A novel electrode architecture for passive direct methanol fuel cells

The supply of cathode reactants in a passive direct methanol fuel cell (DMFC) relies on naturally breathing oxygen from ambient air. The successful operation of this type of passive fuel cell requires the overall mass transfer resistance of oxygen through the layered fuel cell structure to be minimized such that the voltage loss due to the oxygen concentration polarization can be reduced. In this work, we propose a new membrane electrode assembly (MEA), in which the conventional cathode gas diffusion layer (GDL) is eliminated while utilizing a porous metal structure for transporting oxygen and collecting current. We show theoretically that the new MEA enables a higher mass transfer rate of oxygen and thus better performance. The measured polarization and constant-current discharging behavior showed that the passive DMFC with the new MEA yielded better and much more stable performance than did the cell having the conventional MEA. The EIS spectrum analysis further demonstrated that the improved performance with the new MEA was attributed to the enhanced transport of oxygen as a result of the reduced mass transfer resistance in the fuel cell system.     

A novel membrane electrode assembly for improving the efficiency of the unitized regenerative fuel cell

A novel membrane electrode assembly (MEA) for unitized regenerative fuel cell (URFC) has been developed. The MEA was fabricated to improve the efficiency of the URFC by a Nafion-pyrolyzed method. The polarization curves for fuel cell and water electrolysis modes of URFC operation both were investigated. The MEA improved water management and minimized mass transport limitations. The URFC using the novel MEA exhibited a high water electrolysis performance and a much higher fuel cell performance than that of the URFC using the conventional MEA. The efficiency of fuel cell and round-trip enhanced 13.5% and 10.8% at 700 mA/cm² with the novel MEA respectively.     

Investigation of a novel MEA for direct dimethyl ether fuel cell

In this study, we presented the novel membrane electrode assembly (MEA) for direct dimethyl ether fuel cell (DDFC). The anode diffusion layer of the MEA consisted of hydrophilic region and hydrophobic region (with a ratio of region areas of 1:1). The electrochemical impedance spectra analyses revealed that the mass transfer resistance of novel MEA was lower than that of completed hydrophilic or hydrophobic MEA. The performance of novel MEA for DDFC was enhanced due to the promotion the mass transport of DME fuel at 50 °C. The constant current operation curves showed that the performance decay ratio of the novel MEA was lower than that of conventional MEAs. It indicated that the novel MEA benefited the long-term operation of DDFC.     

自呼吸直接甲醇燃料电池膜电极的优化(英文)

针对空气自呼吸式直接甲醇燃料电池甲醇易渗透和阴极易水淹的特点,通过对催化层催化剂载量、阴极微孔层、阳极微孔层和膜等因素进行调控,对膜电极结构和性能的进行了优化.结果表明,使用高载量催化剂能有效降低甲醇渗透,但载量过高会引起传质阻力.当阳极微孔层PTFE含量为30%(bymass)时,可以有效促进CO2的均一析出,从而降低甲醇浓度梯度,减小甲醇透过.综合考虑甲醇渗透和阴极自返水,经优化后所得MEA在室温时自呼吸工作条件下,比功率密度达到33mW·cm-2,最优甲醇工作浓度为4mol·L-1.     

Fabrication of catalyst-coated membrane by modified decal transfer technique

A decal transfer method based on colloidal ink was developed for the fabrication of membrane electrode assemblies (MEAs). The new method requires fewer steps and utilizes H⁺ form of membrane compared to conventional decal method based on solution ink utilizing Na⁺ form of membrane. The structural features of the electrodes made by the modified decal method were investigated by scanning electron microscopy (SEM). The performance of fabricated electrode was evaluated for oxygen reduction reaction in a proton exchange membrane fuel cell. The results indicate that the modified decal method has the potential to be a facile method of fabricating electrodes with high performance.     

Air-breathing laminar flow-based microfluidic fuel cell

This communication reports the design and characterization of an air-breathing laminar flow-based microfluidic fuel cell (LFFC). The performance of previous LFFC designs was cathode-limited due to the poor solubility and slow transport of oxygen in aqueous media. Introduction of an air-breathing gas diffusion electrode as the cathode addresses these mass transfer issues. With this design change, the cathode is exposed to a higher oxygen concentration, and more importantly, the rate of oxygen replenishment in the depletion boundary layer on the cathode is greatly enhanced as a result of the 4 orders of magnitude higher diffusion coefficient of oxygen in air as opposed to that in aqueous media. The power densities of the present air-breathing LFFCs are 5 times higher (26 mW/cm2) than those for LFFCs operated using formic acid solutions as the fuel stream and an oxygen-saturated aqueous stream at the cathode ( approximately 5 mW/cm2). With the performance-limiting issues at the cathode mitigated, these air-breathing LFFCs can now be further developed to fully exploit their advantages of direct control over fuel crossover and the ability to individually tailor the chemical composition of the cathode and anode media to enhance electrode performance and fuel utilization, thus increasing the potential of laminar flow-based fuel cells.     

