Clathrate XI K 58 Zn 122 Sb 207 : A New Branch on the Clathrate Family Tree

Cox, Tori; Gvozdetskyi, Volodymyr; Bertolami, Mark; Lee, Shannon; Shipley, Kristian; Lebedev, Oleg I.; Zaikina, Julia V.

doi:10.1002/ange.202011120

Title: Clathrate XI K ₅₈ Zn ₁₂₂ Sb ₂₀₇ : A New Branch on the Clathrate Family Tree

Journal Article · 29 October 2020 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202011120 · OSTI ID:1691552

Cox, Tori ^[1];

^[1]; Bertolami, Mark ^[1]; Lee, Shannon ^[2]; Shipley, Kristian ^[1]; Lebedev, Oleg I. ^[3];

^[1]

Department of Chemistry Iowa State University Ames Iowa 50011 USA
Department of Chemistry Iowa State University Ames Iowa 50011 USA, Ames Laboratory US DOE Iowa State University Ames Iowa 50011 USA
Laboratoire CRISMAT ENSICAEN CNRS UMR 6508 14050 Caen France

Abstract The compositional screening of K‐Zn‐Sb ternary system aided by machine learning, rapid exploratory synthesis using KH salt‐like precursor and in situ powder X‐ray diffraction yielded a novel clathrate type XI K ₅₈ Zn ₁₂₂ Sb ₂₀₇ . This clathrate consists of a 3D Zn‐Sb framework hosting K ⁺ ions inside polyhedral cages, some of which are reminiscent of known clathrate types while others are unique to this structure type. The complex non‐centrosymmetric structure in the tetragonal space group was solved by means of single crystal X‐ray diffraction as a 6‐component twin due to pseudocubic symmetry and further confirmed by high‐resolution synchrotron powder X‐ray diffraction and state‐of‐the‐art scanning transmission electron microscopy. The electron‐precise composition of this clathrate yields narrow‐gap p ‐type semiconductor with extraordinarily low thermal conductivity due to displacement or “rattling” of K cations inside oversized cages and as well as to twinning, stacking faults and antiphase boundary defects.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1691552

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 1 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (51)

