CN107903575B - 一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法 - Google Patents
一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法 Download PDFInfo
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Abstract
一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法是以生物质活性炭纤维为骨架,乳液小球为模板剂,与氧化石墨烯水溶胶一起加入水和有机溶剂组成的混合溶剂中形成悬浮液,悬浮液进行沉积复合,获得复合柔性膜,复合柔性膜铺覆于石墨夹具中抽真空或惰性气氛下,经热压处理得3D大孔泡状复合膜,3D大孔泡状复合膜铺覆于预浸料酚醛树脂中,室温下抽真空,经热压,在碱液中浸渍、活化,得石墨烯酚醛树脂基复合纤维膜。本发明具有电容器电极储能密度高、循环稳定性好的优点。
Description
技术领域
本发明属于新能源材料领域,涉及一种超级电容器电极材料的制备方法,具体地说涉及一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法。
技术背景
石墨烯是一种以单层或少数层sp2碳构成的二维结构。自2004年被发现以来,因其良好的导电性 (103–104 S﹒m-1)、高电子迁移率(室温下20000 cm2﹒V-1﹒S-1)和高理论比表面积(2630 m2﹒g-1)等优良特性,人们便开始探究这种sp2结构的炭质材料在超级电容器中应用的可能性(Zhang LL, Zhou R, Zhao XS. Graphene-based materials assupercapacitor electrodes.基于石墨烯材料超级电容器电极[J]. J Mater Chem 2010;20(29):5983-92)(Stoller MD, Park SJ, Zhu YW, An JH, Ruoff RS. Graphene-basedultracapacitors. 基于石墨烯的超级电容器[J].Nano Lett 2008;8(10):3498-502.)。
目前现有技术基于石墨烯基超级电容器材料已得到了广泛的研究和关注。王云峰等(专利公开号:CN 103723722 A)通过将去杂质的活性炭与石墨烯混合在有机溶剂中进行高温活化制备了高比表面积的石墨烯改性活性炭电极材料,其展示了高的质量比容量。李璐(专利公开号:CN 103253658 A)将氧化石墨烯与活化剂、碳源物质充分混合,在保护气氛下进行活化,制得了高体积比容量的石墨烯。上述基于石墨烯的电极材料充分发挥了石墨烯二维表面易与电解液充分接触,其片间大孔结构可为电解液提供充足缓冲空间,为离子迁移提供顺畅通道。此外,石墨烯面向的共轭π电子(高密度载流子)可为电荷传输提供低阻通道,从而满足大电流快速充放电的储能需求。然而上述基于石墨烯的电极材料多是固体粉末,在应用于超级电容器的时候,必须先与乙炔黑及粘结剂等物质混合均匀,再涂覆到集流体上,这个过程会导致粉末团聚结块,而且会降低电极材料的导电性,从而导致制备的石墨烯基电极材料储能密度低、循环稳定性差,尚不能满足实际应用的要求。
发明内容
本发明的目的就是为了克服上述现有石墨烯基电极材料存在的不足,提供了一种电容器电极储能密度高、循环稳定性好的电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法。
本发明是通过硬模板导向有序组装法获得一种3D大孔泡状石墨烯/生物质活性炭纤维复合膜;然后将该复合膜铺覆于预浸料酚醛树脂乳液中,再经真空热压成型、碱活化工艺制成石墨烯酚醛树脂基复合纤维膜。该膜结合石墨烯、生物质活性炭和酚醛树脂三方面优势,充分发挥了石墨烯良好的导电性、生物质活性炭纤维多孔结构、高比表面积以及空间骨架结构和酚醛树脂高的残炭率,从而有效提超级电容器的能量存储。同时,该复合膜柔性好,可直接用作超级电容器电极,有效避免了粉体在制备电极过程中添加粘结剂所引起的内阻。
为实现上述目的,本发明通过下述技术方案予以实现:
(1)以生物质活性炭纤维为骨架,乳液小球为模板剂,与氧化石墨烯水溶胶一起加入水和有机溶剂组成的混合溶剂中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1:0.1~20,氧化石墨烯与乳液小球的质量比为1:0.5~5,水与有机溶剂的体积比为1∶0.5~10,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:1.6-26:50~500;
