Percolation behaviors of ionic and electronic transfers in Li3-2xCoxN.

Nitridocobaltates Li3-2xCoxN, with Li3N-type layered structure, are promising compounds as negative electrode materials for Li-ion batteries. In the present paper, we report the first detailed broadband dielectric spectroscopy (BDS) study on lithiated transition metal nitrides. The ionic and electronic conductivities of Li3-2xCox□xN compounds (0 ≤ x ≤ 0.44) are investigated as a function of the concentration x of cobalt ions, cationic vacancies (□) and lithium ions. Dielectric and conductivity spectra were recorded within the frequency range of 60-1010 Hz from 200 to 300 K. Experimental results exhibit two types of electric conduction: the first one is due to lithium ion diffusion (for 0 ≤ x ≤ 0.25) and the second one due to electronic transfers (for x ≥ 0.3). Furthermore, two percolation transitions are evidenced and associated with 3D ionic transfers (threshold at x ≈ 0.11) on the one hand and 2D electronic transfers (threshold at x ≈ 0.30) on the other hand. Upon increasing the frequency, dielectric relaxations appear from larger to smaller sample scales. These successive polarizations appear with increasing frequency in the following order: (a) sample/silver paint interface; (b) particles (aggregates of grains); (c) grains (crystallites); (d) local ionic and electronic motions within the grains. Evolutions of dielectric relaxation parameters (dielectric strength and relaxation frequency) with Co content confirm the two percolation transitions. Surprisingly, the grain conductivity has a large discontinuity immediately below the electronic percolation threshold where any local- and long-range ionic movement disappears without electronic transfer. This discontinuity would be due to a narrow transition from ionic to electronic conduction when x increases.

Redirected charge transport arising from diazonium grafting of carbon coated LiFePO4.

The morphological and the electrical properties of carbon coated LiFePO4 (LFPC) active material functionalized by 4-ethynylbenzene tetrafluoroboratediazonium salt were investigated. For this purpose, FTIR, Raman, XPS, High Resolution Transmission Electron Microscopy (HRTEM) and Broadband Dielectric Spectroscopy (BDS) were considered. Electronic conductivities of LFPC samples at room temperature were found to decrease in a large frequency range upon simple immersion in polar solvents and to decrease further upon functionalization. Due to their high dipole moment, strongly physisorbed molecules detected by XPS likely add barriers to electron hopping. Significant alteration of the carbon coating conductivity was only observed, however, upon functionalization. This effect is most presumably associated with an increase in the sp(3) content determined by Raman spectroscopy, which is a strong indication of the formation of a covalent bond between the organic layer and the carbon coating. In this case, the electron flux appears to be redirected and relayed by short-range (intra chain) and long-range (inter chain) electron transport through molecular oligomers anchored at the LFPC surface. The latter are controlled by tunnelling and slightly activated hopping, which enable higher conductivity at low temperature (T < 250 K). Alteration of the electron transport within the carbon coating also allows detection of a relaxation phenomenon that corresponds to small polaron hopping in bulk LiFePO4. XPS and HRTEM images allow a clear correlation of these findings with the island type oligomeric structure of grafted molecules.

Multiscale electronic transport in Li(1+x)Ni(1/3-u)Co(1/3-v)Mn(1/3-w)O2: a broadband dielectric study from 40 Hz to 10 GHz.

