Nafion/PTFE and zirconium phosphate modified Nafion/PTFE composite membranes for direct methanol fuel cells

We prepared Nafion/PTFE (NF) and zirconium phosphate (ZrP) hybridized Nafion/PTFE composite membranes (NF–ZrP). NF–ZrP composite membranes were prepared via two processes. One is impregnating sub-μm porous PTFE membrane directly in a Nafion/ZrOCl₂ solution (NF–Zr–d). The other is impregnating sub-μm porous PTFE membrane in a Nafion solution to prepare NF composite membrane, and then the NF membrane was impregnated in a ZrOCl₂ aqueous solution via in situ precipitation method (NF–Zr–I). The ZrOCl₂ inserted in NF composite membranes was then reacted with phosphoric acid to form ZrP and thus NF–ZrP–d and NF–ZrP–I composite membranes were obtained. The direct methanol fuel cell (DMFC) performances of membrane electrode assemblies prepared from Nafion-117, NF, NF–ZrP–d, and NF–ZrP–I composite membranes were investigated. The effects of introducing sub-μm porous PTFE film and ZrP particles into Nafion membranes on the DMFC performance were investigated. The influence of ZrP hybridizing process into NF membranes (the process of preparing NF–ZrP–I is inserting ZrOCl₂ into NF membranes after Nafion is annealed and the process of preparing NF–ZrP–d is mixing ZrOCl₂ into a Nafion solution before Nafion is annealed) on the morphology of NF–ZrP composite membranes and thus on the DMFC performance was also discussed.     

直接甲醇燃料电池用PEMs的研究进展

本文介绍了用于直接甲醇燃料电池(DMFCs)的质子交换膜(PEMs)的工作原理与性能要求。讨论了影响DMFCs国PEMs的甲醇渗透性能的因素。综述了Nation、改性Nafion膜以及其它新品种膜的研究进展。     

An NMR and SAXS investigation of DMFC composite recast Nafion membranes containing ceramic fillers

Small angle X-ray scattering (SAXS) and nuclear magnetic resonance (NMR) investigations of recast composite and bare Nafion membranes have been carried out. The self-diffusion coefficients of water and methanol have been determined over a wide temperature range by PFGSE ¹H NMR method. The transport mechanism appears to be influenced by surface properties of inorganic fillers. Acidic silica filler appears to promote proton transport in the membrane with respect to basic alumina. An interaction of the silica surface with methanol molecules is also envisaged from the analysis of proton self diffusion coefficients of methanol. The SAXS analysis revealed a modification of the polymer structure immersed in pure methanol or methanol solution with respect to water. A significant increase of the average ion clusters dimension is observed for the composite SiO₂ membrane.     

An NMR study of methanol diffusion in polymer electrolyte fuel cell membranes

Methanol diffusion in two polymer electrolyte membranes, Nafion 117 and BPSH 40 (a 40% disulfonated wholly aromatic polyarylene ether sulfone), was measured using a modified pulsed field gradient NMR method. This method allowed for the diffusion coefficient of methanol within the membrane to be determined while immersed in a methanol solution of known concentration. A second set of gradient pulses suppressed the signal from the solvent in solution, thus allowing the methanol within the membrane to be monitored unambiguously. Over a methanol concentration range of 0.5–8 M, methanol diffusion coefficients in Nafion 117 were found to increase from 2.9 × 10⁻⁶ to 4.0 × 10⁻⁶ cm² s⁻¹. For BPSH 40, the diffusion coefficient dropped significantly over the same concentration range, from 7.7 × 10⁻⁶ to 2.5 × 10⁻⁶cm² s⁻¹. The difference in diffusion behavior is largely related to the amount of solvent sorbed by the membranes. Increasing the methanol concentration results in an increase in solvent uptake for Nafion 117, while BPSH 40 actually excludes the solvent at higher concentrations. In contrast, diffusion of methanol measured via permeability measurements (assuming a partition coefficient of 1) was lower (1.3 × 10⁻⁶ and 6.4 × 10⁻⁷ cm² s⁻¹ for Nafion 117 and BPSH 40 respectively) and showed no concentration dependence. The differences observed between the two techniques are related to the length scale over which diffusion is monitored and the partition coefficient, or solubility, of methanol in the membranes as a function of concentration. For the permeability measurements, this length is equal to the thickness of the membrane (178 and 132 μm for Nafion 117 and BPSH 40 respectively) whereas the NMR method observes diffusion over a length of approximately 4–8 μm. Regardless of the measurement technique, BPSH 40 is a greater barrier to methanol permeability at high methanol concentrations.     

