SPEEK Membrane Research Articles

Recent Progresses and Challenges to Determine Properties of Sulfonated Polyether Ether Ketone Based Electrolytes for Direct Methanol Fuel Cell Applications

AbstractThis review focuses on fillers, modifications, and methods used in the preparation and development of sulfonated poly(ether ether ketone) (sPEEK) membranes, specifically for direct methanol fuel cell (DMFC) applications as proton exchange membranes in recent years. The primary objective is to evaluate recent advancements by emphasizing key characteristics such as water uptake and swelling capacity, ionic conductivity, methanol permeability, and single cell polarization tests. Additionally, the review aims to provide insights for future researchers by discussing the preparation processes of electrolytes. It presents basic characterizations of membrane electrolytes, including evaluations of the sulfonation degree and ion exchange capacities of sPEEK. High performance of membrane electrolytes is essential for commercialization and to compete with established membranes like Nafion®, which has a perfluorosulfonic acid structure. Therefore, the review also covers detailed characterization methods for assessing long‐term stability when available in the related studies. Numerical results and indicators are categorized and tabulated for easy interpretation and comparative analysis.

Enhanced selectivity of SPEEK membrane incorporated covalent organic nanosheet crosslinked graphene oxide for vanadium redox flow battery

It is difficult for sulfonated poly(ether ether ketone) (SPEEK) to possess both high proton conduction and vanadium resistance owing to the degree of sulfonation. Herein, the composite membranes (S/GO-TpTG) with cationic covalent organic nanosheet (TpTG) crosslinked graphene oxide (GO-TpTG) are prepared to enhance selectivity by optimizing the ion transport channels. The GO-TpTG can efficiently transport protons utilizing its cationic porous structure and acid-base pairs' interaction with SPEEK. Meanwhile, it can block vanadium ions through the Donnan exclusion and physical blocking effects. The S/GO-TpTG membrane with 3 wt% GO-TpTG exhibits excellent proton conductivity (82.7 mS cm−1) and selectivity (77.9 × 10−7 cm2 min−1). The VRFB with this membrane exhibits excellent energy efficiency (88.6–81.0 % at 100–200 mA cm−2), cycle durability, and self-discharge time (209.8 h). This study confirms the great potential of GO-COF to balance proton conductivity and vanadium resistance, and provides an effective strategy to optimize proton channels.

High proton conductivity of sulfonate-amine ionic HOFs and enhancement of SPEEK composite membranes.

Hydrogen-bonded organic frameworks (HOFs) are crystalline materials assembled by intermolecular hydrogen-bonding interactions, and their hydrogen-bonding structures are effective pathways for proton transport. Herein, we synthesize iHOF-45 using 4,4'-diaminodiphenylmethane and 1,3,6,8-pyrenetetrasulfonicacid sodium salt with 2D hydrogen-bonding networks. The introduction of ionic bond based on the weak hydrogen-bonding force was employed to enhance the stability of ionic HOFs (iHOFs). Thermal analyses demonstrated that iHOF-45 exhibited excellent thermal stability up to 332 °C. The proton conductivity of iHOF-45 was evaluated, demonstrating a notable increase with rising temperature and RH. At 100 °C and 98% RH, the conductivity reached 5.25 × 10-3 S cm-1. The activation energy (Ea) of iHOF-45 was calculated to be 0.281 eV for 98% RH, and the proton conduction was attributed to the Grotthuss mechanism, whereby the protons were transported in 2D hydrogen-bonding networks. Moreover, iHOF-45 was doped into SPEEK to prepare composite membranes, the proton conductivity of the 15%-iHOF-45/SPEEK membrane reached 9.52 × 10-2 S cm-1 at 80 °C and 98% RH, representing a 45.1% increase over that of the SPEEK. This suggests that doping enhances the proton conductivity of SPEEK and providing a reference for the development of high proton conductivity materials.

