CN111041602A - 一种基于杂化纤维电极的全固态超级电容器及其制备方法 - Google Patents
一种基于杂化纤维电极的全固态超级电容器及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种基于杂化纤维电极的全固态超级电容器及其制备方法,所述超级电容器以GO/CNT‑TPU杂化纤维为电极,表面涂覆凝胶电解质并缠绕组装获得。本发明制备方法成本低,过程简单,适用于大规模生产。所得杂化纤维电极具有较好的力学性能和电化学性能,所得纤维状全固态超级电容器具有较好的电化学稳定性和可编织性,有望应用于柔性储能和可穿戴设备领域。
Description
技术领域
本发明属于电容器材料及其制备领域,特别涉及一种基于杂化纤维电极的全固态超级电容器及其制备方法。
背景技术
近些年来,柔性电子和可穿戴电子设备的快速发展对储能器件提出了更高的要求。为了满足柔性织物状电子装备的使用需求,储能器件也应当具有相似的织物或纤维形状、突出的柔性、力学稳定性以及轻质等特点。作为重要的储能设备,超级电容器具有高功率密度、快速充放电、结构简单、循环稳定性好等优点,这使得超级电容器在可穿戴织物电子领域具有较大的应用前景。
在众多形状的超级电容器中,纤维状超级电容器因其更易于编织而收到广泛关注。目前,金属线、碳纤维、碳纳米管纤维、石墨烯纤维等都已经成功被应用为纤维状超级电容器电极材料。碳纳米管纤维自从2000年首次被报道以来,因其轻质、优越的柔性、突出的力学性能以及较大的比表面积在超级电容器领域得到广泛应用。Cheng等人基于化学气相沉积法制备了以碳纳米管纤维为基材的非对称纤维状超级电容器,其体积能量密度可达11.3mWh/cm3(The Journal of Physical Chemistry C,2016,120,9685-9691)。同时为了赋予纤维器件可拉伸性能,Yang等人在弹性聚合物纤维基底表面包覆了碳纳米管阵列,拉伸应变为75%循环100次后电化学性能仍能保持95%以上(Angewandte ChemieInternational Edition,2013,52,13453-13457)。但不论是碳纳米管纤维电极还是可拉伸器件,其制备方法都较复杂,成本较高,限制了其在实际生产中的大规模应用。
CN108054442A公开了一种利用丝网印刷技术制备织物状水系锂电池的方法,运用此方法制备的织物状水系锂电池具有一定的局限性。首先,通过丝网印刷技术将活性物质涂敷在织物表面,使得活性物质较易脱落;其次,此锂电池不具有可拉伸性,难以满足各类可穿戴器件的不同需求。
发明内容
本发明所要解决的技术问题是提供一种基于杂化纤维电极的全固态超级电容器及其制备方法,克服了现有可穿戴器件中电极活性物质与织物基底结合不牢固,易脱落以及不可拉伸的缺陷。本发明通过超声及加热搅拌方法制备得到氧化石墨(GO)、碳纳米管(CNT)以及聚氨酯(TPU)均匀分散的纺丝液,再利用湿法纺丝技术制备得到GO/CNT-TPU杂化纤维。以该杂化纤维为电极,表面涂覆凝胶电解质并缠绕组装得到纤维状全固态超级电容器。
本发明的一种杂化纤维,所述纤维为氧化石墨GO/碳纳米管CNT-聚氨酯TPU杂化纤维;将包含氧化石墨GO、碳纳米管CNT、聚氨酯TPU的纺丝液进行纺丝获得。
所述氧化石墨GO/碳纳米管CNT-聚氨酯TPU杂化纤维具体结构为多孔纤维。
所述碳纳米管与氧化石墨的质量比为5:1~5:2;聚氨酯与氧化石墨质量比为200:1~100:1。
本发明的一种杂化纤维的制备方法,包括:
(1)将氧化石墨GO分散在溶剂中,超声,得到氧化石墨分散液;
(2)将步骤(1)分散液中加入碳纳米管CNT,在冰水浴环境下超声,然后加入聚氨酯TPU,加热,搅拌并冷凝回流,冷却至室温,得到GO/CNT-TPU纺丝液,进行湿法纺丝,得到杂化纤维。
上述制备方法的优选方式如下:
所述步骤(1)中氧化石墨分散液的浓度为1~2mg/mL;溶剂为N,N-二甲基甲酰胺。
步骤(2)中加入的碳纳米管与氧化石墨的质量比为5:1~5:2;加入的聚氨酯与氧化石墨质量比为200:1~100:1。
所述步骤(1)中超声时间为2~3h。
所述步骤(2)中超声时间为1~2h。
所述步骤(2)中加热温度为60~70℃,回流时间为1~2h。
所述步骤(2)中湿法纺丝具体为:纺丝液通过注射器注入到去离子水中,其中注射泵推进注射器的速度为1~2mL/min;注射器采用的针头内径为200~840μm。
