Electrochemical performance of an air-breathing direct methanol fuel cell using poly(vinyl alcohol)/hydroxyapatite composite polymer membrane

A novel composite polymer membrane based on poly(vinyl alcohol)/hydroxyapatite (PVA/HAP) was successfully prepared by a solution casting method. The characteristic properties of the PVA/HAP composite polymer membranes were examined by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and AC impedance method. An air-breathing DMFC, comprised of an air cathode electrode with MnO₂/BP2000 carbon inks on Ni-foam, an anode electrode with PtRu black on Ti-mesh, and the PVA/HAP composite polymer membrane, was assembled and studied. It was found that this alkaline DMFC showed an improved electrochemical performance at ambient temperature and pressure; the maximum peak power density of an air-breathing DMFC in 8 M KOH + 2 M CH₃OH solution is about 11.48 mW cm⁻². From the application point of view, these composite polymer membranes show a high potential for the DMFC applications.     

Study of poly(vinyl alcohol)/titanium oxide composite polymer membranes and their application on alkaline direct alcohol fuel cell

The novel poly(vinyl alcohol)/titanium oxide (PVA/TiO₂) composite polymer membrane was prepared using a solution casting method. The characteristic properties of the PVA/TiO₂ composite polymer membrane were investigated by thermal gravimetric analysis (TGA), a scanning electron microscopy (SEM), a micro-Raman spectroscopy, a methanol permeability measurement and the AC impedance method. An alkaline direct alcohol (methanol, ethanol and isopropanol) fuel cell (DAFC), consisting of an air cathode based on MnO₂/C inks, an anode based on PtRu (1:1) black and a PVA/TiO₂ composite polymer membrane, was assembled and examined for the first time. The results indicate that the alkaline DAFC comprised of a cheap, non-perfluorinated PVA/TiO₂ composite polymer membrane shows an improved electrochemical performances. The maximum power densities of alkaline DAFCs with 4 M KOH + 2 M CH₃OH, 2 M C₂H₅OH and 2 M isopropanol (IPA) solutions at room temperature and ambient air are 9.25, 8.00, and 5.45 mW cm⁻², respectively. As a result, methanol shows the highest maximum power density among three alcohols. The PVA/TiO₂ composite polymer membrane with the permeability values in the order of 10⁻⁷ to 10⁻⁸ cm² s⁻¹ is a potential candidate for use on alkaline DAFCs.     

Fabrication and characterization of poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) proton-conducting composite membranes for direct methanol fuel cells

A high performance poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) (PVA/MMT/PSSA) proton-conducting composite membrane was fabricated by a solution casting method. The characteristic properties of these blend composite membranes were investigated by using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, methanol permeability measurement, and the AC impedance method. The ionic conductivities for the composite membranes are in the order of 10⁻³ S cm⁻¹ at ambient temperature. There are two proton sources used on this novel composite membrane: the modified MMT fillers and PSSA polymer, both materials all contain the -SO₃H group. Therefore, the ionic conductivity was greatly enhanced. The methanol permeabilities of PVA/MMT/PSSA composite membranes is of the order of 10⁻⁷ cm² s⁻¹. It is due to the excellent methanol barrier properties of the PVA polymer. The peak power densities of the air-breathing direct methanol fuel cells (DMFCs) with 1M, 2M, 4M CH₃OH fuels were 14.22, 20.00, and 13.09 mW cm⁻², respectively, at ambient conditions. The direct methanol fuel cell with this composite polymer membrane exhibited good electrochemical performance. The proposed PVA/MMT/PSSA composite membrane is therefore a potential candidate for future applications in DMFC.     

Direct methanol fuel cell based on poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO2/PSSA) composite polymer membrane

The high performance poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO₂/PSSA) proton-conducting composite membrane is prepared by a solution casting method. The characteristic properties of these blend composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), micro-Raman spectroscopy, dynamic mechanical analysis (DMA), methanol permeability measurement and AC impedance method. It is found that the peak power densities of the DMFC with 1, 2, and 4 M CH₃OH fuels are 12.85, 23.72, and 10.99 mW cm⁻², respectively, at room temperature and ambient air. Especially, among three methanol concentrations, the 2 M methanol shows the highest peak power density among three methanol concentrations. The results indicate that the air-breathing direct methanol fuel cell comprised of a novel PVA/nt-TiO₂/PSSA composite polymer membrane has excellent electrochemical performance and stands out as a viable candidate for applications in DMFC.     

