scholarly journals Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance

Nanomaterials ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 1386
Author(s):  
Peter Baláž ◽  
Emmanuel Guilmeau ◽  
Marcela Achimovičová ◽  
Matej Baláž ◽  
Nina Daneu ◽  
...  

In this study, we demonstrate the feasibility of Bi-doped tetrahedrite Cu12Sb4−xBixS13 (x = 0.02–0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-energy milling was followed by spark plasma sintering. In all the samples, the prevailing content of tetrahedrite Cu12Sb4S13 (71–87%) and famatinite Cu3SbS4 (13–21%), together with small amounts of skinnerite Cu3SbS3, have been detected. The occurrence of the individual Cu-Sb-S phases and oxidation states of bismuth identified as Bi0 and Bi3+ are correlated. The most prominent effect of the simultaneous milling and doping on the thermoelectric properties is a decrease in the total thermal conductivity (κ) with increasing Bi content, in relation with the increasing amount of famatinite and skinnerite contents. The lowest value of κ was achieved for x = 0.2 (1.1 W m−1 K−1 at 675 K). However, this sample also manifests the lowest electrical conductivity σ, combined with relatively unchanged values for the Seebeck coefficient (S) compared with the un-doped sample. Overall, the lowered electrical performances outweigh the benefits from the decrease in thermal conductivity and the resulting figure-of-merit values illustrate a degradation effect of Bi doping on the thermoelectric properties of tetrahedrite in these synthesis conditions.

2014 ◽  
Vol 616 ◽  
pp. 174-177
Author(s):  
Mei Jun Yang ◽  
Qiang Shen ◽  
Lian Meng Zhang

The single phase of Bi-doped Mg2Si0.3Sn0.7compounds have been successfully fabricated by solid state reaction and spark plasma sintering (SPS). The effect of Bi doping concentration on the thermoelectric properties of Mg2Si0.3Sn0.7is investigated. The doping of Bi atom results in the increase of carrier concentrations and ensures the increase of electrical conductivity. Although the thermal conductivity and Seebeck coefficient shows a slight increase, the figure of merit of Mg2Si0.3Sn0.7compounds still increases with the increasing contents of Bi-doping. When Bi-doping content is 1.5at%, the Mg2Si0.3Sn0.7compound obtained the maximum value,ZT, is 1.03 at 640 K.


2020 ◽  
Vol 20 (6) ◽  
pp. 3902-3908
Author(s):  
Sandeep K. Pundir ◽  
Sukhvir Singh ◽  
Parveen Jain

Thermoelectric properties of high energy ball milled nano structured bismuth telluride (Bi2Te3) have been reported. By high energy ball milling, alloyed bulk crystalline ingots crush into nanopowder and followed by spark plasma sintering (SPS), we have demonstrate high figure of merit (ZT) in bismuth telluride pellet samples. In this work systematic study carried out on three pellet samples of Bi2Te3, synthesized by high ball milling for the time period of 4 hours, 8 hours and 12 hours and followed by SPS at the same processing parameters. A peak value of dimensionless figure of merit of about 1.22 at the temperature of 473 K has been achieved for 8 hours ball milled pellet sample. This enhancement in ZT value is mostly due to decrease in thermal conductivity. Results of this study demonstrate that ball milling and SPS has a major effect in controlling the density of grain boundaries of Bi2Te3 nano particles, while the pressure exerted on the powder samples during SPS introduce stress at the boundaries of the crystallites. These disordered crystallite boundary regions exert scattering of thermal energy carriers which reduced the thermal conductivity of the materials.


2013 ◽  
Vol 743-744 ◽  
pp. 94-99
Author(s):  
Liang Liang Li ◽  
Rui Rui Sun ◽  
Xiao Ying Qin ◽  
Yong Fei Liu ◽  
Guang Lei Guo

The Nd-doped SrO(SrTiO3)n (n=1,2) bulk samples were prepared by combining a sol-gel method and spark plasma sintering (SPS). The microstructures of the precursor powders were characterized by X-ray powder diffraction (XRD) and scanning electron microscope (SEM), thermogravimetric (TG) and differential scanning calorimetry (DSC). The oxides of (Sr1-xNdx)n+1TinO3n+1(n=1,2;x=0.05, 0.1) were prepared by solid-state reaction of the precursor powders with post-spark plasma sintering for the first time and the thermoelectric properties showed that electrical resistivity ρ and the absolute values |S| of Seebeck coefficient increased with temperature and depended on the dopant concentration, indicating a n-type degenerate semiconductor behavior. Compared with the total thermal conductivity κ (4.1-5.2 Wm-1K-1) at room temperature, the estimated electronic thermal conductivity κe(0.2-0.7 Wm-1K-1) were very small, indicating that lattice contribution was predominant in the RP phase compounds. The largest dimensionless figure of merit ZT, 0.13 at 905K, was obtained the 10 at.% Nd-doped Sr3Ti2O7. This synthetic method provides a simple way to prepare thermoelectric oxides.


2014 ◽  
Vol 2 (38) ◽  
pp. 15829-15835 ◽  
Author(s):  
Kriti Tyagi ◽  
Bhasker Gahtori ◽  
Sivaiah Bathula ◽  
A. K. Srivastava ◽  
A. K. Shukla ◽  
...  

