Proton conducting membranes based on semi-interpenetrating polymer network of Nafion and polybenzimidazole

A new strategy to prepare the reinforced composite membranes for polymer electrolyte membrane fuel cells (PEMFCs), which can work both in humidified and anhydrous state, was proposed via constructing semi-interpenetrating polymer network (semi-IPN) structure from polybenzimidazole (PBI) and Nafion^®212, with N-vinylimidazole as the crosslinker. The crosslinkable PBI was synthesized from poly(2,2′-(m-phenylene)-5,5′-bibenzimidazole) and p-vinylbenzyl chloride. The semi-IPN structure was formed during the membrane preparation. The composite membranes exhibit excellent thermal stability, high-dimensional stability, and significantly improved mechanical properties compared with Nafion^®212. The proton transport in the hydrated composite membranes is mainly contributed by the vehicle mechanism, with proton conductivity from ∼10⁻² S/cm to ∼10⁻¹ S/cm. When the temperature exceeds 100 °C, the proton conductivity of the semi-IPN membranes decreases quickly due to the dehydration of the membranes. Under anhydrous condition, the proton conductivity of the membranes will drop to ∼10⁻⁴ S/cm, which is also useful for intermediate temperature (100-200 °C) PEMFCs. The benzimidazole structure of PBI and the acidic component of Nafion^® provide the possibility for the proton mobility via structure diffusion involving proton transfer between the heterocycles with a corresponding reorganization of the hydrogen bonded network.     

Phosphoric acid doped polybenzimidazole membranes: Physiochemical characterization and fuel cell applications

A polymer electrolyte membrane fuel cell operational at temperatures around 150–200 °C is desirable for fast electrode kinetics and high tolerance to fuel impurities. For this purpose polybenzimidazole (PBI) membranes have been prepared and H₃PO₄-doped in a doping range from 300 to 1600 mol %. Physiochemical properties of the membrane electrolyte have been investigated by measurements of water uptake, acid doping level, electric conductivity, mechanical strength and water drag coefficient. Electrical conductivity is found to be insensitive to humidity but dependent on the acid doping level. At 160 °C a conductivity as high as 0.13 S cm^–1 is obtained for membranes of high doping levels. Mechanical strength measurements show, however, that a high acid doping level results in poor mechanical properties. At operational temperatures up to 190 °C, fuel cells based on this polymer membrane have been tested with both hydrogen and hydrogen containing carbon monoxide.     

Synthesis of novel sulfonated polybenzimidazole and preparation of cross-linked membranes for fuel cell application

A novel sulfonated polybenzimidazole, sulfonated poly[2,2′-(p-oxydiphenylene)-5,5′-bibenzimidazole] (SOPBI), was successfully prepared by post-sulfonation reaction of the parent polymer, poly[2,2′-(p-oxydiphenylene)-5,5′-bibenzimidazole] (OPBI), using concentrated and fuming sulfuric acid as the sulfonating reagent at 80 °C, and the degree of sulfonation (DS) could be regulated by controlling the reaction conditions. No significant polymer degradation was observed in the post-sulfonation processes. Direct polymerization of 4,4′-dicarboxydiphenyl ether-2,2′-disulfonic acid disodium salt (DCDPEDS) and 3,3′-diaminobenzidine (DABz), however, resulted in insoluble gels either in polyphosphoric acid (PPA) or in phosphorus pentoxide/methanesulfonic acid (PPMA) in a ratio of 1:10 by weight reaction medium. The SOPBIs prepared by the post-sulfonation method showed good solubility in dimethyl sulfoxide (DMSO), high thermal stability, good film forming ability and excellent mechanical properties. Cross-linked SOPBI membranes were successfully prepared by thermal treatment of phosphoric acid-doped SOPBI membranes at 180 °C in vacuo for 20 h and the resulting cross-linked membranes showed much improved water stability and radical oxidative stability in comparison with the corresponding uncross-linked ones, while the proton conductivity did not change largely. Highly proton conductive (150 mS cm⁻¹, 120 °C in water) and water stable SOPBI membrane was developed.     

