磺化聚酰亚胺酸碱复合膜的制备及其在全钒液流电池中的应用

采用高温一步法合成了一系列不同磺化度的三元共聚磺化聚酰亚胺(SPI),通过控制磺化二胺与非磺化二胺的摩尔比来调节磺化度.选取碱性聚合物聚乙烯吡咯烷酮(PVP)与SPI按质量比1∶9进行共混,制成SPI/PVP酸碱复合膜.对复合膜的吸水率、离子交换容量、钒离子渗透率以及电池性能进行了测试.结果表明,随着磺化度的升高,复合膜的吸水率、离子交换容量、质子电导率升高以及钒离子渗透率升高.复合膜的隔膜选择性比Nafion117的选择性好,其中SPI/PVP-3的选择性是Nafion117的10倍.电池性能测试表明,随磺化度的升高,复合膜能量效率升高.其中SPI/PVP-3膜较Nafion117膜具有较高的库伦效率和能量效率,通过循环测试SPI/PVP-3膜性能稳定,充放电理想.     

质子交换膜对钒氧化还原液流电池性能的影响

采用溶液接枝聚合法制备了一种新型的质子交换膜PVDF-g-PSSA, 测定了PVDF-g-PSSA膜、Nafion 117 膜和PE01均相膜的离子交换能力和电导率, 并分别研究了以这3种膜为隔膜的钒电池的电化学性能. 实验结果表明, PVDF-g-PSSA膜具有优良的质子电导率和离子交换能力, 室温下其离子交换能力和质子电导率分别为1.13 mmol/g和3.22×10-2 S/cm, 在不同的充放电电流密度下, 以PVDF-g-PSSA膜为隔膜的钒电池的库仑效率和能量效率明显高于Nafion 117膜和PE01均相膜为隔膜的钒电池; PVDF-g-PSSA膜阻钒离子的渗透性能与PE01均相膜基本一致, 都明显优于Nafion 117膜的阻钒离子渗透能力.     

全钒氧化还原液流电池Nafion/SiO_2复合膜的研究

采用溶胶-凝胶法制备Nafion117/SiO2复合膜.工艺研究表明:复合膜制备过程中,加入的MeOH与TEOS比例基本不影响复合膜的阻钒性能.但如以水解时间10 min,水解完成后自然晾干24 h制备的复合膜,则其VO2+的渗透率最低,为4.27×10-9cm2/s,比Nafion117膜的渗透率降低了52倍.SEM测试表明,经自然晾干的复合膜,其中SiO2晶粒长大,并填充了Nafion膜中大部分的孔洞.以其作隔膜组装全钒氧化还原液流电池(单电池),测试表明膜掺杂后电池的电力效率提高2.7%.     

全钒液流电池磺化石墨烯/Nafion复合膜的研究

本文通过磺化石墨烯对Nafion膜进行改性,研究了磺化石墨烯/Nafion复合膜（GRS-Nafion复合膜）的吸水率、电阻率和钒离子迁移数. 结果表明,经磺化石墨烯改性之后,GRS-Nafion复合膜的面电阻和钒离子渗透率显著降低. 全钒液流电池的测试结果表明,GRS-Nafion复合膜有着更加优异的电化学性能,展示出GRS-Nafion复合膜在液流电池中的应用潜力.     

磺化聚醚醚酮与氧化石墨烯共混膜的制备以及在全钒液流电池中的应用

以浓硫酸为溶剂和磺化剂制备磺化度(DS)为65%的磺化聚醚醚酮(SPEEK),根据SPEEK和氧化石墨烯(GO)不同质量比制备一系列共混膜(S/GO).对共混膜的含水量、离子交换容量、面电阻、质子电导率、钒离子渗透率、机械强度以及耐氧化性进行研究.采用扫描电子显微镜(SEM)观察S/GO共混膜的形态;通过热重分析(TG)表征共混膜的热稳定性.结果表明随着GO引入量的增加,共混膜的含水量增加,离子交换容量(IEC)降低,质子电导率减小,钒离子渗透率减小,机械性能增强.共混膜能量效率均高于Nafion115,其中S/GO-2(GO含量2 wt%)的电池效率最佳,能量效率达到80%,相比于Nafion115提高近9%.在运行100次循环以后S/GO共混膜电池效率稳定性良好.S/GO共混膜有望在全钒液流电池中得到应用.     

