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鈣鈦礦型鋰離子固體電解質Li2x?ySr1?xTi1?yNbyO3的性能

Performance of perovskite-type Li-ion solid electrolyte Li2x?ySr1?xTi1?yNbyO3

  • 摘要: 采用高溫固相法成功制備了Li2x?ySr1?xTi1?yNbyO3 (x=3y/4, y=0.25, 0.5, 0.6, 0.7, 0.75, 0.8)鋰離子固體電解質,并通過X射線衍射(XRD)、掃描電子顯微鏡(SEM)、交流阻抗圖譜、恒電位極化等分別研究了各個組分的晶體結構、微觀形貌、離子電導率和電子電導率。XRD顯示當y≤0.70時,材料為立方鈣鈦礦型結構,幾乎沒有雜質相生成。SEM表明隨著摻雜含量的增加材料的晶粒尺寸逐漸增大。Li0.35Sr0.475Ti0.3Nb0.7O3鋰離子固體電解質有著高離子電導率,為3.62×10?5 S·cm?1,其電子電導率為2.55×10?9 S·cm?1,活化能僅為0.29 eV。使用以Li0.35Sr0.475Ti0.3Nb0.7O3為隔膜的LiFePO4/Li半電池經過100圈循環后,放電比容量仍有93.9 mA·h·g?1,容量保持率為90.72%。

     

    Abstract: All-solid-state lithium batteries are recognized as the next-generation energy storage batteries due to their high energy density and high security, to which researchers have paid more attention. All-solid-state lithium batteries are composed of solid materials, and the Li-ion solid electrolytes do not contain flammable and explosive organic solvents, which can enhance the safety of the battery. As important components, Li-ion solid electrolytes are widely studied in all-solid-state lithium batteries, which currently include Li-superionic solid electrolyte (LISICON), Na-superionic solid electrolyte (NASICON), garnet-type solid electrolyte, perovskite-type solid electrolyte, sulfide-type solid electrolyte, and polymer solid electrolyte. Li-ion solid electrolytes generally have the advantages of high Li-ion conductivity, low electronic conductivity, wide operating temperatures, wide electrochemical windows, and inhibition of lithium dendrite growth. Among the solid electrolytes, the perovskite-type solid electrolytes have a wide tolerance factor that allows most elements to dope into the ABO3 structure. Additionally, the perovskite-type Li-ion solid electrolytes are summarized into two types: (1) the three-component Li3xLa2/3?xTiO3 (LLTO, 0 < x < 1/6) and (2) the four-component (Li, Sr)(A, B)O3 (A = Zr, Hf, Ti, Sn; B = Nb, Ta). In this paper, the four-component Li2x?ySr1?xTi1?yNbyO3 (x = 3y/4, y = 0.25, 0.5, 0.6, 0.7, 0.75, 0.8) solid electrolytes were prepared by conventional solid-state reaction method. X-ray diffraction (XRD), scanning electron microscopy, alternating current impedance, and potentiostatic polarization methods were adopted to study the crystal structure, micromorphology, ion conductivity, and electronic conductivity, respectively. XRD analysis show the synthesized samples exhibit a cubic perovskite structure when y≤0.70 with almost no impurity phase formed. Li0.35Sr0.475Ti0.3Nb0.7O3 exhibits the highest ion conductivity of 3.62×10?5 S·cm?1, electronic conductivity of 2.55×10?9 S·cm?1 at 20 ℃, and activation energy of only 0.29 eV. The LiFePO4/Li half-cell was fabricated using Li0.35Sr0.475Ti0.3Nb0.7O3 as a separator, exhibiting a capacity of 93.9 mA·h·g?1 and a retention capacity of 90.72% after 100 cycles.

     

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