Proton-Conducting Membranes - 2nd Edition

A special issue of Membranes (ISSN 2077-0375).

Deadline for manuscript submissions: closed (10 January 2024) | Viewed by 14094

Special Issue Editors


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Guest Editor
Petersburg Nuclear Physics Institute (PNPI), Gatchina, Russia
Interests: proton exchange membranes; hydrogen energy; carbon nanostructures
Special Issues, Collections and Topics in MDPI journals

E-Mail Website
Guest Editor
Institute of Macromolecular Compounds of Russian Academy of Sciences, Saint Petersburg, Russia
Interests: proton exchange membranes; hydrogen energy
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Today, modern challenges are provoking a trend of decarbonization, necessitating the development of the hydrogen energy industry over the upcoming decades and a phasing-out of traditional types of fuel. Proton-conducting membranes, such as Nafion®, Aquivion® and their analogues, have already demonstrated excellent performance in the process of converting hydrogen fuel into energy in fuel cells. Further investigations are required to develop membranes that have enhanced conducting properties and are low-cost and sustainable for long-term operation in order to achieve economically effective “green” energy technologies of the future.

This Special Issue aims to contribute to the investigation of high-performance proton-conducting membranes, understanding their structure and properties and finding ways to develop PEMs (proton-exchange membranes or polymer electrolyte membranes) for their application in various electrochemical devices.

In this Special Issue, original research articles and reviews are welcome. Research areas may include (but are not limited to) the following: new types of proton-conducting membranes; original techniques for membrane fabrication, including compositional membranes and novel insights into preparation methods; methods of characterization; and industrial applications, focusing on the study of membranes.

We look forward to receiving your high-quality contributions. 

Dr. Yuri Kulvelis
Dr. Oleg N. Primachenko
Guest Editors

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Keywords

  • proton-conducting membranes
  • proton-exchange membranes
  • polymer electrolyte membranes
  • conductivity
  • hydrogen energy

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Published Papers (7 papers)

