Lithium metal atoms fill vacancies in the germanium network of a type-I clathrate: synthesis and structural characterization of Ba8Li5Ge41

被引:9
作者
Ghosh, Kowsik [1 ]
Ovchinnikov, Alexander [1 ,2 ]
Baitinger, Michael [3 ]
Krnel, Mitja [3 ]
Burkhardt, Ulrich [3 ]
Grin, Yuri [3 ]
Bobev, Svilen [1 ]
机构
[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
[2] Tech Univ Dresden, Fac Chem & Food Chem, D-01062 Dresden, Germany
[3] Max Plank Inst Chem Phys Fester Stoffe, D-01187 Dresden, Germany
基金
美国国家科学基金会;
关键词
ELECTRON LOCALIZATION FUNCTION; THERMOELECTRIC PROPERTIES; CRYSTAL-STRUCTURE; BAND-STRUCTURE; SPACE REPRESENTATION; ANODE MATERIALS; N-TYPE; SILICON; SUPERCONDUCTIVITY; LOCALIZABILITY;
D O I
10.1039/d3dt01168b
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Clathrate phases with crystal structures exhibiting complex disorder have been the subject of many prior studies. Here we report syntheses, crystal and electronic structure, and chemical bonding analysis of a Li-substituted Ge-based clathrate phase with the refined chemical formula Ba8Li5.0(1)Ge41.0, which is a rare example of ternary clathrate-I where alkali metal atoms substitute framework Ge atoms. Two different synthesis methods to grow single crystals of the new clathrate phase are presented, in addition to the classical approach towards polycrystalline materials by combining pure elements in desired stoichiometric ratios. Structure elucidations for samples from different batches were carried out by single-crystal and powder X-ray diffraction methods. The ternary Ba8Li5.0(1)Ge41.0 phase crystallizes in the cubic type-I clathrate structure (space group Pm3n no. 223, a approximate to 10.80 angstrom), with the unit cell being substantially larger compared to the binary phase Ba8Ge43 (Ba83Ge43, a approximate to 10.63 angstrom). The expansion of the unit cell is the result of the Li atoms filling vacancies and substituting atoms in the Ge framework, with Li and Ge co-occupying one crystallographic (6c) site. As such, the Li atoms are situated in four-fold coordination environment surrounded by equidistant Ge atoms. Analysis of chemical bonding applying the electron density/electron localizability approach reveals ionic interaction of barium with the Li-Ge framework, while the lithium-germanium bonds are strongly polar covalent.
引用
收藏
页码:10310 / 10322
页数:14
相关论文
共 80 条
  • [51] Atomic ordering and thermoelectric properties of the n-type clathrate Ba8Ni3.5Ge42.1□0.4
    Nguyen, L. T. K.
    Aydemir, U.
    Baitinger, M.
    Bauer, E.
    Borrmann, H.
    Burkhardt, U.
    Custers, J.
    Haghighirad, A.
    Hoefler, R.
    Luther, K. D.
    Ritter, F.
    Assmus, W.
    Grin, Yu.
    Paschen, S.
    [J]. DALTON TRANSACTIONS, 2010, 39 (04) : 1071 - 1077
  • [52] NOLAS GS, 2001, CHAPTER 6 SEMICONDUC, V69, DOI DOI 10.1016/S0080-8784(01)80152-6
  • [53] Electron localization function in full-potential representation for crystalline materials
    Ormeci, A
    Rosner, H
    Wagner, FR
    Kohout, M
    Grin, Y
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (03) : 1100 - 1105
  • [54] Ormeci A., 2015, J THERMOELECTR, P16
  • [55] Pauling L., 1960, NATURE CHEM BOND, DOI [10.1002/jps.3030300111, DOI 10.1002/JPS.3030300111]
  • [56] First-Principles Study of Lithiation of Type I Ba-Doped Silicon Clathrates
    Peng, Xihong
    Wei, Qun
    Li, Ying
    Chan, Candace K.
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2015, 119 (51) : 28247 - 28257
  • [57] Accurate and simple analytic representation of the electron-gas correlation energy (vol 45, 13244, 1992)
    Perdew, John P.
    Wang, Yue
    [J]. PHYSICAL REVIEW B, 2018, 98 (07)
  • [58] A quantitative measure of bond polarity from the electron localization function and the theory of atoms in molecules
    Raub, S
    Jansen, G
    [J]. THEORETICAL CHEMISTRY ACCOUNTS, 2001, 106 (03) : 223 - 232
  • [59] Reny E, 2002, PHYS REV B, V66, DOI 10.1103/PhysRevB.66.014532
  • [60] Large thermoelectric figure of merit at high temperature in Czochralski-grown clathrate Ba8Ga16Ge30 -: art. no. 023708
    Saramat, A
    Svensson, G
    Palmqvist, AEC
    Stiewe, C
    Mueller, E
    Platzek, D
    Williams, SGK
    Rowe, DM
    Bryan, JD
    Stucky, GD
    [J]. JOURNAL OF APPLIED PHYSICS, 2006, 99 (02)