First-principles studies of atomic dynamics in tetrahedrite thermoelectrics

Li, Junchao; Zhu, Mengze; Abernathy, D. L.; Ke, Xianglin; Morelli, Donald T.; Lai, Wei

doi:10.1063/1.4959961

Cited by 15 publications

(12 citation statements)

References 30 publications

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“…The expressions of τ U , τ N , τ E , τ IF , τ PD , and τ NP are given in Formula (S1)–(S6) (Supporting Information). By using literature values of Debye temperature θ D = 239 K [ 43 ] and average sound velocity v = 2522 m s −1[ 44 ] for Cu 12‐ x In x Sb 4 S 12.8 Se 0.2 samples, we can obtain calculated κ L (dashed lines in Figure 7c). The magnitudes of the prefactor for the scattering from phonon–phonon U‐ and N‐process (A), electron–phonon interaction phonon scattering (B), point defects (C), and other parameters used in Debye–Callaway model are given in Table S2 (Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu₁₂Sb₄S₁₃ Tetrahedrites

Zhu

Ming

Zhang

et al. 2022

Adv Elect Materials

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The thermoelectric properties of dually substituted Cu12−xInxSb4S12.8Se0.2 tetrahedrites are studied in temperature range from 300 to 723 K. The results indicate that dual substitution of In for Cu and Se for S not only causes the enhancement of thermopower S but also gives rise to a significant decrease in lattice thermal conductivity κL. An ultralow κL ≈0.2 W m−1 K−1 is obtained at 723 K in Cu11.95In0.05Sb4S12.8Se0.2 sample due to the enhanced phonon scattering mainly by point defects. Consequently, a high figure of merit ZTmax ≈1.0 is achieved in Cu11.95In0.05Sb4S12.8Se0.2 sample, which is ≈56% larger than that of pristine Cu12Sb4S13, indicating that dual substitution is effective in boosting the thermoelectric properties of tetrahedrites.

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Section: Resultsmentioning

confidence: 99%

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu₁₂Sb₄S₁₃ Tetrahedrites

Zhu

Ming

Zhang

et al. 2022

Adv Elect Materials

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“…25 This results in a Debye temperature of 257 K, comparable to the values of 239 K, obtained using low-temperature diffraction data, 26 244 K, extracted from elastic measurements, 10 and 281 K, determined from first-principle calculations. 27 The Einstein temperatures for the copper cations can be estimated from a plot of Uiso/eq vs. temperature. 25 This results in values of 79 and 82 K for Cu (2), and 88 and 91 K for Cu(1) in Cu12Sb4S13 and Cu11MnSb4S13 respectively, which would correspond to energies ranging between 6.8 and 7.8 meV.…”

Section: Resultsmentioning

confidence: 99%

“…31 First-principle calculations predict two vibrational peaks between 3 and 5 meV for Cu (2), with the partial vibrational density of states for Cu(1) showing a peak at higher energies, close to 10 meV. 27 The absence of the low-energy Cu(2) vibrational mode in inelastic neutron scattering measurements of the tetrahedrite-related phase Cu10Te4S13…”

Section: Resultsmentioning

confidence: 99%

The impact of manganese substitution on the structure and properties of tetrahedrite

Guélou

Powell

Smith

et al. 2019

Journal of Applied Physics

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The crystal structure of the tetrahedrites Cu12-xMnxSb4S13 (x = 0, 1) has been studied by powder neutron diffraction between room temperature and 773 K. At all temperatures investigated, manganese exclusively occupies tetrahedral sites, while the trigonal-planar sites contain only copper. In situ diffraction data confirm the stability of the tetrahedrite phase up to 773 K, with no evidence of copper mobility at elevated temperatures. Analysis of atomic displacement parameters indicate that there are low-energy vibrations associated with the trigonal-planar and the tetrahedral copper cations. The Einstein temperatures for the copper cations range between 79 and 91 K. Manganese substitution increases the electrical resistivity and the Seebeck coefficient, while the thermal conductivity is reduced. This results in a modest improvement in the thermoelectric figure of merit for Cu12MnSb4S13, which reaches ZT=0.56 at 573 K.

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“…Hence, combining phonon scattering of vacancies and the dopant due to their Rayleigh scattering character, one can expresses formula as where A , B , and C are the prefactors of the scattering from point defects (PD), Umklapp-process ( U ), and electron–phonon interaction ( E ), respectively. Literature values of θ D = 239 K and v = 2522 m s –1 are used to estimate the value of κ L for Cu 12‑ x Gd x Sb 4 S 13 samples. The calculated κ L are shown in Figure (solid lines) and magnitudes for parameters A, B and C are shown in Table S8.…”

Section: Discussionmentioning

confidence: 99%

Improved Thermoelectric Performance of Cu₁₂Sb₄S₁₃ through Gd-Substitution Induced Enhancement of Electronic Density of States and Phonon Scattering

Zhu

Chen

Ming

et al. 2021

ACS Appl. Mater. Interfaces

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Cu12Sb4S13 has aroused great interest because of its earth-abundant constituents and intrinsic low thermal conductivity. However, the applications of Cu12Sb4S13 are hindered by its poor thermoelectric performance. Herein, it is shown that Gd substitution not only causes a significant increase in both electrical conductivity σ and thermopower S but also leads to dramatic drop in lattice thermal conductivity κ L. Consequently, large ZT reaches 0.94 at 749 K for Cu11.7Gd0.3Sb4S13, which is ∼41% higher than the ZT value of undoped sample. Rietveld refinements of XRD results show that accompanying inhibition of impurity phase Cu3SbS4, the number of Cu vacancies increases substantially with substituted content x (x ≤ 0.3), which leads to reduced κ L owing to intensive phonon scattering by the point defects and increased σ arising from the charged defects (V Cu ’ ). Crucially, synchrotron radiation photoelectron spectroscopy reveals substantial increment of electronic density of states at Fermi level upon Gd substitution, which is proven, by our first-principle calculations, to originate from contribution of Gd 4f orbit, resulting in enhancement of S. Our study provides us with a new path to enhance thermoelectric performance of Cu12Sb4S13.

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First-principles studies of atomic dynamics in tetrahedrite thermoelectrics

Cited by 15 publications

References 30 publications

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu₁₂Sb₄S₁₃ Tetrahedrites

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu₁₂Sb₄S₁₃ Tetrahedrites

The impact of manganese substitution on the structure and properties of tetrahedrite

Improved Thermoelectric Performance of Cu₁₂Sb₄S₁₃ through Gd-Substitution Induced Enhancement of Electronic Density of States and Phonon Scattering

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First-principles studies of atomic dynamics in tetrahedrite thermoelectrics

Cited by 15 publications

References 30 publications

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu12Sb4S13 Tetrahedrites

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu12Sb4S13 Tetrahedrites

The impact of manganese substitution on the structure and properties of tetrahedrite

Improved Thermoelectric Performance of Cu12Sb4S13 through Gd-Substitution Induced Enhancement of Electronic Density of States and Phonon Scattering

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Product

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Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu₁₂Sb₄S₁₃ Tetrahedrites

Ultralow Lattice Thermal Conductivity and High Thermoelectric Figure of Merit in Dually Substituted Cu₁₂Sb₄S₁₃ Tetrahedrites

Improved Thermoelectric Performance of Cu₁₂Sb₄S₁₃ through Gd-Substitution Induced Enhancement of Electronic Density of States and Phonon Scattering