Recycling of nickel–metal hydride batteries. II: Electrochemical deposition of cobalt and nickel

A combination of hydrometallurgical and electrochemical processes has been developed for the separation and recovery of nickel and cobalt from cylindrical nickel–metal hydride rechargeable batteries. Leaching tests revealed that a 4 mol dm^?3 hydrochloric acid solution at 95 °C was suitable to dissolve all metals from the battery after 3 h dissolution. The rare earths were separated from the leaching solution by solvent extraction with 25% bis(2‐ethylhexyl)phosphoric acid (D2EHPA) in kerosene. The nickel and cobalt present in the aqueous phase were subjected to electrowinning. Galvanostatic tests on simulated aqueous solutions investigated the effect of current density, pH, and temperature with regard to current efficiency and deposit composition and morphology. The results indicated that achieving an Ni? Co composition with desirable properties was possible by varying the applied current density. Preferential cobalt deposition was observed at low current densities. Galvanostatic tests using solutions obtained from treatment of batteries revealed that the aqueous chloride phase, obtained from the extraction, was suitable for recovery of nickel and cobalt through simultaneous electrodeposition. Scanning electron micrography and X‐ray diffraction analysis gave detailed information of the morphology and the crystallographic orientation of the obtained deposits. Copyright © 2004 Society of Chemical Industry     

Recycling of nickel–metal hydride batteries. I: Dissolution and solvent extraction of metals

Nickel–metal hydride batteries contain valuable metallic components and although they are not considered a hazardous waste, recovery of these materials is necessary from an economic point of view. In this work a hydrometallurgical method for the dissolution and separation of the metals from cylindrical nickel–metal hydride rechargeable batteries was investigated. Hydrochloric acid was employed as the leaching agent to dissolve the metals from the batteries. Dissolution of metals was investigated as a function of acid concentration, leaching time and temperature. Suitable conditions for maximum metal dissolution were 3 h leaching with 4.0 mol dm^?3 hydrochloric acid solutions at 95 °C. Extraction of 98% of nickel, 100% of cobalt and 99% of rare earth elements was achieved under these conditions. Separation of the rare earths from nickel and cobalt was preliminarily investigated by single batch solvent extraction with 25% bis(2‐ethylhexyl)phosphoric acid. Efficient separation via complete extraction of the rare earths was obtained at a pH of approximately 2.5 while leaving nickel and cobalt in the raffinate. A shrinking particle model which can enable, under certain conditions, evaluation of the extent of metal dissolution present in nickel–metal hydride batteries was developed. A proposed electrochemical recovery of nickel and cobalt is also briefly discussed. Copyright © 2004 Society of Chemical Industry     

Electrochemical and crystallographic characterization of Co-free hydrogen storage alloys for use in nickel–metal hydride batteries

Electrochemical and crystallographic characterization of Co-free hydrogen storage alloys containing Si and/or Fe was carried out. In the charge–discharge cycle test, the maximum discharge capacity of a Co-free MmNi_4.3Mn_0.4Al_0.3 (Mm=misch metal) alloy electrode was decreased by the partial substitution of Si and/or Fe for Ni, but the cycle performance was improved. The MmNi_3.6Mn_0.4Al_0.3Si_0.1Fe_0.6 electrode showed the most excellent cycle durability in this study. It was found by SEM, EPMA and XRD that Fe and Si contained in these alloys more or less suppressed the dissolution of Al and the lattice expansion with hydrogen absorption, leading to the long cycle life. This effect was strengthened by the simultaneous partial substitution of Si and Fe for Ni in the Co-free alloy.     

High temperature performances of yttrium-doped spherical nickel hydroxide

The regular and yttrium-doped spherical β-phase nickel hydroxides were synthesized by means of chemically co-precipitation. The yttrium-doping with long needle-like nanocrystallites observed by TEM promoted the formation of the spherical nickel hydroxide with the larger diameter of about 5 μm. The discharge capacity of the yttrium-doped spherical nickel hydroxide was measured to be slightly lower than that of the regular spherical nickel hydroxide at room temperature. At temperatures of above 50 °C, however, the discharge capacity of the yttrium-doped nickel hydroxide is much higher than that of the regular spherical nickel hydroxide. The improvement of discharge capacity at elevated temperatures was contributed to the increase of the charge acceptance of yttrium-doped nickel hydroxide. The formation of an yttrium-rich surface layer on nickel hydroxide particles raised the oxygen evolution over-potential, leading to performance improvements of the nickel hydroxide electrode. The improvement of high temperature charge acceptance of yttrium-doped nickel hydroxide remarkably contributed to the high temperature charge-discharge efficiency of the nickel-metal hydride (Ni-MH) batteries with a commercial AAA size.     

