CN104242795B - A kind of tandem type solar power system and manufacture method - Google Patents
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Abstract
本发明公开了一种级联式太阳能发电系统及制作方法，包括染料敏化太阳电池，其特征是：所述染料敏化太阳电池A的下端设置有机太阳电池B，所述有机太阳电池B的下端设置热电器件C，所述染料敏化太阳电池A的负极连接所述有机太阳电池B的正极，所述有机太阳电池B的负极连接所述热电器件C的正极。本发明在生长有透明导电膜FTO一的透明玻璃衬底一上制作具有上转换功能的染料敏化太阳电池，然后在染料敏化太阳电池上制作具有下转换功能的有机太阳电池，然后在有机太阳电池上制作热电器件。利用红外上转换材料能有效将近红外光转换成可见光，进而被染料有效的吸收；利用蓝紫下转换材料能有效将蓝紫光转换成可见光。
The invention discloses a cascaded solar power generation system and a manufacturing method, comprising a dye-sensitized solar cell, characterized in that an organic solar cell B is arranged at the lower end of the dye-sensitized solar cell A, and an organic solar cell B is arranged at the lower end of the organic solar cell B. A thermoelectric device C is arranged at the lower end, the negative electrode of the dye-sensitized solar cell A is connected to the positive electrode of the organic solar cell B, and the negative electrode of the organic solar cell B is connected to the positive electrode of the thermoelectric device C. In the present invention, a dye-sensitized solar cell with up-conversion function is fabricated on a transparent glass substrate with a transparent conductive film FTO-, and then an organic solar cell with a down-conversion function is fabricated on the dye-sensitized solar cell, and then the organic solar cell with a down-conversion function is fabricated on the organic solar cell. Fabrication of thermoelectric devices on solar cells. The use of infrared up-conversion materials can effectively convert near-infrared light into visible light, and then be effectively absorbed by dyes; the use of blue-violet down-conversion materials can effectively convert blue-violet light into visible light.
Description
技术领域technical field
本发明涉及太阳能发电领域，具体地讲，涉及一种级联式太阳能发电系统及制备方法。The invention relates to the field of solar power generation, in particular to a cascaded solar power generation system and a preparation method.
背景技术Background technique
有效利用太阳能对于解决能源问题具有重要意义。近年来，光伏技术作为太阳能利用的重要手段得到了广泛的关注。为了提高光伏器件的转换效率，可以通过材料的合成或器件结构的设计来提高太阳光谱的利用率，特别是太阳光谱的蓝紫及红外区。再者，光伏器件工作中有很大一部分的能量是以热量的形式损失掉，因此可以通过将热电材料和光伏器件集成到一起来进一步减少能量的损失。Effective use of solar energy is of great significance for solving energy problems. In recent years, photovoltaic technology has received widespread attention as an important means of solar energy utilization. In order to improve the conversion efficiency of photovoltaic devices, the utilization rate of the solar spectrum, especially the blue-violet and infrared regions of the solar spectrum, can be improved through the synthesis of materials or the design of device structures. Furthermore, a large part of the energy in the operation of photovoltaic devices is lost in the form of heat, so the energy loss can be further reduced by integrating thermoelectric materials and photovoltaic devices.
基于以上的考虑，将染料敏化太阳电池及有机太阳电池集成在一起，并将上转换发光材料用于染料敏化太阳电池以充分吸收太阳光谱的红外部分，将下转换发光材料用于有机太阳电池以充分吸收太阳光谱的蓝紫部分，最后将热电材料集成到已经集成的光伏器件中以利用太阳光的热量。该发电系统具有如下优势：①利用红外上转换材料能有效将近红外光转换成可见光，进而被染料有效的吸收；②利用蓝紫下转换材料能有效将蓝紫光转换成可见光，进而被有机给体材料有效的吸收；③利用热电材料能有效将热量转换成电能。Based on the above considerations, dye-sensitized solar cells and organic solar cells are integrated, and up-conversion luminescent materials are used in dye-sensitized solar cells to fully absorb the infrared part of the solar spectrum, and down-conversion luminescent materials are used in organic solar cells. Cells to fully absorb the blue-violet part of the solar spectrum, and finally thermoelectric materials are integrated into already integrated photovoltaic devices to harness the heat of sunlight. The power generation system has the following advantages: ①Using infrared up-conversion materials can effectively convert near-infrared light into visible light, which is then effectively absorbed by dyes; ②Using blue-violet down-conversion materials can effectively convert blue-violet light into visible light, which is then absorbed by organic donors The material absorbs effectively; ③The use of thermoelectric materials can effectively convert heat into electrical energy.
