CN104392845B - 一种可拉伸的线状超级电容器和锂离子电池制备方法 - Google Patents
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Abstract
本发明属于微型储能器件技术领域，具体为一种可拉伸的线状超级电容器和锂离子电池及其制备方法。本发明首先制备一种弹簧状的取向碳纳米管纤维，通过过加捻形成螺旋形，可以拉伸超过300%，然后以这种纤维作为电极构建可拉伸超级电容器；这种纤维可以进一步与锰酸锂和钛酸锂纳米颗粒复合形成复合纤维，分别作为正极和负极，构建可拉伸的锂离子电池。本发明得到的线状可拉伸超级电容器和锂离子电池，相比于其他微型器件具有全新的结构，不需要弹性基底就可以实现拉伸性能，减轻了器件的重量和体积，从而提高了器件的比容量和能量密度，是微型器件领域的重要创新；同时，该器件具有良好的柔性，易于编制和集成，因而具有良好的应用前景。
Description
技术领域
本发明属于微型储能器件技术领域，具体涉及一种可拉伸的线状超级电容器和锂离子电池及其制备方法。
背景技术
柔性和可拉伸的电子器件已经成为现代电子学的一个重要分支。它们在智能衣服、电子皮肤、可拉伸显示器、柔性手机等方面有广泛地应用。因此，迫切需要研发出一个与之匹配的提供储存能量的系统如超级电容器和锂离子电池，并且要求其具有质轻、柔性、可拉伸等性能。传统的超级电容器和锂离子电池通常在一个刚性的平板基底上制得，不能满足上述的要求。最近，人们开始尝试使用弹性的高分子材料作为基底，制备可拉伸的超级电容器和锂离子电池。然而，引入非电化学活性的高分子材料后，大大增加了器件的质量和体积，从而使比容量和比能量密度下降。此外，这些高分子材料由于较低的力学强度和工作温度大大限制了器件的使用范围。
发明内容
本发明的目的在于提供一种可拉伸、可弯折、可编织的柔性线状超级电容器和锂离子电池及其制备方法。
本发明提供的可拉伸的超级电容器，其由弹簧状的取向碳纳米管纤维作为电极，以聚乙烯醇-磷酸凝胶作为电解质。
本发明提供的可拉伸的线状超级电容器的制备方法，具体步骤为：
首先，将5-25根直接从碳纳米管阵列中纺出的碳纳米管纤维，通过过加捻形成螺旋形（即弹簧状）纤维束；过加捻形成的螺旋形，拉伸可以超过300%；
然后，将两根弹簧状纤维束分别均匀地涂抹一层聚乙烯醇-磷酸凝胶电解质；
最后，将两根弹簧状的纤维束缠绕在一起，即制备得可拉伸的线状超级电容器。
上述线状超级电容器中，弹簧状取向碳纳米管纤维电极的直径为30-120 μm。
本发明提供的一种可拉伸的线状锂离子电池，其由弹簧状的取向碳纳米管/锰酸锂复合纤维作为电池的正极，碳纳米管/钛酸锂复合纤维作为电池负极，以环氧乙烷/丁二腈/双三氟甲基磺酰亚胺锂凝胶作为电解质。
本发明提供的可拉伸的线状锂离子电池的制备方法，具体步骤为：
首先，分别将锰酸锂分散液和钛酸锂的分散液均匀地滴在碳纳米管膜上，分别加捻，制成碳纳米管/锰酸锂复合纤维和碳纳米管/钛酸锂复合纤维；
然后，将5-25根复合纤维平行排列，并通过过加捻形成螺旋形（即弹簧状）复合纤维束，过加捻形成的螺旋形，拉伸可以超过300%；将两根复合纤维束分别均匀地涂抹一层环氧乙烷/丁二腈/双三氟甲基磺酰亚胺锂凝胶状电解质；
最后，将两根两根复合纤维束缠绕在一起并封装，制备得可拉伸的线状锂离子电池。
本发明制得的可拉伸的线状锂离子电池，锰酸锂和钛酸锂纳米颗粒均匀地分散在弹簧状碳纳米管纤维的内部和表面。
上述线状锂离子电池中，弹簧状取向碳纳米管复合纤维电极的直径为30-120 μm。
本发明中，所述碳纳米管阵列由化学气相沉积法制备得到；碳纳米管阵列高度在200-300μm。 碳纳米管取向排列，没有无定型碳的沉积。碳纳米管为多壁结构，管径为10-20nm。碳纳米管纤维重量密度为0.1-0.7g/cm3，碳纳米管膜的面密度为1-5 μg/cm2。
