Electric field-assisted sintering of tin dioxide with manganese dioxide addition

Green compacts of pure SnO₂ and with addition of 0.25, 0.5 and 1.0 wt.% MnO₂ were sintered by applying 100 V cm⁻¹ at 1 kHz and limiting the current to 5 A during 5 min at 1100 and 1200 °C. The shrinkage was monitored precisely during the electric current pulses. The role played by the additive was clearly seen in the shrinkage data: the higher is the additive content the lower is the onset of the shrinkage and the higher is the attained final shrinkage level. Sintering experiments on cylindrical samples with 0.5 wt.% MnO₂ with different thickness-to-diameter ratio show that the lower is that ratio, the higher is the shrinkage level, showing that the imparted Joule heating play a key role in the mechanisms responsible for sintering. The total electrical resistivity, evaluated by impedance spectroscopy, depends on the maximum attained shrinkage level, due to pore elimination upon sintering.     

Electrospun ZnO–SnO2 composite nanofibers with enhanced electrochemical performance as lithium-ion anodes

ZnO–SnO₂ composite nanofibers with different structures were synthesized by a simple electrospinning approach with subsequent calcination at three different temperatures using polyacrylonitrile as the polymer precursor. The electrochemical performance of the composites for use as anode materials in lithium-ion batteries were investigated. It was found that the ZnO–SnO₂ composite nanofibers calcined at 700 °C showed excellent lithium storage properties in terms of cycling stability and rate capability, compared to those calcined at 800 and 900 °C, respectively. ZnO–SnO₂ composite nanofibers calcined at 700 °C not only delivered high initial discharge and charge capacities of 1450 and 1101 mAh g⁻¹, respectively, with a 75.9% coulombic efficiency, but also maintained a high reversible capacity of 560 mAh g⁻¹ at a current density of 0.1 A g⁻¹ after 100 cycles. Additionally, a high reversible capacity of 591 mAh g⁻¹ was obtained when the current density returned to 0.1 A g⁻¹ after 50 cycling at a high current density of 2 A g⁻¹. The superior electrochemical performance of ZnO–SnO₂ composite nanofibers can be attributed to the unique nanofibrous structure, the smaller particle size and smaller fiber diameter as well as the porous structure and synergistic effect between ZnO and SnO₂.     

High-performance and low-voltage SnO2-based varistors

This paper presents the results of a thorough study conducted on the action mechanism of one-dimensional single-crystalline SnO₂ nanobelts in decreasing the breakdown electric field (E_b) in SnO₂-based varistors. The proposed method has general validity in that our investigation was focused on the traditional varistor composition SnO₂-CoO-Cr₂O₃-Nb₂O₅. To accomplish our study objective, two methods of decreasing E_b value were compared; one involving the increase in average grain size of the varistor through the sintering time and the other one related to the addition of nanobelts. The morphological results show that the method involving the increase in average grain size is limited by the formation of intragranular pores. Furthermore, despite contributing successfully towards decreasing the E_b value (which underwent a decline from 3990 V cm⁻¹ to 1133 V cm⁻¹ with an increase in sintering time from 1 h to 2 h), the reduction obtained by this method is found to be much lower compared to that obtained via the nanobelts insertion method (E_b = 270 V cm⁻¹). Impedance spectroscopy results showed that the insertion of nanobelts caused a decline in the grain boundary resistance while surface potential measurements proved that this decline in resistance is attributed to the absence of potential barriers along the belts which leads to the formation of a lower resistance percolation path in the varistor.     

Shrinkage control of yttria-stabilized zirconia during ac electric field-assisted sintering

Yttria-stabilized zirconia pellets were easily and accurately sintered to a predetermined sintering level, including near full density, in an experimental arrangement consisting of a vertical dilatometer and an ac adjustable power supply. Conventional and electric field-assisted sintering steps can be combined, starting from temperatures above 800 °C and applying 1000 Hz alternating electric fields in the range 80–160 V cm⁻¹. A systematic comparison of the microstructures and impedance diagrams of samples conventionally and electric field-assisted sintered to the same density levels shows that the non-conventional sintering method gives significantly small grains in agreement with previous observations. The results show that this sintering method can be applied to produce materials partially sintered at any desired shrinkage level.     

