Vanadium Redox Flow Battery Application Research Articles

Advanced hybrid membrane constructed with silicon carbide, graphene oxide and functionalized silicon carbide for vanadium permeability, proton conductivity to battery and fuel cell applications

The energy sector is currently exploring eco-friendly energy conversion and storage devices, as an alternative to traditional fossil fuel devices. A unique hybrid proton exchange membrane is developed for proton exchange membrane fuel cells (PEMFC) and vanadium redox flow battery (VRFB) application. Polymeric nanocomposite membranes are effective for the selective and controlled transportation of ions between the electrodes. This study utilizes various modifiers such as GO, SGO, SPES, and SiC, to modify the PES polymer matrix. Analysis of the functional groups confirmed the presence of modifiers and hydroxyl groups on the nanocomposite membrane. Additionally, the use of Field Emission Scanning Electron Microscopy (FESEM) validated the existence of honeycomb and sponge-like voids as well as the surface morphology on the membrane surface. The incorporation of modifiers into the nanocomposite membrane matrix serves as a reliable barrier for the transport of vanadium ions, leading to a significant reduction in vanadium ion permeability across the membrane. The mechanical properties and ion exchange capacity of nanocomposite membranes are enhanced, while the permeability of VO2+ decreases compared to that of the bare PES membrane. The enhancement of proton conductivity is further achieved with the utilization of modifiers in PES polymer. As compared to bare PES membrane, PES/SPES + SGO (5%) exhibits less than half the permeability for vanadium, and PES/SiC shows 44.03 % elongation means twice of bare PES membrane.

2-Acrylamido-2-methylpropane sulfonic acid (AMPS) grafted poly(vinylidene fluoride) (PVDF) membrane for improved vanadium redox flow battery (VRFB) performance

Polymer modification techniques are crucial for customizing material properties to suit specific applications, particularly in energy storage systems. This study investigates the modification of poly(vinylidene fluoride) (PVDF) membranes via atom transfer radical polymerization (ATRP) to graft 2-acrylamido-2-methylpropane sulfonic acid (AMPS) onto the fluorinated backbone. The successful grafting was confirmed via nuclear magnetic resonance (NMR) spectroscopy, while the membrane structure was evaluated using infrared (IR) and X-ray photoelectron spectroscopies (XPS). Thermogravimetric analysis (TGA) and universal testing machine (UTM) tests verified the thermal and mechanical stability of the membranes. Electrochemical analysis showed sustained performance over 300 cycles. The FluorCat-25 membrane demonstrated high coulombic efficiency (>98 %), voltage efficiency (83 %), and energy efficiency (81 %) at a current density of 100 mA cm−2. Notably, FluorCat-25 achieved a peak power density of 353 mW cm⁻², surpassing that of Nafion-117 (304 mW cm⁻²), with >85 % capacity retention, indicating its superior performance and suitability for VRFB applications. These findings position FluorCat-25 as a promising candidate for efficient and durable energy storage solutions in VRFB technology.

In Situ Growth of Amorphous MnO2 on Graphite Felt via Mild Etching Engineering as a Powerful Catalyst for Advanced Vanadium Redox Flow Batteries.

Owing to the advantages of low cost, high safety, and a desirable cycling lifetime, vanadium redox flow batteries (VRFBs) have attracted great attention in the large-scale energy storage field. However, graphite felts (GFs), widely used as electrode materials, usually possess an inferior catalytic activity for the redox reaction of vanadium ions, largely limiting the energy efficiency and rate performance of VRFBs. Here, an in situ growth of amorphous MnO2 on graphite felt (AMO@GF) was designed for application in VRFBs via mild and rapid etching engineering (5 min). After the etching process, the graphite felt fibers showed a porous and defective surface, contributing to abundant active sites toward the redox reaction. In addition, formed amorphous MnO2 can also serve as a powerful catalyst to facilitate the redox couples of VO2+/VO2+ based on density functional theoretical (DFT) calculations. As a result, the VRFB using AMO@GF displayed an elevated energy efficiency and superior stability after 2400 cycles at 200 mA cm-2, and the maximum current density can reach 300 mA cm-2. Such a high-efficiency and convenient design strategy for the electrode material will drive the further development and industrial application of VRFBs and other flow battery systems.

