CN106653384B - 胺基功能化石墨烯量子点/碳纳米管/碳布三维柔性电极的制备方法 - Google Patents
胺基功能化石墨烯量子点/碳纳米管/碳布三维柔性电极的制备方法 Download PDFInfo
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Abstract
本发明涉及一种具有三维结构的胺基功能化石墨烯量子点‑碳纳米管/碳布三维柔性电极的制备方法。该方法首先使用化学气相沉积法制备碳纳米管/碳布复合材料,然后再采用电沉积的方法制备胺基功能化石墨烯量子点‑碳纳米管/碳布三维柔性电极。本方法过程较为简单,所制备的石墨烯量子点‑碳纳米管/碳布三维柔性电极具有高电容性能,电流密度为0.5mA/cm2时,三维电极的面容量可高达842mF/cm2。本发明制备的具有三维结构的胺基功能化石墨烯量子点/碳纳米管/碳布复合柔性电极在新能源纳米器件技术领域展示出诱人的应用前景。
Description
背景技术
本发明涉及一种具有三维结构的胺基功能化石墨烯量子点/碳纳米管/碳布柔性电极制备方法。
背景技术
国内外研究的较多的碳材料是碳纳米管,它具有电阻低、稳定性高、比表面积高、尺寸分布窄等特点。碳纳米管的这些优异性能使其在超级电容器、锂电子电池、复合材料、储氢材料、场发射、催化剂载体、新型电子探针、传感器等领域都有广泛的应用,具有巨大的市场前景。
碳纳米管(Carbon nanotubes)是碳的一种同素异形体。碳纳米管为准一维结构,是一种新型的纳米材料。碳纳米管是类石墨烯结构,管壁呈交织网状分布,巨大的管状外表面,官腔有孔径在2~50nm独特的中空管腔结构,有较高的比表面积,由于碳原子的sp3杂化,其具有优良的电子传导能力。由于碳纳米管比表面积大,呈多孔结构以及高导电性,可以作为超级电容器的理想电极材料运用。通过酸氧化纯化、回流等方法可以在碳纳米管表面加上丰富的官能团,来提高赝电容,也增加碳纳米管的浸润性。在导电基体上直接长碳纳米管制备一体化的电极能够降低内阻,从而提高超级电容器的功率特性。此外,碳纳米管较高的机械强度以及管状结构使得它能够很好地成为活性材料的支撑物,目前通过负载拥有赝电容材料也是提升能量密度的重要方法之一。因此,碳纳米管由于其特殊的管状纳米结构和稳定的化学性质,是石墨烯量子点负载的优秀载体之一。
石墨烯量子点使一种新型量子点,由几个或几十个纳米的单层或少层石墨稀小片组成。石墨烯量子点使一种新型量子点,由几个或几十个纳米的单层或少层石墨稀小片组成,其性质同时由石墨烯和量子点性质共同决定。石墨烯量子点主要是由sp2团簇组成,这些含有sp2杂化碳的纳米结构的化学性质很大程度上取决于sp2团簇的边缘基团和结构。与石墨烯纳米片相比,石墨烯量子点sp2团簇尺寸更小,因此边缘的zigzag结构以及armchair结构浓度更大,这种特殊的结构使碳量子点或石墨烯量子点具有一些独特的性质。由于石墨烯量子点的尺寸小于100nm且层数小于10层,有着量子限域、化学惰性、边界效应、不易光漂白、容易制备、较低的细胞毒性以及更好的表面接枝性质等优点,它表现出了很多与二维石墨烯不同的性质。与传统的半导体量子点比,有很好的生物相容性,使得它们在传感器、细胞成像光学器件等方面有广大的应用前景。石墨烯量子点在各方向上内部电子的运动都受到局限,特别显着的量子局域效应,具有独特的性质,所以在光电器件、传感器等领域有着广阔的应用前景。但是石墨烯量子点同时具有比表面积高、胺基功能团高的电化学活性、容易组装、导电性高、分散性好等优点。这些优点也可应用于超级电容器。
