CN101582302A - 碳纳米管/导电聚合物复合材料 - Google Patents
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Abstract
一种碳纳米管/导电聚合物复合材料,其包括:多个碳纳米管。其中,所述碳纳米管/导电聚合物复合材料进一步包括多个导电聚合物纤维,所述多个碳纳米管相互连接形成一网络结构,所述多个导电聚合物纤维复合在所述碳纳米管的表面或/和附着在所述碳纳米管的管壁上。
Description
技术领域
本发明涉及一种碳纳米管/聚合物复合材料,尤其涉及一种碳纳米管/导电聚合物复合材料。
背景技术
自1991年日本NEC公司的Iijima发现碳纳米管(Carbon Nanotube,CNT)以来(Iilima S.,Nature,1991,354,56-58),立即引起科学界及产业界的极大重视。碳纳米管具有优良的机械和光电性能,被认为是复合材料的理想添加物。碳纳米管/聚合物复合材料已成为世界科学研究的热点(Ajjayan P.M.,StephanO.,Colliex C.,Tranth D.Science.1994,265,1212-1215:Calvert P.,Nature,1999,399,210-211)。碳纳米管作为增强体和导电体,形成的复合材料具有抗静电,微波吸收和电磁屏蔽等性能,具有广泛的应用前景。
现有技术中的碳纳米管/导电聚合物复合材料中的碳纳米管多为棒状物,而导电聚合物以颗粒的形式分布在碳纳米管的间隙中。当所述碳纳米管/导电聚合物复合材料在应用于超级电容器、太阳能电池的电极时,其中的导电聚合物充放电时会引起得体积收缩和膨胀,而碳纳米管的中空结构可缓解由上述导电聚合物的体积收缩和膨胀引起的碳纳米管/导电聚合物复合材料的体积收缩和膨胀,而且碳纳米管的高导电性可降低导电聚合物的电阻。因此,现有技术中的碳纳米管/导电聚合物复合材料具有较好的导电性和较高的比电容量(大于200法拉/克)。然而,现有技术中的碳纳米管/导电聚合物复合材料通过采用将碳纳米管分散于硫酸及硝酸等强氧化性酸或表面活性剂中进行分散,之后再与导电聚合物的单体进行电化学反应,并最终在工作电极上得到一碳纳米管/导电聚合物复合材料的薄膜。通过强酸处理,会使得所述碳纳米管受到一定程度的破坏,而使用表面活性剂处理会使得表面活性剂在最终的碳纳米管/导电聚合物材料中不易除去。因而,经强氧化性酸或表面活性剂处理后得到的碳纳米管/导电聚合物复合材料的性能会受到影响。另外,由于碳纳米管易团聚,目前一直不能很好的分散,故,现有技术所制备得到的碳纳米管/导电聚合物复合材料中的碳纳米管间通常没有形成良好的导电网络,且有些相邻碳纳米管之间间距较大,相互间接触性较差,因而不能充分发挥碳纳米管的优良导电性及导热性能,造成所述碳纳米管/导电聚合物复合材料的内阻较大、比电容量较低。
有鉴于此,确有必要提供一种内阻较小、比电容量较大的碳纳米管/导电聚合物复合材料。
发明内容
一种碳纳米管/导电聚合物复合材料,其包括:多个碳纳米管。其中,所述碳纳米管/导电聚合物复合材料还进一步包括多个导电聚合物纤维,所述多个碳纳米管相互连接形成一网络结构,所述多个导电聚合物纤维复合在所述碳纳米管的表面或/和附着在所述碳纳米管的管壁上。
