CN112735860B - 一种高结晶度高导电率聚吡咯石墨烯复合结构及制备方法 - Google Patents
一种高结晶度高导电率聚吡咯石墨烯复合结构及制备方法 Download PDFInfo
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Abstract
本发明涉及一种高结晶度高导电率聚吡咯石墨烯复合结构及制备方法,包括配制质子酸溶液,溶剂使用去离子水;称取氧化剂溶解于上述酸溶液中,充分搅拌使其完全溶解;取吡咯单体溶于特定的有机溶剂中,充分搅拌使其完全溶解;将溶有氧化剂的酸溶液和溶有吡咯单体的有机溶剂中密度小的倒入密度大的溶液中,两者分层,逐渐可观察到在两者界面有聚吡咯薄膜形成,随着聚合时间的增加,薄膜愈发明显,反应在恒温下进行,最终获得高结晶质量聚吡咯薄膜;将单层石墨烯和聚吡咯薄膜转移到衬底上形成两层或两层以上的复合结构,用去离子水清洗,以除去所述多层复合结构表面的反应溶液残留,然后烘干即可得到聚吡咯/石墨烯复合结构。
Description
技术领域
本发明涉及涉及聚吡咯石墨烯复合结构的制备方法,具体涉及一种通过界面化学氧化后转移的方法制备高结晶度、高导电率聚吡咯石墨烯复合结构的方法。
背景技术
导电聚合物属于一种导电高分子材料,其除了具有传统高分子材料质量轻,易于加工,机械性能好和成本低廉等优点外,其还具有可以通过改变制备条件,使其导电性能连续可调的优点,这极大的拓展了其应用范围。相关报道表明导电聚合物在有机太阳能电池、有机发光二极管、电致变色、超级电容器、化学传感器和生物传感器、柔性透明显示器和电磁屏蔽等方面有极大的应用前途。聚吡咯作为常见导电聚合物之一,它可以通过化学氧化法和电化学法制备,通过改变制备条件可得到电导率连续变化的聚吡咯材料,但化学氧化法制备的聚吡咯多为固体颗粒状,难以成膜,而电化学法可以在电极上氧化聚合形成聚吡咯薄膜。
石墨烯是一种以sp2杂化连接的碳原子紧密连接形成单层的二维蜂窝状晶格结构材料,从发现以来,以其优异的光学、电学和力学特性引起了广泛的研究热潮。实验测得石墨烯在室温下的载流子迁移率可达15000 cm2V-1s-1,是一种极好的导电材料。
发明内容
本发明设计了一种高结晶度高导电率聚吡咯石墨烯复合结构及制备方法,其解决的技术问题是现有化学氧化法难以获得聚吡咯薄膜。
为了解决上述存在的技术问题,本发明采用了以下方案:
一种高结晶度高导电率聚吡咯石墨烯复合结构的制备方法,包括以下步骤:
步骤1、配制质子酸溶液,溶剂使用去离子水;
步骤2、称取氧化剂溶解于上述酸溶液中,充分搅拌使其完全溶解;
步骤3、取吡咯单体溶于特定的有机溶剂中,充分搅拌使其完全溶解;
步骤4、将所述步骤2中溶有氧化剂的酸溶液和所述步骤3中溶有吡咯单体的有机溶剂中密度小的倒入密度大的溶液中,两者分层,逐渐可观察到在两者界面有聚吡咯薄膜形成,随着聚合时间的增加,薄膜愈发明显,反应在恒温下进行,最终获得高结晶质量聚吡咯薄膜;
步骤5、将单层石墨烯和所述步骤4制备的聚吡咯薄膜转移到衬底上形成两层或两层以上的复合结构,用去离子水清洗,以除去所述多层复合结构表面的反应溶液残留,然后烘干即可得到聚吡咯/石墨烯复合结构。
优选地,多层复合结构中层数越多,其透光性能变差;
或者,当应用于电容器的电极材料,多层复合结构层数越多,其存储电荷的能力会提高;
或者,多层复合结构超过两层时,石墨烯层作为中间层,对于提升器件导电性能起到积极作用;
或者,多层复合结构至少包括衬底/聚吡咯/石墨烯或衬底/石墨烯/聚吡咯两种结构,最外层为聚吡咯或石墨烯。
优选地,步骤1中所述质子酸为盐酸、硫酸、高氯酸、十二烷基苯磺酸或樟脑磺酸。
