基于亚氨基芪电子给体的敏化染料及其性能
发布时间：2018-08-01 10:39
【摘要】：染料敏化太阳能电池(DSSCs)是利用吸附在半导体表面的染料分子吸收太阳光,从而将太阳能转换成电能的一种新型太阳能电池,具有制作工艺简单、成本低廉、光电转换效率较高等优势,引起了研究者们的广泛研究。如何有效地提高染料敏化太阳能电池的光电转换效率和使用寿命是目前染料敏化电池研究领域的关键问题。本论文创新性地将亚氨基芪化合物引入染料敏化电池,提高染料稳定性。在以亚氨基芪化合物为电子给体的分子中,系统性地引入了不同的强吸电子基团,并测试了染料的光电性能及器件的光电转换效率。 第一章,简要介绍了有机染料敏化太阳能电池(DSSCs)的结构及其工作原理,评价电池性能的主要指标,纳米晶半导体电极和电解质等的发展概况,综述了目前染料敏化剂的研究进展,在此基础之上提出了本论文的研究思路和主要内容。 第二章,首次将亚氨基二苄和亚氨基芪基团引入染料敏化剂中,并以其为电子给体,噻吩作为π共轭桥链,氰基乙酸为电子受体,合成了IDB-1,ISB-1, IDB-2和ISB-2,研究亚氨基二苄和亚氨基芪基团对染料敏化太阳能电池性能参数的影响。对比亚氨基二苄和亚氨基芪两种基团,基于亚氨基芪的染料具有更宽的吸收光谱,在可见光区具有更好的光捕获能力。并在电子给体与噻吩基团中间引入烯烃键,研究其对染料吸收光谱的影响。烯烃键的引入可以有效地扩宽染料的吸收光谱。在AM1.5G，100mW cm-2光照条件下,染料ISB-2得到13.14mA·cm-2的短路电流、0.649V的开路电压、0.68的填充因子和5.83%的光电转换效率。 第三章,以苯并噻二唑单元作为额外的受体,以亚氨基芪作为电子给体,设计了四个D-A-π-A结构的染料S1～S4,考察引入吸电子基团苯并噻二唑后对染料的吸收光谱和能级、光电性能的影响。吸电子基团苯并噻二唑的引入,使染料的吸收光谱发生红移,增强了染料的光捕获能力。改变与受体相邻的共轭基团,如噻吩和苯基,可以简单有效地调节染料的能级,改进其光电性能。基于染料S1,S2,S3和S4的DSSCs的IPCE在350～550nm的区域内,均达到了60%,最高达到了90%。其中,基于染料S2的DSSCs得到12.11mA·cm-2的短路电流、0.673V的开路电压、0.66的填充因子和5.36%的光电转换效率,在优化条件后,得到13.69mA·cm-2的短路电流、0.722V的开路电压、0.67的填充因子和6.71%的光电转换效率。 第四章,以喹喔啉单元作为额外的受体,以亚氨基芪作为电子给体,设计了两个D-A-兀-A结构的染料Q1和Q2,考察引入吸电子基团喹喔啉后对染料的吸收光谱和能级、光电性能的影响。吸电子基团喹喔啉的引入,有效地减小了染料因吸附时羧基丢失质子而造成的光谱蓝移,保证了染料在Ti02膜上对光的吸收；有效地提高了染料的LUMO能级,更利于染料光电性能的提高。在此喹喔啉体系中,用呋喃取代与受体相邻的共轭桥链噻吩基团,染料分子的HOMO能级向上移动,LUMO能级进一步提高,增大了染料的LUMO与Ti02导带的带隙。基于染料Q1和Q2的DSSCs的IPCE在400～550nm的区域内,均达到了50%。其中,基于染料Q1的DSSC得到11.76mA·cm-2的短路电流、0.734V的开路电压、0.73的填充因子和6.28%的光电转换效率,Q2得到12.89mA·cm-2的短路电流、0.714V的开路电压、0.72的填充因子和6.66%的光电转换效率。 第五章,以吡咯并吡咯二酮单元作为额外的受体,以亚氨基芪作为电子给体,设计了两个D-A-兀-A结构的染料Q1和Q2,考察引入吸电子基团吡咯并吡咯二酮后对染料的吸收光谱和能级、光电性能的影响。吸电子基团吡咯并吡咯二酮的引入,染料的吸收光谱红移了50nm,同时,在400nm附近多出一个吸收带,增强了染料的光捕获能力。DPP染料具有较高的摩尔消光系数。基于染料DPP-1的DSSC的IPCE响应范围达到了700nm。 第六章,在苯并噻二唑和喹喔啉基团上引入己氧基侧链,并以此为额外的受体,设计了两个D-A-π-A结构的染料H1和H2,考察引入己氧基链后对染料的吸收光谱和能级、光电性能的影响。在苯并噻二唑和喹喔啉基团引入己氧基侧链后,吸收光谱都发生了10nm左右的蓝移,染料的LUMO能级有一定的提升。在此苯并噻二唑体系中,引入己氧基侧链后,有效地抑制了染料在Ti02膜上的聚集,并阻止了电子的回传,短路电流和开路电压都有所提高。但在喹喔啉的体系中引入己氧基侧链,却明显没有起到这样的作用。
[Abstract]:Dye sensitized solar cell (DSSCs) is a new type of solar cell which uses the dye molecules adsorbed on the surface of the semiconductor to absorb the sun and convert the solar energy into electric energy. It has the advantages of simple production process, low cost and high photoelectric conversion efficiency. It has caused extensive research in the researchers. How to improve the dye effectively The photoelectric conversion efficiency and service life of sensitized solar cells are the key problems in the current research field of dye-sensitized batteries. This paper introduces aminqi compound into dye sensitized battery to improve the stability of dye. Different strong absorbencies are systematically introduced in the subdivision of the electron donor with amidagalqi compound. The photoelectric properties of the dyes and photoelectric conversion efficiency of the devices were tested.
