Surface modified multi‐walled carbon nanotubes and Nafion nanocomposite membranes for use in fuel cell applications

The preparation and characterization of the nanocomposite polyelectrolyte membranes, based on Nafion, sulfonated multi‐walled carbon nanotubes (MWCNT‐SO₃H) and imidazole modified multi‐walled carbon nanotubes (MWCNT‐Im), for direct methanol fuel cell applications is described. The results showed that the modification of multi‐walled carbon nanotubes (MWCNT) with proton‐conducting groups (sulfonic acid groups or imidazole groups) could enhance the proton conductivity of the nanocomposite membranes in comparison to Nafion 117. Regarding the interactions between the protonated imidazole groups, grafted on the surface of MWCNT, and the negatively charged sulfonic acid groups of Nafion, new electrostatic interactions can be formed in the interface of the Nafion and MWCNT‐Im, which result in both lower methanol permeability and higher proton conductivity. The physical characteristics of these manufactured nanocomposite membranes were investigated by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, water uptake, methanol permeability, and ion exchange capacity, as well as proton conductivity. The Nafion/MWCNT‐Im membranes showed the higher proton conductivity, lower methanol permeability, and, as a consequence, a higher selectivity parameter in comparison to the neat Nafion or Nafion membrane containing MWCNT‐SO₃H or ─OH functionalized multi‐walled carbon nanotubes (MWCNT‐OH) membranes. The obtained results indicated that the Nafion/MWCNT‐Im membranes could be used as efficient polyelectrolyte membranes for direct methanol fuel cell applications.     

Formation and characterization of PEDOT-modified Nafion 117 membranes

Nafion 117 membranes were modified with a thin film of poly(3,4-ethylenedioxythiophene) (PEDOT) by a diffusion-controlled polymerization process using a two-compartment cell with the monomer EDOT on one side of the membrane and the oxidizing agent FeCl₃ on the other side. The methanol permeability and ion conductivity of the composite PEDOT/Nafion membranes were measured as a function of temperature and polymerization time by DC and AC polarization measurements in four-electrode technique and permeation experiments in a diaphragm cell. These modified membranes have lower methanol permeability while maintaining adequate conductivity.     

Poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) based composite electrolytes for lithium batteries

The composite polymer electrolyte (CPE) membranes, comprising of poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP), aluminum oxyhydroxide, (AlO[OH]_n) of two different particle sizes 7 μm/14 nm and LiN(CF₃SO₂)₂ as lithium salt were prepared using solution casting technique. The prepared membranes were subjected to XRD, impedance spectroscopy, compatibility and transport number studies. The incorporation of nanofiller greatly enhanced the ionic conductivity and the compatibility of the composite polymer electrolyte. Also LiCr_0.01Mn_1.99O₄/CPE/Li cells were assembled and their charge-discharge profiles have been made at 70 °C. The film which possesses nanosized filler offered better electrochemical properties than those with micron sized filler. The results are discussed based on Lewis acid-base theory.     

Self-assembled polyelectrolyte multilayered films on Nafion with lowered methanol cross-over for DMFC applications

The paper is concerned with the deposition of self-assembled polyelectrolyte multilayer on Nafion membrane by layer-by-layer (LbL) technique with lowered methanol cross-over for direct methanol fuel cell (DMFC) applications. The formation of self-assembled multilayered film on Nafion was characterized by UV–vis spectroscopy and it was found that the polyelectrolyte layers growth on the Nafion surface regularly. Furthermore, the proton conductivity and methanol cross-over measurements were carried out for characterization of the LbL self-assembled composite membranes. The results showed that the concentration and pH of the polyelectrolytes significantly affect the proton conductivity and methanol barrier properties of the composite membranes. 10⁻¹ monomol polyelectrolyte concentration and pH 1.8 was found to be optimum deposition conditions considering proton conductivity and methanol permeation properties of the LbL self-assembled composite membranes. The methanol permeability of the 10 bi-layers of PAH1.8/PSS1.8 deposited LbL self-assembly composite membrane was significantly suppressed and found to be 4.41 × 10⁻⁷ cm²/s while the proton conductivity value is in acceptable range for fuel cell applications.     

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.     

