Ultralow-resistance electrochemical capacitor for integrable line filtering.

Electrochemical capacitors are expected to replace conventional electrolytic capacitors in line filtering for integrated circuits and portable electronics1-8. However, practical implementation of electrochemical capacitors into line-filtering circuits has not yet been achieved owing to the difficulty in synergistic accomplishment of fast responses, high specific capacitance, miniaturization and circuit-compatible integration1,4,5,9-12. Here we propose an electric-field enhancement strategy to promote frequency characteristics and capacitance simultaneously. By downscaling the channel width with femtosecond-laser scribing, a miniaturized narrow-channel in-plane electrochemical capacitor shows drastically reduced ionic resistances within both the electrode material and the electrolyte, leading to an ultralow series resistance of 39 mΩ cm2 at 120 Hz. As a consequence, an ultrahigh areal capacitance of up to 5.2 mF cm-2 is achieved with a phase angle of -80° at 120 Hz, twice as large as one of the highest reported previously4,13,14, and little degradation is observed over 1,000,000 cycles. Scalable integration of this electrochemical capacitor into microcircuitry shows a high integration density of 80 cells cm-2 and on-demand customization of capacitance and voltage. In light of excellent filtering performances and circuit compatibility, this work presents an important step of line-filtering electrochemical capacitors towards practical applications in integrated circuits and flexible electronics.

Graphene Ionogel Ultra-Fast Filter Supercapacitor with 4 V Workable Window and 150 °C Operable Temperature.

The filtering capacitor plays an essential role in the ever-increasing electronics for current stability in complicated environments. However, because of the low specific capacitance and bulky volume, current filtering devices have difficulty satisfying the harsh temperature environment and small size for supercomputers, electric vehicles, aircraft and so on. Therefore, an ultra-fast electrochemical capacitor is developed on the basis of vertically oriented graphene iongel electrodes (GI-EC), which demonstrates excellent alternate current line-filtering performance with both hot tolerance of up to 150 °C and a wide voltage window of 4 V. Because of the particularly oriented graphene nanosheets induced fast ion transport, this ionic electrochemical capacitor displays a high areal specific energy density of 1784 µF V2  cm-2 with a phase angle of -80.0° (120 Hz) at 150 °C, which is greater than most of the reported electrochemical capacitors. Moreover, it can filter arbitrary waveforms to smooth direct current signals and works well with a wide frequency range from 10 to 104  Hz. The easy integration of GI-ECs in series or parallel can also further deliver desired capacitances or high voltages. The GI-EC with high-rate performance, wide voltage window, and high-temperature adaptability presents a great promise for universally applicable filtering capacitors.

Maximization of Spatial Charge Density: An Approach to Ultrahigh Energy Density of Capacitive Charge Storage.

Capacitive energy storage has advantages of high power density, long lifespan, and good safety, but is restricted by low energy density. Inspired by the charge storage mechanism of batteries, a spatial charge density (SCD) maximization strategy is developed to compensate this shortage by densely and neatly packing ionic charges in capacitive materials. A record high SCD (ca. 550 C cm-3 ) was achieved by balancing the valance and size of charge-carrier ions and matching the ion sizes with the pore structure of electrode materials, nearly five times higher than those of conventional ones (ca. 120 C cm-3 ). The maximization of SCD was confirmed by Monte Carlo calculations, molecular dynamics simulations, and in situ electrochemical Raman spectroscopy. A full-cell supercapacitor was further constructed; it delivers an ultrahigh energy density of 165 Wh L-1 at a power density of 150 WL-1 and retains 120 Wh L-1 even at 36 kW L-1 , opening a pathway towards high-energy-density capacitive energy storage.

Graphene-Based Functional Architectures: Sheets Regulation and Macrostructure Construction toward Actuators and Power Generators.

