Plasma-Driven Selenization for Electrical Property Enhancement in Janus 2D Materials.

The recent emergence of Janus 2D materials like SnSSe, derived from SnS2, reveals unique electrical and optical features, such as asymmetrical electronic structure, enhanced carrier mobility, and tunable bandgap. Previous theoretical studies have discuss the electronic properties of Janus SnSSe, but experimental evidence is limited. This study presents a two-step method for synthesizing Janus SnSSe, involving hydrogen plasma treatment and in situ selenization. Optimized conditions (38 W, 1.5 min, 250 °C) are determined using Raman spectroscopy and AFM analysis. XPS confirmed SnSSe's elemental composition, while KPFM reveals a significant reduction in the work function (from 5.26 down to 5.14 eV) for the first time, indicating asymmetrically induced n-type doping. Finally, field-effect transistors (FETs) derived from SnSSe exhibited significantly enhanced mobility and on-current, as well as n-type doping, compared to SnS2-based FETs. These findings lay a crucial foundation for developing high-performance 2D electronic and optoelectronic devices.

Submicron Memtransistors Made from Monocrystalline Molybdenum Disulfide.

Multiterminal memtransistors made from two-dimensional (2D) materials have garnered increasing attention in the pursuit of low-power heterosynaptic neuromorphic circuits. However, existing 2D memtransistors tend to necessitate high set voltages (>1 V) or feature defective channels, posing concerns regarding material integrity and intrinsic properties. Herein, we present a monocrystalline monolayer MoS2 memtransistor designed for operation within submicron regimes. Under reverse drain bias sweeps, our experiments reveal memristive behavior within the device, further controllable through modulation of the gate terminal. This controllability facilitates the consistent manifestation of multistate memory effects. Notably, the memtransistor behavior becomes more significant as the channel length diminishes, particularly with channel lengths below 1.6 µm, showcasing an increase in the switching ratio alongside a decrease in the set voltage with the decreasing channel length. Our optimized memtransistor demonstrates the ability to exhibit individual resistance states spanning 5 orders of magnitude, with switching drain voltages of approximately 0.05 V. To elucidate these findings, we investigate hot carrier effects and their interplay with oxide traps within the HfO2 dielectric. This work highlights the importance of memtransisor behavior in highly scaled 2D transistors, particularly those featuring low contact resistances. This understanding holds the potential to tailor memory characteristics essential for the development of energy-efficient neuromorphic devices.

Self-powered broadband photodetection enabled by facile CVD-grown MoS2/GaN heterostructures.

Achieving self-powered photodetection without biasing is a notable challenge for photodetectors. In this work, we demonstrate the successful fabrication of large-scale van der Waals epitaxial molybdenum disulfide (MoS2) on a p-GaN/sapphire substrate using a straightforward chemical vapor deposition (CVD) technique. Our research primarily centers on the characterization of these photodetectors produced through this method. The MoS2/GaN heterojunction photodetector showcases a broad and extensive photoresponse spanning from ultraviolet A (UVA) to near-infrared (NIR). When illuminated by a 532 nm laser, its self-powered photoresponse is characterized by a rise time (τr) of ∼18.5 ms and a decay time (τd) of ∼123.2 ms. The photodetector achieves a responsivity (R) of ∼0.13 A W-1 and a specific detectivity (D*) of ∼3.8 × 1010 Jones at zero bias. Additionally, while utilizing a 404 nm laser, the photodetector reaches a maximum R and D* of ∼1.7 × 104 A/W and ∼1.6 × 1013 Jones, respectively, at Vb = 5 V. The operational mechanism of the device can be explained by the diode characteristics involving a tunneling current in the presence of reverse bias. The exceptional performance of these photodetectors can be attributed to the pristine interface between the CVD-grown MoS2 and GaN, providing an impeccably clean tunneling surface. Additionally, our investigation has unveiled that MoS2/GaN heterostructure photodetectors, featuring MoS2 coverage percentages spanning from 20% to 50%, exhibit improved responsivity capabilities at an external bias voltage. As a result, this facile CVD growth technique for MoS2 photodetectors holds significant potential for large-scale production in the manufacturing industry.

