Next generation anion-exchange membranes (AEM) with covalently-bound antiradical functions for enhanced durability

具有共价结合抗自由基功能的下一代阴离子交换膜 (AEM)，可增强耐用性

• 批准号: EP/T009233/1
• 负责人: John Varcoe
• 金额: $ 67.77万
• 依托单位: University of Surrey
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FT009233%2F1
• 关键词: Next; generation; anion; exchange; membranes

The prime motivation in the development of anion-exchange membrane-(AEM)-based fuel cells (AEMFC) and alkaline water electrolysers (AEM-AWE), that use (generate electricity) and produce sustainable hydrogen respectively, is the potential to minimise the use of precious metal electrocatalysts (cf. proton-exchange membrane equivalents); this will reduce costs and lead to systems involving only earth abundant elements (ensures sustainability). Additionally, AEM-AWEs use low-concentration aqueous-alkali or pure-water feeds (cf. traditional non-AEM alkaline water electrolysers), eliminating the need to handle large quantities of highly caustic solution (that comes with significant environmental implications related to leakage and disposal).The AEMFCs will initially be targeted in the backup power stationary sector (including for telecoms) to replace diesel generators with the added consumer convenience of reduced noise and local emissions of pollutants: the current diesel generation market supplies 200 GW of global power demand (valued at £9B in 2015). The global hydrogen electrolyser market is estimated to register a compound annual growth rate of 7.2% between 2018-28 (market expected to reach US$426.3M by 2028), with application in the transport segment expected to grow at a significant pace in Western Europe ["Hydrogen Electrolyzer Market: Alkaline Electrolyzer Expected to Remain Dominant Product Type Through 2028: Global Industry Analysis 2013-17 and Opportunity Assessment 2018-28", Future market insights report, 2019].The applicants are world-leaders in the development of alkaline polymer electrolyte materials (membranes and powdered forms, the latter for use in electrode manufacture), especially radiation-grafted types. Mechanically robust, alkali stable, and high performance (high conductivity, high water transport) materials have been demonstrated for use in both AEMFCs and AEM-AWEs (temperatures up to 80 degC). The recent improvements in alkali stability means that oxidative-radical degradation mechanisms become relatively significant and now need to be a research focus. The focus of this project is to develop two classes of AEM with further enhanced chemical stabilities (both alkali and radical-oxidative), but where mechanical, ion-transport and water transport properties are not sacrificed: (1) next generation radiation-grafted AEMs (RG-AEM) and (2) new dimensionally-stable, mechanically-strong pore-filled AEMs (PF-AEM).Firstly, the focus will be on the co-incorporation of vinyl-phenolic components into RG-AEMs, where such covalently-bound phenolic components can act as radical traps to enhance radical-oxidative stabilities. Secondly, our prior RG-AEM research has also identified several new advanced monomers (such as the 3-vinylbenzyl chloride) that can form RG-AEMs with enhanced alkali stabilities but, unfortunately, poor ion conductivities and water transport properties (as such monomers cannot be made to radiation-graft at adequate levels, due to the crude radical-based nature of such grafting). Hence, these advanced monomers will be used to make PF-AEMs, which can be fabricated using alternative polymerisation methods (e.g. cationic or advanced controlled-radical polymerisation). Thirdly, co-incorporation of vinyl-phenolic monomers will also be possible with these new PF-AEMs to produce materials with maximised chemical and mechanical stabilities.The RG-AEMs and PF-AEMs will be evaluated in both AEMFCs and AEM-AWEs, to maximise the commercialisation opportunities. This will heavily involve our industrial project partners: AFC Energy (Dunsfold, Surrey) will assist with translating the materials developments into pilot scale AEMFC demonstrator systems, using their fuel cell component integration knowhow and IP (for the backup power sector). PV3 Technologies (Cornwall) will assist with AEM-AWE developments by materials exchange and evaluation and scale-up of AEM-AWE technology in their facilities.