Graphene, with large delocalized π electron cloud on a two-dimensional (2D) atom-thin plane, possesses excellent carrier mobility, large surface area, high light transparency, high mechanical strength, and superior flexibility. However, the lack of intrinsic band gap, poor dispersibility, and weak reactivity of graphene hinder its application scope. Heteroatom-doping regulation and surface modification of graphene can effectively reconstruct the sp2 bonded carbon atoms and tailor the surface chemistry and interfacial interaction, while microstructure mediation on graphene can induce the special chemical and physical properties because of the quantum confinement, edge effect, and unusual mass transport process. Based on these regulations on graphene, series of methods and techniques are developed to couple the promising characters of graphene into the macroscopic architectures for potential and practical applications. In this Account, we present our effort on graphene regulation from chemical modification to microstructure control, from the morphology-designed macroassemblies to their applications in functional systems excluding the energy-storage devices. We first introduce the chemically regulative graphene with incorporated heteroatoms into the honeycomb lattice, which could open the intrinsic band gap and provide many active sites. Then the surface modification of graphene with functional components will improve dispersibility, prevent aggregation, and introduce new functions. On the other hand, microstructure mediation on graphene sheets (e.g., 0D quantum dots, 1D nanoribbons, and 2D nanomeshes) is demonstrated to induce special chemical and physical properties. Benefiting from the effective regulation on graphene sheets, diverse methods including dimension-confined strategy, filtration assembly, and hydrothermal treatment have been developed to assemble individual graphene sheets to macroscopic graphene fibers, films, and frameworks. These rationally regulated graphene sheets and well-constructed assemblies present promising applications in energy-conversion materials and device systems focusing on actuators that can convert different energy forms (e.g., electric, chemical, photonic, thermal, etc.) to mechanical actuation and electrical generators that can directly transform environmental energy to electric power. These results reveal that graphene sheets with surface chemistry and microstructure regulations as well as their rationally designed assemblies provide a promising and abundant platform for development of diverse functional devices. We hope that this Account will promote further efforts toward fundamental research on graphene regulation and the wide applications of advanced designed assemblies in new types of energy-conversion materials/devices and beyond.

A Microstructured Graphene/Poly(N-isopropylacrylamide) Membrane for Intelligent Solar Water Evaporation.

Intelligent solar water evaporation (iSWE) was achieved with a thermally responsive and microstructured graphene/poly(N-isopropylacrylamide) (mG/PNIPAm) membrane. As the solar intensity varies, the water evaporation is tuned through reversible transformations of microstructures reminiscent of the stomatal opening and closing of leaves. Consequently, this mG/PNIPAm membrane displays a high water evaporation rate change (ΔWER) of 1.66 kg m-2 h-1 under weak sunlight (intensity<1 sun) and a low ΔWER of 0.24 kg m-2 h-1 under intense sunlight (1 sun

Solution-Processed Ultraelastic and Strong Air-Bubbled Graphene Foams.

Solution-processed ultraelastic graphene foams are prepared via a convenient air-bubble-promoted synthesis. These foams can dissipate external compression through the ordered interconnecting graphene network between the bubbles without causing a local fracture and thus reliably show compressive stress of 5.4 MPa at a very high strain of 99%, setting a new benchmark for solution-processed graphene foams.

A Graphene Fibriform Responsor for Sensing Heat, Humidity, and Mechanical Changes.

Controllable and sensitive perception of environmental changes is essential for the development of smart material and device systems. Herein, a multi-stimuli sensitive responsor has been fabricated on the base of the established double-helix core-sheath graphene-based microfibers (GFs). By combining the tunable conductivity and mechanical robustness of GF coated with graphitic carbon nitride (GF@GCN), a fibriform smart environmental responsor (SER) is prepared by water-assisted GFs-twisting strategy, which can accordingly present conductive state-dependent current responses upon exposure to a variety of stimuli. More importantly, this SER exhibits high current response to small perturbations induced by temperature variations, mechanical interactions, and relative humidity changes, thereby achieving an environmental perceptibility. Based on this finding, a multi-functional respiratory monitor has been built under the stimuli of the human breath.

Uniquely arranged graphene-on-graphene structure as a binder-free anode for high-performance lithium-ion batteries.

