Behaviour of heavy metals in the partial oxidation of heavy fuel oil

The behaviour of heavy metals in the partial oxidation of heavy fuel oils under a pressure of up to 100 bar (10 MPa) has been investigated. The tests were carried out in a 5 MW HP POX (High Pressure Partial Oxidation) test plant, that is operated by the IEC (Department of Energy Process Engineering and Chemical Engineering, TU Bergakademie Freiberg) in cooperation with Lurgi GmbH. In several test campaigns preheated oil with a viscosity of up to 300 cSt (= 300 mm²/s) at the burner inlet has been gasified. The heavy metals nickel Ni, iron Fe and vanadium V occur in heavy residual oils in considerable concentration and may seriously impact the gasification itself and the synthesis gas conditioning and usage. While iron is largely recovered in the gasification residue, the recovery rates of nickel and vanadium depend on the process conditions. Volatile nickel compounds were detected in the raw synthesis gas. It was found that an incomplete carbon conversion enables the capture of nickel Ni and vanadium V in the solid residue phase and can thus mitigate the problem of volatile metal compounds in the raw synthesis gas.     

Microstructure of carbon derived from mangrove charcoal and its application in Li-ion batteries

In this study, the microstructure of mangrove-charcoal-derived carbon (MC) was studied using XRD, STM and TEM. MC was found to consist of aligned quasi-spherical structural units with diameters of around 5-20 nm. It shows typical hard carbon characteristics, including a strongly disoriented single graphene layer and BSU, formed by two or three graphene layers stacked nearly parallel. Some curved and faceted graphene layers, especially closed carbon nanoparticles with fullerene-like, were observed in the as-prepared samples. MC was also evaluated as an anodic material for Li-ion batteries. MC carbonized at 1000 °C possessed the highest available discharge capacity (below 0.5 V) of 335 mAh g⁻¹, the high first-cycle coulombic efficiency of 73.7%, good rate and cyclic capability and PC-based electrolyte compatibility. ⁷Li nuclear magnetic resonance (NMR) spectra of fully lithiated mangrove charcoal-derived carbons indicated the co-existence of three Li species.     

Combination of redox capacity and double layer capacitance in composite electrodes through immobilization of an organic redox couple on carbon black

Carbon electrodes have been modified with 2-nitro-1-naphthol with the aim of producing composite supercapacitor electrodes, which make use of both the electric double layer (EDL) capacitance of high surface area carbon and the redox capacity (pseudocapacitance) of the organic compound. In situ FTIR and cyclic voltammetric data confirm literature reports of the reduction of 2-nitro-1-naphthol to 2-amino-1-naphthol and the subsequent oxidation of the o-aminonaphthol to the corresponding o-naphthaquinoneimine in aqueous acidic media. The measurements also show that the quinoneimine is not stable and hydrolized in sulphuric acid electrolyte to 1,2-naphthaquinone. The chemically highly reversible o-naphthaquinone/o-naphthahydroquinone couple remains immobilized on the carbon electrodes during redox cycling. The organic redox couple contributes a capacity of 35 mA h g⁻¹ of the bare carbon to the overall charge storage capability of the composite electrode. Surprisingly, it does not affect the capacitance of the electric double layer of the carbon. During 1000 charge/discharge cycles, the pseudocapacitance decreases by less than 20% in a normal large-volume electrochemical cell. Electrochemical impedance measurements show that the full capacity of the electrode is accessible at frequencies below 0.1 Hz.     

Rheological phase reaction synthesis and electrochemical performance of Li3V2(PO4)3/carbon cathode for lithium ion batteries

Monoclinic lithium vanadium phosphate/carbon (Li₃V₂(PO₄)₃/C) cathode has been synthesized for applications in lithium ion batteries, via a rheological phase reaction (RPR) method. The sample is characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). This material exhibits high initial discharge capacity of 189 and 177 mAh g⁻¹ at 0.1 and 0.2 C between 3.0 and 4.8 V, respectively. Moreover, it displays good fast rate performance, which discharge capacities of 140, 133, 129 and 124 mAh g⁻¹ can be delivered after 100 cycles between 3.0 and 4.8 V vs. Li at a different rate of 0.5, 1, 2 and 5 C, respectively. The electrochemical impedance spectroscopy (EIS) is also investigated.     

