Fabrication and characterization of supported dual acidic ionic liquids for polymer electrolyte membrane fuel cell applications

In this study, we proposed an innovative and versatile method for preparation of highly stable and conductive supported ionic liquid (IL) membranes for proton exchange fuel cell applications. Novel covalently supported dual acidic IL membranes were prepared by radiation induced grafting of 4-vinyl pyridine (4-VP) onto poly(ethylene-co-tetrafluoroethylene) (ETFE) film followed by post-functionalization via sequential treatments with 1,4-butane sultone and sulfuric acid to introduce pyridinium alkyl sulfonate/hydrogen sulfate moieties. The advantage of our approach lies in grafting polymers with highly reactive functional groups suitable for efficient post-sulfonation. The membranes displayed better swelling and mechanical properties compared to Nafion 112 despite having more than 3 times higher ion exchange capacity (IEC). The proton conductivity reached superior values to Nafion above 80 °C. Particularly, the membrane with ion exchange capacity of 3.41 displayed a proton conductivity of 259 mScm⁻¹ at 95 °C. This desired conductivity value is attributed to the high IEC of the membranes as well as dissociation of the hydrophobic ETFE polymer and hydrophilic pyridinium alkyl sulfonate groups. Such appealing properties make the supported IL membranes promising for proton exchange membrane fuel cells (PEMFC).     

气体扩散层中聚四氟乙烯的分布对质子交换膜燃料电池水淹的影响

通过在不同真空度下进行碳纸的聚四氟乙烯（PTFE）浸渍处理,考察了PTFE在碳纸中的分布对燃料电池水淹情况的影响. 碳纸PTFE浸渍过程中,抽真空作用可以将碳纸微孔中存留的空气移除,使PTFE更均匀地扩散到内部微孔中. 碳纸的断面电镜照片显示真空浸渍可以改善PTFE的分布. 在总浸渍量相同时,由于真空浸渍使更多的PTFE进入到碳纸内部微孔,故其表面的PTFE比例减少. 实验进一步考察了碳纸中亲水孔和憎水孔的分布,结果表明真空浸渍处理的碳纸具有更高比例的憎水孔. 将不同处理方法的碳纸制备成膜电极,通过全尺寸电池考察其性能,结果表明PTFE的均匀分布可以改善电池性能,并且电化学阻抗分析表明其有利于改善水淹问题.     

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).     

Electrochemical pressure impedance spectroscopy for investigation of mass transfer in polymer electrolyte membrane fuel cells

Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.     

New polymer electrolyte membrane for medium-temperature fuel cell applications based on cross-linked polyimide Matrimid and hydrophobic protic ionic liquid

New hydrophobic protic ionic liquid, 2-butylaminoimidazolinium bis(trifluoromethylsulfonyl)imide (BAIM-TFSI), has been synthesized. The ionic liquid showed good thermal stability to at least 350 °C. The conductivity of BAIM-TFSI determined by electrochemical impedance method was found to be 5.6 × 10^?2 S/cm at 140 °C. Homogeneous composite films based on commercial polyimide (PI) Matrimid and BAIM-TFSI containing 30–60 wt% of ionic liquid were prepared by casting from methylene chloride solutions. Thermogravimetric analysis data indicated an excellent thermal stability of PI/BAIM-TFSI composites and thermal degradation points in the temperature range 377 °C–397 °C. The addition of ionic liquid up to 50 wt% in PI films does not lead to any significant deterioration of the tensile strength of the polymer. The dynamic mechanical analysis results indicated both an increase of storage modulus E′ of PI/BAIM-TFSI composites at room temperature and a significant E′ decrease with temperature compared with the neat polymer. The cross-linking of the PI with polyetheramine Jeffamine D-400 allowed to prepare PI/Jeffamine/BAIM-TFSI (50%) membrane with E′ value of 300 MPa at 130 °C. The ionic conductivity of this cross-linked composite membrane reached the level of 10^?2 S/cm at 130 °C, suggesting, therefore, its potential use in medium-temperature fuel cells operating in water-free conditions.     

