A NOVEL KIND OF PROTON EXCHANGE MEMBRANE:CHARACTERS AND PROTON TRANSPORT MECHANISM

A novel proton exchange membrane(PEM) was designed and prepared from a polymer containing calix[4]arene as the functional unit to transport proton.The proton-conductivity of this membrane is about the same order of magnitude as that of Nation~■ 112 membrane.It is of interest to note that very different from most of the currently known PEMs,this membrane can transport proton without the help of water or other solvents.It is deduced that the protons are transported via an ion tunneling model.This opens up a n...

Pore-Scale Investigation of Coupled Two-Phase and Reactive Transport in the Cathode Electrode of Proton Exchange Membrane Fuel Cells

A three-dimensional multicomponent multiphase lattice Boltzmann model(LBM)is established to model the coupled two-phase and reactive transport phenomena in the cathode electrode of proton exchange membrane fuel cells.The gas diff usion layer(GDL)and microporous layer(MPL)are stochastically reconstructed with the inside dynamic distribution of oxygen and liquid water resolved,and the catalyst layer is simplifi ed as a superthin layer to address the electrochemical reaction,which provides a clear description of the fl ooding eff ect on mass transport and performance.Diff erent kinds of electrodes are reconstructed to determine the optimum porosity and structure design of the GDL and MPL by comparing the transport resistance and per-formance under the fl ooding condition.The simulation results show that gradient porosity GDL helps to increase the reactive area and average concentration under fl ooding.The presence of the MPL ensures the oxygen transport space and reaction area because liquid water cannot transport through micropores.Moreover,the MPL helps in the uniform distribution of oxygen for an effi cient in-plane transport capacity.Crack and perforation structures can accelerate the water transport in the assembly.The systematic perforation design yields the best performance under fl ooding by separating the transport of liquid water and oxygen.

Segmented tomographic evaluation of structural degradation of carbon support in proton exchange membrane fuel cells

The variation of the three-dimensional(3D)structure of the membrane electrode of a fuel cell during proton exchange cycling involves the corrosion/compaction of the carbon support.The increasing degradation of the carbon structure continuously reduces the electrocatalytic performance of proton exchange membrane fuel cells(PEM-FCs).This phenomenon can be explained by performing 3D tomographic analysis at the nanoscale.However,conventional tomographic approaches which present limited experimental feasibility,cannot perform such evaluation and have not provided sufficient structural information with statistical significance thus far.Therefore,a reliable methodology is required for the 3D geometrical evaluation of the carbon structure.Here,we propose a segmented tomographic approach which employs pore network analysis that enables the visualization of the geometrical parameters corresponding to the porous carbon structure at a high resolution.This approach can be utilized to evaluate the 3D structural degradation of the porous carbon structure after cycling in terms of local surface area,pore size distribution,and their 3D networking.These geometrical parameters of the carbon body were demonstrated to be substantially reduced owing to the cycling-induced degradation.This information enables a deeper understanding of the degradation phenomenon of carbon supports and can contribute to the development of stable PEM-FC electrodes.

The influence of patterned microporous layer on the proton exchange membrane fuel cell performances

The ordered membrane electrode assembly(MEA)has gained much attention because of its potential in improving mass transfer.Here,a comprehensive study was conducted on the influence of the patterned microporous layer(MPL)on the proton exchange membrane fuel cell performances.When patterned MPL is employed,grooves are generated between the catalyst layer and the gas diffusion layer.It is found that the grooves do not increase the contact resistance,and it is beneficial for water retention.When the MEA works under low humidity scenarios,the MEA with patterned MPL illustrated higher performance,due to the reduced inner resistance caused by improved water retention,leading to increased ionic conductivity.However,when the humidity is higher than 80%or working under high current density,the generated water accumulated in the grooves and hindered the oxygen mass transport,leading to a reduced MEA performance.

