New substituted copper titanates with the CaCu3Ti4O12 structure: Li[Cu3−xLix][Ti3−xMV1+x]O12 (MV = Nb: 0.12 ≤ x ≤ 0.33; MV = Ta: x = 0.33)

doi:10.1016/0022-4596(87)90200-3

Journal of Solid State Chemistry

Volume 66, Issue 2, February 1987, Pages 311-317

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Abstract

New substituted copper titanates with the CaCu₃Ti₄O₁₂ perovskite-like structure were synthesized and characterized. Their formula is Li|Cu_3−xLi_x| |Ti_3−xM^V_1+x|O₁₂. There is a homogeneity range for M^V = Nb, 0.12 ≤ x ≤ 0.33, and a unique composition for M^V = Ta, x = 0.33. The unit cell is cubic: a ∼ 2a_p (parameter of the ideal cubic cell) ∼ 7.40 Å. The CaCu₃Ti₄O₁₂-type structure was confirmed from an X-ray powder structural determination. Lithium occupies both square planar sites where it replaces copper and icosahedral sites, with a probable delocalization. Crystal chemistry of the AC₃B₄O₁₂ structure is considered, taking into account the evolution of anion packing and the distortion of polyhedra. A diagrammatic representation is proposed so that precise information on the regularity of the C₃B₄O₁₂ network can be obtained.

References (15)

P. Mouron et al.
J. Solid State Chem.
(1985)
B. Bochu et al.
J. Solid State Chem.
(1979)
J. Chenavas et al.
J. Solid State Chem.
(1975)
M. Marezio et al.
J. Solid State Chem.
(1973)
R.J. Cava et al.
J. Solid State Chem.
(1983)
H. Vincent et al.
J. Solid State Chem.
(1978)
M.N. Deschizeaux et al.
J. Solid State Chem.
(1976)

There are more references available in the full text version of this article.

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Regular articleNew substituted copper titanates with the CaCu3Ti4O12 structure: Li[Cu3−xLix][Ti3−xMV1+x]O12 (MV = Nb: 0.12 ≤ x ≤ 0.33; MV = Ta: x = 0.33)

Abstract

J. Solid State Chem.

J. Solid State Chem.

J. Solid State Chem.

J. Solid State Chem.

J. Solid State Chem.

J. Solid State Chem.

J. Solid State Chem.

Regular article
New substituted copper titanates with the CaCu₃Ti₄O₁₂ structure: Li[Cu_3−xLi_x][Ti_3−xM^V_1+x]O₁₂ (M^V = Nb: 0.12 ≤ x ≤ 0.33; M^V = Ta: x = 0.33)