发明内容Contents of the invention
本发明要解决的技术问题是提供一种级联式太阳能发电系统及制备方法，提高太阳能的转换效率。The technical problem to be solved by the present invention is to provide a cascaded solar power generation system and a preparation method to improve the conversion efficiency of solar energy.
本发明采用如下技术手段实现发明目的：The present invention adopts following technical means to realize the object of the invention:
一种级联式太阳能发电系统，包括染料敏化太阳电池，其特征是：所述染料敏化太阳电池A的下端设置有机太阳电池B，所述有机太阳电池B的下端设置热电器件C，所述染料敏化太阳电池A的负极连接所述有机太阳电池B的正极，所述有机太阳电池B的负极连接所述热电器件C的正极。A cascaded solar power generation system, comprising a dye-sensitized solar cell, characterized in that: an organic solar cell B is arranged at the lower end of the dye-sensitized solar cell A, and a thermoelectric device C is arranged at the lower end of the organic solar cell B. The negative electrode of the dye-sensitized solar cell A is connected to the positive electrode of the organic solar cell B, and the negative electrode of the organic solar cell B is connected to the positive electrode of the thermoelectric device C.
作为对本技术方案的进一步限定，所述染料敏化太阳电池从上至下依次包括玻璃衬底一、透明导电膜FTO一、TiO2及红外复合薄膜层、电解液层、Pt对电极、透明导电膜FTO二和玻璃衬底二。As a further limitation to this technical solution, the dye-sensitized solar cell includes a glass substrate, a transparent conductive film FTO, a TiO2 and an infrared composite thin film layer, an electrolyte layer, a Pt counter electrode, and a transparent conductive film from top to bottom. Film FTO II and glass substrate II.
作为对本技术方案的进一步限定，所述有机太阳电池包括透明导电膜FTO三、P3HT:PCBM 及蓝紫复合薄膜层，Al电极和玻璃衬底三。As a further limitation to this technical solution, the organic solar cell includes a transparent conductive film FTO3, a P3HT:PCBM and a blue-violet composite film layer, an Al electrode and a glass substrate3.
本发明还公开了一种级联式太阳能发电系统的制备方法，其特征在于，包括如下步骤：The invention also discloses a method for preparing a cascaded solar power generation system, which is characterized in that it includes the following steps:
（1）在生长有透明导电膜FTO一的玻璃衬底一上用丝网印刷法制备染料敏化太阳电池的光阳极，在制备过程中，采用TiO2和上转换发光材料ZnO:Er3+,Yb3+混合浆料，其中TiO2与上转换发光材料ZnO:Er3+,Yb3+的质量百分比是1:0.015然后再放入高温炉内退火；(1) The photoanode of the dye-sensitized solar cell was prepared by screen printing on the glass substrate with the transparent conductive film FTO-. In the preparation process, TiO 2 and the up-conversion luminescent material ZnO:Er 3+ were used , Yb 3+ mixed slurry, wherein the mass percentage of TiO 2 and up-conversion luminescent material ZnO:Er 3+ , Yb 3+ is 1:0.015 and then placed in a high temperature furnace for annealing;
（2）在双面生长有透明导电膜FTO二的玻璃衬底二的一侧用旋涂法制备Pt 对电极5，然后在箱式炉中450 ℃下退火30分钟；(2) Prepare Pt counter electrode 5 by spin coating on one side of glass substrate 2 with transparent conductive film FTO 2 grown on both sides, and then anneal in a box furnace at 450 °C for 30 minutes;
（3）用热熔胶将光阳极和Pt对电极进行封装，并注入电解液;(3) Encapsulate the photoanode and Pt counter electrode with hot melt adhesive, and inject electrolyte;
（4）在双面生长有透明导电膜FTO三 的玻璃衬底二 的另一侧用旋涂的方法制备有机太阳电池的活性层，采用P3HT:PCBM与下转换发光材料ZnO:Eu3+, Tb3+的混合浆料，在制备过程中转速为500RPM,时间60秒，P3HT:PCBM的质量百分比为1:1，P3HT:PCBM与下转换发光材料ZnO:Eu3+, Tb3+按质量百分比为1:0.01的比例混合，然后再放入高温炉内退火，温度小于200℃；(4) On the other side of the glass substrate 2 with the transparent conductive film FTO 3 grown on both sides, the active layer of the organic solar cell was prepared by spin coating, using P3HT:PCBM and the down-converting luminescent material ZnO:Eu 3+ , The mixed slurry of Tb 3+ , during the preparation process, the rotation speed is 500RPM, the time is 60 seconds, the mass percentage of P3HT:PCBM is 1:1, and the mass percentage of P3HT:PCBM and down-conversion luminescent material ZnO:Eu 3+ , Tb 3+ The ratio is 1:0.01, and then put into a high temperature furnace for annealing, the temperature is less than 200 ℃;
（5）用真空蒸镀法制备Al电极10，然后再放入高温炉内退火，温度小于200℃；(5) The Al electrode 10 is prepared by vacuum evaporation, and then placed in a high-temperature furnace for annealing at a temperature lower than 200°C;
（6）在N2保护的手套箱中，用环氧树脂及玻璃封装太阳电池；(6) Encapsulate solar cells with epoxy resin and glass in a N2 protected glove box;
（7）在有机太阳电池B的一侧用热硅膏集成热电元器件C。(7) Integrating thermoelectric components C on one side of organic solar cell B with thermal silicon paste.
