A novel double branched sulfonated polyimide membrane with ultra-high proton selectivity for vanadium redox flow battery

Long, Jun; Xu, Wenjie; Xu, Shoubin; Li, Jun; Wang, Yanlin; Luo, Huan; Zhang, Yaping; Li, Jinchao; Chu, Liang‐Yin

doi:10.1016/j.memsci.2021.119259

Cited by 51 publications

(19 citation statements)

References 60 publications

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“…Therefore, many efforts have been taken to prepare other proton exchange membranes (PEMs) in order to replace or partially replace Nafion membranes for VRFBs. Some ionic polymers, such as sulfonated poly(ether ether ketone)s (SPEEK), − sulfonated polyimides (SPI), − sulfonated poly(aryl sulfone)s (SPAS), , poly(vinylidene fluoride) PVDF, and so forth, were developed and their physicochemical properties were systematically investigated. However, due to the strong hydrophilicity of sulfonic acid groups and their affinity with vanadium ions, these sulfonated PEMs are difficult to achieve an ideal energy efficiency and durability.…”

Section: Introductionmentioning

confidence: 99%

Efficiency and Oxidation Performance of Densely Flexible Side-Chain Piperidinium-Functionalized Anion Exchange Membranes for Vanadium Redox Flow Batteries

Tao

Wang

Cai

et al. 2021

ACS Appl. Energy Mater.

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In order to improve the performance of vanadium redox flow batteries (VRFBs), a series of anion exchange membranes (PAES-8mPip-x) containing multiple flexible side-chain piperidinium structures were selected for use as ionic membranes for VRFBs. The relationship between their battery performance and chemical structure was systematically investigated, and their oxidation stability and degradation mechanism in strong oxidizing solution were studied in detail. These membranes exhibited high SO4 2– conductivity as well as low area specific resistance due to the incorporation of densely flexible side-chain piperidinium. Their SO4 2– conductivity and area-specific resistance are in the range of 9.6–18.1 mS cm–1 and 0.19–0.34 Ω cm2 at 20 °C, respectively. The single battery assembled with the representative PAES-8mPip-0.25 displayed high efficiencies, and its coulombic efficiency, voltage efficiency, and energy efficiency were 94.78, 90.15, and 85.44% at a current density of 60 mA cm–2, respectively, which were higher than those of Nafion 212 (94.19, 89.08, and 83.90%) at the same testing condition. What is more, it was found that these AEMs had good stability in strong oxidizing solution. Although their polymer backbone was degraded to a certain extent in 1.5 mol L–1 VO2 +/3 mol L–1 H2SO4 at 40 °C, the flexible piperidinium in side chains did not undergo significant chemical degradation. Related research results provide a scientific basis for the design of high-performance anion membrane materials for VRFBs.

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Section: Introductionmentioning

confidence: 99%

Efficiency and Oxidation Performance of Densely Flexible Side-Chain Piperidinium-Functionalized Anion Exchange Membranes for Vanadium Redox Flow Batteries

Tao

Wang

Cai

et al. 2021

ACS Appl. Energy Mater.

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“…Membrane Permeability and Water Contact Angle. As a new prevalent method to describe the balance between permeation and conductivity, 41 the selectivity (ratio of proton conductivity and vanadium permeability) values were measured through coin cell assembly (please see Section 3.5) and the diffusion cell setup shown in Figure 4a,b. The configuration of the diffusion cell ensures a similar mass transport mechanism vanadium ions to occur as in a practical zero-gap VRFB with the same electrolyte concentration, in which the same electroactive species diffuse from serpentine flow channels onto and through the membrane electrode assembly (MEA).…”

Section: Resultsmentioning

confidence: 99%

Charge Carrier Molecular Sieve (CCMS) Membranes with Anti-aging Effect for Long-Life Vanadium Redox Flow Batteries

Ghasemiestahbanati

Shaibani

Konstas

et al. 2022

ACS Appl. Energy Mater.

