燃料电池用阴离子交换膜的研究进展

本文简单介分析了燃料电池用阴离子交换膜需要具备的特点,针对AEM电导率和稳定性提升展开了深入的研究,希望可以通过提升AEM电导率和稳定性方式使AEM性能得到改善和加强,更好的满足燃料电池实际需要,降低燃料电池生产成本,提高其性能,为我国社会经济的持续稳定发展做出相应贡献。     

液流电池多孔离子传导膜研究进展

液流电池具有安全性高、性价比高、寿命长、环境友好等特点，是大规模储能的首选技术之一。离子传导膜是液流电池的关键材料之一，其性质和成本与液流电池储能系统的性能和成本直接相关。多孔离子传导膜基于“尺寸筛分”效应实现对活性物质的隔离和对载流子的传导，具有选择性高、离子传导性高和稳定性好等特点，在液流电池中具有良好的应用前景。通过多孔离子传导膜的结构调控，可以进一步优化多孔离子传导膜的选择性、传导性等性能，从而推动液流电池的产业化。本文基于多孔离子传导膜的研究进展，总结不同多孔离子传导膜的修饰策略，包括成膜参数的调节、混合基质多孔离子传导膜的制备、复合多孔离子传导膜的制备和后处理，为离子传导膜进一步的结构调控和性能优化提供理论指导。     

可充电钠离子电池隔膜研究进展

介绍了可充电钠离子电池的工作机理及其在成本、寿命、安全和大规模储能等方面的优势。简述了隔膜性能对电池的电化学性能、耐用性及安全性的影响。回顾了近几年钠离子电池隔膜的研究进展，包括聚烯烃微孔膜、玻璃纤维膜、聚合物电解质膜、静电纺丝膜、纤维素基隔膜和阳离子交换膜等，并分析了各自的优缺点。讨论了隔膜产业化过程面临的问题尤其是在安全方面面临的挑战，指出电解质润湿性更佳、离子电导率更高、耐枝晶性更强、热稳定性更好是隔膜研究的方向。     

多孔离子传导电池隔膜研究进展

具有高离子选择性和高电导率的离子传导膜对于以新能源为主体的新型电力系统（如液流电池、燃料电池、锂电池等）至关重要。近年来，研究者们提出了构建多孔离子传导膜以应对传统隔膜普遍存在的离子选择性和电导率之间的权衡效应。本综述从无机多孔离子传导膜、有机多孔离子传导膜以及多孔离子传导复合膜三个方面简要概述了近年来多孔离子传导膜作为电池隔膜的最新研究进展，总结了多孔离子传导膜在液流电池、燃料电池、锂电池等新能源电池中的前沿性工作，并指出未来多孔离子传导电池隔膜的研究将重点关注多孔膜结构的调控、高性能多孔膜材料的开发以及多孔膜在新型电池中的应用。     

侧链型聚(靛红-联苯)阴离子交换膜水电解性能

对阴离子交换膜(AEM)进行分子结构设计,制备出满足AEM水电解技术需求的高碱稳定性、高电导率的AEM。通过超强酸催化反应制备出具有高碱稳定性的聚(靛红-联苯)(PBPIN)主链;门秀金反应制备出含有高碱稳定性阳离子(哌啶阳离子)以及烷基间隔基的侧链(6C-Pip);门秀金反应将6C-Pip侧链接枝到PBPIN中制备出PBPIN-6C-Pip膜。为了验证PBPIN-6C-Pip膜的高碱稳定性以及高电导率,对其在高温KOH溶液中进行了碱稳定性测试,PBPIN-6C-Pip膜在80 ^oC、1 M KOH溶液中浸泡900 h后离子交换容量保留率高达97.02%;对其进行了电导率测试以及透射电子显微镜表征,PBPIN-6C-Pip膜在80 ^oC的纯水中电导率可达88.2 m S/cm,同时具有良好的微相分离结构。对AEM电解槽运行参数(KOH溶液浓度、温度、循环方式)进行了系统地研究后,在最优运行参数下(80 ^oC、2 M KOH,2.0 V),对PBPIN-6C-Pip膜进行了水电解性能测试,电流密度可达1.20 A/cm     

燃料电池用阴离子交换膜分子结构研究进展

阴离子交换膜（AEMs）作为燃料电池的核心部件,其发展得到了普遍关注。然而,AEMs中聚合物骨架和阳离子基团无序的直接相连的结构导致了膜在应用过程中存在离子电导率低、碱稳定性差和机械性能不足等问题,因此对连接二者的分子结构进行设计,开发综合性能优异的AEMs很有必要。本文介绍了AEMs选择性透过的基本机理,并从不同的分子结构出发,总结了近年来应用较为广泛的嵌段结构、接枝结构、交联结构、局部高密度结构以及由局部高密度结构与其他三种结构组成的复合结构AEMs的研究进展;从离子电导率、碱稳定性、机械性能以及吸水率等方面对AEMs的性能提升进行了归纳,重点关注AEMs离子电导率和吸水率的权衡问题,并从分子结构及其组合使用的角度对燃料电池用AEMs的未来发展方向进行了展望。     

