CN107805254B - 一种卟啉小分子钙钛矿阴极缓冲层材料及其制备方法与应用 - Google Patents
一种卟啉小分子钙钛矿阴极缓冲层材料及其制备方法与应用 Download PDFInfo
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- CN107805254B CN107805254B CN201710842325.8A CN201710842325A CN107805254B CN 107805254 B CN107805254 B CN 107805254B CN 201710842325 A CN201710842325 A CN 201710842325A CN 107805254 B CN107805254 B CN 107805254B
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 38
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- 238000006243 chemical reaction Methods 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- -1 porphyrin small molecule Chemical class 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 20
- CGEYVESOLQQRNM-UHFFFAOYSA-N Brc1c2ccc(n2)c(Br)c2ccc(cc3ccc(cc4ccc1[nH]4)n3)[nH]2 Chemical compound Brc1c2ccc(n2)c(Br)c2ccc(cc3ccc(cc4ccc1[nH]4)n3)[nH]2 CGEYVESOLQQRNM-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 18
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photovoltaic Devices (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
本发明属于钙钛矿太阳电池的技术领域,公开了一种卟啉小分子钙钛矿阴极缓冲层材料及其制备方法与应用。所述卟啉小分子钙钛矿阴极缓冲层材料的结构式为式Ⅰ,其中,M是金属离子或氢;A为带有极性基团的共轭单元;Ar为取代或未取代的芳香基团。所述卟啉小分子钙钛矿阴极缓冲层材料用于制备钙钛矿太阳电池。本发明的材料一层就可替代目前文献中普遍采用的C60、BCP两层界面,同时还能提升器件性能;并且本发明的卟啉小分子钙钛矿阴极缓冲层材料具有水醇溶特性,可溶液旋涂,大大降低器件成本。
Description
技术领域
本发明涉及钙钛矿太阳电池界面材料,具体涉及一种卟啉小分子钙钛矿阴极缓冲层材料及其制备方法,所述阴极缓冲层材料用于钙钛矿太阳电池中,处于钙钛矿太阳电池的PCBM层与金属电极之间,可明显提高钙钛矿太阳电池的光电转换效率。
背景技术
随着传统化石能源日益枯竭,开发可再生能源成为了当前科研工作者的重要研究课题。太阳能是一种可再生的清洁能源,且具有储量大、分布广等优势,是一个巨大的能源宝库,对太阳能的开发利用已经成为各国广泛关注的热点,目前各种光伏电池已经被开发出来,并得到大量的研究与改进。
