Position and oxidation state of tin in Sn-bearing tetrahedrites Cu12-xSnxSb4S13

Nasonova, Daria I.; Sobolev, A. V.; Presniakov, Igor A.; Andreeva, Ksenia D.; Shevelkov, Аndrei V.

doi:10.1016/j.jallcom.2018.11.168

Cited by 9 publications

(10 citation statements)

References 22 publications

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“…However, previous studies have shown that Cu 12−x Sn x Sb 4 S 13 series did not show Sn substitution at Sb site based on Rietveld refinements. 13,14 The reason for this discrepancy could be the inherent Sb deficiency in the present series because our intended compositions were Cu 12 Sb 4−x Sn x S 13 with Sb added in deficiency to accommodate Sn substitution at Sb site. In conclusion, the XRD analysis reveals successful substitution of Sn in tetrahedrite with the possibility of Sn substituting at both Cu(2) 12e and Sb sites.…”

Section: Acs Applied Materials and Interfacesmentioning

confidence: 91%

“…As a result, a maximum zT of 0.65 at 665 K was obtained for the compositions x = 0.3−0.5. 13 Another recent study by Nasonova et al 14 involving high-resolution powder X-ray diffraction (XRD) and Mossbauer spectroscopy reported that Sn in Cu 12−x Sn x Sb 4 S 13 substitutes at Cu(1) 12d site and exhibits a +4 oxidation state. 14 Previously, however, Hansen et al 15 performed a detailed study involving Sn substitution at Cu and Sb sites in tetrahedrite.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite

Tippireddy

Kumar

Karati

et al. 2019

ACS Appl. Mater. Interfaces

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The present study reports the effect of Sn substitution on the structural and thermoelectric properties of synthetic tetrahedrite (Cu 12 Sb 4 S 13) system. The samples were prepared with the intended compositions of Cu 12 Sb 4−x Sn x S 13 (x = 0.25, 0.35, 0.5, 1) and sintered using spark plasma sintering. A detailed structural characterization of the samples revealed tetrahedrite phase as the main phase with Sn substituting at both Cu and Sb sites instead of only Sb site. The theoretical calculations using density functional theory revealed that Sn at Cu(1) 12d or Cu(2) 12e site moves the Fermi level (E F) toward the band gap, whereas Sn at Sb 8c site introduces hybridized hole states near E F. Consequently, a relatively high optimum power factor of 1.3 mW/mK 2 was achieved by the x = 0.35 sample. The Sn-substituted samples exhibited a significant decrease in the total thermal conductivity (κ T) compared to the pristine composition (Cu 12 Sb 4 S 13), primarily because of reduced electronic thermal conductivity. Due to an optimum power factor (1.3 mW/mK 2) and reduced thermal conductivity (0.9 W/mK), a maximum zT of 0.96 at 673 K was achieved for x = 0.35 sample, which is nearly 40% increment compared to that of the pristine (Cu 12 Sb 4 S 13) sample.

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Section: Acs Applied Materials and Interfacesmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite

Tippireddy

Kumar

Karati

et al. 2019

ACS Appl. Mater. Interfaces

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“…Most studies [ 10–33 ] on Cu 12 Sb 4 S 13 have focused on the single‐ or cosubstitution on the Cu, Sb, or S sites. Such as Co, Zn, Fe, Ni, Cd, Hg, Mg, Sn, Ag, and Mn at Cu sites, Bi, Te, As, Ge, and Sn at Sb sites, and Se at S sites have been reported so far.…”

Section: Introductionmentioning

confidence: 99%

“…Among these substituted Cu 12 Sb 4 S 13 systems, Hansen et al [ 32 ] reported that Sn can be substituted Sb sites with a valence state of +2. While, Nasonova et al [ 33 ] found that Sn in Cu 12− x Sn x Sb 4 S 13 substitutes at Cu(1) 12 d site with a + 4 oxidation state by high‐resolution powder X‐ray diffraction (XRD) and Mössbauer spectroscopy. However, Tippireddy et al [ 30 ] discovered that Sn might be substituting at both Cu(2) 12e and Sb 8c sites from a combined analysis of XRD, electron probe microanalysis, X‐ray photoelectron spectroscopy, and Mössbauer spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Substitution Site Selection and Thermoelectric Performance‐Enhancing Mechanism of Cu₁₂Sb₄S₁₃ Doped with Pb/Ge/Sn

Liu

Qin

Liu

2021

Physica Status Solidi (b)