Anion exchange membrane based on poly(arylene ether sulfone)s functionalized with quinuclidinium-piperidinium dual cations for vanadium redox flow battery applications

Vanadium redox flow batteries (VRFBs) have gained significant interest as a prospective energy storage solution due to their scalability and extended cycle durability. The efficient functioning of VRFBs relies significantly on anion exchange membranes (AEMs), which facilitate the selective transport of ions while preventing crossover. In this study, we present a novel AEM based on poly(arylene ether sulfone)s (PAES) functionalized with dual cations (quinuclidinium-piperidinium) (DC-PAES) bearing a butyl spacer, explicitly designed for VRFB applications. The DC-PAES membrane containing dual cations separated by a butyl spacer results in a balanced combination of hydrophilicity and hydrophobicity, which enables efficient ion transport across the membrane. The DC-PAES membrane showed hydroxide conductivity of 0.085 S/cm at 80 °C, having an ion exchange capacity (IEC) of 1.42 mmol/g. The resulting DC-PAES membrane displayed low permeability (2.1 × 10−7 cm2 min−1) and high selectivity (12.3 × 105 S min cm−3) to vanadium. The performance of the AEMs fabricated for VRFB application showed better Coulombic (97.1 %), energy (90.0 %), and voltage efficiency (92.63 %) at 40 mAcm−2 higher than Nafion 117. The reported AEMs revealed excellent stability due to the steric and ring constraints of quinuclidinium and piperidinium cation, hindering the attack of oxidative species. Furthermore, the DC-PAES membrane demonstrated improved battery cycling performance lasting up to 150 cycles under in-situ conditions, making it a promising separator material for VRFB applications.

A highly-selective layer-by-layer membrane modified with polyethylenimine and graphene oxide for vanadium redox flow battery

ABSTRACT A selective composite membrane for vanadium redox flow battery (VRFB) was successfully prepared by layer-by-layer (LbL) technique using a perfluorosulfonic sulfonic acid or Nafion 117 (N117). The composite membrane referred as N117-(PEI/GO)n, was obtained by depositing alternating layers of positively charged polyethylenimine (PEI) and negatively charged graphene oxide (GO) as polyelectrolytes. The physicochemical properties and performance of the pristine and composite membranes were investigated. The membrane showed an enhancement in proton conductivity and simultaneously exhibited a notable 90% reduction in vanadium permeability. This, in turn, results in a well-balanced ratio of proton conductivity to vanadium permeability, leading to high selectivity. The highest selectivity of the LbL membranes was found to be 19.2 × 104 S.min/cm3, which is 13 times higher than the N117 membrane (n = 0). This was translated into an improvement in the battery performance, with the n = 1 membrane showing a 4–6% improvement in coulombic efficiency and a 7–15% improvement in voltage efficiency at current densities ranging from 40 to 80 mA/cm2. Furthermore, the membrane displays stable operation over a long-term stability at around 88% at a current density of 40 mA/cm2, making it an attractive option for VRFB applications using the LbL technique. The use of PEI/GO bilayers maintains high proton conductivity and VE of the battery, opening up possibilities for further optimization and improvement of VRFBs.

Layer-by-layer membranes for vanadium redox flow battery

Layer-by-layer (LbL) is a widely utilized method for enhancing the selectivity, efficiency, and long-term stability of ion exchange membranes (IEMs) in various applications. This technique involves the deposition of charged thin films on IEM surface through electrostatic interactions using polycations and polyanions. The simplicity and straightforwardness of the LbL modification technique make it a preferred choice due to its reduced preparation steps and time. This method is found to be suitable for preparation of IEMs with excellent vanadium barrier properties for vanadium redox flow battery (VRFB), a battery that is highly sought to promote renewable energy to the grid level. The objective of this article provides an overview for progress in the development of IEMs for VRFB using LbL method. This includes not only description of the basics of the LbL method and its pros and cons but also factors affecting membrane functions and stability. The current applications of various LbL prepared membranes in VRFB and the challenges to their performance are pointed out. The research future directions to enhance membranes characteristics are discussed. Overall, this short review offers valuable insights into the exploration of LbL techniques for the preparation of highly selective, efficient, and stable membranes for VRFB applications.

