Porous Polyethylene Supports in Reinforcement of Multiblock Hydrocarbon Ionomers for Proton Exchange Membranes.

Hydrocarbon (HC)-based block copolymers have been recognized as promising candidates for proton exchange membranes (PEMs) due to their distinct hydrophilic-hydrophobic separation, which results in improved proton transport compared to that of random copolymers. However, most PEMs derived from HC-based ionomers, including block copolymers, encounter challenges related to durability in electrochemical cells due to their low mechanical and chemical properties. One method for reinforcing HC-based ionomers involves incorporating the ionomers into commercially available low surface tension PTFE porous substrates. Nevertheless, the high interfacial energy between the hydrocarbon-based ionomer solution and PTFE remains a challenge in this reinforcement process, which necessitates the application of surface energy treatment to PTFE. Here, multiblock sulfonated poly(arylene ether sulfone) (SPAES) ionomers are being reinforced using untreated PE on the surface, and this is compared to reinforcement using surface-treated porous PTFE. The PE support layer exhibits a lower surface energy barrier compared to the surface-treated PTFE layer for the infiltration of the multiblock SPAES solution. This is characterized by the absence of noticeable voids, high translucency, gas impermeability, and a physical and chemical stability. By utilizing a high surface tension PE support with a comparable value to the multiblock SPAES, effective reinforcement of the multiblock SPAES ionomers is achieved for a PEM, which is potentially applicable to various hydrogen energy-based electrochemical cells.

Multi-Block Copolymer Membranes Consisting of Sulfonated Poly(p-phenylene) and Naphthalene Containing Poly(arylene Ether Ketone) for Proton Exchange Membrane Water Electrolysis.

Glassy hydrocarbon-based membranes are being researched as a replacement for perfluorosulfonic acid (PFSA) membranes in proton exchange membrane water electrolysis (PEMWE). Here, naphthalene containing Poly(arylene Ether Ketone) was introduced into the Poly(p-phenylene)-based multi-block copolymers through Ni(0)-catalyzed coupling reaction to enhance π-π interactions of the naphthalene units. It is discovered that there is an optimum input ratio of the hydrophilic monomer and NBP oligomer for the multi-block copolymers with high ion exchange capacity (IEC) and polymerization yield. With the optimum input ratio, the naphthalene containing copolymer exhibits good hydrogen gas barrier property, chemical stability, and mechanical toughness, even with its high IEC value over 2.4 meq g-1. The membrane shows 3.6 times higher proton selectivity to hydrogen gas than Nafion 212. The PEMWE single cells using the membrane performed better (5.5 A cm-2) than Nafion 212 (4.75 A cm-2) at 1.9 V and 80 °C. These findings suggest that naphthalene containing copolymer membranes are a promising replacement for PFSA membranes in PEMWE.

Mesoscale Simulation Based on the Dynamic Mean-Field Density Functional Method on Block-Copolymeric Ionomers for Polymer Electrolyte Membranes.

Block copolymers generally have peculiar morphological characteristics, such as strong phase separation. They have been actively applied to polymer electrolyte membranes for proton exchange membrane fuel cells (PEMFCs) to obtain well-defined hydrophilic regions and water channels as a proton pathway. Although molecular simulation tools are advantageous to investigate the mechanism of water channel formation based on the chemical structure and property relationships, classical molecular dynamics simulation has limitations regarding the model size and time scale, and these issues need to be addressed. In this study, we investigated the morphology of sulfonated block copolymers synthesized for PEM applications using a mesoscale simulation based on the dynamic mean-field density functional method, widely applied to investigate macroscopic systems such as polymer blends, micelles, and multi-block/grafting copolymers. Despite the similar solubility parameters of the monomers in our block-copolymer models, very different morphologies in our 3D mesoscale models were obtained. The model with sulfonated monomers, in which the number of sulfonic acid groups is twice that of the other model, showed better phase separation and water channel formation, despite the short length of its hydrophilic block. In conclusion, this unexpected behavior indicates that the role of water molecules is important in making PEM mesoscale models well-equilibrated in the mesoscale simulation, which results in the strong phase separation between hydrophilic and hydrophobic regions and the ensuing well-defined water channel. PEM synthesis supports the conclusion that using the sulfonated monomers with a high sulfonation degree (32.5 mS/cm) will be more effective than using the long hydrophilic block with a low sulfonation degree (25.2 mS/cm).

Aluminum Diethylphosphinate-Incorporated Flame-Retardant Polyacrylonitrile Separators for Safety of Lithium-Ion Batteries.