Intrinsically ultra-low thermal conductivity and electrical transport in single-phase Cu2SbSe3 synthesized employing a solid state reaction and spark plasma sintering.


2012 ◽  
Vol 512-515 ◽  
pp. 1651-1654 ◽  
Author(s):  
Yu Kun Xiao ◽  
Zhi Xiang Li ◽  
Jun Jiang ◽  
Sheng Hui Yang ◽  
Ting Zhang ◽  
...  

P-type BiSbTe/RuO2 composite was fabricated using a combined process of melting and spark plasma sintering. The XRD patterns showed that RuO2 reacted with the matrix for the RuO2 content of 1.0 wt% and 4.0 wt% samples. The measured thermoelectric properties showed that the highest electrical conductivity was obtained for the sample with 2.0 wt% RuO2. The power factor (α2σ/κ) decreased with the increase of RuO2 below 450 K. The lattice thermal conductivity was lower than that of BiSbTe over the whole temperature range for BiSbTe/2.0 wt% RuO2.


2007 ◽  
Vol 336-338 ◽  
pp. 854-856
Author(s):  
Yong Gao Yan ◽  
Xin Feng Tang ◽  
Hai Jun Liu ◽  
Ling Ling Yin ◽  
Qing Jie Zhang

Ag1-xPbmSbTe2+m (m = 6, 10, 18; x = 0, 0.5, 0.75) compounds were prepared by melting-spark plasma sintering (SPS) process. The effects of m and x on the thermoelectric properties of the compounds were investigated. The results indicate that all samples are n-type conduction. For Ag1-xPb18SbTe20 (x = 0, 0.5, 0.75), the electrical conductivity decreases, whereas Seebeck coefficient increases, with increasing Ag concentration. For AgPbmSbTe2+m (m = 6, 10, 18), as m increases, the Seebeck coefficient slightly decreases and the electrical conductivity increases first, with a maximum at m =10, and then decreases. The thermal conductivity increases with increasing m.


2010 ◽  
Vol 1267 ◽  
Author(s):  
Jeffrey D Germond ◽  
Paul J Schilling ◽  
Nathan J. Takas ◽  
Pierre F. P. Poudeu

AbstractSamples with a composition ZrNiSn were synthesized by a combination of mechanical alloying (MA) and consolidation by either Spark Plasma Sintering (SPS) or hot pressing (HP). Appropriate stoichiometric ratios of the starting materials were milled under an inert atmosphere in a high energy ball mill for 6 hours, achieving a half-Heusler phase. X-Ray diffraction patterns of as milled powders and consolidated samples were compared and analyzed for phase purity. Thermal conductivity, electrical conductivity and Seebeck coefficient were measured as a function of temperature in the range 300 K to 800 K and compared with measurements reported for high temperature solid state reaction synthesis of this compound. HP samples, compared to SPS samples, demonstrate increased grain growth due to longer heating times. Reduced grain size achieved by MA and SPS causes increased phonon scattering due to the increased number of grain boundaries, which lowers the thermal conductivity without doping the base system with addition phonon scattering centers.


2004 ◽  
Vol 449-452 ◽  
pp. 905-908 ◽  
Author(s):  
Dong Choul Cho ◽  
Cheol Ho Lim ◽  
D.M. Lee ◽  
Seung Y. Shin ◽  
Chung Hyo Lee

The n-type thermoelectric materials of Bi2Te2.7Se0.3 doped with SbI3 were prepared by spark plasma sintering technique. The powders were ball-milled in an argon and air atmosphere. Then, powders were reduced in H2 atmosphere. Effects of oxygen content on the thermoelectric properties of Bi2Te2.7Se0.3 compounds have been investigated. Seebeck coefficient, electrical resistivity and thermal conductivity of the sintered compound were measured at room temperature. It was found that the effect of atmosphere during the powder production was remarkable and thermoelectric properties of sintered compound were remarkably improved by H2 reduction of starting powder. The obtained maximum figure of merit was 2.4 x 10-3/K.


Materials ◽  
2019 ◽  
Vol 12 (15) ◽  
pp. 2451 ◽  
Author(s):  
Cristina Artini ◽  
Riccardo Carlini ◽  
Roberto Spotorno ◽  
Fainan Failamani ◽  
Takao Mori ◽  
...  

The structural and thermoelectric properties of the filled skutterudite (Sm,Gd)y(FexNi1-x)4Sb12 were investigated and critically compared to the ones in the Sm-containing system with the aim of unravelling the effect of double filling on filling fraction and thermal conductivity. Several samples (x = 0.50–0.90 and y = 0.15–0.48) were prepared by melting-sintering, and two of them were densified by spark plasma sintering in order to study their thermoelectric features. The crystallographic study enables the recognition of the role of the filler size in ruling the filling fraction and the compositional location of the p/n crossover: It has been found that the former lowers and the latter moves toward lower x values with the reduction of the filler ionic size, as a consequence of the progressively weaker interaction of the filler with the Sb12 cavity. The analysis of thermoelectric properties indicates that, despite the Sm3+/Gd3+ small mass difference, the contemporary presence of these ions in the 2a site significantly affects the thermal conductivity of both p- and n-compositions. This occurs by reducing its value with respect to the Sm-filled compound at each temperature considered, and making the overall thermoelectric performance of the system comparable to several multi-filled (Fe, Ni)-based skutterudites described in the literature.


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