Nanocomposite fuel cell membranes based on Nafion and acid functionalized zeolite beta nanocrystals

We have prepared nanocomposite proton exchange membranes (PEMs) based on Nafion with sulfonic acid functionalized zeolite beta (AFB) as an additive. 2.5 and 5 wt% AFB composite membranes possess proton conductivity/methanol permeability (selectivity) ratios as much as 93% higher than commercial Nafion 117 at 21 °C, and 63% higher at 80 °C. These 2.5 and 5 wt% AFB composite membranes also outperform commercial Nafion 117 in direct methanol fuel cell performance evaluations. The composite membranes are characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, four-electrode impedance for proton conductivity, two-compartment permeation for methanol crossover, and direct methanol fuel cell performance.     

Synthesis and Ex-situ Characterization of Nafion/TiO2 Composite Membranes for Direct Ethanol Fuel Cell

Nafion/TiO₂ composite membranes for different loadings of TiO₂ were prepared by casting method for the possible application in direct ethanol fuel cell (DEFC). The properties of the composite membranes were investigated by scanning electron microscopy (SEM), x-ray diffraction (XRD), thermogravimetric analyser (TGA), ion exchange capacity, water and alcohol uptake, swelling ratio, proton conductivity, and ethanol crossover. The observed characteristics of the membranes were evaluated for DEFC and compared with the direct methanol fuel cell (DMFC) membrane. The analysis reveales a significant influence on the TiO₂ surface characteristics, water and alcohol uptake, and swelling of the membrane. The TiO₂ composite membranes exhibited a sharp decrease in methanol and ethanol crossover for 5% TiO₂ and the proton conductivity was heighest for 1% TiO₂ loading. The best compromise between proton conductivity and crossover has been found out with the help of the characteristic factor ϕ. The optimum loading of 5% TiO₂ composite membrane has shown the maximum characteristic factor.     

Poly(3,4-ethylenedioxythiophene)-modified nafion membrane for direct methanol fuel cells

Membranes Nafion 117 are modified with poly(3,4-ethylenedioxythiophene) (PEDT) by chemical polymerization of EDT with H₂O₂ or FeCl₃ as the oxidants in a two-compartment cell. Depending on the oxidant and polymerization conditions, PEDT is deposited either as a thin film on the membrane surface or inside the Nafion membrane depending on whether FeCl₃ or H₂O₂ is used as the oxidant. The decrease in the ionic conductivity and methanol permeability is studied as a function of the polymerization time. A linear dependence is found with H₂O₂ and a t ^−1/2 dependence, with FeCl₃. The contributions of PEDT and Nafion to the overall conductivity of the composite membranes are separated by impedance measurements. The modified membranes (FeCl₃) are also tested in direct methanol fuel cells (DMFC). The methanol permeation through the membranes is measured by operating the fuel cell in an electrolysis mode. The influence of the modified membranes on the DMFC current-voltage characteristics is studied with 2 M CH₃OH and O₂ at 1.2 bar_abs and 80°C. Membrane electrode assemblies (MEAs) are prepared by hot pressing the modified membrane between two commercial gas diffusion electrodes with 1 mg cm⁻² of Pt loading. A decrease of the methanol permeation of 25% is observed at MEA with the modified membrane (1 h polymerization time), compared with that of MEA with a Nafion membrane. However, the overall DMFC performance decreases in the same relation: a maximal power density of 36 W cm⁻² is measured at MEA with a PEDT-modified membrane compared with 45 W cm⁻² for MEA with a Nafion membrane. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1330–1339. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Sulfonated poly(ether ether ketone)/poly(vinylpyrrolidone) acid–base polymer blends for direct methanol fuel cell application

