CN103748097B - 高电导性的空穴传输材料以及利用其的染料敏化太阳能电池 - Google Patents
高电导性的空穴传输材料以及利用其的染料敏化太阳能电池 Download PDFInfo
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- CN103748097B CN103748097B CN201280038674.XA CN201280038674A CN103748097B CN 103748097 B CN103748097 B CN 103748097B CN 201280038674 A CN201280038674 A CN 201280038674A CN 103748097 B CN103748097 B CN 103748097B
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007070 tosylation reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
本发明提供一种可降低光电子复合反应的高电导性空穴传输材料以及利用其的染料敏化太阳能电池。所述空穴传输材料利用具有根据本发明的化学式(1)或者(2)表示结构的化合物而形成。所述固相染料敏化太阳能电池包括通过光电聚合或者热聚合,将所述化合物涂布于无机氧化物层,从而形成的空穴传输材料层。
Description
技术领域
本发明涉及一种降低光电子复合(photoelectron recombination)反应的高电导性空穴传输材料以及利用其的染料敏化太阳能电池。更详细地说,涉及一种新型的降低光电子复合反应,同时电导性提高的空穴传输材料;以及一种固相(solid state)染料敏化太阳能电池,其通过上述空穴传输材料的光电聚合(photoelectrochemicalpolymerization)或者热聚合(thermal polymerization)形成高分子电导层,未使用具有腐蚀性的碘和碘离子。
背景技术
太阳能电池元件是指将太阳光转换成能量,从而直接产生电的元件。其以1839年,法国物理学家贝克勒尔(Becquerel)发现了光电动势,后又发现了类似的现象还发生在硒等固体上的事实为基础。1991年,瑞士的格雷策尔(Gratzel)研究组公开了将钌(卟啉)(Ru(phophyrine))染料化学吸附至以锐钛型二氧化钛为基础的半导体薄膜上,并利用包括碘和碘盐的溶液作为电解质而制备的染料敏化太阳能电池(DSSC),其光电转换效率(light-to-electrical conversion efficiency)约为10%。由于染料敏化太阳能电池具有优异的光电转换效率,因此被认为是能替代现有的硅二极管的最为先进的技术之一。
一般染料敏化太阳能电池包括:半导体电极,其是通过在掺杂有氟(F)或者铟(In)的具有高电导性的无机氧化物电极上,涂布由吸附有染料的多孔性二氧化钛(TiO2)纳米粒子构成的半导体而成的;相对电极,其涂布有铂金(Pt)或者碳(C);电解质,其填充于上述两个电极之间。即染料敏化太阳能电池具有利用光电化学反应的结构,其是通过在透明电极和金属电极之间***吸附有染料的无机氧化物层和电解质或者空穴传输材料而实现的。虽然染料敏化太阳能电池的制备成本比硅太阳能电池约低廉20%,但其具有与无定型硅系列太阳能电池不相上下的高光电转换效率,因此被认为具有极高的产业化可能性(参见美国专利第4,927721号以及美国专利第5,350,644号)。
有报道称,使用液体电解质的染料敏化太阳能电池具有寿命短、由液体电解质的渗漏液引起的效率的降低等缺点,而上述染料敏化太阳能电池中使用固体电解质或者空穴传输材料(HTM)的固相染料敏化太阳能电池可弥补上述缺点。1997年,柳田(Yanagida)研究组公开的染料敏化太阳能电池是利用光电特性,将电导性材料通过光电聚合涂布在吸附有染料的半导体电极上,并在相对电极达到涂布上述电导性材料的半导体电极之前,涂布少量包含金属盐的离子型液体电解质的结构(参见Murakoshi K,Kogure R,Wada Y,andYanagida S,Chem.Lett.,5,471(1997))。