本发明的一种全固态超级电容器,所述电容器以所述杂化纤维为电极,涂覆凝胶电解质并缠绕组装,获得。
本发明的一种全固态超级电容器的制备方法,包括:将所述杂化纤维浸入聚乙烯醇/硫酸凝胶电解质中,然后取两段以上包覆电解质的杂化纤维缠绕,得到纤维状全固态超级电容器。
所述全固态超级电容器的制备方法中,浸入聚乙烯醇/硫酸凝胶电解质中的时间为12~24h。
本发明提供的一种所述全固态超级电容器的应用,如应用于柔性储能和可穿戴设备领域。
有益效果
(1)本发明利用湿法纺丝技术制备了高度可拉伸高性能导电杂化纤维,即GO/CNT-TPU纤维。杂化纤维可被拉伸至200%结构无明显损坏,拉伸应变为50%循环20次以后最大拉伸强度几乎没有变化。最大电导率可达342S/cm,最大体积比电容可达36.45F/cm3(长度比电容为21.87mF/cm、质量比电容为95F/g)。
(2)以本发明杂化纤维为电极,在表面涂覆聚乙烯醇/硫酸电解质后取两根缠绕即可得纤维状全固态超级电容器。该器件具有较好的电化学性能,最大体积比电容可达14.3F/cm3,5000次充放电循环后仍然保持约97%的电容量。同时器件具有较好的可编制性,能够编入织物。
(3)本发明所得杂化纤维电极具有较好的力学性能和电化学性能,所得纤维状全固态超级电容器具有较好的电化学稳定性和可编织性;本发明中从杂化纤维电极的制备到纤维状全固态超级电容器的组装,过程简单,成本较低,有望大规模应用于柔性储能和可穿戴设备领域。
附图说明
图1为本发明的基于高度可拉伸导电杂化纤维电极的全固态超级电容器制备过程示意图;
图2为实施例1制备得到的GO/CNT-TPU杂化纤维应力应变曲线,(a)为拉伸过程中的数码照片;(b)杂化纤维拉伸循环测试图;
图3为实施例1制备得到的纤维状全固态超级电容器电化学性能表征,(a)为器件在不同电压窗口下的循环伏安曲线;(b)为器件在不同扫速下的循环伏安曲线;(c)为器件在不同电流密度下的恒电流充放电曲线;(d)为器件的倍率性能曲线和循环测试曲线;
图4为实施例1制备得到纤维状全固态超级电容器在织物中的数码照片。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
主要原料的来源及规格参数:氧化石墨(XF205)购于南京先丰纳米材料科技有限公司;碳纳米管(TNGMC2,长度10-50μm,99.9wt%,)购于中科时代纳米科技有限公司;聚氨酯(Elastollan 1185A)购自巴斯夫有限公司。
GO/CNT-TPU杂化纤维的机械性能通过万能材料试验机进行测试(型号5969,Instron),通过华辰电化学工作站对杂化纤维以及纤维状全固态超级电容器进行了电化学测试,如循环伏安(CV),恒电流充放电(GCD)测试等。
实施例1
(1)取20mg氧化石墨分散于10mg N,N-二甲基甲酰胺中,超声3h后,得到2mg/ml的氧化石墨分散液;
(2)在上述分散液中加入50mg碳纳米管,并在冰水浴环境下超声2h;
(3)在上述分散液加入4g聚氨酯,加热至60℃,搅拌并冷凝回流2h,待冷却至室温后即可得到GO/CNT-TPU纺丝液;
(4)采用内径840μm的针头将上述纺丝液通过注射器以2mL/min的速度注入到去离子水中即可得到GO/CNT-TPU多孔杂化纤维,并用圆筒收集起来,自然干燥;
(5)取约8cm长的两段杂化纤维浸入到聚乙烯醇/硫酸凝胶电解质中,为了电解质能在杂化纤维电极表面形成充分包覆,且部分电解质可浸润到电极内部,浸入时间约24h,然后取出,在空气中干燥约30min后将两段纤维缠绕即可得到纤维状全固态超级电容器。
本实施例制备得到的GO/CNT-TPU杂化纤维应力应变曲线,如图2所示,杂化纤维可被拉伸至200%结构无明显破坏,拉伸应变为50%循环20次以后最大拉伸强度几乎没有变化。
本实施例制备得到的纤维状全固态超级电容器电化学性能表征,如图3所示,由(a)可得,在扫速为50mV/s的条件下,电压窗口高于1V时,循环伏安曲线表现出明显的变形,这是由电极及电解质极化现象引起的,因此该超级电容器最合适的电压窗口为0-1V。图(b)为不同扫速下纤维状全固态超级电容器的循环伏安曲线,(c)为不同电流密度下所得的充放电曲线。由(b)、(c)以及(d)中下部曲线可得,当扫描速度或电流密度增大时,器件的比电容逐渐降低,这是由固态电解质离子传输速度较慢引起。由(d)上部曲线可得,在充放电循环5000次以后,器件的电容仍能保持初始值的97%左右,拥有较好的充放电循环稳定性,最大体积比电容可达14.3F/cm3。本实施例制备得到的GO/CNT-TPU多孔杂化纤维最大电导率可达342S/cm,最大体积比电容可达36.45F/cm3(长度比电容为21.87mF/cm、质量比电容为95F/g)。