与现有技术相比较,所述的碳纳米管/导电聚合物复合材料具有以下优点:其一,由于所述碳纳米管/导电聚合物复合材料中的碳纳米管相互连接形成一网络结构,该网络结构中的碳纳米管无序排列或有序排列,使得碳纳米管/导电聚合物复合材料的比电容量大幅度提高。克服了碳纳米管在现有技术中的碳纳米管/导电聚合物复合材料易团聚的缺点。其二,由于采用碳纳米管网络结构作为骨架,从而使得所述的碳纳米管/导电聚合物材料的内阻较小。其三,由于所述的碳纳米管网络结构具有很好的柔性,可以任意卷曲、弯折,从而所述的碳纳米管/导电聚合物复合材料也具有较好的柔性,进一步地,使用上述的碳纳米管/导电聚合物复合材料有利于使得相应地储能元件具有较好的柔性。
附图说明
图1是本技术方案第一实施例的包含无序碳纳米管的碳纳米管/导电聚合物复合材料的结构示意图。
图2是本技术方案第一实施例制备的碳纳米管/聚苯胺复合材料的扫描电镜照片。
图3是本技术方案第一实施例制备的碳纳米管/聚苯胺复合材料的充放电曲线图。
图4是本技术方案第二实施例的包含有序碳纳米管的碳纳米管/导电聚合物复合材料的结构示意图。
具体实施方式
以下将结合附图详细说明本技术方案的碳纳米管/导电聚合物复合材料。
请参阅图1,本技术方案第一实施例所提供一种碳纳米管/导电聚合物复合材料10,其包括多个碳纳米管12及多个导电聚合物纤维14。所述多个碳纳米管12相互连接形成一网络结构16,多个导电聚合物纤维14复合在所述碳纳米管12的表面或/和附着在所述碳纳米管12的管壁上。在上述的碳纳米管/导电聚合物复合材料10中,碳纳米管12形成的网络结构16起到了骨架作用,导电聚合物纤维14依附在所述的碳纳米管网络结构骨架上。进一步地,所述碳纳米管12和导电聚合物纤维14均匀分布于所述碳纳米管/导电聚合物复合材料中。
本实施例中,所述碳纳米管12形成的网络结构16为一无序排列的碳纳米管网络结构16。
所述无序排列的碳纳米管网络结构16中的碳纳米管12为无序或各向同性排列。该无序排列的碳纳米管通过范德华力相互吸引、相互缠绕、均匀分布,该各向同性排列的碳纳米管通过范德华力相互吸引且平行于碳纳米管网络结构16的表面。
所述碳纳米管12包括单壁碳纳米管、双壁碳纳米管及多壁碳纳米管中的一种或几种。单壁碳纳米管的直径为0.5纳米~50纳米,双壁碳纳米管的直径为1.0纳米~50纳米,多壁碳纳米管的直径为1.5纳米~50纳米。所述碳纳米管的长度在100纳米到10毫米之间。
所述导电聚合物纤维14包括聚苯胺、聚吡咯、聚噻吩、聚乙炔、聚对苯及聚对苯撑乙烯中的一种或几种。所述导电聚合物纤维14的长度在100纳米到10毫米之间,直径在30纳米到120纳米之间。所述导电聚合物纤维在所述碳纳米管/导电聚合物复合材料中的质量百分含量为20%~80%。可以理解,所述导电聚合物纤维14的长度与所述碳纳米管12的长度相当,有利于所述导电聚合物物纤维14和所述碳纳米管12相互吸附及均匀分布。
本技术方案第一实施例制备的碳纳米管/聚苯胺复合材料的扫描电镜图片如图2所示。该碳纳米管/聚苯胺复合材料采用聚苯胺纤维作为导电聚合物纤维14与无序碳纳米管网络结构16进行复合。其中,聚苯胺纤维依附在上述的无序碳纳米管网络结构上。聚苯胺纤维的直径在30纳米~120纳米之间,长度为500纳米左右。为了便于测量所述碳纳米管/聚苯胺复合材料的比电容量,将碳纳米管/聚苯胺复合材料裁剪成两个圆形的碳纳米管/聚苯胺复合材料薄片。每个碳纳米管/聚苯胺复合材料薄片的直径为13毫米、厚度为55微米、质量为3.95毫克(mg)。
