Microporous Polypyrrole‐Coated Graphene Foam for High‐Performance Multifunctional Sensors and Flexible Supercapacitors

This study reports on the fabrication of pressure/temperature/strain sensors and all‐solid‐state flexible supercapacitors using only polydimethylsiloxane coated microporous polypyrrole/graphene foam composite (PDMS/PPy/GF) as a common material. A dual‐mode sensor is designed with PDMS/PPy/GF, which measures pressure and temperature with the changes of current and voltage, respectively, without interference to each other. The fabricated dual‐mode sensor shows high sensitivity, fast response/recovery, and high durability during 10 000 cycles of pressure loading. The pressure is estimated using the thermoelectric voltage induced by simultaneous increase in temperature caused by a finger touch on the sensor. Additionally, a resistor‐type strain sensor fabricated using the same PDMS/PPy/GF could detect the strain up to 50%. Flexible, high performance supercapacitor used as a power supply is fabricated with electrodes of PPy/GF for its high surface area and pseudocapacitance. Furthermore, an integrated system of such fabricated multifunctional sensors and a supercapacitor on a skin‐attachable flexible substrate using liquid–metal interconnections operates well, whereas sensors are driven by the power of the supercapacitor. This study clearly demonstrates that the appropriate choice of a single functional material enables fabrication of active multifunctional sensors for pressure, temperature, and strain, as well as the supercapacitor, that could be used in wirelessly powered wearable devices.     

Ultrafast Discharge/Charge Rate and Robust Cycle Life for High‐Performance Energy Storage Using Ultrafine Nanocrystals on the Binder‐Free Porous Graphene Foam

A hierarchical architecture fabricated by integrating ultrafine titanium dioxide (TiO₂) nanocrystals with the binder‐free macroporous graphene (PG) network foam for high‐performance energy storage is demonstrated, where mesoporous open channels connected to the PG facilitate rapid ionic transfer during the Li‐ion insertion/extraction process. Moreover, the binder‐free conductive PG network in direct contact with a current collector provides ultrafast electronic transfer. This structure leads to unprecedented cycle stability, with the capacity preserved with nearly 100% Coulombic efficiency over 10 000 Li‐ion insertion/extraction cycles. Moreover, it is proven to be very stable while cycling 10 to 100‐fold longer compared to typical electrode structures for batteries. This facilitates ultrafast charge/discharge rate capability even at a high current rate giving a very short charge/discharge time of 40 s. Density functional theory calculations also clarify that Li ions migrate into the TiO₂–PG interface then stabilizing its binder‐free interface and that the Li ion diffusion occurs via a concerted mechanism, thus resulting in the ultrafast discharge/charge rate capability of the Li ions into ultrafine nanocrystals.     

Homogeneous CoO on Graphene for Binder‐Free and Ultralong‐Life Lithium Ion Batteries

Ultralong cycle life, high energy, and power density rechargeable lithium‐ion batteries are crucial to the ever‐increasing large‐scale electric energy storage for renewable energy and sustainable road transport. However, the commercial graphite anode cannot perform this challenging task due to its low theoretical capacity and poor rate‐capability performance. Metal oxides hold much higher capacity but still are plagued by low rate capability and serious capacity degradation. Here, a novel strategy is developed to prepare binder‐free and mechanically robust CoO/graphene electrodes, wherein homogenous and full coating of β‐Co(OH)₂ nanosheets on graphene, through a novel electrostatic induced spread growth method, plays a key role. The combined advantages of large 2D surface and moderate inflexibility of the as‐obtained β‐Co(OH)₂/graphene hybrid enables its easy coating on Cu foil by a simple layer‐by‐layer stacking process. Devices made with these electrodes exhibit high rate capability over a temperature range from 0 to 55 °C and, most importantly, maintain excellent cycle stability up to 5000 cycles even at a high current density.     

