Constructing Microporous Ion Exchange Membranes via Simple Hypercrosslinking for pH-Neutral Aqueous Organic Redox Flow Batteries.

Ion exchange membranes (IEMs) play a critical role in aqueous organic redox flow batteries (AORFBs). Traditional IEMs that feature microphase-separated microstructures are well developed and easily available but suffer from the conductivity/selectivity tradeoff. The emerging charged microporous polymer membranes show the potential to overcome this tradeoff, yet their commercialization is still hindered by tedious syntheses and demanding conditions. We herein combine the advantages of these two types of membrane materials via simple in-situ hypercrosslinking of conventional IEMs into microporous ones. Such a concept is exemplified by the very cheap commercial quaternized polyphenylene oxide membrane. The hypercrosslinking treatment turns poor-performance membranes into high-performance ones, as demonstrated by the above 10-fold selectivity enhancement and much-improved conductivities that more than doubled. This turn is also confirmed by the effective and stable pH-neutral AORFB with decreased membrane resistance and at least an order of magnitude lower capacity loss rate. This battery shows advantages over other reported AORFBs in terms of a low capacity loss rate (0.0017% per cycle) at high current density. This work provides an economically feasible method for designing AORFB-oriented membranes with microporosity.

Dual-Function Electrolyte Additive Design for Long Life Alkaline Zinc Flow Batteries.

Alkaline zinc-based flow batteries (AZFBs) have emerged as a promising electrochemical energy storage technology owing to Zn abundance, high safety, and low cost. However, zinc dendrite growth and the formation of dead zinc greatly impede the development of AZFBs. Herein, a dual-function electrolyte additive strategy is proposed to regulate zinc nucleation and mitigate the hydroxide corrosion of zinc depositions for stable AZFBs. This strategy, as exemplified by urea, introduces an electrolyte additive to coordinate with Zn2+/Zn with proper strength, slowing zinc deposition kinetics to induce uniform nucleation and protecting the deposited zinc surface from attack by hydroxide ions through preferable adsorption. The zincate complexes with urea are identified to be Zn(OH)2(urea)(H2O)2 and Zn2(OH)4(H2O)4(urea), which exhibit slow zinc deposition kinetics, allowing instantaneous nucleation. Calculation results reveal an additional energy barrier of 1.29 eV for the subsequent adsorption of an OH- group when a urea molecule absorbs on the zinc cluster, significantly mitigating the formation of dead zinc. Consequently, prolonged cell cycling of the prototype alkaline zinc-iron flow battery demonstrates stable operation for over 130 h and an average coulombic efficiency of 98.5%. It is anticipated that this electrolyte additive strategy will pave the way for developing highly stable AZFBs.

Ultramicroporous Tröger's Base Framework Membranes for pH-Neutral Aqueous Organic Redox Flow Batteries.

Processable polymers of intrinsic microporosity (PIMs) are emerging as promising candidates for next-generation ion exchange membranes (IEMs). However, especially with high ion exchange capacity (IEC), IEMs derived from PIMs suffer from severe swelling, thus, resulting in decreased selectivity. To solve this problem, we report ultramicroporous polymer framework membranes constructed with rigid Tröger's Base network chains, which are fabricated via an organic sol-gel process. These membranes demonstrate excellent antiswelling, with swelling ratios below 4.5% at a high IEC of 2.09 mmol g-1, outperforming currently reported PIM membranes. The rigid ultramicropore confinement and charged modification of pore channels endow membranes with both very high size-exclusion selectivity and competitive ion conductivity. The membranes thus enable the efficient and stable operation of pH-neutral aqueous organic redox flow batteries (AORFBs). This work presents the advantages of polymer framework materials as IEMs and calls for increasing attention to extending their varieties and utilization in other applications.

Advancing Ion Selective Membranes with Micropore Ion Channels in the Interaction Confinement Regime.

