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.     

Stretchable,Skin‐Mountable,and Wearable Strain Sensors and Their Potential Applications: A Review

There is a growing demand for flexible and soft electronic devices. In particular, stretchable, skin‐mountable, and wearable strain sensors are needed for several potential applications including personalized health‐monitoring, human motion detection, human‐machine interfaces, soft robotics, and so forth. This Feature Article presents recent advancements in the development of flexible and stretchable strain sensors. The article shows that highly stretchable strain sensors are successfully being developed by new mechanisms such as disconnection between overlapped nanomaterials, crack propagation in thin films, and tunneling effect, different from traditional strain sensing mechanisms. Strain sensing performances of recently reported strain sensors are comprehensively studied and discussed, showing that appropriate choice of composite structures as well as suitable interaction between functional nanomaterials and polymers are essential for the high performance strain sensing. Next, simulation results of piezoresistivity of stretchable strain sensors by computational models are reported. Finally, potential applications of flexible strain sensors are described. This survey reveals that flexible, skin‐mountable, and wearable strain sensors have potential in diverse applications while several grand challenges have to be still overcome.     

Flexible and Stretchable 3ω Sensors for Thermal Characterization of Human Skin

Characterization of the thermal properties of the surface and subsurface structures of the skin can reveal the degree of hydration, the rate of blood flow in near‐surface micro‐ and macrovasculature, and other important physiological information of relevance to dermatological and overall health status. Here, a soft, stretchable thermal sensor, based on the so‐called three omega (i.e., 3ω) method, is introduced for accurate characterization of the thermal conductivity and diffusivity of materials systems, such as the skin, which can be challenging to measure using established techniques. Experiments on skin at different body locations and under different physical states demonstrate the possibilities. Systematic studies establish the underlying principles of operation in these unusual systems, thereby allowing rational design and use, through combined investigations based on analytical modeling, experimental measurements, and finite element analysis. The findings create broad opportunities for 3ω methods in biology, with utility ranging from the integration with surgical tools or implantable devices to noninvasive uses in clinical diagnostics and therapeutics.     

A Flexible 3D Multifunctional MgO‐Decorated Carbon Foam@CNTs Hybrid as Self‐Supported Cathode for High‐Performance Lithium‐Sulfur Batteries

One of the critical challenges to develop advanced lithium‐sulfur (Li‐S) batteries lies in exploring a high efficient stable sulfur cathode with robust conductive framework and high sulfur loading. Herein, a 3D flexible multifunctional hybrid is rationally constructed consisting of nitrogen‐doped carbon foam@CNTs decorated with ultrafine MgO nanoparticles for the use as advanced current collector. The dense carbon nanotubes uniformly wrapped on the carbon foam skeletons enhance the flexibility and build an interconnected conductive network for rapid ionic/electronic transport. In particular, a synergistic action of MgO nanoparticles and in situ N‐doping significantly suppresses the shuttling effect via enhanced chemisorption of lithium polysulfides. Owing to these merits, the as‐built electrode with an ultrahigh sulfur loading of 14.4 mg cm^?2 manifests a high initial areal capacity of 10.4 mAh cm^?2, still retains 8.8 mAh cm^?2 (612 mAh g^?1 in gravimetric capacity) over 50 cycles. The best cycling performance is achieved upon 800 cycles with an extremely low decay rate of 0.06% at 2 C. Furthermore, a flexible soft‐packaged Li‐S battery is readily assembled, which highlights stable electrochemical characteristics under bending and even folding. This cathode structural design may open up a potential avenue for practical application of high‐sulfur‐loading Li‐S batteries toward flexible energy‐storage devices.     

3D Carbon Nanotube Network Bridged Hetero‐Structured Ni‐Fe‐S Nanocubes toward High‐Performance Lithium,Sodium, and Potassium Storage