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Vanadium crossover hinders widespread commercial adoption of vanadium redox flow batteries (VRFBs). Superglassy polymers have the potential to offer high selectivity needed to control the crossover but as yet do not possess the requisite proton conductivity and stability. Here, we explore nanocomposite separators that can improve this selectivity. We report a dual-function charge carrier molecular sieve (CCMS) membrane, consisting of a high free volume microporous glassy polymer, poly[1-(trimethylsilyl)-1-propyne] (PTMSP)/sulfonated PAF (PAF-1-SO 3 H), that effectively hinders the migration of hydrated vanadium ions. Furthermore, ideally placed PAF-1-SO 3 H pores not only proved excellent for developing proton conductive channels but also suppressed physical aging within the separator. Experiments then linked this to an increased battery cycle life. As a consequence of achieving higher and more stable VRFB performance compared to benchmarked Nafion (Coulombic efficiencies of 97 vs 87% and capacity retention values of 85 vs 58% at a current density of 60 mA cm −2 , respectively), our integrated design heralds a class of stable separators for hydrogen-based energy technologies. KEYWORDS: super glassy polymer, sulfonated porous aromatic framework, thin-film composite mixed matrix membrane, charge carrier molecular sieve (CCMS) separator, H + /V 4+ selectivity, vanadium redox flow battery

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“…The reason is that the IEC with more SPEEK makes the membrane more hydrophilic, so it is easy to hydrolyze and oxidize under strong acidic and oxidizing conditions. 52 The thermal stability of SPEEK and SPEEK-SA-x membranes at a 20 °C min −1 heating rate of 30−800 °C in the N 2 environment was studied by the TGA method. As shown in Figure 6, the original SPEEK and the membranes with different grafting degrees showed three-step degradation.…”

Section: Membrane Morphologymentioning

confidence: 99%

Side-Chain Grafting-Modified Sulfonated Poly(ether ether ketone) with Significantly Improved Selectivity for a Vanadium Redox Flow Battery

Wang

Wei

et al. 2023

Ind. Eng. Chem. Res.

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A sulfonated poly(ether ether ketone) (SPEEK) proton exchange membrane with side-chain grafted sulfamic acid (SA) was designed. The introduction of SA with an amphoteric functional group achieves the purpose of preventing the migration of vanadium ions in the case of a lossless proton conductive group (−SO3H), which is caused by the Donnan repulsion of a protonated −NH– group to a vanadium ion. At the same time, acid–base pairs and hydrogen bonds are formed between the sulfonated side-chain grafted secondary amine (−NH−) group and the sulfonic (−SO3H) group, which hinders the penetration of vanadium ions. The results show that the prepared SPEEK-SA-50 membrane has high proton conductivity (0.099 S cm–1) and vanadium ion selectivity (1.8 × 105 S min cm–3), and its selectivity is significantly improved compared with SPEEK (4.9 × 104 S min cm–3) and the Nafion 212 membrane (4.8 × 104 S min cm–3). Under the condition of 80 mA cm–2, the Coulombic efficiency (CE) of the vanadium redox flow battery with the SPEEK-SA-50 membrane is 95.45%, and the energy efficiency (EE) is 76.11%, which is better than that of the Nafion 212 membrane (CE: 86.39%; EE: 68.26%).

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A novel double branched sulfonated polyimide membrane with ultra-high proton selectivity for vanadium redox flow battery

Cited by 51 publications

References 60 publications

Efficiency and Oxidation Performance of Densely Flexible Side-Chain Piperidinium-Functionalized Anion Exchange Membranes for Vanadium Redox Flow Batteries

Efficiency and Oxidation Performance of Densely Flexible Side-Chain Piperidinium-Functionalized Anion Exchange Membranes for Vanadium Redox Flow Batteries

Charge Carrier Molecular Sieve (CCMS) Membranes with Anti-aging Effect for Long-Life Vanadium Redox Flow Batteries

Side-Chain Grafting-Modified Sulfonated Poly(ether ether ketone) with Significantly Improved Selectivity for a Vanadium Redox Flow Battery

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