B1-Mobilstor: Materials for Sustainable Energy Storage Techniques - Lithium Containing Compounds for Hydrogen and Electrochemical Energy Storage: B1-Mobilstor: Materials for Sustainable Energy Storage Techniques Böhme, Bodo; Bonatto Minella, Christian; Thoss, Franziska Advanced Engineering Materials, Vol. 16, Issue 10 https://doi.org/10.1002/adem.201400182	journal	June 2014
K7B7Si39, ein Borosilicid mit Clathrat-I-Struktur Jung, Walter; Lörincz, Josef; Ramlau, Reiner Angewandte Chemie, Vol. 119, Issue 35 https://doi.org/10.1002/ange.200701028	journal	September 2007
The Antimony-Based Type I Clathrate Compounds Cs8Cd18Sb28 and Cs8Zn18Sb28 Liu, Yi; Wu, Li-Ming; Li, Long-Hua Angewandte Chemie, Vol. 121, Issue 29 https://doi.org/10.1002/ange.200806158	journal	June 2009
Extension of the Clathrate Family: The Type X Clathrate Ge ₇₉ P ₂₉ S ₁₈ Te ₆ Kirsanova, Maria A.; Olenev, Andrei V.; Abakumov, Artem M. Angewandte Chemie, Vol. 123, Issue 10 https://doi.org/10.1002/ange.201007483	journal	January 2011
Denken wie ein Chemiker: Thermoelektrika intuitiv Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M. Angewandte Chemie, Vol. 128, Issue 24 https://doi.org/10.1002/ange.201508381	journal	April 2016
Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba ₈ M ₂₄ P _{28+ δ} ( M =Cu/Zn) Dolyniuk, Juli-Anna; Zaikina, Julia V.; Kaseman, Derrick C. Angewandte Chemie, Vol. 129, Issue 9 https://doi.org/10.1002/ange.201611510	journal	January 2017
Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs Gvozdetskyi, Volodymyr; Bhaskar, Gourab; Batuk, Maria Angewandte Chemie, Vol. 131, Issue 44 https://doi.org/10.1002/ange.201907499	journal	September 2019
K7B7Si39, a Borosilicide with the Clathrate I Structure Jung, Walter; Lörincz, Josef; Ramlau, Reiner Angewandte Chemie International Edition, Vol. 46, Issue 35 https://doi.org/10.1002/anie.200701028	journal	September 2007
The Antimony-Based Type I Clathrate Compounds Cs8Cd18Sb28 and Cs8Zn18Sb28 Liu, Yi; Wu, Li-Ming; Li, Long-Hua Angewandte Chemie International Edition, Vol. 48, Issue 29 https://doi.org/10.1002/anie.200806158	journal	June 2009
Extension of the Clathrate Family: The Type X Clathrate Ge ₇₉ P ₂₉ S ₁₈ Te ₆ Kirsanova, Maria A.; Olenev, Andrei V.; Abakumov, Artem M. Angewandte Chemie International Edition, Vol. 50, Issue 10 https://doi.org/10.1002/anie.201007483	journal	January 2011
Thinking Like a Chemist: Intuition in Thermoelectric Materials Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M. Angewandte Chemie International Edition, Vol. 55, Issue 24 https://doi.org/10.1002/anie.201508381	journal	April 2016
Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba ₈ M ₂₄ P _{28+ δ} ( M =Cu/Zn) Dolyniuk, Juli-Anna; Zaikina, Julia V.; Kaseman, Derrick C. Angewandte Chemie International Edition, Vol. 56, Issue 9 https://doi.org/10.1002/anie.201611510	journal	January 2017
Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs Gvozdetskyi, Volodymyr; Bhaskar, Gourab; Batuk, Maria Angewandte Chemie International Edition, Vol. 58, Issue 44 https://doi.org/10.1002/anie.201907499	journal	September 2019
A Hydride Route to Ternary Alkali Metal Borides: A Case Study of Lithium Nickel Borides Gvozdetskyi, Volodymyr; Hanrahan, Michael P.; Ribeiro, Raquel A. Chemistry – A European Journal, Vol. 25, Issue 16 https://doi.org/10.1002/chem.201805398	journal	February 2019
Ba8Cu16P30 - eine neue tern�re Variante des Clathrat I-Strukturtyps D�nner, J.; Mewis, A. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 621, Issue 2 https://doi.org/10.1002/zaac.19956210205	journal	February 1995
Zintl Phases: Principles and Recent Developments Fässler, Thomas F. Structure and Bonding https://doi.org/10.1007/978-3-642-21150-8	book	June 2011
Estimation of the thermal band gap of a semiconductor from seebeck measurements Goldsmid, H. J.; Sharp, J. W. Journal of Electronic Materials, Vol. 28, Issue 7 https://doi.org/10.1007/s11664-999-0211-y	journal	July 1999
The Smaller the Better: Hosting Trivalent Rare-Earth Guests in Cu–P Clathrate Cages Wang, Jian; He, Yuping; Mordvinova, Natalia E. Chem, Vol. 4, Issue 6 https://doi.org/10.1016/j.chempr.2018.04.001	journal	June 2018
