Thermoelectric Properties of Bi Doped Tetrahedrite

Kumar, Deepak; Chetty, Raju; Femi, Olu Emmanuel; Chattopadhyay, K.; Malar, P.; Mallik, Ramesh Chandra

doi:10.1007/s11664-016-4826-5

Cited by 41 publications

(11 citation statements)

References 21 publications

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“…11 c. This increase in the lattice parameter confirms the substitution of Bi at Sb sites, since ionic radii for Bi 3+ (0.96 Å) is slightly larger than that for Sb 3+ (0.76 Å) 71 . Similar behaviour was reported by Kumar et al 77 for the Bi-doped samples. In this instance the lattice parameter a increases from 10.326 Å for undoped tetrahedrite to 10.375 Å for Bi-doped tetrahedrite Cu 12 Sb 4−x Bi x S 13 with x = 0.8.…”

Section: Resultssupporting

confidence: 90%

Scalable synthesis of Cu–Sb–S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties

Alqahtani

Khan

Lewis

et al. 2021

Sci Rep

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We report a simple, economical and low temperature route for phase-pure synthesis of two distinct phases of Cu–Sb–S, chalcostibite (CuSbS2) and tetrahedrite (Cu12Sb4S13) nanostructures. Both compounds were prepared by the decomposition of a mixture of bis(O-ethylxanthato)copper(II) and tris(O-ethylxanthato)antimony(III), without the use of solvent or capping ligands. By tuning the molar ratio of copper and antimony xanthates, single-phases of either chalcostibite or tetrahedrite were obtained. The tetrahedrite phase exists in a cubic structure, where the Cu and Sb atoms are present in different coordination environments, and tuning of band gap energy was investigated by the incorporation of multivalent cationic dopants, i.e. by the formation of Zn-doped tetrahedrites Cu12−xZnxSb4S13 (x = 0.25, 0.5, 0.75, 1, 1.2 and 1.5) and the Bi-doped tetrahedrites Cu12Sb4−xBixS13 (x = 0.08, 0.15, 0.25, 0.32, 0.4 and 0.5). Powder X-ray diffraction (p-XRD) confirms single-phase of cubic tetrahedrite structures for both of the doped series. The only exception was for Cu12Sb4−xBixS13 with x = 0.5, which showed a secondary phase, implying that this value is above the solubility limit of Bi in Cu12Sb4S13 (12%). A linear increase in the lattice parameter a in both Zn- and Bi-doped tetrahedrite samples was observed with increasing dopant concentration. The estimated elemental compositions from EDX data are in line with the stoichiometric ratio expected for the compounds formed. The morphologies of samples were investigated using SEM and TEM, revealing the formation of smaller particle sizes upon incorporation of Zn. Incorporation of Zn or Bi into Cu12Sb4S13 led to an increase in band gap energy. The estimated band gap energies of Cu12−xZnxSb4S13 films ranges from 1.49 to 1.6 eV, while the band gaps of Cu12Sb4−xBixS13 films increases from 1.49 to 1.72 eV with increasing x.

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Section: Resultssupporting

confidence: 90%

Scalable synthesis of Cu–Sb–S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties

Alqahtani

Khan

Lewis

et al. 2021

Sci Rep

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“…In this work, the calculated values of L are between 1.75 × 10 –8 and 2.04 × 10 –8 V 2 K –2 for all specimens, as shown in Table , which is similar to the L values reported previously. ,, In addition, the κ L decreased after Ge doping: the values are 1.1 W m –1 K –1 at 300 K and 0.8 W m –1 K –1 at 723 K for the undoped samples; and 0.75–0.97 W m –1 K –1 at 300 K and 0.44–0.70 W m –1 K –1 at 750 K for all doped samples, which demonstrated that a ∼40% decrease in κ L was obtained after Ge doping. This decrease may originate from the increased impurity (doped Ge atoms) scattering of phonons.…”

Section: Results and Discussionsupporting

confidence: 89%

Achieving a High Thermoelectric Performance of Tetrahedrites by Adjusting the Electronic Density of States and Enhancing Phonon Scattering

Huang

Kong

Zhang

et al. 2019

ACS Appl. Mater. Interfaces

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Recently, many researchers have focused on tetrahedrite-based compounds due to their intrinsic low thermal conductivity; however, their thermoelectric performance is limited by the lower power factor. In this case, using Ge doping on Sb sites, the power factor is obviously enhanced due to an increment in carrier concentration and density of states; simultaneously, the thermal conductivity is substantially suppressed by atomic defects. Also, ZnO nanoparticles are introduced in the Ge-doped compounds to further weaken the thermal conductivity. As a result, the maximum dimensionless figure of merit (ZT) of ∼1.0 is obtained for the Cu12Sb3.96Ge0.04S13-0.5 wt % ZnO sample at 750 K, which is ∼72% larger than that of Cu12Sb4S13. All results indicate that suitable elemental doping combined with the incorporation of the nanophase is a very promising approach for Cu12Sb4S13 tetrahedrites to improve the thermoelectric performance.

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“…Improved thermoelectric compounds should also have high Seebeck coefficients and electric conductivity, combined with low thermal conductivity to achieve the needed efficiencies. Recently, tetrahedrite, a natural mineral based on the Cu 12 Sb 4 S 13 compound, has been identified as a potentially significant new material, with high thermoelectric performance at midrange temperatures. − This material includes nontoxic, earth-abundant elements and can also be doped with transition metals.…”

Section: Introductionmentioning

confidence: 99%

Copper-Ion Dynamics and Phase Segregation in Cu-Rich Tetrahedrite: an NMR Study

Ghassemi

Tian

et al. 2020

J. Phys. Chem. C

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63 Cu NMR measurements are reported for the Cu-rich phase of Cu 12+x Sb 4 S 13 (x 2) and compared to Cu 12 Sb 4 S 13 . We identify the NMR signatures of the phase segregation into Cu-poor (x ≈ 0) and Cu-rich (x 2) phases, with the metal-insulator transition observed in Cu 12 Sb 4 S 13 suppressed in the Cu-rich phase. Based on NMR T1 and T2 measurements, the results demonstrate Cu-ion hopping below room temperature with an activation energy of ∼150 meV for the Cu-rich phase, consistent with superionic behavior. The NMR results also demonstrate the effects of Cu-ion mobility in the Cu 12 Sb 4 S 13 phase, but with a larger activation barrier. We identify a small difference in NMR Knight shift for the metallic phase of Cu 12 Sb 4 S 13 , compared to the Cu-rich phase, and when compared to DFT calculations the results indicate a mix of hyperfine contributions to the metallic shift.I.

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Thermoelectric Properties of Bi Doped Tetrahedrite

Cited by 41 publications

References 21 publications

Scalable synthesis of Cu–Sb–S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties

Scalable synthesis of Cu–Sb–S phases from reactive melts of metal xanthates and effect of cationic manipulation on structural and optical properties

Achieving a High Thermoelectric Performance of Tetrahedrites by Adjusting the Electronic Density of States and Enhancing Phonon Scattering

Copper-Ion Dynamics and Phase Segregation in Cu-Rich Tetrahedrite: an NMR Study

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