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Ali, Syed Shahbaz
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article
Improved High-Temperature Thermoelectric Properties of Dual-Doped Ca3Co4O9
Abstract
Layered structured Ca<sub>3</sub>Co<sub>4</sub>O<sub>9</sub> has displayed great potential for thermoelectric (TE) renewable energy applications, as it is nontoxic and contains abundantly available constituent elements. In this work, we study the crystal structure and high-temperature TE properties of Ca<sub>3–2<i>y</i></sub>Na<sub>2<i>y</i></sub>Co<sub>4–<i>y</i></sub>Mo<i><sub>y</sub></i>O<sub>9</sub> (0 ≤ <i>y</i> ≤ 0.10) polycrystalline materials. Powder X-ray diffraction (XRD) analysis shows that all samples are single-phase samples and without any noticeable amount of the secondary phase. X-ray photoelectron spectroscopic (XPS) measurements depict the presence of a mixture of Co<sup>3+</sup> and Co<sup>4+</sup> valence states in these materials. The Seebeck coefficient (<i>S</i>) of dual-doped materials is significantly enhanced, and electrical resistivities (<i>ρ</i>) and thermal conductivities (<i>κ</i>) are decreased compared to the pristine compound. The maximum thermoelectric power factor (PF = <i>S</i><sup>2</sup>/<i>ρ</i>) and dimensionless figureof merit (<i>zT</i>) obtained for the <i>y</i> = 0.025 sample at 1000 K temperature are ∼3.2 × 10<sup>–4</sup> W m<sup>–1</sup> K<sup>–2</sup> and 0.27, respectively. The <i>zT</i> value for Ca<sub>2.95</sub>Na<sub>0.05</sub>Co<sub>3.975</sub>Mo<sub>0.025</sub>O<sub>9</sub> is about 2.5 times higher than that of the parent Ca<sub>3</sub>Co<sub>4</sub>O<sub>9</sub> compound. These results demonstrate that dual doping of Na and Mo cations is a promising strategy for improving the high-temperature thermoelectric properties of Ca<sub>3</sub>Co<sub>4</sub>O<sub>9</sub>.