Dominique Bonnin

Effect of Particle Size on Lithium Intercalation into α ­ Fe2 O 3

The electrochemical reaction of lithium with crystallized -Fe2O3 (hematite) has been studied by means of in situ X-ray diffraction. When reacting large particles (~0.5 µm), we observed the well-known transformation of the close-packed anionic array from hexagonal (hc) to cubic (ccp) stacking. At the early stage of the reduction, a very small amount of lithium (xc<0.1 Li/Fe2O3) can be inserted before this structural transformation occurs. Nanosize -Fe2O3 made of fine monolithic particles (200 A) behaves very different, since up to one Li per formula unit (-Li1Fe2O3,xc = 1) can be inserted in the corundum structure without phase transformation. To our knowledge, this is the first time this phase is maintained for such large xc values. This cationic insertion was found to come with a small cell volume expansion evaluated to 1%. Unsuccessful attempts to increase the xc values on large particles by decreasing the applied discharge current density suggest that the particle size is the only parameter involved. The better structural reversibility of this monophasic process compared to the biphasic one was confirmed by electrochemical cycling tests conducted with hematite samples of various particle sizes. Therefore, by using nanosize particles, we can drastically increase the critical Li concentration required to observe the hcccp transition. This work demonstrates that a careful control of the texture/particle size of electrochemically active oxide particles is likely an important variable that has been largely disregarded for such properties. ©2002 The Electrochemical Society. All rights reserved.

The effects of moderate thermal treatments under air on LiFePO 4-based nano powders

The thermal behavior under air of LiFePO4-based powders was investigated through the combination of several techniques such as temperature-controlled X-ray diffraction, thermogravimetric analysis and Mossbauer and NMR spectroscopies. The reactivity with air at moderate temperatures depends on the particle size and leads to progressive displacement of Fe from the core structure yielding nano-size Fe2O3 and highly defective, oxidized LixFeyPO4 compositions whose unit-cell volume decreases dramatically when the temperature is raised between 400 and 600 K. The novel LiFePO4-like compositions display new electrochemical reactivity when used as positive electrodes in Li batteries. Several redox phenomena between 3.4 V and 2.7 V vs.Li were discovered and followed by in-situX-ray diffraction, which revealed two distinct solid solution domains associated with highly anisotropic variations of the unit-cell constants.

Iron oxide nanoparticles with sizes, shapes and compositions resulting in different magnetization signatures as potential labels for multiparametric detection.

Magnetic iron oxide nanoparticles differing in their size, shape (spherical, hexagonal, rods, cubes) and composition have been synthesized and modified using caffeic acid for transfer to aqueous media and stabilization of the particle suspensions at physiological pH. A super quantum interference device and the recently patented magnetic sensor MIAplex®, which registered a signal proportional to the second derivative of the magnetization curve, were used to study the magnetization behavior of the nanoparticles. The differences in the magnetic signatures of the nanoparticles (spheres and rods) make them promising candidates for the simultaneous detection of different types of biological molecules.

Size-dependent nonlinear weak-field magnetic behavior of maghemite nanoparticles.

The magnetic behavior at room temperature of maghemite nanoparticles of variable sizes (from 7 to 20 nm) is compared using a conventional super quantum interference device (SQUID) and a recently patented technology, called MIAplex. The SQUID usually measures the magnetic response versus an applied magnetic field in a quasi-static mode until high field values (from -4000 to 4000 kA m(-1)) to determine the field-dependence and saturation magnetization of the sample. The MIAplex is a handheld portable device that measures a signal corresponding to the second derivative of the magnetization around zero field (between -15 and 15 kA m(-1)). In this paper, the magnetic response of the size series is correlated, both in diluted and powder form, between the SQUID and MIAplex. The SQUID curves are measured at room temperature in two magnetic field ranges from -4000 to 4000 kA m(-1) (-5T to 5T) and from -15 to 15 kA m(-1). Nonlinear behavior at weak fields is highlighted and the magnetic curves for diluted solutions evolve from quasi-paramagnetic to superparamagnetic behavior when the size of the nanoparticles increases. For the 7-nm sample, the fit of the magnetization with the Langevin model weighted with log-normal distribution corresponds closely to the magnetic size. This confirms the accuracy of the model of non-interacting superparamagnetic particles with a magnetically frustrated surface layer of about 0.5 nm thickness. For the other samples (10-nm to 21-nm), the experimental weak-field magnetization curves are modeled by more than one population of magnetically responding species. This behavior is consistent with a chemically uniform but magnetically distinct structure composed of a core and a magnetically active nanoparticle canted shell. Accordingly the weak-field signature corresponds to the total assembly of the nanoparticles. The impact of size polydispersity is also discussed.

Non-linear magnetic behavior around zero field of an assembly of superparamagnetic nanoparticles

The MIAplex® device is a miniaturized detector, devoted to the high sensitive detection of superparamagnetic nanoprobes for multiparametric immunoassays. It measures a signal corresponding to the second derivative of the magnetization around zero field. Like any new technology, the real success of the MIAplex® detector can only be exploited through a deep understanding of the magnetic signature. In this letter, we study the magnetic behavior around zero-field of diluted lab-made and commercial ferrofluids by comparing together conventional SQUID magnetization and MIAplex® signature.

SiO2 versus chelating agent@ iron oxide nanoparticles: interactions effect in nanoparticles assemblies at low magnetic field

Hydrophilic magnetic nanoparticles present many interest for various medical applications due to their unique properties: immunoassays, imaging and hyperthermia. With regards to their applicability in the biomedical field, colloidal stability is a key parameter related to nanoparticle surface functionalization. In this paper, we report the water transfer of hydrophobic oleic acid coated iron oxide nanoparticles comparing two methodologies to obtain water dispersible iron oxide nanoparticles: exchange ligands with small strong chelating agent (caffeic acid) and SiO2 shell passivation. Both strategies are leading to stable aqueous ferrofluid but differing by their interactions. The non linear magnetic behavior at high and low magnetic field and second derivative signature of water dispersed superparamagnetic Fe304 nanoparticles samples are studied using conventional SQUID equipment and miniaturized detector MIAplex® device. We demonstrated those samples differing only by their interparticle interactions present different magnetic behavior at very low magnetic field whereas at high magnetic field both samples are very similar.

Electrochemically reduced cobalt-graphite intercalation compound

Abstract The reactions occurring during electrochemical reduction within a lithium battery system have been studied using a cobalt chloride-graphite intercalation compound as positive electrode. The reduction mechanism is a semi-infinite diffusion of lithium between the graphite layers along with an irreversible charge transfer between lithium ions and graphite. A washing process, intended to remove impurities such as lithium chloride, leads to the cobalt-GIC. Its rough formula is Co0.7C11(CoCl2)0.3(LiC1)0.5 determined through elemental analysis. Structural theoretical calculations, X-ray diffraction (XRD),transmission electron microscopy (TEM) observations, extended X-ray absorption fine structure (EXAFS) and magnetic experiments have been carried out on this compound. The results indicate that the reduced compound is, in its major part, a first-stage cobalt-graphite phase CoC2 with an ABC commensurate structure, constituted of two-dimensional islands, randomly distributed in the graphite structure. The crystallographic parameters for this hexagonal structure are a = 0.248nm, and c = 1.68nm equal to three times the identity period. An elastic balls-elastic graphitic networks model can explain this structure.