Fatigue-Resistant Polymer Electrolyte Membranes for Fuel Cells.

In a hydrogen fuel cell, an electrolyte membrane conducts protons, but blocks electrons, hydrogen molecules, and oxygen molecules. The fuel cell often runs unsteadily, resulting in fluctuating water production, causing the membrane to swell and contract. The cyclic deformation can cause fatigue crack growth. This paper describes an approach to develop a fatigue-resistant polymer electrolyte membrane. The membrane is prepared by forming an interpenetrating network of a plastic electrolyte and a rubber. The former conducts protons, and the latter enhances fatigue resistance. The introduction of the rubber modestly reduces electrochemical performance, but significantly increases fatigue threshold and lifespan. Compared to pristine plastic electrolyte, Nafion, an interpenetrating network of Nafion and perfluoropolyether (PFPE) reduces the maximum power density by 20%, but increases the fatigue threshold by 175%. Under the wet/dry accelerated stress test, the fuel cell with the Nafion-PFPE membrane has a lifespan 1.7 times that of a fuel cell with the Nafion membrane.

Oil-gated isoporous membrane with micro-apertures for controllable pressure-induced passive flow regulator.

The pressure-driven liquid flow controller is one of the key components in diverse applications including microfluidic systems, biomedical drug injection devices, and pressurized water supply systems. Electric feedback loop based flow controllers are fine-tunable but expensive and complex. The conventional safety valves based on spring force are simple and low cost, but their diverse application is limited due to their fixed pressure range, size, and shape. Herein, we propose a simple and controllable liquid-flowing system combining a closed liquid reservoir and an oil-gated isoporous membrane (OGIM). The ultra-thin and flexible OGIM acts as an immediately responsive and precisely controlled gas valve to maintain internal pneumatic pressure as designed to induce constant liquid flow. The oil filling apertures act as a gate for gas flow depending on the applied pressure and the threshold (gating) pressure of the gate is determined by the surface tension of the oil and the gate diameter. It is confirmed that the gating pressure is precisely controlled by varying the gate diameter, which agrees with the theoretically estimated pressures. Based on stably maintained pressure due to the function of OGIM, the constant liquid flow rate is achieved even with the high gas flow rate.

Multiscale Architectured Membranes, Electrodes, and Transport Layers for Next-Generation Polymer Electrolyte Membrane Fuel Cells.

Over the past few decades, considerable advances have been achieved in polymer electrolyte membrane fuel cells (PEMFCs) based on the development of material technology. Recently, an emerging multiscale architecturing technology covering nanometer, micrometer, and millimeter scales has been regarded as an alternative strategy to overcome the hindrance to achieving high-performance and reliable PEMFCs. This review summarizes the recent progress in the key components of PEMFCs based on a novel architecture strategy. In the first section, diverse architectural methods for patterning the membrane surface with random, single-scale, and multiscale structures as well as their efficacy for improving catalyst utilization, charge transport, and water management are discussed. In the subsequent section, the electrode structures designed with 1D and 3D multiscale structures to enable low Pt usage, improve oxygen transport, and achieve high electrode durability are elucidated. Finally, recent advances in the architectured transport layer for improving mass transportation including pore gradient, perforation, and patterned wettability for gas diffusion layer and 3D structured/engineered flow fields are described.

Oxygen Plasma-Mediated Microstructured Hydrocarbon Membrane for Improving Interface Adhesion and Mass Transport in Polymer Electrolyte Fuel Cells.

Developing a method for fabricating high-efficient and low-cost fuel cells is imperative for commercializing polymer electrolyte membrane (PEM) fuel cells (FCs). This study introduces a mechanical and chemical modification technique using the oxygen plasma irradiation process for hydrocarbon-based (HC) PEM. The oxygen functional groups were introduced on the HC-PEM surface through the plasma process in the controlled area, and microsized structures were formed. The modified membrane was incorporated with plasma-treated electrodes, improving the adhesive force between the HC-PEM and the electrode. The decal transfer was enabled at low temperatures and pressures, and the interfacial resistance in the membrane-electrode assembly (MEA) was reduced. Furthermore, the micropillar structured electrode configuration significantly reduced the oxygen transport resistance in the MEA. Various diagnostic techniques were conducted to find out the effects of the membrane surface modification, interface adhesion, and mass transport, such as physical characterizations, mechanical stress tests, and diverse electrochemical measurements.

Reversible Wrinkling Surfaces for Enhanced Grip on Wet/Dry Conditions.