Ultraclean and Facile Patterning of CVD Graphene by a UV-Light-Assisted Dry Transfer Method.

The synthesis of large-area graphene by the chemical vapor deposition (CVD) method is a mature technology; however, a transfer procedure is required to integrate CVD-grown graphene into a functional device. The reported methods for transferring graphene films cause different degrees of defects (cracking, rupture) and ion/polymer residues, which deteriorate or alter the electrical properties of as-grown graphene. Developing a reliable and fast transfer method that can maintain high-quality graphene remains a challenge. In this work, we employed UV light release tape (UV-RT) as the support layer to replace the frequently used thermal release tape (TRT) in a typical roll-to-roll dry transfer process. In this process, we used an easier-to-remove polymer as an adhesion layer to greatly reduce the strain and defects that occur during the transfer process. The cleanliness of graphene transferred by this method is above 99%, and the carrier mobility is 1.6 and 1.1 times higher than that obtained with conventional wet transfer and TRT transfer methods, respectively. UV illumination leads to facile and uniform release of the graphene film onto the target substrate, achieving one-step and selective patterning of graphene (feature size of <100 µm). The UV-assisted decomposition of the polymer molecular structure into small molecules enables a residue-free and ultraclean graphene surface. This proposed transfer method enables facile patterning of graphene and 2D films while maintaining high quality, which paves the way for versatile functional graphene applications.

Dual-mode frequency multiplier in graphene-base hot electron transistor.

Since quantum computers have been gradually introduced in countries around the world, the development of the many related quantum components that can operate independently of temperature has become more important for enabling mature products with low power dissipation and high efficiency. As an alternative to studying cryo-CMOSs (complementary metal-oxide-semiconductors) to achieve this goal, quantum tunneling devices based on 2D materials can be examined instead. In this work, a vertical graphene-based quantum tunneling transistor has been used as a frequency modulator. The transistor can operate via different quantum tunneling mechanisms and generates, by applying the appropriate bias, voltage-resistance curves characteristic of variable nonlinear resistance for both base and emitter voltages. We experimentally demonstrate frequency modulation from input signals over the range of 100 kHz to 10 MHz, enabling a tunable frequency doubler or tripler in just a single transistor. This frequency multiplication with a tunneling mechanism makes the graphene-based tunneling device a promising option for frequency electronics in the emerging field of quantum technologies.

Laser-Induced Graphene Stretchable Strain Sensor with Vertical and Parallel Patterns.

In intelligent manufacturing and robotic technology, various sensors must be integrated with equipment. In addition to traditional sensors, stretchable sensors are particularly attractive for applications in robotics and wearable devices. In this study, a piezoresistive stretchable strain sensor based on laser-induced graphene (LIG) was proposed and developed. A three-dimensional, porous LIG structure fabricated from polyimide (PI) film using laser scanning was used as the sensing layer of the strain sensor. Two LIG pattern structures (parallel and vertical) were fabricated and integrated within the LIG strain sensors. Scanning electron microscopy, an X-ray energy dispersive spectrometer, and Raman scattering spectroscopy were used to examine the microstructure of the LIG sensing layer. The performance and strain sensing properties of the parallel and vertical stretchable LIG strain sensors were investigated in tensile tests. The relative resistance changes and the gauge factors of the parallel and vertical LIG strain sensors were quantified. The parallel strain sensor achieved a high gauge factor of 15.79 in the applied strain range of 10% to 20%. It also had high sensitivity, excellent repeatability, good durability, and fast response times during the tensile experiments. The developed LIG strain sensor can be used for the real-time monitoring of human motions such like finger bending, wrist bending, and throat swallowing.

In Situ Cleaning and Fluorination of Black Phosphorus for Enhanced Performance of Transistors with High Stability.