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).     

Development of polyoxadiazole nanocomposites for high temperature polymer electrolyte membrane fuel cells

Novel nanocomposite membranes were prepared with sulfonated polyoxadiazole and different amounts of sulfonated dense and mesoporous (MCM-41) silica particles. It has been shown that particle size and functionality of sulfonated silica particles play an important role when they are used as fillers for the development of polymer electrolyte nanocomposite membrane for fuel cells. No significant particle agglomerates were observed in all nanocomposite membranes prepared with sulfonated dense silica particles, as analyzed by SEM, AFM, TGA, DMTA and tensile tests. The T_g values of the composite membranes increased with addition of sulfonated silica, indicating an interaction between the sulfonic acid groups of the silica and the polyoxadiazole. Constrained polymer chains in the vicinity of the inorganic particles were confirmed by the reduction of the relative peak height of tan δ. A proton conductivity of 0.034 S cm⁻¹ at 120 °C and 25% RH, which is around two-fold higher than the value of the pristine polymer membrane was obtained.     

Effect of convective channel-to-channel mass flow in a polymer electrolyte fuel cell

The effect of convective channel-to-channel mass flow on the local performance of a polymer electrolyte fuel cell (PEFC) air cathode is determined experimentally by using submillimeter resolved current density distribution measurements in channel and land areas. A special cell is employed, where the two parallel channels of the cathode flow field can be operated at different pressure. For isobaric operation of the channels (Δp = 0 mbar), the lateral current density distribution shows a distinct minimum in the land area between the channels as diffusive mass transport becomes limiting at a higher cell polarization. Toward higher Δp, the local cell performance in the land area improves initially as a result of an improving convective channel-to-channel mass flow. However, as the pressure difference exceeds a value of 10 mbar, no noteworthy additional benefit is observed with further increasing Δp. Under these conditions, the convective mass flow provides an abundant reactant supply in the land area and, since reactant depletion is no longer limiting, the lateral current density distribution is primarily governed by the local ohmic resistance. As a result, the current density exhibits a maximum in the land area, where the local ohmic resistance shows a minimum.     

Side chain crosslinking of aromatic polyethers for high temperature polymer electrolyte membrane fuel cell applications

Novel aromatic polymers bearing polar pyridine units in the main chain and side chain crosslinkable hydroxyl and propargyl groups have been successfully synthesized. The polymers have been investigated in terms of their critical properties related to their application in high temperature polymer electrolyte membrane fuel cells, such as doping ability, mechanical properties, and thermal stability. Crosslinked membranes were prepared by direct crosslinking of hydroxyl side chain groups with decafluorobiphenyl used for the first time as a crosslinking agent. However, further functionalization of hydroxyl groups to the propargyl derivative has also led to crosslinked polymers after thermal curing. Both types of crosslinked membranes exhibited higher glass transition temperatures as well as lower doping levels when doped in phosphoric acid compared with the non crosslinked analogs, confirming the formation of a successfully crosslinked network. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Improved lifetime of PEM fuel cell catalysts through polymer stabilization

A novel approach to increase lifetime of Pt/C catalysts was demonstrated and shown that Nafion-stabilized Pt catalyst (denoted here as Nafion-Pt/C) synthesized by a colloid route gives rise to an enhanced durability as compared to a conventional Pt/C catalysts commonly used in PEM fuel cell. A high catalytic activity of the catalyst is also observed by both CV (cyclic voltammetry) and ORR (oxygen reduction reaction) measurements. This catalyst durability in comparison with conventional Pt/C is increased directly by electrochemically-accelerated durability test (ADT). The loss rate of electrochemical active area (ECA) for Nafion-Pt/C catalysts is only 0.004 m² g⁻¹ cycle⁻¹, compared to a value of 0.012 m² g⁻¹ cycle⁻¹ for Pt/C. This indicates the catalyst is three times higher durability than Pt/C.     

