Current efficiency studies for graphite and SnO2-based anodes for the electro-deoxidation of metal oxides

Studies were performed investigating the electrochemical reduction of chromium oxide (Cr₂O₃) by electro-deoxidation by utilising either a graphite anode or a tin oxide (SnO₂) based anode. Potentiostatic electrolysis was performed at 3.0 V for both a graphite and for a SnO₂-based anode, and also 2.0 V for a graphite anode. The cathode reduction purity, anode mass change, anode potential relative to a glassy carbon pseudo-reference and current efficiency were measured and compared. The key observations are that substituting a SnO₂-based anode for a graphite anode led to greater current efficiencies for electro-deoxidation. This was attributed to the lack of contamination of the melt by carbon and the lower cathode potential due to the higher anodic potential when using tin oxide based anodes for the same applied voltage. The current efficiency was also found to decrease with both anode materials when higher anode surface areas or lower current densities were used. Again this was attributed to a decrease in anodic potentials and a corresponding increase in the cathodic potential resulting in a greater number of parasitic reactions occurring at the cathode.     

Solvothermal synthesis of SnO2/graphene nanocomposites for supercapacitor application

A facile solvent-based synthesis route based on the oxidation–reduction reaction between graphene oxide (GO) and SnCl₂·2H₂O has been developed to synthesize SnO₂/graphene (SnO₂/G) nanocomposites. The reduction of GO and the in situ formation of SnO₂ nanoparticles were achieved in one step. Characterization by X-ray diffraction (XRD), ultraviolet-visible (UV–vis) absorption spectroscopy, Raman spectroscopy, and field emission scanning electron microscopy (FESEM) confirmed the feasibility of using the solvothermally treated reaction system to simultaneously reduce GO and form SnO₂ nanoparticles with an average particle size of 10 nm. The electrochemical performance of SnO₂/graphene showed an excellent specific capacitance of 363.3 F/g, which was five-fold higher than that of the as-synthesized graphene (68.4 F/g). The contributing factors were the synergistic effects of the excellent conductivity of graphene and the nanosized SnO₂ particles.     

SnO2–graphene–carbon nanotube mixture for anode material with improved rate capacities

SnO₂–graphene–carbon nanotube (SnO₂–G–CNT) mixture is synthesized using graphene oxide as precursor for application as anode material in rechargeable Li ion batteries. It is shown that the SnO₂ nanoparticles of 3–6 nm in diameter are not only attached onto the surface of graphene sheets by anchoring with surface functional groups, but they also are encapsulated in pore channels formed by entangled graphene sheets. The incorporation of carbon nanotubes reduces the charge transfer resistance of the anode made from the mixture through the formation of 3D electronic conductive networks. The SnO₂–G–CNT anodes deliver remarkable capacities of 345 and 635 mAh g⁻¹ at 1.5 and 0.25 A g⁻¹, respectively. Flexible electrodes consisting of highly-aligned SnO₂–G–CNT papers are also prepared using a simple vacuum filtration technique. They present a stable capacity of 387 mAh g⁻¹ at 0.1 A g⁻¹ after 50 cycles through the synergy of the high specific capacity of SnO₂ nanoparticles and the excellent cycleability of G–CNT paper.     

Electrochemical behavior of activated-carbon capacitor material loaded with nickel oxide

In order to enhance specific capacitance and energy density of carbon-based supercapacitor, some nanometer-scale amorphous particles of nickel oxide were loaded into activated-carbon by suspending the activated-carbon in a Ni(NO₃)₂ solution followed by neutralization. A hybrid type electrochemical capacitor was made and tested, in which the activated-carbon loaded with nickel oxide was used as cathode material and activated-carbon was used as anode material. Although the BET surface area of the activated-carbon decreased upon nickel oxide loading compared to that of the starting material, its specific capacitance increased 10.84%, from 175.40 to 194.01 F g⁻¹ and the potential of oxygen evolution on the composite material electrode was 0.076 V higher than that of the pure activated-carbon electrode, in the electrolyte of 6 mol/L KOH solution, so the hybrid capacitor had larger energy density. Similar to the pure activated-carbon electrode, no obvious change appears on the specific capacitances of the composite material electrode at various discharge currents and the composite material electrode exhibiting good power characteristics.     