High durable SPEEK/TiO2 nanopaper composite membrane for vanadium redox flow battery

Sulfonated poly (ether ether ketone) (SPEEK) ion exchange membranes for VRFB are promising alternatives to Nafion, but require improved mechanical and chemical stability for long-term operation. Here, we have fabricated composite membranes using SPEEK as proton conductive medium and TiO2 nanopapers as reinforcing framework to improve the mechanical and chemical stabilities of SPEEK membranes. The SPEEK/TiO2 nanopaper composite membranes exhibited almost twice the tensile strength and only one-third the vanadium ion permeability compared to pristine SPEEK (DS=60 %). Due to the excellent cell performance such as high EE, slow capacity degradation and long-term lifetime, these high durable composite membranes could be found their potential use as ion exchange membranes for commercial VRFBs.

High-performance SPEEK membrane with polydopamine-bridged PTFE nanoparticles for vanadium redox flow batteries

With the growing demand of energy storage techniques in carbon-neutral environments, vanadium redox flow batteries (VRFBs) have emerged as outstanding systems for long-duration energy storage. Developing high-performance ion exchange membrane is essential for broad deployment of RFBs. In this work, a SPEEK/PTFE membrane is designed by incorporating polytetrafluoroethylene (PTFE) nanoparticles into sulfonated poly (ether ether ketone) (SPEEK) membrane by bio-inspired polydopamine (PDA) bridge. PDA combines SPEEK membrane and hydrophobic PTFE nanoparticle tightly by its abundant functional groups. The ion selectivity of optimal SPEEK/PTFE-0.5 % membrane is 8.9 times greater than that of Nafion 115. Remarkably, VRFB with optimal SPEEK/PTFE-0.5 % membrane exhibits excellent battery performances including impressive columbic efficiency (CE, 99.5 %) and energy efficiency (EE, 86.3 %) at 100 mA cm−2 surpassing Nafion 115 (CE, 95.8 %; EE, 83.4 %). Besides, VRFB employing SPEEK/PTFE-0.5 % membrane demonstrates excellent cycling stability, with higher capacity retention (71.4 % after 300 cycles) compared to Nafion 115, indicating its capability of extended operation. This work illustrates that the design of PDA bridge in composite membrane is a useful approach for developing high-performance membranes in RFBs.

Breaking the trade-off between proton conductivity and mechanical stability through liquid-crystal-modified aramid fibers in sulfonated polyether ether ketone membranes

In the quest for sustainable and high-performance hydrogen fuel cells, proton exchange membranes (PEMs) stand as a pivotal research focus. To overcome the significant challenge posed by the traditional trade-offs between proton conductivity and mechanical stability, this work introduces liquid-crystal-modified aramid fibers (DBAF) with highly ordered molecular arrangements and abundant sulfonic acid groups on the side chains as proton-hopping sites into a sulfonated poly (ether ether ketone) (SPEEK) matrix. The inclusion of components not only improves the proton conductivity of the membrane, but also boosts its mechanical strength. The results of our study demonstrate that the externally attached sulfonic acid groups create extra channels for the transport of protons. Additionally, the organized and consistently stable hydrogen-bond network enables the Grotthuss transport mechanism within the SPEEK membrane. The 1 wt% DBAF-SPEEK composite membrane exhibits a maximum proton conductivity of 0.23 S cm−1 at 80 °C, representing a 64% increase over the baseline SPEEK membrane's 0.14 S cm−1. Simultaneously, the tensile strength at normal room temperature is 39.7 MPa, exhibiting an improvement of 86% compared to the initial value of 21.3 MPa. Additionally, the swelling ratio is lowered by 18.69%. Compared with the baseline membrane, the DBAF-enhanced SPEEK composite membrane exhibits superior mechanical stability and proton conductivity within a moderate temperature range (30–80 °C). Consequently, this work offers valuable insights for the development of novel proton-conductive materials.

