本文選題：La_2(WO_4)_3 + NaLa(WO_4)_2��； 參考：《南京大學(xué)》2014年博士論文

【摘要】：本論文通過水熱合成法制備了La2(WO4)3納米晶、NaLa(WO4)2微納米晶、MoO2微米空心球以及MoO2納米空心球等幾種鉬鎢(復(fù)合)氧化物的微納米結(jié)構(gòu),并成功實(shí)現(xiàn)了對(duì)NaLa(WO4)2形貌和尺寸以及對(duì)Mo02微米空心球內(nèi)部空間大小的調(diào)控。利用粉末X射線衍射(XRD)、掃描電子顯微鏡(SEM)、透射電子顯微鏡(TEM)、高分辨透射電子顯微鏡(HRTEM)等手段對(duì)所得材料的晶相、結(jié)構(gòu)、尺寸和形貌等進(jìn)行了詳細(xì)的表征,并基于這些表征提出了在不同反應(yīng)條件下所得不同結(jié)構(gòu)的形成機(jī)理。最后,通過熒光光譜(PL)、電化學(xué)工作站和鋰離子電池性能測(cè)試系統(tǒng)等考察了所得材料的光致發(fā)光性能或鋰離子電池陽極材料性能,并揭示微納米材料的性能與其結(jié)構(gòu)之間的內(nèi)在聯(lián)系。主要內(nèi)容概括如下：1.純相La2(WO4)3:Eu3+納米晶和紡錘狀NaLa(WO4)2:Yb3+/Er3+微納米晶：選擇性合成、形貌以及光致發(fā)光性能基于同一反應(yīng)體系選擇性合成了純相La2(WO4)3納米晶和均一的紡錘狀且尺寸可調(diào)的NaLa(WO4)2微納米晶。研究顯示Na+對(duì)選擇性合成起著至關(guān)重要的影響；后續(xù)的水熱處理對(duì)La2(WO4)3的形貌有很大影響；水熱溫度,水熱時(shí)間以及甘油添加量對(duì)NaLa(WO4)2的形貌和尺寸都有很重要的影響�；跁r(shí)間依賴實(shí)驗(yàn),提出了紡錘狀NaLa(WO4)2的形成機(jī)理為奧斯特瓦爾德熟化。所制備的La2(WO4)3:Eu3+納米晶在467 nm激光激發(fā)下能發(fā)射出純度很高的明亮的紅光,更為重要的是其能很好地分散在蒸餾水中。在980 nm紅外激光激發(fā)下,NaLa(WO4)2:Yb3+/Er3+的上轉(zhuǎn)換發(fā)射強(qiáng)度隨其中Yb3+含量的增加而快速增加,表明了從Yb3+到Er3+的高效能量傳遞。另外,隨著其中Yb3+含量的增加,發(fā)光色能從黃綠色變?yōu)榫G色。La2(WO4)3和NaLa(WO4)2的這些獨(dú)特性質(zhì)與它們獨(dú)特的晶體晶格緊密相關(guān)。2.形貌可控合成NaLa(WO4)2:形貌依賴的光致發(fā)光性能以及單相白光熒光粉NaLa(WO4)2:Tm3+/Tb3+/Eu3通過添加極少量的EDTA-2Na,在水熱條件下制備了均一的NaLa(WO4)2單晶微米紡錘。同時(shí),通過簡單的調(diào)節(jié)添加劑用量以及反應(yīng)溶劑的比例可使產(chǎn)物的形貌調(diào)變?yōu)槲⒚灼桨�、納米晶、亞微米啞鈴以及互相連接的孿微米球。通過對(duì)比NaLa(WO4)2:Eu3+微米紡錘和微米平板的光致發(fā)光性能,發(fā)現(xiàn)NaLa(WO4)2:Eu3+微米紡錘有更強(qiáng)烈的熒光發(fā)射強(qiáng)度,并進(jìn)一步探討了其中的可能原因。更重要的是,由于Tm3+, Tb3+向Eu3+的有效能量傳遞,通過調(diào)節(jié)優(yōu)化Tm3+、Tb3+和Eu3+在NaLa(WO4)2微米紡錘基質(zhì)中的摩爾比例,成功制備了新型的近紫外激發(fā)的單相白光熒光粉NaLa(WO4)2:Tm3+/Tb3+/Eu3+。3.MoO2@C微米空心球的合成及其顯著提高的鋰離子電池陽極材料性能以Mo03微米帶取代體相Mo03作為起始原料,通過簡單的水熱過程制備了內(nèi)部空間大小可調(diào)的Mo02微米空心球。實(shí)驗(yàn)結(jié)果表明反應(yīng)物的形貌對(duì)產(chǎn)物的形貌有很重要的影響,且可通過改變NaOH水溶液的添加量來調(diào)節(jié)微米空心球的內(nèi)部空間大小,接著我們進(jìn)一步提出了Mo02微米空心球可能的形成機(jī)理。結(jié)合水熱法及煅燒步驟,在MoO2微米空心球表面包覆了一層無定形碳。所制備的Mo02@C微米空心球作為鋰離子電池的陽極材料顯示了高的比容量及庫侖效率、優(yōu)異的循環(huán)穩(wěn)定性及倍率性能。MoO2@C微米空心球顯著提高的鋰離子電池陽極材料性能可歸因于其合理的結(jié)構(gòu)設(shè)計(jì),如納米尺度的基本構(gòu)建單元、導(dǎo)電碳包覆和中空結(jié)構(gòu)等,尤其是碳包覆與中空結(jié)構(gòu)之間的協(xié)同效應(yīng)。4.均一Mo02@C納米空心球的簡易制備及其優(yōu)異的儲(chǔ)鋰性能通過簡單的軟模板水熱方法結(jié)合后續(xù)的煅燒處理合成了尺寸200 nm左右的MoO2@C納米空心球,并闡述了MoO2@C納米空心球可能的形成機(jī)理。這一方法有效的將材料制備與碳層包覆整合為一個(gè)步驟,有利于材料的工業(yè)化制備。由于MoO2@C納米空心球獨(dú)特的結(jié)構(gòu),如極小的構(gòu)建單元,中空結(jié)構(gòu),碳包覆,因而展現(xiàn)了優(yōu)異的儲(chǔ)鋰性能,如高的可逆容量(909.8 mAh·g-1),良好的循環(huán)穩(wěn)定性以及優(yōu)異的倍率性能。
[Abstract]:In this paper, the microstructures of La2 (WO4) 3 nanocrystals, NaLa (WO4) 2 micronanocrystals, MoO2 micron hollow spheres and MoO2 nano hollow spheres were prepared by hydrothermal synthesis method. The morphology and size of NaLa (WO4) 2 and the internal space size of Mo02 micrometer hollow spheres were successfully realized. Powder X rays were used. Diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM) are used to characterize the crystalline phase, structure, size and morphology of the obtained materials. Based on these characterization, the formation mechanism of different structures under different reaction conditions is proposed. Finally, the fluorescent light is used. Spectrum (PL), electrochemical workstation and lithium ion battery performance testing system have been used to investigate the photoluminescence properties of the materials or the properties of lithium ion battery anode materials, and reveal the internal relations between the properties of the micro and nanomaterials and their structures. The main contents are as follows: 1. pure phase La2 (WO4) 3:Eu3+ nanocrystals and spindle NaLa (WO4) 2:Yb3+/Er 3+ micro nanocrystals: selective synthesis, morphology and photoluminescence properties are selective synthesis of pure phase La2 (WO4) 3 nanocrystals and homogeneous spindle like and adjustable NaLa (WO4) 2 micro nanocrystals based on the same reaction system. Studies show that Na+ plays a vital role in selective synthesis; followed by hydrothermal treatment on the morphology of La2 (WO4) 3. The effect of hydrothermal temperature, hydrothermal time and glycerol