Highly ion selective sulfonated poly(ether ether ketone)/polyzwitterion functionalized graphene oxides hybrid membrane for vanadium redox flow battery

High-density zwitterionic groups functionalized graphene oxides (PSBMA@GO) were incorporated into sulfonated poly(ether ether ketone) (SPEEK) membranes to create continuous channels for efficient proton/vanadium ion selective conduction. The incorporation of zwitterionic polymers, specifically poly(sulfobetaine methacrylate) (PSBMA) combined with graphene oxide (GO) sheets, enhanced the compatibility of additives with the SPEEK matrix. Furthermore, the impact of PSBMA@GO content on the properties of S/PSBMA@GO hybrid membranes for vanadium redox flow battery (VRFB) application was investigated. S/PSBMA@GO-1 hybrid membrane exhibits ultrahigh ion selectivity 55.3×103 S min cm-3, and the cell with this membrane shows excellent coulombic efficiencies (98.2-99.1%), energy efficiencies (83.6-74.5%) at 100-180 mA cm-2, long cycle life and high capacity retention (35.8% after 100 cycles at 100 mA cm-2). This study demonstrates that PSBMA@GO have great application potential to solve the trade-off effect between proton conductivity and vanadium ion permeability of PEM.

Effects of N-functional groups on the electron transfer kinetics of VO2+/VO2+ at carbon: Decoupling morphology from chemical effects using model systems

Carbons and nanocarbons are important electrode materials for vanadium redox flow battery applications, however, the kinetics of vanadium species are often sluggish at these surfaces, thus prompting interest in functionalization strategies to improve performance. Herein, we investigate the effect of N-functionalities on the VO2+/VO2+ redox process at carbon electrodes. We fabricate thin film carbon disk electrodes that are metal-free, possess well-defined geometry and display smooth topography, while featuring different N-site distribution, thus enabling a mechanistic investigation of the intrinsic surface activity towards VO2+/VO2+. Voltammetry and electrochemical impedance spectroscopy show that N-functionalities improve performance, with pyridinic/pyrrolic-N imparting the most significant improvements in charge transfer rates and reversibility, compared to graphitic-N. This was further supported by voltammetry studies on nitrogen-free electrodes modified via aryldiazonium chemistry with molecular pyridyl adlayers. Computational modeling using an electrochemical-chemical mechanism indicates that introduction of surface pyridinic/pyrrolic-N can increase the heterogeneous rate constants by approximately two orders of magnitude relative to those observed at nitrogen-free carbon (k0 = 1.29 × 10−4 vs 9.34 × 10−7 cm/s). Simulations also suggest that these N-functionalities play a role in affecting reaction rates in the chemical step. Our results indicate that nitrogen incorporation via basic functional groups offers an interesting route to the design of advanced carbon electrodes for VRFB devices.

Sulfonated polyimide membranes with branched architecture and unique diamine monomer for implementation in vanadium redox flow battery

In this paper, a new functional diamine monomer 2-methyl-1,4-bis(4-amino-2-trifluoromethyl) benzene (FAPOB) is designed and synthesized for further improving the performance of branched sulfonated polyimide (SPI–B) membrane for implementation in vanadium redox flow battery (VRB). At the same time, the sulfonation levels of SPI-B membranes are accurately regulated by modifying the proportion of FAPOB and 4,4′-diaminobiphenyl-2,2′-disulphonic acid. Among them, the SPI-B-50 membrane with 50 % sulfonation degree exhibits a remarkable proton selectivity of 2.31 × 105 S min/cm3, which is 5.5 times higher than the Nafion 212 (NR212) membrane. Moreover, the SPI-B membrane's stability is significantly improved due to its branched structure and the presence of numerous trifluoromethyl groups. Compared to NR212 membrane, SPI-B-50 membrane demonstrates superior coulomb and energy efficiencies at the same current density. Furthermore, the SPI-B-50 membrane exhibits a higher voltage holding capacity compared to the NR212 membrane. Remarkably, the SPI-B-50 membrane maintains stable efficiencies even after undergoing more than 500 charge-discharge cycles. This research not only involves the innovative synthesis of a novel diamine monomer but also the construction of various SPI-B membranes with a unique molecular structure specifically designed for VRB applications.

