NASICON型固体电解质的合成与改性研究

发布时间：2017-12-28 14:14

本文关键词：NASICON型固体电解质的合成与改性研究　出处：《天津工业大学》2017年硕士论文　论文类型：学位论文

【摘要】：NASICON(Na Super-ionic Conductor)是一类具有三维离子传输通道的无机固体电解质,又称为钠快离子导体,其母体为NaZr_2P_3Ch_2。Si部分取代NaZr_2P_3O_(12)中的P而得到的Na_(1+x)Zr_2Si_xP_3V_xO_(12)(NZSP,0≤x≤3)固溶体具有较高的Na+电导率,当x = 2时,Na_3Zr_2Si_2PO_(12)具有较高的离子电导率,可以和具有二维离子通道的β-Al_2O_3相比较。本文通过TG热重分析、X射线衍射技术、SEM扫描电镜以及电化学工作站等对Na_3Zr_2Si_2PO_(12)固体电解质材料及金属氧化物掺杂过后的NZSP固体电解质材料进行表征。本文分别采用固相法和溶胶凝胶法制备了 NASICON型Na_3Zr_2Si_2PO_(12)固体电解质材料,研究了不同烧结温度和烧结时间对固体电解质材料的微观结构和电化学性能的影响。实验结果表明,利用固相法在1100℃烧结12h得到的Na_3Zr_2Si_2PO_(12)固体电解质材料表现出良好的电化学性能。室温下,其最高晶粒离子电导率和总离子电导率分别为7.41×10~(-4)S cm~(-1)-和5.82×10~(-4) S cm~(-1)。溶胶凝胶法制备Na_3Zr_2Si_2PO_(12)固体电解质材料的最佳烧结温度为1050℃。该温度下焙烧得到的样品具有最佳的离子电导率,其晶粒离子电导率和总离子电导率分别为4.74×10~(-4)和 cm~(-1)和2.93×10-5S cm~(-1)。在上述工艺优化的基础上,采用固相法对Na_3Zr_2Si_2PO_(12)固体电解质进行改性研究。通过不同掺杂含量的金属氧化物对Na_(3+y)Zr_(2-x)M_xSi_2PO_(12)(M = ZnO,MgO,La_2O_3,Nd_2O_3,Y_2O_3,CeO_2和Nb_2O_5等;0≤x≤0.5;y根据电荷平衡计算而得)材料中的Zr~(4+)进行掺杂改性。利用XRD、SEM、EIS等方法对掺杂产物进行物理表征和电化学性能测试。XRD衍射谱阁确定出不同金属氧化物的最佳掺杂含量为x =0.1。在最佳掺杂含量条件下,本文所选金属氧化物对NASICON材料的掺杂均能表现出良好的电化学性能。研究发现,La、Zn和Nb元素对产物有良好的掺杂改性效果。经过La、Zn和Nb掺杂得到的固体电解质材料在室温下的离子电导率分别为 9.14× 1 0~(-4) S cm~(-1)、9.15 × 10~(-4) S cm~(-1) 和 1.14× 1 0-3 S cm~(-1),接近于 10-3 S cm~(-1),是具备较高离子电导率的固体电解质材料。采用分散聚合法制备出粒径为2-6 μm的PS微球,并以PS微球为模板,利用共沉积法将其与Na_3Zr_2Si_2PO_(12)固体电解质材料复合,最终合成Na_3Zr_2Si_2PO_(12)固体电解质三维大孔材料。
[Abstract]:NASICON (Na Super-ionic Conductor) is a kind of inorganic solid electrolyte with three dimensional ion transport channel, also known as sodium fast ionic conductor, its parent body is NaZr_2P_3Ch_2. NaZr_2P_3O_ substituted Si (12) and the P Na_ (1+x) Zr_2Si_xP_3V_xO_ (12) (NZSP, x = 0 ~ 3) solid solution has high conductivity of Na+, when x = 2, Na_3Zr_2Si_2PO_ (12) has high ionic conductivity, and with two-dimensional ion channel beta -Al_2O_3 comparison. In this paper, Na_3Zr_2Si_2PO_ (12) solid electrolyte materials and NZSP doped solid electrolyte materials doped with metal oxides were characterized by TG thermogravimetry, X ray diffraction, SEM scanning electron microscope and electrochemical workstation. NASICON type Na_3Zr_2Si_2PO_ (12) solid electrolyte materials were prepared by solid-phase method and sol-gel method respectively. The effects of sintering temperature and sintering time on the microstructure and electrochemical properties of solid electrolyte materials were studied. The experimental results show that the Na_3Zr_2Si_2PO_ (12) solid electrolyte material obtained by the solid phase method at 1100 C for 12h shows good electrochemical performance. At room temperature, the ionic conductivity and total ionic conductivity of the highest grain are 7.41 * 10~ (-4) S cm~ (-1) - and 5.82 x 10~ (-4) S cm~ (-1), respectively. The optimum sintering temperature of Na_3Zr_2Si_2PO_ (12) solid electrolyte materials prepared by sol-gel method is 1050. The samples obtained by calcination at this temperature had the best ionic conductivity. The ionic conductivity and total ionic conductivity of the samples were 4.74 x 10~ (-4) and cm~ (-1) and 2.93 x 10-5S cm~ (-1), respectively. On the basis of the above process optimization, the solid electrolyte of Na_3Zr_2Si_2PO_ (12) was modified by solid phase method. Through different metal oxides doping content of Na_ (3+y) Zr_ (2-x) M_xSi_2PO_ (12) (M = ZnO, MgO, La_2O_3, Nd_2O_3, Y_2O_3, CeO_2 and Nb_2O_5; 0 = x = 0.5; y according to the charge balance calculation and material) of the Zr~ (4+) doped. The physical and electrochemical properties of the doped products were tested by XRD, SEM, EIS and other methods. The optimum doping content of different metal oxides is x =0.1 by the XRD diffraction spectrum cabinet. Under the optimum doping content, the metal oxide selected in this paper can show good electrochemical performance for the doping of NASICON material. It is found that the La, Zn and Nb elements have good doping effect on the products. The ionic conductivity of the solid electrolyte materials of La, Zn and Nb doped at room temperature was 9.14 * 1 0~ (-4) S cm~ (-1), 9.15 * 10~ (-4) S cm~ (-1) and 1.14 * 10-3 S cm~ (-1), close to 10-3 S cm~ (-1), is have a higher ionic conductivity of solid electrolyte materials. The PS microspheres with particle size of 2-6 micron m were prepared by dispersion polymerization. The PS microspheres were used as templates to synthesize Na_3Zr_2Si_2PO_ (12) solid electrolyte materials by co deposition. Finally, Na_3Zr_2Si_2PO_ (12) solid electrolyte three dimensional macroporous materials were synthesized.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM912;O646

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