XPS study of Li ion intercalation in V2O5 thin films prepared by thermal oxidation of vanadium metal

The intercalation and deintercalation mechanisms of lithium into V₂O₅ thin films prepared by thermal oxidation of vanadium metal have been studied by X-ray photoelectron spectroscopy (XPS) using a direct anaerobic and anhydrous transfer from the glove box (O₂ and H₂O < 1ppm), where the samples were electrochemically treated, to the XPS analysis chamber. Vanadium in the as-prepared oxide films is mostly (from 93 to 96% depending on samples) in a pentavalent state (V⁵⁺) with a stoichiometric O/V concentration ratio fitting that of V₂O₅. Four to seven percent of VO₂ is also observed. After the 1st and the 2nd intercalation steps at E = 3.3 and 2.8 V versus Li/Li⁺, respectively, the V2p core level spectra evidence a partial reduction to V⁴⁺ states with a remaining concentration of 73 and 56% of V⁵⁺, in agreement with the intercalation of about 1/2 mol of Li per V₂O₅ mol at each intercalation step. Intercalated lithium was observed at a binding energy of 56.1 eV for Li1s. Changes of the electronic structure of the V₂O₅ thin film after intercalation are evidenced by the observation, at a binding energy of 1.3 eV, of occupied V3d states (V⁴⁺) originally empty in the pristine film (V⁵⁺). The V2p and Li1s core level spectra show that the process of Li intercalation is partially irreversible. In the first cycle, 34 and 14% of the vanadium ions remain in the V⁴⁺ state after deintercalation at E = 3.4 and 3.8 V versus Li/Li⁺, respectively, indicating a partially irreversible process already after the 1st deintercalation. The analyses of C1s and O1s XP spectra show the formation of a solid-electrolyte interface (SEI). The analyzed surface layer includes lithium carbonate and Li-alkoxides.     

Synthesis and characterisation of nanoporous carbide-derived carbon by chlorination of vanadium carbide

Nanoporous carbide-derived carbon (CDC) was synthesised from vanadium carbide (VC) powder via gas phase chlorination in the temperature range from 500 to 1100 °C. The XRD analysis of nanoporous carbon powder samples was carried out to investigate the structural changes (graphitisation) of nanoporous carbons synthesised. The first-order Raman spectra showed the absorption peak at ∼1582 cm⁻¹ and the disorder-induced (D) peak at ∼1345 cm⁻¹. The low-temperature N₂ adsorption experiments were performed and a specific surface area up to 1305 m² g⁻¹ and total pore volume up to 0.66 cm³ g⁻¹ were obtained.     

Hydrothermal synthesis of carbon-coated lithium vanadium phosphate

A novel hydrothermal synthesis was developed to prepare carbon-coated lithium vanadium phosphate (Li₃V₂(PO₄)₃) powders to be used as cathode material for Li-ion batteries. The structural, morphological and electrochemical properties were investigated by means of X-ray powder diffraction (XRD), thermogravimetry (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and constant current charge-discharge cycling. This material exhibits high initial discharge capacity of 178, 173 and 172 mAh g⁻¹ at 0.1, 0.2 and 0.5 C between 3.0 and 4.8 V, respectively. Moreover, it displays good fast rate performance, which discharge capacities of 136, 132 and 127 mAh g⁻¹ can be delivered after 100 cycles between 3.0 and 4.8 V versus Li at a different rate of 1, 2 and 5 C, respectively. For comparison, the electrochemical properties of carbon-coated lithium vanadium phosphate prepared by traditional solid-state reaction (SSR) method are also studied.     

Nano-composite of polypyrrole/modified mesoporous carbon for electrochemical capacitor application

Nano-thin polypyrrole (PPy) layers were coated on chemically modified ordered mesoporous carbon (m-CMK-3) by an in situ chemical polymerization. Structural and morphological characterizations of m-CMK-3/PPy composites were carried out using field emission scanning electron microscopy. Pseudo-capacitive behavior of the deposited PPy layers on m-CMK-3 was investigated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. As results of this study, the thin layer of PPy in the composite electrode was effective to obtain fully reversible and very fast Faradaic reaction. A maximum discharge capacity of 427 F g⁻¹ or 487 F g⁻¹ after correcting for weight percent of PPy phase at the current density of 5 mA cm⁻², could be achieved in a half-cell setup configuration for the m-CMK-3/PPy composites electrode, suggesting its potential application in electrode material for electrochemical capacitors.     

