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The use of molybdate as a new anionic dopant that replaces phosphate in LiFePO4 was studied. When a small amount of molybdate (0.5 mol%) was used as a dopant, the olivine structure was maintained, while the lattice volume increased by 0.4%. The expanded volume facilitates ionic transfer, because of which the capacity of doped LiFePO4 at high current discharge rates is higher than that of pure LiFePO4. The discharge value increased by 25.2% at a charge rate of 5 C when the material was doped with 0.5 mol% molybdate ions. The slight expansion of the lattice volume in the olivine structure facilitates a fast redox reaction by lowering the charge transfer resistance. The current values from cyclic voltammetry indicate that the oxidation (charge) process of the cathode material is more improved than the corresponding reduction (discharge) process. Increasing the level of doping beyond 0.5 mol% had no effect on the results. At some discharge rates, the discharge capacity became worse. Because molybdate is divalent while phosphate is trivalent, a large number of molybdate ions in the lattice can exert considerable stress on the structure.

Citation

Ketack Kim, Daewoong Kam, Yeonjoo Kim, Sinwoong Kim, Minsoo Kim, Hyun-Soo Kim. Electrochemical studies of molybdate-doped LiFePO4 as a cathode material in Li-ion batteries. Journal of nanoscience and nanotechnology. 2013 May;13(5):3383-6

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PMID: 23858863

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