Nitrogen-doped ordered porous carbon catalyst for oxygen reduction reaction in proton exchange membrane fuel cells

Three different N-doped ordered porous carbons (CNx) were produced by a nanocasting process using polyaniline as the carbon and nitrogen precursor. A pyrolysis treatment of iron chloride-impregnated CNx under nitrogen is used in the preparation of the carbon composite catalysts, and this is followed by posttreatments and optimization of the iron loading and the pore size. Exploration of the catalytic activity of the CNx products for catalyzing the oxygen reduction reaction (ORR) using rotating disk electrode measurements and single-cell tests shows that the onset potential for ORR of the most effective catalyst in 0.5 M H₂SO₄ is as high as 0.9 V vs. the normal hydrogen electrode. A proton exchange membrane fuel cell constructed with the catalyst exhibits a current density as high as 0.52 A cm^?2 at 0.6 V with 2 atm back pressure using a cathode catalyst loading of 6 mg cm^?2. The average pore diameters of synthesized CNx-12, CNx-15, and CNx-16 are 0.7, 4.3, and 14 nm, respectively. It is observed that the pore size and specific surface area are an important factor for increased catalyst activity. The pore size of the most effective catalysts is found to be 4.3 nm.     

Pd-Co-Mo electrocatalyst for the oxygen reduction reaction in proton exchange membrane fuel cells

The catalytic activity of carbon supported Pd-Co-Mo for the oxygen reduction reaction (ORR) in a single cell proton exchange membrane fuel cell (PEMFC) has been investigated at 60 degrees C and compared with data from commercial Pt catalyst and our previously reported Pd-Co-Au and Pd-Ti catalysts. The Pd-Co-Mo catalyst with a Pd:Co:Mo atomic ratio of 70:20:10 exhibits slightly higher catalytic activity like the Pd-Co-Au catalyst than the commercial Pt catalyst, but with excellent chemical stability unlike the Pd-Co-Au catalyst. The Pd-Co-Mo catalyst also exhibits better tolerance to methanol poisoning than Pt. Investigation of the catalytic activity of the Pd-Co-Mo system with varying composition and heat treatment temperature reveals that a Pd:Co:Mo atomic ratio of 70:20:10 with a heat treatment temperature of 500 degrees C exhibits the highest catalytic activity. Although the degree of alloying increases with increasing temperature from 500 to 900 degrees C as indicated by the X-ray diffraction data, the catalytic activity decreases due to an increase in particle size and a decrease in surface area.     

快速微波法制备掺氮石墨烯用于碱性氧还原电催化剂

采用微波法在氨气气氛下快速加热石墨烯（G）制备了含氮量在4.05 wt%-5.47 wt%的掺氮石墨烯（NG）. 将上述的掺氮石墨烯用作碱性电解质条件下的氧还原电催化剂,起始还原电势为0.17 V（vs SHE）,接近商用碳载铂催化剂的0.21 V（vs SHE）. 采用透射电子显微镜、拉曼光谱和X射线光电子能谱研究了掺氮石墨烯的形貌、结构和掺杂氮原子的键合方式. 结果发现,掺氮石墨烯的氧还原起始电位随着石墨氮原子含量的提高而上升,说明石墨类型的氮含量是影响其氧还原催化活性的关键因素. 实验结果表明,微波法快速制备的掺氮石墨烯在碱性条件下表现出较高的氧还原催化活性,具有作为碱性燃料电池阴极催化剂的潜力.     

Enhanced electrocatalytic performance of functionalized carbon nanotube electrodes for oxygen reduction in proton exchange membrane fuel cells

Although nitrogen doped CNTs (N-CNTs) are considered as a promising alternative to platinized carbon for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs), the origin of the enhanced ORR activity with N-CNTs is not clear at present. Among several plausible reasons, the exposure of edge plane and creation of impurity band/surface states near the Fermi level are considered as major causes behind the catalytic activity. However, CNTs without nitrogen doping are not known to catalyze the ORR. In this work, we study the ORR activity of functionalized carbon nanotubes with different functional groups, such as sulfonic acid and phosphonic acid, in order to understand the role of surface functionalities in catalyzing the reaction. Functionalized CNTs show significantly enhanced activity towards the ORR, while CNTs without such surface functional groups do not reveal any such special ORR activity. Linear sweep voltammetry experiments with different rotation rates show diffusion controlled limiting current values for functionalized CNTs, and the 'n' values derived from Koutecky-Levich plots are 3.3 and 1.7 for S-MWCNTs and P-MWCNTs, respectively. This work demonstrates the ORR activity of functionalized MWCNTs, which opens up new strategies for electrocatalyst design in PEMFCs.     