A direct borohydride fuel cell based on poly(vinyl alcohol)/hydroxyapatite composite polymer electrolyte membrane

A new poly(vinyl alcohol)/hydroxyapatite (PVA/HAP) composite polymer membrane was synthesized using a solution casting method. Alkaline direct borohydride fuel cells (DBFCs), consisting of an air cathode based on MnO₂/C inks on Ni-foam, anodes based on PtRu black and Au catalysts on Ni-foam, and the PVA/HAP composite polymer membrane, were assembled and investigated for the first time. It was demonstrated that the alkaline direct borohydride fuel cell comprised of this low-cost PVA/HAP composite polymer membrane showed good electrochemical performance. As a result, the maximum power density of the alkaline DBFC based on the PtRu anode (45 mW cm⁻²) proved higher than that of the DBFC based on the Au anode (33 mW cm⁻²) in a 4 M KOH + 1 M KBH₄ solution at ambient conditions. This novel PVA/HAP composite polymer electrolyte membrane with high ionic conductivity at the order of 10⁻² S cm⁻¹ has great potential for alkaline DBFC applications.     

Direct methanol fuel cell (DMFC) based on PVA/MMT composite polymer membranes

A novel composite polymer electrolyte membrane composed of a PVA polymer host and montmorillonite (MMT) ceramic fillers (2–20 wt.%), was prepared by a solution casting method. The characteristic properties of the PVA/MMT composite polymer membrane were investigated using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and micro-Raman spectroscopy, and the AC impedance method. The PVA/MMT composite polymer membrane showed good thermal and mechanical properties and high ionic conductivity. The highest ionic conductivity of the PVA/10 wt.%MMT composite polymer membrane was 0.0368 S cm⁻¹ at 30 °C. The methanol permeability (P) values were 3–4 × 10⁻⁶ cm² s⁻¹, which was lower than that of Nafion 117 membrane of 5.8 × 10⁻⁶ cm² s⁻¹. It was revealed that the addition of MMT fillers into the PVA matrix could markedly improve the electrochemical properties of the PVA/MMT composite membranes; which can be accomplished by a simple blend method. The maximum peak power density of the DMFC with the PtRu anode based on Ti-mesh in a 2 M H₂SO₄ + 2 M CH₃OH solution was 6.77 mW cm⁻² at ambient pressure and temperature. As a result, the PVA/MMT composite polymer appears to be a good candidate for the DMFC applications.     

Poly (vinyl alcohol)/3-(trimethylammonium) propyl-functionalized silica hybrid membranes for alkaline direct ethanol fuel cells

A novel hybrid membrane based on poly (vinyl alcohol)/3-(trimethylammonium) propyl-functionalized silica (PVA-TMAPS) is prepared by a simple solution-casting method. The properties of the PVA-TMAPS membranes are characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and X-ray diffraction (XRD). It is found that the thermal stability of the membranes increases with the addition of TMAPS particles. Moreover, the study of the effect of different weight ratios of PVA to TMAPS on the OH⁻ conductivity shows that the membrane with a ratio of PVA:TMAPS = 90:10 exhibited the highest OH⁻ conductivity. Finally, it is shown that the application of the alkaline membrane (PVA:TMAPS = 90:10) to an direct ethanol fuel cell can yield a peak power density of about 50 mW cm⁻² at 60 °C.     

Synthesis and characterization of anion exchange membranes for alkaline direct methanol fuel cells

Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics and methanol crossover, which are limiting the development of direct methanol fuel cells. In this work, a novel anion exchange membrane, quaternized poly(aryl ether oxadiazole), was prepared through polycondensation, grafting and quaternization. The ionic conductivity of as-synthesized anion exchange membrane can reach up to 2.79 × 10⁻² S/cm at 70 °C. The physical and chemical stability of the anion exchange membranes could also meet the requirement for alkaline direct methanol fuel cells.     

