CN109104117B - 一种可穿戴织物纳米发电机及其制备方法 - Google Patents
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Abstract
本发明公开了一种可穿戴织物纳米发电机及其制备方法,通过化学电镀的方式对纯棉纱添加镀层制得导电纱线,将导电芯纱线作为包芯纱的芯纱,然后将制得的芯纱材料利用共轭静电纺成纱技术制备包覆纳米纤维的纱线。在此基础上,利用机织的方法将得到的两种包芯纱各自单独编织形成纳米纤维单层织物,后利用超细透明尼龙在两织物层进行连接,给两层留出相应空气层,最终获得可穿戴织物纳米发电机。纳米发电机可以将机械能,特别是低频身体动能的转换电能,由于环保性和普遍可用性,因此在收集小型机械能和大规模能源发电方面得以应用。
Description
技术领域
本发明属于纳米纤维材料领域,涉及一种可穿戴纳米发电机的制备方法,具体涉及一种利用化学镀铜、静电纺丝技术制备的纳米纤维织物摩擦发电机,具体属于摩擦生电发生器制备领域。
背景技术
近年来,解决未使用的机械能,如环境振动,引起了广泛关注。在周边环境中的各种可再生和可持续能源中,机械能是分布最广泛的能源种类和规模,如机械振动,声音,轮胎滚动,行走,海洋潮汐等。人们为了解决能源危机日益严重,实现自给自足的低能耗电子化的问题,开发了多种将机械能有效转换为电能的方法,包括压电效应、静电效应、电磁等。
通过摩擦纳米发电机(TENG)从人类活动中收集机械能是便携式和可穿戴式电子产品的可持续绿色电源的有效方法。据估计,甚至可以获取人体功率的1%-5%而不会显着增加对人体的负荷就足以运行许多身体磨损的装置。摩擦式纳米发电机(TENGs)已经被证明可以从人类活动中获取能量,作为可持续自给自足的纳米力量由于其高效率,低成本,环境友好以及普遍的可用性。随着可穿戴电子设备近年来受到很多关注,对简单,轻便和便携式发电机的需求大大增加。能量收集装置将诸如机械振动,光,热和电磁辐射等环境能量的能量转化为电能,是这种发电机的有希望的候选者。
近来,基于摩擦电效应和静电感应的耦合,已经引入了摩擦纳米发电机(TENG)以从机械能发电。 通过设计特定用途的TENG结构,TENG能够从人体运动,行走,振动,冲击,风和流水等各种机械能量中获取电力。TENG可以通过摩擦电效应来产生电力,这种效应源于两层不同接触材料之间的电荷转移。
发明内容
针对现有技术中存在的问题,本发明提供一种可穿戴织物纳米发电机及其制备方法,设计了具有压电摩擦、交错摩擦发电功能的基于纳米纤维包芯纱结构的可穿戴纳米发电机,以镀铜棉纱线作为导电电极,分别以聚偏氟乙烯(PVDF)、尼龙66纳米纤维作为两种摩擦材料,利用共轭静电纺纳米纤维的成纱工艺,得到分别包覆PVDF、尼龙66的两种纳米纤维包芯纱,利用机织的方法将包芯纱线交织形成纳米纤维织物,获得可穿戴织物纳米发电机。
为解决上述技术问题,本发明采用以下技术方案:
一种可穿戴织物纳米发电机,利用化学电镀的方式对纯棉纱添加镀层制得导电纤维,将制得的导电纤维利用共轭静电纺进行纳米纤维的包覆制得包芯纱线,利用机织的方法将包芯纱线交织形成纳米纤维织物,获得可穿戴织物纳米发电机。
所述导电纤维为镀镍棉纱或镀铜棉纱,导电纱线的直径为100-500μm。
所述纳米纤维由高分子聚合物构成,纳米纤维的直径为100-900nm。
所述聚合物为聚偏氟乙烯和尼龙66,聚合物的分子量≥100000。
所述纳米包芯纱的直径为150-1000μm。
所述纳米纤维发电机织物的层数≥2,单层织物结构为平纹组织、凹凸组织、蜂窝组织的一种或几种,纳米纤维织物的经密10-500根/5cm,纳米纤维织物的纬密10-500根/5cm。
所述可穿戴纳米织物发电机长度≥5 mm,宽度≥5 mm,厚度≥1 mm。
所述的可穿戴纳米织物发电机的制备方法,按以下步骤进行:
(1)利用化学电镀的方式对纯棉纱添加镀层制得导电纱线;
(2)将聚偏氟乙烯颗粒加入到N,N二甲基甲酰胺溶液中加热于20℃-80℃的条件下搅拌2h-15h得到质量分数为5%-30%的聚偏氟乙烯纺丝液,所述聚偏氟乙烯的分子量规格为60万-100万;
