Novel Catalyst Composites of Ni- and Co-Based Nanoparticles Supported on Inorganic Oxides for Fatty Acid Hydrogenations.

In the quest to develop nanometrically defined catalytic systems for applications in the catalytic valorization of agri-food wastes, small Ni-based nanoparticles supported on inorganic solid supports have been prepared by decomposition of organometallic precursors in refluxing ethanol under H2 atmosphere, in the presence of supports exhibiting insulating or semi-conductor properties, such as MgAl2O4 and TiO2, respectively. The efficiency of the as-prepared Ni-based nanocomposites has been evaluated towards the hydrogenation of unsaturated fatty acids under solvent-free conditions, with high selectivity regarding the hydrogenation of C=C bonds. The influence of the support on the catalytic performance of the prepared Ni-based nanocomposites is particularly highlighted.

Composite Mn-Co electrode materials for supercapacitors: why the precursor's morphology matters!

In the energy storage field, an electrode material must possess both good ionic and electronic conductivities to perform well, especially when high power is needed. In this context, the development of composite electrode materials combining an electrochemically active and good ionic conductor phase with an electronic conductor appears as a perfectly adapted approach to generate a synergetic effect and optimize the energy storage performance. In this work, three layered MnO2 phases with various morphologies (veils, nanoplatelets and microplatelets) were combined with electronic conductor cobalt oxyhydroxides with different platelet sizes (∼20 nm vs. 70 nm wide), to synthesize 6 different composites by exfoliation and restacking processes. The influence of precursors' morphology on the distribution of the Mn and Co objects within the composites was carefully investigated and correlated with the electrochemical performance of the final restacked material. Overall, the best performing restacked composite was obtained by combining MnO2 possessing a veil morphology with the smallest cobalt oxyhydroxide nanoplatelets, leading to the most homogeneous distribution of the Mn and Co objects at the nanoscale. More generally, the aim of this work is to understand how the size and morphology of the precursor building blocks influence their distribution homogeneity within the final composite and to find the most compatible building blocks to reach a homogeneous distribution at the nanoscale.

Impact of the Salt Anion on K Metal Reactivity in EC/DEC Studied Using GC and XPS Analysis.

To develop K-ion batteries, the potassium metal reactivity in a half-cells must be understood. Here, it is shown first that the K metal leads to the migration of the electrode degradation species to the working electrode surface so that half-cells' solid electrolyte interphase (SEI) studies cannot be trusted. Then, the K metal reactivity was studied by combining gas chromatography (GC)-mass spectrometry, GC/Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis after storage in ethylene carbonate/diethylene carbonate (EC/DEC) wo/w 0.8 M KPF6 or KFSI. A comparison with Li stored in EC/DEC wo/w 0.8 M LiPF6 was also performed. Overall, full electrolyte degradation pathways were obtained. The results showed a similar alkali reactivity when stored in EC/DEC with the formation of a CH3CH2OCO2M-rich SEI. For a MPF6-based electrolyte, the reactivity was driven by the PF6- anion (i) forming mostly LiF (Li metal) or (ii) catalyzing the solvent degradation into (CH2CH2OCOOK)2 and CH3CH2OCOOK as main SEI products with additional C2H6 release (K metal). This highlights the higher reactivity of the K system. With KFSI, the reactivity was driven by the FSI- anion degradation, leading to an inorganic-rich SEI. These results thus explain the better electrochemical performance often reported in half-cells with KFSI compared to that with KPF6. Finally, the understanding of these chemically driven electrolyte degradation mechanisms should help researchers to design robust carbonate-based electrolyte formulations for KIBs.

Paving the Way for K-Ion Batteries: Role of Electrolyte Reactivity through the Example of Sb-Based Electrodes.