Tin dioxide/carbon nanotube composites with high uniform SnO2 loading as anode materials for lithium ion batteries

SnO₂/multi-walled carbon nanotube (MWCNT) composites were prepared by the solvothermal method and subsequent heat treatment at 360 °C. The samples were characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Results on the higher SnO₂ content composite sample indicate that a uniform layer of SnO₂ nanocrystals with crystal size around 5 nm was deposited on the surface of the carbon nanotubes. The composite demonstrates a reversible lithium storage capacity of 709.9 mAh g⁻¹ at the first cycle and excellent cyclic retention up to 100 cycles as anode for lithium ion batteries.     

Microwave-assisted one-pot synthesis of metal/metal oxide nanoparticles on graphene and their electrochemical applications

An effective synthesis strategy of hybrid metal (PtRu)/metal oxide (SnO₂) nanoparticles on graphene nanocomposites is developed using a microwave-assisted one-pot reaction process. The mixture of ethylene glycol (EG) and water is used as both solvent and reactant. In the reaction system for the synthesis of SnO₂/graphene nanocomposite, EG not only reduces graphene oxide (GO) to graphene, but also results in the formation of SnO₂ facilitated by the presence of a small amount of water. On the other hand, in the reaction system for preparation of PtRu/graphene nanocomposites, EG acts as solvent and reducing agent for reduction of PtRu nanoparticles from their precursors and reduction of graphene from graphene oxide. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) characterizations confirm the feasibility of the microwave-assisted reaction system to simultaneously reduce graphene oxide and to form SnO₂ or PtRu nanoparticles. The as-synthesized SnO₂/graphene hybrid composites show a much higher supercapacitance than the pure graphene, and the as-prepared PtRu/graphene show much better electrocatalytic activity for methanol oxidation compared to the commercial E-TEK PtRu/C electrocatalysts.     

Interconnected SnO2/graphene+CNT network as high performance anode materials for lithium-ion batteries

As a metal oxide with a high theoretical capacity, SnO₂ is considered to be one of the promising alternative anode materials in lithium-ion batteries. However, the pulverization of electrodes caused by the large volume expansion of SnO₂ during repeated charge/discharge hinders its practical application. Here, SnO₂ nanoparticles decorated on a 3D carbon network structure formed by the interconnection of graphene and CNT (SnO₂/G + CNT), which is designed and successfully synthesized via in situ chemical synthesis and thermal treatment. In this structure, the SnO₂ with nanosized can increase energy storage points and decrease the ions transport length, the carbon network can build a high conductive network that facilitates electron transport and alleviate the volume expansion to prevent electrode pulverization. In addition, graphene has a high specific surface area effect that facilitates lithium-ion storage, and the CNT also supports the graphene frame to make the carbon skeleton structure more stable, and provides a large number of ion transport channels, increasing the active sites of the reaction. Due to this excellent structure with synergistic effects, the SnO₂/G + CNT electrode exhibits superior reversible capacity (1227.2 mAh g^-1 at 0.1 A g^-1 after 200 cycles), superior rate capacity (549.3 mAh g^-1 at 3.0 A g^-1) and long cycle stability (1630.1 mAh g^-1 at 0.5 A g^-1 after 1000 cycles).     

Tin antimony oxide @graphene as a novel anode material for lithium ion batteries

Bimetal oxides have attracted much attention due to their unique characteristics caused by the synergistic effect of bimetallic elements, such as adjustable operating voltage and improved electronic conductivity. Here, a novel bimetal oxide Sn_0.918Sb_0.109O₂@graphene (TAO@G) was synthesized via hydrothermal method, and applied as anode material for lithium ion batteries. Compared with SnO₂, the addition of Sb to form a bimetallic oxide Sn_0.918Sb_0.109O₂ can shorten the band gap width, which is proved by DFT calculation. The narrower band gap width can speed up the lithium ions transport and improve the electrochemical performances of TAO@G. TAO@G is a structure in which graphene supports nano-sized TAO particles, and it is conducive to the electrons transport and can improve its electrochemical performances. TAO@G achieved a high initial reversible discharge specific capacity of 1176.3 mA h g^?1 at 0.1 A g^?1 and a good capacity of 648.1 mA h g^?1 at 0.5 A g^?1 after 365 cycles. Results confirm that TAO@G is a novel prospective anode material for LIBs.     

