Abstract
The electrochemical reaction mechanisms of tridymite FePO 4 with Li ions were studied in the voltage range of 2.4–0 V. The lithiation/delithiation of FePO 4 was found to be similar to that of binary 3d-metal oxides, which involve the formation and decomposition of Li 2O along with the reduction and oxidation of nanoscale 3d-metal nanoparticles. In the first discharge, FePO 4 was reduced to metallic Fe nanoparticles dispersed in a lithium compound matrix consisting of Li 3PO 4 and Li 2O. In the subsequent charge, these metallic Fe nanoparticles were partially oxidized to FeO by the decomposition of Li 2O. The Li 3PO 4 matrix was inactive during the change of potential from 0 to 2.4 V. It is notable that the re-oxidation of metallic Fe occurred only in the case of small nanoparticles, and the large Fe particles remained electrochemically inert during the reversible reaction.
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