SSPEEK/Na-MMT复合钒电池质子交换膜的制备与性能研究

以含有异丙基溴侧基的聚醚醚酮为原子转移自由基聚合(ATRP)大分子引发剂,通过ATRP法在聚醚醚酮主链上接枝引入聚苯乙烯磺酸钠侧链,得到侧链型磺化聚醚醚酮质子交换膜(SSPEEK).采用溶液共混法在SSPEEK膜中引入钠基蒙脱土(Na-MMT),制备SSPEEK/Na-MMT钒电池质子交换复合膜.热重分析表明,复合膜具有较好的耐热性;扫描电镜显示,Na-MMT均匀分散在SSPEEK中.复合膜的钒离子渗透率由SSPEEK膜的1.24×10-5cm2·min-1降为4.88×10-6cm2·min-1,低于Nafion117膜的钒离子渗透率,阻钒能力优于Nafion117膜.电流密度为30 m A·cm-2时,以复合膜组装的电池的放电时间为215 min,长于Nafion117膜的198 min.在高放电电流密度下SSPEEK/Na-MMT膜的库伦效率与Nafion117膜相当.     

钒电池用聚胺薄层复合膜研究

钒电池(VRB)具有容量和功率相互独立、易于模块化、寿命长和安全性高等优点,因此特别适合作为大规模储能系统使用.隔膜是VRB的核心部件之一,对电池的综合性能和成本影响巨大.全氟磺酸膜如Nafion(杜邦)具有化学稳定性高、电导率高和机械性能好等优点,因此是当前VRB中所广泛使用的商业化隔膜.然而,Nafion用于VRB时存在着钒离子渗透率高和成本高两大主要缺点,严重制约了VRB的商业化进程.薄层复合(TFC)膜具有皮层和支撑层易调控、制备简单和离子选择性高等特点,特别适合于在VRB中使用.但是传统的聚酰胺型TFC膜在VRB强酸电解液中存在潜在的水解和分解问题.为了制备VRB用高稳定性TFC膜,本工作以聚乙烯亚胺(PEI)和三聚氰氯(CC)作为两相单体,通过界面聚合法制备了不含酰胺基的聚胺型TFC膜并应用于VRB.在此基础上,对所制备复合膜进行了钒离子渗透率、单电池充放电性能、化学稳定性和长期循环稳定性等物化性能及电化学性能研究.结果表明:聚胺TFC膜(M_T)的钒离子渗透系数为3.17×10^-7 cm²·min^-...     

质子交换膜燃料电池Nafion/PTFE复合膜的研究

在聚四氟乙烯(PTFE)多孔膜内浸入Nafion树脂,制成Nafion/PTFE复合膜用于质子交换膜燃料电池(PEMFC).该复合膜的Nafion含量在50%左右,在干态和湿态时的拉伸强度及水化/脱水过程中,其尺寸稳定性比Nafion均有所提高.在80 ℃,H2/O2压力为0.2/0.2 MPa条件下,用25 μm厚复合膜组装的电池性能优于Nafion117膜组装电池的性能.测量了复合膜的O2渗透率和含水量并与Nafion膜的性能作了比较.     

高选择性APSF/rNafion复合膜在全钒液流电池中的应用

以氨化聚砜(APSF)和废弃的Nafion为原料,通过交混流涎的方法制得APSF/rNafion复合膜。采用了扫描电子电镜、拉力测试仪、电化学工作站和充放电测试仪等仪器对复合膜的形貌、力学性能和电化学性能进行表征。结果表明:APSF与rNafion具有很好的兼容性,使得复合膜具有好的力学性能和钒离子选择性。与空白的重铸Nafion膜相比,在不同电流密度下,APSF/rNafion复合膜表现出了突出的电化学性能,同时在40 m A/cm~2的电流密度下,复合膜的库伦效率(80μm,CE=96%)高于商用的Nafion115的库伦效率(125μm,CE=94.4%)。此外,在80 mA/cm~2的电流密度下,用APSF/rNafion复合膜组装的电池经过100圈的循环测试后,仍然具有80%的能量效率和85%放电容量维持率,表现出了很好的化学稳定性。该复合膜制备简单、耗材少、成本低,在全钒液流电池中有很好的应用前景。     

液流电池用季铵化聚醚砜阴离子交换膜材料的研究

离子交换膜是液流电池的关键部件之一,理想的离子交换膜应具有较低的活性物质渗透率(即有较高的选择性)和较低的面电阻(即有较高的离子传导率),同时还应具有较好的化学稳定性和较低的成本[1,2].目前,全钒液流电池主要采用全氟磺酸类阳离子交换膜(如Nafion),其化学稳定性优异,但易造成钒离子的渗透,降低了电池的使用寿命,且Nafion膜价格昂贵;全钒液流电池的电解质溶液由不同钒电解质溶解在硫酸中组成,采用阴离子交换膜时,由于Donan效应钒离子的渗透将受到制约,与阳离子交换膜相比,具有较高的选择性.     

