Synthesis and characterization of polybenzimidazole/α‐zirconium phosphate composites as proton exchange membrane

To improve the high‐temperature performance of proton exchange membranes, the polybenzimidazole (PBI)/α‐zirconium phosphate (α‐Zr(HPO₄)₂·nH₂O, α‐ZrP) proton exchange composite membranes were prepared in this study. PBI polymer containing a large amount of ether units has been synthesized from 3,3′‐ diaminobenzidine (DAB) and 4,4′‐oxybis (benzoic acid) by a direct polycondensation in polyphosphoric acid. The polymer exhibited a good solubility in most polar solvents. Inorganic proton conductor α‐ZrP nanoparticles have been obtained using a synthesis route involving separate nucleation and aging steps (SNAS). The effects of α‐ZrP doping content on the composite membrane performance were investigated. It was found that the introduction of ZrP improved the thermal stability of the composite membranes. The PBI/ZrP composite membranes exhibited excellent mechanical strength. The composite membrane with 10 wt% ZrP showed the highest proton conductivity of 0.192 S cm^?1 at 160°C under anhydrous condition. The proton conducting mechanism of the PBI/ZrP composite membranes was proposed to explain the proton transport phenomena. The experimental results suggested that the PBI/ZrP composite membranes may be a promising polymer electrolyte used in high temperature proton exchange membrane fuel cells (HT‐PEMFCs) under anhydrous condition. POLYM. ENG. SCI., 56:622–628, 2016. © 2016 Society of Plastics Engineers     

Proton exchange composite membranes from blends of brominated and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide)

New composite proton exchange membrane was prepared by mixing a 1‐methyl‐2‐pyrrolidone (NMP) solution of sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) in sodium form and brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (BPPO) for hydrophilic‐hydrophobic balance, then casting the solution as a thin film, evaporating the solvent, and treating the membrane with aqueous hydrochloric acid. The resulting membranes were subsequently characterized using FTIR‐ATR, SEM‐EDXA, and TGA instrumentation as well as measurements of basic properties such as ion exchange capacity (IEC), water uptake, proton conductivity, methanol permeability, and single cell performance. Water uptake, IEC, proton conductivity, and methanol permeability all increased with a corresponding increase of SPPO content. By properly compromising the conductivity and methanol permeability, membranes with 60–80 wt % SPPO content exhibited comparable proton conductivity to that of Nafion^® 117, with only half the methanol permeability, thereby demonstrating higher single cell performance. The membranes developed in this study could thus be a suitable candidate electrolyte for proton exchange membrane fuel cells (PEMFCs). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhanced proton conductivity from phosphoric acid‐incorporated 3D polyacrylamide‐graft‐starch hydrogel materials for high‐temperature proton exchange membranes

To enhance anhydrous proton conductivity of high‐temperature proton exchange membranes (PEMs), we report here the realization of H₃PO₄‐imbibed three‐dimensional (3D) polyacrylamide‐graft‐starch (PAAm‐g‐starch) hydrogel materials as high‐temperature PEMs using the unique absorption and retention of crosslinked PAAm‐g‐starch to concentrated H₃PO₄ aqueous solution. The 3D framework of PAAm‐g‐starch matrix provides enormous space to keep H₃PO₄ into the porous structure, which can be controlled by adjusting crosslinking agent and initiator dosages. Results show that the H₃PO₄ loading and therefore the proton conductivities of the membranes are significantly enhanced by increasing the amount of crosslinking agent and initiator dosages. Proton conductivities as high as 0.109 S cm^?1 at 180°C under fully anhydrous state are recorded. The high conductivities at high temperatures in combination with the simple preparation, low cost, and scalable matrices demonstrate the potential use of PAAm‐g‐starch hydrogel materials in high‐temperature proton exchange membrane fuel cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40622.     

