Ryoji Funahashi

An Oxide Single Crystal with High Thermoelectric Performance in Air.

An oxide single-crystalline whisker with high thermoelectric properties at temperatures (T) higher than 600 K in air has been discovered. This whisker is assigned to Ca2Co2O5 phase (abbreviated to Co-225 whiskers) and has a layered structure in which Co–O layers of two different kinds alternate in the direction of the c-axis. Seebeck coefficient of the whiskers is higher than 100 µVK-1 at 100 K and increases with temperature up to 210 µVK-1. Temperature dependence of electric resistivity shows a semiconducting-like behavior. These results indicate that the electric carriers are transported via hopping conduction. Using thermal conductivity of a Co-225 polycrystalline sample, figure of merit (ZT) of the Co-225 whiskers is estimated 1.2–2.7 at T≥873 K. This compound is characterized with regard to low mobility and high density of carriers, which contradicts the conventional materials with high thermoelectric properties.

Electrical and thermal properties of single-crystalline (Ca2CoO3)0.7CoO2 with a Ca3Co4O9 structure

Single crystals of (Ca2CoO3)0.7CoO2 were grown using a modified strontium chloride flux technique, and their electrical and thermal properties were determined. Growth conditions were established for obtaining plate-like single crystals of a relatively large size (5×10×0.05 mm3). At 973 K, thermoelectric power S and electrical resistivity ρ of the specimens are ≈240 μV K−1 and ≈2.3×10−5 Ω m, respectively, and their thermal conductivity κ is nearly 3 W m1 K−1, as determined by mathematical extrapolation. The figure of merit ZT=S2T/ρκ derived therefrom is ≈0.87 at 973 K. The relatively low κ is likely the result of a misfit structure between the CoO2 layer and the Ca2CoO3 slab.

Thermoelectric properties of Bi2Sr2Co2Ox polycrystalline materials

Bi2Sr2Co2O9 (BC-2202) polycrystalline materials with a layered structure have been prepared by partial melting. The chemical compositions of the samples are Bi2Sr2Co2Ox (2202), Bi1.8Sr2Co2Ox (Bi-1.8), and Bi2Sr1.8Co2Ox (Sr-1.8). All three samples are p-type conductors. The electric properties, namely, the Seebeck coefficient (S) and electric resistivity (ρ), of the samples are dependent on chemical composition. The S values increase with temperature at T>673 K and, at 973 K, reach 100, 110, and 150 μV K−1 for the 2202, the Bi-1.8, and the Sr-1.8 samples, respectively. Thermal conductivity (κ) for all samples is lower than for ordinary conducting oxides. The figure of merit (Z) increases with temperature for all samples. Z values at 973 K are 0.77×10−4, 0.61×10−4, and 2.0×10−4 K−1 for the 2202, Bi-1.8, and Sr-1.8 samples, respectively. The thermoelectric properties depend on the chemical composition of the BC-2202 phase. The BC-2202 material thus appears to be a promising thermoelectric material due to its...

Bi2Sr2Co2Oy whiskers with high thermoelectric figure of merit

Bi2Sr2Co2Oy (BC-222) whiskers were grown with an excellent Seebeck coefficient (S) and electrical resistivity (ρ) for power generation applications at high temperatures in air. The S value of these long BC-222 whiskers reached almost 300 μV K−1 at 973 K. Thermal conductivity (κ) was measured and found to be suppressed to a low value of about 2.0 W m−1 K−1. This is considered due not only to a phonon–phonon interaction but also other scattering processes. The resulting dimensionless thermoelectric figure of merit ZT(=S2T/ρκ) was more than 1.1, which corresponds to a conversion efficiency of almost 10% at 973 K in air.

