Proton exchange membranes containing densely alkyl sulfide sulfonated side chains for vanadium redox flow battery

Cai, Shiju; Wang, Chenyi; Tao, Zhengwang; Qian, Jiafeng; Zhao, Xiaoyan; Li, Jian; Ren, Qiang

doi:10.1016/j.ijhydene.2021.12.263

Cited by 28 publications

(7 citation statements)

References 64 publications

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“…[29][30][31][32][33][34]37 This was mainly because the acid-base interactions of the sPBI-PO membranes between the sulfonic acid groups and the benzimidazole rings led to the binding of some acid protons, reducing the conduction of protons. [29][30][31][32] Although the proton conductivities were much lower than the corresponding values of low-temperature PEMs, the sPBI membranes still exhibited significant advantages at high temperatures and in dry conditions. [55][56][57][58] Moreover, phosphoric acid (PA) doping effectively increased the proton conductivities of the sPBI-PO membranes.…”

Section: 34mentioning

confidence: 99%

“…There are three main methods used to attach sulfonated groups to the PBI backbone and prepare sPBIs by chemical linkage: grafting, post-sulfonation, and direct polycondensation. [29][30][31][32] Direct polycondensation is more advantageous for controlling the sulfonated parts in the polymer backbone and designing the product structure. Thus, the use of direct condensation to prepare soluble sPBIs with high molecular weight in PEM research is very exciting.…”

Section: Introductionmentioning

confidence: 99%

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Soluble sulfonated polybenzimidazoles containing phosphine oxide units as proton exchange membranes

et al. 2023

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Section: 34mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Soluble sulfonated polybenzimidazoles containing phosphine oxide units as proton exchange membranes

et al. 2023

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“…The vanadium redox flow battery (VRFB) is a kind of redox flow battery with vanadium as the active substance in the circulating liquid state. , The electric energy of the VRFB is stored as chemical energy in the electrolytes of vanadium ions with different valence states. , The electrolytes are pressed into the battery stack through an external pump and circulate in the different liquid storage tanks and closed circuits of half batteries under the action of mechanical power to achieve energy storage. , The ion exchange membranes, as a key component of the VRFB, play a role in separating the positive and negative electrolytes inside a single battery and allow the selective penetration of specific ions and conducting ions to form a circuit. , Therefore, the ion exchange membranes need to meet the conditions of high conductivity and stability. , At present, proton exchange membranes (PEMs) are most widely used in the VRFB, among which commercial Nafion is the most representative. However, such membranes have a high cost and VO 2+ permeability. − Li et al prepared a series of PEMs based on polyimides.…”

Section: Introductionmentioning

confidence: 99%

“…16,17 The ion exchange membranes, as a key component of the VRFB, play a role in separating the positive and negative electrolytes inside a single battery and allow the selective penetration of specific ions and conducting ions to form a circuit. 18,19 Therefore, the ion exchange membranes need to meet the conditions of high conductivity and stability. 20,21 At present, proton exchange membranes (PEMs) are most widely used in the VRFB, among which commercial Nafion is the most representative.…”

Section: ■ Introductionmentioning

confidence: 99%

Preparation and Properties of Quaternary Ammonium Anion Exchange Membranes with Flexible Side Chains for the Vanadium Redox Flow Battery

Qian

Cai

et al. 2023

Ind. Eng. Chem. Res.

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In order to promote the conduction and stability of anion exchange membranes (AEMs) for the vanadium redox flow battery (VRFB), a kind of quaternary ammonium AEMs with flexible side chains (PAES-4N-xx, xx represents the proportion of monomers containing an amino structure) are prepared via aromatic nucleophilic polycondensation and grafting reactions. The ion exchange capacity (IEC) values of PAES-4N-xx are in the range of 1.58−2.10 mmol g −1 , and their water uptake, swelling ratio, SO 4 2− conductivity, and VO 2+ permeability at 30 °C are in the range of 15−52%, 5−17%, 13.5−22.4 mS cm −1 , and 8.6−43.3 cm 2 min −1 , respectively. In addition, PAES-4N-xx display good stability, and their retention ratio of IEC and conductivity reach more than 95% after soaking in a solution of 1.5 mol L −1 VO 2 + /3 mol L −1 H 2 SO 4 at RT for 30 days. The typical battery assembled with PAES-4N-40 shows high efficiency; its Coulomb efficiency (CE), voltage efficiency (VE), and energy efficiency (EE) are in the range of 93.5%−97.8%, 88.6%−70.5%, and 69.0%− 84.9% at the fixed current density which is between 40 mA cm −2 and 200 mA cm −2 , respectively. The battery also has good stability for 100 cycles of charging and discharging at a current density of 40 mA cm −2 , and its retention of EE reaches 96.5%. The introduction of flexible side chains and dense cationic structures can effectively improve the performance of the VRFB.

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“…Water diffusion in PCMs has a critical role to improve ion conductivity and fuel cell efficiency. Different strategies (e.g., inclusion of nanoparticles in PCMs) have been employed to increase water retention and ion conductivity. , In recent studies, adding ionic side-chains to the polymer backbone has been found to be a novel design method to dictate the performance of fuel cells by balancing the ion diffusion rate and water content in the PCMs. ,− However, the origin of the increased conductivity of PCMs has not been explored. For example, Li et al proposed a sulfonated poly(arylene ether sulfone) model membrane with two pendant aliphatic sulfonic acid groups (tetramethoxy groups) and two −OH groups per repeating unit.…”

Section: Introductionmentioning

confidence: 99%

Role of Side-Chain Lengths on Hydronium Mobility in Sulfonated Poly(ether sulfone) Proton-Conducting Model Membranes

2023

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Designing novel polymer architectures is a key to maintain high proton conductivity for proton-conducting membranes (PCMs) while reducing fuel permeability at a medium water content. Modifying anion exchange membranes with alkyl side-chains is a common strategy to improve the aforementioned membrane properties. This improvement is attributed to the flexibility and dynamics of alkyl side-chains, which speed up the hand-to-hand process of anion diffusion. In this study, we employed this strategy for PCMs and propose hypothetical model membranes to improve proton conduction. To this end, a series of model sulfonated poly(ether sulfone) block copolymers with sulfonate groups attached to the backbone with 0, 6, 10, and 16 carbon unit spacers have been made. Then, we analyzed the morphological properties of the membranes and dynamical properties of water, hydronium ions (H 3 O + ), and methanol by using molecular dynamics simulations. We find that the morphological parameters of the PCM and the hydrophilic domains are almost robust against alkyl side-chain lengths. Nevertheless, the diffusion coefficients of water and hydronium ions increase with a side-chain length of up to 10 carbon units (around 50%) and decrease for membranes with a spacer length of 16 carbons at λ = 15. Moreover, the methanol diffusion coefficient increase, despite the substantial improvement in sulfonate group mobility, remains marginal (below 15%) with a spacer length; hence, a considerably better membrane selectivity is achieved. The results put forward a new design strategy and produce a general understanding of the structure−function interplay for the new generation of PCMs.

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Proton exchange membranes containing densely alkyl sulfide sulfonated side chains for vanadium redox flow battery

Cited by 28 publications

References 64 publications

Soluble sulfonated polybenzimidazoles containing phosphine oxide units as proton exchange membranes

Soluble sulfonated polybenzimidazoles containing phosphine oxide units as proton exchange membranes

Preparation and Properties of Quaternary Ammonium Anion Exchange Membranes with Flexible Side Chains for the Vanadium Redox Flow Battery

Role of Side-Chain Lengths on Hydronium Mobility in Sulfonated Poly(ether sulfone) Proton-Conducting Model Membranes

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