Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks

Dolyniuk, Juli -Anna; Wang, Jian; Marple, Maxwell A. T.; Sen, Sabyasachi; Cheng, Yongqiang; Ramirez-Cuesta, Anibal J.; Kovnir, Kirill

doi:10.1021/acs.chemmater.8b00966

Title: Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks

Journal Article · Wed Apr 18 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b00966· OSTI ID:1474850

Dolyniuk, Juli -Anna ^[1];

^[2]; Marple, Maxwell A. T. ^[1];

^[1];

^[3];

^[2]

Univ. of California, Davis, CA (United States)
Ames Lab. and Iowa State Univ., Ames, IA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here quaternary clathrate-I phases with an overall composition of Ba₈M_16+yP_30-y (M = Cu,Zn) exhibit complex structural chemistry. Characterization of the electronic structures and chemical bonding using quantum-chemical calculations and ³¹P solid state NMR spectroscopy demonstrated that the Cu–Zn–P framework is flexible and able to accommodate up to six Zn atoms per formula unit via bonding rearrangements, such as partial Zn/P substitution and the formation of Cu–Zn bonds. Such perturbations of the framework’s bonding affect the thermal and charge transport properties. The overall thermoelectric figure-of-merit, ZT, of Ba₈Cu₁₄Zn₂P₃₀ is 0.62 at 800 K, which is 9 times higher than the thermoelectric performance of the ternary parent phase Ba₈Cu₁₆P₃₀. Through a combination of inelastic neutron scattering and single crystal X-ray diffraction experiments at 10 K, low-energy rattling of the Ba guest atoms inside the large tetrakaidecahedral cages are shown to be the reason for the low thermal conductivities observed for the studied clathrates.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1474850

Journal Information:: Chemistry of Materials, Vol. 30, Issue 10; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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