Rational synthesis of 3D coral-like ZnCo2O4 nanoclusters with abundant oxygen vacancies for high-performance supercapacitors.

Transition metal oxides with high theoretical capacitance are regarded as desired electrode materials for supercapacitors, however, the poor conductivity and sluggish charge transfer kinetics constrain their electrochemical performance. The three-dimensional (3D) coral-like ZnCo2O4 nanomaterials with abundant oxygen vacancies were synthesized through a facile hydrothermal method and chemical reduction approach. The introduced oxygen vacancies can provide more active sites and lower the energy barrier, thereby facilitating the kinetics of surface reactions. Furthermore, the abundant oxygen vacancies in metal oxides can function as shallow donors to facilitate charge carrier diffusion, resulting in a faster ion diffusion rate and superior electrochemical conductivity. The electrochemical performance of ZnCo2O4 was optimized by the introduction of oxygen vacancies. The ZnCo2O4 nanoclusters, reduced by 0.5 M NaBH4 (ZnCo2O4-0.5), exhibit a specific capacitance of 2685.7 F g-1 at 1 A g-1, which is nearly twice that of the pristine ZnCo2O4 (1525.7 F g-1 at 1 A g-1). The ZnCo2O4-0.5 exhibits an excellent rate capacity (81.9% capacitance retention at 10 A g-1) and a long cycling stability (72.6% specific capacitance retention after 10 000 cycles at 3 A g-1). Furthermore, the asymmetric supercapacitor (ASC, ZnCo2O4-0.5 nanoclusters//active carbon) delivers a maximum energy density of 50.2 W h kg-1 at the power density of 493.7 W kg-1 and an excellent cycling stability (75.3% capacitance retention after 3000 cycles at 2 A g-1), surpassing the majority of previously reported ZnCo2O4-based supercapacitors. This work is important for revealing the pivotal role of implementing the defect engineering regulation strategy in achieving optimization of both electrochemical activity and conductivity.

Enhanced metal-free photocatalyst performance by synergistic Coupling of internal magnetic field and piezoelectric field.

Graphitic carbon nitride (g-C3N4) is a promising metal-free photocatalyst; however, its high carrier recombination rate and insufficient redox capacity limit its degradation effect on antibiotics. In order to overcome these shortcomings, the photocatalytic activity is improved by regulating the spin polarization state, constructing the internal electric field, and applying the external piezoelectric field. In this paper, the chlorine-doped and nitrogen-deficient porous carbon nitride composite carbon quantum dots (Nv-Cl/UPCN@CQD) has been synthesized successfully. The doping position of chlorine and spin polarization properties are verified by DFT calculation. The key intermediates *O2- and *OOH for the synthesis of reactive oxygen species were detected by in-situ infrared testing, which promotes the production of •O2- and H2O2. The degradation rate constant of Nv-Cl/UPCN@CQD for removal of tetracycline is 8.45 times higher than that of g-C3N4. The active oxygen production and degradation efficiency of piezoelectric photocatalysis under the synergistic effect of intense stirring and vis-light irradiation are much higher than those of photocatalysis and piezoelectric catalysis, and the conversion of H2O2 to •OH is promoted by piezoelectric field. This paper provides a reliable way to improve the performance of piezoelectric photocatalysts by adjusting their energy band, electronic structure and piezoelectric force.

Facile synthesis of morphology-controlled hybrid structure of ZnCo2O4 nanosheets and nanowires for high-performance asymmetric supercapacitors.

Controllable synthesis of electrode materials with desirable morphology and size is of significant importance and challenging for high-performance supercapacitors. Herein, we propose an efficient hydrothermal approach to controllable synthesis of hierarchical porous three-dimensional (3D) ZnCo2O4 composite films directly on Ni foam substrates. The composite films consisted of two-dimensional (2D) nanosheets array anchored with one-dimensional (1D) nanowires. The morphologies of ZnCo2O4 arrays can be easily controlled by adjusting the concentration of NH4F. The effect of NH4F in the formation of these 3D hierarchical porous ZnCo2O4 nanosheets@nanowires films is systematically investigated based on the NH4F-independent experiments. This unique 3D hierarchical structure can help enlarge the electroactive surface area, accelerate the ion and electron transfer, and accommodate structural strain. The as-prepared hierarchical porous ZnCo2O4 nanosheets@nanowires films exhibited inspiring electrochemical performance with high specific capacitance of 1289.6 and 743.2 F g-1 at the current density of 1 and 30 A g-1, respectively, and a remarkable long cycle stability with 86.8% capacity retention after 10 000 cycles at the current density of 1 A g-1. Furthermore, the assembled asymmetric supercapacitor using the as-prepared ZnCo2O4 nanosheets@nanowires films as the positive electrode and active carbon as negative electrode delivered a high energy density of 39.7 W h kg-1 at a power density of 400 W kg-1. Our results show that these unique hierarchical porous 3D ZnCo2O4 nanosheets@nanowires films are promising candidates as high-performance electrodes for energy storage applications.

