Polymer Electrolytes for Energy Storage and Conversion Devices

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (15 July 2019) | Viewed by 27209

Special Issue Editors

CNR-ITAE Institute for Advanced Energy Technologies “N. Giordano”, Via Salita S. Lucia sopra Contesse 5, 98126 Messina, Italy
Interests: polymer electrolyte fuel cells; direct alcohol fuel cells; water electrolysis; metal–air batteries; dye-sensitized solar cells; photo-electrolysis; carbon dioxide electro-reduction
Special Issues, Collections and Topics in MDPI journals
CNR-ITAE Institute for Advanced Energy Technologies “N. Giordano” Via Salita S. Lucia sopra Contesse 5, 98126 Messina, Italy
Interests: polymer electrolyte membrane fuel cells; polymer electolyte membrane electrolysis; anion exchange membranes; photoelectrolysis; batteries
Special Issues, Collections and Topics in MDPI journals
CNR-ITAE, Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”, 98126 Messina, Italy
Interests: nanocarbon materials; metal oxides; polymer electrolyte membrane; energy storage and conversion; supercapacitors; fuel cells; batteries
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

In the last three decades, the development of polymer electrolytes has received great attention due to their potential applications in electrochemical power generation, storage and conversion systems. A polymer electrolyte is often a membrane composed by the dissolution of an ion-conducting salt in a polymer matrix with high molecular weight. Besides this, it can be based on ion-conducting polymers or ionomers containing charged functional groups (e.g. –SO3H, –PO3H2, –COOH), which typically have a multiphase structure containing both hydrophobic and hydrophilic regions. These solid systems possess ionic conduction properties and therefore are widely employed in electrochemical devices such as solid-state batteries, rechargeable batteries, fuel cells, electrolysers, supercapacitors, dye-sensitized solar cells, electrochemical sensors and electrochromic windows.

The technological advancement in the field of polymer electrolytes plays a pivotal role in the development of energy storage/conversion systems. This Special Issue is intended to cover the latest progress in polymer electrolytes for energy-related applications. In particular, this Special Issue aims to gain insights into the development of different types of polymer electrolytes, recent approaches, and their technological applications.

Dr. Vincenzo Baglio
Dr. Antonino S. Aricò
Dr. Francesco Lufrano
Guest Editors

Manuscript Submission Information

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Keywords

  • synthesis and characterization of polymer electrolytes
  • polymer electrolyte membranes
  • proton exchange membranes
  • anion exchange membranes
  • solid polymer ion conductors
  • polymer gel based membranes
  • composite/hybrid membranes
  • ionomers
  • electrolysers
  • fuel cells
  • metal–air batteries
  • redox-flow batteries
  • lithium-ion/sodium-ion batteries
  • supercapacitors
  • dye-sensitized solar cells

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Published Papers (6 papers)

