Band engineering enhances the electrochemical properties by constructing TiO2 NRs-MoS2 NSFs flexible electrode.

Research and development of flexible electrodes with high performance are crucial to largely determine the performance of flexible lithium-ion batteries (FLIBs) to a large extent. In this work, a flexible anode (TiO2 NRs-MoS2 NSFs/CC) is rationally designed and successfully constructed, in which TiO2 nanorods arrays (NRs) vertically grown on CC as a supporting backbone for MoS2 nanosheets flowers (NSFs) to form a TiO2 NRs-MoS2 NSFs heterostructure. The backbone can not only serve as a mechanical support MoS2 and improve its electronic conductivity, but also limit the dissolution of polysulfides issue during cycling. The density functional theory (DFT) analysis manifests that the obvious interaction between O and S at the interface for the TiO2 NRs-MoS2 NSFs heterostructure changes the electronic structure and reduces the band gap of TiO2 NRs-MoS2 NSFs. The small band gap and high electron state at the Fermi level are both beneficial to the transport of electrons, enhancing the kinetics, and giving the long cycling stability at high density and excellent rate capacity. Furthermore, the assembled TiO2 NRs-MoS2 NSFs/CC//NCM622 full cell delivers superior rate capacity and good cycling stability. Meanwhile, the soft-packed cell shows good mechanical flexibility, which can be lighted up successfully and keep brightness when folding with different angles. This result illustrates that it is a highly potential strategy for constructing flexible electrodes with the controlled electronic structure through band engineering to not only improve the electrochemical performance, but also possibly meet the requirements of high-performance FLIBs.

Site-selective occupation, optical spectrum regulation and photoluminescence property investigation of Eu2+-activated blue light-excited yellow-orange emitting phosphors.

We report yellow-orange emitting phosphors Sr9-xCaxMg1.5(PO4)7:0.05Eu2+ (SCxMPO:Eu2+, x = 0.5-2.5) and Sr9-yBayMg1.5(PO4)7:0.05Eu2+ (SByMPO:Eu2+, y = 0.5-3.0) with broad emission bands (450-800 nm). All these phosphors can be excited efficiently by blue light and n-UV light. Their crystal structure, photoluminescence spectra, fluorescence decay curves and thermal stability were investigated in detail. As doping concentrations of Ca2+ or Ba2+ increase, Eu2+ emitting centers will selectively occupy different Sr2+ sites, thus leading to the regulation of optical spectra of SCxMPO:Eu2+ and SByMPO:Eu2+. Accordingly, the emission colors of SCxMPO:Eu2+ and SByMPO:Eu2+ samples can gradually turn from yellow to orange when excited using 460 nm blue light. And the emission colors of a given sample can also be varied under different excitations because there are three kinds of emitting centers in SCxMPO:Eu2+ and SByMPO:Eu2+. In addition, introducing Ca2+ and Ba2+ can enhance the thermal stability of the phosphors obviously, and overall, the thermal stability of SByMPO:Eu2+ is better than that of SCxMPO:Eu2+. We chose SB2.5MPO:zEu2+ as an example to further investigate its photoluminescence properties, and found that the optimal doping concentration of Eu2+ is 0.08, and dipole-quadrupole interaction is dominated in the concentration quenching mechanism. Furthermore, high-quality warm white light can be obtained by two ways: (a) 470 nm blue LED chip + SC1.5MPO:Eu2+ [CCT = 3639 K, Ra = 82.21] and (b) 470 nm blue LED chip + SB2.5MPO:Eu2+ and YAG:Ce3+ [CCT = 4284 K, Ra = 86.69]. The excellent performances indicate that SCxMPO:Eu2+ and SByMPO:Eu2+ are attractive candidates for warm WLEDs.

One-Step Route to Fe2O3 and FeSe2 Nanoparticles Loaded on Carbon-Sheet for Lithium Storage.

Iron-based anode materials, such as Fe2O3 and FeSe2 have attracted widespread attention for lithium-ion batteries due to their high capacities. However, the capacity decays seriously because of poor conductivity and severe volume expansion. Designing nanostructures combined with carbon are effective means to improve cycling stability. In this work, ultra-small Fe2O3 nanoparticles loaded on a carbon framework were synthesized through a one-step thermal decomposition of the commercial C15H21FeO6 [Iron (III) acetylacetonate], which could be served as the source of Fe, O, and C. As an anode material, the Fe2O3@C anode delivers a specific capacity of 747.8 mAh g-1 after 200 cycles at 200 mA g-1 and 577.8 mAh g-1 after 365 cycles at 500 mA g-1. When selenium powder was introduced into the reaction system, the FeSe2 nano-rods encapsulated in the carbon shell were obtained, which also displayed a relatively good performance in lithium storage capacity (852 mAh g-1 after 150 cycles under the current density of 100 mA·g-1). This study may provide an alternative way to prepare other carbon-composited metal compounds, such as FeNx@C, FePx@C, and FeSx@C, and found their applications in the field of electrochemistry.

