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Mechanism of the interfacial reaction between cation-deficient La0.56Li0.33TiO3 and metallic lithium at room temperature

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Abstract

We used x-ray diffractometry (XRD), x-ray photoelectron spectrometry (XPS), and secondary-ion mass spectrometry (SIMS) to investigate the mechanism of the interfacial room-temperature (RT) chemical reaction between cation-deficient La0.56Li0.33TiO3 solid electrolytes and metallic lithium anodes in all-solid-state lithium batteries. A stoichiometric mixture of La2O3, Li2CO3, and TiO2 powders was calcined at 1250 °C for 8 h to obtain a single perovskite structure of La0.56Li0.33TiO3. When this La0.56Li0.33TiO3 sample and lithium were placed in contact at room temperature for 24 h, the phase of the La0.56Li0.33TiO3 remained unchanged. The XPS results indicate that 12% of the tetravalent Ti4+ ions were converted into trivalent Ti3+ ions. The valence conversion and degree of conversion were limited by the structural rigidity of the host crystal. Our SIMS analysis suggests the existence of a local electric field near the contact surface and indicates that the 6Li+ isotope ions were inserted into the specimen through the effect of this field. The change in the electrical properties of La0.56Li0.33TiO3 supports this mechanism for the interfacial reaction. The ionic conductivities of the grain and total grain boundary decreased and increased, respectively, after the insertion of Li+, and the total electronic conductivity increased as a result of the presence of intervalence electron hopping between mixed Ti3+/Ti4+ states. The mechanism of the lithium-activated RT interfacial reaction is associated with the reduction of Ti4+ transition metal ions from tetravalent to trivalent states and the local-electric-field-induced Li+ insertion into La3+/Li+-site vacancies of La0.56Li0.33TiO3.

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Acknowledgments

We thank the National Science Council of Taiwan for financial support (Contracts NSC 92-2120-M-006-003 and NSC 93-2120-M-006-004). We are grateful to Professor M.P. Hung for kindly offering advice and suggestions and to P. Glink (http://www.editchem.com) for polishing the language of our manuscript.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, National Cheng Kung University, Tainan, 70101, Taiwan

    Kai-Yun Yang, Kuan-Zong Fung, Min-Hsiung Hon, Ming-Chi Hsu & Yu-Jen Hsiao

  2. Department of Materials Science and Engineering, National United University, Kung-Ching Li, Miao-Li, 360, Taiwan

    Ing-Chi Leu

  3. Faculty of Fragrance and Cosmetics, Kaohsiung Medical University, Kaohsiung, 807, Taiwan

    Moo-Chin Wang

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Yang, KY., Leu, IC., Fung, KZ. et al. Mechanism of the interfacial reaction between cation-deficient La0.56Li0.33TiO3 and metallic lithium at room temperature. Journal of Materials Research 23, 1813–1825 (2008). https://doi.org/10.1557/JMR.2008.0255

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