Solvothermal Synthesis of Tetrahedrite: Speeding Up the Process of Thermoelectric Material Generation

James, Derak J.; Lu, Xu; Morelli, Donald T.; Brock, Stephanie L.

doi:10.1021/acsami.5b07141

Solvothermal Synthesis of Tetrahedrite: Speeding Up the Process of Thermoelectric Material Generation

Journal Article · Mon Oct 19 00:00:00 EDT 2015 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5b07141· OSTI ID:1370342

James, Derak J. ^[1]; Lu, Xu ^[2]; Morelli, Donald T. ^[2]; Brock, Stephanie L. ^[1]

Wayne State Univ., Detroit, MI (United States)
Michigan State Univ., East Lansing, MI (United States)

Derivatives of synthetic tetrahedrite, Cu₁₂Sb₄S₁₃, are receiving increasing attention in the thermoelectric community due to their exploitation of plentiful, relatively nontoxic elements, combined with a thermoelectric performance that rivals that of PbTe-based compounds. However, traditional synthetic methods require weeks of annealing at high temperatures (450–600 °C) and periodic regrinding of the samples. Here we report a solvothermal method to produce tetrahedrite that requires only 1 day of heating at a relatively low temperature (155 °C). This allows preparation of multiple samples at once and is potentially scalable. The solvothermal material described herein demonstrates a dimensionless figure of merit (ZT) vs temperature curve comparable to that of solid-state tetrahedrite, achieving the same ZT of 0.63 at ~720 K. In conclusion, as with the materials from solid-state synthesis, products from this rapid solvothermal synthesis can be improved by mixing in a 1:1 molar ratio with the Zn-containing natural mineral, tennantite, to achieve 0.9 mol equiv of Zn. This leads to a 36% increase in ZT at ~720 K for solvothermal tetrahedrite, to 0.85.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC)

Sponsoring Organization:: NSF; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001054

OSTI ID:: 1370342

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 42 Vol. 7; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (41)