发明内容
本发明的目的在于提供一种具有三维结构的胺基功能化石墨烯量子点-碳纳米管/碳布复合柔性电极的制备方法。
为达到上述目的,本发明采用下述的技术方案:
一种胺基功能化石墨烯量子点/碳纳米管/碳布三维柔性电极的制备方法,其特征在于该三维柔性电极的结构是以网状结构的导电碳布为支撑、以碳纳米管为网络支架、负载胺基功能化石墨烯量子点,形成三维空间结构的胺基功能化石墨烯量子点/碳纳米管/碳布柔性电极。
一种制备上述的胺基功能化石墨烯量子点/碳纳米管/碳布三维柔性电极的制备方法,其特征在于该方法的具体步骤为:
a.搅拌下,将芘缓慢加入浓硝酸,回流反应15~35h,冷却,过滤,将洗涤后的菊黄色固体在蒸馏水中超声分散2~3h,得到质量分数为0.5%~3.0%的前驱物1,3,6三硝基芘溶液,所述的芘与浓硝酸的质量体积比为(1~2)g:(50~80)mL;
b.搅拌下,将步骤a所得前驱物溶液加入氨水溶液,200~300℃条件下保温10~20h,冷却过滤,得到胺基功能化的石墨烯量子点溶液;所述的前驱物溶液和氨水溶液的体积比为:(10~20)mL:(1~2)mL;利用电沉积的方法,以碳纳米管/碳布复合材料作为正极,铂丝作为负极,步骤b所得的胺基功能化的石墨烯量子点溶液作为电解质,在电压为1~4V的条件下沉积2~3h;用去离子水清洗,烘干,即可得到胺基功能化石墨烯量子点-碳纳米管/碳布三维电极。
上述的多环芳烃芘的结构式为:看作四个苯环连起来的石墨烯分子,分子式为C16H10。
上述的碳纳米管/碳布的制备方法为:
a.将硝酸镍六水化合物溶解在无水酒精和乙二醇按1:1的体积比的混合溶液中,配制成浓度为0.5mol/L~1mol/L的硝酸镍溶液;然后将预处理后的碳布沉浸到硝酸镍溶液,浸泡1-2h来吸收镍盐;
b.将乙醇和乙二醇按1:4~1:5的体积比混合后放在管式炉中的低温区做碳源,将上述步骤a所得的吸收镍盐的碳布放在高温区内;在惰性气体保护下,以30~40℃/min的速率升温至700~800℃,维持20~40min,自然冷却至室温,用去离子水清洗,即得到碳纳米管/碳布复合材料。
本发明涉及一种具有三维结构的胺基功能化石墨烯量子点-碳纳米管/碳布三维柔性电极的制备方法。本方法过程较为简单,所制备的胺基功能化石墨烯量子点-碳纳米管/碳布三维柔性电极具有高电容性能,电流密度为0.5mA/cm2时,三维柔性电极的面容量可高达842mF/cm2。本发明制备的具有三维结构的胺基功能化石墨烯量子点-碳纳米管/碳布三维柔性电极的三维柔性电极在新能源纳米器件技术领域展示出诱人的应用前景。
附图说明
图1为石墨烯量子点的TEM图;石墨烯量子点的TEM图像(a)低倍(b)高倍。
图2为得到的纯碳布、碳纳米管/碳布、石墨烯量子点-碳纳米管/碳布的SEM图;(a)碳布(b)碳纳米管/碳布(c)量子点-碳纳米管/碳布的SEM图。
图3为碳纳米管/碳布、石墨烯量子点-碳纳米管/碳布的TEM图;(a)碳纳米管/碳布的SEM图,石墨烯量子点-碳纳米管/碳布的SEM图(b)低倍,(c)高倍。