3D graphene interconnected frameworks homogeneously connected with a few-layer graphene film (3DG/FLG) constitute a novel hierarchical hybrid structure for anodes in lithium-ion batteries. The pore-rich 3D graphene network is favorable for Li(+) diffusion and electron transport, and the FLG is a non-metallic current collector that effectively collects/transports charge carriers from/to the 3D graphene network and provides an excellent scaffold to support the 3DG.

Graphene quantum dots-three-dimensional graphene composites for high-performance supercapacitors.

Graphene quantum dots (GQDs) have been successfully deposited onto the three-dimensional graphene (3DG) by a benign electrochemical method and the ordered 3DG structure remains intact after the uniform deposition of GQDs. In addition, the capacitive properties of the as-formed GQD-3DG composites are evaluated in symmetrical supercapacitors. It is found that the supercapacitor fabricated from the GQD-3DG composite is highly stable and exhibits a high specific capacitance of 268 F g(-1), representing a more than 90% improvement over that of the supercapacitor made from pure 3DG electrodes (136 F g(-1)). Owing to the convenience of the current method, it can be further used in other well-defined electrode materials, such as carbon nanotubes, carbon aerogels and conjugated polymers to improve the performance of the supercapacitors.

Droplet-Pen Writing of Ultra-Uniform Graphene Pattern for Multi-Spectral Applications.

Artificial optical patterns bring wide benefits in applications like structural color display, photonic camouflage, and electromagnetic cloak. Their scalable coating on large-scale objects will greatly enrich the multimodal-interactive society. Here, a droplet-pen writing (DPW) method to directly write multi-spectral patterns of thin-film graphene is reported. By amphiphilicity regulations of 2D graphene nanosheets, ultra-uniform and ultrathin films can spontaneously form on droplet caps and pave to the substrate, thus inducing optical interference. This allows the on-surface patterning by pen writing of droplets. Specifically, drop-on-demand thin films are achieved with millimeter lateral size and uniformity up to 97% in subwavelength thickness (<100 nm), corresponding to an aspect ratio of over 30 000. The pixelated thin-film patterns of disks and lines in an 8-inch wafer scale are demonstrated, which enable low-emittance structural color paintings. Furthermore, the applications of these patterns for dual-band camouflage and infrared-to-visible encryption are investigated. This study highlights the potential of 2D material self-assembly in the large-scale preparation and multi-spectral application of thin film-based optical patterns.

Inorganic Hydrogel Based on Low-Dimensional Nanomaterials.

Composed of three-dimensional (3D) nanoscale inorganic bones and up to 99% water, inorganic hydrogels have attracted much attention and undergone significant growth in recent years. The basic units of inorganic hydrogels could be metal nanoparticles, metal nanowires, SiO2 nanowires, graphene nanosheets, and MXene nanosheets, which are then assembled into the special porous structures by the sol-gel process or gelation via either covalent or noncovalent interactions. The high electrical and thermal conductivity, resistance to corrosion, stability across various temperatures, and high surface area make them promising candidates for diverse applications, such as energy storage, catalysis, adsorption, sensing, and solar steam generation. Besides, some interesting derivatives, such as inorganic aerogels and xerogels, can be produced through further processing, diversifying their functionalities and application domains greatly. In this context, we primarily provide a comprehensive overview of the current status of inorganic hydrogels and their derivatives, including the structures of inorganic hydrogels with various compositions, their gelation mechanisms, and their exceptional practical performance in fields related to energy and environmental applications.

Moisture-Enabled Electricity from Hygroscopic Materials: A New Type of Clean Energy.

Water utilization is accompanied with the development of human beings, whereas gaseous moisture is usually regarded as an underexploited resource. The advances of highly efficient hygroscopic materials endow atmospheric water harvesting as an intriguing solution to convert moisture into clean water. The discovery of hygroelectricity, which refers to the charge buildup at a material surface dependent on humidity, and the following moisture-enabled electric generation (MEG) realizes energy conversion and directly outputs electricity. Much progress has been made since then to optimize MEG performance, pushing forward the applications of MEG into a practical level. Herein, the evolvement and development of MEG are systematically summarized in a chronological order. The optimization strategies of MEG are discussed and comprehensively evaluated. Then, the latest applications of MEG are presented, including high-performance powering units and self-powered devices. In the end, a perspective on the future development of MEG is given for inspiring more researchers into this promising area.

