Conductivity of Nafion 117 membrane used in polymer electrolyte fuel cells

The membrane electric transport (MC) directly influences the performance of the polymer electrolyte fuel cells (PEMFC). The membrane conductivity is determined by a number of parameters such as: hydration technique, graphite cell geometry and pressure applied when the membrane electrode assembly (MEA) is joined. In addition, the membrane conductivity might be influenced by the electrode position due to the possibility of anisotropic electric conductivity.     

Effect of acid treatment on the physico-chemical properties of Nafion 117 membrane

In this work, the effect on the physico-chemical properties of Nafion 117 membrane due to the treatment with HCl, H₂SO₄ and HNO₃ was studied. Water uptake, crystallinity, proton conductivity and water dynamics were evaluated on treated and non-treated membranes. An increase in the water uptake and conductivity and a decrease in the crystallinity were observed in treated membranes in comparison with the untreated one. The water dynamics, studied by spin-spin NMR relaxometry, suggests that treated membranes have a more uniform channel size distribution. The treatment with HCl and HNO₃ showed higher conductivity and water uptake than H₂SO₄.     

Oxygen permeation through Nafion 117 membrane and its impact on efficiency of polymer membrane ethanol fuel cell

We investigate oxygen permeation through Nafion 117 membrane in a direct ethanol fuel cell and elucidate how it affects the fuel cell efficiency. An obvious symptom of oxygen permeation is the presence of significant amounts of acetaldehyde and acetic acid in the mixture leaving anode when no current was drawn from the fuel cell (i.e. under the open circuit conditions). This parasitic process severely lowers efficiency of the fuel cell because ethanol is found to be directly oxidized on the surface of catalyst by oxygen coming through membrane from cathode in the absence of electric current flowing in the external circuit. Three commonly used carbon-supported anode catalysts are investigated, Pt, Pt/Ru and Pt/Sn. Products of ethanol oxidation are determined qualitatively and quantitatively at open circuit as a function of temperature and pressure, and we aim at determining whether the oxygen permeation or the catalyst's activity limits the parasitic ethanol oxidation. Our results strongly imply the need to develop more selective membranes that would be less oxygen permeable.     

The influence of metal ions on the conductivity of Nafion 112 in polymer electrolyte membrane fuel cell

Nafion 112 membranes were soaked in 1 M H₂SO₄ solutions containing variable amounts of Fe and Cr ions, either individually or mixed. An even distribution of the metal ions on the surface of the membranes was observed with electron probe microanalysis (EPMA) mapping. The proton conductivity of the soaked membranes was investigated using a conductivity cell. For Fe ions, the conductivity was almost constant until the Fe-ion solution concentration reached 300 ppm. Over the 300-ppm threshold, the conductivity decreased significantly. Similar results were obtained with Cr ions in the membrane, but here the threshold was approximately 200 ppm in the solution. Mixed metal ions were found to decrease these threshold values due to the additive effect of the two metals.     

Investigation of gas diffusion layer compression by electrochemical impedance spectroscopy on running polymer electrolyte membrane fuel cells

Two gas diffusion layers based on the same carbon cloth substrate, produced by an Italian Company (SAATI), and coated with microporous layers of different hydrophobicities, were assembled in a polymer electrolyte membrane fuel cell and its performances assessed. For comparison the cell mounting the carbon cloth without microporous layer was also tested. The membrane electrode assembly was made of Nafion^® 212 with Pt load 0.3/0.6 mg cm⁻² (anode/cathode). The cell testing was run at 60 °C and 80 °C with fully humidified air (100%RH) and 80%RH hydrogen feedings. The assembly of gas diffusion layers and membrane with electrodes was compressed to 30% and 50% of its initial thickness. For each configuration polarization and power curves were recorded; in order to evaluate the role of different GDLs, AC impedance spectroscopy of the running cell was also performed.The higher compression ratio caused the worsening of cell performances, partially mitigated when the operating temperature was raised to 80 °C. The presence of the microporous layer onto the carbon cloth resulted extremely beneficial for the operations especially at high current density; moreover, it sensibly reduces the high frequency resistance of the overall assembly.     