Most two-dimensional (2D) semiconductors suffer from intrinsic instability under ambient conditions, especially 2D black phosphorus (BP). Although much effort has been made to study the passivation of 2D materials against corrosion by oxygen and water molecules, facile and effective passivation with long-term stability is still challenging; in particular, selective passivation, which is critical for integration into nanoelectronics, is still lacking. Here, we develop a novel passivation route for BP using a fluorinated self-assembled thin film of PFSA (perfluorosulfonic acid, PFSA), where the surface modifier with high hydrophobicity on BP presents extremely stable characteristics over five months under ambient conditions. Moreover, we report for the first time in situ cleaning and selective fluorination of only BP flakes on a SiO2/Si substrate by a spin-coating process followed by ultrasonication, which was attributed to the formation of P-F covalent bonds on the BP surface. Selectively fluorinated BP shows not only enhanced stability in air but also electrical properties of the BP field-effect transistor (FET), with the on-current of the BP FET increasing and presenting enhanced carrier mobility (125 cm2 V-1 s-1) and on/off ratio (104). This significant finding sheds light on fabricating vertical 2D heterostructures to realize high performance and reliability with versatile 2D materials. This work demonstrates an emerging passivation approach for long-term stability together with superior electrical properties, which paves the way for integrating 2D semiconductors into critical channel materials in FETs that are favorable for next-generation digital logic circuits.

MoSx on Nitrogen-Doped Graphene for High-Efficiency Hydrogen Evolution Reaction: Unraveling the Mechanisms of Unique Interfacial Bonding for Efficient Charge Transport and Stability.

Functional nanostructures with abundant exposed active sites and facile charge transport through conductive scaffolds to active sites are pivotal for developing an advanced and efficient electrocatalyst for water splitting. In the present study, by coating ∼3 nm MoSx on nitrogen-doped graphene (NG) pre-engrafted on a flexible carbon cloth (MNG) as a model system, an extremely low Tafel slope of 39.6 mV dec-1 with cyclic stability up to 5000 cycles is obtained. The specific fraction of N on the NG framework is also analyzed by X-ray photoelectron spectroscopy and X-ray absorption near edge spectroscopy with synchrotron radiation light sources, and it is found that the MoSx particles are selectively positioned on the specific graphitic N sites, forming the unique Mo-N-C bonding state. This Mo-N-C bonding is founded to facilitate highly effective charge transfer directly to the active sulfur sites on the edges of MoSx, leading to a highly improved hydrogen evolution reaction (HER) with excellent stability (95% retention @ 5000 cycles). The functional anchoring of MoSx by such bonding prevents particle aggregation, which plays a significant role in maintaining the stability and activity of the catalyst. Furthermore, it has been revealed that MNG samples with adequately high amounts of both pyridinic and graphitic N result in the best HER performance. This work helps in understanding the mechanisms and bonding interactions within various catalysts and the scaffold electrode.

Manipulation of Nitrogen-Heteroatom Configuration for Enhanced Charge-Storage Performance and Reliability of Nanoporous Carbon Electrodes.

In this study, various nitrogen-containing functional groups, namely, pyridine (N-6), pyrrole (N-5), oxidized N (N-O), and quaternary N (N-Q), are created on activated carbon (AC) surface via melamine, ammonia, and nitric oxide doping methods. N-5 and N-6 groups markedly alter the specific surface area and pore size of AC. N-O is found to affect electrolyte wettability, and the N-Q content is closely associated with AC electronic conductivity. The nitrogen-containing groups do not contribute to pseudocapacitance in propylene carbonate and acetonitrile electrolytes. However, the nitric-oxide-treated carbon (AC-NO) exhibits the best high-rate charge-discharge performance among the investigated materials. The N-Q-enriched and N-5/N-6-depleted AC-NO most effectively suppresses the leakage current and gas evolution of supercapacitors. Online gas chromatography is used to analyze the gaseous species produced from AC electrodes. With an appropriate surface functionality on carbon, the cell voltage can be increased to ∼3 V, increasing the energy and power densities. The aging behavior of the carbon electrodes with and without nitrogen modification after being floated at 2.5 V and 70 °C for 3 days is investigated. An effective strategy for enhancing supercapacitor performance and reliability is proposed.

Sb nanoparticle decorated rGO as a new anode material in aqueous chloride ion batteries.

