CN105819885A - 一种结构稳定的石墨烯凝胶及其制备方法 - Google Patents
一种结构稳定的石墨烯凝胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种结构稳定的石墨烯凝胶及其制备方法,具体是将氧化石墨烯与交联剂经水热反应、交联,最后热处理得到。本发明的有益效果是:制备的共价键交联石墨烯凝胶具有非常稳定的三维多孔结构,用作超级电容器的电极材料具有优异的比电容。
Description
技术领域
本发明涉及一种结构稳定的石墨烯凝胶及其制备方法,属于材料合成技术领域。
背景技术
石墨烯,作为一种新型碳材料,超大而完美的sp2杂化体系使其具有无与伦比的性质,科学家们一直致力于石墨烯和石墨烯复合材料的合成及其应用。随着研究的进展,石墨烯的制备方法从最初的采用产率较低且不容易操作控制的机械剥离发展到还原氧化石墨法、外延生长法、化学气相沉积法等等。与此同时,科学家们也将视线投向了石墨烯的功能化研究。
然而,由于二维平面的石墨烯片层之间存在范德华力及π-π共轭作用,导致石墨烯片相互吸引产生团聚,从而大大限制了石墨烯的应用。石墨烯凝胶可以赋予石墨烯组装体独特的性质,如柔韧性、多孔性、高活性比表面积、优异的传质性能等。因此,近年来国内外对如何将二维平面石墨烯组装成三维网状石墨烯的研究十分活跃。但是存在的问题是组装方法复杂和结构不稳定。
发明内容
针对技术背景中的特点,本发明的目的在于克服目前石墨烯存在的缺陷,制备出结构稳定,性能优异的石墨烯材料。本发明提供一种结构稳定的石墨烯凝胶及其制备方法,通过下述步骤制得:
a、将氧化石墨烯超声分散于水中,制备一定浓度的氧化石墨烯分散液;
b、将步骤a得到的氧化石墨烯分散液与一定量的交联剂混合;
c、将步骤b得到的混合液置于水热反应釜中,在一定温度下水热、交联,得到含石墨烯和交联剂的水凝胶;
d、将步骤c得到的水凝胶在一定条件下干燥,得到交联剂支撑的干凝胶;
e、将步骤d得到的干凝胶在氮气保护,一定温度下煅烧,得到结构稳定的石墨烯凝胶。
上述步骤a所述的氧化石墨烯的浓度为1~20mg/mL;
上述步骤b所述的交联剂为三聚氰胺甲醛树脂,苯酚甲醛树脂,尿醛树脂中的一种或几种;
上述步骤b所述氧化石墨烯和交联剂的质量比为1:1~1:10;
上述步骤c所述的水热反应的温度为120~180℃;
上述步骤d所述的干燥方法为冷冻干燥或80℃加热干燥;
上述步骤e所述的煅烧温度为550~850℃加热。
本发明的有益效果是:制备的共价键交联石墨烯凝胶具有非常稳定的三维多孔结构,用作超级电容器的电极材料具有优异的比电容。
附图说明
下面结合附图对本发明进一步说明。
图1:本发明制备的石墨烯凝胶SEM照片;
图2:本发明制备的石墨烯凝胶经强烈超声前后的TEM照片;
图3:本发明制备的石墨烯凝胶同无交联剂支撑的石墨烯凝胶恒流充放电结果对比;
图4:本发明制备的石墨烯凝胶经10000次循环充放电比电容衰减结果。
具体实施方式
下面结合具体的实施例,进一步详细地描述本发明。应理解,这些实施例只是为了举例说明本发明,而非以任何方式限制本发明的范围。
实施例1:
(1)用改良Hummers法,在500mL容器中依次加入120mL浓硫酸、13.3mL浓磷酸,搅拌,在水浴下慢慢升温至50℃,加入1g石墨粉、6g高锰酸钾,搅拌12h,溶液倒入含10mL过氧化氢溶液的冰块上,搅拌冷却至室温,过滤未反应的固体。离心洗涤至中性,干燥,得氧化石墨烯;
(2)称取0.015gGO,加入15mL二次蒸馏水,超声2min,加入1mL的甲醛和0.15g三聚氰胺,轻轻搅拌;120℃下,水热反应12h。将所得固体在80℃下干燥,得到交联剂支撑的干凝胶;
(3)将干凝胶,在氮气氛下,管式炉先以5℃/min的升温速率升温至300℃,再以10℃/min的升温速率升温至550℃,并保温3h,之后待温度降至室温后去取出产品。
实施例2:
(1)氧化石墨烯的制备方法同实施例1。
(2)称取0.15gGO,加入15mL二次蒸馏水,超声2min,加入1mL的甲醛和0.35g苯酚,轻轻搅拌;160℃下,水热反应12h。将所得固体在冷冻干燥,得到交联剂支撑的干凝胶;(3)将干凝胶,在氮气氛下,管式炉先以5℃/min的升温速率升温至300℃,再以10℃/min的升温速率升温至650℃,并保温3h,之后待温度降至室温后去取出产品。
实施例3:
(1)氧化石墨烯的制备方法同实施例1
(2)称取0.30gGO,加入15mL二次蒸馏水,超声2min,加入2mL的甲醛和1.05g尿素,轻轻搅拌;180℃下,水热反应12h。将所得固体在80℃下干燥,得到交联剂支撑的干凝胶;
(3)将干凝胶,在氮气氛下,管式炉先以5℃/min的升温速率升温至300℃,再以10℃/min的升温速率升温至750℃,并保温3h,之后待温度降至室温后去取出产品。
对比例1:
(1)氧化石墨烯的制备方法同实施例1。
(2)称取0.15gGO,加入15mL二次蒸馏水,超声2min,180℃下,水热反应12h。将所得固体在80℃下干燥,得到无交联剂支撑的干凝胶;