目前,太阳电池按照器件类型来分类,主要有5类。一是传统硅基电池,硅基电池具有光电转化效率高,寿命长,稳定性好等优良性质,但是硅基电池也有制作成本高昂,制作过程高能耗、高污染等缺点;二是量子点太阳电池,量子点太阳电池是结合纳米技术与量子力学理论,发展出来的新型的太阳电池,具有柔性,可溶液加工等优良性质,但是,目前量子点太阳电池器件的光电转化效率并不高,电池效率的提升也很缓慢;三是染料敏化太阳电池,染料敏化太阳电池是模仿光合作用原理,研制出来的一种太阳电池,具有寿命长,结构简单、易于制造,制备电池耗能较少,生产过程中无毒无污染等优点,但是,电池结构中液体电解质的使用,成为染料敏化太阳电池最致命的缺点;四是有机太阳电池,有机太阳电池同样拥有染料敏化电池结构简单、易于制造,制备电池耗能较少等优点,且不使用电解液,是一种前景广阔一种太阳电池;五是钙钛矿太阳电池,钙钛矿太阳电池,具有原料丰富,可溶液加工,加工成本低等优良性质,同时,电池效率在不到8年的时间里提高到超过20%,被业界普遍看好,但是目前钙钛矿太阳电池也还有不耐水汽,电池效率衰减严重等缺点,我们相信随着对钙钛矿太阳电池研究的深入,这些缺点能够被慢慢克服。
近些年来,钙钛矿太阳电池的研究方向主要集中在器件的构造与改进上,对新材料的开发与利用反而比较少见。
发明内容
在现有的技术中,钙钛矿太阳电池通常依次由ITO、阳极界面材料(如PSS:PEDOT和PTAA等)、钙钛矿层、PCBM、阴极缓冲层(C60,BCP,LiF等)和金属电极组成。为了提高钙钛矿太阳电池的光电转换效率,降低器件的成本,本发明的目的在于提供一种卟啉小分子钙钛矿阴极缓冲层材料。所述缓冲层材料可替代C60和BCP(2,9-二甲基-4,7-二苯基-1,10-菲咯啉)两层缓冲层材料,同时还能提高电池效率,并且本发明的卟啉小分子钙钛矿阴极缓冲层材料具有水醇溶特性,可在PCBM层上直接溶液旋涂,而不是真空蒸镀(C60和BCP采用真空蒸镀),从而还大大降低了器件构造成本。
本发明的另一目的在于提供上述卟啉小分子钙钛矿阴极缓冲层材料的制备方法。
本发明的再一目的在于提供上述卟啉小分子钙钛矿阴极缓冲层材料的应用。所述卟啉小分子钙钛矿阴极缓冲层材料用于制备钙钛矿太阳电池,作为钙钛矿太阳电池阴极缓冲层材料。
本发明的目的通过以下技术方案实现:
一种卟啉小分子钙钛矿阴极缓冲层材料,其结构式为式Ⅰ:
其中,M是金属离子或氢;A为带有极性基团的共轭单元;Ar为取代或未取代的芳香基团;
当M为氢时,卟啉小分子钙钛矿阴极缓冲层材料,其结构式为:
当M为金属离子时,M优选为Zn2+,Cu2+,Mg2+和Ni2+,金属离子以其空轨道与氮原子的孤对电子产生配位,提高了卟啉环的稳定性。
所述A优选为以下式(1)~(8)中一种,*为连接处:
所述Ar优选为以下式(Ⅰ)~(Ⅷ)中一种,*为连接处:
其中,R1为氢、羟基、含碳数为1至20的烷基或烷氧基,同一结构中R1相同或不同。
所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,包括以下步骤:
(1)通过Suzuki偶联反应或Sonogashira偶联反应,制备吡啶卟啉化合物;
(2)将吡啶卟啉化合物与含有极性基团的化合物进行离子化反应,得到卟啉小分子钙钛矿阴极缓冲层材料;
所述Suzuki偶联反应的具体步骤为:(a1)在惰性氛围和碱性环境下,将5,10-双溴卟啉与联硼酸频那醇酯在二价钯的催化下进行反应,纯化,得到5,10-双硼酸酯卟啉;
步骤(a1)中所述惰性氛围为氩气氛围,所述碱性环境是指在碳酸铯的1,2-二氯乙烷溶液中反应;所述反应的温度为60~95℃,优选为85℃;时间为12~36h,优选为24h;所述二价钯为双(三苯基膦)二氯化钯,所述5,10-双溴卟啉:联硼酸频那醇酯的摩尔比为1:(3~6),优选为1:5;所述5,10-双溴卟啉:碳酸铯的摩尔比为1:(3~6),优选为1:5;所述5,10-双溴卟啉:双(三苯基膦)二氯化钯的摩尔比为1:(0.05~0.2),优选为1:0.1,所述碳酸铯:1,2-二氯乙烷的摩尔体积比为5mol:(500~1000)mL,优选为5mol:800mL;
(a2)在惰性氛围和碱性环境下,将5,10-双硼酸酯卟啉与3-溴吡啶在钯催化剂的作用下进行反应,纯化,得到5,10-双吡啶卟啉即吡啶卟啉化合物;
步骤(a2)中所述惰性氛围为氩气氛围,所述碱性环境是指在碳酸铯的DMF/甲苯的混合溶液中反应;所述反应的温度为100~120℃,优选为110℃;时间为1~4天,优选为3天;所述二价钯为四(三苯基膦)钯;所述5,10-双硼酸酯卟啉:3-溴吡啶的摩尔比为1:(3~6),优选为1:5,所述5,10-双硼酸酯卟啉:碳酸铯的摩尔比为1:(3~6),优选为1:5;所述5,10-双硼酸酯卟啉:四(三苯基膦)钯的摩尔比为1:(0.08~0.12),优选为1:0.1;所述碳酸铯:DMF与甲苯的混合溶剂的摩尔体积比为5mol:(500~1000)mL,DMF:甲苯的体积比为1:2。