An aqueous chloride ion battery (CIB) is an emerging technology for electrochemical energy storage as well as battery desalination systems. However, the instability and decomposition of electrode materials in an aqueous medium is a major issue in CIBs. Herein, in one step, we synthesized fine antimony nanoparticles with a size of ∼20 nm on reduced graphene oxide (Sb@rGO) sheets using a hydrothermal route with facile and cost-effective processes. It is proposed as a new anode material and coupled with the AgCl cathode in an aqueous CIB. The specific capacity is maintained constantly at 51.6 mA h g-1 at a current density of 400 mA g-1 even after 200 cycles. In addition, characterization methods such as electrochemical analysis, X-ray diffraction, etc. were used to confirm the reaction mechanism. The chloride ion capture material developed in this research work will be significant for CIBs as an energy storage technology or battery desalination system.

Zinc-Air Battery-Based Desalination Device.

Efficiently storing electricity generated from renewable resources and desalinating brackish water are both critical for realizing a sustainable society. Previously reported desalination batteries need to work in alternate desalination/salination modes and also require external energy inputs during desalination. Here, we demonstrate a novel zinc-air battery-based desalination device (ZABD), which can desalinate brackish water and supply energy simultaneously. The ZABD consists of a zinc anode with a flowing ZnCl2 anolyte stream, a brackish water stream, and an air cathode with a flowing NaCl catholyte stream, separated by an anion-exchange membrane and a cation-exchange membrane, respectively. During the discharging, ions in brackish water move to the anolyte and catholyte, and they return to the feed steam during charging. The ZABD can desalt brackish water from 3000 ppm to the drinking water level at 120.1 ppm in one step and concurrently provide an energy output up to 80.1 kJ mol-1 under a discharge current density of 0.25 mA cm-2. Further, the ZABD can be charged/discharged over 20 cycles without significant performance deterioration, demonstrating its reversibility. Moreover, the desalination performances can be adjusted by varying current densities and are also influenced by the initial concentration of salt feeds. Besides, two ZABD devices were connected in series to drive 60 light-emitting diodes during the salt removal process without external power supply over 2000 min. Overall, this ZABD system demonstrates the potential for simultaneous water desalination and energy supply, which is suitable for many urgent situations.

Facile synthesis of core-shell structured Si@graphene balls as a high-performance anode for lithium-ion batteries.

Encapsulating silicon (Si) nanoparticles with graphene nanosheets in a microspherical structure is proposed to increase electrical conductivity and solve stability issues when using Si as an anode material in lithium-ion batteries (LIBs). Currently the main strategies to produce high-quality Si-graphene (Si@Gra) electrodes are (1) chemical vapor deposition (CVD) of graphene grown in situ on Si by hydrocarbon precursors and (2) encapsulating Si with a graphene oxide followed by postannealing. However, both methods require a high-temperature and are costly and time-consuming procedures, which hinders their mass scalability and practical utilization. Herein, we report a Si@Gra composite with a ball-like structure that is assembled by a facile spray drying process without a postannealing treatment. The graphene sheets are synthesized by an electrochemical exfoliation method from natural graphite. The resulting Si@Gra composite exhibits a unique core-shell structure, from which the ball-like morphology and the number of graphene layers in the Si@Gra composites are found to affect both the electric conductivity and ionic conductivity. The Si@Gra composites are found to increase the capacity of the anode and provide excellent cycling stability, which is attributed to the high electrical conductivity and mechanical flexibility of the layered graphene; additionally, a void space in the core-shelled ball structure inside the Si@Gra compensates for the Si volume expansion. As a result, the Si@few-layer graphene ball anode exhibits a high initial discharge capacity of 2882.3 mA h g-1 and a high initial coulombic efficiency of 86.9% at 0.2 A g-1. The combination of few-layer graphene sheets and the spray drying process can effectively be applied for large-scale production of core-shell structured Si@Gra composites as promising anode materials for use in high-performance LIBs.

Pool Boiling Heat Transfer Enhanced by Fluorinated Graphene as Atomic Layered Modifiers.

