CN107603217A - 一种聚二苯胺‑4‑磺酸分散聚3,4‑乙撑二氧噻吩导电复合物及制备与应用 - Google Patents
一种聚二苯胺‑4‑磺酸分散聚3,4‑乙撑二氧噻吩导电复合物及制备与应用 Download PDFInfo
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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
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Abstract
本发明属于复合材料技术领域,公开了一种聚二苯胺‑4‑磺酸分散聚3,4‑乙撑二氧噻吩导电复合物及制备与应用。所述复合物具有式(I)所示的结构式,其通过如下方法制备:将质量浓度为5.0%~10.0%的二苯胺‑4‑磺酸钠水溶液加酸调节pH为2~3,加入氧化剂反应6~12h得到聚二苯胺‑4‑磺酸分散液;然后加入3,4‑乙撑二氧噻吩单体,加入氧化剂反应12~36h,将反应液透析除去无机盐及未反应的单体,得到导电复合物。本发明所得导电复合物具有电导率高,薄膜的结构和导电均匀性好,酸性相对PEDOT:PSS弱等优点,在钙钛矿太阳能电池中具有良好的应用前景。
Description
技术领域
本发明属于复合材料技术领域,具体涉及一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物及制备与应用。
背景技术
PEDOT作为导电聚合物,是一种新型的具有潜力开发成理想柔性透明电极的有机材料,但其不溶不熔的性质限制了它的应用。上世纪80年代,德国Bayer AG公司使用聚苯乙烯磺酸(PSS)分散的聚噻吩的衍生物聚3,4-乙撑二氧噻吩,简称PEDOT:PSS。PEDOT:PSS具有良好的成膜性,较好的环境稳定性和薄膜透明性而受到广泛的关注,并在抗静电涂料、有机电子器件等方面也表现出了广阔的应用前景。聚苯乙烯磺酸(PSS)具有线性规整结构,有利于分散PEDOT,利于PEDOT链上的π-π堆积,增加其导电性能。
PEDOT:PSS在应用过程中显现出许多缺点,如掺杂剂聚苯乙烯磺酸价格相对较高,增加了电子器件的成本;PSS本身不导电,而且分散用量较大,导致聚合物中含有大量不能导电的聚阴离子,使PEDOT:PSS薄膜具有结构和导电不均匀性(专利CN 105336867A,Advanced Energy Materials 2017,7,1601499),影响电荷传输,电导率低;酸性强,腐蚀电极,所以许多人致力于改性PEDOT:PSS或寻找其他掺杂剂替代PSS。
发明内容
针对以上现有技术存在的缺点和不足之处,本发明的首要目的在于提供一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物。
本发明的另一目的在于提供上述聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法。
本发明的再一目的在于提供上述聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物在有机光电器件中的应用。
本发明目的通过以下技术方案实现:
一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物,所述复合物是通过3,4-乙撑二氧噻吩单体在聚二苯胺-4-磺酸(PDAS)载体上聚合分散得到;所述复合物具有式(I)所示的结构式:
上述聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,包括如下制备步骤:
(1)将二苯胺-4-磺酸钠溶于去离子水中配制成质量浓度为5.0%~10.0%的二苯胺-4-磺酸钠水溶液,加酸调节pH为2~3,再加入氧化剂室温搅拌反应6~12h,得到聚二苯胺-4-磺酸分散液;
(2)向步骤(1)的分散液中加入3,4-乙撑二氧噻吩单体,然后加入氧化剂,室温搅拌反应12~36h,得到以聚二苯胺-4-磺酸为载体的聚3,4-乙撑二氧噻吩水分散液;
(3)将步骤(2)的水分散液透析除去无机盐及未反应的单体,得到聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物(PEDOT:PDAS)。
所述的二苯胺-4-磺酸钠具有如下分子结构式:
所述的聚二苯胺-4-磺酸具有如下所示的分子结构式:
上述制备方法中,所述3,4-乙撑二氧噻吩与二苯胺-4-磺酸钠加入的质量比优选为1:(1~100)。
所述的氧化剂优选过硫酸铵、过硫酸钠或过硫酸钾。
优选地,步骤(1)中所述的酸是指盐酸、硫酸、碳酸或醋酸。
优选地,步骤(2)中所述搅拌的速度为500~2000r/min。
优选地,步骤(3)中所述的透析是指用截留分子量为1000的透析袋透析3~7天。
上述聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物在有机光电器件中的应用。
本发明所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物具有如下优点及有益效果:
