Hybrid-Mechanism Synergistic Flexible Nb2O5@WS2@C Carbon Nanofiber Anode for Superior Sodium Storage.

Sodium-ion batteries (SIBs) have demonstrated remarkable development potential and commercial prospects. However, in the current state of research, the development of high-energy-density, long-cycle-life, high-rate-performance anode materials for SIBs remains a huge challenge. Free-standing flexible electrodes, owing to their ability to achieve higher energy density without the need for current collectors, binders, and conductive additives, have garnered significant attention across various fields. In this work, we designed and fabricated a free-standing three-dimensional flexible Nb2O5@WS2@C carbon nanofiber (CNF) anode based on a hybrid adsorption-intercalation-conversion mechanism of sodium storage, using electrospinning and hydrothermal synthesis processes. The hybrid structure, aided by synergistic effects, releases the advantages of all materials, demonstrating a superior rate performance (288, 248, 211, 158, 90, and 48 mA h g-1 at the current density of 0.2, 0.5, 1, 2, 5, and 10 A g-1, respectively) and good cycling stability (160 mA h g-1 after 200 cycles at 1 A g-1). This work provides certain guiding significance for future research on hybrid and flexible anodes of SIBs.

Employing a chelating agent as electrolyte additive with synergistic effects yields highly reversible zinc metal anodes.

Aqueous zinc ion batteries (AZIBs) have attracted sustained attention owing to their intrinsic safety and low cost. Unfortunately, the dendrite growth and parasitic side reactions of metallic zinc anodes severely degrade the cycling stability of the batteries and limit the practical application of AZIBs. In this work, calcium gluconate (CG), a chelating agent, as a novel electrolyte additive was introduced to tackle the thorny issue of zinc anodes in a 2 M ZnSO4 electrolyte by the synergistic effects of gluconate (GA-) anions and Ca2+ cations. Experimental characterization and computational simulations confirmed that the incorporation of GA- can not only mitigate the precipitation of Ca2+ ions, but also affect the primary solvation shell (PSS) of Zn2+ and modulate the electrode/electrolyte interfacial reaction, thereby inhibiting side reactions. Besides, trace amounts of Ca2+ cations can preferentially adsorb on the surface of the zinc anode tip, forming an electrostatic shielding shell that guides the uniform deposition of zinc ions. The Zn//Zn symmetric cells achieved a remarkably prolonged cycling lifespan ranging from 174 h to 3745 h at 6.37 mA cm-2 and 2.88 mA h cm-2 with an ultrahigh cumulative plating capacity (CPC) of about 11 900 mA h cm-2. Even at a higher current density of 5 mA cm-2 and an areal specific capacity of 5 mA h cm-2, Zn//Zn cells with the CG additive cycled for 248 h, about 5 times better than that without the CG additive. These results pave the way for the exploitation of new electrolyte additives with synergistic effects in AZIBs.

A rationally designed 3DTiO2@CdZnS heterojunction photocatalyst for effectively enhanced visible-light-driven hydrogen evolution.

Hydrogen production with higher efficiency and lower cost is of great significance for the sustainable development of energy. Zinc cadmium sulfide (CZS) is gaining more attention owing to its excellent photocatalytic properties. However, its development is greatly limited due to photogenerated charge recombination. In this work, an innovative design with a unique 3D morphology was introduced by integrating 3DTiO2 into CZS to form a novel 3DTiO2/CZS heterojunction photocatalyst. As a result, the optimized composite achieved a very high hydrogen production rate of 75.38 mmol h-1 g-1 under visible light, which is 2.4 times higher than that of the original CZS. It can also be greatly demonstrated through photoelectrochemical tests that this unique 3D morphology contributes to the effective separation of electrons and holes, thus dramatically improving the photocatalytic activity of 3DTiO2/CZS composites. The 3DTiO2/CZS composite has a rational energy band structure, which makes it more favorable for the hydrogen precipitation reaction. It is believed that such a modification strategy based on 3DTiO2 can be applied to other similar photocatalysts as well for boosting hydrogen evolution.

Research on the energy storage performance of laminated composites based on multidimensional co-design in a broad temperature range.

