Post-irradiation time effects on the graft of poly(ethylene-alt-tetrafluoroethylene) (ETFE) films for ion exchange membrane application

Grafting of styrene followed by sulfonation onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) was studied for synthesis of ion exchange membranes. Radiation-induced grafting of styrene onto ETFE films was investigated after simultaneous irradiation (in post-irradiation condition) using a ⁶⁰Co source. The ETFE films were irradiated at 20 kGy dose at room temperature and chemical changes were monitored after contact with styrene for grafting. The post-irradiation time was established at 14 days when the films were remained in styrene/toluene 1:1 v/v. After this period the grafting degree was evaluated in the samples. The grafted films were sulfonated using chlorosulfonic acid and 1, 2-dichloroethane 20:80 (v/v) at room temperature for 5 h. The membranes were analyzed by infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), thermogravimetric measurements (TG) and degree of grafting (DOG). The ion exchange capacity (IEC) of membranes was determined by acid–base titration and the values for ETFE membranes were achieved higher than Nafion^® films. Preliminary single cell performance was made using pure H₂ and O₂ as reactants at a cell temperature of 80 °C and atmospheric gas pressure. The fuel cell performance of ETFE films was satisfactory when compared to state-of-art Nafion^® membranes.     

Solvation of sulphonic acid groups in Nafion® membranes from accurate conductivity measurements

The wide degree of scatter of experimental data shows unambiguously that Nafion^®117 conductivity is very sensitive to climatic conditions, temperature and relative humidity. In order to allow equilibrium with the surrounding atmosphere to be reached rapidly, a conductivity cell, adapted to a small size membrane samples, has been designed. Conductivity measurements have been carried out by electrochemical impedance spectroscopy (EIS) between 10 °C and 95 °C in a broad domain of relative humidity, i.e., 10–98%. The measurement set up provides reproducible data with a total uncertainty of 30% in a large range of conductivity values. These accurate data enable a power relationship to be proposed at constant temperature between conductivity and relative humidity. This suggests that the solvation process of a sulphonic acid group involves four water molecules. Based on the assumption that a proton mobility depends weakly on temperature, a solvation enthalpy of a sulphonic acid group by water of −135 kJ mol⁻¹ is deduced from conductivity variations with the temperature.     

Development of MEMS-based direct methanol fuel cell with high power density using nanoimprint technology

Performance of MEMS-based DMFC is low, because graphite-based porous electrodes show poor compatibility with MEMS technology. Nanoimprint technology was adopted in this paper to prepare fine pattern on proton exchange membrane (PEM) in MEMS-based DMFC as a promising alternative to the graphite-based porous electrodes. Micro-convex with the diameter of about 600 nm and the height of 50–70 nm was prepared on Nafion^® 117 membrane by the nanoimprint at 130 °C using silicon mold. Thick Pt film (20 nm) was deposited as catalyst directly on the nanoimprinted Nafion^® 117 membrane. Then the Pt-coated PEM was sandwiched with micro-channeled silicon plates to form a micro-DMFC. With passively feeding of 1 M methanol solution and air at room temperature, the as-prepared cell had the open circuit voltage (OCV) of 0.74 V and the maximum power density of 0.20 mW/cm². The measured OCV was higher than those (0.1–0.3 V) of the state-of-the-art MEMS-based DMFC with planar electrode and pure Pt catalyst.     

Phosphoric acid doped high temperature proton exchange membranes based on sulfonated polyetheretherketone incorporated with ionic liquids

A composite membrane was fabricated using a novel approach based on the ionic liquids 1-butyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium hexafluorophosphate, sulfonated polyetheretherketone (SPEEK), and phosphoric acid. This proton conducting composite membrane shows promise for operation in high temperature proton exchange membrane fuel cells at working temperatures up to 160 °C without humidification. Proton conductivity at a level of 2.0 × 10^? 2 S/cm was achieved at 160 °C by the composite membrane with a molar ratio of 1:0.6:9 for SPEEK, 1-butyl-3-methylimidazolium (BMIM) cation and phosphoric acid, respectively. The sulfonation degree was 0.643 per polymer repeat unit with over 90% of the sulfate fixed anions forming a salt complex with BMIM cations. The tensile stress at break of the composite membrane was 15.5 MPa at room temperature, and it decreased from 4.1 to 1.9 MPa when the temperature increased from 110 to 160 °C, respectively.     

