Anhydrous proton-conducting polymeric electrolytes for fuel cells

The need to design proton-conducting electrolytes for fuel cells operating at temperatures of 120 degrees C and above has prompted the investigation of various "water-free" polymeric materials. The present study investigates the properties of "water-free" proton-conducting membranes prepared from high-molecular-weight polymeric organic amine salts. Specifically, the properties of bisulfates and dihydrogenphosphates of poly-2-vinylpyridine (P2VP), poly-4-vinylpyridine (P4VP), and polyvinylimidazoline (PVI) have been investigated over the temperature range of 25-180 degrees C. Nanocomposites of these polymeric organic amine salts and hydroxylated silica have also been investigated in this study. These polymers are found to be stable and proton-conducting at temperatures up to 200 degrees C. In all the polymer examples studied herein, the phosphates are more conducting than the bisulfates. The activation energy for ionic conduction was found to decrease with increasing temperature, and this is associated with the increased polymer mobility and ionization of the proton. This is confirmed by the high degree of motional narrowing that is observed in proton NMR experiments. The measured values of conductivity and the differences in pKa values of the polymeric organic amine and the mineral acid are clearly correlated. This observation provides the basis for the design of other water-free acid-base polymer systems with enhanced proton conductivity. The results presented here suggest that anhydrous polymer systems based on acid-base polymer salts could be combined with short-range proton conductors such as nanoparticulate silica to achieve acceptable conductivity over the entire temperature range.     

X-ray absorption spectroscopic studies on solid oxide fuel cells and proton-conducting ceramic fuel cells

X-ray absorption spectroscopy (XAS) is one of the best techniques to obtain the information on the electronic and local structures of materials. In the last few decades, XAS becomes a common analytical technique for the investigation of solid oxide fuel cells and proton-conducting ceramic fuel cells. In particular, operando and/or advanced XAS measurements can be recently available with the increased accessibility of synchrotron radiation. In this article, recent trends of solid oxide fuel cell and proton-conducting ceramic fuel cell researches using XAS are overviewed.     

Materials research and development focus areas for low cost automotive proton-exchange membrane fuel cells

Research and development of fuel cell materials often focuses on designing and discovering materials which will reduce the cost or improve the durability of an individual subcomponent. Examples of recent focus areas include non-Pt group metal catalysts, noncarbon catalyst supports, and nonfluorinated membranes. These studies rarely look at the entire system to comprehend the impact of these materials on the cost of ownership to the customer, including vehicle and fuel costs. This perspective takes a holistic look at the impact of functional materials on automotive fuel-cell systems and provides direction on which material properties will provide the greatest benefit. It also provides guidance on which material classes are the most likely to enable the achievement of systems which will result in the successful commercialization of light-duty fuel-cell vehicles.     

A review on key factors influencing the electrical conductivity of proton exchange membrane fuel cell composite bipolar plates

Fuel cells are gaining increasing importance as a promising alternative to traditional energy sources, primarily due to their exceptional efficiency and environmental advantages. The electrical performance of proton exchange membrane fuel cells (PEMFCs) largely depends on the effectiveness of proton and electron transport within the cell components. A critical factor impacting this efficiency is the electrical conductivity of polymer-based bipolar plates (BPPs), which play a fundamental role as current collectors. BPPs in PEMFCs can be made from various materials including coated metallic materials, graphitic materials, and polymer composites. This review exclusively concentrates on polymer composite BPPs. Enhancing the overall cell performance is achievable through the integration of electrically conductive additives into the polymer matrix of these plates. Graphite (GR), carbon black (CB), carbon fibers (CF), carbon nanotubes (CNT), and graphene (Gr) all emerge as highly promising functional materials capable of substantially elevating BPPs performance. This study, among its various objectives, delves into the synergistic effects of these electrically conductive additives and their capacity to enhance the electrical conductivity within polymeric matrices. Furthermore, this review article thoroughly explores the influence of the polymeric matrix, encompassing co-continuous morphology and processing conditions. In essence, it focuses on the improvement of BPPs electrical conductivity through innovative designs of their polymer-based composites and nanocomposites and the particular selection of the electrically conductive fillers. The insights derived from this study significantly contribute to a more profound understanding of how to effectively harness the potential of this vital PEMFC component.     