addition on the morphology and size of NaLa (WO4) 2 is very important. Based on the time dependence experiment, the formation mechanism of the spindle like NaLa (WO4) 2 is developed in Ostwald. The prepared La2 (WO4) 3:Eu3+ nanocrystals can emit a high purity under the 467 nm laser excitation. Bright red light and more important is that it can be well dispersed in distilled water. Under 980 nm infrared laser excitation, the upconversion intensity of NaLa (WO4) 2:Yb3+/Er3+ increases rapidly with the increase of Yb3+ content, indicating the efficient energy transfer from Yb3+ to Er3+. In addition, with the increase of Yb3+ content, the luminescent color can be from yellowish green. These unique properties changed into green.La2 (WO4) 3 and NaLa (WO4) 2 with their unique crystal lattice closely related to.2. morphology to synthesize the photoluminescence properties of NaLa (WO4) 2: morphologies and the single-phase white light phosphor NaLa (WO4) 2:Tm3+/Tb3+/Eu3 by adding a very small amount of EDTA-2Na, and preparing a homogeneous 2 single crystal under the hydrothermal condition. At the same time, the morphologies of the products can be modulated into micron plates, nanocrystals, submicron dumbbell and interconnected twin microspheres by simply adjusting the amount of additives and the proportion of the reactive solvents. The NaLa (WO4) 2:Eu3+ micron spindle has been found by comparing the photoluminescence properties of the NaLa (WO4) 2:Eu3+ micron spindle and the micron plate. The stronger fluorescence intensity and possible reasons are further discussed. More importantly, the new type of single-phase white phosphor NaLa (WO4) 2:Tm3+/T of a new type of near ultraviolet excitation is successfully prepared by adjusting the effective energy transfer of Tm3+, Tb3+ to Eu3+, and by adjusting the molar ratio of Tm3+, Tb3+ and Eu3+ in the 2 micron spindle matrix of NaLa (WO4). The synthesis of b3+/Eu3+.3.MoO2@C micron hollow sphere and its remarkable improvement in the performance of lithium ion battery anode material with Mo03 micron band instead of the body phase Mo03 as starting materials, the inner space and adjustable Mo02 micrometer hollow spheres are prepared by a simple hydrothermal process. The experimental results show that the morphology of the reactants is very important to the morphology of the products. The internal space of the microspheres can be adjusted by changing the amount of the NaOH aqueous solution. Then we further put forward the possible formation mechanism of the Mo02 microsphere hollow sphere. In combination with the hydrothermal method and the calcination step, a layer of amorphous carbon is coated on the surface of the hollow sphere of the MoO2 micron. The prepared Mo02@C microsphere hollow sphere is used as the lithium separation. The anode material of the subbattery shows a high specific capacity and coulomb efficiency. The excellent performance of the anode material of the.MoO2@C micron hollow sphere is due to its reasonable structural design, such as the basic construction unit of nanoscale, the conductive carbon coating and the hollow structure, especially the carbon coating. The synergistic effect between the hollow structure and the.4. homogeneous Mo02@C nano hollow sphere is easy to be prepared and its excellent lithium storage properties have been synthesized by a simple soft template water heat method combined with subsequent calcination, and the possible formation mechanism of MoO2@C nano hollow spheres is described. This method is effective. The combination of material preparation and carbon coating is beneficial to the industrialization of materials. Due to the unique structure of MoO2@C nanospheres, such as small construction unit, hollow structure, carbon coating, it shows excellent lithium storage properties, such as high reversible capacity (909.8 mAh. G-1), good cyclic stability and excellent multiplier. Performance.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM912;TB383.1

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