BaCe_(0.8)Y_(0.2)O_(3-α)的溶胶-凝胶法合成及其电性能

用溶胶-凝胶法合成了BaCe_(0.8)Y_(0.2)O_(3-α)固体电解质前驱体，并以低 于通常固相反应150～250 ℃的温度（即1400～1500 ℃）进行了烧结。以烧结体样 品为固体电解质、多孔性铂为电极，组成氢及氧浓差电池、氢-空气燃料电池，测 定了BaCe_(0.8)Y_(0.2)O_(3-α)烧结体的质子和氧离子迁移数以及燃料电池的性 能，并与高温固相反应法合成的样品进行了比较。结果表明，烧结温度能显著影响 溶胶-凝胶法合成样品的质子迁移数及燃料电池性能。烧结温度≥ 1450 ℃时，质 子迁移数近似为1，燃料电池性能亦较高，烧结温度< 1450 ℃时，质子迁移数< 1 ，燃料电池性能亦较低。在1400～1500 ℃烧结的样品中，1450 ℃下烧结的样品具 有最高的电池性能，接近于高温固相反应法合成的样品。     

Investigation of the role of the micro-porous layer in polymer electrolyte fuel cells with hydrogen deuterium contrast neutron radiography

In this study, the high resolution hydrogen-deuterium contrast radiography method was applied to elucidate the impact of the micro-porous layer (MPL) on water distribution in the porous fuel cell media. At the steady state, deuterium replaced hydrogen in the anode stream, and the large difference in neutron attenuation of the D(2)O produced at the cathode was used to track the produced water. It was found that the water content peaked in the cathode-side diffusion media (DM) for the cell without MPL, but with an MPL on the anode and cathode DM, the peak water amount was pushed toward the anode, resulting in a relatively flattened water profile through components and demonstrating a liquid barrier effect. Additionally, the dynamic water behavior in diffusion media was analyzed to understand the effect of a MPL and operating conditions. The water content in the DM changed with applied current, although there is a significant amount of residual liquid content that does not appear to be part of capillary channels. The effect of the MPL on irreducible saturation in DM and cell performance was also investigated.     

A new flow field design for polymer electrolyte-based fuel cells

We present a new flow field design, termed convection-enhanced serpentine flow field (CESFF), for polymer electrolyte-based fuel cells, which was obtained by re-patterning conventional single serpentine flow fields. We show theoretically that the CESFF induces larger pressure differences between adjacent flow channels over the entire electrode surface than does the conventional flow field, thereby enhancing in-plane forced flow through the electrode porous layer. This characteristic increases mass transport rates of reactants and products to and from the catalyst layer and reduces the amount of liquid water that is entrapped in the porous electrode, thereby minimizing electrode flooding over the entire electrode surface. We applied this new flow field to a single direct methanol fuel cell and demonstrated experimentally that the new flow field resulted in substantial improvements in both cell performance and operating stability as opposed to the conventional serpentine flow field design.     

Stable Thiophene-sulfur Covalent Organic Frameworks for Oxygen Reduction Reaction(ORR)

Exploring novel materials deriving from earth resources to substitute for platinum(Pt) electrocatalyst to promote oxygen reduction reaction(ORR) of fuel cell cathode is very important. Herein, we have exploited two crystallographic thiophene-sulfur covalent organic frameworks(COFs), termed JUC-607 and JUC-608, as electrocatalysts that exhibited good ORR performances. These thiophene-sulfur COFs exhibited high stability, and their functional groups acting as active centers in the ORR can be precisely determined. Notably, due to a larger aperture for mass transfer and electrons transport, JUC-608 displayed a growing electrochemical performance, leading to a better ORR activity. Thus, this study will provide a new strategy for designing heteroatom-based COF materials for high-performance electrochemical catalysis.     

质子交换膜燃料电池MnO2-Pt/C复合催化剂阴极的富氧作用

质子交换膜燃料电池空气电极阴极催化剂的富氧作用是提高其性能的关键.应用化学氧化法制备MnO2-Pt/C复合催化剂,研究MnO2的富氧作用,应用CV、CP、TEM等方法表征该催化剂,并组装成单电池测试其性能.     

