ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
A continuous flow incubation (perifusion) was used to examine the effect of 5 alpha-androstane-3 beta, 17 beta diol 3 beta diol) on the release of FSH induced by LH-RH. Over a 3 h-period the 3 beta diol exerts inhibitory effects on male and female pituitaries at high dose (1 microgram/ml) and only on male pituitaries at low dose (100 ng/ml).
Subject(s)
Androstane-3,17-diol/pharmacology , Androstanols/pharmacology , Follicle Stimulating Hormone/metabolism , Gonadotropin-Releasing Hormone/pharmacology , Pituitary Gland/metabolism , Animals , Female , Kinetics , Male , Pituitary Gland/drug effects , Rats , Sex FactorsABSTRACT
In vitro (perifusion of rat pituitaries) the 5 alpha-androstane-3 beta, 17 beta diol (3 beta diol) exerts inhibitory effects on Gn-RH stimulated LH secretion. The 3 beta diol is more potent at high dose (1 micrograms/ml) than low dose (100 ng/ml) and in the male rat than in the female rat.
