摘要
The structure evolution and electrochemical performance of Na SICON-type Ca_(0.5)Ti_(2)(PO_(4))_(3) for sodium batteries are presented.This phosphate was synthesized by a solid-state method,and the obtained particles were coated with carbon using sucrose.This compound crystallizes in the rhombohedral system with space group R-3.The presence of carbon in the Ca_(0.5)Ti_(2)(PO_(4))_(3)/C composite was confirmed by Raman and Thermogravimetric analysis.The electrochemical performance of Ca_(0.5)Ti_(2)(PO_(4))_(3)/C was investigated in the potential window 1.5–3.0 V vs.sodium metal at different scan rates.The compound is able to initially intercalate/deintercalate 1.6/1.15 Na per formula unit,respectively.In operando synchrotron diffraction was done in the potential window 0.02–3.0 V vs.Na|Na+and revealed the occurrence of several reaction regions upon first discharge.Up to 4 Na+ion per formula unit can be inserted during the first discharge.An intensive refinement of the synchrotron X-ray diffraction(SXRD)patterns of discharged Ca_(0.5)Ti_(2)(PO_(4))_(3) evidenced the existence of five regions depending on the sodium content while the crystal structures of new phases were elucidated for the first time where sodium insertion occurs in the unusual M3 and M’3 sites of the Na SICON structure.
基金
the project e-STORE(APRD Program)funded by OCP Foundation
was partially funded by the German Research Foundation(DFG)under Project ID 390874152(POLi S Cluster of Excellence)。