One-pot synthesis of core–shell-structured tin oxide–carbon composite powders by spray pyrolysis for use as anode materials in Li-ion batteries

Core–shell-structured tin oxide–carbon composite powders with mixed SnO₂ and SnO tetragonal crystals are prepared by one-pot spray pyrolysis from a spray solution with tin oxalate and polyvinylpyrrolidone (PVP). The aggregate, made up of SnO_x nanocrystals (several tens of nanometers), is uniformly coated with an amorphous carbon layer. The initial discharge capacities of the bare SnO₂ and SnO_x–carbon composite powders at a current density of 1 A g⁻¹ are 1473 and 1667 mA h g⁻¹, respectively; their discharge capacities after 500 cycles are 78 and 1033 mA h g⁻¹, respectively. The SnO_x–carbon composite powders maintain their spherical morphology even after 500 cycles. On the other hand, the bare SnO₂ powder breaks into several pieces after cycling. The structural stability of the SnO_x–carbon composite powders results in a low charge transfer resistance and high lithium ion diffusion rate even after 500 cycles at a high current density of 2 A g⁻¹. Therefore, the SnO_x–carbon composite powders have superior electrochemical properties compared with those of the bare SnO₂ powders with a fine size.     

Synthesis of BaCeO3 and BaCe0.9Y0.1O3−δ from mixed oxalate precursors

An oxalate precipitation route is proposed for the synthesis of BaCe_1−xY_xO₃ (x = 0 and 0.1) after calcination at 1100 °C. The precipitation temperature (70 °C) was a determinant parameter for producing a pure perovskite phase after calcination at 1100 °C for 1 h. TG/DTA measurements showed that the co-precipitated (Ba, Ce and Y) oxalate had a different thermal behaviour from single oxalates. Despite a simple grinding procedure, sintered BaCe_0.9Y_0.1O_3−δ pellets (1400 °C, 48 h) presented 90.7% of relative density and preliminary impedance measurements showed an overall conductivity of around 2 × 10⁻⁴ S cm⁻¹ at 320 °C.     

Carbon coated porous tin peroxide/carbon composite electrode for lithium-ion batteries with excellent electrochemical properties

A porous tin peroxide/carbon (SnO₂/C) composite electrode coated with an amorphous carbon layer is prepared using a facile method. In this electrode, spherical graphite particles act as supporter of electrode framework, and the interspace among particles is filled with porous amorphous carbon derived from decomposition of polyvinylidene fluoride and polyacrylonitrile. SnO₂ nanoparticles are uniformly embedded in the porous amorphous carbon matrix. The pores in amorphous carbon matrix are able to buffer the huge volume expansion of SnO₂ during charge/discharge cycling, and the carbon framework can prevent the SnO₂ particles from pulverization and re-aggregation. The carbon coating layer on the outermost surface of electrode can further prevent porous SnO₂/C electrode from contacting with electrolyte directly. As a result, the repeated formation of solid electrolyte interface is avoided and the cycling stability of electrode is improved. The obtained SnO₂/C electrode presents an initial coulombic efficiency of 77.3% and a reversible capacity of 742 mA h g⁻¹ after 130 cycles at a current density of 100 mA g⁻¹. Furthermore, a reversible capacity of 679 mA h g⁻¹ is obtained at 1 A g⁻¹.     

Microstructure and electrical characteristics of ZnO–B2O3–PbO–V2O5–MnO2 ceramics prepared from ZnO nanopowders

A peculiar kind of ZnO–B₂O₃–PbO–V₂O₅–MnO₂ ceramics was produced from the ZnO nanopowders directly co-doped with the oxides instead of lead zinc borate frit in this investigation. The 8 wt.% (PbO+B₂O₃) co-doped ceramics sintered at 950 °C for 2 h displayed the optimum electrical properties, that is, leakage current density J_L=6.2×10⁻⁶ A/cm², nonlinear coefficient α=22.8 and breakdown voltage V_BK=331 V/mm. The co-doping of 8 wt.% (PbO+B₂O₃) resulted in an increase in nonlinear coefficient and a decrease in leakage current density of the ZnO–V₂O₅ varistors while the sintering temperature showed no evident influence on nonlinear coefficient and leakage current density at the range of 800–950 °C.     

