CN110775957A - A kind of preparation method of bio-based electron transport material - Google Patents
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Abstract
本发明提供一种生物基电子传输材料的制备方法，包括：在反应釜中放入生物质原料、掺氮试剂、有机溶剂，先超声波2‑5分钟；然后盖紧盖子，将反应釜放入马弗炉，缓慢升温至150‑200℃小时，反应6‑8h；反应完毕，降温至20℃；过滤以分离掉大颗粒的碳化物；硅胶柱层析法进行分离和提纯后，通过减压蒸馏脱出反应溶剂，最终制得生物制剂电子传输材料。本发明方法制备得到的生物基电子传输材料电子传输性能高；而且制备原料来源广泛，价格低廉。
The invention provides a method for preparing a bio-based electron transport material, which includes: putting biomass raw materials, nitrogen-doped reagents, and organic solvents into a reaction kettle, first ultrasonicating for 2-5 minutes; then closing the lid, and placing the reaction kettle in Muffle furnace, slowly heat up to 150-200 ℃ for 6-8 hours; after the reaction is completed, lower the temperature to 20 ℃; filter to separate out large particles of carbide; after separation and purification by silica gel column chromatography, reduce the pressure The reaction solvent is removed by distillation, and the electron transport material for biological preparations is finally prepared. The bio-based electron-transporting material prepared by the method of the invention has high electron-transporting performance; and the preparation raw materials have wide sources and low price.
Description
技术领域technical field
本发明涉及材料技术领域，尤其涉及一种可用于有机薄膜太阳能电池的生物基电子传输材料的制备方法。The invention relates to the technical field of materials, in particular to a preparation method of a bio-based electron transport material that can be used in organic thin film solar cells.
背景技术Background technique
将太阳能高效转换为电能仍然是人类所面临的最大挑战之一。尽管近年来在有机薄膜太阳能电池研究取得了飞速的进展，但受到材料制成本的影响，高纯度单晶硅仍然是太阳能电池产业中主导材料。图1中a)显示了有机薄膜太阳能电池的基本构造。与有机发光二极管相似，也是一种有机活性层被两端的电极夹在中间的“三明治”结构。有机活性层一般是由传输正孔的p型材料(例如导电高分子聚噻吩，P3HT)和传输电子的n型材料(富勒姆烯的衍生物，PCBM)所组成。在太阳光激发下产生的正负电荷分别通过P型材料和n型材料运送的各自相应的电极，实现彻底的电荷分离，在外部电路中形成电压以及电流。尽管近年来在有机薄膜太阳能电池研究取得了飞速的进展，但受到PCBM材料昂贵的合成成本的影响，高纯度单晶硅仍然是太阳能电池产业中主导材料。同样具有电子传输能力，而价格低廉的生物基碳纳米点，可代替合成成本昂贵的PCMB，被用于太阳能电池的电子传输材料(图1中b))。Efficient conversion of solar energy into electricity remains one of the greatest challenges facing humanity. Although the research on organic thin-film solar cells has made rapid progress in recent years, high-purity monocrystalline silicon is still the dominant material in the solar cell industry due to the cost of materials. A) in Figure 1 shows the basic structure of an organic thin-film solar cell. Similar to organic light-emitting diodes, it is also a "sandwich" structure in which the organic active layer is sandwiched by electrodes at both ends. The organic active layer is generally composed of p-type materials (such as conductive polymer polythiophene, P3HT) that transport positive holes and n-type materials (derivatives of fullemene, PCBM) that transport electrons. The positive and negative charges generated under the excitation of sunlight pass through the corresponding electrodes of the p-type material and the n-type material, respectively, to achieve complete charge separation, and to form voltage and current in the external circuit. Despite the rapid progress in organic thin-film solar cell research in recent years, high-purity monocrystalline silicon is still the dominant material in the solar cell industry due to the expensive synthesis cost of PCBM materials. The bio-based carbon nanodots also have the same electron transport ability, and the inexpensive bio-based carbon nanodots can be used as electron transport materials for solar cells instead of the expensive PCMB (Fig. 1b)).
碳纳米点(Carbon nanodots)是一种离散的、粒径范围在3-10nm，厚度在1nm以下的准球形纳米粒子，2004年首次被国外研究机构所报道以来，因其独特的荧光特性、极好的生物相容性(无毒性)、快速而廉价的制备方法，已被广泛地研究与报道。生物基碳纳米点，以纤维素、淀粉、壳聚糖、葡萄糖等生物质原料为碳源，利用溶剂法，碳化制备而得。Carbon nanodots are discrete quasi-spherical nanoparticles with a particle size range of 3-10 nm and a thickness of less than 1 nm. Good biocompatibility (non-toxic), fast and inexpensive preparation methods have been widely studied and reported. Bio-based carbon nanodots are prepared by carbonization of cellulose, starch, chitosan, glucose and other biomass raw materials as carbon sources by solvent method.