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Research

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42 pages, 6015 KiB  
Article
Electrochemical Properties and Structure of Membranes from Perfluorinated Copolymers Modified with Nanodiamonds
by Vasily T. Lebedev, Yuri V. Kulvelis, Alexandr V. Shvidchenko, Oleg N. Primachenko, Alexei S. Odinokov, Elena A. Marinenko, Alexander I. Kuklin and Oleksandr I. Ivankov
Membranes 2023, 13(11), 850; https://doi.org/10.3390/membranes13110850 - 25 Oct 2023
Viewed by 1642
Abstract
In this study, we aimed to design and research proton-conducting membranes based on Aquivion®-type material that had been modified with detonation nanodiamonds (particle size 4–5 nm, 0.25–5.0 wt. %). These nanodiamonds carried different functional groups (H, OH, COOH, F) that provided [...] Read more.
In this study, we aimed to design and research proton-conducting membranes based on Aquivion®-type material that had been modified with detonation nanodiamonds (particle size 4–5 nm, 0.25–5.0 wt. %). These nanodiamonds carried different functional groups (H, OH, COOH, F) that provided the hydrophilicity of the diamond surface with positive or negative potential, or that strengthened the hydrophobicity of the diamonds. These variations in diamond properties allowed us to find ways to improve the composite structure so as to achieve better ion conductivity. For this purpose, we prepared three series of membrane films by first casting solutions of perfluorinated Aquivion®-type copolymers with short side chains mixed with diamonds dispersed on solid substrates. Then, we removed the solvent and the membranes were structurally stabilized during thermal treatment and transformed into their final form with –SO3H ionic groups. We found that the diamonds with a hydrogen-saturated surface, with a positive charge in aqueous media, contributed to the increase in proton conductivity of membranes to a greater rate. Meanwhile, a more developed conducting diamond-copolymer interface was formed due to electrostatic attraction to the sulfonic acid groups of the copolymer than in the case of diamonds grafted with negatively charged carboxyls, similar to sulfonic groups of the copolymer. The modification of membranes with fluorinated diamonds led to a 5-fold decrease in the conductivity of the composite, even when only a fraction of diamonds of 1 wt. % were used, which was explained by the disruption in the connectivity of ion channels during the interaction of such diamonds mainly with fluorocarbon chains of the copolymer. We discussed the specifics of the mechanism of conductivity in composites with various diamonds in connection with structural data obtained in neutron scattering experiments on dry membranes, as well as ideas about the formation of cylindrical micelles with central ion channels and shells composed of hydrophobic copolymer chains. Finally, the characteristics of the network of ion channels in the composites were found depending on the type and amount of introduced diamonds, and correlations between the structure and conductivity of the membranes were established. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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16 pages, 5494 KiB  
Article
Effect of Blended Perfluorinated Sulfonic Acid Ionomer Binder on the Performance of Catalyst Layers in Polymer Electrolyte Membrane Fuel Cells
by Beom-Seok Kim, Jong-Hyeok Park and Jin-Soo Park
Membranes 2023, 13(9), 794; https://doi.org/10.3390/membranes13090794 - 13 Sep 2023
Cited by 3 | Viewed by 2102
Abstract
In this study, blended perfluorinated sulfonic acid (PFSA) ionomers with equivalent weights (EWs, g/mol) of ~1000, 980, and 830 are prepared. Catalyst layers (CLs), using blended PFSA ionomers, with different side chain lengths and EWs are investigated and compared to CLs using single [...] Read more.
In this study, blended perfluorinated sulfonic acid (PFSA) ionomers with equivalent weights (EWs, g/mol) of ~1000, 980, and 830 are prepared. Catalyst layers (CLs), using blended PFSA ionomers, with different side chain lengths and EWs are investigated and compared to CLs using single ionomers. The ion exchange capacity results confirm that blended ionomers have the target EWs. As a result, blended ionomers exhibit higher ion conductivity than single ionomers at all temperatures due to the higher water uptake of the blended ionomers. This implies that blended ionomers have a bulk structure to form a competent free volume compared to single ionomers. Blended ionomers with short side chains and low EWs can help reduce the activation energy in proton conduction due to enhanced hydrophobic and hydrophilic segregation. In addition, when using the blended ionomer, the CLs form a more porous microstructure to help reduce the resistance of oxygen transport and contributes to lower mass transfer loss. This effect is proven in fuel cell operations at not a lower temperature (70 °C) and full humidification (100%) but at an elevated temperature (80 °C) and lower relative humidity (50 and 75%). Blended ionomer-based CLs with a higher water uptake and porous CL structure result in improved fuel cell performance with better mass transport than single ionomer-based CLs. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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19 pages, 5806 KiB  
Article
Investigating the Sulfonated Chitosan/Polyvinylidene Fluoride-Based Proton Exchange Membrane with fSiO2 as Filler in Microbial Fuel Cells
by Gowthami Palanisamy, Ajmal P. Muhammed, Sadhasivam Thangarasu and Tae Hwan Oh
Membranes 2023, 13(9), 758; https://doi.org/10.3390/membranes13090758 - 25 Aug 2023
Cited by 8 | Viewed by 1828
Abstract
Chitosan (CS), a promising potential biopolymer with exquisite biocompatibility, economic viability, hydrophilicity, and chemical modifications, has drawn interest as an alternative material for proton exchange membrane (PEM) fabrication. However, CS in its original form exhibited low proton conductivity and mechanical stability, restricting its [...] Read more.
