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Special Issue "Advanced Materials in Polymer Electrolyte Fuel Cells"

A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (15 March 2017)

Special Issue Editors

Guest Editor
Dr. Vincenzo Baglio

CNR-ITAE Institute for Advanced Energy Technologies “N. Giordano”, Via Salita S. Lucia sopra Contesse 5, Messina 98126, Italy
Website | E-Mail
Interests: direct alcohol fuel cells; electrocatalysis; polymer electrolyte fuel cells; water electrolysis; metal–air batteries; dye-sensitized solar cells; photo-electrolysis; carbon dioxide electro-reduction
Guest Editor
Dr. David Sebastián

Institute for Advanced Energy Technologies “Nicola Giordano” (ITAE-CNR), Messina, Italy
Website | E-Mail

Special Issue Information

Dear Colleagues,

Polymer electrolyte fuel cells (PEFCs) have recently attracted much interest due to the need for an efficient, non-polluting power source for vehicles in urban environments. Hydrogen is the most suitable fuel for a fuel cell powered vehicle, providing the highest conversion efficiency for fuel-on-board-to-electric-power and generating zero polluting emission, since water is the only product of the hydrogen/air fuel cell process. Significant efforts have been made in the last decades to investigate the direct electrochemical oxidation of alcohol and hydrocarbon fuels. Among the liquid organic fuels, methanol has promising characteristics in terms of reactivity at low temperatures, storage and handling. Nevertheless, before this technology can reach a large scale diffusion, some drawbacks related to poor electrochemical performance, high cost of fuel cell components, long term stability, etc. must be solved. In a PEFC system, high costs derive from the use of noble metal catalysts, perfluorosulfonic acid polymer electrolyte membranes, bipolar plates and auxiliary components. Therefore, the development of cost-effective and highly performing polymer electrolyte membranes, enhanced electro-catalysts and cheap bipolar plates satisfying the target requirements of high performance and durability represents an important challenge. The research is currently addressed towards cost-effective materials, such as novel hydrocarbon membranes and low precious metal loading electrodes. The key to a sustainable energy future thus lies in the development of advanced materials.

This Special Issue is intended to cover the most recent progress in advanced electro-catalysts, catalytic supports, electrodes, membranes, fillers and bipolar plates for high performance and cost-effective polymer electrolyte fuel cells, including direct alcohol fuel cells.

We look forward to receiving your contribution.

Dr. Vincenzo Baglio
Dr. David Sebastián
Guest Editors

Manuscript Submission Information

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Keywords

  • proton/anion exchange membrane fuel cells
  • direct alcohol fuel cells
  • oxygen electro-reduction
  • alcohol electro-oxidation
  • hydrogen electro-oxidation
  • polymer electrolyte membranes
  • electro-catalysts
  • advanced catalytic supports
  • electrodes
  • bipolar plates

Published Papers (10 papers)

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Editorial

Jump to: Research, Review

Open AccessEditorial Advanced Materials in Polymer Electrolyte Fuel Cells
Materials 2017, 10(10), 1163; doi:10.3390/ma10101163
Received: 6 October 2017 / Revised: 8 October 2017 / Accepted: 8 October 2017 / Published: 10 October 2017
PDF Full-text (711 KB) | HTML Full-text | XML Full-text
Abstract
Polymer electrolyte fuel cells (PEFCs) have attracted much interest due to the need for an efficient, non-polluting power source with high energy density for vehicles in urban environments, as well as portable electronics [...] Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Research