A facile crosslinking method of polybenzimidazole with sulfonyl azide groups for proton conducting membranes

A facile crosslinking method of polybenzimidazole (PBI) with sulfonyl azide groups (sPBI-SA) for proton conducting membranes is proposed. Thermally crosslinkable sPBI-SA is synthesized from sulfonated PBI (sPBI) and sodium azide. The structures of sPBI, sPBI-SA, and crosslinked sPBI are confirmed by FTIR and ¹H NMR. Upon heating, sPBI-SA loses nitrogen and form nitrene, which reacts with CH-bond of the backbone of another chain of PBI via the reactions of hydrogen abstraction, recombination, or CH-bond insertion. The crosslinking structure of PBI membranes is thus formed. Compared with the uncrosslinked membranes, the crosslinked sPBI membranes exhibit improved tensile strength, migration stability of phosphoric acid (PA), dimensional stability, and chemical oxidative stability. Whereas, the doping ability of PA and the proton conductivity of the crosslinked membranes decrease a little.     

Methanol permeability and proton conductivity of polybenzimidazole and sulfonated polybenzimidazole

The preparation of sulfonated polybenzimidazole (sPBI) by the grafting of (4‐bromomethyl) benzenesulfonate onto polybenzimidazole (PBI) has been investigated. The methanol permeability and proton conductivity of PBI and sPBI have been studied, and the effects of methanol concentration and temperature on the methanol permeability of PBI and sPBI membranes are discussed. The results showed that the PBI membrane is a good methanol barrier. Methanol permeability in this membrane decreases with increasing methanol concentration and increases with increasing temperature. The temperature‐dependence of methanol permeability of PBI and sPBI membranes is of the ‘Arrhenius type’. Methanol permeation of sPBI is less sensitive to temperature than that of PBI. However, sPBI is a poorer methanol barrier when compared to PBI. Methanol permeability in sPBI membranes increases with increasing methanol concentration and temperature. The proton conductivity of sPBI is 4.69 × 10^?4 S cm^?1 at room temperature in the hydrated state. The DC conductivity of sPBI–H₃PO₄ increases with increasing temperature. Proton transport in sPBI–H₃PO₄ is less sensitive to temperature than that in PBI–H₃PO₄. Copyright © 2004 Society of Chemical Industry     

磺化聚苯并咪唑/磺化聚醚砜酸碱复合质子交换膜的制备与表征

为提高膜的尺寸稳定性和阻醇性能,以磺化聚苯并咪唑(S-PBI)与高磺化度聚醚砜(ABPS)两种聚合物为原料,采用溶液共混的方法,制备了系列酸碱复合质子交换膜。研究了复合膜的甲醇溶胀性、吸水率、甲醇渗透系数、质子传导率随S-PBI含量的变化规律。研究表明,随着S-PBI含量的增加,膜的阻醇性能和尺寸稳定性明显提高;同时,复合膜具有较好的质子传导率,有望应用于直接甲醇燃料电池。     

Organic/inorganic composite membranes based on polybenzimidazole and nano-SiO2

Organic/inorganic composite membranes based on polybenzimidazole (PBI) and nano-SiO₂ were prepared in this work. However, the preparation of PBI/SiO₂ composite membrane is not easy since PBI is insoluble in water, while nano-SiO₂ is hydrophilic due to the hydrophilicity of nano-SiO₂ and water-insolubility of PBI. Thus, a solvent-exchange method was employed to prepare the composite membrane. The morphology of the composite membranes was studied by scanning electron microscopy (SEM). It was revealed that inorganic particles were dispersed homogenously in the PBI matrix. The thermal stability of the composite membrane is higher than that of pure PBI, both for doped and undoped membranes. PBI/SiO₂ composite membranes with up to 15 wt% SiO₂ exhibited improved mechanical properties compared with PBI membranes. The proton conductivity of the composite membranes containing phosphoric acid was studied. The nano-SiO₂ in the composite membranes enhanced the ability to trap phosphoric acid, which improved the proton conductivity of the composite membranes. The membrane with 15 wt% of inorganic material is oxidatively stable and has a proton conductivity of 3.9 × 10⁻³ S/cm at 180 °C.     