High-consistency proton exchange membrane fuel cells enabled by oxygen-electron mixed-pathway electrodes via digitalization design

Proton exchange membrane(PEM)fuel cell has been regarded as a promising approach to the decarbonization and diversification of energy sources.In recent years,durability and cost issues of PEM fuel cells are increasingly significant with the rapid increase of power density.However,the failure to maintain the cell consistency,as one major cause of the above issue,has attracted little attention.Therefore,this study intends to figure out the underlying cause of cell inconsistency and provide solutions to it from the perspective of multi-physics transport coupled with electrochemical reactions.The PEM fuel cells with electrodes under two compression modes are firstly discussed to fully explain the relationship of cell performance and consistency to electrode structure and multi-physics transport.The result indicates that one main cause of cell inconsistency is the intrinsic conflict between the separated transport and cooperated consumption of oxygen and electron throughout the active area.Then,a mixed-pathway electrode design is proposed to reduce the cell inconsistency by enhancing the mixed transport of oxygen and electron in the electrode.It is found that the mixing of pathways in electrodes at under-rib region is more effective than that at the under-channel region,and can achieve an up to 40%reduction of the cell inconsistency with little(3.3%)sacrificed performance.In addition,all the investigations are implemented based on a self-developed digitalization platform that reconstructs the complex physical–chemical system of PEM fuel cells.The fully observable physical information of the digitalized cells provides strong support to the related analysis.

基于电-热特性的质子交换膜电解槽模型研究进展

“电-氢”转换为能源领域低碳转型提供了一种新型、绿色、高效的解决方案,质子交换膜电解槽因具备产氢纯度高、制氢效率优、高度集成化以及与波动性电源耦合程度好等优点而备受关注,模型构建是对其机理研究、特性分析、系统运行控制模拟的重要手段。基于质子交换膜电解槽电化学特性和热传输特性,对国内外已有的质子交换膜电解槽电化学模型和热传输模型建模方法进行综述,并简要分析多物理场耦合模型研究进展,对未来质子交换膜电解槽建模研究发展方向进行展望。

燃料电池部分堵塞通道内液滴的动态行为

为了有效去除通道内液态水,采用流体体积模型(volume of fluid model,VOF)方法研究了燃料电池通道内部分堵塞对液滴运输过程的影响,探讨了堵塞块形状参数、液滴尺寸和气体扩散层(gas diffusion layer,GDL)表面润湿性对通道内两相输运特性的影响.结果表明:堵塞块的存在会影响液滴在通道内运输,堵塞块的引入导致液滴受到y方向的剪切力增大,液滴的运输速率提高,有利于GDL表面液态水的去除;随着堵塞比和纵向比的增大,通道内压降增大,液滴运输速率加快;随着液滴直径和GDL表面接触角的增大,液滴运输速率增大;当液滴直径为0.8 cm和GDL表面接触角为150°时,通道内液滴的运输速率越快.

基于金字塔池化网络的质子交换膜燃料电池气体扩散层组分推理方法

针对质子交换膜燃料电池气体扩散层(gas diffusion layer composition,GDL)形貌划分与制备工艺改进问题,提出了一种基于金字塔池化网络(pyramid scene parsing network,PSPNet)与多层感知器(multi-layer perception,MLP)的气体扩散层组分识别与比例推理方法:首先将带标签的气体扩散层扫描电镜(scanning electron microscope,SEM)图片输入神经网络,得到特征图;得到的图像特征层进入金字塔池化模块后,获取SEM图像的深层和浅层特征;随后将深层和浅层特征图层融合输入全卷积网络(fully convolutional network,FCN)模块,得到预测图像;最后统计各个组分上的像素点比例,通过MLP完成组分比例推理。结果表明:所提方法组分识别像素准确率达81.24%;在5%偏差范围内,比例推理准确率为88.89%。该方法解决了气体扩散层多组分无法区分、比例无法获知的问题,可有效应用于气体扩散层的质检、数值重构以及制备工艺改进。

高电流密度PEM水电解OER催化材料研究现状与分析

因强酸性、高过电位以及强氧化环境等问题,商业化质子交换膜(PEM)水电解析氧(OER)阳极需采用高载量的贵金属材料,且目前尚无替代的非贵金属催化剂,导致成本居高不下。以高电流密度(HCD)提升功率密度是PEM水电解未来发展趋势,但随着电流密度升高,水电解反应过电位也近似线性增长,需要催化材料更高的电导率和更快的物质运输,以降低电流和电解效率的损失。因此,开发高性能OER催化剂对推动PEM水电解制氢产业的发展意义重大。介绍了PEM水电解与可再生能源的契合性,从OER四电子反应机理出发,揭示OER催化剂研究意义;结合已有的研究报道,从形貌尺寸、表面结构、传电能力、电化学反应微环境等四方面,分析了高电流密度下OER催化材料的研究现状及其提高PEM水电解传输效率的原因;对高电流密度PEM水电解OER催化材料未来的发展趋势提出建议并进行了展望。