SnO2 Anchored in S and N Co-Doped Carbon as the Anode for Long-Life Lithium-Ion Batteries.

Tin dioxide (SnO2) has been the focus of attention in recent years owing to its high theoretical capacity (1494 mAh g-1). However, the application of SnO2 has been greatly restricted because of the huge volume change during charge/discharge process and poor electrical conductivity. In this paper, a composite material composed of SnO2 and S, N co-doped carbon (SnO2@SNC) was prepared by a simple solid-state reaction. The as-prepared SnO2@SNC composite structures show enhanced lithium storage capacity as compared to pristine SnO2. Even after cycling for 1000 times, the as-synthesized SnO2@SNC can still deliver a discharge capacity of 600 mAh g-1 (current density: 2 A g-1). The improved electrochemical performance could be attributed to the enhanced electric conductivity of the electrode. The introduction of carbon could effectively improve the reversibility of the reaction, which will suppress the capacity fading resulting from the conversion process.

One-pot thermal decomposition of commercial organometallic salt to Fe2O3@C-N and MnO@C-N for lithium storage.

Iron oxide (Fe2O3) nanoparticles encapsulated in the N-doped carbon framework (Fe2O3@C-N) were synthesized via a one-step thermal decomposition reaction of commercial C10H12FeN2NaO8 (ethylenediaminetetraacetic acid monosodium ferric salt), which can serve as the source of Fe, O, C, and N. As an anode material for lithium storage, the Fe2O3@C-N sample exhibits a reversible capacity of 1072 mA h g-1 after 200 cycles at 0.2 A g-1 and 553 mA h g-1 after 500 cycles at 0.5 A g-1. Furthermore, the synthetic strategy can be simply extended to prepare other similar products, e.g. MnO@C-N and ZnO@C-N. The MnO@C-N anode also shows good cycling performances (915 mA h g-1 after 200 cycles at 0.2 A g-1 and 768 mA h g-1 after 500 cycles at 0.5 A g-1).

Effects of Carbon Content and Current Density on the Li+ Storage Performance for MnO@C Nanocomposite Derived from Mn-Based Complexes.

In this study, a simple method was adopted for the synthesis of MnO@C nanocomposites by combining in-situ reduction and carbonization of the Mn3O4 precursor. The carbon content, which was controlled by altering the annealing time in the C2H2/Ar atmosphere, was proved to have great influences on the electrochemical performances of the samples. The relationships between the carbon contents and electrochemical performances of the samples were systematically investigated using the cyclic voltammetry (CV) as well as the electrochemical impedance spectroscopy (EIS) method. The results clearly indicated that the carbon content could influence the electrochemical performances of the samples by altering the Li+ diffusion rate, electrical conductivity, polarization, and the electrochemical mechanism. When being used as the anode materials in lithium-ion batteries, the capacity retention rate of the resulting MnO@C after 300 cycles could reach 94% (593 mAh g-1, the specific energy of 182 mWh g-1) under a current density of 1.0 A g-1 (1.32 C charge/discharge rate). Meanwhile, this method could be easily scaled up, making the rational design and large-scale application of MnO@C possible.

FeS2 crystal lattice promotes the nanostructure and enhances the electrocatalytic performance of WS2 nanosheets for the oxygen evolution reaction.

The control of surface elements and nanostructures is one of the effective ways to design and synthesize high performance catalysts. Herein, we, for the first time, prepare FeS2 crystal lattices on WS2 nanosheets (FeS2 CL@WS2 NS) by solvothermal methods for the oxygen evolution reaction (OER). The FeS2 CLs effectively prevent the oxidation and aggregation of WS2 nanosheets and increase the electrochemically active surface area. The abundant surface defect in the FeS2 CL@WS2 NS electrocatalyst reduces the stress between the crystal lattices of FeS2 and that of WS2. The overpotential (260 mV) of the FeS2 CL@WS2 NS electrocatalyst for the OER at a current density of 10 mA cm-2 is superior to those of WS2 NS/Ni foam (310 mV) and IrO2/Ni foam (300 mV) in 1.0 M KOH solution. An electrochemical-kinetic study shows that the Tafel slope of 54 mV per decade for the FeS2 CL@WS2 NS electrocatalyst is lower than those of WS2 NS (102 mV per decade) and IrO2/Ni foam (77 mV per decade). In addition, the charge transport resistor (2.3 Ω) of the FeS2 CL@WS2 NS electrocatalyst for the OER is smaller than that of WS2 NS. These faster kinetic properties, in turn, explain the high catalytic activity of the FeS2 CL@WS2 NS electrocatalyst for the OER. The XPS and HRTEM results of the post stability sample confirm that Fe2+ and W4+ are oxidized after durability measurement. Thus, we think that the FeS2 CL@WS2 NS electrocatalyst is a promising candidate for efficient, low-cost, and stable non-noble-metal-based OER electrocatalysts.

