Effect of cesium salt of tungstophosphoric acid (Cs-TPA) on the properties of sulfonated polyether ether ketone (SPEEK) composite membranes for fuel cell applications

We have prepared composite membranes for fuel cell applications. Cesium salt of tungstophosphoric acid (Cs-TPA) particles was synthesized by aqueous solutions of tungstophosphoric acid and cesium hydroxide and, Cs-TPA particles and sulfonated (polyether ether ketone) (SPEEK) with two sulfonation degrees (DS), 60 and 70%have been used. We examined both the effects of Cs-TPA in SPEEK membranes as functions of sulfonation degrees of SPEEK and the content of Cs-TPA. The performance of the composite membranes was evaluated in terms of water uptake, ion exchange capacity, proton conductivity, chemical stability, hydrolytic stability, thermal stability and methanol permeability. The morphology of the membranes was investigated with SEM micrographs. Increasing sulfonation degree of SPEEK from 60 to 70 caused agglomeration of the Cs-TPA particles. The methanol permeability was reduced to 4.7 × 10⁻⁷ cm²/s for SPEEK (DS: 60%)/Cs-TPA membrane with 10 wt.% Cs-TPA concentration, and acceptable proton conductivity of 1.3 × 10⁻¹ S/cm was achieved at 80 °C under 100% RH. The weight loss at 900 °C increased with the addition of inorganic particles, as expected. The hydrolytic stability of the SPEEK/Cs-TPA based composite membranes was improved with the incorporation of the Cs-TPA particles into the matrix. We also noted that SPEEK60/Cs-TPA composite membranes were hydrolytically more stable than SPEEK70/Cs-TPA composite membranes. On the other hand, Methanol, water vapor, and hydrogen permeability values of SPEEK60 composite membranes were found to be lower than that of Nafion^®.     

Influence of water and degree of sulfonation on the structure and dynamics of SPEEK studied by solid-state C and H NMR

The molecular motions of sulfonated poly(ether-ether ketone) (SPEEK), synthesized by conventional method with a range of degree of sulfonation (DS) between 42 and 70%, as a function of DS and hydration were studied by ¹H-¹³C dipolar recoupling by rotor-encoded longitudinal magnetization (RELM) and ¹³C spin-lattice relaxations. The proton conductivity increased linearly with increasing DS from 52% and was comparable to that of Nafion 115 measured in the same condition for DS higher than 65%. The RELM dipolar patterns analyzed by the SIMPSON simulation program indicated that the population of phenyl rings in large amplitude motions such as 180°-flips was reduced with increasing DS. On the other hand, T_1ρ (¹³C) and T₁ (¹³C) results suggested that the dynamic chains in both 66 kHz and 100 MHz regimes were more populated with increasing DS, possibly in small-amplitude oscillations.     

SPEEK膜与Nafion膜在钒液流电池中的应用研究

研究了Nafion膜与SPEEK膜两种质子交换膜的含水率、膨胀率、阻钒性能以及在钒液流电池样机中的充放电性能,并结合两种隔膜的基本化学结构对产生这些差异的原因进行了分析.静态测试结果表明.SPEEK膜的含水率、膨胀率大于Nafion膜,其阻钒性能也比Nafion膜好.在钒液流电池样机中的充放电测试结果表明,Nafion膜的质子交换能力优于SPEEK膜.SPEEK膜与Nafion膜性能的差异可能与两者化学骨架结构以及磺化基团差异有关.     

测试介质对纳米CeO_2改性SPEEK膜质子电导率的影响

采用纳米氧化铈(CeO2)改性磺化度48.3%的磺化聚醚醚酮(SPEEK),通过溶液浇铸法制备用于直接甲醇燃料电池的质子交换膜.在两种介质中测试改性膜的电导率均随温度的升高而增大,与未改性膜相比却大小正好相反:在1 mol/L以盐酸溶液为电解液的测试介质中,改性膜的电导率是未改性膜的15倍,在水蒸气测试介质中,却仅为40%.红外光谱分析表明,CeO2中的铈原子与—SO3H基团中的氧原子发生配位作用.X射线衍射仪(XRD)分析可见,当复合膜浸入1 mol/L盐酸4 h前后,纳米CeO2的晶体结构未见明显变化,表明所发生的配位作用仅处于CeO2和SPEEK两个固相界面上.扫描电子显微镜(SEM)观察改性膜和未改性膜均无网络结构和微相分离,质子在膜内通过—SO3H基团之间的跃迁传导,酸溶液介质远比水蒸气有利于质子在纳米CeO2改性SPEEK膜内磺酸基团之间的跃迁.     