将吸附有染料的半导体电极和相对电极(铂金等),浸渍于溶解了电导性材料的前体和电解质的溶液中,并同时照射可激发染料的波长的光,在两个电极上施加电流或者电压,从而实现依赖光电聚合的电导性材料涂布。光电聚合的原理是从被光激发的染料中生成电子和空穴,通过施加在两个电极的电流或者电压,溶解于电解质的前体在染料周边发生氧化,从而实现聚合。
以上述结构形成的染料敏化太阳能电池元件的驱动原理是:向吸附有染料的钛氧化物层照射光后,吸收光子的染料形成激发子(exciton),从基态变化为激发态。此时,电子-空穴对各自分离,其中电子注入到电极的无机氧化物层,空穴移至空穴传输材料层。注入的电子通过外部电路的导线向相对电极移动产生电流,后被空穴传输材料还原,其不断的移动激发态的电子,从而形成电路。
为提高染料敏化太阳能电池的光电变换效率需要提高短路电流、开放电压以及最大输出功率。在固相染料敏化太阳能电池中,由于注入到半导体氧化物的电子和移动至空穴传输材料的空穴间的复合反应非常大,因此提高上述因素的最佳方法为防止复合反应。由此已开发出了很多防止光电子和空穴的复合,或者提高空穴传输材料能力等方法。首先,有一种技术,其在染料或者p-型半导体的空穴传输材料中,导入对锂进行螯合的乙二醇,从而可通过屏障效果防止复合(参见Henry J.Snaith,Adam J.Moule,Cedric Klein,KlausMeerholz,Richard H.Friend,and Michael Gratzel,Nano Letters,7,3372(2007);TaihoPark,Saif A.Haque,Roberto J.Potter,Andrew B.Holmes,and James R.Durrant,Chem,Chem.Comm.11,2878(2003))。其次,还有一种技术,其使用用于掺杂光电聚合用空穴传输材料的盐的阴离子(例如磺酰胺)提升空穴传输材料的电导性,从而由此增大短路电流以及开放电压(参见Jiangbin Xia,Naruhiko Masaki,Monica Lira-Cantu,Yukyeong Kim,KejianJiang,and Shozo Yanagida,J.Am.Chem.Soc.,130,1258(2008))。然而制备同时能满足上述两种优点的固相染料敏化太阳能电池元件非常困难。
发明内容
本发明要解决的技术问题
本发明的目的在于,提供一种减少光电子复合反应的同时,还能提高电导性的空穴传输材料以及为此提供一种新型的化合物。
并且,本发明的目的在于,提供一种固相染料敏化太阳能电池,其具有通过所述化合物的聚合而形成的高分子层,在不使用碘和碘盐的条件下,还能显著提高光电转换效率。
技术方案
本发明提供一种聚合了下述由化学式(1)或者化学式(2)表示的化合物的空穴传输材料。
其中,R1、R2以及R4是各自独立的为氢、包括1-20个碳原子的寡聚乙二醇包括1-20个碳原子的寡聚丙二醇C1-C20烷基、C1-C20杂烷基、C3-C20环烷基、C1-C20杂环烷基、C1-C20芳基或者C1-C20杂芳基;R3是氢或者卤原子;n是1-5的自然数,可包含杂原子替代氢原子;m是1或者2;X是氮原子、硫原子或者硒原子。
在所述化学式(1)或者(2)中,优选R1、R2以及R4中至少有一个是包含1-20个碳原子的寡聚乙二醇。更优选的是,所述化学式(1)中,R1以及R2中有一个是包含1-20个碳原子的寡聚乙二醇;而所述化学式(2)中,R1、R2以及R4中有一个是包含1-20个碳原子的寡聚乙二醇。
所述化学式(1)或者(2)的化合物,例如可包括:1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-(2-甲氧基乙氧基)苯[1,4--2-(3,4- )-2-(2-)];1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-[2-(2-甲氧基乙氧基)乙氧基]苯{1,4--2-(3,4- )-2[2-(2-)};1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-{2-[2-(2-甲氧基乙氧基)乙氧基]乙氧基}苯{1,4--2-(3,4-)-2-{2-[2-(2-)]} };1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚{1,4- [2-(3,4-)]-2,5- bis-EDOT-TB};1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]-2,5-双四甘醇苯{1,4--2,5-[(3,4-) ]-2,5-};1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]三甘醇苯{1,4--2,5-[(3,4-) ]}等,但并不仅限于此。