Friction is important in material design for robotic systems that need to perform tasks regardless of environmental changes. Generally, robotic systems lose their friction in wet environments and fail to accomplish their tasks. Despite the significance of maintaining friction in dry and wet environments, it is still challenging. Here, we report a smart switching surface, which helps to complete missions in both wet and dry environments. Inspired by the reversible wrinkling mechanism of a human finger, the surface reversibly generates and removes wrinkles to adapt to both environments using volume-changing characteristics of the Nafion film. The switchable surfaces with manipulated wrinkle morphologies via patterns of diverse densities, sizes, and shapes induce a relationship between the wrinkle morphologies and friction: wrinkles on denser and smaller hexagonal patterns generate six times more friction than non-switching flat surfaces in wet environments and a similar amount of friction to the flat surfaces in dry environments. In addition, the wrinkle morphologies according to the patterns are predicted through numerical simulation, which is in good agreement with experimental results. This work presents potential applications in robotic systems that are required to perform in and out of water and paves the way for further understanding of wrinkling dynamics, manipulation, and evolutionary function in skin.

Formation of non-base-pairing DNA microgels using directed phase transition of amphiphilic monomers.

Programmability of DNA sequences enables the formation of synthetic DNA nanostructures and their macromolecular assemblies such as DNA hydrogels. The base pair-level interaction of DNA is a foundational and powerful mechanism to build DNA structures at the nanoscale; however, its temperature sensitivity and weak interaction force remain a barrier for the facile and scalable assembly of DNA structures toward higher-order structures. We conducted this study to provide an alternative, non-base-pairing approach to connect nanoscale DNA units to yield micrometer-sized gels based on the sequential phase transition of amphiphilic unit structures. Strong electrostatic interactions between DNA nanostructures and polyelectrolyte spermines led to the formation of giant phase-separated aggregates of monomer units. Gelation could be initiated by the addition of NaCl, which weakened the electrostatic DNA-spermine interaction while attractive interactions between cholesterols created stable networks by crosslinking DNA monomers. In contrast to the conventional DNA gelation techniques, our system used solid aggregates as a precursor for DNA microgels. Therefore, in situ gelation could be achieved by depositing aggregates on the desired substrate and subsequently initiating a phase transition. Our approach can expand the utility and functionality of DNA hydrogels by using more complex nucleic acid assemblies as unit structures and combining the technique with top-down microfabrication methods.

Design Rule for Constructing Buckling-Free Polymeric Stencil with Microdot Apertures.

A polymeric stencil with microdot apertures made by using polydimethylsiloxane (PDMS) molds with pillar patterns has many advantages, including conformal contact, easy processability, flexibility, and low cost compared to conventional silicon-based membranes. However, due to the inherent deformability of PDMS materials in response to external pressure, it is challenging to construct structurally stable stencils with high structural fidelity. Here, we propose a design rule on the buckling pressure for constructing polymeric stencils without process failure. To investigate the critical buckling pressure (Pcr), stencils are fabricated by using different PDMS molds with aspect ratio variations (AR: 1.6, 2.0, 4.0, and 5.3). By observing the buckled morphology of apertures, the structures can be classified into two groups: low (AR 1.6 and 2.0) and high (AR 4.0 and 5.3) AR groups, and Pcr decreases as AR increases in each group. To investigate the results theoretically, the analysis based on Euler's buckling theory and slenderness ratio is conducted, indicating that the theory is only valid for the high-AR group herein. Besides, considering the correction factor, Pcr agrees well with the experimental results.

Investigation on the Microscopic/Macroscopic Mechanical Properties of a Thermally Annealed Nafion® Membrane.

The Nafion® electrolyte membrane, which provides a proton pathway, is an essential element in fuel cell systems. Thermal treatment without additional additives is widely used to modify the mechanical properties of the membrane, to construct reliable and durable electrolyte membranes in the fuel cell. We measured the microscopic mechanical properties of thermally annealed membranes using atomic force microscopy with the two-point method. Furthermore, the macroscopic property was investigated through tensile tests. The microscopic modulus exceeded the macroscopic modulus over all annealing temperature ranges. Additionally, the measured microscopic modulus increased rapidly near 150 °C and was saturated over that temperature, whereas the macroscopic modulus continuously increased until 250 °C. This mismatched micro/macroscopic reinforcement trend indicates that the internal reinforcement of the clusters is induced first until 150 °C. In contrast, the reinforcement among the clusters, which requires more thermal energy, probably progresses even at a temperature of 250 °C. The results showed that the annealing process is effective for the surface smoothing and leveling of the Nafion® membrane until 200 °C.

Artificial Perspiration Membrane by Programmed Deformation of Thermoresponsive Hydrogels.