Performance of high sulfonated poly(ether ether ketone) improved with microcrystalline cellulose and 2,3-dialdehyde cellulose for proton exchange membranes

Sulfonated poly (ether ether ketone) (SPEEK) has received substantial attention for its potential to improve the electrochemical behavior and thermomechanical capabilities of direct methanol fuel cells. This study examines how the integration by solution casting of microcrystalline cellulose (MCC) and 2,3-dialdehyde cellulose (DAC) onto highly sulfonated PEEK (with a sulfonation degree of 80%) affects its physicochemical properties and morphological structures. The mechanical attributes and proton conductivity of the polymer matrix are impacted by MCC and DAC inclusion into SPEEK membrane. The maximum proton conductivity was seen in the SPEEK/MCC membranes at 70 °C (up to 0.1 S cm−1). The proton conductivity in methanol vapor was increased by SPEEK/DAC membranes at high temperatures as opposed to pristine SPEEK and SPEEK/MCC membranes.

Comparative study of random and block SPEEK copolymers for high-temperature proton exchange membrane electrolysis

Traditionally, High-temperature proton Exchange Membrane Electrolysis (HT-PEME) has relied on costly and exceptionally hydrogen-permeable PFSA ionomers like Nafion®, Flemion®, and Aciplex®. Sulfonated Poly (ether ether ketone) (SPEEK) membranes have been developed as potential substitutes for the highly hydrogen permeable Nafion® membranes. The ion exchange capacity (IEC) of SPEEK membranes has been varied, ranging from 0.5 to 2.2 meq/g, to enhance their performance. Furthermore, the incorporation of ion-conducting units into these polymers is explored using both random and block copolymerization approaches. At 75 °C, SPEEK membranes exhibit significantly lower hydrogen diffusivity (35–50 barriers) compared to Nafion® and Flemion® membranes (∼202 barriers). Among SPEEK yttria-stabilized zirconia membranes (YSZM), those produced through random copolymerization exhibit marginally greater proton-to-hydrogen selectivity than YSZM derived from block SPEEK copolymers with a similar ion exchange capacity (IEC). This could be ascribed to the improved hydrogen-blocking capability resulting from an underdeveloped hydrophilic component. Among the SPEEK membranes tested, the random SPEEK membrane with an IEC of approximately 1.9 meq/g demonstrates superior performance (6.8 A/cm2) compared to a similarly thick (∼45 μm) Flemion® membrane (4.4 A/cm2) at 2.2 V. However, during an accelerated stress test involving 410 successive fluctuating flow densities of 2.8 and 0.04 A/cm2 imitating the alternating period's cycles of a water electrolyzer, the random SPEEK membrane exhibits a higher degradation rate (860 μV/h) compared to Flemion® and Nafion® (505 μV/h).

Nucleobase-mediated hydrogen bonding crosslinked highly sulfonated poly(ether ether ketone) electrodialysis membranes for efficient waste acid recovery

Electrodialysis is a promising technology for waste acid recovery with the advantages of low energy consumption and high efficiency. In this work, two nucleobase-modified highly sulfonated poly(ether ether ketone) with adenine (SPEEK-50A) and thymine (SPEEK-50T) were successfully synthesized. Then, a series of blending SPEEK-50Ax/50Ty membranes with varying molar ratios of these two functionalized SPEEKs were fabricated by solution casting. The hydrogen bonding crosslinked structure of ‘A-T base pairs’, as well as the acid-base interactions between the incorporated nucleobases and SO3H groups of the polymer backbone, not only enhanced the mechanical properties and thermal stability of the blending membranes, but more importantly, it successfully addressed the over-swelling issue of highly sulfonated SPEEK membrane. The SPEEK-50Ax/50Ty membranes exhibited tensile strengths between 59.3 and 72.3 MPa, which is 2.2–2.6 times that of the pristine SPEEK membrane. And the water uptake of the blending membranes reduced from 116 % to 14.6–19.2 %, while the swelling ratio decreased from 27.1 % to 5.86–6.60 %. The proton affinity of the multiple basic N atoms in nucleobases, as well as the ‘A-T base pairs’ hydrogen bonding network and acid-base interactions between nucleobases and SO3H groups, all can serve as effective proton transport channels. Additionally, the charge repulsion effect of protonated nucleobases and the crosslinking structure is beneficial to the permselectivity. Therefore, the fabricated blending SPEEK-50Ax/50Ty membranes exhibited superior H+ flux (1.66–1.73 mmol m−2 s−1) and enhanced H+/Fe2+ permselectivity (40.3–43.2). The SPEEK-50A0.5/50T0.5 membrane demonstrated a H+ flux of 1.70 mmol m−2 s−1 and a H+/Fe2+ permselectivity of 43.2, which is 2.8 times that of the pristine SPEEK membrane, surpassing both commercially available and recently reported membranes. Therefore, the nucleobase-modified blending SPEEK-50Ax/50Ty membranes might be potential candidates for the efficient recovery of acid from pickling wastewater.