Rapid diagnostics of characteristics and stability of fuel cells with proton-conducting electrolyte

Processes underlying the degrading of membrane-electrode assemblies of hydrogen-air fuel cells with Nafion 212 and MF-4SK membranes under the conditions of their accelerated stress testing and long-term life tests are analyzed. The cathode platinum catalyst corrosion was shown to be the main cause of the degrading of the fuel cell’s kinetically controlled current-voltage characteristics; the corrosion is accompanied by the platinum nanoparticles’ growth and the platinum ion partial transfer into the membrane. The overvoltage components of the membrane-electrode assembly and their changing during accelerated stress testing are determined. The voltage decrease at currents >0.5 A/cm² is shown to be mainly caused by the transport and ohmic resistance growth. The transport resistance components are calculated; the dependence of the cathode active layer resistance on the platinum catalyst surface area is revealed.     

Ti/(Ti,Cr)N/CrN multilayer coated 316L stainless steel by arc ion plating as bipolar plates for proton exchange membrane fuel cells

Arc ion plating(AIP) is applied to form Ti/(Ti,Cr)N/Cr N multilayer coating on the surface of 316 L stainless steel(SS316L) as bipolar plates for proton exchange membrane fuel cells(PEMFCs). The characterizations of the coating are analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Interfacial contact resistance(ICR) between the coated sample and carbon paper is 4.9 m cm~2 under 150 N/cm~2,which is much lower than that of the SS316 L substrate. Potentiodynamic and potentiostatic tests are performed in the simulated PEMFC working conditions to investigate the corrosion behaviors of the coated sample. Superior anticorrosion performance is observed for the coated sample, whose corrosion current density is 0.12 μA/cm2. Surface morphology results after corrosion tests indicate that the substrate is well protected by the multilayer coating. Performances of the single cell with the multilayer coated SS316 L bipolar plate are improved significantly compared with that of the cell with the uncoated SS316 L bipolar plate, presenting a great potential for PEMFC application.     

Polysulfone ionomers for proton-conducting fuel cell membranes: sulfoalkylated polysulfones

Polysulfones (PSUs) carrying short pendant alkyl side-chains with terminal sulfonic acid units have been prepared and studied as proton-conducting membrane materials. The first step in the preparation involved quenching of lithiated PSU with SO₂ gas, resulting in sulfinated PSU. In the second step, the lithium sulfinate units on the polymer were reacted with sodium 2-bromoethanesulfonate, sodium 3-bromopropanesulfonate, or 1,4-butane sultone to produce sulfoethylated, sulfopropylated, or sulfobutylated PSUs, respectively. Analysis by thermogravimetry showed that membranes based on the sulfoalkylated polymers were stable up to approximately 300 °C under N₂ atmosphere. Calorimetry measurements revealed that the modified polymers absorbed large amounts of non-freezing water, corresponding to 11–14 mol H₂O/mol SO₃H under immersed conditions. The proton conductivity of a membrane based on a PSU carrying 0.9 sulfopropyl chains per repeating unit was measured to be 77 mS/cm at 70 °C under humidifying conditions.     

Synthetic strategies for the preparation of proton-conducting hybrid polymers based on PEEK and PPSU for PEM fuel cells

Synthetic strategies for the preparation of proton-conducting hybrid polymers based on Poly-Ether-Ether-Ketone (PEEK) and Poly-Phenyl-Sulfone (PPSU) are presented. Sulfonation reactions are discussed as a function of sulfonating agents and reaction conditions. Metalation reactions are also described, specifically the introduction of silanol units into the macromolecules. The objective is to improve the proton conductivity of the hybrid polymers by sulfonation, and the mechanical and thermal stabilities by introduction of silicon moieties. Examples of NMR spectra and thermogravimetric curves are shown and discussed in view of the macromolecular structure.     