Electrical properties of new tin dioxide varistor ceramics at high currents

New dense SnO₂-based varistor ceramics with high nonlinear current–voltage characteristics (nonlinearity coefficients are of approximately 50) in a system of SnO₂–CoO–Nb₂O₅–Cr₂O₃–Y₂O₃–SrO–MgO are reported. The current–voltage behaviour at high currents is studied by using exponential voltage pulses. The obtained SnO₂ varistor ceramics exhibit low grain resistivity values of 0.23–0.64 ohm cm. To date, such values are the lowest known for SnO₂ varistors, and are closely approaching the grain resistivity of the ZnO varistor. The current–voltage characteristics of the obtained SnO₂-based varistor materials are reproducible in a wide current range from 10^?11 to approximately 10⁴ A cm^?2. The minimum current density and the minimum electric field necessary to cause the irreversible electrical breakdown are measured. It is established that a decrease in the grain resistivity leads to an increase in the minimum current density necessary for irreversible electrical breakdown to occur.     

Electrochemical energy storage performance of heterostructured SnO2@MnO2 nanoflakes

In this work, we report synthesis of SnO₂@MnO₂ nanoflakes grown on nickel foam through a facile two-step hydrothermal route. The as-obtained products are characterized by series of techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-obtained SnO₂@MnO₂ nanoflakes are directly used as supercapacitor electrode materials. The results show that the electrode possesses a high discharge areal capacitance of 1231.6 mF cm⁻² at 1 mA cm⁻² and benign cycling stability with 67.2% of initial areal capacitance retention when the current density is 10 mA cm⁻² after 6000 cycles. Moreover, the heterostructured electrode shows 41.1% retention of the initial capacitance when the current densities change from 1 to 10 mA cm⁻², which reveals good rate capability. SnO₂@MnO₂ nanoflakes products which possess excellent electrochemical properties might be used as potential electrode materials for supercapacitor applications.     

Tubular graphene nanoribbons with attached manganese oxide nanoparticles for use as electrodes in high-performance supercapacitors

Graphene nanoribbons (GNRs) with tubular shaped thin graphene layers were prepared by partially longitudinal unzipping of vapor-grown carbon nanofibers (VGCFs) using a simple solution-based oxidative process. The GNR sample has a similar layered structure to graphene oxide (GO), which could be readily dispersed in isopropyl alcohol to facilitate electrophoretic deposition (EPD). GO could be converted to graphene after heat treatment at 300 °C. The multilayer GNR electrode pillared with open-ended graphene tubes showed a higher capacitance than graphene flake and pristine VGCF electrodes, primarily due to the significantly increased surface area accessible to electrolyte ions. A GNR electrode with attached MnO₂ nanoparticles was prepared by EPD method in the presence of hydrated manganese nitrate. The specific capacitance of GNR electrode with attached MnO₂ could reach 266 F g⁻¹, much higher than that of GNR electrode (88 F g⁻¹) at a discharge current of 1 A g⁻¹. The hydrophilic MnO₂ nanoparticles attached to GNRs could act as a redox center and nanospacer to allow the storage of extra capacitance.     

Fabrication of manganese oxide/three-dimensional reduced graphene oxide composites as the supercapacitors by a reverse microemulsion method

Manganese oxide (MnO₂)/three-dimensional (3D) reduced graphene oxide (RGO) composites were prepared by a reverse microemulsion (water/oil) method. MnO₂ nanoparticles (3–20 nm in diameter) with different morphologies were produced and dispersed homogeneously on the macropore surfaces of the 3D RGO. Scanning electron microscopy and transmission electron microscopy were applied to characterize the microstructure of the composites. The MnO₂/3D RGO composites, which were annealed at 150 °C, displayed a significantly high specific capacitance of 709.8 F g⁻¹ at 0.2 A g⁻¹. After 1000 cycles, the capacitance retention was measured to be 97.6%, which indicates an excellent long-term stability of the MnO₂/3D RGO composites.     