Boosting the potassium-ion storage performance of a carbon anode by chemically regulating oxygen-containing species.

The oxygen-containing species in melamine foam carbons are chemically regulated by oxidizing-acid treatment. The optimized carbon anode shows an enhanced potassium-storage performance in terms of reversible capacity, rate performance, and long-term cycling stability. Both structural analysis and theoretical calculations highlight the roles of quinone- and ether-type oxygen species in boosting the potassium-ion storage performance.

Nanostructures inducing distinctive photocatalytic and photoelectrochemical performance via the introduction of rGO into CdxZn1-xS.

It is well known that efficient charge separation is a crucial factor for the enhancement of photocatalytic activity for hydrogen evolution, and the internal electric field is commonly designed to improve charge separation. The microstructure of a catalyst has a significant effect on the photocatalytic and photoelectrochemical (PEC) performance. Herein, two samples are engineered with similar morphology but different crystal structures. Small wurtzite (WZ)/zinc blende (ZB) -Cd0.6Zn0.4S nanorods are featured with dense type-II homojunctions. By utilizing the excellent thermal conductivity of graphene to eliminate thermal fluctuations, WZ-Cd0.6Zn0.4S/RGO is obtained by anchoring Cd0.6Zn0.4S nanorods on the graphene sheets. The elongated WZ/ZB-Cd0.6Zn0.4S nanorods with an internal electric field formed by the heterophase homojunction greatly improve the photocatalytic hydrogen production rate to 36.33 mmol h-1 g-1, much higher than that of WZ-Cd0.6Zn0.4S-RGO. On the contrary, WZ-Cd0.6Zn0.4S/RGO shows superior photoelectrochemical performance under an external electric field, benefiting from the excellent electric conduction and the 2D network of RGO as electron transportation channels. The study strategy and synthetic route for the Cd0.6Zn0.4S nanorods with a homojunction and a homogenous structure in our work may open up new avenues for the fabrication of other semiconductor materials with distinctive photocatalytic and PEC applications.

New Insights into the Electrochemistry Superiority of Liquid Na-K Alloy in Metal Batteries.

The significant issues with alkali metal batteries arise from their poor electrochemical properties and safety problems, limiting their applications. Herein, TiO2 nanoparticles embedded into N-doped porous carbon truncated ocatahedra (TiO2 ⊂NPCTO) are engineered as a cathode material with different metal anodes, including solid Na or K and liquid Na-K alloy. Electrochemical performance and kinetics are systematically analyzed, with the aim to determine detailed electrochemistry. By using a galvanostatic intermittent titration technique, TiO2 ⊂NPCTO/NaK shows faster diffusion of metal ions in insertion and extraction processes than that of Na-ions and K-ions in solid Na and K. The lower reaction resistance of liquid Na-K alloy electrode is also examined. The higher b-value of TiO2 ⊂NPCTO/NaK confirms that the reaction kinetics are promoted by the surface-induced capacitive behavior, favorable for high rate performance. This superiority highly pertains to the distinct liquid-liquid junction between the electrolyte and electrode, and the prohibition of metal dendrite growth, substantiated by symmetric cell testing, which provides a robust and homogeneous interface more stable than the traditional solid-liquid one. Hence, the liquid Na-K alloy-based battery exhibits to better cyclablity with higher capacity, rate capability, and initial coulombic efficiency than solid Na and K batteries.

Room temperature synthesis of CdS/SrTiO3 nanodots-on-nanocubes for efficient photocatalytic H2 evolution from water.

Spontaneous solar-driven water splitting to generate H2 with no pollution discharge is an ideal H2 generation approach. However, its efficiency remains far from real application owing to the poor light-harvesting and ultrafast charge recombination of photocatalysts. To address these issues, herein, we employed a novel but simple chemical bath deposition (CBD) method to construct CdS/SrTiO3 nanodots-on-nanocubes at room temperature (ca. 25 °C). The as-synthesized nanohybrids not only expand light absorption from ultraviolet (UV) to visible light but also significantly retard charge recombination owing to the well-defined heterostructure formation. As a result, the CdS/SrTiO3 exhibits high photocatalytic performance with H2 evolution rate of 1322 µmol g-1 h-1, which is 2.8 and 12.2 times higher than that of pristine CdS and SrTiO3, respectively. This work provides a universal approach for the heterostructure construction, and inspired by this, higher efficient photocatalysts for H2 evolution may be developed in the near future.

