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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 no. 223, a  10.80 Å), with the unit cell being substantially larger compared to the binary phase Ba8Ge43 (Ba8□3Ge43, a  10.63 Å). 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. 

A ternary derivative of Li 3 Bi with the composition Li 3– x – y In x Bi ( x  ≃ 0.14, y  ≃ 0.29) was produced by a mixed In+Bi flux approach. The crystal structure adopts the space group Fd \overline{3} m (No. 227), with a = 13.337 (4) Å, and can be viewed as a 2 × 2 × 2 superstructure of the parent Li 3 Bi phase, resulting from a partial ordering of Li and In in the tetrahedral voids of the Bi fcc packing. In addition to the Li/In substitutional disorder, partial occupation of some Li sites is observed. The Li deficiency develops to reduce the total electron count in the system, counteracting thereby the electron doping introduced by the In substitution. First-principles calculations confirm the electronic rationale of the observed disorder. 

Four novel ternary phases have been prepared in the system Ca–Li–Sn using both the metal flux method and conventional high-temperature synthesis. Each of the obtained compositions represents its own (new) structure type, and the structures feature distinct polyanionic Sn units. Ca 4 LiSn 6 (space group Pbcm , Pearson symbol oP 44) accommodates infinite chains, made up of cyclopentane-like [Sn 5 ]-rings, which are bridged by Sn atoms. The Sn atoms in this structure are two- and three-bonded. The anionic substructure of Ca 9 Li 6+x Sn 13–x ( x ≈ 0.28, space group C 2/ m , Pearson symbol mS 56) displays extensive mixing of Li and Sn and combination of single-bonded and hypervalent interactions between the Sn atoms. Hypervalent bonding is also pronounced in the structure of the third compound, Ca 2 LiSn 3 (space group Pmm 2, Pearson symbol oP 18) with quasi-two-dimensional polyanionic subunits and a variety of coordination environments of the Sn atoms. One-dimensional [Sn 10 ]-chains with an intricate topology of cis - and trans -Sn–Sn bonds exist in the structure of Ca 9–x Li 2 Sn 10 ( x ≈ 0.16, space group C 2/ m , Pearson symbol mS 42), and the Sn–Sn bonding in this case demonstrates the characteristics of an intermediate between single- and double- bond-order. The peculiarities of the bonding are discussed in the context of the Zintl approach, which captures the essence of the main chemical interactions. The electronic structures of all four compounds have also been analyzed in full detail using first-principles calculations. 

The crystal structure of the ternary germanide Li₂MnGe has been re‐evaluated from single‐crystal X‐ray diffraction data. This compound crystallizes in a non‐centrosymmetric superstructure of the ZrCuSiAs type (space groupP4bm, Pearson codetP16), with the lattice parametersa= 6.088(4) Å,c= 6.323(4) Å. First‐principle calculations for the idealized structure predict antiferromagnetic exchange in the square Mn nets and semimetallic ground state. In addition, a new ternary phase with the composition Li_2–xMn_4+xGe₅(x≈ 1.2) was discovered. It adopts the V₆Si₅structure type (space groupIbam, Pearson codeoI44), with the lattice parametersa= 7.570(2) Å,b= 16.323(3) Å,c= 5.057(1) Å. DSC/TG measurements show that this compound is thermally stable below 995 K. 

The guest‐free, type‐II Si clathrate (Si₁₃₆) is an open cage polymorph of Si with structural features amenable to electrochemical Li storage. However, the detailed mechanism for reversible Li insertion and migration within the vacant cages of Si₁₃₆is not established. Herein, X‐ray characterization and density functional theory (DFT) calculations are used to understand the structural origin of electrochemical Li insertion into the type‐II clathrate structure. At low Li content, instead of alloying with Si, topotactic Li insertion into the empty cages occurs at ≈0.3 V versus Li/Li⁺with a capacity of ≈231 mAh g⁻¹(corresponding to composition Li₃₂Si₁₃₆). A synchrotron powder X‐ray diffraction analysis of electrodes after lithiation shows evidence of Li occupation within the Si₂₀and Si₂₈cages and a volume expansion of 0.22%, which is corroborated by DFT calculations. Nudged elastic band calculations suggest a low barrier (0.2 eV) for Li migration through interconnected Si₂₈cages, whereas there is a higher barrier for Li migration into Si₂₀cages (2.0 eV). However, if Li is present in a neighboring cage, a cooperative migration pathway with a barrier of 0.65 eV is possible. The results show that the type‐II Si clathrate displays unique electrochemical properties for potential applications as Li‐ion battery anodes.