Electrochemically Driven Transformation of Olivine LiFePO4 to Olivine NaFePO4 in Cells with Sodium Anode and Carbonate Electrolyte

The direct electrochemical transformation of commercial LiFePO4 to NaxFePO4 olivine in a Na||LiFePO4 electrochemical cell with sodium electrolyte has been studied. Electrolytes containing 1 M of NaClO4 in ethylene carbonate (EC), dimethyl carbonate (DEC) and fluoroethylene carbonate (FEC) have been probed, and in the solvents with the ratio of EC:DMC:FEC = 0.4:0.5:0.1 by volume, maximal values of the specific capacity (113 mAh g‐1) with good cycling stability and maximal discharge currents are achieved upon sodiation. To determine the composition of the cathode material and utilization factor of LiFePO4, the dependence of open circuit voltage on specific capacity has been investigated. The general formula of the sodiation product can be written as Na0.88FePO4. Its theoretic specific capacity may be estimated as 135 mAh g‐1. The composition of the products obtained is supported by XRD analysis, which suggests that in discharged cathodes, Coulombic influence of LiFePO4 crystallites on neighboring NaxFePO4 crystallites may enlarge the unit cell of the former and reduce its size of the latter. Probably, shrinkage in the presence of LiFePO4 stabilizes the olivine structure of NaxFePO4 and prevents its transformation from electrochemically active olivine to inactive maricite.