Enhancing water flux through semipermeable polybenzimidazole membranes by adding surfactant‐treated CNTs

In this study, surfactant‐treated carbon nanotubes (CNTs) were incorporated into polybenzimidazole (PBI) matrix to prepare the PBI/CNT composite membranes with CNT content in the range of 0 to 15 wt %. The composite membranes were fabricated by spin‐coating. The membrane morphology, mechanical property, and water and salt transport properties were investigated to characterize the additive effect of CNTs. The tensile strength of all the PBI/CNT composite membranes was lower than that of pristine PBI membrane, indicating the weak interaction between CNT and PBI. In addition, water flux increased without reducing the salt rejection when CNTs were homogeneously dispersed in the PBI matrix at a less than 7.5 wt % content. On the other hand, at 10 wt % and higher CNT content, submicro‐scaled cellular structure was formed, and both the water flux and salt rejection decreased. The well‐dispersed CNTs in the PBI matrix via weak interaction preferentially improve the water permeability by 1.7 times without depressing the salt rejection. The incorporation of well‐dispersed CNTs in polymer matrix provides a promising and facile option for improvement in the water transport properties through the polymeric semipermeable membranes with intrinsically low water permeability such as PBI. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45875.     

Recent advances in polybenzimidazole/phosphoric acid membranes for high‐temperature fuel cells

Proton exchange membrane fuel cells are one of the most promising technologies for sustainable power generation in the future. In particular, high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs) offer several advantages such as increased kinetics, reduced catalyst poisoning and better heat management. One of the essential components of a HT‐PEMFC is the proton exchange membrane, which has to possess good proton conductivity as well as stability and durability at the required operating temperatures. Amongst the various membrane candidates, phosphoric acid‐impregnated polybenzimidazole‐type polymer membranes (PBI/PA) are considered the most mature and some of the most promising, providing the necessary characteristics for good performance in HT‐PEMFCs. This review aims to examine the recent advances made in the understanding and fabrication of PBI/PA membranes, and offers a perspective on the future and prospects of deployment of this technology in the fuel cell market. © 2014 Society of Chemical Industry     

Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries

Polybenzimidazole(PBI) is a kind of proton transport membrane material, and its ion conductivity is a key factor affecting its application in vanadium redox flow batteries(VRFBs). The casting solvent of PBI has a significant influence on the acid doping level of PBI membranes which is closely related to ionic conductivity. In this paper, 3,3′-diaminobenzidine(DABz) and 4,4′-Dicarboxydiphenylether(DCDPE) were used as raw materials by solution condensation to prepare the PBI with ether bond groups. The chemical structure of PBI was determined by1~H NMR and FT-IR, and the prepared PBI had good solubility which can be dissolved in a variety of solvents. The PBI proton exchange membranes were prepared by solution coating with 5 different solvents of N,N-dimethylformamide(DMF), N,N-dimethylacetamide(DMAc), dimethyl sulfoxide(DMSO), 1-methyl-2-pyrrolidone(NMP), methane sulfonic acid(MSA). The effects of different solvents on the ion conductivity and physicochemical properties were discussed in detail. The results showed that the PBI membrane prepared by using MSA as solvent(the PBI + MSA membrane) exhibits high water uptake, acid doping level and low vanadium ion permeability. The VRFB assembled with the PBI + MSA membrane exhibited higher coulombic efficiency(CE) 99.87% and voltage efficiency(VE) 84.50% than that of the commercial Nafion115 membrane at100 m A·cm~(-2), and after 480 cycles, the EE value can still be maintained at 83.73%. The self-discharge time of a single battery was recorded to be as long as 1000 h. All experimental data indicated that MSA is the best solvent for casting PBI membrane.     

