清洁能源的储存和转化是人类应对能源危机的重要手段,其中电化学能源转化(如燃料电池)及储存(如液流电池(redox flow batteries,RFBs)、锂基动力电池等)技术受到广泛关注.然而,其商业化应用面临稳定性差、功率低及成本高等挑战.自具微孔聚合物(polymers of intrinsic microporosity,PIMs)中高度扭曲的刚性链结构赋予其超高比表面积(Brunauer-Emmett-Teller specific surface area,SABET)及埃米级微孔,可被应用于离子交换膜(ion-exchange membranes,IEMs)、电活性物质及界面功能层等关键部件,以提高电化学能源装置的性能,是一种极具应用前景的多孔材料.本文根据反应原理分类现有的PIMs材料,总结了经典PIMs的合成、官能团化及其微孔结构、性质的调控策略,对PIMs分子结构、孔结构及膜结构的表征方法,以及先进的原位表征和理论模拟手段,以推动对PIMs微孔中传质机理的认识,重点综述了 PIMs在电化学能源转化和储存技术中的应用进展,并提出了未来的发展方向,以指导PIMs在能源领域的广泛应用.
Application of polymers of intrinsic microporosity in electrochemical energy conversion and storage
Increasing concerns about global warming and the climate crisis emphasize the significance of the decarbonization of electric grids and transportation with clean energy resources,such as solar,wind and hydrogen,etc.Clean energy storage and conversion technologies are critical enablers for reducing greenhouse gas emissions and addressing the energy crisis.Electrochemical energy conversion technologies(e.g.,fuel cells)and energy storage technologies(e.g.,redox flow batteries,lithium-based batteries,etc.)have attracted wide attention from both academic and industrial fields.However,their commercialization is greatly challenged by poor stability,insufficient power capability,high costs,etc.Polymers of intrinsic microporosity(PIMs)have an ultra-high specific surface area(＞500 m2 g-1)and abundant sub-nanometer-sized micropores(0.2-0.8 nm)from the insufficient packing of their highly rigid twisted chain structures.In addition to the advantages of high porosity,PIMs are solution-processable and low-cost,rendering them a promising material that can be widely employed as ion-exchange membranes,electroactive materials,and interface functional layers,etc.,to facilitate the commercialization of the electrochemical energy storage and conversion devices.In this review,we first categorized the existing PIMs according to their synthetic mechanisms to dibenzodioxane-PIMs(such as PIM-1),Tröger's base-PIMs(TB-PIMs)and catalytic arene-norbomene annulation(CANAL)ladder PIMs,etc.We highlighted the synthesis,functionalization methods,and the manipulation strategies of the microporous structure of typical PIMs including PIM-1 and TB-PIMs.In addition,we provided a comprehensive summarization of the characterization methods of PIMs to probe their molecular structures,pore structures,and membrane structures,as well as the advanced in-situ characterization techniques and theoretical simulations to facilitate the in-depth investigations of the ion transportation in the sub-nanometer-sized micropores of PIMs.Next,we reviewed the latest progress of the applications of PIMs in electrochemical energy conversion technologies(fuel cells including proton-exchange membrane fuel cells(PEMFC)and alkaline anion-exchange membrane fuel cells(AAEMFC))and energy storage technologies(aqueous and nonaqueous redox flow batteries,aprotic Li-S batteries,etc.).First,PIMs are widely employed as efficient ion-exchange membranes owing to their high porosity and narrow distribution of the sub-nanometer-sized pore structure,which is preferential to break the trade-off of ion selectivity and ionic conductivity in conventional ion-exchange membranes.We provided a fundamental understanding of the ion transportation mechanism of PIMs compared to traditional membrane materials,and further summarized the cell-level characterization protocols,the design principles of PIM-based membranes in different working environments and the strategies for functionalization of PIMs in fuel cells,redox flow batteries and Li-S batteries.Additionally,PIMs are also developed as novel redox active materials,dendrite prohibited coatings for lithium or zinc anodes,porous carbon electrodes,and catalysts protective layer,etc.,in recent years to promote the performances of the electrochemical energy conversion and storage technologies.Finally,we highlighted our perspectives on the future development directions of PIMs to guide their wide contributions in the energy storage and conversion fields.This review provides the fundamental understanding of the design strategies,characterization matrix,mechanism understandings and applications of PIMs in advanced electrochemical energy conversion and storage systems,which will pave the way of the wide applications of PIMs for a cleaner landscape of the energy utilization in the future.
polymers of intrinsic microporosityion-exchange membranesredox flow batteriesfuel cellslithium-sulfur batteries
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