The composites were synthesized by combustion method. The aqueous solution of stoichiometric values of sodium nitrate (98%), manganese (II) nitrate hexahydrate (97%), and nickel (II) nitrate hexahydrate (98%) were added to aqueous citric acid solution (nitrates : citric acid, 1 : 0.5 in weight). The solution was heated on a hot plate at 100 °C for overnight under constant stirring to evaporate the solvent. Then dried powder was further heated to 200 °C for auto combustion of citric acid. Burnt powder further heated at 500 °C for 3 h to decompose the nitrates and yield a homogeneously mixed amorphous powder containing carbon residues. The obtained decomposition product was pelletized and heated in a tube furnace at 900 °C (heating rate – 5 °C / min) for 10 h in air atmosphere and then slowly cooled to room temperature. The obtained powder was transferred to Ar-filled glove box to avoid the contact with moisture in the air.
X-ray diffraction (XRD, Xpert, PANalitical) using Cu-Kα radiation was employed to characterize the crystal structure of the synthesized powders. XRD measurement was carried out in the 2θ range of 10−80° with a step size of 0.03°. The FULLPROF Rietveld program was used to analyze the observed powder diffraction patterns. Structural studies during cycle were examined by means of in-situ synchrotron X-ray diffraction (XRD) and ex-situ X-ray Absorption Spectroscopy (XAS). In-situ XRD and ex-situ XAS measurement was respectively carried out at 9B beamline and 8C beamline of Pohang Accelerator Laboratory (PAL), Pohang, South Korea.
Electrochemical properties were studied in an half-cell configuration assembling a R2032 coin-type cell using sodium metal as the negative electrode in an Ar-filled glove box. The electrolyte solution comprised 0.5 M NaPF6 in propylene carbonate and fluorinated ethylene carbonate (PC:FEC, 98:2 in volume). The cells were charged and discharged between 2.0 V and 4.3 V at a rate of 0.1C at 25 °C.
Among the successfully synthesized samples Na0.7Mn0.8Ni0.2O2 composite displayed better electrochemical performance. As shown in Figure 1 the composite delivered initial discharge capacity of 160 mAh g-1 at 0.1C between voltage of 2.0 V and 4.3 V and the capacity retention is remarkably improved compared to bare composite. Data on structural change during cycling and other detailed studies will be presented at the meeting.
Figure 1. Initial charge-discharge profiles of P2-Na0.7Mn1-xNixO2 composites at 0.1C.