作为对本技术方案的进一步限定，所述上转换发光材料ZnO:Er3+,Yb3+采用共沉淀法制备，其中Zn2+:Er3+摩尔比是1:0.02，Zn2+:Yb3+摩尔比是1:0.02，Er3+:Yb3+摩尔比是1:1。As a further limitation to this technical solution, the up-conversion luminescent material ZnO:Er 3+ , Yb 3+ is prepared by co-precipitation method, wherein the molar ratio of Zn 2+ :Er 3+ is 1:0.02, Zn 2+ :Yb 3 + molar ratio is 1:0.02, Er 3+ :Yb 3+ molar ratio is 1:1.
作为对本技术方案的进一步限定，所述下转换发光材料ZnO:Eu3+, Tb3+是用共沉淀法制备的，其中Zn2+:Eu3+摩尔比是1:0.02，Zn2+:Tb3+摩尔比是1:0.02，Eu3+:Tb3+摩尔比是1:1。As a further limitation to this technical solution, the down-conversion luminescent material ZnO:Eu 3+ , Tb 3+ is prepared by co-precipitation method, wherein the molar ratio of Zn 2+ :Eu 3+ is 1:0.02, Zn 2+ : The molar ratio of Tb 3+ is 1:0.02, and the molar ratio of Eu 3+ :Tb 3+ is 1:1.
作为对本技术方案的进一步限定，所述步骤（2）旋涂法的转速为1000 RPM，时间20秒。As a further limitation of the technical solution, the rotation speed of the step (2) spin coating method is 1000 RPM, and the time is 20 seconds.
作为对本技术方案的进一步限定，所述上转换发光材料ZnO:Er3+,Yb3+中稀土的掺杂的摩尔比为2%。As a further limitation to the technical solution, the molar ratio of rare earth doping in the up-conversion luminescent material ZnO:Er 3+ , Yb 3+ is 2%.
作为对本技术方案的进一步限定，所述下转换发光材料ZnO:Eu3+, Tb3+中稀土的掺杂的摩尔比为2%。As a further limitation to the technical solution, the molar ratio of rare earth doping in the down-converting luminescent material ZnO:Eu 3+ , Tb 3+ is 2%.
与现有技术相比，本发明的优点和积极效果是：本发明在生长有透明导电膜FTO一的透明玻璃衬底一上制作具有上转换功能的染料敏化太阳电池 ，然后在染料敏化太阳电池上制作具有下转换功能的有机太阳电池，然后在有机太阳电池上制作热电器件。利用上转换材料能有效将近红外光转换成可见光，进而被染料有效的吸收；利用下转换材料能有效将蓝紫光转换成可见光，进而被有机给体材料有效的吸收；利用热电材料能有效将热量转换成电能。Compared with the prior art, the advantages and positive effects of the present invention are: the present invention makes the dye-sensitized solar cell with up-conversion function on the transparent glass substrate that grows transparent conductive film FTO-, then dye-sensitized An organic solar cell with down-conversion function is fabricated on the solar cell, and then a thermoelectric device is fabricated on the organic solar cell. The use of up-conversion materials can effectively convert near-infrared light into visible light, which can then be effectively absorbed by dyes; the use of down-conversion materials can effectively convert blue-violet light into visible light, and then be effectively absorbed by organic donor materials; converted into electrical energy.
附图说明Description of drawings
图1为本发明优选实施例的结构示意图。Fig. 1 is a schematic structural diagram of a preferred embodiment of the present invention.
图2为本发明的上转换发光材料的发射光谱图。Fig. 2 is an emission spectrum diagram of the up-conversion luminescent material of the present invention.
图3为本发明的下转换发光材料的发射光谱图。Fig. 3 is an emission spectrum diagram of the down conversion luminescent material of the present invention.