Contribution of nanoclays to the barrier properties of a model proton exchange membrane for fuel cell application

Direct methanol fuel cells (DMFCs) that use a proton exchange membrane (PEM) as electrolyte, is a promising alternative source of energy for the future. However, methanol crossover from the anodic side to the cathodic one is a major problem in DMFC. Proper dispersion of layered silicates within the fuel cell membrane has been proposed as a strategy for improving the barrier properties of the membrane. The validity of this approach has been tested in case of a model membrane consisting of phosphotungstic acid doped poly(vinyl alcohol). A solvent casting technique has been used, which allows the nanofiller to be delaminated by an ultrasonic pre-treatment, as confirmed by TEM and XRD analysis. The layered silicates have a favourable impact on the methanol permeability, whose the decrease overcompensates some loss in ionic conductivity.     

Perfluorosulfonic acid-functionalized Pt/graphene as a high-performance oxygen reduction reaction catalyst for proton exchange membrane fuel cells

Platinum nanoparticles (Pt NPs) on carbon black (CB) have been used as catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells for a while. However, this catalyst has suffered from aggregation and dissolution of Pt NPs as well as CB dissolution. In this study, we resolve those issues by developing perfluorosulfonic acid (PFSA)-functionalized Pt/graphene as a high-performance ORR catalyst. The noncovalently bonded PFSA remarkably decreases the dissolution and aggregation of Pt NPs. Moreover, unlike typical NP functionalization with other capping agents, PFSA is a proton conductor and thus efficiently develops a triple-phase boundary. These advantageous features are reflected in the improved cell performance in electrochemical active surface area, catalytic activity, and long-term durability, compared to those of the commercial Pt/C catalysts and graphene-based catalysts with no such treatment.     

Current challenges related to the deployment of shape-controlled Pt alloy oxygen reduction reaction nanocatalysts into low Pt-loaded cathode layers of proton exchange membrane fuel cells

The reduction of the amount of platinum used in proton exchange membrane fuel cell cathodes at constant power density helps lower the cell stack cost of fuel cell electric vehicles. Recent screening studies using the thin film rotating disk electrode technique have identified an ever-growing number of Pt-based nanocatalysts with oxygen reduction reaction Pt-mass activities that allow for a substantial projected decrease in the geometric platinum loading at the cathode layer. However, the step from a rotating disk electrode test to a membrane electrode assembly test has proved a formidable task. The deployment of advanced, often shape-controlled dealloyed Pt alloy nanocatalysts in actual cathode layers of proton exchange membrane fuel cells has remained extremely challenging with respect to their actual catalytic activity under hydrogen/oxygen flow, their hydrogen/air performance at high current densities, and their morphological stability under prolonged fuel cell operations. In this review, we discuss some of these challenges, yet also propose possible solutions to understand the challenges and to eventually unfold the full potential of advanced Pt-based alloy oxygen reduction reaction catalysts in fuel cell electrode layers.     

Preparation and characterization of fluorine-containing polybenzimidazole/imidazole hybrid membranes for proton exchange membrane fuel cells

Polybenzimidazole (PBI)/imidazole (Im) hybrid membranes were prepared from an organosoluble, fluorine-containing PBI with Im. The thermal decomposition of the PBI/Im hybrid membranes occurred at about 160 °C. The conductivities of the acid doped PBI/Im hybrid membranes increased with both the temperature and the Im content. The conductivity of acid doped PBI-40Im (molar ratio of Im/PBI = 40) reached 3.1 × 10⁻³ (S/cm) at 160 °C. The proton conductivities of PBI/Im hybrid membranes were over 2 × 10⁻³ (S/cm) at 90 °C and 90% relative humidity. The addition of Im could reduce the mechanical properties and methanol barrier ability of the PBI membranes.     

Doped graphene/carbon black hybrid catalyst giving enhanced oxygen reduction reaction activity with high resistance to corrosion in proton exchange membrane fuel cells

Nitrogen doping of the carbon is an important method to improve the performance and durability of catalysts for proton exchange membrane fuel cells by platinum–nitrogen and carbon–nitrogen bonds. This study shows that p-phenyl groups and graphitic N acting bridges linking platinum and the graphene/carbon black(the ratio graphene/carbon black = 2/3) hybrid support materials achieved the average size of platinum nanoparticles with(4.88 ± 1.79) nm. It improved the performance of the lower-temperatu...     