Performance of plasma sputtered fuel cell electrodes with ultra-low Pt loadings

Ultra-low Pt content PEMFC electrodes have been manufactured using magnetron co-sputtering of carbon and platinum on a commercial E-Tek^® uncatalyzed gas diffusion layer in plasma fuel cell deposition devices. Pt loadings of 0.16 and 0.01 mg cm^?2 have been realized. The Pt catalyst is dispersed as small clusters with size less than 2 nm over a depth of 500 nm. PEMFC test with symmetric electrodes loaded with 10 μg cm^?2 led to maximum reproducible power densities as high as 0.4 and 0.17 W cm^?2 with Nafion^®212 and Nafion^®115 membranes, respectively.     

SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究

通过在磺化聚醚醚酮(SPEEK,DS=61.68%)中分别混入酚酞型聚醚砜(PES-C)、磺化酚酞型聚醚砜(SPES-C,DS=53.7%)制备出SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜.结果表明,共混的两种聚合物之间均具有较好的相容性.PES-C、SPES-C的混入能有效降低膜的溶胀及甲醇透过,且随着共混量的增加,这种作用越趋明显.纯SPEEK膜在75℃左右溶解,而SPEEK/PES-C(30wt%)、SPEEK/SPES-C(30wt%)共混膜在80℃时溶胀度仅为22.5%、26.32%.在室温至80℃范围内,纯SPEEK及共混膜的甲醇透过系数都在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,温度大于90℃时,SPEEK/PES-C(20wt%)共混膜电导率超过Nafion115膜;温度大于110℃时,SPEEK/SPES-C(30wt%)共混膜电导率与Nafion115膜相当,达到0.11S.cm-1.高电导率,低透醇系数以及明显提高了的可使用温度表明该类共混膜有望在DMFC中使用.     

TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene-co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 °C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 °C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6×10^?1 S/cm.     

Polymeric proton conducting membranes for medium temperature fuel cells (110–160°C)

The availability of stable polymeric membranes with good proton conductivity at medium temperatures is very important for the development of methanol PEM fuel cells. In view of this application, a systematic investigation of the conductivity of Nafion 117 and sulfonated polyether ether ketone (S-PEEK) membranes was performed as a function of relative humidity (r.h.) in a wide range of temperature (80–160°C). The occurrence of swelling/softening phenomena at high r.h. values prevented conductivity determinations above certain temperatures. Nevertheless, when r.h. was maintained at values lower than 80%, measurements were possible up to 160°C. The results showed that Nafion is a better proton conductor than S-PEEK at low r.h. values, especially at temperatures lower than 120°C. The differences in conductivity were, however, leveled out with the increasing r.h. and temperature. While at 100°C and 35% r.h. the conductivity of S-PEEK 2.48 was about 30 times lower than the conductivity of Nafion, both membranes reached a comparable conductivity (4×10⁻² S cm⁻¹) at 160°C and 75% r.h. The effect of superacidity and crystallization of the polymers on the conductivity, as well as the possibility of using Nafion and S-PEEK membranes in medium temperature fuel cells, are discussed.     

