On the Conductivity of Proton-Exchange Membranes Based on Multiblock Copolymers of Sulfonated Polysulfone and Polyphenylsulfone: An Experimental and Modeling Study

The effect of relative humidity (RH) and degree of sulfonation (DS) on the ionic conductivity and water uptake of proton-exchange membranes based on sulfonated multiblock copolymers composed of polysulfone (PSU) and polyphenylsulfone (PPSU) is examined experimentally and numerically. Three membranes with a different DS and ion-exchange capacity are analyzed. The heterogeneous structure of the membranes shows a random distribution of sulfonated (hydrophilic) and non-sulfonated (hydrophobic) domains, whose proton conductivity is modeled based on percolation theory. The mesoscopic model solves simplified Nernst–Planck and charge conservation equations on a random cubic network. Good agreement is found between the measured ionic conductivity and water uptake and the model predictions. The ionic conductivity increases with RH due to both the growth of the hydrated volume available for conduction and the decrease of the tortuosity of ionic transport pathways. Moreover, the results show that the ionic conductivity increases nonlinearly with DS, experiencing a strong rise when the DS is varied from 0.45 to 0.70, even though the water uptake of the membranes remains nearly the same. In contrast, the increase of the ionic conductivity between DS=0.70 and DS=0.79 is significantly lower, but the water uptake increases sharply. This is explained by the lack of microphase separation of both copolymer blocks when the DS is exceedingly high. Encouragingly, the copolymer membranes demonstrate a similar performance to Nafion under well hydrated conditions, which can be further optimized by a combination of numerical modeling and experimental characterization to develop new-generation membranes with better properties.

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Characterization of Multiblock Sulfonated Poly(Arylene Ether Sulfone) as Proton Exchange Membranes

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.805-806.1321 ◽

2013 ◽

Vol 805-806 ◽

pp. 1321-1324

Author(s):

Hai Dan Lin ◽

Xiao Ying Yang ◽

Cheng Xun Sun

Keyword(s):

Ion Exchange ◽

Water Uptake ◽

Proton Exchange Membranes ◽

Exchange Capacity ◽

Proton Exchange ◽

Membrane Properties ◽

Multiblock Copolymers ◽

Arylene Ether ◽

Ether Ketone ◽

Sulfonated Poly

A new series of hydrophobic-hydrophilic multiblock sulfonated poly (arylene ether ketone)-b-poly (arylene ether ketone) copolymers were successfully synthesized and evaluated for use as proton exchange membranes (PEMs). The membrane properties of block copolymers including ion exchange capacities (IECs), water uptake and proton conductivities were characterized for the multiblock copolymers and compared with random sulfonated poly (arylene ether) s and other multiblock copolymer membranes at similar ion exchange capacity value. This series of multiblock copolymers showed moderate conductivities up to 0.063 S/cm at 80 °C with very low water uptake of 19%. Therefore, they are considered to be promising PEM materials for fuel cells.

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Synthesis of proton exchange membranes for dual-chambered microbial fuel cells

Journal of the Serbian Chemical Society ◽

10.2298/jsc170902016d ◽

2018 ◽

Vol 83 (5) ◽

pp. 611-623 ◽

Cited By ~ 4

Author(s):

Sandeep Dharmadhikari ◽

Prabir Ghosh ◽

Manivannan Ramachandran

Keyword(s):