Sulfonated polysulfone with 1,3-1H-dibenzimidazole-benzene additive as a membrane for direct methanol fuel cells

1,3-1H-Dibenzimidazole-benzene (DBImBenzene) has been synthesized using phosphorus pentoxide-methanesulfonic acid (PPMA) as a solvent and dehydration agent and investigated as an additive (up to 2.0 wt.%) in sulfonated polysulfone (SPSf) membranes to promote proton conduction via acid–base interactions. The SPSf/DBImBenzene blend membranes with various DBImBenzene contents (0–2.0 wt.%) have been prepared and characterized by proton conductivity measurement and electrochemical polarization and methanol crossover measurements in direct methanol fuel cells (DMFCs). The blend membranes with DBImBenzene content of 0.5 and 1.0 wt.% show higher proton conductivities (3.4 and 2.9 × 10⁻⁴ S/cm, respectively) than plain SPSf (2.4 × 10⁻⁴ S/cm) even though the blend membranes have lower ion exchange capacity (0.81 and 0.75 mequiv./g, respectively) than plain SPSf (0.86 mequiv./g). The blend membranes exhibit better electrochemical performance in DMFC than plain SPSf membrane due to an enhancement in proton conductivity through acid–base interactions and lower methanol crossover.     

Nafion含量对直接甲醇燃料电池阴极催化剂性能表达的影响

燃料电池是一种将燃料反应的化学能转化为电能的装置,可分为氢氧质子交换膜燃料电池(PEMFCs)、直接甲醇燃料电池(DMFCs)和直接甲酸燃料电池等.与 PEMFCs相比, DMFCs以甲醇为燃料,燃料的储存运输和电池操作运行具有较高的安全性,所以近年来受到人们的广泛关注.
　　膜电极组件(MEA)是 DMFCs的核心部分,由气体扩散层(GDL)、催化层(CL)和质子交换膜(PEM)三部分组成. GDL用于提高电池传质能力,并同时作为 MEA的集流体. PEM主要用于隔离燃料和氧气,进行质子传导. CL是 MEA中的主要组成部分,为电化学反应提供场所.
　　催化层由催化剂,质子传输介质和电子传输介质组成.通常,阳极催化剂采用 PtRu/C,阴极采用 Pt/C,质子传输介质为全氟磺酸树脂,如 Nafion. CL的结构对电池性能有直接的影响,因此人们对 CL的结构进行了详细的研究,并通过调节 CL亲水性能、梯度催化层的结构设计等优化其结构.研究表明,当 CL中 Nafion含量为33 wt.%, PEMFCs具有最佳的电池性能. DMFCs与 PEMFCs对 MEA要求不同,其阴极更容易发生水淹现象.本文结合非接触式三维光学轮廓仪、接触角测试系统和电化学测试对阴极不同 Nafion含量的膜电极进行了表面形貌、亲水性、循环伏安和 DMFC性能测试.
　　本文利用喷涂法制备了 GDE,然后与 Nafion115热压形成 MEA.由三维表面形貌图可以看出,随着催化层中 Nafion含量的增加, GDE表面的粗糙度变大,尤其是 N35和 N45.理论上,表面粗糙有利于 Pt的暴露和传质扩散,但是其电池性能并未与粗糙度呈现出正相关的关系,因为 Nafion含量高于35 wt.%, Pt被 Nafion过度包裹,抑制了 O2至催化剂表面的传输,且随着 Nafion含量由15 wt.%增加至45 wt.%,其 GDE表面的接触角由166.8o减至143.1o,说明 CL的亲水性增强,易导致阴极产生的水无法及时排出,从而造成阴极水淹现象.
　　从不同 Nafion含量制备 MEA的 CV图可以看出,随着 Nafion含量的增加, Pt的电化学活性面积(ESA)增加.当 Nafion含量较少时, Nafion无法对全部 Pt纳米粒子(NPs)形成包覆或无法形成连贯的质子传输通道,从而导致大部分的 Pt NPs催化活性较低变为无效 Pt.而有效 Pt NPs要求与连贯的质子传输通道相连接.当 Nafion含量高于35 wt.%时,其 ESA基本保持不变,因为 Pt载量一定,从而限制了 ESA,此时达到该载量条件下的极限 ESA.但是电池极化曲线表明,30 wt.% Nafion含量的 MEA具有最佳的电池性能.因为有效 Pt NPs不一定是高效的,当他们全部被 Nafion包裹后, O2只能依靠溶解在 Nafion中才可以到达催化剂表面,从而阻碍传质.只有 Pt NPs表面包裹和暴露面积达到一定比例时才变得高效.所以当 Nafion含量低于30 wt.%时,主要由质子传输通道导致的有效 Pt NPs较少;当 Nafion含量高于30 wt.%时,出现 Nafion过度包裹 Pt NPs,阻碍 O2传质.因此, Nafion含量30 wt.%时, Pt的包裹面积和裸露面积达到所研究的最佳状态.     

