The kinetics and mechanism of methanol adsorption and oxidation on real Pt/Ru (1:1) electrodes were investigated. In model electrode systems, the addition of supporting proton‐conducting electrolyte is necessary. Therefore, the influence of sulphuric acid on the kinetics of methanol adsorption and oxidation was also investigated. It turns out that the steady state adsorption is not significantly affected by the addition of sulphuric acid. However, if sulphuric acid is used as an additional electrolyte, the rate of methanol adsorption and steady state oxidation decreases, whereas the active surface of the catalyst increases. The mechanism of methanol oxidation is not affected by the addition of sulphuric acid. At low potentials, the adsorption of methanol is found to be much faster than its oxidation. Hence, the oxidation of the methanol intermediate species is believed to be the rate‐determining step under these conditions. This result is confirmed by apparent orders of reaction of about 0.5. At potentials in the range of 0.3–0.5 V, a mixed activation‐adsorption control is supposed, whereas at potentials more positive than 0.5 V, the adsorption of methanol is probably the rds. This is supported by the apparent reaction orders and apparent activation energies of methanol oxidation.
A new route for the preparation of nickel and cobalt substituted spinel cathode materials (LiMn1.95Co0.025Ni0.025O4 and Li1.1Mn1.95Co0.025Ni0.025O4) by freeze-drying of acetate precursors followed by heat treatment was suggested in the present work. The experimental conditions for the preparation single-phase material with small particle size were optimized. Single-phase spinel was formed by low-temperature annealing at 700 °C. For discharge rate 0.2 C, the reversible capacities 109 and 112 mAh g−1 were obtained for LiMn1.95Co0.025Ni0.025O4 and Li1.1Mn1.95Co0.025Ni0.025O4, respectively. A good cycle performance and capacity retention about 90% after 30 cycles at discharge rate 0.2–4 C were observed for the materials cycled from 3 to 4.6 V vs. Li/Li+. Under the same conditions pure LiMn2O4 cathode materials represent a reversible capacity 94 mAh g−1 and a capacity retention about 80%. Two independent experimental techniques (cyclic voltammetry at different scan rates and electrochemical impedance spectroscopy) were used in order to investigate the diffusion kinetics of lithium. This study shows that the partial substitution of Mn in LiMn2O4 with small amounts of Ni and Co allows the cyclability and the performance of LiMn2O4-based cathode materials to be improved.
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