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Polymers
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Polymers for Electrochemical Applications
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Polymers for Electrochemical Applications

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (1 October 2023) | Viewed by 19054

Special Issue Editors

Prof. Dr. Andrey B. Yaroslavtsev

E-Mail Website
Guest Editor
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
Interests: ion-exchange membranes; hybrid membranes; solid electrolytes; composites; fuel cells; electrodialysis; reverse electrodialysis; metal-ion batteries; sensors
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Irina A. Stenina

E-Mail Website
Guest Editor
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
Interests: reverse electrodialysis; flow batteries; metal-ion batteries; electrolysis; sensors; solid electrolytes; composites
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Ion-exchange membranes are traditionally used in such popular technologies as the processes of separation, purification, and electrolytic synthesis. One of the most important applications is wastewater desalination, as well as the concentration and separation of valuable chemical products from natural waters and industrial waste. At the same time, significant efforts have been made in recent years to improve the environmental situation. In this regard, chemical current sources and energy storage devices, including fuel cells and flow batteries, are becoming extremely popular. The need to improve the efficiency and safety of such highly demanded devices as metal-ion batteries is leading to increased interest in the development of polymer electrolytes and separators. New areas of application of electromembrane technologies are also emerging, such as, reverse electrodialysis. At the same time, constant monitoring of the environment is necessary to prevent its pollution. In this regard, electromembrane sensors and multisensor devices based on them are increasingly in demand. These critical issues will be the subject of this Special Issue, “Polymers for electrochemical applications”.

We would like to invite you to submit your contribution to the Special Issue “Polymers for electrochemical applications” in Polymers.

This Special Issue aims to highlight the rapid progress in electrochemical applications of modern polymeric materials, including primarily ion-exchange membranes, hybrid and composite electrolytes. A wide range of various electrochemical devices and technologies associated with the purification and separation, production and accumulation of energy, sensors, and a number of other processes are developed on their basis. The subject of this Special Issue will be related to both fundamental and applied research aimed at the development of electrochemically active polymers and devices based on them, which will include, but not be limited to:

  • Fuel cells;
  • Desalination;
  • Electrodialysis;
  • Reverse electrodialysis;
  • Flow batteries;
  • Metal-ion batteries;
  • Electrolysis.

Prof. Dr. Andrey B. Yaroslavtsev
Prof. Dr. Irina A. Stenina
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • ion-exchange membranes 
  • hybrid membranes
  • composites
  • fuel cells
  • desalination
  • electrodialysis
  • reverse electrodialysis
  • flow batteries
  • metal-ion batteries
  • electrolysis
  • sensors

Published Papers (8 papers)

