Significantly Increased Specific Discharge Capacitance at Carbon Fibers Created via Architected Ultramicropores.

Carbon is commonly used as an electrode material for supercapacitors operating on an electrical double-layer energy storage mechanism. However, the low specific capacitance limits its application. Increasing the specific surface area is by far the most common expansion method, and surprisingly, they are not always positively correlated. The overmuch specific surface will show the characteristics of nanoconfinement, and the potential synergistic enhancement mechanism of various key parameters is still controversial. In this work, carbon fiber electrodes with different ultramicropore structures were designed in order to improve the utilization rate and the discharge capacitance. It has been found that when the ultramicropore entrance's surface is too small, it will lead to the decrease of the external charge of the pore transport channel, and then, the selectivity of the opposite ions will decrease. The numerical simulation based on Poisson and Nernst-Planck equations also indicates that ions have difficulty diffusing into the micropores when their entrance surface decreases. Surface properties within the nanocontainment space become critical factors influencing ion transport and adsorption. The specific discharge capacitance of carbon fiber is increased from 3 to 1430 mF cm-2.

Novel Fluorinated Anion Exchange Membranes Based on Poly(Pentafluorophenyl-Carbazole) with High Ionic Conductivity and Alkaline Stability for Fuel Cell Applications.

Constructing good microphase separation structures by designing different polymer backbones and ion-conducting groups is an effective strategy for improving the ionic conductivity and chemical stability of anion exchange membranes (AEMs). In this study, a series of AEMs based on the poly(pentafluorophenylcarbazole) backbone grafted with different cationic groups are designed and prepared to construct well-defined microphase separation morphology and improve the trade-off between the properties of AEMs. Highly hydrophobic fluorinated backbone and alkyl spaces enhance phase separation and construct interconnected hydrophilic channels for anion transport. The ionic conductivity of the PC-PF-QA membrane is 123 mS cm-1 at 80 °C, and the ionic conductivity of the PC-PF-QA membrane decreased by only 6% after 960 h of immersion at 60 °C in 1 M NaOH aqueous solution. The maximum peak power density of the single cell based on PC-PF-QA is 214 mW cm-2 at 60 °C.

Sulfonated Polyimide Membranes Constructed by Main-Chain and Molecular-Network Engineering Strategy for Direct Methanol Fuel Cell.

Excessive swelling is one important factor that leads to high fuel permeability and limited operating concentration of methanol for proton exchange membranes. Herein, a collaborative strategy of main-chain and molecular-network engineering is applied to lower swelling ratio and improve methanol resistance for highly sulfonated polyimide. Two m-phenylenediamine monomers (4-(2,3,5,6-tetrafluoro-4-vinylphenoxy)benzene-1,3-diamine and 4,6-bis(2,3,5,6-tetrafluoro-4-vinylphenoxy)benzene-1,3-diamine) with tetrafluorostyrol groups are designed and synthesized. Two series of cross-linked sulfonated polyimides (CSPI-Ts, CSPI-Bs) are prepared from the two diamines, 4,4'-diaminostilbene-2,2'-disulfonic acid and 1,4,5,8-naphthalenetetracarboxylicdianhydride. The rigid main-chain structure is cornerstone for wet CSPI-Ts and CSPI-Bs remaining stable at elevated temperatures. The introduction of hydrophobic cross-linked network further improves their dimensional stability and methanol resistance. CSPI-Ts and CSPI-Bs show obviously improved performances containing high proton conductivity (121 ± 0.27-158 ± 0.35 S cm-1 ), low swelling ratio (9.6 ± 0.40%-16.1 ± 0.01%) and methanol permeability (4.14-7.69 × 10-7 cm2 s-1 ) at 80 °C. The direct methanol fuel cell (DMFC) is assembled from CSPI-T-10 with balanced properties, and it exhibits high maximum power density (PDmax ) of 82.3 and 72.6 mW cm-2 in 2 and 10 m methanol solution, respectively. The ratio of PDmax in 10 m methanol solution to the value in 2 m methanol solution is as high as 88%. The CSPI-T-10 is promising proton exchange membrane candidate for DMFC application.

ZnO Nanoneedle-Modified PEEK Fiber Felt for Improving Anti-fouling Performance of Oil/Water Separation.

Membrane separation has been considered to be the most effective decontamination method for oily waste water. The most significant point of membrane separation is the resistance against membrane fouling. Fabricating hierarchical architectures on the membrane surface is an available approach to improving its anti-fouling property. In this study, ZnO nanoneedles were successfully anchored onto surface-sulfonated poly(ether-ether-ketone) (PEEK) felt via UV/ozone cleaning and hydrothermal synthesis. The modified felt (PEEK-f-Z) showed much better anti-fouling properties and far higher rejection height (33 cm) than the unmodified felt (17 cm) with a separation efficiency up to 99.99%. The enhanced separation properties could be attributed to the stronger water locking capability of the hierarchical architectures on the surface. Furthermore, benefiting from the great chemical stability of PEEK substrates and ZnO nanoneedles, the as-prepared membrane exhibited admirable solvent resistance, mechanical strength, and thermal stability. As a result, PEEK-f-Z could even separate immiscible organic liquids with different polarities and collect hot water from the oil/water mixture, promising to be used under severe conditions.

