本文選題：染料敏化太陽能電池 + 光陽極改性��； 參考：《哈爾濱工業(yè)大學》2017年博士論文

【摘要】：染料敏化太陽能電池(DSSC)自1991年誕生以來,得到了長足的發(fā)展,但是也存在一定的問題。TiO2基的DSSC光陽極只能吸收波長小于387 nm的紫外光,使得電池的吸收光譜與太陽光光譜不匹配,TiO2較寬的帶隙降低了光生電子的注入效率,在光陽極界面間的載流子的復合作用,限制了電池光電流密度的提升。釕基N719染料在可見光區(qū)的吸收較弱,影響了電池光電轉換性能的進一步提高。傳統(tǒng)的Pt對電極不但儲量有限價格昂貴,電池的高生產(chǎn)成本,限制了染料敏化太陽能電池的發(fā)展。因此,制備新型的光陽極復合材料、提高對電極的催化性能及穩(wěn)定性顯得尤為重要。本論文針對上述DSSC存在的問題,將結構和性能優(yōu)異的多金屬氧酸鹽材料引入到染料敏化太陽能電池的電極中,合成了三種多金屬氧酸鹽化合物,并對它們進行了光電化學性質研究。從能級匹配、提高電池對太陽光譜的響應范圍、改善電池對電極的催化作用角度考察了其應用于傳統(tǒng)TiO2基染料敏化太陽能電池體系中的可能性;從能級結構、電子壽命、電池穩(wěn)定性等方面研究了改性后電池效率提高的原因。研究結果表明,多金屬氧酸鹽修飾的TiO2光陽極將電池的光吸收范圍拓展到了可見光區(qū),起到了光譜補償和光譜增效的雙重作用,降低了TiO2的禁帶寬度,提高了電子由N719染料注入到TiO2導帶的效率,抑制了電池內部載流子的反向復合作用,使得電子壽命得以延長;多金屬氧酸鹽復合的對電極,增強了其催化活性,進一步提高了電池的光電轉化性能。采用溶劑熱的方法制備了SiW11Ni和SiW11Cu兩種多金屬氧酸鹽,通過紫外可見近紅外以及光譜電化學的測試手段分析了它們應用到DSSC中的可能性,通過電流-電壓曲線,表面光電壓、電化學阻抗,開路電壓衰減、單色光效率譜等方法研究了多金屬氧酸鹽在TiO2基DSSC光陽極中的作用機理。實驗結果表明,這兩種多金屬氧酸鹽改性后的光陽極,其禁帶寬度變窄,進而提高了激發(fā)態(tài)電子注入到光陽極導帶的驅動力,擴寬了器件對太陽光的吸收范圍,提高了電池的光電流密度;同時,提高了電池中光生電子與空穴的分離能力,促進了電子傳輸、延長了電子壽命。多酸鹽改性后的TiO2光陽極電池其光電轉換效率比空白電池提高了22%,短路電流密度提升了31%。將多酸鹽SiW11Ni引入到染料敏化太陽電池的光陰極中,制備了SiW11Ni復合的Pt對電極,減少了貴金屬Pt的用量。采用循環(huán)伏安、塔菲爾極化曲線和電化學阻抗的測試方法研究了復合對電極SiW11Ni/Pt的催化性質,同時也研究了電池的穩(wěn)定性。實驗結果表明:SiW11Ni復合的Pt對電極具有較高的催化活性,促進了對電極電解液中I-/I3-的循環(huán)速度,加快染料再生的速度,與傳統(tǒng)的Pt對電極電池相比,電池的光電轉換性能提高了16%,短路電流密度提升了34%。在多金屬氧酸鹽修飾光陽極和對電極的基礎上,我們將SiW11Cu多酸鹽同時引入到DSSC的兩個光電極上,優(yōu)化了電池結構,組裝DSSC并測試了電池性能。結果表明,SiW11Cu多酸鹽在DSSC中起到了雙重作用,降低了電池的生產(chǎn)成本(以克為單位計算,其生產(chǎn)成本約為Pt的1/50),提高了對電極對電解液的催化作用,采用SiW11Cu復合的Pt對電極電池的光電性能提升了16%,短路電流密度提升了34%。針對多酸鹽較好的吸光性能,在水熱合成的條件下,選擇合成了吸光性能更好、能級匹配的Na3.5Co4[Bi2Co2W19.75O70(H2O)6]·39.5H2O(BiWCo)多酸鹽,進一步提升了電池在可見光區(qū)的吸收范圍,將光吸收范圍擴展至約800 nm,BiWCo多酸鹽可以起到敏化劑的作用,提高電子注入TiO2中的數(shù)量,抑制電子的復合,提高電子的注入效率。與空白電池相比,以BiWCo/TiO2作為光陽極電池的光電轉化效率由6.38%提高到了8.16%,短路電流密度提高了32%。
[Abstract]:Dye-sensitized solar cell (DSSC) has been greatly developed since its birth in 1991. However, there are some problems with the.TiO2 based DSSC photoanode that only absorbs ultraviolet light less than 387 nm, which makes the absorption spectrum of the battery do not match the solar light spectrum. The wide band gap of TiO2 reduces the injection efficiency of the photoelectron, in Guangyang The recombination between the carriers in the polar interface limits the increase of the photocurrent density of the battery. The weak absorption of the ruthenium based N719 dye in the visible light area affects the further improvement of the photoelectric conversion performance of the battery. The traditional Pt has limited reserves and high cost, and the high production cost of the battery limits the hair of the dye sensitized solar cells. Therefore, it is very important to prepare a new type of photo anode composite to improve the catalytic performance and stability of the electrode. In this paper, three kinds of polyoxometalate compounds are synthesized by introducing the polyoxometalate material with excellent structure and performance into the electrode of the dye sensitized solar cell for the problems of the DSSC. They have studied the photoelectric chemical properties. From the energy level matching, the increase of the response range of the solar spectrum to the solar spectrum and the improvement of the catalytic action of the battery to the electrode, the possibility of its application in the traditional TiO2 based dye sensitized solar cell system is investigated. The modified electric power is studied from the energy level structure, the electronic life life, the battery stability and so on. The research results show that the TiO2 photo anode modified by polyoxometalate extends the light absorption range of the battery to the visible light area, which plays the dual role of spectral compensation and spectral synergy, reduces the band gap of TiO2, improves the efficiency of the electron from N719 dye into the conduction band of the TiO2, and inhibits the internal load of the battery. The reverse recombination of the flow