Ion exchange membranes allowing the passage of charge-carrying ions have established their critical role in water, environmental, and energy-relevant applications. The design strategies for high-performance ion exchange membranes have evolved beyond creating microphase-separated membrane morphologies, which include advanced ion exchange membranes to ion-selective membranes. The properties and functions of ion-selective membranes have been repeatedly updated by the emergence of materials with subnanometer-sized pores and the understanding of ion movement under confined micropore ion channels. These research progresses have motivated researchers to consider even greater aims in the field, i.e., replicating the functions of ion channels in living cells with exotic materials or at least targeting fast and ion-specific transmembrane conduction. To help realize such goals, we briefly outline and comment on the fundamentals of rationally designing membrane pore channels for ultrafast and specific ion conduction, pore architecture/chemistry, and membrane materials. Challenges are discussed, and perspectives and outlooks are given.

Alkaline Membranes toward Electrochemical Energy Devices: Recent Development and Future Perspectives.

Anion-exchange membranes (AEMs) that can selectively transport OH-, namely, alkaline membranes, are becoming increasingly crucial in a variety of electrochemical energy devices. Understanding the membrane design approaches can help to break through the constraints of undesired performance and lab-scale production. In this Outlook, the research progress of alkaline membranes in terms of backbone structures, synthesis methods, and related applications is organized and discussed. The evaluation of synthesis methods and description of membrane stability enhancement strategies provide valuable insights for structural design. Finally, to accelerate the deployment of relevant technologies in alkaline media, the future priority of alkaline membranes that needs to be addressed is presented from the perspective of science and engineering.

Upscaled production of an ultramicroporous anion-exchange membrane enables long-term operation in electrochemical energy devices.

The lack of high-performance and substantial supply of anion-exchange membranes is a major obstacle to future deployment of relevant electrochemical energy devices. Here, we select two isomers (m-terphenyl and p-terphenyl) and balance their ratio to prepare anion-exchange membranes with well-connected and uniformly-distributed ultramicropores based on robust chemical structures. The anion-exchange membranes display high ion-conducting, excellent barrier properties, and stability exceeding 8000 h at 80 °C in alkali. The assembled anion-exchange membranes present a desirable combination of performance and durability in several electrochemical energy storage devices: neutral aqueous organic redox flow batteries (energy efficiency of 77.2% at 100 mA cm-2, with negligible permeation of redox-active molecules over 1100 h), water electrolysis (current density of 5.4 A cm-2 at 1.8 V, 90 °C, with durability over 3000 h), and fuel cells (power density of 1.61 W cm-2 under a catalyst loading of 0.2 mg cm-2, with open-circuit voltage durability test over 1000 h). As a demonstration of upscaled production, the anion-exchange membranes achieve roll-to-roll manufacturing with a width greater than 1000 mm.

Near-frictionless ion transport within triazine framework membranes.

The enhancement of separation processes and electrochemical technologies such as water electrolysers1,2, fuel cells3,4, redox flow batteries5,6 and ion-capture electrodialysis7 depends on the development of low-resistance and high-selectivity ion-transport membranes. The transport of ions through these membranes depends on the overall energy barriers imposed by the collective interplay of pore architecture and pore-analyte interaction8,9. However, it remains challenging to design efficient, scaleable and low-cost selective ion-transport membranes that provide ion channels for low-energy-barrier transport. Here we pursue a strategy that allows the diffusion limit of ions in water to be approached for large-area, free-standing, synthetic membranes using covalently bonded polymer frameworks with rigidity-confined ion channels. The near-frictionless ion flow is synergistically fulfilled by robust micropore confinement and multi-interaction between ion and membrane, which afford, for instance, a Na+ diffusion coefficient of 1.18 × 10-9 m2 s-1, close to the value in pure water at infinite dilution, and an area-specific membrane resistance as low as 0.17 Ω cm2. We demonstrate highly efficient membranes in rapidly charging aqueous organic redox flow batteries that deliver both high energy efficiency and high-capacity utilization at extremely high current densities (up to 500 mA cm-2), and also that avoid crossover-induced capacity decay. This membrane design concept may be broadly applicable to membranes for a wide range of electrochemical devices and for precise molecular separation.