High Electroactive Material Loading on a Carbon Nanotube@3D Graphene Aerogel for High‐Performance Flexible All‐Solid‐State Asymmetric Supercapacitors

Freestanding carbon‐based hybrids, specifically carbon nanotube@3D graphene (CNTs@3DG) hybrid, are of great interest in electrochemical energy storage. However, the large holes (about 400 µm) in the commonly used 3D graphene foams (3DGF) constitute as high as 90% of the electrode volume, resulting in a very low loading of electroactive materials that is electrically connected to the carbon, which makes it difficult for flexible supercapacitors to achieve high gravimetric and volumetric energy density. Here, a hierarchically porous carbon hybrid is fabricated by growing 1D CNTs on 3D graphene aerogel (CNTs@3DGA) using a facile one‐step chemical vapor deposition process. In this architecture, the 3DGA with ample interconnected micrometer‐sized pores (about 5 µm) dramatically enhances mass loading of electroactive materials comparing with 3DGF. An optimized all‐solid‐state asymmetric supercapacitor (AASC) based on MnO₂@CNTs@3DGA and Ppy@CNTs@3DGA electrodes exhibits high volumetric energy density of 3.85 mW h cm^?3 and superior long‐term cycle stability with 84.6% retention after 20 000 cycles, which are among the best reported for AASCs with both electrodes made of pseudocapacitive electroactive materials.     

Multifunctional Three‐Dimensional T‐Junction Graphene Micro‐Wells: Energy‐Efficient,Plasma‐Enabled Growth and Instant Water‐Based Transfer for Flexible Device Applications

The “third‐generation” 3D graphene structures, T‐junction graphene micro‐wells (T‐GMWs) are produced on cheap polycrystalline Cu foils in a single‐step, low‐temperature (270 °C), energy‐efficient, and environment‐friendly dry plasma‐enabled process. T‐GMWs comprise vertical graphene (VG) petal‐like sheets that seemlessly integrate with each other and the underlying horizontal graphene sheets by forming T‐junctions. The microwells have the pico‐to‐femto‐liter storage capacity and precipitate compartmentalized PBS crystals. The T‐GMW films are transferred from the Cu substrates, without damage to the both, in de‐ionized or tap water, at room temperature, and without commonly used sacrificial materials or hazardous chemicals. The Cu substrates are then re‐used to produce similar‐quality T‐GMWs after a simple plasma conditioning. The isolated T‐GMW films are transferred to diverse substrates and devices and show remarkable recovery of their electrical, optical, and hazardous NO₂ gas sensing properties upon repeated bending (down to 1 mm radius) and release of flexible trasparent display plastic substrates. The plasma‐enabled mechanism of T‐GMW isolation in water is proposed and supported by the Cu plasma surface modification analysis. Our GMWs are suitable for various optoelectronic, sesning, energy, and biomedical applications while the growth approach is potentially scalable for future pilot‐scale industrial production.     

Iron Oxide Nanoparticle and Graphene Nanoribbon Composite as an Anode Material for High‐Performance Li‐Ion Batteries

A composite material made of graphene nanoribbons and iron oxide nanoparticles provides a remarkable route to lithium‐ion battery anode with high specific capacity and cycle stability. At a rate of 100 mA/g, the material exhibits a high discharge capacity of ~910 mAh/g after 134 cycles, which is >90% of the theoretical li‐ion storage capacity of iron oxide. Carbon black, carbon nanotubes, and graphene flakes have been employed by researchers to achieve conductivity and stability in lithium‐ion electrode materials. Herein, the use of graphene nanoribbons as a conductive platform on which iron oxide nanoparticles are formed combines the advantages of long carbon nanotubes and flat graphene surfaces. The high capacity over prolonged cycling achieved is due to the synergy between an electrically percolating networks of conductive graphene nanoribbons and the high lithium‐ion storage capability of iron oxide nanoparticles.     

A Lyotropic Liquid‐Crystal‐Based Assembly Avenue toward Highly Oriented Vanadium Pentoxide/Graphene Films for Flexible Energy Storage

A novel lyotropic liquid‐crystal (LC) based assembly strategy is developed for the first time, to fabricate composite films of vanadium pentoxide (V₂O₅) nanobelts and graphene oxide (GO) sheets, with highly oriented layered structures. It is found that similar lamellar LC phases can be simply established by V₂O₅ nanobelts alone or by a mixture of V₂O₅ nanobelts and GO nanosheets in their aqueous dispersions. More importantly, the LC phases can be retained with any proportion of V₂O₅ nanobelts and GO, which allows facile optimization of the ratio of each component in the resulting films. Named VrGO, composite films manifest high electrical conductivity, good mechanical stability, and excellent flexibility, which allow them to be utilized as high performance electrodes in flexible energy storage devices. As demonstrated in this work, the VrGO films containing 67 wt% V₂O₅ exhibit excellent capacitance of 166 F g^?1 at 10 A g^?1; superior to those of the previously reported composites of V₂O₅ and nanocarbon. Moreover, the VrGO film in flexible lithium ion batteries delivers a high capacity of 215 mAh g^?1 at 0.1 A g^?1; comparable to the best V₂O₅ based cathode materials.     