In the first chapter, the structure and working principle of the organic dye sensitized solar cell (DSSCs), the main indexes of the battery performance, the development of nanocrystalline semiconductor electrodes and electrolytes, and the progress in the research of the current dye sensitizers are reviewed. On the basis of this, the research ideas and main contents of this paper are put forward.
In the second chapter, IDB-1, ISB-1, IDB-2 and ISB-2 were synthesized by the introduction of subininyl two benzyl and aminoastragalus group in the dye sensitizer, and thiophene as the conjugated bridge chain and cyanoacetic acid as the electron acceptor. The effect of subamino two benzyl and amiaminqi groups on the performance parameters of dye-sensitized solar cells was studied. Two groups of amino two benzyl and amiaminqi, the dyestuff based dyestuff has a wider absorption spectrum and better optical capture in the visible region. The introduction of olefin bonds between the electron donor and thiophene group is used to study the effect of the dye on the absorption spectrum of the dye. The introduction of olefin bonds can effectively broaden the absorption spectrum of the dye. Under the conditions of AM1.5G, 100mW cm-2, the dye ISB-2 gets the short-circuit current of 13.14mA / cm-2, the open circuit voltage of 0.649V, 0.68 filling factor and 5.83% photoelectric conversion efficiency.
In the third chapter, using the BENZOTHIAZOL two azole unit as an additional receptor, the dye S1 ~ S4 of four D-A- PI -A structures was designed with amithagqi as an electron donor. The absorption spectrum and energy level and the photoelectric property of the dye were investigated after the introduction of the electronic group benzothiazide two azole. The absorption of the dyestuff group, benzothiazole, two azole, was introduced to make the dye absorption light The red shift of the spectrum increases the light capture ability of the dye. Changing the conjugated groups adjacent to the receptor, such as thiophene and phenyl, can easily and effectively regulate the dye's energy level and improve its photoelectric properties. The IPCE based on the DSSCs of the dye S1, S2, S3 and S4 has reached 60% in the 350 to 550nm region, and the highest reaches 90%., based on the S2 DS of the dye. SCs gets the short circuit current of 12.11mA cm-2, the open circuit voltage of 0.673V, 0.66 filling factor and 5.36% photoelectric conversion efficiency. After the optimization, the short-circuit current of 13.69mA / cm-2, the open circuit voltage of 0.722V, the filling factor of 0.67 and the photoelectric conversion efficiency of 6.71% are obtained.