Activated carbon produced from Sasol-Lurgi gasifier pitch and its application as electrodes in supercapacitors

A pyrolysis product derived from Sasol-Lurgi gasifier pitch was activated using different proportions of KOH. The increase of the amount of KOH used for activation caused the activation degree of the carbons to increase very significantly. The activated carbons obtained using lower amounts of KOH were mainly microporous, while the amount of mesopores developed in the samples progressively increased for the carbons activated with higher proportions of KOH. The gravimetric specific capacitance of samples obtained with (2:1), (3:1) and (5:1) KOH to carbon ratio were rather similar at low current densities (∼400 F/g at low current densities), despite the significant differences observed in their textural characteristics. Supercapacitors built with the activated carbons obtained with (2:1) and (3:1) KOH to carbon ratio yielded the highest volumetric capacitance (higher than 200 F/cm³ at low current densities), while the most activated sample yielded the lowest values, due to the significant reduction in density caused by activation. The high values of capacitance observed result from the combination of two mechanisms of energy storage: double layer formation and pseudocapacitance.     

Electrochemical studies of LiB compound as anode material for lithium-ion battery

Electrochemical studies of LiB compound were carried out for its application as anode for lithium-ion battery. The compound exhibited a reversible discharge-charge behavior between 0 and 0.75 V versus Li/Li⁺ with a first discharge capacity of 293 mA h g⁻¹. Discharging to 1.0 V, the first discharge capacity of LiB compound was 660 mA h g⁻¹, but a part of this capacity was irreversible. Impedance spectra were measured at several potentials corresponding to different discharge plateaus. The impedance spectra obtained below and above 0.8 V presented significantly different features. The solid electrolyte interphase layer (SEI) was formed below 0.8 V and assumed a good performance of LiB electrode in this potential range. The SEI was found to deteriorate above 0.8 V, which might be associated with the irreversible discharge capacity.     

A dilatometric study of the voltage limitation of carbonaceous electrodes in aprotic EDLC type electrolytes by charge-induced strain

The strain induced by electrochemical charging was studied for a series of carbon materials in two different aprotic electrochemical double layer capacitor electrolytes: 1 M tetraethylammoniumtetrafluoroborate in propylene carbonate and in acetonitrile. Five different carbon samples were investigated: a powder of mesocarbon microbeads (MCMB), a high surface area graphite, an activated carbon (AC)-based proprietary electrode material, an AC black, and an AC fibre cloth. The charge specific expansion was determined by means of electrochemical dilatometry in combination with linear sweep voltammetry. A simple and fast semi-quantitative method is used to estimate the coulombic efficiency and the charge capacity of the different systems. For MCMB distinct intercalation and de-intercalation current peaks and simultaneous height changes are observed for either scan direction with the onset more than 1.5 V remote from zero charge (about 3.0 V vs. Li/Li⁺). The porous carbons show the typical capacitive charging behaviour within a potential window of at least ±1 V around zero charge. In this regime a small but noticeable height change in the order of 1% is seen with the onset close to zero charge. At more remote potentials a steep expansion and decrease of coulombic efficiency is observed. For all systems, the potential stability window appears to be asymmetric with respect to zero charge. The smaller anodic stability range is likely to be governed by the onset of solvent oxidation. The wider cathodic range is apparently limited by the strong expansion caused by cation insertion.     

The mediation reaction between the external couple Ferri/Ferrocyanide and Os(II) bipyridile poly-vinylpyridile films coated onto glassy carbon electrodes

The oxidation-reduction of the Ferri/Ferrocyanide couple in solution onto modified glassy carbon Rotating Disk Electrodes (RDE) covered by Os(II) bipyridile poly-vinylpyridile (OsBPP) polymer was studied at room temperature. Steady state polarization curves were carried out as a function of the rotation speed, the polymer thickness and the concentration of redox centers within the polymer. This system has the characteristic that the formal redox potentials of both the external redox couple (E⁰′(Fe(CN)₆^3−/4−) = + 0.225 V vs. SCE) and the mediator polymer (E⁰′(OsBPP) = 0.260 V vs. SCE) lie very close. It is demonstrated that diffusion of the Ferri/Ferrocyanide inside the polymer can be ruled out. Since the processes of charge transfer at the metal/polymer and the mediating reaction are fast, the experimental results can be interpreted in terms of a kinetics in which the charge transport in the polymer or the diffusion in the solution may be the rate determining step, according to the experimental conditions. A simple model is considered that allows interpreting the experimental results quantitatively. Application of this model allows the determination of the diffusion coefficient of the electrons within the film, D_e ≈ 10⁻¹⁰ cm² s⁻¹.     