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     

Regulation of micromorphology and proton conductivity of sulfonated polyimide/crosslinked PNIPAm semi‐interpenetrating networks by hydrogen bonding

A series of novel sulfonated polyimide (SPI)/crosslinked poly(N‐isopropylacrylamide) (cPNIPAm) semi‐interpenetrating polymer networks (semi‐IPNs) were synthesized as the proton exchange membranes for direct methanol fuel cells via in situ polymerization. The micromorphology and properties of the semi‐IPN membranes were characterized. The results indicated that the hydrogen bonds between cPNIPAm and SPI in the semi‐IPN structure were a crucial factor for regulating the micromorphology, proton conductivity and other properties of the semi‐IPN membranes. A more uniform sulfonic ionic cluster distribution was observed in the membrane of SPI‐20‐cPNIPAm with equimolar ratio of sulfonic acid groups and amido bonds, which could provide effective proton transport channels. The SPI‐20‐cPNIPAm exhibited a maximum proton conductivity of 0.331 S cm^?1 at 80 ^oC (relative humidity 100%), an optimal selectivity of 8.01 × 10⁵ S s cm^?3 and an improved fuel cell performance of 72 mW cm^?2 compared with both pristine SPI and other semi‐IPN membranes. The SPI‐20‐cPNIPAm semi‐IPN membranes also retained good mechanical properties and thermal stabilities on the whole. © 2014 Society of Chemical Industry     

Sulfonated graphene oxide‐doped proton conductive membranes based on polymer blends of highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole

Simultaneously improving the proton conductivity and mechanical properties of a polymer electrolyte membrane is a considerable challenge in commercializing proton exchange membrane fuel cells. In response, we prepared a new series of miscible polymer blends and thus the corresponding crosslinked membranes based on highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole. The blended membranes showed more compact structures, due to the acid‐base interactions between the two constituents, and improved mechanical and morphological properties. Further efforts by doping sulfonated graphene oxide (s‐GO) forming composite membranes led to not only significantly elevated proton conductivity and electrochemical performance, but also better mechanical properties. Notably, the composite membrane with the filler content of 15 wt % exhibited a proton conductivity of 0.217 S cm^?1 at 80 °C, and its maximum power density tested by the H₂/air single PEMFC cell at room temperature reached 171 mW cm^?2, almost two and half folds compared with that of the native membrane. As a result, these polymeric membranes provided new options as proton exchange membranes for fuel‐cell applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46547.     

Theoretical investigation of a water‐gas‐shift catalytic membrane for diesel reformate purification

The novel application of a catalytic water‐gas‐shift membrane reactor for selective removal of CO from H₂‐rich reformate mixtures for achieving gas purification solely via manipulation of reaction and diffusion phenomena, assuming Knudsen diffusion regime and the absence of hydrogen permselective materials, is described. An isothermal, two‐dimensional model is developed to describe a tube‐and‐shell membrane reactor supplied with a typical reformate mixture (9% CO, 3% CO₂, 28% H₂, and 15% H₂O) to the retentate volume and steam supplied to the permeate volume such that the overall H₂O:CO ratio within the system is 9:1. Simulations indicate that apparent CO:H₂ selectivities of 90:1 to >200:1 at H₂ recoveries of 20% to upwards of 40% may be achieved through appropriate design of the catalytic membrane and selection of operating conditions. Under these conditions, simulations predict an apparent hydrogen permeability of 2.3 × 10^?10 mol m^?1 Pa, which compares favorably against that of competing hydrogen‐permselective membranes. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4334–4345, 2013     

A CO2‐stable hollow‐fiber membrane with high hydrogen permeation flux

A Mo‐substituted lanthanum tungstate mixed proton‐electron conductor, La_5.5W_0.6Mo_0.4O_11.25?δ (LWM04), was synthesized using solid state reactions. Dense U‐shaped LWM04 hollow‐fiber membranes were successfully prepared using wet‐spinning phase‐inversion and sintering. The stability of LWM04 in a CO₂‐containing atmosphere and the permeation of hydrogen through the LWM04 hollow‐fiber membrane were investigated in detail. A high hydrogen permeation flux of 1.36 mL/min cm² was obtained for the U‐shaped LWM04 hollow‐fiber membranes at 975°C when a mixture of 80% H₂?20% He was used as the feed gas and the sweep side was humidified. Moreover, the hydrogen permeation flux did not significantly decrease over 70 h of operation when fed with a mixture containing 25% CO₂, 50% H₂, and 25% He, indicating that the LWM04 hollow‐fiber membrane has good stability under a CO₂‐containing atmosphere. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1997–2007, 2015     

