CN110563904B - 一种聚合物包覆碳纳米管复合材料、制备方法和应用 - Google Patents
一种聚合物包覆碳纳米管复合材料、制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种聚合物包覆碳纳米管复合材料、制备方法和应用。首先,通过席夫碱反应,将含有醛基官能团的单体与氨基化的碳纳米管反应。其次,加入适当摩尔量的含氨基官能团的单体,通过化学反应和氢键作用力制备高分子聚合物包覆碳纳米管的复合材料。最后,将其用于电极材料,研究高分子聚合物包覆碳纳米管的复合材料的电化学行为。
Description
技术领域
本发明涉及一种聚合物包覆碳纳米管复合材料、制备方法和应用。
背景技术
随着科技的发展,社会的进步,人类对能源的需求量越来越大,因而由能源危机引发的问题也日益严重。碳材料作为能源材料的一种,被广泛的应用在超级电容器,氧化还原反应等领域中。但是,碳材料表面润湿性差,电荷分布均匀的特点使得其电化学性能表现不佳。因此,需要对纯碳材料进行改性,以期获得优异的电化学性能。近年来,通过杂原子改性碳材料的策略屡见不鲜,并且已经逐渐成为了能源领域的一大研究热点。杂原子的掺杂不仅可以改善碳材料的表面润湿性,改变碳材料的电荷分布,而且还可以提供赝电容,从而提高碳材料的电化学性能。但是,此类能源材料的制备方法复杂且耗能高。
互穿网络结构高分子聚合物的孔结构有利于电解质的传输,但该类材料大都不导电,不利于电荷传输,很难将其直接应用于电极材料。因此,如何改善互穿网络结构高分子聚合物的导电性决定高分子材料能否直接应用于电极材料。碳纳米管具有诸多的优异性能,如:力学、电学和化学性能,并且将其与其他工程材料复合,制成碳纳米管复合材料,可使复合材料表现出良好的强度、弹性、抗疲劳性及各向同性,给复合材料的性能带来极大的改善。因此,近年来碳纳米管的复合材料被科研人员广泛关注,其广阔的应用前景也不断地展现出来。然而,目前可用于超级电容器的高分子聚合物包覆碳纳米管的复合材料的制备鲜有报道。
发明内容
本发明的目的在于提供一种聚合物包覆碳纳米管复合材料、制备方法和应用。
本发明解决其技术问题所采用的技术方案之一是:提供了一种聚合物包覆碳纳米管复合材料的制备方法,包括如下步骤:
1)反应体系的制备:将醛基单体溶解于溶剂中,加入氨基化碳纳米管,于25~35℃下搅拌,得到反应体系,所述反应体系中氨基化碳纳米管均匀分散于醛基单体的溶液;其中,所述醛基单体和溶剂配比为0.01mmol:30~50mL,醛基单体和氨基化碳纳米管的质量比为1:10~20;
2)高分子聚合物的包覆:向反应体系中加入氨基单体,室温搅拌5~8h,得到聚合物包覆碳纳米管的复合材料;其中,氨基单体和醛基单体的摩尔比为1:0.85~1.25。
在本发明一较佳实施例中,所述醛基单体包括:
在本发明一较佳实施例中,所述溶剂包括甲醇、乙醇、四氢呋喃、N,N-二甲基甲酰胺。
在本发明一较佳实施例中,所述氨基单体包括:
在本发明一较佳实施例中,所述步骤1)将醛基单体溶解于溶剂中,30~35℃下搅拌10~15分钟,再将氨基化碳纳米管分散于醛基单体的溶液中,室温下搅拌10~15分钟。
在本发明一较佳实施例中,所述步骤2)将搅拌后得到黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。
本发明还提供了上述制备方法制备的聚合物包覆碳纳米管复合材料,其结构单元为碳纳米管外部包覆具有互穿网络聚合物高分子。所述聚合物包覆碳纳米管复合材料电容值为90~125F/g。
本发明还提供了上述聚合物包覆碳纳米管复合材料在电化学材料中的应用。
在本发明一较佳实施例中,用于超级电容器。
本发明与现有技术相比具有如下优点:
(1)本发明制备的高分子聚合物包覆碳纳米管复合材料,通过对反应单体调控,实现聚合物壳层厚度的调节,利于研究聚合物壳层厚度对复合材料超级电容器性能的影响;
(2)本发明制备的产物具有多孔结构和优秀的导电性能,可应用于电化学材料;
(3)传统多孔结构的高分子聚合物因为导电性差无法直接作为超级电容器的电极材料,具有导电性能的碳纳米管的表面润湿性差,使得其超电性能差;本发明克服了现有高分子聚合物导电性差的缺陷,将两者的优点结合起来,制备出超电性能优异的超电复合材料,通过选择不同的醛基和氨基单体改变聚合物的原子含量,进而调控复合材料的超电性能。
附图说明
图1为实施例1制备的聚合物包覆碳纳米管复合材料的投射电镜图,其中,a-20000x,b-200000x;
图2为实施例1制备的聚合物包覆碳纳米管复合材料的电化学性能图,其中,a-横坐标为电位,纵坐标电流密度;b-横坐标为时间,纵坐标为电位。
具体实施方式
下面结合实施例对本发明作进一步详细的描述。
实施例1
(1)将0.01mmol的对苯二醛溶解于30mL乙醇溶液当中,35℃搅拌10分钟;缓慢加入0.2g氨基化碳纳米管分散在对苯二醛乙醇溶液中,并且在室温条件下搅拌10分钟。
