Optimizing the surfactant for the aqueous processing of LiFePO4 composite electrodes

Aqueous processing would reduce the costs associated with the making of the composite electrode. To achieve the incorporation and the dispersion of the carbon black (CB) conductive agent in aqueous slurries, a surfactant is needed. In this paper, three surfactants are compared, an anionic one, the sodium dodecyle sulphate (SDS), a non-ionic one, the isooctylphenylether of polyoxyethylene called commercially Triton X-100 and a cationic one, the hexadecyltrimethylammonium bromide (CTAB), by using rheology and laser granulometry measurements on electrode slurries on one hand, and SEM observations, porosity and adhesion measurements and electrochemical testing on composite electrodes on the other hand. Ionic surfactants were found to be not suitable because a corrosion of the aluminium current collector occurred. The utilization of Triton X-100 favoured a more homogeneous CB distribution, resulted in a better electronic wiring of the active material particles and higher rate behavior of the electrode. Optimal electrochemical performances are obtained for an optimal surfactant concentration which depends on the BET surface area of the CB powder.     

Improvement of the identification of four heavy metals in environmental samples by using predictive decision tree models coupled with a set of five bioluminescent bacteria

A primary statistical model based on the crossings between the different detection ranges of a set of five bioluminescent bacterial strains was developed to identify and quantify four metals which were at several concentrations in different mixtures: cadmium, arsenic III, mercury, and copper. Four specific decision trees based on the CHAID algorithm (CHi-squared Automatic Interaction Detector type) which compose this model were designed from a database of 576 experiments (192 different mixture conditions). A specific software, 'Metalsoft', helped us choose the best decision tree and a user-friendly way to identify the metal. To validate this innovative approach, 18 environmental samples containing a mixture of these metals were submitted to a bioassay and to standardized chemical methods. The results show on average a high correlation of 98.6% for the qualitative metal identification and 94.2% for the quantification. The results are particularly encouraging, and our model is able to provide semiquantitative information after only 60 min without pretreatments of samples.     

Alternative splicing in fibroblast growth factor receptor 2 is associated with induced epithelial-mesenchymal transition in rat bladder carcinoma cells

We described previously that acidic fibroblast growth factor (aFGF), but not basic fibroblast growth factor (bFGF), can induce the rat carcinoma cell line NBT-II to undergo a rapid and reversible transition from epithelial to mesenchymal phenotype (EMT). We now find that NBT-II EMT is stimulated by keratinocyte growth factor (KGF) in cells grown at low density. Accordingly, a high-affinity receptor showing 98% homology to mouse FGF receptor 2b/KGF receptor was cloned and sequenced from NBT-II cells. Northern analysis indicated that mRNA for FGF receptor 2b/KGF receptor was drastically down-regulated within 1 wk in aFGF-induced mesenchymal NBT-II cells. This decrease coincided with an up-regulation of FGF receptor 2c/Bek, a KGF-insensitive, alternatively spliced form of FGF receptor 2b/KGF receptor. Functional studies confirmed that KGF could not maintain EMT induction on mesenchymal NBT-II cells. FGF receptor 1 and FGF receptor 2c/Bek could also support EMT induction when transfected into NBT-II cells in response to aFGF or bFGF. Such transfected cells could bind bFGF as well as aFGF. Therefore, EMT can be induced through different FGF receptors, but EMT may also regulate FGF receptor expression itself.     

Carbon nanofibers improve both the electronic and ionic contributions of the electrochemical performance of composite electrodes

The impact of carbon nanofibers as conductive additive on the electrochemical performance of a LiFePO₄-based composite electrode for lithium battery is investigated here. We use a new method that allows discriminating between the electronic and the ionic wirings contributions to the polarization and the specific capacity at different discharge rates [C. Fongy, et al., J. Electrochem. Soc., 157 (2010) A885; C. Fongy, et al., J. Electrochem. Soc., 157 (2010) A1347]. Results show this conductive additive is not only beneficial in terms of electronic wiring but it also enables to reach better high rate performance by improving the ionic wiring as it decreases the tortuosity of the porosity within the composite electrode architecture.     

Characterization of a 2[4Fe-4S] ferredoxin obtained by chemical insertion of the Fe-S clusters into the apoferredoxin II from Rhodobacter capsulatus

The Rhodobacter capsulatus ferredoxin II (FdII) belongs to a family of 7Fe ferredoxins containing one [3Fe-4S] cluster and one [4Fe-4S] cluster. This protein, encoded by the fdxA gene, has been overproduced in Escherichia coli as a soluble apoferredoxin. The purified recombinant protein was subjected to reconstitution experiments by chemical incorporation of the Fe-S clusters under anaerobic conditions. A brown protein was obtained, the formation of which was dependent upon the complete unfolding of the polypeptide prior to incorporation of iron and sulfur atoms. The yield of the reconstituted product was higher when the reaction was carried out at slightly basic pH. The reconstituted ferredoxin was purified and shown to be distinct from the native [7Fe-8S] ferredoxin, based on several biochemical and spectroscopic criteria. In the oxidized state, EPR revealed the quasi-absence of [3Fe-4S] cluster. 1H-NMR spectroscopic analyses provided evidence that the protein was reconstituted as a 2[4Fe-4S] ferredoxin. This conclusion was further supported by the determination by electrospray mass spectrometry of the molecular mass of the reconstituted protein, which matched within 2 Da to the mass of the FdII polypeptide incremented of eight atoms each of iron and sulfur. Exposure of the reconstituted protein to air resulted in a fast and irreversible oxidative denaturation of the Fe-S clusters, without formation of [7Fe-8S] form. Unlike the natural 7Fe ferredoxin, the reconstituted ferredoxin appeared incompetent in an electron-transfer assay coupled to nitrogenase activity. The fact that the apoFdII was reconstituted as a highly unstable 8Fe ferredoxin instead of the 7Fe naturally occurring FdII is discussed in relation to the results obtained with other types of ferredoxins.     

