CN110136994A - 一种高能量密度的纤维状超级电容器及其制备方法 - Google Patents
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Abstract
本发明公开了一种高能量密度的纤维状超级电容器及其制备方法,属于能源储存技术领域,该发明首先以柔性长条状电极及电解质膜来制备薄膜型全固态超级电容器,再通过“费马螺线”式加捻将其制成纤维状超级电容器。与现有的纤维状超级电容器相比,该电容器的突出特点是有且只有一层薄膜型固态电解质(同时充当隔膜),而不嵌入其他任何辅助成纤组分,减小了纤维状超级电容器的质量和体积;并且两个电极都是以薄膜状与电解质紧密接触,充分利用了电极活性材料在充放电过程中的使用率,可显著提高纤维状超级电容器能量密度和功率密度,具有广泛的应用前景。
Description
技术领域
本发明属于能源储存技术领域,尤其涉及一种高能量密度的纤维状超级电容器及其制备方法。
背景技术
可持续发展和大规模高效率的利用能源需要能源收集,转换和储存系统的快速进步和升级。超级电容器是正在稳健开发的能量存储装置。它比传统电容器存储更多的能量,比电池和燃料电池等可以更高的速率提供能量。纤维状超级电容器与传统的三维大尺寸超级电容器和二维平面型超级电容器相比,具有体积小,重量轻,柔韧性好,可以很容易地编织成透气的面料/纺织品等,并且可与其它形式的纤维状能源设备集成到电力供应系统中。因此,纤维状超级电容器是未来便携式和可穿戴电子设备中最有前途的能量存储装置之一。
目前纤维状超级电容器的结构主要可分为三类,即同轴式、缠绕式、平行式(刘连梅等,纤维状超级电容器的发展现状,中国材料进展,2016,35,81-90)。如复旦大学的彭慧胜等 (A highly stretchable,fiber-shaped supercapacitor,Angew. Chem. Int. Ed.2013,125,13695-13699) 通过在橡胶纤维上涂上一层薄薄的PVA-H3PO4凝胶电解质,之后用CNT薄膜缠绕作为内电极;继而用第二层电解质涂覆,并用另一层CNT薄膜卷绕作为与内电极对应的外电极,最后用第三层电解质涂覆,制备成同轴式纤维状超级电容器。但是这类纤维状超级电容器使用多层电解质涂层,并且电极纤维的核心是橡胶纤维/碳纤维/金属丝等(Nano. Energy,2014,8,44–51; J. Power. Sources,2016,324,325-333;Chem.Electro.Chem,2015,2,1042-1047; Adv. Mater. 2014,26,8126-8132;专利:公开号为CN103247446A,一种具有同轴结构的纤维状超级电容器及其制备方法与应用);它们不仅显著增加了器件的质量,而且本身也不提供电容,大大降低了纤维状电容器的能量密度和功率密度。另外如彭慧胜等 (Flexible,weavable and efficient microsupercapacitorwires based on polyaniline composite fibers incorporated with aligned carbonnanotubes, J. Mater. Chem. A,2013,1,258-261) 通过电化学方法将聚苯胺沉积到碳纳米管纤维上制成复合纤维,再将两根复合纤维电极涂上电解质涂层后,同时加捻以制备缠绕式的纤维状超级电容器。但是该类电容器同样需要在每个纤维状电极上涂覆电解质,如此将增加组装后的电容器的质量;并且为了防止短路的发生,通常还需要在纤维状电容器的外表面加上绝缘套筒(如 Angew. Chem. Int. Ed. 2016,55,6762-6766; ACS Nano,2015,9,6242-6251),这无疑增加了器件的重量,降低了其能量密度和功率密度。平行式纤维状超级电容器的缺点非常明显,因为其通常是将两根纤维状电极并排放置在以平板基底上,再在两根电极之间涂覆电解质。这类纤维状超级电容器不属于自支撑型,需要依赖平板基底,不仅限制的器件的能量密度和功率密度,还使得器件最终无法编织。目前发展的纤维状超级电容器,除了上述论述的前线之外,还有部分器件在制备成纤维时,引入了额外使电容器易于成纤的组分,如尼龙纤维、聚酯纤维等(Small,2016,12,1024-1033; Adv. EnergyMater. 2014,4,1300759),这对器件在储能方面上毫无贡献,但是却显著增加了器件的整体重量,使得能量密度和功率密度不高。因此,制备高能量密度的纤维状超级电容器仍需要开发新的方法。
发明内容
本发明为了弥补现有技术的不足,提供一种高能量密度的纤维状超级电容器及其制备方法。
为了实现上述的目的,本发明提供以下技术方案:
一种高能量密度的纤维状超级电容器,所述电容器由柔性薄膜电极和柔性固态电解质隔膜构成,先制备出平面薄膜状超级电容器,再按照类似“费马螺线”的方式将其加捻卷制成纤维状超级电容器。
一种上述高能量密度的纤维状超级电容器的制备方法,包括以下步骤:
(1)柔性薄膜电极的制备:将电极薄膜,如碳纳米管(CNT)薄膜等,通过酸洗或高温煅烧等方法除去其中的杂质,然后用乙醇和去离子水清洗数次后干燥备用;