(2)将0.085mmol的2,4,6-三(4-氨基苯基)-1,3,5-三嗪加入到氨基化碳纳米管均匀分散的对苯二醛乙醇溶液中;室温搅拌5h,将黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。(电容值:112F/g)
实施例2
(1)将0.015mmol的对苯二醛溶解于50mL甲醇溶液当中,25℃搅拌10分钟;缓慢加入0.2g氨基化碳纳米管分散在对苯二醛乙醇溶液中,并且在室温条件下搅拌15分钟。
(2)将0.01mmol的1,3,5-三(4-氨苯基)苯加入到氨基化碳纳米管均匀分散的对苯二醛甲醇溶液中;室温搅拌6h,将黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。(电容值:90F/g)
实施例3
(1)将0.02mmol的1,3,5-三(4-甲酰基苯基)苯溶解于60mL四氢呋喃/乙醇的混合溶液当中,30℃搅拌10分钟;缓慢加入0.12g氨基化碳纳米管分散在1,3,5-三(4-甲酰基苯基)苯四氢呋喃/乙醇溶液中,并且在室温条件下搅拌15分钟。
(2)将0.025mmol的1,3,5-三(4-氨苯基)苯加入到氨基化碳纳米管均匀分散的对苯二醛乙醇溶液中;室温搅拌7h,将黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。(电容值:100F/g)
实施例4
(1)将0.015mmol的对苯二醛溶解于50mL乙醇溶液当中,32℃搅拌12分钟;缓慢加入0.2g氨基化碳纳米管分散在对苯二醛N,N-二甲基甲酰胺溶液中,并且在室温条件下搅拌20分钟。
(2)将0.015mmol的三(4-氨苯基)胺加入到氨基化碳纳米管均匀分散的对苯二醛N,N-二甲基甲酰胺溶液中;室温搅拌7h,将黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。(电容值:118F/g)
实施例5
(1)将0.01mmol的1,3,5-三(4-甲酰基苯基)苯溶解于30mL四氢呋喃溶液当中,30℃搅拌5分钟;缓慢加入0.08g氨基化碳纳米管分散在1,3,5-三(4-甲酰基苯基)苯四氢呋喃溶液中,并且在室温条件下搅拌15分钟。
(2)将0.01mmol的2,4,6-三(4-氨基苯基)-1,3,5-三嗪加入到氨基化碳纳米管均匀分散的1,3,5-三(4-甲酰基苯基)苯四氢呋喃溶液中;室温搅拌5h,将黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。(电容值:125F/g)
以上所述,仅为本发明较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (8)
1.一种聚合物包覆碳纳米管复合材料的制备方法,其特征在于,包括如下步骤:
1)反应体系的制备:将醛基单体溶解于溶剂中,加入氨基化碳纳米管,于25~35℃下搅拌,得到反应体系,所述反应体系中氨基化碳纳米管均匀分散于醛基单体的溶液;其中,所述醛基单体和溶剂配比为0.01mmol:30~50mL,醛基单体和氨基化碳纳米管的质量比为1:10~20;
2)高分子聚合物的包覆:向反应体系中加入氨基单体,室温搅拌5~8h,得到聚合物包覆碳纳米管的复合材料;其中,氨基单体和醛基单体的摩尔比为1:0.85~1.25;
其中,所述醛基单体为1,3,5-三(4-甲酰基苯基)苯,所述氨基单体包括三(4-氨苯基)胺、1,3,5-三(4-氨苯基)苯、2,4,6-三(4-氨基苯基)-1,3,5-三嗪。
2.根据权利要求1所述的一种聚合物包覆碳纳米管复合材料的制备方法,其特征在于:所述溶剂包括甲醇、乙醇、四氢呋喃、N,N-二甲基甲酰胺。
3.根据权利要求1所述的一种聚合物包覆碳纳米管复合材料的制备方法,其特征在于:所述步骤1)将醛基单体溶解于溶剂中,30~35℃下搅拌10~15分钟,再将氨基化碳纳米管分散于醛基单体的溶液中,室温下搅拌10~15分钟。
4.根据权利要求1所述的一种聚合物包覆碳纳米管复合材料的制备方法,其特征在于:所述步骤2)将搅拌后得到黑褐色沉淀离心,得到聚合物包覆碳纳米管的复合材料。
5.如权利要求1~4所述方法制备的一种聚合物包覆碳纳米管复合材料,其特征在于:其结构单元为碳纳米管外部包覆具有互穿网络聚合物高分子。
6.根据权利要求5所述的一种聚合物包覆碳纳米管复合材料,其特征在于:所述聚合物包覆碳纳米管复合材料电容值为90~125F/g。
7.如权利要求5~6所述的一种聚合物包覆碳纳米管复合材料在电化学材料中的应用。
8.根据权利要求7所述的应用,其特征在于:用于超级电容器。
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