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Research

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18 pages, 4279 KiB  
Article
Study of the Thermochemical Effect on the Transport and Structural Characteristics of Heterogeneous Ion-Exchange Membranes by Combining the Cell Model and the Fine-Porous Membrane Model
by Anatoly N. Filippov, Elmara M. Akberova and Vera I. Vasil’eva
Polymers 2023, 15(16), 3390; https://0-doi-org.brum.beds.ac.uk/10.3390/polym15163390 - 13 Aug 2023
Cited by 2 | Viewed by 1508
Abstract
For the first time, based on the joint application of the fine-porous and cell models, a theoretical analysis of the changing transport and structural characteristics of heterogeneous polymeric ion-exchange membranes (IEMs) MK-40, MA-40, and MA-41 after exposure to elevated temperatures in water and [...] Read more.
For the first time, based on the joint application of the fine-porous and cell models, a theoretical analysis of the changing transport and structural characteristics of heterogeneous polymeric ion-exchange membranes (IEMs) MK-40, MA-40, and MA-41 after exposure to elevated temperatures in water and aggressive media (H2SO4 and NaOH solutions), as well as after long-term processing in electrodialyzers of various types, was carried out. The studied membranes are composites of ion-exchange polymers with polyethylene and nylon reinforcing mesh. The external influences provoke the aging of IEMs and the deterioration of their characteristics. The transport properties of IEMs are quantitatively described using five physicochemical parameters: counterion diffusion and equilibrium distribution coefficients in the membrane, characteristic exchange capacity, which depends on the microporosity of ion-exchanger particles, and macroscopic porosity at a known exchange capacity of IEMs. Calculations of the physicochemical parameters of the membranes were performed according to a specially developed fitting technique using the experimental concentration dependences of integral diffusion permeability and specific electrical conductivity, and their model analogs. This made it possible to identify and evaluate changes in the membrane micro- and macrostructure and examine the process of artificial aging of the IEM polymer material due to the abovementioned external impacts. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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23 pages, 4718 KiB  
Article
How Chemical Nature of Fixed Groups of Anion-Exchange Membranes Affects the Performance of Electrodialysis of Phosphate-Containing Solutions?
by Natalia Pismenskaya, Olesya Rybalkina, Ksenia Solonchenko, Evgeniia Pasechnaya, Veronika Sarapulova, Yaoming Wang, Chenxiao Jiang, Tongwen Xu and Victor Nikonenko
Polymers 2023, 15(10), 2288; https://0-doi-org.brum.beds.ac.uk/10.3390/polym15102288 - 12 May 2023
Cited by 5 | Viewed by 1757
Abstract
Innovative ion exchange membranes have become commercially available in recent years. However, information about their structural and transport characteristics is often extremely insufficient. To address this issue, homogeneous anion exchange membranes with the trade names ASE, CJMA-3 and CJMA-6 have been investigated in [...] Read more.
Innovative ion exchange membranes have become commercially available in recent years. However, information about their structural and transport characteristics is often extremely insufficient. To address this issue, homogeneous anion exchange membranes with the trade names ASE, CJMA-3 and CJMA-6 have been investigated in NaxH(3−x)PO4 solutions with pH 4.4 ± 0.1, 6.6 and 10.0 ± 0.2, as well as NaCl solutions with pH 5.5 ± 0.1. Using IR spectroscopy and processing the concentration dependences of the electrical conductivity of these membranes in NaCl solutions, it was shown that ASE has a highly cross-linked aromatic matrix and mainly contains quaternary ammonium groups. Other membranes have a less cross-linked aliphatic matrix based on polyvinylidene fluoride (CJMA-3) or polyolefin (CJMA-6) and contain quaternary amines (CJMA-3) or a mixture of strongly basic (quaternary) and weakly basic (secondary) amines (CJMA-6). As expected, in dilute solutions of NaCl, the conductivity of membranes increases with an increase in their ion-exchange capacity: CJMA-6 < CJMA-3 << ASE. Weakly basic amines appear to form bound species with proton-containing phosphoric acid anions. This phenomenon causes a decrease in the electrical conductivity of CJMA-6 membranes compared to other studied membranes in phosphate-containing solutions. In addition, the formation of the neutral and negatively charged bound species suppresses the generation of protons by the “acid dissociation” mechanism. Moreover, when the membrane is operated in overlimiting current modes and/or in alkaline solutions, a bipolar junction is formed at the CJMA- 6/depleted solution interface. The CJMA-6 current-voltage curve becomes similar to the well-known curves for bipolar membranes, and water splitting intensifies in underlimiting and overlimiting modes. As a result, energy consumption for electrodialysis recovery of phosphates from aqueous solutions almost doubles when using the CJMA-6 membrane compared to the CJMA-3 membrane. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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12 pages, 2329 KiB  
Article
Improvement of Selectivity of RALEX-CM Membranes via Modification by Ceria with a Functionalized Surface
by Irina Stenina, Polina Yurova, Aslan Achoh, Victor Zabolotsky, Liang Wu and Andrey Yaroslavtsev
Polymers 2023, 15(3), 647; https://0-doi-org.brum.beds.ac.uk/10.3390/polym15030647 - 27 Jan 2023
Cited by 4 | Viewed by 1565
Abstract
Ion exchange membranes are widely used for water treatment and ion separation by electrodialysis. One of the ways to increase the efficiency of industrial membranes is their modification with various dopants. To improve the membrane permselectivity, a simple strategy of the membrane surface [...] Read more.
Ion exchange membranes are widely used for water treatment and ion separation by electrodialysis. One of the ways to increase the efficiency of industrial membranes is their modification with various dopants. To improve the membrane permselectivity, a simple strategy of the membrane surface modification was proposed. Heterogeneous RALEX-CM membranes were surface-modified by ceria with a phosphate-functionalized surface. Despite a decrease in ionic conductivity of the prepared composite membranes, their cation transport numbers slightly increase. Moreover, the modified membranes show a threefold increase in Ca2+/Na+ permselectivity (from 2.1 to 6.1) at low current densities. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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16 pages, 4104 KiB  
Article
Stability of Properties of Layer-by-Layer Coated Membranes under Passage of Electric Current
by Ksenia Solonchenko, Olesya Rybalkina, Daria Chuprynina, Evgeniy Kirichenko, Ksenia Kirichenko and Victor Nikonenko
Polymers 2022, 14(23), 5172; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14235172 - 28 Nov 2022
Cited by 4 | Viewed by 1305
Abstract
Electrodialysis with layer-by-layer coated membranes is a promising method for the separation of monovalent and polyvalent ions. Since the separation selectivity is significantly reduced in the presence of defects in the multilayer system, the stability of the modifiers becomes an important issue. This [...] Read more.
