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A tellurate compound with Co II /Co III mixed valence states and lithium ions within orthogonally oriented channels was realized in Li 3 Co 1.06(1) TeO 6 . The single-crystal structure determination revealed two independent and interpenetrating Li/O and (Co,Te)/O substructures with octahedral oxygen coordination of the metal atoms. In contrast to other mixed oxides, a honeycomb-like ordering of CoO 6 and TeO 6 octahedra was not observed. Li 3 Co 1.06(1) TeO 6 crystallizes orthorhombically with the following unit cell parameters and refinement results: Fddd, a = 588.6(2), b = 856.7(2), c = 1781.5(4) pm, R 1 = 0.0174, wR 2 = 0.0462, 608 F 2 values, and 33 variables. Additional electron density in tetrahedral voids in combination with neighboring face-linked and under-occupied octahedral lithium sites offers an excellent possible diffusion pathway for lithium ions. According to the symmetry of the crystal structure the diffusion pathways in Li 3 Co 1.06(1) TeO 6 were found in two orthogonal orientations. The Co II /Co III mixed valence was investigated via X-ray photoelectron spectroscopy (XPS), revealing a composition comparable to that derived from single-crystal X-ray diffractometry. Magnetic susceptibility measurements underlined the coexistence of Co II and Co III , the title compound, however, showed no magnetic ordering down to low temperatures. The ionic conductivity of Li 3 Co 1.06(1) TeO 6 was determined via alternating current (AC) electrochemical impedance spectroscopy and was found to be in the range of 1.6 × 10 -6 S cm -1 at 573 K.

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Li3Co1.06(1)TeO6: synthesis, single-crystal structure and physical properties of a new tellurate compound with CoII/CoIIImixed valence and orthogonally oriented Li-ion channels