Polycondensation of structurally divergent tetraamine monomers with dicarboxylic acids to synthesize polybenzimidazole copolymers for polymer electrolyte membranes

In our effort to promote 2,6‐bis(3,4‐diaminophenyl)‐4‐phenylpyridine (Py‐TAB) as an alternative tetraamine monomer to conventionally used 3,3′,4,4′‐tetraaminobiphenyl (TAB) for synthesizing readily processable pyridine bridged polybenzimidazoles (Py‐PBIs), two series of random copolymers (PBI‐co‐Py‐PBI) were synthesized by polymerizing Py‐TAB and TAB with isophthalic acid or terephthalic acid to produce meta (mPBI‐co‐mPy‐PBI) and para (pPBI‐co‐pPy‐PBI) connected copolymers, respectively. For the first time in the PBI literature, copolymers were synthesized by varying the relative compositions of tetraamines (TAB and Py‐TAB) in the polymerization feed with a single dicarboxylic acid (DCA) instead of the traditionally used method where two DCAs with variable compositions were polymerized with a single tetraamine. The solubility and hence the processability of the copolymers were improved significantly upon introduction of Py‐PBI in the copolymer. The detailed characterizations of both meta and para series copolymers compellingly established that thermal, chemical and mechanical stabilities can be easily modulated according to need by altering the relative compositions of PBI and Py‐PBI. The phosphoric acid (PA) loading of the copolymers increased gradually with increasing Py‐PBI content since the bulky pyridine moiety facilitated the absorption of PA. The presence of pyridine functionality and a larger PA loading caused a higher proton conductivity of PA doped copolymer membranes. © 2014 Society of Chemical Industry     

Properties and performance of composite electrolyte membranes based on sulfonated poly(arylenethioethersulfone) and sulfonated polybenzimidazole

A novel composite membranes comprising a sulfonated polyarylenethioethersulfone homopolymer (SPTES-100) and a sulfonated poly(p-phenylene benzobisimidazole) (SPBI), was described in this article. The composite membrane was obtained via a solution cast process in a mixture solvent of N, N-Dimethylacetamide (DMAc) and methanol (MeOH). The proton conductivity of the composite membranes was found to increase with the SPTES-100 content increased. The higher proton conductivity was ∼110 mS/cm at 85 °C and 85% relative humidity for the SPTES/SPBI 70/30 (wt) composite membrane which was considerably less than that of the 300 mS/cm of the SPTES-100 membrane. The mechanical properties indicated that the swelling of the composite membranes was reduced, which is relative to the SPTES-100 polymers, due to the reduced water uptake of the composite membrane by introducing the SPBI into the SPTES polymer matrix. The morphology of the SPTES/SPBI composite membranes was examined by a combination of techniques such as scanning electron microscopy (SEM) and elemental mapping to confirm the dispersion of the SPBI and study the micro-structure of the composite. The membrane electrode assembly (MEA) performance of the composite membranes was preliminary studied for H₂/Air fuel cells applications.     

聚苯并咪唑的改性及其应用

为了提高聚苯并咪唑(PBI)的溶解性、化学稳定性和导电性等,需对PBI进行改性。介绍了通过单体改性、在聚合物主链上引入柔性链(基团或原子)、在—N—H上引入脂肪族和芳香族磺酸盐侧基等方法提高PBI的溶解性;通过调节PBI的相对分子质量或者用甲基取代咪唑环上的氢,提高PBI的稳定性能;通过物理改性和化学改性(单体改性、掺杂改性、磺化改性)提高PBI的导电性能。综述了PBI在纤维、膜材料、基体树脂、粘结剂等方面的应用情况,并对其进行了展望;指出了PBI的改性大部分属于化学改性,通过单体改性和聚合物主链改性对PBI性能影响很大,应进一步加大PBI物理改性的开发,如低温等离子体改性,拓宽PBI应用范围。     

A comparative experimental study of the hygroscopic and mechanical behaviors of electrospun nanofiber membranes and solution-cast films of polybenzimidazole