Emulsifier‐Free Graphene Dispersions with High Graphene Content for Printed Electronics and Freestanding Graphene Films

A novel and highly versatile synthetic route for the production of functionalized graphene dispersions in water, acetone, and isopropanol (IPA), which exhibit long‐term stability and are easy to scale up, is reported. Both graphene functionalization (wherein the oxygen content can be varied from 4 to 16 wt%) and dispersion are achieved by the thermal reduction of graphite oxide, followed by a high‐pressure homogenization (HPH) process. For the first time, binders, dispersing agents, and reducing agents are not required to produce either dilute or highly concentrated dispersions of single graphene sheets with a graphene content of up to 15 g L^?1. High graphene content is essential for the successful printing of graphene dispersions by 3D microextrusion. Free‐standing graphene films and micropatterned graphene materials are successfully prepared using this method. Due to the absence of toxic reducing agents, the graphene exhibits no cytotoxicity and is biocompatible. Furthermore, the electrical conductivity of graphene is significantly improved by the absence of binders. Flexible microarrays can be printed on different substrates, producing microarrays that are mechanically stable and can be bent several times without affecting electrical conductivity.     

Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.     

High‐Performance Polypyrrole/Graphene/SnCl2 Modified Polyester Textile Electrodes and Yarn Electrodes for Wearable Energy Storage

Flexible supercapacitors have potential for wearable energy storage due to their high energy/power densities and long operating lifetimes. High electrochemical performance with robust mechanical properties is highly desired for flexible supercapacitor electrodes. Usually, the mechanical properties are improved by choosing high flexible textile substrates but at the much expense of electrochemical performance due to the nonideal contact between conductive materials and textile substrates. Herein, the authors present an efficient, scalable, and general strategy for the simultaneous fabrication of high‐performance textile electrodes and yarn electrodes. It is interesting to find that the conformal reduced graphene oxide (RGO) layer is uniformly and successively painted on the surface of SnCl₂ modified polyester fibers (M‐PEF) via a repeated “dyeing and drying” strategy. The large‐area textile electrodes and ultralong yarn electrodes are fabricated by using RGO/M‐PEF as substrate with subsequent deposition of polypyrrole. This work provides new opportunities for developing high flexible textile electrodes and yarn electrodes with further increased electrochemical performance and scalable production.     

In‐Plane Assembled Orthorhombic Nb2O5 Nanorod Films with High‐Rate Li+ Intercalation for High‐Performance Flexible Li‐Ion Capacitors

Organic hybrid supercapacitors that consist of a battery electrode and a capacitive electrode show greatly improved energy density, but their power density is generally limited by the poor rate capability of battery‐type electrodes. In addition, flexible organic hybrid supercapacitors are rarely reported. To address the above issues, herein an in‐plane assembled orthorhombic Nb₂O₅ nanorod film anode with high‐rate Li⁺ intercalation to develop a flexible Li‐ion hybrid capacitor (LIC) is reported. The binder‐/additive‐free film exhibits excellent rate capability (≈73% capacity retention with the rate increased from 0.5 to 20 C) and good cycling stability (>2500 times). Kinetic analyses reveal that the high rate performance is mainly attributed to the excellent in‐plane assembly of interconnected single‐crystalline Nb₂O₅ nanorods on the current collector, ensuring fast electron transport, facile Li‐ion migration in the porous film, and greatly reduced ion‐diffusion length. Using such a Nb₂O₅ film as anode and commercial activated carbon as cathode, a flexible LIC is designed. It delivers both high gravimetric and high volumetric energy/power densities (≈95.55 Wh kg^?1/5350.9 W kg^?1; 6.7 mW h cm^?3/374.63 mW cm^?3), surpassing previous typical Li‐intercalation electrode‐based LICs. Furthermore, this LIC device still keeps good electrochemical attributes even under serious bending states (30°–180°).     

