All-solid-state sodium-ion batteries operating at room temperature based on NASICON-type NaTi2(PO4)3 cathode and ceramic NASICON solid electrolyte: A complete in situ synchrotron X-ray study

Abstract

All-solid-state sodium-ion batteries that work at ambient temperature are a potential approach for large-scale energy storage systems. Nowadays, ceramic solid electrolytes are gaining attention because of their good ionic conductivity and excellent mechanical and chemical stabilities. Furthermore, a good interface between electrode and solid electrolyte is also required to achieve successful cell performances. In this work, sintered ceramic layer electrolyte Na3.16Zr1.84Y0.16Si2PO12, with high ionic conductivity (0.202 mS/cm at room temperature), are prepared by using uniaxial pressing followed by a sintering process. The conductive carbon coated NASICON material (NaTi2(PO4)3/C) exhibits, as cathode material, enhanced rate capability and stability for sodium ion batteries for high carbon (18.95 %) coated sample. At C/10, the optimized cathode (with higher carbon content) achieves a remarkable initial discharge capacity of 107.3 mAh/g (reversible capacity of 101.4 mAh/g), a sufficient rate capability up to a rate of 10C, and a long cycle life (capacity retention of 58% after 950 cycles). The one-stage reversible biphasic reaction mechanism and potential-dependent structure–property of NaTi2(PO4)3 can be explained by employing in situ X-ray synchrotron method. Sequential Rietveld refinements of the in situ data show the evolution of the Na-poor NaTi2(PO4)3 and Na-rich Na3Ti2(PO4)3 phase fractions (wt%), unit cell characteristics, and unit cell volume. The design of an all-solid-state sodium ion half-cell with a NaTi2(PO4)3/C cathode and a Na3.16Zr1.84Y0.16Si2PO12 solid-state electrolyte interface results in stable capacity of 83.6 mAh/g at C/10 and excellent reversible capacity at high C-rate. The results show that sintered NASICON-based electrolytes can significantly contribute for the fabrication of all-solid-state sodium-ion battery due to the superior conductivity and stability.