Performance of passive direct methanol fuel cell with poly(vinyl alcohol)-based polymer electrolyte membranes

Polymer electrolyte membranes (PEMs) were prepared from poly(vinyl alcohol) (PVA) and a modified PVA polyanion containing 2 mol% of 2-methyl-1-propanesulfonic acid (AMPS) groups as a copolymer. The effect of the AMPS content and the crosslinking conditions on the properties of the membranes was investigated in PEMs with various AMPS contents prepared under various crosslinking conditions. The proton conductivity and the permeability of methanol through the PEMs increased with increasing AMPS content, C_AMPS, and with decreasing annealing temperature, T_a, because of the increase in the degree of swelling. The permeability coefficient of methanol through the PEM prepared under the conditions of C_AMPS = 2.0 mol% and T_a 190 °C was approximately 30 times lower than that of Nafion^® 117 under the same measurement conditions. A maximum proton permselectivity of 96 × 10³ S cm⁻³ s, which is defined as the ratio of the proton conductivity to the permeability of methanol, was obtained for this PEM. The permselectivity value is about three times higher than that of Nafion^® 117. A passive air-breathing-type DMFC test cell constructed using the PEM delivered 2.4 mW cm⁻² of maximum power density, P_max, at 2 M methanol concentration, which is smaller than the value obtained with Nafion^® 117. However, at high methanol concentrations (>10 M), the P_max of the PEM decreases slightly to 1.6 mW cm⁻² (at a methanol concentration of 20 M), whereas the P_max of Nafion^® 117 falls to almost zero.     

Functionalized carbon nanotube-poly(arylene sulfone) composite membranes for direct methanol fuel cells with enhanced performance

A new type of composite membrane, consisting of functionalized carbon nanotubes (CNTs) and sulfonated poly(arylene sulfone) (sPAS), is prepared for direct methanol fuel cell (DMFC) applications. The CNTs modified with sulfonic acid or PtRu nanopaticles are dispersed within the sPAS matrix by a solution casting method to afford SO₃CNT-sPAS or PtRu/CNT-sPAS composite membranes, respectively. Characterization of the composite membranes reveals that the functionalized CNTs are homogeneously distributed within the sPAS matrix and the composite membranes contain smaller ion clusters than the neat sPAS. The composite membranes exhibit enhanced mechanical properties in terms of tensile strength, strain and toughness, which leads to improvements in ion conductivity and methanol permeability compared with the neat sPAS membrane. In DMFC performance tests, the use of a PtRu/CNT-sPAS membrane yields high power density compared with the neat sPAS membrane, which demonstrates that the improved properties of the composite membranes induce an increase in power density. The strategy for CNT-sPAS composite membranes presented in this work can potentially be extended to other CNT-polymer composite systems.     

Fabrication and properties of poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cell applications

A series of poly(vinyl alcohol) (PVA)-based organic–inorganic crosslinked polymer electrolyte membranes with PVA and poly(methacrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid-vinyltriethoxysilicone) (PMAV) are prepared for direct methanol fuel cell applications. Fourier transform infrared (FTIR) spectroscopy measurements clearly reveal the existence of crosslinking reactions and molecular interactions in PVA–PMAV membranes. The results of TGA show that the PVA–PMAV membranes possess good thermal stability. The uptake behavior, methanol diffusion coefficient, proton conductivity and selectivity of membranes also are investigated as function of PMAV content. The results indicate that the PVA-based organic–inorganic crosslinked membranes are particularly promising to be used as polymer electrolyte membranes due to their excellent methanol barrier property, suitable proton conductivity and high selectivity.     

Synthesis and characterization of crosslinked poly (vinyl alcohol)/layered double hydroxide composite polymer membranes for alkaline direct ethanol fuel cells

The low ionic conductivity and low thermal stability of conventional quaternary ammonium group functionalized anion-exchange membranes (AEM) are two key parameters that limit the performance of AEM direct ethanol fuel cells (AEM DEFCs). The present work is to address these issues by synthesizing crosslinked poly (vinyl alcohol)/layered double hydroxide (PVA/LDH) hybrid membranes with solution casting method. The experimental results indicate that incorporating 20 wt.% LDH into the PVA resulted in not only a higher ionic conductivity, but also a lower ethanol permeability. The performance test of the DEFC using the PVA/LDH hybrid membrane shows that the fuel cell can yield a power density of 82 mW cm⁻² at 80 °C, which is much higher than that of the AEM DEFC employing the quaternary ammonium group functionalized membrane. A constant current discharge test shows that the PVA/20LDH membrane can be operated stably at relatively high temperatures.     

