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Composite Polybenzimidazole Membrane with High Capacity Retention for Vanadium Redox Flow Batteries.

ABSTRACT: Currently, energy storage technologies are becoming essential in the transition of replacing fossil fuels with more renewable electricity production means. Among storage technologies, redox flow batteries (RFBs) can represent a valid option due to their unique characteristic of decoupling energy storage from power output. To push RFBs further into the market, it is essential to include low-cost materials such as new generation membranes with low ohmic resistance, high transport selectivity, and long durability. This work proposes a composite membrane for vanadium RFBs and a method of preparation. The membrane was prepared starting from two polymers, meta-polybenzimidazole (6 μm) and porous polypropylene (30 μm), through a gluing approach by hot-pressing. In a vanadium RFB, the composite membrane exhibited a high energy efficiency (~84%) and discharge capacity (~90%) with a 99% capacity retention over 90 cycles at 120 mA·cm^-2, exceeding commercial Nafion^® NR212 (~82% efficiency, capacity drop from 90% to 40%) and Fumasep^® FAP-450 (~76% efficiency, capacity drop from 80 to 65%).

SUBMITTER: Duburg JC

PROVIDER: S-EPMC8002762 | biostudies-literature |

REPOSITORIES: biostudies-literature

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An Economical Composite Membrane with High Ion Selectivity for Vanadium Flow Batteries.

Project description:The ion exchange membrane of the Nafion series widely used in vanadium flow batteries (VFBs) is characterized by its high cost and high vanadium permeability, which limit the further commercialization of VFBs. Herein, a thin composite membrane enabled by a low-cost microporous polyethylene (PE) substrate and perfluorosulfonic acid (PFSA) resin is proposed to reduce the cost of the membrane. Meanwhile, the rigid PE substrate limits the swelling of the composite membrane, which effectively reduces the penetration of vanadium ions and improves the ion selectivity of the composite membrane. Benefiting from such a rational design, a VFB assembled with the PE/PFSA composite membrane exhibited a higher coulombic efficiency (CE ≈ 96.8%) compared with commercial Nafion212 at 200 mA cm-2. Significantly, the energy efficiency maintained stability within 200 cycles with a slow decay rate. In practical terms, the thin PE/PFSA composite membrane with low cost and high ion selectivity can make an ideal membrane candidate in VFBs.

| S-EPMC10057319 | biostudies-literature

Polybenzimidazole/Nafion hybrid membrane with improved chemical stability for vanadium redox flow battery application.

Project description:In order to increase the chemical stability of polybenzimidazole (PBI) membrane against the highly oxidizing environment of a vanadium redox flow battery (VRFB), PBI/Nafion hybrid membrane was developed by spray coating a Nafion ionomer onto one surface of the PBI membrane. The acid-base interaction between the sulfonic acid of the Nafion and the benzimidazole of the PBI created a stable interfacial adhesion between the Nafion layer and the PBI layer. The hybrid membrane showed an area resistance of 0.269 Ω cm2 and a very low vanadium permeability of 1.95 × 10-9 cm2 min-1. The Nafion layer protected the PBI from chemical degradation under accelerated oxidizing conditions of 1 M VO2 +/5 M H2SO4, and this was subsequently examined in spectroscopic analysis. In the VRFB single cell performance test, the cell with the hybrid membrane showed better energy efficiency than the Nafion cell with 92.66% at 40 mA cm-2 and 78.1% at 100 mA cm-2 with no delamination observed between the Nafion layer and the PBI layer after the test was completed.

| S-EPMC9082649 | biostudies-literature

PVDF/Graphene Composite Nanoporous Membranes for Vanadium Flow Batteries.

Project description:The development of chemically stable and high conductive membranes is one of the most important issues to improve the performance of vanadium flow batteries (VFBs). Herein, poly(vinylidene fluoride) (PVDF)/graphene composite nanoporous membranes were easily fabricated by manipulating crystallization processes. The graphene was used to enhance membrane selectivity and conductivity. In the nanoscale channels of the membranes, the graphene nanosheets reduced the apertures among the crystal grains, thus restraining vanadium ions crossover due to the size exclusion effect. Moreover, the oxygen groups on the graphene improved the surface hydrophilicity and formed hydrogen bonds with the PVDF polymer chains, which facilitated the proton transport. The composite membranes, with a 0.15 wt % graphene loading, showed a selectivity of 38.2 and conductivity of 37.1 mS/cm. The single cell exhibited a coulomb efficiency of 94.7%, a voltage efficiency of 88.5%, and an energy efficiency of 83.8%, which was 13% higher than that of the pristine PVDF membranes. The composite membranes showed excellent stability during 100 charge-discharge cycles. All these results indicate that the PVDF/graphene composite membrane is a promising candidate for VFB applications.

