Solvent-Controlled Morphology of Zinc-Cobalt Bimetallic Sulfides for Supercapacitors.

Bimetallic sulfides offer high theoretical specific capacitance and good stability as electrode materials due to their diverse redox reactions, larger specific surface areas, and better conductivity. The morphology of the electrode material is an important influencing factor for the electrochemical properties. Herein, a series of ZnCoS electrode materials with different morphologies were prepared by varying the solvent in the solvothermal reaction, and the effects of different microstructures on the electrochemical properties of ZnCoS were investigated. The ratio of water and ethanol in the solvent was controlled to modulate the microstructure of the as-prepared ZnCoS materials. XRD and XPS revealed the physical and chemical structure of the ZnCoS materials. SEM and TEM observations showed that the microstructure of ZnCoS transformed from one-dimensional wires to two-dimensional sheets with increasing amounts of ethanol. The maximum specific capacitance of the as-prepared ZnCoS materials is 6.22 F cm-2 at a current density of 5 mA cm-2, which is superior to that of most previously reported bimetallic sulfides. The enhanced electrochemical performance could be ascribed to its sheet-assembled spherical structure, which not only shortens the path of ion diffusion but also increases the contact between surface active sites and the electrolyte. Moreover, the spherical structure provides numerous void spaces for buffering the volume expansion and penetration of the electrolyte, which would be favorable for electrochemical reactions. Furthermore, the ZnCoS electrodes were coupled with activated carbon (AC) electrodes to build asymmetric supercapacitors (ASCs). The ASC device exhibits a maximum energy density of 0.124 mWh cm-2 under a power density of 2.1 mW cm-2. Moreover, even under a high-power density of 21 mW cm-2, the energy density can still reach 0.055 mWh cm-2.

High-Performance Dual-Ion Battery Based on Silicon-Graphene Composite Anode and Expanded Graphite Cathode.

Dual-ion batteries (DIBs) are a new kind of energy storage device that store energy involving the intercalation of both anions and cations on the cathode and anode simultaneously. They feature high output voltage, low cost, and good safety. Graphite was usually used as the cathode electrode because it could accommodate the intercalation of anions (i.e., PF6-, BF4-, ClO4-) at high cut-off voltages (up to 5.2 V vs. Li+/Li). The alloying-type anode of Si can react with cations and boost an extreme theoretic storage capacity of 4200 mAh g-1. Therefore, it is an efficient method to improve the energy density of DIBs by combining graphite cathodes with high-capacity silicon anodes. However, the huge volume expansion and poor electrical conductivity of Si hinders its practical application. Up to now, there have been only a few reports about exploring Si as an anode in DIBs. Herein, we prepared a strongly coupled silicon and graphene composite (Si@G) anode through in-situ electrostatic self-assembly and a post-annealing reduction process and investigated it as an anode in full DIBs together with home-made expanded graphite (EG) as a fast kinetic cathode. Half-cell tests showed that the as-prepared Si@G anode could retain a maximum specific capacity of 1182.4 mAh g-1 after 100 cycles, whereas the bare Si anode only maintained 435.8 mAh g-1. Moreover, the full Si@G//EG DIBs achieved a high energy density of 367.84 Wh kg-1 at a power density of 855.43 W kg-1. The impressed electrochemical performances could be ascribed to the controlled volume expansion and improved conductivity as well as matched kinetics between the anode and cathode. Thus, this work offers a promising exploration for high energy DIBs.

1T/2H Mixed Phase MoS2 Nanosheets Integrated by a 3D Nitrogen-Doped Graphene Derivative for Enhanced Electrocatalytic Hydrogen Evolution.

Molybdenum disulfide (MoS2) has become one of the most promising non-platinum-based electrocatalysts for the hydrogen evolution reaction (HER) because of its unique layered structure. However, the catalytic performance of the thermodynamically stable MoS2 is hindered by its poor conductivity and scarce active sites. We developed a 3D porous N-doped graphene derivative-integrated metal-semiconductor (1T-2H) mixed phase MoS2 (MNG) using urea as a doping reagent. The highly exposed active sites were achieved by inducing the phase transition of MoS2 from 2H phase to 1T phase and the inclusion of highly N-incorporated reduced graphene oxide, both of which were simultaneously realized by optimizing the concentration of the doping reagent. Moreover, the charge/proton transfer was enhanced by the well-designed porous architecture and hydrophilic 1T-MoS2. With these advantages, the optimized MNG-40 catalyst has a small overpotential of 157 mV at a cathodic current density of 10 mA cm-2, a relatively low Tafel slope of 45.8 mV dec-1, and an excellent stability. This work represents a new strategy to design higher-performance HER catalysts and provides new insights into the structural regulation of metal composite transitions.

Enhancing Capacitance Performance of Ti3C2Tx MXene as Electrode Materials of Supercapacitor: From Controlled Preparation to Composite Structure Construction.

