Novel highly efficient branched polyfluoro sulfonated polyimide membranes for application in vanadium redox flow battery

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

doi:10.1016/j.jpowsour.2020.229354

Cited by 35 publications

(14 citation statements)

References 53 publications

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“…Recently,aseries of branched polyfluorosulfonated polyimide membranes with mono-branch and double-branch motifs were reported by Zhang,L ie ta l. (BPFSPI-X-Y and dbSPI-X in Figure 2). [28] Theb ranched polymer structure similar to ac rosslinked network made it difficult for the membrane to swell, and thus al ow swelling ratio of 9.09 %a tI EC of 1.14 mmol g À1 was obtained (dbSPI-X in Table 1). [28a] TheY -shaped motifs on the backbone made the membrane more entangled and denser on the molecular level, thus narrowing the ion transport channels and suppressing the vanadium permeation.…”

Section: Molecular Design Of Backbonesmentioning

confidence: 99%

A Chemistry and Microstructure Perspective on Ion‐Conducting Membranes for Redox Flow Batteries

et al. 2021

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Redox flow batteries (RFBs) are among the most promising grid‐scale energy storage technologies. However, the development of RFBs with high round‐trip efficiency, high rate capability, and long cycle life for practical applications is highly restricted by the lack of appropriate ion‐conducting membranes. Promising RFB membranes should separate positive and negative species completely and conduct balancing ions smoothly. Specific systems must meet additional requirements, such as high chemical stability in corrosive electrolytes, good resistance to organic solvents in nonaqueous systems, and excellent mechanical strength and flexibility. These rigorous requirements put high demands on the membrane design, essentially the chemistry and microstructure associated with ion transport channels. In this Review, we summarize the design rationale of recently reported RFB membranes at the molecular level, with an emphasis on new chemistry, novel microstructures, and innovative fabrication strategies. Future challenges and potential research opportunities within this field are also discussed.

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Section: Molecular Design Of Backbonesmentioning

confidence: 99%

A Chemistry and Microstructure Perspective on Ion‐Conducting Membranes for Redox Flow Batteries

et al. 2021

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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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“…For the application of the VRFB, a membrane with high efficiency, stability, and high VRFB performance can be obtained by intelligently optimizing proton conductivity and vanadium ion permeability. ,, Vanadium ions passing through the proton exchange membrane will cause self-discharge, resulting in a low EE for the VRFB . Therefore, it is very desirable to develop membranes with lower vanadium ion permeation.…”

Section: Resultsmentioning

confidence: 99%

“…The density of exchangeable charged groups, which are responsible for ion conduction, was assessed by the IEC. 46 We designed the SPEEK-SA membrane in which the −SO 3 H group maintains the proton conductivity,while the −NH− group hinders the crossover of VO 2+ due to the enhancement of acid−base interface interactions, 47 which increases the charge−discharge time. For the SPEEK-grafted membrane, the IEC decreased gradually with the increase of the grafting degree.…”

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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Novel highly efficient branched polyfluoro sulfonated polyimide membranes for application in vanadium redox flow battery

Cited by 35 publications

References 53 publications

A Chemistry and Microstructure Perspective on Ion‐Conducting Membranes for Redox Flow Batteries

A Chemistry and Microstructure Perspective on Ion‐Conducting Membranes for Redox Flow Batteries

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