This article reports a comparative experimental study of the hygroscopic and mechanical behaviors of electrospun polybenzimidazole (PBI) nanofiber membranes and solution-cast PBI films. As-electrospun nonwoven PBI nanofiber mats (with the nanofiber diameter of ~250 nm) were heat-pressed under controlled temperature, pressure and duration for the study; lab-made solution-cast PBI films and commercially available PBI films (the PBI Performance Product Inc., Charlotte, NC) were used as the control samples. Thermogravimetric and microtensile tests were utilized to characterize the hygroscopic (moisture absorption) and mechanical properties of the PBI nanofiber membranes at varying heat-pressing conditions, which were further compared to those of solution-cast PBI films. Experimental results indicated that the PBI nanofiber membranes carried slightly higher thermal stability and less hygroscopic properties than those of solution-cast PBI films. In addition, heat-pressing conditions significantly influenced the mechanical properties of the resulting PBI nanofiber membranes. The stiffness and tensile strength increase with increasing either the heat-pressing pressure or duration, and relevant mechanisms were explored. The present study provides a rational understanding of the hygroscopic and mechanical behaviors of electrospun PBI nanofiber membranes and solution-cast PBI films that are beneficial to their reliable cutting-edge applications in high-temperature filtration, polymer electrolyte membranes (PEMs), etc.     

Phosphonic acid functionalized siloxane crosslinked with 3‐glycidoxyproyltrimethoxysilane grafted polybenzimidazole high temperature proton exchange membranes

Phosphonic acid functionalized siloxane crosslinked with 3‐glycidoxypropyltrimethoxysilane (GPTMS) grafted polybenzimidazole (PBI) membranes are prepared by sol–gel process. The structure of the membranes is characterized by Fourier‐transform infrared spectroscopy and X‐ray diffraction spectroscopy. SEM images of the membranes show that the membranes are homogeneous and compact. The crosslinked membranes exhibit excellent thermal stability, chemical stability and mechanical property. The proton conductivity of the crosslinked membranes increases by an order of magnitude over range of 20 °C to 160 °C under anhydrous condition, which can reach 3.15 × 10^?2 S cm^?1 at 160 °C under anhydrous condition. The activation energy of proton conductivity for membranes decreases with increase of PBI, because the formation of hydrogen bond network between the phosphonic acid and the imidazole ring can enhance the continuity of hydrogen bond in the membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44818.     

Enhanced forward osmosis from chemically modified polybenzimidazole (PBI) nanofiltration hollow fiber membranes with a thin wall

To develop high-flux and high-rejection forward osmosis (FO) membranes for water reuses and seawater desalination, we have fabricated polybenzimidazole (PBI) nanofiltration (NF) hollow fiber membranes with a thin wall and a desired pore size via non-solvent induced phase inversion and chemically cross-linking modification. The cross-linking by p-xylylene dichloride can finely tune the mean pore size and enhance the salt selectivity. High water permeation flux and improved salt selectivity for water reuses were achieved by using the 2-h modified PBI NF membrane which has a narrow pore size distribution. Cross-linking at a longer time produces even a lower salt permeation flux potentially suitable for desalination but at the expense of permeation flux due to tightened pore sizes. It is found that draw solution concentration and membrane orientations are main factors determining the water permeation flux. In addition, effects of membrane morphology and operation conditions on water and salt transport through membrane have been investigated.     

Preparation and proton conductivity of phosphoric acid‐doped blend membranes composed of sulfonated block copolyimides and polybenzimidazole

A series of phosphoric acid (PA)‐doped blend membranes composed of block or random sulfonated polyimides (SPIs) and polybenzimidazole (PBI) were prepared with similar PA contents to investigate the influence of chemical structures of SPIs on proton conductivity. The proton conductivity of a PA‐doped blend membrane containing block‐type SPI, PA‐bSPI(80/20)/oPBI, was higher than that of the corresponding pristine block‐type SPI, PA‐SPI/PBI containing random‐type SPI and Nafion membranes over a wide temperature range, and reached 0.37 S cm^?1 at 90 °C and 98% relative humidity. The PA‐bSPI(80/20)/oPBI membrane also showed distinct proton conductivity even at low humidity due to a new proton transport pathway among PA and sulfonic acid groups. Also, the novel PA‐doped blend membrane showed higher proton conductivity than Nafion at both above 100 °C and below 0 °C under low relative humidity conditions. © 2013 Society of Chemical Industry