Pd-Ti and Pd-Co-Au electrocatalysts as a replacement for platinum for oxygen reduction in proton exchange membrane fuel cells

Fuel cells are appealing for a variety of energy needs, but the high materials and manufacturing costs have hampered their commercialization. The limited availability and the high cost of the currently used platinum catalysts, for example, pose a serious problem in their practical application. We report here non-platinum electrocatalyst systems, such as Pd-Co-Au and Pd-Ti, that are proposed from simple thermodynamic guidelines and selected by a rapid screening technique, which show electrochemical performance in proton exchange membrane fuel cells (PEMFC) similar to that found with commercial platinum catalysts. This finding opens up a new avenue to develop potentially less expensive electrocatalysts.     

Synthesis of boron and nitrogen co-doped graphene nano-platelets using a two-step solution process and catalytic properties for oxygen reduction reaction

Chemically modified graphenes (CMGs) show great promise for various applications owing to the feasibility of their low-cost mass production and good solution processability. Recently, hetero-atom-doped CMGs have been suggested as good candidate materials for electrochemical catalysts in oxygen reduction reaction (ORR). In this study, we synthesized B, N co-doped graphene nano-platelets (BN-rG-O) using a two-step solution process with sequential reaction of graphene oxide with borane tetrahydrofuran and hydrazine monohydrate. In the ORR measured in a basic medium (0.1 M KOH), BN-rG-O exhibits an onset potential of 0.81 V (vs. reversible hydrogen electrode), follows near four electron pathway, and shows excellent stability against methanol poisoning and during durability tests.     

气体扩散层中聚四氟乙烯的分布对质子交换膜燃料电池水淹的影响

通过在不同真空度下进行碳纸的聚四氟乙烯（PTFE）浸渍处理,考察了PTFE在碳纸中的分布对燃料电池水淹情况的影响. 碳纸PTFE浸渍过程中,抽真空作用可以将碳纸微孔中存留的空气移除,使PTFE更均匀地扩散到内部微孔中. 碳纸的断面电镜照片显示真空浸渍可以改善PTFE的分布. 在总浸渍量相同时,由于真空浸渍使更多的PTFE进入到碳纸内部微孔,故其表面的PTFE比例减少. 实验进一步考察了碳纸中亲水孔和憎水孔的分布,结果表明真空浸渍处理的碳纸具有更高比例的憎水孔. 将不同处理方法的碳纸制备成膜电极,通过全尺寸电池考察其性能,结果表明PTFE的均匀分布可以改善电池性能,并且电化学阻抗分析表明其有利于改善水淹问题.     

Effect of load-cycling amplitude on performance degradation for proton exchange membrane fuel cell

Durability is one of the critical issues to restrict the commercialization of proton exchange membrane fuel cells (PEMFCs) for the vehicle application. The practical dynamic operation significantly affects the PEMFCs durability by corroding its key components. In this work, the degradation behavior of a single PEMFC has been investigated under a simulated automotive load-cycling operation, with the aim of revealing the effect of load amplitude (0.8 and 0.2 A/cm² amplitude for the current density range of 0.1−0.9 and 0.1−0.3 A/cm², respectively) on its performance degradation. A more severe degradation on the fuel cell performance is observed under a higher load amplitude of 0.8 A/cm² cycling operation, with ∼10.5% decrease of cell voltage at a current density of 1.0 A/cm². The larger loss of fuel cell performance under the higher load amplitude test is mainly due to the frequent fluctuation of a wider potential cycling. Physicochemical characterizations analyses indicate that the Pt nanoparticles in cathodic catalyst layer grow faster with a higher increase extent of particle size under this circumstance because of their repeated oxidation/reduction and subsequent dissolution/agglomeration process, resulting in the degradation of platinum catalyst and thus the cell performance. Additionally, the detected microstructure change of the cathodic catalyst layer also contributes to the performance failure that causes a distinct increase in mass transfer resistance.     