Carbon-coated SnO2/graphene nanosheets as highly reversible anode materials for lithium ion batteries

A simple approach is reported to prepare carbon-coated SnO₂ nanoparticle–graphene nanosheets (Gr–SnO₂–C) as an anode material for lithium ion batteries. The material exhibits excellent electrochemical performance with high capacity and good cycling stability (757 mA h g^?1 after 150 cycles at 200 mA g^?1). The likely contributing factors to the outstanding charge/discharge performance of Gr–SnO₂–C could be related to the synergism between the excellent conductivity and large area of graphene, the nanosized particles of SnO₂, and the effects of the coating layer of carbon, which could alleviate the effects of volume changes, keep the structure stable, and increase the conductivity. This work suggests a strategy to prepare carbon-coated graphene–metal oxide which could be used to improve the electrochemical performance of lithium ion batteries.     

In situ fabrication of spherical porous tin oxide via a spray pyrolysis technique

Spherical porous tin oxide was fabricated via a spray pyrolysis technique. TEM revealed that the primary SnO₂ crystals had an average size of 5-10 nm. Good interconnection between SnO₂ crystals is also observed. The electrochemical measurements showed that the spherical porous SnO₂ samples have excellent cyclability, which can deliver a reversible capacity of 410 mAh/g for up to 50 cycles as a negative electrode for lithium batteries. Our approach for enhancing the structural stability of tin oxide is to incorporate spherical porous structures as a buffer zone to alleviate the volume expansion of the tin oxide anode during lithiation/delithiation.     

High reversible capacity of SnO2/graphene nanocomposite as an anode material for lithium-ion batteries

A gas–liquid interfacial synthesis approach has been developed to prepare SnO₂/graphene nanocomposite. The as-prepared nanocomposite was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller measurements. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (2–6 nm in size) on graphene matrix. The electrochemical performances were evaluated by using coin-type cells versus metallic lithium. The SnO₂/graphene nanocomposite prepared by the gas–liquid interface reaction exhibits a high reversible specific capacity of 1304 mAh g⁻¹ at a current density of 100 mA g⁻¹ and excellent rate capability, even at a high current density of 1000 mA g⁻¹, the reversible capacity was still as high as 748 mAh g⁻¹. The electrochemical test results show that the SnO₂/graphene nanocomposite prepared by the gas–liquid interfacial synthesis approach is a promising anode material for lithium-ion batteries.     

Structural and electrochemical characterization of SnOx thin films for Li-ion microbattery

SnO_x thin films were prepared by reactive radio frequency magnetron sputtering with different sputtering powers. X-ray photoelectron spectroscopy suggested that all the films have similar chemical stoichiometry as SnO_1.5. X-ray diffraction and transmission electro microscopy results showed that crystal size of the SnO_x thin films gradually increases with increase of sputtering power from 50 to 150 W. Cyclic voltammetry and galvanostatic charge/discharge cycling measurements indicated that the electrochemical properties of SnO_x films strongly rely on their crystal sizes as well as surface morphologies. The SnO_x film deposited at sputtering power of 120 W exhibits the best electrochemical performances. It could deliver a reversible capacity of 670 μAh cm⁻² μm⁻¹ at 50 μA cm⁻² in the voltage range of 0.1-1.2 V up to 50 cycles.     

