全钒液流电池VO2+离子跨膜渗透行为

采用静止型全钒氧化还原液流电池,利用紫外分光光度法,研究电解液钒离子跨膜渗透行为,讨论浓度、温度、荷电状态(SOC)、电场以及渗透压等对VO²⁺离子跨膜传质的影响,关联相应的钒离子渗透系数。研究结果表明,提高钒电解液浓度可以有效减缓钒离子跨膜传递速率,提高能量效率;适当降低体系温度,可以抑制钒离子的跨膜渗透,减小电池化学短路的发生;VO²⁺离子渗透系数随SOC值增加而迅速减小;正向电场存在会促进VO²⁺离子透膜扩散,加剧电池自放电;隔膜两侧液面渗透压的作用会加速钒离子跨膜渗透,造成电池容量衰减。     

聚偏氟乙烯纳米多孔膜结构调控及离子传递特性

在纳微米尺度调控膜孔结构对发展高性能膜分离材料具有重要意义。使用半结晶性高分子材料聚偏氟乙烯（PVDF）,利用非溶剂诱导相分离（NIPS）、蒸汽诱导相分离（VIPS）、溶剂蒸发诱导相分离（EIPS）方法,成功制备了不同形貌的多孔膜。提出了根据聚合物的结晶生长机制调控膜孔结构概念,根据溶剂蒸发时间调控结晶生长。利用SEM和BET对膜孔形貌进行表征,XRD和DSC对结晶进行检测,氢离子（H⁺）和四价钒离子（VO²⁺）以及其他常用离子的扩散系数表征传质特性。在溶剂蒸发诱导结晶的过程中,随着溶剂蒸发时间的延长,膜断面的球晶比例逐渐增加,最后至球晶完全融合,膜孔结构发生了显著变化,且膜的结晶度和结晶形态随之发生变化,离子选择性能随膜孔尺寸减小而逐渐增大。     

协同场作用下钒离子在质子交换膜中的传质过程

研究了VO²⁺在Nafion117质子交换膜中的传质过程, 重点考察了不同操作工况下浓度场和电场的协同作用。定量了电场对钒离子透膜传质过程的影响大小, 并根据实验数据拟合出了VO²⁺在Nafion117膜中的表观电迁移率。结果表明:电场对高浓度电解液的离子透膜过程影响较大, 升高温度和增加电解液对流均强化了电场作用在钒离子透膜传质的影响, 加入的正向电场越强, 跨膜渗透越剧烈, 且电场因子随着时间的增加而增加。反向电场有利于缓解钒离子透膜传递过程。     

全钒液流电池开路电压模型

建立全钒液流电池六参数开路电压计算模型,揭示开路电压由电池总电势和VO₂⁺/VO²⁺电极电势决定,并与电解液中钒离子透膜扩散行为密切相关。模型计算得到开路电压存在两个电压平台和一个转折点,与实验结果较为一致。利用该模型计算了电池开路时电解液中4种钒离子浓度随时间的变化关系,指出电池电解液不均衡性是由不同价态钒离子在膜相的Donnan平衡和透膜扩散系数不同产生的。该模型可为优化电池操作提供理论指导,并可为电池长期运行时电解液管理提供工程指导。     

锑离子添加剂对低共熔溶剂(DES)电解液液流电池的性能改善研究

非水系氧化还原液流电池（NARFB）的广泛应用受制于其较低的性能。在电解液中加入一些金属离子添加剂是一种可能的解决方案。实验研究了Sb³⁺离子对低共熔溶剂（DES）电解液液流电池电化学性能的影响。结果表明,添加Sb³⁺离子可以强化V（Ⅲ）/V（Ⅱ）氧化还原离子对的电化学反应动力学（最高可达22.6％）过程,钒离子在DES中的扩散系数提高了63.3％,并且电荷转移电阻降低了11.9％。场发射扫描电子显微镜表明,Sb³⁺离子电沉积在石墨毡的表面,对电化学反应起催化作用,从而改善了电化学性能。考虑增强的动力学和降低的活性比表面积之间的平衡,确定了Sb³⁺的最佳浓度为15 mmol·L^-1。此外,当使用含有Sb³⁺的负极电解液液流电池时,液流电池的功率密度提高了31.2%,从含原始电解质的3.08 mW·cm^-2到含15 mmol·L^-1 Sb³⁺离子的4.04 mW·cm^-2。这些结果为改善NARFB的电池性能提供了一个便捷而有前景的方法。     