Construction of thermal, chemical and mechanically stable ion exchange membranes with improved ion selectivity for vanadium redox flow batteries applications

As an alternative to expensive Nafion membrane, SPEEK (Sulfonated Poly Ether Ether Ketone) membrane reinforced with hydroxylated boron nitride is investigated as a potential proton exchange membrane for vanadium redox flow battery (VRFB). SPEEK based hybrid membranes are characterized for their thermal, mechanical and chemical stability along with proton conductivity and vanadium permeability. The results reveal that the hydroxylated boron nitride enhances the physicochemical properties of SPEEK and shown to improve selectivity of ions (52.629 *103. S.cm−3.min) with better stability. The improved properties are attributed to hydrogen bond formation between hydroxyl moieties of born nitride and sulfonic acid group in SPEEK. Among the hybrid membrane, SPEEK reinforced with 0.05 wt % of hydroxylated boron nitride exhibits a higher coulombic efficiency of 93.6 % (91.8 % for Nafion), higher self-discharge time of 14.21 h (11.36 h for Nafion) in VRFB single cell performance study. Cyclic performance study in VRFB with hybrid membrane shows stable characteristics during 50 cycles and it reaffirms the structural, thermal and chemical stability of hybrid membranes. Thus, this study provides insight into replacing commercial Nafion with hydroxylated boron nitride reinforced SPEEK hybrid membrane for vanadium redox flow battery.

Cost estimation and performance evaluation of 3D printed membranes for vanadium redox flow batteries

AbstractThe membrane is a central component in the commercialization of vanadium redox flow batteries (VRFB), with Nafion being the preferred material for those membranes. Nafion suffers however from high vanadium crossover and high cost, thus limiting its wider commercial application in VRFB. To address this, studies have focused on sulfonated polyether ether ketone (SPEEK) as an alternative material. This work presents an economic study on the production costs of 3D printed SPEEK (3D‐SPEEK) membranes for VRFB, with multiple production scenarios evaluated. This analysis relies on the performances of 3D‐SPEEK membranes prepared in our laboratory, which have shown higher Coulombic efficiency and lower vanadium ions diffusion than Nafion membranes. Results from the economic analysis revealed that the cost of the 3D‐SPEEK membrane varies from 567.77 to 79.35 €/m2 depending on the production scheme and scale used. Production costs lower than commercial Nafion membranes are achieved when a large production scheme is used. Further analysis shows that 3D‐SPEEK membranes might even be cheaper than conventional SPEEK membranes if their printing time is reduced.

A sulfonated polyimide containing flexible aliphatic segments with high chemical stability for vanadium redox flow battery application

To improve sulfonated polyimide (SPI) chemical stability, the SPI containing flexible aliphatic segments is successfully designed and synthesized. The highest occupied molecular orbital (HOMO) energy, lowest unoccupied molecular orbital (LUMO) energy and their energy gaps (HOMO-LUMO gap (ΔE)) can quantitatively compare the molecular reactivity, which are calculated and used to compare firstly in the SPIs for vanadium redox flow battery (VRFB) application. Furthermore, the natural bond orbital (NBO) charge of SPIs is also used to calculate and compare, respectively. Theoretical calculation shows SPI(DAD) has higher chemical stability. Obtained by experimental results that the retention time in water of SPI(DAD)-60 membrane is 23.58 h at 80 °C, which is nearly four times than conventional SPI under the same conditions. The SPI(DAD)-60 membrane at a current density of 100 mA cm−2 shows higher columbic efficiency (CE: 96.83%), and energy efficiency (EE: 79.47%) than that of N212 membrane (CE: 93.14%, EE: 74.13%). Besides, the SPI(DAD)-60 membrane has 479.1 mA h more charging capacity after 100 cycles compared to N212 membrane. The theoretical calculation of the LUMO energy, HOMO-LUMO gap may be a potential tool that is used to analyze and evaluate the chemical stability of membranes for VRFB application.