酞菁铁对MH/Ni电池浮充性能的影响

研究了酞菁铁(FePc)对金属氢化物-镍电池浮充性能的影响。添加适量FePc的电池具有较好的浮充浮放性能,其中添加1mgFePc的电池显示了最好的充电效率和循环性能;2000次浮充以后其内压升高速度也最低。     

Ca3(PO4)2 coating of spherical Ni(OH)2 cathode materials for Ni-MH batteries at elevated temperature

Calcium phosphate was used for surface modification of spherical nickel hydroxide to improve its high temperature performance at the first time due to its low cost. The Ca₃(PO₄)₂ and Co(OH)₂ coated nickel hydroxides were prepared by precipitation of Ca₃(PO₄)₂ on the surface of spherical nickel hydroxide, followed by precipitation of Co(OH)₂ on its surface. The optimum coating content of calcium was around 2% (atomic concentration) to obtain high discharge capacity both at 25 and 60 °C. It was shown that the discharge capacity of nickel hydroxide at higher temperatures was improved by coating of Ca₃(PO₄)₂ and cobalt hydroxide. The high temperature performances of the sealed AA-sized nickel-metal hydride (Ni-MH) batteries using Ca/Co coated nickel hydroxide as positive electrodes were carried out, showing much better than those using uncoated or only Co(OH)₂ coated nickel hydroxide electrodes. The charge acceptance of the battery using 2% Ca and 2% Co coated nickel hydroxide reached 81% at 60 °C, where the charge acceptances for uncoated and only Co(OH)₂ coated nickel hydroxide were only 42 and 48%, respectively. It has shown that the Ca/Co coating is an effective way to improve the high temperature performance of nickel hydroxide for nickel-metal hydride batteries. It is a promising cathode material of Ni-MH batteries for EV applications due to the cost.     

Electrochemical investigations of bare and Pd-coated LaNi4.25Al0.75 electrodes in alkaline solution

Electrochemical investigations were carried out on electrodes made from both bare and Pd-coated LaNi4.25Al0.75 particles. Experimental results showed that the Pd-coating significantly decreases the electrode resistance and increases the electrode discharge capacity. The electrochemical impedance spectroscopy technique was used to determine various resistive components in the electrodes and electrolyte by fitting an equivalent circuit to the experimental data. The results indicated that an electrode made from the Pd-coated alloy has much less ohmic resistance (particle-to-particle contact resistance and current collector to electrode pellet contact resistance) compared to the electrodes made from bare alloy.     

纳米b-Ni(OH)2的制备及其储锂性能

以Ni(NO₃)₂·6H₂O和NaOH为原料采用化学沉淀法制备了Ni(OH)₂电极材料。采用X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)表征了样品的微观结构,结果表明该样品是具有片状纳米次级结构的β-Ni(OH)₂。采用循环伏安(CV)和电化学充放电测试研究了该β-Ni(OH)₂样品的储锂性能,结果发现该样品作为锂离子电池负极材料具有非常高的储锂活性,在50 mA·g^-1电流密度下其第3次循环放电比容量高于1550 mA·h·g^-1;样品电极中的碳含量对其循环性能和倍率性都有显著影响,通过交流阻抗(EIS)测试分析了样品电极中碳含量的作用机理。     

Development of a novel metal hydride–air secondary battery

A laboratory metal hydride/air cell was evaluated. Charging was via a bifunctional air gas-diffusion electrode. Mixed nickel and cobalt oxides, supported on carbon black and activated carbon, were used as catalysts in this electrode. At 30mAcm–2 in 6m KOH, the air electrode potentials were –0.2V (oxygen reduction) and +0.65V (oxygen evolution) vs Hg/HgO. The laboratory cell was cycled for 50 cycles at the C/2 rate (10mAcm–2). The average discharge/charge voltages of the cell were 0.65 and 1.6V, respectively. The initial capacity of the metal hydride electrode decreased by about 15% after 50 cycles.     