Fluorinated polyoxadiazole for high-temperature polymer electrolyte membrane fuel cells

For the first time a fluorinated polyoxadiazole doped with phosphoric acid as a proton-conducting membrane for operation at temperatures above 100 °C and low humidities for fuel cells has been reported. Fluorinated polyoxadiazole with remarkable chemical stability was synthesized. No changes in the molecular weight (about 200,000 g mol⁻¹) can be observed when the polymer is exposed for 19 days to mixtures of sulfuric acid and oleum. Protonated membranes with low doping level (0.34 mol of phosphoric acid per polyoxadiazole unit, 11.6 wt.% H₃PO₄) had proton conductivity at 120 °C and RH = 100% in the order of magnitude of 10⁻² S cm⁻¹. When experiments are conducted at lower external humidity, proton conductivity values drop an order of magnitude. However still a high value of proton conductivity (6 × 10⁻³ S cm⁻¹) was obtained at 150 °C and with relative humidity of 1%. In an effort to increase polymer doping, nanocomposite with sulfonated silica containing oligomeric fluorinated-based oxadiazole segments has also been prepared. With the addition of functionalized silica not only doping level but also water uptake increased. For the nanocomposite membranes prepared with the functionalized silica higher proton conductivity in all range of temperature up to 120 °C and RH = 100% (in the order of magnitude of 10⁻³ S cm⁻¹) was observed when compared to the plain membrane (in the order of magnitude of 10⁻⁵ S cm⁻¹).     

Silica-facilitated proton transfer for high-temperature proton-exchange membrane fuel cells

High-temperature proton-exchange membrane fuel cells (HT-PEMFCs) have shown a broad prospect of applications due to the enhanced reaction kinetics and simplifie...     

质子交换膜燃料电池Pt纳米线电催化剂研究现状

质子交换膜燃料电池(PEMFC)能直接将化学能转换为电能,具有能量转换效率高、环境友好、启动快等优点.其中电催化剂是决定PEMFC性能、寿命及成本的关键材料之一.目前所采用的Pt催化剂成本较高,是阻碍其商业化的主要因素.而Pt纳米线电催化剂的Pt利用率和催化剂活性高,抗CO毒性以及耐久性好.本文综述了Pt纳米线电催化剂的制备及其电化学催化性能的研究现状.     

A strategy of tailoring stable electrolyte material for high performance proton-conducting solid oxide fuel cells (SOFCs)

A facile strategy was proposed to synthesize Nb-containing BaCeO₃-based material, which is a potential electrolyte for proton-conducting solid oxide fuel cells (SOFCs), via a wet chemical route while the conventional synthesis of Nb-containing oxides relied on the solid state reaction method due to the unavailability of suitable Nb-precursors such as Nb-nitrates resulting in a less desirable fuel cell performance when used as an electrolyte. The BaCe_0.7Nb_0.1Y_0.2O_3 − δ (BCNY) electrolyte material in this study persisted a good chemical stability against CO₂ and exhibited good performance in the fuel cell application. The fuel cell with BCNY electrolyte film showed a high performance of 533 mW cm^− 2 at 700 °C. This cell performance based on BCNY electrolyte was superior to that of many stable modified BaCeO₃-based proton-conducting SOFCs where the electrolytes were tailored by other strategies. This result indicated that the strategy presented in this study could be an effective way to prepare a stable electrolyte for high performance proton-conducting SOFCs, which could advance the development of proton-conducting SOFCs.     

A novel composite Nafion membrane for direct alcohol fuel cells

Trifluoromethanesulfonic acid or triflate acid, chemical formula CF₃SO₃H, is regarded as one of the strongest acids and resembles Nafion^® in structure. Erbium triflate, a lanthanum salt of triflate, is thermally stable. This paper reports data on the formation of membranes by the fixation of erbium triflate salts (ErTfO) into the Nafion structure. Five different loadings of ErTfO were used to fabricate ErTfO/Nafion composite membranes and these were characterized, extensively for possible use in direct alcohol fuel cells. The membranes were characterized using XRD, TGA, FTIR, and for mechanical strength, water uptake, ion exchange capacity, alcohol uptake, swelling, proton conductivity, alcohol permeability and oxygen stability. The ErTfO/Nafion composite membranes reduced alcohol permeability by 77–80%. The proton conductivity of 3% ErTfO/Nafion composite membranes was 38% higher than that of a pure cast Nafion membrane. The oxygen stability of the ErTfO/Nafion composite membranes was higher than pure cast Nafion. However, the mechanical strength of 7% and 9% ErTfO/Nafion was lower than that of pure cast Nafion. The composite membrane was chemically stable and has potential for use in direct alcohol fuel cells.     