Self‐Assembly of Flexible Free‐Standing 3D Porous MoS2‐Reduced Graphene Oxide Structure for High‐Performance Lithium‐Ion Batteries

Flexible freestanding electrodes are highly desired to realize wearable/flexible batteries as required for the design and production of flexible electronic devices. Here, the excellent electrochemical performance and inherent flexibility of atomically thin 2D MoS₂ along with the self‐assembly properties of liquid crystalline graphene oxide (LCGO) dispersion are exploited to fabricate a porous anode for high‐performance lithium ion batteries. Flexible, free‐standing MoS₂–reduced graphene oxide (MG) film with a 3D porous structure is fabricated via a facile spontaneous self‐assembly process and subsequent freeze‐drying. This is the first report of a one‐pot self‐assembly, gelation, and subsequent reduction of MoS₂/LCGO composite to form a flexible, high performance electrode for charge storage. The gelation process occurs directly in the mixed dispersion of MoS₂ and LCGO nanosheets at a low temperature (70 °C) and normal atmosphere (1 atm). The MG film with 75 wt% of MoS₂ exhibits a high reversible capacity of 800 mAh g^?1 at a current density of 100 mA g^?1. It also demonstrates excellent rate capability, and excellent cycling stability with no capacity drop over 500 charge/discharge cycles at a current density of 400 mA g^?1.     

A Composite of Carbon‐Wrapped Mo2C Nanoparticle and Carbon Nanotube Formed Directly on Ni Foam as a High‐Performance Binder‐Free Cathode for Li‐O2 Batteries

Cathode design is indispensable for building Li‐O₂ batteries with long cycle life. A composite of carbon‐wrapped Mo₂C nanoparticles and carbon nanotubes is prepared on Ni foam by direct hydrolysis and carbonization of a gel composed of ammonium heptamolybdate tetrahydrate and hydroquinone resin. The Mo₂C nanoparticles with well‐controlled particle size act as a highly active oxygen reduction reactions/oxygen evolution reactions (ORR/OER) catalyst. The carbon coating can prevent the aggregation of the Mo₂C nanoparticles. The even distribution of Mo₂C nanoparticles results in the homogenous formation of discharge products. The skeleton of porous carbon with carbon nanotubes protrudes from the composite, resulting in extra voids when applied as a cathode for Li‐O₂ batteries. The batteries deliver a high discharge capacity of ≈10 400 mAh g^?1 and a low average charge voltage of ≈4.0 V at 200 mA g^?1. With a cutoff capacity of 1000 mAh g^?1, the Li‐O₂ batteries exhibit excellent charge–discharge cycling stability for over 300 cycles. The average potential polarization of discharge/charge gaps is only ≈0.9 V, demonstrating the high ORR and OER activities of these Mo₂C nanoparticles. The excellent cycling stability and low potential polarization provide new insights into the design of highly reversible and efficient cathode materials for Li‐O₂ batteries.     

Functionally Antagonistic Hybrid Electrode with Hollow Tubular Graphene Mesh and Nitrogen‐Doped Crumpled Graphene for High‐Performance Ionic Soft Actuators

Ionic soft actuators, which exhibit large mechanical deformations under low electrical stimuli, are attracting attention in recent years with the advent of soft and wearable electronics. However, a key challenge for making high‐performance ionic soft actuators with large bending deformation and fast actuation speed is to develop a stretchable and flexible electrode having high electrical conductivity and electrochemical capacitance. Here, a functionally antagonistic hybrid electrode with hollow tubular graphene meshes and nitrogen‐doped crumpled graphene is newly reported for superior ionic soft actuators. Three‐dimensional network of hollow tubular graphene mesh provides high electrical conductivity and mechanically resilient functionality on whole electrode domain. On the contrary, nitrogen‐doped wrinkled graphene supplies ultrahigh capacitance and stretchability, which are indispensably required for improving electrochemical activity in ionic soft actuators. Present results show that the functionally antagonistic hybrid electrode greatly enhances the actuation performances of ionic soft actuators, resulting in much larger bending deformation up to 620%, ten times faster rise time and much lower phase delay in a broad range of input frequencies. This outstanding enhancement mostly attributes to exceptional properties and synergistic effects between hollow tubular graphene mesh and nitrogen‐doped crumpled graphene, which have functionally antagonistic roles in charge transfer and charge injection, respectively.     