(2)柔性固态电解质隔膜的制备:如聚乙烯醇(PVA)-H3PO4固态电解质的制备,需要首先取适量的PVA缓慢加入去离子水中搅拌,加热至PVA溶解形成水凝胶,再向凝胶中加入一定量的H3PO4搅拌均匀;最后取适量的PVA-H3PO4水凝胶均匀地涂在基底上,待溶剂挥发后得到固态电解质隔膜;
(3)裁取一定尺寸的柔性薄膜电极,与电解质隔膜一起首先组装成全固态的条状薄膜型超级电容器,在条状薄膜电容器的一边的中间处将其夹住,并通过“费马螺线”的扭转方式将其加捻,进而卷制成纤维状超级电容器。
所述步骤1中的电极薄膜包括但不限于CNT薄膜、石墨烯薄膜、导电高分子薄膜、聚合物碳化后的导电碳薄膜、钛碳类化合物薄膜等具有电容活性的柔性薄膜。
所述步骤2中的柔性固态电解质的材料包括但不限于PVA-H3PO4、PVA-KOH、PVA-H2SO4、PVP-H3PO4等。
所述步骤3中的电解质隔膜只用一层,且在加捻成纤维状超级电容器时该器件可独立自支撑,同时不使用任何其他如聚合物纤维、金属纤维等辅助成纤的结构。
本发明的优点是:
(1)本发明卷制成的纤维状超级电容器有且只有一层薄膜型固态电解质,并同时充当隔膜,而不嵌入其他任何辅助成纤组分,可独立自支撑,减小了纤维状超级电容器的质量和体积;并且两个电极都是以薄膜状与电解质紧密接触,充分利用了电极活性材料在充放电过程中的使用率,可显著提高纤维状超级电容器能量密度和功率密度,具有广泛的应用前景。
(2)在柔性薄膜电极上可选择负载金属氧化物、导电高分子、金属氢氧化物等具有电容活性的材料,制备非对称结构,进一步提高此类纤维状超级电容器的能量密度和功率密度。
附图说明
图1所示为费马螺线曲线图,其中a为“费马螺线”式加捻后的纤维截面结构图,b为“费马螺线”式加捻薄膜的俯视图。
图2所示为本发明所述的纤维状全固态超级电容器的制备过程及结构示意图。
图3所示为本发明实施实例1中CNT薄膜的扫描电镜形貌图。
图4所示为本发明实施实例1中卷制成纤维状全固态超级电容器的照片。
图5所示为本发明实施实例1中卷制成纤维状全固态超级电容器的循环伏安曲线。
具体实施方式
为使本发明的实质性特点及其所具的实用性更易于理解,以下结合附图及若干具体实施例对本发明的技术方案作进一步的详细说明。但以下关于实施实例的描述及说明对本发明保护范围不构成任何限制,本领域普通技术人员根据这些实施方式所作的功能、方法、或者结构上的等效变换或替代,均属于本发明的保护范围之内:
本发明所述的纤维状全固态超级电容器的制备过程及结构示意图如图2所示。
实施例1
首先,用浓硝酸清洗条状CNT薄膜电极并将其干燥备用;继而将两片CNT条状电极分别粘附在PVA-H3PO4固态电解质隔膜的两面,并稍加压实使电极和隔膜相互紧密接触,如此获得一个条状的柔性全固态超级电容器。再用细夹夹住条状薄膜型电容器短边的中间处,将该电容器加捻卷制成纤维状超级电容器。
其中CNT薄膜的扫描电镜形貌图如图3所示,所得卷制成纤维状全固态超级电容器的照片如图4所示,所得卷制成纤维状全固态超级电容器的循环伏安曲线如图5所示。
实施例2
首先,用电化学沉积的方法,将电容活性材料MnO2沉积到浓硝酸清洗干燥之后的CNT薄膜上制备柔性复合电极,再与PVA-KOH凝胶电解质隔膜一起组装成条状的全固态超级电容器。再用细夹夹住条状薄膜型电容器短边的中间处,将该电容器加捻卷制成纤维状超级电容器。
实施例3
首先,通过电化学聚合法将聚苯胺(PANI)沉积到石墨烯薄膜上以制备柔性复合电极,再制备一层MXene涂覆的CNT薄膜电极,分别粘附在PVA-H2SO4凝胶电解质隔膜的两侧,制备成条状的全固态超级电容器。再用细夹夹住条状薄膜型电容器短边的中间处,将该电容器加捻卷制成纤维状超级电容器。
Claims (5)
1.一种高能量密度的纤维状超级电容器,其特征在于,所述电容器由柔性薄膜电极和柔性固态电解质隔膜构成,先制备出平面薄膜状超级电容器,再按照类似“费马螺线”的方式将其加捻卷制成纤维状超级电容器。
2.一种权利要求1所述的高能量密度的纤维状超级电容器的制备方法,其特征在于,包括以下步骤:
(1)柔性薄膜电极的制备:将电极薄膜,通过酸洗或高温煅烧的方法除去其中的杂质,然后用乙醇和去离子水清洗数次后干燥备用;
(2)柔性固态电解质隔膜的制备:将柔性固态电解质的材料制成水凝胶,并将其均匀地涂在基底上,待溶剂挥发后得到固态电解质隔膜;
(3)裁取一定尺寸的柔性薄膜电极,与电解质隔膜一起首先组装成全固态的条状薄膜型超级电容器,在条状薄膜电容器的一边的中间处将其夹住,并通过“费马螺线”的扭转方式将其加捻,进而卷制成纤维状超级电容器。
3.根据权利要求2所述的制备方法,其特征在于,所述步骤1中的电极薄膜包括CNT薄膜、石墨烯薄膜、导电高分子薄膜、聚合物碳化后的导电碳薄膜、钛碳类化合物薄膜中的任意一种。
4.根据权利要求2所述的制备方法,其特征在于,所述步骤2中的柔性固态电解质的材料包括PVA-H3PO4、PVA-KOH、PVA-H2SO4、PVP-H3PO4中的任意一种。
5.根据权利要求2所述的制备方法,其特征在于,所述步骤3中的电解质隔膜只用一层,且在加捻成纤维状超级电容器时该器件可独立自支撑,同时不使用任何其他如聚合物纤维、金属纤维等辅助成纤的结构。
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