Selective Recovery of Cadmium,Cobalt, and Nickel from Spent Ni–Cd Batteries Using Adogen® 464 and Mesoporous Silica Derivatives

Spent Ni–Cd batteries are now considered an important source for many valuable metals. The recovery of cadmium, cobalt, and nickel from spent Ni–Cd Batteries has been performed in this study. The optimum leaching process was achieved using 20% H₂SO₄, solid/liquid (S/L) 1/5 at 80 °C for 6 h. The leaching efficiency of Fe, Cd, and Co was nearly 100%, whereas the leaching efficiency of Ni was 95%. The recovery of the concerned elements was attained using successive different separation techniques. Cd(II) ions were extracted by a solvent, namely, Adogen^® 464, and precipitated as CdS with 0.5% Na₂S solution at pH of 1.25 and room temperature. The extraction process corresponded to pseudo-2nd-order. The prepared PTU-MS silica was applied for adsorption of Co(II) ions from aqueous solution, while the desorption process was performed using 0.3 M H₂SO₄. Cobalt was precipitated at pH 9.0 as Co(OH)₂ using NH₄OH. The kinetic and thermodynamic parameters were also investigated. Nickel was directly precipitated at pH 8.25 using a 10% NaOH solution at ambient temperature. FTIR, SEM, and EDX confirm the structure of the products.     

Effect of Ethane and Propane in Simulated Natural Gas on the Operation of Ni–YSZ Anode Supported Solid Oxide Fuel Cells

Solid oxide fuel cells with Ni–yittria‐stabilised zirconia (YSZ) anode supports were tested on surrogate natural gas fuels (methane containing 2.5–10% ethane and 1.25–5% propane) and compared with results for pure methane. Inert anode‐side diffusion barriers were found to help suppress coking on the Ni–YSZ anodes. However, carbonaceous deposits were observed on anode compartment surfaces and the barrier layers for all of the natural gas compositions tested. The addition of air to the natural gas was shown to suppress this coking. For natural gas with 5% ethane and 2.5% propane, the addition of 33% air yielded stable, coke‐free operation at 750 °C and 800 mA cm^–2. Cell performance on this fuel was only slightly worse than for the same cell operated with dry hydrogen.     

Performance of sol–gel Titanium Mixed Metal Oxide electrodes for electro-catalytic oxidation of phenol

Mixed metal oxides SnO₂–RuO₂–IrO₂, Ta₂O₅–IrO₂ and RhO₂–IrO₂ were immobilised on a Ti substrate using sol–gel techniques. The Ti mixed metal oxides were characterized in terms of morphology using scanning electron microscopy. Cyclic voltammetric responses of phenol at Ti/SnO₂–RuO₂–IrO₂, Ti/Ta₂O₅–IrO₂ and Ti/RhO₂–IrO₂ electrodes were evaluated and showed significantly low potentials for Ti/Ta₂O₅–IrO₂ (+100 mV), Ti/SnO₂–RuO₂–IrO₂ (+200 mV) and Ti/RhO₂–IrO₂ (−100 mV). The degradation of phenol in aqueous solution and its intermediates were investigated by bulk electrolysis and quantitatively assessed by HPLC analysis to elucidate the decomposition pathways and to develop a kinetic model for the electro-catalytic oxidation of phenol over Ti mixed metal oxides. Ring compounds, benzoquinone/hydroquinone, catechol, and short chain organics, carboxylic acids, have been identified as intermediate products for the electro-catalytic oxidation of phenol. Fundamental kinetic data were obtained for the conversion of phenol at these electrodes and was found to proceed in accordance with the pseudo-first-order kinetics with respect to the phenol concentration.     