(2)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行沉积复合,获得复合柔性膜;
(3)将步骤(2)中所得复合柔性膜铺覆于石墨夹具中抽真空或惰性气氛下,经500-1000℃热压处理0.1-15h得3D大孔泡状复合膜;
(4)将步骤(3)中所制备的3D大孔泡状复合膜铺覆于预浸料酚醛树脂中,室温下抽真空,经150~180℃热压30-120min,并进一步在碱液中浸渍、活化,得石墨烯酚醛树脂基复合纤维膜。
如上所述的步骤(1)中有机溶剂为无水乙醇、丙酮、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种。
如上所述的步骤(1)中生物质活性炭纤维包括采用杨絮、柳絮、香蒲、木棉中的一种制备的生物质活性炭纤维。
如上所述的步骤(1)中氧化石墨烯水溶胶,将氧化石墨在去离子水中超声处理,超声时间为10-120min,超声功率为100-800W,得到0.1-10mg/ml的氧化石墨烯水溶胶。
如上所述的步骤(1)中乳液小球为聚甲基丙烯酸甲酯乳状小球(PMMA)或聚苯乙烯乳状小球(PS)。
如上所述的步骤(2)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行沉积复合,这里的沉积复合采用喷涂、涂覆、压滤或真空抽滤。
如上所述的步骤(3)中惰性气氛为氩气、氮气或氦气。
如上所述的步骤(4)石墨烯与酚醛树脂质量比为0.5~10:100。
如上所述的步骤(4)碱液中浸渍中的膜与碱的质量比为1∶0.5~6,浸渍时间6-12h。
如上所述的步骤(4)活化温度为500-900℃,活化时间0.5-6h。
本发明的有益效果:
本发明的一种电容器电极用石墨烯酚醛树脂基复合纤维膜制备方法,通过硬模板导向有序组装法获得一种3D大孔泡状石墨烯/生物质活性炭纤维复合膜;然后将该复合膜铺覆于预浸料酚醛树脂乳液中,再经真空热压成型、碱活化工艺制成石墨烯酚醛树脂基复合纤维膜。该方法制备的复合膜结合了石墨烯、生物质活性炭和酚醛树脂三方面优势,充分发挥了石墨烯良好的导电性、生物质活性炭纤维多孔结构、高比表面积以及空间骨架结构和酚醛树脂高的残炭率,从而有效提高超级电容器的能量存储。同时,该复合膜柔性好,可直接用作超级电容器电极,有效避免了粉体在制备电极过程中添加粘结剂所引起的内阻。其比容量在100-300 F/g之间;经2000圈循环后电容量仍能达到初始容量的90%-98.5%。
附图说明
图1实施例1制备的石墨烯酚醛树脂基复合纤维膜的吸脱附曲线与孔径分布曲线。
图2实施例1制备的石墨烯酚醛树脂基复合纤维膜直接用作电极组装超级电容器在不同扫速下的循环伏安曲线。
具体实施方式
下面用实施例来进一步说明本发明,但本发明的保护范围并不仅限于实施例。对本领域的技术人员在不背离本发明的精神和保护范围情况下做出的其它的变化和修改,仍包括在本发明保护范围之内。
实施例1
(1)将氧化石墨在去离子水中超声处理,超声时间为10min,超声功率为800W,得到10mg/ml的氧化石墨烯水溶胶;
(2)以基于杨絮的生物质活性炭纤维为骨架,聚甲基丙烯酸甲酯乳状小球(PMMA)为模板剂,与氧化石墨烯水溶胶一起加入水和无水乙醇的混合溶剂中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1∶0.1,氧化石墨烯与乳液小球的质量比为1∶0.5,水与有机溶剂的体积比为1∶0.5,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:1.6∶50;
(3)将悬浮液进行真空抽滤,获得复合柔性膜;
(4)将步骤(3)中所得复合柔性膜铺覆于石墨夹具中抽真空,经500℃热压处理15h得3D大孔泡状石墨烯/生物质活性炭纤维复合膜;
(5)将步骤(4)中制备的3D大孔泡状石墨烯/生物质活性炭纤维复合膜铺覆于预浸料酚醛树脂中(石墨烯与酚醛树脂质量比为4:100),室温下抽真空,经150℃热压120min,并进一步在碱液中浸渍12h(膜与碱的质量比为1∶2)、800℃活化1h,得石墨烯酚醛树脂基复合纤维膜。
实施例1制备的石墨烯酚醛树脂基复合纤维膜比表面积为698 m2/g。将制备的石墨烯酚醛树脂基复合纤维膜直接用作电极组装超级电容器。经测试,该复合膜在电流密度为1Ag-1时质量比容量为284 Fg-1,经过2000次循环后电容量仍能达到初始容量的98.5%。
实施例2
(1)将氧化石墨在去离子水中超声处理,超声时间为120min,超声功率为100W,得到0.1mg/ml的氧化石墨烯水溶胶;
(2)以基于香蒲的生物质活性炭纤维为骨架,聚甲基丙烯酸甲酯乳状小球(PMMA)为模板剂,与氧化石墨烯水溶胶一起加入水和N-甲基吡咯烷酮的混合体系中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1∶20,氧化石墨烯与乳液小球的质量比为1∶5,水与有机溶剂的体积比为1∶10,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:26∶500;
