Carbon-free nanoporous gold based membrane electrocatalysts for fuel cells

Nanoporous gold (NPG) membranes made by dealloying consist of a bicontinuous network of Au ligaments and open pore channels, which have gained considerable attention as a platform for the design of carbon-free electrodes for proton exchange membrane fuel cells (PEMFCs). Benefiting from a unique combination of high electronic conductivity, high surface area, and modifiable surface chemistry, these self-supporting membrane type electrodes allow integration of various structural functions required for specific electrode reactions and simultaneously facilitate the entire fuel cell kinetic process. In this review, we summarize the major research progresses in this area, with an emphasis on how to customize the surface structures of these three-dimensional electrocatalysts for desired fuel molecule oxidation and oxidant reduction. We will also discuss these designed structural characteristics that can be readily accommodated in membrane electrode assemblies (MEA), thus effectively bridging the technological gap between electrocatalysts’ intrinsic activities and their actual performances in fuel cells.     

交流阻抗法测试质子交换膜电导率的研究

介绍了交流阻抗谱法测试质子交换膜质子电导率的原理与等效电路.并以Nafion117膜为例介绍了采用交流阻抗法测试其电导率的测试夹具及测试平台的设计和搭建,给出了Nafion117膜的交流阻抗谱图以及膜质子电导率随温度的变化曲线.采用交流阻抗法测试质子交换膜的电导率是质子交换膜燃料电池性能测试的重要手段.     

质子交换膜燃料电池膜电极再发电性能的研究

对质子交换膜燃料电池(PEMFC)膜电极(MEA)的二次发电性能进行了研究.由单电池的电性能测试表明,二次使用时MEA的开路电压下降5.0%,最大电流密度和最大功率均降低约50.0%.SEM的测试结果显示,二次使用的MEA的表面有催化层脱落现象,减少了电极的活性反应区域,降低了其发电性能.     

质子交换膜燃料电池膜电极的关键技术

 膜电极是多相物质传输和电化学反应场所,决定着燃料电池的性能、寿命及成本。本文分析膜电极当前技术现状与商业化目标,梳理膜电极分类及经过梯度化膜电极向有序化膜电极发展的技术脉络,介绍近年来超低Pt载量的第三代膜电极-有序化膜电极的新进展,比较各种有序化膜电极制备方法的优缺点。目前有序化膜电极在铂族元素总载量为0.118 mg/cm²下取得的最好性能为861 mW/cm²@0.692 V,0.137 g/kW,成本降至5美元/kW,Q/ΔT值从2013年的1.9下降到1.45。从降低Pt用量及简化燃料电池发电系统、降低系统成本的角度看,自增湿有序化膜电极是未来膜电极开发的重要方向。     

Janus few layered graphene with asymmetric wettability as anti-flooding cathode supports in proton exchange membrane fuel cells

Water balance in cathode catalyst layer (CCL) is crucial for proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel strategy to develop a Janus few layered graphene particles (FLGP) with asymmetric wettability by varying the carbon precursors in the chemical vapor deposition (CVD) process. Using the Janus FLGP supported Pt with asymmetric wettability as the cathode of a PEMFC, a peak power density of 632 mW cm⁻² was achieved, which was about two-folds of the hydrophobic FLGP and three-folds of hydrophilic FLGP based cathode, respectively. The enhanced performance could be ascribed to the well-constructed three-phase boundary in an anti-flooding cathode, leading to enlarged electrochemical active surface area and facilitated mass transfer. This work may provide new clues for improving water management in PEMFCs.     

Electrolyte membranes for intermediate temperature proton exchange membrane fuel cell

An overview of intermediate temperature (100–300 °C) proton conducting membrane electrolyte materials for fuel cells is presented in this review. The fuel cells operated in intermediate temperature range could enhance the electrochemical kinetics, simplify water management, and improve impurities resistance. Polyfluorosulfonic acid polymer membrane represented by Nafion, and non-fluorinated arylene polymer membranes represented by polybenzimidazole are the two most widely polymer electrolyte membranes for intermediate temperature membrane. The structure regulation and fillers addition are two effective ways to maintain the conductivity and mechanical properties of membranes at intermediate temperature. Moreover, heteropolyacids, metal pyrophosphates and inorganic membranes also have attracted widespread attention when they operate at intermediate temperature.     