In situ sol–gel route to novel sulfonated polyimide?SiO2 hybrid proton‐exchange membranes for direct methanol fuel cells

Polyimides (PIs) as high‐performance organic matrices are used in the preparation of PI composites because of their excellent mechanical, thermal and dielectric properties. The sol–gel method is a promising technique for preparing these PI composites due to the mild reaction conditions and the process being controllable. Although sulfonated polyimide (SPI) proton‐exchange membranes have attracted much attention recently, studies on preparing SPI‐based hybrid proton‐exchange membranes for fuel cells have been rare. A series of SPI? SiO₂ hybrid proton‐exchange membranes were prepared from amino‐terminated SPI pre‐polymers, 3‐glycidoxypropyltrimethoxysilane (KH‐560) and tetraethylorthosilicate through a co‐hydrolysis and condensation process using an in situ sol–gel method. The reactive silane KH‐560 was used to react with amino‐terminated SPI to form silane‐capped SPI in order to improve the compatibility between the polymer matrix and the inorganic SiO₂ phase. The microstructure and mechanical, thermal and proton conduction properties were studied in detail. The hybrid membranes were highly uniform without phase separation up to 30 wt% SiO₂. The storage modulus and tensile strength of the hybrid membranes increased with increasing SiO₂ content. The introduction of SiO₂ improved the methanol resistance while retaining good proton conductivity. The hybrid membrane with 30 wt% SiO₂ exhibited a proton conductivity of 10.57 mS cm^?1 at 80 °C and methanol permeability of 2.3 × 10^?6 cm² s^?1 possibly because the crosslinking structure and SiO₂ phases formed in the hybrids could retain water and were helpful to proton transport. Copyright © 2010 Society of Chemical Industry     

Novel Proton Conducting Membranes from the Combination of Sulfonated Polymers of Polyetheretherketones and Polyphosphazenes Doped with Sulfonated Single‐Walled Carbon Nanotubes

Intent on developing efficient proton exchange membranes used for direct methanol fuel cells as well as hydrogen fuel cells, a series of membranes based on sulfonated polyetheretherketone and sulfonated polyphosphazene‐graft copolymers is prepared by cross‐linking reaction because the former material has good enough mechanical property, while the latter is excellent in the proton transfer. The cross‐linked membranes combine the advantages of the two kinds of polymers. Among them, the membrane poly[(4‐trifluoromethylphenoxy)(4‐methylphenoxy)phosphazene]‐g‐poly {(styrene)₁₁‐r‐[4‐(4‐sulfobutyloxy)styrene]₃₃‐sulfonated poly(ether ether ketone)75 (CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75) shows a proton conductivity at 0.143 S cm⁻¹ under fully hydrated conditions at 80 °C and performs tensile strength about five times as much as did the sulfonated polyphosphazene membrane CF₃‐PS₁₁‐PSBOS₃₃. Further doping of sulfonated single‐walled carbon nanotubes (S‐SWCNTs) into the cross‐linked membranes on the screening of additives gives composite membrane CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75‐SWCNT possessing proton conductivity of 0.196 S cm⁻¹, even higher than that of Nafion 117 and a tensile strength comparable to that of Nafion 117. However, this significance of the composite membrane in the proton conduction is not observed in the test with a H₂/air fuel cell when it shows a maximal power density of 280 mW cm⁻² at 80 °C, whereas 294 mW cm⁻² is observed for CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75.

