Highly ion-selective sulfonated polyimide membranes with covalent self-crosslinking and branching structures for vanadium redox flow battery

Li, Jinchao; Li, Jun; Xu, Wenjie; Long, Jun; Huang, Wenheng; Zhang, Yaping; Chu, Liang‐Yin

doi:10.1016/j.cej.2022.135414

Cited by 35 publications

(18 citation statements)

References 47 publications

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Section: Introductionmentioning

confidence: 99%

“…Widely used commercial perfluorinated membranes, such as Nafion, possess excellent chemical stability and high proton conductivity; however, a few drawbacks, including high cost and low ion selectivity, impede the practical application of Nafion. 10 The non-fluorinated alternatives, with low cost and high efficiency, have attracted considerable attention in recent years. 11 Sulfonated poly(ether ether ketone) (SPEEK) is considered one of the most promising proton-conductive materials owing to its good membrane-forming properties, excellent mechanical properties, and low cost.…”

Section: ■ Introductionmentioning

confidence: 99%

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Sulfonated Poly(ether Ether Ketone)/Sulfonated Covalent Organic Framework Composite Membranes with Enhanced Performance for Application in Vanadium Redox Flow Batteries

Chen

et al. 2022

ACS Appl. Energy Mater.

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In this study, a series of sulfonated poly(ether ether ketone) (SPEEK)-based ionic exchange membranes were prepared by introducing sulfonated Schiff base network-type (SSNW-1) covalent organic frameworks, which exhibited enhanced properties for application in vanadium redox flow batteries (VRFBs). Compared with the pure SPEEK and Nafion 212 membranes, the SPEEK/SSNW-x% composite membranes showed lower vanadium permeability owing to the size screening of SSNW-1. The vanadium permeability of the SPEEK/SSNW-x% composite membranes decreased with an increase in the SSNW-1 content; the lowest vanadium permeability of 4.02 × 10 −9 cm 2 s −1 was observed with SPEEK/SSNW-3%. However, the vanadium permeability of the composite membranes increased when the SSNW-1 content exceeded 3 wt % because of the aggregation of SSNW-1. In addition, the SPEEK/SSNW-x% composite membrane exhibited good thermal stability and mechanical properties. The VRFB assembled with the SPEEK/SSNW-3% composite membrane showed a Coulombic efficiency (CE) of 99.8% at a current density of 80 mA cm −2 . In contrast, the values with the pure SPEEK and Nafion 212 membranes under the same conditions were 95.4 and 90.4%, respectively. The VRFBs assembled with the SPEEK/ SSNW-3% membrane also exhibited higher voltage efficiency (VE) (85.9%) than that of Nafion 212 (85.0%) and SPEEK (82.6%). Finally, the capacity retention rate of VRFB assembled with the SPEEK/SSNW-3% composite membrane was observed to be superior to that with the pure SPEEK and Nafion 212 membranes. Hence, this study provides a direction for preparing membranes with enhanced performance for VRFB applications.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Sulfonated Poly(ether Ether Ketone)/Sulfonated Covalent Organic Framework Composite Membranes with Enhanced Performance for Application in Vanadium Redox Flow Batteries

Chen

et al. 2022

ACS Appl. Energy Mater.

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“…To be noted, for sulfonated PBI membranes, the self-discharge time increases with increased degree of sulfonation, which is opposite to the Fe 3+ and Cr 3+ permeability. Generally, a higher crossover of active ions through the membranes in RFB means less self-charge period. , The inconsistent result may be caused by the combination of the formed ferric chloride complex (such as FeCl 4 –1 , FeCl 5 –2 , and FeCl 6 –3 ) with the positively charged benzimidazoliums which is believed to be detrimental to the electrolyte and thus the cell’s stability . In the sulfonated PBI membrane matrix, there exists an intermolecular acid–base interaction between the sulfonic acid and imidazole groups, which strengthens with the increased sulfonation degree, thus leading to fewer free imidazole groups to form imidazolium and thus bonding with the ferric chloride complex.…”

Section: Results and Discussionmentioning

confidence: 99%

Highly Ion Selective Proton Exchange Membrane Based on Sulfonated Polybenzimidazoles for Iron–Chromium Redox Flow Battery

Wang

Geng

Tan

et al. 2022

ACS Appl. Energy Mater.