A New Structure with Localized sp2 Bonding for Fivefold Twinning in Diamond.

Changes in atomic bonding configuration in carbon from sp3 to sp2 are known to exist in certain structural defects in diamond, such as twin boundaries, grain boundaries, and dislocations, which have a significant impact on many properties of diamond. In this work, the atomic structure of fivefold twinning in detonation synthesized ultra-dispersed diamonds is investigated using a combination of techniques, including spherical aberration-corrected high-resolution electron microscopy (HREM), HREM image simulations, and molecular mechanics (MM) calculations. The experimental HREM images reveal clearly that the fivefold twinning in diamond has two distinct structures. In addition to the concentric fivefold twins, where the core structure is the intersection of five {111} twinning boundaries, a new extended core structure with co-hybridization of bonding is identified and analyzed in fivefold twinning. The atomic structure forming these fivefold twinning boundaries and their respective core structures is proposed to involve both the tetrahedral sp3 and planar graphitic sp2 bonding configurations, in which a co-hybridized planar hexagon of carbon serves as a fundamental structural unit. The presence of this sp2 -bonded planar unit of hexagonal carbon rings in general grain boundaries is also discussed.

Tuning oxygen-containing functional groups of graphene for supercapacitors with high stability.

To investigate the relationship between the oxygen-containing functional groups of graphene and the stability of supercapacitors, reduced graphene oxide (rGO) containing different oxygenic functional groups was prepared by varying the reduction time of GO using hydrazine as the reducing agent. TEM, XRD, Raman, and XPS characterizations revealed that, as the reduction time increased, the sp2 structure in the rGO sheet was restored and the obtained rGO had good crystallinity accompanied by removal of the oxygenic functional groups. The analysis of the content of the different functional groups also suggested that the reduction rate of the oxygenic functional group was C-O > C[double bond, length as m-dash]O > O-C[double bond, length as m-dash]O. The supercapacitive performance of rGO showed that the oxygenic functional groups contributed to some pseudocapacitance and resulted in a larger specific capacitance. At the same time, however, it is also accompanied by poorer rate performance and durability, which will be improved by removing the oxygenic functional groups by extending the reduction time. With an optimized reaction condition of a reduction time of 24 h, the obtained rGO exhibited excellent stability in floating tests at 3.0 V and 45 °C for 60 days. These findings pave the way for the development of high quality graphene materials for cost-effective and practical graphene supercapacitors.

Achieving High-Energy-Density Graphene/Single-Walled Carbon Nanotube Lithium-Ion Capacitors from Organic-Based Electrolytes.

Developing electrode materials with high voltage and high specific capacity has always been an important strategy for increasing the energy density of lithium-ion capacitors (LICs). However, organic-based electrolytes with lithium salts limit their potential for application in LICs to voltages below 3.8 V in terms of polarization reactions. In this work, we introduce Li[N(C2F5SO2)2] (lithium Bis (pentafluoroethanesulfonyl)imide or LiBETI), an electrolyte with high conductivity and superior electrochemical and mechanical stability, to construct a three-electrode LIC system. After graphite anode pre-lithiation, the anode potential was stabilized in the three-electrode LIC system, and a stable solid electrolyte interface (SEI) film formed on the anode surface as expected. Meanwhile, the LIC device using LiBETI as the electrolyte, and a self-synthesized graphene/single-walled carbon nanotube (SWCNT) composite as the cathode, showed a high voltage window, allowing the LIC to achieve an operating voltage of 4.5 V. As a result, the LIC device has a high energy density of up to 182 Wh kg-1 and a 2678 W kg-1 power density at 4.5 V. At a current density of 2 A g-1, the capacity retention rate is 72.7% after 10,000 cycles.