用Potentiostat/Galvanostat model 1273A电化学工作站对第一实施例中包含有无序碳纳米管的碳纳米管/聚苯胺复合材料薄片进行恒流充放电测量。其中,CELGARD隔膜纸(聚乙烯薄膜)作隔膜,1mol/L(摩尔每升)的硫酸溶液作电解液,恒流电流为1mA(毫安),电压范围为0-0.6V(伏)。测量数据曲线如图3所示,从充放电部分曲线可知,所述碳纳米管/聚苯胺复合材料的放电时间大约为550s。
在对上述的碳纳米管/聚苯胺复合材料薄片的放电过程中,流过电路中的电荷总量与碳纳米管/聚苯胺复合材料上存储的电荷量相等可知:
C×ΔU=I×t (1)
其中,C代表电路中的电容量,ΔU代表电路中的电压降,I代表上述电路中的电流,t为放电时间。每个碳纳米管/聚苯胺复合材料薄片的电容量为C′,因此,整个充电电路中的电容量为:
根据比电容的定义可知,每个碳纳米管/聚苯胺复合材料薄片的比电容量CS为:
其中,m为每一个碳纳米管/聚苯胺复合材料薄片的质量。
将上述的公式(1)和公式(2)分别代入公式(3)中,可得:
本实施例中,电流I为1mA,放电时间t为550s,每个碳纳米管/聚苯胺复合材料薄片的质量m为3.95mg,施加的电压ΔU为0.6V,将上述的数据代入公式(4)计算可知,每个碳纳米管/聚苯胺复合材料薄片的比电容量CS约为464F/g(法拉每克)。
可以理解,由于聚苯胺具有的法拉第电容明显地大于碳纳米管的双电层电容,因此,所述碳纳米管/聚苯胺复合材料的比电容量随着其中的聚苯胺的质量分数的增加而增加。具体地,在本实施例中,随着聚苯胺在所述碳纳米管/聚苯胺复合材料中所占的质量分数从20%~80%增加,所得的碳纳米管/聚苯胺复合材料的比电容量也相应地在200F/g~600F/g范围内增加。
本技术方案第一实施例所获得的碳纳米管/聚苯胺复合材料的比电容量有了明显的提高。进而,所述的碳纳米管/导电聚合物复合材料可用作超级电容器、太阳能电池、燃料电池、锂离子电池等储能元件的电极材料。
请参阅图4,本技术方案第二实施例所提供的一种碳纳米管/导电聚合物复合材料20,该碳纳米管/导电聚合物复合材料20包括多个碳纳米管22及多个导电聚合物24,所述多个碳纳米管22相互连接形成一有序排列的网络结构26。所述碳纳米管/导电聚合物复合材料20与第一实施例所提供的碳纳米管/导电聚合物复合材料10结构大体相同,其不同之处在于,第二实施例中的碳纳米管/导电聚合物复合材料20包括一有序排列的碳纳米管网络结构26,该有序排列的碳纳米管网络结构26中的碳纳米管22沿一个方向或多个方向择优取向排列。导电聚合物纤维24依附在所述有序排列的碳纳米管网络结构26上。
具体地,所述有序排列的碳纳米管网络结构为一有序排列的碳纳米管层。该碳纳米管层包括至少一有序碳纳米管薄膜,该有序碳纳米管薄膜通过直接拉伸一碳纳米管阵列获得。该有序碳纳米管薄膜包括沿同一方向择优取向排列的碳纳米管。所述相邻的碳纳米管之间通过范德华力紧密结合。可以理解,所述有序碳纳米管层可以进一步包括至少两个重叠设置的有序碳纳米管薄膜。相邻的两个有序碳纳米管薄膜中的碳纳米管沿同一方向或沿不同方向排列,具体地,相邻的两个有序碳纳米管薄膜中的碳纳米管具有一交叉角度α,且0度≤α≤90度,具体可依据实际需求制备。可以理解,由于有序排列的碳纳米管层中的有序碳纳米管薄膜可重叠设置,故,上述有序碳纳米管层的厚度不限,可根据实际需要制成具有任意厚度的有序排列的碳纳米管层。