Selenium/interconnected porous hollow carbon bubbles composites as the cathodes of Li-Se batteries with high performance.

A kind of Se/C nanocomposite is fabricated by dispersing selenium in interconnected porous hollow carbon bubbles (PHCBs) via a melt-diffusion method. Such PHCBs are composed of porous hollow carbon spheres with a size of ∼70 nm and shells of ∼12 nm thickness interconnected to each other. Instrumental analysis shows that the porous shell of the PHCBs could effectively disperse and sequester most of the selenium, while the inner cavity remains hollow. When evaluated as cathode materials in a carbonate-based electrolyte for Li-Se batteries, the Se/PHCBs composites exhibit significantly excellent cycling performance and a high rate capability. Especially, the Se/PHCBs composite with an optimal content of ∼50 wt% selenium (Se50/PHCBs) displays a reversible discharge capacity of 606.3 mA h g(-1) after 120 cycles at 0.1 C charge-discharge rate. As the current density increased from 0.1 to 1 C (678 mA g(-1)), the reversible capacity of the Se50/PHCBs composite can still reach 64% of the theoretical capacity (431.9 mA h g(-1)). These outstanding electrochemical features should be attributed to effective sequestration of Se in the PHCBs, as well as to the ability to accommodate volume variation and enhance the electronic transport by making Se have close contact with the carbon framework.

Low temperature chemical reduction of fusional sodium metasilicate nonahydrate into a honeycomb porous silicon nanostructure.

Honeycomb porous silicon (hp-Si) has been synthesized by a low temperature (200 °C) magnesiothermic reduction of Na2SiO3·9H2O. This process can be regarded as a general synthesis method for other silicide materials. Significantly, hp-Si features excellent electrochemical properties after graphene coating.

One-pot hydrothermal synthesis of peony-like Ag/Ag(0.68)V2O5 hybrid as high-performance anode and cathode materials for rechargeable lithium batteries.

A peony-like Ag/Ag0.68V2O5 hybrid assembled from nanosheets with the thickness of 40 nm was synthesized through a one-pot hydrothermal approach from vanadium pentoxide (V2O5), oxalic acid (H2C2O4), and silver nitrate (AgNO3) at 180 °C for 24 h. The hybrid exhibits high performance as both anode and cathode materials for rechargeable lithium batteries. Electrochemical measurements revealed that the as-prepared Ag/Ag0.68V2O5 hybrid displayed excellent cycling stability, especially as an anode material. The resulting anode retains 100% of the initial capacity after 1000 cycles under a current density of 400 mA g(-1). This phenomenon may be attributed to electron conductivity improvement by the existence of metallic silver in the hybrid in addition to the convenient access to lithium ion ingress/egress because of its unique structure.

Stable Cycling of Fe2 O3 Nanorice as an Anode through Electrochemical Porousness and the Solid-Electrolyte Interphase Thermolysis Approach.

A new thread for improving the cycling stability of Fe2 O3 nanorice is proposed through combining the electrochemical porousness (EP) effect and solid-electrolyte interphase (SEI) thermolysis approach. Starting from solid Fe2 O3 nanorice, this process could be applied to prepare porous Fe2 O3 nanorice with a good coating of a porous SEI thermolysis layer composed of carbon and Li2 O. The interconnecting pores and full coating of the SEI thermolysis layer provides not only mechanical resistance of the Fe2 O3 nanorice against pulverization, but also high electrical and ionic conductivity over the electrode throughout long cell cycles. This method results in the enhancement of cycling ability and capacity, which is demonstrated by comparison with the starting Fe2 O3 nanorice. After the EP and SEI thermolysis approach, the Fe2 O3 nanorice exhibits an energy capacity retention about of 680 mAh g-1 at a current density of 1000 mA g-1 over 250 cycles, which is more than 82 % of the initial reversible capacity. Moreover, it also has an excellent rate capability and high coulombic efficiency. This strategy provides a simple and convenient route toward stable charge/discharge cycling for not only Fe2 O3 , but also for other electrode materials that are subject to large volume changes and low charge voltages. At the same time, it also contributes to a fundamental understanding of improved cycling stability and reversible capacity for electrode materials.