本发明提供一种固相染料敏化太阳能电池,其在金属氧化物表面,通过使所述化合物发生光电聚合或者热聚合,形成高分子空穴传输材料,从而克服了现有的使用碘和碘盐的液相染料敏化太阳能电池的缺点。
一方面,本发明中的所述固相染料敏化太阳能电池包括半导体电极、相对电极以及空穴传输材料,而所述半导体电极包括金属氧化物半导体,并且还包括电导性高分子薄膜,所述电导性高分子薄膜是在吸附有染料的多孔性薄膜上,将所述化学式(1)以及/或者(2)的化合物进行光电聚合或者热聚合而形成。
所述金属氧化物半导体优选微粒形态,且所述多孔性薄膜优选染料分子和反应型化合物均匀分散的。当所述化学式(1)或者(2)中,R1、R2或者R4是包括1-20个碳原子的寡聚乙二醇时,能够与金属离子螯合,且所述化合物聚合后具有电导性提高的特性。所述电导性高分子薄膜还可将染料分子坚固地固定于金属氧化物表面。
一方面,本发明的固相染料敏化太阳能电池包括:电导性第1电极;无机氧化物半导体电极,其在所述第1电极上,吸附有一种或者两种以上的染料分子;电导性物质层,其在所述无机氧化物半导体电极上,其包括所述化学式(1)以及/或者(2)的化合物;以及相对电极,其在所述电导性物质层上,其包括金属。所述电导性物质层优选通过所述化学式(1)以及/或者(2)的化合物的光电聚合或者热聚合反应而成。
本发明提供一种固相染料敏化太阳能电池的制备方法,其包括在所述半导体电极上,通过光电聚合或者热聚合反应,涂布所述化学式(1)以及/或者(2)的化合物,并其上将第2电极进行接合或者涂布第2电极物质的步骤。
一方面,本发明的所述化学式(1)的化合物通过包括使下述化学式(3)表示的化合物和下述化学式(4)表示的化合物进行反应的步骤制备:
其中,R是氢或者烷基,X是卤族元素,m是1-10的整数;以及
其中,n是1-5的整数,X是卤族元素。
有益效果
本发明提供一种新型的空穴传输材料,其具有固相染料敏化太阳能电池中作为重要的因素而作用的空穴传输能力以及由此得到的高复合反应率的结构。
并且,本发明可制备高效、价廉以及长期稳定的染料敏化太阳能电池,其中空穴传输材料层主要形成于染料周边,可与染料高效地接触;且通过由乙二醇引起的结构平面性而提高的电导性和通过由金属离子螯合的复合反应的延迟,可同时提高短路电流和填充系数,从而大大提高光电转换效率。
附图说明
图1是图示根据本发明的一个实施例制备的染料敏化太阳能电池元件的结构的截面图。
图2是图示根据本发明的一个实施例制备的导入空穴传输材料层的钛氧化物电极。
图3是比较根据本发明的实施例和比较例的电压-电流特性的曲线图。
具体实施方式
A.空穴传输材料
根据本发明的空穴传输材料利用下述化学式(1)或者(2)表示的化合物形成:
其中,R1、R2以及R4是各自独立的为氢、包括1-20个碳原子的寡聚乙二醇、C1-C20烷基、C1-C20杂烷基、C3-C20环烷基、C1-C20杂环烷基、C1-C20芳基或者C1-C20杂芳基;R3是氢或者卤原子;n是1-5的自然数,可包含杂原子替代氢原子;m是1或者2;X是氮原子、硫原子或者硒原子。
对于所述化学式(1)或者(2)的取代基,优选R1、R2以及R4中有一个是包含1-20个碳原子的寡聚乙二醇。
所述化合物例如可包括:1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-(2-甲氧基乙氧基)苯;1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-[2-(2-甲氧基乙氧基)乙氧基]苯;1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-{2-[2-(2-甲氧基乙氧基)乙氧基]乙氧基}苯;1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚;1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]-2,5-双四甘醇苯;1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]三甘醇苯等。