Thermoelectric properties of the Bi- and Na- substituted Ca3Co4O9 system

Bi- and Na-substituted Ca3Co4O9 polycrystalline samples have been prepared using a hot-pressing technique and their thermoelectric properties were carefully studied in air from room temperature to 1000 K. The substitutions of Bi3+ and Na+ for Ca2+, as well as Bi3+ and Na+ double substitution, cause both the electrical conductivity (σ) and thermoelectric power (S) to increase simultaneously. The double substitution has also been demonstrated to be effective to decrease the thermal conductivity (κ). The dimensionless figure of merit ZT (=S2σT/κ) reaches 0.32 at 1000 K in the double-substituted sample.

Thermoelectrical properties of A-site substituted Ca1−xRexMnO3 system

CaMnO3 is an electron-doped compound which belongs to the perovskite family. Despite its high Seebeck coefficient S value, the figure of merit at high temperature remains low due to its large resistivity ρ(ρ300K=2Ωcm). To optimize the performance of this material in terms of thermoelectric properties, several substitutions have been attempted on the Ca site to decrease the ρ. Structure and thermoelectric properties of polycrystalline samples Ca1−xAxMnO3 (A=Yb, Tb, Nd, and Ho) have been investigated. Although ρ strongly depends on the ionic radius ⟨rA⟩ and carrier concentration, we have shown that the thermal conductivity κ is mainly driven by the atomic weight of the A site and decreases with it. Therefore, it seems that the S, ρ, and κ could be controlled separately. For instance, the highest dimensionless ZT (=0.16) has been obtained at 1000K in the air for Ca0.9Yb0.1MnO3.

High temperature thermoelectric properties of oxide Ca9Co12O28

The electrical conductivity, Seebeck coefficient and thermal conductivity of oxide Ca 9 Co 12 O 28 with Ca 2 Co 2 O 5 -type structure are 84 S cm –1 , 118 µV K –1 and 1.73 W m –1 K –1 respectively at 700 °C, and its figure of merit is 0.67×10 –4 K –1 , showing that Ca 9 Co 12 O 28 is a potential material for high temperature thermoelectric energy conversion.

Fabrication of an all-oxide thermoelectric power generator

An oxide thermoelectric device was fabricated using Gd-doped Ca3Co4O9 p-type legs and La-doped CaMnO3 n-type legs on a fin. The power factors of p legs and n legs were 4.8×10−4 Wm−1 K−2 and 2.2×10−4 Wm−1 K−2 at 700 °C in air, respectively. With eight p–n couples the device generated an output power of 63.5 mW under the thermal condition of hot side temperature Th=773 °C and a temperature difference ΔT=390 °C. This device proved to be operable for more than two weeks in air showing high durability.

Ca2.7Bi0.3Co4O9∕La0.9Bi0.1NiO3 thermoelectric deviceswith high output power density

Different versions of a thermoelectric unicouple composed of p-type Ca2.7Bi0.3Co4O9 (Co-349) and n-type La0.9Bi0.1NiO3 (Ni-113) bulks were constructed using Ag paste containing p- and n-type oxide powders, prepared from the same bulks, for connection of the p and n legs, respectively. Internal resistance (RI) of the unicouple corrected using Ag paste containing 6 wt. % of the oxide powders is 26.2mΩ at 1073K in air and decreases with increasing temperature. Maximum output power (Pmax), evaluated using the formula Pmax=VO2∕4RI, (VO is open-circuit voltage), is 94mW at 1073K (ΔT=500K) and increases with temperature. This value corresponds to a volume power density of 0.66W∕cm3.

Thermoelectric properties of highly grain-aligned and densified Co-based oxide ceramics

Highly grain-aligned Ca3Co4O9 and (Ca2.7Sr0.2La0.1)(Co3.9Cu0.1)O9 ceramics were prepared by the magnetic alignment technique, and then treated by a spark plasma sintering process to increase their bulk densities. Thermoelectric properties were investigated from room temperature to 700 °C in air. Grain alignment is effective in lowering the electrical resistivity and has no obvious influence on the Seebeck coefficient, thus resulting in enhancement of the thermoelectric power factor. Substitution of Sr, La and Cu does not appreciably change the electrical resistivity and Seebeck coefficient, but significantly reduces the thermal conductivity.