CN108690366B - 一种新型的n,n-二乙基苯胺类太阳能染料敏化剂及其制备与应用 - Google Patents
一种新型的n,n-二乙基苯胺类太阳能染料敏化剂及其制备与应用 Download PDFInfo
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- 230000001235 sensitizing effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylphenylamine Natural products CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003480 eluent Substances 0.000 claims abstract description 14
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003053 piperidines Chemical class 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
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- 238000000034 method Methods 0.000 claims description 5
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- 239000000463 material Substances 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
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- DFGWJCZWKBGVOX-UHFFFAOYSA-N [Cl+].[O-2].[O-2].[Ti+4] Chemical compound [Cl+].[O-2].[O-2].[Ti+4] DFGWJCZWKBGVOX-UHFFFAOYSA-N 0.000 description 1
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- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 125000001544 thienyl group Chemical group 0.000 description 1
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
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Abstract
本发明公开了一类N,N‑二乙基苯胺类太阳能染料敏化剂及其制备与应用,所述N,N‑二乙基苯胺类太阳能染料敏化剂如式I、式II或式III所示;
Description
(一)技术领域
本发明涉及一类N,N-二乙基苯胺类太阳能染料敏化剂及其制备与应用。
(二)背景技术
染料敏化太阳能电池(Dye Sensitized Solar Cell,DSSC)凭借其成本低、可弱光发电、光电转化率不受温度影响等特点,极有希望替代硅半导体光电转换部件,成为下一代实用型高性能太阳能电池。染料敏化剂是DSSC中决定可见光吸收和光电转换效率的关键结构材料,具有结构易设计修饰和加工、成本低、稳定性好等特点。
国内外染料敏化剂的研究主要分两类,一类为有机金属配合物,典型结构为功能性多吡啶钌化合物。这类染料敏化剂在可见光区吸收较强,氧化还原性能可逆,氧化稳定性高,但钌作为稀有金属成本较高,其染料吸收光谱窄。第二类为非金属有机染料,具有摩尔吸光系数高、吸收光谱宽和可通过结构修饰调变产生优良电化学性能等优点,是近年来染料敏化剂的研究热点。传统的非金属有机染料敏化剂的结构通式为“给体-π共轭桥-受体”(Donor-πBridge-Acceptor, D-π-A),根据给体的不同,已有香豆素型、吲哚啉型、三芳胺型等非金属染料敏化剂得以设计和开发。
新型的“D-A-π-A”结构是在“D-π-A”结构基础上增加一个额外受体,不仅扩大π共轭体系,促进有机染料敏化剂分子吸收光谱红移,同时相较于π共轭桥的扩大而言,更有利于染料敏化剂分子的稳定性的提高。弥补了“D-π-A”结构染料分子的缺陷。本发明以合成高光电转换效率的染料敏化剂为目标,以N,N-二乙基苯胺类衍生物为电子供体,苯并噻二唑为额外引入的受体,呋喃、苯基或噻吩基为桥键,氰基乙酸为键合受体,合成得到了三个“D-A-π-A”结构的N,N-二乙基苯胺类染料敏化色素染料敏化剂。目前,尚无文献报道该结构的太阳能电池应用。