图4为纯碳布、碳纳米管/碳布、石墨烯量子点/碳布、石墨烯量子点-碳纳米管/碳布的XRD图;
图5为纯碳布、碳纳米管/碳布、石墨烯量子点/碳布、石墨烯量子点-碳纳米管/碳布的拉曼光谱图;
图6为碳纳米管/碳布、石墨烯量子点/碳布、石墨烯量子点-碳纳米管/碳布电极的循环伏安曲线、恒流充放电曲线、面容量与充放电电流密度间的变化关系图。(a)10mV s-1扫描速率下CV图,(b)1mA cm-2电流密度的恒电流充放电图,(c)不同电流密度下的电极面容量曲线。
图7为碳纳米管/碳布、石墨烯量子点/碳布、石墨烯量子点-碳纳米管/碳布电极的充放电循环性能图。
具体实施方式
实施例一:本发明的具体制备步骤如下:
a.将碳布(1.5cm×1.7cm)依次用丙酮、无水乙醇、去离子水超声清洗后,烘干备用。
b.将处理后的碳布沉浸在0.5mol/L或者1mol/L的硝酸镍溶液1-2h。将乙醇和乙二醇混合液(体积比为1:4或者1:5)放在管式炉中石英管的低温区做碳源,将多片吸收完镍盐的碳布放在高温区内。通入氩气,待空气排除后,以30-40℃/min的速率升温至700-800℃,维持20-40min,自然冷却至室温,用去离子水清洗,烘干,得到了碳纳米管/碳布三维复合材料。
c.然后利用电沉积的方法,将事先制备好的碳纳米管/碳布复合材料正极,铂丝作为负极,量子点溶液为电解质,在电压为1-4V的条件下沉积2-3h。用去离子水将清洗干净,烘干,即可得到胺基功能化石墨烯量子点-碳纳米管/碳布三维柔性电极。
上述实施例中所制得的样品经仪器检测进行表征,其结果如下:
1.由图1可知,从上部的高度尺寸图看出石墨烯量子点的厚度大约在4-5nm左右,是多层石墨烯。在这一尺寸大小下,石墨烯量子点可以很轻易的进入碳纳米管的内部,并且也可以大量地负载在碳纳米管上。
2.由图2可知,(a)中看出碳布是由许多表面光滑的碳纤维组成的,在我们使用化学气相沉积法之后,碳纳米管与碳布可以较为紧密的结合起来,如(b)图。经过电沉积过程,(c)可以看出量子点大量均匀的负载在碳纳米管上,但是由于在电沉积过程中发生了的量子点聚集和结合,完全将碳纳米管和碳布纤维包覆在里面。
3.由图3可知,成功制备出了长度在100-200nm直径在20-30nm左右的碳纳米管,同时它具有7nm左右的中空结构。我们从图中可以清楚地看出量子点负载在碳纳米管上,并且可以在碳纳米管内部观察到石墨烯量子点的存在。
4.由图4可知,所有的电极材料包括碳纳米管/碳布、石墨烯量子点/碳布、石墨烯量子点-碳纳米管/碳布电极在26°(002)和43°(100)都属于碳的标准峰位,同时在44.4°和51.8°出现镍的标准衍射峰,说明了我们成功的使用了化学气相沉积法来制备碳纳米管。
5.图5中分别表示了未复合碳纳米管和复合碳纳米管、未负载量子点和负载量子点的拉曼图,仔细观察,它们都属于碳材料D峰和G峰的区域。对于在碳布上复合碳纳米管,我们发现在1610cm-1存在一个小峰,这是由于碳纳米管的多壁特征所造成的。