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Polymer Membranes for All-Vanadium Redox Flow Batteries: A Review.

Project description:Redox flow batteries such as the all-vanadium redox flow battery (VRFB) are a technical solution for storing fluctuating renewable energies on a large scale. The optimization of cells regarding performance, cycle stability as well as cost reduction are the main areas of research which aim to enable more environmentally friendly energy conversion, especially for stationary applications. As a critical component of the electrochemical cell, the membrane influences battery performance, cycle stability, initial investment and maintenance costs. This review provides an overview about flow-battery targeted membranes in the past years (1995-2020). More than 200 membrane samples are sorted into fluoro-carbons, hydro-carbons or N-heterocycles according to the basic polymer used. Furthermore, the common description in membrane technology regarding the membrane structure is applied, whereby the samples are categorized as dense homogeneous, dense heterogeneous, symmetrical or asymmetrically porous. Moreover, these properties as well as the efficiencies achieved from VRFB cycling tests are discussed, e.g., membrane samples of fluoro-carbons, hydro-carbons and N-heterocycles as a function of current density. Membrane properties taken into consideration include membrane thickness, ion-exchange capacity, water uptake and vanadium-ion diffusion. The data on cycle stability and costs of commercial membranes, as well as membrane developments, are compared. Overall, this investigation shows that dense anion-exchange membranes (AEM) and N-heterocycle-based membranes, especially poly(benzimidazole) (PBI) membranes, are suitable for VRFB requiring low self-discharge. Symmetric and asymmetric porous membranes, as well as cation-exchange membranes (CEM) enable VRFB operation at high current densities. Amphoteric ion-exchange membranes (AIEM) and dense heterogeneous CEM are the choice for operation mode with the highest energy efficiency.

| S-EPMC8003036 | biostudies-literature

Performances of Anion-Exchange Blend Membranes on Vanadium Redox Flow Batteries.

Project description:Anion exchange blend membranes (AEBMs) were prepared for use in Vanadium Redox Flow Batteries (VRFBs). These AEBMs consisted of 3 polymer components. Firstly, PBI-OO (nonfluorinated PBI) or F6-PBI (partially fluorinated PBI) were used as a matrix polymer. The second polymer, a bromomethylated PPO, was quaternized with 1,2,4,5-tetramethylimidazole (TMIm) which provided the anion exchange sites. Thirdly, a partially fluorinated polyether or a non-fluorinated poly (ether sulfone) was used as an ionical cross-linker. While the AEBMs were prepared with different combinations of the blend polymers, the same weight ratios of the three components were used. The AEBMs showed similar membrane properties such as ion exchange capacity, dimensional stability and thermal stability. For the VRFB application, comparable or better energy efficiencies were obtained when using the AEBMs compared to the commercial membranes included in this study, that is, Nafion (cation exchange membrane) and FAP 450 (anion exchange membrane). One of the blend membranes showed no capacity decay during a charge-discharge cycles test for 550 cycles run at 40 mA/cm² indicating superior performance compared to the commercial membranes tested.

| S-EPMC6410199 | biostudies-literature

Design of polybenzimidazolium membranes for use in vanadium redox flow batteries.

Project description:In recent years, polybenzimidazole (PBI) membranes have been proposed for vanadium redox flow batteries (VRFBs) as an alternative to perfluoroalkylsulfonic acid membranes such as Nafion™. Despite their excellent capacity retention, PBI membranes tend to suffer from a low ionic conductivity. The formation of a polybenzimidazolium through an N-alkylation of the benzimidazole core is shown to improve the ionic conductivity of the membrane, with this class of materials having found uses in alkaline fuel cell and water electrolysis systems. However, much less is known about their incorporation into a VRFB. This article describes the use of hexamethyl-p-terphenyl polybenzimidazolium (HMT-PMBI) membranes for a vanadium redox flow battery, with the membrane characteristics in acidic media being related to their performance in a single-cell VRFB setup. A change of the degree of methylation from 56 to 65, 75, and 89% leads to an increase in ionic conductivity, correlated with an increased fraction of free water in the ionomer. The corresponding increase in cell performance is, however, accompanied by a drop in capacity retention. The membrane with a degree of methylation of 65% shows balanced properties, with a 5% higher efficiency and a two times improved capacity retention compared to Nafion™ NR212 over 200 charge-discharge cycles at 200 mA cm-2.

| S-EPMC10929584 | biostudies-literature

Hierarchical Carbon Micro/Nanonetwork with Superior Electrocatalysis for High-Rate and Endurable Vanadium Redox Flow Batteries.