Anion exchange membranes derived from nafion precursor for the alkaline fuel cell

Robust hydroxide conducting membranes are required for long‐lasting, low‐cost solid alkaline fuel cells (AFCs). In this study, we synthesize Nafion‐based anion exchange membranes (AEMs) via amination of the Nafion precursor membrane with 1,4‐dimethylpiperazine. This initial reaction produces an AEM with covalently attached dimethylpiperazinium cations neutralized with fluoride anions, while a subsequent ion exchange reaction produces a hydroxide ion conducting membrane. These AEMs possess high thermal stability and different thermal transition temperatures compared to Nafion, while small‐angle X‐ray scattering reveals a similar ionic morphology. The hydroxide ion conductivity of the Nafion‐based AEM is fivefold lower than the proton conductivity of Nafion at 80 °C and 90% relative humidity. More importantly, the hydroxide conductivity is insensitive to drying and rehydrating the membrane, which is atypical of other AEMs with quaternary ammonium cations. The high chemical and thermal stability of this hydroxide conducting Nafion‐based AEM provides a promising alternative for AFCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Current progress in membranes for fuel cells and reverse electrodialysis

The deterioration of the environmental situation has led to the need to restructure the world’s power industry, and clean renewable power sources are coming to the forefront. This review deals with recent advances in the development of promising ion-exchange membrane materials for two types of application that have been intensely developing recently, namely, hydrogen energy and reverse electrodialysis. Special attention is paid to the comparison of two properties of membranes, conductivity and selectivity, that are competing but fundamentally important in both areas. Perfluorinated sulfonic acid membranes now play a dominant role in hydrogen power engineering, as they provide not only high proton conductivity but also chemical stability and low gas permeability. The review also covers other types of membrane materials, including anion exchange membranes, polybenzimidazoles and hybrid membranes containing inorganic nanoparticles that have been actively developed in recent years. The milder operating conditions of membranes in reverse electrodialysis units allow one to use less expensive non-perfluorinated membranes, including grafted ones. It is of note that in devices of this type, the selectivity of membranes to the transfer of oppositely charged ions is a more important parameter.     

