Synthesis and characterization of sulfonated block copolyimides derived from 4,4'‐sulfide‐bis(naphthalic anhydride) for proton exchange membranes

A series of sulfonated copolyimides (SPIs) with hydrophilic segment length of 20–60 based on 4,4′‐sulfide‐bis(naphthalic anhydride) (SBNA) have been successfully synthesized to improve hydrolytic stability and proton conductivity. The SPI membranes were cast from their m‐cresol solutions, and they were characterized by determining the water uptake, water swelling ratio, mechanical properties, hydrolytic stability, oxidative stability, and proton conductivity. It was found that the water uptake of SPI membranes was low and decreased as the hydrophilic segment length increased, which led to good dimensional stability. In addition, the SPI membranes with low ion‐exchange capacity (IEC) value displayed excellent hydrolytic stability and retained good mechanical properties even after harsh hydrolysis testing, in which the block SPI with hydrophilic segment length of 40 had the best hydrolytic stability, while those with high IEC value showed an apparent decrease. All of the block SPI membranes show better conductivity than the random ones at the temperature range from 30 to 70°C. Interestingly, the proton conductivities of random SPI membranes were higher than that of corresponding block ones at 90°C. The block SPI with hydrophilic segment length of 40 gave the highest proton conductivity as the temperature increased among the block SPIs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41501.     

Synthesis and characterization of partially fluorinated poly(fluorenyl ether ketone)s with different degrees of sulfonation as proton exchange membranes

Partially fluorinated poly(fluorenyl ether ketone)s with different degree of sulfonation were successfully synthesized by the sulfonation of the designed parent polymer. The sulfonation took place only at the specific (2, 7)-position on the fluorenyl groups due to the positions adjacent to the ether bond occupied by methyl groups. The sulfonated polymers are soluble in common organic solvents and can readily be cast into tough and smooth films from their solutions. The properties of proton conductivity, water uptake, thermal and oxidative stability for the membranes were investigated. It was found that the oxidative stability of the membrane decreased with increasing the degree of sulfonation. However, the partially fluorinated membrane with high degree of sulfonation exhibited better oxidative stability compared to the non-fluorinated analogy with low degree of sulfonation. The proton conductivity of the membranes increased with increasing the degree of sulfonation and temperature. Moreover, the membranes also showed good thermal and hydrolytic stabilities.     

Proton conductive reinforced poly(ethylene‐co‐styrene) membranes

Polymers with ionic conductivity are useful materials for ion exchange membranes, separators, and electrolytes in electrochemical cells. New ionomers are currently being sought to replace the ionomers, which contain fluorine and are harmful to environment and expensive. A new and promising ionomer is a sulfonated ethylene/styrene copolymer. A nearby alternating copolymer with styrene content of 47 mol % was polymerized with metallocene/MAO catalyst. Membranes were prepared by hot‐pressing copolymer films with a glassfiber tissue. Phenyl rings in the copolymers were sulfonated with chlorosulfonic acid as a sulfonating agent. As the alternating structure of the copolymer, sulfonic groups were evenly distributed along the membranes. The membranes were characterized by determining water uptake, ion exchange capacity, proton conductivity, and mechanical properties. The studies revealed that the sulfonated copolymers have promising properties for proton‐conducting applications. All membranes had good ion exchange capacity, ～ 3.5 meq/g, and proton conductivity, over 50 mS/cm. Due to the high water uptake of the sulfonated copolymer, mechanical properties of the membranes were improved by using the glassfiber tissue as reinforcement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

一种新型的燃料电池用质子交换膜--磺化聚酰亚胺膜

综述了磺化聚酰亚胺作为质子交换膜燃料电池中膜材料的研究概况。介绍了其制备方法,总结了磺化聚酰亚胺结构对膜性能的影响。重点讨论了提高磺化聚酰亚胺质子交换膜电导率的途径和影响水解稳定性的因素,结果表明：纳米孔和相分离结构有助于提高质子电导率;磺化聚酰亚胺的水解稳定性不仅与吸水率有关,还与分子链的柔性和二胺单体的碱性有关。     

Anisotropic membranes from electrospun mats of sulfonated/nonsulfonated poly (ether ketone)s containing ion-rich paths as proton exchange membranes

Anisotropic proton exchange membranes composed of five layers with different contents of ionic groups across the membrane were prepared by simultaneous electrospinning of sulfonated and nonsulfonated poly(ether ketone) (PEK)s. To prepare nonporous and defect- free membranes from electrospun mats, nonsulfonated fibers as hydrophobic part of the membrane were melted by hot-pressing so that covered sulfonated fibers (hydrophilic part). Prepared membranes showed better thermal and dimensional stability compared to Nafion 115. Proton conductivity of membranes was comparable with Nafion especially at higher temperatures. Water uptake of prepared membranes and mechanical strength of them were in an acceptable range. The results showed that the difference between sulfonated PEK fibers in surface and center of the membranes affect proton conductivity and mechanical properties of the membranes.     

