Progress and perspective of single-atom catalysts for membrane electrode assembly of fuel cells

A fuel cell is an energy conversion device that can continuously input fuel and oxidant into the device through an electrochemical reaction to release electrical energy.Although noble metals show good activity in fuel cell-related electrochemical reactions,their ever-increasing price considerably hinders their industrial application.Improvement of atom utilization efficiency is considered one of the most effective strategies to improve the mass activity of catalysts,and this allows for the use of fewer catalysts,saving greatly on the cost.Thus,single-atom catalysts(SACs)with an atom utilization efficiency of 100%have been widely developed,which show remarkable performance in fuel cells.In this review,we will describe recent progress on the development of SACs for membrane electrode assembly of fuel cell applications.First,we will introduce several effective routes for the synthesis of SACs.The reaction mechanism of the involved reactions will also be introduced as it is highly determinant of the final activity.Then,we will systematically summarize the application of Pt group metal(PGM)and nonprecious group metal(non-PGM)catalysts in membrane electrode assembly of fuel cells.This review will offer numerous experiences for developing potential industrialized fuel cell catalysts in the future.

Experimental Study on the Electrochemical Performance of PEMFC under Different Assembly Forces

Proton exchange membrane fuel cell(PEMFC)is of paramount significance to the development of clean energy.The components of PEMFC are assembled using many pairs of nuts and bolts.The assembly champing bolt torque is critical to the electrochemical performance and mechanical stability of PEMFC.In this paper,a PEMFC with the threechannel serpentine flow field was used and studied.The different assembly clamping bolt torques were applied to the PEMFC in three uniform assembly bolt torque and six non-uniform assembly bolt torque conditions,respectively.And then,the electrochemical performance experiments were performed to study the effect of the assembly bolt torque on the electrochemical performance.The test results show that the assembly bolt torque significantly affected the electrochemical performance of the PEMFC.In uniform assembly bolt torque conditions,the maximal power density increased initially as the assembly bolt torque increased,and then decreased on further increasing the assembly torque.It existed the optimum assembly torque which was found to be 3.0 N·m in this work.In non-uniform assembly clamping bolt torque conditions,the optimum electrochemical performance appeared in the condition where the assembly torque of each bolt was closer to be 3.0 N·m.This could be due to the change of the contact resistance between the gas diffusion layer and bipolar plate and mass transport resistance for the hydrogen and oxygen towards the catalyst layers.This work could optimize the assembly force conditions and provide useful information for the practical PEMFC stack assembly.

Probing the Efficiency of PPMG-Based Composite Electrolytes for Applications of Proton Exchange Membrane Fuel Cell

PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.

Performance Investigation of Membrane Electrode Assemblies for High Temperature Proton Exchange Membrane Fuel Cell

Different types of ABPBI (poly(2,5-benzimidazole)) membranes and polymer binders were evaluated to investigate the performance of MEAs for high temperature proton exchange membrane fuel cell (HT-PEMFC). The properties of the prepared MEAs were evaluated and analyzed by polarization curve, electrochemistry impedance spectroscopy (EIS), cyclic voltammetry (CV) and durability test. The results showed that MEA with modified ABPBI membrane (AM) has satisfactory performance and durability for fuel cell application. Compare to conventional PBI or Nafion binders, polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) are more attractive as binders in the catalyst layer (CL) of gas diffusion electrode (GDE) for HT-PEMFC.

Stiffness Evaluation of the Welded Connection between Guide Thimbles and the Spacer Grids for 16 × 16 Fuel Assemblies Types, Using the Finite Element Method

