结论：甲烷水蒸气重整耦合MT-SOFC电堆发电的工艺可提高燃料的利用效率，对发展新能源和保护环境具有现实意义。     

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。     

Sulfonated polybenzimidazole/amine functionalized titanium dioxide (sPBI/AFT) composite electrolyte membranes for high temperature proton exchange membrane fuel cells usage

The novel sulfonated polybenzimidazole (sPBI)/amine functionalized titanium dioxide (AFT) composite membrane is devised and studied for its capability of the application of high temperature proton exchange membrane fuel cells (HT-PEMFCs), unlike the prior low temperature AFT endeavors. The high temperature compatibility was actualized because of the filling of free volumes in the rigid aromatic matrix of the composite with AFT nanoparticles which inhibited segmental motions of the chains and improved its thermal stability. Besides, amine functionalization of TiO₂ enhanced their dispersion character in the sPBI matrix and shortened the interparticle separation gap which finally improved the proton transfer after establishing interconnected pathways and breeding more phosphoric acid (PA) doping. In addition, the appeared assembled clusters of AFT flourished a superior mechanical stability. Thus, the optimized sPBI/AFT (10 wt%) showed 65.3 MPa tensile strength; 0.084 S·cm^-1 proton conductivity (at 160 °C; in anhydrous conditions), 28.6% water uptake and PA doping level of 23 mol per sPBI repeat unit. The maximum power density peak for sPBI/AFT-10 met the figure of 0.42 W·cm^-2 at 160 °C (in dry conditions) under atmospheric pressure with 1.5 and 2.5 stoichiometric flow rates of H₂/air. These results affirmed the probable fitting of sPBI/AFT composite for HT-PEMFC applications.     

Poly (ether ether ketone ketone) based imidazolium as anion exchange membranes for alkaline fuel cells

An imidazolium functionalized poly (ether ether ketone ketone) (PEEKK-DImOH) anion exchange membrane (AEM) readily soluble in certain low-boiling-point solvents (isopropanol) is prepared. The solubility results are consistent with the results of molecular dynamics simulations. By varying the chloromethylation reaction temperature or concentrated sulfuric acid concentration of PEEKK, the degrees of chloromethylation of PEEKK are changed from 54% to 92%, the corresponding PEEKK-DImOH AEMs with the ion exchange capacities (IECs) of 1.14-1.65 mmol·g^-1. The PEEKK-DImOH 92% AEM shows high hydroxide conductivity (31 mS·cm^-1), suitable water uptake (94%) and acceptable swelling ratio (39%) at 60℃. In addition, the PEEKK-DImOH AEMs possess good thermal and alkaline stability. The maximum power density (46.16 mW·cm^-2) of fuel cell prepared with PEEKK-DImOH 92% AEM as exchange membrane and ionomer is much higher than that with commercial AHA membranes. All the above results indicate that the PEEKK used in this study is a promising AEM matrix material for alkaline fuel cells.     

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。     

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.     

A new long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)/polybenzimidazole (PBI) amphoteric membrane for vanadium redox flow battery

A new amphoteric membrane was prepared by blending long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide)(S-L-PPO) and polybenzimidazole(PBI) for vanadium redox flow battery(VRFB) application.An acid–base pair structure formed between the imidazole of PBI and sulfonic acid of S-L-PPO resulted in lowered swelling ratio. It favors to reduce the vanadium permeation. While, the increased sulfonic acid concentration ensured that proton conductivity was still at a high level. As a result, a better balance between the vanadium ion permeation(6.1 × 10-9 cm~2·s~(-1)) and proton conductivity(50.8 m S·cm~(-1)) in the S-L-PPO/PBI-10% membrane was achieved. The VRFB performance with S-L-PPO/PBI-10% membrane exhibited an EE of 82.7%, which was higher than those of pristine S-L-PPO(81.8%) and Nafion 212(78.0%) at 120 m A·cm~(-2). In addition, the S-LPPO/PBI-10% membrane had a much longer self-discharge duration time(142 h) than that of Nafion 212(23 h).     

原位浸渍法制备NiO-BZCYYb阳极支撑SOFCs及电化学性能

采用原位浸渍法一步烧结成型制备了NiO-BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ（BZCYYb）/SDC/LSCF管状结构阳极支撑型SDC电解质膜固体氧化物燃料电池（SOFCs）。以加湿H₂（约含有体积分数为3%的水）为燃料,空气为氧化剂,研究了电池的电化学性能、热循环性能和工作电压下运行的稳定性。结果表明：电池在600、650、700、750、800℃的开路电压分别为1.084、1.074、1.067、1.058、1.046 V;最大输出功率密度分别为0.12、0.25、0.38、0.54和0.70 W·cm^-2。单电池在700℃和0.7 V连续放电测试过程中稳定运行,没有明显的下降和衰退。单电池经历了11次热循环,输出功率稳定,能够经受住重复启动考验。     

NiMn2O4尖晶石氧化物阴极的制备及电化学性能研究

高性能阴极材料的开发对推动中温固体氧化物燃料电池（intermediate temperature solid oxide fuel cells, IT-SOFCs）的发展具有重要意义。本文采用溶胶-凝胶法制备了尖晶石型NiMn₂O₄（NMO）电子-离子混合导体材料，并作为IT-SOFCs阴极进行了系统的研究，通过X射线衍射表征确定NMO材料呈稳定的立方相结构，并采用电导弛豫方法对其氧离子传导能力进行了研究。发现NMO具有优秀的氧离子传导能力，为其电化学性能提供了保障。对称电池的电化学阻抗谱测试结果表明，800℃时NMO阴极材料的界面电阻值为0.27 Ω·cm^-2，同时作为阳极支撑型SOFC的阴极材料进行放电时的最大功率密度可以达到864.9 mW·cm^-2。上述结果表明，NiMn₂O₄是一种极具潜力的IT-SOFCs阴极材料。