High‐κ Solid‐Gate Transistor Configured Graphene Biosensor with Fully Integrated Structure and Enhanced Sensitivity

A fully integrated graphene field‐effect transistor (GFET) nanosensor utilizing a novel high‐κ solid‐gating geometry for a practical biosensor with enhanced sensitivity is presented. Herein, an “in plane” gate supplying electrical field through a 30 nm HfO₂ dielectric layer is employed to eliminate the cumbrous external wire electrode in conventional liquid‐gate GFET nanosensors that undesirably limits the device potential in on‐site sensing applications. In addition to the advantage in the device integration degree, the transconductance level is found to be increased by about 50% over liquid‐gate GFET devices in aqueous‐media, thereby improves the sensitivity performance in sensor applications. As the first demonstration of biosensing applications, a small‐molecule antibiotic, kanamycin A, is detected by means of an aptameric competitive affinity principle. It is experimentally shown that the label‐free and specific quantification of kanamycin A with a concentration resolution at 11.5 × 10^?9 m is achievable through a single direct observation of the 200 s fast bioassay without any further noise canceling. These results demonstrate the utility and practicability of the new devices in label‐free biosensing as a novel analytical tool, and potentially hold great promise in other significant biomedical applications.     

Ultralight and Binder‐Free All‐Solid‐State Flexible Supercapacitors for Powering Wearable Strain Sensors

Flexible energy storage devices play a pivotal role in realizing the full potential of flexible electronics. This work presents high‐performance, all‐solid‐state, flexible supercapacitors by employing an innovative multilevel porous graphite foam (MPG). MPGs exhibit superior properties, such as large specific surface area, high electric conductivity, low mass density, high loading efficiency of pseudocapacitive materials, and controlled corrugations for accommodating mechanical strains. When loaded with pseudocapacitive manganese oxide (Mn₃O₄), the MPG/Mn₃O₄ (MPGM) composites achieve a specific capacitance of 538 F g^?1 (1 mV s^?1) and 260 F g^?1 (1 mV s^?1) based on the mass of pure Mn₃O₄ and entire electrode composite, respectively. Both are among the best of Mn₃O₄‐based supercapacitors. The MPGM is mechanically robust and can go through 1000 mechanical bending cycles with only 1.5% change in electric resistance. When integrated as all‐solid‐state symmetric supercapacitors, they offer a full cell specific capacitance as high as 53 F g^?1 based on the entire electrode and retain 80% of capacitance after 1000 continuous mechanical bending cycles. Furthermore, the all‐solid‐state flexible supercapacitors are incorporated with strain sensors into self‐powered flexible devices for detection of both coarse and fine motions on human skins, i.e., those from finger bending and heart beating.     

Enhanced Light‐Harvesting by Integrating Synergetic Microcavity and Plasmonic Effects for High‐Performance ITO‐Free Flexible Polymer Solar Cells

In this work, a high‐performance ITO‐free flexible polymer solar cell (PSC) is successfully described by integrating the plasmonic effect into the ITO‐free microcavity architecture. By carefully controlling the sizes of embedded Ag nanoprisms and their doping positons in the stratified device, a significant enhancement in power conversion efficiency (PCE) is shown from 8.5% (reference microcavity architecture) to 9.4% on flexible substrates. The well‐manipulated plasmonic resonances introduced by the embedded Ag nanoprisms with different LSPR peaks allow the complementary light‐harvesting with microcavity resonance in the regions of 400–500 nm and 600–700 nm, resulting in the substantially increased photocurrent. This result not only signifies that the spectral matching between the LSPR peaks of Ag nanoprisms and the relatively low absorption response of photoactive layer in the microcavity architecture is an effective strategy to enhance light‐harvesting across its absorption region, but also demonstrates the promise of tailoring two different resonance bands in a synergistic manner at desired wavelength region to enhance the efficiency of PSCs.