Cycling performance of layered oxide cathode materials for sodium-ion batteries

Layered oxide is a promising cathode material for sodium-ion batteries because of its high-capacity,high operating voltage,and simple synthesis.Cycling performance is an important criterion for evaluating the application prospects of batteries.However,facing challenges,including phase transitions,ambient stability,side reactions,and irreversible anionic oxygen activity,the cycling performance of layered oxide cathode materials still cannot meet the application requirements.Therefore,this review proposes several strategies to address these challenges.First,bulk doping is introduced from three aspects:cationic single doping,anionic single doping,and multi-ion doping.Second,homogeneous surface coating and concentration gradient modification are reviewed.In addition,methods such as mixed structure design,particle engineering,high-entropy material construction,and integrated modification are proposed.Finally,a summary and outlook provide a new horizon for developing and modifying layered oxide cathode materials.

Structural and electrochemical stabilization enabling high-energy P3-type Cr-based layered oxide cathode for K-ion batteries

Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe structural change by de/intercalation and diffusion of K^(+)ions with large ionic size,which results in not only much lower reversible capacity than the theoretical capacity but also poor power capability.Thus,it is important to enhance the structural stability of the layered-type TM oxides for outstanding electrochemical behaviors under the K-ion battery system.Herein,it is investigated that the substitution of the appropriate Ti^(4+)contents enables a highly enlarged reversible capacity of P3-type KxCrO_(2) using combined studies of first-principles calculation and various experiments.Whereas the pristine P3-type KxCrO_(2) just exhibits the reversible capacity of∼120 mAh g^(−1) in the voltage range of 1.5-4.0 V(vs.K^(+)/K),the∼0.61 mol K^(+)corresponding to∼150 mAh g^(−1) can be reversible de/intercalated at the structure of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) under the same conditions.Furthermore,even at the high current density of 788 mA g^(−1),the specific capacity of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) is∼120 mAh g^(−1),which is∼81 times larger than that of the pristine P3-type KxCrO_(2).It is believed that this research can provide an effective strategy to improve the electrochemical performances of the cathode materials suffered by severe structural change that occurred during charge/discharge under not only K-ion battery system but also other rechargeable battery systems.

Thermodynamic Analysis on Interaction between Molten Ti Alloys and Oxide Molding Materials

A thermodynamic model has been built up for the interactions between molten Ti alloys and oxide molding materials in the way of decomposition and solution of molding materials, then the influences on the reaction free energy changes have been calculated and discussed.

Effect of Atmosphere on Sintering Behavior of Chromium Oxide Materials

The chromium oxide materials were prepared using Cr2O3 micropowder as main starting material, TiO2 micropowder as sintering aid, polyvinyl alcohol as binder, by a series of processes such as slurrying, spraying granulation, machine moulding and cold isostatic pressing, and firing at 1 500 ℃ for 3 h in air （ oxygen partial pressure was 2. 1× 10^4 Pa ）, industrial nitrogen （ oxygen partial pressure was 1×10^3 Pa ） , pure nitrogen （ oxygen partial pressure was 10 Pa） , high purity nitrogen （ oxygen partial pressure was 0.1 Pa ） , and carbon cake embedded atmosphere （ oxygen partial pressure wtas 2.3×10-12 Pa ）. Effects of oxygen partial pressures on the sintering behavior of Cr2 O3 materials were investiga- ted. The results show that （ 1 ） for 3 wt% TiO2-doped specimeas, there is a substantial dependence of sintering on oxygen partial pressure （0. 1 Pa - 2. 1 ×10^4 Pa ） , and the bulk density increases and apparent porosity decreases with oxygen partial pressure decreasing; （2） even if the oxygen partial pressure is 0. 1 Pa, the specimen without TiO2 cannot reach densification sintering; （3） under very low oxygen partial pressure of carbon embedded atmosphere, Cr2O3 materials containing TiO2 or not can attain denzification.

Preparation and Characterization of Multi Shape ZnO/PVDF Composite Materials

Two different morphologies of ZnO（lotus-shaped, rod-shaped） and ZnO/PVDF composite materials were prepared. The morphologies of ZnO and composite materials were characterized by scanning electron microscopy（SEM） and transmission electron microscopy（TEM）. Fourier transform infrared spectroscopy（FT-IR）, thermal gravimetry（TG）, and X-ray diffraction（XRD） were also used to characterize the chemical structures and phase composites of ZnO and ZnO/PVDF composite materials. Breakdown voltage, dielectric constant and dielectric loss of ZnO/PVDF composite materials were also tested. Microstructure analysis showed that ZnO nanoparticles dispersed uniformly in the matrix. And the dielectric constant expresses a significantly improvement while the dielectric loss and breakdown voltage expresses no significant change. Moreover, dielectric constant keeps an improvement tendency with increasing content of ZnO.

