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

We have prepared powder samples of NaxCoO2 x yH2O using a new synthesis route. Superconductivity was observed in Na0.3CoO2 x 1.3H2O between 4 and 5K as indicated by the magnetic susceptibility. The bulk compressibilities of Na0.3CoO2 x 1.3H2O, Na0.3CoO2 x 0.6H2O and Na0.3CoO2 were determined using a diamond anvil cell and synchrotron powder diffraction. Chemical changes occurring under pressure when using different pressure transmitting media are discussed and further transpo...

Poly- and single-crystalline Na$_x$CoO$_2$ has been successfully intercalated with H$_2$O and D$_2$O as confirmed by X-ray diffraction and thermogravimetric analysis. Resistivity, magnetic susceptibility, and specific heat measurements show bulk superconductivity with T$_c$ close to 5 K in both cases. The substitution of deuterium for hydrogen has an effect on T$_c$ of less than 0.2 K. Investigation of the resistivity anisotropy of Na$_x$CoO$_2\cdot$yH$_2$O single crystals sh...

In order to investigate the role of the water molecules in Na$_{0.35}$CoO$_{2}\cdot$1.3H$_{2}$O, we synthesized superconducting Na$_{0.35}$CoO$_{2}\cdot$1.3H$_{2}$O and nonsuperconducting Na$_{0.35}$CoO$_{2}\cdot$0.7H$_{2}$O, and measured their normal-state magnetic susceptibilities. The susceptibility of Na$_{0.35}$CoO$_{2}\cdot$1.3H$_{2}$O has an enhancement below ~150 K probably caused by ferromagnetic fluctuation, whereas no such enhancement was observed in Na$_{0.35}$CoO...

We report a successful tuning of Co valence state in cobalt oxyhydrate superconductor via a facile post reduction using NaOH as reducing agent. The change in Co valence was precisely determined by measuring the volume of the released oxygen. The possible hydronium-incorporation was greatly suppressed in concentrated NaOH solution, making the absolute Co valence determinable. As a result, an updated superconducting phase diagram was obtained, which shows that the superconducti...

Charge ordering behavior is observed in the crystal prepared through the immersion of the $Na_{0.41}CoO_2$ crystal in distilled water. Discovery of the charge ordering in the crystal with Na content less than 0.5 indicates that the immersion in water brings about the reduction of the $Na_{0.41}CoO_2$. The formal valence of Co changes from +3.59 estimated from the Na content to +3.5, the same as that in $Na_{0.5}CoO_2$. The charge compensation is confirmed to arise from th...

We succeeded in synthesizing the powder samples of bilayer-hydrate sodium cobalt oxide superconductors NaxCoO2-yH2O with Tc = 0 ~ 4.6 K by systematically changing the keeping duration in a 75 % relative humidity atmosphere after intercalation of water molecules. From the magnetic measurements, we found that the one-day duration sample does not show any superconductivity down to 1.8 K, and that the samples kept for 2 ~ 7 days show superconductivity, in which Tc increases up to...

We have used electron and neutron powder diffraction to elucidate the structural properties of superconducting \NaD. Our measurements show that our superconducting sample exhbits a number of supercells ranging from ${1/3}a^{*}$ to ${1/15}a^{*}$, but the most predominant one, observed also in the neutron data, is a double hexagonal cell with dimensions \dhx. Rietveld analysis reveals that \deut\space is inserted between CoO$_{2}$ sheets as to form a layered network of NaO$_{6}...

Superconducting single crystal samples of Na_xCoO_2 + yH_2O have been produced using an electrochemical technique which dispenses with the usual bromine chemical de-intercalation step and permits much more precise control of the Na content. After careful hydration, nearly single-phase crystals have been obtained in which over 90% of the sample's volume corresponds to the superconducting Na_{0.3}CoO_2 + 1.3H_2O structure. Susceptibility and specific heat measurements confirm t...

We report ^{59}Co NMR studies in single crystals of cobalt oxide superconductor Na_{0.42}CoO_{2}\cdot1.3H_{2}O (T_c=4.25K) and its parent compound Na_{0.42}CoO_{2}. We find that both the magnitude and the temperature (T) dependence of the Knight shifts are identical in the two compounds above T_c. The spin-lattice relaxation rate (1/T_1) is also identical above T_0 \sim60 K for both compounds. Below T_0, the unhydrated sample is found to be a non-correlated metal that well co...

The structure of a new member of the AxCoO2 x nH2O family (A=Li,Na,K) was determined by high-resolution synchrotron X-ray powder diffraction. Layered lithium cobalt oxide hydrate LixCoO2 x 2H2O crystallizes in a disordered monoclinic structure (space group C2/m) with lattice parameters a = 4.8915(2) A, b = 2.8239(1) A, c = 10.7033(9) A, beta = 112.386(4)deg. Unlike the superconducting sodium cobalt oxide hydrate, this material possesses a structure with lithium-water layers i...