In the fourth chapter, with the quinoaline unit as an additional receptor and amiimara as an electron donor, two dyes Q1 and Q2 of D-A- -A structure were designed, and the absorption spectra and energy levels of the dyes were introduced after introducing the electronic group of quinozolin. The introduction of quinozoline, the absorption group, effectively reduced the carboxyl dye when the dye was adsorbed. The blue shift of the spectrum caused by the loss of the proton, ensures the absorption of the dye on the Ti02 film, effectively improves the LUMO energy level of the dye and is more conducive to the improvement of the photoelectrical properties of the dye. In this system, the thiophene group of the conjugated bridge chain adjacent to the receptor is substituted with furan, the HOMO energy level of the dye molecules moves upwards, and the LUMO level is entered. The step increases the band gap between the dye LUMO and the Ti02 guide band. 50%. based on the DSSCs of dye Q1 and Q2 has reached 50%. in the region of 400 to 550nm. Based on the DSSC of the dye Q1, the short-circuit current of 11.76mA cm-2 is obtained, the open circuit voltage, the filling factor of 0.73 and the photoelectric conversion efficiency of 6.28% are obtained. The open circuit voltage of 0.714V, the fill factor of 0.72 and the photoelectric conversion efficiency of 6.66%.
The fifth chapter, using pyrrole and pyrrole two one unit as an additional receptor, using amiimalin as an electron donor, designed two D-A- -A dyes Q1 and Q2. The absorption spectra and energy levels of the dye, the effect of the absorption spectrum and energy level on the dye were investigated. The introduction of the electron group pyrrole and pyrrole two ketone was introduced. The absorption spectrum of the material redshifted 50nm, and at the same time, there was an absorption band near 400nm, which enhanced the light capture ability of the dye and.DPP dye had a higher molar extinction coefficient. The IPCE response range of DSSC based on dyestuff DPP-1 reached 700nm.
In the sixth chapter, two D-A- PI -A dyes H1 and H2 were designed by introducing the side chain of benzothiazolyl and oloxaline groups and taking it as an additional receptor. The absorption spectra and energy levels of the dyes were investigated and the effects of the photoelectrical properties were investigated after the introduction of the alkoxyl chain. The absorption of light after the BENZOTHIAZOL and the Chloroalkyl group was introduced into the side chain of the oxygen group. The blue shift of the spectrum is about 10nm, and the LUMO level of the dye has a certain increase. In the benzothiazole two azole system, after the introduction of the side chain of the oxygen group, the aggregation of the dye on the Ti02 membrane is effectively inhibited and the return of the electrons is prevented. The short circuit current and the open circuit voltage are raised. But the oxygen group side chain is introduced in the system of the oxaline. It was obvious that it did not play such a role.
【学位授予单位】：华东理工大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.4
本文编号：2157304
[Abstract]:Dye sensitized solar cell (DSSCs) is a new type of solar cell which uses the dye molecules adsorbed on the surface of the semiconductor to absorb the sun and convert the solar energy into electric energy. It has the advantages of simple production process, low cost and high photoelectric conversion efficiency. It has caused extensive research in the researchers. How to improve the dye effectively The photoelectric conversion efficiency and service life of sensitized solar cells are the key problems in the current research field of dye-sensitized batteries. This paper introduces aminqi compound into dye sensitized battery to improve the stability of dye. Different strong absorbencies are systematically introduced in the subdivision of the electron donor with amidagalqi compound. The photoelectric properties of the dyes and photoelectric conversion efficiency of the devices were tested.
In the first chapter, the structure and working principle of the organic dye sensitized solar cell (DSSCs), the main indexes of the battery performance, the development of nanocrystalline semiconductor electrodes and electrolytes, and the progress in the research of the current dye sensitizers are reviewed. On the basis of this, the research ideas and main contents of this paper are put forward.
In the second chapter, IDB-1, ISB-1, IDB-2 and ISB-2 were synthesized by the introduction of subininyl two benzyl and aminoastragalus group in the dye sensitizer, and thiophene as the conjugated bridge chain and cyanoacetic acid as the electron acceptor. The effect of subamino two benzyl and amiaminqi groups on the performance parameters of dye-sensitized solar cells was studied. Two groups of amino two benzyl and amiaminqi, the dyestuff based dyestuff has a wider absorption spectrum and better optical capture in the visible region. The introduction of olefin bonds between the electron donor and thiophene group is used to study the effect of the dye on the absorption spectrum of the dye. The introduction of olefin bonds can effectively broaden the absorption spectrum of the dye. Under the conditions of AM1.5G, 100mW cm-2, the dye ISB-2 gets the short-circuit current of 13.14mA / cm-2, the open circuit voltage of 0.649V, 0.68 filling factor and 5.83% photoelectric conversion efficiency.