(3)将无交联剂支撑的干凝胶,在氮气氛下,管式炉先以5℃/min的升温速率升温至300℃,再以10℃/min的升温速率升温至750℃,并保温3h,之后待温度降至室温后去取出产品。
实施例4:
(1)将制得的石墨烯凝胶研磨,在去离子水中分散,配成1mg/mL溶液,移取10μL均匀滴涂在玻碳电极上,制成石墨烯修饰电极;
(2)在1M的硫酸溶液中,以上述制备的石墨烯修饰电极为工作电极,饱和甘汞电极为参比电极,铂片为辅助电极,充放电电压为0-0.4V,室温下,1A/g恒流充放电实验,测得比电容为509F/g,结果见图3。经10000次循环充放电后,比电容损失不到4%,结果见图4。
对比例2:
(1)将制得的无交联剂支撑的石墨烯凝胶研磨,在去离子水中分散,配成1mg/mL溶液,移取10μL均匀滴涂在玻碳电极上,制成无交联剂支撑石墨烯修饰电极。恒流充放电测试同实施例4,测得比电容仅为180F/g,结果见图3。
Claims (7)
1.一种电化学剥离制备氮掺杂石墨烯的制备方法,其特征在于,步骤如下一种结构稳定石墨烯凝胶及其制备方法,其特征在于,制备过程包括以下步骤:
a、将氧化石墨烯超声分散于水中,制备一定浓度的氧化石墨烯分散液;
b、将步骤a得到的氧化石墨烯分散液与一定量的交联剂混合;
c、将步骤b得到的混合液置于水热反应釜中,在一定温度下水热、交联,得到含石墨烯和交联剂的水凝胶;
d、将步骤c得到的水凝胶在一定条件下干燥,得到交联剂支撑的干凝胶;
e、将步骤d得到的干凝胶在氮气保护,一定温度下煅烧,得到结构稳定的石墨烯凝胶。
2.根据权利要求1所述的一种结构稳定石墨烯凝胶及其制备方法,其特征在于步骤a所述的氧化石墨烯的浓度为1~20mg/mL。
3.根据权利要求1所述的一种结构稳定石墨烯凝胶及其制备方法,其特征在于步骤b所述的交联剂为三聚氰胺甲醛树脂,苯酚甲醛树脂,尿醛树脂中的一种或几种。
4.根据权利要求1所述的一种结构稳定石墨烯凝胶及其制备方法,其特征在于步骤b所述氧化石墨烯和交联剂的质量比为1:1~1:10。
5.根据权利要求1所述的一种结构稳定石墨烯凝胶及其制备方法,其特征在于步骤c所述的水热反应的温度为120~180℃。
6.根据权利要求1所述的一种结构稳定石墨烯凝胶及其制备方法,其特征在于步骤d所述的干燥方法为冷冻干燥或80℃加热干燥。
7.根据权利要求1所述的一种结构稳定石墨烯凝胶及其制备方法,其特征在于步骤e所述的煅烧温度为550~850℃加热。
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CN106732732A (zh) * | 2017-01-03 | 2017-05-31 | 福州大学 | 一种抗堆叠氮掺杂的三维石墨烯及其制备方法 |
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CN107376837A (zh) * | 2017-07-27 | 2017-11-24 | 武汉工程大学 | 一种石墨烯/金属有机框架气凝胶吸附/催化材料的制备方法 |
CN108548619A (zh) * | 2018-03-30 | 2018-09-18 | 华中科技大学 | 基于碎片化结构提升压阻式传感器灵敏度的方法 |
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Cited By (7)
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CN106732732A (zh) * | 2017-01-03 | 2017-05-31 | 福州大学 | 一种抗堆叠氮掺杂的三维石墨烯及其制备方法 |
CN107342421A (zh) * | 2017-06-19 | 2017-11-10 | 苏州大学 | 一种高含量吡啶氮掺杂多孔碳负极材料、制备方法及其应用 |
CN107342421B (zh) * | 2017-06-19 | 2020-05-01 | 苏州大学 | 一种高含量吡啶氮掺杂多孔碳负极材料、制备方法及其应用 |
CN107376837A (zh) * | 2017-07-27 | 2017-11-24 | 武汉工程大学 | 一种石墨烯/金属有机框架气凝胶吸附/催化材料的制备方法 |
CN108548619A (zh) * | 2018-03-30 | 2018-09-18 | 华中科技大学 | 基于碎片化结构提升压阻式传感器灵敏度的方法 |
CN108548619B (zh) * | 2018-03-30 | 2020-02-14 | 华中科技大学 | 基于碎片化结构提升压阻式传感器灵敏度的方法 |
WO2022065493A1 (ja) * | 2020-09-28 | 2022-03-31 | パナソニックIpマネジメント株式会社 | キャパシタ用電極およびその製造方法ならびにキャパシタ |
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