It is desirable to develop electrode materials for advanced rechargeable batteries with low cost, long life, and high-rate capability. Pyrite FeS2, as an easily obtained natural mineral, has been already commercialized in primary lithium batteries, but encountered problems in rechargeable batteries with carbonate-based electrolytes due to the limited cycle life caused by the conversion-type reaction (FeS2 + 4M → Fe + 2M2S (M = Li or Na)). Herein, we demonstrate that FeS2 microspheres can be applied in room-temperature rechargeable sodium batteries with only the intercalation reaction by simultaneously selecting a compatible NaSO3CF3/diglyme electrolyte and tuning the cut-off voltage to 0.8 V. A surprisingly high-rate capability (170 mA h g−1 at 20 A g−1) and unprecedented long-term cyclability (∼90% capacity retention for 20000 cycles) has been obtained. We suggest that a stable electrically conductive layer-structured NaxFeS2 was formed during cycling, which enables the highly reversible sodium intercalation and deintercalation. Moreover, 18650-type sodium batteries were constructed exhibiting a high capacity of ∼4200 mA h (corresponding to 126 W h kg−1 and 382 W h L−1) and a capacity retention of 97% after an initial 200 cycles at 4 A during charge–discharge. This shows that the production of rechargeable sodium batteries with FeS2 microspheres is viable for commercial utilization.