Carbon-supported ultrafine Pt nanoparticles modified with trace amounts of cobalt as enhanced oxygen reduction reaction catalysts for proton exchange membrane fuel cells

To accelerate the kinetics of the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells, ultrafine Pt nanoparticles modified with trace amounts of cobalt were fabricated and decorated on carbon black through a strategy involving modified glycol reduction and chemical etching. The obtained Pt₃₆Co/C catalyst exhibits a much larger electrochemical surface area (ECSA) and an improved ORR electrocatalytic activity compared to commercial Pt/C. Moreover, an electrode prepared with Pt₃₆Co/C was further evaluated under H₂-air single cell test conditions, and exhibited a maximum specific power density of 10.27 W mg_Pt^?1, which is 1.61 times higher than that of a conventional Pt/C electrode and also competitive with most state-of-the-art Pt-based architectures. In addition, the changes in ECSA, power density, and reacting resistance during the accelerated degradation process further demonstrate the enhanced durability of the Pt₃₆Co/C electrode. The superior performance observed in this work can be attributed to the synergy between the ultrasmall size and homogeneous distribution of catalyst nanoparticles, bimetallic ligand and electronic effects, and the dissolution of unstable Co with the rearrangement of surface structure brought about by acid etching. Furthermore, the accessible raw materials and simplified operating procedures involved in the fabrication process would result in great cost-effectiveness for practical applications of PEMFCs.     

Reinforced and self-humidifying composite membrane for fuel cell applications

A novel preparation method for a composite proton exchange membrane with reinforced strength and self-humidifying property was developed. Using self-assembly method, highly dispersed poly(diallyldimethylammonium chloride) (PDDA) stabilized Pt nanoparticles were mounted onto the pores of poly(tetrafluoroethylene) (PTFE) porous film to serve the self-humidifying purpose. With Pt nanoparticles fixed on the PTFE pores, the potential problem of any short circuit because of the use of metal nanoparticles can be prevented. Pt-PDDA/PTFE substrate in the composite membrane can enhance the mechanical strength of the membrane and distribute self-humidifying layer adjacent to the anode side. Compared with the cells fabricated with conventional Nafion^® and PTFE/Nafion membranes, the performance of the cells with this composite membrane is dramatically improved under dry conditions. Electrochemical impedance spectroscopy technique revealed that these self-humidifying composite membranes could minimize membrane conductivity loss under dry conditions.     

ZnCl2辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性

Fe、N掺杂的碳材料(FeNC)是最有希望取代贵金属用作氧还原反应的催化剂之一.然而,传统FeNC材料制备过程中所采用的高温碳化-蚀刻步骤会造成相邻Fe原子随温度升高而逐渐团聚,形成较大尺寸金属铁单质、铁氧化物或碳化物的聚集颗粒,并在后续酸刻蚀处理中被移出,铁元素损失严重,无法形成有效活性位点.同时高温下含N小分子物质也容易分解并从产物中逸出,导致N元素掺杂量较低.直接焙烧还加重了碳的团聚,造成材料内部孔道有限,比表面积低,活性位难以暴露于三相界面.因此,焙烧处理过程中如何形成Fe、N元素的高含量、均匀分散掺杂,同时构建大量内部联通孔道,是形成高活性Fe NC催化剂的关键.本文采用ZnCl2辅助焙烧方法制备出具有高活性位点密度和大材料孔隙率的Fe NC催化剂;通过TEM、N2吸附和XPS等一系列物理手段对所制备样品进行了形貌、结构及组成表征,提出了ZnCl2辅助催化剂合成机理;结合CV和LSV等电化学测试结果详细探讨了ZnCl2辅助方法对催化剂结构和催化性能的影响.普通共价盐ZnCl2在283–732°C的较宽温度范围内呈现熔融态,同卟啉铁(Fe Pc)碳化温度区间恰好匹配,可以辅助Fe NC催化剂进行元素掺杂和多级孔结构的构建.首先,在熔融状态下,过量的ZnCl2形成分支结构,阻止相邻Fe物种直接接触和聚集,有利于形成高度分散的FeNx活性位点.其次,熔融的ZnCl2像盖子一样包封住催化剂前驱体,避免了挥发性含N小分子的快速逸出,使得N原子在高温下有可能重新在碳骨架中形成掺杂,有助于在材料中保留更高比例的活性N物质.在ZnCl2的辅助下碳化Fe Pc得到的Sphere-FeNC样品具有高达4.37%的总N含量,并且Fe-Nx含量也高达0.71%,分别是不使用ZnCl2制备的对比催化剂FeNC-none的3.2和13倍.同时, ZnCl2辅助合成方法将Fe NC材料的比表面积增加4.5倍,总孔体积增加7倍.三电极氧还原反应性能测试表明, Sphere-Fe NC在碱性和酸性介质的初始电位分别为1.080和1.015 V(vsRHE),半波电位分别为0.906和0.799 V (vs RHE),活性优异.以Sphere-FeNC为阴极催化剂组装的单电池功率达到0.72 W mg–1,高于已报道的Fe NC和Pt/C催化剂.因此, ZnCl2辅助焙烧碳化的方法可以作为一种普适手段用于构建具有高密度活性元素掺杂和大量微孔介孔分布的碳基催化材料,并应用于各类催化反应.     