Pulsed plasma-polymerized alkaline anion-exchange membranes for potential application in direct alcohol fuel cells

Pulsed plasma polymerization is adopted to synthesize alkaline anion-exchange membranes (AAEMs) with high contents of functional groups. The attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and thermo gravimetric analysis demonstrate that the benzyltrimethylammonium cationic groups can be successfully introduced into the polymer matrix. The content of the quaternary nitrogen in pulsed plasma-polymerized membrane is up to 1.93 atom%. The ultra-flat and undamaged morphology structure of the AAEMs indicates a low plasma ablation effect in the pulsed plasma polymerization. The excellent properties of the pulsed plasma-polymerized AAEMs, including good adhesion to the substrate, acceptable chemical stability and thermal stability, high ion-exchange capacity (1.42 mmol g⁻¹) and water uptake (59.73 wt%), interesting ionic conductivity (0.0205 S cm⁻¹ in deionized water at 20 °C) and ethanol permeability (3.37 × 10⁻¹¹ m² s⁻¹), suggest a great potential for application in direct alcohol fuel cells.     

Nafion-impregnated electrospun polyvinylidene fluoride composite membranes for direct methanol fuel cells

Composite membranes consisting of polyvinylidene fluoride (PVdF) and Nafion have been prepared by impregnating various amounts of Nafion (0.3–0.5 g) into the pores of electrospun PVdF (5 cm × 5 cm) and characterized by scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, and proton conductivity measurements. The characterization data suggest that the unique three-dimensional network structure of the electrospun PVdF membrane with fully interconnected fibers is maintained in the composite membranes, offering adequate mechanical properties. Although the composite membranes exhibit lower proton conductivity than Nafion 115, the composite membrane with 0.4 g Nafion exhibits better performance than Nafion 115 in direct methanol fuel cell (DMFC) due to smaller thickness and suppressed methanol crossover from the anode to the cathode through the membrane. With the composite membranes, the cell performance increases on going from 0.3 to 0.4 g Nafion and then decreases on going to 0.5 g Nafion due to the changes in proton conductivity.     

A novel organic/inorganic polymer membrane based on poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid/3-glycidyloxypropyl trimethoxysilane polymer electrolyte membrane for direct methanol fuel cells

Poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS)/3-glycidyloxypropyl)trimethoxysilane (PVA/PAMPS/GPTMS) organic/inorganic proton-conducting polymer membranes are prepared by a solution casting method. PAMPS is a polymeric acid commonly used as a primary proton donor, while 3-(glycidyloxypropyl)trimethoxysilane (GPTMS) is an inorganic precursor forming a semi-interpenetrating network (SIPN). Varying amounts of sulfosuccinic acid (SSA) are used as the cross-linker and secondary proton source. The characteristic properties of PVA/PAMPS/GPTMS composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), micro-Raman spectroscopy and the AC impedance method. Direct methanol fuel cells (DMFCs) made of PVA/PAMPS/GPTMS composite membranes are assembled and examined. Experimental results indicate that DMFCs employing an inexpensive, non-perfluorinated, organic/inorganic SIPN membrane achieve good electrochemical performance. The highest peak power density of a DMFC using PVA/PAMPS/GPTMS composite membrane with 2 M CH₃OH solution fuel at ambient temperature is 23.63 mW cm⁻². The proposed organic/inorganic proton-conducting membrane based on PVA/PAMPS/GPTMS appears to be a viable candidate for future DMFC applications.     

Improving the direct methanol fuel cell performance with poly(vinyl alcohol)/titanium dioxide nanocomposites as a novel electrolyte additive

The present investigation deals with the fabrication of new poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposites (NCs) with different titanium dioxide (TiO₂) loading by using ultrasound irradiation. For the improvement of nanoparticles (NPs) dispersion and increasing possible interactions between NPs and PVA, the surface of TiO₂ NPs was modified by γ-aminopropyltriethoxy silane. The as-prepared NCs were characterized by spectroscopic, thermogravimetric analysis and electron microscopy methods. The results demonstrate that NPs dispersed homogeneously within the PVA matrix on nanoscale, which could be assigned to the hydrogen and covalent bonds formed between PVA and NPs. The results indicated that heat stability of NCs was improved in the presence of modified TiO₂ NPs. The mechanisms of surface modification and a possible mechanism of ultrasonic induced interaction between polymer and NPs have been analyzed.     

