CN110176582B - 一种树枝状石墨烯/碳纳米管复合结构的制备方法 - Google Patents
一种树枝状石墨烯/碳纳米管复合结构的制备方法 Download PDFInfo
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Abstract
本发明涉及一种树枝状石墨烯/碳纳米管复合结构的制备方法,包括下面的步骤:制备石墨烯/碳纳米管阵列基底:以金属箔片作为催化基底,利用石英管式炉进行石墨烯的化学气相沉积制备,制得石墨烯基底;得到FeAlOx液相二元催化剂;得石墨烯/碳纳米管阵列基底;制备树枝状石墨烯/碳纳米管复合结构;去除金属基底,得呈现自支撑状态的树枝状石墨烯/碳纳米管复合结构。
Description
技术领域
本发明属于碳纳米材料的电化学应用领域,具体涉及一种具有树枝状三维微观结构的碳纳米材料的可控制备方法。
背景技术
随着现代社会高速发展,环境危机日益加重,可再生绿色能源及高性能储能器件的需求空前高涨。近年来,以风能、核能、太阳能等为代表的新能源产业蓬勃发展,有望取代传统化石能源的主导地位。与此同时,新兴储能器件的发展也在不断加速,其中以二次电池、超级电容器为代表的电化学储能器件可实现高效率、低污染的能量转换过程,是广受认可的新一代储能器件,随着研究的不断推进,正在逐步实现商业化进程。为实现电化学储能器件性能最优化,电极材料纳米化是有力手段之一。其中,碳纳米材料原料丰富、导电性好,在电化学储能器件领域的适用性强。由于其制备技术水平较高,配套的产业线也在不断发展完善,目前电化学储能用碳纳米材料的项目投入呈现逐年增长趋势。
以石墨烯、碳纳米管为代表的电化学储能器件电极用碳纳米材料,具有轻质高强、高比表面积、高导电性等优点。然而,单一材料在实际应用中易团聚,结构优势不明显,性能难以达到实际需求。而由石墨烯和碳纳米管组装而成的复合结构,不仅在一定程度上减轻了团聚所造成的比表面积减小的问题,而且可以优化电子传输路径,提高电子的传导效率,进而提高电极材料的导电性。石墨烯与碳纳米管可以通过多种形式进行复合,但在目前的相关报道中,复合结构的空间设计还存在很大的发展空间,如何提高电极空间的利用率是实现高性能器件制备亟待解决的难题之一。
发明内容
针对现有技术的不足,本发明拟提供一种树枝状石墨烯/碳纳米管复合结构,该复合结构制备工艺过程简单,适合工业化生产,将其用作锂二次电池、超级电容器、锂离子电容器等电化学储能器件的电极材料,可有效提高电极导电率和比表面积,进而提升器件整体性能。
一种树枝状石墨烯/碳纳米管复合结构的制备方法,包括下面的步骤:
(1)制备石墨烯/碳纳米管阵列基底
以金属箔片作为催化基底,利用石英管式炉进行石墨烯的化学气相沉积制备,得到石墨烯基底;
按照10~50毫升:0.05~0.5克:0.05~0.5克:0.5~2克:0.1~5毫升:0.1~5毫升的体积质量配比称取二苄醚、乙酰丙酮铁、乙酰丙酮铝、十六烷二醇、油酸、油胺进行回流反应,回流温度设定为180~250摄氏度,冷却后将产物离心清洗,溶解在正己烷中,得到FeAlOx液相二元催化剂;
在所得的石墨烯基底上涂布FeAlOx液相二元催化剂,随后将其置于管式炉中,以流量比为(1~500):(1~100):1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为0~760托,设置温度为500~900摄氏度;将涂布FeAlOx液相二元催化剂的石墨烯基底推入管式炉恒温区内,停留20~60分钟后移至管口区域,冷却至室温,取出后得石墨烯/碳纳米管阵列基底;
(2)制备树枝状石墨烯/碳纳米管复合结构
将步骤(1)制备的石墨烯/碳纳米管阵列基底浸渍在FeAlOx液相二元催化剂中,1~120分钟后取出并干燥。随后将其置于管式炉中,以流量比为(1~500):(1~100):1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为0~760托,设置温度为500~900摄氏度。将石墨烯/碳纳米管阵列基底推入管式炉恒温区内,停留1~30分钟后移至管口区域,冷却至室温,取出后得树枝状石墨烯/碳纳米管复合结构。
(2)去除金属基底
