Pressureless all‐solid‐state sodium‐ion battery consisting of sodium iron pyrophosphate glass‐ceramic cathode and β″‐alumina solid electrolyte composite

Abstract In recent years, the expansion of demand for lithium ion batteries has resulted in soaring prices of the constituent resources. From the viewpoint of safety, studies on all‐solid‐state batteries are actively being carried out. In this study, we succeeded in driving all‐solid‐state batteries derived from nontoxic oxide glasses at room temperature without requiring scarce resources such as lithium and cobalt. The main structure of the ceramic batteries with a simple structure in which Na 2 FeP 2 O 7 crystallized glass and β″‐alumina solid solution are joined by pressureless cofiring at 550°C. During the crystallization of Na 2 O‐Fe 2 O 3 ‐P 2 O 5 glass, fusion with the β″‐alumina solid solution is achieved. Reversible charge and discharge of 80 mAh/g were achieved at room temperature. It is not necessary to apply pressure during cell preparation or the use of the batteries. Furthermore, the strong junction at the cathode and electrolyte interface does not peel off during charge and discharge over a long period of 623 cycles. Ex situ X‐ray photoelectron spectroscopy revealed partial Fe 4+ induction and a reversible charge and discharge reaction even after overcharging to 9 V. It was demonstrated that Na 2 FeP 2 O 7 is very stable against overcharging to 9 V.