Cyclic voltammetry study of arsenic in acidic solutions

An electrochemical investigation of arsenic species in acidic solutions, using cyclic voltammetry at a platinum rotating disk electrode, has been carried out. A well defined peak at about 1 V_SCE, with a large overpotential (>0.5 V) is attributed to the oxidation of As(III) to As(V). The reaction is under the mixed control of ionic transport and charge transfer. The corresponding reduction of As(V) is not observed in the potential range of the study (−0.6 to +1.2 V_SCE). As(V) is not electrochemically active in this range and it has no effect on hydrogen evolution. With As(III) in solution, hydrogen evolution on Pt is shifted towards more negative potentials and it takes place simultaneously with arsine production. A small cathodic peak at −0.2 V_SCE and a corresponding anodic peak at +0.3 V_SCE are attributed to the deposition of a thin layer of As by reduction of As(III) and its dissolution.     

Synthesis, electron mobility, and electroluminescence of a polynorbornene-supported silole

A solution-processable polynorbornene with pendant fluorescent and electron-transport silole groups was synthesized using ruthenium-complex-initiated ring-opening metathesis polymerization. A weight-average molecular weight around 59,300 and a low polydispersity index of 1.4 were estimated for the polymer using gel permeation chromatography. The thermal, electronic, photo- and electroluminescence properties of the polymer were investigated and compared with those of a small-molecule reference compound. The polymer exhibits better thermal stability than the small molecule and exhibits a glass transition temperature of 91 °C, while retaining the optical and electronic properties of the corresponding small-molecule silole. The room temperature electron mobility was measured using the time-of-flight technique to be 3.5 × 10⁻⁵ cm²/V/s at an applied electric field of 7.5 × 10⁵ V/cm. Organic light-emitting diodes fabricated using the polymer as the electron transport and emissive layer have low efficiencies; introduction of an additional tris(8-hydroxyquinolinato)aluminum (Alq₃) electron-transport layer leads not only to increased efficiency, but also to increased contributions to the electroluminescence from the Alq₃.     

The formation of two Ag UPD layers on stepped Pt single crystal electrodes and their restructuring by co-adsorption of CO

We have investigated the underpotential deposition (UPD) of silver on high-index platinum single crystals vicinal to the (1 1 1) plane. Carbon monoxide displacement experiments were carried out on Ag-modified Pt(6 6 5) and Pt(3 3 2) stepped single crystal electrodes and examined by means of electrochemical scanning tunneling microscopy (EC-STM) and cyclic voltammetry (CV) in 0.05 M sulfuric acid. Analogous to studies of Pt(1 1 1) by Klein [L.H. Klein, Etude des etats d’adsorption electrochimique sur les electrodes de platine et de rhodium monocristallins modifiees ou non par les adatomes, Ecole Nationale de Chimie de Paris, Universite Paris 6, Paris, 1997] and Domke et al. [K.F. Domke, X.-Y. Xiao, H. Baltruschat, PCCP 10 (2008) 1555], carbon monoxide displaces Ag from stepped Pt electrodes. The present STM studies reveal the formation of small, biatomic thick or thicker Ag clusters on Pt(6 6 5) and Pt(3 3 2) after co-adsorption of CO, extending across step edges, They have a narrow size distribution centred around 10 nm diameter independent of the substrate step density. The desorption of the second Ag adlayer and of CO are monitored electrochemically in two well-separated oxidation peaks at around 0.68 and 0.9 V vs RHE, respectively, whereas the desorption peak of Ag of the first adlayer cannot be completely separated from the early onset of Pt oxidation at approximately 1.13 V vs RHE.     

Improved capacitance characteristics during electrochemical charging of carbon nanotubes modified with polyoxometallate monolayers

By modification of surfaces of multi-walled carbon nanotubes with ultra-thin monolayer-type films of phosphododecamolybdic acid, H₃PMo₁₂O₄₀, an electrode material with improved capacitance properties is produced. It is apparent from three distinct test experiments (based on cyclic voltammetry, galavanostatic charging-discharging and AC impedance) that capacitors utilizing H₃PMo₁₂O₄₀-modified carbon nanotubes are characterized by specific capacitances and energy densities on the levels of 40 F g⁻¹ and 1.3 Wh kg⁻¹, whereas the respective values for the systems built from bare carbon nanotubes are lower, 22 F g⁻¹ and 0.7 Wh kg⁻¹. It is reasonable to expect that fast and reversible multi-electron transfers of the Keggin-type H₃PMo₁₂O₄₀ account for the pseudocapacitance effect and significantly contribute to the observed overall capacitance.     