Effect of ionomer content and relative humidity on polymer electrolyte membrane fuel cell (PEMFC) performance of membrane-electrode assemblies (MEAs) prepared by decal transfer method

Membrane-electrode assemblies (MEAs) were fabricated by the decal transfer method with various Nafion ionomer contents (10–40 wt%) and their single cell performance and electrochemical characteristics were examined in atmospheric air at relative humidities of 25–95%. At high humidity (95%), the MEA performance was the highest with a cathode ionomer content of 30 and 20 wt% at 0.6 and 0.4 V, respectively. The optimum ionomer content of the decal MEAs increased with decreasing humidity, because of the change in the oxygen transport rate (water flooding) and number of active sites (ionic resistance). The concentration overpotential gradually increased with relative humidity up to about 0.4 V at 0.8 A/cm², which was not considered in previous studies using pressurized air and oxygen. The combined effect of the electrochemical active surface area and ionic resistance of the cathodes on the activation overpotential was also investigated, focusing on intermediate and low humidity levels, using a newly developed impedance analysis method.     

Dynamics and spatial distribution of water in Nafion 117 membrane investigated by NMR spin-spin relaxation

The dynamics and spatial distribution of water molecules in Nafion 117 membrane has been investigated by ¹H NMR. To this end, 1D and 2D spin-spin (T₂) relaxometry experiments were carried out as a function of the relative humidity ranging from 9 to 100%. The inverse Laplace transform was successfully applied to obtain the 1D T₂ distributions and 2D relaxation maps. The 1D T₂ distributions show two peaks at low RH and mainly one at high water content, which can be associated with the rearrangement of the exchange sites inside the polymeric channels with the amount of water. From the T₂ distribution at 70% RH three types of water were identified corresponding to different degree of molecular mobility. The 2D T₂-T₂ maps show molecular exchange between the two water populations found at low RH, while at 70% the exchange between only the two more mobile water populations takes place.     

Effect of operating conditions on carbon corrosion in polymer electrolyte membrane fuel cells

The influence of humidity, cell temperature and gas-phase O₂ on the electrochemical corrosion of carbon in polymer electrolyte membrane fuel cells is investigated by measuring CO₂ emission at a constant potential of 1.4 V for 30 min using on-line mass spectrometry. Carbon corrosion shows a strong positive correlation with humidity and cell temperature. The presence of water is indispensable for electrochemical carbon corrosion. By contrast, the presence of gas-phase O₂ has little effect on electrochemical carbon corrosion. With increased carbon corrosion, changes in fuel cell electrochemical characteristics become more prominent and thereby indicate that such corrosion significantly affects fuel cell durability.     

Nafion/poly(1-vinyl-1,2,4-triazole) blends as proton conducting membranes for polymer electrolyte membrane fuel cells

In this study, proton conducting Nafion-poly(1-vinyl-1,2,4-triazole) blends are produced. Nafion/polymer blend membranes are prepared by means of film casting from the Nafion-PVTri solutions at several molar ratios of PVTri repeat unit to -SO₃H. The chemical structure of the homopolymer PVTri is confirmed by FT-IR and ¹³C NMR. Thermal properties are investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and the results illustrated that all these Nafion-PVTri electrolytes are thermally stable at least up to 300 °C. The membrane properties are further characterized for their morphology by scanning electron microscopy (SEM) and water uptake measurements. The methanol permeability of these membranes is measured and the results exhibited that they have quite lower methanol permeability compared to pristine Nafion112. The electrochemical properties of PVTri are investigated by cyclic voltammetry. The conductivity of Nafion-P(VTri)₁ blend membranes is measured to be 5.3 × 10⁻⁴ S cm⁻¹ at 220 °C, in anhydrous state. The conductivity of blend increased at least three orders of magnitude up on hydration, i.e., exceeding 10⁻³ S cm⁻¹ with RH = 50% at ambient temperature.     