纳米TiO2增强阴离子导电膜中碱性离子液体的稳定性研究

首先，以N-甲基吡咯烷为原料，通过两步法合成碱性甲基吡咯烷离子液体（[DMPy]OH）。然后，通过物理掺杂方式在聚乙烯醇（PVA）膜基质中引入[DMPy]OH碱性离子液体和纳米二氧化钛（TiO2），最后引入戊二醛（GA）交联PVA，制得PVA-[DMPy][OH]-TiO2复合膜。利用纳米二氧化钛（Nano-TiO2）表面分布的未配位饱和的Ti4+、O2-与[DMPy]OH中阴阳离子间的自组装效应，以及戊二醛（GA）交联PVA形成半互穿结构来降低膜内碱性离子液体的流失率，增加膜内“阳离子活性点位”数量，加快OH-的迁移速率，提高电导率。借助X射线衍射(XRD)和Mapping测试证实了Nano-TiO2和[DMPy]OH间自组装作用的存在，同时对复合膜的机械性能、热稳定性能、电导率、耐碱性等指标进行测试。结果表明，该系列复合膜，形貌平整、均一；当离子液体添加量为25wt%，Nano-TiO2添加量为1wt%时，80℃下PVA-[DMPy][OH]-TiO2复合膜的电导率为2.78×10-3 S.cm-1，室温下浸渍于水中12h后，离子液体流失率为23.2%；与未添加Nano-TiO2的PVA-[DMPy][OH]膜相比，电导率提高了19.4%，离子液体流失率降幅约为34.3%；室温下，3M KOH中耐碱性测试120h后，电导率和初始值相比并无明显变化，表现出优异的耐碱稳定性。热稳定性测试结果表明，该膜分解温度高于200℃，具有良好的热稳定性。     

大连化物所研制出长寿命锌基液流电池用复合离子传导膜

正锌基液流电池(ZFBs)储能技术因其具有成本低、安全性高、环境友好等特点,在分布式储能领域展现出良好的应用前景。但是,由于锌枝晶/锌累积的问题,该类电池的发展受到循环寿命差和充放电性能差的限制。离子传导膜可调控锌沉积形貌和抑制枝晶生长,在提高电池循环稳定性方面发挥了重要作用。前期,研究团队发现通过膜材料荷电特性可实现对锌沉积方向和形貌的调控,从而大幅度提高锌基液流电池的面容量和电池的循环稳定性。     

燃料电池用阴离子交换膜的研究进展

碱性阴离子交换膜燃料电池(AEMFC)是一种以碱性阴离子交换膜为电解质的新型燃料电池。结合了质子交换膜燃料电池(PEMFC)和传统碱性燃料电池(AFC)的优点,从根本上摆脱了对贵金属催化剂的依赖,具有广阔的应用前景。阴离子交换膜是阴离子交换膜燃料电池的核心材料之一,其电导率及稳定性制约了碱性阴离子交换膜(AEM)的发展。从提高AEM的电导率及耐碱稳定性两个方面,对近期报道的研究工作进行梳理总结。     

用于燃料电池的碱性阴离子交换膜研究进展

针对当前碱性阴离子交换膜离子电导率低和高温耐碱性较差的问题,本文综述了碱性功能基团和聚合物主链结构对阴离子交换膜离子电导率、碱性稳定性等主要性能的影响,主要介绍了季铵盐型、胍型、季盐型、咪唑盐型、锍盐型碱性功能基团以及嵌段共聚物、侧链型聚合物为基体材料的阴离子交换膜的研究进展,重点分析了上述因素对离子电导率的影响机理。综合分析表明,为了制备高电导率且强耐碱性的阴离子交换膜,进一步改性研究提高碱性功能基团离子电导率和碱性稳定性,优化聚合物主链结构,构建高效、有序的离子传输通道是未来的主要研究方向。     

Crosslinked anion exchange membrane with improved membrane stability and conductivity for alkaline fuel cells