From Bonding Asymmetry to Anharmonic Rattling in Cu ₁₂ Sb ₄ S ₁₃ Tetrahedrites: When Lone-Pair Electrons Are Not So Lonely Lai, Wei; Wang, Yuxing; Morelli, Donald T. Advanced Functional Materials, Vol. 25, Issue 24 https://doi.org/10.1002/adfm.201500766	journal	May 2015
Enhancement in Thermoelectric Figure of Merit in Nanostructured Bi2Te3 with Semimetal Nanoinclusions Sumithra, S.; Takas, Nathan J.; Misra, Dinesh K. Advanced Energy Materials, Vol. 1, Issue 6 https://doi.org/10.1002/aenm.201100338	journal	September 2011
High Performance Thermoelectricity in Earth-Abundant Compounds Based on Natural Mineral Tetrahedrites Lu, Xu; Morelli, Donald T.; Xia, Yi Advanced Energy Materials, Vol. 3, Issue 3, p. 342-348 https://doi.org/10.1002/aenm.201200650	journal	October 2012
The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite Makovicky, E.; Forcher, K.; Lottermoser, W. Mineralogy and Petrology, Vol. 43, Issue 1 https://doi.org/10.1007/BF01164223	journal	August 1990
Effect of NiTe Nanoinclusions on Thermoelectric Properties of Bi2Te3 Sumithra, S.; Takas, Nathan J.; Nolting, Westly M. Journal of Electronic Materials, Vol. 41, Issue 6 https://doi.org/10.1007/s11664-012-2003-z	journal	March 2012
Theoretical study on the thermal decomposition of thiourea Wang, Zerong Daniel; Yoshida, Motoko; George, Ben Computational and Theoretical Chemistry, Vol. 1017 https://doi.org/10.1016/j.comptc.2013.05.007	journal	August 2013
Structural stability of the synthetic thermoelectric ternary and nickel-substituted tetrahedrite phases Barbier, Tristan; Lemoine, Pierric; Gascoin, Stéphanie Journal of Alloys and Compounds, Vol. 634 https://doi.org/10.1016/j.jallcom.2015.02.045	journal	June 2015
Structure–property relationships along the Fe-substituted CuInS2 series: Tuning of thermoelectric and magnetic properties Burnett, Johanna D.; Gourdon, Olivier; Ranmohotti, Kulugammana G. S. Materials Chemistry and Physics, Vol. 147, Issue 1-2 https://doi.org/10.1016/j.matchemphys.2014.03.034	journal	September 2014
Enhanced Thermoelectric Performance of Synthetic Tetrahedrites Heo, Jaeseok; Laurita, Geneva; Muir, Sean Chemistry of Materials, Vol. 26, Issue 6 https://doi.org/10.1021/cm404026k	journal	March 2014
Selective Nanocrystal Synthesis and Calculated Electronic Structure of All Four Phases of Copper–Antimony–Sulfide Ramasamy, Karthik; Sims, Hunter; Butler, William H. Chemistry of Materials, Vol. 26, Issue 9 https://doi.org/10.1021/cm5005642	journal	April 2014
Increasing the Thermoelectric Figure of Merit of Tetrahedrites by Co-Doping with Nickel and Zinc Lu, Xu; Morelli, Donald T.; Xia, Yi Chemistry of Materials, Vol. 27, Issue 2 https://doi.org/10.1021/cm502570b	journal	January 2015
Structure of copper(II) ethylenediamine complexes in aqueous and neat ethylenediamine solutions and solvent-exchange kinetics of the copper(II) ion in ethylenediamine as studied by EXAFS and NMR methods Inada, Yasuhiro; Ozutsumi, Kazuhiko; Funahashi, Shigenobu Inorganic Chemistry, Vol. 32, Issue 14 https://doi.org/10.1021/ic00066a009	journal	July 1993
Spinodal Decomposition and Nucleation and Growth as a Means to Bulk Nanostructured Thermoelectrics: Enhanced Performance in Pb _1- _x Sn _x Te−PbS Androulakis, John; Lin, Chia-Her; Kong, Hun-Jin Journal of the American Chemical Society, Vol. 129, Issue 31 https://doi.org/10.1021/ja071875h	journal	August 2007
Large Enhancements of Thermopower and Carrier Mobility in Quantum Dot Engineered Bulk Semiconductors Liu, Yuanfeng; Sahoo, Pranati; Makongo, Julien P. A. Journal of the American Chemical Society, Vol. 135, Issue 20 https://doi.org/10.1021/ja311059m	journal	May 2013
Near-Infrared Absorbing Cu ₁₂ Sb ₄ S ₁₃ and Cu ₃ SbS ₄ Nanocrystals: Synthesis, Characterization, and Photoelectrochemistry van Embden, Joel; Latham, Kay; Duffy, Noel W. Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja402702x	journal	July 2013
Semiconductor Nanocrystals Functionalized with Antimony Telluride Zintl Ions for Nanostructured Thermoelectrics Kovalenko, Maksym V.; Spokoyny, Boris; Lee, Jong-Soo Journal of the American Chemical Society, Vol. 132, Issue 19 https://doi.org/10.1021/ja909591x	journal	May 2010
PbS/PbSe Hollow Spheres: Solvothermal Synthesis, Growth Mechanism, and Thermoelectric Transport Property Jin, Rencheng; Chen, Gang; Pei, Jian The Journal of Physical Chemistry C, Vol. 116, Issue 30 https://doi.org/10.1021/jp302206q	journal	July 2012
Synthesis and Characterization of Telluride Aerogels: Effect of Gelation on Thermoelectric Performance of Bi ₂ Te ₃ and Bi _{2– x} Sb _x Te ₃ Nanostructures Ganguly, Shreyashi; Zhou, Chen; Morelli, Donald The Journal of Physical Chemistry C, Vol. 116, Issue 33 https://doi.org/10.1021/jp3055608	journal	August 2012
Flexible Nanocrystal-Coated Glass Fibers for High-Performance Thermoelectric Energy Harvesting Liang, Daxin; Yang, Haoran; Finefrock, Scott W. Nano Letters, Vol. 12, Issue 4 https://doi.org/10.1021/nl300524j	journal	January 2012