6.图6(a)图中黑色曲线表示的是原始的碳布载体CV图,绿色曲线表示的是复合碳纳米管之后的碳纳米管/碳布的CV图,蓝线表示的是在纯碳布上负载石墨烯量子点之后的CV图,红色线表示的是在碳纳米管/碳布复合材料上负载石墨烯量子点的CV图。很明显不管是复合碳纳米管还是负载量子点的复合材料的CV面积要大很多,即表明其容量要高出很多,从图中可以看出同时复合碳纳米管和石墨烯量子点的三元电极材料与两元复合材料相比容量要高得多。同时我们在0.285V和0.102V观察到了明显的氧化还原峰,可以说石墨烯量子点在石墨烯量子点-碳纳米管/碳布三维柔性电极中展现了比较高的赝电容。图6(b)图是的循环伏安对比图,从中可以看出我们制备材料展现了比较好的循环稳定性,负载量子点之后,材料的性能有了一个显著的提升。图6(c)图为碳纳米管/碳布、石墨烯量子点/碳布、石墨烯量子点-碳纳米管/碳布在不同电流密度下的面容量图,在电流密度为0.5mA/cm2时,三维柔性电极的面容量可以高达842mF/cm2。即使在电流密度在为20mA/cm2时,三维柔性电极的面容量可以高达772mF/cm2,容量剩余为初始的91.7%,展示了良好的电化学性能。
7.由图7可知,在纯碳布上利用电沉积方法负载石墨烯量子点的石墨烯量子点/碳布电极经过5000次循环后面容量保有首次容量的89.7%。
Claims (3)
1.一种胺基功能化石墨烯量子点/碳纳米管/碳布三维柔性电极的制备方法,其特征在于,该方法的具体步骤为:
a.搅拌下,将芘缓慢加入浓硝酸,回流反应15~35 h,冷却,过滤,将洗涤后的菊黄色固体在蒸馏水中超声分散2~3 h,得到质量分数为0.5 %~3.0 %的前驱物1,3,6 三硝基芘溶液,所述的芘与浓硝酸的质量体积比为(1~2) g: (50~80) mL;
b.搅拌下,将步骤a所得前驱物溶液加入氨水溶液,200~300 ℃条件下保温10~20 h,冷却过滤,得到胺基功能化的石墨烯量子点溶液;所述的前驱物溶液和氨水溶液的体积比为:(10~20) mL :(1~2) mL;利用电沉积的方法,以碳纳米管/碳布复合材料作为正极,铂丝作为负极,步骤b所得的胺基功能化的石墨烯量子点溶液作为电解质,在电压为1~4 V的条件下沉积2~3 h;用去离子水清洗,烘干,即可得到胺基功能化石墨烯量子点-碳纳米管/碳布三维电极;该三维柔性电极的结构是以网状结构的导电碳布为支撑、以碳纳米管为网络支架、负载胺基功能化石墨烯量子点,形成三维空间结构的胺基功能化石墨烯量子点/碳纳米管/碳布柔性电极;所述石墨烯量子点的厚度为4-5 nm,碳纳米管长度为100-200 nm并且直径为20-30 nm,使石墨烯量子点进入碳纳米管的内部,并且石墨烯量子点还负载在碳纳米管上。
2.根据权利要求1所述的方法,其特征在于,所述芘的结构式为:看作四个苯环连起来的石墨烯分子,分子式为C16H10。
3.根据权利要求1所述的方法,其特征在于所述的碳纳米管/碳布的制备方法为:
a. 将硝酸镍六水化合物溶解在无水酒精和乙二醇按1:1的体积比的混合溶液中,配制成浓度为0.5 mol/L~1 mol/L的硝酸镍溶液;然后将预处理后的碳布沉浸到硝酸镍溶液,浸泡1-2 h来吸收镍盐;
b. 将乙醇和乙二醇按1:4~1:5的体积比混合后放在管式炉中的低温区做碳源,将上述步骤a所得的吸收镍盐的碳布放在高温区内;在惰性气体保护下,以30~40 ℃/min的速率升温至700~800 ℃,维持20~40 min,自然冷却至室温,用去离子水清洗,即得到碳纳米管/碳布复合材料。
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