Continuous Flow Electrochemical Synthesis of Olivine‐Structured NaFePO₄ Cathode Material for Sodium‐Ion Batteries from Recycle LiFePO₄

Abstract

To mitigate the environmental impact of the improper disposal of spent LiFePO4 batteries and reduce resource waste, the development of LiFePO4 recycling technologies is of paramount importance. Meanwhile, olivine‐structured NaFePO4 in sodium‐ion batteries has received great attention, due to its high theoretical specific capacity of 154 mAh g−1 and excellent stability. However, olivine NaFePO4 only can be synthesized from olivine LiFePO4. Accordingly, in this proposal, developing the continuous flow electrochemical solid‐liquid reactor‐based metal ion insertion technology is to utilize the olivine FePO4, recycled from LiFePO4, and to synthesize NaFePO4. Additionally, by employing I− as the reducing agent, NaFePO4 is successfully synthesized with a discharge‐specific capacity of 134 mAh g−1 at 0.1C and a remarkable capacity retention rate of 86.5% after 100 cycles at 0.2C. And the reasons for sodium deficiency in the synthesized NFP are elucidated through first‐principles calculations. Furthermore, the kinetics of the solid‐solution reaction 2 (Na2/3+βPO4→ Na1‐αFePO4) mechanism improve with cycling and are sensitive to temperature. Utilizing a minimal amount of reducing agent in the electrochemical reactor, NaFePO4 synthesis is successfully achieved. This innovative approach offers a new, cost‐effective, and environmentally friendly strategy for preparing NaFePO4 from recycling LiFePO4.