开发基于阴离子交换膜(AEM)的燃料电池(AEMFC)和碱性水电解液(AEM-AWE)的主要动机是尽可能减少贵金属电催化剂的使用，这两种电池分别使用(发电)和生产可持续氢气。质子交换膜的等价物)；这将降低成本，并导致系统只使用富含地球的元素(确保可持续性)。此外，AEM-AWE使用低浓度的水碱或纯水饲料(参见AEMFC最初将针对备用电力固定部门(包括电信)，以取代柴油发电机，从而增加消费者的便利性，降低噪音和本地污染物排放：目前的柴油发电市场供应全球200千兆瓦的电力需求(2015年价值为GB 9B)。全球氢电解槽市场预计在2018-28年间将录得7.2%的复合年增长率(市场预计到2028年将达到4.263亿美元)，西欧运输领域的应用预计将大幅增长[《2019年未来市场洞察报告》，氢电解槽市场：碱性电解槽预计到2028年仍将是主导产品类型：全球行业分析2013-17年和机遇评估2018-28年“。申请者在碱性聚合物电解质材料(膜和粉末形式，后者用于电极制造)，特别是辐射接枝类型的开发方面处于世界领先地位。机械坚固、碱稳定和高性能(高导电性、高水分传输)材料已被证明可用于AEMFC和AEM-AWE(温度高达80℃)。最近碱稳定性的改善意味着氧化-自由基降解机理变得相对重要，现在需要成为研究的重点。本项目的重点是开发两类化学稳定性进一步增强的AEM(碱和自由基氧化)，但机械、离子传输和水传输性能不会受到影响：(1)新一代辐射接枝AEMS(RG-AEM)和(2)新的尺寸稳定、机械填充孔较强的AEMS(PF-AEM)。首先，重点将集中在RG-AEMS中共掺乙烯基酚类成分，其中这种共价结合的酚类成分可以作为自由基陷阱来增强自由基氧化稳定性。其次，我们先前的RG-AEM研究也发现了几种新的先进单体(如3-乙烯基氯化苄)，它们可以形成具有增强的碱稳定性的RG-AEMS，但不幸的是，较差的离子传导性和水传输性能(因为此类单体不能在适当的水平上进行辐射接枝，因为这种接枝的性质是基于粗自由基的)。因此，这些先进的单体将被用于制造PF-AEMS，可以使用替代聚合方法(例如阳离子聚合或先进的受控自由基聚合)来制造PF-AEMS。第三，乙烯基酚醛单体与这些新的PF-AEMS共掺也将有可能生产出具有最大化学和机械稳定性的材料。RG-AEMS和PF-AEMS将在AEMFC和AEM-AWE中进行评估，以最大限度地增加商业化机会。这将极大地涉及我们的工业项目合作伙伴：AFC Energy(位于萨里的邓斯福尔德)将协助将材料开发转化为中试规模的AEMFC演示系统，利用他们的燃料电池组件集成技术和IP(用于备用电力部门)。PV3技术公司(康沃尔)将通过材料交换和评估以及在其设施中扩大AEM-AWE技术来协助AEM-AWE的开发。

项目成果

Changes in permselectivity of radiation-grafted anion-exchange membranes with different cationic headgroup chemistries are primarily due to water content differences

具有不同阳离子头基化学性质的辐射接枝阴离子交换膜的选择性渗透性的变化主要是由于水含量的差异

• DOI: 10.1039/d3ma00082f
• 发表时间: 2023
• 期刊: Materials Advances
• 影响因子: 5
• 作者: Chakraborty A

Isoindolinium Groups as Stable Anion Conductors for Anion-Exchange Membrane Fuel Cells and Electrolyzers.

• DOI: 10.1021/acsmaterialsau.2c00002
• 发表时间: 2022-05-11
• 期刊: ACS MATERIALS AU
• 作者: Aggarwal, Kanika;Gjineci, Nansi;Kaushansky, Alexander;Bsoul, Saja;Douglin, John C;Li, Songlin;Salam, Ihtasham;Aharonovich, Sinai;Varcoe, John R;Dekel, Dario R;Diesendruck, Charles E
• 通讯作者: Diesendruck, Charles E

Radiation-grafted anion-exchange membranes for CO 2 electroreduction cells: an unexpected effect of using a lower excess of N -methylpiperidine in their fabrication

用于CO 2 电还原电池的辐射接枝阴离子交换膜：在其制造中使用较低过量的N-甲基哌啶的意想不到的效果

• DOI: 10.1039/d3ta04915a
• 发表时间: 2023
• 期刊: Journal of Materials Chemistry A
• 影响因子: 11.9
• 作者: Willson T