Supercritical carbon dioxide treated Nafion 212 commercial membranes for direct methanol fuel cells

Supercritical carbon dioxide (Sc-CO₂) thermal treatment to enhance performance of Nafion 212 (NR212) commercial membranes for direct methanol fuel cells (DMFCs) is described. It is shown that the microstructure of NR212 membranes is re-organized after the Sc-CO₂ treatment, and then the performance of NR212 membranes is improved. Specifically the thinner NR212 membranes after the Sc-CO₂ treatments have higher proton conductivity and better capacity of barrier to methanol crossover compared with the thicker Nafion 117 membranes. It is demonstrated that the DMFC performance of the Sc-CO₂ treated NR212 membranes is better than that of Nafion 117 membranes.     

Nafion perfluorinated membranes in fuel cells

Increasing global energy requirements, localized power issues and the need for less environmental impact are now providing even more incentive to make fuel cells a reality. A number of technologies have been demonstrated to be feasible for generation of power from fuel cells over the last several years. Proton exchange membranes (PEM) have emerged as an essential factor in the technology race. DuPont has supplied Nafion^® perfluorinated membranes in fuel cells for space travel for more than 35 years and they have played an integral part in the success of recent work in portable, stationary and transportation applications. The basis for PEM fuel cell emergence and DuPont technology utilization will be discussed.     

Transport properties of Nafion membranes modified with tetrapropylammonium ions for direct methanol fuel cell application

This work presents a study of transport properties (proton conductivity, methanol permeability, and water uptake) and acid-base properties of commercial Nafion-112, -115, and -117 membranes modified with tetrapropylammonium (TPA) cations. In the interaction between TPA hydroxide and protons of sulfonate groups in the Nafion matrix, some of the protons are shown to be bound to sulfonate groups and do not participate in transport processes. These findings are confirmed by IR spectroscopy, acid-base titration, and data on proton conductivity of the modified membranes. Proton conductivity of the modified membranes is shown to be effectively described by a percolation model with parameters that agree with published data for commercial Nafion membranes. Based on these results, a model is proposed for the interaction of TPA cations with the sulfonate groups in Nafion membranes. According to this model, TPA cations form hydrophobic clusters in hydrophilic regions of the polymer matrix, thus preventing some of the protonated sulfonate groups from participating in transport processes.     

Direct methanol fuel cells for vehicular applications

Dramatic technological advances for the proton exchange membrane fuel cell have focused attention on this technology for motor vehicles. The fuel cell vehicles (FCVs) have the potential to compete with the petroleum-fueled internal combustion engine vehicles (ICEVs) in cost and performance while effectively addressing air quality, energy insecurity, and global warming concerns. Methanol being a liquid can be easily transported and can be supplied from the existing network of oil company distribution sites. Recently, combining improved catalysts with fuel cell engineering, it has been possible to overcome some of the difficulties that have frustrated previous research and development efforts in realizing a commercially viable direct methanol fuel cell. Direct methanol fuel cells (DMFCs) with power densities between 0.2 and 0.4 W/cm² at operational temperatures in the range 95–130 °C have been developed. These power densities are sufficient to suggest that stack construction is well worth while. This paper reviews recent advances and technical challenges in the field of DMFCs. Received: 27 May 1997 / Accepted: 25 November 1997     

Performance of direct dimethyl ether fuel cells at low temperature

The performance of direct dimethyl ether fuel cells (DDMEFC) is presented in this study at the relatively low temperature of 80 °C. At temperatures lower than 100 °C, since water exists as liquid but DME as a gas, it is difficult for them to use simultaneously as fuel for DDMEFCs even with the low solubility of DME in water at atmospheric pressure. It has been found that the use of an interdigitated flow field enhances the performance of DDMEFC by facilitating the phase mixing of DME and water. Palladium (Pd) catalyst is not nearly electrochemically active to the anode reaction of DDMEFC and platinum–ruthenium (Pt–Ru) catalyst has been found to be effective anode catalysts for DDMEFC at low temperature.     

