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CN104059432B - 透明碳纳米管高分子复合导电墨水及其制备方法 - Google Patents

透明碳纳米管高分子复合导电墨水及其制备方法 Download PDF

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CN104059432B
CN104059432B CN201310089765.2A CN201310089765A CN104059432B CN 104059432 B CN104059432 B CN 104059432B CN 201310089765 A CN201310089765 A CN 201310089765A CN 104059432 B CN104059432 B CN 104059432B
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CN104059432A (zh
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郝海燕
戴雷
蔡丽菲
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Beijing Aglaia Technology Development Co Ltd
Guangdong Aglaia Optoelectronic Materials Co Ltd
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Guangdong Aglaia Optoelectronic Materials Co Ltd
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Priority to DE112014001525.3T priority patent/DE112014001525T5/de
Priority to JP2016503525A priority patent/JP6244006B2/ja
Priority to US14/778,064 priority patent/US20160280947A1/en
Priority to PCT/CN2014/072623 priority patent/WO2014146534A1/zh
Priority to TW103110032A priority patent/TW201437301A/zh
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Abstract

本发明涉及透明碳纳米管高分子复合导电墨水及其制备方法。该导电墨水由改性后的碳纳米管、导电高分子、水溶性高分子助溶剂、高分子改性助剂、表面活性剂和去离子水组成，且通过溶液的共混工艺技术，实现了碳纳米管与导电高分子溶液的均匀分散，制备的墨水稳定性和再分散性良好。本发明可以在室温条件下，采用spin？coating、喷墨打印等设备制备精细的电极图案，也可以通过光刻工艺实现精细的电极图案制备，也可配制成光刻型的导电墨水，实现微细结构电极图案的一次性制备。该墨水可应用于柔性OLED显示器件、太阳能电池、液晶显示，触摸屏面板等器件中的极透明电极材料，与透明高分子基底相容性好，附着力强，确保柔性电极的使用寿命。