Designing Versatile Superhydrophilic Structures via an Alginate-Based Hydrophilic Plasticene.

The rational design of superhydrophilic materials with a controllable structure is a critical component in various applications, including solar steam generation, liquid spontaneous transport, etc. The arbitrary manipulation of the 2D, 3D, and hierarchical structures of superhydrophilic substrates is highly desirable for smart liquid manipulation in both research and application fields. To design versatile superhydrophilic interfaces with various structures, here we introduce a hydrophilic plasticene that possesses high flexibility, deformability, water absorption, and crosslinking capabilities. Through a pattern-pressing process with a specific template, 2D prior fast spreading of liquids at speeds up to 600 mm/s was achieved on the superhydrophilic surface with designed channels. Additionally, 3D superhydrophilic structures can be facilely designed by combining the hydrophilic plasticene with a 3D-printed template. The assembly of 3D superhydrophilic microstructure arrays were explored, providing a promising route to facilitate the continuous and spontaneous liquid transport. The further modification of superhydrophilic 3D structures with pyrrole can promote the applications of solar steam generation. The optimal evaporation rate of an as-prepared superhydrophilic evaporator reached ~1.60 kg·m-2·h-1 with a conversion efficiency of approximately 92.96%. Overall, we envision that the hydrophilic plasticene should satisfy a wide range of requirements for superhydrophilic structures and update our understanding of superhydrophilic materials in both fabrication and application.

Multilayer Dielectric Nanocomposites with Cross-Linked Dielectric Transition Interlayers for High-Temperature Applications.

In energy storage and transportation systems, polymer dielectrics are widely applied in smart grids, electric vehicles, and power conditioning owing to their incomparable power density and high reliability. However, the dielectric constant (ε) and breakdown strength (Eb) normally cannot be increased simultaneously, which results in insufficient discharged energy density especially at high temperatures. In this work, enhanced Eb and high energy density are archived in multilayer polymer nanocomposites by introducing cross-linked dielectric transition layers. Specifically, the sandwiched composite achieves a huge discharge energy density of 4.64 J cm-3 with a charged-discharged efficiency of 84% at 150 °C and 500 MV m-1. The formation of cross-linked dielectric transition layers between layers of the multilayer nanocomposite could effectively restrain the growth of the electrical tree and greatly increase the Eb. This work presents a strategy for designing high-performance multilayered dielectric polymer nanocomposites by introducing cross-linked dielectric transition layers to reduce the loss from interlayer interfaces.

Ultraviolet Photodetectors Based on Polymer Microwire Arrays toward Wearable Medical Devices.

Polymer micro/nanoarchitectures have attracted intense interest for wearable medical applications due to their excellent mechanical flexibility, solution processability, and tunable optoelectronic properties. Based on polymer micro/nanostructures, high-performance ultraviolet (UV) photodetectors can not only functionalize the accurate image sensing but also sustain the biocomfortable flexible devices for real-time health monitoring. The main challenges are focused on the integration of medical wearable devices, which requires large-scale assembly of polymer micro/nanostructures with controlled morphology and strict alignment. Herein, we utilized a confined assembly system through the cautious regulation for the growth of high-quality polymer 1D arrays. UV photodetectors based on these polymer microwire arrays perform a high on/off ratio of 137 and responsivity of 19.1 mA W-1. Polymer microarray photodetectors facilitate the scale-up fabrication of 14 × 18 multiplexed image sensors for highly accurate capturing the signals of Arabic numerals "1," "2," and "3." Flexible UV photodetectors based on these arrays present excellent flexibility and bending durability, maintaining 97% of their original on/off ratio after 4000 cycles with a 10 mm bending radius. UV photodetection signals were also collected from the attached flexible devices on the back skin of the mouse, demonstrating the great potential in wearable medical photodetection.

A universal strategy to improve interfacial kinetics of solid supercapacitors used in high temperature.

The growing application domain of energy storage devices (ESDs) is leading research to temperature tolerant supercapacitors. To realize reliable and safe devices, high modulus solid electrolytes are favored by most researchers. However, the inferior infiltrating ability of such electrolytes usually results in poor electrochemical performances of the ESDs. Herein, we adopted a hierarchical optimization strategy to address the aforementioned interfacial issues. Continuous ionic percolation throughout the hierarchical pores of the 3D electrode was formed by in-situ introducing an ionogel buffer layer. Benefiting from this, the rate of ions diffusing within electrodes was increased by 5 times. Furthermore, the kinetics of ions entering into nanopores was improved via introducing small size ions into ionic liquids (ILs) and adjusting the solvated structures. Both the capacity and rate performance of the electrochemical double layer capacitors (EDLCs) were improved. Additionally, the buffer layer exhibited sufficient thermostability to cooperate with poly(ether ether ketone) (PEEK)-based solid electrolyte. Consequently, the EDLCs exhibited excellent cycling stability (79% capacitance retention after 5000 cycles) at 120 °C and delivered a maximum energy density of 46.9 Wh kg-1 with a power density of 926.9 W kg-1. Our strategy is believed to be effective to cooperate with various solid electrolyte systems and offer a general design principle for durable and high performance EDLCs.