Designing Robust Two-Electron Storage Extended Bipyridinium Anolytes for pH-Neutral Aqueous Organic Redox Flow Batteries.

Bipyridinium derivatives represent the most extensively explored anolyte materials for pH-neutral aqueous organic redox flow batteries, and most derivatives feature two separate electron-transfer steps that cause a sharp decrease in cell voltage during discharge. Here, we propose a strategy to fulfill the concurrent two-electron electrochemical reaction by designing extended bipyridinium derivatives (exBPs) with a reduced energy difference between the lowest unoccupied molecular orbital of exBPs and the ß-highest occupied molecular orbital of the singly reduced form. To demonstrate, a series of exBPs are synthesized and exhibit a single peak at redox potentials of -0.75 to -0.91 V (vs standard hydrogen electrode (SHE)), as opposed to the two peaks of most bipyridinium derivatives. Cyclic voltammetry along with diffusion-ordered spectroscopy and rotating disk electrode experiments confirm that this peak corresponds to a concurrent two-electron transfer. When examined in full-flowing cells, all exBPs demonstrate one charge/discharge plateau and two-electron storage. Continuous galvanostatic cell cycling reveals the side reactions leading to capacity fading, and we disclose the underlying mechanism by identifying the degradation products. By prohibiting the dimerization/ß-elimination side reactions, we acquire a 0.5 M (1 M e-) exDMeBP/FcNCl cell with a high capacity of 22.35 Ah L-1 and a capacity retention rate of 99.95% per cycle.

Functioning Water-Insoluble Ferrocenes for Aqueous Organic Flow Battery via Host-Guest Inclusion.

Ferrocene (Fc) is one of the very limited organic catholyte options for aqueous organic flow batteries (AOFBs), a potential electrochemical energy storage solution to the intermittency of renewable electricity. Commercially available Fc derivatives are barely soluble in water, while existing methods for making water-soluble Fc derivatives by appending hydrophilic or charged moieties are tedious and time-consuming, with low yields. Here, a strategy was developed based on host-guest inclusion to acquire water-soluble Fc-based catholytes by simply mixing Fc derivatives with ß-cyclodextrins (ß-CDs) in water. Factors determining the stability and the electrochemical behavior of the inclusion complexes were identified. When adopted in a neutral pH AOFB, the origin of capacity loss was identified to be a chemical degradation caused by the nucleophilic attack on the center FeIII atom of the oxidized Fc derivatives. By limiting the state of charge, a low capacity fade rate of 0.0073 % h-1 (or 0.0020 % per cycle) was achieved. The proposed strategy may be extended to other families of electrochemically active water-insoluble organic compounds, bringing more electrolyte options for practical AOFB applications.

Designer Ferrocene Catholyte for Aqueous Organic Flow Batteries.

The aqueous organic flow battery (AOFB) holds enormous potential as an energy storage device for fluctuating renewable electricity by exploiting the redox reactions of water-soluble organic molecules. The current development is impeded by lack of organic molecules adequate as catholyte, yet how the catholyte structure impacts the battery lifetime remains unexplored. Here, six ferrocene derivatives with deliberately tuned chemical structure were devised. They underwent reversible redox reactions in water, and the redox potentials were inversely related to the lowest unoccupied molecular orbital (LUMO) energy of their energized forms. The stability of the ferrocene derivatives was evaluated in full flow cells and in symmetric cells. Density function theory calculations, along with experimental results, revealed that the localized LUMO density on Fe led to fast capacity fading. BQH-Fc, which has the lowest LUMO density on Fe, showed the highest stability. No capacity loss was observed for the BQH-Fc/BTMAP-Vi cell at 0.1 m, and a high capacity retention rate of 99.993 % h-1 was recorded at 1.5 m, which could be attributed to electrolyte crossover. To facilitate explorations of robust and high capacity catholytes, a method was established to predict the water solubility of ferrocene molecules, and calculations were in good accordance with measured values.