优选地,步骤1中所述质子酸溶液pH值范围为0.5-3。
优选地,步骤2中所述氧化剂可以为过硫酸铵、高锰酸钾、过氧化氢或三氯化铁。
优选地,步骤2中所述溶液中氧化剂浓度范围为0.01-0.1 mol/L。
优选地,步骤3中的反应时间范围为1-60 min;或者/和,步骤3中选择反应温度的范围为0-60 ℃。
优选地,步骤4中所述衬底为玻璃、硅片、云母或聚酰亚胺等刚性或柔性沉底。
一种高结晶质量聚吡咯薄膜,其特征在于:使用所述步骤1-步骤3进行制备。
一种复合结构,其特征在于:其使用上述制备方法制备,并且材质包括上述高结晶质量聚吡咯薄膜和单层或多层石墨烯材料。
该高结晶度高导电率聚吡咯石墨烯复合结构及制备方法具有以下有益效果:
(1)本发明通过界面化学氧化法制备聚吡咯薄膜,可大面积制备,且结晶质量高、薄膜表面平整度高、分子链有序程度高。
(2)本发明因为薄膜在两种溶液接触面形成,所以薄膜面积的大小可以通过改变两溶液界面的面积来调节,同时选择特定的有机溶剂相比于普通水溶剂,其制备的膜会更加完整。之前有尝试过将吡咯单体溶解于去离子水中,效果不理想,制备出的聚吡咯薄膜分散开来,不连续。
(3)本发明通过将聚吡咯和石墨烯结合,可以极大提高导电性,有利于在导电电极方面的应用。
(4)本发明通过界面化学氧化的方法获得了导电聚吡咯薄膜,并在此基础上与石墨烯形成层状复合结构,与单一聚吡咯薄膜相比,其导电性能显著提高。该方法制备的聚吡咯薄膜面积大、结晶度高、表面平整,聚吡咯石墨烯复合结构导电率高,方便转移,适应用于导电电极材料。
附图说明
图1为本发明所制备的聚吡咯薄膜的扫描电镜图。
图2为所制备的聚吡咯石墨烯复合结构的XRD图谱。
图3分别为聚吡咯薄膜和聚吡咯石墨烯复合结构的电流-电压曲线。
图4为本发明制备的聚吡咯石墨烯复合结构示意图。
具体实施方式
下面结合图1至图4,对本发明做进一步说明:
实施例1:
使用量筒量取99mL去离子水倒入烧杯中,然后使用移液枪量取833μL浓度为12mol/L的浓盐酸溶液加入去离子水中,配制pH=1的盐酸水溶液。称取1.4g过硫酸铵固体,将其溶于上述制备的稀盐酸溶液中,搅拌使其充分溶解,过硫酸铵浓度为 0.05mol/L,在0℃下保存。使用量筒量取100mL氯仿溶剂倒入烧杯中,取139μL吡咯单体滴入氯仿中,充分搅拌使其完全溶解,于0℃下保存。将石墨烯转移到洁净的石英玻璃衬底上。在0℃下,将溶有过硫酸铵的盐酸溶液倒入溶有吡咯单体的氯仿溶液溶液中,两者分层,逐渐可观察到在两者界面有聚吡咯薄膜形成。5分钟后使用带有石墨烯的石英玻璃片将聚吡咯薄膜捞出,使聚吡咯薄膜覆盖于石墨烯上,用去离子水冲洗薄膜以去除残留物,清洗完毕后,将带有聚吡咯和石墨烯的石英玻璃衬底放入烘箱烘干,设置温度为60℃,时长30min。即可得到聚吡咯石墨烯复合结构。
结果分析:图1为本发明所制备的聚吡咯薄膜的扫描电镜图。图中可以看出薄膜致密无空洞,表面平整。图2为所制备的聚吡咯石墨烯复合结构的XRD图谱。从图中可以看出所制备的聚吡咯薄膜和复合结构都有明显的衍射峰,表示所制备的聚吡咯薄膜具有较高的结晶质量。高的结晶质量表明聚合物薄膜长链的有序程度高,更有利于载流子的传输。图3分别为聚吡咯薄膜和聚吡咯石墨烯复合结构的电流-电压曲线。图中可以看出聚吡咯和石墨烯复合都具有较高的导电能力。霍尔测试显示聚吡咯的电导率为0.3 S/cm,迁移率为2cm2/(V·s),而聚吡咯石墨烯复合结构的电导率为36S/cm,迁移率为1.1×102 cm2/(V·s),表明相比聚吡咯薄膜,加入石墨烯形成复合结构后其电导率和载流子迁移率都有两个数量级的提高,而此更有利于其在导电电极材料方面的应用。