The present work aims to evaluate the increase in the number of spot welds in the 16 × 16 type fuel assembly structure that connects guide thimbles and spacer grids, in order to provide a proper joint for this connection. This new and improved process can provide more stiffness to the whole structure, since the number of spots raised from four to eight. A 3-D geometric model of a guide thimble section was generated in a CAD （computer aided design） program （SolidWorks）. After that, the geometric model was imported to a CAE （computer aided engineering） program （ANSYS Mechanical APDL, Release 14.0）, where the finite element model was built, considering the guide thimble geometry assembled with the spacer grid through the welded connections. Boundaries conditions were implemented in the model in order to simulate the correct physical behavior due to the operation of the fuel assembly inside the reactor. The analysis covered specific loads and displacements acting on the entire structure. The method used to solve this finite element analysis was a linear static simulation in order to perform the connection between a spacer grid cell and a guide thimble section. Hence, four models was evaluated, differing on the spot weld number in the spacer grid and guide thimble connection. The rotational stiffness results of each model were compared. The results acquired from four and eight spot weld were validated with physical test results. The behavior of the structure under the acting force/displacement and the related results of the analysis, mainly the stiffness, were satisfied. The results of this analysis were used to prove that the increasing spot welds number is an improvement in the dimensional stability when submitted to loads and displacements required on the fuel assembly design. This analysis aid to get more information of extreme importance such as, the pursuance to develop better manufacturing process and to improve the fuel assembly performance due to the increasing of the bum-up.

PtNi-W/C with Atomically Dispersed Tungsten Sites Toward Boosted ORR in Proton Exchange Membrane Fuel Cell Devices

The performance of proton exchange membrane fuel cells is heavily dependent on the microstructure of electrode catalyst especially at low catalyst loadings.This work shows a hybrid electrocatalyst consisting of PtNi-W alloy nanocrystals loaded on carbon surface with atomically dispersed W sites by a two-step straightforward method.Single-atomic W can be found on the carbon surface,which can form protonic acid sites and establish an extended proton transport network at the catalyst surface.When implemented in membrane electrode assembly as cathode at ultra-low loading of 0.05 mgPt cm^(−2),the peak power density of the cell is enhanced by 64.4%compared to that with the commercial Pt/C catalyst.The theoretical calculation suggests that the single-atomic W possesses a favorable energetics toward the formation of*OOH whereby the intermediates can be efficiently converted and further reduced to water,revealing a interfacial cascade catalysis facilitated by the single-atomic W.This work highlights a novel functional hybrid electrocatalyst design from the atomic level that enables to solve the bottle-neck issues at device level.

Thermal Hydraulic Analysis Improvement for the IEA-R1 Research Reactor and Fuel Assembly Design Modification

This paper presents the sequence of activities to improve the thermal hydraulic analysis of the IEA-R1 research reactor to operate in safe conditions after power upgrade from 2 to 5 MW and core size reduction from 30 to 24 fuel assemblies. A realistic analysis needs the knowledge of the actual operation conditions (heat flow, flow rates) beyond the geometric data and the uncertainties associated with manufacturing and measures. A dummy fuel assembly was designed and constructed to measure the actual flow rate through the core fuel assemblies and its pressure drop. First results showed that the flow distribution over the core is nearly uniform. Nevertheless, the values are below than the calculated ones and the core bypass flow rate is greater than those estimated previously. Based on this, several activities were performed to identify and reduce the bypass flow, such as reduction of the flow rate through the sample irradiators, closing some unnecessary secondary holes on the matrix plate, improvement in the primary flow rate system and better fit of the core components on the matrix plate. A sub-aquatic visual system was used as an important tool to detect some bypass flow path. After these modifications, the fuel assemblies flow rate increased about 13%. Additional tests using the dummy fuel assembly were carried out to measure the internal flow distribution among the rectangular channels. The results showed that the flow rate through the outer channels is 10% - 15% lower than the internal ones. The flow rate in the channel formed between two adjacent fuel assemblies is an estimated parameter and it is difficult to measure because this is an open channel. A new thermal hydraulic analysis of the outermost plates of the fuel assemblies takes into account all this information. Then, a fuel design modification was proposed with the reduction of 50% in the uranium quantity in the outermost fuel plates. In order to avoid the oxidation of the outermost plates by high temperature, low flow rate, a reduction of 50% in the uranium density in the same ones was shown to be adequate to solve the problem.