Acid–base polymer blends for polymer electrolyte membranes have been prepared by blending sulfonated poly(ether ether ketone) (SPEEK) with poly(vinylpyrrolidone) (PVP) to reduce methanol uptake and to decrease methanol permeability while maintaining high proton conductivity. The acid‐base interaction occurring on the sulfonic acid group and on the tertiary amide group was characterized by FTIR and DMA. As the composition of PVP lowered than 20 wt % in the blends, the acid–base interaction causes great reduction on methanol uptake and the methanol permeability; however, the proton conductivity is still high. In this work, membrane–electrode assemblies (MEAs) have been prepared for direct methanol fuel cell (DMFC) from both blend membrane and Nafion 117. DMFC single cell performance was also evaluated. Results confirmed that SPEEK (with the degree of sulfonation (DS) = 69%) blended with PVP (M_n = 1,300,000) with a ratio of 80/20 (w/w) exhibits higher open‐circuit voltages (OCV) and lower polarization loss than those of Nafion 117. These acid–base blends will be suitable for DMFC application. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 565–572, 2006     

Blend membranes of Nafion/sulfonated poly(aryl ether ketone) for direct methanol fuel cell

Sulfonated poly(aryl ether ketone) (sPAEK) synthesized by LG Chem. was confirmed by FT-IR. To estimate the thermal stability, glass transition temperature and decomposition temperature were investigated. They showed that sPAEK had good thermal properties. The proton conductivity, methanol permeability and water uptake of sPAEK were also measured. Nafion/sulfonated poly(aryl ether ketone) composite membranes were prepared by blending two materials. The blend ratios of sPAEK and Nafion were 2:1, 3:1, 5:1, and 7:1. The blend membranes showed phase separated morphology since they became immiscible during the solvent evaporation process. Due to the differences in specific gravity and solvent concentration profile during the solvent evaporation process, the upper region had lower Nafion volume fraction with smaller domains and the lower region had higher Nafion volume fraction with larger domains. Mechanical properties such as the stress at break, yield stress, Young's modulus, and elongation at break were measured. The sPAEK had better mechanical properties than Nafion. The mechanical properties increased with increasing sPAEK content. Proton conductivity and methanol permeability of the blend membranes were lower than those of Nafion. Both decreased with decreasing Nafion content. Since the methanol permeability of sPAEK was lower than that of Nafion, sPAEK acted as the methanol barrier. Water uptake of sPAEK was higher than that of Nafion.     

Novel proton-conductive nanochannel membranes with modified SiO2 nanospheres for direct methanol fuel cells

A novel approach is proposed to prepare a proton-conductive nanochannel membrane based on polyvinylidene difluoride (PVDF) porous membrane with modified SiO₂ nanospheres. The hydrophilic PVDF porous membrane with a 450-nm inner pore size was chosen as the supporting structure. Pristine SiO₂ with a uniform particle size of 95–110 nm was synthesized and functionalized with –NH₂ and –COOH, respectively. Through-plane channels of porous membrane and arranged functional nanoparticles in pores could contribute to constituting efficient proton transfer channels. The characteristics such as morphology, thermal stability, water uptake, dimensional swelling, proton conductivity and methanol permeability as proton exchange membranes, of the SiO₂ nanospheres, and the composite membrane were investigated. The formation of ionic channels in membrane enhanced the water uptakes and proton conduction abilities of the composite membranes. PVDF/Nafion/SiO₂–NH₂ exhibited superior proton conductivities (0.21 S cm^?1) over other samples due to several proton sites and the acid–base pairs formed between –NH₂ and –SO₃H. Furthermore, all the composite membranes exhibited improved methanol resistance compared with Nafion. Therefore, such a design based on porous membrane provided feasibility for high-performance proton exchange membrane in fuel cell applications.     

PPO-based acid–base polymer blend membranes for direct methanol fuel cells

New acid–base polymer blend membranes for direct methanol fuel cells (DMFC) have been designed using a very accessible commercial polymer, poly(2,6-dimethyl-1,4-phenylene oxide) (PPO). The preparation begins with the sulfonation and bromination of PPO to sulfonated PPO (SPPO) and bromomethylated PPO (BrPPO), respectively. Blend membranes are formed by mixing n-propylamine(PrNH₂)-neutralized SPPO and PrNH₂-aminated BrPPO solutions in N-methyl-2-pyrrolidone (NMP), and casting the mixed solution on glass petri dishes followed by acidification with aqueous hydrochloric acid. The compatibility between the acid and base components of the blend is assured by using acidic and basic polymers deriving from the same parent polymer (PPO). Ionic crosslinking is established between the sulfonic groups of SPPO and the amine groups of aminated BrPPO. The ionic crosslinking strengthens the membrane dimensional stability by reducing water uptake and membrane swelling up to temperatures as high as 80 °C. The membranes fabricated as such display good resistance to methanol crossover amidst some, but acceptable loss of proton conductivity. The characteristic factor (i.e. the ratio of proton conductivity to methanol permeability) increases noticeably with the BrPPO content, with the sample containing 30 wt.% BrPPO showing a 16-fold improvement over Nafion 117. The mechanical properties and oxidative stability of the blend membranes also satisfy the requirements for fuel cell assembly and operation.     