Hydrophilic Microporous Polymer Membranes: Synthesis and Applications.

Ion and water transfer in subnanometer-sized confined channels of hydrophilic microporous polymer membranes show enormous potential in tackling the ubiquitous trade-off between permeability and selectivity for energy and environment-related membrane technologies. To this end, a variety of hydrophilic polymers of intrinsic microporosity (HPIMs) have been developed. Herein, the synthetic strategies toward HPIMs are summarized, including post-synthetic modification of polymers to introduce polar groups (e. g., amines, hydroxy groups, carboxylic acids, tetrazoles) or charged moieties (e. g., quaternary ammonium salts, sulfonic acids), and the polymerization of hydrophilic monomers. The advantages of HPIM membranes over others when employed in energy conversion and storage, acid gas capture and separation, ionic diodes, and ultrafiltration, are highlighted.

Sulfonated Microporous Polymer Membranes with Fast and Selective Ion Transport for Electrochemical Energy Conversion and Storage.

Membranes which allow fast and selective transport of protons and cations are required for a wide range of electrochemical energy conversion and storage devices, such as proton-exchange membrane (PEM) fuel cells (PEMFCs) and redox flow batteries (RFBs). Herein we report a new approach to designing solution-processable ion-selective polymer membranes with both intrinsic microporosity and ion-conductive functionality. Polymers are synthesized with rigid and contorted backbones, which incorporate hydrophobic fluorinated and hydrophilic sulfonic acid functional groups, to produce membranes with negatively charged subnanometer-sized confined ionic channels. The ready transport of protons and cations through these membranes, and the high selectivity towards nanometer-sized redox-active molecules, enable efficient and stable operation of an aqueous alkaline quinone redox flow battery and a hydrogen PEM fuel cell.

Screening Viologen Derivatives for Neutral Aqueous Organic Redox Flow Batteries.

Viologen derivatives have been developed as negative electrolyte for neutral aqueous organic redox flow batteries (AOFBs), but the structure-performance relationship remains unclear. Here, it was investigated how the structure of viologens impacts their electrochemical behavior and thereby the battery performance, by taking hydroxylated viologens as examples. Calculations of frontier molecular orbital energy and molecular configuration promise to be an effective tool in predicting potential, kinetics, and stability, and may be broadly applicable. Specifically, a modified viologen derivative, BHOP-Vi, was proved to be the most favorable structure, enabling a concentrated 2 m battery to exhibit a power density of 110.87 mW cm-2 and an excellent capacity retention rate of 99.953 % h-1 .

Advances in Artificial Layers for Stable Lithium Metal Anodes.

Lithium (Li) metal is considered as the most promising anode material for rechargeable high-energy batteries. Nevertheless, the practical implement of Li anodes is significantly hindered by the growth of Li dendrites, which can cause severe safety issues. To inhibit the formation of Li dendrites, coating an artificial layer on the Li metal anode has been shown to be a facile and effective approach. This review mainly focuses on recent advances in artificial layers for stable Li metal anodes. It summarizes the progress in this area and discusses the different types of artificial layers according to their mechanisms for Li dendrite inhibition, including regulation of uniform deposition of Li metal and suppression of Li dendrite growth. By doing this, it is hoped that this contribution will provide instructional guidance for the future design of new artificial layers.

Endowing g-C3 N4 Membranes with Superior Permeability and Stability by Using Acid Spacers.

g-C3 N4 membranes were modulated by intercalating molecules with SO3 H and benzene moieties between layers. The intercalation molecules break up the tightly stacking structure of g-C3 N4 laminates successfully and accordingly the modified g-C3 N4 membranes give rise to two orders magnitude higher water permeances without sacrificing the separation efficiency. The sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO)/g-C3 N4 with a thickness of 350 nm presents an exceptionally high water permeance of 8867 L h-1 m-2 bar-1 and 100 % rejection towards methyl blue, while the original g-C3 N4 membrane with a thickness of 226 nm only exhibits a permeance of 60 L h-1 m-2 bar-1 . Simultaneously, SO3 H sites firmly anchor nitrogen with base functionality distributing onto g-C3 N4 through acid-base interactions. This enables the nanochannels of g-C3 N4 based membranes to be stabilized in acid, basic, and also high-pressure environments for long periods.