Ti3C2Tx, a novel two-dimensional layer material, is widely used as electrode materials of supercapacitor due to its good metal conductivity, redox reaction active surface, and so on. However, there are many challenges to be addressed which impede Ti3C2Tx obtaining the ideal specific capacitance, such as restacking, re-crushing, and oxidation of titanium. Recently, many advances have been proposed to enhance capacitance performance of Ti3C2Tx. In this review, recent strategies for improving specific capacitance are summarized and compared, for example, film formation, surface modification, and composite method. Furthermore, in order to comprehend the mechanism of those efforts, this review analyzes the energy storage performance in different electrolytes and influencing factors. This review is expected to predict redouble research direction of Ti3C2Tx materials in supercapacitors.

Photo-Promoted Platinum Nanoparticles Decorated MoS2@Graphene Woven Fabric Catalyst for Efficient Hydrogen Generation.

Hydrogen production from water splitting has been considered as an effective and sustainable method to solve future energy related crisis. Molybdenum sulfides (e.g., MoS2) show promising catalytic ability in hydrogen evolution reaction (HER). Combining MoS2 with conductive carbon-based materials has aroused tremendous research interest recently. In this work, a highly efficient multiple-catalyst is developed for HER by decorating Pt nanoparticles (Pt NPs) on MoS2@graphene protected nickel woven fabrics (NiWF) substrate, which comprises the following components: (i) Graphene protected NiWF acts as the underlying substrate, supporting the whole structure; (ii) MoS2 nanoplates serve as a central and essential photosensitive component, forming a heterostructure with graphene simultaneously; and (iii) on the basis of the intrinsic photoluminescence effect of MoS2, together with the photoelectric response at the MoS2/graphene interface, Pt NPs are successfully deposited on the whole structure under illumination. Particularly and foremost, this work emphasizes on discussion and verification of the underlying mechanism for photopromoted electroless Pt NPs deposition. Due to this assembly approach, the usage amount of Pt is controlled at ∼5 wt % (∼0.59 at. %) with respect to the whole catalyst. MoS2@Substrate with Pt NPs deposited under 643 nm illumination, with the synergistic effect of MoS2 active sites and Pt NPs, demonstrates the most superior electrocatalytic performance, with negligible overpotential and low Tafel slope of 39.4 mV/dec.

Role of hydrogen in the chemical vapor deposition growth of MoS2 atomic layers.

Hydrogen plays a crucial role in the chemical vapor deposition (CVD) growth of graphene. Here, we have revealed the roles of hydrogen in the two-step CVD growth of MoS2. Our study demonstrates that hydrogen acts as the following: (i) an inhibitor of the thermal-induced etching effect in the continuous film growth process; and (ii) a promoter of the desulfurization reaction by decreasing the S/Mo atomic ratio and the oxidation reaction of the obtained MoSx (0 < x < 2) films. A high hydrogen content of more than 100% in argon forms nano-sized circle-like defects and damages the continuity and uniformity of the film. Continuous MoS2 films with a high crystallinity and a nearly perfect S/Mo atomic ratio were finally obtained after sulfurization annealing with a hydrogen content in the range of 20%-80%. This insightful understanding reveals the crucial roles of hydrogen in the CVD growth of MoS2 and paves the way for the controllable synthesis of two-dimensional materials.

Graphene/polyaniline woven fabric composite films as flexible supercapacitor electrodes.

We report the design and preparation of graphene and polyaniline (PANI) woven-fabric composite films by in situ electropolymerization. The introduction of PANI greatly improves the electrochemical properties of solid-state supercapacitors which possess capacitances as high as 23 mF cm(-2), and exhibit excellent cycling stability with ∼ 100% capacitance retention after 2000 cycles. The devices have displayed superior flexibility with improved areal specific capacitances to 118% during deformation.

All carbon coaxial supercapacitors based on hollow carbon nanotube sleeve structure.

All carbon coaxial supercapacitors based on hollow carbon nanotube (CNT) sleeve structure are assembled and tested. The key advantage of the structure is that the inner core electrode is variable from CNT sleeve sponges, to CNT fibers, reduced graphene oxide fibers, and graphene woven fabrics. By changing core electrodes from sleeve sponges to CNT fibers, the electrochemical performance has been significantly enhanced. The capacitance based on sleeve sponge + CNT fiber double the capacitances of double-sleeve sponge supercapacitors thanks to reduction of the series and internal resistances. Besides, the coaxial sleeve structure possesses many other features, including high rate capacitance, long cycle life, and good flexibility.

Vertical junction photodetectors based on reduced graphene oxide/silicon Schottky diodes.

Reduced graphene oxide (RGO) has been employed as an electrode for a series of vertically structured photodetectors. Compared with mechanically exfoliated or chemical vapor deposited graphene, RGO possesses more oxygen containing groups and defects, which are proved to be favorable to enhance the performance of photodetectors. As a matter of fact, RGO with different reduction levels can be readily obtained by varying the annealing temperature. The synthesis procedures for the RGO material are suitable for large scale production and its performance can be effectively improved by functionalization or element doping. For RGO-based devices, the Schottky junction properties and photoelectric conversion have been investigated, primarily by analyzing their current-voltage characteristics. Subsequently, the ON/OFF ratio, responsivity and detectivity of the photodetectors were closely examined, proving that the RGO material could be effectively utilized as the electrode material; also, their relationship with the RGO reduction levels has also been explored. By analyzing the response/recovery speed of the RGO-based photodetectors, we have studied the effects of oxygen-containing functional groups and crystalline defects on the photoelectric conversion.