Facile solvothermal synthesis of a graphene nanosheet-bismuth oxide composite and its electrochemical characteristics

This work demonstrates a novel and facile route for preparing graphene-based composites comprising of metal oxide nanoparticles and graphene. A graphene nanosheet-bismuth oxide composite as electrode materials of supercapacitors was firstly synthesized by thermally treating the graphene-bismuth composite, which was obtained through simultaneous solvothermal reduction of the colloidal dispersions of negatively charged graphene oxide sheets in N,N-dimethyl formamide (DMF) solution of bismuth cations at 180 °C. The morphology, composition, and microstructure of the composites together with pure graphite oxide, and graphene were characterized using powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetry and differential thermogravimetry (TG-DTG). The electrochemical behaviors were measured by cyclic voltammogram (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS). The specific capacitance of 255 F g⁻¹ (based on composite) is obtained at a specific current of 1 A g⁻¹ as compared with 71 F g⁻¹ for pure graphene. The loaded-bismuth oxide achieves a specific capacitance as high as 757 F g⁻¹ even at 10 A g⁻¹. In addition, the graphene nanosheet-bismuth oxide composite electrode exhibits the excellent rate capability and well reversibility.     

Synthesis of single-crystal SnO2 nanowires for NOx gas sensors application

Single-crystal SnO₂ nanowires (NWs) were successfully synthesized and characterized as sensing materials for long-term NO_x stability detection in environmental monitoring. Reproducible and selective growths of the SnO₂ NWs on a patterned, 5 nm-thick gold catalyst coated on a SiO₂/Si wafer as substrate were conducted by evaporating SnO powder source at 960 °C in a mixture of argon/oxygen ambient gas (Ar: 50 sccm/O₂: 0.5 sccm). The as-obtained products were characterized by field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman scattering, and photoluminescence (PL). The SEM and HRTEM images revealed that the products are single-crystal SnO₂ NWs with diameter and length ranges of 70 nm–150 nm and 10 μm–100 μm, respectively. The three observed Raman peaks at 476, 633, and 774 cm⁻¹ indicated the typical rutile phase, which is in agreement with the XRD results. The NWs showed stable PL with an emission peak centered at around 620 nm at room-temperature, indicating the existence of oxygen vacancies in the NW samples. The electrical properties of synthesized SnO₂ NWs sensor were also investigated and it exhibited a negative temperature coefficient of resistance in the measured range (300–525 K). The calculated activation energy E_c of SnO₂ NWs was 0.186 eV. Moreover, the SnO₂ NW sensors exhibited good response to NO_x gas. The response of the sensors to 5 ppm NO_x reached 105% at an operating temperature of 200 °C.     

Synthesis of uniform polycrystalline tin dioxide nanofibers and electrochemical application in lithium-ion batteries

Under optimized synthesis conditions, very large area uniform SnO₂ nanofibers consisting of orderly bonded nanoparticles have been obtained for the first time by thermal pyrolysis and oxidization of electrospun tin(II)2-ethylhexanoate/polyacrylonitrile (PAN) polymer nanofibers in air. The structure and morphology were elaborated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The SnO₂ nanofibers delivered a reversible capacity of 446 mAh g⁻¹ after 50 cycles at the 100 mA g⁻¹ rate and excellent rate capability of 477.7 mAh g⁻¹ at 10.0 C. Owing to the improved electrochemical performance, this electrospun SnO₂ nanofiber could be one of the most promising candidate anode materials for the lithium-ion battery.     

SnO2 nano-spheres/graphene hybrid for high-performance lithium ion battery anodes

SnO₂ nano-spheres/graphene composite was fabricated via a simple one-step hydrothermal method with graphene oxide and SnCl₄·5H₂O as the precursors. The composite was characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and surface area measurement. It is shown that fine SnO₂ nano-spheres with an average size of 50–100 nm could be homogeneously deposited on graphene nano-sheets layer by layer. The structural feature enabled SnO₂ nano-spheres/graphene hybird as an excellent anode material in lithium ion battery. The composite possesses 1306 mA h g^?1 of initial discharge capacity and good capacity retention of 594 mA h g^?1 up to the 50th cycle at a current density of 100 mA g^?1. These results indicate that the composite is a promising anode material in high-performance lithium ion batteries.     