Phase separation-hydrogen etching-derived Cu-decorated Cu-Mn bimetallic oxides with oxygen vacancies boosting superior sodium-ion storage kinetics

Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anode of the Cu-decorated Cu-Mn bimetallic oxides with oxygen vacancies(Ov-BMO-Cu)are in-situ generated by phase separation and hydrogen etching using nanoporous Cu-Mn alloy as selfsacrificial templates.On this basis,we have elucidated the relationship between the phase evolution,oxygen vacancies and sodium-ion storage mechanisms,further demonstrating the evolution of oxygen vacancies and the inhibition effect of manganese oxides as an“anchor”on grain aggregation of copper oxides.The kinetic analyses confirm that the expanded lattice space and increased oxygen vacancies of cycled Ov-BMO-Cu synergistically guarantee effective sodium-ion diffusion and storage mechanisms.Therefore,the Ov-BMO-Cu electrode exhibits higher reversible capacities of 4.04 mA h cm^(-2)at 0.2 mA cm^(-2)after 100 cycles and 2.20 m A h cm^(-2)at 1.0 mA cm^(-2)after 500 cycles.Besides,the presodiated Ov-BMO-Cu anode delivers a considerable reversible capacity of 0.79 m A h cm^(-2)at 1.0 mA cm^(-2)after 60 cycles in full cells with Na_(3)V_(2)(PO_(4))_(3)cathode,confirming its outstanding practicality.Thus,this work is expected to provide enlightenment for designing high-capacity bimetallic oxide anodes.

Synthesis and Photoluminescence of Eu-doped ZnO Nanosheets

Eu-doped ZnO nanosheets were synthesized successfully by means of the hydrothermal method. The X-ray diffraction（XRD） pattern shows that the sample is a single phase with the ZnO-like wurtzite structure. And the X-ray photoelectron spectrum suggests that there are Eu3＋ ions in the matrix of the sample. Eu3＋-related red emissions resulted from energy transfer were observed for the nanosheets under UV laser excitation. The UV, green and yellow emissions were also seen in the photoluminescence spectra.

Synthesis and characterization of Fe_3O_4@SiO_2 magnetic composite nanoparticles by a one-pot process

Fe3O4@SiO2 core–shell composite nanoparticles were successfully prepared by a one-pot process. Tetraethyl-orthosilicate was used as a surfactant to synthesize Fe3O4@SiO2 core–shell structures from prepared Fe3O4 nanoparticles. The properties of the Fe3O4 and Fe3O4@SiO2 composite nanoparticles were studied by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy, and Fourier transform infrared spectroscopy. The prepared Fe3O4 particles were approximately 12 nm in size, and the thickness of the SiO2 coating was approximately 4 nm. The magnetic properties were studied by vibrating sample magnetometry. The results show that the maximum saturation magnetization of the Fe3O4@SiO2 powder（34.85 A·m^2·kg^–1） was markedly lower than that of the Fe3O4 powder（79.55 A·m^2·kg^–1）, which demonstrates that Fe3O4 was successfully wrapped by SiO2. The Fe3O4@SiO2 composite nanoparticles have broad prospects in biomedical applications; thus, our next study will apply them in magnetic resonance imaging.

The roles of graphene in advanced Li-ion hybrid supercapacitors

Lithium-ion hybrid supercapacitors （LIHSs）, also called Li-ion capacitors, are electrochemical energy stor- age devices that combining the advantages of high power density of supercapacitor and high energy density of Li-ion battery. However, high power density and long cycle life are still challenges for the cul~ rent LIHSs due to the imbalance of charge-storage capacity and electrode kinetics between capacitor-type cathode and battery-type anode. Therefore, great efforts have been made on designing novel cathode materials with high storage capacity and anode material with enhanced kinetic behavior for LIHSs. With unique two-dimensional form and numerous appealing properties, for the past several years, the rational designed graphene and its composites materials exhibit greatly improved electrochemical performance as cathode or anode for LIHSs. Here, we summarized and discussed the latest advances of the state- of-art graphene-based materials for LIHSs applications. The major roles of graphene are highlighted as （1） a superior active material, （2） ultrathin 2D flexible support to remedy the sluggish reaction of the metal compound anode, and （3） good 2D building blocks for constructing macroscopic 3D pOFOUS car- bonjgraphene hybrids. In addition, some high performance aqueous LIHSs using graphene as electrode were also summarized. Finally, the perspectives and challenges are also proposed for further develop- ment of more advanced graphene-based LIHSs.