Gas diffusion electrodes for polymer electrolyte fuel cell using sulfonated polyimide

Gas diffusion electrodes for high temperature polymer electrolyte fuel cells (PEFCs) have been prepared by using a novel proton conductive sulfonated polyimide (SPI) electrolyte. The catalyst layer was composed of Pt-loaded carbon black (Pt-CB) and SPI ionomer. The polarization properties and the microstructure of the catalyst layer were investigated as a function of the SPI/CB weight ratio. The anodic polarization was found to be negligibly small for all the compositions examined. The highest cathode performance was obtained at SPI/CB = 0.5 (by weight), where the best balance of high catalyst utilization and oxygen gas diffusion rate through the ionomer was obtained.     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

An NMR study of methanol diffusion in polymer electrolyte fuel cell membranes

Methanol diffusion in two polymer electrolyte membranes, Nafion 117 and BPSH 40 (a 40% disulfonated wholly aromatic polyarylene ether sulfone), was measured using a modified pulsed field gradient NMR method. This method allowed for the diffusion coefficient of methanol within the membrane to be determined while immersed in a methanol solution of known concentration. A second set of gradient pulses suppressed the signal from the solvent in solution, thus allowing the methanol within the membrane to be monitored unambiguously. Over a methanol concentration range of 0.5–8 M, methanol diffusion coefficients in Nafion 117 were found to increase from 2.9 × 10⁻⁶ to 4.0 × 10⁻⁶ cm² s⁻¹. For BPSH 40, the diffusion coefficient dropped significantly over the same concentration range, from 7.7 × 10⁻⁶ to 2.5 × 10⁻⁶cm² s⁻¹. The difference in diffusion behavior is largely related to the amount of solvent sorbed by the membranes. Increasing the methanol concentration results in an increase in solvent uptake for Nafion 117, while BPSH 40 actually excludes the solvent at higher concentrations. In contrast, diffusion of methanol measured via permeability measurements (assuming a partition coefficient of 1) was lower (1.3 × 10⁻⁶ and 6.4 × 10⁻⁷ cm² s⁻¹ for Nafion 117 and BPSH 40 respectively) and showed no concentration dependence. The differences observed between the two techniques are related to the length scale over which diffusion is monitored and the partition coefficient, or solubility, of methanol in the membranes as a function of concentration. For the permeability measurements, this length is equal to the thickness of the membrane (178 and 132 μm for Nafion 117 and BPSH 40 respectively) whereas the NMR method observes diffusion over a length of approximately 4–8 μm. Regardless of the measurement technique, BPSH 40 is a greater barrier to methanol permeability at high methanol concentrations.     

Water management strategies for PGM-free catalyst layers for polymer electrolyte fuel cells

Platinum group metal–free (PGM-free) catalysts are promising candidates to catalyze the oxygen reduction reaction in polymer electrolyte fuel cells (PEFCs). Because of their low activity, larger loadings are used resulting in thicker catalyst layers. Transport, particularly water management, thereby becomes a more prominent performance factor. Currently, very few works attempted to understand water management in PGM-free catalyst layers, mainly because of other challenges that had to be overcome first, such as enhancing their activity and durability. The field has also been active in a hypothesis discussion of micropores flooding that led to the belief that poor stability of the PEFC performance is linked to active sites flooding within the micropores. We present here an overview of recent advances in understanding water management in the PGM-free catalyst layer for oxygen reduction reaction in PEFCs and provide an opinion on design guidance in optimizing catalyst layers to avoid flooding.     