Highly Conductive and Water-Swelling Resistant Anion Exchange Membrane for Alkaline Fuel Cells.

To ameliorate the trade-off effect between ionic conductivity and water swelling of anion exchange membranes (AEMs), a crosslinked, hyperbranched membrane (C-HBM) combining the advantages of densely functionalization architecture and crosslinking structure was fabricated by the quaternization of the hyperbranched poly(4-vinylbenzyl chloride) (HB-PVBC) with a multiamine oligomer poly(N,N-Dimethylbenzylamine). The membrane displayed well-developed microphase separation morphology, as confirmed by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Moreover, the corresponding high ionic conductivity, strongly depressed water swelling, high thermal stability, and acceptable alkaline stability were achieved. Of special note is the much higher ratio of hydroxide conductivity to water swelling (33.0) than that of most published side-chain type, block, and densely functionalized AEMs, implying its higher potential for application in fuel cells.

Biomimetic Nanocones that Enable High Ion Permselectivity.

Artificial counterparts of conical-shaped transmembrane protein channels are of interest in biomedical sciences for biomolecule detection and selective ion permeation based on ionic size and/or charge differences. However, industrial-scale applications such as seawater desalination, separation of mono- from divalent cations, and treatment of highly-saline industrial waste effluents are still big challenges for such biomimetic channels. A simple monomer seeding experimental approach is used to grow ionically conductive biomimetic charged nanocone pores at the surface of an acid-functionalized membrane. These readily scalable nanocone membranes enable ultra-fast cation permeation (Na+ =8.4× vs. Mg2+ =1.4×) and high ion charge selectivity (Na+ /Mg2+ =6×) compared to the commercial state-of-the-art permselective membrane (CSO, Selemion, Japan) owing to negligible surface resistance and positively charged conical pore walls.

An Interfacial Layer Based on Polymers of Intrinsic Microporosity to Suppress Dendrite Growth on Li Metal Anodes.

The performance and safety of lithium (Li) metal batteries can be compromised owing to the formation of Li dendrites. Here, the use of a polymer of intrinsic microporosity (PIM) is reported as a feasible and robust interfacial layer that inhibits dendrite growth. The PIM demonstrates excellent film-forming ability, electrochemical stability, strong adhesion to a copper metal electrode, and outstanding mechanical flexibility so that it relieves the stress of structural changes produced by reversible lithiation. Importantly, the porous structure of the PIM, which guides Li flux to obtain uniform deposition, and its strong mechanical strength combine to suppress dendrite growth. Hence, the electrochemical performance of the anode is significantly enhanced, promising excellent performance and extended cycle lifetime for Li metal batteries.

Thermally triggered polyrotaxane translational motion helps proton transfer.

Synthetic polyelectrolytes, capable of fast transporting protons, represent a challenging target for membrane engineering in so many fields, for example, fuel cells, redox flow batteries, etc. Inspired by the fast advance in molecular machines, here we report a rotaxane based polymer entity assembled via host-guest interaction and prove that by exploiting the thermally triggered translational motion (although not in a controlled manner) of mechanically bonded rotaxane, exceptionally fast proton transfer can be fulfilled at an external thermal input. The relative motion of the sulfonated axle to the ring in rotaxane happens at ~60 °C in our cases and because of that a proton conductivity (indicating proton transfer rate) of 260.2 mS cm-1, which is much higher than that in the state-of-the-art Nafion, is obtained at a relatively low ion-exchange capacity (representing the amount of proton transfer groups) of 0.73 mmol g-1.