Fabrication of Tri-Directional Poly(2,5-benzimidazole) Membrane Using Direct Casting for Vanadium Redox Flow Battery.

In vanadium redox flow batteries (VRFBs), simultaneously achieving high proton conductivity, low vanadium-ion permeability, and outstanding chemical stability using electrolyte membranes is a significant challenge. In this study, we report the fabrication of a tri-directional poly(2,5-benzimidazole) (T-ABPBI) membrane using a direct casting method. The direct-cast T-ABPBI (D-T-ABPBI) membrane was fabricated by modifying the microstructure of the membrane while retaining the chemical structure of ABPBI, having outstanding chemical stability. The D-T-ABPBI membrane exhibited lower crystallinity and an expanded free volume compared to the general solvent-cast T-ABPBI (S-T-ABPBI) membrane, resulting in enhanced hydrophilic absorption capabilities. Compared to the S-T-ABPBI membrane, the enhanced hydrophilic absorption capability of the D-T-ABPBI membrane resulted in a decrease in the specific resistance (the area-specific resistance of S-T-ABPBI and D-T-ABPBI membrane is 1.75 and 0.98 Ωcm2, respectively). Additionally, the D-T-ABPBI membrane showed lower vanadium permeability (3.40 × 10-7 cm2 min-1) compared to that of Nafion 115 (5.20 × 10-7 cm2 min-1) due to the Donnan exclusion effect. Owing to the synergistic effects of these properties, the VRFB assembled with D-T-ABPBI membrane had higher or equivalent coulomb efficiencies (>97%) and energy efficiencies (70-91%) than Nafion 115 at various current densities (200-40 mA cm-2). Furthermore, the D-T-ABPBI membrane exhibited stable performance for over 300 cycles at 100 mA cm-2, suggesting its outstanding chemical stability against the highly oxidizing VO2+ ions during practical VRFB operation. These results indicate that the newly fabricated D-T-ABPBI membranes are promising candidates for VRFB application.

Optimization through response surface methodology of 3D printed membrane preparation conditions for use in vanadium redox flow battery: A vanadium/proton selectivity study

AbstractSPEEK membrane applicable in Vanadium Redox Flow Battery (VRFB) have been 3D printed via Fused Deposition Modeling (FDM). Response Surface Methodology (RSM) has been used to optimize conditions for 3D printing membrane. Good membranes characteristics were obtained by manipulating three parameters, namely the printing temperature, the orientation of the printing layer and the sulfonation time. We evaluated the effects of these three variables on the permeability of membranes to protons and vanadium ions. Results have shown that sulfonation is the most significant variable influencing vanadium and proton permeability. The optimal printing conditions were found at 408°C temperature with a horizontal layer orientation, while the best sulfonation is obtained at 6 min. The optimal membrane has an ion exchange capacity of 0.86 mmolg−1, a water uptake ratio of 22%, a VO2+ permeability of 6.1 × 10−8 cm2 min−1, a H+ permeability of 7.0 × 10−6 cm2 min−1, excellent mechanical stability and better H+/VO2+ perm selectivity than conventional sulfonated polyether ether ketone (SPEEK), Fap450 and Nafion211 membranes. The above results show that the 3D‐SPEEK membrane has great advantages and broad prospects for VRFB applications.

