May 12, 2004
We have first succeefully synthesized the sodium cobalt oxyhydrate superconductors using KMnO4 as a de-intercalating and oxidizing agent. It is a novel route to form the superconductive phase of NaxCoO2.yH2O without resorting to the commonly used Br2/CH3CN solution. The role of the KMnO4 is to de-intercalate the Na+ from the parent compound Na0.7CoO2 and oxidize the Co ion as a result. The higher molar ratio of KMnO4 relative to the sodium content tends to remove more Na+ from the parent compound and results in a slight expansion of the c-axis in the unit cell. The superconducting transition temperature is 4.6-3.8 K for samples treated by the aqueous KMnO4 solution with the molar ratio of KMnO4 relative to the sodium content in the range of 0.3 and 2.29.
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July 16, 2004
We have first used the aquesous KMnO4 solutions to de-intercalate and oxideze gamma-phase of Na0.7CoO2 and successfully form the superconductive phase of cobalt oxyhydrate hydrates (Na,K)xCoO2.yH2O with Tc=3.2-4.6K based on the magnetization measurements. The higher molar ratio of KMnO4/Na used to treat Na0.7CoO2 results in more removal of Na+ and leads to a partial or even complete replacement of K+ for Na+. The low molar ratio of KMnO4/Na forms a superconductive phase with ...
April 11, 2006
By deintercalation of Na+ followed by inserting bilayers of water molecules into the host lattice, the layered cobalt oxide of gamma-Na0.7CoO2 undergoes a topotactic transformation to a layered cobalt oxyhydrate of Na0.35(H2O)1.3CoO2-delta with the c-axis expanded from c = 10.9 anstrom to c = 19.6 anstrom. In this paper, we demonstrate that the superconducting phase of c = 19.6 anstrom can be directly obtained by simply immersing gamma-Na0.7CoO2 powders in electrolyzed/oxidiz...
June 22, 2005
We report the synthesis and superconducting properties of a metastable form of the known superconductor NaxCoO2*yH2O (x ~ 1/3, y ~ 4x). Instead of using the conventional bromine-acetonitrile mixture for sodium deintercalation, we use an aqueous bromine solution. Using this method, we oxidize the sample to a point that the sodium cobaltate becomes unstable, leading to formation of other products if not controlled. This compound has the same structure as the reported supercondu...
January 30, 2004
A systematic study of NaxCoO2 (x=0.50 - 0.90) and NaxCoO2 yH(D)2O (x=0.26 - 0.42, y=1.3) has been performed to determine phase stability and the effect of hydration on the structural and superconducting properties of this system. We show that a careful control of the Na deintercalation process and hydration dynamics is possible in single crystals of this system. Furthermore, we give experimental evidence that the dependence of the superconducting transition temperature on Na ...
February 18, 2004
Here we present results of accurate wet-chemical redox analyses, revealing that the oxidation number of cobalt in the newly discovered CoO2-layer superconductor, NaxCoO2 yH2O (x ~ 0.36, y ~ 1.3) is ~ 3.46. This value is significantly lower than the one (~ 3.64) expected on the basis of the value determined for the Na to Co stoichiometry ratio, x. The "lower-than-expected" value for the Co oxidation state may be alternatively explained by presence of oxygen vacancies or excess...
February 26, 2004
We report the evidence of proton incorporations in a newly-discovered cobalt oxyhydrate superconductor. During the hydration process for Na$_{0.32}$CoO$_{2}$ by the direct reaction with water liquid, it was shown that substantial NaOH was gradually liberated, indicating that H$^{+}$ is incorporated into the hydrated compound. Combined with the thermogravimetric analysis, the chemical composition of the typical sample is Na$_{0.22}$H$_{0.1}$CoO$_{2}\cdot 0.85$H$_{2}$O, which s...
November 17, 2005
Various samples of sodium cobalt oxyhydrate with relatively large amounts of Na$^{+}$ ions were synthesized by a modified soft-chemical process in which a NaOH aqueous solution was added in the final step of the procedure. From these samples, a superconducting phase diagram was determined for a section of a cobalt valence of $\sim$+3.48, which was compared with a previously obtained one of $\sim$+3.40. The superconductivity was significantly affected by the isovalent exchange...
July 24, 2003
Neutron and x-ray powder diffraction have been used to investigate the crystal structures of a sample of the newly-discovered superconducting sodium cobaltate deuterate compound with composition Na0.31(3)CoO2o1.25(2)D2O and its anhydrous parent compound Na0.61(1)CoO2. The deuterate superconducting compound is formed by coordinating four D2O molecules (two above and two below) to each Na ion in a way that gives Na-O distances nearly equal to those in the parent compound. One d...
June 3, 2003
The structural properties of NaxCoO2 and NaxCoO2yH2O have been investigated. The NaxCoO2yH2O samples in general show up the superconducting transitions at around 3.5K. EDAX analyses suggest our samples have the average composition of Na0.65CoO2 for the parent compound and Na0.26CoO2yH2O for the superconducting crystals. TEM observation reveals a superstructure with wave vector q=<1/2,0, 0> in the parent Na0.65CoO2 materials. This superstructure becomes very weak in the superc...
March 27, 2006
This paper has been withdrawn by the author due to a data error in Fig 5.