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Title: Energy factors governing the partial irreversibility of lithium intercalation in layered trichalcogenides MX sub 3 (M = Ti, Zr, Hf; X = S, Se) and the structural changes in the intercalated species Li sub 3 MX sub 3

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00314a035· OSTI ID:7031111
; ;  [1];  [2]
  1. Universite de Paris, Orsay (France)
  2. North Carolina State Univ., Raleigh (USA)

The two-step mechanism proposed to explain the results of electrochemical intercalation of layered trichalcogenides MX{sub 3} (M = Ti, Zr, Hf; X = S, Se) cannot explain the results of chemical intercalation. Thus, we propose a one-step mechanism for chemical intercalation in which each metal of MX{sub 3} is affected by three lithium atoms at a time and analyze the merits of the one- and two-step mechanisms. State correlation diagrams show that the one- and two-step mechanisms are symmetry-allowed and symmetry-forbidden, respectively. This conclusion is supported by tight-binding band electronic structure calculations on the model ZrS{sub 5} chain. The cell parameter changes from a, b, and c in MX{sub 3} to approximately 2a + 1, b, and c + 0.3 in Li{sub 3}MX{sub 3} are explained by considering how the X-X bond breaking affects the interchain X...X and M...X interactions. 21 refs., 7 figs.

OSTI ID:
7031111
Journal Information:
Inorganic Chemistry; (USA), Vol. 28:15; ISSN 0020-1669
Country of Publication:
United States
Language:
English