Robustly and Intrinsically Stretchable Ionic Gel-Based Moisture-Enabled Power Generator with High Human Body Conformality.

Direct harvesting of energy from moist air will be a promising route to supply electricity for booming wearable and distributed electronics, with the recent rapid development of the moisture-enabled electricity generator (MEG). However, the easy spatial distortion of rigid MEG materials under severe deformation extremely inconveniences the human body with intense physical activity, seriously hindering the desirable applications. Here, an intrinsically stretchable moisture-enabled electricity generator (s-MEG) is developed based on a well-fabricated stretchable functional ionic gel (SIG) with a flexible double-network structure and reversible cross-linking interactions, demonstrating stable electricity output performance even when stretched up to 150% strain and high human body conformality. This SIG exhibits ultrahigh tensile strain (∼600%), and a 1 cm × 1 cm SIG film-based s-MEG can generate a voltage of ∼0.4 V and a current of ∼5.7 µA when absorbing water from humidity air. Based on the strong adhesion and the excellent interface combination of SIG and rough fabric electrodes induced by the fabrication process, s-MEG is able to realize bending or twisting deformation and shows outstanding electricity output stability with ∼90% performance retention after 5000 cycles of bending tests. By connecting s-MEG units in series or parallel, an integrated device of "moisture-powered wristband" is developed to wear on the wrist of humans and drive a flexible sensor for tracking finger motions. Additionally, a comfortable "moisture-powered sheath" based on s-MEGs is created, which can be worn like clothing on human arms to generate energy while walking and flexing the elbow, which is promising in the field of wearable electronics.

Moisture-enabled self-charging and voltage stabilizing supercapacitor.

Supercapacitor is highly demanded in emerging portable electronics, however, which faces frequent charging and inevitable rapid self-discharging of huge inconvenient. Here, we present a flexible moisture-powered supercapacitor (mp-SC) that capable of spontaneously moisture-enabled self-charging and persistently voltage stabilizing. Based on the synergy effect of moisture-induced ions diffusion of inner polyelectrolyte-based moist-electric generator and charges storage ability of inner graphene electrochemical capacitor, this mp-SC demonstrates the self-charged high areal capacitance of 138.3 mF cm-2 and ~96.6% voltage maintenance for 120 h. In addition, a large-scale flexible device of 72 mp-SC units connected in series achieves a self-charged 60 V voltage in air, efficiently powering various commercial electronics in practical applications. This work will provide insight into the design self-powered and ultra-long term stable supercapacitors and other energy storage devices.

Evaporate-casting of curvature gradient graphene superstructures for ultra-high strength structural materials.

In contemporary manufacturing, the processing of structural materials plays a pivotal role in enabling the creation of robust, tailor-made, and precise components suitable for diverse industrial applications. Nonetheless, current material forming technologies face challenges due to internal stress and defects, resulting in a substantial decline in both mechanical properties and processing precision. We herein develop a processing strategy toward graphene superstructure with a curvature gradient, which allows us to fabricate robust structural materials with meticulously designed functional shapes. The structure consists of an arc-shaped assembly of graphene nanosheets positioned at co-axial curvature centers. During the dehydration-based evaporate-casting process, the assembly is tightened via capillary effect, inducing local bending. By precisely tuning the axis-center distance and tilt angle, we achieve accurate control over the shape of obtained structure. Notably, internal stress is harnessed to reinforce a designed mortise and tenon structure, resulting in a high joining strength of up to ~200 MPa. This innovative approach addresses the challenges faced by current material forming technologies and opens up more possibilities for the manufacturing of robust and precisely shaped components.

Bio-Inspired Ultrathin Perfect Absorber for High-Performance Photothermal Conversion.

