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The Effect of Cobalt Doping on Physicochemical Properties of La1.5Sr0.5Ni1–yCoyO4+d

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Abstract

The La1.5Sr0.5Ni1–yCoyO4+δ (y = 0, 0.1, 0.2, 0.3, 0.4) complex oxides were synthesized by the citrate-nitrate route. The phase purity of the samples was confirmed by the powder X-ray diffraction (PXRD). All studied samples possess the K2NiF4-type structure with space group I4/mmm. The cobalt doping in La1.5Sr0.5Ni1–yCoyO4+δ leads to the expansion of oxygen octahedra in the ab plane and their shrinkage in the c direction, thus, decreasing the structural microstrain. The increase in cobalt concentration results in a gradual increase in oxygen over-stoichiometry, while the oxygen content in La1.5Sr0.5Ni1–yCoyO4+δ shows weak temperature dependence. It is shown that the majority of cobalt cations in these oxides are in the Co3+ state in the whole temperature range studied. The fitting results for the temperature dependencies of the Seebeck coefficient show that the Ni3+ cations are mostly in the low-spin state in La1.5Sr0.5Ni1–yCoyO4+δ in the range of 25–1000°C, although the increase in cobalt content leads to the non-monotonous increase in the fraction of high-spin Ni3+ cations at T > 600°C. The cobalt doping of La1.5Sr0.5Ni1–yCoyO4+δ decreases total conductivity due to the increase in localization of electron holes on the 3d-metal cations.

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Funding

The work was financially supported by Russian Foundation for Basic Research, project no. 19-03-00753 А.

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  1. Ural Federal University, Yekaterinburg, Russia

    A. R. Gilev, E. A. Kiselev & V. A. Cherepanov

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  1. A. R. Gilev
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  2. E. A. Kiselev
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  3. V. A. Cherepanov
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Correspondence to E. A. Kiselev.

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Gilev, A.R., Kiselev, E.A. & Cherepanov, V.A. The Effect of Cobalt Doping on Physicochemical Properties of La1.5Sr0.5Ni1–yCoyO4+d . Russ. J. Phys. Chem. 94, 2474–2481 (2020). https://doi.org/10.1134/S0036024420120110

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