Effect of sodium phosphate on stability and electrochemical performance of the positive electrolyte for a vanadium redox flow battery at 50°C

This report suggests that the addition of sodium phosphate (Na3PO4) into the electrolyte of vanadium redox flow battery (VRFB) can effectively enhance the thermal stability of the electrolyte and significantly improve the discharge capacity at high temperatures. The introduction of Na3PO4 enables the positive electrolytes with 2 M vanadium ions to maintain stability at 50 °C for over 7 days, while the electrolytes without Na3PO4 show significant precipitation on the first day. In addition, a cell containing 0.3 M Na3PO4 exhibits a capacity retention of 83.02% after undergoing 100 cycles, which is nearly 13.2% higher than the pristine cell. After investigating the electrochemical performance of a cell containing 0.3 M Na3PO4 at 50 °C, it is discovered that the energy efficiency of 80% can be maintained at 150 mA cm−2. Additionally, the capacity retention rate of the cell after 100 cycles is 28.47% higher than that of the pristine cell. Therefore, Na3PO4 is a potentially effective additive for VRFB in long-term thermal stability and capacity retention, thereby reducing the thermal management cost of energy storage systems and providing a broad prospect for the application of VRFB.

VRFBs based on benzotriazole grafted polybenzimidazole / polymeric ionic liquid with high ion selectivity

A series of innovative branching OPBI composite membranes (OPBI-BTZ-PIL) were created based on benzotriazole side chain grafted OPBI (OPBI-BTZ) and double-bond ionic liquids for vanadium redox flow battery applications. The benzotriazole contained three nitrogen sites, which helped enhance the proton conductivity and low area resistance. The cation in the polymeric ionic liquid in the matrix and the vanadium ion produces the Donnan effect, which reduces vanadium permeability. Moreover, the hydrogen bond cross-linking network formed by the polymeric ionic liquid in the membrane further helps proton transport. The vanadium permeability of OPBI-BTZ10-PIL10 is as low as 1.51 × 10−9 cm2 min−1, which is one 40th of the Nafion117 (62.54 × 10−9 cm2 min−1). Its ion selectivity is up to 2.45 × 106 S min cm−3. The OPBI-BTZ10-PIL10 membrane performs well at 60 mA cm−2, with CE of 94.12% and EE of 86.2%, both of which are higher than the Nafion117 membrane.

Anion Exchange Membranes Based on Bis-Imidazolium and Imidazolium-Functionalized Poly(phenylene oxide) for Vanadium Redox Flow Battery Applications.

Although the Nafion membrane has a high energy efficiency, long service life, and operational flexibility when applied for vanadium redox flow battery (VRFB) applications, its applications are limited due to its high vanadium permeability. In this study, anion exchange membranes (AEMs) based on poly(phenylene oxide) (PPO) with imidazolium and bis-imidazolium cations were prepared and used in VRFBs. PPO with long-pendant alkyl-side-chain bis-imidazolium cations (BImPPO) exhibits higher conductivity than the imidazolium-functionalized PPO with short chains (ImPPO). ImPPO and BImPPO have a lower vanadium permeability (3.2 × 10-9 and 2.9 × 10-9 cm2 s-1) than Nafion 212 (8.8 × 10-9 cm2 s-1) because the imidazolium cations are susceptible to the Donnan effect. Furthermore, under the current density of 140 mA cm-2, the VRFBs assembled with ImPPO- and BImPPO-based AEMs exhibited a Coulombic efficiency of 98.5% and 99.8%, respectively, both of which were higher than that of the Nafion212 membrane (95.8%). Bis-imidazolium cations with long-pendant alkyl side chains contribute to hydrophilic/hydrophobic phase separation in the membranes, thus improving the conductivity of membranes and the performance of VRFBs. The VRFB assembled with BImPPO exhibited a higher voltage efficiency (83.5%) at 140 mA cm-2 than that of ImPPO (77.2%). These results of the present study suggest that the BImPPO membranes are suitable for VRFB applications.