Dynamic monitoring of structural changes in nickel hydroxide electrodes during discharge in batteries

The nickel hydroxide electrode is used as the positive plate of many rechargeable battery systems such as the nickel/cadmium, nickel/hydrogen, and nickel/metal hydrides. The electrochemical energy storage in the nickel hydroxide electrodes is related to the reversible characteristics of the redox couple nickel hydroxide/ox hydroxide. In the present work we describe the use of the electrochemical impedance spectroscopy (EIS) technique as a tool to characterize the dynamic behaviour of nickel hydroxide electrodes at different states of discharge (SOD) in KOH 7 M electrolytic solutions. The parameter identification procedure allows the estimation of the active area per unit volume, the solution conductivity as well as diffusion and kinetic constants related to the process, that represent very important parameters to evaluate the electrode performance.     

Electrodeposition of Ni, Fe and Ni–Fe alloys on a 316 stainless steel surface in a fluorborate bath

Electrodeposition processes of Ni, Fe and Ni–Fe alloys on 316 stainless steel surfaces in fluorborate baths were studied using conventional electrochemical techniques and atomic force microscopy. The results showed that these processes occurred under mass transfer control, associated with nucleation and growth process. Cathodic current–time transients indicated that the nucleation and growth of Ni–Fe alloy was different from that of the single metal (Ni or Fe). For one, two nucleation and growth processes occurred during Ni–Fe alloy codeposition. Also, there was a nucleation and growth process of Ni–Fe alloy on Ni–Fe clusters, due to a change of the Ni–Fe alloy composition and phase. Homogeneous Ni–Fe alloy deposits could be obtained by pulse potential plating. AFM images of Ni, Fe and Ni–Fe deposits prepared by pulse potential plating revealed the following results: (1) the growth rate of Ni nuclei was faster in parallel than in perpendicular to the 316 electrode surface; (2) for Fe nuclei, the preferential growth direction was perpendicular to the 316 electrode surface; and (3) for Ni–Fe nuclei, there was no preferential growth direction and uniformly hemispherical Ni–Fe clusters were obtained.     

High temperature water–gas shift reaction over hollow Ni–Fe–Al oxide nano-composite catalysts prepared by the solution-spray plasma technique

The effect of Fe content in Ni–Fe–Al oxide nano-composites prepared by the solution-spray plasma technique on their catalytic activity for the high temperature water–gas shift reaction was investigated. The composites showed a hollow sphere structure, with highly dispersed Fe–Ni particles supported on the outer surface of the spheres. When the water–gas shift reaction was performed over an Ni–Al oxide composite catalyst without Fe, undesired CO methanation took place predominantly compared to the water–gas shift reaction, and significant amounts of hydrogen were consumed. When appropriate amounts of Fe were added to the Ni–Al oxide composite catalyst during the plasma process, methanation was suppressed remarkably, without serious loss of activity for the water–gas shift reaction. The catalyst was characterized by STEM, XRD and H₂ chemisorption measurements.     

Removal of SO2 in Semi‐Dry Flue Gas Desulfurization Process with a Powder‐Particle Spouted Bed

Semi‐dry flue gas desulfurization was investigated with several kinds of SO₂ sorbents, such as slaked lime, limestone, Mg(OH)₂ and concrete pile sludge, in a powder‐particle spouted bed. Slurry droplets including sorbent fine particles were fed to a spouted bed of coarse inert particles spouted with hot gas containing SO₂. SO₂ removal efficiency was strongly affected by the approach to saturation temperature, Ca/S molar ratio and particle size of sorbent. Slaked lime showed the highest desulfurization efficiency. In this process, despite very short gas residence time, more than 90% SO₂ removal was easily achieved by choosing appropriate conditions.     

The morphology of MoS2, WS2, Co–Mo–S, Ni–Mo–S and Ni–W–S nanoclusters in hydrodesulfurization catalysts revealed by HAADF-STEM

HAADF-STEM studies have provided detailed morphological insight regarding MoS₂, WS₂, Co–Mo–S, Ni–Mo–S and Ni–W–S nanostructures in graphite-supported catalysts. It is found that the technique allows the catalytically active edges to be imaged even for single layer metal sulfide structures. Unpromoted MoS₂ and WS₂ are predominantly present as slightly truncated triangular clusters containing only a single S–M–S layer (M = Mo, W). The addition of promoter atoms results in more heavy truncations consistent with the expected tendency for the Co–Mo–S structures to expose promoted S-type edges at the expense of unpromoted Mo-type edges. However, the HAADF-STEM (High-Angle Annular Dark-field Scanning Transmission Electron Microscopy) results show for the first time that Co–Mo–S and Ni–W–S may also expose extended high index truncations.     