As a core component of anion exchange membrane (AEM) fuel cells, it has practical significance to improve the performance of AEMs. However, it is difficult to obtain AEM with both good stability and high conductivity. In this study, a series of AEMs were prepared by chloromethylation, quaternization, and crosslinking reactions. The quaternization reaction was carried out first to ensure that there are abundant quaternary ammonium groups on AEM and enhance the conductivity of membrane. N,N,N′,N′-tetramethylethylenediamine was used as a crosslinker to improve membrane stability and mechanical property. A simple, mild, and cost-effective AEM synthetic route was developed. This strategy achieves a certain balance of electrochemical and physical properties. The effect of the crosslinking reactions on the property of membrane was evaluated. Crosslinked membranes have better dimensional stability (water uptake: 20.2% and swelling ratio: 2.1%), mechanical properties (55.84 MPa), and alkaline stability because crosslinked structures result in large steric hindrance. The mutually independent quaternization and crosslinking reaction do not affect the electrochemical performance of membranes; in the crosslinking reaction stage, crosslinker also reacted as quaternization agent and increased the number of reactive groups in AEM. Thus, the resulting crosslinked AEM exhibits higher ion exchange capacity and ionic conductivities (46.4 mS cm⁻¹). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48169.     

An easy method for the preparation of anion exchange membranes: Graft‐polymerization of ionic liquids in porous supports

A novel way for anion exchange membrane (AEM) preparation has been investigated, avoiding the use of expensive and toxic chemicals. This new synthetic approach to prepare AEMs was based on the use of a porous polybenzylimidazole membrane as support in which functionalized ILs were introduced and subsequently grafted on the polymer backbone. These new AEMs were prepared and their chemical structures and properties including morphology, thermal stability, and ionic conductivity were characterized. The hydroxyl ionic conductivity of the synthesized membranes can reach values upto 6.62 × 10^?3 S cm^?1 at 20°C. Although the ionic conductivity is not very high yet, the work shows the strength of the concept. Membrane properties can be easily tailored toward specific applications by choosing the proper chemistry, i.e., porous polymer support, ionic liquid, and method of initiation and polymerization. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly (ether ether ketone ketone) based imidazolium as anion exchange membranes for alkaline fuel cells

An imidazolium functionalized poly (ether ether ketone ketone) (PEEKK-DImOH) anion exchange membrane (AEM) readily soluble in certain low-boiling-point solvents (isopropanol) is prepared. The solubility results are consistent with the results of molecular dynamics simulations. By varying the chloromethylation reaction temperature or concentrated sulfuric acid concentration of PEEKK, the degrees of chloromethylation of PEEKK are changed from 54% to 92%, the corresponding PEEKK-DImOH AEMs with the ion exchange capacities (IECs) of 1.14-1.65 mmol·g^-1. The PEEKK-DImOH 92% AEM shows high hydroxide conductivity (31 mS·cm^-1), suitable water uptake (94%) and acceptable swelling ratio (39%) at 60℃. In addition, the PEEKK-DImOH AEMs possess good thermal and alkaline stability. The maximum power density (46.16 mW·cm^-2) of fuel cell prepared with PEEKK-DImOH 92% AEM as exchange membrane and ionomer is much higher than that with commercial AHA membranes. All the above results indicate that the PEEKK used in this study is a promising AEM matrix material for alkaline fuel cells.     

燃料电池阴离子交换膜高效离子传输通道构建进展

阴离子交换膜燃料电池因具有可使用非贵金属催化剂及催化反应动力学快等优点,是一种清洁高效的能源来源,但其商业化进展一直受制于高性能阴离子交换膜的开发。目前,阴离子交换膜主要面临着离子传导率低和稳定性差问题。研究者们分别围绕提高离子传导率（同时维持机械稳定性）和增加碱性稳定性开展了大量的研究工作。其中构建高效离子传输通道被认为是一种有效解决阴离子交换膜离子传导率和机械稳定性平衡问题的有效方法。本文综述了构建离子通道的常见方法,包括纳米复合、微相分离、构建互穿聚合物网络、构建离子簇。     

Facile Fabrication of Poly(vinyl alcohol)/Polyquaternium-10 (PVA/PQ-10) Anion Exchange Membrane with Semi-Interpenetrating Network

Anion exchange membranes (AEMs) are one of the core components of AEM fuel cells. A series of poly(vinyl alcohol)/polyquaternium-10 (PVA/PQ-10) AEMs with semi-interpenetrating networks (s-IPNs) are prepared by a simple solution-casting method using glutaraldehyde (GA) as a cross-linking agent. Subsequently, the prepared PVA/PQ-10 cross-linked membranes are characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, mechanical analysis, water uptake and swelling ratio tests, ion exchange capacity (IEC) tests, ionic conductivity measurements, and oxidative/alkaline stability tests. The effects of the mass ratio of PVA and PQ-10 and the amount of cross-linking agent GA on the performance of the PVA/PQ-10 cross-linked membranes are systematically explored. The results show that the cross-linked PVA/PQ-10 AEMs have high IEC and low water uptake and swelling ratio, and its maximum ionic conductivity can reach 79.37 mS cm^–1 at 80 °C. In addition, the PVA/PQ-10 cross-linked membrane has good oxidative and alkaline stability under optimal preparation conditions. These results may provide valuable insights toward more effective scheme designs and new, simple preparation methods for AEMs with s-IPN structures.     