Developing potassium-ion batteries remains a challenge so far due to the lack of efficient electrolytes. Moreover, the high reactivity of K metal and the use of half-cells may greatly alter both the electrochemical performance and the solid electrolyte interphase formation. Here, it is shown that in K metal/Sb half-cells, Coulombic efficiency improvement is achieved by the addition of fluoroethylene carbonate + vinylene carbonate to propylene carbonate (PC), the replacement of PC by ethylene carbonate/diethyl carbonate, and the replacement of KPF6 by potassium bis(fluorosulfonyl)imide. Surprisingly, however, storage of cells containing K metal leads to the coloration of K metal, separators, and Sb electrodes, whereas no change occurs for cells prepared without K metal. These results demonstrate that for all electrolytes, the high electrolyte reactivity with K metal also influences the Sb/electrolyte interface via a cross-talk mechanism. This observation is supported by gas chromatography/mass spectrometry analysis of electrolytes and X-ray photoelectron spectroscopy analysis of Sb electrodes. In summary, these results indicate that the search for efficient electrolytes for potassium-ion batteries must be carried out in full cells if one wants to obtain meaningful correlations between electrochemical performance and electrode/electrolyte interfacial properties. Overall, the results presented here are also likely to benefit the development of other emerging Na- and Mg-ion cell chemistries.

Novel nanoporous MnOx (x=∼1.75) sorbent for the removal of SO2 and NH3 made from MnC2O4·2H2O.

In this work, nanoporous manganese oxides (MnOx) were prepared by thermal decomposition of MnC2O4·2H2O at 225°C for 6h in air. The manganese oxalate dihydrate precipitate was made from manganese sulfate and ammonium oxalate during ultrasonication and stirring. The physical properties of the oxalate precursors and the resulting MnOx samples were characterized with SEM, TGA-DSC, FTIR and powder XRD. The specific surface areas and porosity of MnOx were studied by single-point BET and multi-point N2 adsorption-desorption measurements. The amorphous MnOx from oxalate prepared by sonication showed a specific surface area as large as 499.7m(2)/g. Dynamic SO2 and NH3 flow tests indicated that the adsorption capacity of MnOx, especially for SO2, can be increased by increased surface area. Compared to the best Mn3O4-impregnated activated carbon adsorbent, nanoporous MnOx could remove approximately three times as much SO2 and a comparable amount of NH3 per gram of adsorbent. This could lead to respirators of lower weight and smaller size which will be attractive to users.

Synergistic effect in carbon coated LiFePO4 for high yield spontaneous grafting of diazonium salt. Structural examination at the grain agglomerate scale.

Molecular grafting of p-nitrobenzene diazonium salt at the surface of (Li)FePO4-based materials was thoroughly investigated. The grafting yields obtained by FTIR, XPS, and elemental analysis for core shell LiFePO4-C are found to be much higher than the sum of those associated with either the LiFePO4 core or the carbon shell alone, thereby revealing a synergistic effect. Electrochemical, XRD, and EELS experiments demonstrate that this effect stems from the strong participation of the LiFePO4 core that delivers large amounts of electrons to the carbon substrate at a constant energy, above the Fermi level of the diazonium salt. Correspondingly large multilayer anisotropic structures that are associated with outstanding grafting yields could be observed from TEM experiments. Results therefore constitute strong evidence of a grafting mechanism where homolytic cleavage of the N2(+) species occurs together with the formation and grafting of radical nitro-aryl intermediates. Although the oxidation and concomitant Li deintercalation of LiFePO4 grains constitute the main driving force of the functionalization reaction, EFTEM EELS mapping shows a striking lack of spatial correlation between grafted grains and oxidized ones.

Non-aqueous carbon black suspensions for lithium-based redox flow batteries: rheology and simultaneous rheo-electrical behavior.

We report on the rheological and electrical properties of non-aqueous carbon black (CB) suspensions at equilibrium and under steady shear flow. The smaller the primary particle size of carbon black is, the higher the magnitude of rheological parameters and the conductivity are. The electrical percolation threshold ranges seem to coincide with the strong gel rather than the weak gel rheological threshold ones. The simultaneous measurements of electrical properties under shear flow reveal the well-known breaking-and-reforming mechanism that characterises such complex fluids. The small shear rate breaks up the network into smaller agglomerates, which in turn transform into anisometric eroded ones at very high shear rates, recovering the network conductivity. The type of carbon black, its concentration range and the flow rate range are now precisely identified for optimizing the performance of a redox flow battery. A preliminary electrochemical study for a composite anolyte (CB/Li4Ti5O12) at different charge-discharge rates and thicknesses is shown.