Effects of structural changes of new organophosphorus cationic exchangers on a solvent extraction of cobalt, nickel and manganese from acidic chloride media

The effects of structural changes of organophosphorus cationic exchangers on metal-distribution curves (extraction efficiency vs. pH) have been investigated for the recovery of cobalt(II), nickel(II) and manganese(II) from acidic chloride solutions. By using alkyl groups with different branching and hydrophobicity and by including oxygen atoms in the hydrophobic chains of the cationic exchangers, it has been shown that the change of the chemical structure in the hydrophobic chains plays an important role in the extraction behaviours and causes more specifically a shift of the extraction curves to higher or lower pH depending on pKa values of extracting agents (evaluated by using QSPR calculations), distribution constants of metal–ligand complexes between organic and aqueous phases and the formation constant of the metal–ligand complexes. Based on the present results, interest in the new cationic exchangers synthesized in the present work for cobalt(II), nickel(II) and manganese(II) separation is also discussed

Interphase chemistry of Si electrodes used as anodes in Li-ion batteries

International audienceThe effect of the Si electrode morphology (amorphous hydrogenated silicon thin films - a-Si:H as a model electrode and Si nanowires - SiNWs electrode) on the interphase chemistry was thoroughly investigated by the surface science techniques: X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS analysis shows a strong attenuation and positive shift of the Si 2p peaks after a complete charge/discharge performed in PC- and EC:DMC-based electrolytes for both electrodes (a-Si:H and SiNW), confirming a formation of a passive film (called solid electrolyte interphase - SEI layer). As evidenced from the XPS analysis performed on the model electrode, the thicker SEI layer was formed after cycling in PC-based electrolyte as compared to EC:DMC electrolyte. XPS and ToF-SIMS investigations reveal the presence of organic carbonate species on the outer surface and inorganic salt decomposition species in the inner part of the SEI layer. Significant modification of the surface morphol- ogy for the both electrodes and a full surface coverage by the SEI layer was confirmed by the scanning electron microscopy (SEM) analysis

Multinuclear solid-state NMR investigation of Hexaniobate and Hexatantalate compounds

This work determines the potential of solid-state NMR techniques to probe proton, alkali, and niobium environments in Lindqvist salts. Na7HNb6O19·15H2O (1), K8Nb6O19·16H2O (2), and Na8Ta6O19·24.5H2O (3) have been studied by solid-state static and magic angle spinning (MAS) NMR at high and ultrahigh magnetic field (16.4 and 19.9 T). 1H MAS NMR was found to be a convenient and straightforward tool to discriminate between protonated and nonprotonated clusters AxH8–xM6O19·nH2O (A = alkali ion; M = Nb, Ta). 93Nb MAS NMR studies at different fields and MAS rotation frequencies have been performed on 1. For the first time, the contributions of NbO5Oμ2H sites were clearly distinguished from those assigned to NbO6 sites in the hexaniobate cluster. The strong broadening of the resonances obtained under MAS was interpreted by combining chemical shift anisotropy (CSA) with quadrupolar effects and by using extensive fitting of the line shapes. In order to obtain the highest accuracy for all NMR parameters (CSA and quadrupolar), 93Nb WURST QCPMG spectra in the static mode were recorded at 16.4 T for sample 1. The 93Nb NMR spectra were interpreted in connection with the XRD data available in the literature (i.e., fractional occupancies of the NbO5Oμ2H sites). 1D 23Na MAS and 2D 23Na 3QMAS NMR studies of 1 revealed several distinct sodium sites. The multiplicity of the sites was again compared to structural details previously obtained by single-crystal X-ray diffraction (XRD) studies. The 23Na MAS NMR study of 3 confirmed the presence of a much larger distribution of sodium sites in accordance with the 10 sodium sites predicted by XRD. Finally, the effect of Nb/Ta substitutions in 1 was also probed by multinuclear MAS NMR (1H, 23Na, and 93Nb)

Recycling supercapacitors based on shredding and mild thermal treatment

Supercapacitors are widely used in electric and hybrid vehicles, wind farm and low-power equipment due to their high specific power density and huge number of charge–discharge cycles. Waste supercapacitors should be recycled according to EU directive 2002/96/EC on waste electric and electronic equipment. This paper describes a recycling approach for end-of-life supercapacitors based on shredding and mild thermal treatment. At first, supercapacitors are shredded using a Retsch cutting mill. The shredded mixture is then undergone thermal treatment at 200 °C to recycle the organic solvent contained in the activated carbon electrodes. After the thermal treatment, the mixture is roughly separated using a fluidized bed method to remove the aluminium foil particles and paper particles from the activated carbon particles, which is subsequently put into water for a wet shredding into fine particles that can be re-used. The recycled activated carbon has a BET surface area of up to 1200 m2/g and the recycled acetonitrile has a high purity

Soft X ray spectroscopy of light elements in energy storage materials

The increasing demand for electrochemical energy storage devices continuously promotes the development of new electrode materials and electrolytes. As a result, understanding their structural and electronic properties affecting electrochemical performance becomes crucial. The role of light elements, which are found in anode and cathode materials, in electrolytes and hence in the solid-electrolyte interphases, requires a special attention. Soft X-ray spectroscopies are particularly relevant to probe selectively light elements in complex environment. Here, the recent advances in the characterization of light elements in energy storage materials by soft X-ray spectroscopy and microscopy techniques are reviewed. After introducing the main X-ray spectroscopic methods and their application to ex situ/in situ/operando characterization of electrochemical processes, the role of light elements in the electrode for supercapacitors and Li/Na-ion storage applications is described. The characterization of electrolytes and related ion solvation is then briefly reviewed before describing how the formation and evolution of solid-electrolyte interphases can be monitored with these methods. Finally, major challenges and future opportunities for soft X-rays spectroscopy in the context of electrochemical energy storage are highlighted

Simulation of Solvent Extraction Flowsheets by a Global Model Combining Physicochemical and Engineering Approaches-Application to Cobalt(II) Extraction by D2EHPA

International audienceThe liquid-liquid extraction of cobalt(II) from an acidic chloride solution by using bis-(2ethylhexyl) phosphoric acid (D2EHPA) diluted in kerosene has been modelled by means of a combination of physicochemical and engineering approaches. This model is able to calculate the performance of solvent extraction flowsheets (residual fraction at the outlet of the flowsheet and concentration factor between the feed solution and eluate) as a function of pH, leach solution flowrate, solvent flowrate and stripping solution flowrate. The influence of these parameters and mixer-settlers arrangements on the performance of eleven flowsheets is discussed

Les sels de lithium, à la base du stockage d'électricité

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