Polymer dielectrics play an irreplaceable role in electronic power systems because of their high power density and fast charge-discharge capability, but it is limited by their low stability in the temperature range of 25-200 °C. Rather than the introduction of one-dimensional fillers in polymers, we used a kind of multidimensional synergistic design to prepare Al2O3-TiO2-Al2O3/PI composites with layered structures by introducing multi-dimensional materials in polyimide (PI). In fact, the composite achieves much higher temperature stability than the pure PI film. The optimally proportioned composite has an energy density of 3.41 J cm-3 (vs. 1.48 J cm-3 for pure PI) even at 200 °C. Additionally, it reaches an impressive energy density retention of up to 90% and maintains an energy efficiency as high as 86% at 400 MV m-1 in the temperature range of 25-200 °C. The multidimensional coordination design is proposed to obtain composite films, and provides a feasible strategy in the study of polymer-based composites with high-temperature performance.

In Situ Growth of CdZnS Nanoparticles@Ti3C2Tx MXene Nanosheet Heterojunctions for Boosted Visible-Light-Driven Photocatalytic Hydrogen Evolution.

Using natural light energy to convert water into hydrogen is of great significance to solving energy shortages and environmental pollution. Due to the rapid recombination of photogenerated carriers after separation, the efficiency of photocatalytic hydrogen production using photocatalysts is usually very low. Here, efficient CdZnS nanoparticles@Ti3C2Tx MXene nanosheet heterojunction photocatalysts have been successfully prepared by a facile in situ growth strategy. Since the CdZnS nanoparticles uniformly covered the Ti3C2Tx Mxene nanosheets, the agglomeration phenomenon of CdZnS nanoparticles could be effectively inhibited, accompanied by increased Schottky barrier sites and an enhanced migration rate of photogenerated carriers. The utilization efficiency of light energy can be improved by inhibiting the recombination of photogenerated electron-hole pairs. As a result, under the visible-light-driven photocatalytic experiments, this composite achieved a high hydrogen evolution rate of 47.1 mmol h-1 g-1, which is much higher than pristine CdZnS and Mxene. The boosted photocatalytic performances can be attributed to the formed heterojunction of CdZnS nanoparticles and Ti3C2Tx MXene nanosheets, as well as the weakened agglomeration effects.

Two-Dimensional Fillers Induced Superior Electrostatic Energy Storage Performance in Trilayered Architecture Nanocomposites.

Dielectric capacitors with ultrahigh power densities and fast charging/discharging rates are of vital relevance in advanced electronic markets. Nevertheless, a tradeoff always exists between breakdown strength and polarization, which are two essential elements determining the energy storage density. Herein, a novel trilayered architecture composite film, which combines outer layers of two-dimensional (2D) BNNS/poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) with high breakdown strength and an intermediate layer made of blended 2D MoS2 nanosheets/P(VDF-HFP) with large polarization, is fabricated using the layer-by-layer casting method. The insulating BNNS with a wide band gap is able to largely alleviate the distortion of the local electric field, thereby suppressing the leakage current and effectively reducing the conductivity loss, while the 2D MoS2 nanosheets act as microcapacitors in the polymer composites, thus significantly increasing the permittivity. A finite element simulation is carried out to further analyze the evolution process of electrical treeing in the experimental breakdown of the polymer nanocomposites. Consequently, the nanocomposites possess an excellent discharged energy density of 25.03 J/cm3 accompanied with a high charging/discharging efficiency of 77.4% at 650 MV/m, which greatly exceeds those of most conventional single-layer films. In addition, the corresponding composites exhibit an outstanding reliability of energy storage performance under continuous cycling. The excellent performances of these polymer-based nanocomposite films could pave a way for widespread applications in advanced capacitors.

Ultrahigh Energy Storage Performance of Layered Polymer Nanocomposites over a Broad Temperature Range.