Nafion/TiO<Subscript>2</Subscript> hybrid membrane fabricated via hydrothermal method for vanadium redox battery

To improve the performance of Nafion membrane as a separator in vanadium redox battery (VRB) system, a Nafion/TiO₂ hybrid membrane was fabricated by a hydrothermal method. The primary properties of this hybrid membrane were measured and compared with the Nafion membrane. The Nafion/TiO₂ hybrid membrane has a dramatic reduction in crossover of vanadium ions compared with the Nafion membrane. The results of scanning electron microscope, energy dispersive X-ray spectroscopy, and X-ray diffraction of the hybrid membrane revealed that the TiO₂ phase was formed in the bulk of the prepared membrane. Cell tests identified that the VRB with the Nafion/TiO₂ hybrid membrane presented a higher coulombic efficiency (CE) and energy efficiency (EE), and a lower self-discharge rate compared with that of the Nafion system. The CE and EE of the VRB with the hybrid membrane were 88.8% and 71.5% at 60 mA cm⁻², respectively, while those of the VRB with Nafion membrane were 86.3% and 69.7% at the same current density. Furthermore, cycling tests indicated that the Nafion/TiO₂ hybrid membrane can be applied in VRB system.     

Preparation of perfluoro‐1,3‐propanedisulfonic acid/Nafion/silica hybrid nanoparticles—thermally stable Nafion in these silica hybrid nanoparticles even after calcination at 800 °C

Perfluoro‐1,3‐propanedisulfonic acid (PFPS)/Nafion/silica hybrid particles were prepared by the sol–gel reactions of PFPS with tetraethoxysilane and silica nanoparticles in the presence of Nafion under alkaline conditions. These obtained composites exhibited a good dispersibility and stability in not only water but also traditional organic media such as methanol, ethanol, 1,2‐dichloroethane, tetrahydrofuran, and dimethyl sulfoxide. Dynamic light scattering measurements and field‐emission scanning electron microscopy show that these hybrid particles are nanometer size‐controlled fine particles before and even after calcination at 800 °C. Nafion/silica hybrid nanoparticles were also prepared in the absence of PFPS under similar conditions. The weight of original Nafion markedly dropped around 350 °C and decomposed gradually, reaching 0% around 450 °C, and Nafion in the Nafion/silica nanocomposites exhibited a similar weight loss behavior to that of the original one. However, Nafion/PFPS/silica hybrid nanoparticles were found to exhibit no weight loss corresponding to the contents of Nafion and PFPS in the silica gel matrices even after calcination at 800 °C. It was demonstrated that the pH value (3.77 at 25 °C) of Nafion/PFPS/silica hybrid nanoparticles after calcination is smaller than that (5.66 at 25 °C) before calcination, and this hybrid nanoparticles exhibited a higher proton conductivity (5.8 × 10^?3 S/cm at 85 °C) than that (4.1 × 10^?3 S/cm at 85 °C) before calcination. In addition, Nafion/PFPS/silica hybrid nanoparticles after calcination at 800 °C were applied to the Friedel‐Crafts acylation of thiophene with acetic anhydride to give the expected 2‐acetylthiophene, of whose yield was similar to that before calcination under similar conditions. These findings suggest that Nafion in PFPS/silica hybrid nanoparticle cores should exhibit a nonflammable characteristic even after calcination at 800 °C to act as an effective acid catalyst. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1869–1877     

A modified Nafion membrane with extremely low methanol permeability via surface coating of sulfonated organic silica

We developed a method to significantly decrease the methanol permeability of a Nafion membrane that does not require sacrificing its proton conductivity and mechanical stability. The Nafion membrane modified by the coating of a thin layer of sulfonated organic silica on the membrane surface exhibits significantly decreased methanol permeability--the permeability is decreased to an undetectable level--while retaining an acceptable ionic conductivity of 0.029 S cm(-1).     