(1)本发明首次采用导电物质聚二苯胺-4-磺酸用于导电聚合物PEDOT的分散掺杂,并成功制备了聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩(PEDOT:PDAS)导电复合物。相比传统的绝缘的PSS掺杂剂,聚二苯胺-4-磺酸自身导电,所得PEDOT:PDAS导电复合物具有电导率高,薄膜的结构和导电均匀性好,酸性相对PEDOT:PSS弱等优点,在钙钛矿太阳能电池中作为空穴收集层,表现出较好的性能,具有良好的应用前景。
(2)本发明的制备方法工艺简单,所使用的二苯胺-4-磺酸钠原料价格低廉,生产成本低。
附图说明
图1为本发明实施例1、3所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物(PEDOT:PDAS)与聚二苯胺-4-磺酸(PDAS)、PEDOT:PSS(4083)的紫外吸收光谱图;
图2为实施例1、3所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物(PEDOT:PDAS)与聚二苯胺-4-磺酸(PDAS)、3,4-乙撑二氧噻吩单体(EDOT)的红外光谱图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
取2g二苯胺-4-磺酸钠溶于去离子水中配制成质量浓度为7.0%的水溶液,室温搅拌10min,用盐酸调节其pH值为2;再加2.5g过硫酸铵;室温搅拌反应10h;向上述溶液加入2g单体3,4-乙撑二氧噻吩,边搅拌边加入4.8g过硫酸铵,1500转/分钟的搅拌速度下室温搅拌反应36小时。反应结束后,将所得水分散液用截留分子量1000的透析带透析5天,除去无机盐及未反应的单体,得到聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物。
实施例2
取4g二苯胺-4-磺酸钠溶于去离子水中配制成质量浓度为7.0%的水溶液,室温搅拌10min,用盐酸调节其pH值为2;再加5.0g过硫酸铵;室温搅拌反应10h;向上述溶液加入2g单体3,4-乙撑二氧噻吩,边搅拌边加入4.8g过硫酸铵,1500转/分钟的搅拌速度下室温搅拌反应36小时。反应结束后,将所得水分散液用截留分子量1000的透析带透析5天,除去无机盐及未反应的单体,得到聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物。
实施例3
取5g二苯胺-4-磺酸钠溶于去离子水中配制成质量浓度为7.0%的水溶液,室温搅拌10min,用盐酸调节其pH值为2;再加6.2g过硫酸铵;室温搅拌反应10h;向上述溶液加入2g单体3,4-乙撑二氧噻吩,边搅拌边加入4.8g过硫酸铵,1500转/分钟的搅拌速度下室温搅拌反应36小时。反应结束后,将所得水分散液用截留分子量1000的透析带透析5天,除去无机盐及未反应的单体,得到聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物(PEDOT:PDAS)。
实施例4
取6g二苯胺-4-磺酸钠溶于去离子水中配制成质量浓度为7.0%的水溶液,室温搅拌10min,用盐酸调节其pH值为2;再加7.5g过硫酸铵;室温搅拌反应10h;向上述溶液加入2g单体3,4-乙撑二氧噻吩,边搅拌边加入3g过硫酸铵,1500转/分钟的搅拌速度下室温搅拌反应36小时。反应结束后,将所得水分散液用截留分子量1000的透析带透析5天,除去无机盐及未反应的单体,得到聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物。
性能测试及表征:以下为部分实施例产品的性能测试及表征,其他实施例性能测试结果及表征谱图基本相同,不一一提供。
(1)实施例3所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物(PEDOT:PDAS)作为空穴传输材料在钙钛矿太阳能电池器件中应用性能测试:
其器件结构为:ITO/PEDOT:PDAS/MAPbI3/PCBM/PEI/Ag。其中PCBM表示[6,6]-苯基-C61-丁酸甲酯,PEI代表聚乙烯亚胺。
器件制作步骤:氧化铟锡(ITO)玻璃依次用洗洁精、去离子水、丙酮、异丙醇超声清洗10min,氧气等离子体处理1min,然后通过旋涂法,在3000rpm的转速下将PEDOT:PDAS溶液旋涂于ITO表面,并于130℃下退火15min得到PEDOT:PDAS的薄膜,之后在手套箱中用反溶剂法旋涂钙钛矿薄膜,100℃退火10min,之后依次旋涂氯苯溶液(2000rpm,20mg/ml)和PEI溶液(5000rpm,0.1wt%),最后将器件转移至高真空腔内,以0.5nm/s的速度蒸镀银电极。得到钙钛矿太阳能电池,并以没有旋涂PEDOT:PDAS空穴传输层的器件作为空白对比。所得器件的光电性能测试结果如表1所示。
表1