Herein, we developed polyacrylonitrile (PAN)-based nanoporous composite membranes incorporating aluminum diethylphosphinate (ADEP) for use as a heat-resistant and flame-retardant separator in high-performance and safe lithium-ion batteries (LIBs). ADEP is phosphorus-rich, thermally stable, and flame retardant, and it can effectively suppress the combustibility of PAN nanofibers. Nanofibrous membranes were obtained by electrospinning, and the content of ADEP varied from 0 to 20 wt%. From the vertical burning test, it was demonstrated that the flame retardancy of the composite membranes was enhanced when more than 5 wt% of ADEP was added to PAN, potentially increasing the safety level of LIBs. Moreover, the composite membrane showed higher ionic conductivity and electrolyte uptake (0.83 mS/cm and 137%) compared to those of commercial polypropylene (PP) membranes (Celgard 2400: 0.65 mS/cm and 63%), resulting from interconnected pores and the polar chemical composition in the composite membranes. In terms of battery performance, the composite membrane showed highly stable electrochemical and heat-resistant properties, including superior discharge capacity when compared to Celgard 2400, indicating that the PAN/ADEP composite membrane has the potential to be used as a heat-resistant and flame-retardant separator for safe and high-power LIBs.

Alcohol-Treated Porous PTFE Substrate for the Penetration of PTFE-Incompatible Hydrocarbon-Based Ionomer Solutions.

For a mechanically tough proton exchange membrane, a composite membrane incorporated with a porous polymer substrate is of great interest to suppress the ionomer swelling and to improve the dimensional stability and mechanical strength of the ionomers. For the composite membranes, good impregnation of substrate-incompatible ionomer solution into the substrate pores still remains one of the challenges to be solved. Here, we demonstrated a facile process (surface treatment with solvents compatible with both substrate and the ionomer solution) for the fabrication of the composite membranes using polytetrafluoroethylene (PTFE) as a porous substrate and poly(arylene ether sulfone) (SPAES) as a hydrocarbon-based (HC) ionomer. Appropriate solvents for the surface treatment were sought through the contact angle measurement, and it was found that alcohol solvents effectively tuned the surface property of PTFE pores to facilitate the penetration of the SPAES/N-methyl-2-pyrrolidone (NMP) solution into ∼300 nm pores of the substrate. Using this simple alcohol treatment, the SPAES/NMP contact angle was reduced in half, and we could fabricate the mechanically tough PTFE/HC composite membranes, which were apparently translucent and microscopically almost void-free composite membranes.

Reinforced anion exchange membrane based on thermal cross-linking method with outstanding cell performance for reverse electrodialysis.

A poly(ethylene)-reinforced anion exchange membrane based on cross-linked quaternary-aminated polystyrene and quaternary-aminated poly(phenylene oxide) was developed for reverse electrodialysis. Although reverse electrodialysis is a clean and renewable energy generation system, the low power output and high membrane cost are serious obstacles to its commercialization. Herein, to lower the membrane cost, inexpensive polystyrene and poly(phenylene oxide) were used as ionomer backbones. The ionomers were impregnated into a poly(ethylene) matrix supporter and were cross-linked in situ to enhance the mechanical and chemical properties. Pre-treatment of the porous PE matrix membrane with atmospheric plasma increased the compatibility between the ionomer and matrix membrane. The fabricated membranes showed outstanding physical, chemical, and electrochemical properties. The area resistance of the fabricated membranes (0.69-1.67 Ω cm2) was lower than that of AMV (2.58 Ω cm2). Moreover, the transport number of PErC(5)QPS-QPPO was comparable to that of AMV, despite the thinness (51 µm) of the former. The RED stack with the PErC(5)QPS-QPPO membrane provided an excellent maximum power density of 1.82 W m-2 at a flow rate of 100 mL min-1, which is 20.7% higher than that (1.50 W m-2) of the RED stack with the AMV membrane.

Hydrophilic Channel Alignment of Perfluoronated Sulfonic-Acid Ionomers for Vanadium Redox Flow Batteries.

It is known that uniaxially drawn perfluoronated sulfonic-acid ionomers (PFSAs) show diffusion anisotropy because of the aligned water channels along the deformation direction. We apply the uniaxially stretched membranes to vanadium redox flow batteries (VRFBs) to suppress the permeation of active species, vanadium ions through the transverse directions. The aligned water channels render much lower vanadium permeability, resulting in higher Coulombic efficiency (>98%) and longer self-discharge time (>250 h). Similar to vanadium ions, proton conduction through the membranes also decreases as the stretching ratio increases, but the thinned membranes show the enhanced voltage and energy efficiencies over the range of current density, 50-100 mA/cm2. Hydrophilic channel alignment of PFSAs is also beneficial for long-term cycling of VRFBs in terms of capacity retention and cell performances. This simple pretreatment of membranes offers an effective and facile way to overcome high vanadium permeability of PFSAs for VRFBs.

Pore-Size-Tuned Graphene Oxide Frameworks as Ion-Selective and Protective Layers on Hydrocarbon Membranes for Vanadium Redox-Flow Batteries.