纯化是指用氯仿萃取出目标产物,通过硅胶柱层析和GPC纯化。
步骤(a1)中所述5,10-双溴卟啉的结构为
所述5,10-双硼酸酯卟啉的结构为
步骤(a2)中所述吡啶卟啉化合物的结构为
所述Sonogashira偶联反应的具体制备步骤为:(b1)在惰性氛围和有机溶剂中,将5,10-双溴卟啉与三甲基硅乙炔在催化体系的作用下进行反应,纯化,得到5,10-双硅乙炔卟啉;
步骤(b1)中所述惰性氛围为氩气氛围,所述催化体系为双(三苯基膦)二氯化钯和碘化亚铜;所述有机溶剂为四氢呋喃和三乙胺的混合溶剂;所述反应的温度为常温,时间为1~3天,优选为48h;所述5,10-双溴卟啉:三甲基硅乙炔的摩尔比为1:(3~6),优选为1:5;所述5,10-双溴卟啉:双(三苯基膦)二氯化钯:碘化亚铜的摩尔比为1:(0.08~0.12):(0.08~0.12),优选为1:0.1:0.1,所述5,10-双溴卟啉:有机溶剂的摩尔体积比为1mmol:(100~1000)mL;有机溶剂中四氢呋喃:三乙胺的体积比为2:1;
(b2)在有机溶剂中,将四丁基氟化铵与5,10-双硅乙炔卟啉进行反应,纯化,得到5,10-乙炔卟啉;步骤(b2)中所述有机溶剂为四氢呋喃;
(b3)在惰性氛围和有机溶剂中,将5,10-乙炔卟啉与3-溴吡啶在催化体系的作用下进行反应,纯化,得到5,10-双炔吡啶卟啉即含有炔基的吡啶卟啉化合物;
步骤(b3)中所述催化体系为四(三苯基膦)钯和碘化亚铜,所述有机溶剂为四氢呋喃和三乙胺的混合溶剂;所述5,10-乙炔卟啉与3-溴吡啶的摩尔比为1:(3~6);所述5,10-乙炔卟啉:四(三苯基膦)钯:碘化亚铜的摩尔比为1:(0.08~0.12):(0.08~0.12),优选为1:0.1:0.1,所述5,10-乙炔卟啉:有机溶剂的摩尔体积比为1mmol:(100~1000)mL;有机溶剂中四氢呋喃:三乙胺的体积比为2:1;所述反应的温度为70~90℃,优选为80℃,时间为1~3天。
步骤(b1)中所述5,10-双硅乙炔卟啉的结构式为
步骤(b2)中所述5,10-乙炔卟啉的结构式为
步骤(b3)中所述5,10-双炔吡啶卟啉的结构式为
离子化反应中所述含有极性基团的化合物为溴乙烷、碘乙烷、3-溴丙醇或1,3-丙磺酸内酯;所述离子化反应的条件为:以超干DMF或者超干DMSO为溶剂,惰性气体保护,反应温度为50~80℃;所述吡啶卟啉化合物与溶剂(DMF或DMSO)的质量体积为(4~5)mg:1ml。
离子化反应后,需进行提纯,具体为将反应液与沉淀剂(如四氢呋喃)混合,离心,获得所需产物。
本发明的反应方程式如下:
Suzuki偶联反应:
Songashira偶联反应:
离子化反应:
卟啉小分子钙钛矿阴极缓冲层材料的制备方法中Suzuki偶合反应和Sonogashira偶合反应,两种反应所使用的溶剂均需无水无氧,反应开始前,反应体系均需抽气-换气3次,最终在惰性气体氮气或氩气的保护之中。
与现有技术相比,本发明具有以下优点和有益效果:
(1)本发明的卟啉小分子钙钛矿阴极缓冲层材料一层就可替代目前文献中普遍采用的C60、BCP两层界面,同时,器件性能还有所提升;
(2)本发明的卟啉小分子钙钛矿阴极缓冲层材料具有水醇溶特性,可溶液旋涂,而不必采用C60、BCP的真空蒸镀,大大降低器件成本;
(3)本发明卟啉小分子钙钛矿阴极缓冲层材料为卟啉类小分子界面材料,由于卟啉环有4个活泼氢位点和1个金属配位位点,因此卟啉类小分子存在着多种多样的组合形式,本发明所涉及的材料也还存在着广阔的改进空间。
附图说明
图1为实施例1制备的5,15-双(乙基溴吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉(m-PYBrZnPor)的乙醇溶液和薄膜的紫外-可见吸收光谱;
图2为实施例1制备的以m-PYBrZnPor为阴极缓冲层的光伏电池和BCP作为阴极缓冲层的光伏电池在AM 1.5,100mW/cm2光照下的电流-电压曲线。
