Tunable BaxSr1-xTiO3 nanoparticles induced high energy storage density in layer-structured asymmetric polymer-based nanocomposites

In order to solve the problem of low charging and discharging energy density of dielectric capacitors, the structure design of layered polymer matrix composites is carried out in this paper. Ba_0.7Sr_0.3TiO₃, Ba_0.8Sr_0.2TiO₃ and Ba_0.9Sr_0.1TiO₃ nanoparticles were successfully prepared by the oxalate coprecipitation method. The surface of Ba_xSr_1-xTiO₃ was successfully coated with dopamine, which promoted the dispersion of the polymer matrix of the ceramic powder. Monolayer Ba_xSr_1-xTiO₃/PVDF composites containing Ba_xSr_1-xTiO₃ with different Ba/Sr ratios were successfully prepared by the casting method. Three-layer asymmetric composites with different fillers were successfully prepared by layer-by-layer casting. The phase and microstructure of the as-prepared materials were analyzed by XRD and SEM. The dielectric, electrical conductivity, ferroelectric and energy storage properties of the composites were tested. The effects and laws of the design of the three-layer asymmetric structure on the dielectric properties and energy storage properties of the layered composites are mainly studied. When the structure of the three-layer asymmetric composite is 1-2-3, the breakdown field strength reaches 330 kV/mm, the discharge energy density reaches 8.51 J/cm³, and the charge-discharge efficiency is 67%. This work demonstrates that layered composites with asymmetric properties can facilitate the development of electrical energy storage.     

Formation of single-crystalline BaTiO3 nanorods from glycolate by tuning the supersaturation conditions

We have studied peculiarities in the formation of single-crystalline barium titanate (BaTiO₃) nanorods from a glycolate-mediated complex via a single-step hydrothermal process under different supersaturation (S_R) conditions. X-ray diffraction (XRD) showed the formation of pure BaTiO₃ with an S_R of above 19. The tetragonality for the BaTiO₃ (c/a) reached 1.013 at S_R = 19–29 and dropped to 1.010 for S_R = 39. According to the transmission electron microscopy (TEM) and XRD analyses, the rod-shaped particles exhibited single crystallinity and crystal growth along the [001] plane. With scanning electron microscopy (SEM), the morphological evolution from a plate-shaped intermediate precursor (S_R = 6–9) to a rod-shaped product with an aspect ratio of 6–9 (S_R = 19–29), and to non-polar material with an irregular structure (S_R = 39), was observed. The negative slope, linear dependence of the particles’ width and length on the supersaturation level in the range S_R = 19–39 was established for the first time. The replacement of the prevailing crystallization mechanism from in-situ topotactic transformation into dissolution-precipitation above S_R = 19 was observed. It was shown that with a simple regulation of the S_R, the structural and morphological characteristics of the obtained BaTiO₃ nanoparticle can be effectively tuned.     

Effect of nickel addition on the physicochemical properties of SrTiO3-based materials

Synthesis of materials in Ni/SrTiO₃ system was undertaken. Perovskite structure material with nominal composition SrTi_0.98O₃ was synthesised by the sol-gel method. Nickel was introduced into the system by the wet impregnation method followed by proper thermal treatment. Two research paths were carried out: the evaluation of sintering conditions on material properties (sintering temperature: 1100, 1200, 1300 and 1400 °C; sintering time: 1, 3 and 5 h for sintering at 1300 °C) and the effect of nickel addition on the material properties - 1, 2, and 5 mol% of Ni compared to the amount of Ti was introduced into the analysed system. The microstructures of the materials, together with their structural (XRD analysis) and electrical (total conductivity and Seebeck coefficient) properties, were determined. Furthermore, temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPOx) measurements were performed to evaluate the materials’ redox properties. It was shown that less than 1 mol% of Ni could be incorporated into the strontium titanate structure when a wet impregnation was chosen as the method for the introduction of Ni into the SrTiO₃-based system. NiO and, for the highest amount of introduced nickel, also NiTiO₃ were the main additional nickel-containing phases. For all materials synthesised in the Ni/SrTiO₃ system, the positive value of the Seebeck coefficient was observed, suggesting that nickel is an acceptor-type dopant while incorporated into the perovskite structure. However, the TPR measurements clearly imply that nickel can be incorporated into the strontium titanate structure in various oxidation states.     

Novel polymer composites of RuO2@nBaTiO3/PVDF with a high dielectric constant

The dielectric properties of a novel polymer dielectric material were investigated. The conductive phase of RuO₂ was synthesized for deposition on the surface of a nanosized BaTiO₃ (nBT). The RuO₂@nBT hybrid particles were incorporated into a poly (vinylidene fluoride) (PVDF) as a three-phase composite (RuO₂@nBT/PVDF). The obtained dielectric constant (ε′) was significantly high (3837.16) for the composite with a volume fraction of $f_{Ru{O}_2@nBT}$ = 0.50. The large interfacial polarization between the RuO₂?nBT and RuO₂?PVDF interfaces considerably increased the value of ε′. Therefore, interfacial polarization is a critical factor in improving the dielectric properties. The dielectric behavior of the RuO₂@nBT/PVDF composites can be described using the effective medium percolation theory model, which indicates the significant contributions of the conductive RuO₂ phase and high-permittivity nBT phase.     