由表1结果可以看出,对比不存在空穴传输层的器件,本发明所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物具有显著的空穴传输能力。
实施例3所得PEDOT:PDAS复合物溶液的酸性和电导率数据与现有导电复合物PEDOT:PSS对比如表2所示。
表2
由表2结果可以看出,本发明所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物相比现有的PEDOT:PSS具有较弱的酸性及较高的电导率。尤其是电导率的提高,对比工业化的4083最高电导率还提高了一个数量级。
(2)实施例1、3所得聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物(PEDOT:PDAS)的表征:
图1为PDAS、PEDOT:PSS(4083)、实施例1、3所得PEDOT:PDAS的紫外吸收光谱。紫外吸收光谱采用UV-2450紫外分光光度计(日本岛津)测试。其中PEDOT:PSS(4083)为聚(3,4-乙撑二氧噻吩)导电复合物商业化产品,聚(3,4-乙撑二氧噻吩)的紫外特征吸收峰为在500-950nm的宽峰,而3,4-乙撑二氧噻吩单体和聚二苯胺-4-磺酸在波长为500-950nm的区域没有吸收。由图1可以看出实施例1,3复合物在500-950nm的区域存在明显吸收,说明聚(3,4-乙撑二氧噻吩)/聚二苯胺-4-磺酸已成功制备。
图2为3,4-乙撑二氧噻吩单体(EDOT)、聚二苯胺-4-磺酸(PDAS)、实施例1、3所得复合物的红外光谱。实验采用仪器AutosystemXL/I-series/Spectrum2000红外光谱仪,用溴化钾压片法进行表征。3050~3125cm-1处的特征尖峰为单体噻吩环上C-H的伸缩振动峰,892cm-1处的尖峰为单体噻吩环上C-H的弯曲振动,1510、1400和760cm-1处的吸收峰为噻吩骨架上的特征峰,1200和1100cm-1处的吸收峰为3,4-乙撑二氧噻吩的含氧取代基的特征峰。实施例3的PEDOT:PDAS复合物的红外谱图与EDOT单体及PDAS对照来看,3050~3125cm-1、892cm-1两个单体特征尖峰消失,说明噻吩单体反应完全,且出现了噻吩骨架和3,4-乙撑二氧噻吩的含氧取代基的特征峰,说明3,4-乙撑二氧噻吩已经成功聚合得到聚(3,4-乙撑二氧噻吩)。
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上述实施例的限制,其它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)
1.一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物,其特征在于所述复合物是通过3,4-乙撑二氧噻吩单体在聚二苯胺-4-磺酸载体上聚合分散得到;所述复合物具有式(I)所示的结构式:
2.权利要求1所述的一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,其特征在于包括如下制备步骤:
(1)将二苯胺-4-磺酸钠溶于去离子水中配制成质量浓度为5.0%~10.0%的二苯胺-4-磺酸钠水溶液,加酸调节pH为2~3,再加入氧化剂室温搅拌反应6~12h,得到聚二苯胺-4-磺酸分散液;
(2)向步骤(1)的分散液中加入3,4-乙撑二氧噻吩单体,然后加入氧化剂,室温搅拌反应12~36h,得到以聚二苯胺-4-磺酸为载体的聚3,4-乙撑二氧噻吩水分散液;
(3)将步骤(2)的水分散液透析除去无机盐及未反应的单体,得到聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物。
3.根据权利要求2所述的一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,其特征在于:所述3,4-乙撑二氧噻吩与二苯胺-4-磺酸钠加入的质量比为1:(1~100)。
4.根据权利要求2所述的一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,其特征在于:所述的氧化剂为过硫酸铵、过硫酸钠或过硫酸钾。
5.根据权利要求2所述的一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,其特征在于:步骤(1)中所述的酸是指盐酸、硫酸、碳酸或醋酸。
6.根据权利要求2所述的一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,其特征在于:步骤(2)中所述搅拌的速度为500~2000r/min。
7.根据权利要求2所述的一种聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物的制备方法,其特征在于:步骤(3)中所述的透析是指用截留分子量为1000的透析袋透析3~7天。
8.权利要求1所述的聚二苯胺-4-磺酸分散聚3,4-乙撑二氧噻吩导电复合物在有机光电器件中的应用。
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