Analysis of fixation method of fuel assembly for lead-alloy cooled reactor

As a potential candidate for generation IV reactors, lead-alloy cooled reactor has attracted much attentions in recent years. The China LEAd-based research Reactor(CLEAR) is proposed as the primary choice for the accelerator driven subcritical system project launched by Chinese Academy of Sciences. Lead-bismuth eutectic(LBE) is selected as the coolant of CLEAR owing to its efficient heat conductivity properties and high production rate of neutrons. In order to compensate the buoyancy due to the high density of lead-alloy, fixation methods of fuel assembly(FA) have become a research hotspot worldwide. In this paper, we report an integrated system of ballast and fuel element for CLEAR FA. It guarantees the correct positioning of each FA in normal and refueling operations. Force calculation and temperature analysis prove that the FA will be stable and safe under CLEAR operation conditions.

标准核燃料组件几何轮廓校准装置的研制

针对标准核燃料组件竖直状态下几何参数溯源需求,研制了一种标准核燃料组件几何轮廓校准装置。该装置以空间坐标测量为理念,利用多路接触式传感器作为轮廓测量采集单元,结合测量工作台高度位置获得轮廓坐标。通过直线度及扭转度测量与误差补偿,进一步提高了几何轮廓测量精度;并使用集成运动控制和专用测量软件,实现了标准核燃料组件几何轮廓参数(直线度、扭转度、垂直度、平行度)的自动检测。通过分析及实验验证,几何轮廓参数中直线度和平行度测量标准不确定度为0.01 mm,扭转度测量标准不确定度为0.007 mm,垂直度测量标准不确定度为0.017 mm,说明该装置能够满足标准核燃料组件的溯源需求。

加长加宽的PEMFC电堆应力分布一致性仿真与优化

质子交换膜燃料电池可以通过扩大电堆的活性区域反应面积来获得更高的功率,但电堆反应面积扩大后,容易导致膜电极应力分布的不均匀性增加,从而引起燃料电池电化学性能的下降.为此,本研究设计了4种不同结构尺寸的燃料电池电堆,结合等效刚度模型法和有限元软件,分析了扩大反应面积的电堆结构对膜电极应力分布均匀性的影响,并进一步优化电堆内钢带的安装位置,以提升电堆内部接触压力分布均匀性.研究结果表明,膜电极接触压力分布的均匀性对反应区域宽度的变化较为敏感,当活性区域尺寸加宽,电堆内部活性区域的平均应力标准差增加了23.2%.而当活性区域加长,或同时加长和加宽时,相应增加一根捆扎钢带使电堆内部活性区域的平均应力标准差分别减小了8.6%和8.7%,表明适当增加捆扎钢带的数量可以提高电堆内部接触压力分布的均匀性.此外,钢带位置优化结果显示,电堆外侧钢带越靠近端板侧面时,电堆内部活性区域的应力分布越均匀.

交混因子对CHF关系式开发及安全裕量影响研究

采用最小偏离泡核沸腾比(MDNBR)点法开发了与子通道分析程序FLICA-ⅢF匹配的临界热流密度(CHF)关系式,利用Owen准则确定了其DNBR限值并进行统计评估。在掌握了一套完整的CHF关系式开发方法后,对比分析了不同交混因子其对应关系式的预测效果、DNBR限值以及实际最大功率。结果表明:基于实验获得的精确交混因子开发的CHF关系式具有更高的精确度与经济性。因此考虑格架交混效应的精细化子通道的工作是有价值和意义的。

压水堆乏燃料组件中主要同位素含量分析计算

绝大多数的特种可裂变材料钚均存在于商用乏燃料组件中,在核保障领域,对于乏燃料组件中钚含量的核实显得尤为重要。为分析计算乏燃料组件中易裂变核素钚的含量,以31组AFA-2G典型压水堆乏燃料组件为研究对象,通过分析核燃料在反应堆运行过程中的U-Pu循环燃耗链的特点,分析计算了乏燃料组件中主要同位素的含量和固有中子本底,同时利用蒙特卡罗模拟方法计算了239Pu等效质量的等效系数。本文工作为中子质询乏燃料组件易裂变核素含量非破坏性测量的方法研究及测量装置的设计打下了基础。

