Ultra-Stable Sodium-Ion Battery Enabled by All-Solid-State Ferroelectric-Engineered Composite Electrolytes

Highlights The capacity fading mechanism of the conventional Na 3 V 2 (PO 4 ) 3 //Na 3 V 2 (PO 4 ) 3 (NVP//NVP) cell has been investigated. All-solid-state ferroelectric-engineered composite electrolyte could improve the electrolyte–electrode interfacial stability as well as the interfacial ion conduction of the Na-ion battery using the NVP anode. Outstanding cyclic stability has been achieved in the all-solid-state Na-ion battery using the NVP anode, with a capacity fading rate as low as 0.005% per cycle. Symmetric Na-ion cells using the NASICON-structured electrodes could simplify the manufacturing process, reduce the cost, facilitate the recycling post-process, and thus attractive in the field of large-scale stationary energy storage. However, the long-term cycling performance of such batteries is usually poor. This investigation reveals the unavoidable side reactions between the NASICON-type Na 3 V 2 (PO 4 ) 3 (NVP) anode and the commercial liquid electrolyte, leading to serious capacity fading in the symmetric NVP//NVP cells. To resolve this issue, an all-solid-state composite electrolyte is used to replace the liquid electrolyte so that to overcome the side reaction and achieve high anode/electrolyte interfacial stability. The ferroelectric engineering could further improve the interfacial ion conduction, effectively reducing the electrode/electrolyte interfacial resistances. The NVP//NVP cell using the ferroelectric-engineered composite electrolyte can achieve a capacity retention of 86.4% after 650 cycles. Furthermore, the electrolyte can also be used to match the Prussian-blue cathode Na x Fe y Fe(CN) 6− z ·nH 2 O (NFFCN). Outstanding long-term cycling stability has been obtained in the all-solid-state NVP//NFFCN cell over 9000 cycles at a current density of 500 mA g −1 , with a fading rate as low as 0.005% per cycle.