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

The hydration phase diagram for sodium cobalt oxyhydrate, Na0.3CoO2*yH2O (y=0, 0.6, 1.3), was determined as a function of relative humidity at 298K. It is found that greater than 75% relative humidity is needed for complete hydration of anhydrous Na0.3CoO2 to the superconducting phase Na0.3CoO2*1.3H2O. Dehydration studies show that a minimum of 43% relative humidity is needed to maintain the stability of the fully hydrated superconducting phase. The intermediate hydrate, Na0....

Single crystals of sodium cobaltates Na$_{x}$CoO$_{2}$ with $x \approx 0.8$ were grown by the floating zone technique. Using electrochemical Na de-intercalation method we reduced the sodium content in the as-grown crystals down to pure phase with 22 K N\'eel temperature and $x \approx 0.77$. The $^{59}$Co NMR study in the paramagnetic state of the $T_{N}=22$ K phase permitted us to evidence that at least 6 Co sites are differentiated. They could be separated by their magnetic...

We report 23Na NMR studies of the polycrystalline samples of double-layer hydrated cobalt oxides NaxCoO2.yH2O (x ~ 0.35 and y ~ 1.3) with the superconducting transition temperatures Tc < 1.8K and ~4.5K, and the dehydrated NaxCoO2 (x ~ 0.35). The hyperfine field and the electric field gradient at the Na sites in the non-hydrated Na0.7CoO2 and the dehydrated Na0.35CoO2 are found to be significantly reduced by the hydration, which indicates a strong shielding effect of the inter...

We have studied the superconducting phase diagram of \NaH\space as a function of electronic doping, characterizing our samples both in terms of Na content $x$ and the Co valence state. Our findings are consistent with a recent report that intercalation of \oxp\space ions into Na$_{x}$CoO$_{2}$, together with water, act as an additional dopant indicating that Na sub-stochiometry alone does not control the electronic doping of these materials. We find a superconducting phase di...

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 ...

The observation of superconductivity at 4.3 K in a new crystalline form of Na0.3CoO2*1.3H2O is reported. The new superconductor has three layers of CoO6 octahedra per crystallographic unit cell, in contrast to the previously reported two-layer superconductor. The three-layer cell occurs because the relative orientations of neighboring CoO2 layers are distinctly different from what is seen in the two-layer superconducting phase. This type of structural difference in materials ...

We synthesized the five batches of the samples of the novel P3 type superconductor, Na$_{x}$(H$_{3}$O)$_{y'}$CoO$_{2}\cdot y''$H$_{2}$O, by the soft chemical process starting from $\alpha$-NaCoO$_{2}$. The chemical and structural properties varied rather widely from batch to batch, with a result that $T_{c}$ varied from 4.6 K to 3.2 K. The magnetic susceptibility above $T_{c}$ shows upturn at low temperature as in the case of the P2 phase. The $T_{c}$ seems to be well correla...

Single-phase bulk samples of the "exotic" CoO2, the x = 0 phase of the AxCoO2 systems (A = Li, Na), were successfully synthesized through electrochemical de-intercalation of Li from pristine LiCoO2 samples. The samples of pure CoO2 were found to be essentially oxygen stoichiometric and possess a hexagonal structure consisting of stacked triangular-lattice CoO2 layers only. The magnetism of CoO2 is featured with a temperature-independent susceptibility of the magnitude of 10-3...

Co nuclear-quadrupole-resonance (NQR) measurements were performed on various bilayered hydrate cobaltate Na_x(H_3O)_zCoO_2\cdot yH_2O with different values of the superconducting and magnetic-ordering temperatures, T_c and T_M, respectively. From measurements of the temperature and sample dependence of the NQR frequency, it was revealed that the NQR frequency is changed by the change of the electric field gradient (EFG) along the c axis \nu_{zz} rather than the asymmetry of E...

We have investigated a set of sodium cobaltates (NaxCoO2) samples with various sodium content (0.67 \le x \le 0.75) using Nuclear Quadrupole Resonance (NQR). The four different stable phases and an intermediate one have been recognized. The NQR spectra of 59Co allowed us to clearly differentiate the pure phase samples which could be easily distinguished from multi-phase samples. Moreover, we have found that keeping samples at room temperature in contact with humid air leads t...