• Journal of the Korean Electrochemical Society
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• v.24 no.3
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• pp.52-64
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• 2021

The effect of Fe and BO₃ doping on structure, thermal, and electrical properties of Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y (x = 0.2, 0.5)-based glass and glass ceramics was investigated. In addition, their crystallization behavior during sintering and ionic conductivity were also investigated in terms of sintering temperature. FT-IR and XPS results indicated that Fe²⁺ and Fe³⁺ ions in Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y glass worked as a network modifier (FeO₆ octahedra) and also as a network former (FeO₄ tetrahedra). In the case of the glass with low substitution of BO₃, boron formed (PB)O₄ network structure, while boron preferred BO₃ triangles or B₃O₃ boroxol rings with increasing the BO₃ content owing to boic oxide anomaly, which can result in an increased non-bridging oxygen. The glass transition temperature (GTT) and crystallization temperature (CT) was lowered as the BO₃ substitution was increased, while Fe²⁺ lowered the GTT and raised the CT. The ionic conductivity of Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y glass ceramics were 8.85×10^-4 and 1.38×10^-4S/cm for x = 0.2 and 0.5, respectively. The oxidation state of doped Fe and boric oxide anomaly were due to the enhanced lithium ion conductivity of glass ceramics.