Anion exchange membranes derived from nafion precursor for the alkaline fuel cell: Effect of cation type on properties

Highly stable hydroxide conducting membranes are necessary for solid‐state alkaline fuel cells to have long performance lifetimes. In this study, we used solid‐state chemistry to synthesize Nafion‐based anion exchange membranes (AEMs) with a variety of covalently attached cations, including trimethylammonium, trimethylphosphonium, piperazinium, pyrrolidinium, pyridinium, and quaternized 1,4‐diazabicyclo[2.2.2]octane. Infrared spectroscopy confirms a partial asymmetric functionalization of all cations with the exception of pyridinium. The AEMs that were successfully synthesized all exhibited sufficient water uptake and conductivity. The effect of cation type on AEM chemical and thermal stability was investigated as a function of various conditions (e.g., hydration levels, temperature, and pH). High chemical and thermal stability was observed for all successfully synthesized AEMs with the exception of the trimethylphosphonium cation AEM. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

不同侧链BPPO阴离子交换膜的制备及其抗污染性能

采用含有不同碳链长度的4-乙基吡啶、3-丁基吡啶与3-己基吡啶,通过亲核取代反应分别对溴化聚苯醚（BPPO）进行季铵化,制得三种阴离子交换膜（QBPPO-1、QBPPO-2、QBPPO-3）并对其电化学性能、脱盐性能以及抗污染性能进行了研究。实验结果表明随着吡啶环上烷基碳链的增长,制得的离子交换膜的离子交换容量呈现下降趋势,由1.92 mmol/g降至1.34 mmol/g,而膜面电阻逐渐增加,由2.99 Ω·cm²增加到10.59 Ω·cm²;在电渗析实验中,与商业日本Fuji阴离子交换膜相比,本实验制备的三种离子交换膜均呈现出较高的脱盐率;在污染实验中,随着高分子骨架侧链碳链的增长,离子交换膜在污染实验中的的转折时间逐渐变短,抗污染能力下降;计算模拟结果表明疏水作用在有机污染物（十二烷基苯磺酸钠）与离子交换膜内高分子骨架侧链的亲和相互作用中占有重要地位。     

Polystyrene‐based anion exchange membranes via click chemistry: improved properties and AEM performance

Polystyrene‐based anion exchange membranes (AEMs) have been fabricated using in situ click chemistry between azide and alkyne moieties introduced as side groups on functionalized polymers. The membrane properties such as water uptake, swelling ratio and conductivity were affected by the number of cations and the degree of crosslinking. The membranes containing a larger amount of trimethylammonium cationic groups (i.e. higher ion exchange capacity) showed high hydroxide conductivity when immersed in KOH solution, exhibiting a peak in conductivity (156 mS cm^?1) in 3 mol L^–1 KOH solution. A higher degree of crosslinking tended to decrease conductivity. These membranes demonstrated relatively good stability in 8 mol L^–1 KOH at 60 °C and maintained 33%–62% of initial conductivity after 49 days with most of the loss in conductivity occurring in early stages of the test. In an alkaline fuel cell, the areal specific resistance was constant indicating good stability of the membranes. The observed peak power density (157 mW cm^?2) was comparable to that of other AEM‐based fuel cells reported. © 2018 Society of Chemical Industry     

离子交换纤维微观形貌特点及结构修饰研究

利用比表面积测试仪、扫描电子显微镜等物理化学方法对颗粒与纤维状离子交换剂的链间交联与微观形貌进行了研究,通过刚性交联剂对聚丙烯-苯乙烯-二乙烯基苯(PP-ST-DVB)离子交换纤维骨架结构进行了修饰改造。结果表明:离子交换纤维由于不能通过交联剂与致孔剂参与下的单体聚合构建具有丰富微孔的高分子骨架,所以不存在丰富孔结构和高比表面积特征,其内部为连续凝胶相结构;外比表面积大、传质距离短、交联键分布均匀是其反应动力学和渗透压稳定性能优异的主要原因;刚性交联剂在PP-ST-DVB纤维上的附加交联反应使其比表面积从原来的0.5 m~2/g提高到200 m~2/g以上,附加交联反应所形成的分子尺度微孔孔径分布窄,具有超高交联树脂的结构特点。