Ionic Liquid Electrolytes with Various Sodium Solutes for Rechargeable Na/NaFePO₄ Batteries Operated at Elevated Temperatures

NaFePO4 with an olivine structure is synthesized via chemical delithiation of LiFePO4 followed by electrochemical sodiation of FePO4. Butylmethylpyrrolidinium-bis(trifluoromethanesulfonyl)imide (BMP-TFSI) ionic liquid (IL) with various sodium solutes, namely NaBF4, NaClO4, NaPF6, and NaN(CN)2, is used as an electrolyte for rechargeable Na/NaFePO4 cells. The IL electrolytes show high thermal stability (>350 °C) and nonflammability, and are thus ideal for high-safety applications. The highest conductivity and the lowest viscosity of the electrolyte are obtained with NaBF4. At an elevated temperature (above 50 °C), the IL electrolyte is more suitable than a conventional organic electrolyte for the sodium cell. At 75 °C, the measured capacity of NaFePO4 in a NaBF4-incorporated IL electrolyte is as high as 152 mAh g(-1) (at 0.05 C), which is near the theoretical value (154 mAh g(-1)). Moreover, 60% of this capacity can be retained when the charge-discharge rate is increased to 1 C.