Proton-conducting membranes with high selectivity from cross-linked poly(vinyl alcohol) and poly(vinyl pyrrolidone) for direct methanol fuel cell applications

A series of hydrocarbon membranes consisting of poly(vinyl alcohol) (PVA), sulfosuccinic acid (SSA) and poly(vinyl pyrrolidone) (PVP) were synthesized and characterized for direct methanol fuel cell (DMFC) applications. Fourier transform infrared (FT-IR) spectra confirm a semi-interpenetrating (SIPN) structure based on a cross-linked PVA/SSA network and penetrating PVP molecular chains. A SIPN membrane with 20% PVP (SIPN-20) exhibits a proton conductivity value comparable to Nafion^® 115 (1.0 × 10⁻² S cm⁻¹ for SIPN-20 and 1.4 × 10⁻² S cm⁻¹ for Nafion^® 115). Specifically, SIPN membranes reveal excellent methanol resistance for both sorption and transport properties. The methanol self-diffusion coefficient through a SIPN-20 membrane conducted by pulsed field-gradient nuclear magnetic resonance (PFG-NMR) technology measures 7.67 × 10⁻⁷ cm² s⁻¹, which is about one order of magnitude lower than that of Nafion^® 115. The methanol permeability of SIPN-20 membrane is 5.57 × 10⁻⁸ cm² s⁻¹, which is about one and a half order of magnitude lower than Nafion^® 115. The methanol transport behaviors of SIPN-20 and Nafion^® 115 membranes correlate well with their sorption characteristics. Methanol uptake in a SIPN-20 membrane is only half that of Nafion^® 115. An extended study shows that a membrane-electrode assembly (MEA) made of SIPN-20 membrane exhibits a power density comparable to Nafion^® 115 with a significantly higher open current voltage. Accordingly, SIPN membranes with a suitable PVP content are considered good methanol barriers, and suitable for DMFC applications.     

Homogeneous polymer/filler composite membrane by spraying method for enhanced direct methanol fuel cell performance

In this work, composite membranes for a direct methanol fuel cell (DMFC) were prepared using a spraying method to improve cell performance especially at a high methanol concentration. Nafion polymer and mordenite as a filler were used for the composite membrane preparation using a spraying method and a conventional solution casting method and the membranes from the two methods were compared. SEM images showed that a more homogeneous composite membrane could be obtained using the spraying method. The effect of mordenite content was also studied. The membranes were consequently characterized and tested in DMFC operation. The results were compared to those prepared using the solution casting method at 30, 50, and 70 °C with methanol concentrations of 2, 4, and 8 M. It was found that the membrane with 5 wt.% mordenite from the spraying method showed a vast improvement in DMFC performance. When the cell was operated at 70 °C, the maximum power density of 5 wt.% mordenite from the spraying method was higher than that of commercial membrane and 5 wt.% from the solution casting method. Power densities from the 5 wt.% sprayed membrane were higher by around 29%, 40%, and 60% at 2, 4, and 8 M methanol concentration, respectively.     

Synthesis and characterization of cross-linked quaternized poly(vinyl alcohol)/chitosan composite anion exchange membranes for fuel cells

Novel cross-linked composite membranes were synthesized to investigate their applicability in anion exchange membrane fuel cells. These membranes consist of quaternized poly(vinyl alcohol) (QAPVA) and quaternized chitosan (2-hydroxypropyltrimethyl ammonium chloride chitosan, HACC) with glutaraldehyde as the cross-linking reagent. The membranes were characterized in term of their water content, ion exchange capacity (IEC), ion conductivity and methanol permeability. FTIR, X-ray diffraction and scanning electron microscopy (SEM) were also used to investigate the relation between the structure and performance of the composite membranes. The composite membranes have a high conductivity (10⁻³ to 10⁻² S cm⁻¹), and a low methanol permeability (from 5.68 × 10⁻⁷ to 4.42 × 10⁻⁶ cm² s⁻¹) at 30 °C. After reviewing all pertinent characteristics of the membranes, we find that the membrane structure is the principal factor affecting the conductivity and methanol permeability of these membranes.     

Poly(vinyl alcohol)/poly(vinyl chloride) composite polymer membranes for secondary zinc electrodes

A microporous composite polymer membrane composed of poly(vinyl alcohol) (PVA) and poly(vinyl chloride) (PVC), was prepared by a solution casting method and a partial dissolution process. The characteristic properties of microporous PVA/PVC composite polymer membranes containing 2.5-10 wt.% PVC polymers as fillers were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), capillary flow porometry (CFP), micro-Raman spectroscopy, dynamic mechanical analyzer (DMA) and the AC impedance method. The electrochemical properties of a secondary Zn electrode with the PVA/PVC composite polymer membrane were studied using the galvanostatic charge/discharge method. The PVA/PVC composite polymer membrane showed good thermal, mechanical and electrochemical properties. As a result, the PVA/PVC composite polymer membrane appears to be a good candidate for use on the secondary Zn electrodes.