To reach the full potential of polymer dielectrics in advanced electronics and electrified transportation, it calls for efficient operation of high-energy-density dielectric polymers under high voltages over a wide temperature range. Here, the polymer composites consisting of the boron nitride nanosheet/polyetherimide and TiO2 nanorod arrays/polyetherimide layers are reported. The layered composite exhibits a much higher dielectric constant than the current high-temperature dielectric polymers and composites, while simultaneously retaining low dielectric loss at elevated temperatures and high applied fields. Consequently, the layered polymer composite presents much improved capacitive performance than the current dielectric polymers and composites over a temperature range of 25-150 °C. Moreover, the excellent capacitive performance of the layered composite is achieved at an applied field that is about 40% lower than the typical field strength of the current polymer composites with the discharged energy densities of >3 J cm-3 at 150 °C. Remarkable cyclability and dielectric stability are established in the layered polymer nanocomposites. This work addresses the current challenge in the enhancement of the energy densities of high-temperature dielectric polymers and demonstrates an efficient route to dielectric polymeric materials with high energy densities and low loss over a broad temperature range.

Simultaneously enhanced discharge energy density and efficiency in nanocomposite film capacitors utilizing two-dimensional NaNbO3@Al2O3 platelets.

With rapid developments in the consumer electronics market, electrostatic capacitors need to store as much energy as possible within a rather restricted space. In this work, nanocomposite films combining two-dimensional core-shell NaNbO3@Al2O3 platelets (2D NN@AO Ps) and poly(vinylidene-fluoride hexafluoropropylene) (P(VDF-HFP)), featuring excellent energy storage capability, high efficiency, and ultrafast discharge performance, are designed and fabricated. Both the experimental results and finite element simulations confirm the superiority of these 2D NN@AO Ps nanocomposite films in improving the breakdown strength (Eb) and energy storage capability. In particular, the introduction of 3 vol% 2D NN@AO Ps results in much enhanced discharge energy density of 14.59 J cm-3 and outstanding discharge efficiency of 70.1% in NN@AO Ps/P(VDF-HFP) nanocomposite films, which is much greater than that of pure P(VDF-HFP) (7.74 J cm-3). The corresponding nanocomposite films exhibit excellent reliability in energy storage performance under consecutive cycling. Therefore, this research could reveal a new chapter in the study and application of polymer nanocomposites in energy-storage dielectric capacitors.

Interfacial Coupling Effect in Organic/Inorganic Nanocomposites with High Energy Density.

Organic/inorganic nanocomposites (OINs) can be potentially used as high-performance capacitors due to their rapid charge-discharge capability along with respectable power density. The coupling effect of the filler/matrix interface plays a prominent role in the dielectric and electric properties of OINs. Along with a review of contemporary theoretical models, recent advances in interfacial optimization to improve energy density through careful interface control and design are also presented. Possible mechanisms that may improve energy density and potential applications for high-energy-density capacitors are also highlighted.

Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C-H borylation of aromatic imines.

As a major challenge in C-H borylation, how to control the selectivity has attracted lots of attention, however, the related mechanistic information still needs to be uncovered. Herein, density functional theory (DFT) has been used to study the mechanism for the ligand controlled regioselectivity in the iridium-catalyzed C-H borylation of aromatic imines, which is inspired by experimental observations (R. Bisht, B. Chattopadhyay, J. Am. Chem. Soc., 2016, 138, 84-87). The proposed Ir(i)-Ir(iii) catalytic cycle includes (i) the oxidative addition of the C-H bond to iridium(i); (ii) the reductive elimination of a C-B bond; (iii) the oxidative addition of B2pin2 to an iridium(i) hydride complex; and (iv) the reductive elimination of a B-H bond. The oxidative addition of a C-H bond to the iridium center is the determining step. For the ligand AQ, ortho-selectivity is proposed to be attributed to the decreased steric hindrance and increased electron donating effect of AQ (8-aminoquinoline) which promotes proton-transfer in the ortho-transition state of C-H activation. While, for the TMP ligand, the steric repulsion between the TMP (4,5,7,8-tetramethyl-1, 10-phenanthroline) ligand and the ortho-substituted imine hinders the ortho C-H activation and favors meta borylation. Our calculations provide insights into further ligand design to achieve different regioselective borylation of aromatics. Guided by the results, the regioselectivity in the borylation of aromatics may be achieved by accordingly modifying the electronic and steric substituents of the ligand.

Co3O4-NP embedded mesoporous carbon rod with enhanced electrocatalytic conversion in lithium-sulfur battery.