Zwitterion-functionalized nanofiber-based composite proton exchange membranes with superior ionic conductivity and chemical stability for direct methanol fuel cells

Proton exchange membranes with high ionic conductivity and good chemical stability are critical for achieving high power density and long lifespan of direct methanol cells (DMFCs). Herein, a zwitterionic molecule was grafted onto the surface of polyvinylidene fluoride (PVDF) nanofibers to obtain functionalized PVDF porous substrate (SBMA-PDA@PVDF). Then, sulfonated poly(ether ether ketone) (SPEEK) was filled into the pores of SBMA-PDA@PVDF, and further ionic cross-linked via H2SO4 to prepare the composite membrane (SBMA-PDA@PVDF/SPEEK). The basic groups on the zwitterionic interface could not only establish ionic cross-linking with SPEEK to increase chemical stability and reduce swelling, but also serve as the adsorption sites for subsequent H2SO4 cross-linking to significantly enhance proton conductivity. Super-high proton conductivity (165.34 mS cm−1, 80 °C) was achieved for the membrane, which was 2.12 times higher than that of the pure SPEEK. Moreover, the SBMA-PDA@PVDF/SPEEK membrane exhibited remarkably improved oxidative stability of 91.6 % mass retention after soaking in Fenton’s agent for 12 h, while pure SPEEK completely decomposed. Satisfactorily, the DMFC assembled with SBMA-PDA@PVDF/SPEEK exhibited a peak power density of 99.01 mW cm−2, which was twice as much as that of commercial Nafion 212 (48.88 mW cm−2). After 235 h durability test, only 11 % voltage loss was observed.

Synthesis, Characterization, and Fabrication of Nickel Metal-Organic Framework-Incorporated Polymer Electrolyte Membranes for Fuel-Cell Applications.

Proton-conducting sulfonated polymer metal-organic framework (MOF)-based composite membranes were synthesized by anchoring the nickel MOF (Ni-MOF) to the aromatic sulfonated polymer backbone. In this work, we sulfonated two different polymers, poly(1,4-phenylene ether ether sulfone) (PEES) and poly ether ether ketone (PEEK), with a controllable sulfonation degree, and the synthesized Ni-MOF was incorporated into the sulfonated polymers to prepare a polymer electrolyte membrane. The effect of an MOF as a pendant moiety on the polymer backbone had a significant effect on properties such as water uptake, thermal, mechanical, and oxidative stabilities, swelling ratio, ion-exchange capacity (IEC), morphology, proton conductivity, and fuel-cell performance. The presence of an MOF structure enhanced the water retention capacity of the composite membranes. Adding Ni-MOF to the composite membrane improved the fuel-cell performance by increasing the OCV and power density. Among the synthesized electrolytes, the 3 wt % Ni-MOF-incorporated sPEEK membrane displayed a power density of 319 mW/cm2 with a cell voltage of 0.79 V, which was higher than the pure sulfonated polymer. Thus, the developed composite membranes are suitable for fuel-cell applications.

