Highly proton conductive, dense polybenzimidazole membranes with low permeability to vanadium and enhanced H<sub>2</sub>SO<sub>4</sub>absorption capability for use in vanadium redox flow batteries

Jang, Jeong Gook; Kim, Sang Woo; Yoon, Sang Jun; Lee, Jang Yong; Lee, Jong-Chan; Hong, Young Taik

doi:10.1039/c6ta05080h

Cited by 112 publications

(91 citation statements)

References 63 publications

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“…It should be noted that AEMs do not always show high CEs, as this would also require a high dimensional stability of the membrane [21]. In addition, more dense PBI membranes yielded higher CEs due to the low vanadium ion permeability [34]. Accordingly, the M-PPFSt-MTZ-Me 4 membrane with the highest F6-PBI content also showed the highest CE, of almost 100%.…”

Section: Vanadium Redox Flow Battery Evaluationmentioning

confidence: 99%

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

et al. 2020

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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.Polymers 2020, 12, 915 2 of 14 and superior chemical stability; however, it has been found that Nafion ® type membranes suffer from high vanadium ion cross-over, resulting in fast capacity fade when used in VRFBs [4,5].In the last decade, interest in using AEMs in various applications, such as alkaline anion exchange membrane fuel cells [6], alkaline anion exchange membrane water electrolysis [7], ionic polymer membrane actuators [8], dye-sensitized solar cells [9], CO 2 pumps [10] and redox flow batteries [11] has strongly increased. In a recent review paper, the number of journal articles published in the field of anion exchange membranes was analyzed using Web of Science (SCI-EXPANDED), showing a steady growth since 2007 [12]. The significant advantage of AEMs when applied in a VRFB is that their positively charged fixed ion groups (commonly quaternary ammonium) exclude positively charged, strongly oxidizing vanadium ions from the membrane interior due to the Donnan exclusion effect, leading to extremely low vanadium ion cross-over [11].Additionally, modified poly(pentafluorostyrene) (PPFSt) was applied in proton exchange membrane fuel cells as sulfonated [13] or phosphonated [14] CEMs, exhibiting outstanding oxidative and thermal stabilities, which were better than those of their non-fluorinated styrene polymer analogs due to the higher bond strengths of the C-F bonds compared to those of C-H bonds [15]. The outstanding stability of PPFSt-based CEMs inspired us to find a route to prepare a PPFSt-based anion exchange polymer with the advantages of AEMs. Introducing spacer units between the polymer backbone and the side chains in an AEM was thought to lead to an enhanced ion-conductivity, which might be facilitated by an improved phase separation between the hydrophobic polymer backbone and the cation-carrying side chains [16]. Tetrazole tethered polymers showed an improved conductivity compared to that of tetramethylammonium-based quaternized poly(phenylene oxide) AEMs, which is thought to be caused by the long-range hydrogen bond network formation by the tetrazole moiety contributing to the ion conductivity [17].In this study, we synthesize...

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Section: Vanadium Redox Flow Battery Evaluationmentioning

confidence: 99%

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

et al. 2020

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“…The influence of GF and CF on the performance of vanadium redox flow battery (VRFB) has been widely reported, while there is less literature on this issue for the application of ICRFBs, as shown in Table S1. Liu et al reported that in comparison with GF, the VRFB adopted with CF exhibits much higher electrochemical activity .…”

Section: Introductionmentioning

confidence: 99%

“…13 More and more researchers are attempting various means for enhancing the electrochemical activity of GF or CF electrode. [18][19][20][21][22][23] The influence of GF and CF on the performance of vanadium redox flow battery (VRFB) has been widely reported, [24][25][26][27] while there is less literature on this issue for the application of ICRFBs, as shown in Table S1. Liu et al reported that in comparison with GF, the VRFB adopted with CF exhibits much higher electrochemical activity.…”

