卢佳垚, 厉英, 倪培远, 唐甜甜. 钙钛矿型锂离子固体电解质Li2xySr1−xTi1−yNbyO3的性能[J]. 工程科学学报, 2021, 43(8): 1024-1031. DOI: 10.13374/j.issn2095-9389.2020.12.03.004
引用本文: 卢佳垚, 厉英, 倪培远, 唐甜甜. 钙钛矿型锂离子固体电解质Li2xySr1−xTi1−yNbyO3的性能[J]. 工程科学学报, 2021, 43(8): 1024-1031. DOI: 10.13374/j.issn2095-9389.2020.12.03.004
LU Jia-yao, LI Ying, NI Pei-yuan, TANG Tian-tian. Performance of perovskite-type Li-ion solid electrolyte Li2xySr1−xTi1−yNbyO3[J]. Chinese Journal of Engineering, 2021, 43(8): 1024-1031. DOI: 10.13374/j.issn2095-9389.2020.12.03.004
Citation: LU Jia-yao, LI Ying, NI Pei-yuan, TANG Tian-tian. Performance of perovskite-type Li-ion solid electrolyte Li2xySr1−xTi1−yNbyO3[J]. Chinese Journal of Engineering, 2021, 43(8): 1024-1031. DOI: 10.13374/j.issn2095-9389.2020.12.03.004

钙钛矿型锂离子固体电解质Li2xySr1−xTi1−yNbyO3的性能

Performance of perovskite-type Li-ion solid electrolyte Li2xySr1−xTi1−yNbyO3

  • 摘要: 采用高温固相法成功制备了Li2xySr1−xTi1−yNbyO3 (x=3y/4, y=0.25, 0.5, 0.6, 0.7, 0.75, 0.8)锂离子固体电解质,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、交流阻抗图谱、恒电位极化等分别研究了各个组分的晶体结构、微观形貌、离子电导率和电子电导率。XRD显示当y≤0.70时,材料为立方钙钛矿型结构,几乎没有杂质相生成。SEM表明随着掺杂含量的增加材料的晶粒尺寸逐渐增大。Li0.35Sr0.475Ti0.3Nb0.7O3锂离子固体电解质有着高离子电导率,为3.62×10−5 S·cm−1,其电子电导率为2.55×10−9 S·cm−1,活化能仅为0.29 eV。使用以Li0.35Sr0.475Ti0.3Nb0.7O3为隔膜的LiFePO4/Li半电池经过100圈循环后,放电比容量仍有93.9 mA·h·g−1,容量保持率为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 Li2xySr1−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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