Self-Assembly DBS Nanofibrils on Solution-Blown Nanofibers as Hierarchical Ion-Conducting Pathway for Direct Methanol Fuel Cells

In this work, we reported a novel proton exchange membrane (PEM) with an ion-conducting pathway. The hierarchical nanofiber structure was prepared via in situ self-assembling 1,3:2,4-dibenzylidene-d-sorbitol (DBS) supramolecular fibrils on solution-blown, sulfonated poly (ether sulfone) (SPES) nanofiber, after which the composite PEM was prepared by incorporating hierarchical nanofiber into the chitosan polymer matrix. Then, the effects of incorporating the hierarchical nanofiber structure on the thermal stability, water uptake, dimensional stability, proton conductivity, and methanol permeability of the composite membranes were investigated. The results show that incorporation of hierarchical nanofiber improves the water uptake, proton conductivity, and methanol permeability of the membranes. Furthermore, the composite membrane with 50% hierarchical nanofibers exhibited the highest proton conductivity of 0.115 S cm−1 (80 °C), which was 69.12% higher than the values of pure chitosan membrane. The self-assembly allows us to generate hierarchical nanofiber among the interfiber voids, and this structure can provide potential benefits for the preparation of high-performance PEMs.

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Highly selective sulfonated Poly (arylene ether nitrile) composite membranes containing copper phthalocyanine grafted graphene oxide for direct methanol fuel cell

High Performance Polymers ◽

10.1177/09540083211039412 ◽

2021 ◽

pp. 095400832110394

Author(s):

Yan Ma ◽

Kaixu Ren ◽

Ziqiu Zeng ◽

Mengna Feng ◽

Yumin Huang

Keyword(s):

Graphene Oxide ◽

Proton Conductivity ◽

Direct Methanol Fuel Cells ◽

Copper Phthalocyanine ◽

Composite Membranes ◽

Proton Exchange ◽

Methanol Permeability ◽

Arylene Ether ◽

Direct Methanol ◽

Sulfonated Poly

To improve the performances of sulfonated poly (arylene ether nitrile) (SPEN)–based proton exchange membranes (PEMs) in direct methanol fuel cells (DMFCs), the copper phthalocyanine grafted graphene oxide (CP-GO) was successfully prepared via in situ polymerization and subsequently incorporated into SPEN as filler to fabricate a series of SPEN/CP-GO-X (X represents for the mass ratio of CP-GO) composite membranes. The water absorption, swelling ratio, mechanical properties, proton conductivity, and methanol permeability of the membranes were systematically studied. CP-GO possesses good dispersion and compatibility with SPEN matrix, which is propitious to the formation of strong interfacial interactions with the SPEN, so as to provide more efficient transport channels for proton transfer in the composite membranes and significantly improve the proton conductivity of the membranes. Besides, the strong π–π conjugation interactions between CP-GO and SPEN matrix can make the composite membranes more compact, blocking the methanol transfer in the membranes, and significantly reducing the methanol permeability. Consequently, the SPEN/CP-GO-1 composite membrane displayed outstanding tensile strength (58 MPa at 100% RH and 25°C), excellent proton conductivity (0.178 S cm−1 at 60°C), and superior selectivity (5.552 × 105 S·cm−3·s). This study proposed a new method and strategy for the preparation of high performance PEMs.

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Constructing Continuous Proton-Conducting Highways within Sulfonated Poly(Arylene Ether Nitrile) Composite Membrane by Incorporating Amino-Sulfo-Bifunctionalized GO

Polymers ◽

10.3390/polym10091005 ◽

2018 ◽

Vol 10 (9) ◽

pp. 1005 ◽

Cited By ~ 10

Author(s):

Tao Cheng ◽

Xuechun Zhang ◽

Yan Ma ◽

Yumin Huang ◽

Xiaobo Liu

Keyword(s):

