Search Results (13)

The pseudocapacitive effect can improve the electrochemical lithium storage capacity at high-rate current density. However, the cycle stability is still unsatisfactory. To overcome this issue, a multivalent oxide with a carbon coating represents a plausible technique. In this work, a CuO–Cu₂O@C composite has been constructed by a one-step bilayer salt-baking process and utilized as anode material for lithium-ion batteries. At a current density of 2.0 A g⁻¹, the as-prepared composite delivered a stable discharge capacity of 431.8 mA h g⁻¹ even after 600 cycles. The synergistic effects of the multivalence, the pseudocapacitive contribution from copper, and the carbon coating contribute to the enhanced electrochemical lithium storage performance. Specifically, the existence of cuprous suboxide improves the electrochemical conductivity, the pseudocapacitive effect enhances the lithium storage capacity, and the presence of carbon ensures cycle stability. The testing results show that CuO–Cu₂O@C composite has broad application prospects in portable energy storage devices. The present work provides an instructive precedent for the preparation of transition metal oxides with controllable electronic states and excellent electrochemical performance. Full article

Electrochemical (EC) detection is a powerful tool supporting simple, low-cost, and rapid analysis. Although screen printing is commonly used to mass fabricate disposable EC chips, its mask is relatively expensive. In this research, we demonstrated a method for fabricating three-electrode EC chips using 3D printing of relatively high-viscosity paste. The electrodes consisted of two layers, with carbon paste printed over silver/silver chloride paste, and the printed EC chips were baked at 70 °C for 1 h. Engineering challenges such as bulging of the tubing, clogging of the nozzle, dripping, and local accumulation of paste were solved by material selection for the tube and nozzle, and process optimization in 3D printing. The EC chips demonstrated good reversibility in redox reactions through cyclic voltammetry tests, and reliably detected heavy metal ions Pb(II) and Cd(II) in solutions using differential pulse anodic stripping voltammetry measurements. The results indicate that by optimizing the 3D printing of paste, EC chips can be obtained by maskless and flexible 3D printing techniques in lieu of screen printing. Full article

Producing consistent quality pre-baked carbon anodes for the Hall–Héroult aluminum reduction process is challenging due to the decreasing quality and increasing variability of anode raw materials. Non-destructive testing techniques (NDT) have been developed and recently implemented in manufacturing plants to establish better suited and more efficient quality control schemes than core sampling and characterization. These technologies collect measurements representing effective properties of the materials located along a pathway between two transducers (emitter and receiver), and not spatially-resolved distribution of properties within the anode volume. A method to interpolate pathway-based measurements and provide spatially-resolved distribution of properties is proposed in this work to help NDT technologies achieve their full potential. The interpolation method is tested by simulating acousto-ultrasonic data collected from a large number of 2D and 3D toy examples representing simplified anode internal structures involving randomly generated defects. Experimental validation was performed by characterizing core samples extracted from a set of industrial anodes and correlating their properties with interpolated speed of sound by the algorithm. The method is shown to be successful in determining the defect positions, and the interpolated results are shown to correlate significantly with mechanical properties. Full article

In the Hall–Héroult process, prebaked carbon anodes are utilized to produce primary aluminium. The quality of the anode plays a crucial role in the efficiency of electrowinning primary aluminium. In the production of anodes, the anode baking is considered as the stage most frequently causing anode problems. During the baking process, the anode undergoes complex physicochemical transformations. Moreover, the anode at a lower position, imposed by loading pressures from upper anodes, will creep during this process. Thus, the production of high-quality anodes demands efficient control of their baking process. This paper aims to investigate the thermo-chemo-mechanical properties of the anode paste mixture at high temperatures. These properties include kinetic parameters of pitch pyrolysis such as the activation energy and the pre-exponential factor, the thermal expansion coefficient (TEC) and relevant mechanical parameters related to the elastic, the viscoelastic and the viscoplastic behaviours of the anode. For this purpose, experiments consisting of the thermogravimetric analysis, the dilatometry and the creep test were carried out. Based on the obtained results, the forementioned parameters were identified. Relevant mechanical parameters were expressed as a function of a new variable, called the shrinking index, which is related to the volatile released in open and closed pores of the anode. This variable would be used to highlight the chemo-mechanical coupling effect of the anode mixture. New insights into the phenomena such as the expansion due to the increase of the pore pressure and the chemical shrinkage of the anode during the baking process were also gained in this work. These investigations pave the way for modeling the thermo-chemo-poromechanical behaviour of the anode during the baking process. Full article