B.化合物的合成
Bis-EDOT:2,2’-双(3,4-亚乙二氧基噻吩)
在圆底烧瓶中加入无水四氢呋喃(THF)30mL和3.0mM的3,4-亚乙二氧基噻吩(1)后,用氮气排空。将上述溶液降温至-78℃后,缓慢滴加7mL的2.5M丁基锂,后搅拌45分钟。待溶液变成黄色的透明液体后,一次性添加7.0mM的CuCl2,之后缓慢升温至45℃,并在此温度下搅拌2小时。反应结束后利用减压旋转蒸发器去除THF,之后加入蒸馏水和二氯甲烷萃取有机溶液层。对于萃取出的溶液,利用减压旋转蒸发器再次去除萃取溶剂后,使用干燥硅胶并以氯仿作为洗脱液,进行柱层析,获得白色固体。产率:70%;mp 183-185℃;1H N MR(CDCl3)δ6.93(s,2H),4.34-4.32(m,4H),4.25-4.23(m,4H);此外,相关数据与下述参考文献的数据一致(Sotzing,G.A.,R eynolds,J.R.,and Steel,P.J.,Adv.Mater.,9,795-798(1997))。
甲苯磺酰化三乙二醇(Tosylated TEG):三乙二醇甲酯砜基甲苯
在50mL的二氯甲烷溶剂中添加57.8mM的对甲苯磺酰氯后进行搅拌。0℃条件下维持搅拌的情况下,缓慢加入溶解了61mM的三乙二醇甲酯和91.3mM的三乙胺的100mL二氯甲烷溶液,后继续搅拌5小时。反应结束后,倒入到0.1M的盐酸水溶液去除未反应物后,利用二氯甲烷萃取水层。之后收集的有机层利用硫酸镁去除水,通过减压旋转蒸发器获得浅黄色的物质。产率:93%;1H NMR(DMSO d6)δ7.76-7.79(d,2H),7.46-7.49(d,2H),4.08-4.11(t,2H),3.54-3.57(t,2H),3.33-3.47(m,8H),3.23(s,3H),2.41(s,3H);此外,相关数据与下述参考文献的数据一致(Gentilini,C.,Boccalan,M.,and Pasquato,L.,Eur.J.Org.Chem.,3308(2008))。
4)1,4-二溴-2,5-双-三甘醇苯甲醚(1,4--2,5- )
将24.5mM的1,4-二溴-2,5-羟基苯(3)溶于60mL的THF的溶液,在氮气条件下,缓慢加入至30mL的加入了50mM氢氧化钾的乙醇溶液中。常温下搅拌3小时后,缓慢加入溶解50mM的三乙二醇甲酯砜基甲苯的60mL的THF,后升温至50℃,搅拌24小时。反应结束后加入氯化钠水溶液和***分离出有机层,之后用硫酸镁去除水。之后通过柱层析,利用己烷:乙酸乙酯(1:1)的溶液作为洗脱液,获得浅黄色液体。产率:91%;1H NMR(CDCl3)δ7.31(s,2H),3.76-3.80(t,4H),3.61-3.66(m,12H),3.52-3.54(t,4H),3.42-3.46(t,4H),3.36(s,6H);13C NMR(CDCl3)δ150.3,119.2,111.4,71.9,71.1,70.7,70.6,70.2,69.6,59.0;元素分析理论值:C,42.87;H,5.76;实际值:C,42.87;H,5.76;m/e理论值:C20H32Br2O8,558.0464,实际值:559.0440([M]+)。
Bis-EDOT-TB:1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚
在-78℃以及氮气条件下,将30mL的丁基锂缓慢滴加至溶解了30mM的EDOT的75mL的THF溶液中。待溶液的颜色变成黄色后,在20分钟的时间里,缓慢的将溶液加入至溶解了33mM的ZnCl2的75mL的THF溶液,搅拌1小时,制备EDOT-ZnCl(2)的混合体。之后将溶液缓慢加入至溶解有6.91mM的1,4-二溴-2,5-双-三甘醇苯甲醚和0.03m M的Pd(PPh3)4的50mL的THF溶液中,并缓慢升温至50℃后,搅拌3天。反应结束后,利用1M的盐酸水溶液去除未反应物后,用二氯甲烷进行萃取,利用硫酸镁去除水。之后,用二氧化硅板进行过滤,并用二氯甲烷进行重结晶,获得橙色的结晶。