稀土材料應(yīng)用于染料敏化太陽(yáng)能電池的研究
發(fā)布時(shí)間：2018-08-15 13:53
【摘要】：染料敏化太陽(yáng)能電池與傳統(tǒng)硅基太陽(yáng)能電池相比具有許多明顯的優(yōu)勢(shì)，例如：原材料豐富、成本低、制備工藝簡(jiǎn)單，可制備柔性器件等。但是由于染料敏化太陽(yáng)能電池的光譜響應(yīng)范圍窄，與太陽(yáng)光譜不匹配，使得染料敏化太陽(yáng)能電池的效率依然比較低，這極大限制了其產(chǎn)業(yè)化進(jìn)程。作為電池核心組成部分的染料光敏化劑，吸收光譜的長(zhǎng)波限一般都不超過(guò)750nm，而太陽(yáng)光譜中有55%-60%分布于800nm-2400nm的近紅外區(qū)域，所以要想從根本上提高染料敏化太陽(yáng)能電池的效率就必須拓展電池的光譜響應(yīng)范圍。利用上轉(zhuǎn)換發(fā)光材料將近紅外光轉(zhuǎn)換為可見(jiàn)光以及開(kāi)發(fā)新的紅外染料是拓展光譜響應(yīng)范圍的兩種有效方法。目前，公認(rèn)的效率最高的稀土摻雜上轉(zhuǎn)換發(fā)光材料當(dāng)屬β-NaYF4:Yb3+,Er3+，但是其4f-4f躍遷窄帶發(fā)光還是相對(duì)較弱，所以研究具有超強(qiáng)上轉(zhuǎn)換發(fā)射的新型發(fā)光材料是非常必要的。染料敏化太陽(yáng)能電池中染料分子必須要與被吸附的納米半導(dǎo)體相匹配才能實(shí)現(xiàn)有效的電荷分離，所以研究新的半導(dǎo)體材料具有重要意義，并且對(duì)于以后新的紅外染料的開(kāi)發(fā)具有潛在的應(yīng)用價(jià)值。針對(duì)以上兩點(diǎn)，本論文從尋找適合于染料敏化太陽(yáng)能電池的新型超強(qiáng)上轉(zhuǎn)換發(fā)光材料和新半導(dǎo)體材料出發(fā)，研究了以下主要內(nèi)容： (1)系統(tǒng)研究了Yb2O3材料的超強(qiáng)白光上轉(zhuǎn)換發(fā)射，利用980nm激光作為激發(fā)光，對(duì)比研究了Yb2O3和β-NaYF4:Yb3+,Er3+在不同激發(fā)光功率密度激發(fā)下發(fā)射光譜的變化，發(fā)現(xiàn)在高功率密度激發(fā)下Yb2O3表現(xiàn)出超強(qiáng)的上轉(zhuǎn)換白光發(fā)射，，其發(fā)射光積分強(qiáng)度比在同條件下β-NaYF4:Yb3+,Er3+的要強(qiáng)近一個(gè)數(shù)量級(jí)。通過(guò)對(duì)樣品溫度的研究，發(fā)現(xiàn)Yb2O3的白光發(fā)射的來(lái)源并不是黑體輻射，為此提出了新的發(fā)光機(jī)理模型，認(rèn)為Yb2O3的白光發(fā)射來(lái)源于激發(fā)態(tài)Yb3+-Yb3+電子與價(jià)帶中空穴的復(fù)合。最后分別將Yb2O3和β-NaYF4:Yb3+,Er3+作為光轉(zhuǎn)換層應(yīng)用于染料敏化太陽(yáng)能電池，研究了兩種器件在980nm激光激發(fā)下的I-V特性，發(fā)現(xiàn)隨著激光功率密度的增加，基于Yb2O3的電池效率的增加速率要高于NaYF4器件，激光功率密度為4.737W/mm2時(shí)，Yb2O3器件效率約為NaYF4器件2.4倍。 (2)使用靜電紡絲的方法制備了In2O3納米管，通過(guò)稀土離子的摻雜成功的對(duì)In2O3納米管的帶隙進(jìn)行了調(diào)節(jié)，并將其作為陽(yáng)極半導(dǎo)體材料制備了In2O3基染料敏化太陽(yáng)能電池，發(fā)現(xiàn)稀土離子摻雜能夠使染料敏化太陽(yáng)能電池的效率得到明顯提高，通過(guò)對(duì)器件電化學(xué)阻抗譜的測(cè)試，發(fā)現(xiàn)電池效率提高的主要原因是稀土離子的摻雜抑制了In2O3中傳輸?shù)碾娮优c激發(fā)態(tài)染料以及電解質(zhì)之間的復(fù)合。最終發(fā)現(xiàn)，摻雜Er3+離子的電池效率達(dá)到1.447%，與純的In2O3電池相比提高了近3倍，是目前In2O3基染料敏化太陽(yáng)能電池的最高效率。
[Abstract]:Compared with traditional silicon based solar cells, dye sensitized solar cells have many advantages, such as abundant raw materials, low cost, simple preparation process, flexible devices and so on. However, due to the narrow spectral response range of dye sensitized solar cells, which does not match the solar spectrum, the efficiency of dye sensitized solar cells is still relatively low, which greatly limits the industrialization process of dye sensitized solar cells. As a core component of the battery, Guang Min dye has a long wavelength limit of less than 750 nm, and 55% to 60% of the solar spectrum is distributed in the near infrared region of 800nm-2400nm. Therefore, in order to improve the efficiency of dye-sensitized solar cells, we must expand the spectral response range of the cells. Up-conversion of near-infrared light to visible light and the development of new infrared dyes are two effective methods to expand the spectral response range. At present, the most efficient rare-earth doped up-conversion luminescent material is 尾 -NaYF4: Yb3 + Er3, but its 4f-4f transition narrowband luminescence is still relatively weak, so it is very necessary to study new luminescent materials with super-strong up-conversion emission. Dye molecules in dye sensitized solar cells must match the adsorbed nanocrystalline semiconductors in order to achieve effective charge separation, so