低铂膜电极结构优化途径

膜电极是质子交换膜燃料电池的核心组件,长期以来,在衣院士的指导下,我国高度重视膜电极技术的开发. 目前,燃料电池的研发和产业化进入了一个新的时代,对膜电极提出来更高的要求,特别是在降低铂载量方面,提出了0.125 mg·W^-1的挑战性指标. 本文从活化极化、欧姆极化和传质极化三个方面分析了低铂载量情况下电池性能下降的原因,提出应重点关注催化剂在燃料电池工作区间（0.6 V ~ 0.8 V)的催化活性,并讨论了用电荷传输阻抗作为催化剂活性指示符的合理性. 从优化潜力来说,传质极化优化>活化极化优化>欧姆极化优化. 催化层结构优化是实现低铂目标的关键,重点是解决离子聚合物（ionomer）传递质子和阻碍气体的矛盾.     

Effects of ionomer coverage on agglomerate effectiveness in catalyst layers of polymer electrolyte fuel cells

A large proportion of voltage losses in polymer electrolyte fuel cells (PEFCs) originates in cathode catalyst layers. Catalyst utilization and performance of conventional catalyst layers depend largely on their ionomer content and distribution. The present study explores effects of agglomerate size and ionomer distribution on reaction rate distributions and effectiveness factor of Pt utilization. To study the oxygen reduction reaction, we have developed an agglomerate model, which consists of coupled relations for proton and oxygen transport, metal charging behavior, and interfacial charge transfer kinetics. The model is considered under steady state conditions. Results show that higher effectiveness factor is attained for agglomerates with smaller size and larger oxygen partial pressure on the surface. In addition, low to medium coverage of the ionomer skin layer is beneficial in view of high effectiveness factors due to the optimized interplay of oxygen and proton supply.     

Progress on the development of uniform distributed Pd electroless based catalysts on MEA for PEMFC application

Envisaging the scale-up production of fuel cell electrodes, it was established an electrode manufacturing method that enables a uniform distribution of Pd-based catalyst over the MEA, ensuring simultaneously a low catalyst loading. The new procedure relies on the direct immobilization of the catalyst on the gas diffusion substrate by the electroless deposition after substrate activation by the electrodeposition of metal nucleus of Pd using the galvanostatic mode. The effect of the novel method on the catalyst distribution uniformity, morphology, and electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M HClO₄ solution is compared to samples prepared by the conventional Sn/Pd sensitization—activation route. The performance of the PEMFC containing the same Pd load (0.09 mg cm^?2) reveals to be slightly higher on depositing the Pd nucleus by the galvanostatic electrodeposition than by the conventional sensitization/activation method. The new method opens up new approaches to extend the electroless deposition to the preparation of a wide range of alloy catalysts for the cathode and anode sides of PEMFCs.     

Supportless PdFe nanorods as highly active electrocatalyst for proton exchange membrane fuel cell

The PdFe nanorods (PdFe-NRs) with tunable length were synthesized by an organic phase reaction of [Pd(acac)₂] and thermal decomposition of [Fe(CO)₅] in a mixture of oleyamine and octadecene at 160 °C. They show a better proton exchange membrane fuel cell (PEMFC) performance than commercial Pt/C in working voltage region of 0.80–0.65 V, due to their high intrinsic activity to oxygen reduction reaction (ORR), reduced cell inner resistance, and improved mass transport.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-hydroxy-imidamide-functionalized graphene: an efficient metal-free electrocatalyst for oxygen reduction

Metal-free electrocatalysts for oxygen reduction reaction (ORR) are key to the development of efficient, durable, and low-cost alternatives to noble-metal-based electrocatalysts in fuel cell cathodes. In recent years, many efforts are directed to the metal-free catalyst based on heteroatom-doped graphene. In this work, we demonstrate that the graphene surface can be converted into the catalyst for the oxygen reduction by chemical functionalization. In this context, we first synthesized malononitrile-functionalized graphene oxide. Amidoximation of nitrile group and reduction in graphene oxide were then carried out by hydroxylamine in one step. The electrochemical behavior of functionalized graphene-modified electrode for the reduction in oxygen was studied. The results showed that the electrocatalyst fabricated by this method exhibited striking catalytic activities in alkaline solution. In alkaline solution, this catalyst showed a competitive activity to the commercial Pt catalyst via four-electron transfer pathway with better ORR selectivity and stability. In addition, this metal-free electrocatalyst exhibited tolerance to methanol crossover effect. Based on its outstanding performance, this functionalized graphene electrocatalyst showed the promising prospect of a metal-free catalyst for fuel cell with much lower cost than currently used Pt/C catalyst.     