Tungsten oxide embedded graphene oxide doped with SPEEK composite membrane for zinc–bromine redox flow batteries

Zinc-bromine redox flow batteries (Zn/Br2 RFBs) are fingerprint candidates for large-scale energy storage applications owing to their low cost, flexibility, high energy density, and astonishing round-trip efficiency. However, during the charging and discharging process, the diffusion of bromine through the porous membrane creates significant capacity decay and reduces the membrane efficiency of Zn/Br2 RFBs. In this respect, we developed various amounts of tungsten trioxide (WO3) nanoparticle-decorated graphene oxide (WO3@GO)-loaded sulfonated poly (ether ether ketone) (SPEEK) membranes and investigated their Zn/Br2 redox flow battery performance. The optimum amount of WO3@GO-loaded WO3@GO/SPEEK-3 membrane exhibits higher mechanical stability and ionic conductivity, significantly restricting the bromine crossover through the membrane. Due to their higher hydrophilic ability and uniform dispersion, WO3-loaded GO nanosheets provide strong interaction between the sulfonic acid group of the SPEEK membrane, which acts as an effective barrier for bromine crossover and significantly alters the Zn/Br2 battery performance. As a result, at a current density of 40 mA cm−2, the Zn/Br2 single cell of the WO3@GO/SPEEK-3 demonstrated higher coulombic efficiency (96.6 %), voltage efficiency (89.6 %), and energy efficiency (86.6 %), better than the WO3@GO/SPEEK-5 and pristine SPEEK membranes. These performances indicate that the proposed low-cost WO3@GO/SPEEK membrane can be highly applicable to other energy-related fields, including fuel cells and water treatment.

Homogeneous-strengthened SPEEK membrane with ultrahigh conductivity regulated by main/side-chain bisulfonated PEEK for vanadium flow battery

A comblike polymer (SPOS) with a main/side-chain bisulfonated structure has been synthesized with 1,3-propane sulfonate as the pendant chains and poly (ether ketone) (PEEK) as the reactant by the combined post-sulfonation and ring-opening grafting reaction. Taking sulfonated PEEK as a membrane matrix, the composite membranes (S/SPOS) are prepared by the solution-blending method with varied contents of bisulfonic SPOS polymer from 10 to 25 wt%. The S/SPOS composite membranes display superior conductivity owing to synergistic enhancement in the intermolecular chain interactions and the homogeneous strengthened transportation channels from main/side-chain bisulfonic acid interconnected networks. S/SPOS-15 shows better CE (96.5–98.5 %) and EE (84.7–69.9 %) than that of Nafion 212 (CE: 92.3–95.0 %, EE: 76.1–63.7 %) at 100–200 mA cm−2. Moreover, 600-cycled durability and 77.3 % EE at 150 mA cm−2, and 71.8 h self-discharge time demonstrate its improved reliable structure and cyclic stability. This provides a promising method to prepare high-performance and low-cost membranes with desirable conductivity by homogeneous structural regulation and molecular chain synergistic interactions.

Carbon black-coated SPEEK membrane for efficient vanadium flow batteries

Ion exchange membrane is a key component of vanadium flow batteries (VFB). Development of low-cost and high ion selectivity membrane is essential to promote practical application of VFB. Here we report a kind of carbon-coated membrane by spraying coating Super P/polyvinylidene fluoride slurries on the surface of sulfonated poly(ether ether ketone) membrane (SPEEK/SP@PVDF). The SP attached to the membrane surface or infiltrated into the membrane matrix can synergistically promote the transport of protons while inhibiting the penetration of vanadium ions. In addition, the surface SP@PVDF layer can effectively shield the strong oxidizing VO2+ in the posolyte. As a result, the VFB with the optimized SPEEK/SP@PVDF membrane demonstrates a stable energy efficiency of >80 % at 200 mA cm−2 and a peak power density of 1073.79 mW cm−2 at 1300 mA cm−2, indicating the great potential of this carbon black-coated membrane for potential application in VFB.