双面冷却熔盐堆组件热工分析程序开发与验证

新型液态燃料熔盐堆双面冷却组件相比传统熔盐堆组件具有更大的换热面积和更短的石墨导热距离,因而具有更低的石墨温度热点,然而由于其不同的几何结构特征和熔盐自发热特性,组件内存在独特的热量分配和冷却剂流量分配的问题。为准确高效评估新型组件的热安全边界,有必要开发新的计算分析工具。本研究基于MATLAB开发了适用于熔盐堆双面冷却组件的一维稳态热工分析程序THDA-MSR(Thermal-Hydraulic Analysis Code for Dual Cooled Assembly-Molten Salt Reactor),考虑熔盐自发热的特点,建立了组件内外流道内熔盐的一维温度分布模型和熔盐石墨对流换热模型以及石墨导热模型,根据并联通道压损相等原则建立流量分配模型,通过CFD(Computational Fluid Dynamics)数值模拟对程序计算结果进行了验证,并初步分析了各结构参数对组件最大熔盐出口温度和石墨温度热点的影响。THDA-MSR的计算结果与CFD结果吻合较好,压损偏差小于4.84%,石墨温度热点偏差小于0.15%,分析结果发现:外通道截面积占总流道截面积比是影响最大熔盐出口温度和石墨温度热点的关键参数。以上研究结果表明,自编程序能很好地预测组件流量分布、组件压损、熔盐温度分布和石墨温度热点。THDA-MSR能够应用于熔盐堆双面冷却组件热工水力性能分析评估,对于组件选型设计有较大工程参考价值。

颗粒床反应堆燃料组件瞬态特性研究

核热推进系统不仅要像传统动力堆产生预期功率,还需具备快速启动与推力调节的能力,以满足其变轨与机动的需求。因此,瞬态分析对于核热推进系统的方案设计、运行策略和集成试验等有重要作用。以颗粒床反应堆燃料组件为研究对象,建立了一维瞬态热工水力模型,并分析了功率提升过程以及反应性引入后的响应特性。研究发现由于颗粒床反应堆热量载出能力强,且燃料颗粒自身热容小,因此在启动等瞬态过程中换热滞后现象较弱,从而避免了堆芯内由于蓄热效应显著可能造成的超温或热应力过大等现象,有利于实现快速启动。额定工况下引入阶跃反应性,冷却剂载热滞后于堆芯释热约0.1 s,同样有利于系统功率和推力的快速调节。此外,颗粒床反应堆堆芯阻力会随着功率升高而增大,因此在启动和推力调节等过程中需要进一步研究反应性引入与推进剂供应量的匹配技术,以实现核热推进系统的运行与控制。

MC法校正高能X射线核燃料组件无损检测系统散射

高能X射线无损检测技术能在不破坏检测物体的前提下获取其内部结构信息。核燃料组件的多棒束特性导致产生的散射射线严重影响检测图像质量。为了校正散射射线的干扰,本研究分析了多种解决散射射线干扰的方法在核燃料组件无损检测中的局限性,使用Geant4仿真模拟核燃料组件无损检测过程,构建ComptonFlag类标记发生康普顿散射的散射射线并去除其干扰。模拟结果表明,在去除散射射线干扰后,投影图像中的缺陷与完整燃料棒的对比度信噪比提高了69.02%,能有效提升核燃料组件无损检测图像质量。

湿空气在全尺寸压水堆燃料组件中的自然循环特性试验及理论研究

为开发一种不依赖于计算流体力学(Computational Fluid Dynamics,CFD)结果的燃料组件自然循环特性分析模型,以研究乏燃料水池在发生冷却剂丧失事故后的自然循环特性,本研究基于全尺寸压水堆燃料组件压降实验结果对Darcy-Forchheimer模型进行了修正,以预测湿空气流过燃料组件的压降,然后建立了燃料组件自然循环流量和峰值包壳温度的分析预测模型,并考虑了空气的相对湿度对模型计算结果的影响。结果表明:该模型可较为准确地预测不同加热功率下燃料组件的自然循环流量和峰值包壳温度,与实验测量值相比误差分别在25%和20%以内。并利用该模型研究了总加热功率、环境温度和相对湿度对燃料组件自然循环流量和峰值包壳温度的影响。因此,本研究所开发的模型可用于压水堆全尺寸燃料组件的自然循环特性研究。

