Effect of Free Volume on Water and Salt Transport Properties in Directly Copolymerized Disulfonated Poly(arylene ether sulfone) Random Copolymers

Xie, Wei; Ju, Hao; Geise, Geoffrey M.; Freeman, Benny D.; Mardel, J.; Hill, Anita J.; McGrath, James E.

doi:10.1021/ma102745s

Cited by 142 publications

(140 citation statements)

References 91 publications

(186 reference statements)

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“…However, a salt molecule can be more restricted by crosslinked structure because a salt molecule is usually hydrated and shows larger the dynamic radius than water molecules. 28,[37][38][39] Similar results have been previously reported by McGrath et al, where covalent crosslinking of disulfonated poly(arylene ether sulfone)s by the reaction of multifunctional epoxy agent with phenoxide end group improved R value while maintaining water permeability. 32 The results obtained here suggest that the covalent crosslinking of sulfonated PBI is a promising method to prepare the ultrathin semipermeable membrane with enhanced water transport properties.…”

Section: Effect Of the Hydrophilic Group And Crosslinked Structure Onsupporting

confidence: 88%

“…14,16,[28][29][30] For example, thick single membranes (20-40 lm) based on disulfonated poly(arylene ether sulfone) 16,28,29 and sulfonated poly(arylene ether) 29 were previously studied and these membranes showed the improvement of water permeability according to the ratio of introducing hydrophilic groups into the polymer chains. These previous observations prompted us to study the effect of the hydrophilic group on water transport properties of PBI membranes.…”

Section: Effect Of the Hydrophilic Group And Crosslinked Structure Onmentioning

confidence: 99%

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Effect of primary structure on permselectivity of ultrathin semipermeable polybenzimidazole membrane

Aiba

Tokuyama

Matsumoto

et al. 2014

J of Applied Polymer Sci

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A series of polybenzimidazoles (PBIs) with different main chains and sulfonated PBI were successfully synthesized from the corresponding dicarboxylic acids and 3,3'-diaminobenzidine for the formation of ultrathin, single-component, and semipermeable membranes. Furthermore, the covalently crosslinked PBI membrane was prepared by the reaction of sulfonated PBI with divinyl sulfone. Their water transport properties were evaluated under a reverse osmosis mode and compared with the primary structure based on the water permeability (A) and salt permeability (B) values normalized by the membrane thickness. It was found that the A and B values of the PBIs were improved with increasing the weight ratio of the imidazole rings per repeating unit, the introduction of sulfonate group as the hydrophilic group to the PBI was an effective way to enhance the A value, and the crosslinked structure enhanced the salt rejection rate (R) value while maintaining the water flux.

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Section: Effect Of the Hydrophilic Group And Crosslinked Structure Onsupporting

confidence: 88%

Section: Effect Of the Hydrophilic Group And Crosslinked Structure Onmentioning

confidence: 99%

Effect of primary structure on permselectivity of ultrathin semipermeable polybenzimidazole membrane

Aiba

Tokuyama

Matsumoto

et al. 2014

J of Applied Polymer Sci

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“…The size selectivity, which is also known as steric hindrance, of a membrane affects the mass transfer of molecules / ions by the difference between the size of pores and the solvated diameter of the crossover species. 41 The charge selectivity of Li-N117, according to the principle of Donnan exclusion, 42 functions such that the negative charged RSO − 3 group attracts counter-ions and repels co-ions, and thus facilitates the mass transfer of cations and retards that of anions. Size effect.-In line with Figure 5a, the increase of salt concentration (trend 1) or the change of solvent from DMSO to PC : EC to PC (trend 2) reduces the solvent volume fraction in Li-N117, and consequently, constricts pores of the membrane, which results in larger mass transfer resistance, and experimentally, lower crossover rate of the redox active species.…”