大功率质子交换膜燃料电池建模及仿真

针对70 kW大功率燃料电池系统进行建模,基于Simulink平台搭建质子交换膜燃料电池电堆系统模型。基于该模型在稳态下研究温度、膜含水量、压力对电池输出性能的影响,分析水气跨膜运输情况。仿真结果表明电流密度在0.4~1.0 A/cm范围内时,电堆输出电压保持稳定。然后在新欧洲驾驶循环(NEDC)动态工况下,分析电池系统输出性能和水气跨膜传输情况,结果表明所建模型可用于大功率车用PEMFC研究。

二维材料复合质子膜的制备及其氕氚分离性能研究

采用溶液浇铸法分别制备了Graphene-Nafion和hBN-Nafion 2种二维纳米复合质子交换膜,利用XRD､ATR-FT-IR和SEM对复合膜的结构及微观形貌进行表征,并对复合膜的离子交换容量､质子电导率､机械性能和热稳定性进行测试,结果表明,Graphene和hBN纳米片均匀地分散于Nafion基体内部。相较于重铸Nafion膜(空白对照样品),复合膜的离子交换容量､质子电导率以及机械性能均有不同程度的提升,特别是在掺入质量分数为0.50%时,Graphene-Nafion和hBN-Nafion复合膜的质子传导性能约为重铸Nafion膜的1.25倍和1.14倍。通过对比Graphene-Nafion和hBN-Nafion 2种复合膜的氕氚分离性能发现,在初始氚水比活度为3.51×10^(7)Bq/L时,持续电解超过60 h,2种复合膜的氕氚分离系数分别为5.73和8.46,氚回收率分别为78.53%和85.35%,表明hBN-Nafion复合膜具有更好的氕氚分离性能。

面向控制的一维非等温两相流燃料电池模型研究

经验模型不能反映电池内部复杂的物理化学耦合过程及其导致的响应迟滞,这给燃料电池系统精确控制策略的开发带来了一定困难。针对此问题,建立了面向控制的一维非等温两相流模型,考虑了流道内气体瞬态效应、电池内部水相变,研究了电流密度对气体浓度以及水热分布特性的影响,分析了运行条件和模型参数对电池输出电压的影响,探究了电流阶跃下该模型相比于集总参数模型在输出性能方面的优势。结果表明,该模型具有更好的适用性,可为燃料电池系统层面的模型优化及控制策略设计提供可靠依据。

全钒液流电池用磺化聚芴醚酮质子交换膜的制备及性能

首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。

Fe/N/C材料在质子交换膜燃料电池中阴极催化剂的研究进展

从ORR反应的机理出发,结合Fe/N/C材料的制备方式,从活性位点角度分析了Fe/N/C材料高效氧还原电催化的机制,并针对在高性能Fe/N/C材料开发过程中存在的各种稳定性问题进行阐述。对于Fe/N/C催化剂在燃料电池中的应用前景提出建议和展望,为今后Fe/N/C材料的发展提供了参考。

质子交换膜燃料电池钛双极板研究进展

双极板是质子交换膜燃料电池(PEMFC)中的重要组成部件,其性能对PEMFC的结构稳定性、耐久性、效率和功率密度等起关键作用。金属双极板由于成本较低、力学性能优异以及导电导热性能良好等优点而备受关注。其中,钛金属具有密度低、气密性好、抗拉强度高等特性,且在酸性环境下具有优异的耐蚀性,在PEMFC中有很高的应用价值。钛双极板的耐蚀、导电、疏水、传热、传质等性能受到涂层材料和成形方法的显著影响。因此,文章首先介绍了双极板在PEMFC中的功能及相关要求,然后综述了近年来在PEMFC钛双极板涂层材料和成形方法两个方面的主要研究成果,并对其未来的研究方向进行了展望。

