质子交换膜燃料电池研究进展

由于质子交换膜燃料电池（PEMFC）具有能量转化效率高、寿命长、比功率和比能量高、以及对环境友好等优点,近年来得到迅速发展.笔者综述了PEMFC的特点,分析了PEMFC在国内外的最新研究进展,介绍了PEMFC的应用前景,并指出了PEMFC研究当前需要解决的技术问题及其发展趋势.     

Cobalt based non-precious electrocatalysts for oxygen reduction reaction in proton exchange membrane fuel cells

Cobalt based non-precious metal catalysts were synthesized using chelation of cobalt (II) by imidazole followed by heat-treatment process and investigated as a promising alternative of platinum (Pt)-based electrocatalysts in proton exchange membrane fuel cells (PEMFCs). Transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements were used to characterize the synthesized CoN_x/C catalysts. The activities of the catalysts towards oxygen reduction reaction (ORR) were investigated by electrochemical measurements and single cell tests, respectively. Optimization of the heat-treatment temperature was also explored. The results indicate that the as-prepared catalyst presents a promising electrochemical activity for the ORR with an approximate four-electron process. The maximum power density obtained in a H₂/O₂ PEMFC is as high as 200 mW cm⁻² with CoN_x/C loading of 2.0 mg cm⁻².     

Preparation of highly dispersed PEM fuel cell catalysts using electroless deposition methods

A methodology for the electroless deposition (ED) of PtCl₆²⁻ using dimethylamine borane (DMAB) on a Rh-seeded carbon support has been developed for electrochemical and fuel cell applications. This procedure required seeding the carbon with a Rh-precursor catalyst via wet impregnation prior to the exposure of an aqueous ED bath containing PtCl₆²⁻, DMAB, and sodium citrate (complexing/stabilizing agent). Kinetic parameters that affect the extent and rate of PtCl₆²⁻ deposition include concentrations of PtCl₆²⁻, DMAB, and sodium citrate as well as pH and concentrations of Rh seed sites. A linear relationship between rate and extent of PtCl₆²⁻ deposition and DMAB and Rh concentrations was found while the citrate concentration had little effect on rate and a modest effect on extent. Lastly, extent of PtCl₆²⁻ deposition showed a maximum with respect to pH. Characterization of the Rh-seeded, carbon support by transmission electron microscopy (TEM) shows that the Rh particle diameters remain constant at 33–43 Å as the Rh weight loading increases from 0.4% to 2.2% to 4.4%. Further, after deposition of similar loadings of Pt, TEM analysis shows Pt particle diameters decrease with increasing Rh loading, since equal amounts of Pt were deposited on greater numbers of Rh seed particles. This pattern suggests a shell-core geometry, where Pt is deposited more or less uniformly around a Rh core.     

Synthesis of Pt nanocatalyst with micelle-encapsulated multi-walled carbon nanotubes as support for proton exchange membrane fuel cells

Micelle-encapsulated multi-walled carbon nanotubes (MWCNTs) with sodium dodecyl sulfate (SDS) were used as catalyst support to deposit platinum nanoparticles. High resolution transmission electron microscopy (HRTEM) images reveal the crystalline nature of Pt nanoparticles with a diameter of ∼4 nm on the surface of MWCNTs. A single proton exchange membrane fuel cell (PEMFC) with total catalyst loading of 0.2 mg Pt cm⁻² (anode 0.1 and cathode 0.1 mg Pt cm⁻², respectively) has been evaluated at 80 °C with H₂ and O₂ gases using Nafion-212 electrolyte. Pt/MWCNTs synthesized by using modified SDS-MWCNTs with high temperature treatment (250 °C) showed a peak power density of 950 mW cm⁻². Accelerated durability evaluation was carried out by conducting 1500 potential cycles between 0.1 and 1.2 V with 50 mV s⁻¹ scan rate, H₂/N₂ at 80 °C. The membrane electrode assembly (MEA) with Pt/MWCNTs showed superior performance stability with a power density degradation of only ∼30% compared to commercial Pt/C (70%) after potential cycles.     

Basic examination of membrane electrode assembly of proton exchange membrane fuel cell considering heat deterioration

The purpose of this research is to develop a standard preparation method for membrane electrode assemblies (MEAs). Therefore, the preparation method for multilayered MEAs with gas diffusion layers (GDLs) and the degree to which polymer membranes deteriorate by heating were studied. As a result, improvement of power density by making multi catalyst layers provides a solution to some problems found in thin polymer membranes. In addition, it was found that improving the diffusion of gas through two-layer GDLs in cathode (duct side: carbon paper, catalyst layer side: carbon cross) results in a cross leak reduction. Moreover, a making condition of MEAs was optimized by varying the temperatures used for the multi catalyst layers and two-layer GDLs. The analysis of heat deterioration of the Nafion membrane using X-ray photoelectron spectroscopy (XPS) indicates that the optimal hot press temperature is 130 °C.     