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Research

13 pages, 2342 KiB  
Article
Preparation of Graft Poly(Arylene Ether Sulfone)s-Based Copolymer with Enhanced Phase-Separated Morphology as Proton Exchange Membranes via Atom Transfer Radical Polymerization
by Yang Zhao, Xue Li, Zhongyang Wang, Xiaofeng Xie and Wei Qian
Polymers 2019, 11(8), 1297; https://doi.org/10.3390/polym11081297 - 02 Aug 2019
Cited by 10 | Viewed by 3643
Abstract
Novel proton exchange membranes (PEMs) based on graft copoly(arylene ether sulfone)s with enhanced phase-separated morphology were prepared using atom transfer radical polymerization (ATRP). A series of PEMs with different graft lengths and sulfonation degrees were prepared. The phase-separated morphologies were confirmed by transmission [...] Read more.
Novel proton exchange membranes (PEMs) based on graft copoly(arylene ether sulfone)s with enhanced phase-separated morphology were prepared using atom transfer radical polymerization (ATRP). A series of PEMs with different graft lengths and sulfonation degrees were prepared. The phase-separated morphologies were confirmed by transmission electron microscopy. Among the membranes prepared and evaluated, PAESPS18S2 exhibited considerably high proton conductivity (0.151 S/cm, 85 °C), benefitting from the graft polymer architecture and phase-separated morphology. The membranes also possessed excellent thermal and chemical stabilities. Highly conductive and stable copoly(arylene ether sulfone)-based membranes would be promising candidates as polymer electrolytes for fuel cell applications. Full article
(This article belongs to the Special Issue Polymer Electrolytes for Energy Storage and Conversion Devices)
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13 pages, 2241 KiB  
Article
Polymer Electrolyte Membranes Prepared by Graft Copolymerization of 2-Acrylamido-2-Methylpropane Sulfonic Acid and Acrylic Acid on PVDF and ETFE Activated by Electron Beam Treatment
by Xi Ke, Yufei Zhang, Uwe Gohs, Marco Drache and Sabine Beuermann
Polymers 2019, 11(7), 1175; https://doi.org/10.3390/polym11071175 - 11 Jul 2019
Cited by 11 | Viewed by 4611
Abstract
Polymer electrolyte membranes (PEM) for potential applications in fuel cells or vanadium redox flow batteries were synthesized and characterized. ETFE (poly (ethylene-alt-tetrafluoroethylene)) and PVDF (poly (vinylidene fluoride)) serving as base materials were activated by electron beam treatment with doses ranging from 50 to [...] Read more.
Polymer electrolyte membranes (PEM) for potential applications in fuel cells or vanadium redox flow batteries were synthesized and characterized. ETFE (poly (ethylene-alt-tetrafluoroethylene)) and PVDF (poly (vinylidene fluoride)) serving as base materials were activated by electron beam treatment with doses ranging from 50 to 200 kGy and subsequently grafted via radical copolymerization with the functional monomers 2-acrylamido-2-methylpropane sulfonic acid and acrylic acid in aqueous phase. Since protogenic groups are already contained in the monomers, a subsequent sulfonation step is omitted. The mechanical properties were studied via tensile strength measurements. The electrochemical performance of the PEMs was evaluated by electrochemical impedance spectroscopy and fuel cell tests. The proton conductivities and ion exchange capacities are competitive with Nafion 117, the standard material used today. Full article
(This article belongs to the Special Issue Polymer Electrolytes for Energy Storage and Conversion Devices)
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10 pages, 1744 KiB  
Article
Polymer Electrolyte Membranes Based on Nafion and a Superacidic Inorganic Additive for Fuel Cell Applications
by Lucia Mazzapioda, Stefania Panero and Maria Assunta Navarra
Polymers 2019, 11(5), 914; https://doi.org/10.3390/polym11050914 - 22 May 2019
Cited by 33 | Viewed by 5083
Abstract
Nafion composite membranes, containing different amounts of mesoporous sulfated titanium oxide (TiO2-SO4) were prepared by solvent-casting and tested in proton exchange membrane fuel cells (PEMFCs), operating at very low humidification levels. The TiO2-SO4 additive was originally [...] Read more.
Nafion composite membranes, containing different amounts of mesoporous sulfated titanium oxide (TiO2-SO4) were prepared by solvent-casting and tested in proton exchange membrane fuel cells (PEMFCs), operating at very low humidification levels. The TiO2-SO4 additive was originally synthesized by a sol-gel method and characterized through x-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and ion exchange capacity (IEC). Peculiar properties of the composite membranes, such as the thermal transitions and ion exchange capacity, were investigated and here discussed. When used as an electrolyte in the fuel cell, the composite membrane guaranteed an improvement with respect to bare Nafion systems at 30% relative humidity and 110 °C, exhibiting higher power and current densities. Full article
(This article belongs to the Special Issue Polymer Electrolytes for Energy Storage and Conversion Devices)
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14 pages, 2561 KiB  
Article
Ionic Liquid Composite Polybenzimidazol Membranes for High Temperature PEMFC Applications
by Jorge Escorihuela, Abel García-Bernabé, Álvaro Montero, Óscar Sahuquillo, Enrique Giménez and Vicente Compañ
Polymers 2019, 11(4), 732; https://doi.org/10.3390/polym11040732 - 22 Apr 2019
Cited by 40 | Viewed by 5650
Abstract
A series of proton exchange membranes based on polybenzimidazole (PBI) were prepared using the low cost ionic liquids (ILs) derived from 1-butyl-3-methylimidazolium (BMIM) bearing different anions as conductive fillers in the polymeric matrix with the aim of enhancing the proton conductivity of PBI [...] Read more.