本发明中，碳纳米管纤维由碳纳米管阵列通过干法纺丝得到：首先，把可纺碳纳米管阵列固定在样品台上，样品台可以旋转以实现纤维加捻；然后，使用刀片从阵列边缘拉出连续的碳纳米管膜，并将碳纳米管膜加捻形成纤维后固定在用于收集的辊筒上；然后，打开控制样品台的电机，使样品以1000-2000 r/min 转动，同时打开控制辊筒的电机，从而连续拉出碳纳米管纤维，拉伸速率为10-20cm/min；若不加捻, 则得到连续的取向碳纳米管膜。5-20根得到的碳纳米管纤维平行排列，继续加捻，直到形成弹簧状的碳纳米管纤维束。
本发明首先设计制备了一种弹簧状的取向碳纳米管纤维，这种纤维是由取向的多壁碳纳米管组成，通过过加捻形成螺旋形，可以拉伸超过300%；然后以这种纤维作为电极构建可拉伸超级电容器。这种纤维可以进一步与锰酸锂和钛酸锂纳米颗粒复合形成复合纤维，分别作为正极和负极，构建可拉伸的锂离子电池。本发明得到的线状可拉伸超级电容器和锂离子电池，相比于其他微型器件具有全新的结构，不需要弹性基底就可以实现拉伸性能，减轻了器件的重量和体积，从而提高了器件的比容量和能量密度，是微型器件领域的重要创新。同时，该器件具有良好的柔性，易于编制和集成，因而具有良好的应用前景，尤其可用于可穿戴、便携式移动设备中。在其它很多领域，也有广泛的应用价值。
附图说明
图1为弹簧状碳纳米管纤维的扫描电镜。其中，a，b和c分别是弹簧状碳纳米管纤维在不同放大倍数下的扫描电镜；d，e和f分别是弹簧状碳纳米管纤维拉伸前和拉伸50%、100%的扫描电镜。
图2为可拉伸的线状超级电容器的电化学性能。其中，a为超级电容器在不同电压扫速下的CV图形；b为比容量与循环次数的关系；c为比容量与拉伸量的关系。d为比容量与拉伸次数的关系。
图3为弹簧状的碳纳米管/钛酸锂复合纤维在不同放大倍数下的扫描电镜。
图4为可拉伸的线状锂离子电池的电化学性能。其中，a为锂离子电池的充放电曲线；b为比容量与循环次数的关系；c为比容量与拉伸量的关系；d为比容量与拉伸次数的关系。
图5为柔性线状超级电容器和锂离子电池结构图示。
具体实施方式
碳纳米管是通过化学气相沉淀法制备的。催化剂采用结构形式为Si/SiO2/Al2O3/Fe的复合材料，其中Al2O3位于硅片和Fe的中间，作为缓冲层，Fe作为催化剂的活性成份，它们分别通过电子束蒸发镀膜仪在硅片（Si）上沉积一层纳米厚度的薄膜制备获得。其中，SiO2层厚度为200-1200 μm，Al2O3层厚度为10-50 nm，Fe层厚度为0.5-2.0 nm。将镀有催化剂的硅基底催化剂面向上，用一片较大的二氧化硅托底承载，放入管式炉的石英管中，靠近管式炉的温度传感装置。调节通气管道流量为:氩气：300-600sccm氢气：20-100sccm；乙烯气：60-200sccm。连接管路。先打开氩气，关闭氢气和乙烯气体。在室温下通气5-15min，以确保排除管路之中的氧气及水蒸气。打开氢气和乙烯，10-25min从室温升至500-900℃，稳定5-25min，待程序开始自行降温时关掉乙烯和氢气。温度降至50-150℃时打开炉子，取出长在基底上的高度取向的可纺碳纳米管阵列。
碳纳米管纤维都是由碳纳米管阵列通过干法纺丝得到的。首先把可纺碳纳米管阵列固定在样品台上, 样品台可以旋转以实现纤维加捻; 然后使用刀片从阵列边缘拉出连续的碳纳米管膜, 并将碳纳米管膜加捻形成纤维后固定在用于收集的辊筒上. 然后打开控制样品台的电机, 使样品以1000-2000 r/min 转动, 同时打开控制辊筒的电机, 从而连续拉出碳纳米管纤维, 拉伸速率为10-20cm/min. 若不加捻, 则得到连续的取向碳纳米管膜。5-20根得到的碳纳米管纤维平行排列，继续加捻，直到形成弹簧状的碳纳米管纤维纤维。