(3)将尼龙66颗粒加入到甲酸溶液中常温搅拌3h-20h得到质量分数为10%-30%的尼龙66纺丝液;
(4)以步骤(1)制得的导电纱线为导电芯纱,将步骤(2)所得聚偏氟乙烯纺丝液、步骤(3)所得尼龙66纺丝液分别作为外层纺丝溶液,利用静电纺丝装置分别进行同轴静电纺丝,得到捻度为30捻/10cm-60捻/10cm的聚偏氟乙烯纳米纤维纱线和尼龙66纳米纤维纱线;
(5)利用机织的方法将步骤(4)中的纳米纤维纱线编织成聚偏氟乙烯纳米纤维织物和尼龙66纳米纤维织物两种织物层,两层织物中间利用超细透明的尼龙线进行连接得到可穿戴织物纳米发电机,所述组装后纳米纤维发电机织物的层数≥2,织物层经密10-150根/5cm,纬密10-150根/5cm。
所述步骤(1)中利用化学电镀的方式对纯棉纱添加镀层制得导电纱线的方法如下:将纯棉股纱进行碱性溶液中进行碱处理、敏化、活化为下一步镀铜/镍做准备;利用化学镀铜液进行棉纱镀铜1-10min,利用化学镀镍液棉纱棉纱镀镍1h-5h,为棉纱添加导电性能,导电纤维的导电性是1-10Ω/cm。
所述步骤(3)中PVDF纺丝溶液流量为0.3ml/h-0.9 ml/h,尼龙纺丝液流量为0.1ml/h-0.3ml/h;纺丝电压为10 kV -30 kV,纺丝温度为20℃-40℃,喇叭转速50-180 r/min,卷绕速度10-50 r/min。
本发明的有益效果:(1)将静电纺丝技术与传统纺织技术相结合,制备具有纳米结构的编织物,并应用于传统纺织品,提高传统纺织品的附加值。(2)由于制备的纳米纤维织物具有微纳米分级结构,因此摩擦纳米发电机显示了较宽的摩擦频率范围。应用在人们服装领域中,可实现对人体所产生的机械能的一种收集。(3)制备的纳米纤维织物具有较好的力学自适应性,可实现真正意义上的可穿戴纳米摩擦发电机。(4)本发明的可穿戴织物纳米发电机可以将机械能,特别是低频身体动能的转换电能,由于环保性和普遍可用性,因此在收集小型机械能和大规模能源发电方面得以应用。
附图说明
图1纳米发电机示意图:1、PVDF纳米纤维包芯纱编织的织物层;2、两层织物的连接线透明尼龙线;3、尼龙纳米纤维包芯纱编织的织物层。
图2 纳米纤维织物及单根纤维的SEM图片。
具体实施方式
下面结合具体实施例,对本发明做进一步说明。应理解,以下实施例仅用于说明本发明而非用于限制本发明的范围,该领域的技术熟练人员可以根据上述发明的内容作出一些非本质的改进和调整。
实施例1
本实施例的可穿戴织物纳米发电机的制备方法如下:
(1)将纯棉股纱进行碱性溶液中进行碱处理、敏化、活化为下一步镀铜做准备:
a.将纯棉股纱在10g/L NaOH溶液中,80℃处理1h,后用去离子水冲洗并60℃的干燥箱里烘干;
b.将清洗干燥好的棉纱放入浓度为0.05g/mL 硫酸镍和浓度为0.02g/mL的盐酸混合水溶液中浸渍10min后,取出置于50mL浓度为0.01g/mL的硼氢化钠和浓度为0.01g/mLNaOH混合水溶液中浸渍10min后,取出来并用去离子水清洗后为下一步操作做准备;
(2)将步骤(1)准备好的纯棉股纱浸入以下化学镀铜溶液: 9. 663 g/L CuSO4·5H2O、16. 271 g /L NiSO4·6H2O、 115 g /L NaH2PO2·H2O、50g /L Na3C6H5O7、PH值11. 6,0. 40 mg /L亚铁氰化钾中0. 2 mL中,温度70℃,时间5 min,为棉纱添加导电性能;
(3)将聚偏氟乙烯(PVDF)颗粒加入到N,N二甲基甲酰胺溶液中加热80℃搅拌8h得到纺丝溶液,所述聚偏氟乙烯(PVDF)的分子量规格为100万分子量,纺丝液质量分数为15.5%;
(4)将尼龙66颗粒加入到甲酸溶液中常温搅拌10h直指颗粒消失得到纺丝液,所述的尼龙66纺丝液质量分数为22.5%;
(5)利用共轭静电纺丝装置,正负喷丝头之间的距离14cm-20cm,喷头距离喇叭口边缘的垂直距离4cm-10cm;
(6)步骤(2)所得镀铜棉纱作为导电芯纱,将步骤(3)、(4)所得混合溶液分别作为外层纺丝溶液,利用共轭静电纺丝装置分别进行同轴静电纺丝,PVDF纺丝溶液流量0.5ml/h,尼龙纺丝流量为0.4 ml/h,纺丝电压为20 kV,纺丝温度为25℃,喇叭转速60 r/min,卷绕速度50mm/min;