用Cluster-Continuum模型计算水溶液中VO2+/VO2+电对溶剂化自由能

利用Cluster-Continuum模型,通过B3LYP方法计算出VO₂⁺/VO²⁺电对的第一溶剂化层的水分子数分别为3和5个,并得到了水溶液中VO₂⁺、VO²⁺离子的溶剂化自由能。利用此计算数值并通过热力学计算推算出VO₂⁺/VO²⁺电对的标准反应电势为1.29 V,与理论值相差不大。这表明利用Cluster-Continuum模型可以较为准确地描述VO₂⁺、VO²⁺离子的溶剂化作用。     

阳离子类型对粉煤灰混凝土氯离子扩散性能的影响

通过快速氯离子迁移系数法(RCM法)和自然扩散法研究了钾、钠、钙、镁四种阳离子类型的氯盐对粉煤灰混凝土氯离子扩散性能的影响,基于分子动力学模拟,对比分析了K⁺、Na⁺、Ca²⁺、Mg²⁺、Cl^-五种离子在水溶液中的径向分布函数和均方位移曲线。结果表明:粉煤灰混凝土的氯离子扩散系数主要受阳离子价态的影响,价态越高,扩散系数越大;扩散系数随着氯离子浓度增加先增大后减小,随着粉煤灰掺量增加先减小后增大;阳离子类型影响氯离子扩散性能的原因是离子扩散能力不同,其中各离子水合能力强弱顺序为Mg²⁺＞Ca²⁺＞Na⁺＞K⁺>Cl^-,自扩散系数大小顺序为Mg²⁺＞Ca²⁺＞Cl^-＞K⁺>Na⁺。MgCl₂中的Mg²⁺和Cl^-对粉煤灰混凝土都有侵蚀作用,且Mg²⁺会抑制粉煤灰活性的激发。     

连续共价有机框架筛分复合膜及全钒电池性能

设计了应用于全钒液流电池的尺寸筛分效应共价有机框架/聚醚砜(COF/PES)复合膜,利用纳米片的有序交错堆叠在聚醚砜支撑层上构建了具有均匀埃米级离子传输通道的连续COF分离层。连续COF层的规整刚性骨架赋予了膜极低的溶胀比,有序的埃米级孔道(有效孔径约为0.6 nm)对氢/钒离子具有精确的尺寸筛分作用。COF/PES筛分复合膜的钒渗透率仅有0.61×10^-8 cm^-2·s^-1,质子/钒离子选择性为Nafion 212的4.0倍。电流密度为80 mA·cm^-2下复合膜的能量效率达到82.9%,优于Nafion 212(81.2%)。100 mA·cm^-2下的长循环测试中,复合膜电池容量保持率相比于Nafion 212电池提高了16.2%,表明连续COF/PES筛分复合膜在全钒液流电池中具有广阔的应用前景。     

连续共价有机框架筛分复合膜及全钒电池性能

设计了应用于全钒液流电池的尺寸筛分效应共价有机框架/聚醚砜(COF/PES)复合膜,利用纳米片的有序交错堆叠在聚醚砜支撑层上构建了具有均匀埃米级离子传输通道的连续COF分离层。连续COF层的规整刚性骨架赋予了膜极低的溶胀比,有序的埃米级孔道(有效孔径约为0.6 nm)对氢/钒离子具有精确的尺寸筛分作用。COF/PES筛分复合膜的钒渗透率仅有0.61×10^-8 cm^-2·s^-1,质子/钒离子选择性为Nafion 212的4.0倍。电流密度为80 mA·cm^-2下复合膜的能量效率达到82.9%,优于Nafion 212(81.2%)。100 mA·cm^-2下的长循环测试中,复合膜电池容量保持率相比于Nafion 212电池提高了16.2%,表明连续COF/PES筛分复合膜在全钒液流电池中具有广阔的应用前景。     