Clathrate thermoelectrics Dolyniuk, Juli-Anna; Owens-Baird, Bryan; Wang, Jian Materials Science and Engineering: R: Reports, Vol. 108 https://doi.org/10.1016/j.mser.2016.08.001	journal	October 2016
Unconventional Clathrates with Transition Metal–Phosphorus Frameworks Wang, Jian; Dolyniuk, Juli-Anna; Kovnir, Kirill Accounts of Chemical Research, Vol. 51, Issue 1 https://doi.org/10.1021/acs.accounts.7b00469	journal	December 2017
Twisted Kelvin Cells and Truncated Octahedral Cages in the Crystal Structures of Unconventional Clathrates, AM ₂ P ₄ (A = Sr, Ba; M = Cu, Ni) Dolyniuk, Juli-Anna; Wang, Jian; Lee, Kathleen Chemistry of Materials, Vol. 27, Issue 12 https://doi.org/10.1021/acs.chemmater.5b01592	journal	June 2015
Tuning Thermoelectric Properties of Type I Clathrate K _{8– x} Ba _x Al _{8+ x} Si _{38– x} through Barium Substitution Sui, Fan; Kauzlarich, Susan M. Chemistry of Materials, Vol. 28, Issue 9 https://doi.org/10.1021/acs.chemmater.6b00566	journal	April 2016
Rapid Phase Screening via Hydride Route: A Discovery of K _{8– x} Zn _{18+3 x} Sb ₁₆ Cox, Tori; Gvozdetskyi, Volodymyr; Owens-Baird, Bryan Chemistry of Materials, Vol. 30, Issue 23 https://doi.org/10.1021/acs.chemmater.8b04211	journal	November 2018
Synthesis, Structure, and Electrical Properties of the Single Crystal Ba ₈ Cu ₁₆ As ₃₀ Wei, Kaya; Khabibullin, Artem R.; Hobbis, Dean Inorganic Chemistry, Vol. 57, Issue 15 https://doi.org/10.1021/acs.inorgchem.8b01314	journal	July 2018
Hydride Synthesis and Thermoelectric Properties of Type-I Clathrate K ₈ E ₈ Ge ₃₈ (E = Al, Ga, In) Perez, Christopher J.; Bates, Victor J.; Kauzlarich, Susan M. Inorganic Chemistry, Vol. 58, Issue 2 https://doi.org/10.1021/acs.inorgchem.8b02977	journal	December 2018
Anodes for Lithium-Ion Batteries Based on Type I Silicon Clathrate Ba ₈ Al ₁₆ Si ₃₀ - Role of Processing on Surface Properties and Electrochemical Behavior Zhao, Ran; Bobev, Svilen; Krishna, Lakshmi ACS Applied Materials & Interfaces, Vol. 9, Issue 47 https://doi.org/10.1021/acsami.7b12810	journal	November 2017
Synthesis, Structural Characterization, and Physical Properties of the Type-I Clathrates A ₈ Zn ₁₈ As ₂₈ ( A = K, Rb, Cs) and Cs ₈ Cd ₁₈ As ₂₈ He, Hua; Zevalkink, Alex; Gibbs, Zachary M. Chemistry of Materials, Vol. 24, Issue 18 https://doi.org/10.1021/cm3020226	journal	September 2012
High-Pressure Synthesis of a New Silicon Clathrate Superconductor, Ba ₈ Si ₄₆ Yamanaka, Shoji; Enishi, Eiji; Fukuoka, Hiroshi Inorganic Chemistry, Vol. 39, Issue 1 https://doi.org/10.1021/ic990778p	journal	January 2000
Clathrate Ba ₈ Au ₁₆ P ₃₀ : The “Gold Standard” for Lattice Thermal Conductivity Fulmer, James; Lebedev, Oleg I.; Roddatis, Vladimir V. Journal of the American Chemical Society, Vol. 135, Issue 33 https://doi.org/10.1021/ja4052679	journal	August 2013
Facile Synthesis of Ba _{1– x} K _x Fe ₂ As ₂ Superconductors via Hydride Route Zaikina, Julia V.; Batuk, Maria; Abakumov, Artem M. Journal of the American Chemical Society, Vol. 136, Issue 48 https://doi.org/10.1021/ja509907r	journal	November 2014
Disentangling Structural Confusion through Machine Learning: Structure Prediction and Polymorphism of Equiatomic Ternary Phases ABC Oliynyk, Anton O.; Adutwum, Lawrence A.; Rudyk, Brent W. Journal of the American Chemical Society, Vol. 139, Issue 49 https://doi.org/10.1021/jacs.7b08460	journal	November 2017
Crystal Structure Prediction via Deep Learning Ryan, Kevin; Lengyel, Jeff; Shatruk, Michael Journal of the American Chemical Society, Vol. 140, Issue 32 https://doi.org/10.1021/jacs.8b03913	journal	June 2018
III–V Clathrate Semiconductors with Outstanding Hole Mobility: Cs ₈ In ₂₇ Sb ₁₉ and A ₈ Ga ₂₇ Sb ₁₉ ( A = Cs, Rb) Owens-Baird, Bryan; Wang, Jian; Wang, Suyin Grass Journal of the American Chemical Society, Vol. 142, Issue 4 https://doi.org/10.1021/jacs.9b12351	journal	December 2019
Prediction and accelerated laboratory discovery of previously unknown 18-electron ABX compounds Gautier, Romain; Zhang, Xiuwen; Hu, Linhua Nature Chemistry, Vol. 7, Issue 4 https://doi.org/10.1038/nchem.2207	journal	March 2015