Ultrathin perfect absorber (UPA) enables efficient photothermal conversion (PC) in renewable chemical and energy systems. However, it is challenging so far to obtain efficient absorption with thickness significantly less than the wavelength, especially considering the common view that an ultrathin film can absorb at most 50% of incident light. Here, a highly light-absorbing and mechanically stable UPA is reported by learning from the honeycomb mirror design of the crab compound eyes. With the hollow apertures enclosed by the self-supporting ultrathin film of reduced graphene oxide and gold nanoparticles, the absorber achieves spoof-plasmon enhanced broadband absorption in solar spectrum and low radiative decay in infrared. Specifically, a strong absorption (87%) is realized by the apertures with cross-section thickness of 1/20 of the wavelength, which is 7.3 times stronger than a planar counterpart with the identical material. Its high PC efficiency up to 64%, with hot-electron temperature as high as 2344 K, is also experimentally demonstrated. Utilizing its low thermal mass nature, a high-speed visible-to-infrared converter is constructed. The absorber can enable high-performance PC processes for future interfacial catalysis and photon-detection.

An all-cotton-derived, arbitrarily foldable, high-rate, electrochemical supercapacitor.

The pure natural cotton provides a low-cost material platform for the facile assembly of all-cotton-derived electrochemical supercapacitors (allC-ECs) with a remarkable character of arbitrary foldability and high response rate, which can be bent, rolled-up, and fully folded without loss of high-rate (<50 ms) capacitive performance.

Graphene microtubings: controlled fabrication and site-specific functionalization.

Manipulating graphene through engineering for macroscopic assemblies of practical importance is a big challenge. We develop a dually geometric confinement approach for the scalable preparation of meter-long graphene microtubings (µGTs) with a tunable diameter. They have strength comparable to graphene fiber and can be shaped to hierarchical multichannel µGT systems in a straightforward way. Of particular importance, µGTs can be selectively functionalized in a site-specific outer-wall, inner-wall, outer/inner-wall, and within-wall fashion, which endows the µGTs with unique properties for desirable applications. Apart from the magnetically and photoelectronically responsive µGTs developed here, a self-powered micromotor made of Pt inner-wall modified µGT showing agile motion in aqueous medium has been also achieved. Beyond the applications demonstrated in this study, the well-defined µGT systems can also play essential role in other important fields such as fluidics, catalysis, purification, separation, and sensing.

Graphene fibers with predetermined deformation as moisture-triggered actuators and robots.

Enough to make your hair curl! Moisture-responsive graphene (G) fibers can be prepared by the positioned laser reduction of graphene oxide (GO) counterparts. When exposed to moisture, the asymmetric G/GO fibers display complex, well-controlled motion/deformation in a predetermined manner. These fibers can function not only as a single-fiber walking robot under humidity alternation but also as a new platform for woven devices and smart textiles.

Multistage coupling water-enabled electric generator with customizable energy output.

Constant water circulation between land, ocean and atmosphere contains great and sustainable energy, which has been successfully employed to generate electricity by the burgeoning water-enabled electric generator. However, water in various forms (e.g. liquid, moisture) is inevitably discharged after one-time use in current single-stage water-enabled electric generators, resulting in the huge waste of inherent energy within water circulation. Herein, a multistage coupling water-enabled electric generator is proposed, which utilizes the internal liquid flow and subsequently generated moisture to produce electricity synchronously, achieving a maximum output power density of ~92 mW m-2 (~11 W m-3). Furthermore, a distributary design for internal water in different forms enables the integration of water-flow-enabled and moisture-diffusion-enabled electricity generation layers into mc-WEG by a "flexible building blocks" strategy. Through a three-stage adjustment process encompassing size control, space optimization, and large-scale integration, the multistage coupling water-enabled electric generator realizes the customized electricity output for diverse electronics. Twenty-two units connected in series can deliver ~10 V and ~280 µA, which can directly lighten a table lamp for 30 min without aforehand capacitor charging. In addition, multistage coupling water-enabled electric generators exhibit excellent flexibility and environmental adaptability, providing a way for the development of water-enabled electric generators.