具体实施方式
下面结合具体实施例和附图对本发明作进一步的描述,但本发明的实施方式不限于此。
实施例1
(1)5,15-双(5-(2-丁基)噻吩-2-辛烷)卟啉的合成
反应方程式如下:
在2L三口圆底烧瓶中,加入噻吩醛(4.2g,15.0mmol),联吡咯甲烷(2.19g,15.0mmol)和1.5L的二氯甲烷,用氮气通气30分钟,然后加入0.18mL的三氟乙酸,在室温下搅拌反应12小时,再加入5.55g 2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ),继续搅拌反应1小时。反应结束后,用硅胶/(二氯甲烷为洗脱剂)柱层析,旋干后得到粗产物,再用氯仿/甲醇重结晶,得暗红色固体(5,15-双(5-(2-丁基)噻吩-2-辛烷)卟啉)。1H NMR(500MHz,Chloroform-d)δ10.28(s,2H),9.44–9.28(m,8H),7.75(d,J=3.3Hz,2H),7.21(d,J=3.3Hz,2H),3.10(d,J=6.7Hz,4H),1.93(h,J=6.3Hz,2H),1.65–1.34(m,32H),1.01(t,J=7.0Hz,6H),0.98–0.91(m,6H),-2.96(s,2H).
(2)5,15-双溴-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉的合成
反应方程式如下:
将5,15-双(5-(2-丁基)噻吩-2-辛烷)卟啉(1.8g,2.2mmol)溶解在400mL的氯仿里,加入5mL的吡啶,避光充分溶解后,然后加入溴代丁二酰亚胺(NBS)(1.17g,6.6mmol),在0℃反应60分钟,后在室温下继续反应过夜,最后用丙酮淬灭反应。反应完毕,加入水,用氯仿萃取,无水硫酸钠干燥,旋干溶剂后溶解在60mL的氯仿溶液中,后加入15mL的醋酸锌甲醇溶液(1.2g,6.5mmol的醋酸锌溶解在15mL的甲醇溶剂里),避光回流6小时。反应完毕,水洗,并用无水硫酸钠干燥,旋干溶剂,使用硅胶柱层析纯化后得到亮红色的固体(5,15-双溴-10,20-双(5-(2-丁基)噻吩-2-辛基)锌卟啉)。
1H NMR(500MHz,Chloroform-d)δ9.64–9.36(m,4H),9.03(ddd,J=9.8,4.6,2.3Hz,4H),7.58(q,J=3.2Hz,2H),7.15(d,J=3.3Hz,2H),3.07(d,J=6.7Hz,4H),1.91(p,J=6.2Hz,2H),1.66–1.34(m,32H),1.03(t,J=6.9Hz,6H),0.96(t,J=4.9Hz,6H).
(3)5,15-双(三甲基硅乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉的合成
反应方程式如下:
在100mL的两口圆底烧瓶中,加入5,15-双溴-10,20-双(5-(2-丁基)噻吩-2-辛基)锌卟啉(429mg,0.416mmol),30mL无水四氢呋喃和15mL无水三乙胺,通氮气30分钟,然后加入双(三苯基膦)二氯化钯(29.5mg,0.042mmol),碘化亚铜(CuI)(8.0mg,0.042mmol)和三甲基硅乙炔(180mg,1.84mmol),避光,反应在室温下搅拌反应三天。反应完毕,用三氯甲烷萃取,水洗,再用硅胶/(二氯甲烷/二氯甲烷=3.5/1到3/1为洗脱剂)柱层析,加压过柱,旋干得到绿色粘稠固体(5,15-双(三甲基硅乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉)。1HNMR(500MHz,Chloroform-d)δ9.66(d,J=4.6Hz,4H),9.16(d,J=4.6Hz,4H),7.67(d,J=3.3Hz,2H),7.15(d,J=3.3Hz,2H),3.08(dd,J=6.8,1.7Hz,4H),1.91(p,J=6.1Hz,2H),1.62–1.36(m,32H),1.00(t,J=7.0Hz,6H),0.97–0.92(m,6H),0.61(d,J=1.2Hz,18H).
