Enhanced thermoelectric properties of NaxCoO2 whisker crystals

Single-crystalline whiskers of thermoelectric cobalt oxide, NaxCoO2, have been grown by an unconventional method from potassium-containing compositions, and their transport properties, and chemical compositions were determined. The growth mechanism was analyzed and interpreted by means of thermogravimetric analysis. At 300 K, electrical resistivity r and thermoelectric power S of the whisker are 102 u ohm cm and 83 uV/K, respectively. The power-factor, S2/r, thus is enhanced up to ~ 68 uW/K2 cm.Comment: 8 pages, 4 figures, to appear in Appl. Phys. Let

Electrochemical synthesis and properties of CoO2, the x = 0 phase of the AxCoO2 systems (A = Li, Na)

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 emu/mol Oe, being essentially identical to that of a Li-doped phase, Li0.12CoO2. It is most likely that the CoO2 phase is a Pauli-paramagnetic metal with itinerant electrons.Comment: 12 pages, 3 figure

Impact of lithium composition on the thermoelectric properties of the layered cobalt oxide system LixCoO2

Thermoelectric properties of the layered cobalt oxide system LixCoO2 were investigated in a wide range of Li composition, 0.98 >= x >= 0.35. Single-phase bulk samples of LixCoO2 were successfully obtained through electrochemical deintercalation of Li from the pristine LiCoO2 phase. While LixCoO2 with x >= 0.94 is semiconductive, the highly Li-deficient phase (0.75 >= x >= 0.35) exhibits metallic conductivity. The magnitude of Seebeck coefficient at 293 K (S293K) significantly depends on the Li content (x). The S293K value is as large as +70 ~ +100 uV/K for x >= 0.94, and it rapidly decreases from +90 uV/K to +10 uV/K as x is lowered within a Li composition range of 0.75 >= x >= 0.50. This behavior is in sharp contrast to the results of x <= 0.40 for which the S293K value is small and independent of x (+10 uV/K), indicating that a discontinuous change in the thermoelectric characteristics takes place at x = 0.40 ~ 0.50. The unusually large Seebeck coefficient and metallic conductivity are found to coexist in a narrow range of Li composition at about x = 0.75. The coexistence, which leads to an enhanced thermoelectric power factor, may be attributed to unusual electronic structure of the two-dimensional CoO2 block.Comment: 29 pages, 1 table, 8 figure

Electronic phase diagram of the layered cobalt oxide system, LixCoO2 (0.0 <= x <= 1.0)

Here we report the magnetic properties of the layered cobalt oxide system, LixCoO2, in the whole range of Li composition, 0 <= x <= 1. Based on dc-magnetic susceptibility data, combined with results of 59Co-NMR/NQR observations, the electronic phase diagram of LixCoO2 has been established. As in the related material NaxCoO2, a magnetic critical point is found to exist between x = 0.35 and 0.40, which separates a Pauli-paramagnetic and a Curie-Weiss metals. In the Pauli-paramagnetic regime (x <= 0.35), the antiferromagnetic spin correlations systematically increase with decreasing x. Nevertheless, CoO2, the x = 0 end member is a non-correlated metal in the whole temperature range studied. In the Curie-Weiss regime (x >= 0.40), on the other hand, various phase transitions are observed. For x = 0.40, a susceptibility hump is seen at 30 K, suggesting the onset of static AF order. A magnetic jump, which is likely to be triggered by charge ordering, is clearly observed at Tt = 175 K in samples with x = 0.50 (= 1/2) and 0.67 (= 2/3), while only a tiny kink appears at T = 210 K in the sample with an intermediate Li composition, x = 0.60. Thus, the phase diagram of the LixCoO2 system is complex, and the electronic properties are sensitively influenced by the Li content (x).Comment: 29 pages, 1 table, 9 figure

Synthesis, Characterization, and Magnetic Properties of gamma-NaxCoO2 (0.70 < x <0.84)

Powder Na$_{x}$CoO$_{2}$ ($0.70\leq x\leq 0.84$) samples were synthesized and characterized carefully by X-ray diffraction analysis, inductive-coupled plasma atomic emission spectroscopy, and redox titration. It was proved that $\gamma$-Na$_{x}$CoO$_{2}$ is formed only in the narrow range of $0.70\leq x\leq 0.78$. Nevertheless, the magnetic properties depend strongly on $x$. We found, for the first time, two characteristic features in the magnetic susceptibility of Na$_{0.78}$CoO$_{2}$, a sharp peak at $T_{p}=16$ K and an anomaly at $T_{k}=9$ K, as well as the transition at $T_{c}=22$ K and the broad maximum at $T_{m}=50$ K which had already been reported. A type of weak ferromagnetic transition seems to occur at $T_{k}$. The transition at $T_{c}$, which is believed to be caused by spin density wave formation, was observed clearly for $x\geq 0.74$ with constant $T_{c}$ and $T_{p}$ independent of $x$. On the other hand, ferromagnetic moment varies systematically depending on $x$. These facts suggest the occurrence of a phase separation at the microscopic level, such as the separation into Na-rich and Na-poor domains due to the segregation of Na ions. The magnetic phase diagram and transition mechanism proposed previously should be reconsidered.Comment: 4 pages (2 figures included) and 2 extra figures (gif), to be published in J. Phys. Soc. Jpn. 73 (8) with possible minor revision

Quantum Dynamics of Atom-molecule BECs in a Double-Well Potential

We investigate the dynamics of two-component Bose-Josephson junction composed of atom-molecule BECs. Within the semiclassical approximation, the multi-degree of freedom of this system permits chaotic dynamics, which does not occur in single-component Bose-Josephson junctions. By investigating the level statistics of the energy spectra using the exact diagonalization method, we evaluate whether the dynamics of the system is periodic or non-periodic within the semiclassical approximation. Additionally, we compare the semiclassical and full-quantum dynamics.Comment: to appear in JLTP - QFS 200

Measurement of electron correlations in LixCoO2 (x=0.0 - 0.35) using 59Co nuclear magnetic resonance and nuclear quadrupole resonance techniques

CoO2 is the parent compound for the superconductor NaxCoO2\cdot1.3H2O and was widely believed to be a Mott insulator. We performed 59Co nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) studies on LixCoO2 (x = 0.35, 0.25, 0.12, and 0.0) to uncover the electronic state and spin correlations in this series of compounds which was recently obtained through electrochemical de-intercalation of Li from pristine LiCoO2. We find that although the antiferromagnetic spin correlations systematically increase with decreasing Li-content (x), the end member, CoO2 is a non-correlated metal that well satisfies the Korringa relation for a Fermi liquid. Thus, CoO2 is not simply located at the limit of x->0 for AxCoO2 (A = Li, Na) compounds. The disappearance of the electron correlations in CoO2 is due to the three dimensionality of the compound which is in contrast to the highly two dimensional structure of AxCoO2.Comment: 4pages, 4figures, to be published in Phys.Rev.B. Rapid