Project description:Vanadium redox flow batteries (VRFBs) are receiving increasing interest in energy storage fields because of their safety and versatility. However, the electrocatalytic activity of the electrode is a pivotal factor that still restricts the power and cycling capabilities of VRFBs. Here, a hierarchical carbon micro/nanonetwork (HCN) electrode codoped with nitrogen and phosphorus is prepared for application in VRFBs by cross-linking polymerization of aniline and physic acid, and subsequent pyrolysis on graphite felt. Due to the hierarchical electron pathways and abundant heteroatom active sites, the HCN exhibits superior electrocatalysis toward the vanadium redox couples and imparts the VRFBs with an outstanding energy efficiency and extraordinary stability after 2000 cycles at 250 mA cm-2 and a discharge capacity of 10.5 mA h mL-1 at an extra-large current density of 400 mA cm-2. Such a micro/nanostructure design will force the advancement of durable and high-power VRFBs and other electrochemical energy storage devices.

| S-EPMC6299713 | biostudies-literature

Dataset on performance of large-scale vanadium redox flow batteries with serpentine flow fields.

Project description:The dataset presented in this article are related to research articles "Effect of electrolyte convection velocity in the electrode on the performance of vanadium redox flow battery cells with serpentine flow fields" [1] and "Effect of channel dimensions of serpentine flow fields on the performance of a vanadium redox flow battery" [2]. The combined dataset on the pressure drop and electrochemical behavior of the vanadium flow battery cells with active areas of 400 cm2, 900 cm2 and 1500 cm2 were obtained using battery life cycler for the circulation of vanadium electrolyte of concentration 1.61 M VOSO4 dissolved in 5 M H2SO4. The cells were designed with various combinations of flow-channel dimensions of serpentine flow field and the electrochemical performance has been obtained at various flow rates and current densities. In addition to the experimental data, computational fluid dynamics simulations have been performed to investigate the electrolyte distribution across the cell. The shared data enables the reader of research articles to delve into the life cycle behavior at various operating conditions and emphasize the importance of flow-channel dimensions, flow rate and uniform distribution of electrolyte in combating the concentration over-potential.

| S-EPMC7890134 | biostudies-literature

Novel Anion Exchange Membrane Based on Poly(Pentafluorostyrene) Substituted with Mercaptotetrazole Pendant Groups and Its Blend with Polybenzimidazole for Vanadium Redox Flow Battery Applications.

Project description:In order to evaluate the performance of the anion exchange membranes in a vanadium redox flow battery, a novel anion exchange polymer was synthesized via a three step process. Firstly, 1-(2-dimethylaminoethyl)-5-mercaptotetrazole was grafted onto poly(pentafluorostyrene) by nucleophilic F/S exchange. Secondly, the tertiary amino groups were quaternized by using iodomethane to provide anion exchange sites. Finally, the synthesized polymer was blended with polybenzimidazole to be applied in vanadium redox flow battery. The blend membranes exhibited better single cell battery performance in terms of efficiencies, open circuit voltage test and charge-discharge cycling test than that of a Nafion 212 membrane. The battery performance results of synthesized blend membranes suggest that those novel anion exchange membranes are promising candidates for vanadium redox flow batteries.

| S-EPMC7240731 | biostudies-literature

Influence of Membrane Equivalent Weight and Reinforcement on Ionic Species Crossover in All-Vanadium Redox Flow Batteries.

Project description:One of the major sources of lost capacity in all-vanadium redox flow batteries (VRFBs) is the undesired transport (usually called crossover) of water and vanadium ions through the ion-exchange membrane. In this work, an experimental assessment of the impact of ion-exchange membrane properties on vanadium ion crossover and capacity decay of VRFBs has been performed. Two types of cationic membranes (non-reinforced and reinforced) with three equivalent weights of 800, 950 and 1100 g·mol-1 were investigated via a series of in situ performance and capacity decay tests along with ex situ vanadium crossover measurement and membrane characterization. For non-reinforced membranes, increasing the equivalent weight (EW) from 950 to 1100 g·mol-1 decreases the V(IV) permeability by ~30%, but increases the area-specific resistance (ASR) by ~16%. This increase in ASR and decrease in V(IV) permeability was accompanied by increased through-plane membrane swelling. Comparing the non-reinforced with reinforced membranes, membrane reinforcement increases ASR, but V(IV) permeability decreases. It was also shown that there exists a monotonic correlation between the discharge capacity decay over long-term cycling and V(IV) permeability values. Thus, V(IV) permeability is considered a representative diagnostic for assessing the overall performance of a particular ion-exchange membrane with respect to capacity fade in a VRFB.

| S-EPMC5489863 | biostudies-other

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