用EIS研究PEMFC膜电极的运行条件对其性能的影响

在质子交换膜燃料电池（PEMFC）中，采用电化学阻抗谱（EIS）研究了膜电极（MEA）的一些运行条件对其工作性能的影响，并探讨了其作用机理．通过测量数据的解析和等效电路的数学模拟，得到了与MEA结构关联的电极诸参数随电池温度和反应气体压力的变化规律．研究表明，MEA的氧电极的电化学反应电阻随电池温度的升高显著减小，氧电极的双电层电容随电池温度的升高有所增加，表明电极有效面积得以增加，有利于MEA工作性能的提高．     

质子交换膜燃料电池三维气液两相流数值模拟

质子交换膜燃料电池液态水的生成和传输过程研究,是进行电池水管理的关键。该文基于多相混合流理论,建立了质子交换膜燃料电池三维气液两相流动与传热的数学模型。该模型不仅能模拟燃料电池内部反应气的流动、扩散和化学反应过程,还能模拟液态水的传输和相变过程。应用该模型模拟了电池内液态水的分布及其对燃料电池性能的影响,结果表明液态水主要分布在阴极侧,在大电流密度下,液态水阻碍了氧的扩散过程,导致电池性能下降。模拟结果与实验结果吻合较好。     

静电场对碗豆幼苗膜透性影响与跨膜电导率

根据静电场作用下碗豆幼苗膜透性的试验结果,应用分子力学方法研究了离子跨膜输运能量,将植物细胞膜内部模拟为两个介电常烽不同的空间电荷区,建立离子跨膜模型,导出了界面势垒的静电荷密度与界面电导率,并从电子水平研究植物细胞畸变机理。     

磺化聚醚醚酮(sPEEK)/SiO2杂化质子交换膜的制备与表征

为提高磺化聚醚醚酮(sPEEK)质子交换膜的耐甲醇渗透性能,用正硅酸乙酯为前驱体制得硅溶胶,在sPEEK中原位生成SiO2,制备了直接甲醇燃料电池用sPEEK/SiO2杂化质子交换膜材料,用核磁共振(1H-NMR)和Fourier红外光谱(FT-IR)表征了膜的化学结构,用扫描电子显微镜(SEM)观察了sPEEK与SiO2的复合形态,用交流阻抗仪和气相色谱仪分别测定了膜的质子传导率和甲醇渗透系数。实验结果表明,在质子传导率没有严重降低的同时,杂化膜的阻醇性得到了较好的改善。     

Pt含量对燃料电池膜电极组件结构及性能的影响

本文基于Catalyst Coated Membrane（CCM）技术,采用70%Pt/C催化剂制备质子交换膜燃料电池（PEMFC）的核心部件膜电极组件（Membrane electrolyte assembly,MEA）。考察了电池的放电性能,并利用循环伏安（CV）、电化学阻抗谱（EIS）、扫描电镜（SEM）等技术对电池的电化学性能进行了表征。研究表明采用质量分数为70%的Pt/C催化剂与Nafion的最佳质量比例为6：1,MEAΩ在600mA/cm~2电流密度下,电压能达到0.69V,催化层的厚度显著降低,性能也明显优于40%Pt/C催化剂制备的MEA。     

Central electron-enriched NO-FeN4 sites as superior acidic oxygen reduction reaction electrocatalysts for proton exchange membrane fuel cells

Developing nobel-metal-free catalysts, especially for iron-nitrogen on carbon (FeNC) materials, has been an urgent demand for wide applications of proton exchange membrane fuel cells (PEMFCs). However, the inferior oxygen reduction reaction (ORR) activity of traditional iron-nitrogen sites in acidic conditions seriously impedes the further improvement of their performance. Herein, we synthesized FeN₄ with NO (nitric oxide) group axial modification (denoted as NO-FeN₄) on a large scale through a confined small molecule synthesis strategy. Benefitting from the strong electron-withdrawing effect of the NO group, the central electron-rich FeN₄ site exhibits ultrahigh ORR activity with a three times higher mass activity (1.1 A·g?1 at 0.85 V) compared to the traditional FeN₄ sample, as well as full four-electron reaction selectivity. Moreover, the PEMFC assembled with the as-prepared electrocatalyst also exhibits a greatly enhanced peak power density (>725 mW·cm?2). This work provides a new approach to rationally design advanced M-N_x nonnoble electrocatalysts for the ORR.     

Crystal structure of the plasma membrane proton pump

A prerequisite for life is the ability to maintain electrochemical imbalances across biomembranes. In all eukaryotes the plasma membrane potential and secondary transport systems are energized by the activity of P-type ATPase membrane proteins: H+-ATPase (the proton pump) in plants and fungi, and Na+,K+-ATPase (the sodium-potassium pump) in animals. The name P-type derives from the fact that these proteins exploit a phosphorylated reaction cycle intermediate of ATP hydrolysis. The plasma membrane proton pumps belong to the type III P-type ATPase subfamily, whereas Na+,K+-ATPase and Ca2+-ATPase are type II. Electron microscopy has revealed the overall shape of proton pumps, however, an atomic structure has been lacking. Here we present the first structure of a P-type proton pump determined by X-ray crystallography. Ten transmembrane helices and three cytoplasmic domains define the functional unit of ATP-coupled proton transport across the plasma membrane, and the structure is locked in a functional state not previously observed in P-type ATPases. The transmembrane domain reveals a large cavity, which is likely to be filled with water, located near the middle of the membrane plane where it is lined by conserved hydrophilic and charged residues. Proton transport against a high membrane potential is readily explained by this structural arrangement.     