Thermal management is essential for living organisms and electronic devices to survive and maintain their own functions. However, developing flexible cooling devices for flexible electronics or biological systems is challenging because conventional coolers are bulky and require rigid batteries. In nature, skins help to maintain a constant body temperature by dissipating heat through perspiration. Inspired by nature, an artificial perspiration membrane that automatically regulates evaporation depending on temperature using the programmed deformation of thermoresponsive hydrogels is presented. The thermoresponsive hydrogel is patterned into pinwheel shapes and supported by a polymeric rigid frame with stable adhesion using copolymerization. Both shape of the valve and mechanical constraint of the frame allow six times larger evaporation area in the open state compared to the closed state, and the transition occurs at a fast rate (≈1 s). A stretchable membrane is selectively coated to prevent unintended evaporation through the hydrogel while allowing swelling or shrinking of the hydrogel by securing path of water. Consequently, a 30% reduction in evaporation is observed at lower temperature, resulting in regulation of the skin temperature at the thermal model of human skins. This simple, small, and flexible cooler will be useful for maintaining temperature of flexible devices.

Membrane/Electrode Interface Design for Effective Water Management in Alkaline Membrane Fuel Cells.

The recent development of ultrathin anion exchange membranes and optimization of their operating conditions have significantly enhanced the performance of alkaline-membrane fuel cells (AMFCs); however, the effects of the membrane/electrode interface structure on the AMFC performance have not been seriously investigated thus far. Herein, we report on a high-performance AMFC system with a membrane/electrode interface of novel design. Commercially available membranes are modified in the form of well-aligned line arrays of both the anode and cathode sides by means of a solvent-assisted molding technique and sandwich-like assembly of the membrane and polydimethylsiloxane molds. Upon incorporating the patterned membranes into a single-cell system, we observe a significantly enhanced performance of up to ∼35% compared with that of the reference membrane. The enlarged interface area and reduced membrane thickness from the line-patterned membrane/electrode interface result in improved water management, reduced ohmic resistance, and effective utilization of the catalyst. We believe that our findings can significantly contribute further advancements in AMFCs.

Fabrication and design of mechanically stable and free-standing polymeric membrane with two-level apertures.

Herein, we report the fabrication process and the investigation of mechanically stable, flexible and free-standing polymeric membranes with two-level apertures. By using overlapped oxygen inhibition layers (OILs) with variation in diameters of the micro-sized supporting layer, we successfully fabricated the mechanically stable and free-standing polymeric membrane with micro/nano two-level apertures. The nano aperture membrane was stably sustained on the micro aperture membrane with a diameter of 50 µm and 100 µm, but was torn off in the case of 300 µm and 500 µm sized supporting layers. To analyze the results, we propose a simple model to set the criteria of the geometrical features which are mechanically stable during the demolding process. It is worth noting that an appropriate material modulus, length, and thickness of the membrane are required for designing and achieving the robust free-standing hierarchical polymeric membrane.

Guided cracking of electrodes by stretching prism-patterned membrane electrode assemblies for high-performance fuel cells.

Guided cracks were successfully generated in an electrode using the concentrated surface stress of a prism-patterned Nafion membrane. An electrode with guided cracks was formed by stretching the catalyst-coated Nafion membrane. The morphological features of the stretched membrane electrode assembly (MEA) were investigated with respect to variation in the prism pattern dimension (prism pitches of 20 µm and 50 µm) and applied strain (S ≈ 0.5 and 1.0). The behaviour of water on the surface of the cracked electrode was examined using environmental scanning electron microscopy. Guided cracks in the electrode layer were shown to be efficient water reservoirs and liquid water passages. The MEAs with and without guided cracks were incorporated into fuel cells, and electrochemical measurements were conducted. As expected, all MEAs with guided cracks exhibited better performance than conventional MEAs, mainly because of the improved water transport.

Ultra-sensitive Pressure sensor based on guided straight mechanical cracks.

Recently, a mechanical crack-based strain sensor with high sensitivity was proposed by producing free cracks via bending metal coated film with a known curvature. To further enhance sensitivity and controllability, a guided crack formation is needed. Herein, we demonstrate such a ultra-sensitive sensor based on the guided formation of straight mechanical cracks. The sensor has patterned holes on the surface of the device, which concentrate the stress near patterned holes leading to generate uniform cracks connecting the holes throughout the surface. We found that such a guided straight crack formation resulted in an exponential dependence of the resistance against the strain, overriding known linear or power law dependences. Consequently, the sensors are highly sensitive to pressure (with a sensitivity of over 1 × 105 at pressures of 8-9.5 kPa range) as well as strain (with a gauge factor of over 2 × 106 at strains of 0-10% range). A new theoretical model for the guided crack system has been suggested to be in a good agreement with experiments. Durability and reproducibility have been also confirmed.

Artificial Slanted Nanocilia Array as a Mechanotransducer for Controlling Cell Polarity.