配制盐酸-氯化铁溶液作为腐蚀液,将步骤(2)所得的树枝状石墨烯/碳纳米管复合结构置于腐蚀液的液面上,使得生长碳纳米管的一面向上,静置待金属基底腐蚀完全,用去离子水漂洗,得呈现自支撑状态的树枝状石墨烯/碳纳米管复合结构。
优选地,(1)中,石墨烯基底的制备方法如下:在常压氩气气氛下,将管式炉升温至600-1200摄氏度,以流量比为(1~50):(1~50):1通入氩气、氢气和甲烷,控制真空泵调节管内压力为0~760托,将金属箔片推入管式炉恒温区,停留5~120分钟得到金属箔片/三维基底;最后,将金属箔片/三维基底从恒温区移至管口区域,冷却至室温,取出制得石墨烯基底。
本发明首先采用石墨烯/碳纳米管阵列作为基底,通过液相二元催化剂辅助化学气相沉积法,制备得到了树枝状石墨烯/碳纳米管复合结构,可用作电化学储能器件电极材料,实现电极空间利用率的最大化。与现有技术相比,通过FeAlOx液相二元催化剂辅助化学气相沉积法,在石墨烯/碳纳米管阵列基底上实现了树枝状复合结构,本发明方法具有以下优势:(1)本方法得到的树枝状石墨烯/碳纳米管复合结构具有丰富的孔结构,在与电解液接触时展现出高浸润性,加速了电解液离子的传输;(2)树枝状结构获得的高比表面积为电解液离子提供了大量的吸附位点,提高了材料的能量密度;(3)本方法得到的树枝状石墨烯-碳纳米管复合结构中,石墨烯基底与碳纳米管无缝键合,降低了材料内阻,提高了电子传输效率,从而在高倍率下拥有稳定的性能。(4)本方法采用的FeAlOx液相二元催化剂可满足工业化大批量生产的要求。
附图说明
图1为本发明实施例1所制得的石墨烯/碳纳米管阵列基底的扫描电子显微镜表征图像;
图2为本发明实施例1所制备的树枝状石墨烯/碳纳米管复合结构的扫描电子显微镜表征图像;
图3为本发明实施例1所制备的树枝状石墨烯/碳纳米管复合结构的透射电子显微镜表征图像;
图4为本发明实施例1所制备的树枝状石墨烯/碳纳米管复合结构的拉曼光谱表征图。
具体实施方式
本发明未述及之处适用于现有技术。
以下给出本发明制备方法的具体实施例。这些实施例仅用于详细说明本发明制备方法,并不限制本申请权利要求的保护范围。
实施例1
(1)制备石墨烯/碳纳米管阵列基底
以镍箔作为催化基底(也可以选用铜箔等金属箔片),利用石英管式炉进行石墨烯的化学气相沉积制备。首先在常压氩气气氛下,将管式炉升温至800摄氏度。随后以流量比为10:10:1通入氩气、氢气和甲烷,控制真空泵调节管内压力为0托,将镍箔推入管式炉恒温区,停留10分钟,冷却至室温后取出,得石墨烯基底。
在40毫升二苄醚加入乙酰丙酮铁0.1克、乙酰丙酮铝0.1克、十六烷二醇1克、油酸1毫升、油胺1毫升进行回流反应,回流温度设定为250摄氏度,回流时间设定为90分钟,冷却后将产物离心清洗,溶解在正己烷中,得FeAlOx液相二元催化剂。
在第一步所得的石墨烯基底上旋涂第二步制得的FeAlOx液相二元催化剂,随后将其置于石英管式炉中,以流量比为100:100:1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为20托,设置温度为700摄氏度。将样品推入管式炉恒温区内,停留30分钟后移至管口区域,冷却至室温,得石墨烯/碳纳米管阵列基底。
(2)制备树枝状石墨烯/碳纳米管复合结构
将步骤(1)制备的石墨烯/碳纳米管阵列基底浸渍在FeAlOx液相二元催化剂中,60分钟后取出并干燥。随后将其置于石英管式炉中,以流量比为100:100:1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为20托,设置温度为700摄氏度。将样品推入管式炉恒温区内,停留30分钟后移至管口区域,冷却至室温,得树枝状石墨烯/碳纳米管复合结构。
(3)去除金属基底
在100毫升去离子水中加入1克氯化铁、1毫升盐酸作为腐蚀液,将步骤(2)所得的树枝状石墨烯/碳纳米管复合结构置于腐蚀液的液面上(生长碳纳米管的一面向上),静置1~3天后,镍箔腐蚀完全,用去离子水反复漂洗三次,得呈现自支撑状态的树枝状石墨烯/碳纳米管复合结构。
实施例2
(1)制备石墨烯/碳纳米管阵列基底
以铜箔作为催化基底,利用石英管式炉进行石墨烯的化学气相沉积制备。首先在常压氩气气氛下,将管式炉升温至800摄氏度。随后以流量比为10:10:1通入氩气、氢气和甲烷,控制真空泵调节管内压力为0托,将铜箔推入管式炉恒温区,停留10分钟后移至管口区域,冷却至室温,取出后得石墨烯基底。