Anode baking is critical in carbon anode production for aluminium extraction. Operational and geometrical parameters have a direct impact on the performance of anode baking furnaces (ABF), and hence on the resulting anode quality. Gas flow patterns, velocity field, pressure drop, shear stress and turbulent dissipation rate are the main operational parameters to be optimised, considering a specific geometry that is discretised as a mesh. Therefore, this paper aims to establish the need to generate an appropriate mesh to perform accurate numerical simulations of three-dimensional turbulent flow in a single section of an ABF. Two geometries are considered for generating three meshes, using COMSOL and cfMesh, with different refinement zones. The three meshes are used for creating nine incompressible isothermal turbulent flow models, with varying operational parameters. Velocity field, convergence and turbulent viscosity ratio in the outlet of fuel inlet pipes are the quantification criteria. Quantification criteria have shown that a better physical representation is obtained by refining in the whole combustion zone. COMSOL Multiphysics’ built-in mesh generator allows quadrilateral, tetrahedron and hexahedron shapes. Adaptive cell sizes and shapes have a place within modelling, since refining a mesh in appropriate zones brings the Peclet number down when the incompressible isothermal turbulent flow is simulated. Full article

The Hall-Héroult process uses prebaked carbon anodes as electrodes. The anode’s quality plays a crucial role in the efficiency of the aluminium production process. During the baking process, the anode undergoes complex physicochemical transformations. Thus, the production of high-quality anodes depends, among others, on the efficient control of their baking process. This paper aims to investigate the evolution of some physical properties of the anode paste mixture during the baking process. These properties include the mass loss fraction, real and apparent densities, the ratio of apparent volume, the permeability, and porosities. For this purpose, experiments consisting of thermogravimetric analysis, dilatometry, air permeability, and helium-pycnometric measurements were carried out. The anode permeability at high temperatures was linked to the air permeability through a permeability correlator due to experimental limitations. Moreover, the real density at high temperatures was estimated by combining real densities of the coal tar pitch and coke aggregates. Different porosities, such as the open porosity and the closed porosity related to the pitch binder, were estimated by taking the permeability at high temperatures into account. In this context, the effect of the permeability correlator, which was introduced to link the permeability at high temperatures to the air permeability, was investigated through a sensitivity analysis. These results allow an estimation of the shrinking index, a new variable introduced to reflect the baking level of the anode mixture, which is linked to the volatile that is released in both open and closed pores. Afterwards, the pore pressure inside closed pores in the coal tar pitch was estimated. The obtained results highlight some new insights related to the baking process of the anode mixture. Moreover, they pave the way for better modeling of the thermo-chemo-mechanical behavior of anodes at high temperatures. Full article

Reduction cell operation in primary aluminum production is strongly influenced by the properties of baked anodes. Producing consistent anode quality is more challenging nowadays due to the increasing variability of raw materials. Taking timely corrective actions to attenuate the impact of raw material fluctuations on anode quality is also difficult based on the core sampling and characterization scheme currently used by most anode manufacturers, because it is applied on a very small proportion of the anode production (about 1%), and long-time delays are required for lab characterization. The objective of this work is to develop rapid and non-destructive methods for the inspection of baked anodes. Previous work has established that sequential excitation of smaller parts collected from an industrial sized anode using acousto-ultrasonic signals at different frequencies allowed detecting and discriminating anode defects (pores and cracks). This was validated qualitatively using X-ray computed tomography. This work improves the method by using frequency-modulated excitation and building quantitative relationships between the acousto-ultrasonic signals and defects extracted from tomography images using Wavelet Transforms and Partial Least Squares (PLS) regression. The new excitation approach was found to provide similar or better inspection performance compared with sequential excitation, while requiring a shorter cycle time. Full article

Carbon anodes play an important role in the electrolytic production of aluminum. They have a significant economic and environmental impact. Carbon anodes are made of dry aggregates, composed of petroleum coke, recycled rejects, and butts, bound by coal tar pitch. Due to several factors, defects (cracks/pores) appear in anodes during the fabrication process, affecting their quality. It is thus essential to control the quality of anodes before their use in the electrolysis cell. Current practice for the quality evaluation (visual inspection, core analysis) gives limited information. As an alternative to this practice, electrical resistivity measurements can be used. Electrical resistivity is one of the key indicators for anode quality and its homogeneity. A simple and non-destructive method has been developed for the specific electrical resistivity measurement of anodes (SERMA) for on-line control of anode quality. Various tests have been carried out at both lab scale and industrial scale. In this study, the electrical resistivity distributions in the lab-scale anodes were measured and compared with those of the tomography analysis. The method is able to detect defective anodes even before the baking process. Full article

