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The Sn rich ternary intermetallic compounds Li 3 Cu 6 Sn 4  (CSD-427097) and Li 2 CuSn 2  (CSD-427098) were synthesized from the pure elements by induction melting and annealing at 400°C. Structural investigations were performed by powder- and single-crystal XRD. Li 3 Cu 6 Sn 4  crystallizes in space group  P 6/ mmm ; it is structurally related to but not isotypic with MgFe 6 Ge 6  ( a  = 5.095(2) Å,  c  = 9.524(3) Å;  w R 2  = 0.059; 239 unique F 2 -values, 17 free variables). Li 3 Cu 6 Sn 4  is characterized by two sites with a mixed Cu:Sn occupation. In contrast to all other Cu-Li-Sn compounds known so far, any mixed occupation was found for Cu-Li pairs only. In addition, one Li site is only half occupied. The second Sn rich phase is Li 2 CuSn 2  (space group  I 4 1 / amd ,  a  = 4.4281(15) Å,  c  = 19.416(4) Å;  w R 2  = 0.033; 213 unique F 2 -values, 12 atom free variables); it is the only phase in the Cu-Li-Sn system which is noted for full ordering. Both crystal structures exhibit 3D-networks which host Li atoms in channels. They are important for understanding the lithiation mechanism in Cu-Sn electrodes for Li-ion batteries.

The tin-rich copper lithium stannides: Li 3 Cu 6 Sn 4 and Li 2 CuSn 2