Enhanced light extraction of GaN-based light-emitting diodes with periodic textured SiO_2 on Al-doped ZnO transparent conductive layer

We report an effective enhancement in light extraction of Ga N-based light-emitting diodes（LEDs） with an Al-doped Zn O（AZO） transparent conductive layer by incorporating a top regular textured SiO2 layer. The 2 inch transparent throughpore anodic aluminum oxide（AAO） membrane was fabricated and used as the etching mask. The periodic pore with a pitch of about 410 nm was successfully transferred to the surface of the SiO2 layer without any etching damages to the AZO layer and the electrodes. The light output power was enhanced by 19% at 20 m A and 56% at 100 m A compared to that of the planar LEDs without a patterned surface. This approach offers a technique to fabricate a low-cost and large-area regular pattern on the LED chip for achieving enhanced light extraction without an obvious increase of the forward voltage.

Highly stable two-dimensional graphene oxide:Electronic properties of its periodic structure and optical properties of its nanostructures

According to first principle simulations, we theoretically predict a type of stable single-layer graphene oxide（C_2O）.Using density functional theory（DFT）, C_2O is found to be a direct gap semiconductor. In addition, we obtain the absorption spectra of the periodic structure of C_2O, which show optical anisotropy. To study the optical properties of C_2O nanostructures, time-dependent density functional theory（TDDFT） is used. The C_2O nanostructure has a strong absorption near 7 eV when the incident light polarizes along the armchair-edge. Besides, we find that the optical properties can be controlled by the edge configuration and the size of the C_2O nanostructure. With the elongation strain increasing, the range of light absorption becomes wider and there is a red shift of absorption spectrum.

Characterization of structural and electrical properties of ZnO tetrapods

ZnO tetrapods were synthesized by a typical thermal vapor-solid deposition method in a horizontal tube furnace.Structural characterization was carried out by transmission electron microscopy （TEM） and select-area electron diffraction （SAED）,which shows the presence of zinc blende nucleus in the center of tetrapods while the four branches taking hexagonal wurtzite structure.The electrical transport property of ZnO tetrapods was investigated through an in-situ nanoprobe system.The three branches of a tetrapod serve as source,drain,and ＂gate＂,respectively;while the fourth branch pointing upward works as the force trigger by vertically applying external force downward.The conductivity of each branch of ZnO-tetrapods increases 3-4 times under pressure.In such situation,the electrical current through the branches of ZnO tetrapods can be tuned by external force,and therefore a simple force sensor based on ZnO tetrapods has been demonstrated for the first time.

Investigation of structural, morphological and electrochemical properties of mesoporous La2CuCoO6 rods fabricated by facile hydrothermal route

This work introduces the facile hydrothermal synthesis of double perovskite La2CuCoO6.X-ray diffraction pattern confirmed the formation of a monoclinic phase with P121/c1 symmetry.Transmission electron microscopy results revealed that the self-assembled porous rods were composed of nanocrystallite aggregates.The estimated specific surface area of these mesoporous rods with an average pore diameter of 6 nm was^41 m^2·g^–1.The presence of ions with oxidation states of La^3+,Cu^2+,and Co^2+/Co^3+on the surface of the mesoporous La2CuCoO6 rods was confirmed by X-ray photoelectron spectroscopic analysis.Via cyclicvoltammetry and chronopotentiometry,the electrode fabricated from the mesoporous La2CuCoO6 rods were found to exhibit pseudocapacitive behavior with a specific capacitance of 259.4 F·g^–1 at a current density of 0.5 A·g^–1.An^89%retention in specific capacitance was achieved after 1000 charge/discharge cycles at a constant current density of4 A·g^–1.