实施例1制备得到纤维状全固态超级电容器在织物中的数码照片,如图4所示,多根器件一起编织到织物中,展现出较好的可编织性能。
实施例2
(1)取10mg氧化石墨分散于10mg N,N-二甲基甲酰胺中,超声2h后,得到1mg/ml的氧化石墨分散液;
(2)在上述分散液中加入50mg碳纳米管,并在冰水浴环境下超声1h;
(3)在上述分散液加入2g聚氨酯,加热至70℃,搅拌并冷凝回流1h,待冷却至室温后即可得到GO/CNT-TPU纺丝液;
(4)采用内径400μm的针头将上述纺丝液通过注射器以1mL/min的速度注入到去离子水中即可得到GO/CNT-TPU杂化纤维,并用圆筒收集起来,自然干燥;
(5)取约8cm长的两段杂化纤维浸入到聚乙烯醇/硫酸凝胶电解质中,为了电解质能在杂化纤维电极表面形成充分包覆,且部分电解质可浸润到电极内部,浸入时间约12h,然后取出,在空气中干燥约30min后将两段纤维缠绕即可得到纤维状全固态超级电容器。在充放电循环5000次以后,器件的电容仍能保持初始值的90%左右,拥有较好的充放电循环稳定性。
实施例3
(1)取15mg氧化石墨分散于10mg N,N-二甲基甲酰胺中,超声1.5h后,得到1.5mg/ml的氧化石墨分散液;
(2)在上述分散液中加入50mg碳纳米管,并在冰水浴环境下超声2.5h;
(3)在上述分散液加入3g聚氨酯,加热至65℃,搅拌并冷凝回流1.5h,待冷却至室温后即可得到GO/CNT-TPU纺丝液;
(4)采用内径600μm的针头将上述纺丝液通过注射器以1.5mL/min的速度注入到去离子水中即可得到GO/CNT-TPU杂化纤维,并用圆筒收集起来,自然干燥;
(5)取约8cm长的两段杂化纤维浸入到聚乙烯醇/硫酸凝胶电解质中,为了电解质能在杂化纤维电极表面形成充分包覆,且部分电解质可浸润到电极内部,浸入时间约18h,然后取出,在空气中干燥约30min后将两段纤维缠绕即可得到纤维状全固态超级电容器。在充放电循环5000次以后,器件的电容仍能保持初始值的95%左右,拥有较好的充放电循环稳定性,在循环拉伸50%的状态下,循环200次比电容可保持初始状态的83%左右。
Claims (10)
1.一种杂化纤维,其特征在于,所述纤维为氧化石墨GO/碳纳米管CNT-聚氨酯TPU杂化纤维;将包含氧化石墨GO、碳纳米管CNT、聚氨酯TPU的纺丝液进行纺丝获得。
2.根据权利要求1所述杂化纤维,其特征在于,所述碳纳米管与氧化石墨的质量比为5:1~5:2;聚氨酯与氧化石墨质量比为200:1~100:1。
3.一种杂化纤维的制备方法,包括:
(1)将氧化石墨GO分散在溶剂中,超声,得到氧化石墨分散液;
(2)将步骤(1)分散液中加入碳纳米管CNT,在冰水浴环境下超声,然后加入聚氨酯TPU,加热,搅拌并冷凝回流,冷却至室温,得到GO/CNT-TPU纺丝液,进行湿法纺丝,得到杂化纤维。
4.根据权利要求3所述制备方法,其特征在于,所述步骤(1)中氧化石墨分散液的浓度为1~2mg/mL;溶剂为N,N-二甲基甲酰胺。
5.根据权利要求3所述制备方法,其特征在于,步骤(2)中加入的碳纳米管与氧化石墨的质量比为5:1~5:2;加入的聚氨酯与氧化石墨质量比为200:1~100:1。
6.根据权利要求3所述制备方法,其特征在于,所述步骤(2)中加热温度为60~70℃,回流时间为1~2h。
7.根据权利要求3所述制备方法,其特征在于,所述步骤(2)中湿法纺丝具体为:纺丝液通过注射器注入到去离子水中,其中注射泵推进注射器的速度为1~2mL/min;注射器采用的针头内径为200~840μm。
8.一种全固态超级电容器,其特征在于,所述电容器以权利要求1所述杂化纤维为电极,涂覆凝胶电解质并缠绕组装,获得。
9.一种全固态超级电容器的制备方法,包括:将权利要求1所述杂化纤维浸入聚乙烯醇/硫酸凝胶电解质中,然后取两段以上包覆电解质的杂化纤维缠绕,得到全固态超级电容器。
10.一种权利要求8所述全固态超级电容器的应用。
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