High voltage spinel oxides for Li-ion batteries: From the material research to the application

Li-ion batteries are already used in many nomad applications, but improvement of this technology is still necessary to be durably introduced on new markets such as electric vehicles (EVs), hybrid electric vehicles (HEVs) or eventually photovoltaic solar cells. Modification of the nature of the active materials of electrodes is the most challenging and innovative aspect. High voltage spinel oxides for Li-ion batteries, with general composition LiMn_2−xM_xO₄ (M a transition metal element), may be used to face increasing power source demand. It should be possible to obtain up to 240 Wh kg⁻¹ at cell level when combining a nickel manganese spinel oxide with graphite (even more with silicon/carbon nanocomposites at the anode). Specific composition and material processing have to be selected with care, as discussed in this paper. It is demonstrated that ‘LiNi_0.5Mn_1.5O₄’ and LiNi_0.4Mn_1.6O₄ have remarkable properties such as high potential, high energy density, good cycle life and high rate capability. Choice of the electrolyte is also of primary importance in order to prevent its degradation at high voltage in contact with active surfaces. We showed that a few percents of additive in the electrolyte were suitable for protecting the positive electrode/electrolyte interface, and reducing the self-discharge. High voltage materials are also possibly interesting to be used in safe and high power Li-ion cells. In this case, the negative electrode may be made of Li₄Ti₅O₁₂ or TiO₂ to give a ‘3 V’ system.     

Dissolution du nickel en transpassivité—I. Méthode de calcul

The behaviour of nickel has been studied in 0,5 M H₂SO₄, 25°C, in the transpassive region. The experimental polarisation curves were determined by a potentiostatic technique over the potential range 1000–1800 mV/sce; the dissolution curves were determined directly by the nickel weight loss per unit time at each potential; the oxygen discharge curves were determined by the volume of gas evolved per unit time. In the transpassive region several reactions occur simultaneously. In order to explain the nickel dissolution, and the depassivation of the metal, in this potential range, a model of the mechanism is proposed, and the method of calculation described. The experimental current voltage curves are compared and are in good accord with the calculated curves.     

New insights into the structure of hybrid κ-/μ-carrageenan and its alkaline conversion

Hybrid κ-/μ-carrageenan, water-extracted from Kappaphycus alvarezzi, was incubated with Pseudoalteromonas carrageenovora κ-carrageenase. The five most abundant hybrid κ-/μ-carrageenan oligosaccharides were purified and their structure was determined by NMR and mass spectrometry. Since the enzyme-resistant fraction was small, these five oligosaccharides were representative of the distribution of the μ-carrabiose moieties along the carrageenan chain. Three main distributions of μ-carrabiose were found: -μ-, -μ-μ- and -μ-μ-μ-. Interestingly, the chemical shifts of the anomeric proton and carbon were strongly influenced by the identity of the adjacent carrabiose, which explains the asymmetrical D6S-H1 NMR signal that we observed. Although μ-carrabiose chemical shifts are usually attributed to blocks of μ-carrabiose as expected in ideal μ-carrageenan, we demonstrate that they are in fact due to μ-carrabiose units positioned between κ-carrabiose units. Using NMR and chromatography to monitor the alkaline conversion of μ- to κ-carrabiose, we found that the μ-carrabiose distribution (-μ-, -μ-μ-, -μ-μ-μ-) did not influence the conversion rate.     

Dissolution du nickel en transpassivite 2eme partie: etude du degagement d'oxygene simultane et influence du pH

The oxygen discharge was studied in the transpassive range of nickel on 0·5M H₂SO₄. The potential range is separated into two parts, the experimental data indicating that, above 1650 mV/sce the oxygen discharge occurs alone and between 1360 and 1650 mV/sce two reactions namely nickel dissolution and oxygen discharge occur simultaneously. A model is proposed where two OH^? ions are simultaneous adsorbed on the first formed layer of Ni(OH), a fraction of the surface is covered by Ni(OH)₃. The oxygen discharge is also a multistep reaction. Between 1360 and 1650 mV/sce, the dissolution of metal and the oxygen discharge are in competition at all times, the surface is covered simultaneously by Ni(OH)₂ and Ni(OH)₃.The calculated curves are in good accord with the potentiostatic curves, the influence of pH is correlated with the experimental data.     

Comparison between the dissolution and passivity of nickel in sulphuric and hydrofluoric acids

The purpose of this paper is to study the anodic passivity of the nickel in sulphuric and hydrofluoric acids. Theoretical expressions for the current and the impedance are established and compared with experimental data. We conclude, that, in anodic range, the electrode surface is always covered by an intermediate of reaction where the nickel cation is partial or full oxided.