Study of intercalation and deintercalation of Na_xCoO_2 yH_2O single crystals

Abstract

Single crystals of NaxCoO2 with beta-phase (x=0.55, 0.60 and 0.65), alpha'-phase (x=0.75) and alpha-phase (x=0.9, 1.0) have been grown by the floating zone technique. The Na-extraction and hydration were carried out for the alpha'-sample to get superconducting phase of NaxCoO2.yH2O (x~0.3, y~1.3). Hydrated single crystals exhibit cracked layers perpendicular to the c-axis due to a large expansion when the water is inserted into the structure. A study of intercalation/deintercalation was performed to determine the stability of the hydrated phase and effects of hydration on the structure of the compound. X-ray diffraction and Thermogravimetric experiments are used to monitor the process of water molecules accommodated in and removed from the crystal lattice. The initial intercalation process takes place with two-water molecules corresponding to y=0.6) inserted in a formula unit, followed by a group of four (y=1.3) to form a cluster of Na(H2O)4. Thermogravimetric analysis suggests that the deintercalation occurs with the removal of the water molecules one by one from the hydrated cluster at elevated temperatures of approximately 50, 100, 200 and 300 C, respectively. Our investigations reveal that the hydration process is dynamic and that water molecule inter- and deintercalation follow different reaction paths in an irreversible way.

15 pages, 6 figures, figures with higher resolution by email request from the corresponding author

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Cited by in corpus (3)

• Electron-phonon interaction in the lamellar cobaltate Na${}_x$CoO${}_2$
• Thermal Expansion and Compressibility in Superconducting NaxCoO2o4xD2O (x?1/3): Evidence for Pressure-Induced Charge Redistribution
• Influence of water intercalation on the electronic structure of the hydrated Na0.3CoO2.yH2O using a local spin density approximation