基于亞氨基芪電子給體的敏化染料及其性能
發(fā)布時(shí)間：2018-08-01 10:39
【摘要】：染料敏化太陽能電池(DSSCs)是利用吸附在半導(dǎo)體表面的染料分子吸收太陽光,從而將太陽能轉(zhuǎn)換成電能的一種新型太陽能電池,具有制作工藝簡單、成本低廉、光電轉(zhuǎn)換效率較高等優(yōu)勢,引起了研究者們的廣泛研究。如何有效地提高染料敏化太陽能電池的光電轉(zhuǎn)換效率和使用壽命是目前染料敏化電池研究領(lǐng)域的關(guān)鍵問題。本論文創(chuàng)新性地將亞氨基芪化合物引入染料敏化電池,提高染料穩(wěn)定性。在以亞氨基芪化合物為電子給體的分子中,系統(tǒng)性地引入了不同的強(qiáng)吸電子基團(tuán),并測試了染料的光電性能及器件的光電轉(zhuǎn)換效率。 第一章,簡要介紹了有機(jī)染料敏化太陽能電池(DSSCs)的結(jié)構(gòu)及其工作原理,評(píng)價(jià)電池性能的主要指標(biāo),納米晶半導(dǎo)體電極和電解質(zhì)等的發(fā)展概況,綜述了目前染料敏化劑的研究進(jìn)展,在此基礎(chǔ)之上提出了本論文的研究思路和主要內(nèi)容。 第二章,首次將亞氨基二芐和亞氨基芪基團(tuán)引入染料敏化劑中,并以其為電子給體,噻吩作為π共軛橋鏈,氰基乙酸為電子受體,合成了IDB-1,ISB-1, IDB-2和ISB-2,研究亞氨基二芐和亞氨基芪基團(tuán)對(duì)染料敏化太陽能電池性能參數(shù)的影響。對(duì)比亞氨基二芐和亞氨基芪兩種基團(tuán),基于亞氨基芪的染料具有更寬的吸收光譜,在可見光區(qū)具有更好的光捕獲能力。并在電子給體與噻吩基團(tuán)中間引入烯烴鍵,研究其對(duì)染料吸收光譜的影響。烯烴鍵的引入可以有效地?cái)U(kuò)寬染料的吸收光譜。在AM1.5G，100mW cm-2光照條件下,染料ISB-2得到13.14mA·cm-2的短路電流、0.649V的開路電壓、0.68的填充因子和5.83%的光電轉(zhuǎn)換效率。 第三章,以苯并噻二唑單元作為額外的受體,以亞氨基芪作為電子給體,設(shè)計(jì)了四個(gè)D-A-π-A結(jié)構(gòu)的染料S1～S4,考察引入吸電子基團(tuán)苯并噻二唑后對(duì)染料的吸收光譜和能級(jí)、光電性能的影響。吸電子基團(tuán)苯并噻二唑的引入,使染料的吸收光譜發(fā)生紅移,增強(qiáng)了染料的光捕獲能力。改變與受體相鄰的共軛基團(tuán),如噻吩和苯基,可以簡單有效地調(diào)節(jié)染料的能級(jí),改進(jìn)其光電性能。基于染料S1,S2,S3和S4的DSSCs的IPCE在350～550nm的區(qū)域內(nèi),均達(dá)到了60%,最高達(dá)到了90%。其中,基于染料S2的DSSCs得到12.11mA·cm-2的短路電流、0.673V的開路電壓、0.66的填充因子和5.36%的光電轉(zhuǎn)換效率,在優(yōu)化條件后,得到13.69mA·cm-2的短路電流、0.722V的開路電壓、0.67的填充因子和6.71%的光電轉(zhuǎn)換效率。 第四章,以喹喔啉單元作為額外的受體,以亞氨基芪作為電子給體,設(shè)計(jì)了兩個(gè)D-A-兀-A結(jié)構(gòu)的染料Q1和Q2,考察引入吸電子基團(tuán)喹喔啉后對(duì)染料的吸收光譜和能級(jí)、光電性能的影響。吸電子基團(tuán)喹喔啉的引入,有效地減小了染料因吸附時(shí)羧基丟失質(zhì)子而造成的光譜藍(lán)移,保證了染料在Ti02膜上對(duì)光的吸收；有效地提高了染料的LUMO能級(jí),更利于染料光電性能的提高。在此喹喔啉體系中,用呋喃取代與受體相鄰的共軛橋鏈噻吩基團(tuán),染料分子的HOMO能級(jí)向上移動(dòng),LUMO能級(jí)進(jìn)一步提高,增大了染料的LUMO與Ti02導(dǎo)帶的帶隙。基于染料Q1和Q2的DSSCs的IPCE在400～550nm的區(qū)域內(nèi),均達(dá)到了50%。其中,基于染料Q1的DSSC得到11.76mA·cm-2的短路電流、0.734V的開路電壓、0.73的填充因子和6.28%的光電轉(zhuǎn)換效率,Q2得到12.89mA·cm-2的短路電流、0.714V的開路電壓、0.72的填充因子和6.66%的光電轉(zhuǎn)換效率。 第五章,以吡咯并吡咯二酮單元作為額外的受體,以亞氨基芪作為電子給體,設(shè)計(jì)了兩個(gè)D-A-兀-A結(jié)構(gòu)的染料Q1和Q2,考察引入吸電子基團(tuán)吡咯并吡咯二酮后對(duì)染料的吸收光譜和能級(jí)、光電性能的影響。吸電子基團(tuán)吡咯并吡咯二酮的引入,染料的吸收光譜紅移了50nm,同時(shí),在400nm附近多出一個(gè)吸收帶,增強(qiáng)了染料的光捕獲能力。DPP染料具有較高的摩爾消光系數(shù)�；谌玖螪PP-1的DSSC的IPCE響應(yīng)范圍達(dá)到了700nm。 第六章,在苯并噻二唑和喹喔啉基團(tuán)上引入己氧基側(cè)鏈,并以此為額外的受體,設(shè)計(jì)了兩個(gè)D-A-π-A結(jié)構(gòu)的染料H1和H2,考察引入己氧基鏈后對(duì)染料的吸收光譜和能級(jí)、光電性能的影響。在苯并噻二唑和喹喔啉基團(tuán)引入己氧基側(cè)鏈后,吸收光譜都發(fā)生了10nm左右的藍(lán)移,染料的LUMO能級(jí)有一定的提升。在此苯并噻二唑體系中,引入己氧基側(cè)鏈后,有效地抑制了染料在Ti02膜上的聚集,并阻止了電子的回傳,短路電流和開路電壓都有所提高。但在喹喔啉的體系中引入己氧基側(cè)鏈,卻明顯沒有起到這樣的作用。
[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.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM914.4
本文編號(hào)：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.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM914.4
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 褚道葆,周幸福,林昌健,譚建光;電化學(xué)法制備高熱穩(wěn)定性銳鈦礦型納米TiO_2[J];電化學(xué);1999年04期
2 ;Advances in dye-sensitized solar cell[J];Chinese Science Bulletin;1997年23期
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