Tin–Zinc oxide composite ceramics for selective CO sensing

Composite metal oxide gas sensors were intensely studied over the past years having superior performance over their individual oxide components in detecting hazardous gases. A series of pellets with variable amounts of SnO₂ (0–50 mol%) was prepared using wet homogenization of the component oxides leading to the composite tin-zinc ceramic system formation. The annealing temperature was set to 1100 °C. The samples containing 2.5 mol% SnO₂ and 50 mol% SnO₂ were annealed also at 1300 °C, in order to observe/to investigate the influence of the sintering behaviour on CO detection. The sensor materials were morphologically characterized by scanning electron microscopy (SEM). The increase in the SnO₂ amount in the composite ceramic system leads to higher sample porosity and an improved sensitivity to CO. It was found that SnO₂ (50 mol%) - ZnO (50 mol%) sample exhibits excellent sensing response, at a working temperature of 500 °C, for 5 ppm of CO, with a fast response time of approximately 60 s and an average recovery time of 15 min. Sensor selectivity was tested using cross-response to CO, methane and propane. The results indicated that the SnO₂ (50 mol%)-ZnO (50 mol%) ceramic compound may be used for selective CO sensing applications.     

Semiconducting properties of cold sintered V2O5 ceramics and Co-sintered V2O5-PEDOT:PSS composites

Recently we established a sintering approach, namely Cold Sintering Process (CSP), to densify ceramics and ceramic-polymer composites at extraordinarily low temperatures. In this work, the microstructures and semiconducting properties of V₂O₅ ceramic and (1-x)V₂O₅-xPEDOT:PSS composites cold sintered at 120 °C were investigated. The electrical conductivity (25 °C), activation energy (25 °C), and Seebeck coefficient (50 °C) of V₂O₅ are 4.8 × 10⁻⁴ S/cm, 0.25 eV, and −990 μV/K, respectively. The conduction mechanism was studied using a hopping model. A reversible metal-insulator transition (MIT) was observed with V₂O₅ samples exposed to a N₂ atmosphere, whereas in a vacuum atmosphere, no obvious MIT could be detected. With the addition of 1–2 Vol% PEDOT:PSS, the electrical conductivity (50 °C) dramatically increases from 10⁻⁴ to 10⁻³ ∼ 10⁻² S/cm, and the Seebeck coefficient (50 °C) shifts from −990 to −(600 ∼ 250) μV/K. All the results indicate that CSP may offer a new processing route for the semiconductor electroceramic development without a compromise to the all-important electrical properties.     

The effect of annealing on electrical properties of fluorinated amorphous carbon films

Fluorinated amorphous carbon (a–C:F) films have been deposited by electron cyclotron resonance chemical vapor deposition (ECR–CVD) at room temperature using C₄F₈ and CH₄ as precursor gases. The chemical compositions and electrical properties of a–C:F films have been studied by X-ray photoelectron spectroscopy (XPS), capacitance–voltage (C–V) and current-voltage (I–V) measurements. The results show that C–CF_x and C–C species of a–C:F films increase and fluorine content decreases after annealing. The dielectric constant of the annealed a–C:F films increases as a result of enhancement of film density and reduction of electronic polarization. The densities of fixed charges and interface states decrease from 1.6 × 10¹⁰ cm^− 2 and (5–9) × 10¹¹ eV^− 1 cm^− 2 to 3.2 × 10⁹ cm^− 2 and (4–6) × 10¹¹ eV^− 1 cm^− 2 respectively when a–C:F films are annealed at 300 °C. The magnitude of C–V hysteresis decreases due to reduced dangling bonds at the a–C:F/Si interfaces after heat treatment. The conduction of a–C:F films shows ohmic behavior at lower electric fields and is explained by Poole–Frankel (PF) mechanism at higher electric fields. The PF current increases indicative of reduced trap energy when a–C:F films are subjected to higher annealing temperatures.     

High performance MnO2 nanoflower supercapacitor electrode by electrochemical recycling of spent batteries

MnO₂ nanoflower is prepared by electrochemical conversion of Mn₃O₄ obtained by heat treatment of spent zinc‒carbon batteries cathode powder. The heat treated and converted powders were characterized by TGA, XRD, FTIR, FESEM and TEM techniques. XRD analyses show formation of Mn₃O₄ and MnO₂ phases for the heat treated and converted powders, respectively. FESEM images indicate the formation of porous nanoflower structure of MnO_2, while, condensed aggregated particles are obtained for Mn₃O₄. The energy band gap of MnO₂ is obtained from UV‒Vis spectra to be 2.4 eV. The electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge‒discharge and electrochemical impedance techniques using three-electrode system. The specific capacitance of MnO₂ nanoflower (309 F g⁻¹ at 0.1 A g⁻¹) is around six times higher than those obtained from the heat treated one (54 F g⁻¹ at 0.1 A g⁻¹). Moreover, it has high capacitance retention up to 93% over 1650 cycles. Impedance spectra of MnO₂ nanoflower show very small resistances and high electrochemical active surface area (340 m² g⁻¹). The present work demonstrates a novel electrochemical approach to recycle spent zinc-carbon batteries into high value supercapacitor electrode.     