质子交换膜燃料电池膜电极关键材料研究进展

膜电极是质子交换膜燃料电池(PEMFC)的关键技术部件,本文根据其构造综述了近几年国内外在膜材料、电极催化剂和气体扩散层方面的研究进展,包括Nafion改良膜、磺化聚芳烃（SPA/SPE）类膜、Pt改性催化剂、非贵金属催化剂以及气体扩散层。对各种材料进行了评价和比较,并指出今后应着眼于Nafion膜的简便改良方法、芳香烃聚合物共混膜的研制、含有Co、N等电极催化剂的研究以及具微孔层、表面较粗糙、疏水性较大的扩散层的研发。     

质子交换膜燃料电池空气流场的优化设计

质子交换膜燃料电池空气流场的合理设计可以使电流密度、气体浓度等均匀分布,有利于提高性能。采用数值模拟与测试相结合的方法,对5种常见的空气流场进行了综合评价。结果显示,模拟结果与测试结果反映的电池性能变化趋势基本相同,性能由低到高依次为:平行流场、网格流场、平行蛇形流场、渐缩流场。串并联流场的模拟和实验结果略有差异。该方法可用于质子交换膜燃料电池空气流场的优化设计。     

Ca2+对质子交换膜燃料电池性能的影响

质子交换膜燃料电池(PEMFC)长期运行过程中,其部件因损伤产生的杂质金属离子对燃料电池的电化学性能有重要影响。模拟PEMFC中Ca2+污染燃料电池工况,研究了Ca2+对PEMFC电化学性能的影响。实验结果表明:随着污染时间的增加,燃料电池性能逐渐衰减,当污染时间超过9 h,电池电压急剧降低;在高电流密度区(电流密度>400 mA/cm2),电压衰减最明显。在500 mA/cm2电流密度下恒电流放电2 h后,电压降低了41%。Ca2+的存在及其积累对质子交换膜燃料电池有明显的毒化作用。     

质子交换膜燃料电池建模研究评述

车用动态工况下,质子交换膜燃料电池(PEMFC)内部压力、温度和气体浓度直接影响整个系统的性能和耐久性,因此需要借助数学模型分析电池内部传质、传热和化学反应过程,以优化燃料电池系统设计及控制。然而,燃料电池是一个非线性、多输入、强耦合的系统,模型的建立涉及从原子分子级尺度,到材料晶格结构级尺度,再到部件、电堆和系统级尺度。针对多尺度建模问题,从关键部件、单体、电堆及系统等角度,对不同尺度的建模方法进行全面梳理,并阐述了未来建模的挑战及发展趋势。     

PEMFC阴极催化层电化学性能的数学模拟

质子交换膜燃料电池(PEMFC)的膜电极中包含多种传输过程,且传输过程与电化学反应过程在相互交错的区域内进行,本文建立了质子交换膜燃料电池的阴极数学模型,运用MATLAB和C语言编写了模拟程序,探讨了电极结构和电极制备工艺对电极电化学性能的影响.     

三维聚合物电解质膜燃料电池中水的输运模拟

针对新型螺旋形加压聚合物电解质膜燃料电池,提出了一种液态水生成和输运效应的数值模型.该数值模型基于燃料电池的物理机理、流体流动、传热导、多孔介质中的传质、电化学反应、含相变的多相流动、电流输运、多孔介质和固体导电区域中的位势场以及穿过聚合物膜的水的输运设计优化过程.在分析中还使用了燃料电池模型.例如,电化学模型--用于预测局部电流密度和电压分布;位势场模型--用于预测多孔介质以及固体导电区中的电流和电压;多相混合物模型--用于预测在多孔扩散层中的液态水和气体流;薄膜多相模型--用于研究气体流道中的液态水流.最后给出了聚合物电解质膜燃料电池液态水生成和输运的理论模型的数值结果,包括催化层和膜中的H2,O2和H2O的质量和克分子数的等值线图.     

高温质子交换膜燃料电池催化层孔尺度模拟

为了研究磷酸在高温质子交换膜燃料电池催化层中再分布对电极性能的影响,使用聚焦离子束电子扫描显微镜对自制的扩散电极成像,重构得到了三维的催化层几何模型;采用多弛豫时间格子玻尔兹曼模型对磷酸在催化层的迁移行为进行仿真,模拟得到递减型和准均匀型2种不同的磷酸分布形式;采用孔尺度模型求解不同条件下的电极传输性质。结果表明在磷酸含量较低时,准均匀型的磷酸分布具有稍优的电化学活性表面积和稍差的氧气和水蒸气有效扩散系数;在磷酸含量较高时,2种分布的电化学活性表面积相似,但是准均匀型分布具有更好的氧气和水蒸气有效扩散系数。