Comparative study of microwave absorption properties of Ni–Zn ferrites obtained from different synthesis technologies

Spinel ferrites are widely used for electromagnetic wave (EMW) absorption applications. In this study, spinel Ni–Zn ferrites with excellent microwave absorption properties were synthesized. Their EMW absorption characteristics and interaction mechanisms were studied to lay the foundation for the study of the role of Ni–Zn ferrite as a magnetic substrate for composites. Herein, Ni_0·5Zn_0·5Fe₂O₄ was prepared by the hydrothermal method (H-NZFO) and the sol–gel auto-combustion method (S-NZFO); both samples exhibited distinct microwave absorption properties. The S-NZFO absorber (thickness = 3.72 mm) demonstrated the best dual-zone microwave absorption with two strong reflection loss peaks at 5.1 and 10.5 GHz. The corresponding effective absorption bandwidth (EAB) reached 9.0 GHz, which covered part of the S-band and all of the C- and X-bands. These results were attributed to the high saturation magnetization, outstanding complex permeability, and multiple magnetic loss channels of S-NZFO. The H-NZFO sample exhibited excellent absorption capability and matching thickness. At a thickness as low as 1.71 mm, the minimum reflection loss (RL_min) of the H-NZFO absorber reached -60.2 dB at 13.1 GHz. The maximum bandwidth corresponding to RL below -10 dB was 4.6 GHz. These results can be attributed to small particle size, high complex permittivity, and multiple dielectric loss channels of H-NZFO. The observed wide effective absorption bandwidth of S-NZFO and strong microwave absorption capability of H-NZFO suggest the potential of both materials as substrates for efficient microwave absorbers in military as well as civilian absorption applications.     

Magnetodielectric coupling in barium titanate–cobalt ferrite composites obtained via thermally-assisted high-energy ball milling

In this work, a magnetodielectric coupling observed in barium titanate–cobalt ferrite composites synthesized using high-energy ball milling assisted via a thermal treatment is discussed. Vibrating sample magnetometry and dielectric spectroscopy showed that multiferroic composites possess both ferromagnetic and dielectric behaviors inherited from the parent ferromagnetic cobalt ferrite and ferroelectric barium titanate phases. The magnetocapacitance (up to 35%) recorded for x = 0.3, (1-x)BaTiO₃–xCoFe₂O₄, can be attributed to the spin-dependent filtering mechanism. The composite with the aforementioned composition exhibited a homogeneous matrix–particle composite microstructure, which was achieved via high-energy ball milling during the mixing stage.     

Recycling spent lead acid batteries into aqueous zinc-ion battery material with ultra-flat voltage platforms

The harmless disposal of lead paste in the spent lead-acid batteries (LABs) remains an enormous challenge in traditional pyrometallurgical recycling. Here, we introduced a hydrometallurgical method for the recycling of the spent LABs’ waste to obtain the β-PbO as a novel zinc ion batteries (ZIBs) active material. The obtained β-PbO exhibits ultra-flat charge/discharge voltage platforms (0.21 mV/(mAh g^?1)) and stable specific capacity. During the charge/discharge, the β-PbO spontaneously triggers the formation of (ZnSO₄)[Zn(OH)₂]₃·5H₂O (ZHS) micro-sheets as a surface passivation layer. Moreover, the ex-situ X-ray spectra reveal that the reversible phase transformation occurs between PbSO₄ and Pb with the assistance of ZHS by adjusting the PH value on the electrode-electrolyte interface. The synergistic two-phase-reaction mechanism generates ultra-flat voltage platforms upon the charge/discharge. This “energy-saving and environment-friendly” recycling route eliminates the major source of emission of pollution particulates/gases compared to the traditional pyrometallurgical recycling, while at the same time replacing energy-consuming and environmentally detrimental processes of synthesis of current ZIBs cathodes.     

Transformation of sputtered calcium copper titanate thin film into nanorods by sequential annealing

Rapid synthesis of long calcium copper titanate (CCTO) nanorods was carried out by sequential annealing. CCTO thin films have been deposited on p-Si substrate by RF sputtering technique and afterwards, the samples were thermally treated using a preheated furnace by varying the annealing temperature from 850 °C to 1100 °C. CCTO nanorods of 12 µm lengths and 400–600 nm diameters were synthesized at 1100 °C. Based on the FESEM observations, a plausible growth mechanism has been proposed to explain the formation of nanorods. The (220) XRD peak of the CCTO film became prominent for the annealing temperature of 950 °C. The presence of nanoscale crystals in amorphous matrix has been observed by HRTEM studies. The elemental mapping of CCTO nanorod has shown a spatial variation of elements throughout the nanorod. The oxide and interface charge density was found to be increased with the rise in annealing temperature.     

滇南兰坪南厂铅锌矿矿床成因及成矿作用

南厂铅锌矿位于兰坪—思茅中生代坳陷北端，构造格局复杂，成矿条件优越。通过对矿床进行野外地质调查，对成矿地质背景、矿床地质特征、成矿机制和矿床成因进行了分析，发现南厂铅锌矿体主要呈透镜状赋存于第三系云龙组（Eyb）及下白垩统景星组（K1j1）地层中，与围岩接触部位发育微弱褪色蚀变，云龙组下段（Eya）是矿体底板有效的“屏蔽层”；区内发育原生砂岩型矿石、灰岩型矿石和氧化矿石，沉积构造特征明显，局部具有热液、变质作用改造特征；矿区地层、构造是矿床形成的重要因素，断裂构造是主要的容矿、导矿构造，高盐度热卤水沿导矿构造循环至有利层位、构造部位富集成矿，综合分析认为南厂矿床属热卤水为主的多成因层控型铅锌矿床。