subsides makes the electronic life longer, and the polyoxometalate compound pair electrode enhances its catalytic activity and further improves the photoelectric conversion performance of the battery. Two kinds of SiW11Ni and SiW11Cu polyoxometalate are prepared by the solvent heat method, and the ultraviolet visible near infrared and spectroelectrochemistry are tested through the ultraviolet light. The possibility of their application to DSSC was analyzed by means of the method. The action mechanism of Polyoxometalates in the TiO2 based DSSC photoanode was studied through the current voltage curve, the surface photovoltage, the electrochemical impedance, the open circuit voltage attenuation, and the monochromatic light efficiency spectrum. The experimental results showed that the two kinds of polyoxometalates modified by the photoanode were forbidden. With the narrowing of the width, the driving force of the excited state electron injection into the photoanode guide band is enhanced, the absorption range of the solar light is widened and the photocurrent density of the battery is increased. At the same time, the separation ability of the photoelectron and hole in the battery is improved, the electron transport is promoted and the electronic life is extended. The TiO2 Guangyang after the polyacid salt modification is extended. The photoelectric conversion efficiency of the polar battery is 22% higher than that of the blank battery, the short circuit current density increases 31%. and the polyacid SiW11Ni is introduced into the photocathode of the dye-sensitized solar cell. The SiW11Ni composite Pt pair electrode is prepared, and the amount of the precious metal Pt is reduced. The measurement method of the cyclic voltammetry, Tafel polarization curve and electrochemical impedance is used. The catalytic properties of the composite electrode SiW11Ni/Pt are studied and the stability of the battery is also studied. The experimental results show that the SiW11Ni compound Pt has high catalytic activity to the electrode, promotes the circulation speed of I-/I3- in the electrode electrolyte, speeds up the speed of the dye regeneration, and compares the photoelectric conversion of the battery with the traditional Pt electrode battery. The performance increased by 16%, the short circuit current density increased 34%. on the basis of the polyoxometalate modified photoanode and the pair electrode. We introduced the SiW11Cu polyacid to the two optoelectronic poles of DSSC, optimized the battery structure, assembled the DSSC and tested the battery performance. The results showed that the SiW11Cu polyacid played a dual role in DSSC and decreased. The production cost of the battery is lower (the cost of the production cost is about Pt 1/50), which improves the catalytic activity of the electrode to the electrolyte. The SiW11Cu composite Pt has improved the photoelectric performance of the electrode battery by 16%. The short circuit current density improves the better absorbability of 34%. against the polyacid, and is selected under the condition of hydrothermal synthesis. Na3.5Co4[Bi2Co2W19.75O70 (H2O) 6] / 39.5H2O (BiWCo) polyacid is synthesized with better absorbability and energy level, which further improves the absorption range of the battery in the visible light area, extending the light absorption range to about 800 nm. BiWCo polyacid can play the role of sensitizer, increase the number of electron injected TiO2, inhibit the recombination of electrons, and lift the recombination of electrons. The efficiency of high electron injection. Compared with the blank battery, the photoelectric conversion efficiency of the BiWCo/TiO2 as an anodic battery increased from 6.38% to 8.16%, and the short circuit current density increased by 32%.
【學位授予單位】：哈爾濱工業(yè)大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O646;TM914.4

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