• 한국결정성장학회지
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• 제31권5호
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• pp.197-202
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• 2021

Z형 육방정 페라이트인 Ba₃Co₂Fe₂₄O₄₁(Ba₃Z)와 Ba_1.5La_1.5Co₂Fe₂₄O₄₁(Ba_1.5La_1.5Z) 분말을 1차 하소 후 용융염 합성법을 통해 합성하였다. Ba₃Z의 경우, 1000℃에서 하소한 결과 M형 육방정 페라이트와 Y형 육방정 페라이트가 합성되었으며, 이후 1150℃와 1200℃에서 소결했을 때 Z형 육방정 페라이트를 얻을 수 있었다. 하지만 Ba_1.5La_1.5Z의 경우 1000℃에서 하소하였을 때 M형 육방정 페라이트와 CoFe₂O₄(Spinel 상) 그리고 LaFeO₃으로 합성되었으며, Z형 육방정 페라이트는 용융염 합성 과정에서 합성되지 않았다. 또한 입자 형상의 종횡비는 용융염 합성 시 소결온도가 증가함에 따라 감소하는 경향을 보였다. 따라서 높은 종횡비를 갖는 단상의 Ba_1.5La_1.5Z를 합성하기 위해서는 용융염 합성 전 1차 하소 온도가 Spinel 상이 형성되는 온도보다 낮아야 될 것으로 판단된다.

• 한국재료학회지
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• 제34권4호
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• pp.185-193
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• 2024

In this study, NASICON-type Li_1+XGa_XTi_2-X(PO₄)₃ (x = 0.1, 0.3 and 0.4) solid-state electrolytes for all-solid-state batteries were synthesized through the sol-gel method. In addition, the influence on the ion conductivity of solid-state electrolytes when partially substituted for Ti⁴⁺ (0.61Å) site to Ga³⁺ (0.62Å) of trivalent cations was investigated. The obtained precursor was heat treated at 450 ℃, and a single crystalline phase of Li_1+XGa_XTi_2-X(PO₄)₃ systems was obtained at a calcination temperature above 650 ℃. Additionally, the calcinated powders were pelletized and sintered at temperatures from 800 ℃ to 1,000 ℃ at 100 ℃ intervals. The synthesized powder and sintered bodies of Li_1+XGa_XTi_2-X(PO₄)₃ were characterized using TG-DTA, XRD, XPS and FE-SEM. The ionic conduction properties as solid-state electrolytes were investigated by AC impedance. As a result, Li_1+XGa_XTi_2-X(PO₄)₃ was successfully produced in all cases. However, a GaPO₄ impurity was formed due to the high sintering temperatures and high Ga content. The crystallinity of Li_1+XGa_XTi_2-X(PO₄)₃ increased with the sintering temperature as evidenced by FE-SEM observations, which demonstrated that the edges of the larger cube-shaped grains become sharper with increases in the sintering temperature. In samples with high sintering temperatures at 1,000 ℃ and high Ga content above 0.3, coarsening of grains occurred. This resulted in the formation of many grain boundaries, leading to low sinterability. These two factors, the impurity and grain boundary, have an enormous impact on the properties of Li_1+XGa_XTi_2-X(PO₄)₃. The Li_1.3Ga_0.3Ti_1.7(PO₄)₃ pellet sintered at 900 ℃ was denser than those sintered at other conditions, showing the highest total ion conductivity of 7.66 × 10^-5 S/cm at room temperature. The total activation energy of Li-ion transport for the Li_1.3Ga_0.3Ti_1.7(PO₄)₃ solid-state electrolyte was estimated to be as low as 0.36 eV. Although the Li_1+XGa_XTi_2-X(PO₄)₃ sintered at 1,000 ℃ had a relatively high apparent density, it had less total ionic conductivity due to an increase in the grain-boundary resistance with coarse grains.