(3)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行涂覆复合,获得氧化石墨烯/乳液小球/生物质活性炭纤维复合柔性膜;
(4)将步骤(3)中所得氧化石墨烯/生物质活性炭纤维复合柔性膜铺覆于石墨夹具中抽真空,经1000℃热压处理0.1h得3D大孔泡状石墨烯/生物质活性炭纤维复合膜;
(5)将步骤(4)中制备的3D大孔泡状石墨烯/生物质活性炭纤维复合膜铺覆于预浸料酚醛树脂中(石墨烯与酚醛树脂质量比为2:100),室温下抽真空,经180℃热压30min,并进一步在碱液中浸渍6h(膜与碱的质量比为1:6)、500℃活化2h,得石墨烯酚醛树脂基复合纤维膜。
实施例2制备的石墨烯酚醛树脂基复合纤维膜比表面积为542 m2/g。将制备的石墨烯酚醛树脂基复合纤维膜直接用作电极组装超级电容器。经测试,该复合膜在电流密度为1Ag-1时质量比容量为211 Fg-1,经过2000次循环后电容量仍能达到初始容量的90.5%。
实施例3
(1)将氧化石墨在去离子水中超声处理,超声时间为30min,超声功率为500W,得到3mg/ml的氧化石墨烯水溶胶;
(2)以基于柳絮的生物质活性炭纤维为骨架,聚苯乙烯乳状小球(PS)为模板剂,与氧化石墨烯水溶胶一起加入水和N,N-二甲基甲酰胺的混合体系中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1∶10,氧化石墨烯与乳液小球的质量比为1∶3,水与有机溶剂的体积比为1∶5,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:14∶300;
(3)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行喷涂复合,获得氧化石墨烯/乳液小球/生物质活性炭纤维复合柔性膜;
(4)将步骤(3)中所得氧化石墨烯/生物质活性炭纤维复合柔性膜铺覆于石墨夹具中抽真空,经800℃热压处理1h得3D大孔泡状石墨烯/生物质活性炭纤维复合膜;
(5)将步骤(4)中制备的3D大孔泡状石墨烯/生物质活性炭纤维复合膜铺覆于预浸料酚醛树脂中(石墨烯与酚醛树脂质量比为10:100),室温下抽真空,经140℃热压100min,并进一步在碱液中浸渍12h(膜与碱的质量比为1:4)、900℃活化0.5h,得石墨烯酚醛树脂基复合纤维膜。
实施例3制备的石墨烯酚醛树脂基复合纤维膜比表面积为980 m2/g。将制备的石墨烯酚醛树脂基复合纤维膜直接用作电极组装超级电容器。经测试,该复合膜在电流密度为1Ag-1时质量比容量为103 Fg-1,经过2000次循环后电容量仍能达到初始容量的98.5%。
实施例4
(1)将氧化石墨在去离子水中超声处理,超声时间为45min,超声功率为300W,得到3.5mg/ml的氧化石墨烯水溶胶。
(2)以基于木棉的生物质活性炭纤维为骨架,聚苯乙烯乳状小球(PS)为模板剂,与氧化石墨烯水溶胶一起加入水和N,N-二甲基乙酰胺的混合体系中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1∶5,氧化石墨烯与乳液小球的质量比为1∶2,水与有机溶剂的体积比为1∶1,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:8∶200;
(3)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行真空抽滤,获得氧化石墨烯/乳液小球/生物质活性炭纤维复合柔性膜;
(4)将步骤(3)中所得氧化石墨烯/生物质活性炭纤维复合柔性膜铺覆于石墨夹具中抽真空,经600℃热压处理4h得3D大孔泡状石墨烯/生物质活性炭纤维复合膜;
(5)将步骤(4)中制备的3D大孔泡状石墨烯/生物质活性炭纤维复合膜铺覆于预浸料酚醛树脂中(石墨烯与酚醛树脂质量比为8:100),室温下抽真空,经170℃热压60min,并进一步在碱液中浸渍8h(膜与碱的质量比为1:2)、850℃活化1h,得石墨烯酚醛树脂基复合纤维膜。
实施例4制备的石墨烯酚醛树脂基复合纤维膜比表面积为720 m2/g。将制备的石墨烯酚醛树脂基复合纤维膜直接用作电极组装超级电容器。经测试,该复合膜的在电流密度为1Ag-1时质量比容量为189 Fg-1,经过2000次循环后电容量仍能达到初始容量的95.2%。
实施例5
(1)将氧化石墨在去离子水中超声处理,超声时间为60min,超声功率为100W,得到4mg/ml的氧化石墨烯水溶胶。