全钒液流电池用多氟聚噁二唑芳醚阴离子交换膜的制备

离子交换膜的钒离子渗透是制约全钒液流电池效率的因素之一。制备了一种新型的、低钒离子渗透的氟化聚芳醚阴离子交换膜。以六氟双酚A、四甲基联苯二酚、含氟单体合成了多氟聚噁二唑芳醚。以N-溴代丁二酰亚胺（NBS）为溴化试剂,过氧化二苯甲酰（BPO）为引发剂,将多氟聚噁二唑芳醚上的甲基进行溴化、功能化得到多氟聚噁二唑芳醚阴离子交换膜（QFOAEM）。研究了该膜的钒离子渗透率、离子传导率、吸水率、溶胀度和离子交换容量（IEC）等性能。研究结果表明：QFOAEM的钒离子渗透率为1.1×10^-8cm²·min^-1,低于Nafion117的3.8×10^-7cm²·min^-1,具有在全钒液流电池中应用的潜力。     

Adsorption and Diffusion of VO2+ and VO2 + across Cation Membrane for All‐Vanadium Redox Flow Battery

A method based on a selectivity coefficient and the Nernst‐Planck equation is proposed to determine diffusion coefficients of vanadium ions across a cation exchange membrane in VO²⁺/H⁺ and VO₂ ⁺/H⁺ systems. This simplified method can be applied to high concentrations of vanadium ions. Three cation exchange membranes were studied. The logarithmic value of the selectivity coefficient was linearly dependent on the molar fraction of vanadium ions in solution. The diffusion coefficient of vanadium ions decreased with decreasing water content. The membrane with the lowest diffusion coefficient was selected as a battery separator and showed the lowest capacity loss of the studied membranes.     

Effect of crosslinking on the physicochemical properties of proton conducting PVDF-g-PSSA membranes

Poly(vinylidene fluoride) (PVDF) membranes, radiation-grafted with styrene and sulfonated, were studied as a candidate material for polymer electrolyte fuel cell (PEFC). In particular the effect of the use of crosslinkers in the polymer structure was investigated using bis(vinyl phenyl)ethane (BVPE) and divinylbenzene (DVB) as reagents. Water uptake in the H+ form, proton conductivity and ion exchange capacity of the PVDF-g-PSSA membranes, as well as transport properties of oxygen and hydrogen were determined at room temperature. Crosslinking with DVB resulted in a more pronounced decrease in the properties; the use of BVPE had no significant influence. Even on the permeation of oxygen and hydrogen the BVPE had little effect: the diffusion coefficient and solubility remained at the same level as for the non-crosslinked membranes. Increasing the membrane thickness was found to be at least as effective in reducing the oxygen permeation rate as using crosslinkers.     

Cost effective cation exchange membranes: A review

This paper will look at developments of new polymer electrolyte membranes to replace high cost ion exchange membranes such as Nafion^®, Flemion^® and Aciplex^®. These perfluorinated polymer electrolytes are currently the most commercially utilized electrolyte membranes for polymer electrolyte fuel cells, with high chemical stability, proton conductivity and strong mechanical properties. While perfluorinated polymer electrolytes have satisfactory properties for fuel cell applications, they limit commercial use due to significant high costs as well as reduced performance at high temperatures and low humidity. A promising alternative to obtain high performance proton-conducting polymer electrolyte membranes is through the use of hydrocarbon polymers. The need for inexpensive and efficient materials with high thermal and chemical stability, high ionic conductivity, miscibility with other polymers, and good mechanical strength is reviewed in this paper. Though it is difficult to evaluate the true cost of a product based on preliminary research, this paper will examine several of the more promising materials available as low cost alternatives to ion exchange membranes. These alternative membranes represent a new generation of cost effective electrolytes that can be used in various ion exchange systems. This review will cover recent and significant patents regarding low cost polymer electrolytes suitable for ion exchange membrane applications. Promising candidates for commercial applications will be discussed and the future prospects of cost effective membranes will be presented.     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Characterization of Flemion® membranes for PEFC

Perfluorinated ion exchange membranes were studied to clarify the characteristics of membranes required for polymer electrolyte fuel cells (PEFC). The influence of membrane thickness on gas permeability and the influence of incorporation of cations on water content and ac specific resistance of Flemion® and Nafion®117 were estimated. Gas permeation rates of the membranes decreased in inverse proportion to the increase of the membrane thickness and gas permeability coefficients were nearly constant and independent of the thickness. Hydrogen permeation rates of Flemion®S at 70°C were converted to 2.1 mA/cm² as current density. Water content changed by only 5% in the region of the ion exchange ratio from 0% to 100% and was independent on the kinds of incorporated cations in the region of the ion exchange ratio under 40% except for K⁺. Ac specific resistance increased markedly when the ion exchange ratio exceeded 50%. In the case that the ion exchange ratio was under 30%, ac specific resistance increased with decrease of the numbers of protons having no relation with the kinds of cations. Area resistance of Flemion® was smaller because it has higher ion exchange capacity and thinner thickness than Nafion®117.     