High performance nitrile copolymers for polymer electrolyte membrane fuel cells

This paper reports the fuel cells (DMFC and PEMFC) performance using sulfonated poly(arylene ether ether nitrile) (SPAEEN) copolymers containing sulfonic acid group arranged in structurally different ways. The membrane electrode assembly (MEA) fabricated from SPAEEN containing 60 mol% of angled naphthalenesulfonic acid group (m-SPAEEN-60) had superior performance over those derived from pendent naphthalenesulfonic acid group (p-SPAEEN) or sulfonated hydroquinone (HQ-SPAEEN) in H₂/air and/or DMFC conditions. For example, the current density of the MEA using m-SPAEEN-60 at 0.5 V and 2.0 M methanol was 250 mA/cm², whereas the current densities of the MEAs using p-SPAEEN-50 and HQ-SPAEEN-56 were 185 and 190 mA/cm², respectively. In addition, compared with the sulfonated polysulfone (BPSH-35) and Nafion membranes, the copolymer containing nitrile group showed the improved cell performance. For example, the power density of the MEA using m-SPAEEN-60 at 250 mA/cm² and 2.0 M methanol was 125 mW/cm², whereas the power densities of the MEAs using sulfonated polysulfone (BPSH-35) and Nafion were 115 and 113 mW/cm², respectively. m-SPAEEN-60 showed stable cell performance during extended operation (>100 h).     

Corrosion analysis of graphite sinter as bipolar plates in the low-temperature PEM fuel cell simulated environments

Journal of Solid State Electrochemistry - The article presents the results of research and an analysis of the possibility of using sinters made of graphite powder as a material dedicated to the...     

A membrane electrode assembly with high fuel coulombic efficiency for passive direct borohydride fuel cells

Here, we report the development of a new membrane electrode assembly (MEA) structure for passive direct borohydride fuel cells (DBFCs). The anode of this type of MEA includes upper and lower parts for the electro-oxidation of borohydride and hydrogen, respectively. In comparison to conventional MEAs, the maximum power of this MEA is increased by 28.1%, and the anode polarization is decreased due to the current contribution of hydrogen electro-oxidation. The hydrogen generated from borohydride hydrolysis can be oxidized inside the cell, and the fuel coulombic efficiency reaches 100%. Therefore, high fuel utilization and cell safety can be obtained by employing this novel MEA in DBFCs.     

Single-wall carbon nanotube-based proton exchange membrane assembly for hydrogen fuel cells

A membrane electrode assembly (MEA) for hydrogen fuel cells has been fabricated using single-walled carbon nanotubes (SWCNTs) support and platinum catalyst. Films of SWCNTs and commercial platinum (Pt) black were sequentially cast on a carbon fiber electrode (CFE) using a simple electrophoretic deposition procedure. Scanning electron microscopy and Raman spectroscopy showed that the nanotubes and the platinum retained their nanostructure morphology on the carbon fiber surface. Electrochemical impedance spectroscopy (EIS) revealed that the carbon nanotube-based electrodes exhibited an order of magnitude lower charge-transfer reaction resistance (R(ct)) for the hydrogen evolution reaction (HER) than did the commercial carbon black (CB)-based electrodes. The proton exchange membrane (PEM) assembly fabricated using the CFE/SWCNT/Pt electrodes was evaluated using a fuel cell testing unit operating with H(2) and O(2) as input fuels at 25 and 60 degrees C. The maximum power density obtained using CFE/SWCNT/Pt electrodes as both the anode and the cathode was approximately 20% better than that using the CFE/CB/Pt electrodes.