Observation of water transport in the micro-porous layer of a polymer electrolyte fuel cell with a freezing method and cryo-scanning electron microscope

Micro-porous layers (MPLs) play an important role in the water management of polymer electrolyte fuel cells (PEFCs), however, the detailed mechanism of how the produced water is drained from these layers is not well understood. This paper observed the cross-sectional distribution of liquid water inside the cathode MPL to elucidate details of the phase state of the water transported through the MPL. The freezing method and cryo-scanning electron microscope (cryo-SEM) are used for the observations; the freezing method enables immobilization of the liquid water in the cell as ice forms by the freezing, and the cryo-SEM can visualize the water distribution in the vicinity of the MPL at high resolution without the ice melting. It was shown that no liquid water accumulates inside the MPL in operation at 35 °C, while the pores of the MPL are filled with liquid water under very low cell temperature operation, at 5 °C. These results indicate that the produced water passes through the MPL not as a liquid but in the vapor state in usual PEFC operation. Additionally, liquid water at the interface between the MPL and a catalyst layer (CL) was identified, and the effect of the interfacial contact on the water distribution was examined.     

Carbon nanotube film by filtration as cathode catalyst support for proton-exchange membrane fuel cell

A simple filtration method is developed to prepare a partially oriented superhydrophobic film of carbon nanotubes (CNTs) that have been catalyzed with uniform small Pt nanoparticles (2.8 nm) at high metal loading (30 wt %). A proton-exchange membrane fuel cell with the oriented CNT film as the cathode achieves higher single-cell performance than those with carbon black and a disordered CNT-film-based cathode probably because of the enhanced electrocatalytic activity of Pt/CNT and improved mass transport within the oriented film.     

铂纳米棒有序阵列催化电极在被动式直接甲醇燃料电池中的应用

直接甲醇燃料电池(DMFC)具有能量密度高、无需充电、液体燃料添加便捷及环境友好等优点,是新一代便携式移动电源研究热点. DMFC规模应用的主要技术挑战是如何进一步提高电池性能、显著降低成本和可靠延长寿命.催化电极作为 DMFC发电核心和成本的集中体现,其电催化活性和贵金属用量直接影响 DMFC的性能和成本,开发高性能、低成本的催化电极对推进 DMFC实用化进程具有重要意义.特别是在被动式 DMFC中,阴极催化电极不仅需要提高电催化活性和大幅降低贵金属用量,而且还面临内部严重的“水淹”和氧传质受限等问题.近年来,随着纳米技术发展,有序纳米结构已逐渐应用于 DMFC催化电极的构筑中,电池性能得到显著提高.然而,目前的研究主要集中在膜电极纳米有序微孔层、纳米有序改性膜和纳米有序阳极催化电极及其阳极贵金属载量降低等方面,关于阴极催化电极在有序纳米结构以及载量降低等方面的研究相对较少.
　　本文采用模板法直接在微孔层上电沉积定向生长排列有序、直径可控的铂纳米棒阵列,并作为阴极催化电极应用于被动式 DMFC. X射线衍射和透射电镜结果表明,该铂纳米棒结构稳定,表面含有丰富的纳米晶须结构,有利于催化电极比表面积增加和电催化活性提高.不同催化电极上氧还原的极化曲线表明电极性能依下列次序变化：直径为200 nm铂纳米棒阵列电极>100 nm铂纳米棒阵列电极>商业化铂黑催化电极.电池性能表征表明,长度为1–3μm、直径分别为200和100 nm、载量为1.0 mg/cm2的铂纳米棒阵列作为阴极催化电极的 DMFC最大功率密度分别为17.3和12.0 mW/cm2.通过催化电极电化学活性面积和阻抗测试,分析其性能提高的原因可归结于有序排列的铂纳米棒阵列结构提高了电化学活性面积、增强了氧还原电催化活性并促进了阴极氧的传质.     

操作条件对DMFC阴极电化学阻抗谱参数的影响

通过降低阴极催化剂载量强化了阴极氧还原反应的电化学极化, 测量了不同操作条件下直接甲醇燃料电池(DMFC)的极化曲线和交流阻抗谱,并提出了改进的等效电路模型LR(CR)(QR(LR))用以分析温度、空气流量和甲醇流量对DMFC阴极电化学反应和传质极化过程的影响. 研究结果表明, 提高工作温度会导致更多的甲醇渗透到阴极, 加大阴极氧气还原反应的电荷转移电阻; 只有采用大的空气流量,才会有效地防止水淹, 加大氧气向催化剂层的传质, 促进阴极反应的进行; 适当提高甲醇的流量可以促进阳极和阴极电化学反应的进行, 但是过高的甲醇流速可能会降低电极表面的温度, 加剧甲醇的渗透.