(4)5,15-双(乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉
反应方程式如下:
将5,15-双(三甲基硅乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉(578mg,0.54mmol)溶解在45mL的四氢呋喃里,加入四丁基氟化铵(1.3mL,1M in THF),在室温下搅拌反应5分钟,加水淬灭反应。用氯仿萃取,无水硫酸钠干燥,旋干,通过凝胶柱分离杂质,旋干得到绿色的固体(5,15-双(乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉)。
(5)5,15-双(吡啶-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉的合成
反应方程式为:
在氩气的保护下,往50mL的两口圆底烧瓶中加入锌卟啉(即5,15-双(乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉)(307mg,0.333mmol)、无水THF(36mL)、无水三乙胺(18mL)、3-溴吡啶(180uL,1.998mmol)、碘化亚铜(6.3mg,0.033mmol)和四(三苯基膦)钯(零价钯)(38.5mg,0.033mmol),反应体系避光,在80℃下搅拌反应三天。反应完毕,冷却至室温,加水猝灭,用氯仿萃取,水洗,无水硫酸钠干燥,旋干,过硅胶柱分离粗产物(二氯甲烷装柱,二氯甲烷冲柱,再用二氯甲烷/甲醇=100/1,过出二氯甲烷冲不下来的点),再用凝胶渗透色谱(Gel Permeation Chromatography,GPC)柱层析(四氢呋喃为洗脱剂),得到蓝黑色的固体(5,15-双(吡啶-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉)。1H NMR(500MHz,Chloroform-d)δ9.59(d,J=4.6Hz,4H),9.11(dd,J=2.1,0.9Hz,2H),9.09(d,J=4.5Hz,4H),8.53(dd,J=4.9,1.6Hz,2H),8.13(dt,J=7.8,1.9Hz,2H),7.59(d,J=3.3Hz,2H),7.34(ddd,J=7.8,4.9,0.9Hz,2H),7.07(d,J=3.3Hz,2H),2.99(d,J=6.7Hz,4H),1.82(h,J=6.3Hz,2H),1.52–1.27(m,32H),0.91(t,J=7.0Hz,6H),0.88–0.82(m,6H).
(6)终产物5,15-双(乙基溴吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉的合成
反应方程式如下:
取50ml两口瓶,充氮气保护,加入卟啉(5,15-双(吡啶-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉)(67mg,0.062mmol),无水DMF15ml,溴乙烷3ml,加热到50℃反应12h,再补加溴乙烷2ml,并将温度升至80℃反应4h,然后冷却到室温,反应液50℃旋转蒸发掉过量溴乙烷,然后反应液用瓶装THF沉析,高速离心机离心,产物为蓝色固体(5,15-双(乙基溴吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉(m-PYBrZnPor))。1HNMR(500MHz,DMSO-d6)δ10.04(s,2H),9.91(d,J=4.6Hz,4H),9.36(dt,J=8.0,1.4Hz,2H),9.24(dt,J=6.1,1.4Hz,2H),9.12(d,J=4.6Hz,4H),8.42(dd,J=8.1,6.0Hz,2H),7.83(d,J=3.3Hz,2H),7.34(d,J=3.3Hz,2H),4.83(q,J=7.3Hz,4H),1.90(q,J=6.2Hz,2H),1.75(t,J=7.4Hz,6H),1.63–1.31(m,32H),0.98(t,J=7.1Hz,6H),0.94–0.87(m,6H).
图1为实施例1制备的5,15-双(乙基溴吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉(m-PYBrZnPor)的乙醇溶液和薄膜的紫外-可见吸收光谱。
实施例2
5,15-双(乙基碘吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉的合成
反应方程式如下:
反应步骤同实施例1的步骤(6)5,15-双(乙基溴吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉的合成,不同之处为碘乙烷代替溴乙烷进行离子化,产物为蓝色固体(5,15-双(乙基碘吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉)。1H NMR(500MHz,DMSO-d6)δ10.03(s,2H),9.91(d,J=4.6Hz,4H),9.36(dt,J=8.2,1.4Hz,2H),9.24(dt,J=6.1,1.3Hz,2H),9.12(d,J=4.6Hz,4H),8.42(dd,J=8.1,6.0Hz,2H),7.83(d,J=3.3Hz,2H),7.35(d,J=3.3Hz,2H),4.83(q,J=7.3Hz,4H),1.90(q,J=6.2Hz,2H),1.75(t,J=7.4Hz,4H),1.64–1.18(m,32H),0.98(t,J=7.1Hz,6H),0.93–0.84(m,6H).