Graphene has been applied to thermal technology including boiling and condensation heat transfer, from which the pool boiling enhancement relies on adjusting the surface morphology and wettability that is favorable to catalyze the vaporization on the fluid/graphene interface. However, previous works using graphene or reduced graphene oxide (RGO) flake coatings, where the morphology of graphene coating is nonuniform and most of the underlying structured cavities are sealed by graphene flakes. For a long time, this hampered the unraveling of the mechanism behind the enhanced boiling performance by graphene coatings. Moreover, the previous work relied on using water-based pool boiling, which limits the scope of its practical applications since the versatile nonpolar refrigerant has been widely used in boiling heat transfer. The pool boiling was carried out on a plain copper surface to study the effect of fluorinated graphene (F-graphene) coating using nonpolar refrigerant R-141b as the working fluid along with bubble dynamic visualization. It was found that the increase of contact angle leads to more active cavities and enhances heat transfer performance up to twice as much, by applying the F-graphene coating. Moreover, the mechanism of graphene-enhanced heat transfer performance was unraveled and mainly attributed to the hydrophobic surface and effective cavity structure. This research provides a practical and reliable route for enhancing the heat transfer through F-graphene-coatings, which paves the way for potential application in graphene-based thermal technologies.

Spectroscopic and Electrical Characterizations of Low-Damage Phosphorous-Doped Graphene via Ion Implantation.

Development of n-/p-type semiconducting graphenes is a critical route to implement in graphene-based nanoelectronics and optronics. Compared to the p-type graphene, the n-type graphene is more difficult to be prepared. Recently, phosphorous doping was reported to achieve air-stable and high mobility of n-typed graphene. The phosphorous-doped graphene (P-Gra) by ion implantation is considered as an ideal method for tailoring graphene due to its IC compatible process; however, for a conventional ion implanter, the acceleration energy is in the order of kiloelectron volts (keV), thus severely destroys the sp2 bonding of graphene owing to its high energy of accelerated ions. The introduced defects, therefore, degrade the electrical performance of graphene. Here, for the first time, we report a low-damage n-typed chemical vapor deposition (CVD) graphene by an industrial-compatible ion implanter with an energy of 20 keV where the designed protection layer (thin Au film) covered on as-grown CVD graphene is employed to efficiently reduce defect formation. The additional post-annealing is found to heal the crystal defects of graphene. Moreover, this method allows transferring ultraclean and residue-free P-Gra onto versatile target substrates directly. The doping configuration, crystallinity, and electrical properties on P-Gra were comprehensively studied. The results indicate that the low-damaged P-Gra with a controllable doping concentration of up to 4.22 at % was achieved, which is the highest concentration ever recorded. The doped graphenes with tunable work functions (4.85-4.15 eV) and stable n-type doping while keeping high-carrier mobility are realized. This work contributes to the proof-of-concept for tailoring graphene or 2D materials through doping with an exceptional low defect density by the low energy ion implantation, suggesting a great potential for unconventional doping technologies for next-generation 2D-based nanoelectronics.

Nanocatalyst-Assisted Fine Tailoring of Pore Structure in Holey-Graphene for Enhanced Performance in Energy Storage.

Nanoporous holey-graphene (HG) shows potential versatility in several technological fields, especially in biomedical, water filtration, and energy storage applications. Particularly, for ultrahigh electrochemical energy storage applications, HG has shown promise in addressing the issue of low gravimetric and volumetric energy densities by boosting of the ion-transport efficiency in a high-mass-loaded graphene electrode. However, there are no studies showing complete control over the entire pore architecture and density of HG and their effect on high-rate energy storage. Here, we report a unique and cost-effective method for obtaining well-controlled HG, where a copper nanocatalyst assists the predefined porosity tailoring of the HG and leads to an extraordinary high pore density that exceeds 1 × 103 µm-2. The pore architectures of the hierarchical and homogenous pores of HG were realized through a rationally designed nanocatalyst and the annealing procedure in this method. The HG electrode with a high mass loading results in improved supercapacitor performance that is at least 1 order of magnitude higher than conventional graphene flakes (reduced electrochemically exfoliated graphene (rECG)) in areal capacitance (∼100% retention of capacitance until 15 000 cycles), energy density, and power density. The diffusion coefficient of the HG electrode is 1.5-fold higher than that of rECG at a mass loading of 15 mg cm-2, indicating excellent ion-transport efficiency. The excellent ion-transport efficiency of HG is further proved by nearly 4-fold magnitude lowering of its Rion (the ionic resistance in the electrolyte-filled pores) value as compared with rECG when estimated for equivalent high-mass-loaded electrodes. Furthermore, the HG exhibits a packing density that is 2 orders of magnitude higher than rECG, revealing the utility of the maximum electrode mass and possessing higher volumetric capacitance. The perfect tailoring of HG with optimized porosity allows the achievement of high areal capacitance and excellent cycling stability due to the facile ion- and charge-transport at high-mass-loaded electrodes, which could open a new avenue for addressing the long-existing issue of practical application of graphene-based energy storage devices.