本技术方案实施例所述的碳纳米管/导电聚合物复合材料具有以下优点:其一,由于所述碳纳米管/导电聚合物复合材料中的碳纳米管相互连接形成一网络结构,该网络结构中的碳纳米管无序排列或有序排列,使得碳纳米管/导电聚合物复合材料的比电容量大幅度提高。克服了碳纳米管在现有技术中的碳纳米管/导电聚合物复合材料易团聚的缺点。其二,由于采用碳纳米管网络结构作为骨架,从而使得所述的碳纳米管/导电聚合物材料的内阻较小。其三,由于所述的碳纳米管网络结构具有很好的柔性,可以任意卷曲、弯折,从而所述的碳纳米管/导电聚合物复合材料也具有较好的柔性,进一步地,使用上述的碳纳米管/导电聚合物复合材料有利于使得相应地储能元件具有较好的柔性。
另外,本领域技术人员还可以在本发明精神内做其它变化,当然,这些依据本发明精神所做的变化,都应包含在本发明所要求保护的范围之内。
Claims (11)
1.一种碳纳米管/导电聚合物复合材料,其包括:多个碳纳米管,其特征在于,该碳纳米管/导电聚合物复合材料进一步包括多个导电聚合物纤维,所述多个碳纳米管相互连接形成一网络结构,所述多个导电聚合物纤维复合在所述碳纳米管的表面或/和附着在所述碳纳米管的管壁上。
2.如权利要求1所述的碳纳米管/导电聚合物复合材料,其特征在于,所述的网络结构包括无序排列的碳纳米管网络结构或有序排列的碳纳米管网络结构。
3.如权利要求2所述的碳纳米管/导电聚合物复合材料,其特征在于,所述无序排列的网络结构包括多个无序或各向同性排列的碳纳米管,该无序排列的碳纳米管通过范德华力相互吸引、相互缠绕、均匀分布,该各向同性排列的多个碳纳米管通过范德华力相互吸引且平行于碳纳米管网络结构的表面。
4.如权利要求2所述的碳纳米管/导电聚合物复合材料,其特征在于,所述有序排列的网络结构包括沿一个方向或多个方向择优取向排列的碳纳米管。
5.如权利要求4所述的碳纳米管/导电聚合物复合材料,其特征在于,所述有序排列的网络结构为一有序排列的碳纳米管层,该碳纳米管层包括至少一个有序碳纳米管薄膜。
6.如权利要求5所述的碳纳米管/导电聚合物复合材料,其特征在于,所述有序碳纳米管薄膜包括沿同一方向择优取向排列的碳纳米管,且相邻的碳纳米管之间通过范德华力紧密结合。
7.如权利要求6所述的碳纳米管/导电聚合物复合材料,其特征在于,所述有序碳纳米管层包括至少两个重叠设置的有序碳纳米管薄膜,相邻的两个有序碳纳米管薄膜中的碳纳米管具有一交叉角度α,且0度≤α≤90度。
8.如权利要求1所述的碳纳米管/导电聚合物复合材料,其特征在于,所述碳纳米管包括单壁碳纳米管、双壁碳纳米管及多壁碳纳米管中的一种或几种,单壁碳纳米管的直径为0.5纳米~50纳米,双壁碳纳米管的直径为1.0纳米~50纳米,多壁碳纳米管的直径为1.5纳米~50纳米。
9.如权利要求1所述的碳纳米管/导电聚合物复合材料,其特征在于,所述碳纳米管的长度为100纳米~10毫米。
10.如权利要求1所述的碳纳米管/导电聚合物复合材料,其特征在于,所述导电聚合物纤维为聚苯胺、聚吡咯、聚噻吩、聚乙炔、聚对苯及聚对苯撑乙烯中的一种或几种。
11.如权利要求1所述的碳纳米管/导电聚合物复合材料,其特征在于,所述导电聚合物纤维的长度为100纳米~10毫米,直径为30纳米~120纳米。
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JP2009275225A (ja) | 2009-11-26 |
US7972537B2 (en) | 2011-07-05 |
CN101582302B (zh) | 2011-12-21 |
US20100019209A1 (en) | 2010-01-28 |
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