Proton Conductivity ◽

Composite Membrane ◽

High Performance ◽

Fold Increase ◽

Composite Membranes ◽

Proton Exchange ◽

Methanol Permeability ◽

Proton Conducting ◽

Arylene Ether ◽

Sulfonated Poly

To obtain a proton exchange membrane (PEM) with high proton conductivity and low methanol permeability, a novel amino-sulfo-bifunctionalized GO (NSGO) was synthesized and explored as a filler for sulfonated poly(arylene ether nitrile) (SPEN). The result indicated that the microstructure of composite membranes was rearranged by NSGO and strong acid–base interactions were formed between fillers and the SPEN matrix, affording enhanced thermal, mechanical, and dimensional stabilities. Moreover, it was found that NSGO fillers were uniformly dispersed in the SPEN matrix, generating efficient proton-conducting paths along the SPEN/NSGO interface. Meanwhile, the sulfonic and amino groups of NSGO served as additional proton hopping sites to connect the ionic clusters in the SPEN matrix, creating interconnected and long-range ionic pathways. In such a way, proton-conducting highways with low energy barriers are constructed, which enhance the proton conductivity of the composite membranes via the Grotthuss mechanism. Furthermore, the composite membranes also effectively prevent methanol permeation, and therefore high selectivity (the ratio of proton conductivity and methanol permeability) is endowed. Compared to SPEN membrane, a 3.6-fold increase in selectivity is obtained for the optimal composite membrane. This study will provide a new strategy for the preparation of high-performance PEM.

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Composite Sulfonated Polyether-Ether Ketone Membranes with SBA-15 for Electrochemical Energy Systems

Materials ◽

10.3390/ma13071570 ◽

2020 ◽

Vol 13 (7) ◽

pp. 1570 ◽

Cited By ~ 1

Author(s):

A. Rico-Zavala ◽

J. L. Pineda-Delgado ◽

A. Carbone ◽

A. Saccà ◽

E. Passalacqua ◽

...

Keyword(s):

Proton Conductivity ◽

Proton Exchange Membrane ◽

Energy Systems ◽

Composite Membranes ◽

Exchange Capacity ◽

Proton Exchange ◽

Inorganic Materials ◽

Methanol Permeability ◽

Ether Ketone ◽

Electrochemical Energy

The aim of this work is the evaluation of a Sulfonated Poly Ether-Ether Ketone (S-PEEK) polymer modified by the addition of pure Santa Barbara Amorphous-15 (SBA-15, mesoporous silica) and SBA-15 previously impregnated with phosphotungstic acid (PWA) fillers (PWA/SBA-15) in order to prepare composite membranes as an alternative to conventional Nafion® membranes. This component is intended to be used as an electrolyte in electrochemical energy systems such as hydrogen and methanol Proton Exchange Membrane Fuel Cell (PEMFC) and Electrochemical Hydrogen Pumping (EHP). The common requirements for all the applications are high proton conductivity, thermomechanical stability, and fuel and oxidant impermeability. The morphology of the composite membranes was investigated by Scanning Electron Microscopy- Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Water Uptake (Wup), Ion Exchange Capacity (IEC), proton conductivity, methanol permeability and other physicochemical properties were evaluated. In PEMFC tests, the S-PEEK membrane with a 10 wt.% SBA-15 loading showed the highest performance. For EHP, the inclusion of inorganic materials led to a back-diffusion, limiting the compression capacity. Concerning methanol permeability, the lowest methanol crossover corresponded to the composites containing 5 wt.% and 10 wt.% SBA-15.

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Hybrid polymers based on sulfonated polynorbornene with enhanced proton conductivity for direct methanol fuel cells

High Performance Polymers ◽

10.1177/0954008312451478 ◽

2012 ◽

Vol 24 (8) ◽

pp. 756-764 ◽

Cited By ~ 1

Author(s):

Rong Zeng ◽

Shuqin Xiao ◽

Lie Chen ◽

Yiwang Chen

Keyword(s):

Proton Conductivity ◽

Direct Methanol Fuel Cells ◽

Sol Gel ◽

Weight Ratio ◽

Proton Exchange ◽

Methanol Permeability ◽

Relative Humidity Condition ◽

Conduction Pathway ◽

Direct Methanol ◽

Order Of Magnitude

Sulfonated polynorbornene (SPNB) and 3-aminopropyltriethoxysilane (KH550) hybrid cross-linked proton exchange membranes doped with different weight ratio of phosphotungstic acid (PWA) were prepared by a simple sol-gel process. The cross-linked structures led to low methanol permeability and good stability of the nanocomposites. Incorporation of PWA has significantly improved the proton conductivity of the hybrid membrane due to an extra provided conductive proton-conduction pathway to facilitate proton transportation. In particular, the conductivity of SPNB/KH550/PWA25 reached the maximum of 0.02 S.cm−1 at 80°C under the 100% relative humidity condition, and this value is on the same order of magnitude as that of Nafion117. Furthermore, SPNB /KH550/PWA20 owns the lowest proton transport activation energy (8.39 kJ.mol−1).