Preparation of Sulfonated Poly(arylene ether)/SiO2 Composite Membranes with Enhanced Proton Selectivity for Vanadium Redox Flow Batteries

Proton exchange membranes (PEMs) are an important type of vanadium redox flow battery (VRFB) separator that play the key role of separating positive and negative electrolytes while transporting protons. In order to lower the vanadium ion permeability and improve the proton selectivity of PEMs for enhancing the Coulombic efficiency of VRFBs, herein, various amounts of nano-sized SiO2 particles were introduced into a previously optimized sulfonated poly(arylene ether) (SPAE) PEMs through the acid-catalyzed sol-gel reaction of tetraethyl orthosilicate (TEOS). The successful incorporation of SiO2 was confirmed by FT-IR spectra. The scanning electron microscopy (SEM) images revealed that the SiO2 particles were well distributed in the SPAE membrane. The ion exchange capacity, water uptake, and swelling ratio of the PEMs were decreased with the increasing amount of SiO2, while the mechanical properties and thermal stability were improved significantly. The proton conductivity was reduced gradually from 93.4 to 76.9 mS cm-1 at room temperature as the loading amount of SiO2 was increased from 0 to 16 wt.%; however, the VO2+ permeability was decreased dramatically after the incorporation of SiO2 and reached a minimum value of 2.57 × 10-12 m2 s-1 at 12 wt.% of SiO2. As a result, the H+/VO2+ selectivity achieved a maximum value of 51.82 S min cm-3 for the composite PEM containing 12 wt.% of SiO2. This study demonstrates that the properties of PEMs can be largely tuned by the introduction of SiO2 with low cost for VRFB applications.

Novel microporous sulfonated polyimide membranes with high energy efficiency under low ion exchange capacity for all vanadium flow battery

High proton conductivity and low vanadium permeation created great challenges in designing of highly efficient membranes for all vanadium redox flow battery. To overcome this trade-off phenomenon, a series of novel microporous sulfonated polyimides (SPI) with gradient sulfonic acid group concentrations (6FTMA-X) were prepared by a simple one-step polymerization. They demonstrated high molecular weight (Mn of 23 to 59 KDa), modest microporosity (SBET = 437.2 - 39.4 m2 g−1) and suitable interchain space (between 3.7 and 5.2 Å), which provided excellent ion sieving for proton and vanadium ions (2.4 and 6.0 Å). Consequently, although the ion exchange capacities (0.38 - 1.47 mmol g−1) of 6FTMA-Xs were low compared with the reported SPIs, they still achieved high energy efficiency (80.4%) under high current density (100 mA cm−2), which was comparable to Nafion 117 (N117, 81.7%) at the same current density. This was because of the acceptable proton conductivity and ultra-low vanadium permeation (0.59 - 3.56 × 10−7 cm2 min−1). We suppose the micropore inside the sulfonated polyimides behaviors as ion channel for proton transport and a vanadium barrier. All these results demonstrate that the 6FTMA-X membranes show great potential for vanadium redox flow battery applications. This polymer design strategy provided new insight for highly efficient membranes for VRFB applications.

Low Vanadium Permeability Membranes Based on Flexible Hydrophilic Side Chain Grafted Polybenzimidazole/Polymeric Ionic Liquid for VRFBs

Based on amino polybenzimidazoles with flexible hydrophilic side chains (AmPBI-MOE) and polymeric ionic liquid (PIL), a series of composite membranes (AmPBI-MOE-PIL-X) were fabricated for vanadium redox flow battery applications. Here, 1-Bromo-2-(2-methoxyethoxy)ethane was grafted onto amino polybenzimidazole (AmPBI) by the method of halogenated hydrocarbons, and PIL was synthesized from ionic liquids by in situ radical polymerization to build a hydrogen-bonded cross-linked network within the film. The hydrophilic side chain improves the proton conductivity. With the increase in ionic liquids, the vanadium transmittance and the proton conductivity increase. The AmPBI-MOE-PIL-5 membrane not only exhibits a vanadium ions permeability of 0.88 × 10−9 cm2 min−1, which is much lower than Nafion117 (6.07 × 10−8 cm2 min−1), but also shows a very excellent blocking ability for vanadium ion. The AmPBI-MOE-PIL-5 membrane shows excellent performances at 60 mA cm−2, with VE of 87.93% and EE of 82.87%, both higher than that of Nafion117 membrane in VRFB.