Characterization of internal wetting in polymer electrolyte membrane gas diffusion layers

Capillary pressure vs. saturation (P_C(S_L)) curves are fundamental to understanding liquid water transport and flooding in PEM gas diffusion layers (GDLs). P_C(S_L) curves convolute the influence of GDL pore geometry and internal contact angles at the three-phase liquid/solid/gas boundary. Even simple GDL materials are a spatially non-uniform mixture of carbon fiber and binder, making a Gaussian distribution of contact angles likely, based on the Cassie–Baxter equation. For a given Gaussian contact angle distribution with mean (θ_Mean) and standard deviation (σ), a realistic P_C(S_L) curve can be computed using a bundle of capillaries model and GDL pore size distribution data. As expected, computed P_C(S_L) curves show that θ_Mean sets the overall hydrophilic (θ_Mean < 90°) or hydrophobic (θ_Mean > 90°) character of the GDL (i.e., liquid saturation level at a given capillary pressure), and σ affects the slope of the P_C(S_L) curve. The capillary bundle model also can be used with (θ_Mean, σ) as unknown parameters that are best-fit to experimentally acquired P_C(S_L) and pore size distribution data to find (θ_Mean, σ) values for actual GDL materials. To test this, pore size distribution data was acquired for Toray TGP-H-090 along with hysteretic liquid and gas intrusion capillary pressure curve data. High quality best-fits were found between the model and combined datasets, with GDL liquid intrusion showing fairly neutral internal surface wetting properties (θ_Mean = 92° and σ = 10°) whereas gas intrusion displayed a hydrophilic character (θ_Mean = 52° and σ = 8°). External liquid advancing and receding contact angles were also measured on this same material and they also showed major hysteresis. The new methods described here open the door for better understanding of the link between GDL material processing and the wetting properties that affect flooding.     

Role of the glass transition temperature of Nafion 117 membrane in the preparation of the membrane electrode assembly in a direct methanol fuel cell (DMFC)

The glass transition temperature (T_g) of the Nafion 117 membrane was traced by DSC step by step during the preparation of the membrane electrode assembly (MEA). Wide-angle x-ray diffraction and frequency response analysis were used for the determination of the crystallinity and proton conductivity of the membrane. As-received Nafion 117 membrane showed two glass transition temperatures in the DSC thermogram. The first T_g, caused by the mobility of the main chain in the polymer matrix, was 125 °C; the second T_g, derived from the side chain due to the strong interaction between the sulfonic acid functional groups, was 195 °C. During the pretreatment of the membrane, the T_g of the Nafion 117 membrane drastically decreased because of the plasticizer effect of water. In the hot-pressing process, the T_g of the Nafion 117 membrane gradually increased due to the loss of water. When the Nafion 117 was completely dried, the T_g of the membrane finally reached 132 °C. Thermal heat treatment was then applied to the MEA to obtain high interfacial stability; however, the membrane developed a crystalline morphology that led to reduced water uptake and proton conductivity. Therefore, the thermal heat treatment of the MEA should be carefully controlled in the region of the glass transition temperature (120–140 °C) of the Nafion 117 membrane to ensure the high performance of the MEA.     

Ex situ measurements of through-plane thermal conductivities in a polymer electrolyte fuel cell

In this paper thermal properties for materials typically used in the proton exchange membrane fuel cell (PEMFC) are reported. Thermal conductivities of Nafion membranes were measured ex situ at 20 °C to be 0.177 ± 0.008 and 0.254 ± 0.016 W K⁻¹ m⁻¹ for dry and maximally wetted membranes respectively. This paper also presents a methodology to determine the thermal conductivity of compressible materials as a function of applied load. This technique was used to measure the thermal conductivity of an uncoated SolviCore porous transport layer (PTL) at various compaction pressures. For the dry PTL at 4.6, 9.3 and 13.9 bar compaction pressures, the thermal conductivity was found to be 0.27, 0.36 and 0.40 W K⁻¹ m⁻¹ respectively and the thermal contact resistivity to the apparatus was determined to be 2.1, 1.8 and 1.1 × 10⁻⁴ m² K W⁻¹, respectively. It was shown that the thermal contact resistance between two PTLs is negligible compared to the apparatus’ thermal contact resistivity. For a humidified PTL, the thermal conductivity increases by up to 70% due to a residual liquid saturation of 25%.     

