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Register a new userValence and Na content dependences of superconductivity in NaxCoO2.yH2O
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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 exchanger of Na$^{+}$ and H$_{3}$O$^{+}$, rather than by variation of Co valence, suggesting the presence of multiple kinds of Fermi surface. Furthermore, the high-field magnetic susceptibility measurements for one sample up to 30 T indicated an upper critical field much higher than the Pauli limit supporting the validity of the spin-triplet pairing mechanism.
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The Raman spectra of the parent compound NaxCoO2 (x=0.75) and the superconducting oxyhydrates NaxCoO2.yH2O with different superconducting temperatures (Tc) have been measured. Five Raman active phonons around 195 cm-1 (E1g), 482 cm-1, 522 cm-1, 616 cm-1 (3E2g), 663 cm-1 (A1g) appear in all spectra. These spectra change systematically along with the intercalation of H2O and superconducting properties. In particular, the Raman active phonons (A1g and E1g) involving the oxygen motions within the Co-O layers show up monotonous decrease in frequency along with superconducting temperature Tc. The fundamental properties and alternations of other active Raman phonons in the superconducting materials have also been discussed.
We synthesized powder samples of Na$_{x}$CoO$_{2}cdot y$H$_{2}$O changing the volume of the water in the hydration process, then investigated their superconducting properties,. It was proved that the volume of water is one of key parameters to obtain a single phase of Na$_{x}$CoO$_{2}cdot y$H$_{2}$O with good superconducting properties. The transition temperature, $T_{c}$, of the sample changed gradually while it was stored in the atmosphere of 70% humidity. Superconducting behavior under high magnetic field was very sensitive to $T_{c}$. $H_{c2}$ of a high quality sample with high $T_{c}$ seemed very high.
We synthesized Nax(H3O)zCoO2yH2O samples with various Na/H3O ratios but with the constant Co valence of s = +3.40, and measured their magnetic properties to draw phase diagrams of the system. The superconductivity is very sensitive to the Na/H3O ratio. With varying x under fixed s of +3.40, magnetically ordered phase appears in the intermediate range of x sandwiched by two separated superconducting phases, suggesting that the superconductivity is induced by moderately strong magnetic interactions. In the vicinity of the magnetic phase, transition from the superconducting state to the magnetically ordered state was induced by applying high magnetic field. This transition is of the second order, at least, above 1.8 K. The upper-critical field is expected to be much higher than the Pauli limit for a phase located far away from the magnetic phase regarding the Na/H3O ratio.
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 protons. Moreover, the result implies that rather than an electron-doped Co(IV) lattice the phase should be considered as a hole-doped Co(III) lattice.
We report here the correlation between the water content and superconductivity in Na0.3CoO2*yH2O under the influences of elevated temperature and cold compression. The x-ray diffraction of the sample annealed at elevated temperatures indicates that intergrowths exist in the compound at equilibrium when 0.6 < y < 1.4. Its low-temperature diamagnetization varies linearly with y, but is insensitive to the intergrowth, indicative of quasi-2D superconductivity. The Tc-onset, especially, shifts only slightly with y. Our data from cold compressed samples, on the other hand, show that the water-loss non-proportionally suppresses the diamagnetization, which is suggestive of weak links.
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