Unique ion rectification in hypersaline environment: A high-performance and sustainable power generator system.

The development of membrane science plays a fundamental role in harvesting osmotic power, which is considered a future clean and renewable energy source. However, the existing designs of the membrane cannot handle the low conversion efficiency and power density. Theory has predicted that the Janus membrane with ionic diode-type current would be the most efficient material. Therefore, rectified ionic transportation in a hypersaline environment (the salt concentration is at least 0.5 M in sea) is highly desired, but it still remains a challenge. Here, we demonstrate a versatile strategy for creating a scale-up Janus three-dimensional (3D) porous membrane-based osmotic power generator system. Janus membranes with tunable surface charge density and porosity were obtained by compounding two kinds of ionomers. Under electric fields or chemical gradients, the Janus membrane has ionic current rectification properties and anion selectivities in a hypersaline environment. Experiments and theoretical calculation demonstrate that abundant surface charge and narrow pore size distribution benefit this unique ionic transport behavior in high salt solution. Thus, the output power density of this membrane-based generator reaches 2.66 W/m2 (mixing seawater and river water) and up to 5.10 W/m2 at a 500-fold salinity gradient (i.e., flowing salt lake into river water). Furthermore, a generator, built by connecting a series of membranes, could power a calculator for 120 hours without obvious current decline, proving the excellent physical and chemical stabilities. Therefore, we believe that this work advances the fundamental understanding of fluid transport and materials design as a paradigm for a high-performance energy conversion generator.

3D Porous Hydrogel/Conducting Polymer Heterogeneous Membranes with Electro-/pH-Modulated Ionic Rectification.

Heterogeneous membranes composed of asymmetric structures or compositions have enormous potential in sensors, molecular sieves, and energy devices due to their unique ion transport properties such as ionic current rectification and ion selectivity. So far, heterogeneous membranes with 1D nanopores have been extensively studied. However, asymmetric structures with 3D micro-/nanoscale pore networks have never been investigated. Here, a simple and versatile approach to low-costly fabricate hydrogel/conducting polymer asymmetric heterogeneous membranes with electro-/pH-responsive 3D micro-/nanoscale ion channels is introduced. Due to the asymmetric heterojunctions between positively charged nanoporous polypyrrole (PPy) and negatively charged microscale porous hydrogel poly (acrylamide-co-acrylic acid) (P(AAm-co-AA)), the membrane can rectify ion transmembrane transport in response to both electro- and pH-stimuli. Numerical simulations based on coupled Poisson and Nernst-Plank equations are carried out to explain the ionic rectification mechanisms for the membranes. The membranes are not dependent on elaborately fabricated 1D ion channel substrates and hence can be facilely prepared in a low-cost and large-area way. The hybridization of hydrogel and conducting polymer offers a novel strategy for constructing low-cost, large-area and multifunctional membranes, expanding the tunable ionic rectification properties into macroscopic membranes with micro-/nanoscale pores, which would stimulate practical applications of the membranes.

A Charge-Density-Tunable Three/Two-Dimensional Polymer/Graphene Oxide Heterogeneous Nanoporous Membrane for Ion Transport.

The design and fabrication of a robust nanoporous membrane in large scale is still a challenge and is of fundamental importance for practical applications. Here, a robust three/two-dimensional polymer/graphene oxide heterogeneous nanoporous membrane is constructed in large scale via the self-assembly approach by chemically designing a robust charge-density-tunable nanoporous ionomer with uniform pore size. To obtain a nanoporous polymer that maintains high mechanical strength and promotes multifunctionality, we designed a series of amphiphilic copolymers by introducing a positively charged pyridine moiety into the engineered polymer polyphenylsulfone. The multiphysical-chemical properties of the membrane enable it to work as a nanogate switch with synergy between wettability and surface charge change in response to pH. Then we systematically studied the transmembrane ionic transport properties of this two-/three-dimensional porous system. By adjusting the charge density of the copolymer via chemical copolymerization through a controlled design route, the rectifying ratio of this asymmetric membrane could be amplified 4 times. Furthermore, we equipped a concentration-gradient-driven energy harvesting device with this charge-density-tunable nanoporous membrane, and a maximum power of ≈0.76 W m-2 was obtained. We expect this methodology for construction of a charge-density-tunable heterogeneous membrane by chemical design will shed light on the material design, and this membrane may further be used in energy devices, biosensors, and smart gating nanofluidic devices.