实施例3器件的构造
将实施例1制备的离子化吡啶卟啉-5,15-双(乙基溴吡啶季铵盐-3-乙炔)-10,20-双(5-(2-丁基)噻吩-2-辛烷)锌卟啉(m-PYBrZnPor)作为钙钛矿太阳电池的阴极缓冲层材料。
以m-PYBrZnPor作为阴极缓冲层的钙钛矿太阳电池器件的结构为ITO/PTAA/钙钛矿层(CH3NH3PbI3)/PCBM/m-PYBrZnPor/电极Ag。
以m-PYBrZnPor作为阴极缓冲层的钙钛矿太阳电池器件的制备方法:
(1)PTAA层的制备:通过溶液法,在ITO透明玻璃基底上旋涂了一层PTAA(聚三乙胺)作为阳极界面,PTAA溶液浓度为5mg/ml,在4000r/min的转速下,旋涂40秒,在100℃下退火10分钟,得到一层17nm厚的PTAA层;
(2)光活性层即钙钛矿层的构造:在PTAA层上,将PbI2的DMF溶液以4800r/min的转速,旋涂30秒,90℃退火5分钟,待冷却后,再旋涂一层CH3NH3I的DMF溶液,转速为3500r/min,旋涂时间是30秒,然后于150℃退火2h,期间需不时在薄膜边缘滴几滴DMF,获得一层~300nm厚的钙钛矿薄膜;
(3)冷却后,在钙钛矿层上旋涂一层PCBM(溶剂为氯苯,20mg/ml),以1000r/min的转速旋涂30秒,并在100℃下退火1h,得到一层40nm厚的PCBM薄膜;
(4)将m-PYBrZnPor的乙醇溶液(0.4mg/ml)旋涂在PCBM层上,转速为3500r/min,旋涂30秒,得到一层8nm厚的卟啉层作为阴极缓冲层;
(5)在阴极缓冲层上通过热蒸镀的方法,蒸镀了一层100nm厚的金属银作为阴极。
实施例1制备的以m-PYBrZnPor为阴极缓冲层的光伏电池和BCP作为阴极缓冲层的光伏电池在AM 1.5,100mW/cm2光照下的电流-电压曲线如图2所示。
在此种器件结构中,以离子化吡啶卟啉(即m-PYBrZnPor)为阴极缓冲层,高效钙钛矿太阳电池器件的最高光电转化效率为17.5%(开路电压1.067V,短路电流19.98mA/cm2,填充因子77.5%),平均光电转化效率为16.8%。而在现有的相似结构的器件中,使用蒸镀法构造C60、BCP双层阴极缓冲层的器件的平均光电转化效率为15%左右;使用单层BCP作为阴极缓冲层,构造了同样结构的钙钛矿电池器件,BCP层厚度为10nm,其他层的构造方法不变,最终基于BCP的钙钛矿太阳电池的最高光电转化效率为15.56%(开路电压1.024V,短路电流21.15mA/cm2,填充因子76.0%)。由此可知,本发明的离子化吡啶卟啉作为钙钛矿太阳电池中的阴极缓冲层具有成本低(可溶液旋涂),效果好等明显优势。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受所述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
2.根据权利要求1所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,其特征在于:包括以下步骤:
(1)通过Suzuki偶联反应或Sonogashira偶联反应,制备吡啶卟啉化合物;
(2)将吡啶卟啉化合物与含有极性基团的化合物进行离子化反应,得到卟啉小分子钙钛矿阴极缓冲层材料;
所述Suzuki偶联反应的具体步骤为:(a1)在惰性氛围和碱性环境下,将5,10-双溴卟啉与联硼酸频那醇酯在二价钯的催化下进行反应,纯化,得到5,10-双硼酸酯卟啉;
(a2)在惰性氛围和碱性环境下,将5,10-双硼酸酯卟啉与3-溴吡啶在钯催化剂的作用下进行反应,纯化,得到5,10-双吡啶卟啉即吡啶卟啉化合物;
步骤(a1)中所述5,10-双溴卟啉的结构为
所述5,10-双硼酸酯卟啉的结构为
步骤(a2)中所述吡啶卟啉化合物的结构为
所述Sonogashira偶联反应的具体制备步骤为:
(b1)在惰性氛围和有机溶剂中,将5,10-双溴卟啉与三甲基硅乙炔在催化体系的作用下进行反应,纯化,得到5,10-双硅乙炔卟啉;