The carbon anode, used in aluminum electrolysis (Hall–Héroult process), is over-consumed by air oxidation and carboxy-reaction (with CO₂). Several anode features may affect this over-consumption, such as impurity content, graphitization level and anode porosity features (e.g., porosity volume fraction or pore size distribution). The two first parameters are basically related to the quality of raw materials and coke calcination conditions. Anode porosity is, however, greatly affected by anode manufacturing conditions, and is possible to be modified, to some extent, by adjusting the anode recipe and the processing parameters. This work aims to investigate the effect of anode porosity on its air reactivity. Baked anode samples were prepared in laboratory scale and then crushed into powder form (−4760 + 4000 µm). The recipe for anode preparation was similar to a typical industrial recipe, except that in the lab scale no butt particles were used in the recipe. Anode particles were then gasified at six different conversion levels (0, 5, 15, 25, 35 and 50 wt %) under air at 525 °C. The porosity was characterized in several pore size ranges, measured by nitrogen adsorption and mercury intrusion (0.0014–0.020, 0.002–0.025, 0.025–0.100, 0.1–40.0 and superior at 40 µm). The volume variation of each pore range, as a function of carbon conversion, was assessed and used to determine the size of the most active pores for air oxidation. The most active pore size was found to be the pores inferior at 40 µm before 15 wt % of gasification and pores superior at 40 µm between 15 and 50 wt % of carbon conversion. Limitation of pore size range could be used as an additional guideline, along with other targets such as high homogeneity and density, to set the optimum anode manufacturing parameters. Full article

Identifying optimum anode baking level and mixing temperature are important when producing high quality anodes. The effect of varying mixing temperature and baking level were investigated in terms of the resulting apparent anode density, specific electrical resistivity (SER), air permeability, coefficient of thermal expansion (CTE), air reactivity, and CO₂ reactivity. Six pilot-scale anodes were prepared at Hydro Aluminium using a single source petroleum coke and <2 mm coke fractions. A coal tar pitch was used with Mettler softening point of 119.1 °C. The aggregate was mixed at 150 °C or 210 °C and baked to a low, medium, or high baking level. A 2² full-factorial design analysis was performed to determine the response of the analyzed properties to the applied mixing and baking temperature. Apparent density, SER, and air permeability were found to be highly dependent on mixing temperature. Apparent density and SER were also slightly affected by baking level. CTE was found to be independent of both baking level and mixing temperature. Air reactivity was found to be mainly dependent on baking level, while CO₂ reactivity was dependent on both mixing temperature and baking level. Full article

Carbon anodes used in the aluminium industry were imaged through destructive and non-destructive testing (NDT) methods. For the latter case, computed tomography (CT), which has previously been used to map the 3D apparent density distribution, was extended to crack detection. Previous work has shown how to overcome technical hurdles related to crack detection by using percolation-based algorithms operating on low-resolution images of full-scale baked carbon anodes. The previous application to 2D images was extended here to the 3D case. The crack detection algorithm has been performed on anode slices containing several independent macro cracks with different morphologies. Full article

High quality baked carbon anodes contribute to the optimal performance of aluminum reduction cells. However, the currently decreasing quality and increasing variability of anode raw materials (coke and pitch) make it challenging to manufacture the anodes with consistent overall quality. Intercepting faulty anodes (e.g., presence of cracks and pores) before they are set in reduction cells and deteriorate their performance is therefore important. This is a difficult task, even in modern and well-instrumented anode plants, because lab testing using core samples can only characterize a small proportion of the anode production due to the costly, time-consuming, and destructive nature of the analytical methods. In addition, these results are not necessarily representative of the whole anode block. The objective of this work is to develop a rapid and non-destructive method for quality control of baked anodes using acousto-ultrasonic (AU) techniques. The acoustic responses of anode samples (sliced sections) were analyzed using a combination of temporal features computed from AU signals and principal component analysis (PCA). The AU signals were found sensitive to pores and cracks and were able to discriminate the two types of defects. The results were validated qualitatively by submitting the samples to X-ray Computed Tomography (CT scan). Full article

Carbon anodes are consumed in electrolysis cells during aluminum production. Carbon consumption in pre-bake anode cells is 400–450 kg C/t Al, considerably higher than the theoretical consumption of 334 kg C/t Al. This excess carbon consumption is partly due to the anode manufacturing processes. Net carbon consumption over the last three years at Emirates Aluminium (EMAL, also known as Emirates Global Aluminium (EGA) Al Taweelah) was analyzed with respect to anode manufacturing processes/parameters. The analysis indicates a relationship between net carbon consumption and many manufacturing processes, including anode desulfurization during anode baking. Anode desulfurization appears to increase the reaction surface area, thereby helping the Boudouard reaction between carbon and carbon dioxide in the electrolysis zone, as well as reducing the presence of sulfur which could inhibit this reaction. This paper presents correlations noted between anode manufacturing parameters and baked anode properties, and their impact on the net carbon consumption in electrolytic pots. Anode reactivities affect the carbon consumption in the pots during the electrolysis of alumina. Pitch content in anodes, impurities in anodes, and anode desulfurization during baking were studied to find their influence on anode reactivities. The understanding gained through this analysis helped reduce net carbon consumption by adjusting manufacturing processes. For an aluminum smelter producing one million tonnes of aluminum per year, the annual savings could be as much as US $0.45 million for every kg reduction in net carbon consumption. Full article