Lithium‐ion, sodium‐ion, and potassium‐ion batteries have captured tremendous attention in power supplies for various electric vehicles and portable electronic devices. However, their practical applications are severely limited by factors such as poor rate capability, fast capacity decay, sluggish charge storage dynamics, and low reversibility. Herein, hetero‐structured bimetallic sulfide (NiS/FeS) encapsulated in N‐doped porous carbon cubes interconnected with CNTs (Ni‐Fe‐S‐CNT) are prepared through a convenient co‐precipitation and post‐heat treatment sulfurization technique of the corresponding Prussian‐blue analogue nanocage precursor. This special 3D hierarchical structure can offer a stable interconnect and conductive network and shorten the diffusion path of ions, thereby greatly enhancing the mobility efficiency of alkali (Li, Na, K) ions in electrode materials. The Ni‐Fe‐S‐CNT nanocomposite maintains a charge capacity of 1535 mAh g^?1 at 0.2 A g^?1 for lithium ion batteries, 431 mAh g^?1 at 0.1 A g^?1 for sodium ion batteries, and 181 mAh g^?1 at 0.1 A g^?1 for potassium‐ion batteries, respectively. The high performance is mainly attributed to the 3D hierarchically high‐conductivity network architecture, in which the hetero‐structured FeS/NiS nanocubes provide fast Li⁺/Na⁺/K⁺ insertion/extraction and reduced ion diffusion paths, and the distinctive 3D networks maintain the electrical contact and guarantee the structural integrity.     

3D Conformal Printing and Photonic Sintering of High‐Performance Flexible Thermoelectric Films Using 2D Nanoplates

Flexible thermoelectric (TE) devices hold great promise for energy harvesting and cooling applications, with increasing significance to serve as perpetual power sources for flexible electronics and wearable devices. Despite unique and superior TE properties widely reported in nanocrystals, transforming these nanocrystals into flexible and functional forms remains a major challenge. Herein, demonstrated is a transformative 3D conformal aerosol jet printing and rapid photonic sintering process to print and sinter solution‐processed Bi₂Te_2.7Se_0.3 nanoplate inks onto virtually any flexible substrates. Within seconds of photonic sintering, the electrical conductivity of the printed film is dramatically improved from nonconductive to 2.7 × 10⁴ S m^?1. The films demonstrate a room temperature power factor of 730 µW m^?1 K^?2, which is among the highest values reported in flexible TE films. Additionally, the film shows negligible performance changes after 500 bending cycles. The highly scalable and low‐cost fabrication process paves the way for large‐scale manufacturing of flexible devices using a variety of high‐performing nanoparticle inks.     

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.     

Versatile,High‐Power,Flexible, Stretchable Carbon Nanotube Sheet Heating Elements Tolerant to Mechanical Damage and Severe Deformation

A macroscopic carbon nanotube (CNT) sheet‐based heating element having flexible, stretchable, and damage‐tolerant features, and wide applicability in harsh environments, is introduced. Because of the intrinsic connection of extremely flexible CNT bundles throughout the sample by van der Waals interactions without use of a binder, the electrical resistance variation of the CNT sheet on elastomer heating element as a function of strain is completely suppressed to some extent, even when stretched under up to 400% strain, which guarantees electrical stability under severe mechanical deformation. In addition, the spatial uniformity of the heat generated from the microaligned CNT bundles reduces the temperature variation inside the sample, which also guarantees thermal stability and operation at a higher average temperature. Such exceptional performance is achieved by the passivation of the elastomer layer on the CNT sheets. Furthermore, the mechanical robustness of this flexible, stretchable heating element is demonstrated by stable heater operation, even when the heating element is damaged. In addition, this design concept of CNT sheet on elastomer is extended to transparent flexible heaters and electric‐thermochromic windows.     

3D Carbonaceous Current Collectors: The Origin of Enhanced Cycling Stability for High‐Sulfur‐Loading Lithium–Sulfur Batteries

The cycling stability of high‐sulfur‐loading lithium–sulfur (Li–S) batteries remains a great challenge owing to the exaggerated shuttle problem and interface instability. Despite enormous efforts on design of advanced electrodes and electrolytes, the stability issue raised from current collectors has been rarely concerned. This study demonstrates that rationally designing a 3D carbonaceous macroporous current collector is an efficient and effective “two‐in‐one” strategy to improve the cycling stability of high‐sulfur‐loading Li–S batteries, which is highly versatile to enable various composite cathodes with sulfur loading >3.7 mAh cm^?2. The best cycling performance can be achieved upon 950 cycles with a very low decay rate of 0.029%. Moreover, the origin of such a huge enhancement in cycling stability is ascribed to (1) the inhibition of electrochemical corrosion, which severely occurs on the typical Al foil and disables its long‐term sustainability for charge transfer, and (2) the passivation of cathode surface. The role of the chemical resistivity against corrosion and favorable macroscopic porous structure is highlighted for exploiting novel current collectors toward exceptional cycling stability of high‐sulfur‐loading Li–S batteries.     