Description

透明碳纳米管高分子复合导电墨水及其制备方法
技术领域
本发明涉及有机电致发光器件领域，特别是涉及一种透明电极用透明碳纳米管高分子复合导电墨水及其制备方法。
背景技术
在液晶面板、OLED面板、触摸屏、电子纸、太阳能电池等显示器件和光伏器件中，透明电极都是不可缺少的部分。氧化铟锡(ITO)在玻璃基底上形成ITO薄膜显示出优异的透光性和导电性，因此目前其在商业化透明电极的应用领域里占有主导地位。但随着科技的发展及透明电极应用领域的多元化，透明电极必须具备低方阻，可见光范围内良好的透过率、柔性、可实现大面积精细涂布成膜的简单操作工艺等要求。这使得ITO薄膜的拓展应用中存在技术上难以克服的问题。In是稀有元素，世界储存量较少而且薄膜中In2O3的含量比较高，所以制备成本较高；由于ITO薄膜比较脆，在经过周期性多次弯曲或者压缩后，容易产生裂缝，致使导电性失效。当ITO薄膜低温沉积在相匹配的塑料衬底时，膜层表现出相对高的表面电阻和粗糙度。因此，开发新型柔性透明电极材料来替代ITO电极是电子显示领域和光伏等应用领域发展所必须解决技术难点。
碳纳米管是一种具有典型的层状中空结构特征的碳材料,构成碳纳米管的管身由六边形石墨碳环结构单元组成,是一种具有特殊结构（径向尺寸为纳米量级，轴向尺寸为微米量级）的一维量子材料。它的管壁构成主要为数层到数十层的同轴圆管。层与层之间保持固定的距离，约为0.34nm，直径一般为2～20nm。碳纳米管上碳原子的P电子形成大范围的离域π键，由于共轭效应显著，碳纳米管具有一些特殊的电学性质。由于碳纳米管的结构与石墨的片层结构相同，所以具有很好的电学性能。碳纳米管材料因为其高电子迁移率，低电阻率及高透明度，已被科研和产业界认定为可代替ITO的透明电极。
碳纳米管与导电材料制成复合层，可增加透明电极的导电性能，现在的方法一般是将碳纳米管与导电材料制成混合液然后再喷涂，或是印刷在电极上，但由于碳纳米管结构的特殊性，跟其它物质的相容性较差，混合液中碳纳米管的分散性较差，而且混合液不稳定，且容易沉积。
发明内容
本发明开发了一种新型的透明碳纳米管高分子导电墨水，此墨水采用改性的碳纳米管及导电高分子为原材料，采用特选的助溶剂，且通过溶液的共混工艺技术，实现了碳纳米管与导电高分子溶液的均匀分散，制备的墨水稳定性和再分散性良好。
本发明还提供该透明碳纳米管高分子导电墨水的制备方法。
透明碳纳米管高分子导电墨水，其组分及其重量份如下：
1.改性后的碳纳米管0.01%-1%，
2.导电高分子0.17%-2%，
3.水溶性高分子助溶剂0.43%-5%，
4.表面活性剂0.01%-0.05%，
5.高分子改性助剂0.037%-0.44%，
6.去离子水加至100%，
所述改性后的碳纳米管采用下述方法制成：在碳纳米管中加入30%HNO3溶液，通过超声波分散40min后，在50-70℃搅拌30min，用200μm的多孔滤膜过滤，清洗至中性，于100℃下烘干，得到纯化的改性后的碳纳米管。
所述碳纳米管为单壁碳纳米管、双壁碳纳米管或多壁碳纳米管粉体。
所述导电高分子为聚苯胺、聚3，4-乙撑二氧噻吩、聚乙炔或聚吡咯。
所述相应的导电高分子助溶剂为聚苯乙烯磺酸盐、樟脑磺酸、十二烷基苯磺酸、十六烷基苯磺酸或萘磺酸。
所述高分子改性助剂为：丙二醇、丙三醇、乙二醇丁醚、山梨醇、二甲基亚砜、N-N二甲基甲酰胺中的一种或几种。
所述表面活性剂为十二烷基苯磺酸钠或聚吡咯烷酮。
所述导电高分子为聚3,4-乙撑二氧噻吩，导电高分子助溶剂为聚苯乙烯磺酸钠，所述表面活性剂为聚吡咯烷酮。
该透明碳纳米管高分子导电墨水的制备方法，采用如下步骤：
1）碳纳米管纯化改性：在碳纳米管中加入30%HNO3溶液，通过超声波分散40min后，在50-70℃搅拌30min，用200μm的多孔滤膜过滤，清洗至中性。于100℃下烘干，得到纯化的改性后的碳纳米管；
2）将一定量的纯化的改性后的碳纳米管与表面活性剂混合溶解在一定量的水中，利用超声分散仪和机械搅拌的方法进行充分分散，所得分散液经过200μm的过孔滤膜进行多次过滤，所得的滤液为碳纳米管分散液；
3）导电高分子：导电高分子助溶剂高分子体改性：将一定量的高分子改性助剂加入导电高分子：导电高分子助溶剂中，通过超声分散和机械搅拌，形成澄清的溶液，溶液经过200μm的过孔滤膜进行多次过滤；
4）将步骤2和步骤3所得的溶液进行共混，通过超声和机械搅拌的方法形成稳定均匀的透
明碳纳米管高分子导电墨水。
所述导电高分子：导电高分子助溶剂为聚3，4-乙撑二氧噻吩（PEDOT）：聚苯乙烯磺酸钠（PSS）。
本发明配方中除了基本的改性后的碳纳米管、导电高分子和去离子水外，另加入了导电高分子助溶剂，以及高分子改性助剂和表面活性剂，使该碳纳米管的分散性能显著提高，同时该墨水的稳定性好和再分散性好。
碳纳米管作为导电薄膜的导电传输材料，其在导电高分子体系中的分散至关重要。但是由于碳纳米管表面张力较大，容易团聚形成颗粒状。由此，碳纳米管较均匀的分散在此墨水体系中非常关键。本专利技术采用酸化的方法，去除了碳纳米管表面的无定形态碳，同时也在碳纳米管的表面嫁接了如OH、COOH类官能团，降低了碳纳米管的团聚，增加了碳纳米管的溶解性。并且在表面活性剂的对碳纳米管表面张力的调整下，可增加碳纳米管在墨水体系的稳定分散性。
导电高分子本身是难溶于水的物质，在高分子助溶剂的键合作用下，可形成一种可溶解的溶液体系。为调整其导电特性，可加入一些高熔点的物质来增强其导电性能即导电助剂。
本发明开发了一种新型的透明碳纳米管高分子导电墨水，此墨水采用改性的碳纳米管及导电高分子为原材料，通过溶液的共混工艺技术，实现了碳纳米管与导电高分子溶液的均匀分散，制备的墨水稳定性和再分散性良好。该透明的碳纳米管高分子导电墨水，可以在室温条件下，采用spincoating、喷墨打印等设备制备精细的电极图案，也可以通过光刻工艺实现精细的电极图案制备，也可配制成光刻型的导电墨水，实现微细结构电极图案的一次性制备。
该透明CNT墨水可应用于柔性OLED显示器件、太阳能电池、液晶显示，触摸屏面板等器件中的极透明电极材料，与透明高分子基底相容性好，附着力强，确保柔性电极的使用寿命。
附图说明
图1碳纳米管（CNT）及CNT/PEDOT：PSS（实施例1）薄膜的表面形貌测试图，
图2实施例1制备薄膜光学透过率测试结果。
具体实施方式
下面结合实施例对本发明做进一步的详细说明。
实施例1：
制备方法：
工艺步骤：
1）碳纳米管纯化改性：在碳纳米管中加入30%HNO3溶液，通过超声波分散40min后，在50-70℃搅拌30min，用200μm的多孔滤膜过滤，清洗至中性。于100℃下烘干，得到纯化的碳纳米管。
2）将一定量的纯化的碳纳米管与表面活性剂PVP混合溶解在一定量的水中，利用超声分散仪和机械搅拌的放射进行充分分散，所得分散液经过200μm的过孔滤膜进行多次过滤。所得的滤液为碳纳米管分散液。
3）PEDOT：PSS高分子体改性。将一定量的高分子改性助剂加入PEDOT：PSS溶液中。通过超声分散和机械搅拌，形成澄清的蓝色溶液。溶液经过200μm的过孔滤膜进行多次过滤。
4）按照一定比例将步骤2和步骤3所得的溶液进行共混，通过超声和机械搅拌的方法形成稳定均匀的透明碳纳米管高分子复合导电墨水制备。
实施例2：
制备方法同实施例1。
透明的碳纳米管高分子导电墨水，可以在室温条件下，采用spincoating、喷墨打印等设备制备精细的电极图案，也可以通过光刻工艺实现精细的电极图案制备，也可配制成光刻型的导电墨水，实现微细结构电极图案的一次性制备。
实验例：将实施例1的导电墨水在电子玻璃基底上旋涂导电膜。见图1。实施工艺：转速3000rpm，时间30s，烘烤温度120℃，烘烤时间20min。
所得单层膜厚度为19-23nm，三层膜厚度为55-60nm，在300-600nm波长范围内，光学透过率（相对于基底）均大于90%。三层薄膜方阻达到150-200Ω/□。见表1、图2。
表1实施例1所制备薄膜导电性及薄膜厚度测试结果
IJ1005-MWNTCOOH-1layer 1132.5Ω/□ 19.7nm
IJ1005-MWNTCOOH-2layers 317.1Ω/□ 40.3nm
IJ1005-MWNTCOOH-3layers 181.2Ω/□ 52.7nm