介孔碳掺杂磺化聚酰亚胺质子膜的制备与性能

以有序介孔碳(CMK)为掺杂剂,在乙醇中超声分散后与磺化聚酰亚胺的间甲酚溶液直接混合,然后采用流延法制备掺杂质子交换膜。环镜扫描电子显微镜表征发现CMK在膜中分散均匀。通过吸水率、溶剂吸收率、尺寸变化、电导率、甲醇透过率、力学性能及稳定性等测试发现掺杂膜虽然电导率有所下降,但其吸水率下降了15%~26%;抗溶胀性提高了15%~30%;热稳定性提高了约20~30℃;抗氧化性增大了1.3~1.5倍;水稳定性和力学性能也显著提高。     

Composite membranes of chitosan and titania‐coated carbon nanotubes as promising materials for new proton‐exchange membranes

Titania‐coated carbon nanotubes (TCNTs) were obtained by a simple sol–gel method. Then chitosan/TCNT (CS/TCNT) composite membranes were prepared by stirring chitosan/acetic acid and a TCNT/ethanol suspension. The morphology, thermal and oxidative stabilities, water uptake and proton conductivity, and mechanical properties of CS/TCNT composite membranes were investigated. The CNTs coated with an insulated and hydrophilic titania layer eliminated the risk of electronic short‐circuiting. Moreover, the titania layer enhanced the interaction between TCNTs and chitosan to ensure the homogenous dispersion of TCNTs in the chitosan matrix. The water uptake of CS/TCNT composite membranes was reduced owing to the decrease of the effective number of the ? NH₂ functional groups of chitosan. However, the CS/TCNT composite membranes exhibited better performance than a pure CS membrane in thermal and oxidative stability, proton conductivity, and mechanical properties. These results suggest that CS/TCNT composite membranes are promising materials for new proton‐exchange membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43365.     

Improved proton conductivity and methanol permeability of PVA-based proton exchange membranes using diphenylamine-4-sulfonic acid sodium salt and silica nanoparticles

ABSTRACT

A novel series of PVA/DPA-4-SASS/SiO₂ composite membranes were fabricated and characterized in the present study. Compared to the neat PVA, water uptake, proton conductivity, and ion exchange capacity of the membranes were enhanced. The membrane containing 5 Wt. % of SiO₂ nanoparticles and 80 Wt. % of the DPA-4-SASS showed the highest values of water uptake, proton conductivity (1.5 × 10^?1 S/cm) and ion exchange capacity (1.47 mmol/g). The results also indicated that methanol permeability was decreased by increasing the DPA-4-SASS content in the hybrid membranes. Thermal stability and mechanical properties of the cross-linked membranes were also improved.     

Stable anion exchange membranes derived from fluorinated poly(aryl ethers) with quaternized fluorene units for fuel cell applications

A series of fluorinated poly(aryl ethers) containing benzyltrimethyl quaternary ammonium functionalized fluorene units (QPFAE) are synthesized via condensation polymerization, chloromethylation, and quaternization. Ionomer structure and the ion exchange capacity are confirmed by ¹H‐nuclear magnetic resonance spectroscopy. Other characterization techniques such as Fourier transform infrared spectroscopy, atomic force microscopy, thermogravimetric analysis, gel permeation chromatography, electrochemical impedance spectroscopy, Fenton, water‐swelling, and hydrolytic aging tests are used to evaluate the physicochemical properties of the as‐prepared QPFAE membranes. For the QPFAE membranes with ion exchange capacity of 0.95–1.94 mmol/g, they displayed low water uptake and methanol permeability (4.59–26.1 × 10⁻⁸ cm²/s at 25 °C), fairly good dimensional stability, high mechanical toughness, as well as fine thermal‐oxidative‐hydrolytic stability and ion conductivity at least 10 mS/cm. The membranes also showed clear hydrophilic/hydrophobic phase‐separation morphology. Furthermore, the QPFAE membranes could endure harsh basic conditions (1–4 mol/L NaOH solution) at 60 and 80 °C at least 240 h, keeping rather high mechanical toughness and ion conduction capability during the aging test. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46301.     