Jump to: Editorial, Review

Open AccessFeature PaperArticle N-Doped Carbon Xerogels as Pt Support for the Electro-Reduction of Oxygen
Materials 2017, 10(9), 1092; doi:10.3390/ma10091092
Received: 28 July 2017 / Revised: 4 September 2017 / Accepted: 14 September 2017 / Published: 17 September 2017
Cited by 1 | PDF Full-text (2256 KB) | HTML Full-text | XML Full-text
Abstract
Durability and limited catalytic activity are key impediments to the commercialization of polymer electrolyte fuel cells. Carbon materials employed as catalyst support can be doped with different heteroatoms, like nitrogen, to improve both catalytic activity and durability. Carbon xerogels are nanoporous carbons that
[...] Read more.
Durability and limited catalytic activity are key impediments to the commercialization of polymer electrolyte fuel cells. Carbon materials employed as catalyst support can be doped with different heteroatoms, like nitrogen, to improve both catalytic activity and durability. Carbon xerogels are nanoporous carbons that can be easily synthesized in order to obtain N-doped materials. In the present work, we introduced melamine as a carbon xerogel precursor together with resorcinol for an effective in-situ N doping (3–4 wt % N). Pt nanoparticles were supported on nitrogen-doped carbon xerogels and their activity for the oxygen reduction reaction (ORR) was evaluated in acid media along with their stability. Results provide new evidences of the type of N groups aiding the activity of Pt for the ORR and of a remarkable stability for N-doped carbon-supported Pt catalysts, providing appropriate physico-chemical features. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessArticle Manufacturing the Gas Diffusion Layer for PEM Fuel Cell Using a Novel 3D Printing Technique and Critical Assessment of the Challenges Encountered
Materials 2017, 10(7), 796; doi:10.3390/ma10070796
Received: 7 June 2017 / Revised: 26 June 2017 / Accepted: 10 July 2017 / Published: 14 July 2017
Cited by 1 | PDF Full-text (1390 KB) | HTML Full-text | XML Full-text
Abstract
The conventional gas diffusion layer (GDL) of polymer electrolyte membrane (PEM) fuel cells incorporates a carbon-based substrate, which suffers from electrochemical oxidation as well as mechanical degradation, resulting in reduced durability and performance. In addition, it involves a complex manufacturing process to produce
[...] Read more.
The conventional gas diffusion layer (GDL) of polymer electrolyte membrane (PEM) fuel cells incorporates a carbon-based substrate, which suffers from electrochemical oxidation as well as mechanical degradation, resulting in reduced durability and performance. In addition, it involves a complex manufacturing process to produce it. The proposed technique aims to resolve both these issues by an advanced 3D printing technique, namely selective laser sintering (SLS). In the proposed work, polyamide (PA) is used as the base powder and titanium metal powder is added at an optimised level to enhance the electrical conductivity, thermal, and mechanical properties. The application of selective laser sintering to fabricate a robust gas diffusion substrate for PEM fuel cell applications is quite novel and is attempted here for the first time. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessFeature PaperCommunication Probing Transition-Metal Silicides as PGM-Free Catalysts for Hydrogen Oxidation and Evolution in Acidic Medium
Materials 2017, 10(6), 661; doi:10.3390/ma10060661
Received: 3 May 2017 / Revised: 10 June 2017 / Accepted: 13 June 2017 / Published: 16 June 2017
Cited by 1 | PDF Full-text (1963 KB) | HTML Full-text | XML Full-text
Abstract
In this experimental study, we investigate various transition-metal silicides as platinum-group-metal-(PGM)-free electrocatalysts for the hydrogen oxidation reaction (HOR), and for the hydrogen evolution reaction (HER) in acidic environment for the first time. Using cyclic voltammetry in 0.1 M HClO4, we first
[...] Read more.
In this experimental study, we investigate various transition-metal silicides as platinum-group-metal-(PGM)-free electrocatalysts for the hydrogen oxidation reaction (HOR), and for the hydrogen evolution reaction (HER) in acidic environment for the first time. Using cyclic voltammetry in 0.1 M HClO4, we first demonstrate that the tested materials exhibit sufficient stability against dissolution in the relevant potential window. Further, we determine the HOR and HER activities for Mo, W, Ta, Ni and Mo-Ni silicides in rotating disk electrode experiments. In conclusion, for the HOR only Ni2Si shows limited activity, and the HER activity of the investigated silicides is considerably lower compared to other PGM-free HER catalysts reported in the literature. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessArticle Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes
Materials 2017, 10(6), 580; doi:10.3390/ma10060580
Received: 17 March 2017 / Revised: 12 May 2017 / Accepted: 22 May 2017 / Published: 25 May 2017
Cited by 1 | PDF Full-text (4165 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active
[...] Read more.
Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM) and X-ray techniques such as photoelectron spectroscopy (XPS), diffraction (XRD) and energy dispersive spectroscopy (EDX). The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M) and temperatures (60 °C and 90 °C). The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessFeature PaperArticle Transport in Proton Exchange Membranes for Fuel Cell Applications—A Systematic Non-Equilibrium Approach
Materials 2017, 10(6), 576; doi:10.3390/ma10060576
Received: 20 March 2017 / Revised: 15 May 2017 / Accepted: 19 May 2017 / Published: 25 May 2017
Cited by 1 | PDF Full-text (8180 KB) | HTML Full-text | XML Full-text
Abstract
We hypothesize that the properties of proton-exchange membranes for fuel cell applications cannot be described unambiguously unless interface effects are taken into account. In order to prove this, we first develop a thermodynamically consistent description of the transport properties in the membranes, both
[...] Read more.
We hypothesize that the properties of proton-exchange membranes for fuel cell applications cannot be described unambiguously unless interface effects are taken into account. In order to prove this, we first develop a thermodynamically consistent description of the transport properties in the membranes, both for a homogeneous membrane and for a homogeneous membrane with two surface layers in contact with the electrodes or holder material. For each subsystem, homogeneous membrane, and the two surface layers, we limit ourselves to four parameters as the system as a whole is considered to be isothermal. We subsequently analyze the experimental results on some standard membranes that have appeared in the literature and analyze these using the two different descriptions. This analysis yields relatively well-defined values for the homogeneous membrane parameters and estimates for those of the surface layers and hence supports our hypothesis. As demonstrated, the method used here allows for a critical evaluation of the literature values. Moreover, it allows optimization of stacked transport systems such as proton-exchange membrane fuel cell units where interfacial layers, such as that between the catalyst and membrane, are taken into account systematically. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessArticle Towards Highly Performing and Stable PtNi Catalysts in Polymer Electrolyte Fuel Cells for Automotive Application
Materials 2017, 10(3), 317; doi:10.3390/ma10030317
Received: 28 December 2016 / Revised: 13 March 2017 / Accepted: 15 March 2017 / Published: 21 March 2017
Cited by 2 | PDF Full-text (6692 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In order to help the introduction on the automotive market of polymer electrolyte fuel cells (PEFCs), it is mandatory to develop highly performing and stable catalysts. The main objective of this work is to investigate PtNi/C catalysts in a PEFC under low relative
[...] Read more.
In order to help the introduction on the automotive market of polymer electrolyte fuel cells (PEFCs), it is mandatory to develop highly performing and stable catalysts. The main objective of this work is to investigate PtNi/C catalysts in a PEFC under low relative humidity and pressure conditions, more representative of automotive applications. Carbon supported PtNi nanoparticles were prepared by reduction of metal precursors with formic acid and successive thermal and leaching treatments. The effect of the chemical composition, structure and surface characteristics of the synthesized samples on their electrochemical behavior was investigated. The catalyst characterized by a larger Pt content (Pt3Ni2/C) presented the highest catalytic activity (lower potential losses in the activation region) among the synthesized bimetallic PtNi catalysts and the commercial Pt/C, used as the reference material, after testing at high temperature (95 °C) and low humidification (50%) conditions for automotive applications, showing a cell potential (ohmic drop-free) of 0.82 V at 500 mA·cm−2. In order to assess the electro-catalysts stability, accelerated degradation tests were carried out by cycling the cell potential between 0.6 V and 1.2 V. By comparing the electrochemical and physico-chemical parameters at the beginning of life (BoL) and end of life (EoL), it was demonstrated that the Pt1Ni1/C catalyst was the most stable among the catalyst series, with only a 2% loss of voltage at 200 mA·cm−2 and 12.5% at 950 mA·cm−2. However, further improvements are needed to produce durable catalysts. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessArticle Novel PEFC Application for Deuterium Isotope Separation
Materials 2017, 10(3), 303; doi:10.3390/ma10030303
Received: 18 February 2017 / Revised: 14 March 2017 / Accepted: 15 March 2017 / Published: 16 March 2017
Cited by 1 | PDF Full-text (1706 KB) | HTML Full-text | XML Full-text
Abstract
The use of a polymer electrolyte fuel cell (PEFC) with a Nafion membrane for isotopic separation of deuterium (D) was investigated. Mass analysis at the cathode side indicated that D diffused through the membrane and participated in an isotope exchange reaction. The exchange
[...] Read more.
The use of a polymer electrolyte fuel cell (PEFC) with a Nafion membrane for isotopic separation of deuterium (D) was investigated. Mass analysis at the cathode side indicated that D diffused through the membrane and participated in an isotope exchange reaction. The exchange of D with protium (H) in H2O was facilitated by a Pt catalyst. The anodic data showed that the separation efficiency was dependent on the D concentration in the source gas, whereby the water produced during the operation of the PEFC was more enriched in D as the D concentration of the source gas was increased. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Open AccessFeature PaperArticle Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction
Materials 2017, 10(2), 197; doi:10.3390/ma10020197
Received: 11 January 2017 / Revised: 11 February 2017 / Accepted: 14 February 2017 / Published: 17 February 2017
Cited by 2 | PDF Full-text (4656 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
2D nitrogen-doped mesoporous carbon (NMC) is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR). The effect of the synthesis conditions on the silica template and carbon
[...] Read more.
2D nitrogen-doped mesoporous carbon (NMC) is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR). The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates—viz. graphene oxide and triblock copolymer F127—to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM), nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and rotating disk electrode measurements (RDE). The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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Review

