A novel route to phase formation of cobalt oxyhydrates using KMnO4 as an oxidizing agent

We present our NMR studies of double-layer hydrated cobalt oxides NaxCoO2-yH2O (x ~ 0.35, y ~ 1.3) with various Tc = 0 - 4.8 K and magnetic transition temperatures. High-resolution $^{1}$H NMR spectrum served as an evidence for the existence of H$_{3}$O$^{+}$ oxonium ions. $^{23}$Na nuclear spin-lattice relaxation rates served to detect local field fluctuations sensitive to Tc. $^{59}$Co nuclear quadrupole resonance (NQR) spectra served to classify the various Tc samples. Fro...

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 m...

We report results of specific heat measurements on polycrystalline samples of the layered superconductor, Na(0.3)CoO(2).1.3H(2)O. The electronic contribution to the specific heat, gamma, is found to be 12.2 mJ/mol-K2. The feature at the superconducting transition is rather sharp, becoming broad and strongly suppressed in an applied magnetic field. The data indicate a residual normal state electronic specific heat at low temperatures, implying that there is a sizable populatio...

Muon spin relaxation ($\mu$SR) measurements on the new layered cobalt oxide superconductor Na$_{0.35}$CoO$_{2}\cdot$1.3H$_{2}$O and its parent, non-superconducting compounds, have revealed unconventional nature of superconductivity through: (1) a small superfluid energy which implies a surprisingly high effective mass of the charge carriers, approximately 100 times the bare electron mass; (2) the superconducting transition temperature $T_{c}$ scaling with the superfluid energ...

Magnetic properties of the novel layered superconductor, Na$_{0.35}$CoO$_{2}$$\cdot$1.3H$_{2}$O have been investigated. From the temperature dependence and field dependence of the magnetization, the superconducting transition temperature, as well as upper- and lower-critical fields have been estimated to be $T_{C}=4.6$ K, $H_{C2}(0)=61.0$ T and $H_{C1}(0)=28.1$ Oe. These values give quite unusual phenomenological parameters, \textit{i.e.}, coherent length, penetration depth a...

Density functional theory (DFT) within the local density approximation (LDA) is used to understand the electronic properties of Na1/3CoO2 and Na1/3CoO2(H2O)4/3, which was recently found to be superconducting1. Comparing the LDA charge density of CoO2 and the Na doped phases indicates that doping does not simply add electrons to the t2g states. In fact, the electron added in the t2g state is dressed by hole density in the eg state and electron density in the oxygen states via ...

We report a detailed study of de-intercalation of Na from the compound NaxCoO2-d using an electrochemical technique. We find evidence for stable phases with Na contents near the fractions ~1/3, 1/2, 5/8, 2/3, and 3/4. Details regarding the floating-zone crystal growth of Na0.75CoO2 single crystals are discussed as well as results from magnetic susceptibility measurements. We observe the presence of significant oxygen deficiencies in powder samples of Na0.75CoO2-d prepared in ...

We report a precise $^{59}$Co nuclear quadrupolar resonance (NQR) measurement on the recently discovered cobalt oxyhydrate Na$_{0.35}$CoO$_{2}$$\cdot y$H$_{2}$O superconductor from $T$=40 K down to 0.2 K. We find that in the normal state the spin-lattice relaxation rate $1/T_1$ follows a Curie-Weiss type temperature ($T$) variation, $1/T_1T=C/(T-\theta)$, with $\theta$=-42 K, suggesting two-dimensional antiferromagnetic spin correlations. Below $T_c$=3.9 K, $1/T_1$ decreases ...

We report on first investigation of the lattice dynamics in the novel superconducting material Na$\_{0.35}$CoO$\_2$$\cdot$1.3H$\_2$O and the non-hydrated parent compound Na$\_{0.7}$CoO$\_2$ by inelastic x-ray scattering. The measured phonon dispersion along the $\Gamma-M$ direction show a marked softening with hole doping of two optical phonon branches close to the Brillouin zone boundary. The phonon spectra, dispersion, and softening are well reproduced by first-principle ca...

Single crystals of Na$_{0.5}$CoO$_2$ were obtained through a flux method followed by de-intercalation of sodium. The Na$_{0.5}$CoO$_2$ samples were found to be vulnerable to water in the air and a hydration process in which H$_2$O molecules fill oxygen vacancies in CoO$_2$ layers is suggested to be responsible for the unusual vulnerability to water. The transport properties, including resistivity (\emph{$\rho$}), thermopower (\emph{S}) and Hall coefficient (\emph{R$_H$}), wer...