Effects of low work-function lanthanum oxides on stable electron field emissions from nanoscale emitters.

Nanoscale electron field emitters are known to produce more stable electron emissions than conventional emitters. This has been attributed to size effects; nanoscale emitters can operate with a small emission current and a low extraction voltage, which reduces the bombardment of residual gas ions on the emitter tip. However, our experiments discovered that nanoscale LaB6 emitters had extremely stable emissions, suggesting that chemical effects are present in addition to size effects. This suggests that during operations, a material other than LaB6 may be deposited on the surface of the tip to enhance the stability of emissions. Therefore, we searched for possible materials theoretically within the La-B-O ternary system and found that lanthanum oxides (LaO) and oxygen-deficient La2O3 (La2O3-x ) had good electrical conductivity and a low work function comparable to that of LaB6. These lanthanum oxides are chemically less reactive to residual gases than LaB6. Thus, if they are present on the LaB6 surface, they could stabilize electron emissions without diminishing the emission performance. These findings suggest that lanthanum oxides could be used for electron field emitters.

Facile preparation of flexible binder-free graphene electrodes for high-performance supercapacitors.

A facile two-step strategy to prepare flexible graphene electrodes has been developed for supercapacitors using thermal reduction of graphene oxide (GO) and thermally reduced graphene oxide (TRGO) composite films. The tunable porous structure of the GO/TRGO film provided channels to release the high pressure generated by CO2 gas. The graphene electrode obtained from reduced-GO/TRGO (1 : 1 in mass ratio) film showed great flexibility and high film density (0.52 g cm-3). Using the EMI-BF4 electrolyte with a working voltage of 3.7 V, the as-fabricated free-standing reduced-GO/TRGO (1 : 1) film achieved a great gravimetric capacitance of 180 F g-1 (delivering a gravimetric energy density of 85.6 W h kg-1), a volumetric capacitance of 94 F cm-3 (delivering a volumetric energy density of 44.7 W h L-1), and a 92% retention after 10 000 charge/discharge cycles. In addition, the solid state flexible supercapacitor with the free-standing reduced-GO/TRGO (1 : 1) film as the electrodes and the EMI-BF4/poly (vinylidene fluoride hexafluopropylene) (PVDF-HFP) gel as the electrolyte also demonstrated a high gravimetric capacitance of 146 F g-1 with excellent mechanical flexibility, bending stability, and electrochemical stability. The strategy developed in this study provides great potentials for the synthesis of flexible graphene electrodes for supercapacitors.

Stable field-emission from a CeB6 nanoneedle point electron source.

A single CeB6 nanoneedle structure has been fabricated using a focused ion beam (FIB) and its field emission characteristics have been evaluated. A converged electron beam has been obtained, attributed to its sharpened tip with a radius of curvature of about 10 nm. Combined with its low work function, the required electric field is as low as 1.6 V nm-1 to generate a field emission current of 50 nA. The most outstanding feature of the CeB6 nanoneedle emitter is its excellent current stability that enabled continuous emission for 16 hours with a fluctuation of 1.6% and without deterioration even in a vacuum of 10-7 Pa. The stable field-emission is attributed to the nanometric tip radius that led to reduction in gas adsorption and desorption. In addition, the downward dipolar structure on the emission surface is also beneficial for making the surface inert. These performance factors make CeB6 a practical field-emission point electron source for microscopy applications.

A stable LaB6 nanoneedle field-emission point electron source.

A material with a low work function exhibiting field-emission of electrons has long been sought as an ideal point electron source to generate a coherent electron beam with high brightness, long service life, low energy spread, and especially stable emission current. The quality and performance of the electron source are now becoming limiting factors for further improving the spatial resolution and analytical capabilities of the electron microscope. While tungsten (W) is still the only material of choice as a practically usable field emission filament since it was identified more than six decades ago, its electron optical performance remains unsatisfactory, especially the poor emission stability (>5% per hour), rapid current decay (20% in 10 hours), and relatively large energy spread (0.4 eV), even in an extremely high vacuum (10-9 Pa). Herein, we report a LaB6 nanoneedle structure having a sharpened tip apex with a radius of curvature of about 10 nm that is fabricated and finished using a focused ion beam (FIB) and show that it can produce a field emission electron beam meeting the application criteria with a high reduced brightness (1010 A m-2 sr-1 V-1), small energy spread (0.2 eV), and especially high emission stability (<1% fluctuation in 16 hours without decay). It can now be used practically as a next-generation field-emission point electron source.