Preparation of highly H+ permeable sulfonated poly(ether ether ketone) cation exchange membranes and their applications in electro‐generation of thioglycolic acid

BACKGROUND: Sulfonated poly(ether ether ketone) (SPEEK) was successfully synthesized from sulfonated 4,4′‐difluorobenzophenone, 4,4′‐difluorobenzophenone and bisphenol A. SPEEK cation exchange membranes were prepared by the casting method. The composition and morphology of SPEEK were characterized using Fourier transform infrared and ¹H NMR spectroscopies, respectively. The ion exchange capacity (IEC), water uptake and degree of swelling of the membranes were also investigated. SPEEK120 was used as a separator in an electrolysis cell to produce thioglycolic acid (TGA). RESULTS: SPEEK polymerization was carried out at 145 and 175 °C for 10 h. The IEC of the SPEEK membranes was measured as 0.24–2.02 meq g^?1 and the water uptake as 2.26–26.45%. The degree of swelling of the membranes was 1.71–15.28%. TGA was effectively prepared by electro‐reduction of dithioglycolic acid. The current efficiency peaked at 58.31% at room temperature with a current density of 15 mA cm^?2. CONCLUSION: SPEEK120 membrane shows good dimensional stability and H⁺ permeability. Compared to the traditional metal‐reduction method, the current electro‐reduction technique avoids the use of zinc powder and so reduces environmental pollution. Copyright © 2009 Society of Chemical Industry     

磺化聚醚醚酮/聚乙烯复合膜的制备及对生菜的贮藏保鲜

以磺化聚醚醚酮（SPEEK）为涂层,聚乙烯（PE）为基底,制备了自发式气体调节SPEEK/PE复合膜,研究不同磺化度SPEEK对SPEEK/PE复合膜的透气性、透湿性、防雾性能等气调特性的影响,并将SPEEK/PE复合膜应用于生菜的气调气调保藏。结果表明,与SPEEK膜相比,不同磺化度SPEEK/PE气调复合膜对CO2和O2的透气系数均有轻微下降,SPEEK/PE复合膜对CO2/O2的分离系数从0.73增加到5.58。不同磺化度的SPEEK/PE复合膜对水蒸气的透过系数在1.50×10-14~4.00×10-14 g?cm/(cm?s?Pa)之间,与SPEEK膜2.00×10-12~2.46×10-12 g?cm/(cm?s?Pa)相比,水蒸气透过系数下降两个数量级,且SPEEK/PE复合膜具有良好的防雾性能。高磺化度SPEEK/PE复合膜对生菜具有良好的气调保藏效果,与空白对照和PE膜组相比,保藏20 d后生菜失重率分别降低92.25%、22.06%,叶绿素损失分别减少85.00%、50.00%,总酚含量下降分别减少73.97%、26.98%,维生素C含量损失分别降低50.00%、31.48%,可溶性固形物含量下降分别减少67.21%、21.31%。4 ℃时SPEEK/PE复合膜能将生菜保藏环境中的CO2和O2含量分别维持在10.00%~12.00%和4.00%~5.00%,并将生菜保藏期期延长到20 d。     

An inorganic/organic self-humidifying composite membranes for proton exchange membrane fuel cell application

With an aim to operate the proton exchange membrane fuel cells (PEMFCs) with dry reactants, an inorganic/organic self-humidifying membrane based on sulfonated polyether ether ketone (SPEEK) hybrid with Cs_2.5H_0.5PW₁₂O₄₀ supported Pt catalyst (Pt-Cs2.5 catalyst) has been investigated. The Pt-Cs2.5 catalysts incorporated in the SPEEK matrix provide the site for catalytic recombination of permeable H₂ and O₂ to form water, and meanwhile avoid short circuit through the whole membrane due to the insulated property of Cs_2.5H_0.5PW₁₂O₄₀ support. Furthermore, the Pt-Cs2.5 catalyst can adsorb the water and transfer proton inside the membrane for its hygroscopic and proton-conductive properties. The structure of the SPEEK/Pt-Cs2.5 composite membrane was characterized by XRD, FT-IR, SEM and EDS. Comparison of the physicochemical and electrochemical properties, such as ion exchange capacity (IEC), water uptake and proton conductivity between the plain SPEEK and SPEEK/Pt-Cs2.5 composite membrane were investigated. Additive stability measurements indicated that the Pt-Cs2.5 catalyst showed improved stability in the SPEEK matrix compared to the PTA particle in the SPEEK matrix. Single cell tests employing the SPEEK/Pt-Cs2.5 self-humidifying membrane and the plain SPEEK membrane under wet or dry operation conditions and primary 100 h fuel cell stability measurement were also conducted in the present study.     