Lithium-sulfur battery has been considered to be one of the promising alternatives to the traditional lithium-ion battery due to its high theoretical energy density and saving-cost. However, the sluggish reaction during the decomposition of lithium sulfide results in a low specific capacity and poor cycling stability. Herein Co3O4 nano-particle embedded mesoporous carbon rod (Co3O4@MCR) was prepared through a template method to accommodate sulfur as cathode of lithium-sulfur battery. The resultant composite was characterized by Raman spectra, XRD, TEM, SEM, etc. The electrochemical investigation demonstrated that Co3O4@MCR composite exhibits enhanced electrocatalytic performance in lithium-sulfur battery, which was confirmed by cyclic voltammograms, galvanostatic charge-discharge testing, and study of sulfide oxidation using linear sweep voltammetry. With the current density of 0.2 A/g, the specific discharge capacity can be achieved up to more than 1000 mAh/g after 100 cycles. The enhanced electrocatalytic conversion from Co3O4@MCR leads to a low over-potential, fast lithium-ion kinetics and sulfide oxidation reaction.

Ultra Uniform Pb0.865La0.09(Zr0.65Ti0.35)O3 Thin Films with Tunable Optical Properties Fabricated via Pulsed Laser Deposition.

Ferroelectric thin films have been utilized in a wide range of electronic and optical applications, in which their morphologies and properties can be inherently tuned by a qualitative control during growth. In this work, we demonstrate the evolution of the Pb0.865La0.09(Zr0.65Ti0.35)O3 (PLZT) thin films on MgO (200) with high uniformity and optimized optical property via the controls of the deposition temperatures and oxygen pressures. The perovskite phase can only be obtained at the deposition temperature above 700 °C and oxygen pressure over 50 Pa due to the improved crystallinity. Meanwhile, the surface morphologies gradually become smooth and compact owing to spontaneously increased nucleation sites with the elevated temperatures, and the crystallization of PLZT thin films also sensitively respond to the oxygen vacancies with the variation of oxygen pressures. Correspondingly, the refractive indices gradually develop with variations of the deposition temperatures and oxygen pressures resulted from the various slight loss, and the extinction coefficient for each sample is similarly near to zero due to the relatively smooth morphology. The resulting PLZT thin films exhibit the ferroelectricity, and the dielectric constant sensitively varies as a function of electric filed, which can be potentially applied in the electronic and optical applications.

Novel design of highly [110]-oriented barium titanate nanorod array and its application in nanocomposite capacitors.

Nanocomposites in capacitors combining highly aligned one dimension ferroelectric nanowires with polymer would be more desirable for achieving higher energy density. However, the synthesis of the well-isolated ferroelectric oxide nanorod arrays with a high orientation has been rather scant, especially using glass-made substrates. In this study, a novel design that is capable of fabricating a highly [110]-oriented BaTiO3 (BT) nanorod array was proposed first, using a three-step hydrothermal reaction on glass-made substrates. The details for controlling the dispersion of the nanorod array, the orientation and the aspect ratio are also discussed. It is found that the alkaline treatment of the TiO2 (TO) nanorod array, rather than the completing transformation into sodium titanate, favors the transformation of the TO into the BT nanorod array, as well as protecting the glass-made substrate. The dispersity of the nanorod array can be controlled by the introduction of a glycol ether-deionized water mixed solvent and soluble salts. Moreover, the orientation of the nanorod arrays could be tuned by the ionic strength of the solution. This novel BT nanorod array was used as a filler in a nanocomposite capacitor, demonstrating that a large energy density (11.82 J cm-3) can be achieved even at a low applied electric field (3200 kV cm-1), which opens us a new application in nanocomposite capacitors.

High-Energy-Density Polymer Nanocomposites Composed of Newly Structured One-Dimensional BaTiO3@Al2O3 Nanofibers.