Electrodialysis with layer-by-layer coated membranes is a promising method for the separation of monovalent and polyvalent ions. Since the separation selectivity is significantly reduced in the presence of defects in the multilayer system, the stability of the modifiers becomes an important issue. This article reports the i-V curves of layer-by-layer coated membranes based on the heterogeneous MK-40 membrane before and after 50 h long electrodialysis of a solution containing sodium and calcium ions at an underlimiting current density, and the values of concentrations of cations in the desalination chamber during electrodialysis. It is shown that the transport of bivalent ions through the modified membranes is reduced throughout the electrodialysis by about 50%, but the operation results in decreased resistance of the membrane modified with polyethylenimine, which may suggest damage to the modifying layer. Even after electrodialysis, the modified membrane demonstrated experimental limiting current densities higher than that of the substrate, and in case of the membrane modified with polyallylamine, the limiting current density 10% higher than that of the substrate membrane. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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12 pages, 3634 KiB  
Article
Physically and Chemically Stable Anion Exchange Membranes with Hydrogen-Bond Induced Ion Conducting Channels
by Chengpeng Wei, Weisheng Yu, Liang Wu, Xiaolin Ge and Tongwen Xu
Polymers 2022, 14(22), 4920; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14224920 - 15 Nov 2022
Cited by 13 | Viewed by 2444
Abstract
Anion exchange membranes (AEMs) with desirable properties are the crucial components for numerous energy devices such as AEM fuel cells (AEMFCs), AEM water electrolyzers (AEMWEs), etc. However, the lack of suitable AEMs severely limits the performance of devices. Here, a series of physically [...] Read more.
Anion exchange membranes (AEMs) with desirable properties are the crucial components for numerous energy devices such as AEM fuel cells (AEMFCs), AEM water electrolyzers (AEMWEs), etc. However, the lack of suitable AEMs severely limits the performance of devices. Here, a series of physically and chemically stable AEMs have been prepared by the reaction between the alkyl bromine terminal ether-bond-free aryl backbone and the urea group-containing crosslinker. Morphology analyses confirm that the hydrogen bonding interaction between urea groups is capable of driving the ammonium cations to aggregate and further form continuous ion-conducting channels. Therefore, the resultant AEM demonstrates remarkable OH− conductivity (59.1 mS cm−1 at 30 °C and 122.9 mS cm−1 at 90 °C) despite a moderate IEC (1.77 mmol g−1). Simultaneously, due to the adoption of ether-bond-free aryl backbone and alkylene chain-modified trimethylammonium cation, the AEM possesses excellent alkaline stability (87.3% IEC retention after soaking in 1 M NaOH for 1080 h). Moreover, the prepared AEM shows desirable mechanical properties (tensile stress > 25 MPa) and dimensional stability (SR = 20.3% at 90 °C) contributed by the covalent-bond and hydrogen-bond crosslinking network structures. Moreover, the resulting AEM reaches a peak power density of 555 mW cm−2 in an alkaline H2/O2 single fuel cell at 70 °C without back pressure. This rational structural design presented here provides inspiration for the development of high-performance AEMs, which are crucial for membrane technologies. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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16 pages, 3747 KiB  
Article
Effect of Ultrasonication on the Morphology, Mechanical Property, Ionic Conductivity, and Flame Retardancy of PEO-LiCF3SO3-Halloysite Nanotube Composites for Use as Solid Polymer Electrolyte
by Pattranuch Pongsuk and Jantrawan Pumchusak
Polymers 2022, 14(18), 3710; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14183710 - 6 Sep 2022
Cited by 10 | Viewed by 2010
Abstract
PEO-LiCF3SO3-halloysite nanotube (HNT) composites were fabricated by solution casting together with hot compression to form a solid polymer electrolyte (SPE) membrane. Different ultrasonic exposure times were used to disperse HNT nanoparticles in the PEO-20%LiCF3SO3-HNT composite [...] Read more.
PEO-LiCF3SO3-halloysite nanotube (HNT) composites were fabricated by solution casting together with hot compression to form a solid polymer electrolyte (SPE) membrane. Different ultrasonic exposure times were used to disperse HNT nanoparticles in the PEO-20%LiCF3SO3-HNT composite solutions prior to casting. An exposure time of 15 min gave the highest ionic conductivity in the SPE membrane, the ionic conductivity significantly increased by two orders of magnitude from 6.6 × 10−6 to 1.1 × 10−4 S/cm. TEM, FE-SEM, and EDS-mapping were used to study the dispersion of HNTs in the SPE membrane. ATR-FTIR revealed that the bonding of PEO-LiCF3SO3 and PEO-HNT was created. XRD and DSC showed a reduction in the crystallinity of PEO due to HNT addition. The ultrasonication for an optimal period gave uniform dispersion of HNT, reduced the polymer crystallinity and strengthened the tensile property of SPE membrane. Moreover, the electrochemical stability, flame retardance and dimensional stability were improved by the addition of HNT and by ultrasonication. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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21 pages, 3722 KiB  
Article
Multisensory Systems Based on Perfluorosulfonic Acid Membranes Modified with Polyaniline and PEDOT for Multicomponent Analysis of Sulfacetamide Pharmaceuticals
by Anna Parshina, Anastasia Yelnikova, Tatyana Titova, Tatyana Kolganova, Polina Yurova, Irina Stenina, Olga Bobreshova and Andrey Yaroslavtsev
Polymers 2022, 14(13), 2545; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14132545 - 22 Jun 2022
Cited by 6 | Viewed by 1688
Abstract
The degradation of sulfacetamide with the formation of sulfanilamide leads to a deterioration in the quality of pharmaceuticals. In this work, potentiometric sensors for the simultaneous determination of sulfanilamide, sulfacetamide and inorganic ions, and for assessing the degradation of pharmaceuticals were developed. A [...] Read more.
The degradation of sulfacetamide with the formation of sulfanilamide leads to a deterioration in the quality of pharmaceuticals. In this work, potentiometric sensors for the simultaneous determination of sulfanilamide, sulfacetamide and inorganic ions, and for assessing the degradation of pharmaceuticals were developed. A multisensory approach was used for this purpose. The sensor cross-sensitivity to related analytes was achieved using perfluorosulfonic acid membranes with poly(3,4-ethylenedioxythiophene) or polyaniline as dopants. The composite membranes were prepared by oxidative polymerization and characterized using FTIR and UV-Vis spectroscopy, and SEM. The influence of the preparation procedure and the dopant concentration on the membrane hydrophilicity, ion-exchange capacity, water uptake, and transport properties was investigated. The characteristics of the potentiometric sensors in aqueous solutions containing sulfanilamide, sulfacetamide and alkali metals ions in a wide pH range were established. The introduction of proton-acceptor groups and π-conjugated moieties into the perfluorosulfonic acid membranes increased the sensor sensitivity to organic analytes. The relative errors of sulfacetamide and sulfanilamide determination in the UV-degraded eye drops were 1.2 to 1.4 and 1.7 to 4%, respectively, at relative standard deviation of 6 to 9%. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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Review

