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Extra info for An Attempt to establish a pure scientific system of mineralogy by the application electro-chemical theory
28). Thus, besides the mixed valence Co3þ/Co4þ, the ordering of Naþ and vacancies that governs the charge ordering on cobalt sites has a great impact upon the physical properties of these lamellar oxides, as will be discussed in section 6. Besides the NaxCoO2 bronzes that have been extensively studied, some other alkaline cobaltites exhibit the same type of structure. 28 Two-dimensional CoO2 layers separated by a thick insulating layer of Naþ ions and H2O molecules in superconducting NaxCoO2ÁyH2O.
Extensive experimental and computational investigations have been carried out to ﬁnd out the stable sodium vacancy orderings at various sodium concentrations [220–224]. However, a few experimental evidences of long-range ordering, either commensurate or incommensurate, have been given using neutron or electron diffraction and most of the reported works are devoted to theoretical considerations using various methods of calculation [221–223]. A detailed electron diffraction study on powder samples revealed several new structures .
However, the presence of some octahedra cannot be ruled out. The coordination around cobalt may be tetrahedral if the O(4) site is unoccupied . 14b), the anionic vacancies between the pyramidal layers being ﬁlled at 13% only by oxygen. 2 Co2O6 . 14b). It is this smaller size of Y3þ and Ca2þ cations that favors the formation of such double pyramidal cobalt layers . 2Co2O6 both tetragonal I4/mmm. The first one is nonstoichiometric and exhibits 87% oxygen vacancies on the apical oxygen sites of the double layers (&), whereas the second one exhibits double pyramidal cobalt layers, similar to La2SrCu2O6.