Planar Heterojunction Solar Cell Employing a Single-Source Precursor Solution-Processed Sb2S3 Thin Film as the Light Absorber.

We discuss here a solution-processed thin film of antimony trisulphide (Sb2S3; band gap ≈ 1.7 eV; electronic configuration: ns2np0) for applications in planar heterojunction (PHJ) solar cells. An alternative solution processing method involving a single-metal organic precursor, viz., metal-butyldithiocarbamic acid complex, is used to grow the thin films of Sb2S3. Because of excess sulphide in the metal complex, the formation of any oxide is nearly retarded. Sb2S3 additionally displays structural anisotropy with a ribbon-like structure along the [001] direction. These ribbon-like structures, if optimally oriented with respect to the electron transport layer (ETL)/glass substrate, can be beneficial for light-harvesting and charge-transport properties. A PHJ solar cell is fabricated comprising Sb2S3 as the light absorber and CdS as an ETL coated on to FTO. With varying film sintering temperature and thickness, the typical ribbon-like structures predominantly with planes hkl: l = 0 stacked horizontally along with respect to CdS/FTO are obtained. The morphology of the films is observed to be a function of the sintering temperature, with higher sintering temperatures yielding compact and smooth films with large-sized grains. Maximum photon to electricity efficiency of 2.38 is obtained for PHJ solar cells comprising 480 nm thick films of Sb2S3 sintered at 350 °C having a grain size of few micrometers (>5 µm). The study convincingly shows that improper grain orientation, which may lead to nonoptimal alignments of the intrinsic structure with regard to the ETL/glass substrate, is not the sole parameter for determining photovoltaics performance. Other solution-processing parameters can still be suitably chosen to generate films with optimum morphology, leading to high photon to electricity efficiency.

Solution-processed black phosphorus nanoflakes for integrating nonvolatile resistive random access memory and the mechanism unveiled.

In this study, we demonstrated the integration of black phosphorus (BP) nanoflakes in a resistive random access memory (RRAM) with a facile and complementary metal-oxide-semiconductor-compatible process. The solution-processed BP nanoflakes embedded in polystyrene (PS) as an active layer were sandwiched between aluminum electrodes (Al/BP:PS/Al). The device shows a figure of merit with typical bipolar behavior and forming-free characteristics as well as excellent memory performances such as nonvolatile, low operation voltage (1.75 V) and high ON/OFF ratio (>102) as well as the long retention time (>1500 s). The improved device performances were attributed to the formation of effective trap sites from the hybrid structure of the active layer (BP:PS), especially the BP nanoflakes and the partly oxidized species (P x O y ). Moreover, the extrinsic aluminum oxide layer was observed after the device operation. The mechanism of switching behavior was further unveiled through the carrier transport models, which confirms the conductive mechanisms of space-charge-limited current and Ohmic conductance at high resistance state (HRS) and low resistance state, respectively. Additionally, in the high electric field at HRS, the transfer curve was well fitted with the Poole-Frenkel emission model, which could be attributed to the formation of the aluminum oxide layer. Accordingly, both the trapping/de-trapping of carriers and the formation/rupture of conductive filaments were introduced as transport mechanisms in our devices. Although the partial P x O y species on BP were inevitable during the liquid phase exfoliation process, which was regarded as the disadvantages for various applications, it turns to a key point for improving performances in memory devices. The proposed approach to integrating BP nanoflakes in the active layer of the RRAM device could pave the way for next-generation memory devices.

Revisiting graphene-polymer nanocomposite for enhancing anticorrosion performance: a new insight into interface chemistry and diffusion model.