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33 pages, 7068 KiB  
Review
Tuning Alkaline Anion Exchange Membranes through Crosslinking: A Review of Synthetic Strategies and Property Relationships
by Auston L. Clemens, Buddhinie S. Jayathilake, John J. Karnes, Johanna J. Schwartz, Sarah E. Baker, Eric B. Duoss and James S. Oakdale
Polymers 2023, 15(6), 1534; https://0-doi-org.brum.beds.ac.uk/10.3390/polym15061534 - 20 Mar 2023
Cited by 12 | Viewed by 5820
Abstract
Alkaline anion exchange membranes (AAEMs) are an enabling component for next-generation electrochemical devices, including alkaline fuel cells, water and CO2 electrolyzers, and flow batteries. While commercial systems, notably fuel cells, have traditionally relied on proton-exchange membranes, hydroxide-ion conducting AAEMs hold promise as [...] Read more.
Alkaline anion exchange membranes (AAEMs) are an enabling component for next-generation electrochemical devices, including alkaline fuel cells, water and CO2 electrolyzers, and flow batteries. While commercial systems, notably fuel cells, have traditionally relied on proton-exchange membranes, hydroxide-ion conducting AAEMs hold promise as a method to reduce cost-per-device by enabling the use of non-platinum group electrodes and cell components. AAEMs have undergone significant material development over the past two decades; however, challenges remain in the areas of durability, water management, high temperature performance, and selectivity. In this review, we survey crosslinking as a tool capable of tuning AAEM properties. While crosslinking implementations vary, they generally result in reduced water uptake and increased transport selectivity and alkaline stability. We survey synthetic methodologies for incorporating crosslinks during AAEM fabrication and highlight necessary precautions for each approach. Full article
(This article belongs to the Special Issue Polymers for Electrochemical Applications)
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