it is of great significance to study new semiconductor materials. And it has potential application value for the development of new infrared dyes in the future. In view of the above two points, this thesis starts from looking for new ultra-strong up-conversion luminescent materials and new semiconductor materials suitable for dyestuff sensitized solar cells. The main contents are as follows: (1) the ultrastrong white light up-conversion emission of Yb2O3 materials is studied systematically. The changes of emission spectra of Yb2O3 and 尾 -NaYF4: Yb3 + Er3 under different excitation power densities are compared by using 980nm laser as excitation light. It is found that under the excitation of high power density, Yb2O3 exhibits superstrong up-conversion white light emission, and the intensity of optical integral emission is nearly one order of magnitude higher than that of 尾 -NaYF4: Yb3 Er3 under the same conditions. It is found that the white light emission of Yb2O3 is not black body radiation through the study of sample temperature. A new luminescence mechanism model is proposed. It is considered that the white light emission of Yb2O3 comes from the combination of excited Yb3 -Yb 3 electrons and holes in valence band. Finally, Yb2O3 and 尾 -NaYF _ 4: Yb _ 3 er _ 3 are used as optical conversion layers for dye sensitized solar cells. The I-V characteristics of two kinds of devices excited by 980nm laser are studied. It is found that the laser power density increases with the increase of laser power density. The increase rate of cell efficiency based on Yb2O3 is higher than that of NaYF4 devices. When the laser power density is 4.737W/mm2, the efficiency of Yb _ 2O _ 3 devices is about 2.4 times that of NaYF4 devices. (2) In2O3 nanotubes are fabricated by electrospinning. The band gap of In2O3 nanotubes was successfully adjusted by doping rare earth ions and used as anode semiconductor material to prepare In2O3 based dye sensitized solar cells. It is found that rare earth ion doping can improve the efficiency of dye sensitized solar cells. It is found that the main reason for the increase of cell efficiency is that the doping of rare earth ions inhibits the recombination of electrons, excited dyes and electrolytes transported in In2O3. Finally, it was found that the efficiency of Er3 ion doped solar cells reached 1.447um, which was nearly three times higher than that of pure In2O3 cells, which was the highest efficiency of In2O3 based dye-sensitized solar cells at present.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM914.4
[Abstract]:Compared with traditional silicon based solar cells, dye sensitized solar cells have many advantages, such as abundant raw materials, low cost, simple preparation process, flexible devices and so on. However, due to the narrow spectral response range of dye sensitized solar cells, which does not match the solar spectrum, the efficiency of dye sensitized solar cells is still relatively low, which greatly limits the industrialization process of dye sensitized solar cells. As a core component of the battery, Guang Min dye has a long wavelength limit of less than 750 nm, and 55% to 60% of the solar spectrum is distributed in the near infrared region of 800nm-2400nm. Therefore, in order to improve the efficiency of