质子交换膜燃料电池研究及应用现状

介绍了国内外质子交换膜燃料电池(PEMFC)研究的整体现状及水平,分别讨论了PEMFC的3个关键部件:质子交换膜的材料要求,电化学反应催化剂的特点,膜电极的组成、制备工艺和最新进展,重点讨论了全氟磺酸型质子交换膜的类型、优缺点和当前的研究方向。在此基础上,追述了近年来国内外以PEMFC作为电动汽车动力源的实际应用情况,并指出应用PEMFC存在的问题。可以看到,PEMFC具有广阔的应用前景,将会在电动汽车方面得到最早的商业化应用。     

Development of a residence time distribution method for proton exchange membrane fuel cell evaluation

New in situ and minimally invasive methods are needed to quantify the presence of liquid water and ice within operating proton exchange membrane fuel cells. A volume sensitive residence time distribution technique was developed based on CO₂ tracer and infrared detection. The method, components and operation are detailed (tracer injection and detection, data scaling, calibration, and pressure correction). The measurement system was characterized by an electronic signal processing response time of 43 ms, accuracy and repeatability better than 0.5-5% error in transit time measurement and sufficient sensitivity to detect less than 10% changes in flow field channel and gas diffusion electrode void volumes. Results obtained with a simplified model fuel cell (single flow field channel, absence and presence of a gas diffusion layer) revealed the presence of two time resolved mechanistic steps for negative tracer step cases (convective tracer removal from flow field channel, diffusive tracer removal from gas diffusion layer). A one-dimensional model was derived using convective diffusion in flow field channels and cross-flow tracer exchange proportional to the concentration difference between flow field channel and gas diffusion electrode. Numerical computations showed good agreement with the model fuel cell experimental results.     

质子交换膜燃料电池膜中气态水管理模型

分析质子交换膜燃料电池的膜水含量与运行参数的关系,从工程方法的角度建立水传输模型.模型分析得到,要提高膜的水合程度,需要通过增湿反应气体.过高的增湿反应气体又会引起阴极扩散层水的泛滥,需通过调节反应气体流量来缓解水的泛滥.为保证膜的高水合程度和低的阴极扩散层水的泛滥,建立了膜水含量的神经网络控制模型,为电池水管理奠定了基础.     

Effect of gas diffusion layer compression on the performance in a proton exchange membrane fuel cell

This study investigates the gas permeability, bulk density, thickness and conductivity of two types of gas diffusion layer (OC14, NC14) as a function of the compressed thickness. The compression of a gas diffusion layer reduces gas permeability and contact resistance. The performance is measured using a single proton exchange membrane fuel cell (PEMFC) with an active area of 25 cm². The results provide an optimum value of compression ratio that maximizes the cell performance. For OC14 the optimum compression ratio is about 64%, whereas for NC14 it is 59%. The best performances are 375 mA/cm² and 296 mA/cm² at 0.7 V, respectively. These results concerning the balance between compression and performance provide vital information for the fabrication of stacks and support for industrial applications.     

中压氢-氧质子交换膜燃料电池的运行特性

通过设计阴极流道宽度为1 mm与2 mm的单电池,研究了不同温度下闭口中压氢-氧质子交换膜燃料电池的运行特性。结果表明：(1)2 mm的电池有较好的闭口稳定运行特性,在800 mA·cm-2下,1 mm的电池闭口运行时,大约经过3 min,电压从0.7 V下降到0.5V,而2 mm的流场结构能实现电池53 min的运行;(2)电池性能随温度的升高而下降,相对于65℃运行,温度为80℃时,1mm的电池闭口运行时,大约经过1.7 min,电压从0.69 V下降到0.5 V,此时为维持电池的高性能运行,氧气侧所需的排放时间越短;(3)电池的内阻随温度的升高而增大,高温时增幅较小。     

