Operando Synchrotron X-ray Diffraction in Calcium Batteries: Insights into the Redox Activity of 1D Ca(3)CoMO(6) (M = Co and Mn)

[Image: see text] 1D Ca(3)Co(2–z)M(z)O(6) (M = Co z = 0, M = Mn z = 1, and M = Fe z = 0.4) were prepared and tested electrochemically. While the iron-containing phase was not found to be active, the iron- and manganese-containing phases were found to be potentially interesting as positive electrode materials for calcium metal-based high-energy battery technologies and were investigated by operando synchrotron X-ray diffraction. Results indicate that electrochemically driven calcium deintercalation from the crystal structure (ca. 0.7 mol per formula unit) takes place upon oxidation in both cases. The oxidized phases have incommensurate modulated crystal structures with the space group R 3m(00γ)0s and a = 9.127(1) Å, c(1) = 2.4226(3) Å and c(2) = 4.1857(3) Å, and γ = 0.579 (M = Co) and a = 9.217(1) Å, c(1) = 4.9076(4) Å and c(2) = 4.3387(4) Å, and γ = 1.139 (M = Mn), which exhibit differences due to the presence of manganese and Mn/Co ordering. The degree of calcium re-intercalation within the structure was found to be extremely limited, if any. Complementary experiments carried out in lithium cells did not show any reversibility either, thus pointing at intrinsic structural/migration constraints in the oxidized phase rather than slow kinetics of high desolvation energies associated with divalent ion charge carriers.