Amelioration of PEMFC performance at high temperature by incorporation of nanofiller (sepiolite/layered double hydroxide) in Nafion membrane

Nanoheterostructured material composed of sepiolite clay mineral in which is assembled a MgAl layered double hydroxide (LDH) was used in the preparation of Nafion composite electrolyte membranes and their behavior compared to those of membranes filled with the LDH alone. Both, the neat MgAl LDH and the MgAl LDH-sepiolite hybrid materials were obtained via the co-precipitation method. Sepiolite fibers provide a large external surface area for bonding MgAl LDH particles while maintaining high microporosity and water molecules. The nanocomposite membranes were prepared incorporating different amount of LDH or LDH-sepiolite hybrid. Composite membranes present better water retention, good thermal properties and high proton conductivities at high temperatures than the pure Nafion membrane. The proton conductivity at 100 °C and 100% RH reaches a value of 0.13 S/cm for the LDH-sepiolite Nafion membrane whereas is only 0.010 S/cm in the case of the Nafion membrane. Fuel cell tests using Nafion membranes containing LDH or LDH-sepiolite hybrid as composite electrolytes show a good result for the operation of the PEMFC at 80 °C, 100 °C and 110 °C, with a clear favoring effect of the LDH-sepiolite filler for operation at the highest temperatures.     

The development of PTFE/Nafion/TEOS membranes for application in moderate and high temperature proton exchange membrane fuel cells

PTFE/Nafion (PN) and PTFE/Nafion/TEOS (PNS) membranes were fabricated for the application of moderate and high temperature proton exchange membrane fuel cells (PEMFCs), respectively. Membrane electrode assemblies (MEAs) were fabricated by PTFE/Nafion (and PTFE/Nafion/TEOS) membranes with commercially available low and high temperature gas diffusion electrodes (GDEs). The effects of relative humidity, operation temperature, and back pressure on the performance and durability test of the as-prepared MEAs were investigated. Incorporating TEOS into a PNS membrane and adding another layer of carbon onto a GDE would result in low membrane conductivity and low fuel cell performance respectively. However, in this work it is shown that HT-PNS MEAs demonstrate a higher performance than LT-PN MEAs in severe conditions - high temperature (118 °C) and low humidity (25% RH). The TEOS and additional carbon layer function as water retaining agents which are especially important for high temperature and low humidity conditions. The HT-PNS MEA showed good stability in a 50 h fuel cell test at high temperature, moderate relative humidity (50% RH) and back pressure of 14.7 psi.     

Measurement of deuterium isotope separation by polymer electrolyte fuel cell stack

Processes for separating hydrogen isotopes are important for future energy applications. Several separation methods are based on electrolytic process; however, electrolysis consumes large amounts of electric energy. In this study, we demonstrate deuterium isotope separation from a mixture of H₂ and D₂ gases using a polymer electrolyte fuel cell stack. To identify the most efficient process, we investigated two flow patterns for the fuel gas, namely, parallel and serial flow. The electrical power of the stacks depended on the flow pattern when a high current was generated. We attribute this dependence on membrane dehydration and water droplet formation in the serial flow, which passed through the single cells in a straight path. However, the stack with the serial path showed a high separation factor (α = 6.6) indicating enrichment of deuterium water during the operation. The long reaction path of the fuel gas contributed to effective separation. The fuel utilization in individual cells suggested the potential for even more effective separation processes by a serial flow path.     