基于钛毡的多孔传输层不同参数对PEMWE极化性能的影响

研究了不同参数的阳极多孔传输层在质子交换膜水电解中的极化特性。结果发现,铱钌镀层可降低电解池的欧姆极化和电荷转移极化。同时,钛毡厚度为0.2 mm,通孔面积集中在40μm^(2),孔隙率为60%时,其欧姆极化和传质极化有所降低。基于上述结论,设计了一款性能良好的定制钛毡。在3 A/cm^(2)的电流密度下,该阳极钛毡的水电解电压为2.11 V,而普通钛毡的水电解电压为2.40 V。

Self-healing and highly elastic fluorine-free proton exchange membranes comprised of poly(vinyl alcohol) derivative and phytic acid for durable fuel cells

Fluorine-free proton exchange membranes(PEMs)capable of healing from physical damage are important for PEM fuel cells(PEMFCs)with extended service life and enhanced reliability.Herein,highly elastic fluorine-free PEMs with excellent self-healing ability and high proton conductivity are fabricated through complexation of phytic acid(PA)with sulfonated polyvinyl alcohol(SPVA),followed by subsequent grafting of SPVA with positively charged 4-(1H-imidazol-1-yl)benzenecarbaldehyde(IBZ).Compared with recast Nafion membranes,the as-prepared SPVA-IBZ/PA membranes exhibit an enhanced mechanical strength and elasticity and can spontaneously recover from a^50%strain to their initial states within^30 s at room temperature.Meanwhile,the SPVA-IBZ/PA membranes have a proton conductivity of^0.095 S cm-1at^70°C,which is higher than that of recast Nafion membranes.The hydrogen-powered PEMFCs using the SPVA-IBZ/PA membranes,which show an open circuit voltage of^0.98 V and maximum power density of^609 mW cm-2,exhibit a satisfactory cell performance.Importantly,the SPVA-IBZ/PA membranes can spontaneously heal mechanical damage of several tens of micrometers in size and restore their original proton conductivity and cell performance under the working conditions of PEMFCs.

Cathode Design for Proton Exchange Membrane Fuel Cells in Automotive Applications

An advanced cathode design can improve the power performance and durability of proton exchange membrane fuel cells(PEMFCs),thus reducing the stack cost of fuel cell vehicles(FCVs).Recent studies on highly active Pt alloy catalysts,short-side-chain polyfluorinated sulfonic acid(PFSA)ionomer and 3D-ordered electrodes have imparted PEMFCs with boosted power density.To achieve the compacted stack target of 6 kW/L or above for the wide commercialization of FCVs,developing available cathodes for high-power-density operation is critical for the PEMFC.However,current developments still remain extremely challenging with respect to highly active and stable catalysts in practical operation,controlled distribution of ionomer on the catalyst surface for reducing catalyst poisoning and oxygen penetration losses and 3D(three-dimensional)-ordered catalyst layers with low Knudsen diffusion losses of oxygen molecular.This review paper focuses on impacts of the cathode development on automotive fuel cell systems and concludes design directions to provide the greatest benefit.

质子交换膜电解池阳极钛基气体扩散层研究进展

气体扩散层在质子交换膜(PEM)水电解池中有着支撑膜组件、供给反应水、移除气体产物以及降低欧姆电阻的重要作用。PEM水电解池阳极区具有酸性、富氧且高电位的工作环境,对阳极区的气体扩散层具有严苛的要求。气体扩散层结构特性、导电性与耐腐蚀性是决定其电化学性能的关键。本文总结了可用于PEM电解池阳极气体扩散层的材料,简述了其结构特性对PEM电解池电化学性能的影响,分析了各种镀层材料在提高气体扩散层的导电性、耐腐蚀性以及电解池阳极氧析出反应(OER)性能方面的作用。最后,展望了气体扩散层在降低成本和提高电解池性能方面的研究趋势。

质子交换膜燃料电池双极板密封研究进展

作为质子交换膜燃料电池(PEMFC)的核心组件,双极板的密封性能是影响电堆工作效率的关键。在目前燃料电池的应用中,因密封不良引发泄漏而导致的电堆失效是不容忽视的问题。综述近年来燃料电池双极板常用密封材料的性能差异、不同密封结构的特点、密封元件的设计等方面的研究进展,探讨密封性能对PEMFC电堆性能的影响,并对未来发展方向进行展望。