Sodium-metal batteries (SMBs) are considered a potential alternative to high-energy lithium-metal batteries (LMBs). However, the high reactivity of metallic sodium towards common liquid organic electrolytes renders such battery technology particularly challenging. Herein, we propose a multi-block single-ion conducting polymer electrolyte (SIPE) doped with ethylene carbonate as suitable electrolyte system for SMBs. This novel SIPE provides a very high ionic conductivity (2.6 mS cm$^{−1}$) and an electrochemical stability window of about 4.1 V at 40 °C, enabling stable sodium stripping and plating and excellent rate capability of Na | | Na$_3$V$_2$(PO$_4$)$_3$ cells up to 2 C. Remarkably, such cells provide a capacity retention of about 85 % after 1,000 cycles at 0.2 C thanks to the very high Coulombic efficiency (99.9 %), resulting from an excellent interfacial stability towards sodium metal and the Na$_3$V$_2$(PO$_4$)$_3$ cathode.