Chitosan (CS), a promising potential biopolymer with exquisite biocompatibility, economic viability, hydrophilicity, and chemical modifications, has drawn interest as an alternative material for proton exchange membrane (PEM) fabrication. However, CS in its original form exhibited low proton conductivity and mechanical stability, restricting its usage in PEM development. In this work, chitosan was functionalized (sulfonic acid (-SO3H) groups)) to enhance proton conductivity. The sulfonated chitosan (sCS) was blended with polyvinylidene fluoride (PVDF) polymer, along with the incorporation of functionalized SiO2 (–OH groups), for fabricating chitosan-based composite proton exchange membranes to enhance microbial fuel cell (MFC) performances. The results show that adding functionalized inorganic fillers (fSiO2) into the membrane enhances the mechanical, thermal, and anti-biofouling behavior. From the results, the PVDF/sCS/fSiO2 composite membrane exhibited enhanced proton conductivity 1.0644 × 10−2 S cm−1 at room temperature and increased IEC and mechanical and chemical stability. Furthermore, this study presents a revolutionary way to generate environmentally friendly natural polymer-based membrane materials for developing PEM candidates for enhanced MFC performances in generating bioelectricity and wastewater treatment. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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18 pages, 1543 KiB  
Article
Perfluorosulfonic Acid Membranes with Short and Long Side Chains and Their Use in Sensors for the Determination of Markers of Viral Diseases in Saliva
by Anna V. Parshina, Ekaterina Yu. Safronova, Svetlana A. Novikova, Nastasia Stretton, Anastasia S. Yelnikova, Timur R. Zhuchkov, Olga V. Bobreshova and Andrey B. Yaroslavtsev
Membranes 2023, 13(8), 701; https://doi.org/10.3390/membranes13080701 - 27 Jul 2023
Viewed by 1128
Abstract
The development of accessible express methods to determine markers of viral diseases in saliva is currently an actual problem. Novel cross-sensitive sensors based on Donnan potential with bio-comparable perfluorosulfonic acid membranes for the determination of salivary viral markers (N-acetyl-L-methionine, [...] Read more.
The development of accessible express methods to determine markers of viral diseases in saliva is currently an actual problem. Novel cross-sensitive sensors based on Donnan potential with bio-comparable perfluorosulfonic acid membranes for the determination of salivary viral markers (N-acetyl-L-methionine, L-carnitine, and L-lysine) were proposed. Membranes were formed by casting from dispersions of Nafion or Aquivion in N-methyl-2-pyrollidone or in a mixture of isopropyl alcohol and water. The influence of the polymer equivalent weight and the nature of dispersing liquid on water uptake, ion conductivity, and slope of Donnan potential for the membranes in H+ and Na+ form was investigated. The varying of the sorption and transport properties of perfluorosulfonic acid membranes provided a change in the distribution of the sensor sensitivity to N-acetyl-L-methionine, L-carnitine, and L-lysine ions, which was necessary for multisensory system development. The simultaneous determination of three analytes, and the group analysis of them in artificial saliva solutions, was performed. The errors of N-acetyl-L-methionine and L-carnitine determination were 4–12 and 3–11%, respectively. The determination of L-lysine was complicated by its interaction with Ca2+ ions. The error of the group analysis was no greater than 9%. The reverse character of the viral markers’ sorption by the membranes provided long-term sensor operation. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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11 pages, 2960 KiB  
Article
Permselectivity and Ionic Conductivity Study of Na+ and Br Ions in Graphene Oxide-Based Membranes for Redox Flow Batteries
by Raphael Flack, Anna Aixalà-Perelló, Alessandro Pedico, Kobby Saadi, Andrea Lamberti and David Zitoun
Membranes 2023, 13(8), 695; https://doi.org/10.3390/membranes13080695 - 26 Jul 2023
Cited by 2 | Viewed by 2212
Abstract
Permselectivity of a membrane is central for the development of electrochemical energy storage devices with two redox couples, such as redox flow batteries (RFBs). In RFBs, Br3/Br couple is often used as a catholyte which can cross over to [...] Read more.
Permselectivity of a membrane is central for the development of electrochemical energy storage devices with two redox couples, such as redox flow batteries (RFBs). In RFBs, Br3/Br couple is often used as a catholyte which can cross over to the anolyte, limiting the battery’s lifetime. Naturally, the development of permselective membranes is essential to the success of RFBs since state-of-the-art perfluorosulfonic acid (PFSA) is too costly. This study investigates membranes of graphene oxide (GO), polyvinylpyrrolidone (PVP), and imidazole (Im) as binder and linker, respectively. The GO membranes are compared to a standard PFSA membrane in terms of ionic conductivity (Na+) and permselectivity (exclusion of Br). The ionic conduction is evaluated from electrochemical impedance spectroscopy and the permselectivity from two-compartment diffusion cells in a four-electrode system. Our findings suggest that the GO membranes reach conductivity and permselectivity comparable with standard PFSA membranes. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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15 pages, 2515 KiB  
Article
NMR Investigation of Water Molecular Dynamics in Sulfonated Polysulfone/Layered Double Hydroxide Composite Membranes for Proton Exchange Membrane Fuel Cells
by Cataldo Simari
Membranes 2023, 13(7), 684; https://doi.org/10.3390/membranes13070684 - 22 Jul 2023
Cited by 1 | Viewed by 1514
Abstract
The development of nanocomposite membranes based on hydrocarbon polymers is emerging as one of the most promising strategies for overcoming the performance, cost, and safety limitations of Nafion, which is the current benchmark in proton exchange membranes for fuel cell applications. Among the [...] Read more.
The development of nanocomposite membranes based on hydrocarbon polymers is emerging as one of the most promising strategies for overcoming the performance, cost, and safety limitations of Nafion, which is the current benchmark in proton exchange membranes for fuel cell applications. Among the various nanocomposite membranes, those based on sulfonated polysulfone (sPSU) and Layered Double Hydroxides (LDHs) hold promise regarding their successful utilization in practical applications due to their interesting electrochemical performance. This study aims to elucidate the effect of LDH introduction on the internal arrangement of water molecules in the hydrophilic clusters of sPSU and on its proton transport properties. Swelling tests, NMR characterization, and Electrochemical Impedance Spectroscopy (EIS) investigation allowed us to demonstrate that LDH platelets act as physical crosslinkers between -SO3H groups of adjacent polymer chains. This increases dimensional stability while simultaneously creating continuous paths for proton conduction. This feature, combined with its impressive water retention capability, allows sPSU to yield a proton conductivity of ca. 4 mS cm−1 at 90 °C and 20% RH. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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Review