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confidence: 99%

Investigations on physicochemical properties and electrochemical performance of graphite felt and carbon felt for iron‐chromium redox flow battery

et al. 2020

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Summary In this paper, polyacrylonitrile‐based graphite felt (GF), carbon felt (CF) and the effect of thermal activation on them with or without the catalyst (BiCl3) are comprehensively investigated for iron‐chromium redox flow battery (ICRFB) application. The physical‐chemical parameters of GF and CF after the thermal activation is affected significantly by their graphitization degree, oxygen functional groups, and surface area. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results manifest that GF and CF before and after the thermal activation have different electrocatalytic activities owing to oxygen functional groups number increase and the graphitization degree decrease. In terms of the capacity decay rate, as oxygen functional groups provide shorter electrocatalytic pathways than bismuth ions, the performance of GF and CF after the thermal activation is more ideal. As a result, GF before and after the thermal activation exhibits higher efficiency (EE: 86%) and better stability at a charge‐discharge current density of 60 mA·cm−2 than those of CF during charge‐discharge cycling, as the dominant limitation in an ICRFB is ohmic and activation polarization. Therefore, GF after thermal activation together with the addition of BiCl3 in the electrolyte is a more promising electrode material for ICRFBs application than CF.

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“…In order to reduce the area resistance (AR) of dense PBI membranes for VFB, our previous work 45 proposed a concentrated acid preswelling strategy to improve the acid-doping level (ADL) of dense PBI membranes and demonstrated the importance of ADL in the performance of acid-doped PBI systems. Very recently, Hong et al 48 developed dense PBI membranes containing benzimidazole side groups for VFB. The introduction of additional benzimidazole side groups changed the PBI membrane from a semi-crystalline structure to a completely amorphous structure, improving its acid absorption capability and proton conductivity.…”

Section: -15mentioning

confidence: 99%

“…31,33,34,36,41,42 Recently, polybenzimidazoles (PBI) as membrane materials have attracted much attention in VFB applications. [43][44][45][46][47][48] A pristine PBI membrane is an ionic non-conductor. When doped with strong acid solutions, it could transfer protons owing to the existence of -N] groups in the imidazole rings of PBI.…”

Section: -15mentioning

confidence: 99%

Thin skinned asymmetric polybenzimidazole membranes with readily tunable morphologies for high-performance vanadium flow batteries

Peng

Yan

et al. 2017

RSC Adv.

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A series of thin skinned asymmetric polybenzimidazole (PBI) membranes with readily tunable morphologies are fabricated by leaching out the porogen dibutyl phthalate (DBP), for vanadium flow batteries (VFBs). The ultrathin defect-free skin layer fully guarantees high ion selectivity of the membrane. Meanwhile, the area resistance (AR) of the asymmetric PBI membrane is dramatically reduced compared to that of the dense one because of interconnected macro-pores in the sublayer. The membrane morphologies and properties are readily adjusted by varying the porogen content (0-300 wt%), thus managing well the trade-off between AR and ion selectivity. The membrane prepared by adding 200 wt% porogen has a high porosity of 74.9 vol% and an appropriately dense skin thickness of 4.9 mm, and yields the best balance between AR and ion selectivity, assembled with which the flow battery achieves excellent cell performances (coulombic efficiency, CE: 99.0%; energy efficiency, EE: 82.3%) as well as a moderate capacity decay rate (CDR, 0.4% per cycle) at 80 mA cm À2 over cycling. The thin skinned asymmetric PBI membranes prepared here surpass the commercial Nafion 211 membrane (CE: 84.6%; EE: 68.1%; CDR:1.3% per cycle) in terms of cell performances and cost, becoming a promising candidate for VFBs.

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Highly proton conductive, dense polybenzimidazole membranes with low permeability to vanadium and enhanced H₂SO₄absorption capability for use in vanadium redox flow batteries

Cited by 112 publications

References 63 publications

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

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

Investigations on physicochemical properties and electrochemical performance of graphite felt and carbon felt for iron‐chromium redox flow battery

Thin skinned asymmetric polybenzimidazole membranes with readily tunable morphologies for high-performance vanadium flow batteries

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Highly proton conductive, dense polybenzimidazole membranes with low permeability to vanadium and enhanced H2SO4absorption capability for use in vanadium redox flow batteries

Cited by 112 publications

References 63 publications

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

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

Investigations on physicochemical properties and electrochemical performance of graphite felt and carbon felt for iron‐chromium redox flow battery

Thin skinned asymmetric polybenzimidazole membranes with readily tunable morphologies for high-performance vanadium flow batteries

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Highly proton conductive, dense polybenzimidazole membranes with low permeability to vanadium and enhanced H₂SO₄absorption capability for use in vanadium redox flow batteries