EB‐crosslinked Polymer Electrolyte Membranes Based on Highly Sulfonated Poly(ether ether ketone) and Poly(vinylidene fluoride)/Triallyl Isocyanurate

In this study, crosslinked polymer electrolyte membranes for polymer electrolyte membrane fuel cell (PEMFC) applications are prepared using electron beam irradiation with a mixture of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and triallyl isocyanurate (TAIC) at a dose of 300 kGy. The gel‐fraction of the irradiated SPEEK/PVDF/TAIC (95/4.5/0.5) membrane is 87% while the unirradiated membrane completely dissolves in DMAc solvent. In addition, the water uptake of the irradiated membrane is 221% at 70 °C while that of the unirradiated membrane completely dissolves in water at above 70 °C. The ion exchange capacity and proton conductivity of the crosslinked membrane are 1.57 meq g⁻¹, and 4.0 × 10⁻² S cm⁻¹ (at 80 °C and RH 90%), respectively. Furthermore, a morphology study of the membranes is conducted using differential scanning calorimetry and X‐ray diffractometry. The cell performance study with the crosslinked membrane demonstrates that the maximum power density is 518 mW cm⁻² at 1036 mA cm⁻² and the maximum current density at applied voltage of 0.4 V is 1190 mA cm⁻².     

全钒液流电池用SPEEK／PES共混膜的制备

通过将PES掺入高磺化度的SPEEK进行共混改性,采用流延法制备了一系列不同PES含量的SPEEK／PES共混膜,获得了SPEEK／PES共混膜的离子交换容、含水率、质子电导率等参数,特别测定了在全钒液流电池工作条件下钒（IV）离子渗透率。综合考察发现,当磺化温度为45℃,磺化时间控制为4h,得到SPEEK的DS为55％,掺入10％的PES,此时共混膜的电导率为0．08S／cm,钒（IV）离子渗透率为0．38×10^-6cm2／min,对钒（IV）离子选择性为Nation膜的5倍,含水率为35％,共混膜综合性能最好,基本满足全钒液流电池（VRB）的使用需求。     

Organic-inorganic nanocomposite polymer electrolyte membranes for fuel cell applications

Organic-inorganic nanocomposite polymer electrolyte membrane (PEM) contains nano-sized inorganic building blocks in organic polymer by molecular level of hybridization. This architecture has opened the possibility to combine in a single solid both the attractive properties of a mechanically and thermally stable inorganic backbone and the specific chemical reactivity, dielectric, ductility, flexibility, and processability of the organic polymer. The state-of-the-art of polymer electrolyte membrane fuel cell technology is based on perfluoro sulfonic acid membranes, which have some key issues and shortcomings such as: water management, CO poisoning, hydrogen reformate and fuel crossover. Organic-inorganic nanocomposite PEM show excellent potential for solving these problems and have attracted a lot of attention during the last ten years. Disparate characteristics (e.g., solubility and thermal stability) of the two components, provide potential barriers towards convenient membrane preparation strategies, but recent research demonstrates relatively simple processes for developing highly efficient nanocomposite PEMs. Objectives for the development of organic-inorganic nanocomposite PEM reported in the literature include several modifications: (1) improving the self-humidification of the membrane; (2) reducing the electro-osmotic drag and fuel crossover; (3) improving the mechanical and thermal strengths without deteriorating proton conductivity; (4) enhancing the proton conductivity by introducing solid inorganic proton conductors; and (5) achieving slow drying PEMs with high water retention capability. Research carried out during the last decade on this topic can be divided into four categories: (i) doping inorganic proton conductors in PEMs; (ii) nanocomposites by sol-gel method; (iii) covalently bonded inorganic segments with organic polymer chains; and (iv) acid-base PEM nanocomposites. The purpose here is to summarize the state-of-the-art in the development of organic-inorganic nanocomposite PEMs for fuel cell applications.