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31 pages, 2761 KiB  
Review
Approaches to the Modification of Perfluorosulfonic Acid Membranes
by Ekaterina Yu. Safronova, Anna A. Lysova, Daria Yu. Voropaeva and Andrey B. Yaroslavtsev
Membranes 2023, 13(8), 721; https://doi.org/10.3390/membranes13080721 - 7 Aug 2023
Cited by 14 | Viewed by 2940
Abstract
Polymer ion-exchange membranes are featured in a variety of modern technologies including separation, concentration and purification of gases and liquids, chemical and electrochemical synthesis, and hydrogen power generation. In addition to transport properties, the strength, elasticity, and chemical stability of such materials are [...] Read more.
Polymer ion-exchange membranes are featured in a variety of modern technologies including separation, concentration and purification of gases and liquids, chemical and electrochemical synthesis, and hydrogen power generation. In addition to transport properties, the strength, elasticity, and chemical stability of such materials are important characteristics for practical applications. Perfluorosulfonic acid (PFSA) membranes are characterized by an optimal combination of these properties. Today, one of the most well-known practical applications of PFSA membranes is the development of fuel cells. Some disadvantages of PFSA membranes, such as low conductivity at low humidity and high temperature limit their application. The approaches to optimization of properties are modification of commercial PFSA membranes and polymers by incorporation of different additive or pretreatment. This review summarizes the approaches to their modification, which will allow the creation of materials with a different set of functional properties, differing in ion transport (first of all proton conductivity) and selectivity, based on commercially available samples. These approaches include the use of different treatment techniques as well as the creation of hybrid materials containing dopant nanoparticles. Modification of the intrapore space of the membrane was shown to be a way of targeting the key functional properties of the membranes. Full article
(This article belongs to the Special Issue Proton-Conducting Membranes - 2nd Edition)
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