Graphene is impermeable to all molecules and has high chemical stability, which makes it an excellent anticorrosion coating for metals. However, current studies have indicated that galvanic coupling between graphene and a metal actually accelerates corrosion at the interface. Due to the insulating nature of polymers, graphene-polymer composite coatings with a strong interaction between the filler and the polymer matrix are an alternative means of addressing this issue. Nevertheless, such coatings require well-dispersed graphene flakes to lengthen the diffusion paths of gases or liquids, while preventing the formation of a conducting network from graphene to the metal. The difficulty in preparing such coatings was mainly due to problems with the control of the assembled phase during interfacial reactions. Herein, the interactions between the filler and the polymer were found to be a key factor governing anticorrosion performance, which has scarcely been previously reported. The advantage of graphene as a filler in anticorrosion coatings lies in its dispersibility and miscibility with both the casting solvent and the polymer. Electrochemically exfoliated graphene (EC-graphene) with appropriate surface functionalities that allow high miscibility with waterborne polyurethane (PU) and hydrophobic epoxy has been found to be an ideal filler that outperforms other graphene materials such as graphene oxide (GO) and reduced graphene oxide (rGO). Furthermore, a bilayer coating with EC-graphene additives for PU over epoxy has been found to reduce the corrosion rate (CR) to 1.81 × 10-5 mm per year. With a graphene loading of less than 1%, this represents the lowest CR ever achieved for copper and steel substrates and a diffusion coefficient that is lower by a factor of nearly 2.2 than that of the pristine polymer. Furthermore, we have shown that by controlling the amount of graphene loaded in the polymer galvanic corrosion favored by the formation of an interconnected graphene percolation network can successfully be limited. The present study, together with a facile and eco-friendly method of nanocomposite synthesis, may pave the way toward practical applications in the development of graphene-based anticorrosion coatings.

Controlled multimodal hierarchically porous electrode self-assembly of electrochemically exfoliated graphene for fully solid-state flexible supercapacitor.

Supercapacitors constructed from three-dimensional (3D) graphene electrodes with high ion-accessible surface area and durable mechanical flexibility have great potential for wearable devices. For the development of a highly efficient graphene electrode for electrical double layer capacitors (EDLCs), proper control over not only the specific surface area but also the type of pore (macro-, meso- and micro-porous networks) adapted for an appropriate type of electrolyte is crucial to ensure an ideal performance in terms of both energy density and power delivery rate. However, there is still a lack of technology to create graphene structures that combine macro-, meso- and micro-pores by a one-step and facile method. In addition, the ion/electron transport of a solid state electrolyte among such multimodal pore structures is not fully investigated. Here, we report a novel cost-effective technique of concentration dependent self-assembly of electrochemically exfoliated graphene (EC-graphene) to obtain a 3D architecture with controllable macropores (0.39-4.99 µm) and multimodal hierarchical meso- and micro-pores. The better performance of the 3D architecture is obtained due to its optimum micron-sized macropore diameter (∼5 µm) that serves as an ion buffering reservoir, followed by facile ion diffusion kinetics through the well-modulated combination of macro-, meso- and micro-pores. The binder and conductive carbon additive free supercapacitor constructed from the 3D graphene electrode exhibited a specific capacitance of 45.40 F g-1 (6 M KOH) and 23.89 F g-1 (1 M H2SO4 gel electrolyte). A capacitance retention of above 90% (up to 180° folding angle) after 50 bending-relaxing cycles is obtained, implying the superior durability of the device and the worthiness of the synthesis procedure. The method reported here may pave the way for the development of an environment friendly, large scale producible and controlled porous graphene-based architecture for the high performance next generation flexible, all-solid-state and binder-free energy storage devices.

Electrolyte Engineering: Optimizing High-Rate Double-Layer Capacitances of Micropore- and Mesopore-Rich Activated Carbon.

Various types of electrolyte cations as well as binary cations are used to optimize the capacitive performance of activated carbon (AC) with different pore structures. The high-rate capability of micropore-rich AC, governed by the mobility of desolvated cations, can outperform that of mesopore-rich AC, which essentially depends on the electrolyte conductivity.