A series of proton exchange membranes based on polybenzimidazole (PBI) were prepared using the low cost ionic liquids (ILs) derived from 1-butyl-3-methylimidazolium (BMIM) bearing different anions as conductive fillers in the polymeric matrix with the aim of enhancing the proton conductivity of PBI membranes. The composite membranes prepared by casting method (containing 5 wt. % of IL) exhibited good thermal, dimensional, mechanical, and oxidative stability for fuel cell applications. The effects of anion, temperature on the proton conductivity of phosphoric acid-doped membranes were systematically investigated by electrochemical impedance spectroscopy. The PBI composite membranes containing 1-butyl-3-methylimidazolium-derived ionic liquids exhibited high proton conductivity of 0.098 S·cm−1 at 120 °C when tetrafluoroborate anion was present in the polymeric matrix. This conductivity enhancement might be attributed to the formed hydrogen-bond networks between the IL molecules and the phosphoric acid molecules distributed along the polymeric matrix. Full article
(This article belongs to the Special Issue Polymer Electrolytes for Energy Storage and Conversion Devices)
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11 pages, 2937 KiB  
Article
Solvent-Free Procedure for the Preparation under Controlled Atmosphere Conditions of Phase-Segregated Thermoplastic Polymer Electrolytes
by Álvaro Miguel, Francisco González, Víctor Gregorio, Nuria García and Pilar Tiemblo
Polymers 2019, 11(3), 406; https://doi.org/10.3390/polym11030406 - 01 Mar 2019
Cited by 7 | Viewed by 2800
Abstract
A solvent-free method that allows thermoplastic solid electrolytes based on poly(ethylene oxide) PEO to be obtained under controlled atmosphere conditions is presented. This method comprises two steps, the first one being the melt compounding of PEO with a filler, able to physically crosslink [...] Read more.
A solvent-free method that allows thermoplastic solid electrolytes based on poly(ethylene oxide) PEO to be obtained under controlled atmosphere conditions is presented. This method comprises two steps, the first one being the melt compounding of PEO with a filler, able to physically crosslink the polymer and its pelletizing, and the second the pellets’ swelling with an electroactive liquid phase. This method is an adaptation of the step described in previous publications of the preparation of thermoplastic electrolytes by a single melt compounding. In comparison to the single step extrusion methodology, this new method permits employing electroactive species that are very sensitive to atmospheric conditions. The two-step method can also be designed to produce controlled phase-segregated morphologies in the electrolyte, namely polymer-poor and polymer-rich phases, with the aim of increasing ionic conductivity over that of homogeneous electrolytes. An evaluation of the characteristics of the electrolytes prepared by single and two-step procedures is done by comparing membranes prepared by both methods using PEO as a polymeric scaffold and a solution of the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMI TFSI) and the bis(trifluoromethanesulfonyl) imide lithium salt (Li TFSI) as liquid phase. The electrolytes prepared by both methods have been characterized by Fourier transform infrared spectroscopy and optic microscopy profilometry, differential scanning calorimetry, self-creep experiments, and dielectric spectroscopy. In this way, the phase separation, rheology, and ionic conductivity are studied and compared. It is striking how the electrolytes prepared with this new method maintain their solid-like behavior even at 90 °C. Compared to the single step method, the two-step method produces electrolytes with a phase-separated morphology, which results in higher ionic conductivity. Full article
(This article belongs to the Special Issue Polymer Electrolytes for Energy Storage and Conversion Devices)
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14 pages, 4674 KiB  
Communication
Constructing Continuous Proton-Conducting Highways within Sulfonated Poly(Arylene Ether Nitrile) Composite Membrane by Incorporating Amino-Sulfo-Bifunctionalized GO
by Tao Cheng, Xuechun Zhang, Yan Ma, Yumin Huang and Xiaobo Liu
Polymers 2018, 10(9), 1005; https://doi.org/10.3390/polym10091005 - 10 Sep 2018
Cited by 20 | Viewed by 3528
Abstract
To obtain a proton exchange membrane (PEM) with high proton conductivity and low methanol permeability, a novel amino-sulfo-bifunctionalized GO (NSGO) was synthesized and explored as a filler for sulfonated poly(arylene ether nitrile) (SPEN). The result indicated that the microstructure of composite membranes was [...] Read more.
To obtain a proton exchange membrane (PEM) with high proton conductivity and low methanol permeability, a novel amino-sulfo-bifunctionalized GO (NSGO) was synthesized and explored as a filler for sulfonated poly(arylene ether nitrile) (SPEN). The result indicated that the microstructure of composite membranes was rearranged by NSGO and strong acid–base interactions were formed between fillers and the SPEN matrix, affording enhanced thermal, mechanical, and dimensional stabilities. Moreover, it was found that NSGO fillers were uniformly dispersed in the SPEN matrix, generating efficient proton-conducting paths along the SPEN/NSGO interface. Meanwhile, the sulfonic and amino groups of NSGO served as additional proton hopping sites to connect the ionic clusters in the SPEN matrix, creating interconnected and long-range ionic pathways. In such a way, proton-conducting highways with low energy barriers are constructed, which enhance the proton conductivity of the composite membranes via the Grotthuss mechanism. Furthermore, the composite membranes also effectively prevent methanol permeation, and therefore high selectivity (the ratio of proton conductivity and methanol permeability) is endowed. Compared to SPEN membrane, a 3.6-fold increase in selectivity is obtained for the optimal composite membrane. This study will provide a new strategy for the preparation of high-performance PEM. Full article
(This article belongs to the Special Issue Polymer Electrolytes for Energy Storage and Conversion Devices)
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