(三)发明内容
本发明的目的之一是提供一类具有新颖结构的N,N-二乙基苯胺类太阳能染料敏化剂及其制备方法。
本发明提供了具有新颖结构的N,N-二乙基苯胺类染料敏化剂,具有式Ⅰ、式II或式III所示的结构:
本发明还提供了上述染料敏化剂的制备方法,所述的方法具体按照如下步骤进行制备:
将氰基乙酸分别与式Iva、式Ivb或式Ivc所示的化合物,哌啶溶于极性有机溶剂中混合均匀,在60~80℃下进行缩合反应,反应完全后,所得反应混合液经后处理分别得到式I、式II或式III所示的化合物;所述氰基乙酸、哌啶与式Iva、式Ivb或式Ivc所示的化合物的物质的量之比为2~4:3~5:1;
进一步,所述极性有机溶剂为乙腈、氯仿和四氢呋喃中的一种或任意几种的混合物。
再进一步,所述的有机溶剂的体积用量以式IVa、IVb或IVc所示的化合物的物质的量计为10~20mL/mmol。
再进一步,优选的,所述缩合反应的反应时间为6~8h。
更进一步,本发明所述反应混合液的后处理方法为:反应结束后,所得反应混合液蒸除溶剂后,残余物用洗脱剂溶剂进行硅胶柱层析,以任意体积比二氯甲烷与甲醇及醋酸组成的混合液为洗脱剂,收集含目标化合物的洗脱液,浓缩干燥得式I、式II或式III所示的化合物。
优选的,所述的洗脱剂为体积比为400:4:1的二氯甲烷、甲醇和醋酸的混合液。
本发明对所述式IV所示化合物的来源没有特殊要求,采用市售或本领域技术人员公知的制备方法制备均可;
在本发明实施例中,所述式IV所示化合物优选采用如下方法制备得到,包括以下步骤:
在N2保护的条件下,将具有式V所示的化合物、四三苯基膦钯分别与式VIa、VIb或VIc所示的甲酰基芳基硼酸化合物溶于四氢呋喃中,得到混合液,将所述混合液与碳酸钾水溶液混合进行加热回流,反应完全后将所得反应混合液冷却至室温,加入水,用二氯甲烷萃取3次,合并有机相并用饱和食盐水洗涤3~5次,干燥旋蒸后过柱(溶剂PE: DCM=5:1),分别得到式IVa、IVb或IVc所示的化合物所示结构的化合物;所述的式V所示结构的化合物、四三苯基膦钯与式VIa、VIb或 VIc所示的甲酰基芳基硼酸化合物的物质的量之比为1:0.1:1.52;
进一步,所述的四氢呋喃的加入量以式V所示的化合物的物质的量计为15ml/mmol。
进一步,所述的碳酸钾水溶液的加入量以式V所示的化合物的物质的量计为2.5mL/mmol。
再进一步,所述的碳酸钾的水溶液的浓度为2mol/L。
本发明还提供了所述的N,N-二乙基苯胺类化合物作为染料敏化剂在染料敏化太阳能电池中的应用,具体的应用如下:
将式I、式II或式III所示的所述的N,N-二乙基苯胺类太阳能染料敏化剂溶于氯仿-甲醇(V:V=10:1)的混合溶剂中,加入二氧化钛纳米粒子膜光电极,浸泡24小时,分别得到负载了式I、式II或式 III所示的N,N-二乙基苯胺类太阳能染料敏化剂的二氧化钛电极,再将其与铂对电极组装成三明治结构的电池,并在电池边缘滴入电解质,利用毛细渗透原理将电解质引入电池内部,与100mV/cm2光强照射下,测定光电压-电流特性曲线。其结果表明,此类太阳能染料敏化剂制作的染料敏化太阳能电池的光电转化效率在2.60-5.38%之间。
与现有技术相比,本发明的有益效果主要体现在:使用易得的二乙基苯胺作为电子给体,设计合成了新的N,N-二乙基苯胺类化合物用作染料敏化剂。该类化合物合成方法简单,原料便宜,且组装成的
染料敏化太阳能电池具有较好的光电转换效率,为染料敏化剂的筛选增添了新的可应用物质。
(四)附图说明
图1为基于式I、式II或式III所示的染料敏化剂的太阳能电池的光电流-电压曲线图。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1:
将化合物V(1.0g,2.7mmol)、5-甲酰基噻吩-2-硼酸VIa(0.65g, 4.1mmol)、四三苯基膦钯(0.31g,0.27mmol)加入到100mL的三口烧瓶中,抽真空换氮气。在氮气保护下,注入四氢呋喃(30mL)和2 mol/L的碳酸钾水溶液(1.49g,10.8mmol),加热回流12h。反应结束后冷却至室温,加入200ml水,用DCM(50ml×3)萃取,有机层用大量饱和食盐水洗涤,无水硫酸镁干燥,旋蒸后过柱(溶剂PE: DCM=5:1),得到暗红色固体IVa 253mg,收率23.4%,熔点139.0~140.5℃;1H NMR(500MHz,CDCl3)δ9.98(s,1H),8.22(d,J= 4.0Hz,1H),8.05(d,J=7.6Hz,1H),7.97(d,J=9.0Hz,2H),7.86(d,J =4.1Hz,1H),7.72(d,J=7.6Hz,1H),6.85(d,J=9.0Hz,2H),3.47(q, J=7.1Hz,4H),1.25(t,J=7.3Hz,6H).