Predicting crystal structure by merging data mining with quantum mechanics Fischer, Christopher C.; Tibbetts, Kevin J.; Morgan, Dane Nature Materials, Vol. 5, Issue 8 https://doi.org/10.1038/nmat1691	journal	July 2006
The high-throughput highway to computational materials design Curtarolo, Stefano; Hart, Gus L. W.; Nardelli, Marco Buongiorno Nature Materials, Vol. 12, Issue 3 https://doi.org/10.1038/nmat3568	journal	February 2013
Thermopower enhancement by encapsulating cerium in clathrate cages Prokofiev, A.; Sidorenko, A.; Hradil, K. Nature Materials, Vol. 12, Issue 12 https://doi.org/10.1038/nmat3756	journal	September 2013
ElemNet: Deep Learning the Chemistry of Materials From Only Elemental Composition Jha, Dipendra; Ward, Logan; Paul, Arindam Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-35934-y	journal	December 2018
Si-based Earth abundant clathrates for solar energy conversion He, Yuping; Sui, Fan; Kauzlarich, Susan M. Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00256C	journal	January 2014
Computer-aided design of metal chalcohalide semiconductors: from chemical composition to crystal structure Davies, Daniel W.; Butler, Keith T.; Skelton, Jonathan M. Chemical Science, Vol. 9, Issue 4 https://doi.org/10.1039/C7SC03961A	journal	January 2018
A versatile low temperature synthetic route to Zintl phase precursors: Na₄Si₄, Na₄Ge₄ and K₄Ge₄ as examples Ma, Xuchu; Xu, Fen; Atkins, Tonya M. Dalton Transactions, Vol. 0, Issue 46, p. 10250-10255 https://doi.org/10.1039/b913320h	journal	January 2009
“Glass-like” thermal conductivity gradually induced in thermoelectric Sr ₈ Ga ₁₆ Ge ₃₀ clathrate by off-centered guest atoms Christensen, Sebastian; Schmøkel, Mette Stokkebro; Borup, Kasper Andersen Journal of Applied Physics, Vol. 119, Issue 18 https://doi.org/10.1063/1.4948334	journal	May 2016
Structural, magnetic, thermal, and transport properties of X 8 Ga 16 Ge 30 ( X = E u , S r , Ba ) single crystals Sales, B. C.; Chakoumakos, B. C.; Jin, R. Physical Review B, Vol. 63, Issue 24 https://doi.org/10.1103/PhysRevB.63.245113	journal	June 2001
Structural, transport, magnetic, and thermal properties of Eu 8 Ga 16 Ge 30 Paschen, S.; Carrillo-Cabrera, W.; Bentien, A. Physical Review B, Vol. 64, Issue 21 https://doi.org/10.1103/PhysRevB.64.214404	journal	November 2001
Combinatorial screening for new materials in unconstrained composition space with machine learning Meredig, B.; Agrawal, A.; Kirklin, S. Physical Review B, Vol. 89, Issue 9 https://doi.org/10.1103/PhysRevB.89.094104	journal	March 2014
Glasslike Heat Conduction in High-Mobility Crystalline Semiconductors Cohn, J. L.; Nolas, G. S.; Fessatidis, V. Physical Review Letters, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevLett.82.779	journal	January 1999
Synthesis of Group IV Clathrates for Photovoltaics Martinez, Aaron D.; Krishna, Lakshmi; Baranowski, Lauryn L. IEEE Journal of Photovoltaics, Vol. 3, Issue 4 https://doi.org/10.1109/JPHOTOV.2013.2276478	journal	October 2013
Notizen: Eine Käfigstruktur als gemeinsames Bauprinzip der Verbindungen K8E46 (E = Si, Ge, Sn) Gallmeier, J.; Schäfer, Herbert; Weiss, Armin Zeitschrift für Naturforschung B, Vol. 24, Issue 6 https://doi.org/10.1515/znb-1969-0603	journal	June 1969
Notizen: Elektrovalente temarnäre Phasen des Natriums bzw. Kaliums mit 2 B- und 5 B-Elementen / Ternary Phases of Sodium or Potassium with Elements of the 2 b- and 5 b-Group Kahlert, Holger; Schuster, Hans-Uwe Zeitschrift für Naturforschung B, Vol. 31, Issue 11 https://doi.org/10.1515/znb-1976-1122	journal	November 1976
Ternäre Pnictide und Chalkogenide von Alkalimetallen und IB-bzw. IIB-Elementen / On Ternary Pnictides and Chalkogenides of Alkaline Metals and IB-resp. II B-Elements Savelsberg, Gerhard Zeitschrift für Naturforschung B, Vol. 33, Issue 4 https://doi.org/10.1515/znb-1978-0404	journal	April 1978
Thermal Stability and Thermoelectric Properties of NaZnSb Gvozdetskyi, Volodymyr; Owens-Baird, Bryan; Hong, Sangki Materials, Vol. 12, Issue 1 https://doi.org/10.3390/ma12010048	journal	December 2018

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