Preparation of Nafion/PTFE/Zr(HPO4)2 composite membranes by direct impregnation method

The viscosities of as received 5.1 wt.% Nafion solutions (EW = 1100, Du Pont Co) blended with various concentrations of ZrOCl₂ were studied. We show the solution viscosity decreases as the wt. ratio of [ZrOCl₂]/[Nafion] is increased from 0.0 to 0.03, then the viscosity does not change significantly as the wt. ratio of [ZrOCl₂]/[Nafion] is increased from 0.03 to 0.16, and then the viscosity increases dramatically as the wt. ratio of [ZrOCl₂]/[Nafion] is increased above 0.16. Four Nafion solutions consisting of 5.1 wt.% Nafion and ZrOCl₂ with [ZrOCl₂]/[Nafion] wt. ratios of 0.019–0.24 were used with porous poly(tetrafluoroethylene) (PTFE) film to prepare zirconium hydrogenphosphate (ZrP) hybridized Nafion/PTFE (NF–ZrP) composite membranes by direct impregnating porous PTFE in Nafion/ZrOCl₂ solutions. The influence of [ZrOCl₂]/[Nafion] wt. ratio of Nafion/ZrOCl₂ solution on the membrane morphology of NF–ZrP and polyelectrolyte membrane fuel cell (PEMFC) performance at temperatures of 110–130 °C with relative humidity of 51.7–28.8% RH was investigated.     

Nafion/PTFE and zirconium phosphate modified Nafion/PTFE composite membranes for direct methanol fuel cells

We prepared Nafion/PTFE (NF) and zirconium phosphate (ZrP) hybridized Nafion/PTFE composite membranes (NF–ZrP). NF–ZrP composite membranes were prepared via two processes. One is impregnating sub-μm porous PTFE membrane directly in a Nafion/ZrOCl₂ solution (NF–Zr–d). The other is impregnating sub-μm porous PTFE membrane in a Nafion solution to prepare NF composite membrane, and then the NF membrane was impregnated in a ZrOCl₂ aqueous solution via in situ precipitation method (NF–Zr–I). The ZrOCl₂ inserted in NF composite membranes was then reacted with phosphoric acid to form ZrP and thus NF–ZrP–d and NF–ZrP–I composite membranes were obtained. The direct methanol fuel cell (DMFC) performances of membrane electrode assemblies prepared from Nafion-117, NF, NF–ZrP–d, and NF–ZrP–I composite membranes were investigated. The effects of introducing sub-μm porous PTFE film and ZrP particles into Nafion membranes on the DMFC performance were investigated. The influence of ZrP hybridizing process into NF membranes (the process of preparing NF–ZrP–I is inserting ZrOCl₂ into NF membranes after Nafion is annealed and the process of preparing NF–ZrP–d is mixing ZrOCl₂ into a Nafion solution before Nafion is annealed) on the morphology of NF–ZrP composite membranes and thus on the DMFC performance was also discussed.     

A new anhydrous proton conducting material based on phosphoric acid doped polyimide

A new anhydrous proton conducting material based on polyimide and phosphoric acid composite was prepared. The interaction between polyimide (PI) and phosphoric acid was investigated by FTIR. The results show that phosphoric acid interacts with polyimides mainly by hydrogen bonds rather than by protonation of PI at room temperature. Environmental scanning electron microscopy (ESEM) was employed to study the surface morphology of the membranes. The results show that the surface of PI-xH₃PO₄ membranes is very compact and homogeneous. Proton conductivity and methanol permeability of PI doped with phosphoric acid (PI-xH₃PO₄) were also studied. Proton conductivity of PI-xH₃PO₄ membranes increases with increasing concentration of phosphoric acid. Hydrogen bond seems to play an important role in the proton conductivity of this system. Effects of osmotic on the direct diffusion process of methanol in the membranes can be negligible due to the absence of micro-pore structure as already shown in ESEM results. Effects of methanol concentration and temperature on the methanol permeability of PI-xH₃PO₄ membranes were also discussed. Methanol permeability in PI-xH₃PO₄ membranes decreases with increasing methanol concentration, and increases with increasing temperature.     