Improvement of Li/Mg monovalent ion selectivity of cation-exchange membranes by incorporation of cerium or zirconium phosphate particles

To improve the selectivity of cation-exchange membranes to the transfer of lithium with respect to magnesium during the electrodialysis desalination of lithium and magnesium sulfates solutions, the surface of a commercial cation-exchange membrane based on sulfated polystyrene was modified with cerium(III, IV) and zirconium phosphates. Upon incorporation of phosphate particles, the Li/Mg selectivity coefficients of the membranes increased up to 113%.     

Crosslinked sulfonated polyimide networks as polymer electrolyte membranes in fuel cells

Sulfonated polyimides with tertiary nitrogen in the polymer backbone were synthesized with 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid, 2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, and diaminoacrydine hemisulfate. They were crosslinked with a series of dibromo alkanes to improve the hydrolytic stability. The crosslinked sulfonated polyimide films were characterized for their thermal stability, ion‐exchange capacity (IEC), water uptake, hydrolytic stability, and proton conductivity. All the sulfonated polyimides had good thermal stability and exhibited a three‐step degradation pattern. With an increase in the alkyl chain length of the crosslinker, IEC decreased as 1.23 > 1.16 > 1.06 > 1.01, and the water uptake decreased as 7.29 > 6.70 > 6.55 > 5.63. The order of the proton conductivity of the crosslinked sulfonated polyimides at 90 °C was as follows: polyimide crosslinked with dibromo butane (0.070) > polyimide crosslinked with dibromo hexane (0.055) > polyimide crosslinked with dibromo decane (0.054). The crosslinked polyimides showed higher hydrolytic stability than the uncrosslinked polyimides. Between the crosslinked polyimides, the hydrolytic stability decreased with an increase in the alkyl chain length of the crosslinker. The crosslinked and uncrosslinked sulfonated polyimides exhibited almost the same proton conductivities. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2370–2379, 2005     

直接甲醇燃料电池纳米结构电催化材料及多孔电极研究

直接甲醇燃料电池(DMFC)因其燃料能量密度高,工作温度低,低污染排放等优点被认为是用作移动设备电源的最佳选择之一,至今已有美国的Oorja Protonics公司和丹麦的IRD公司等新能源相关企业相继发布了多款用于手机、电脑、通信基站、叉式装卸机或房车的商业产品.然而, DMFC内部的复杂情况造成的多种不同的电压损失仍旧使得其实际电压效率远低于理论值.其中从阳极渗透到阴极的甲醇造成的混合电位导致的电压损失尤为明显.目前,众多研究人员都致力于开发高稳定性、高耐久性、高性能且低成本的催化材料体系,以克服传统Pt催化剂存在的各种问题.除了催化剂本身之外, DMFC的问题还与其中膜电极的微结构和电化学特性息息相关.膜电极是化学能通过电催化氧化还原反应转化为电能的反应场所,通常由阳极扩散层、阳极催化层、质子交换膜、阴极催化层和阴极扩散层依序组合而成.通过对MEA中的各层进行优化,如传质管理和甲醇渗透等问题都能得到有效解决.
　　近年来,纳米技术常被用于改进DMFC性能的研究.具备纳米结构的金属-碳/金属氧化物载体类催化材料得到了广泛研究.这些电催化材料在制备方法、结构和组分上都有较大区别.结构方面,许多研究都证明制备纳米级多孔网络结构或者有序阵列结构的催化层有助于提高催化性能和Pt的利用率.组分方面,许多研究人员都开展了引入Pt以外金属成分或金属氧化物来改变Pt催化剂的表面电子状态的研究.引入这些组分导致的配位体效应可以通过弱化Pt与H+, OH-或COads等的相互作用来起到抗催化毒化和提高催化效率的作用.尽管对于DMFC领域的认知逐渐完善,但是仍有许多问题有待解决.因此,本文介绍了目前用于DMFC的纳米结构电催化材料和多孔电极的研究进展.重点介绍了纳米结构催化剂和载体材料的合成及表征.
　　通过对比不同催化材料的特性可以发现,在本文涉及到的催化材料中, In0.1SnO2-Pt和(MoO3)0.2SnO2-Pt/C表现出了最高的催化活性,但是它们高效催化甲醇电氧化所需的碱性环境与现在占绝对主流地位的Nafion质子交换膜所必须的酸性环境相冲突,所以其实际应用价值在碱性阴离子交换膜研究取得突破前都难以有效发挥.而另一类表现较好的采用溶致液晶模板法合成的纳米树枝状和纳米星形Pt催化剂则存在制备工艺难以商业规模化的问题.总的来说,采用溶剂热合成法制备的Pt-NRCeO2/GNs和Pt/Ti0.9Sn0.1O2-C等纳米结构金属氧化物、碳材料复合载体和Pt基贵金属催化剂组成的催化材料体系不仅催化性能相对于商业化Pt纳米颗粒有很大提高,而且制备方法易于商业规模化,值得进一步关注.此外,本文还介绍了如内部传质过程的理论建模计算和膜电极中功能结构的制备等优化DMFC中多孔电极内传质过程的方法.通过计算机模拟得到优化DMFC内部传质过程所需的扩散层、催化层的传质特性相关参数,再通过改进MEA制备工艺,有效控制各层的结构参数向模拟的优化值靠拢,能够实现DMFC性能的有效提升.综合模拟、实验研究及工艺研究结果,根据实际需要,设计和制备包含新功能层的MEA的相关研究也更进一步提高了DMFC的性能和实用性.就目前的研究情况而言,如果在性能提升的基础上,使用寿命再取得突破, DMFC一定会有很好的商业应用前景.     