图中，A、染料敏化太阳电池，B、机太阳电池，C、热电器件，1、玻璃衬底一，2、透明导电膜FTO一，3、TiO2及红外复合薄膜层，4、电解液层,5、Pt对电极，6、透明导电膜FTO二,7、玻璃衬底二，8、透明导电膜FTO三，9、P3HT:PCBM 及蓝紫复合薄膜层，10、Al电极，11、玻璃衬底三。In the figure, A, dye-sensitized solar cell, B, organic solar cell, C, thermoelectric device, 1, glass substrate 1, 2, transparent conductive film FTO 1, 3, TiO 2 and infrared composite thin film layer, 4, electrolytic Liquid layer, 5, Pt counter electrode, 6, transparent conductive film FTO 2, 7, glass substrate 2, 8, transparent conductive film FTO 3, 9, P3HT:PCBM and blue-violet composite film layer, 10, Al electrode, 11 , Glass substrate three.
具体实施方式detailed description
下面结合附图和优选实施例对本发明作更进一步的详细描述。The present invention will be further described in detail below in conjunction with the accompanying drawings and preferred embodiments.
参见图1，本发明包括染料敏化太阳电池A，所述染料敏化太阳电池A的下端设置有机太阳电池B，所述有机太阳电池B的下端设置热电器件C，所述染料敏化太阳电池A的负极连接所述有机太阳电池B的正极，所述有机太阳电池B的负极连接所述热电器件C的正极。Referring to Fig. 1, the present invention includes a dye-sensitized solar cell A, an organic solar cell B is arranged at the lower end of the dye-sensitized solar cell A, a thermoelectric device C is arranged at the lower end of the organic solar cell B, and the dye-sensitized solar cell The negative electrode of A is connected to the positive electrode of the organic solar cell B, and the negative electrode of the organic solar cell B is connected to the positive electrode of the thermoelectric device C.
所述染料敏化太阳电池从上至下依次包括玻璃衬底一、透明导电膜FTO一、TiO2及红外复合薄膜层、电解液层、Pt对电极、透明导电膜FTO二和玻璃衬底二。其中，TiO2及红外复合薄膜层的厚度为1微米左右，The dye-sensitized solar cell includes glass substrate 1, transparent conductive film FTO 1, TiO 2 and infrared composite film layer, electrolyte layer, Pt counter electrode, transparent conductive film FTO 2 and glass substrate 2 from top to bottom. . Among them, the thickness of TiO 2 and infrared composite film layer is about 1 micron,
所述有机太阳电池包括透明导电膜FTO三、P3HT:PCBM 及蓝紫复合薄膜层，Al电极和玻璃衬底三。P3HT:PCBM 及蓝紫复合薄膜层的厚度为3微米左右。The organic solar cell includes a transparent conductive film FTO3, P3HT:PCBM and a blue-violet composite thin film layer, an Al electrode and a glass substrate3. The thickness of P3HT: PCBM and blue-violet composite film layer is about 3 microns.
本发明还公开了一种级联式太阳能发电系统的制备方法，包括如下步骤：The invention also discloses a method for preparing a cascaded solar power generation system, which includes the following steps:
（1）在生长有透明导电膜FTO一的玻璃衬底一上用丝网印刷法制备染料敏化太阳电池的光阳极，在制备过程中，采用TiO2和上转换发光材料ZnO:Er3+,Yb3+混合浆料，其中TiO2与上转换发光材料ZnO:Er3+,Yb3+的质量百分比是1:0.015然后再放入高温炉内退火；(1) The photoanode of the dye-sensitized solar cell was prepared by screen printing on the glass substrate with the transparent conductive film FTO-. In the preparation process, TiO 2 and the up-conversion luminescent material ZnO:Er 3+ were used , Yb 3+ mixed slurry, wherein the mass percentage of TiO 2 and up-conversion luminescent material ZnO:Er 3+ , Yb 3+ is 1:0.015 and then placed in a high temperature furnace for annealing;
（2）在双面生长有透明导电膜FTO二的玻璃衬底二的一侧用旋涂法制备Pt 对电极5，然后在箱式炉中450 ℃下退火30分钟；(2) Prepare Pt counter electrode 5 by spin coating on one side of glass substrate 2 with transparent conductive film FTO 2 grown on both sides, and then anneal in a box furnace at 450 °C for 30 minutes;
（3）用热熔胶将光阳极和Pt对电极进行封装，并注入电解液;(3) Encapsulate the photoanode and Pt counter electrode with hot melt adhesive, and inject electrolyte;