Synthesis of sulfonated poly(fluorenyl ether thioether ketone)s with bulky-block structure and its application in vanadium redox flow battery

High-molecular-weight bulky-block poly(fluorenyl ether thioether ketone)s were successfully synthesized by a two steps one-pot protocol using N,N′-dimethy-S-carbamate masked dithiols for vanadium redox flow battery (VRB) application. The followed sulfonation procedure gave birth to novel sulfonated block poly(fluorenyl ether thioether ketone)s (SPFETKs) with controlled ionic exchange capacities (IEC). Membranes with proton conductivities higher than (IEC > 1.66 mequiv. g⁻¹) or comparable to (IEC < 1.66 mequiv. g⁻¹) that of Nafion117 membrane were achieved. The VO²⁺ permeabilities of SPFETKs membranes were much lower than that of Nafion117 membrane. The thermal properties, mechanical properties, oxidative stability, water uptake, proton conductivity, VO²⁺ permeability and cell performance were investigated in detail.     

Synthesis and properties of novel sulfonated poly(phenylquinoxaline)s as proton exchange membranes

Two series of sulfonated poly(phenylquinoxaline)s (SPPQ-x and SPPQ(O)-x, x refers to molar percentage of sulfonated tetraamine monomer) were first synthesized from a sulfonated tetraamine (4,4′-bis(3,4-diaminophenoxy)biphenyl-3.3′-disulfonic acid) and two aromatic bisbenzils (4-phenylglyoxalylbenzil and p,p′-oxydibenzil) in a mild condition. The structures of SPPQ-x and SPPQ(O)-x were characterized by IR and ¹H NMR spectra. The properties of these polymer films, such as water uptake, water swelling ratio, proton conductivity, thermal properties, methanol permeability, hydrolytic and oxidative stability were also investigated. The resulting polymers generally showed good solubility in DMAc and DMSO. Flexible and tough membranes with high mechanical strength were prepared. They show very high thermal, thermooxidative, hydrolytic stabilities and low methanol permeability. SPPQ-100 with the IEC value (2.41 mmol/g) displays the conductivity of 0.1 S/cm and a swelling ratio of 7.3% at 100 °C. The low swelling was attributed to the high rigid of polymer backbones and the strong intermolecular interaction between the basic nitrogen atoms of quinoxaline units and sulfonic acid groups. Moreover, we found that the conductivities of SPPQ(O)-x membranes were higher than SPPQ-x membranes at the similar IEC value. The highest conductivity of 0.2 S/cm was obtained for SPPQ(O)-100 at 140 °C. A combination of excellent dimensional and hydrolytic stabilities indicated that the SPPQ ionomers were good candidate materials for proton exchange membrane in fuel cell applications.     

Novel aromatic polyimide ionomers for proton exchange membranes: Enhancing the hydrolytic stability

In the pursuit of the hydrolytically stable sulfonated polyimide (SPI) membranes with high proton conductivity for fuel cell applications, a series of novel SPI ionomers derived from benzophenone-4,4′-bis(4-thio-1,8-naphthalic anhydride) (BPBTNA) were conveniently synthesized. The accelerated water stability tests demonstrated that the resultant SPI membranes kept highly the original mechanical properties even after 24 h in water at 140 °C. The membranes exhibited a microphase-separated structure with high morphological stability, and well-collected hydrophilic domains that could work as proton transport channels. The proton conductivity of 1c with an IEC of 1.90 meq g⁻¹ was higher than that of Nafion at 100% relative humidity (RH).     

Investigation on structure and properties of anion exchange membranes based on tetramethylbiphenol moieties containing copoly(arylene ether)s

Quaternary ammonium functionalized poly(arylene ether)s (QPAEs) containing 2,2′,6,6′‐tetramethylbiphenol moieties were designed and successfully synthesized via nucleophilic substitution polycondensation, bromination, quaternization and alkalization. The structure, water uptake, ion exchange capacities (IECs), hydroxide ion conductivities, and mechanical properties, as well as thermal and chemical stabilities of obtained QPAEs membranes were investigated. The QPAE‐a membrane with IEC value of 0.98 meq g^?1 demonstrated the highest ion conductivity (47.4 mS cm^?1) at 80°C. The ion transport activation energy (E_a) of QPAEs membranes varied from 8.57 to 19.95 kJ mol^?1. After chemical stability test conditioned in 1M NaOH at 60°C for 7 days, the QPAEs membranes except QPAE‐c (IEC = 0.88 meq g^?1) still exhibited high hydroxide ion conductivities (over 15 mS cm^?1) and acceptable tensile strength (～10 MPa). These properties indicate that the ionomers membranes are potential candidates for anion exchange membranes in anion exchange membrane fuel cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41525.     

