Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3固态电解质的制备及表征
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摘要
固态电池是未来电池技术发展方向之一,而固态电解质是研究固态电池的重点。采用溶胶凝胶法和固相法制备Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3(LATP)作为固态电解质。通过X射线衍射、扫描电子显微镜、交流阻抗法对不同烧结工艺条件下的LATP玻璃-陶瓷粉的结构、形貌和电导率进行分析表征。结果表明,通过溶胶凝胶法和固相法合成的样品都具有钠离子快导体(NASICON)结构(空间结构群R-3C),结晶程度良好,粒径均匀,晶粒之间相连形成纳米多孔结构。固相法制备的样品呈现立方颗粒形态。溶胶凝胶法制备的样品电导率总体都高于固相法制备的样品。
Solid state battery is one of the future development direction of battery technology, and solid electrolyte isthe focus of solid state battery research. NASICON type solid electrolyte of Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3(LATP) powders wasprepared by Sol-gel method and solid-state reaction. The structures and morphologies of the powders werecharacterized using XRD and SEM and ionic conductivities were measured by EIS. The results show that thesamples synthesized by sol-gel method and solid-phase method are all with NASICON structure(space structuregroup R-3 C), and the crystallization degree is good, the particle size is uniform, and the grains are connected to formnanoporous structure. The samples prepared by solid phase method show cubic particle morphology. Theconductivity of the samples prepared by sol gel method is higher than that of the solid-state method.
Solid state battery is one of the future development direction of battery technology, and solid electrolyte isthe focus of solid state battery research. NASICON type solid electrolyte of Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3(LATP) powders wasprepared by Sol-gel method and solid-state reaction. The structures and morphologies of the powders werecharacterized using XRD and SEM and ionic conductivities were measured by EIS. The results show that thesamples synthesized by sol-gel method and solid-phase method are all with NASICON structure(space structuregroup R-3 C), and the crystallization degree is good, the particle size is uniform, and the grains are connected to formnanoporous structure. The samples prepared by solid phase method show cubic particle morphology. Theconductivity of the samples prepared by sol gel method is higher than that of the solid-state method.
引文
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[2]BIRKE P,SALAM F,D魻RING S,et al.A first approach to a monolithic all solid state inorganic lithium battery[J].Solid State Ionics,1999,118(1/2):149-157.
[3]HAGMAN L O,KIERKEGAARD P,KARVONEN P,et al.The crystal structure of Na M2IV(PO4)3;M2IV=Ge,Ti,Zr[J].Acta Chemica Scandinavica,1968,22:1822-1832.
[4]FERGUS J W.Ceramic and polymeric solid electrolytes for lithium-ion batteries[J].Journal of Power Sources,2010,195(15):4554-4569.á??á??
[5]MONCHAK M,HUPFER T,SENYSHYN A,et al.Lithium diffusion pathway in Li1.3Al0.3Ti1.7(PO4)3(LATP)superionic conductor[J].Inorganic Chemistry,2016,55(6):2941-2950.
[6]CRETIN M,FABRY P.Comparative study of lithium ion conductors in the system Li1+xAlxA2-x IV(PO4)3,with AIV=Ti or Ge and 0≤x≤0.7 for use as Li+sensitive membranes[J].Journal of the European Ceramic Society,1999,19(16):2931-2950.
[7]赵正远.磷酸钛铝锂的制备及其在锂空气二次电池中的应用[D].哈尔滨:哈尔滨工业大学,2014.
[8]吴显明.锂离子电池材料LiMn2O4及Li1.3Al0.3Ti1.7(PO4)3粉末与薄膜的合成及性质研究[D].长沙:中南大学,2003.
[9]吴显明,陈上,刘金练,等.不同热处理方式对Li1.3Al0.3Ti1.7(PO4)3薄膜性质的影响[J].精细化工,2012,29(3):24-27.
[10]BROUSSE T,FRAGNAUD P,MARCHAND R,et al.All oxide solid-state lithium-ion cells[J].Journal of Power Sources,1997,68(2):412-415.
[11]THOKCHOM J S,KUMAR B.The effects of crystallization parameters on the ionic conductivity of a lithium aluminum germanium phosphate glass-ceramic[J].Journal of Power Sources,2010,195(9):2870-2876.
[12]刘红霞,苏凤莲,周圣明,等.溶胶-凝胶法制备MgxZn1-xO及其特性[J].人工晶体学报,2005,34(5):849-852.
[13]朱宇豪,王珲,郑春满.流延法制备高致密固态电解质LATP的研究[J].广州化工,2016,44(15):58-61.
[14]ZHAO E,MA F,GUO Y,et al.Stable LATP/LAGP double-layer solid electrolyte prepared via a simple dry-pressing method for solid state lithium ion batteries[J].Rsc Advances,2016,6(95):92579-92585.