The effect of the magnitude of cathodic polarization and the temperature of a solution of lanthanum salicylate on the kinetics of the formation of elecrode LаyMn1-yO2 has been described. It has been established that two phases are formed on the electrode: the phase of the solid solution of the introduced lanthanum in MnO2 at potentials negative -2.5V turns into a new phase LаyMn1-yO2; last on the curve Eб/т-Ек the potential delay characteristic of the process of forming a new phase with an independent crystal lattice corresponds. Thus, to obtain a time-stable phase of the introduction of lanthanum into the structure of the electrode LаyMn1-yO2 the potential range from –2.9 V to –2.5 V can be recommended. The influence of the solution temperature on the kinetic characteristics of the process is ambiguous and is associated with a change in the degree of disorder in the structure of the forming phase at the boundary MnO2 electrode/solution (La3+), which hampers diffusion of ions La3+ into the electrode and leads to a decrease in ion concentration La3+, involved in the act of electrochemical introduction and, accordingly, to a decrease in the value of i (0). At temperatures above 10 °С the structure is stabilized and the characteristics (k, i (0)) increase. The composition of the formed phases is determined LixMnO2, LayMn1-yO2, LixLayMn1-yO2, current-free chronopotentiometry method calculated on the basis of equilibrium potentials Ep of these phases with pulsed galvanostatic polarization mode. Stability formed in the structure of MnO2 electrode chemical compounds of lanthanum was established. The activating effect of fullerene additives С60 composed of modified lanthanum LаyMn1-yO2 electrodes due to the high redox activity and the unusual structure of the molecules С60. Data on the effect of modified MnO2 electrodes on their potentials in an open circuit and during polarization in the working solution are in good agreement in terms of increasing the capacity of lithium with the results of cycling LiхMnO2, LiхLayMn1-yO2, LiхLayMn1-yO2-σ(C60)n in galvanostatic mode. The results of galvanostatic cycling showed that the discharge capacity of the electrodes increases in the series: LixMnO2 > LixLayMn1-yO2 > LiхLayMn1-yO2-σ(C60)n. With the help of cyclic chronovamperometry a good reversibility for LiхLayMn1-yO2-σ(C60)n electrode was established.
Irreversible Capacity and Lithium-ion Insertion/Extraction Kinetics of a High Potential Negative Electrode TiO2(B)