将化合物IVa(0.253g,0.64mmol)、氰乙酸(0.115g,1.35mmol) 加入到50mL的两口烧瓶中,抽真空换氮气。在氮气保护下,注入 10mL氯仿和0.25mL(2.5mmol)哌啶,加热回流6h。反应结束后,加入20mL二氯甲烷,旋蒸过柱(洗脱剂DCM:CH3OH: CH3COOH=400:4:1),得到深黑色固体I 180mg,收率62.1%,熔点 220.3~221.1℃;1H NMR(500MHz,DMSO)δ8.52(s,1H),8.32(d,J= 7.6Hz,1H),8.27(d,J=3.8Hz,1H),8.09(d,J=3.7Hz,1H),8.01(d,J=8.6Hz,2H),7.89(d,J=7.7Hz,1H),6.84(d,J=8.7Hz,2H),3.44(q, J=6.0Hz,4H),1.16(t,J=6.9Hz,6H);HREIMS m/z 461.1103[M+H]+, cacld C24H21N4O2S2for:461.1100
实施例2:
将化合物V(0.5g,1.38mmol)、4-甲酰基苯基硼酸VIb(0.52g, 3.46mmol)、四三苯基膦钯(0.16g,0.138mmol)加入到50mL的两口烧瓶中,抽真空换氮气。在氮气保护下,注入四氢呋喃(14mL)和 2mol/L的碳酸钾水溶液(0.57g,4.14mmol),加热回流12h。反应结束后冷却至室温,加入200mL水,用DCM(50ml×3)萃取,有机层用大量饱和食盐水洗涤,无水硫酸镁干燥,旋蒸后柱层析(洗脱剂 PE:DCM=5:1),得到砖红色固体IVb 310mg,收率58.5%,熔点 175~177℃;1H NMR(500MHz,CDCl3)δ10.12(s,1H),8.19(d,J=8.2 Hz,2H),8.06(d,J=8.0Hz,2H),7.96(d,J=9.0Hz,2H),7.85(d,J= 7.4Hz,1H),7.76(d,J=7.4Hz,1H),6.86(d,J=8.5Hz,2H),3.47(q,J =7.1Hz,4H),1.25(d,J=7.5Hz,6H).
将化合物IVb(0.30g,0.775mmol)、氰乙酸(0.2g,2.33mmol)加入到50mL的两口烧瓶中,抽真空换氮气。在氮气保护下,注入20mL 四氢呋喃和0.23mL(2.3mmol)哌啶,加热回流8h。反应结束后,加入20mL二氯甲烷,旋蒸后柱层析(洗脱剂DCM:CH3OH: CH3COOH=400:4:1),得到灰黑色固体II 100mg,收率28.41%,熔点200.1~203.4℃;1H NMR(500MHz,DMSO)δ8.42(s,1H),8.27(d,J =8.5Hz,2H),8.22(d,J=8.5Hz,2H),8.06(t,J=7.5Hz,1H),7.98(d, J=8.9Hz,2H),7.89(d,J=7.5Hz,1H),6.84(d,J=9.0Hz,2H),3.44 (q,J=7.0Hz,4H),1.16(t,J=7.0Hz,6H);HREIMS m/z 455.1536 [M+H]+,cacld C26H23N4O2S for:455.1539
实施例3:
将化合物V(0.4g,1.11mmol)、5-甲酰基呋喃-2-硼酸VIc(0.39g, 2.77mmol)、四三苯基膦钯(0.13g,0.11mmol)加入到50mL的两口烧瓶中,抽真空换氮气。在氮气保护下,注入四氢呋喃(12mL)和2 mol/L的碳酸钾水溶液(0.46g,3.33mmol),加热回流12h。反应结束后冷却至室温,加入200mL水,用DCM(50mL×3)萃取,有机层用大量饱和食盐水洗涤,无水硫酸镁干燥,旋蒸后柱层析(洗脱剂 PE:DCM=5:1),得到砖红色固体IVc 139.4mg,收率33.27%,熔点 136.1~137.2℃;1H NMR(500MHz,CDCl3)δ9.73(s,1H),8.35(d,J= 7.7Hz,1H),7.97(d,J=9.0Hz,2H),7.89(d,J=3.7Hz,1H),7.75(d,J =7.6Hz,1H),7.46(d,J=3.8Hz,1H),6.84(d,J=8.9Hz,2H),3.47(q, J=7.1Hz,4H),1.25(t,J=7.1Hz,6H).