Enhanced proton conductivity of sulfonated poly(ether ether ketone) membranes by constructing cation‐π through doping ammonium ionic liquid and graphene oxide

AbstractIn this paper, sulfonic acid functionalized benzothiazole ionic liquid ([(CH2)3SO3HBth] [H2PO4]) and graphene oxide were combined together through the cation‐π. The sulfonated poly (ether ether ketone) was doped with ionic liquid‐modified GO (IL‐GO) to prepare the SPEEK/IL‐GO composite membrane through the solution casting method. The SO3H and benzothiazole rings act as both proton acceptors and proton donors during proton transport and can replace the role of water in medium‐ and high‐temperature environments, increasing the proton transport sites to a certain extent and increasing the proton conductivity of the SPEEK/IL‐GO composite membrane. The proton conductivity of the SPEEK/IL‐GO‐2 composite membrane achieved an 18.02 mS/cm at 120°C, which is 2.43 times higher than that of the pristine SPEEK membrane. This paper provided a method for increasing proton conductivity and limiting IL loss of the SPEEK membrane.Highlights [(CH2)3SO3HBth][H2PO4] and graphene oxide were combined through cation‐π. The benzothiazole ring and SO3H form acid–base pairs. The proton conductivity of SPEEK/IL‐GO‐2 membrane achieved 18.02 mS/cm.

Charge-Gradient Sulfonated Poly(ether ether ketone) Membrane with Enhanced Ion Selectivity for Osmotic Energy Conversion.

Engineered asymmetric heterogeneous ion-selective membranes have become a focal point for their improved efficiency in harnessing osmotic energy from ionic solutions with varying salinity. However, achieving both energy conversion efficiency and excellent chemical stability necessitates effectively mitigating the formation of detrimental interface cracks between two different layers. We develop a charge-gradient sulfonated poly(ether ether ketone) (SPEEK) membrane (CG-SPEEK) on a large-scale using a straightforward coating method. As an osmotic energy generator, CG-SPEEK membrane achieves an impressive output power density of 9.2 W m-2 and exhibits ultrahigh cation selectivity (0.99), with an energy conversion efficiency of 48% at a 50-fold NaCl concentration gradient. The results highlight the ion diode effects of CG-SPEEK, driven by a charge density gradient that accelerates cation transport while suppressing ion concentration polarization. Density functional theory simulations provide further insights, revealing that the energy barrier for Na+ ion transport through CG-SPEEK membrane is lower than that through a homogeneous SPEEK membrane. This work not only enhances our understanding of ion transport dynamics but also establishes the CG-SPEEK membrane as a promising candidate for efficient osmotic energy conversion applications.

Synthesis of potassium-zinc hexacyanoferrate and their SPEEK composite cation exchange membranes for selective recovery of cesium from aqueous system

Potassium-Zinc hexacyanoferrate adsorbent was prepared by precipitation method and further its composite membrane has been fabricated using sulphonated poly (ether ether ketone) (SPEEK) to investigate cesium (Cs+) recovery from aqueous media. The formation of desired adsorbent material was confirmed by Powder X-ray diffraction (PXRD) while chemical structure was assessed by Fourier-transform infrared spectroscopy (FT-IR). The BET surface area, pore volume and pore diameter found as 298.6 m2/g, 0.1034 cm3/g and 3.04 nm respectively calculated by Brunauer and Emmett and Teller (BET) surface area analyzer. The adsorbent synthesized was observed to work efficiently with maximum adsorption capacity of 54.64 mg Cs/g of adsorbent for Langmuir isotherm model. There was no effect of competing ion (Na+, K+, Mg2+, Ca2+) on adsorption performance during Cs+ removal. Cs+ recovery from the aqueous system in presence of 1000 ppm NaCl was performed using SPEEK composite membrane by electrodialysis. Observing the electrodialysis performance, composite membrane exhibited a high removal/recovery for Cs+ ions than Na+, K+, Mg2+ and Ca2+. The composite membrane exhibited a remarkable removal efficiency for Cs+ ion, which is 33.85 times larger than pristine SPEEK membrane. These results confirm composite membrane as promising candidate for the selective recovery/removal of cesium ions from aqueous solution in existence of intrusive ions and can effectively be applicable for industrial applications.