Preparation,photocatalytic activity and mechanism of nano-Titania/Nafion hybrid membrane

Nano-Titania/Nafion (TiO₂/Nafion) hybrid membranes were prepared by recasting, using Nafion solution and TiO₂ anatase hydrosol as the raw materials. The microstructure of the hybrid membrane was characterized by X-ray diffraction, high-resolution transmission electron microscopy (HR-TEM), X-ray Photoelectron Spectroscopy and Fourier Transform Infrared Spectroscopy (FT-IR). The photocatalytic properties of TiO₂/Nafion hybrid membranes were evaluated. Furthermore, endurance of photocatalytic activity of the hybrid membrane was investigated. The results indicate that the TiO₂ Nanoparticles are bounded to Nafion molecule via Ti-O-S bonds and the formed flocculates are distributed homogeneously throughout the recasting Nafion membrane, while the initial pure anatase TiO₂ nanoparticles remain intact in re-crystallized membrane. The hybrid membranes possessed excellent photocatalytic activities with and without H₂O₂. Moreover, the degradation of photocatalytic activities has been better controlled with the presence of H₂O₂.     

Preparation and characterization of Nafion/SPEEK layered composite membrane and its application in vanadium redox flow battery

In order to reduce the cost of membrane used in vanadium redox flow battery (VRB) system while keeping its chemical stability, Nafion/sulfonated poly(ether ether ketone) (SPEEK) layered composite membrane (N/S membrane) consisting of a thin layer of recast Nafion membrane and a layer of SPEEK membrane were prepared by chemical crosslink the sulfonic acid groups of different ionomer membranes. Scanning electron microscopy (SEM) and IR spectra analysis of the membrane showed that Nafion layer was successfully deposited on the SPEEK membrane surface and an integral layered membrane structure was formed. The area resistance and permeability of vanadium ions of membrane were also measured. It was found that N/S membrane have a very low permeability of vanadium ions accompanied by a little higher area resistance compared with Nafion membrane. As a result, the VRB single cell with N/S membrane exhibited higher coulombic efficiency and lower voltage efficiency compared with VRB single cell with Nafion membrane. Although N/S membrane delivered relatively lower energy efficiency compared with Nafion membrane, its good chemical stability and low cost make it a suitable substitute for Nafion membrane used in VRB system.     

Design of Interpenetrated Networks of Mesostructured Hybrid Silica and Nonconductive Poly(vinylidene fluoride)–Cohexafluoropropylene (PVdF–HFP) Polymer for Proton Exchange Membrane Fuel Cell Applications

Organic–inorganic hybrid membranes of poly(vinylidene fluoride)–cohexafluoropropylene (PVdF–HFP) and mesostructured silica containing sulfonic acid groups were synthesized by using the sol‐gel process. These hybrid membranes were prepared by in situ co‐condensation of tetraethoxysilane and an organically modified silane (ormosil) by a self‐assembly route using organic surfactants as templates for tuning the architecture of the hybrid organosilica component. In this paper, we describe the elaboration and characterization of hybrid membranes all the way from the precursor solution to the evaluation of the fuel cell performances. These hybrid materials were extensively characterized by using NMR and IR spectroscopy, electron microscopy, or impedance spectroscopy so as to determinate their physicochemical and electrochemical properties. Even though the ion‐exchange capacity (IEC) was quite weak, the first fuel cell tests performed with these hybrid membranes show promising results relative to optimized Nafion 112 thanks to great water management of the silica inside the hydrophobic polymer.     

表面修饰模式对Nafion离子选择性影响及在VRFB中的应用

本文采用壳聚糖-磷钨酸层对Nafion膜表面分别进行单面和双面修饰改性,研究了修饰模式对Nafion膜钒离子渗透率、电导率及离子选择性的影响. 结果表明,单面、双面修饰改性均会使Nafion膜的钒离子渗透率显著降低,最高降幅分别达到89.9% (单面修饰) 和92.7% (双面修饰);单面、双面修饰改性均会使Nafion膜的电导率下降,但存在明显差异,在相同修饰厚度条件下,双面修饰改性对Nafion膜电导率的影响比单面修饰改性更小。因此,双面修饰复合膜展示出了比单面修饰复合膜更高的离子选择性,并且在修饰层厚度为17 μm时达到最大值（1.12×10⁵ S•min•cm^-3）. 基于优化的双面修饰Nafion膜的全钒液流电池,在充放电流密度30 mA•cm^-2 时,库伦效率和能量效率分别达到93.5%和 80.7%, 并且在测试时间内展示出良好的循环稳定性.     

