本文選題：氧化鋅 + 納米陣列��； 參考：《西南交通大學(xué)》2014年博士論文

【摘要】：能源與環(huán)境的可持續(xù)發(fā)展是社會發(fā)展和人類文明的兩大重要戰(zhàn)略。隨著人類對化石資源的不斷消耗和對能源需求的日益增加,使得人們對清潔新能源的開發(fā)越來越重視。其中,太陽能具有資源豐富、分布廣泛、綠色環(huán)保等特點,被認(rèn)為是最具潛力的新能源之一。染料敏化太陽能電池(Dye-sensitized Solar Cells, DSSC)具有制作工藝簡單和成本低廉等優(yōu)點,因而具有良好的發(fā)展前景。納米結(jié)構(gòu)光陽極薄膜是DSSC的重要組成部分,其結(jié)構(gòu)與組成直接影響電池的光伏性能,因此如何優(yōu)化與設(shè)計光陽極結(jié)構(gòu)是近年來DSSC領(lǐng)域研究的熱點問題之一。本文針對優(yōu)化和設(shè)計光陽極薄膜結(jié)構(gòu)的關(guān)鍵問題,以ZnO微/納結(jié)構(gòu)材料為研究對象,通過水熱法控制合成ZnO納米陣列及ZnO多級納米陣列結(jié)構(gòu),探討了ZnO納米結(jié)構(gòu)的可控生長機(jī)制,系統(tǒng)研究了ZnO納米結(jié)構(gòu)對DSSC光電轉(zhuǎn)換性能的影響規(guī)律。本文的具體工作和主要研究結(jié)果包括：1.通過水熱法制備了ZnO納米草陣列結(jié)構(gòu),研究了添加劑對ZnO納米草形貌、尺寸、長徑比的影響規(guī)律。結(jié)果表明,延長水熱生長時間,ZnO納米棒的直徑和長度都呈增大趨勢；進(jìn)一步研究發(fā)現(xiàn),向生長溶液中添加非極性聚乙烯亞胺(Polyethyleneimine, PEI)可以調(diào)控ZnO納米結(jié)構(gòu)的形貌和長徑比：當(dāng)PEI濃度由0增加至7 mM,ZnO納米棒尖端形貌由六棱柱狀逐漸轉(zhuǎn)變?yōu)殄F體狀,長徑比由34.34提高至93.83。此外,本文的研究還發(fā)現(xiàn),Al3+也可以調(diào)控ZnO納米結(jié)構(gòu)的生長,向生長液中添加少量硝酸鋁(0.25 mM), ZnO納米棒的直徑由465 nm顯著地降低至210 nm；進(jìn)一步增加硝酸鋁濃度時,ZnO納米棒的直徑?jīng)]有明顯的變化。作者分析認(rèn)為,ZnO晶核的晶面選擇性吸附添加劑是調(diào)控ZnO納米結(jié)構(gòu)生長的主要原因。2.采用檸檬酸三鈉輔助晶體二次生長,在ZnO納米棒表面原位生長ZnO納米片,制備了ZnO納米棒-納米片(ZnO NR-NS)多級納米陣列結(jié)構(gòu),發(fā)展了基于檸檬酸三鈉輔助ZnO異相成核原位制備ZnO多級納米陣列結(jié)構(gòu)新方法。表征結(jié)果表明,ZnO納米棒表面均勻包覆ZnO納米片,ZnO納米片由納米顆粒定向排列而成；同時,二次生長的溫度對ZnO NR-NS多級納米陣列結(jié)構(gòu)具有重要影響。在此基礎(chǔ)上,成功地將檸檬酸三鈉輔助二次生長技術(shù)拓展至柔性金屬基體(鋅片、不銹鋼網(wǎng)),制備出ZnO NR-NS多級納米陣列結(jié)構(gòu)。3.利用不同長徑比的ZnO納米草、ZnO NR-NS多級納米陣列以及柔性基體ZnONR-NS多級納米陣列制備了DSSC,并系統(tǒng)比較了其光伏性能。研究發(fā)現(xiàn)：用長徑比大的ZnO納米草制備的DSSC具有更高的短路電流密度和光電轉(zhuǎn)換效率,其短路電流密度由1.93提高至2.90 mA·cm-2,光電轉(zhuǎn)換效率由0.47%提高至0.73%,其原因是大的長徑比具有更高比表面積能夠吸附更多的染料；比較了利用ZnO納米草與ZnO NR-NS多級納米陣列所制備DSSC的光伏性能,發(fā)現(xiàn)后者的光電轉(zhuǎn)換效率提高了近70%,由0.66%提高至1.13%,其原因在于ZnO NR-NS多級納米陣列結(jié)構(gòu)光陽極進(jìn)一步提高了染料的負(fù)載量,同時還具有較高的光散射能力；基于柔性鋅片ZnO NR-NS多級納米陣列DSSC的光伏性能結(jié)果也表明,ZnO NR-NS多級納米陣列有利于提高光電轉(zhuǎn)換效率。4.通過檸檬酸三鈉輔助水熱生長技術(shù)制備了微米棒、多維結(jié)構(gòu)微球和空心微球等ZnO低維結(jié)構(gòu),研究了基于不同形貌ZnO微/納結(jié)構(gòu)的DSSC光伏性能。系統(tǒng)研究結(jié)果表明：引入檸檬酸根離子能夠改變ZnO晶核的本征生長方向,由原來的[001]晶向變?yōu)閇100]晶向擇優(yōu)生長；當(dāng)檸檬酸根離子濃度為1 mM時,得到直徑為2-3 gm的ZnO多維結(jié)構(gòu)微球,其形成機(jī)理經(jīng)歷了ZnO納米顆粒的定向自組裝形成納米片,ZnO納米片再自組裝形成多維微球結(jié)構(gòu)；當(dāng)檸檬酸根離子濃度為4 mM時,形成直徑為2-4 μm的ZnO空心微球,其生長過程則是先形成ZnO實心微球,經(jīng)歷Ostwald熟化過程演變成空心微球。研究了基于三種ZnO微/納結(jié)構(gòu)的DSSC光伏性能,結(jié)果表明ZnO多維結(jié)構(gòu)微球的光電轉(zhuǎn)換效率達(dá)到1.42%,明顯高于ZnO微米棒和空心微球的光電轉(zhuǎn)換效率(分別為0.41%和0.79%),分析認(rèn)為這是多維結(jié)構(gòu)微球內(nèi)部高的染料負(fù)載量、優(yōu)異的光散射能力以及較長的電子壽命共同作用的結(jié)果。5.采用浸漬法制備了導(dǎo)電聚苯胺(PANi)雜化ZnO納米草結(jié)構(gòu),并研究了PANi雜化ZnO納米草對光伏性能的影響。經(jīng)FT-IR和Raman光譜證實PANi和ZnO之間存在類化學(xué)鍵的雜化作用；當(dāng)PANi的濃度為100 mg·L-1時,經(jīng)PANi雜化后的ZnO納米草電極的光電轉(zhuǎn)換效率提高了60%,由0.40%升高至0.64%。研究還發(fā)現(xiàn),PANi與ZnO之間的雜化作用能夠有效促進(jìn)光生電子在界面的分離,這是雜化電極光電轉(zhuǎn)換效率提高的重要原因。
[Abstract]:The sustainable development of energy and environment is the two important strategy of social development and human civilization. With the continuous consumption of fossil resources and the increasing demand for energy, people pay more and more attention to the development of clean energy. Among them, the solar energy is rich in resources, widely distributed, green and environmental protection, and is considered as a kind of characteristics. One of the most potential new energy sources. The Dye-sensitized Solar Cells (DSSC) has the advantages of simple process and low cost, so it has good