产率:产率:84%;mp 85.0-86.2;1H NMR(CDCl3)δ7.69(s,2H),6.36(s,2H)4.31-4.29(m,4H),4.26-4.24(m,4H),4.22-4.20(t,4H),3.96-3.93(t,4H),3.77-3.74(m,4H),3.69-3.63(m,8H),3.55-3.52(m,4H),3.37(s,6H);13C NMR(CDCl3);元素分析理论值:C,56.29;H,6.20;S,9.39;实际值:C,56.28;H,6.16,S,9.37;m/e理论值:C32H42O12S2,682.2118,实际值:683.4300([M]+)。
C.固相染料敏化太阳能电池的结构以及制作
图1是概述了根据本发明的一个实施例的固相染料敏化太阳能电池元件的层结构,其将本发明的化学式(1)或者(2)的化合物进行光电聚合或者热聚合而形成的电导性空穴传输材料层涂布于吸附有染料分子的金属氧化物半导体电极而成。参照图1,所述染料敏化太阳能电池元件包括:第1电极1002,其位于作为透明基板的第1基板1001之上;在所述第1电极1002之上以此为无机氧化物层1003;染料层1004;导入有乙二醇的电导性空穴传输材料层1005;离子型电解质以及添加物层1006;以及第2电极1007。所述第2电极1007是涂布有金(Au)、银(Ag)等金属的多层薄膜形态。
所述第1基板1001可由玻璃、或者聚对苯二甲酸乙二醇酯(polye thyleneterephthalate,PET)、聚萘二甲酸乙二醇酯(polyethylene na phthelate,PEN)、聚丙烯(polypropylene,PP)、聚酰胺(polyamide,PI),三乙酰纤维素(tri acetyl cellulose,TAC)等透明的高分子物质制备。上述基板优选由玻璃制备。
第1电极1002是形成于作为透明基板的第1基板1001一面的金属氧化物形成的透明电极。第1电极1002发挥阴极的功能。第1电极的功函数(work function)较第2电极1007小,且具有透明性以及电导性。第1电极1002可通过喷溅涂覆法(sputtering)、旋转涂覆法(spin coating)等本领域已知的方法涂布于第1基板1001的一面而形成。作为第1电极1002的材料可使用例如氧化铟锡(indium-tin oxide,ITO)、氟掺杂氧化锡(fluorine dopedtin oxide)、ZnO-Ga2O3、ZnO-Al2O3、S nO2-Sb2O3等,优选ITO或者FTO。
元件的无机氧化物层1003优选由纳米粒子形态的金属氧化物形成。上述金属氧化物可包括例如钛氧化物、钪氧化物、钒氧化物、锌氧化物、镓氧化物、钇氧化物、锆氧化物、铌氧化物、钼氧化物、铟氧化物、锡氧化物、镧类氧化物、钨氧化物、铱氧化物等过渡金属氧化物,还可包括镁氧化物、锶氧化物等碱土金属氧化物,以及铝氧化物等。所述无机氧化物层的物质优选纳米粒子形态的钛氧化物。
所述无机氧化物层1003是将包括无机氧化物的糊状物涂布于所述第1电极1002的一面后进行热处理,从而涂布于第1电极1002上。一般将所述糊状物采用刮匀涂装法或者丝网印刷方法,以约5-30μm,优选约10-15μm的厚度涂布于第1电极1002的一面。此外,还可使用本领域技术人员可理解的旋转涂布法、喷雾方法、湿式涂布方法等。
在所述无机氧化物层1003上化学吸附光敏原料,从而形成染料层1004。参照图2,吸附于无机氧化物层1003(其为多孔性膜)的光敏染料优选可吸收紫外线以及可见光区域的光的物质。作为上述材料,可使用钌复合体等染料,例如包括钌535染料、钌535双-TBA染料、钌620-1H3TBA染料等钌络合物构成的光敏染料。所述染料优选为钌535双-TBA染料。可化学吸附于无机氧化物层1003的光敏染料除了钌类染料之外,还可使用具有电荷分离功能的任意的染料,例如呫吨染料、花青染料、卟啉染料、蒽醌染料、有机染料等。
为将上述染料吸附于无机氧化物层1003,可使用通常的方法,优选将上述染料溶解于乙醇、腈、卤化烃、***、酰胺、酯、酮、N-甲基吡咯烷酮等溶剂,或者溶解于乙腈和叔丁醇的共溶剂后,浸渍涂布有无机氧化物1003的光电极的方法。
吸附有染料的所述无机氧化物层1003的上部形成执行元件的空穴传输,且为了防止复合导入了乙二醇的空穴传输材料层1005。所述空穴传输材料层1005可通过所述化学式(1)或者(2)结构化合物的光聚合反应而形成。