Proton transport properties of poly(aspartic acid) with different average molecular weights

We synthesized seven partially protonated poly(aspartic acids)/sodium polyaspartates (P-Asp) with different average molecular weights to study their proton transport properties. The number-average degree of polymerization (DP) for each P-Asp was 30 (P-Asp30), 115 (P-Asp115), 140 (P-Asp140), 160 (P-Asp160), 185 (P-Asp185), 205 (P-Asp205), and 250 (P-Asp250). The proton conductivity depended on the number-average DP. The maximum and minimum proton conductivities under a relative humidity of 70% and 298 K were 1.7 · 10^?3 S cm^?1 (P-Asp140) and 4.6 · 10^?4 S cm^?1 (P-Asp250), respectively. Differential thermogravimetric analysis (TG-DTA) was carried out for each P-Asp. The results were classified into two categories. One exhibited two endothermic peaks between t = (270 and 300) °C, the other exhibited only one peak. The P-Asp group with two endothermic peaks exhibited high proton conductivity. The high proton conductivity is related to the stability of the polymer. The number-average molecular weight also contributed to the stability of the polymer.     

Anhydrous proton conducting membranes based on electron-deficient nanoparticles/PBI-OO/PFSA composites for high-temperature PEMFC

PEMFC operating at high temperature (100–200 °C) are expected to have significant advantages but face big challenges in the development of suitable proton exchange membranes. This communication describes novel PBI-OO/PFSA blend membranes, which facilitate proton conduction under anhydrous conditions based on a “proton donor–proton acceptor” concept. The proton conductivity of the blends under anhydrous conditions exceeded that of PFSA by a factor of 50 at ambient temperature and of 2–4 at elevated temperature. Intermolecular interaction between two polymer components was investigated by FT-IR spectroscopy. After incorporation of inorganic electron-deficient compounds (BN nanoparticles), the anhydrous proton conductivity of the composites was higher than that of the bare PFSA by three orders of magnitude at ambient temperature and more than one order of magnitude at 140 °C.     

Anhydrous solid proton conductors based on perfluorosulfonic ionomer with polymeric solvent for polymer electrolyte fuel cell

Novel anhydrous polymeric proton conductors have been prepared from perfluorosulfonic acid ionomer with polymer solvent as supplying proton pathway through the segmental motion of polymer chains for polymer electrolyte fuel cell (PEFC) application. Since the membranes do not contain liquid-state acid or solvent, the membranes may promise more stable performances during the operation of PEFC. The Nafion-based anhydrous proton conductors showed maximum proton conductivity of about 4.0 × 10^?3 S cm^?1 at 130 °C under anhydrous condition. The mechanical properties of the membranes were enhanced by introducing H⁺-doped TiO₂ nanoparticles without the conductivity degradation. In addition, the electrochemical properties of the membrane electrode assembly (MEA) employing the anhydrous membrane as ionomer have been investigated, showing stable open circuit voltages (OCVs) over 0.9 V under non-humidified condition.     

Nafion–polyfurfuryl alcohol nanocomposite membranes for direct methanol fuel cells

Commercial Nafion 115 membranes were successfully modified by in situ acid-catalyzed polymerization of furfuryl alcohol (PFA) within Nafion structures. FT-IR and AFM were used to characterize the chemical and morphological structures of the Nafion–PFA nanocomposite membrane obtained. The methanol permeation experiments showed that the methanol flux through the Nafion–PFA nanocomposite membranes dropped by a factor of 2.2–2.7 when PFA loading was 3.9–8.0 wt.%. Importantly, the proton conductivity of the membranes decreased only slightly at a low PFA loading (<8 wt.%). The nanocomposite membranes with higher selectivity (e.g., proton conductivity/methanol crossover) achieved a much higher DMFC performance at both room temperature and 60 °C.     

Oxygen permeability and the state of water in Nafion® membranes with alkali metal and amino sugar counterions

The mobility of hydration water and the dissolved oxygen permeability through different cation forms of the Nafion^® membranes were determined. Two alkali metals (Na and K) and two amino sugars (an equivalent molar mixture of d-glucopyranosyl-α(1′ → 6)-2-amino-2-deoxy-d-mannitol and its sorbitol (GPA)and d-glucosamine (GLU)) were used as counterions. Based on the two-state model, the content and mobility of hydration water were determined using DSC and ¹⁷O NMR. The dissolved oxygen permeability through the Nafion^® membrane containing GPA was the lowest value in this study because, for the membrane, the fraction of hydration water was the greatest and the mobility of hydration water was the lowest. The amount and location of the hydrophilic group contained in substances as well as the kind of hydrophilic group affected the fraction and mobility of hydration water and dissolved oxygen permeability through the membranes.     