目前，生物基碳纳米点荧光增白剂最大的技术问题是，与传统的电子传输材料PCBM相比，电子传输效率偏低。通常的做法是碳纳米点的表面引入N元素等富电子基团(例如尿素，乙二胺等掺氮试剂)，增加碳纳米点表面的电子云密度，以此提高材料的电子流动性，可以使电子传输性能提高10–100倍。At present, the biggest technical problem of bio-based carbon nanodot fluorescent whitening agents is that compared with the traditional electron transport material PCBM, the electron transport efficiency is low. The usual practice is to introduce electron-rich groups such as N element (such as urea, ethylenediamine and other nitrogen-doping reagents) on the surface of carbon nanodots to increase the electron cloud density on the surface of carbon nanodots, thereby improving the electron mobility of the material. Improves electron transport performance by a factor of 10–100.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于解决上述现有技术存在的缺陷，提供一种更为廉价的、电子传输效率更为高效的生物基电子传输材料的制备方法。The purpose of the present invention is to solve the above-mentioned defects of the prior art, and to provide a preparation method of a bio-based electron transport material with a cheaper and more efficient electron transport efficiency.
一种生物基电子传输材料的制备方法，包括：A preparation method of a bio-based electron transport material, comprising:
在反应釜中放入生物质原料、掺氮试剂、有机溶剂，先超声波2-5分钟；Put biomass raw materials, nitrogen-doping reagents, and organic solvents into the reactor, and ultrasonicate for 2-5 minutes first;
然后盖紧盖子，将反应釜放入马弗炉，缓慢升温至150-200℃小时，反应6-8h；Then cover the lid tightly, put the reaction kettle into the muffle furnace, slowly heat up to 150-200 °C for 6-8 hours, and react for 6-8 hours;
反应完毕，降温至20℃；过滤以分离掉大颗粒的碳化物；After the reaction is completed, the temperature is lowered to 20°C; filtered to separate out large particles of carbides;
硅胶柱层析法进行分离和提纯后，通过减压蒸馏脱出反应溶剂，最终制得生物制剂电子传输材料。After separation and purification by silica gel column chromatography, the reaction solvent is removed by distillation under reduced pressure, and the electron transport material for biological preparations is finally prepared.
进一步地，如上所述的生物基电子传输材料的制备方法，所述的生物质原料为纤维素、淀粉、壳聚糖、木质素、半纤维素或葡萄糖中的任意一种。Further, in the above-mentioned preparation method of a bio-based electron transport material, the biomass raw material is any one of cellulose, starch, chitosan, lignin, hemicellulose or glucose.
进一步地，如上所述的生物基电子传输材料的制备方法，所述有机溶剂为丙酮、己酮或环己酮中的一种或几种的组合。Further, in the above-mentioned preparation method of a bio-based electron transport material, the organic solvent is one or a combination of acetone, hexanone or cyclohexanone.
进一步地，如上所述的生物基电子传输材料的制备方法，所述掺氮试剂为尿素或乙二胺中的任意一种。Further, in the above-mentioned preparation method of a bio-based electron transport material, the nitrogen-doped reagent is any one of urea or ethylenediamine.
进一步地，如上所述的生物基电子传输材料的制备方法，所述的反应釜为不锈钢反应釜。Further, in the above-mentioned preparation method of the bio-based electron transport material, the reaction kettle is a stainless steel reaction kettle.
根据如上任一方法制备得到的生物基电子传输材料。The bio-based electron transport material prepared according to any of the above methods.
与现有技术相比，本发明具有如下优点:Compared with the prior art, the present invention has the following advantages:
用于有机薄膜太阳能电池的传统的电子传输材料是富勒姆烯的衍生物(PCBM)，合成成本昂贵，而本发明的生物基电子传输材料组分是碳纳米点，而且制备碳纳米点的原料也是来自于天然产物，而不是传统的石油化学品，因此取材广泛，价格低廉；更重要的是本发明生物基碳纳米电子传输材料利用氮元素的富电子性来增加碳纳米点表面的电子云密度、增加分子的电子流动性，使得材料的导电率较高。The traditional electron transport material used in organic thin film solar cells is a derivative of fullemene (PCBM), which is expensive to synthesize, while the bio-based electron transport material component of the present invention is carbon nanodots, and the preparation of carbon nanodots The raw materials are also from natural products, not traditional petrochemicals, so the materials are widely available and the price is low; more importantly, the bio-based carbon nano-electron transport material of the present invention utilizes the electron-rich nature of nitrogen to increase the electrons on the surface of carbon nano-dots The cloud density, increasing the electron mobility of the molecules, makes the material more conductive.