对于根据本发明的原件的离子型电解质以及添加物层1006,最好使用BF4 -,ClO4 -,Br-,(CF3SO2)2N-等阴离子,与可作为离子型电解质的咪唑鎓盐(imidazolium)、四烷基铵(tetra-alkyl ammonium)、吡啶(pyridinium)、***鎓(triazolium)等阳离子铵化合物配对,从而具有盐的形态,但并不仅限于此。并且还可混合两种以上的上述物质使用。作为构成金属盐的金属阳离子可使用锂、钠、钾、镁、钙、铯等。
尤其是,可使用组合了Li(CF3SO2)2N和咪唑鎓盐双三氟磺酰胺的离子型液体电解质。本发明可使用的电解质中,可作为离子型液体使用的化合物有正甲基咪唑鎓盐双三氟磺酰胺(n- )、正乙基咪唑鎓盐双三氟磺酰胺(n- )、1-苄基-2-咪唑鎓盐双三氟磺酰胺(1--2-)、1-乙基-3-咪唑鎓盐双三氟磺酰胺(1--3- )、1-丁基-3-咪唑鎓盐双三氟磺酰胺(1--3- )等,尤其优选将1-乙基-3-咪唑鎓盐双三氟磺酰胺与Li(CF3SO2)2N组合使用。当使用上述离子型液体,即溶解盐时可构成在电解质组合物中不使用溶剂的固体电解质。
所述第2电极1007是涂布在第2基板1008的一面或者涂布于离子型液体电解质以及添加物层1006的电极,可使用为元件的阳极。其可使用喷溅涂覆法或者旋转涂覆法的方法,将第2电极1007涂布或者包被于第2基板1008的一面,或者利用毛笔涂布于离子型液体电解质以及添加物层。
可用于第2电极1007的物质,其功函数值比可用于第1电极1002的物质要大,可以是铂金(Pt)、金(Au)、银(Ag)、碳(C)等,其中优选银(Ag)。所述第2基板(1008)是与所述第1基板1001类似的透明物质,可由玻璃或者包括PET、PEN、PP、PI、TAC等塑料类的透明物质制备,其中优选由玻璃制备。
并且,电子从被光激发的染料转移至无机氧化物,空穴则从氧化的染料移动至空穴传输材料。空穴传输材料层1005接收离子型电解质以及添加物层1006和第2电极1007接收电子,从而完成元件的电路。
根据本发明一个实施例的染料敏化太阳能电池的制备工艺如下。
首先,在涂布有ITO、FTO等第1电极物质的,如透明玻璃的第1基板1001上,优选以5-30μm的厚度涂布或者铸造(casting)作为无机氧化物的胶体状钛氧化物,在约450-550℃的温度条件下进行煅烧,形成依次涂覆/层压去除有机物的第1基板1001-第1电极1002-无机氧化物层1003的的光电极。接着,为在所形成的无机氧化物层1003吸附染料,在预先准备好的乙醇溶液中添加染料(例如钌类染料Z907)制备染料溶液后,在此溶液中放入涂布有无机氧化物层的透明基板所述光电极,吸附染料,从而形成染料层1004。
之后,所述基板可通过以下方式制备:将吸附有染料的透明基板浸渍于包括由本发明化学式(1)或者(2)表示的,摩尔比约为0.005-0.05的空穴传输材料的前体和摩尔比约为0.05-1的金属盐电解质的溶液中,后施加光以及电压,使所述前体发生聚合,形成空穴传输材料层1005。在涂布有所述空穴传输材料的半导体电极上,涂布所述离子型液体电解质以及金属盐添加物1006后,与形成于第2基板1008的第2电极1007发生接合或者涂布第2电极1007物质,从而制备固相染料敏化太阳能电池元件。
实施例
实施例1
利用刮匀涂装法,在基板电阻为15Ω/□的,包被了掺杂有氟的ITO的透明玻璃基板上,涂布二氧化钛(TiO2,Solaronix)多孔性膜形成组合物。干燥后,在500℃条件下进行30分钟的热处理,从而形成包括TiO2的多孔性膜。制备的多孔性膜的厚度约为6μm。之后将所述形成了多孔性膜的第1电极,在将乙腈和叔丁醇(1:1体积比)作为溶剂的0.30mM的(4,4-二羧基-2,2’-二吡啶基)(4,4-二壬基-2,2-二吡啶基)钌(NCS)染料溶液中浸渍18小时,从而将染料吸附于多孔性膜。之后将在所述多孔性膜上吸附有染料的第1电极浸渍于溶解了0.1M的双三氟磺酸亚酰胺锂电解质和0.01M的1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚(bis-EDOT-TB)的乙腈溶液中后,在第1电极的后面照射22mW强度以及520-1000nm波长的光的状态下,将铂金线连接于相对电极,施加+0.2V的电压(以Ag/AgCl基准电极为基准),进行20分钟的光电反应。在所述涂布了空穴传输材料的半导体电极上,滴加3滴添加了0.2M的双三氟磺酸亚酰胺锂和叔丁基吡啶的1-乙基-3-甲基咪唑鎓盐双三氟磺酸亚酰胺离子型液体电解质,后在氮气条件下保存24小时。
