本文關(guān)鍵詞：NASICON型固體電解質(zhì)的合成與改性研究　出處：《天津工業(yè)大學》2017年碩士論文　論文類型：學位論文

  更多相關(guān)文章： 鈉離子電池 固體電解質(zhì) NASICON 離子電導率 摻雜

【摘要】：NASICON(Na Super-ionic Conductor)是一類具有三維離子傳輸通道的無機固體電解質(zhì),又稱為鈉快離子導體,其母體為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)固溶體具有較高的Na+電導率,當x = 2時,Na_3Zr_2Si_2PO_(12)具有較高的離子電導率,可以和具有二維離子通道的β-Al_2O_3相比較。本文通過TG熱重分析、X射線衍射技術(shù)、SEM掃描電鏡以及電化學工作站等對Na_3Zr_2Si_2PO_(12)固體電解質(zhì)材料及金屬氧化物摻雜過后的NZSP固體電解質(zhì)材料進行表征。本文分別采用固相法和溶膠凝膠法制備了 NASICON型Na_3Zr_2Si_2PO_(12)固體電解質(zhì)材料,研究了不同燒結(jié)溫度和燒結(jié)時間對固體電解質(zhì)材料的微觀結(jié)構(gòu)和電化學性能的影響。實驗結(jié)果表明,利用固相法在1100℃燒結(jié)12h得到的Na_3Zr_2Si_2PO_(12)固體電解質(zhì)材料表現(xiàn)出良好的電化學性能。室溫下,其最高晶粒離子電導率和總離子電導率分別為7.41×10~(-4)S cm~(-1)-和5.82×10~(-4) S cm~(-1)。溶膠凝膠法制備Na_3Zr_2Si_2PO_(12)固體電解質(zhì)材料的最佳燒結(jié)溫度為1050℃。該溫度下焙燒得到的樣品具有最佳的離子電導率,其晶粒離子電導率和總離子電導率分別為4.74×10~(-4)和 cm~(-1)和2.93×10-5S cm~(-1)。在上述工藝優(yōu)化的基礎(chǔ)上,采用固相法對Na_3Zr_2Si_2PO_(12)固體電解質(zhì)進行改性研究。通過不同摻雜含量的金屬氧化物對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根據(jù)電荷平衡計算而得)材料中的Zr~(4+)進行摻雜改性。利用XRD、SEM、EIS等方法對摻雜產(chǎn)物進行物理表征和電化學性能測試。XRD衍射譜閣確定出不同金屬氧化物的最佳摻雜含量為x =0.1。在最佳摻雜含量條件下,本文所選金屬氧化物對NASICON材料的摻雜均能表現(xiàn)出良好的電化學性能。研究發(fā)現(xiàn),La、Zn和Nb元素對產(chǎn)物有良好的摻雜改性效果。經(jīng)過La、Zn和Nb摻雜得到的固體電解質(zhì)材料在室溫下的離子電導率分別為 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),是具備較高離子電導率的固體電解質(zhì)材料。采用分散聚合法制備出粒徑為2-6 μm的PS微球,并以PS微球為模板,利用共沉積法將其與Na_3Zr_2Si_2PO_(12)固體電解質(zhì)材料復合,最終合成Na_3Zr_2Si_2PO_(12)固體電解質(zhì)三維大孔材料。
[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.
【學位授予單位】：天津工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TM912;O646

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