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Development of proton-exchange polymer nanocomposite membranes for fuel cell applications

Polymers and Polymer Composites ◽

10.1177/0967391119888319 ◽

2019 ◽

Vol 28 (7) ◽

pp. 492-501

Author(s):

Sivasubramanian Gandhimathi ◽

Hariharasubramanian Krishnan ◽

Deivanayagam Paradesi

Keyword(s):

Proton Conductivity ◽

Water Uptake ◽

Thermal Studies ◽

Polymer Nanocomposite ◽

Composite Membranes ◽

Exchange Capacity ◽

Proton Exchange ◽

Nanocomposite Membranes ◽

Electron Microscopic ◽

Electrolyte Membranes

The design and development of proton conducting polymer electrolyte membranes from a linear constituent, sulfonated poly (ether ether ketone) (SPEEK), and inorganic additive, niobium oxide (NBO), have been achieved. The degree of sulfonation of SPEEK was measured by back titration method and found to be 57%. The physicochemical properties such as water uptake ability, ion-exchange capacity, swelling ratio, proton conductivity, and thermal stability of the prepared polymer nanocomposite membranes were studied in detail. The distribution of NBO throughout the polymer matrix has been examined by scanning electron microscopic and X-ray diffraction analyses and found to be uniform. The SP-NBO-10 composite membrane shows 38.4% of water uptake, whereas the pristine membrane limits to 27.1%. The prepared electrolyte membranes exhibit good proton conductivity at temperature varying from 30°C to 90°C and possess less activation energy for the transportation of proton by the incorporation of NBO filler. The thermal studies demonstrated that the stability of the composite membranes was significantly enhanced by the impregnation of NBO. The filler NBO shows excellent improvements on the polymer nanocomposite, making it a very promising additive for other polymers and offers new roads for energy applications.

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Synthesis and Characterization of Polystyrene-Poly(arylene ether sulfone)-Polystyrene Triblock Copolymer for Proton Exchange Membrane Applications

Journal of Nanoscience and Nanotechnology ◽

10.1166/jnn.2006.17989 ◽

2006 ◽

Vol 6 (11) ◽

pp. 3594-3598

Author(s):

Jung-Eun Yang ◽

Young Taik Hong ◽

Jae-Suk Lee

Keyword(s):

Proton Conductivity ◽

Triblock Copolymer ◽

Proton Exchange Membrane ◽

Direct Methanol Fuel Cells ◽

Condensation Reaction ◽

Acid Group ◽

Proton Exchange ◽

Methanol Permeability ◽

Arylene Ether ◽

Exchange Membrane

The polystyrene-poly(arylene ether sulfone)-polystyrene (PS-PAES-PS) coil-semirod-coil triblock copolymer was synthesized by the condensation reaction of PS-COCl and H2N-PAES-NH2 telechelic polymers. The reaction was facile characterized by high yields with a perfect control over the block lengths. Following a known reaction protocol it was possible to selectively sulfonate the PS block of the triblock copolymer that led to the sulfonated copolymer sPS-PAES-sPS. Studies on its proton conductivity and methanol permeability were carried out to evaluate its use as the proton exchange membrane in direct methanol fuel cells. Proton conductivity of the membranes was increased depending on the sulfonic acid group content in the sulfonated polymer. The membranes exhibited good dimensional and thermal stability, and low methanol permeability compared to Nafion 117.

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Suppression of methanol cross-over in novel composite membranes for direct methanol fuel cells

Pure and Applied Chemistry ◽

10.1351/pac-con-08-12-01 ◽

2009 ◽

Vol 81 (12) ◽

pp. 2309-2316 ◽

Cited By ~ 5

Author(s):

Yong Fang ◽

Ruiying Miao ◽

Tongtao Wang ◽

Xindong Wang

Keyword(s):

Fuel Cells ◽

Proton Conductivity ◽

Direct Methanol Fuel Cells ◽

Base Material ◽

Proton Conductor ◽

Composite Membranes ◽

Methanol Permeability ◽

Poly Vinyl Alcohol ◽

Direct Methanol ◽

Methanol Fuel Cells

A series of novel composite membranes was prepared by using poly(vinyl alcohol) (PVA) with polyimide (PI) as base material and 8-trimethoxysilylpropyl glycerine ether-1,3,6-pyrenetrisulfonic acid (TSGEPS) as proton conductor for direct methanol fuel cells (DMFCs). The parameters of membranes, including water sorption, hydrolysis stability, dimensional stability, proton conductivity, and methanol permeability were studied. The proton conductivity of the membranes is in the order of 10–2 S/cm, and the membranes show better resistance to methanol permeability (1.51 × 10–7 cm2 s–1) and better selectivity (20.6 × 104 S cm–3 s) than those of Nafion115 under the same measurement conditions.

