NASICON型固体电解质Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3的SPS烧结及性能
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摘要
采用溶胶-凝胶法合成NASICON型固体电解质Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3粉体.研究了不同烧结方式对Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3电解质的性能影响.通过差热分析仪分析前驱体的热性能,采用X射线衍射仪、扫描电子显微镜、交流阻抗仪对固体电解质的物相、结构及电化学性能进行表征.结果表明,溶胶-凝胶法成功制备出纯相的NASICON型Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3,并且颗粒均匀;相比传统的无压烧结,SPS烧结明显提高了样品致密度(致密度达94.38%),室温离子电导率高达8.99×10~(-5)S/cm.
Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3 powder was prepared by the sol-gel method.The effects of sintering methods on the performance of Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3 electrolyte were investigated. The thermal properties of the precursors were analyzed by differential scanning calorimetry. The phase, the structure as well as the electrochemical properties of the solid electrolyte were characterized by X-ray diffraction, scanning electron microscopy and electrochemical impedance spectroscopy. The results show that the pure phase of NASICON type Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3 is successfully prepared by the sol-gel method. Compared with the conventional pressureless sintering, SPS sintering can obviously increase the density of the sample(94.38 % of the theoretical density), and the ionic conductivity reaches as high as 8.99 × 10~(-5) S/cm at room temperature.
Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3 powder was prepared by the sol-gel method.The effects of sintering methods on the performance of Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3 electrolyte were investigated. The thermal properties of the precursors were analyzed by differential scanning calorimetry. The phase, the structure as well as the electrochemical properties of the solid electrolyte were characterized by X-ray diffraction, scanning electron microscopy and electrochemical impedance spectroscopy. The results show that the pure phase of NASICON type Li_(1.1)Y_(0.1)Zr_(1.9)(PO_4)_3 is successfully prepared by the sol-gel method. Compared with the conventional pressureless sintering, SPS sintering can obviously increase the density of the sample(94.38 % of the theoretical density), and the ionic conductivity reaches as high as 8.99 × 10~(-5) S/cm at room temperature.
引文
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[2]钟盛文,钟风娣,张骞.锂离子正极材料Li Ni0.5Mn0.3Co0.2O2的合成与掺杂Al的性能研究[J].有色金属科学与工程,2013,4(4):11-16.
[3]梅佳,钟盛文,张骞,等.高性能Li Co O2的制备与性能表征[J].电源技术,2007,31(2):128-130.
[4]SOLOVEICHIK G L.Battery technologies for large-scale stationary energy storage[J].Annual Review of Chemical&Biomolecular Engineering,2011,2(2):503-27.
[5]黄峰,周运鸿.锂离子电池电解质现状与发展[J].电池,2001,31(6):32-35.
[6]GOODENOUGH J B,KIM Y.Challenges for rechargeable Li batteries[J].Chemistry of Materials,2015,22(3):587-603.
[7]KAMAYA N,HOMMA K,YAMAKAWA Y,et al.A lithium super ionic conductor[J].Nature Materials,2011,10(9):682.
[8]ANANTHARAMULU N,RAO K K,RAMBABU G,et al.A wideranging review on Nasicon-type materials[J].Journal of Materials Science,2011,46(9):2821-2837.
[9]刘玉龙,张鸿,薛丹,等.Li1.3Al0.3Ti1.7(PO4)3基锂离子导电材料的制备与表征[J].中国有色金属学报,2012,22(1):144-149.
[10]KOTOBUKI M,KOISHI M.Sol-gel synthesis of Li1.5Al0.5Ge1.5(PO4)3,solid electrolyte[J].Ceramics International,2015,41(7):8562-8567.
[11]LI Y T,LIU M J,LIU K A,et al.High Li+conduction in NASICONtype Li1+xYxZr2-x(PO4)3at room temperature[J].Journal of Power Sources,2013,240(240):50-53.
[12]KNAUTH P.Inorganic solid Li ion conductors:An overview[J].Solid State Ionics,2009,180(14/15/16):911-916.
[13]郑子山,张中太,唐子龙,等.锂无机固体电解质[J].化学进展,2003,15(2):101-106.
[14]RUFFO R,MARI C M,CATTI M.Structural and electrical characterization of the NASICON-type Li2Fe Zr(PO4)3,and Li2Fe Ti(PO4)3compounds[J].Ionics,2001,7(1/2):105-108.
[15]LEE S D,JUNG K N,KIM H,et al.Composite electrolyte for allsolid-State lithium batteries:low-temperature fabrication and conductivity enhancement[J].Chemsuschem,2017,10(10):2175.
[16]XIE H,GOOGENOUGH J B,LI Y.Li1.2Zr1.9Ca0.1(PO4)3,a roomtemperature Li-ion solid electrolyte[J].Journal of Power Sources,2011,196(18):7760-7762.
[17]KALI R,MUKHOPADHYAY A.Spark plasma sintered/synthesized dense and nanostructured materials for solid-state Li-ion batteries:Overview and perspective[J].Journal of Power Sources,2014,45(4):920-931.
[18]CHANG C M,HONG S H,PARK H M.Spark plasma sintering of Al substituted Li Hf2(PO4)3solid electrolytes[J].Solid State Ionics,2005,176(35):2583-2587.
[19]CHANG C M,LEE Y I,SEONG-HYEON H0NG,et al.Spark plasma sintering of Li Ti2(PO4)3-based solid electrolytes[J].Journal of the American Ceramic Society,2005,88(7):1803–1807.
[20]KUMAR S,BALAYA P.Improved ionic conductivity in NASICON-type Sr2+doped Li Zr2(PO4)3[J].Solid State Ionics,2016,296:1-6.