Measuring cycle efficiency and capacitance of chemically activated carbons in propylene carbonate

The cycle efficiency and capacitance of two KOH-activated carbons have been tested in 0.5 M tetraethylammonium tetrafluoroborate in propylene carbonate (TEABF₄/PC) under different conditions of temperature (room temperature and 70 °C) and voltage (0-3 V). The materials tested include a KOH-activated carbon before and after treatment with different acids and hydrogen at high temperature to remove most of the oxygen groups and inorganic impurities. Porous texture and surface chemistry characterization have been carried out before and after cycling to understand the changes in the properties of activated carbons during the cycles. It has been observed that the treatment with different acids and hydrogen at high temperature produces materials with higher cycling stability. The results point out that the observed electrode degradation is mainly due to some pore blockage caused by reaction of the solvent with the functional groups on the carbon. The blockage of porosity is higher for the sample with higher oxygen content, indicating that the treatment carried out to remove the oxygen groups has an important positive effect, giving electrodes with a much lower degradation under very aggressive conditions in a TEABF₄/PC medium.     

1-Methyl-3-butylimidazolium tetraflouroborate with activated carbon for electrochemical double layer supercapacitors

This article presents the main features of electrochemical double layer supercapacitors, made of nanostructured carbon materials with specially selected and optimized porosity structure and electrolyte based on solvent-free ionic liquid as follows 1-methyl-3-butylimidazolium tetrafluoroborate (1Me3BuImBF₄). The performance of supercapacitor was carried out by cyclic voltammetry and galvanostatic charge/discharge measurements. The main characteristics of stacked supercapacitors exhibit a nominal voltage 3.0 V and a maximum cell voltage 3.5 V as well as a specific capacitance (individual electrode of supercapacitor) of 111 F/g. The specific energy of 4.1 Wh/kg and specific power of 1.7 W/kg for industrial stacked supercapacitor has been achieved.     

The effect of Mo2C derived carbon pore size on the electrical double-layer characteristics in propylene carbonate-based electrolyte

Carbide-derived carbon (CDC) was synthesised from molybdenum carbide by extracting Mo atoms in a high-temperature chlorine atmosphere. A systematic study of the influence of pore size on the electrical double layer (EDL) performance was carried out with carbons synthesised in the temperature interval of 500-900 °C. Strong effect of chlorination conditions on the pore-size distribution was noticed that gives wide possibilities to vary the pore structure of Mo₂C derived carbons. An average pore size of carbons varied between 1 nm and 2 nm depending on chlorination temperature. The relationships were established between the pore-size distribution and the electrochemical performance of micro/mesoporous carbons. The EDL characteristics of carbon materials in a propylene carbonate solution of triethylmethylammonium tetrafluoroborate were obtained using the cyclic voltammetry at ΔE of 3.8 V and the constant current methods in a 3-electrode test cell. A novel test method was developed to demonstrate the power characteristics of the electrode materials. The results of this study affirmed the great potential of Mo₂C derived carbons, whose EDL capacitance reaches ∼65 F cm⁻³ and 132 F g⁻¹ and the 20-s discharge power density is 2.1 W cm⁻³.     

Highly hydroxylated carbon fibres as electrode materials of all-vanadium redox flow battery

A highly effective hydroxylated-functionalization of carbon fibres for use as electrodes of all-vanadium redox flow battery (VRFB) was developed. Carbon paper made of carbon fibres was hydroxylated ultrasonically with mixed acids (H₂SO₄/HNO₃, V_H2SO4/V_HNO3 = 3/1) in a Teflon-lined stainless steel autoclave for different time at 80 °C. The structure, composition, and electrochemical properties of the treated samples for positive and negative electrodes of VRFB were characterized with Fourier transformation infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectrometry, scanning electron microscopy, X-ray diffraction, cyclic voltammetry, electrochemical impedance spectroscopy, and cell charge and discharge tests. The content of hydroxyl group changes from 3.8% for the untreated sample to 14.3% for the carbon paper treated in mixed acids for 10 h. The highly hydroxylated sample shows its high activity toward the redox reactions of V(II)/V(III) and V(IV)/V(V). The VRFB using the carbon paper treated for 8 h as the electrodes exhibits excellent performance under a current density of 10 mA cm⁻². The average voltage efficiency reaches 91.3%, and the average energy efficiency reaches 75.1%. The mechanisms for the high hydroxylation of the carbon fibres with the mixed acids and the high activity of the treated sample toward the vanadium redoxs are discussed.