如图4所示,复合层结构显示为衬底/聚吡咯/石墨烯、衬底/石墨烯/聚吡咯或衬底/聚吡咯/石墨烯/聚吡咯。若后续有新物质的加入,希望得到的是石墨烯作为中间层,对于提升器件导电性能起到积极作用。
实施例2:
使用量筒量取99mL去离子水倒入烧杯中,然后使用移液枪量取833μL浓度为12mol/L的浓盐酸溶液加入去离子水中,配制pH=1的盐酸水溶液。称取2.7 g六水合氯化铁固体,将其溶于上述制备的稀盐酸溶液中,搅拌使其充分溶解,氯化铁浓度为0.1 mol/L,在0℃下保存。使用量筒量取100mL环己烷剂倒入烧杯中,取139μL吡咯单体滴入环己烷中,充分搅拌使其完全溶解,于0℃下保存。剪取1×1 cm带有单层石墨烯的铜箔,将铜箔放到步骤2所配制的氯化铁酸溶液中,在0℃下静置待铜箔被完全腐蚀,此时石墨烯漂浮于溶液表面,铜箔已溶解结束,将氯化铁溶液稀释至0.05 mol/L。将含有吡咯单体的环己烷溶液倒入含有氯化铁的盐酸溶液上,两者分层,逐渐可观察到在两者界面有聚吡咯薄膜形成,此时石墨烯上下会有聚吡咯薄膜形成三明治型结构。10分钟后使用石英玻璃片将聚吡咯石墨烯复合结构捞出,用去离子水冲洗薄膜以去除残留物,清洗完毕后,将放入烘箱烘干,设置温度为60℃,时长30min。即可得到聚吡咯石墨烯三明治型复合结构。
采用本发明方法所制备的聚吡咯石墨烯复合结构结晶质量高,导电性能好,适合大面积制备,可作为电极材料应用于微电子器件或者超级电容器的制备。
上面结合附图对本发明进行了示例性的描述,显然本发明的实现并不受上述方式的限制,只要采用了本发明的方法构思和技术方案进行的各种改进,或未经改进将本发明的构思和技术方案直接应用于其它场合的,均在本发明的保护范围内。
Claims (5)
1.一种高结晶度高导电率聚吡咯石墨烯复合结构的制备方法,包括以下步骤:
步骤1、配制质子酸溶液,溶剂使用去离子水;步骤1中所述质子酸为盐酸、硫酸、高氯酸、十二烷基苯磺酸或樟脑磺酸;步骤1中所述质子酸溶液pH值范围为0.5-3;
步骤2、称取氧化剂溶解于上述酸溶液中,充分搅拌使其完全溶解;步骤2中所述氧化剂为过硫酸铵、高锰酸钾、过氧化氢或三氯化铁;步骤2中所述溶液中氧化剂浓度范围为0.01-0.1 mol/L;
步骤3、取吡咯单体溶于特定的有机溶剂中,充分搅拌使其完全溶解;特定的有机溶剂为氯仿或环己烷;
步骤4、将所述步骤2中溶有氧化剂的酸溶液和所述步骤3中溶有吡咯单体的有机溶剂中密度小的倒入密度大的溶液中,两者分层,逐渐可观察到在两者界面有聚吡咯薄膜形成,随着聚合时间的增加,薄膜愈发明显,反应在恒温下进行,最终获得高结晶质量聚吡咯薄膜;
步骤5、将单层石墨烯和所述步骤4制备的聚吡咯薄膜转移到衬底上形成两层以上的复合结构,用去离子水清洗,以除去所述多层复合结构表面的反应溶液残留,然后烘干即可得到聚吡咯/石墨烯复合结构。
2.根据权利要求1所述的高结晶度高导电率聚吡咯石墨烯复合结构的制备方法,其特征在于:
多层复合结构超过两层时,石墨烯层作为中间层;或者,最外层为聚吡咯或石墨烯。
3.根据权利要求1所述的高结晶度高导电率聚吡咯石墨烯复合结构的制备方法,其特征在于:步骤3中的反应时间范围为1-60 min;或者/和,步骤3中选择反应温度的范围为0-60 ℃。
4.根据权利要求1所述的高结晶度高导电率聚吡咯石墨烯复合结构的制备方法,其特征在于:步骤4中所述衬底为玻璃、硅片、云母或聚酰亚胺。
5.一种高结晶度高导电率聚吡咯石墨烯复合结构,其特征在于:其使用权利要求1-4中任何一项所述制备方法制得。
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