Roles of water in the formation and preparation of graphene oxide.

The functional groups and physical properties of graphene oxide (GO) are found to be sensitive to and can be controlled by the water content in the reactions when GO samples are prepared at different concentrations of sulfuric acid using a modified Hummers method. GO prepared with 93% sulfuric acid (H2SO4) showed fewer structural defects, less π-π conjugation, and larger interlayer spacing than GO prepared with 99% H2SO4. The intensity ratio of the D-band to the G-band of the Raman spectrum is 0.89 ± 0.01 and 1.02 ± 0.01, corresponding to average interlayer spacing of 0.91 nm and 0.86 nm, respectively. The yield and carbon to oxygen ratio of the GO sheets prepared from different concentrations of H2SO4 are nearly identical. More importantly, compared with GO synthesized with 99% H2SO4, GO prepared with 93% H2SO4 contains more carbon-oxygen single bonds, such as epoxy groups and hydroxyl groups, but fewer carbonyl groups.

Correction: Roles of water in the formation and preparation of graphene oxide.

[This corrects the article DOI: 10.1039/D0RA10026A.].

Effect of porous structural properties on lithium-ion and sodium-ion storage: illustrated by the example of a micro-mesoporous graphene1-x (MoS2) x anode.

In this work, we synthesized micro-mesoporous graphene1-x (MoS2) x with different compositional ratios via co-reduction of graphite oxide and exfoliated MoS2 platelets. We systematically studied the performance of the micro-mesoporous graphene1-x (MoS2) x as anodes in lithium-ion batteries and sodium-ion batteries. The results show that the specific surface areas of the composites decrease with introducing MoS2. The irreversible capacitance, which is related to the formation of solid electrolyte interphases, also decreases. Besides specific surface area, we found that micropores can benefit the lithiation and sodiation. We demonstrated that a specific charge capacity of 1319.02 mA h g-1 can be achieved at the 50th cycle for the graphene½(MoS2)½ anode in lithium-ion batteries. Possible relationships between such a high specific capacity and the micro-mesoporous structure of the graphene1-x (MoS2) x anode are discussed. This work may shed light on a general strategy for the structural design of electrode materials in lithium-ion batteries and sodium-ion batteries.

Electrical conduction and field emission of a single-crystalline GdB44Si2 nanowire.

The electronic transport and field emission properties of a single-crystalline GdB44Si2 nanowire are studied. The atomic structure and elemental composition of the GdB44Si2 nanowire are characterized by transmission electron microscopy (TEM) using atomic imaging, energy-dispersive X-ray spectroscopy (EDS), and electron energy-loss spectroscopic (EELS) mapping. The electrical conductivity of the single GdB44Si2 nanowire is in the range of 46.8-60.1 S m-1. The in situ TEM field emission measurement reveals that it has a low work function of 2.4 eV. To realize a converged electron emission, a field evaporation pretreatment was used to clean the emission surface and to make a sharpened tip. The field emission probe measurement results show that the electron emission from the sharp GdB44Si2 nanowire is converged to a single field emission spot and it has a work function of 2.6 eV which is in agreement with the in situ TEM measurement. The stability of field emission current is also very good with a fluctuation of 1.4% in 20 min. With a low work function and stable emission current, the GdB44Si2 nanowire shows great promise for field emission applications.

A controllable and efficient method for the fabrication of a single HfC nanowire field-emission point electron source aided by low keV FIB milling.

A single hafnium carbide (HfC) nanowire field-induced electron emitter with a sharp tip apex is fabricated by Pt deposition and focused ion beam (FIB) milling. The structure of the electron emitter is characterized by scanning transmission electron microscopy (STEM) and atom probe tomography (APT). The HfC nanowire is single-crystalline with a thin oxide layer on its tip surface. The field emission properties are determined by using both in situ transmission electron microscopy (TEM) and a field-emission probe in a high-vacuum chamber. A high current of 173 nA was obtained at a low extraction voltage of 631 V with an emission gap of 5 mm. The emission current is stable at 60 nA for 100 min with a fluctuation of 0.7%. The deduced work function was 3.1 eV. It is suggested that the implanted Ga ions and the oxide layer induce more downward dipoles that are beneficial for lowering the work function and creating a stable surface. When the low keV FIB processing is applied, it takes within 30 minutes to finish a HfC nanowire emitter, establishing an efficient procedure for the preparation of nanowire emitters. These results provide a controllable and fast production method for the fabrication of single nanowire field-emission point electron sources.