     

Poly(vinyl alcohol) modified by KE reactive dyes as a novel proton‐exchange membrane for potential fuel‐cell applications

A new type of proton‐exchange membrane based on poly(vinyl alcohol) (PVA) modified KE reactive dyes (KE‐4BD) was prepared and evaluated as H⁺‐conducting polymer electrolytes. The effects of the content of KE‐4BD on the membrane H⁺ conductivity and water uptake were studied with an alternating‐current impedance technique and the method of weighing, respectively. Fourier transform infrared and scanning electron microscopy were used for the chemical and structural characterization of these membranes. With all of these properties, the optimal mass ratio between PVA and KE‐4BD was 1:0.5, and the resulting membrane exhibited a high proton conductivity (0.109 S/cm) at room temperature; this afforded a power density of 83.9 mW/cm² at 210.4 mA/cm² and an open‐circuit voltage of 810.8 mV. The PVA/KE‐4BD membranes showed a high oxidative stability in Fenton's reagent (3% H₂O₂ v/v, 2 ppm FeSO₄). Thermal analysis also showed that the membranes exhibited a significant improvement in thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43019.     

A “proton pump” concept for the investigation of proton transport and anode kinetics in proton exchange membrane fuel cells

A novel concept for the measurement of proton transport properties and electrode kinetics in proton exchange membrane fuel cells (PEMFC) is presented. The “proton pump” is essentially a fuel cell operated with pure nitrogen or very low hydrogen partial pressure instead of oxygen-containing gas on the cathode side, avoiding the complicated electrode kinetics of oxygen reduction. In this first study using this concept, we investigated the proton transport in high temperature PEMFC based on polybenzimidazole (PBI)/phosphoric acid membranes. The impedance spectra of the proton pump allow the clear distinction between anode and cathode kinetics and proton transport in the membrane. Identifying and analyzing the contribution of the anodic processes in the impedance spectra enabled the quantitative investigation of anode kinetics based on the Butler-Volmer equation. The proton transport was investigated in more detail in the current saturation region, where proton transport turned out to be the limiting process in case of sufficient H₂ supply at the anode. The maximum proton transport capacity of the PBI/phosphoric acid membrane was found to be comparable to those of Nafion^® membranes.     

Study of high-temperature proton exchange membrane through one-step encapsulation of ionic liquid in sulfonated poly(ether ether ketone)

The proton exchange membrane (PEM) is the core component of a high-performance proton exchange membrane fuel cell (PEMFC). Since the traditional PEM has the disadvantages of poor cell performance and high cost, a new kind of PEM with good proton conductivity, low cost and simple preparation should be explored. In this paper, several different binary hybrid membranes were successfully prepared through one-step encapsulation of different ionic liquids (ILs) in sulfonated poly(ether ether ketone) (SPEEK). The prepared membranes were characterized by scanning electron microscope (SEM), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), proton conductivity measurements and dynamic mechanical analysis (DMA). SEM images showed that ILs were fully doped into SPEEK. FT-IR and XPS proved that SPEEK and IL formed a new chemical bond combined with intermolecular hydrogen bonds. The TG results showed that the binary hybrid membranes could maintain stability even at 300°C. The water uptake and swelling ratio showed that the water absorption capacity of the binary composite membrane played a vital role in improving proton conductivity. The proton conductivity study showed that ILs doping also helped to improve the proton conductivity of the SPEEK membrane. When the doping amount of IL was maintained at 30 wt.%, it has the highest proton conductivity, 25 mS cm⁻¹ at 120°C. It was proved that anhydrous hybrid membrane tetraphenyl imidazole sulfate/SPEEK ([IM2][H₂PO₄]/SPEEK) could be used in PEMFC at medium temperature.     