(2)以基于柳絮的生物质活性炭纤维为骨架,聚苯乙烯乳状小球(PS)为模板剂,与氧化石墨烯水溶胶一起加入水和丙酮的混合体系中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1∶15,氧化石墨烯与乳液小球的质量比为1∶4,水与有机溶剂的体积比为1∶6,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:20∶400;
(3)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行压滤,获得氧化石墨烯/乳液小球/生物质活性炭纤维复合柔性膜;
(4)将步骤(3)中所得氧化石墨烯/生物质活性炭纤维复合柔性膜铺覆于石墨夹具中抽真空,经600℃热压处理2h得3D大孔泡状石墨烯/生物质活性炭纤维复合膜;
(5)将步骤(4)中制备的3D大孔泡状石墨烯/生物质活性炭纤维复合膜铺覆于预浸料酚醛树脂中(石墨烯与酚醛树脂质量比为0.5:100),室温下抽真空,经170℃热压70min,并进一步在碱液中浸渍8h(膜与碱的质量比为1:3)、900℃活化6h,得石墨烯酚醛树脂基复合纤维膜。
实施例5制备的石墨烯酚醛树脂基复合纤维膜比表面积为685 m2/g。将制备的石墨烯酚醛树脂基复合纤维膜直接用作电极组装锂离子超级电容器。将制备的石墨烯/生物质活性炭纤维复合柔性膜直接用作电极组装超级电容器。经测试该复合膜的在电流密度为1Ag-1时质量比容量为220 Fg-1,经过2000次循环后电容量仍能达到初始容量的95.3%。
Claims (9)
1.一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于包括如下步骤:
(1)以生物质活性炭纤维为骨架,乳液小球为模板剂,与氧化石墨烯水溶胶一起加入水和有机溶剂组成的混合溶剂中形成悬浮液,氧化石墨烯与生物质活性炭纤维的质量比为1:0.1~20,氧化石墨烯与乳液小球的质量比为1:0.5~5,水与有机溶剂的体积比为1:0.5~10,生物质活性炭纤维、乳液小球与氧化石墨烯的质量之和与混合溶剂的质量比为:1.6~26:50~500;所述乳液小球为聚甲基丙烯酸甲酯乳状小球或聚苯乙烯乳状小球;
(2)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行沉积复合,获得复合柔性膜;
(3)将步骤(2)中所得复合柔性膜铺覆于石墨夹具中抽真空或惰性气氛下,经500-1000℃热压处理0.1-15h得3D大孔泡状复合膜;
(4)将步骤(3)中所制备的3D大孔泡状复合膜铺覆于预浸料酚醛树脂中,室温下抽真空,经150~180℃热压30-120min;并进一步在碱液中浸渍、活化,得石墨烯酚醛树脂基复合纤维膜。
2.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(1)中有机溶剂为无水乙醇、丙酮、N-甲基吡咯烷酮、N ,N-二甲基甲酰胺、N ,N-二甲基乙酰胺中的一种。
3.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(1)中生物质活性炭纤维包括采用杨絮、柳絮、香蒲、木棉中的一种制备的生物质活性炭纤维。
4.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(1)中氧化石墨烯水溶胶,将氧化石墨在去离子水中超声处理,超声时间为10-120min,超声功率为100-800W,得到0.1-10mg/ml的氧化石墨烯水溶胶。
5.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(2)将氧化石墨烯水溶胶、乳液小球与生物质活性炭纤维悬浮液进行沉积复合,这里的沉积复合采用喷涂、涂覆、压滤或真空抽滤。
6.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(3)中惰性气氛为氩气、氮气或氦气。
7.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(4)石墨烯与酚醛树脂质量比为0.5~10:100。
8.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(4)碱液中浸渍中的膜与碱的质量比为1:0.5~6,浸渍时间6-12h。
9.如权利 要求1所述的一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法,其特征在于所述的步骤(4)活化温度为500-900℃,活化时间0.5-6h。
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