Claims (3)

1.透明碳纳米管高分子导电墨水，其组分及其重量份如下：
1）．改性后的碳纳米管0.01%-1%，
2）．导电高分子0.17%-2%，
3）．水溶性高分子助溶剂0.43%-5%，
4）．表面活性剂0.01%-0.05%，
5）．高分子改性助剂0.037%-0.44%，
6）．去离子水加至100%，
所述改性后的碳纳米管采用下述方法制成：在碳纳米管中加入30％HNO3溶液，通过超声波分散40min后，在50-70℃搅拌30min，用200μm的多孔滤膜过滤，清洗至中性，于100℃下烘干，得到纯化的改性后的碳纳米管；
所述导电高分子为聚3，4-乙撑二氧噻吩，导电高分子助溶剂为聚苯乙烯磺酸钠，所述表面活性剂为聚乙烯吡咯烷酮；
所述高分子改性助剂为：丙二醇、丙三醇、乙二醇丁醚、山梨醇、二甲基亚砜、N-N二甲基甲酰胺中的一种或几种。
2.根据权利要求1所述的透明碳纳米管高分子导电墨水，所述碳纳米管为单壁碳纳米管、双壁碳纳米管或多壁碳纳米管粉体。
3.权利要求1-2任一所述透明碳纳米管高分子导电墨水的制备方法，采用如下步骤：
1)碳纳米管纯化改性：在碳纳米管中加入30％HNO3溶液，通过超声波分散40min后，在50-70℃搅拌30min，用200μm的多孔滤膜过滤，清洗至中性；于100℃下烘干，得到纯化的改性后的碳纳米管；
2)将一定量的纯化的改性后的碳纳米管与表面活性剂混合溶解在一定量的水中，利用超声分散仪和机械搅拌的方法进行充分分散，所得分散液经过200μm的多孔滤膜进行多次过滤，所得的滤液为碳纳米管分散液；
3)导电高分子/导电高分子助溶剂高分子体改性：将一定量的高分子改性助剂加入导电高分子/导电高分子助溶剂中，通过超声分散和机械搅拌，形成澄清的溶液，溶液经过200μm的多孔滤膜进行多次过滤；
4)将步骤2和步骤3所得的溶液进行共混，通过超声和机械搅拌的方法形成稳定均匀的透明碳纳米管高分子导电墨水。
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