Ultrastable and High Energy Calcium Rechargeable Batteries Enabled by Calcium Intercalation in a NASICON Cathode

Abstract Ca‐ion batteries (CIBs) have been considered a promising candidate for the next‐generation energy storage technology owing to the abundant calcium element and the low reduction potential of Ca 2+ /Ca. However, the large size and divalent nature of Ca 2+ induce significant volume change and sluggish ion mobility in intercalation cathodes, leading to poor reversibly and low energy/power densities for CIBs. Herein, a polyanionic Na superionic conduction (NASICON)‐typed Na‐vacant Na 1 V 2 (PO 4 ) 2 F 3 (N 1 PVF 3 ) with sufficient interstitial spaces is reported as ultra‐stable and high‐energy Ca ion cathodes. The N 1 PVF 3 delivers exceptionally high Ca storage capacities of 110 and 65 mAh g ‐1 at 10 and 500 mA g –1 , respectively, and a record‐long cyclability of 2000 cycles. More interestingly, by tailoring the fluorine content in N 1 PVF x (1 ≤ x ≤ 3), the high working potential of 3.5 V versus Ca 2+ /Ca is achievable. In conjunction with Ca metal anode and a compatible electrolyte, Ca metal batteries with N 1 VPF 3 cathodes are constructed, which deliver an initial energy density of 342 W h kg ‐1 , representing one of the highest values thus far reported for CIBs. Origins of the uncommonly stable and high‐power capabilities for N 1 PVF 3 are elucidated as the small volume changes and low cation diffusion barriers among the cathodes.