Section: Resultsmentioning

confidence: 99%

An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes

Darling

Gallagher

et al. 2015

J. Electrochem. Soc.

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Nonaqueous redox flow batteries are a fast-growing area of research and development motivated by the need to develop lowcost energy storage systems. The identification of a highly conductive, yet selective membrane, is of paramount importance to enabling such a technology. Herein, we report the swelling behavior, ionic conductivity, and species crossover of lithiated Nafion 117 membranes immersed in three nonaqueous electrolytes (PC, PC : EC, and DMSO). Our results show that solvent volume fraction within the membrane has the greatest effect on both conductivity and crossover. An approximate linear relationship between diffusive crossover of neutral redox species (ferrocene) and the ionic conductivity of membrane was observed. As a secondary effect, the charge on redox species modifies crossover rates in accordance with Donnan exclusion. The selectivity of membrane is derived mathematically and compared to experimental results reported here. The relatively low selectivity for lithiated Nafion 117 in nonaqueous conditions suggests that new membranes are required for competitive nonaqueous redox flow batteries to be realized. Large scale energy storage for the electricity grid is widely considered to be necessary for enabling the use of intermittent renewables as primary power sources, for stabilizing power delivery in developing economies, and for facilitating a range of high-value grid services aimed at improving efficiency and lifetime.1 To date, broad market penetration of energy storage systems has been hindered primarily by high installation and operation costs, resulting in only ∼2.5% of the total electricity production in the US relying on grid energy storage predominantly in the form of pumped hydro-electric.2 However, the rapid and sustained growth of renewable electricity generation (e.g., solar photovoltaic, wind) continues to drive the need for advanced low cost energy storage.3-5 While certain energy storage technologies, such as lithium-ion (Li-ion) batteries, are currently at a price point to fulfill niche markets, 6 present electrical energy storage technologies, in general, are still not economically viable for wide-scale deployment, spurring research and development efforts worldwide. 7Redox flow batteries (RFBs) are electrochemical systems wellsuited for multi-hour energy storage and offer several key advantages over enclosed batteries (e.g., Li-ion, Lead-acid) including independent scaling of power and energy, long service life, improved safety, and simplified manufacturing. [8][9][10][11] Since their advent in the 1970s, 12 numerous aqueous redox chemistries have been developed but none has experienced widespread commercial success. The use of nonaqueous electrolytes in flow batteries is a nascent, yet burgeoning, concept.Transitioning from aqueous to nonaqueous electrolytes offers an extended window of electrochemical stability (> 3 V) and an enriched selection of redox materials due to the broader design space. However, this approach is not without technical hurdles such as the identificati...

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“…Introduction of polymer charge through, for example, sulfonation of a polymer backbone or side chains can profoundly influence salt permeability and sorption properties of a polymer in part because these charged groups markedly increase water uptake in such polymers, and water content has a strong impact on both water and ion transport [10,12,13,[38][39][40][41][42][43]. Additionally, these charged groups can interact with ions that sorb into and diffuse through the polymer [12,[44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Sodium chloride diffusion in sulfonated polymers for membrane applications

Geise

Freeman²,

Paul³

2013

Journal of Membrane Science

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107

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a b s t r a c tSodium chloride permeability and sorption measurements were used to calculate average salt diffusion coefficients for charged, sulfonated polymers of interest for membrane applications. A sulfonated polysulfone random copolymer and two phase-separated, sulfonated styrenic pentablock copolymers were considered, and data for these materials were compared with those for an uncharged cross-linked poly(ethylene glycol diacrylate) hydrogel. The average salt diffusion coefficients reported for the block copolymers are apparent salt diffusion coefficients because the values have not been adjusted for the polymer's phase separated morphology. The sodium chloride permeability of the uncharged hydrogel decreases by about 16% as upstream salt concentration increases from 0.01 to 1 mol L À 1 . This salt permeability change results from a decrease in the salt diffusion coefficient with increasing salt concentration because the polymer's water content decreases as salt concentration increases (i.e., osmotic de-swelling). This decrease in salt diffusion coefficient is consistent with free volume theory, wherein a decrease in water content leads to a decrease in free volume, thereby decreasing the salt diffusion coefficient and, in turn, salt permeability. In contrast, the sodium chloride permeability of the charged polymers increases by more than an order of magnitude as upstream salt concentration increases from 0.01 to 1 mol L À 1 . This salt permeability increase is due to increases in both mobile salt sorption and diffusion coefficients with increasing salt concentration, despite the fact that water content (and, therefore, free volume) in the polymer decreases as salt concentration increases. Thus, the increase in salt diffusion coefficient with increasing salt concentration in the charged polymers results from factors (which are currently poorly understood) other than simply water uptake or free volume.

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Effect of Free Volume on Water and Salt Transport Properties in Directly Copolymerized Disulfonated Poly(arylene ether sulfone) Random Copolymers

Cited by 142 publications

References 91 publications

Effect of primary structure on permselectivity of ultrathin semipermeable polybenzimidazole membrane

Effect of primary structure on permselectivity of ultrathin semipermeable polybenzimidazole membrane

An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes

Sodium chloride diffusion in sulfonated polymers for membrane applications

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