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Tetrahedrite Cu12Sb4S13 has attracted much attention as an earth‐abundant and ecofriendly thermoelectric material with intrinsic low thermal conductivity. Herein, the effects of carbon group elements Pb, Ge, and Sn on the electronic structure and thermoelectric properties of Cu12Sb4S13 are extensively investigated based on first‐principles electronic structure calculations and Boltzmann transport theories. It is found that the most energetically favorable sites for the elements Pb and Ge are the Cu(1) sites, while for Sn atoms they are the Cu(2) sites. And the engineered electronic density of states by Pb/Ge/Sn doping results in a sharp increase of the Seebeck coefficient and a great decrease in carrier thermal conductivity of the host. In addition, the Cu12Sb4S13 compounds substituted with Pb/Ge at Cu(2) sites and Sn at Cu(1) sites have a preferable optimizing thermoelectric performance in a whole. Especially, the optimizing ZT of the host could get an about 15‐time improvement at T = 470 K upon Sn substituting at Cu(1) sites.

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“…Single phase Cu 12 Sb 4 S 13 was obtained from natural minerals such as the "seed matrix" [4,16] which demonstrated a novel route for the preparation of Cu 12 Sb 4 S 13 [4,16]. On the other hand, transition metal elements (Mn [7,10,17,18], Fe [19,20], Co [21], Ni [8,22], Sn [23], Pb [24] Bi [25] and Zn [26]) used for doping Cu 12 Sb 4 S 13 have been extensively studied to enhance the thermoelectric properties of the material. Moreover, higher amounts of Fe-doped tetrahedrite [19,20] and tetrahedrites co-doped with Ni and Zn [27] demonstrated improved ZT values.…”

Section: Introductionmentioning

confidence: 99%

The influence of self-doping of stibnite ore with impurities on the preparation, heat capacity, magnetic and transport properties of tetrahedrite Cu₁₂Sb₄S₁₃

Chen

Zhang

et al. 2020

Materials Science-Poland

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Stibnite mineral (mainly Sb2S3) has been employed for the synthesis of tetrahedrite Cu12Sb4S13 bulk material by spark plasma sintering. High purity Cu12Sb4S13 can be quickly obtained by two sintering procedures at temperatures from the range of 420 °C to 440 °C for 1 h. Appropriate reduction of Cu content (Cu12+xSb4S13, x ⩽−0.05) or CuS content (Cu12−ySb4S13−y, y = 0.1 or 0.3) was beneficial to fabricate Cu12Sb4S13. The secondary resintering improved the purity of Cu12Sb4S13 material. The first-order magnetic phase transformation with magnetic hysteresis effect was confirmed by the behavior of susceptibility, heat capacity and resistivity. The magnetization showed a linear increase with increasing field (up to 7 T) and non-saturation behavior was observed. The impurities in stibnite mineral Sb2S3 had a weak influence on the transformation temperature but affected the low-temperature magnetization value (~0.15, close to natural tetrahedrite). Similar transformation was observed by the analysis of heat capacity. The properties such as electrical resistivity, Seebeck coefficient and thermal conductivity were also measured for Cu11:9Sb4S13 and Cu11:9Sb4S12:9. The maximum figure of merit ZT of Cu11:9Sb4S12:9 was 0.22 at 367 K.

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Position and oxidation state of tin in Sn-bearing tetrahedrites Cu12-xSnxSb4S13

Cited by 9 publications

References 22 publications

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite

Substitution Site Selection and Thermoelectric Performance‐Enhancing Mechanism of Cu₁₂Sb₄S₁₃ Doped with Pb/Ge/Sn

The influence of self-doping of stibnite ore with impurities on the preparation, heat capacity, magnetic and transport properties of tetrahedrite Cu₁₂Sb₄S₁₃

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Position and oxidation state of tin in Sn-bearing tetrahedrites Cu12-xSnxSb4S13

Cited by 9 publications

References 22 publications

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite

Substitution Site Selection and Thermoelectric Performance‐Enhancing Mechanism of Cu12Sb4S13 Doped with Pb/Ge/Sn

The influence of self-doping of stibnite ore with impurities on the preparation, heat capacity, magnetic and transport properties of tetrahedrite Cu12Sb4S13

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Resources

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Substitution Site Selection and Thermoelectric Performance‐Enhancing Mechanism of Cu₁₂Sb₄S₁₃ Doped with Pb/Ge/Sn

The influence of self-doping of stibnite ore with impurities on the preparation, heat capacity, magnetic and transport properties of tetrahedrite Cu₁₂Sb₄S₁₃