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

Published online by Cambridge University Press:  31 January 2011

Kai-Yun Yang ,
Ing-Chi Leu ,
Kuan-Zong Fung ,
Min-Hsiung Hon ,
Ming-Chi Hsu ,
Yu-Jen Hsiao  and
Moo-Chin Wang
Kai-Yun Yang*
Affiliation:
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan
Ing-Chi Leu
Affiliation:
Department of Materials Science and Engineering, National United University, Kung-Ching Li, Miao-Li 360, Taiwan
Kuan-Zong Fung
Affiliation:
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan
Min-Hsiung Hon
Affiliation:
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan
Ming-Chi Hsu
Affiliation:
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan
Yu-Jen Hsiao
Affiliation:
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan
Moo-Chin Wang
Affiliation:
Faculty of Fragrance and Cosmetics, Kaohsiung Medical University, Kaohsiung 807, Taiwan
*
a)Address all correspondence to this author. e-mail: KYY@mail.mse.ncku.edu.tw
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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.

Keywords

Chemical reactionIonic conductorLi
Type
Articles
Information
Journal of Materials Research , Volume 23 , Issue 7 , July 2008 , pp. 1813 - 1825
Copyright
Copyright © Materials Research Society 2008

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