氧化石墨烯在燃料电池质子交换膜中的应用

保护环境，开发环保型能源，对人类和社会具有重要意义。质子交换膜燃料电池由于其能量转化率高，可实现零排放，近年来引起了电池领域研究者们的兴趣。氧化石墨烯（GO）由于存在活性氧官能团，可以和离子型聚合物进行复合以制备复合质子交换膜。氧化石墨烯类的复合质子交换膜应用于燃料电池时可以提高膜在高温低湿度条件下的质子传导率，降低甲醇渗透率，提高电池的功率密度。本文首先介绍了氧化石墨烯的制备方法，然后从不同的离子型聚合物基质复合质子交换膜的类别出发，详细介绍了氧化石墨烯在Nafion、聚醚醚酮、聚苯并咪唑和壳聚糖等不同种类的离子型聚合物中的应用现状及作用机理，同时对其在质子交换膜的应用方面存在的问题及应用前景做了评论和展望。     

In situ grown carbon nanotubes on carbon paper as integrated gas diffusion and catalyst layer for proton exchange membrane fuel cells

In situ grown carbon nanotubes (CNTs) on carbon paper as an integrated gas diffusion layer (GDL) and catalyst layer (CL) were developed for proton exchange membrane fuel cell (PEMFC) applications. The effect of their structure and morphology on cell performance was investigated under real PEMFC conditions. The in situ grown CNT layers on carbon paper showed a tunable structure under different growth processes. Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) demonstrated that the CNT layers are able to provide extremely high surface area and porosity to serve as both the GDL and the CL simultaneously. This in situ grown CNT support layer can provide enhanced Pt utilization compared with the carbon black and free-standing CNT support layers. An optimum maximum power density of 670 mW cm⁻² was obtained from the CNT layer grown under 20 cm³ min⁻¹ C₂H₄ flow with 0.04 mg cm⁻² Pt sputter-deposited at the cathode. Furthermore, electrochemical impedance spectroscopy (EIS) results confirmed that the in situ grown CNT layer can provide both enhanced charge transfer and mass transport properties for the Pt/CNT-based electrode as an integrated GDL and CL, in comparison with previously reported Pt/CNT-based electrodes with a VXC72R-based GDL and a Pt/CNT-based CL. Therefore, this in situ grown CNT layer shows a great potential for the improvement of electrode structure and configuration for PEMFC applications.     

Medium-chain-length poly-3-hydroxyalkanoates-carbon nanotubes composite as proton exchange membrane in microbial fuel cell

Medium-chain-length poly-3-hydroxyalkanoates (PHA) and carboxyl group-functionalized multiwalled carbon nanotubes (MC) were used to fabricate a composite membrane for application in a double-chambered microbial fuel cell (MFC). MC was composited into PHA at 5%, 10%, and 20% w/w via ultrasound dispersion blending method. PHA-MC composite was compared with Nafion 117 as proton exchange membrane in MFC operated with palm oil mill effluent (POME) wastewater. The composite exhibited prerequisite separator membrane characteristics. The dispersion of MC in the polymer matrix increased its interfacial surface area and water uptake properties. PHA-MC10% membrane in MFC showed maximum power density of 361?mW/m², which was comparable with Nafion 117 (372?mW/m²). Internal resistance decrease, chemical oxygen demand (COD) removal, coulombic efficiency (CE), and conductivity of the PHA-MC10% were superior to Nafion 117. The environmental-friendly material could provide an alternative towards realizing practical MFC application.     

质子交换膜燃料电池动态过程的数值模拟

为描述质子交换膜燃料电池的动态过程,发展了一个基于计算流体动力学的非稳态、非等温的三维两相流数学模型.应用模型对一蛇形流道结构的质子交换膜燃料电池单体进行了数值计算,得到了电池启动过程中电池阴极侧膜表面温度和电流密度等特征参数的动态过程变化曲线.最后,分析了阴极入口速度、湿度和电池电压阶跃变化后电池特性的动态响应特性.结果表明：电池的启动时间和阶跃响应时间均为秒的数量级,与大多数模型模拟的结果相一致.     

质子交换膜燃料电池研究进展

质子交换膜燃料电池（proton exchange membrane fuel cell, PEMFC）因具有效率高、功率密度大、排放产物仅为水、低温启动性好等多方面优点,被公认为下一代车用动力的发展方向之一。然而,目前PEMFC在耐久性和成本方面距离商业化的要求还存在一定差距。为攻克上述两大难题,需要燃料电池全产业链的共同努力和进步。本文回顾了近年来质子交换膜燃料电池从催化剂、膜电极组件、电堆到燃料电池发动机全产业链的研究进展和成果,梳理出单原子催化剂、非贵金属催化剂、特殊形貌催化剂、有序化催化层、高温质子交换膜、膜电极层间界面优化、一体化双极板-扩散层、氢气系统循环等研究热点。文章指出,催化层低铂/非铂化、质子交换膜超薄化、膜电极组件梯度化/有序化、燃料电池运行高温化、自增湿化是未来的发展趋势,迫切需要进一步的创新与突破。     