The laminated structure of graphene oxide (GO) membranes provides exceptional ion-separation properties due to the regular interlayer spacing ( d) between laminate layers. However, a larger effective pore size of the laminate immersed in water (∼11.1 Å) than the hydrated diameter of vanadium ions (>6.0 Å) prevents its use in vanadium redox-flow batteries (VRFB). In this work, we report an ion-selective graphene oxide framework (GOF) with a d tuned by cross-linking the GO nanosheets. Its effective pore size (∼5.9 Å) excludes vanadium ions by size but allows proton conduction. The GOF membrane is employed as a protective layer to address the poor chemical stability of sulfonated poly(arylene ether sulfone) (SPAES) membranes against VO2+ in VRFB. By effectively blocking vanadium ions, the GOF/SPAES membrane exhibits vanadium-ion permeability 4.2 times lower and a durability 5 times longer than that of the pristine SPAES membrane. Moreover, the VRFB with the GOF/SPAES membrane achieves an energy efficiency of 89% at 80 mA cm-2 and a capacity retention of 88% even after 400 cycles, far exceeding results for Nafion 115 and demonstrating its practical applicability for VRFB.

Polybenzimidazole/Nafion hybrid membrane with improved chemical stability for vanadium redox flow battery application.

In order to increase the chemical stability of polybenzimidazole (PBI) membrane against the highly oxidizing environment of a vanadium redox flow battery (VRFB), PBI/Nafion hybrid membrane was developed by spray coating a Nafion ionomer onto one surface of the PBI membrane. The acid-base interaction between the sulfonic acid of the Nafion and the benzimidazole of the PBI created a stable interfacial adhesion between the Nafion layer and the PBI layer. The hybrid membrane showed an area resistance of 0.269 Ω cm2 and a very low vanadium permeability of 1.95 × 10-9 cm2 min-1. The Nafion layer protected the PBI from chemical degradation under accelerated oxidizing conditions of 1 M VO2 +/5 M H2SO4, and this was subsequently examined in spectroscopic analysis. In the VRFB single cell performance test, the cell with the hybrid membrane showed better energy efficiency than the Nafion cell with 92.66% at 40 mA cm-2 and 78.1% at 100 mA cm-2 with no delamination observed between the Nafion layer and the PBI layer after the test was completed.

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10-3 S cm-1) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g-1 at 0.1 A g-1), better rate capability (64% capacity retention until 20 A g-1), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg-1 at 1 A g-1) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

Three-Dimensional Interlocking Interface: Mechanical Nanofastener for High Interfacial Robustness of Polymer Electrolyte Membrane Fuel Cells.

A scalable nanofastener featuring a 3D interlocked interfacial structure between the hydrocarbon membrane and perfluorinated sulfonic acid based catalyst layer is presented to overcome the interfacial issue of hydrocarbon membrane based polymer electrolyte membrane fuel cells. The nanofastener-introduced membrane electrode assembly (MEA) withstands more than 3000 humidity cycles, which is 20 times higher durability than that of MEA without nanofastener.

Interlocking membrane/catalyst layer interface for high mechanical robustness of hydrocarbon-membrane-based polymer electrolyte membrane fuel cells.

A physical interlocking interface that can tightly bind a sulfonated poly(arylene ether sulfone) (SPAES) membrane and a Nafion catalyst layer in polymer electrolyte fuel cells is demonstrated. Owing to higher expansion with hydration for SPAES than for Nafion, a strong normal force is generated at the interface of a SPAES pillar and a Nafion hole, resulting in an 8-fold increase of the interfacial bonding strength at RH 50% and a 4.7-times increase of the wet/dry cycling durability.

Highly flexible, proton-conductive silicate glass electrolytes for medium-temperature/low-humidity proton exchange membrane fuel cells.

We demonstrate highly flexible, proton-conductive silicate glass electrolytes integrated with polyimide (PI) nonwoven fabrics (referred to as "b-SS glass electrolytes") for potential use in medium-temperature/low-humidity proton exchange membrane fuel cells (PEMFCs). The b-SS glass electrolytes are fabricated via in situ sol-gel synthesis of 3-trihydroxysilyl-1-propanesulfonic acid (THPSA)/3-glycidyloxypropyl trimethoxysilane (GPTMS) mixtures inside PI nonwoven substrates that serve as a porous reinforcing framework. Owing to this structural uniqueness, the b-SS glass electrolytes provide noticeable improvements in mechanical bendability and membrane thickness, in comparison to typical bulk silicate glass electrolytes that are thick and easily fragile. Another salient feature of the b-SS glass electrolytes is the excellent proton conductivity at harsh measurement conditions of medium temperature/low humidity, which is highly important for PEMFC-powered electric vehicle applications. This beneficial performance is attributed to the presence of a highly interconnected, proton-conductive (THPSA/GPTMS-based) silicate glass matrix in the PI reinforcing framework. Notably, the b-SS glass electrolyte synthesized from THPSA/GPTMS = 9/1 (mol/mol) exhibits a higher proton conductivity than water-swollen sulfonated polymer electrolyte membranes (here, sulfonated poly(arylene ether sulfone) and Nafion are chosen as control samples). This intriguing behavior in the proton conductivity of the b-SS glass electrolytes is discussed in great detail by considering its structural novelty and Grotthuss mechanism-driven proton migration that is strongly affected by ion exchange capacity (IEC) values and also state of water.