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Open AccessFeature PaperReview Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review
Materials 2017, 10(7), 687; doi:10.3390/ma10070687
Received: 6 April 2017 / Revised: 22 May 2017 / Accepted: 14 June 2017 / Published: 22 June 2017
Cited by 1 | PDF Full-text (3859 KB) | HTML Full-text | XML Full-text
Abstract
Polymer fuel cells operating above 100 °C (High Temperature Polymer Electrolyte Membrane Fuel Cells, HT-PEMFCs) have gained large interest for their application to automobiles. The HT-PEMFC devices are typically made of membranes with poly(benzimidazoles), although other polymers, such as sulphonated poly(ether ether ketones)
[...] Read more.
Polymer fuel cells operating above 100 °C (High Temperature Polymer Electrolyte Membrane Fuel Cells, HT-PEMFCs) have gained large interest for their application to automobiles. The HT-PEMFC devices are typically made of membranes with poly(benzimidazoles), although other polymers, such as sulphonated poly(ether ether ketones) and pyridine-based materials have been reported. In this critical review, we address the state-of-the-art of membrane fabrication and their properties. A large number of papers of uneven quality has appeared in the literature during the last few years, so this review is limited to works that are judged as significant. Emphasis is put on proton transport and the physico‐chemical mechanisms of proton conductivity. Full article
(This article belongs to the Special Issue Advanced Materials in Polymer Electrolyte Fuel Cells)
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