High performance wire-shaped supercapacitive electrodes based onactivated carbon fibers core/manganese dioxide shell structures

Micro/nano hierarchical structures with uniformly patterned nanostructures shell and activated internal core are promising for boosting electrochemical performance. Here we report the fabrication of wire-shaped supercapacitive electrodes with manganese dioxide (MnO₂) nanostructures shell integrated onto activated carbon fiber (ACF) core. The ACF core is doped with nitrogen heteroatom and shows good conductivity and hydrophilicity, which endow fast ion and electron transport and high accessibility of electrolyte. The MnO₂ nanostructures shell integrated on the ACF core by electrodeposition method together provide significant pseudocapacitive contribution associated with fast faradaic reactions. The electrochemical performance of the fabricated electrodes was evaluated by cyclic voltammetry, galvanostatic charging/discharging and electrochemical impedance spectroscopy techniques. The integrated wire-shaped electrodes, which boost the synergetic effect of MnO₂ nanostructures and ACF, have excellent current collecting capabilities thus resulting high electrochemical performance (with the specific capacitance of 26.64 mF cm⁻¹ at the current density of 0.1 mA cm⁻¹ and 96% capacitance retention after 8000 charging/discharging cycles at the current density of 1 mA cm⁻¹).     

Decoration of carbon cloth by manganese oxides for flexible asymmetric supercapacitors

Here we describe the production of carbon cloth coated with MnO₂ nanosheets or MnOOH nanorods through a normal temperature reaction or a hydrothermal approach, respectively. Of note, the electrochemical performance of MnO₂-coated carbon cloth was better (429.2 F g⁻¹) than that of MnOOH-coated carbon cloth. When the MnO₂-coated carbon cloth is introduced as the positive electrode and the Fe₂O₃-coated carbon cloth as the negative electrode, a flexible asymmetric supercapacitor was obtained with an energy density of 22.8 Wh kg⁻¹ and a power density of 159.4 W kg⁻¹. Therefore, such a hierarchical MnO₂-coated carbon cloth nanocomposite is a promising high-performance electrode for flexible supercapacitors.     

Nitrate–citrate combustion synthesis of Ce1−xGdxO2−x/2 powder and its characterization

The structure, thermal expansion coefficients, and electric conductivity of Ce_1−xGd_xO_2−x/2 (x = 0–0.6) solid solution, prepared by the gel-combustion method, were investigated. The uniform small particle size of the gel-combustion prepared materials allows sintering into highly dense ceramic pellets at 1300 °C, a significantly lower temperature compared to that of 1600–1650 °C required for ceria solid electrolytes prepared by traditional solid state techniques. XRD showed that single-phase solid solutions formed in all the investigated range. The maximum conductivity, σ_600 °C = 5.26 × 10⁻³ S/cm, was found at x = 0.2. The thermal expansion coefficient, determined from high-temperature X-ray data, was 8.125 × 10⁻⁶ K⁻¹ at x = 0.2.     

Encapsulation of manganese oxides nanocrystals in electrospun carbon nanofibers as free-standing electrode for supercapacitors

Flexible composites with manganese oxides (MnO_x) nanocrystals encapsulated in electropun carbon nanofibers were successfully fabricated via a simple and practical combination of electrospinning and carbonization process. The as-formed MnO_x/carbon nanofibers composites have a rough surface with MnO_x nanoparticles well embedded in the carbon nanofibers backbones. When used as electrodes for supercapacitor, the resulting MnO_x/carbon nanofiber composites exhibit good electrochemical performance with a specific capacitance of 174.8 F g⁻¹ at 2 mV s⁻¹ in 0.5 M Na₂SO₄ electrolyte, a good rate capability at high current density and long-term cycling stability. It is expected that such freestanding composites could be promising electrodes for high-performance supercapacitors.