Active transport of Na + and K + through animal cell membranes

The transport of Na⁺ out of the cell and K⁺ into the cell against a concentration gradient is catalyzed by a (Na⁺ + K⁺)-activated ATPase. The way in which the cations pass through the cell membrane has not yet been elucidated. Studies on the ATP hydrolysis revealed a Na⁺-dependent phosphorylation of the enzyme protein; the conformation of the enzyme also appears to change. The energy required for transport of the cations against their concentration gradients is probably provided by K⁺-dependent hydrolysis of the enzyme-bound phosphate. The enzyme can synthesize ATP from inorganic phosphate and ADP on reversal of the cation concentration gradient. By keeping the enzyme in a particular conformation, the cardiac glycoside ouabain specifically inhibits the Na⁺ pump.     

Dynamic behavior of water within a polymer electrolyte fuel cell membrane at low hydration levels

Protonic conduction across the membrane of a polymer electrolyte fuel cell is intimately related to the dynamic behavior of water present within the membrane. To further the understanding of water dynamics in these materials, quasielastic neutron scattering (QENS) has been used to investigate the picosecond dynamic behavior of water within a perfluorosulfonated ionomer (PFSI) membrane under increasing hydration levels from dry to saturation. Evaluation of the elastic incoherent structure factor (EISF) reveals an increase in the characteristic length-scale of confinement as the number of water molecules in the membrane increases, tending to an asymptotic value at saturation. The fraction of elastic incoherent scattering observed at high Q over all hydration levels is well fit by a simple model that assumes a single, nondiffusing hydronium ion per membrane sulfonic acid site. The quasielastic component of the fitted data indicates confined dynamic behavior for scattering vectors less than 0.7 A(-1). As such, the dynamic behavior was interpreted using continuous diffusion confined within a sphere at Q < 0.7 A(-1) and random unconstrained jump diffusion at Q > 0.7 A(-1). As the number of water molecules in the membrane increases, the characteristic residence times obtained from both models is reduced. The increased dynamical frequency is further reflected in the diffusion coefficients predicted by both models. Between low hydration (2 H2O/SO3H) and saturation (16 H2O/SO3H), the continuous spherical diffusion coefficient changes from 0.46 +/- 0.12 to 1.04 +/- 0.12 (10(-5) cm2/s) and jump diffusion indicates an increase from 1.21 +/- 0.03 to 2.14 +/- 0.08 (10(-5) cm2/s). Overall, the dynamic behavior of water has been quantified over different length scale regimes, the results of which may be rationalized on the basis of the formation of water clusters in the hydrophilic domain that expand toward an asymptotic upper limit with increased hydration.     

Higher order hydrodynamic interactions in the calculation of polymer transport properties

Higher order hydrodynamics interactions are short-range modifications to the Oseen tensor T _ij and its self-interaction counterpart T _ii. They differ from the Oseen tensor in having terms of higher order than the first in a/R, a being a bead radius and R being a bead-bead distance. Effects of higher order hydrodynamic interactions on whole chain–whole chain hydrodynamic interactions are here computed. Higher order hydrodynamic interactions are shown to lead to a concentration dependence of the diffusion and friction coefficients of a free monomer. However, while higher order interactions make contributions of the same nature to the drag coefficients of a monomer and of a whole chain, the contributions are not simply multiplicative, removing a justification for the common practice of correcting polymer solution transport data for “monomer friction effects” via a normalization with data on friction coefficients of free monomers. © 1993 John Wiley & Sons, Inc.     

Limitations of aqueous model systems in the stability assessment of electrocatalysts for oxygen reactions in fuel cell and electrolyzers

Cost and stability remain the greatest technical barriers to sustainably commercialize low-temperature fuel cells and electrolyzers. For tackling this problem, numerous advanced electrocatalysts have been proposed and tested in aqueous model systems. There are, however, increasing and evident concerns regarding the value of stability data coming from such studies. Hence, we anticipate that finding new approaches to assess degradation will be a major undertaking in electrocatalysis research in the next years. Specifically, existing differences between fundamental and actual systems have to be addressed first: (a) electrode architecture; (b) electrolyte; (c) reactant and product transport; and (d) operating conditions. In this perspective, we discuss their influence on the stability of electrocatalysts using the challenging oxygen reduction and oxygen evolution reactions as illustrative cases.