Fuel Cells ◽

Water Uptake ◽

Microbial Fuel Cells ◽

Oxygen Demand ◽

Proton Exchange Membranes ◽

Exchange Capacity ◽

Proton Exchange ◽

Poly Vinyl Alcohol ◽

Precursor Material ◽

Anodic Chamber

Proton exchange membranes (PEMs) were synthesized using three different compositions of poly(oxyethylene) (POE), poly(vinyl alcohol) (PVA), chitosan (CS) and phosphoric acid (PA) in weight ratios of 1:1:1:1, 1:2:1:1 and 1:3:1:1 by physical blending and the casting method. Water uptake of the membrane increases with increasing concentration of PVA. A higher percentage of water uptake signifies a higher ion exchange capacity (IEC) of the synthesized membrane. The synthesized membranes were evaluated in microbial fuel cells (MFCs) and the performance observed. The synthesized membranes were characterized for identification of precursor material and inter polymer interactions using X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy analysis, respectively. The removal of chemical oxygen demand (COD) depends on the microbial activity in the anodic chamber. In the present study, the composition of the membrane was optimized and compared with other membranes that had been synthesized by different compositions of all materials. COD removal in the MFC-3 setup connected with an M-3 membrane was found to be 88 %.

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Intercalated Poly (2-acrylamido-2-methyl-1-propanesulfonic Acid) into Sulfonated Poly (1,4-phenylene ether-ether-sulfone) Based Proton Exchange Membrane: Improved Ionic Conductivity

Molecules ◽

10.3390/molecules26010161 ◽

2020 ◽

Vol 26 (1) ◽

pp. 161

Author(s):

Murli Manohar ◽

Prem P. Sharma ◽

Dukjoon Kim

Keyword(s):

Ionic Conductivity ◽

Proton Conductivity ◽

Water Uptake ◽

Polymer Chain ◽

Proton Exchange Membrane ◽

In Situ Polymerization ◽

Exchange Capacity ◽

Proton Exchange ◽

Swelling Ratio ◽

Sulfonated Poly

A series of hybrid proton exchange membranes were synthesized via in situ polymerization of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS with sulfonated poly (1,4-phenylene ether-ether-sulfone) (SPEES). The insertion of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS, between the rigid skeleton of SPEES plays a reinforcing role to enhance the ionic conductivity. The synthesized polymer was chemically characterized by fourier-transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR spectroscopy to demonstrate the successful grafting of PMPS with the pendent polymer chain of SPEES. A variety of physicochemical properties were also investigated such as ion exchange capacity (IEC), proton conductivity, water uptake and swelling ratio to characterize the suitability of the formed polymer for various electrochemical applications. SP-PMPS-03, having the highest concentration of all PMPS, shows excellent proton conductivity of 0.089 S cm−1 at 80 °C which is much higher than SPEES which is ~0.049 S cm−1. Optimum water uptake and swelling ratio with high conductivity is mainly attributed to a less ordered arrangement polymer chain with high density of the functional group to facilitate ionic transport. The residual weight was 93.35, 92.44 and 89.56%, for SP-PMPS-01, 02 and 03, respectively, in tests with Fenton’s reagent after 24 h. In support of all above properties a good chemical and thermal stability was also achieved by SP-PMPS-03, owing to the durability for electrochemical application.

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Synthesis and Properties of Fluorenyl-Containing Multiblock Sulfonated Poly(Arylene Ether Sulfone) Membranes for Fuel Cell Applications

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.391-392.308 ◽

2011 ◽

Vol 391-392 ◽

pp. 308-312

Author(s):

Shan Shan Chen ◽

Jian Mei Liu ◽

Ying Ling ◽

Shi Chao Fang ◽

Hui Yang ◽

...

Keyword(s):

Coupling Reaction ◽

Proton Exchange Membranes ◽

Exchange Capacity ◽

Proton Exchange ◽

Water Stability ◽

Multiblock Copolymers ◽

Dmso Solution ◽

Ion Exchange Capacity ◽

Arylene Ether ◽

Sulfonated Poly

A series of novel multiblock copolymers containing rigid hydrophilic/soft hydrophobic blocks were synthesized and evaluated for use as proton exchange membranes (PEMs). The multiblock copolymers were prepared by a coupling reaction between phenoxide-terminated sulfonated poly(arylene ether sulfone) oligomer (OSO) and fluorine-terminated poly(arylene ether sulfone) oligomer (FNO). All copolymers produced tough, flexible and transparent membranes by casting from DMSO solution. The resulting membranes displayed good water stability and enhanced proton conductivities comparable to that of the corresponding random ones with similar ion exchange capacity (IEC) values. They also showed slight anisotropic swelling behavior, while isotropic behavior for the random ones. The results revealed that these multiblock copolymers were potential candidates for PEM materials.