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The iron–chromium redox flow battery (ICRFB) has great potential for large-scale energy storage, due to its low capital cost of redox-active materials. However, the trade-off between conductivity and selectivity in the membranes limits its applications. Herein, a series of sulfonated polybenzimidazoles with exactly controlled sulfonation degree (SD) (S-PBI-x, x refers to SD) are designed and synthesized via direct copolymerization from the sulfonated monomer. Combined with the electrostatic repulsion of the formed imidazoliums, the S-PBIx membranes facilitate the proton transport and repel the redox-active ion crossover efficiently. Especially, when compared with Nafion 212 membrane, the S-PBI-100 membrane displays a comparable conductivity and more than an order of magnitude lower Fe3+ and Cr3+ permeabilities. Thus, a higher columbic efficiency (CE) of 98.2% and energy efficiency (EE) of 83.17% are achieved at 80 mA cm–2 for the corresponding ICRFB. Most importantly, no chemical degradation is observed for the S-PBI-100 membrane after in situ and ex situ stability tests.

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“…31 Li et al prepared a series of new membranes with covalent self-cross-linking and branching structure. 32 The obtained membrane with a cross-linking degree of 14% exhibited a high ion selectivity of 2.78 × 10 5 S min cm −3 .…”

Section: Introductionmentioning

confidence: 90%

Dual Cross-Linked Poly(vinyl alcohol)-Based Anion Exchange Membranes with High Ion Selectivity for Vanadium Flow Batteries

Liu

Shi

et al. 2023

ACS Appl. Polym. Mater.

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As a widely used, low-cost, and environmentally friendly carbohydrate polymer, poly(vinyl alcohol) (PVA) is employed to prepare dual cross-linked anion exchange membranes (AEMs) for vanadium flow batteries (VFBs). Tertiary amine group functionalized PVA (i.e., poly(vinyl acetal) (PVAc)) is first synthesized via the acetalization reaction between 4dimethylaminobenzaldehyde (DMABA) and PVA. Then (5-bromopentyl)-trimethylammonium bromide (BPTMA) is used as the quaternary ammonium reagent, while α,α′-dibromo-p-xylene (DBPX) is adopted as the first cross-linker. Meanwhile, glutaraldehyde (GA) is used as the second cross-linker to further improve the dimensional stability of AEMs. The formed dual cross-linked PVAc-BPTMA-DBPX-GA membranes display enhanced sulfonic acid (SA) uptake and low area resistance (AR), and maintain low VO 2+ permeability and suitable mechanical strength simultaneously. For example, the PVAc-0.5BPTMA-0.5DBPX-GA membrane shows a low AR of 0.27 Ω cm 2 and an ultralow vanadium ion permeability of 8.09 × 10 −8 cm 2 min −1 . Therefore, the above membrane exhibits a significant ion selectivity of 5.95 × 10 5 S min cm −3 , which is nearly 2 orders of magnitude higher than that of Nafion 115 (i.e., 6.66 × 10 3 S min cm −3 ). The VFB based on PVAc-0.5BPTMA-0.5DBPX-GA displays a higher energy efficiency of 85.2% at 100 mA cm −2 than the cell with Nafion 115 (71.1%). Meanwhile, the battery also maintains a stable performance in a long-term operation of 150 cycles.

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Highly ion-selective sulfonated polyimide membranes with covalent self-crosslinking and branching structures for vanadium redox flow battery

Cited by 35 publications

References 47 publications

Sulfonated Poly(ether Ether Ketone)/Sulfonated Covalent Organic Framework Composite Membranes with Enhanced Performance for Application in Vanadium Redox Flow Batteries

Sulfonated Poly(ether Ether Ketone)/Sulfonated Covalent Organic Framework Composite Membranes with Enhanced Performance for Application in Vanadium Redox Flow Batteries

Highly Ion Selective Proton Exchange Membrane Based on Sulfonated Polybenzimidazoles for Iron–Chromium Redox Flow Battery

Dual Cross-Linked Poly(vinyl alcohol)-Based Anion Exchange Membranes with High Ion Selectivity for Vanadium Flow Batteries

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