prospects. The nanostructured photo anode film is an important part of DSSC. Its structure and composition directly affect the photovoltaic performance of the battery, so how to optimize the photovoltaic performance of the battery. In recent years, the design of the structure of the photo anode is one of the hot issues in the DSSC field. In this paper, the key problem of optimizing and designing the structure of the photo anode film is to control the synthesis of the ZnO nanowire array and the ZnO multistage nanoarray structure by the hydrothermal method. The controllable growth machine of the ZnO nanostructure is discussed. The effect of ZnO nanostructures on the photoelectric conversion performance of DSSC was systematically studied. The specific work and main results of this paper were as follows: 1. the structure of ZnO nanograss array was prepared by hydrothermal method, and the influence of additives on the morphology, size and length diameter ratio of ZnO nanoscale was studied. The results showed that the time of hydrothermal growth was prolonged, ZnO nanorods were prolonged. The diameter and length are all increasing, and further study shows that the addition of non polar polyethyleneimine (Polyethyleneimine, PEI) to the growth solution can regulate the morphology and length to diameter ratio of ZnO nanostructures: when the PEI concentration increases from 0 to 7 mM, the tip morphology of ZnO nanorods gradually transforms from six prism to cones, and the ratio of length to diameter is raised by 34.34. In addition to 93.83., the study also found that Al3+ could also regulate the growth of ZnO nanostructures, adding a small amount of aluminum nitrate (0.25 mM) into the growth liquid, and the diameter of ZnO nanorods decreased significantly from 465 nm to 210 nm, and there was no significant change in the diameter of ZnO nanorods when the concentration of aluminum nitrate was further increased. The crystal surface selective adsorption additive is the main reason for the regulation of the growth of ZnO nanostructures..2. uses sodium citrate three to grow the crystal two times, and the ZnO nanorods on the surface of ZnO nanorods are grown in situ. The ZnO nanorod nanoscale (ZnO NR-NS) multistage nanoarray structure is prepared, and the presence of sodium citrate three sodium is used to assist ZnO heterogenous nucleation in situ. A new ZnO multistage nanoarray structure was prepared. The results showed that the surface of the ZnO nanorods was uniformly coated with ZnO nanoscale, and the ZnO nanoscale was arranged by the nanoparticles. At the same time, the temperature of the two growth was important to the structure of ZnO NR-NS multilevel nanoscale arrays. On this basis, the sodium citrate three sodium was successfully assisted by two times. The technology is extended to the flexible metal matrix (zinc sheet, stainless steel mesh), and the ZnO NR-NS multistage nanoarray structure.3. is prepared by using different length to diameter ratio of ZnO nanoscale, ZnO NR-NS multistage nanoscale arrays and flexible matrix ZnONR-NS multilevel nanoscale arrays, and its photovoltaic performance is compared systematically. The study shows that the length to diameter ratio of ZnO nanometers is large. The DSSC prepared by grass has higher short circuit current density and photoelectric conversion efficiency. The short circuit current density is increased from 