在涂布第2电极之前,利用擦拭辊擦去半导体电极的离子型液体电解质层,从而以薄的薄膜形态形成后,涂布银浆料,并进行干燥后,利用银浆料粘附银线,从而制备固相染料敏化太阳能电池。
实施例2
除了实施光电反应的时间为30分钟,其余方法均与所述实施例1相同。
实施例3
使用了与实施例1使用的空穴传输材料前体具有不同结构的1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-{2-[2-(2-甲氧基乙氧基)乙氧基]乙氧基}苯。且除了在相同的条件下实施光电反应,制备染料敏化太阳能电池,其余均与实施例2相同。
实施例4
除了将实施例3的光电反应时间改为30分钟,其余方法均与实施例3相同。
实施例5
向通过实施例1制备的多孔性膜上吸附有染料的第1电极,滴加几滴溶解了0.01M的1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]-2,5-双四甘醇苯的乙醇溶液后,在80℃条件下进行30分钟的热聚合。之后,在制备的薄膜上,再滴加几滴上述溶液后,在80℃条件下进行24小时的热聚合后,以实施例1的方法进行制备。
实施例6
使用了与实施例5使用的空穴传输材料前体具有不同结构的1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]-2,5-双四甘醇苯。
比较例1
利用刮匀涂装法,在基板电阻为15Ω/□的,包被了掺杂有氟的ITO的透明玻璃基板上,涂布二氧化钛(TiO2,Solaronix)多孔性膜形成组合物。干燥后,在500℃条件下进行30分钟的热处理,从而形成包括TiO2的多孔性膜。制备的多孔性膜的厚度约为6μm。之后将所述形成了多孔性膜的第1电极,在将乙腈和叔丁醇作为溶剂的0.30mM的(4,4-二羧基-2,2’-二吡啶基)(4,4-二壬基-2,2-二吡啶基)钌(NCS)溶液中浸渍18小时,从而将染料吸附于多孔性膜。之后将在所述多孔性膜上吸附有染料的第1电极,浸渍于溶解了0.1M的双三氟磺酸亚酰胺锂电解质和0.01M的双-3,4-亚乙二氧基噻吩的乙腈溶液后,在第1电极的后面照射22mW强度以及520-1000nm波长的光的状态下,将铂金线连接于相对电极,施加+0.2V的电压(以Ag/AgCl基准电极为基准),进行20分钟的光电反应。在所述涂布了空穴传输材料的半导体电极上,滴加3滴添加了0.2M的双三氟磺酸亚酰胺锂和叔丁基吡啶的1-乙基-3-甲基咪唑鎓盐双三氟磺酸亚酰胺离子型液体电解质,后在氮气条件下保存24小时。
在涂布第2电极之前,利用擦拭辊擦去半导体电极的离子型液体电解质层,从而以薄的薄膜形态形成后,涂布银浆料,并进行干燥后,利用银浆料粘附银线,从而制备固相染料敏化太阳能电池。
比较例2
除了实施光电反应的时间为30分钟,其余方法均与所述比较例1相同。
比较例3
向通过比较例1制备的多孔性膜上吸附有染料的第1电极,滴加几滴溶解了0.01M的2,5-二溴-3,4-亚乙二氧基噻吩的乙醇溶液后,在80℃条件下进行30分钟的热聚合。之后,在制备的薄膜上,再滴加几滴上述溶液后,在80℃条件下进行24小时的热聚合后,以比较例1的方法进行制备。
根据上述实施例1以及比较例制备的固相染料敏化太阳能电池的特性如下述表1所示。电流密度如图3的曲线图所示。
[表1]
开放电压(V) | 短路电流(mA/cm2) | 填充系数 | 效率(%) | |
实施例1 | 0.543 | 7.7 | 64.3 | 2.7 |
实施例2 | 0.570 | 4.6 | 74.4 | 1.9 |
实施例3 | 0.523 | 1.2 | 69.4 | 0.4 |
实施例4 | 0.585 | 1.1 | 68.8 | 0.5 |
实施例5 | 0.473 | 7.1 | 67.2 | 2.2 |
实施例6 | 0.485 | 5.4 | 69.4 | 1.8 |
比较例1 | 0.385 | 3.6 | 40.0 | 0.6 |
比较例2 | 0.543 | 4.5 | 60.0 | 1.5 |