Temperature Performance of Doping‐Free Top‐Gate CNT Field‐Effect Transistors: Potential for Low‐ and High‐Temperature Electronics

High‐performance top‐gate carbon nanotube (CNT) field‐effect transistors (FETs) have been fabricated via a doping‐free fabrication process in which the polarity of the CNT FET is controlled by the injection of carriers from the electrodes, instead of using dopants. The performance of the doping‐free CNT FETs is systemically investigated over a wide temperature range, from very low temperatures of down to 4.3 K up to 573 K, and analyzed using several temperature‐dependent key device parameters including the ON/OFF state current and ratio, carrier mobility, and subthreshold swing. It is demonstrated that for ballistic and quasi‐ballistic CNT FETs, the operation of the CNT FETs is largely independent of the presence of dopant, thus avoiding detrimental effects due to dopant freeze‐out at low temperature and dopant diffusion at high temperature, and making it possible to use doping‐free CNT FETs in both low‐ and high‐temperature electronics. A new method is also proposed for extracting the band‐gap and diameter of a semiconducting CNT from the temperature dependent OFF‐state current and shown to yield results that are consistent with AFM measurements.     

Finely Crafted 3D Electrodes for Dendrite‐Free and High‐Performance Flexible Fiber‐Shaped Zn–Co Batteries

Rechargeable aqueous Zn‐based batteries, benefiting from their good reliability, low cost, high energy/power densities, and ecofriendliness, show great potential in energy storage systems. However, the poor cycling performance due to the formation of Zn dendrites greatly hinders their practical applications. In this work, a trilayer 3D CC‐ZnO@C‐Zn anode is obtained by in situ growing ZIFs (zeolitic‐imidazolate frameworks) derived ZnO@C core–shell nanorods on carbon cloth followed by Zn deposition, which exhibits excellent antidendrite performance. Using CC‐ZnO@C‐Zn as the anode and a branch‐like Co(CO₃)_0.5(OH)_x·0.11H₂O@CoMoO₄ (CC‐CCH@CMO) as the cathode, a Zn–Co battery is rationally designed, displaying excellent energy/power densities (235 Wh kg^?1, 12.6 kW kg^?1) and remarkable cycling performance (71.1% after 5000 cycles). Impressively, when using a gel electrolyte, a highly customizable, fiber‐shaped flexible all‐solid‐state Zn–Co battery is assembled for the first time, which presents a high energy density of 4.6 mWh cm^?3, peak power density of 0.42 W cm^?3, and long durability (82% capacity retention after 1600 cycles) as well as excellent flexibility. The unique 3D electrode design in this study provides a novel approach to achieve high‐performance Zn‐based batteries, showing promising applications in flexible and portable energy‐storage systems.     

Gas Sensing of NiO‐SCCNT Core–Shell Heterostructures: Optimization by Radial Modulation of the Hole‐Accumulation Layer

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al₂O₃ dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al₂O₃–SCCNT, Al₂O₃–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region.     

In Situ Construction of 3D Interconnected FeS@Fe3C@Graphitic Carbon Networks for High‐Performance Sodium‐Ion Batteries

Iron sulfides have been attracting great attention as anode materials for high‐performance rechargeable sodium‐ion batteries due to their high theoretical capacity and low cost. In practice, however, they deliver unsatisfactory performance because of their intrinsically low conductivity and volume expansion during charge–discharge processes. Here, a facile in situ synthesis of a 3D interconnected FeS@Fe₃C@graphitic carbon (FeS@Fe₃C@GC) composite via chemical vapor deposition (CVD) followed by a sulfuration strategy is developed. The construction of the double‐layered Fe₃C/GC shell and the integral 3D GC network benefits from the catalytic effect of iron (or iron oxides) during the CVD process. The unique nanostructure offers fast electron/Na ion transport pathways and exhibits outstanding structural stability, ensuring fast kinetics and long cycle life of the FeS@Fe₃C@GC electrodes for sodium storage. A similar process can be applied for the fabrication of various metal oxide/carbon and metal sulfide/carbon electrode materials for high‐performance lithium/sodium‐ion batteries.