ABSTRACT
We present a systematic study of the lithium-ion transport upon the mixed manganese-iron oxide phosphate glasses 3Li2O-xMn2O3-(2-x)Fe2O3-3P2O5(LMxF2−xPO; 0≤ x ≤2.0) proposed for the use in a cathode for lithium secondary batteries. The glasses have been fabricated using a solid reaction process. The electrical characteristics of the glass samples have been characterized by electrical impedance in the frequency range from 100 Hz to 30 MHz and temperature from 30 °C to 240 °C. Differential thermal analysis and X-ray diffraction were used to determine the thermal and structural properties. It has been observed that the dc conductivity decreases, but the activation energies of dc and ac and the glass-forming ability increase with the increasing Mn2O3 content in LMxF2−xPO glasses. The process of the ionic conduction and the relaxation in LMxF2−xPO glasses are determined by using power−law, Cole−Cole, and modulus methods. The Li+ ions migrate via the conduction pathway of the non-bridging oxygen formed by the depolymerization of the mixed iron−manganese−phosphate network structure. The mixed iron−manganese content in the LMxF2−xPO glasses constructs the sites with different depths of the potential well, leading to low ionic conductivity.
ABSTRACT
We investigate the role of tellurite on a lithium-silicate glass 0.1 TeO2 -0.90.1 TeO2 -0.9 (Li2O-2SiO2) (LSTO) system proposed for the use in solid electrolyte for lithium ion batteries. The measurements of electrical impedance are performed in the frequency 100 Hz-30 MHz and temperature from 50 to 150 °C. The electrical conductivity of LSTO glass increases compared with that of Li2O-2SiO2 (LSO) glass due to an increase in the number of Li+ ions. The ionic hopping and relaxation processes in disordered solids are generally explained using Cole-Cole, power law and modulus representations. The power law conductivity analysis, which is driven by the modified Rayleigh equation, presents the estimation of the number of ionic charge carriers explicitly. The estimation counts for direct contribution of about a 14% increase in direct current conductivity in the case of TeO2 doping. The relaxation process by modulus analysis confirms that the cations are trapped strongly in the potential wells. Both the direct current and alternating current activation energies (0.62-0.67 eV) for conduction in the LSO glass are the same as those in the LSTO glass.
ABSTRACT
We have investigated the transition kinetics of Sr0.25Ba0.75Nb2O6 (SBN) and Li2B4O7 (LBO) crystals from 0.25SrO-0.75BaO-Nb2O5-Li2O-2B2O3 (SBNLBO) glass under isothermal and non-isothermal processes. With increasing temperature, there are two consecutive steps of crystallization of SBN and LBO from the glass. The Johnson-Mehl-Avrami function indicates that the crystallization mechanism of SBN belongs to an increasing nucleation rate with diffusion-controlled growth. The crystallite size of SBN ranges from 40 to 140 nm but it is confined to within 30-45 nm for LBO during the whole crystallization process. The relationship between the nano size and strain of SBN based on the Williamson-Hall method, and the change of activation energies of SBN and LBO crystallization analyzed by using the isoconversional model are discussed. A comparison of phonon modes between as-quenched glass and fully transformed crystals clearly shows that the low dimensional vibration modes in the structurally disordered glass change to highly dimensional network units with the formation of crystals.