Eggshell-membrane-templated synthesis of hierarchically-ordered NiO–Ce0.8Gd0.2O1.9 composite powders and their electrochemical performances as SOFC anodes

Hierarchically-ordered NiO-Ce_0.8Gd_0.2O_1.9 (GDC) composite anode powders were synthesized using eggshell membranes as biotemplates. The morphology of the as-synthesized powders depended on the kind of Ni precursor and the use of EDTA as a chelating agent. Hierarchically-ordered anode powders were obtained from Ni chloride and Ni acetate precursors with EDTA. The Ni–GDC anode synthesized from Ni chloride precursor with EDTA exhibited the lowest polarization resistance at 800 °C and an activation energy of 0.01 Ω cm² and 0.74 eV, respectively, in humidified H₂. In accordance with the polarization resistance results, the 0.5-mm thick GDC electrolyte-supported single cell with the Ni–GDC anode synthesized from Ni chloride precursor with EDTA showed a maximum power density of 0.34 W cm⁻² at 800 °C with humidified H₂ fuel.     

Electrochemical study of activated carbon-semiconducting oxide composites as electrode materials of double-layer capacitors

The energy storage of activated carbon modified with a semiconducting oxide TiO₂ is studied. The composite was prepared by mixing nanosize TiO₂ and activated carbon through a means of ultrasonic vibration in ethanol solution for 30 min. It was found that with modification of TiO₂, the specific capacitance of activated carbon measured at 0.65 mA/cm² was increased from 47.2 to 63.1 F g⁻¹. This method is unique in comparison the conventional method because it uses semiconducting TiO₂ other than electrochemically active materials such as RuO₂. The later has been adopted to make electrochemical-double-layer hybrid supercapacitors, however, the former is attributed to a pure double-layer supercapacitor.     

Electrochemical behaviour of propane-fed solid oxide fuel cells based on low Ni content anode catalysts

Two different low Ni content (10 wt.%) anode catalysts were investigated for intermediate temperature (800 °C) operation in solid oxide fuel cells fed with dry propane. Both catalysts were prepared by the impregnation of a Ni-precursor on different oxide supports, i.e. gadolinia doped ceria (CGO) and La_0.6Sr_0.4Fe_0.8Co_0.2O₃ perovskite, and thermal treated at 1100 °C for 2 h. The Ni-modified perovskite catalyst was mixed with a CGO powder and deposited on a CGO electrolyte to form a composite catalytic layer with a proper triple-phase boundary. Anode reduction was carried out in-situ in H₂ at 800 °C for 2 h during cell conditioning. Electrochemical performance was recorded at different times during 100 h operation in dry propane. The Ni-modified perovskite showed significantly better performance than the Ni/CGO anode. A power density of about 300 mW cm⁻² was obtained for the electrolyte supported SOFC in dry propane at 800 °C. Structural investigation of the composite anode layer after SOFC operation indicated a modification of the perovskite structure and the occurrence of a La₂NiO₄ phase. The occurrence of metallic Ni in the Ni/CGO system caused catalyst deactivation due to the formation of carbon deposits.     

Electrodeposition of iron oxide nanorods on carbon nanofiber scaffolds as an anode material for lithium-ion batteries

Iron oxide film with spaced radial nanorods is formed on the VGCF (vapor-grown carbon nanofiber) scaffolds by means of anodic electrodeposition. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy show that the iron oxide film deposited on the VGCF surface is α-Fe₂O₃ and consists of spaced radial nanorods having 16-21 nm in diameter after annealing at 400 °C. Galvanostatic charge/discharge results indicate that the α-Fe₂O₃/VGCF anode (970 mAh g⁻¹) has higher capacity than bare α-Fe₂O₃ anode (680 mAh g⁻¹) at 10 C current discharge. VGCF scaffolds fabricated by electrophoretic deposition favor the electron conduction, and the spaced radial nanorods on VGCFs facilitate the migration of lithium ion from the electrolyte. Electrochemical reactions between α-Fe₂O₃ and lithium ion are therefore improved significantly by this tailored architecture.