比较例3 | 0.489 | 6.2 | 68.7 | 2.1 |
评价及观察
本发明的空穴传输材料具有在固相染料敏化太阳能电池中作为重要的因素而作用的空穴传输能力以及由此得到的高复合反应率的结构。被激发的燃料生成的空穴移动至空穴传输材料层,快速远离表面时,复合反应减少;而类似地,由于对金属进行螯合,可延迟通过金属盐的阳离子具有的筛选效果的电子和空穴的复合。由此,可提供一种高效的固相染料敏化太阳能电池的开发技术,其可同时提升短路电流和填充系数,从而提高光电转换效率。
以上,通过优选实施例详细说明了本发明,但本发明并不仅限于此。在权利要求书和发明的详细说明以及所附的附图的范围内,可进行多种变形而实施,其也显然包含在本发明的范围内。
Claims (9)
1.一种固相染料敏化太阳能电池,其特征在于,在吸附有染料的无机氧化物半导体电极上,形成下述化学式(1)所示的化合物进行聚合而得的空穴传输层,在所述空穴传输层依次形成有离子型液体电解质层及第2电极;
其中,所述化合物为1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-(2-甲氧基乙氧基)苯;1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-[2-(2-甲氧基乙氧基)乙氧基]苯;1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-{2-[2-(2-甲氧基乙氧基)乙氧基]乙氧基}苯;1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚;1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]-2,5-双四甘醇苯;1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]三甘醇苯或1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚。
2.根据权利要求1所述的固相染料敏化太阳能电池,其特征在于,所述无机氧化物半导体电极是二氧化钛纳米粒子。
3.根据权利要求1或2所述的固相染料敏化太阳能电池,其特征在于,所述染料包括钌类染料、呫吨染料、花青染料、卟啉染料和蒽醌染料。
4.根据权利要求1或2所述的固相染料敏化太阳能电池,其特征在于,所述染料包括有机染料。
5.根据权利要求1或2所述的固相染料敏化太阳能电池,其特征在于,所述空穴传输层掺杂有锂离子。
6.根据权利要求1或2所述的固相染料敏化太阳能电池,其特征在于,所述空穴传输层是光电聚合层。
7.一种固相染料敏化太阳能电池的制备方法,其特征在于,包括:
在吸附有染料分子的无机氧化物半导体电极上,形成包含下述化学式(1)所示的化合物中的一种以上的化合物的空穴传输层的步骤;
在所述空穴传输层形成离子型液体电解质层的步骤;以及
形成第2电极的步骤;
其中,所述化学式(1)所示的化合物为1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-(2-甲氧基乙氧基)苯;1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-[2-(2-甲氧基乙氧基)乙氧基]苯;1,4-双-2-(3,4-亚乙二氧基噻吩基)-2-{2-[2-(2-甲氧基乙氧基)乙氧基]乙氧基}苯;1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚;1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]-2,5-双四甘醇苯;1,4-二溴-2,5-双[(3,4-亚乙二氧基)苯硫基]三甘醇苯或1,4-双[2-(3,4-亚乙二氧基)噻吩基]-2,5-双三甘醇苯甲醚。
8.根据权利要求7所述的固相染料敏化太阳能电池的制备方法,其特征在于,所述形成空穴传输层的步骤包括将所述化合物进行光电聚合或者热聚合的步骤。
9.根据权利要求7或8所述的固相染料敏化太阳能电池的制备方法,其特征在于,所述离子型液体电解质包括锂离子。
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