稀土材料应用于染料敏化太阳能电池的研究
发布时间：2018-08-15 13:53
【摘要】：染料敏化太阳能电池与传统硅基太阳能电池相比具有许多明显的优势，例如：原材料丰富、成本低、制备工艺简单，可制备柔性器件等。但是由于染料敏化太阳能电池的光谱响应范围窄，与太阳光谱不匹配，使得染料敏化太阳能电池的效率依然比较低，这极大限制了其产业化进程。作为电池核心组成部分的染料光敏化剂，吸收光谱的长波限一般都不超过750nm，而太阳光谱中有55%-60%分布于800nm-2400nm的近红外区域，所以要想从根本上提高染料敏化太阳能电池的效率就必须拓展电池的光谱响应范围。利用上转换发光材料将近红外光转换为可见光以及开发新的红外染料是拓展光谱响应范围的两种有效方法。目前，公认的效率最高的稀土掺杂上转换发光材料当属β-NaYF4:Yb3+,Er3+，但是其4f-4f跃迁窄带发光还是相对较弱，所以研究具有超强上转换发射的新型发光材料是非常必要的。染料敏化太阳能电池中染料分子必须要与被吸附的纳米半导体相匹配才能实现有效的电荷分离，所以研究新的半导体材料具有重要意义，并且对于以后新的红外染料的开发具有潜在的应用价值。针对以上两点，本论文从寻找适合于染料敏化太阳能电池的新型超强上转换发光材料和新半导体材料出发，研究了以下主要内容： (1)系统研究了Yb2O3材料的超强白光上转换发射，利用980nm激光作为激发光，对比研究了Yb2O3和β-NaYF4:Yb3+,Er3+在不同激发光功率密度激发下发射光谱的变化，发现在高功率密度激发下Yb2O3表现出超强的上转换白光发射，，其发射光积分强度比在同条件下β-NaYF4:Yb3+,Er3+的要强近一个数量级。通过对样品温度的研究，发现Yb2O3的白光发射的来源并不是黑体辐射，为此提出了新的发光机理模型，认为Yb2O3的白光发射来源于激发态Yb3+-Yb3+电子与价带中空穴的复合。最后分别将Yb2O3和β-NaYF4:Yb3+,Er3+作为光转换层应用于染料敏化太阳能电池，研究了两种器件在980nm激光激发下的I-V特性，发现随着激光功率密度的增加，基于Yb2O3的电池效率的增加速率要高于NaYF4器件，激光功率密度为4.737W/mm2时，Yb2O3器件效率约为NaYF4器件2.4倍。 (2)使用静电纺丝的方法制备了In2O3纳米管，通过稀土离子的掺杂成功的对In2O3纳米管的带隙进行了调节，并将其作为阳极半导体材料制备了In2O3基染料敏化太阳能电池，发现稀土离子掺杂能够使染料敏化太阳能电池的效率得到明显提高，通过对器件电化学阻抗谱的测试，发现电池效率提高的主要原因是稀土离子的掺杂抑制了In2O3中传输的电子与激发态染料以及电解质之间的复合。最终发现，掺杂Er3+离子的电池效率达到1.447%，与纯的In2O3电池相比提高了近3倍，是目前In2O3基染料敏化太阳能电池的最高效率。
[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.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：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.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.4
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