Regulating Na/NASCION electrolyte interface chemistry for stable solid-state Na metal batteries at room temperature

Abstract

It is critical for solid-state alkaline metal batteries to solve the issues of large interfacial resistance and poor interfacial stability between the alkaline metal anode and the solid electrolyte. We tune the interface chemistry between Na metal and a NASICON-type solid electrolyte by a facile Cu2+-ion doping method. It is demonstrated that the Cu2+-ion incorporation into Na3Zr2Si2PO12 (NZSP) significantly reduces the interfacial resistance (Rinter) and boosts the interfacial stability during charge/discharge cyles at 25 °C. The optimal Na3.4Zr1.8Cu0.2Si2PO12 (NZSP-0.2Cu) realizes an increased critical current density of 0.5 mA cm−2 and an impressively low Rinter value of 19 Ω cm2 at 25 °C, which is only 1/35 of the undoped one (665 Ω cm2). Moreover, the symmetrical Na|NZSP-0.2Cu|Na cell maintains steady Na plating/stripping cycles for as long as 1450 h under 0.2 mA cm−2, clearly indicating the desired chemical compatibility at the Na metal anode interface. A self-formed dynamically stable Cu3PO4-dominant interphase layer at the Na metal/NZSP-0.2Cu interface is verified to explain for the outstanding interfacial performance. Furthermore, a room-temperature solid-state NaCrO2|NZSP-0.2Cu|Na metal battery is assembled, exhibiting excellent cycling performance at 5 C for 660 cycles with a capacity retention of 86.5% and an overall Coulombic efficiency of 99.5%.