Preparation of semi-interpenetrating polymer networks with adjustable mesh width and hydrophobicity

Proton exchange membranes (PEMs) with a semi-interpenetrating polymer network (SIPN) structure were prepared by cross-linking brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) with different aliphatic α,ω-diamine cross-linkers in the presence of sulfonated PPO (SPPO). The alkylation of the α,ω-diamine with BPPO resulted in a covalently cross-linked BPPO network where SPPO could be immobilized by interlocking. The interlocked structure was also strengthened by ion pair interactions between the sulfonic acid groups of SPPO and the amine moieties formed in cross-linking. The length of the aliphatic α,ω-diamine cross-linker was varied to modify the hydrophobicity and the mesh width (the average distance between two cross-linked polymer segments) of the cross-linked network host. The effects of these adjustments on the structure of the cross-linked network host were evaluated by the morphology of the hydrophilic domains, and transport properties such as proton conductivity and methanol permeability. It was found that the increase in mesh width and hydrophobicity of networks formed by long cross-linkers resulted in more scattered hydrophilic domains and fewer contiguous connections. On the contrary, the hydrophilic domains in networks with short cross-linkers were closer and more extensively-connected to facilitate proton transport. Methanol crossover in the SIPN membranes, on the other hand, could be suppressed by downsizing the size of the hydrophilic domains. Overall water uptake and dimensional swelling of the membranes were also affected by the cross-linker length. Some of the SIPN membranes delivered better performance than the Nafion^® 117 membrane in single stack fuel cell tests, demonstrating the potential of SIPNs for the construction of fuel cell PEMs.     

Sulfonated polyimide and poly (ethylene glycol) diacrylate based semi‐interpenetrating polymer network membranes for fuel cells

Semi‐interpenetrating polymer network (semi‐IPN) membranes based on novel sulfonated polyimide (SPI) and poly (ethylene glycol) diacrylate (PEGDA) have been prepared for the fuel cell applications. SPI was synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid, and 2‐bis [4‐(4‐aminophenoxy) phenyl] hexafluoropropane. PEGDA was polymerized in the presence of SPI to synthesize semi‐IPN membranes of different ionic contents. These membranes were characterized by determining, ion exchange capacity, water uptake, water stability, proton conductivity, and thermal stability. The proton conductivity of the membranes increased with increasing PEGDA content in the order of 10^?1 S cm^?1 at 90°C. These interpenetrating network membranes showed higher water stability than the pure acid polyimide membrane. This study shows that semi‐IPN SPI membranes based on PEGDA which gives hydrophilic group and structural stability can be available candidates comparable to Nafion® 117 over 70°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of chitosan/acidified attapulgite composite proton exchange membranes for fuel cell applications

A composite proton exchange membrane chitosan (CS)/attapulgite (ATP) was prepared with the organic–inorganic compounding of ATP and CS. The composite membranes were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). The mechanical properties, thermal stability, water uptake, and proton conductivity of the composite membranes were fully investigated. The composite membranes exhibited an enhanced mechanical property, dimensional and thermal stability compared to CS membrane, owing to the interface interaction between ATP and CS. The maximum tensile strength of 53.1 MPa and decomposition temperature of 223.4°C was obtained, respectively. More importantly, the proton conductivity of the composite membrane is also enhanced, the composite membrane with 4 wt% ATP content (CS/ATP-4) exhibited the highest proton conductivity of 26.2 mS cm⁻¹ at 80°C with 100% relative humidity, which is 25.1% higher than pure CS membrane. These results may explore a simple and green strategy to prepare CS-based PEMs, which have a great potential in the application of proton exchange membrane fuel cells.     