Electrodeposited Pt and Pt-Sn nanoparticles on Ti as anodes for direct methanol fuel cells

Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Pt_x-Sn_y catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5mol/L H₂SO₄ and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt.  Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Pt_x-Sn_y/Ti towards the methanol oxidation reaction is reported. Consequently, the Pt_x-Sn_y/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.     

New anion conducting membranes based on functionalized styrene–butadiene–styrene triblock copolymer for fuel cells applications

In this work, the functionalization of polystyrene‐b‐poly(butadiene)‐b‐polystyrene triblock copolymer (SBS) with vinylbenzyl chloride and benzoyl peroxide (BPO) or α,α′‐azo‐bis‐isobutyronitrile (AIBN) as free radical initiators was reported. The functionalization degree (FD), calculated by ¹H NMR spectroscopy and confirmed by elemental analysis, was highly tunable (from 4 to 10 mol %) and positively correlated to the starting percentage of radical initiator. More specifically, at the same initiator molar percentage grafting efficiency is higher using BPO rather than AIBN. Quaternization reaction of the grafted benzyl chloride groups with the bifunctional tertiary amine 1,4‐diazabicyclo[2.2.2]octane (Dabco) led to a chemically and thermally stable homogeneous anion‐exchange membrane. Electrochemical parameters were evaluated for Dabco‐quaternized grafted copolymers having different FDs, and compared with a commercial Tokuyama benchmark membrane. Experimental data showed a positive correlation between FD and both water swelling and ionic conductivity. Best trade‐off between ionic conductivity and water swelling was found for membrane having FD 9.1 mol %, which conductivity is comparable with the Tokuyama benchmark one and water uptake is only slightly higher. The results are discussed based on the molecular parameters with particular reference to ionic content and distribution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

磷酸锆催化甘油气相脱水制备丙烯醛

以沉淀法、水热合成法和浸渍法制备了磷酸锆催化剂,通过X射线衍射、热重分析、氮气物理吸附、红外光谱和Hammett指示剂法对催化剂进行了表征,并将该催化剂用于甘油气相脱水反应.研究表明,由沉淀法得到的磷酸锆经过400℃焙烧后能达到最佳催化活性,在温和条件下,甘油可完全转化,丙烯醛选择性为81%,反应24h内催化剂失活不明显.不同方法制备的磷酸锆其结构和表面酸性显著不同,催化剂表面酸性对催化剂活性、丙烯醛选择性和催化剂的寿命均有较大影响.