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.     

Water transport mechanisms through asymmetric membranes

Permeability coefficients and activation energy values for the transport of water through asymmetric cellulose acetate membranes were determined in order to establish the mechanism of the process when different driving forces are applied. A stirred Lucite cell with controlled temperature was used to measure the membrane transport properties under hydraulic and osmotic pressure differences and also in the presence of a tracer concentration gradient across the membrane. The experimental results based on the temperature dependence of water flow show that the controlling step for water transport is diffusion with net flux in the dense zone of the membrane under hydraulic or osmotic pressure gradients. When a tracer concentration gradient is used, equimolar diffusion of water in the thicker, porous zone of the membrane is the controlling mechanism. A mass transport model based on the composed structure of the membrane is presented to provide a general framework for treating the particular cases. Finally, the difference in the controlling barriers, in agreement with a previous work by Hays,¹⁸ is shown to account for the much higher absolute values of osmotic than tracer water permeabilities determined here and frequently reported in the literature.     

Behavior of sulfonated poly(ether ether ketone) in ethanol–water systems

The behavior of sulfonated poly(ether ether ketone) (sPEEK) membranes in ethanol–water systems was studied for possible application in direct ethanol fuel cells (DEFCs). Polymer membranes with different degrees of sulfonation were tested by means of uptake, swelling, and ethanol transport with dynamic measurements (liquid–liquid and liquid–gas systems). Ethanol permeability was determined in an liquid–liquid diffusion cell. For membranes with an ion‐exchange capacity (IEC) between 1.15 and 1.75 mmol/g, the ethanol permeability varied between 5 × 10^?8 and 1 × 10^?6 cm²/s, being dependent on the measuring temperature. Ethanol and water transport in liquid–gas systems was tested with pervaporation as a function of IEC and temperature. Higher IEC accounted for higher fluxes and lower water/ethanol selectivity. The temperature had a large effect on the fluxes, but the selectivity remained constant. Furthermore, the membranes were characterized with proton conductivity measurements. The proton diffusion coefficient was calculated, and a transition in the proton transfer mechanism was found at a water number of 12. Membranes with high IEC (>1.6 mmol/g) exhibited larger proton diffusion coefficients in ethanol–water systems than in water systems. The membrane with the lowest IEC exhibited the best proton transport to ethanol permeability selectivity. The use of sPEEK membranes in DEFC systems depends on possible modifications to stabilize the membranes in the higher conductive region rather than on modifications to increase the proton conductivity in the stable region. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Sulfonated poly(ether ether ketone)/s–TiO2 composite membrane for a vanadium redox flow battery

The SPEEK/s-TiO₂ composite membrane was prepared by blending sulfonated poly(ether ether ketone) (SPEEK) and sulfonated titanium dioxide (s-TiO₂) nanoparticles. The important physiochemical parameters such as proton conductivity, water uptake, swelling degree and ion exchange capacity of the composite membrane were measured. The thermal stability and chemical stability were also tested. It was observed that the SPEEK/s-TiO₂ composite membrane exhibited the best selectivity (7.13 × 10⁴ S·min·cm⁻³) accompanying high proton conductivity (0.061 S·cm⁻¹) and low tetravalent vanadium ion (VO²⁺) permeability (8.55 × 10⁻⁷ cm²·min⁻¹) compared with Nafion117, SPEEK and SPEEK/TiO₂ membranes. The battery performance with these membranes was characterized by charge–discharge cycling tests and it was found that the SPEEK/s-TiO₂ composite membrane showed the highest energy efficiency (EE) up to 82.3%, indicating the SPEEK/s-TiO₂ composite membrane is a candidate for vanadium redox flow battery (VRFB) application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48830.