附图说明Description of drawings
图1为有机太阳能电池结构以及所用到的电池材料结构图。Figure 1 shows the structure of an organic solar cell and the structure of the cell materials used.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面对本发明中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g纤维素、100mL丙酮，尿素，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在200℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为25％；测得：电导率(电子传输性)为2.2×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为3.10％。A preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of cellulose, 100 mL of acetone and urea into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is mixed evenly, the reaction kettle is placed in a muffle furnace, react at 200 °C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 °C, suction filtration, separate the large particles of carbides, and distill under reduced pressure to remove the reaction solvent; put the product solution in dichloromethane solvent, use silica gel Separation and purification were carried out by column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 25%; it was found that the electrical conductivity (electron transport) was 2.2×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 3.10%.
实施例2Example 2
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g纤维素、100mL丙酮，乙二胺，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在200℃反应，反应时间为8小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为22％；测得：电导率(电子传输性)为2.8×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为2.50％。The preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of cellulose, 100 mL of acetone, and ethylenediamine into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is uniformly mixed, put into the reaction kettle Muffle furnace, react at 200 ° C, the reaction time is 8 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; put the product solution in the dichloromethane solvent, The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthetic yield was 22%; it was found that the electrical conductivity (electron transport) was 2.8×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 2.50%.
实施例3Example 3
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g淀粉、100mL丙酮，尿素，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在200℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为20％；测得：电导率(电子传输性)为1.5×10- 4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为2.80％。A preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of starch, 100 mL of acetone, and urea into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is uniformly mixed, the reaction kettle is placed in a muffle furnace , react at 200 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and remove the reaction solvent by vacuum distillation; put the product solution in dichloromethane solvent, use silica gel column The separation and purification were carried out by chromatography (a mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthetic yield was 20%; it was found that the electrical conductivity (electron transport) was 1.5×10 - 4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 2.80%.
实施例4Example 4
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g壳聚糖、100mL丙酮，尿素，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在150℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为28％；测得：电导率(电子传输性)为2.5×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为3.20％。The preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of chitosan, 100 mL of acetone, and urea into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is uniformly mixed, the reaction kettle is placed in a horse Furnace, react at 150 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 28%; it was found that the electrical conductivity (electron transport) was 2.5×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 3.20%.
实施例5Example 5
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g木质素、100mL丙酮，尿素，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在180℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为20％；测得：电导率(电子传输性)为1.0×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为1.60％。A preparation method of a bio-based electron transport material of the present invention comprises the following steps: put 10 g of lignin, 100 mL of acetone and urea into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is uniformly mixed, the reaction kettle is placed in a muffle Furnace, react at 180 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the large particles of carbide, and distill under reduced pressure to remove the reaction solvent; put the product solution in dichloromethane solvent, use silica gel Separation and purification were carried out by column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 20%; it was measured that the electrical conductivity (electron transport) was 1.0×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 1.60%.
实施例6Example 6
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g壳聚糖、100mL己酮，尿素，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在150℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为30％；测得：电导率(电子传输性)为2.8×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为3.5％。A preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of chitosan, 100 mL of hexanone, and urea into a reaction kettle, ultrasonically sonicated for 2 minutes, and after the system is uniformly mixed, put into the reaction kettle Muffle furnace, react at 150 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the large particles of carbide, and distill under reduced pressure to remove the reaction solvent; put the product solution in the dichloromethane solvent, The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 30%; it was found that the electrical conductivity (electron transport) was 2.8×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 3.5%.
实施例7Example 7
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g壳聚糖、100mL己酮，乙二胺，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在150℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为20％；测得：电导率(电子传输性)为1.7×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为2.60％。The preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of chitosan, 100 mL of hexanone, and ethylenediamine into a reaction kettle, ultrasonically sonicated for 2 minutes, and after the system is evenly mixed, the reaction kettle Put it in a muffle furnace and react at 150°C for a reaction time of 6 hours. After the reaction is completed, cool down to 20°C, filter with suction, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; the product solution is dichloromethane solvent. , separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 20%; it was found that the electrical conductivity (electron transport) was 1.7×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 2.60%.
实施例8Example 8
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将10g淀粉、100mL丙酮，乙二胺，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在180℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为20％；测得：电导率(电子传输性)为1.0×10- 4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为2.00％。The preparation method of a bio-based electron transport material of the present invention includes the following steps: put 10 g of starch, 100 mL of acetone, and ethylene diamine into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is mixed uniformly, put the reaction kettle into a horse Furnace, react at 180 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 20%; it was found that the electrical conductivity (electron transport) was 1.0×10 - 4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 2.00%.