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On the Synthesis and Characterization of Silica-Doped/Sulfonated Poly-(2,6-Dimethyl-1,4-Phenylene Oxide) Composite Membranes for Fuel Cells

Journal of Fuel Cell Science and Technology ◽

10.1115/1.4026931 ◽

2014 ◽

Vol 11 (4) ◽

Cited By ~ 4

Author(s):

Daniela Ebrasu ◽

Irina Petreanu ◽

Mihai Varlam ◽

Dorin Schitea ◽

Ioan Stefanescu ◽

...

Keyword(s):

Fuel Cells ◽

Proton Conductivity ◽

Water Uptake ◽

Sol Gel ◽

Composite Membranes ◽

Proton Exchange ◽

Differential Scanning Calorimetric ◽

Gravimetric Analysis ◽

Phenylene Oxide ◽

Sulfonated Poly

The objective of this investigation is to study silica-doped/sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) composite membranes for operation in hydrogen/oxygen proton-exchange membrane fuel cells ranging from room temperature (RT) up to 120 °C. The sulfonated PPO composite membranes were prepared using a sol–gel process employing reaction with tetra-ethoxysilane (TEOS) followed by heat treatment at 60, 90, and 120 °C, respectively. The presence of silicon oxide in the composite membranes was evaluated using FTIR spectroscopy, while thermal properties were studied using thermal gravimetric analysis-differential scanning calorimetric (TGA-DSC) measurements. Additionally, ion exchange capacity, water uptake, and proton conductivity characterizations were also carried out. It was observed that water uptake for 75% PPO sulfonated composite membrane treated at 120 °C is higher than that of NafionTM membrane and the proton conductivity value measured at 120 °C is 0.35·10−1 S/cm. Therefore, the composite membranes are potentially suitable for high temperature fuel cell applications.

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Effects of Concentration of Organically Modified Nanoclay on Properties of Sulfonated Poly(vinyl alcohol) Nanocomposite Membranes

International Journal of Electrochemistry ◽

10.4061/2011/785282 ◽

2011 ◽

Vol 2011 ◽

pp. 1-6 ◽

Cited By ~ 9

Author(s):

Apiradee Sanglimsuwan ◽

Narumon Seeponkai ◽

Jatuphorn Wootthikanokkhan

Keyword(s):

Fuel Cells ◽

Proton Conductivity ◽

Vinyl Alcohol ◽

Direct Methanol Fuel Cells ◽

Proton Exchange ◽

Methanol Permeability ◽

Poly Vinyl Alcohol ◽

Nanocomposite Membranes ◽

Organically Modified ◽

Sulfonated Poly

Electrolyte nanocomposite membranes for proton exchange membrane fuel cells and direct methanol fuel cells were prepared by carrying out a sulfonation of poly(vinyl alcohol) with sulfosuccinic acid and adding a type of organically modified montmorillonite (layered silicate nanoclay) commercially known as Cloisite 93A. The effects of the different concentrations (0, 2, 4, 6, 8 wt. %) of the organoclay in the membranes on water uptake, ion exchange capacity (IEC), proton conductivity, and methanol permeability were measured, respectively, via gravimetry, titration, impedance analysis, and gas chromatography techniques. The IEC values remained constant for all concentrations. Water uptakes and proton conductivities of the nanocomposite membranes changed with the clay content in a nonlinear fashion. While all the nanocomposite membranes had lower methanol permeability than Nafion115, the 6% concentration of Cloisite 93A in sulfonated poly(vinyl alcohol) membrane displayed the greatest proton conductivity to methanol permeability ratio.

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Nanocomposite SPEEK/Titania Nanosheets (TNS) Proton Exchange Membranes for Fuel Cell Applications

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.421-422.447 ◽

2009 ◽

Vol 421-422 ◽

pp. 447-450 ◽

Cited By ~ 1

Author(s):

Debora Marani ◽

S. Licoccia ◽

Enrico Traversa ◽

Masaru Miyayama

Keyword(s):

Fuel Cell ◽

Proton Conductivity ◽

Water Uptake ◽

Proton Exchange Membrane ◽

Composite Membranes ◽

Proton Exchange Membranes ◽

Structural Features ◽

Proton Exchange ◽

Unique Nature ◽

Exchange Membrane

SPEEK-based composite membranes containing various amounts of titania nanosheets (TNS) as inorganic fillers were investigated for proton exchange membrane fuel cell applications. The samples were characterized for water uptake, proton conductivity (EIS), and structural features (SEM and XRD). Composites at low inorganic additive contents exhibited improved properties in terms of proton conductivity and water uptake behavior. Best improvements were observed for the composite containing only 0.95 wt% of TNS. This result could be associated to the unique nature of the two dimensional nanostructure of the inorganic additive.

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