Phosphate-based composite electrodes for Li/Na-ion batteries: upscalable solution syntheses with in-situ solid carbon addition

Since the success story of lithium iron phosphate, other phosphate-based compounds have attracted a lot of interest as promising candidates for positive electrodes in lithium-ion or sodium-ion batteries. Their electronic conductivity usually has to be improved through the preparation of composite powders ensuring intimate contact between the active material and conductive carbon. We report on the one-step synthesis of composite precursors using spray-drying or hydrothermal synthesis routes, two techniques which offer easy scaling-up of production. We show that addition of a solid carbon source (carbon black or carbon nanotubes) into the solution has a strong influence on the powder microstructure and is very effective in improving the battery cycling performance, taking our recent results on phosphates [Fex(PO4)(OH)y.zH2O)] and fluorophosphates [Na2FePO4F, Na3V2(PO4)2F3] as examples. We also compare this approach with the addition of the carbon source as a soluble precursor (such as ascorbic acid or citric acid) where the in situ formation of carbon is achieved by a heat treatment in inert atmosphere (typically argon)

Hybrid lamellar silica: Combined template extraction and hydrophilic silanation

peer reviewedThe surface modification of lamellar silica prepared by liquid crystal templating has been investigated. Two hydrophilic surface modifier agents, 2-glycidoxypropyltrimethoxysilane and 2-[methoxy(polyethyleneoxy)propyl)] trimethoxysilane, have been tested. Characterizations of the modified silica include thermal analysis, C-13 and Si-29 solid state NMR, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The different characterizations confirmed the preservation of the lamellar morphology and the Successful surface modification with both silanes along with the template elimination. The results also indicate that the structure and length of the silanes influence the final lamellar organization as well as the grafting yields and mechanisms. (C) 2008 Elsevier Inc. All rights reserved

Spray Drying-­Assisted Synthesis of Na2FePO4F/CB and Na2FePO4F/CNT Composite Cathodes for Lithium Ion Battery

Fluorophosphates are considered among the most interesting series of cathode materials for Li/Na-ion batteries. Na2FePO4F, with layered structure and two-dimensional pathways for facile Na+/Li+ transport [1], exhibits minimal structural changes (3.7%) upon reduction/oxidation. The average working voltage is 3.3 V versus Li+/Li. However, one of the key drawbacks of Na2FePO4F electrodes is their low intrinsic electronic conductivity. In this work, we report on the synthesis of Na2FePO4F by spray-drying, a technique which is easily scaled-up from the lab- to the industrial-scale and ensures a good homogeneity of all precursors. We are investigating the replacement of the grinding step by the addition of conductive carbon (carbon black and carbon nanotubes) to the solution containing the inorganic precursors of the Na2FePO4F phase in order to prepare Na2FePO4F/CB and Na2FePO4F/CNT with different ratios of CB and CNT (10 and 20%) and enhanced conductivity. The electrochemical performance shows that the addition of CNT improves remarkably the capacity of the NFPF electrode material thanks to better CNT dispersion inside and at the surface of the NFPF particles which enhances the electronic conductivity. Acknowledgements: The authors thank the Walloon Region for support under the “PE Plan Marshall 2.vert” program (BATWAL -1318146). A. Mahmoud is grateful to the Walloon region for a Beware Fellowship Academia 2015-1, RESIBAT n° 1510399. References [1] M. Brisbois, S. Caes, M-T. Sougrati, B. Vertruyen, A. Schrijnemakers, R. Cloots, N. Eshraghi, R-P. Hermann, A. Mahmoud, F. Boschini, Solar Energy Materials & Solar Cells 148 (2015) 11-19.RESIBAT n° 151039

Nuclear probes for battery materials investigations: Mössbauer spectroscopy, nuclear scattering, and neutron scattering

peer reviewedSelected examples of application of Mössbauer spectroscopy, nuclear resonance scattering of synchrotron radiation, and neutron scattering to battery and related materials research are presented. The charms of Mössbauer spectroscopy as a technique for screening materials, for detailed structure investigations, and for in situ measurements are illustrated. New developments of nuclear resonance scattering for isotopes with 30-90 keV resonant energy are presented. Structural, diffusive and dynamic studies utilizing neutron scattering are exemplified. © 2014 IEEE