A green strategy for the preparation of a honeycomb-like silicon composite with enhanced lithium storage properties.

The high-performance silicon (Si) composite electrodes are being widely developed due to their considerable theoretical capacity. Coating with carbon-based materials is an efficient way to solve the common issues of Si-based materials. Currently, most of the reported strategies are complicated, pollutive, or uneconomic, which hamper their practical applications. Herein, a honeycomb-like Si-based composite was prepared to address these issues via a facile and green reduction approach at room temperature. The pre-anchored Si nanoparticles could be packed and interconnected through a three-dimensional graphene network to further enhance the electrochemical properties of the active materials. As an electrode, this composite shows good rate capabilities upon lithium storage and cycling stability. The continued cycling measurement delivers a -0.049% capacity decay rate per cycle within 600 cycles. A direct comparison further exhibits the obviously improved performance between the as-designed Si-based composite and naked Si, suggesting a potential application of this convenient strategy for other high-performance electrode materials.

Accurate measurement of the chirality of WS2 nanotubes.

We describe the structural parameters and atomic positions of a single-walled WS2 nanotube. The structure factor is calculated in detail using analytic expressions for both single-walled and multi-walled WS2 nanotubes. A zoning scheme has been developed to obtain the ratio m/n from the electron diffraction patterns. The procedure for determination of the chiral indices of both single-walled and multi-walled WS2 nanotubes and the tilt angle is illustrated in detail for either normal incidence or inclined incidence. As an example of application, the determination of the chiral indices of a five-shell WS2 nanotube was carried out and the tilt angle was obtained as 17.7°. The method developed here is useful and valid to determine the atomic structure of WS2 nanotubes.

Unique interconnected graphene/SnO2 nanoparticle spherical multilayers for lithium-ion battery applications.

We have designed and synthesized a unique structured graphene/SnO2 composite, where SnO2 nanoparticles are inserted in between interconnected graphene sheets which form hollow spherical multilayers. The hollow spherical multilayered structure provides much flexibility to accommodate the configuration and volume changes of SnO2 in the material. When it is used as an anode material for lithium-ion batteries, such a novel nanostructure can not only provide a stable conductive matrix and suppress the mechanical stress, but also eliminate the need of any binders for constructing electrodes. Electrochemical tests show that the unique graphene/SnO2 composite electrode as designed could exhibit a large reversible capacity over 1000 mA h g-1 and long cycling life with 88% retention after 100 cycles. These results indicate the great potential of the composite for being used as a high performance anode material for lithium-ion batteries.

Comparison of reduction products from graphite oxide and graphene oxide for anode applications in lithium-ion batteries and sodium-ion batteries.

Hydrazine-reduced graphite oxide and graphene oxide were synthesized to compare their performances as anode materials in lithium-ion batteries and sodium-ion batteries. Reduced graphite oxide inherits the layer structure of graphite, with an average spacing between neighboring layers (d-spacing) of 0.374 nm; this exceeds the d-spacing of graphite (0.335 nm). The larger d-spacing provides wider channels for transporting lithium ions and sodium ions in the material. We showed that reduced graphite oxide as an anode in lithium-ion batteries can reach a specific capacity of 917 mA h g-1, which is about three times of 372 mA h g-1, the value expected for the LiC6 structures on the electrode. This increase is consistent with the wider d-spacing, which enhances lithium intercalation and de-intercalation on the electrodes. The electrochemical performance of the lithium-ion batteries and sodium-ion batteries with reduced graphite oxide anodes show a noticeable improvement compared to those with reduced graphene oxide anodes. This improvement indicates that reduced graphite oxide, with larger interlayer spacing, has fewer defects and is thus more stable. In summary, we found that reduced graphite oxide may be a more favorable form of graphene for the fabrication of electrodes for lithium-ion and sodium-ion batteries and other energy storage devices.