实施例9Example 9
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将生物质原料、溶剂，掺氮试剂，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在150℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为20％；测得：电导率(电子传输性)为1.5×10- 4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为2.80％。The preparation method of a bio-based electron transport material of the present invention includes the following steps: putting biomass raw materials, a solvent and a nitrogen-doped reagent into a reaction kettle, ultrasonically sonicating for 2 minutes, and after the system is uniformly mixed, the reaction kettle is placed in a horse Furnace, react at 150 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthetic yield was 20%; it was found that the electrical conductivity (electron transport) was 1.5×10 - 4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 2.80%.
所述的生物质原料为壳聚糖。所述的溶剂为丙酮、己酮中的两种组合。所述的掺氮试剂为尿素。所述的反应釜为不锈钢反应釜。The biomass raw material is chitosan. The solvent is a combination of acetone and hexanone. The nitrogen-doped reagent is urea. The reaction kettle is a stainless steel reaction kettle.
实施例10Example 10
本发明的一种生物基电子传输材料的制备方法，包括如下步骤：将生物质原料、溶剂，掺氮试剂，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在150℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为18％；测得：电导率(电子传输性)为1.3×10- 4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为2.60％。The preparation method of a bio-based electron transport material of the present invention includes the following steps: putting biomass raw materials, a solvent and a nitrogen-doped reagent into a reaction kettle, ultrasonically sonicating for 2 minutes, and after the system is uniformly mixed, the reaction kettle is placed in a horse Furnace, react at 150 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthetic yield was 18%; it was found that the electrical conductivity (electron transport) was 1.3×10 - 4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by hybrid P3HT was 2.60%.
所述的生物质原料为壳聚糖。所述的溶剂为丙酮、环己酮中的两种组合。所述的掺氮试剂为尿素。所述的反应釜为不锈钢反应釜。The biomass raw material is chitosan. The solvent is a combination of acetone and cyclohexanone. The nitrogen-doped reagent is urea. The reaction kettle is a stainless steel reaction kettle.
对比例：Comparative ratio:
没有使用掺氮试剂的生物基电子传输材料的制备方法，包括如下步骤：将10g壳聚糖、100mL己酮，放入反应釜中，超声波超声2分钟，体系混合均匀后，反应釜放入马弗炉，在150℃反应，反应时间为6小时，反应完毕，降温至20℃，抽滤，将大颗粒的碳化物分离，减压蒸馏脱出反应溶剂；将产品溶液二氯甲烷溶剂中，用硅胶柱层析法进行分离和提纯(二氯甲烷和乙醇混合物作为流动相)。最后，真空度0.04-0.08MPa的条件下减压蒸馏脱除溶剂，制得生物基碳纳米点电子传输材料。合成产率为18％；测得：电导率(电子传输性)为1.0×10- 6cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为0.40％。The preparation method of the bio-based electron transport material without using nitrogen-doped reagents includes the following steps: put 10 g of chitosan and 100 mL of hexanone into a reaction kettle, ultrasonically sonicate for 2 minutes, and after the system is uniformly mixed, the reaction kettle is placed in a horse Furnace, react at 150 ° C, the reaction time is 6 hours, after the reaction is completed, cool down to 20 ° C, suction filtration, separate the carbides of large particles, and distill under reduced pressure to remove the reaction solvent; The separation and purification were carried out by silica gel column chromatography (mixture of dichloromethane and ethanol as mobile phase). Finally, under the condition of vacuum degree of 0.04-0.08MPa, the solvent is removed by vacuum distillation, and the electron transport material of bio-based carbon nanodots is prepared. The synthesis yield was 18%; it was found that the electrical conductivity (electron transport ) was 1.0×10 -6 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of the solar cell prepared by the hybrid P3HT was 0.40%.
将对比例1与使用掺氮试剂的实施例6(电导率为2.8×10-4cm2V-1s-1，混合P3HT制备的太阳能电池的光电转化效率为3.5％)作对比，可发现本发明电子传输材料的导电率和光电转化效率均显著提高。Comparing Comparative Example 1 with Example 6 using nitrogen-doped reagents (conductivity of 2.8×10 -4 cm 2 V -1 s -1 , and the photoelectric conversion efficiency of solar cells prepared by hybrid P3HT is 3.5%), it can be found that Both the electrical conductivity and the photoelectric conversion efficiency of the electron transport material of the present invention are significantly improved.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be The technical solutions described in the foregoing embodiments are modified, or some technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
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