Investigation of the interaction between hydrogen and irradiation defects in titanium by using positron annihilation spectroscopy

The formation of mono-vacancy, vacancy clusters and hydrogen-vacancy complexes with 30 keV H ion-irradiated pure titanium at different doses and temperatures was measured using by Positron annihilation spectroscopy (PAS). Results show a large number of H_mV_n clusters and vacancy-like defects in the samples irradiated at for room temperature, and that the formation of H_mV_n (m > n) at the sample irradiated at a high dose inhibits the increase of the S parameter. At increased irradiation temperature, the shrinkage of vacancy clusters and the effective open volume of defects decrease the S parameters. The high-temperature irradiation results in decreased vacancy-type defect concentration, and some hydrogen atoms diffuse from the cascade region to the track region, forming a large number of hydrogen-vacancy complexes in the track region. The coincidence Doppler broadening spectroscopy, an element analysis method, used to detect hydrogen in the ion-irradiated pure titanium sample, and results show hydrogen-related peaks in the high-momentum region, which may be due to the information of positron annihilation in the covalent bond formed by the H and the Ti elements. The increased radiation dose and temperature contribute to the formation of the hydrogen vacancy-complex, and the positron annihilation in high-momentum regions easily obtain hydrogen-related information.     

Nafion nanofibers and their effect on polymer electrolyte membrane fuel cell performance

Current fuel cell research is focused on reducing manufacturing costs by reducing platinum catalyst loading without sacrificing performance. Although improvements have been demonstrated by using platinum supported on porous carbon nanoparticles, significant losses in “active” platinum surface area within the catalyst layer (CL) still occur. Optimizing the reactant gas/Nafion^®/platinum triple phase boundary (TPB) in the CL (i.e., CL morphology) will result in increased “active” catalyst area and overall fuel cell performance. In this study, the effect of temperature on the formation of Nafion^® nanofibers in the CL during fuel cell operation and its subsequent improvement on fuel cell performance was clearly characterized. Post mortem scanning electron micrographs clearly show that Nafion^® nanofibers improve the TPB, where Nafion^® nanofibers act as a more efficient proton transport route from the catalyst particles to the polymer electrolyte membrane reducing ohmic and mass transport resistance.     

Effect of cations (Na, Ca, Fe) on the conductivity of a Nafion membrane

It is known that trace amounts of cations have a detrimental effect on the liquid-phase conductivity of perfluorosulfonated membranes at room temperature. However, the conditions used were very different from typical fuel cell conditions. Recent research has shown the impact of conductivity measurement conditions on NH₄⁺ contaminated membranes. In this study, the impact of nonproton-containing cations (Mⁿ⁺ = Na⁺, Ca²⁺, and Fe³⁺) on Nafion membrane (N-211) conductivity was investigated both in deionized (DI) water at room temperature (∼25 °C) and in the gas phase at 80 °C under conditions similar to in a PEMFC. These conductivities were compared with those of Nafion membranes contaminated with NH₄⁺ ions. Under the same conditions, the conductivity of a metal cationic-contaminated membrane having the same proton composition (yH⁺m) was similar, but slightly lower than that of an NH₄⁺-contaminated membrane. The conductivity in the purely H⁺-form of N-211 was more than 12 times greater than the Mⁿ⁺-form form at 25 °C in DI water. At 80 °C, the gas-phase conductivity was 6 times and 125 times greater at 100%RH and 30%RH, respectively. The quantitative results for conductivity and activation energy of contaminated membranes under typical fuel cell conditions are reported here for the first time.     

Mechanical behavior of the membrane during the polymer electrolyte fuel cell operation

A computational modeling framework is developed to represent the transport phenomena, electrochemistry and the mechanical stresses in a polymer electrolyte fuel cell (PEFC). The model is able to predict the mechanical stresses developed in the polymer electrolyte due to hydration changes, and restriction of the membrane swelling as a result of these hydration changes in the PEFC assembly. Anisotropy in the mechanical properties of the gas diffusion layers is accounted in the stress calculations. It is seen that hydration variations during the PEFC operation can cause significant mechanical stresses. The effects of operating voltage and relative humidities of reactants are investigated. It is observed that high inlet humidities result in a better performance; however, it can potentially cause the polymer electrolyte membrane to go through plastic deformation irreversibly. Thermal stresses due to temperature variations are also calculated and compared with hygral stresses; and it is found that thermal stresses are not negligible but are typically a fraction of the hygral stresses in a typical PEFC operation.