Synthesis, testing, and characterization of a novel Nafion membrane with superior performance in photoassisted immobilized Fenton catalysis

A new type of Nafion/Fe structured membrane ensuring faster kinetics, higher efficiency, and mechanical properties has been prepared and will be compared in its performance with the Fe-exchanged commercial Dupont 117 Nafion/Fe membrane during the abatement of model organic compounds. During the casting of the laboratory Nafion sample, the iron ions were introduced directly into the Nafion oligomer solution. This novel laboratory Nafion/Fe was tested as an immobilized catalyst in the degradation of several toxic pollutants showing a faster photoassisted degradation kinetics and a wider effective photocatalytic pH range compared to the Fe-exchanged commercial Dupont 117 Nafion/Fe membrane. When carrying out Ar ion sputtering of the 50 topmost catalyst layers, evidence is presented by X-ray photoelectron spectroscopy that Fe ions are found in the inner Nafion layers and seem to be responsible for the immobilized photoassisted Fenton processes leading to the degradation of 4-chorophenol (4-CP) taken as a model organic pollutant for the degradation process reported in this study. In the laboratory sample, the iron oxy/hydroxy Nafion moiety undergoes a transition to a more stable Nafion/Fe species during 4-CP degradation as determined by X-ray diffraction. This more stable form shows a higher iron dispersion and crystallinity compared to the fresh sample and is stabilized by the Nafion matrix avoiding the formation of separate iron phases. By infrared absorption (Fourier transform infrared), evidence is presented for the band of akaganeite-like species at 870 cm(-1) on the laboratory Nafion/Fe sample. This band disappears after 4-CP degradation because of the formation of the more highly dispersed iron species. Sputtering experiments show a decrease of F-containing groups in the laboratory Nafion/Fe samples closer to the catalyst upper layer while the amounts of Fe, C, and in particular O species increase in the topmost layer(s). In particular, the oxygenated species develop in the Nafion/Fe up to approximately 50 A below the catalyst surface. These species remain stable during the long-term Nafion/Fe degradation of 4-CP. Dynamo-mechanical analysis performed on laboratory Nafion/ Fe membrane samples revealed that these membranes possessed a greater mechanical modulus and resistance than the commercial Dupont 117 Nafion membrane.     

An Interface‐Bridged Organic–Inorganic Layer that Suppresses Dendrite Formation and Side Reactions for Ultra‐Long‐Life Aqueous Zinc Metal Anodes

Aqueous zinc (Zn) batteries (AZBs) are widely considered as a promising candidate for next‐generation energy storage owing to their excellent safety features. However, the application of a Zn anode is hindered by severe dendrite formation and side reactions. Herein, an interfacial bridged organic–inorganic hybrid protection layer (Nafion‐Zn‐X) is developed by complexing inorganic Zn‐X zeolite nanoparticles with Nafion, which shifts ion transport from channel transport in Nafion to a hopping mechanism in the organic–inorganic interface. This unique organic–inorganic structure is found to effectively suppress dendrite growth and side reactions of the Zn anode. Consequently, the Zn@Nafion‐Zn‐X composite anode delivers high coulombic efficiency (ca. 97 %), deep Zn plating/stripping (10 mAh cm^?2), and long cycle life (over 10 000 cycles). By tackling the intrinsic chemical/electrochemical issues, the proposed strategy provides a versatile remedy for the limited cycle life of the Zn anode.     

Evaluation of hybrid silica sols for stable microporous membranes using high-throughput screening

Microporous membranes are a promising option for energy-efficient molecular separations. Long-term hydrothermal stability of the membrane material is of prime importance for several industrial processes. Here, a short overview of silica-based membrane materials and their hydrothermal stability is presented. Following this, the development of a series of organic–inorganic hybrid silica sols is described, based on α,ω-bis(triethoxysilyl)-precursors with bridging methane, ethane, propane, and benzene groups. High-throughput screening was used to scan a range of sol parameters, followed by membrane preparation from the most promising sols. These organic–inorganic hybrid silica (HybSi^®) membranes were used in dewatering of lower alcohols by pervaporation. Separation factors up to 200 were found for ethanol/water mixtures, and up to 23 for methanol/water mixtures. Modest permselectivity values for hydrogen over nitrogen were found, ranging up to 20.7 for the shortest bridging group. It was concluded that the length of the organic bridge has a clear effect on the pore size distribution and the selectivity of the membrane.