Thermodynamically stable lithium silicides and germanides from density functional theory calculations

被引:81
作者
Morris, Andrew J. [1 ]
Grey, C. P. [2 ]
Pickard, Chris J. [3 ]
机构
[1] Univ Cambridge, Cavendish Lab, Condensed Matter Theory Grp, Cambridge CB3 0HE, England
[2] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
[3] UCL, Dept Phys & Astron, London WC1E 6BT, England
基金
英国工程与自然科学研究理事会;
关键词
CRYSTAL-STRUCTURE; 1ST PRINCIPLES; ELECTRONIC-STRUCTURE; STRUCTURAL-CHANGES; HIGH-CAPACITY; AB-INITIO; SILICON; PHASE; LI; ANODES;
D O I
10.1103/PhysRevB.90.054111
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
High-throughput density functional theory (DFT) calculations have been performed on the Li-Si and Li-Ge systems. Lithiated Si and Ge, including their metastable phases, play an important technological role as Li-ion battery (LIB) anodes. The calculations comprise structural optimizations on crystal structures obtained by swapping atomic species to Li-Si and Li-Ge from the X-Y structures in the International Crystal Structure Database, where X = {Li, Na, K, Rb, Cs} and Y = {Si, Ge, Sn, Pb}. To complement this at various Li-Si and Li-Ge stoichiometries, ab initio random structure searching (AIRSS) was also performed. Between the groundstate stoichiometries, including the recently found Li17Si4 phase, the average voltages were calculated, indicating that germanium may be a safer alternative to silicon anodes in LIB due to its higher lithium insertion voltage. Calculations predict high-density Li1Si1 and Li1Ge1 P4/mmm layered phases which become the ground states above 2.5 and 5 GPa, respectively, and reveal silicon and germanium's propensity to form dumbbells in the LixSi, x = 2.33-3.25, stoichiometry range. DFT predicts the stability of the Li11Ge6 Cmmm, Li12Ge7 Pnma, and Li7Ge3 P32(1)2 phases and several new Li-Ge compounds, with stoichiometries Li5Ge2, Li13Ge5, Li8Ge3 and Li13Ge4.
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页数:9
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