Proton conductive thin films prepared by plasma polymerization

Proton conductive membranes were prepared as thin films of about 10 μm thickness by an ion beam assisted plasma polymerization process. Argon ions were generated in a high frequency plasma and accelerated towards a PTFE target where CF fragments were released as a consequence of the ion impact. Various sulfur components (SO₂, CF₃SO₃H or ClSO₃H) were added to achieve proton conductivity by the formation of sulfonic acid groups. The CF fragments combined with the sulfur components to form a coherent thin film on a substrate. Mass spectrometric investigations revealed, however, that sulfur oxygen compounds were extremely delicate towards reduction to sulfur carbon compounds like CS₂ or SCF₂. The best membrane conductivities (>10⁻⁴ S/cm) and highest ion exchange capacities (0.15 mmol/g) were achieved with chlorosulfonic acid involved in the plasma polymerization process. Ultra-thin layers of these of these plasma polymers (ca. 300 nm) were subsequently deposited onto Nafion^® membranes in order to suppress methanol permeation for a potential application in a direct methanol fuel cell (DMFC). The ratio of proton conductivity and methanol diffusion coefficient was employed for an assessment of the transport characteristics of the coated membrane. Diffusion coefficients were determined in a flow cell coupled to a mass spectrometer. The plasma polymer coating decreased both the methanol permeation and the proton conductivity. With a proton conductive plasma polymer coating the decrease of methanol diffusion could outweigh the loss of proton conductivity. Plasma coating offers a way to suppress methanol crossover in DMFCs and to maintaining the proton conductivity.     

磺化酚酞型聚醚砜膜的制备及其阻醇和质子导电性能

直接甲醇燃料电池 (Directmethanolfuelcell,DMFC)以高效、清洁和燃料储运方便等优点适宜于作为各种用途的可移动动力源 ,成为 2 0世纪 90年代以来研究与开发的热点[1,2 ] .目前 ,这种电池的研究难点主要集中在催化剂不稳定和质子交换膜透醇上 .一张好的DMFC膜不但要可传递质子、绝缘电子 ,还应具有良好的阻醇性能 .如果膜的阻醇性能不好 ,甲醇会穿过膜到达阴极 ,与氧直接反应而不产生电流 ,不但造成燃料的浪费 ,同时也影响阴极的正常反应 ,使电池效率下降[3 ] .目前广泛应用于燃料电池中的Nafion 系列膜是由美国DuPont公司生产的一种…     

Characterization and evaluation of commercial poly (vinylidene fluoride)‐g‐sulfonatedPolystyrene as proton exchange membrane

The possibility of developing low‐cost commercial grafted and sulfonated Poly(vinylidene fluoride) (PVDF‐g‐PSSA) membranes as proton exchange membranes for fuel cell applications have been investigated. PVDF‐g‐PSSA membranes were systematically prepared and examined with the focus of understanding how the polymer microstructure (degree of grafting and sulfonation, ion‐exchange capacity, etc) affects their methanol permeability, water uptake, and proton conductivity. Fourier transform infrared spectroscopy was used to characterize the changes of the membrane's microstructure after grafting and sulfonation. The results showed that the PVDF‐g‐PSSA membranes exhibited good thermal stability and lower methanol permeability. The proton conductivity of PVDF‐g‐PSSA membranes was also measured by the electrochemical impedance spectroscopy method. It was found that the proton conductivity of PVDF‐g‐PSSA membranes depends on the degree of sulfonation. All the sulfonated membranes show high proton conductivity at 92°C, in the range of 27 to 235 mScm⁻¹, which is much higher than that of Nafion212 (102 mScm⁻¹ at 80°C). The results indicated that the PVDF‐g‐PSSA membranes are particularly promising membranes to be used as polymer electrolyte membranes due to their excellent stability, low methanol permeability, and high proton conductivity.     