1.93 to 2.90 mA. Cm-2, and the photoelectric conversion efficiency is increased from 0.47% to 0.73%. The reason is that the larger diameter ratio is higher than the surface area and can adsorb more dyes; compared with the use of ZnO nanoscale and ZnO NR-NS multilevel nanoscale array It is found that the photovoltaic performance of DSSC is improved by nearly 70%, from 0.66% to 1.13%. The reason is that the ZnO NR-NS multi-stage nanoarray photoanode further improves the load of the dye, and also has high light scattering ability; based on the flexible zinc chip ZnO NR-NS multistage nanoscale array DSSC The performance results also show that the ZnO NR-NS multistage nanoarray is beneficial to the improvement of the photoelectric conversion efficiency (.4.) through the ZnO low dimensional structure, such as micron rods, multidimensional structure microspheres and hollow microspheres, through the technology of sodium citrate three sodium assisted hydrothermal growth. The research results of the DSSC photovoltaic performance based on the different morphology of ZnO micro / nano structures have been studied. Citric acid ions can change the intrinsic growth direction of ZnO nucleation, and grow from the original [001] crystal to [100] crystal. When the concentration of citric acid ion is 1 mM, the ZnO multidimensional microspheres with a diameter of 2-3 GM are obtained. The formation mechanism experienced the directional self-assembly of ZnO nanoparticles and the formation of nanoscale fragments and the self-assembly of ZnO nanoscale. A multi-dimensional microsphere structure was formed. When the concentration of citric acid ion was 4 mM, the ZnO hollow microspheres with a diameter of 2-4 m were formed. The growth process was first formed by the formation of ZnO solid microspheres, which evolved into hollow microspheres through the process of Ostwald ripening. The photovoltaic properties based on three ZnO micro / nano structures were studied. The results showed that the photoelectric microspheres of ZnO multidimensional structure were optoelectronic. The conversion efficiency is 1.42%, obviously higher than the photoelectric conversion efficiency of ZnO micron rods and hollow microspheres (0.41% and 0.79% respectively). It is considered that this is the high dye load in the multidimensional structure microspheres, the excellent light scattering ability and the longer electron life effect..5. is prepared by the impregnation method to prepare the conductive polyaniline (PANi) hybrid. The structure of ZnO nano grass and the effect of PANi hybrid ZnO nano grass on the photovoltaic performance were investigated. FT-IR and Raman spectra confirmed the presence of chemical bonds between PANi and ZnO. When PANi concentration was 100 mg L-1, the photoelectric conversion efficiency of ZnO nanoscale electrode after PANi hybrid increased by 60%, from 0.40% to the study. Now, the hybridization between PANi and ZnO can effectively promote the separation of photoelectrons in the interface, which is an important reason for the improvement of photoelectric conversion efficiency of hybrid electrodes.

【學(xué)位授予單位】：西南交通大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TM914.4;TB383.1

【參考文獻(xiàn)】

相關(guān)博士學(xué)位論文 前1條

1 李政道;基于微/納結(jié)構(gòu)Zn、Sn基氧化物的染料敏化太陽能電池光陽極制備、性能研究[D];南京大學(xué);2013年

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本文編號：1850237