Preparation and properties of bisphenol A‐based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell

Novel bisphenol A‐based sulfonated poly(arylene ether sulfone) (bi A‐SPAES) copolymers were successfully synthesized via direct copolymerization of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone, 4,4′‐dichlorodiphenylsulfone, and bisphenol A. The copolymer structure was confirmed by Fourier transform infrared spectra and ¹H NMR analysis. The series of sulfonated copolymers based membranes were prepared and evaluated for proton exchange membranes (PEM). The membranes showed good thermal stability and mechanical property. Transmission electron microscopy was used to obtain the microstructures of the synthesized polymers. The membranes exhibit increased water uptake from 8% to 66%, ion exchange capacities from 0.41 to 2.18 meq/g and proton conductivities (25°C) from 0.012 to 0.102 S/cm with the degree of sulfonation increasing. The proton conductivities of bi A‐SPAES‐6 membrane (0.10–0.15 S/cm) with high‐sulfonated degree are higher than that of Nafion 117 membrane (0.095–0.117 S/cm) at all temperatures (20–100°C). Especially, the methanol diffusion coefficients of membranes (1.7 × 10^?8 cm²/s–8.5 × 10^?7 cm²/s) are much lower than that of Nafion 117 membrane (2.1 × 10^?6 cm²/s). The new synthesized copolymer was therefore proposed as a candidate of material for PEM in direct methanol fuel cell. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of sulfonated block‐graft copolyimide/sulfonated polybenzimidazole blend membranes for fuel cell application

Polymer electrolyte blend membranes composed of sulfonated block‐graft polyimide (S‐bg‐PI) and sulfonated polybenzimidazole (sPBI) were prepared and characterized. The proton conductivity and oxygen permeability coefficient of the novel blend membrane S‐bg‐PI/sPBI (7 wt%) were 0.38 S cm^?1 at 90 °C and 98% relative humidity and 7.2 × 10^?13 cm³(STP) cm (cm² s cmHg)^?1 at 35 °C and 76 cmHg, respectively, while those of Nafion^® were 0.15 S cm^?1 and 1.1 × 10^?10 cm³(STP) cm (cm² s cmHg)^?1 under the same conditions. The apparent (proton/oxygen transport) selectivity calculated from the proton conductivity and the oxygen permeability coefficient in the S‐bg‐PI/sPBI (7 wt%) membrane was 300 times larger than that determined in the Nafion membrane. Besides, the excellent gas barrier properties based on an acid ? base interaction in the blend membranes are expected to suppress the generation of hydrogen peroxide and reactive oxygen species, which will degrade fuel cells during operation. The excellent proton conductivity and gas barrier properties of the novel membranes promise their application for future fuel cell membranes. © 2015 Society of Chemical Industry     

Nafion‐115/aromatic poly(etherimide) with isopropylidene groups/imidazole membranes for polymer fuel cells

Proton exchange membrane fuel cells (PEMFCs) with Pt/C gas diffusion electrodes and graphite single‐serpentine monopolar plates were constructed based on an aromatic poly(etherimide) with isopropylidene groups (PI)/imidazole (Im) and a popular Nafion‐115 matrix. The electrochemical properties of PEMFCs were tested at 25 and 60°C. The maximum power density of 171 mW/cm² and the maximum current density of 484 mA/cm² were detected for Nafion‐115/PI membrane. For both constructed PEMFCs the efficiency at 0.6 V was found about 41%. Immersion of Nafion‐115 in PI or PI/Im increased the thermal stability and mechanical properties of membranes. Thermal, mechanical properties and morphology of membranes were characterized by TGA, and AFM techniques including force spectroscopy. Interactions between the components in composite membranes were established by FT‐IR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42436.     