Pore parameter selection for fused deposition modeling of gas diffusion layers in proton exchange membrane fuel cells

Because of the global energy crisis, many researchers have focused their efforts on fuel cells. The gas diffusion layer (GDL) is a fundamental component of proton exchange membrane (PEM) fuel cells. The manufacturing procedures for traditional carbon-based GDLs are sophisticated and energy-intensive, and have design flexibility constraints, making it difficult to build complicated forms and structures. Additive manufacturing is widely used in a variety of fields, with the fused deposition modeling (FDM) technique being the most popular method. Prior to conducting systematic research on the printed GDLs, it is necessary to investigate the pore parameters with the support of FDM technique. In this research, the initial step involves material selection, FDM printer selection, and modeling. Subsequently, printing analysis and sample characterization are conducted to select an acceptable pore shape. A water drainage test determines the appropriate pore size, followed by additional tests for acceptable porosity range. The square pore shape is determined to be more suitable. A pore side length of 1.0 mm is identified. Furthermore, a suitable pore range of 10.9%–30.3% is identified. Next step, the printed GDLs will undergo further testing to investigate their suitability to be used in PEM fuel cells.     

质子交换膜燃料电池可视化研究进展

质子交换膜燃料电池(包括氢氧质子交换膜燃料电池和直接甲醇燃料电池)内的两相流动以及相应的水管理、气管理对燃料电池的性能和寿命有很大的影响,而可视化方法是研究流场槽道内两相流动非常重要的方法之一。可视化实验可以真实地展示气泡或液滴在流场槽道内的生成以及发展过程,有利于了解其进化机制,从而进一步优化气管理、水管理并提高电池性能。本文主要综述了质子交换膜燃料电池两极流场内两相流动的可视化研究进展,讨论了扩散层的润湿性以及扩散层内水的传递机理,还介绍了实现可视化的方法,并提出了可视化研究的不足及发展方向。     

Non-isothermal effects of single or double serpentine proton exchange membrane fuel cells

Mathematical models on transport processes and reactions in proton exchange membrane (PEM) fuel cell generally assume an isothermal cell behavior for sake of simplicity. This work aims at exploring how a non-isothermal cell body affects the performance of PEM fuel cells with single and double serpentine cathode flow fields, considering the effects of flow channel cross-sectional areas. Low thermal conductivities of porous layers in the cell and low heat transfer coefficients at the surface of current collectors, as commonly adopted in cell design, increase the cell temperature. High cell temperature evaporates fast the liquid water, hence reducing the cathode flooding; however, the yielded low membrane water content reduces proton transport rate, thereby increasing ohmic resistance of membrane. An optimal cell temperature is presented to maximize the cell performance.     

Preparation of proton exchange membranes based on crosslinked polytetrafluoroethylene for fuel cell applications

We prepared proton exchange membranes by the γ-ray-induced post grafting of styrene into crosslinked polytetrafluoroethylene (PTFE) films and subsequent sulfonation. The degree of grafting was controlled in the range of 7-75% by the crosslinking density of the PTFE matrix as well as the grafting conditions. Under our preparation conditions, the films at the grafting yield of ≥30% were found to produce ion exchange membranes with a homogeneous distribution of sulfonic acid groups. The resulting membranes showed a large ion exchange capacity up to 2.9 meq g⁻¹, which exceeded the performance of commercially available perfluorosulfonic acid films such as Nafion; nevertheless, they appeared to be dimensionally stable in water. These should undoubtedly result from the use of the crosslinked PTFE films as graft substrates and make our ion exchange membranes promising for applications to polymer electrolyte fuel cells.     

Platinum electroless deposition on nafion membrane for PEM fuel cells

The aim of this research was to study the deposition of platinum on Nafion117 membrane by using an electroless technique. The investigated parameters were electroless time (30 to 90 min) and Pt : N₂H₄ ratio (from 1 : 1 to 1 : 3.85). The results indicated that the platinum deposition on the 1st side of membrane was lower than that on the 2nd side because of the effect of N₂H₄ on the property of membrane. Platinum deposition increased when the Pt : N₂H₄ ratio decreased. The optimum condition was found at electroless time of 60 min and Pt : N₂H₄ ratio of 1 : 1.95. At this condition, more than 89% of platinum was deposited on both surfaces. The coated membrane was used to make a membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEMFC) which was tested at 60 ‡C in a saturated H₂/O₂ system. The maximum current density was 80 mA/cm² at 0.3 V.