（4）在双面生长有透明导电膜FTO三 的玻璃衬底二 的另一侧用旋涂的方法制备有机太阳电池的活性层，采用P3HT:PCBM与下转换发光材料ZnO:Eu3+, Tb3+的混合浆料，在制备过程中转速为500RPM,时间60秒，P3HT:PCBM的质量百分比为1:1，P3HT:PCBM与下转换发光材料ZnO:Eu3+, Tb3+按质量百分比为1:0.01的比例混合，然后再放入高温炉内退火，温度小于200℃；(4) On the other side of the glass substrate 2 with the transparent conductive film FTO 3 grown on both sides, the active layer of the organic solar cell was prepared by spin coating, using P3HT:PCBM and the down-converting luminescent material ZnO:Eu 3+ , The mixed slurry of Tb 3+ , during the preparation process, the rotation speed is 500RPM, the time is 60 seconds, the mass percentage of P3HT:PCBM is 1:1, and the mass percentage of P3HT:PCBM and down-conversion luminescent material ZnO:Eu 3+ , Tb 3+ The ratio is 1:0.01, and then put into a high temperature furnace for annealing, the temperature is less than 200 ℃;
（5）用真空蒸镀法制备Al电极10，然后再放入高温炉内退火，温度小于200℃；(5) Prepare the Al electrode 10 by vacuum evaporation, and then put it into a high-temperature furnace for annealing at a temperature lower than 200°C;
（6）在N2保护的手套箱中，用环氧树脂及玻璃封装太阳电池；(6) Encapsulate solar cells with epoxy resin and glass in a N2 protected glove box;
（7）在有机太阳电池B的一侧用热硅膏集成热电元器件C。(7) Integrating thermoelectric components C on one side of organic solar cell B with thermal silicon paste.
所述上转换发光材料ZnO:Er3+,Yb3+采用共沉淀法制备，其中Zn2+:Er3+摩尔比是1:0.02，Zn2+:Yb3+摩尔比是1:0.02，Er3+:Yb3+摩尔比是1:1，颗粒尺寸大小约为30 nm，具体光谱图参见图2，用于将红外光转换成可见光。The up-conversion luminescent material ZnO:Er 3+ , Yb 3+ is prepared by co-precipitation method, wherein the molar ratio of Zn 2+ :Er 3+ is 1:0.02, and the molar ratio of Zn 2+ :Yb 3+ is 1:0.02, The molar ratio of Er 3+ : Yb 3+ is 1:1, and the particle size is about 30 nm. See Figure 2 for the specific spectrum, which is used to convert infrared light into visible light.
所述下转换发光材料ZnO:Eu3+, Tb3+是用共沉淀法制备的，其中Zn2+:Eu3+摩尔比是1:0.02，Zn2+:Tb3+摩尔比是1:0.02，Eu3+:Tb3+摩尔比是1:1，颗粒尺寸大小约为30 nm，具体光谱图参见图3，用于将蓝紫光转换成可见光。The down conversion luminescent material ZnO:Eu 3+ , Tb 3+ is prepared by co-precipitation method, wherein the molar ratio of Zn 2+ :Eu 3+ is 1:0.02, and the molar ratio of Zn 2+ :Tb 3+ is 1: 0.02, the Eu 3+ : Tb 3+ molar ratio is 1:1, and the particle size is about 30 nm. See Figure 3 for the specific spectrum, which is used to convert blue-violet light into visible light.
所述步骤（2）旋涂法的转速为1000 RPM，时间20秒。The rotation speed of the step (2) spin coating method is 1000 RPM, and the time is 20 seconds.
所述上转换发光材料ZnO:Er3+,Yb3+中稀土的掺杂的摩尔比为2%。The molar ratio of rare earth doping in the up-conversion luminescent material ZnO:Er 3+ and Yb 3+ is 2%.
所述下转换发光材料ZnO:Eu3+, Tb3+中稀土的掺杂比例的摩尔比为2%。The molar ratio of the rare earth doping ratio in the down-conversion luminescent material ZnO:Eu 3+ , Tb 3+ is 2%.
本发明未经描述的技术特征可以通过或采用现有技术实现，在此不再赘述，当然，上述说明并非是对本发明的限制，本发明也并不仅限于上述举例，本技术领域的普通技术人员在本发明的实质范围内所做出的变化、改型、添加或替换，也应属于本发明的保护范围。The undescribed technical features of the present invention can be realized by or using the prior art, and will not be repeated here. Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Those of ordinary skill in the art Changes, modifications, additions or substitutions made within the essential scope of the present invention shall also belong to the protection scope of the present invention.
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