Characterization of Ionic Transport in LiO-(Mn:Fe)O-PO Glasses for Li Batteries.

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.