Sulfur doped reduced graphene oxide as metal-free catalyst for the oxygen reduction reaction in anion and proton exchange fuel cells

Sulfur doped reduced graphene oxide (S-rGO) is investigated for catalytic activity towards the oxygen reduction reaction (ORR) in acidic and alkaline electrolytes. X-ray photoelectron spectroscopy shows that sulfur in S-rGO is predominantly integrated as thiophene motifs within graphene sheets. The overall sulfur content is determined to be approximately 2.2 at.% (elemental analysis). The catalytic activity of S-rGO towards the ORR is investigated by both rotating disc electrode (RDE) and polymer electrolyte fuel cell (PEFC) measurements. RDE measurements reveal onset potentials of 0.3 V and 0.74 V (vs. RHE) in acidic and alkaline electrolyte, respectively. In a solid electrolyte fuel cell with S-rGO as cathode material, this is reflected in an open circuit voltage of 0.37 V and 0.78 V and a maximum power density of 1.19 mW/cm² and 2.38 mW/cm² in acidic and alkaline polymer electrolyte, respectively. This is the first report investigating the catalytic activity of a sulfur doped carbon material in both acidic and alkaline liquid electrolyte, as well as in both proton and anion exchange polymer electrolyte fuel cells.     

Materials research and development focus areas for low cost automotive proton-exchange membrane fuel cells

Research and development of fuel cell materials often focuses on designing and discovering materials which will reduce the cost or improve the durability of an individual subcomponent. Examples of recent focus areas include non-Pt group metal catalysts, noncarbon catalyst supports, and nonfluorinated membranes. These studies rarely look at the entire system to comprehend the impact of these materials on the cost of ownership to the customer, including vehicle and fuel costs. This perspective takes a holistic look at the impact of functional materials on automotive fuel-cell systems and provides direction on which material properties will provide the greatest benefit. It also provides guidance on which material classes are the most likely to enable the achievement of systems which will result in the successful commercialization of light-duty fuel-cell vehicles.     

基于质子交换膜燃料电池的热电联产系统的研究进展

基于质子交换膜燃料电池的热电联产系统利用电池发电时产生的余热供热,提高了能源利用率,实现了热电供能的可持续发展。本文介绍了基于质子交换膜燃料电池的热电联产系统工作原理,概述了各子系统的组成及功能,重点围绕建模方法、操作模式、运行策略、评价方法及系统优化等方向综述了当前研究的进展情况,指明了后续研究可从多尺度综合性建模、完善配置细节及增加集成选项、预测能源需求及运行智能化、多维度系统评价以及节能降耗等方面进行。     

Current understanding of catalyst/ionomer interfacial structure and phenomena affecting the oxygen reduction reaction in cathode catalyst layers of proton exchange membrane fuel cells

To improve the performance of membrane electrode assemblies used in proton exchange membrane fuel cells, a better understanding is necessitated regarding the nano/microstructure of the catalyst layer and the physicochemical phenomena responsible for the oxygen reduction reaction (ORR) occurring on this layer. In particular, it is very important to understand catalyst/ionomer interfaces in the cathode catalyst layer to apply the advanced ORR catalysts to the cathode catalyst layer in membrane electrode assemblies, which have solid-phase electrolytes; these catalysts are primarily developed under liquid electrolyte conditions. A closer observation of the catalyst/ionomer interfacial structure shows that all the transport processes required for ORR are controlled by the ionomer thin film covering the catalyst. Therefore, this review addresses this issue and introduces recent studies on catalyst/ionomer interfaces. We discuss the current understanding of the structure of the catalyst/ionomer interface, which depends on the surface characteristics of the catalyst and the ionomer, as well as transport of water, ions, and gas; these factors are in turn dependent on the structure of the interface. In addition, we introduce research efforts for improving the properties of catalyst inks, which form the basis for controlling the catalyst/ionomer interfacial structure. Based on the findings of these studies, we propose further opportunities and challenges in the study of catalyst/ionomer interfaces.