This work is the first detailed study concerning the multiscale electronic transport and its temperature dependence in the LiNi1/3Co1/3Mn1/3O2 (NMC) family, high-capacity electrode materials for lithium ion batteries. Powders with two different mean cluster sizes (3 µm and 10 µm) but the same particle sizes (0.4 to 1.3 µm) were measured. The detailed formula of the studied compound is Li1.04Ni(2+)0.235Ni(3+)0.09Mn(4+)0.315Co(3+)0.32O2. Different electrical relaxations are evidenced, resulting from the polarizations at the different scales of the powder architecture. When the frequency increases, three dielectric relaxations are detected in the following order due to: (a) space-charge polarization (low-frequency range) owing to the interface between the sample and the conductive metallic layer deposited on it; (b) polarization of NMC clusters (micronic scale) induced by the existence of resistive junctions between them; and (c) polarization of NMC particles (at sub-micronic scale) induced by resistive junctions between them. High interatomic level conductivity of about 20 S m(-1) was evidenced and attributed to the contribution of the extended states and to a Brownian motion of the charge carriers with mean free path similar to the lattice constant. The ratio between sample and local conductivity is more than 10(5). The large conductivity drop of 3 to 4 orders of magnitude is observed from the particle to the cluster scale. A very large number of charge carriers are blocked by the interparticle junctions within the clusters. The conductivity drop from the cluster to the sample scale is comparatively very small, owing to the dense architecture of the NMC sample in which the spherical clusters are very piled up on each other.

Influence of adsorbed polar molecules on the electronic transport in a composite material Li(1.1)V3O8-PMMA for lithium batteries.

The broadband dielectric spectroscopy (BDS) technique (40 to 10(10) Hz) is used here to measure the electronic transport across all observed size scales of a Li(1.1)V(3)O(8)-polymer-gel composite material for lithium batteries. Different electrical relaxations are evidenced, resulting from the polarizations at the different scales of the architecture: (i) atomic lattice (small-polaron hopping), (ii) particles, (iii) clusters of particles, and finally (iv) sample-current collector interface. A very good agreement with dc-conductivity measurements on a single macro-crystal [M. Onoda and I. Amemiya, J. Phys.: Condens. Matter, 2003, 15, 3079.] shows that the BDS technique does allow probing the bulk (intrinsic) electrical properties of a material in the form of a network of particles separated by boundaries in a composite. Moreover, this study highlights a lowering of the surface electronic conductivity of Li(1.1)V(3)O(8) particles upon adsorption of polar ethylene carbonate (EC) and propylene carbonate (PC) that trap surface polarons. This result is meaningful as EC and PC are typical constituents of a liquid electrolyte of lithium batteries. It is thus suggested that interactions between active material particles and the liquid electrolyte play a role in the electronic transport within composite electrodes used in a lithium battery.

Broadband dielectric and resistivity spectroscopy of WO(3) x H(2)O in the range of 10(3)-10(10) Hz: particle size effect.

The interest in studying the electrical properties of WO(3) x H(2)O powders is made absolutely necessary because their infrared modulation properties depend on their morphologies and electronic populations. Broadband dielectric and resistivity spectra of WO(3) x H(2)O powders were recorded in a frequency range of 10(3)-10(10) Hz at temperatures varying between 200 and 300 K. Complex resistivity and permittivity diagrams have permitted thermal behavior of both dc-conductivity and permittivity to be obtained. A dielectric relaxation is found, attributed to water molecules motions. The role of the powder morphology has been investigated on two types of compounds: the first one being constituted by nanometric particles and the second by micrometric particles. Strong differences are observed in the thermal behaviors of the dc-conductivities (activation energies). Particle size effect is evidenced, giving rise to stronger electron localization on the nanometric particles. The permittivity values and the dynamical behavior of the structural water are also influenced by the particle size effect. A strong interaction between moving polarons and water molecules has been determined.

An analytical model for probing ion dynamics in clays with broadband dielectric spectroscopy.

A simple two-state model is proposed to explicitly derive the ionic contribution to the frequency-dependent dielectric permittivity of clay. This model is based on a separation of time scales and accounts for two possible solvation modes (inner/outer-sphere complexes) for ions in the interlayer spacing and a possible chemical exchange between both forms. The influence on the permittivity of thermodynamic (distribution constant K(d)) and dynamic (diffusion coefficient, chemical relaxation rate) parameters is discussed. In turn, this model is used to analyze experimental data obtained with Na-montmorillonite for two relative humidities. The values of the parameters extracted from these measurements, and their variation with water content, show that the proposed model is at least reasonable.