In the third chapter, using the BENZOTHIAZOL two azole unit as an additional receptor, the dye S1 ~ S4 of four D-A- PI -A structures was designed with amithagqi as an electron donor. The absorption spectrum and energy level and the photoelectric property of the dye were investigated after the introduction of the electronic group benzothiazide two azole. The absorption of the dyestuff group, benzothiazole, two azole, was introduced to make the dye absorption light The red shift of the spectrum increases the light capture ability of the dye. Changing the conjugated groups adjacent to the receptor, such as thiophene and phenyl, can easily and effectively regulate the dye's energy level and improve its photoelectric properties. The IPCE based on the DSSCs of the dye S1, S2, S3 and S4 has reached 60% in the 350 to 550nm region, and the highest reaches 90%., based on the S2 DS of the dye. SCs gets the short circuit current of 12.11mA cm-2, the open circuit voltage of 0.673V, 0.66 filling factor and 5.36% photoelectric conversion efficiency. After the optimization, the short-circuit current of 13.69mA / cm-2, the open circuit voltage of 0.722V, the filling factor of 0.67 and the photoelectric conversion efficiency of 6.71% are obtained.
In the fourth chapter, with the quinoaline unit as an additional receptor and amiimara as an electron donor, two dyes Q1 and Q2 of D-A- -A structure were designed, and the absorption spectra and energy levels of the dyes were introduced after introducing the electronic group of quinozolin. The introduction of quinozoline, the absorption group, effectively reduced the carboxyl dye when the dye was adsorbed. The blue shift of the spectrum caused by the loss of the proton, ensures the absorption of the dye on the Ti02 film, effectively improves the LUMO energy level of the dye and is more conducive to the improvement of the photoelectrical properties of the dye. In this system, the thiophene group of the conjugated bridge chain adjacent to the receptor is substituted with furan, the HOMO energy level of the dye molecules moves upwards, and the LUMO level is entered. The step increases the band gap between the dye LUMO and the Ti02 guide band. 50%. based on the DSSCs of dye Q1 and Q2 has reached 50%. in the region of 400 to 550nm. Based on the DSSC of the dye Q1, the short-circuit current of 11.76mA cm-2 is obtained, the open circuit voltage, the filling factor of 0.73 and the photoelectric conversion efficiency of 6.28% are obtained. The open circuit voltage of 0.714V, the fill factor of 0.72 and the photoelectric conversion efficiency of 6.66%.
The fifth chapter, using pyrrole and pyrrole two one unit as an additional receptor, using amiimalin as an electron donor, designed two D-A- -A dyes Q1 and Q2. The absorption spectra and energy levels of the dye, the effect of the absorption spectrum and energy level on the dye were investigated. The introduction of the electron group pyrrole and pyrrole two ketone was introduced. The absorption spectrum of the material redshifted 50nm, and at the same time, there was an absorption band near 400nm, which enhanced the light capture ability of the dye and.DPP dye had a higher molar extinction coefficient. The IPCE response range of DSSC based on dyestuff DPP-1 reached 700nm.
In the sixth chapter, two D-A- PI -A dyes H1 and H2 were designed by introducing the side chain of benzothiazolyl and oloxaline groups and taking it as an additional receptor. The absorption spectra and energy levels of the dyes were investigated and the effects of the photoelectrical properties were investigated after the introduction of the alkoxyl chain. The absorption of light after the BENZOTHIAZOL and the Chloroalkyl group was introduced into the side chain of the oxygen group. The blue shift of the spectrum is about 10nm, and the LUMO level of the dye has a certain increase. In the benzothiazole two azole system, after the introduction of the side chain of the oxygen group, the aggregation of the dye on the Ti02 membrane is effectively inhibited and the return of the electrons is prevented. The short circuit current and the open circuit voltage are raised. But the oxygen group side chain is introduced in the system of the oxaline. It was obvious that it did not play such a role.
【学位授予单位】：华东理工大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM914.4
【参考文献】
相关期刊论文 前2条
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2 ;Advances in dye-sensitized solar cell[J];Chinese Science Bulletin;1997年23期
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