We present a method to induce cell directional behavior using slanted nanocilia arrays. NIH-3T3 fibroblasts demonstrated bidirectional polarization in a rectangular arrangement on vertical nanocilia arrays and exhibited a transition from a bidirectional to a unidirectional polarization pattern when the angle of the nanocilia was decreased from 90° to 30°. The slanted nanocilia guided and facilitated spreading by allowing the cells to contact the sidewalls of the nanocilia, and the directional migration of the cells opposed the direction of the slant due to the anisotropic bending stiffness of the slanted nanocilia. Although the cells recognized the underlying anisotropic geometry when the nanocilia were coated with fibronectin, collagen type I, and Matrigel, the cells lost their directionality when the nanocilia were coated with poly-d-lysine and poly-l-lysine. Furthermore, although the cells recognized geometrical anisotropy on fibronectin coatings, pharmacological perturbation of PI3K-Rac signaling hindered the directional elongation of the cells on both the slanted and vertical nanocilia. Furthermore, myosin light chain II was required for the cells to obtain polarized morphologies. These results indicated that the slanted nanocilia array provided anisotropic contact guidance cues to the interacting cells. The polarization of cells was controlled through two steps: the recognition of underlying geometrical anisotropy and the subsequent directional spreading according to the guidance cues.

Flexible and Shape-Reconfigurable Hydrogel Interlocking Adhesives for High Adhesion in Wet Environments Based on Anisotropic Swelling of Hydrogel Microstructures.

This study presents wet-responsive, shape-reconfigurable, and flexible hydrogel adhesives that exhibit strong adhesion under wet environments based on reversible interlocking between reconfigurable microhook arrays. The experimental investigation on the swelling behavior and structural characterization of the hydrogel microstructures reveal that the microhook arrays undergo anisotropic swelling and shape transformation upon contact with water. The adhesion between the interlocked microhook arrays is greatly enhanced under wet conditions because of the hydration-triggered shape reconfiguration of the hydrogel microstructures. Furthermore, wet adhesion monotonically increases with water-exposure time. A maximum adhesion force of 79.9 N cm-2 in the shear direction is obtained with the hydrogel microhook array after 20 h of swelling, which is 732.3% greater than that under dry conditions (i.e., 9.6 N cm-2). A simple theoretical model is developed to describe the measured adhesion forces. The results are in good agreement with the experimental data.

Directional Clustering of Slanted Nanopillars by Elastocapillarity.

The unidirectional clustering induced by capillary force of drying liquids between pillars is investigated and a theoretical model to set a criterion of the unidirectional clustering of the slanted nanopillars is proposed.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode.

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

Facile Multiscale Patterning by Creep-Assisted Sequential Imprinting and Fuel Cell Application.

The capability of fabricating multiscale structures with desired morphology and incorporating them into engineering applications is key to realizing technological breakthroughs by employing the benefits from both microscale and nanoscale morphology simultaneously. Here, we developed a facile patterning method to fabricate multiscale hierarchical structures by a novel approach called creep-assisted sequential imprinting. In this work, nanopatterning was first carried out by thermal imprint lithography above the glass transition temperature (Tg) of a polymer film, and then followed by creep-assisted imprinting with micropatterns based on the mechanical deformation of the polymer film under the relatively long-term exposure to mechanical stress at temperatures below the Tg of the polymer. The fabricated multiscale arrays exhibited excellent pattern uniformity over large areas. To demonstrate the usage of multiscale architectures, we incorporated the multiscale Nafion films into polymer electrolyte membrane fuel cell, and this device showed more than 10% higher performance than the conventional one. The enhancement was attributed to the decrease in mass transport resistance because of unique cone-shape morphology by creep-recovery effects and the increase in interfacial surface area between Nafion film and electrocatalyst layer.

Robust microzip fastener: repeatable interlocking using polymeric rectangular parallelepiped arrays.

We report a highly repeatable and robust microzip fastener based on the van der Waals force-assisted interlocking between rectangular parallelepiped arrays. To investigate zipperlike interlocking behaviors, various line arrays were fabricated with three different spacing ratios (1, 3, and 5 of 800 nm in width) and width of parallelepipeds (400 nm, 800 nm, and 5 µm with the spacing ratio of 1). In addition, the different rigidity of line arrays was inspected for a repeatable microzip fastener. The normal and shear locking forces were measured with variation of the material rigidity as well as geometry of the array, in good agreement with a proposed theory based on the contact area and force balance. The maximum adhesion forces as high as ∼8.5 N cm(-2) in the normal direction and ∼29.6 N cm(-2) in the shear direction were obtained with high stability up to 1000 cycles. High stability of our fastening system was confirmed for preventing critical failures such as buckling and fracture in practical applications.

In situ realization of asymmetric ratchet structures within microchannels by directionally guided light transmission and their directional flow behavior.

An asymmetric ratchet structure within microchannels is demonstrated by directionally guided light transmission for controlled liquid flow. A direct and facile method is presented to realize programmed asymmetric structures, which control the fluid direction and speed.