Structural and thermodynamic similarities of phases in the Li–Tt (Tt = Si, Ge) systems: Redetermination of the lithium-rich side of the Li–Ge phase diagram and crystal structures of LiSiGe for x = 2.3, 3.1, 3.5, and 4 as well as LiGe
Journal of the Chemical Society. Dalton Transactions, ISSN: 1477-9226, Vol: 43, Issue: 40, Page: 14959-14970
2014
- 28Citations
- 25Captures
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Article Description
A reinvestigation of the lithium-rich section of the Li–Ge phase diagram reveals the existence of two new phases, LiGe and LiGe (LiGe). Their structures are determined by X-ray diffraction experiments of large single crystals obtained from equilibrated melts with compositions LiGe and LiGe. Excess melt is subsequently removed through isothermal centrifugation at 400 °C and 530 °C, respectively. LiGe crystallizes in the space group F4 3m (a = 18.8521(3) Å, V = 6700.1(2) Å, Z = 20, T = 298 K) and LiGe (LiGe) in Cmcm (a = 4.5511(2) Å, b = 22.0862(7) Å, c = 13.2751(4) Å, V = 1334.37(8) Å, Z = 16, T = 123 K). Both phases are isotypic with their Si counterparts and are further representative of the LiPb and LiSi structure types. Additionally, the solid solutions LiSiGe follows Vegard's law. A comparison of the GeLi coordination polyhedra shows that isolated Ge atoms are 13- and 14-coordinated in LiGe, whereas in LiGe the Ge atoms possess coordination numbers 12 and 13. Regarding the thermodynamic stability, LiGe is assigned a high-temperature phase existing between ∼400 °C and 627 °C, whereas LiGe decomposes peritectically at 520–522 °C. Additionally, the decomposition of LiGe below ∼400 °C was found to be very sluggish. These findings are manifested by differential scanning calorimetry, long-term annealing experiments and the results from melt equilibration experiments. Interestingly, the thermodynamic properties of the lithium-rich tetrelides LiTt and LiTt (LiTt) are very similar (Tt = Si, Ge). Besides LiTt, LiTt, LiTt, and LiTt, the title compounds are further examples of isotypic tetrelides in the systems Li–Tt. © 2014 the Partner Organisations.
Bibliographic Details
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=84907921088&origin=inward; http://dx.doi.org/10.1039/c4dt00743c; http://www.ncbi.nlm.nih.gov/pubmed/24901027; http://xlink.rsc.org/?DOI=C4DT00743C; http://pubs.rsc.org/en/content/articlepdf/2014/DT/C4DT00743C; https://xlink.rsc.org/?DOI=C4DT00743C; https://dx.doi.org/10.1039/c4dt00743c; https://pubs.rsc.org/en/content/articlelanding/2014/dt/c4dt00743c
Royal Society of Chemistry (RSC)
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