燃料组件堵流工况下铅铋-氩气两相流的传热压降特性分析

带绕丝燃料组件的堵流事故是铅冷快堆安全分析的重要工况之一。由于在铅铋自由液面处的气体夹带或在气体增强自然循环条件下存在铅铋-氩气的两相流情况,可能引起燃料组件堵流工况下的局部热工水力特性变化。本文通过计算流体力学软件Fluent,对带绕丝19棒束燃料组件进行建模,模拟分析了堵流工况下的铅铋-氩气两相流传热压降特性,并对两相流模型进行了对比验证,对入口雷诺数、堵块孔隙率、氩气气泡直径等因素进行参数敏感性分析。结果表明:在堵流条件下氩气气泡的流动行为包括逃逸、耗散和受限,在气相体积分率较高的区域会产生局部微正压及过热现象。研究结果可为铅冷快堆堵流事故的安全分析提供参考。

乳液自组装法制备Al/B/PTFE含能微球及其性能表征

为了探究高活性金属含能微球的制备工艺以及燃烧性能,以Viton为黏结剂,聚四氟乙烯(PTFE)、硼粉(B)和铝粉(Al)为高能组分,采用乳液自组装技术制备了Al/B/PTFE含能微球,并对溶剂的挥发温度、乳化剂的种类、水相和油相的体积比和搅拌速度等工艺进行了优化;采用扫描电子显微镜(SEM)对Al/B/PTFE含能微球形貌进行了表征;采用TG-DSC法分析了Al/B/PTFE含能微球的热分解性能;通过高速摄影和密闭爆发器表征了Al/B/PTFE含能微球的燃烧反应性能。结果表面,水浴温度为25℃、乳化剂为PVA、水油比为80∶30和搅拌速度为700 r/min是Al/B/PTFE含能微球的最佳制备工艺;所制备的Al/B/PTFE含能微球的粒径均匀、球形度高且粒径可控,主要粒径分布范围在约300~900μm;微球的流散性、反应热、燃烧火焰面积和压力输出性能随着粒径的增加,出现先增加后减弱的现象;Al/B/PTFE含能微球的最大反应热,最大火焰面积和最高峰值压力为1097.97 J/g,186.06 cm^(2)和213.3 kPa,分别是物理混合样品的1.77倍、5.16倍和1.37倍。

基于线激光三维视觉的燃料组件水下在位变形测量方法

为了解决燃料组件弯曲与扭曲变形水下在位测量难题,提出了基于线激光三维视觉的燃料组件水下在位变形测量方法。通过基于单层折射的水下相机标定、基于平面约束的光平面标定算法研究解决单个测量单元的标定问题;研究基于三维标定工装的10组测量单元在位快速标定方法,解决测量系统全局坐标统一问题,并利用激光跟踪仪测量标定工装的弯扭精度,进行测量精度对比试验验证。研究表明,研制的基于线激光三维视觉的燃料组件水下在位变形测量系统扭曲测量误差限为0.15°,弯曲测量误差限为0.3 mm,且整个测量时间约在1 s,测量效率和测量误差限优于现有的测量系统。

PtIr双功能催化剂膜电极制备及抗反极性能研究

燃料供应不足会导致质子交换膜燃料电池膜电极电压反转,造成阳极催化层中的碳载体发生严重腐蚀,进而给燃料电池带来不可逆的损伤。为了解决该问题,采用双功能PtIr合金作为阳极催化剂制备膜电极,并对其进行了电极极化性能、反极和交流阻抗等测试。结果表明,PtIr/C电极的峰值功率密度可达1.49 W/cm^(2),较Pt/C-IrO_(2)(50%)电极(1.46 W/cm^(2))提高2.1%。反极结果表明,PtIr/C电极抗反极时间725 s,较掺杂IrO_(2)的Pt/C电极反极性能略差,但在整个反极过程中PtIr/C电极呈现出更低的绝对反转电压,以及反极后保持更高的结构稳定性。反极后PtIr/C电极峰值功率密度降为1.18 W/cm^(2),衰减约20.80%,而Pt/C-IrO_(2)(50%)电极的峰值功率密度降至1.09 W/cm^(2),衰减约25.34%。PtIr/C电极相较掺杂IrO_(2)的Pt/C电极具有更佳的初始极化性能和优异的抗反极能力。该研究结果对质子交换膜燃料电池高性能长寿命膜电极催化层设计具有重要的意义。