(b2)在有机溶剂中,将四丁基氟化铵与5,10-双硅乙炔卟啉进行反应,纯化,得到5,10-乙炔卟啉;
(b3)在惰性氛围和有机溶剂中,将5,10-乙炔卟啉与3-溴吡啶在催化体系的作用下进行反应,纯化,得到5,10-双炔吡啶卟啉即含有炔基的吡啶卟啉化合物;
步骤(b1)中所述5,10-双硅乙炔卟啉的结构式为
步骤(b2)中所述5,10-乙炔卟啉的结构式为
步骤(b3)中所述5,10-双炔吡啶卟啉的结构式为
步骤(2)中所述离子化反应中所述含有极性基团的化合物为溴乙烷、碘乙烷、3-溴丙醇或1,3-丙磺酸内酯。
3.根据权利要求2所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,其特征在于:步骤(a1)中所述碱性环境是指在碳酸铯的1,2-二氯乙烷溶液中反应;所述反应的温度为60~95℃,时间为12~36h;
所述二价钯为双(三苯基膦)二氯化钯,所述5,10-双溴卟啉:联硼酸频那醇酯的摩尔比为1:(3~6);所述5,10-双溴卟啉:碳酸铯的摩尔比为1:(3~6);所述5,10-双溴卟啉:双(三苯基膦)二氯化钯的摩尔比为1:(0.05~0.2),所述碳酸铯:1,2-二氯乙烷的摩尔体积比为5mol:(500~1000)mL。
4.根据权利要求2所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,其特征在于:步骤(a2)中所述碱性环境是指在碳酸铯的DMF/甲苯的混合溶液中反应;所述反应的温度为100~120℃,时间为1~4天;所述二价钯为四(三苯基膦)钯;所述5,10-双硼酸酯卟啉:3-溴吡啶的摩尔比为1:(3~6),所述5,10-双硼酸酯卟啉:碳酸铯的摩尔比为1:(3~6);所述5,10-双硼酸酯卟啉:四(三苯基膦)钯的摩尔比为1:(0.08~0.12);所述碳酸铯:DMF与甲苯的混合溶剂的摩尔体积比为5mol:(500~1000)mL,DMF:甲苯的体积比为1:2。
5.根据权利要求2所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,其特征在于:步骤(b1)中所述催化体系为双(三苯基膦)二氯化钯和碘化亚铜;所述有机溶剂为四氢呋喃和三乙胺的混合溶剂;所述反应的温度为常温,时间为1~3天;所述5,10-双溴卟啉:三甲基硅乙炔的摩尔比为1:(3~6);所述5,10-双溴卟啉:双(三苯基膦)二氯化钯:碘化亚铜的摩尔比为1:(0.08~0.12):(0.08~0.12),所述5,10-双溴卟啉:有机溶剂的摩尔体积比为1mmol:(100~1000)mL;有机溶剂中四氢呋喃:三乙胺的体积比为2:1。
6.根据权利要求2所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,其特征在于:步骤(b2)中所述有机溶剂为四氢呋喃;
步骤(b3)中所述催化体系为四(三苯基膦)钯和碘化亚铜,所述有机溶剂为四氢呋喃和三乙胺的混合溶剂;所述5,10-乙炔卟啉与3-溴吡啶的摩尔比为1:(3~6);所述5,10-乙炔卟啉:四(三苯基膦)钯:碘化亚铜的摩尔比为1:(0.08~0.12):(0.08~0.12),所述5,10-乙炔卟啉:有机溶剂的摩尔体积比为1mmol:(100~1000)mL;有机溶剂中四氢呋喃:三乙胺的体积比为2:1;所述反应的温度为70~90℃,时间为1~3天。
7.根据权利要求2所述卟啉小分子钙钛矿阴极缓冲层材料的制备方法,其特征在于:步骤(2)中所述离子化反应的条件为:以超干DMF或者超干DMSO为溶剂,惰性气体保护,反应温度为50~80℃;所述吡啶卟啉化合物与溶剂的质量体积为(4~5)mg:1ml。
8.根据权利要求1所述卟啉小分子钙钛矿阴极缓冲层材料的应用,其特征在于:所述卟啉小分子钙钛矿阴极缓冲层材料用于制备钙钛矿太阳电池。
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