Magnetically aligned composite membranes based on sulfonated poly(ether ether ketone) and phosphotungstic acid-loaded magnetic nanoparticles for fuel cell

In this work, phosphotungstic acid (HPW)-loaded polydopamine-coated magnetic nanoparticles (DMNPs@HPW) were prepared and incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix with magnetic field assistance to construct aligned channels to shorten proton transport pathways. The structure of the prepared composite membranes (M-SP/DMNPs@HPW) with magnetic field-induced proton channels was confirmed by SEM. The proton conductivity of M-SP/DMNPs@HPW-2 was significantly improved, with in-plane proton conductivity (σ//) of 159.3 mS/cm and through-plane proton conductivity (σ⊥) of 129.2 mS/cm in the hydrated state at 80 °C, which were 1.31 and 1.57 times higher than the pristine SPEEK membrane, due to the strong acidity of HPW and acid-base interaction of amine and sulfonic acid groups. Meanwhile, the σ⊥ of M-SP/DMNPs@HPW-2 was 1.14 times higher than that of SP/DMNPs@HPW-2 membrane prepared without magnetic field assistance. The fuel cell power output of M-SP/DMNPs@HPW-2 was 433 mW/cm2, while SP/DMNPs@HPW-2 and pristine SPEEK membranes tested under the same conditions were 360 mW/cm2 and 277 mW/cm2, respectively. The hydrogen crossover of M-SP/DMNPs@HPW-2 was slightly increased compared to SP/DMNPs@HPW-2 due to the construction of through-plane proton transport channels in the membrane.

Electrospinning-assisted construction of rapid proton conduction channels in halloysite nanotube-encapsulated ionic liquid-embedded sulfonated poly(ether ether ketone) proton exchange membranes

The most fatal drawback of traditional sulfonated polymer proton-exchange membranes (PEMs) is their heavy dependence on water molecules to conduct protons, which causes a sharp decrease in their proton conductivity in low-humidity environments. Here, composite membranes were fabricated by electrostatically spinning halloysite nanotube-encapsulated ionic-liquids (IL@HNTs) incorporated into sulfonated poly(ether ether ketone) (SPEEK) (SPEEK/IL@HNTs). Using electrospinning, one-dimensional IL@HNTs ionogels with good water absorption were axially and uniformly aligned along the fiber filament direction. This formed long-range uninterrupted proton conduction pathways that greatly improved the proton conductivity of the composite membrane under various humidity environments. The axially-aligned structure facilitated crystallization, which improved the mechanical properties and thermal stability of the composite membrane. The SPEEK/6IL@HNTs membrane exhibited a through-plane proton conductivity of 139.2 mS cm−1 at 90 °C/98 % RH, representing a significant increase compared with the intrinsic SPEEK membrane. The SPEEK/6IL@HNTs membrane demonstrated a maximum power density of 732 mW cm−2, which exceeded that of the Nafion115 membrane (328 mW cm−2) by a factor of 2.2. It exhibited a single-cell performance equivalent to that of the Nafion212 membrane (723 mW cm−2), demonstrating that this provides a feasible approach to operating fuel cells in low-humidity environments without additional humidification.

Radiation stability of electron beam irradiated high degree sulfonated poly(ether ether ketone) membranes for the applications in nuclear facilities

Sulfonated poly(ether ether ketones) (SPEEK) have raised interest as a replacement of Nafion® proton exchange membranes (PEM) for the application in harsh environments involving material exposure to ionizing radiation, for example, radioactive hydrogen isotope separation from water. This study is dedicated to evaluate the effects of high dose (500 kGy) electron beam irradiation on the physico-chemical and thermomechanical properties of highly sulfonated (degree of sulfonation 60–90 %) SPEEK membranes irradiated in air and water. Spectrometric and thermogravimetric analysis indicated slight changes in the material properties after irradiation with increase of the degree of sulfonation (DS). Tensile tests and thermomechanical analysis of irradiated samples indicated notable deterioration of properties at higher DS values. Results demonstrate that SPEEK membranes with DS around 70 % could be a replacement of the traditional PEM for the applications where exposure to ionizing radiation occurs.