Relationship between ionic conductivity of perfluorinated ionomeric membranes and nonaqueous solvent properties

Ionic conductivity and swelling data are measured for Nafion^® perfluorinated ionomeric membranes in nonaqueous solvents and solvent mixtures and correlated with solvent physical properties. The dependence of ionic conductivity on solvent uptake and cation type is examined for Nafion^® 117 membranes with a nominal equivalent weight of 1100 g/eq. The most important factors determining ionic conductivity in membranes swollen with polar nonaqueous solvents are the solvent viscosity, molar volume, donor properties, and the solvent uptake by the membrane. Ionic conductivity is generally limited by dissociation of the cation from the fixed anion site indicating that the ionomer fixed anion site basicity is the critical membrane property. Means for increasing membrane ionic conductivity are discussed.     

Proton exchange membrane using partially sulfonated polystyrene-b-poly(dimethylsiloxane) for direct methanol fuel cell

A diblock copolymer ionomer containing a rubbery poly(dimethylsiloxane) block has been developed as a proton exchange membrane for direct methanol fuel cell (DMFC). The partially sulfonated polystyrene-b-poly(dimethylsiloxane) (sPS-b-PDMS) membrane with 38% sulfonation degree exhibited 3 times lower methanol permeability and 2.6 times higher membrane selectivity (proton conductivity/methanol permeability) compared to Nafion^® 115 at 25 °C. Coexistence of microphase domains and ionic clusters was confirmed from the morphological studies by small-angle X-ray scattering and tapping-mode atomic force microscopy. Gas chromatographic analysis revealed that water/methanol selectivity of sPS-b-PDMS was 20 times higher than that of Nafion^® 115. Such a high water/methanol selectivity can be attributed to the existence of PDMS microdomains minimizing methanol permeation through hydrophilic ion channels. sPS-b-PDMS membranes were fabricated into membrane electrode assembly (MEA), and air-breathing DMFC test for these MEAs showed a better performance compared to the MEA composed of Nafion^® 115.     

Preparation via microemulsion method and proton conduction at intermediate-temperature of BaCe1−xYxO3−α

The ceramic powders of BaCe_1?xY_xO_3?α (x = 0.05, 0.10, 0.15, 0.20) have been prepared via a microemulsion method. Green compacts of the powders were sintered to densities higher than 95% of theoretical at the lower temperature (1500 °C). The obtained ceramics showed a single-phase of orthorhombic perovskite. The proton conduction was investigated by employing the techniques of AC impedance and electrochemical hydrogen permeation (hydrogen pumping) at 300–600 °C. It was found that the ceramics were almost pure proton conductors in wet hydrogen, and the highest proton conductivity was observed for x = 0.15 at 600 °C. Ammonia was synthesized successfully from nitrogen and hydrogen at atmospheric pressure in the electrolytic cell using BaCe_0.85Y_0.15O_3?α. The maximum rate of NH₃ formation was found to be 2.1 × 10^?9 mol s^?1 cm^?2 at 500 °C with an applied current of 0.75 mA.     

A new promising high temperature lithium battery solid electrolyte

Lithium lanthanoid silicates find importance as a solid electrolyte in high temperature lithium batteries in view of its high ionic conductivity at high temperatures. An first ever attempt is made to synthesis a new high temperature solid electrolyte viz., lithium samarium holmium silicate by sol–gel process and it has been characterized by thermal analysis (TGA–DTA), X-ray diffraction (XRD), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Lithium ion conductivity of 0.8087 × 10⁻⁷ Ω⁻¹ cm⁻¹ at 25 °C was obtained and it increases with increasing temperature. For the first time a highest conductivity of 0.1095 × 10⁻² Ω⁻¹ cm⁻¹ was obtained at 850 °C which is high compared to other high temperature lithium battery solid electrolytes.