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Modeling and Characterization of the Ionic Conductivity of Proton-Exchange Membranes Based on Multiblock Copolymers of Sulfonated PSU/Ppsu Poly(Ether Sulfone)s

ECS Meeting Abstracts ◽

10.1149/ma2021-0127973mtgabs ◽

2021 ◽

Vol MA2021-01 (27) ◽

pp. 973-973

Author(s):

Nieves Ureña ◽

Teresa Pérez-Prior ◽

Pablo Garcia-Salaberri

Keyword(s):

Ionic Conductivity ◽

Proton Exchange Membranes ◽

Proton Exchange ◽

Multiblock Copolymers

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Novel proton exchange membranes based on PVC for microbial fuel cells (MFCs)

Journal of Polymer Engineering ◽

10.1515/polyeng-2018-0276 ◽

2019 ◽

Vol 39 (4) ◽

pp. 360-367 ◽

Cited By ~ 1

Author(s):

Kumar Gaurav ◽

Ram Singh ◽

Brajesh Kumar Tiwari ◽

Richa Srivastava

Keyword(s):

Fuel Cells ◽

Water Uptake ◽

Microbial Fuel Cells ◽

Low Cost ◽

Proton Exchange Membranes ◽

Exchange Capacity ◽

Proton Exchange ◽

Membrane Properties ◽

Potential Applications ◽

New Material

Abstract Proton exchange membranes (PEMs), used as separators, are one of the important components in microbial fuel cells (MFCs). The efficiency of MFC is greatly influenced by PEM. Nafion, which is a commonly used membrane, has several disadvantages in addition to its high cost. The aim of the present work was to develop low-cost PEMs with higher conductivity. In the current work, membranes were prepared using comparatively cheaper material polyvinyl chloride with different concentrations of silica (SiO2), citric acid and phosphotungstic acid (PWA) by the solution casting method. Different membrane properties such as surface morphology, water uptake capacity, ion exchange capacity (IEC), tensile strength, leaching test and potential applications in MFCs were investigated. The results showed that the prepared membrane with 10% silica has the highest water uptake of 55.8%. The IEC of prepared membranes was found to vary from 0.024 to 0.875 meq/g. The membranes showing better IEC were applied to the MFC. The maximum power density obtained was 43.91 m W/cm2 in the case of a membrane with both 5% PWA and 5% silica. The results obtained make this membrane a promising and economically viable new material in MFC applications.

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A Study of the Nitrogen-Containing Heterocycles on Copolyimide Properties for Proton Exchange Membranes

Applied Mechanics and Materials ◽

10.4028/www.scientific.net/amm.401-403.563 ◽

2013 ◽

Vol 401-403 ◽

pp. 563-566 ◽

Cited By ~ 1

Author(s):

Yu Han Li ◽

Wei Jian Wang ◽

Yu Fei Chen ◽

Lei Wang

Keyword(s):

Mechanical Properties ◽

Thermal Stability ◽

Proton Conductivity ◽

Water Uptake ◽

Main Chain ◽

Proton Exchange Membranes ◽

Proton Exchange ◽

Membrane Properties ◽

Dimensional Changes ◽

Sulfonated Polyimide

Containing pyrimidine and pyridine monomers were incorporated respectively into the main chain of a sulfonated polyimide in order to investigate the effect of nitrogen-containing heterocycles on membrane properties such as water uptake and proton conductivity. With increasing content of the nitrogen-containing heterocycles, water uptake of membranes and dimensional changes remarkable decrease. The copolymer showed higher thermal stability (desulfonation temperature up to 330 °C) and reasonable good mechanical properties. These membranes also showed higher proton conductivity, which was comparable or even higher than Nafion 117.

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