dye-sensitized solar cells, we must expand the spectral response range of the cells. Up-conversion of near-infrared light to visible light and the development of new infrared dyes are two effective methods to expand the spectral response range. At present, the most efficient rare-earth doped up-conversion luminescent material is 尾 -NaYF4: Yb3 + Er3, but its 4f-4f transition narrowband luminescence is still relatively weak, so it is very necessary to study new luminescent materials with super-strong up-conversion emission. Dye molecules in dye sensitized solar cells must match the adsorbed nanocrystalline semiconductors in order to achieve effective charge separation, so it is of great significance to study new semiconductor materials. And it has potential application value for the development of new infrared dyes in the future. In view of the above two points, this thesis starts from looking for new ultra-strong up-conversion luminescent materials and new semiconductor materials suitable for dyestuff sensitized solar cells. The main contents are as follows: (1) the ultrastrong white light up-conversion emission of Yb2O3 materials is studied systematically. The changes of emission spectra of Yb2O3 and 尾 -NaYF4: Yb3 + Er3 under different excitation power densities are compared by using 980nm laser as excitation light. It is found that under the excitation of high power density, Yb2O3 exhibits superstrong up-conversion white light emission, and the intensity of optical integral emission is nearly one order of magnitude higher than that of 尾 -NaYF4: Yb3 Er3 under the same conditions. It is found that the white light emission of Yb2O3 is not black body radiation through the study of sample temperature. A new luminescence mechanism model is proposed. It is considered that the white light emission of Yb2O3 comes from the combination of excited Yb3 -Yb 3 electrons and holes in valence band. Finally, Yb2O3 and 尾 -NaYF _ 4: Yb _ 3 er _ 3 are used as optical conversion layers for dye sensitized solar cells. The I-V characteristics of two kinds of devices excited by 980nm laser are studied. It is found that the laser power density increases with the increase of laser power density. The increase rate of cell efficiency based on Yb2O3 is higher than that of NaYF4 devices. When the laser power density is 4.737W/mm2, the efficiency of Yb _ 2O _ 3 devices is about 2.4 times that of NaYF4 devices. (2) In2O3 nanotubes are fabricated by electrospinning. The band gap of In2O3 nanotubes was successfully adjusted by doping rare earth ions and used as anode semiconductor material to prepare In2O3 based dye sensitized solar cells. It is found that rare earth ion doping can improve the efficiency of dye sensitized solar cells. It is found that the main reason for the increase of cell efficiency is that the doping of rare earth ions inhibits the recombination of electrons, excited dyes and electrolytes transported in In2O3. Finally, it was found that the efficiency of Er3 ion doped solar cells reached 1.447um, which was nearly three times higher than that of pure In2O3 cells, which was the highest efficiency of In2O3 based dye-sensitized solar cells at present.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM914.4
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