Flexible electrostatic capacitors are potentially applicable in modern electrical and electric power systems. In this study, flexible nanocomposites containing newly structured one-dimensional (1D) BaTiO3@Al2O3 nanofibers (BT@AO NFs) and the ferroelectric polymer poly(vinylidene fluoride) (PVDF) matrix were prepared and systematically studied. The 1D BT@AO NFs, where BaTiO3 nanoparticles (BT NPs) were embedded and homogeneously dispersed into the AO nanofibers, were successfully synthesized via an improved electrospinning technique. The additional AO layer, which has moderating dielectric constant, was introduced between BT NPs and PVDF matrixes. To improve the compatibility and distributional homogeneity of the nanofiller/matrix, dopamine was coated onto the nanofiller. The results show that the energy density due to high dielectric polarization is about 10.58 J cm-3 at 420 MV m-1 and the fast charge-discharge time is 0.126 µs of 3.6 vol % BT@AO-DA NFs/PVDF nanocomposite. A finite element simulation of the electric-field and electric current density distribution revealed that the novel-structured 1D BT@AO-DA NFs significantly improved the dielectric performance of the nanocomposites. The large extractable energy density and high dielectric breakdown strength suggest the potential applications of the BT@AO-DA NFs/PVDF nanocomposite films in electrostatic capacitors and embedded devices.

Ultrafast Discharge and Enhanced Energy Density of Polymer Nanocomposites Loaded with 0.5(Ba0.7Ca0.3)TiO3-0.5Ba(Zr0.2Ti0.8)O3 One-Dimensional Nanofibers.

One-dimensional (1D) materials as fillers introduced into polymer matrixes have shown great potential in achieving high energy storage capacity because of their large dipole moments. In this article, 1D lead-free 0.5(Ba0.7Ca0.3)TiO3-0.5Ba(Zr0.2Ti0.8)O3 nanofibers (BCZT NFs) were prepared via electrospinning, and their formation mechanism was systematically studied. Polypropylene acyl tetraethylene pentamine (PATP) grafted into the surface of BCZT NFs was embedded in the polymer matrixes, which effectively improved the distribution and compatibility of the fillers via chemical bonding and confined the movement of the charge carriers in the interface filler-matrix. The energy density at a relatively low electric field 380 MV m-1 was increased to 8.23 J cm-3 by small loading of fillers, far more than that of biaxially oriented polypropylene (BOPP) (≈ 1.2 J cm-3 at 640 MV m-1). Moreover, the nanocomposite loaded with 2.1 vol % BCZT@PATP NFs exhibits a superior discharge speed of ≈0.189 µs, which indicates the potential application in practice. The finite element simulation of electric potential and electric current density distribution revealed that the PATP grafted into the BCZT NFs surface could significantly improve the dielectric performances. This work could provide a new design strategy for high-performance dielectric polymer nanocomposite capacitors.

Significantly Enhanced Energy Density in Nanocomposite Capacitors Combining the TiO2 Nanorod Array with Poly(vinylidene fluoride).

A novel inorganic/polymer nanocomposite, using 1-dimensional TiO2 nanorod array as fillers (TNA) and poly(vinylidene fluoride) (PVDF) as matrix, has been successfully synthesized for the first time. A carefully designed process sequence includes several steps with the initial epitaxial growth of highly oriented TNA on the fluorine-doped tin oxide (FTO) conductive glass. Subsequently, PVDF is embedded into the nanorods by the spin-coating method followed by annealing and quenching processes. This novel structure with dispersive fillers demonstrates a successful compromise between the electric displacement and breakdown strength, resulting in a dramatic increase in the electric polarization which leads to a significant improvement on the energy density and discharge efficiency. The nanocomposites with various height ratios of fillers between the TNA and total film thickness were investigated by us. The results show that nanocomposite with 18% height ratio fillers obtains maximum increase in the energy density (10.62 J cm-3) at a lower applied electric field of 340 MV m-1, and it also illustrates a higher efficiency (>85%) under the electric field less than 100 MV m-1. Even when the electric field reached 340 MV m-1, the efficiency of nanocomposites can still maintained at ∼70%. This energy density exceeds most of the previously reported TiO2-based nanocomposite values at such a breakdown strength, which provides another promising design for the next generation of dielectric nanocomposite material, by using the highly oriented nanorod array as fillers for the higher energy density capacitors. Additionally, the finite element simulation has been employed to analyze the distribution of electric fields and electric flux density to explore the inherent mechanism of the higher performance of the TNA/PVDF nanocomposites.