The Effects of the Size and the Doping Concentration on the Power Factor of n-type Lead Telluride Nanocrystals for Thermoelectric Energy Conversion Fang, Haiyu; Luo, Zhiqiang; Yang, Haoran Nano Letters, Vol. 14, Issue 3, p. 1153-1157 https://doi.org/10.1021/nl403677k	journal	February 2014
Thermoelectric Properties of Lead Chalcogenide Core–Shell Nanostructures Scheele, Marcus; Oeschler, Niels; Veremchuk, Igor ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn2017183	journal	October 2011
Core–Shell Nanoparticles As Building Blocks for the Bottom-Up Production of Functional Nanocomposites: PbTe–PbS Thermoelectric Properties Ibáñez, Maria; Zamani, Reza; Gorsse, Stéphane ACS Nano, Vol. 7, Issue 3 https://doi.org/10.1021/nn305971v	journal	March 2013
Synergism in binary nanocrystal superlattices leads to enhanced p-type conductivity in self-assembled PbTe/Ag₂Te thin films Urban, Jeffrey J.; Talapin, Dmitri V.; Shevchenko, Elena V. Nature Materials, Vol. 6, Issue 2, p. 115-121 https://doi.org/10.1038/nmat1826	journal	January 2007
A new class of doped nanobulk high-figure-of-merit thermoelectrics by scalable bottom-up assembly Mehta, Rutvik J.; Zhang, Yanliang; Karthik, Chinnathambi Nature Materials, Vol. 11, Issue 3 https://doi.org/10.1038/nmat3213	journal	January 2012
Lone pair electrons minimize lattice thermal conductivity Nielsen, Michele D.; Ozolins, Vidvuds; Heremans, Joseph P. Energy Environ. Sci., Vol. 6, Issue 2 https://doi.org/10.1039/C2EE23391F	journal	January 2013
Thermoelectric properties of a Mn substituted synthetic tetrahedrite Chetty, Raju; D. S., Prem Kumar; Rogl, Gerda Physical Chemistry Chemical Physics, Vol. 17, Issue 3 https://doi.org/10.1039/C4CP04039B	journal	January 2015
From crystal to glass-like thermal conductivity in crystalline minerals Bouyrie, Y.; Candolfi, C.; Pailhès, S. Physical Chemistry Chemical Physics, Vol. 17, Issue 30 https://doi.org/10.1039/C5CP02900G	journal	January 2015
Rapid direct conversion of Cu _2−x Se to CuAgSe nanoplatelets via ion exchange reactions at room temperature Moroz, N. A.; Olvera, A.; Willis, G. M. Nanoscale, Vol. 7, Issue 21 https://doi.org/10.1039/C5NR01451D	journal	January 2015
Selective synthesis and characterization of famatinite nanofibers and tetrahedrite nanoflakes An, Changhua; Jin, Ying; Tang, Kaibin Journal of Materials Chemistry, Vol. 13, Issue 2 https://doi.org/10.1039/b210703a	journal	January 2003
Natural mineral tetrahedrite as a direct source of thermoelectric materials Lu, Xu; Morelli, Donald T. Physical Chemistry Chemical Physics, Vol. 15, Issue 16 https://doi.org/10.1039/c3cp50920f	journal	January 2013
Preparation of sintered degenerate n -type PbTe with a small grain size and its thermoelectric properties Kishimoto, Kengo; Koyanagi, Tsuyoshi Journal of Applied Physics, Vol. 92, Issue 5 https://doi.org/10.1063/1.1499206	journal	September 2002
Systematic study of electronic and magnetic properties for Cu _12– _x TM _x Sb ₄ S ₁₃ (TM = Mn, Fe, Co, Ni, and Zn) tetrahedrite Suekuni, K.; Tomizawa, Y.; Ozaki, T. Journal of Applied Physics, Vol. 115, Issue 14 https://doi.org/10.1063/1.4871265	journal	April 2014
Low-temperature heat capacity and localized vibrational modes in natural and synthetic tetrahedrites Lara-Curzio, E.; May, A. F.; Delaire, O. Journal of Applied Physics, Vol. 115, Issue 19 https://doi.org/10.1063/1.4878676	journal	May 2014
Bonding relationships in some ternary and quarternary phosphide and tetrahedrite structures: (Ag ₆ M ₄ P ₁₂ )M ₆ ', Cu _12+x Sb ₄ S ₁₃ and Cu _14-x Sb ₄ S ₁₃ , Ln ₆ Ni ₆ P ₁₇ Bullett, D. W.; Dawson, W. G. Journal of Physics C: Solid State Physics, Vol. 19, Issue 29 https://doi.org/10.1088/0022-3719/19/29/008	journal	October 1986
Low thermal conductivity and improved figure of merit in fine-grained binary PbTe thermoelectric alloys Cao, Y. Q.; Zhu, T. J.; Zhao, X. B. Journal of Physics D: Applied Physics, Vol. 42, Issue 1 https://doi.org/10.1088/0022-3727/42/1/015406	journal	December 2008
Thermopower enhancement in lead telluride nanostructures Heremans, Joseph P.; Thrush, Christopher M.; Morelli, Donald T. Physical Review B, Vol. 70, Issue 11 https://doi.org/10.1103/PhysRevB.70.115334	journal	September 2004
Thermoelectric properties of p -type CuInSe 2 chalcopyrites enhanced by introduction of manganese Yao, Jinlei; Takas, Nathan J.; Schliefert, Megan L. Physical Review B, Vol. 84, Issue 7 https://doi.org/10.1103/PhysRevB.84.075203	journal	August 2011
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors Talapin, D. V. Science, Vol. 310, Issue 5745, p. 86-89 https://doi.org/10.1126/science.1116703	journal	October 2005
Recent Developments in Semiconductor Thermoelectric Physics and Materials Shakouri, Ali Annual Review of Materials Research, Vol. 41, Issue 1 https://doi.org/10.1146/annurev-matsci-062910-100445	journal	August 2011
Characterization of Hydrophobic Forces for in Liquid Self-Assembly of Micron-Sized Functional Building Blocks Gullo, M. R.; Jacot-Descombes, L.; Aeschimann, L. MRS Proceedings, Vol. 1299 https://doi.org/10.1557/opl.2011.466	journal	January 2011

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