The role of in situ generated nano-sized metal particles on the coulombic efficiency of MGeO3 (M = Cu, Fe, and Co) electrodes

To improve the coulombic efficiency of GeO₂ electrode, a Cu-containing ternary metal oxide (CuGeO₃) was prepared and the electrochemical behavior of Cu component was studied. The GeO₂ electrode shows a low coulombic efficiency in the first cycle (43%), which is mainly caused by a poor Ge oxidation kinetics (Ge + 2Li₂O → GeO₂ + 2Li⁺ + 2e⁻). The X-ray absorption spectroscopy (XAS) data illustrate that the Cu component in CuGeO₃ is converted to nano-sized metallic Cu in the earlier stage of lithiation but idles thereafter. In contrast, the Ge component in CuGeO₃ behaves like the GeO₂ electrode. It is converted to nano-sized Ge by a conversion reaction and further lithiated by alloying reaction. The de-lithiation proceeds in the reverse order. The CuGeO₃ electrode shows a much improved coulombic efficiency (74%) in the first cycle, which is indebted to a facilitated Ge oxidation with a much reduced electrode polarization. This feature has been explained by the favorable roles provided by the in situ generated nano-sized metallic Cu particles that make such an intimate contact with the nano-sized Ge and Li₂O that they can catalyze Li₂O decomposition and provide an electronic conductive network for Ge oxidation. A similar favorable effect was observed with the other ternary oxides (FeGeO₃ and CoGeO₃), wherein the formation of nano-sized metallic Fe and Co can be assumed.     

Reaction path of ethanol and acetic acid steam reforming over Ni–Zn–Al catalysts. Flow reactor studies

Ethanol steam reforming (ESR) experiments have been performed in dilute conditions over a NiZnAl catalyst. Experiments have been performed by varying catalyst surface area, reactants flow rate, contact time, reactants feed composition and temperature. Acetic acid steam reforming experiments have also been performed. The data suggest that adsorbed acetaldehyde and acetic acid play an important role as intermediates of ESR, while also acetone may have a role in the ESR reaction. The key step for high hydrogen yield during ESR is represented by the evolution of acetate species, either towards decomposition giving rise to methane + CO_x, or to steam reforming to CO₂ and H₂. At high temperature hydrogen production depends on approaching methane steam reforming and reverse water gas shift equilibria. Ethylene end dimethylether are parallel products found at low conversion. With excess water acetaldehyde is not found among the products, and hydrogen yields as high as 95% have been obtained at 853 K.     

Deactivation patterns of Mo/Al2O3, Ni–Mo/Al2O3 and Ni–MoP/Al2O3 catalysts in atmospheric residue hydrodesulphurization

In the present work, a comparative study on the deactivation behavior of three types of industrial hydrotreating catalysts, namely, Mo/Al₂O₃, Ni–Mo/Al₂O₃ and Ni–MoP/Al₂O₃, that are used to promote primarily hydrodemetallization (HDM), hydrodesulphurization (HDS) and hydrodesulphurization + hydrodenitrogenation (HDS/HDN) reactions, respectively, in the first, second and third reactor of commercial atmospheric residue desulfurization (ARDS) units was carried out. The main objective of the study was to contribute to a better understanding of the relationship between catalyst type and catalyst deactivation patterns. The used catalysts from these experiments were fully characterized to determine the extent and the cause of deactivation. Special emphasis was paid to understanding the nature of the coke and metal deposition on the used catalysts by applying chemical analysis and various advanced analytical techniques, such as solid-state carbon-13 nuclear magnetic resonance spectroscopy (¹³C NMR), temperature-programmed oxidation (TPO), electron probe micro-analysis (EPMA), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The results are discussed scientifically based on the physico–chemical properties of the three catalysts.