Zirconium meta-sulfonphenyl phosphonic acid-incorporated Nafion membranes for reduction of methanol permeability

Zirconium meta-sulfonphenyl phosphonic acid (Zr-msPPA)/Nafion^® composite membranes were prepared to reduce methanol permeability of the Nafion^® 117 membrane in direct methanol fuel cell (DMFC) applications. Zr-msPPA crystalline nano proton conductors were synthesized inside the membranes via the reaction of zirconium chloride octahydrate and meta-sulfonphenyl phosphonic acid that had been soaked prior. Synthesis of the Zr-msPPA in the membranes was identified from a series of chemical and physical structure characterizations using FTIR, NMR, EDS, and XRD spectroscopy. The thermal stability of the composite membranes was enhanced by addition of the Zr-msPPA, with considerable reduction in methanol permeability with increasing Zr-msPPA content, as the Zr-msPPA nano conductors acted as crystalline barriers to methanol permeation. The ion conductivity also decreased with increasing Zr-msPPA content, but its effect was not as strong as with methanol permeation given the innate, high conductivity of Zr-msPPA.     

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.     

掺杂纳米SiO2的PVDF-g-PSSA质子交换膜

以聚偏氟乙烯(PVDF)为骨架, 采用溶液接枝苯乙烯磺酸, 合成了掺杂纳米SiO₂颗粒的复合质子交换膜(PVDF/xSiO₂-g-PSSA). 利用红外光谱、热失重分析方法、扫描电镜, 对膜的结构、热稳定性、表面及断面形态进行了表征. 考察了膜的吸水率、电导率、甲醇渗透性等性质. 结果表明, 纳米SiO₂颗粒能提高膜的阻醇性能, 掺杂质量分数10%的适量SiO₂颗粒所得的复合膜的甲醇渗透系数达1.0×10^－7 cm²/s, 低于聚偏氟乙烯接枝苯乙烯磺酸(PVDF-g-PSSA)膜的1.7×10^－7 cm²/s, 仅为Nafion-117的渗透系数的二十分之一. PVDF/10% SiO₂-g-PSSA复合膜具有较高的选择性, 在直接甲醇燃料电池中具有良好的应用前景.     

Low water/methanol permeable Nafion/CHP organic-inorganic composite membrane with high crystallinity

High methanol crossover is one of the main issues of the polyelectrolyte in direct methanol fuel cells (DMFCs). In order to decrease methanol crossover, we introduced a new method that crystallinity control was performed with incorporating CHP (calcium hydroxyphosphate) into Nafion solution. As a result, crystallinity in the composite membranes increased with CHP content compared to cast Nafion accompanying the formation of new crystalline peaks in the original amorphous region of Nafion. On the other hand, water uptake content, methanol sorption/desorption permeability and methanol crossover in the composite membranes remarkably decreased. We conclude that an increase in crystallinity due to the strong interfacial adhesion between Nafion and CHP can suppress the methanol crossover.     

Supercritical carbon dioxide treated Nafion 212 commercial membranes for direct methanol fuel cells

Supercritical carbon dioxide (Sc-CO₂) thermal treatment to enhance performance of Nafion 212 (NR212) commercial membranes for direct methanol fuel cells (DMFCs) is described. It is shown that the microstructure of NR212 membranes is re-organized after the Sc-CO₂ treatment, and then the performance of NR212 membranes is improved. Specifically the thinner NR212 membranes after the Sc-CO₂ treatments have higher proton conductivity and better capacity of barrier to methanol crossover compared with the thicker Nafion 117 membranes. It is demonstrated that the DMFC performance of the Sc-CO₂ treated NR212 membranes is better than that of Nafion 117 membranes.