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Magnetic phase transformation induced by electrochemical lithium intercalation in Li1 + x EuTiO4 and Li2 + 2x Eu2Ti3O10 (0 ≤ x ≤ 1) compounds

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Abstract

Ion exchange of Li for Na in the layered compounds NaEuTiO4 and Na2Eu2Ti3O10 transforms the (NaO)2 rock-salt layers into Li2O2 antifluorite layers. Li can be inserted reversibly into the Li2O2 layers to reduce the Eu3+ to Eu2+, not the Ti(IV) to Ti(III). An internal electric field perpendicular to the layers is reduced by Li insertion; this field induces a ferroic displacement of the Ti(IV) toward the alkali-ion layers that is eliminated as the internal electric field vanishes in Li2 + 2x Eu2Ti3O10 with x ≈ 1. The spins of the (EuO)2 and the (EuTiO3)2 bilayers of Li1 + x EuTiO4 and Li2 + 2x Eu2Ti3O10 with x ≈ 1 order at low temperature into ferromagnetic Eu–Eu chains that form a 2D ferromagnetic spiral spin configuration in zero magnetic field. The M-H curve shows zero coercivity and zero remanence, but the M of a polycrystalline sample rises to 4 μB/Eu in an H = 1 T and approaches saturation above 5 μB/Eu in 5 T.

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Acknowledgments

The authors would like to thank Jian-Shi Zhou for his help in the magnetic measurements. This work was supported by the Robert A. Welch Foundation (Grant No. F-1066). JAA thanks the financial support of the Spanish Ministry of Education to the project MAT2010-16404.

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Authors and Affiliations

  1. Texas Materials Institute, University of Texas at Austin, Austin, TX, 78712, USA

    Sang-Hoon Song, Jin-Guang Cheng & John B. Goodenough

  2. Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049, Madrid, Spain

    José Antonio Alonso

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  1. Sang-Hoon Song
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  2. José Antonio Alonso
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  3. Jin-Guang Cheng
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  4. John B. Goodenough
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Correspondence to John B. Goodenough.

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Song, SH., Alonso, J.A., Cheng, JG. et al. Magnetic phase transformation induced by electrochemical lithium intercalation in Li1 + x EuTiO4 and Li2 + 2x Eu2Ti3O10 (0 ≤ x ≤ 1) compounds. J Solid State Electrochem 18, 2047–2060 (2014). https://doi.org/10.1007/s10008-014-2432-0

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  • DOI: https://doi.org/10.1007/s10008-014-2432-0

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