Synthesis and Characterisation of Sulphonated Poly(arylene sulphone) Terpolymers with Triphenylphosphine Oxide Moieties for Proton Exchange Membrane Fuel Cells

For application in fuel cells, a series of sulphonated poly(phenylene sulphone) terpolymers with triphenylphosphine oxide moieties as constitutional units in the polymer backbone have been prepared. The synthesis of the terpolymers represents a two‐step process including: (i) an aromatic nucleophilic substitution polycondensation of three difluoro monomers with varying ratios, i.e. 3,3′‐disulphonate‐4,4′‐difluorodiphenylsulphone, 4,4′‐difluorodiphenylsulphone and bis(4‐fluorophenyl)phenyl phosphine oxide (BFPPO), with 4,4′‐thiobisbenzenethiol yielding sulphonated poly(phenylene sulphide) terpolymers (sPPSPO) and (ii) their following oxidation with hydrogen peroxide in acidic solution to yield sulphonated poly(phenylene sulphone) terpolymers (sPPSO2PO). The structures and molecular compositions were confirmed by ¹H and ¹³C NMR spectroscopy. The ion exchange capacity (IEC) was adjusted at will choosing the appropriate ratio of sulphonated and unsulphonated monomers. Terpolymers with 1.72 ≤ IEC ≤ 2.32 have been obtained. Sulphonated poly(arylene) ionomers containing only sulphone (–SO₂–) linkages and phosphine oxide (–PO–) units rather than ether or sulphide in the backbone reveal a high thermal and oxidative stability. Membranes were cast either from dimethylformamide (DMF) or from dimethyl sulphoxide (DMSO) solutions. For all terpolymers some general characteristic trends were observed, such as an increase of the proton conductivity with increasing IEC, water uptake and temperature. The series of sPPSO2PO membranes offered high conductivities at high humidification, however, their performance strongly depends on the relative humidity. The mechanical properties of sulphonated poly(phenylene sulphone)s have been considerably improved by means of terpolymerisation with phenylene oxide moieties. Even under high humidification the terpolymers form clear, flexible membranes the stress at break of some membranes exceeds that of Nafion® under the same conditions by 40%.     

Preparation Polyelectrolyte Complexes of Chitosan-Polyacrylic Acid-Modified Iron Sand Leachate for Proton Exchange Membranes

ABSTRACT

Polyelectrolyte complex (PEC) of chitosan (Chi) and poly (acrylic acid) (PAA)-modified iron sand leachate were prepared and considered for applicability as a proton exchange membrane in fuel cells. Chi-PAA-hematite blended in different weight ratios and the resulting membranes were treated to enable the formation of the polyelectrolyte. The membranes of Chi-PAA polyblend were treated using iron sand leachate and reveal high ion exchange capacity (IEC), proton conductivity, water uptake, and good mechanical stability. The result of research indicated that the membrane with 40 wt% of Chi and 60 wt% of PAA blend which its conductivity of 6.10 × 10^?2 S cm^?1 was potentially for a proton exchange membrane in fuel cell applications.     

Thermo and electrochemical characterization of sulfonated PEEK–WC membranes and Krytox-Si-Nafion® composite membranes

Two types of membranes, the sulfonated PEEK-WC (poly(oxa-p-phenylene-3,3-phthalido-p-phenylene-oxyphenylene)(SPWC) and Krytox-Si-Nafion® (KSiN) composite membranes are proposed for DMFC applications.The properties based on water uptake, ion exchange capacity, proton conductivity, gas permeability, thermal stabilityand methanol crossover are summarized. The comparative studies on SPWC and Nafion® 117 membranes clarify us that the amorphous sulfonated PEEK-WC polymer shows thermal and mechanical stability with less methanol flux and gas permeability. The membrane also exhibits the increase in water uptake, ion exchange capacity and proton conductivity as sulfuric acid doping agent concentration was increased. The KSiN is unique in term of its miscible hybrid structure of silica particles modified with Nafion® structured Krytox 157 FSL chain (KSi) andNafion®. Based on the KSiN membranes with different KSi content, it was found that when KSi content increased, the reduction of gas permeability, methanol crossover and thermal stability are improved. The composite membrane performs the proton conductivity in the wide range of high temperature (60–130°C).     

Novel hydrophilic–hydrophobic multiblock copolyimides as proton exchange membranes: Enhancing the proton conductivity

A series of novel multiblock copolymers based on sulfonated copolyimides were developed and evaluated for use as proton exchange membranes (PEMs). In these multiblock copolyimides, the hydrophilic blocks were composed of the sulfonated dianhydride and the sulfonated diamine, with sulfonic acid groups on every aromatic ring (i.e., fully sulfonated). This molecular design was implemented to effectively enhance the proton conductivity. The properties of the multiblock copolyimides with varying IEC values or block lengths were investigated to obtain a better understanding of the relationship between molecular structure and properties of proton exchange membranes. The water uptake and proton conductivity were found to be highly dependent upon their structure. The block copolymers displayed significantly higher proton conductivities, especially at low relative humidity than the random copolymers with a similar IEC. The results indicated that the distribution of sulfonic acid and the length of the blocks play a key role on properties of proton exchange membranes.