将化合物IVc(0.1394g,0.369mmol)、氰乙酸(0.13g,1.48mmol) 加入到50mL的两口烧瓶中,抽真空换氮气。在氮气保护下,注入 10mL乙腈和0.18mL(1.8mmol)哌啶,加热回流7h。反应结束后,加入20mL二氯甲烷,旋蒸后柱层析(洗脱剂DCM:CH3OH: CH3COOH=400:4:1),得到黑色固体III 78mg,收率48.8%,熔点 180.1~181.3℃;1H NMR(500MHz,DMSO)δ8.28(d,J=7.7Hz,1H), 8.16(s,1H),8.06(d,J=8.9Hz,2H),7.97(d,J=7.7Hz,1H),7.91(d,J =3.7Hz,1H),7.67(d,J=3.8Hz,1H),6.83(d,J=9.0Hz,2H),3.45(q, J=7.0Hz,4H),1.16(t,J=7.0Hz,6H);HREIMS m/z 445.1329[M+H]+, cacld C24H21N4O2S2for:445.1333
实施例4:
如式I、式II或式III所示的N,N-二乙基苯胺类化合物作为染料敏化剂的应用:
利用丝网印刷制备的双层TiO2纳米粒子膜作为光电极:首先在导电玻璃FTO上印一层12μm厚的20nm的TiO2粒子,于450℃下马弗炉内煅烧30min,将煅烧后形成的膜浸入0.04mol·L-1的TiCl4水溶液 70℃预处理30min,然后分别用水和乙醇冲洗,电吹风吹干。经马弗炉450℃下再次煅烧30min后,冷却至80℃后浸入3×10-4 mol·L-1染料的氯仿-甲醇(V:V=10:1)溶液室温敏化24h。
对电极的制备:采用丝网印刷方法,将H2PtCl6溶液印刷在FTO 导电玻璃上,然后在400℃马弗炉中烧结20min。吸附染料的TiO2电极和铂对电极组装成三明治结构,并在边缘滴入电解质,利用毛细管渗透原理引入电池内部。于100mW/cm2光强照射下,测定光电压 -电流特性曲线。其结果如表1所示:
表1 N,N-二乙基苯胺类化合物组装得到的DSSC性能参数
a:Jsc为短路电流密度;b:Voc为开路电压;c:ff为填充因子;d:η为光电转换效率。
由图1和表1可以看出,本发明所提供的染料敏化剂均具有光电转化能力,可以作为染料敏化太阳能电池的染料敏化剂,且其光电转化效率可达为2.60-5.38%,具有优异的光电转化性能。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种结构如式I、式II或式III所示的N,N-二乙基苯胺类化合物,
2.一种如权利要求1所述的N,N-二乙基苯胺类化合物的制备方法,其特征在于,所述的方法按如下步骤进行:
将氰基乙酸分别与式Iva、式Ivb或式Ivc所示的化合物,哌啶溶于极性有机溶剂中混合均匀,在60~80℃下进行缩合反应,反应完全后,所得反应混合液经后处理分别得到式I、式II或式III所示的化合物;所述氰基乙酸、哌啶与式Iva、式Ivb或式Ivc所示的化合物的物质的量之比为2~4:3~5:1;
3.如权利要求2所述的制备方法,其特征在于,所述的有机溶剂为氯仿、乙腈或四氢呋喃中的一种或任意几种的混合物。
4.如权利要求2或3所述的制备方法,其特征在于,所述的有机溶剂的体积用量以式IVa、IVb或IVc所示的化合物的物质的量计为10~20mL/mmol。
5.如权利要求2所述的制备方法,其特征在于,所述的反应时间为6~8h。
6.如权利要求2所述的制备方法,其特征在于,所述的反应混合液的后处理方法为:反应结束后,所得反应混合液蒸除溶剂后,残余物用洗脱剂溶剂进行硅胶柱层析,以任意体积比的二氯甲烷和甲醇及醋酸的混合液为洗脱剂,收集含目标化合物的洗脱液,浓缩干燥分别得式I、式II或式III所示的N,N-二乙基苯胺类化合物。
7.如权利要求6所述的制备方法,其特征在于,所述的洗脱剂为体积比为400:4:1的二氯甲烷和甲醇及醋酸的混合液。
8.一种如权利要求1所述的N,N-二乙基苯胺类化合物作为染料敏化剂在染料敏化太阳能电池中的应用。
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