LiMn2O4颗粒是通过水热法合成的。0.2-1.2g的氢氧化锂溶解在50-80mL的去离子水中，然后，加入0.5-2.5g二氧化锰。搅拌1-3h后加入1-5g的葡萄糖和50-80mL的去离子水。最后，在100-400℃的温度下在反应釜中反应20-50个小时。Li4Ti5O12颗粒是通过固态法合成的，TiO2 和 Li2CO3以一定比例混合后，在500-1000℃N2气氛下加热20-50h。最后球磨处理即可得到纳米级别的碳酸锂颗粒。
为了制备复合纤维，分别将锰酸锂和钛酸锂的分散液均匀地滴在碳纳米管膜上，分别加捻制成碳纳米管/锰酸锂复合纤维和碳纳米管/钛酸锂复合纤维。
可拉伸的线状超级电容器的制备：首先，将5-25根直接从碳纳米管阵列中纺出的碳纳米管纤维过加捻形成弹簧状的纤维；然后，将两根纤维分别均匀地涂抹一层聚乙烯醇-磷酸凝胶电解质；最后，将两根纤维缠绕在一起，即得可拉伸的线状超级电容器。如图5所示。
可拉伸的线状锂离子电池的制备：将5-25根复合纤维平行排列并过加捻形成弹簧状的复合纤维；将两根纤维分别均匀地涂抹一层环氧乙烷/丁二腈/双三氟甲基磺酰亚胺锂凝胶状电解质；最后，将两根纤维缠绕在一起并封装，制得可拉伸的线状锂离子电池。
碳纳米管复合纤维的结构由扫描电子显微镜(SEM, Hitachi FE-SEM S-4800operated at 1 kV)来表征。电化学性能通过Arbin多通道电化学测试仪（Arbin,MSTAT-5V/10mA/16Ch）测试，拉伸性能是在拉力测试机（HY-0350）上完成。
Claims (6)
1.一种可拉伸的线状超级电容器，其特征在于由弹簧状的取向碳纳米管纤维作为电极，以聚乙烯醇-磷酸凝胶作为电解质；并由如下步骤制备得到：
首先，将5-25根直接从碳纳米管阵列中纺出的碳纳米管纤维过加捻形成弹簧状的纤维束；
然后，将两根弹簧状纤维束分别均匀地涂抹一层聚乙烯醇-磷酸凝胶电解质；
最后，将两根弹簧状的纤维束缠绕在一起，即制备得可拉伸的线状超级电容器。
2. 根据权利要求1所述的可拉伸的线状超级电容器，其特征在于：弹簧状取向碳纳米管纤维电极的直径为30-120 μm。
3.一种如权利要求1所述的可拉伸的线状超级电容器的制备方法，其特征在于具体步骤如下：
首先，将5-25根直接从碳纳米管阵列中纺出的碳纳米管纤维过加捻形成弹簧状的纤维束；
然后，将两根弹簧状纤维束分别均匀地涂抹一层聚乙烯醇-磷酸凝胶电解质；
最后，将两根弹簧状的纤维束缠绕在一起，即制备得可拉伸的线状超级电容器。
4.一种可拉伸的线状锂离子电池，其特征在于由弹簧状的取向碳纳米管/锰酸锂复合纤维作为电池的正极，碳纳米管/钛酸锂复合纤维作为电池负极，以环氧乙烷/丁二腈/双三氟甲基磺酰亚胺锂凝胶作为电解质，并由如下步骤制备得到：
首先，分别将锰酸锂分散液和钛酸锂的分散液均匀地滴在碳纳米管膜上，分别加捻，制成碳纳米管/锰酸锂复合纤维和碳纳米管/钛酸锂复合纤维；
然后，将5-25根复合纤维平行排列并过加捻形成弹簧状的复合纤维束，将两根复合纤维束分别均匀地涂抹一层环氧乙烷/丁二腈/双三氟甲基磺酰亚胺锂凝胶状电解质；
最后，将两根两根复合纤维束缠绕在一起并封装，制备得可拉伸的线状锂离子电池。
5. 根据权利要求4所述的可拉伸的线状锂离子电池，其特征在于：弹簧状取向碳纳米管复合纤维电极的直径为30-120 μm。
6.一种如权利要求4所述的可拉伸的线状锂离子电池的制备方法，其特征在于具体步骤如下：
首先，分别将锰酸锂分散液和钛酸锂的分散液均匀地滴在碳纳米管膜上，分别加捻，制成碳纳米管/锰酸锂复合纤维和碳纳米管/钛酸锂复合纤维；
然后，将5-25根复合纤维平行排列并过加捻形成弹簧状的复合纤维束，将两根复合纤维束分别均匀地涂抹一层环氧乙烷/丁二腈/双三氟甲基磺酰亚胺锂凝胶状电解质；
最后，将两根两根复合纤维束缠绕在一起并封装，制备得可拉伸的线状锂离子电池。
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