Structural, Magnetic, and Electrical Properties of Al3＋ Substituted CuZn-ferrites

NanocrystallineCuo5Zno5Fe2-xAlxO2（x=0.0,0.1,0.2,0.3,0.45 and 0.5） ferrite materials were synthesized using standard solid state reaction technique. The effects of Al3＋ contents on the structural, electrical, and magnetic properties were investigated. Single phase cubic spinel structure was revealed by X-ray diffraction analysis. The crystallite size was evaluated considering the most intense diffraction peak （311） using Scherrer formula. Lattice constant decreased, whereas porosity increased with the increase in Al3＋ concentration. The value of saturation magnetization decreased with increasing aluminum contents. Temperature dependent value of direct current electrical resistivity has been determined. It is observed that the substitution of Al3＋ has significant impact on the dielectric constant, tangent of dielectric loss angle and dielectric loss factor. The variation in dielectric properties was attributed to space charge polarization.

Synthesis and sintering of indium tin oxide nanoparticles by citrate-nitrate combustion method

Spherical indium tin oxide （ITO） nanoparticles were synthesized by combustion method using citric acid as fuel and nitrates as oxidizer. The obtained ITO nanoparticles were characterized by TG-DSC, FT-IR, XRD, BET, TEM, and SEM. The ITO nanoparticles grew steadily with the increase of heat treatment temperature, and the 700~C calcined particles had a crystallite size of 25.3 nm and a specific surface area of 26.1 m2.g i The avoidance of chlorine ions in the synthesis process decreases particle agglomeration and promotes powder densification. The 900~C sintered pellet had a density of 67.6% of theoretical density （TD） and increased steadily to 97.3% for the 1400℃ sintered ceramics, respectively.

Recent progress on Ge oxide anode materials for lithium-ion batteries

1 Introduction As environmental pollution continues to worsen,governments are increasing their efforts to develop green transport vehicles,such as electric vehicles and hybrid cars.

Coal and coal byproducts:A large and developable unconventional resource for critical materials—Rare earth elements

Rare earth elements（REEs） are critical materials and provide significant values to national security,energy production, environmental protection and economic growth. The supply of REEs in U.S. solely relies on import as domestic production of REEs was ceased because of the environmental concerns during mining and lack of competitiveness. Nonetheless, unconventional REEs-containing resources,including produced water. acid mine drainage, and coal and coal byproducts（C＆CBs） contain significant amounts of REEs. However, the concentrations of REEs in these resources are several orders of magnitude lower than that of REEs ores. Thus, extraction of REEs from these materials is challenging. Here we report REEs extraction with environmentally friendly method that successfully concentrated REEs from312 ppm in fly ash to 99.4% in the final product. Especially, the five critically important REEs（Dy, Eu, Nd.Tb. and Y） account for up to ～63% of the total weight of all REEs in the final 99.4%-purity product. Coal fly ash is one of the major solid coal utilization byproducts, representing great potential resources for REEs extraction. Extraction of REEs from these unconventional resources could be the way to secure domestic supply of these critical materials.

Flexible,robust and highly efficient broadband nonlinear optical materials based on graphene oxide impregnated polymer sheets

We report a simple solution-processed method for the fabrication of low-cost,flexible optical limiting materials based on graphene oxide(GO) impregnated polyvinyl alcohol(PVA) sheets.Such GO–PVA composite sheets display highly efficient broadband optical limiting activities for femtosecond laser pulses at 400,800,and 1400 nm with very low limiting thresholds.Femtosecond pump–probe measurement results revealed that nonlinear absorption played an important role for the observed optical limiting activities.High flexibility and efficient optical limiting activities of these materials allow these composite sheets to be attached to nonplanar optical sensors in order to protect them from light-induced damage.

Rapid determination of iron oxide content in magnetically modified particulate materials

Magnetically responsive composite materials have been used in interesting applications in various areas of bioscience, biotechnology, and environmental technology. In this work, a simple method to determine the amount of magnetic iron oxide nano- and microparticles attached to magnetically-modified partic- ulate diamagnetic materials has been developed using a commercially available magnetic permeability meter, The procedure is fast and enables dry particulate magnetically modified materials to be analysed without any modification or pretreatment. We show that the magnetic permeability can be measured for materials containing up to 20% magnetic iron oxide, The magnetic permeability measurements are highly reproducible.

Magnetic modification of diamagnetic agglomerate forming powder materials

A simple method for the magnetic modification of various types of powdered agglomerate forming dia- magnetic materials was developed. Magnetic iron oxide particles were prepared from ferrous sulfate by microwave assisted synthesis. A suspension of the magnetic particles in water soluble organic solvent （methanol, ethanol, propanol, isopropyl alcohol, or acetone） was mixed with the material to be modified and then completely dried at elevated temperature. The magnetically modified materials were found to be stable in water suspension at least for 2 months.