SPES‐SiO2 hybrid proton exchange membranes from in situ sol–gel process of negatively charged alkoxysilane

One type of negatively charged alkoxysilane, that is, sulfonated 3‐(mercaptopropyl)trimethoxysilane (SMPTS), has been developed from 3‐(mercaptopropyl)trimethoxysilane (MPTS) and hydrogen peroxide. SMPTS is used to modify sulfonated poly(ether sulfone) (SPES) through in situ sol–gel process. The membranes with proper SMPTS dosage show enhanced ion exchange capacity (IEC), hydrophilicity, mechanical strength, chemical stability, and proton conductivity, which prove that SMPTS is an effective modifier for preparing proton‐exchange hybrid membranes. With MPTS of 5–20%, the hybrid membranes exhibit IEC 1.34–1.50 mmol g^?1, thermal stability 264–316°C, and proton conductivity 0.0015–0.0102 S cm^?1 and thus recommended for potential application in fuel cells. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Free‐standing hybrid anion‐exchange membranes for application in fuel cells

A series of free‐standing hybrid anion‐exchange membranes were prepared by blending brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (BPPO) with poly(vinylbenzyl chloride‐co‐γ‐methacryloxypropyl trimethoxy silane) (poly(VBC‐co‐γ‐MPS)). Apart from a good compatibility between organic and inorganic phases, the hybrid membranes had a water uptake of 32.4–51.8%, tensile strength around 30 MPa, and T_d temperature at 5% weight loss around 243–261°C. As compared with the membrane prepared from poly (VBC‐co‐γ‐MPS), the hybrid membranes exhibited much better flexibility, and larger ion‐exchange capacity (2.19–2.27 mmol g^?1) and hydroxyl (OH^?) conductivity (0.0067–0.012 S cm^?1). In particular, the hybrid membranes with 60–75 wt % BPPO had the optimum water uptake, miscibility between components, and OH^? conductivity, and were promising for application in fuel cells. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel crosslinked AB‐type polyphenylquinoxaline membranes for high‐temperature proton exchange membrane fuel cells

AB‐type polyphenylquinoxaline (ABPPQ) membranes exhibit great mechanical properties and thermal properties for high‐temperature proton exchange membranes (PEMs). However, they dissolve in high‐concentration phosphoric acid (PA) during acid doping. In order to improve the PA resistant of ABPPQ, crosslinked ABPPQ membranes were prepared using sulfuric acid. The crosslinked ABPPQ membranes showed high PA resistance. The acid content of PA‐doped membranes decreased slightly with crosslinking, but the crosslinked polyphenylquinoxaline (CPPQ)‐20 membrane could reach 2.5 × 10^?2 S/cm proton conductivity at 160°C. Membrane electrode assemblies were fabricated with an active area of 4 cm² and Pt loading of 1 mg/cm². A startup and shutdown test (operated at 150°C with 0.2 A/cm² for 12 h and then 12 h off at room temperature) and a 30‐day long‐term durability test (150°C with 0.2 A/cm²) were conducted. In the startup and shutdown test, the crosslinked membranes showed a low open‐circuit voltage decay rate of 0.15 mV/h. In the 30‐day long‐term durability test, the voltage decay rate was 0.039 mV/h. In both tests, the crosslinked membranes showed a stable performance. Therefore, the crosslinked ABPPQ membranes can be regarded as a novel material for high‐temperature PEM fuel cells. POLYM. ENG. SCI., 59:2169–2173, 2019. © 2019 Society of Plastics Engineers     

Adsorption of CO2+ by stylene‐g‐polyethylene membrane bearing sulfonic acid groups modified by radiation‐induced graft copolymerization

Cation‐exchange hollow fiber membrane was prepared by radiation‐induced grafting polymerization of styrene onto polyethylene hollow fiber membrane and its sulfonation. Adsorption characteristics for the cation‐exchange membranes are examined when the solution of Co²⁺ permeates across the cation‐exchange fiber membrane. The maximum grafting peak was obtained from 70% styrene concentration at 50°C. The degree of grafting (%) was enhanced with additives such as H₂SO₄ and divinylbenzene. The content of  SO₃H groups ranged from 2 to 5 mmol g⁻¹ with chlorosulfonic acid (ClSO₃H) in dichloroethane, from 0.5 to 6 mmol g⁻¹ with ClSO₃H in H₂SO₄, respectively. The adsorption of Co²⁺ by the cation‐exchange membranes increased with increasing  SO₃H content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2227–2235, 1999