在40毫升二苄醚加入乙酰丙酮铁0.1克、乙酰丙酮铝0.1克、十六烷二醇1克、油酸1毫升、油胺1毫升进行回流反应,回流温度设定为250摄氏度,回流时间设定为90分钟,冷却后将产物离心清洗,溶解在正己烷中,得FeAlOx液相二元催化剂。
在第一步所得的石墨烯基底上旋涂第二步制得的FeAlOx液相二元催化剂,随后将其置于石英管式炉中,以流量比为100:100:1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为20托,设置温度为700摄氏度。将样品推入管式炉恒温区内,停留30分钟后移至管口区域,冷却至室温后取出,得石墨烯/碳纳米管阵列基底。
(2)树枝状石墨烯/碳纳米管复合结构
将步骤(1)制备的石墨烯/碳纳米管阵列基底浸渍在FeAlOx液相二元催化剂中,60分钟后取出并干燥。随后将其置于石英管式炉中,以流量比为100:100:1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为20托,设置温度为700摄氏度。将样品推入管式炉恒温区内,停留30分钟后移至管口区域,冷却至室温,得树枝状石墨烯/碳纳米管复合结构。
(3)去除金属基底
在100毫升去离子水中加入1克氯化铁、1毫升盐酸作为腐蚀液,将步骤(2)所得树枝状石墨烯/碳纳米管阵列复合结构置于腐蚀液的液面上(生长碳纳米管的一面向上),静置1~3天后,铜箔基底腐蚀完全,用去离子水反复漂洗三次,得呈现自支撑状态的树枝状石墨烯/碳纳米管复合结构。
对比例1
为说明树枝状结构的优势,特制备此对比例,与实施例1不同的是:只进行石墨烯/碳纳米管阵列基底的生长,不进行树枝状结构的制备,即只进行步骤(1)、步骤(3)的操作,不进行步骤(2)的操作,具体不再赘述。
Claims (2)
1.一种树枝状石墨烯/碳纳米管复合结构的制备方法,包括下面的步骤:
(1)制备石墨烯/碳纳米管阵列基底
以金属箔片作为催化基底,利用石英管式炉进行石墨烯的化学气相沉积制备,得到石墨烯基底;
按照10~50毫升:0.05~0.5克:0.05~0.5克:0.5~2克:0.1~5毫升:0.1~5毫升的体积质量配比称取二苄醚、乙酰丙酮铁、乙酰丙酮铝、十六烷二醇、油酸、油胺进行回流反应,回流温度设定为180~250摄氏度,冷却后将产物离心清洗,溶解在正己烷中,得到FeAlOx液相二元催化剂;
在所得的石墨烯基底上涂布FeAlOx液相二元催化剂,随后将其置于管式炉中,以流量比为(1~500):(1~100):1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为0~760托,设置温度为500~900摄氏度;将涂布FeAlOx液相二元催化剂的石墨烯基底推入管式炉恒温区内,停留20~60分钟后移至管口区域,冷却至室温,取出后得石墨烯/碳纳米管阵列基底;
(2)制备树枝状石墨烯/碳纳米管复合结构
将步骤(1)制备的石墨烯/碳纳米管阵列基底浸渍在FeAlOx液相二元催化剂中,1~120分钟后取出并干燥;随后将其置于管式炉中,以流量比为(1~500):(1~100):1通入氢气、乙炔和水蒸气,控制真空泵调节管内压力为0~760托,设置温度为500~900摄氏度;将石墨烯/碳纳米管阵列基底推入管式炉恒温区内,停留1~30分钟后移至管口区域,冷却至室温,取出后得树枝状石墨烯/碳纳米管复合结构;
(3)去除金属基底
配制盐酸-氯化铁溶液作为腐蚀液,将步骤(2)所得的树枝状石墨烯/碳纳米管复合结构置于腐蚀液的液面上,使得生长碳纳米管的一面向上,静置待金属基底腐蚀完全,用去离子水漂洗,得呈现自支撑状态的树枝状石墨烯/碳纳米管复合结构。
2.根据权利要求1所述的树枝状石墨烯/碳纳米管复合结构的制备方法,其特征在于,步骤(1)中,石墨烯基底的制备方法如下:在常压氩气气氛下,将管式炉升温至600-1200摄氏度,以流量比为(1~50):(1~50):1通入氩气、氢气和甲烷,控制真空泵调节管内压力为0~760托,将金属箔片推入管式炉恒温区,停留5~120分钟得到金属箔片/三维基底;最后,将金属箔片/三维基底从恒温区移至管口区域,冷却至室温,取出制得石墨烯基底。
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