(7)利用机织的方法将步骤(6)中的纳米纤维纱线编织成聚偏氟乙烯纳米纤维织物和尼龙66纳米纤维织物两种织物层,两层织物中间利用超细透明的尼龙线(0.08mm)进行连接(如图1),所述组装后纳米纤维发电机织物的层数为2层,经密90根/5cm,纬密90根/5cm。
实施例2
本实施例的可穿戴织物纳米发电机的制备方法如下:
(1)将纯棉股纱进行碱性溶液中进行碱处理、敏化、活化为下一步镀铜做准备:
a.将纯棉股纱在10g/L NaOH溶液中,80℃处理1h,后用去离子水冲洗并60℃的干燥箱里烘干;
b.将清洗干燥好的棉纱放入浓度为0.05g/mL 硫酸镍和浓度为0.02g/mL的盐酸混合水溶液中浸渍10min后,取出置于50mL浓度为0.01g/mL的硼氢化钠和浓度为0.01g/mLNaOH混合水溶液中浸渍10min后,取出来并用去离子水清洗后为下一步操作做准备;
(2)将步骤(1)准备好的纯棉股纱浸入以下化学镀铜溶液: 9. 663 g/L CuSO4·5H2O、16. 271 g /L NiSO4·6H2O、 115 g /L NaH2PO2·H2O、50g /L Na3C6H5O7、PH值11. 6,0. 40 mg /L亚铁氰化钾中0. 2 mL中,温度70℃,时间5 min,为棉纱添加导电性能;
(3)将聚偏氟乙烯(PVDF)颗粒加入到N,N二甲基甲酰胺溶液中加热80℃搅拌8h得到纺丝溶液,所述聚偏氟乙烯(PVDF)的分子量规格为100万分子量,纺丝液质量分数为30%;
(4)将尼龙66颗粒加入到甲酸溶液中常温搅拌10h直指颗粒消失得到纺丝液,所述的尼龙66纺丝液质量分数为30%;
(5)利用共轭静电纺丝装置,正负喷丝头之间的距离14cm-20cm,喷头距离喇叭口边缘的垂直距离4cm-10cm。
(6)步骤(2)所得镀铜棉纱作为导电芯纱,将步骤(3)、(4)所得混合溶液分别作为外层纺丝溶液,利用共轭静电纺丝装置分别进行同轴静电纺丝,PVDF纺丝溶液流量0.5ml/h,尼龙纺丝流量为0.4 ml/h,纺丝电压为20 kV,纺丝温度为25℃,喇叭转速60 r/min,卷绕速度50mm/min;
(7)如图1所示,利用机织的方法将步骤(6)中的纳米纤维纱线编织成聚偏氟乙烯纳米纤维织物和尼龙66纳米纤维织物两种织物层,两层织物中间利用超细透明的尼龙线(0.08mm)进行连接,所述组装后纳米纤维发电机织物的层数为2层,经密90根/5cm,纬密90根/5cm。
实施例3
本实施例的可穿戴织物纳米发电机的制备方法如下:
(1)将纯棉股纱进行碱性溶液中进行碱处理、敏化、活化为下一步镀铜做准备,将棉单纱置于氢氧化钠(KOH, 浓度10 g/L)的溶液中60 min,取出后用去离子水清洗,然后置于50℃的真空烘箱中干燥;
(2)将步骤(1)中的棉纱线浸泡在浓度为0.05g/mL 硫酸镍和0.02g/mL的盐酸混合水溶液中浸渍2-30min,取出后置于浓度为0.01g/mL的硼氢化钠和浓度为0.01g/mL氢氧化钠混合水溶液中2-30min,取出后用去离子水清洗置于PH为9的水合硫酸镍(NiSO4•6H2O,30g/L),次亚磷酸钠(NaHPO2 ,12 g/L),氯化铵(NH4Cl,45 g/L),柠檬酸三钠的(25 g/L)的化学电镀液中4h,取出后置于60℃的真空烘箱中干燥;
(3)将聚偏氟乙烯(PVDF)颗粒加入到N,N二甲基甲酰胺溶液中加热80℃搅拌8h得到纺丝溶液,所述聚偏氟乙烯(PVDF)的分子量规格为100万分子量,纺丝液质量分数为5%;
(4)将尼龙66颗粒加入到甲酸溶液中常温搅拌10h直指颗粒消失得到纺丝液,所述的尼龙66纺丝液质量分数为10%;
(5)利用共轭静电纺丝装置,正负喷丝头之间的距离14cm-20cm,喷头距离喇叭口边缘的垂直距离4cm-10cm;
(6)步骤(2)所得镀铜棉纱作为导电芯纱,将步骤(3)、(4)所得混合溶液分别作为外层纺丝溶液,利用共轭静电纺丝装置分别进行同轴静电纺丝,PVDF纺丝溶液流量0.5ml/h,尼龙纺丝流量为0.4 ml/h,纺丝电压为20 kV,纺丝温度为25℃,喇叭转速60 r/min,卷绕速度50mm/min;
(7)利用机织的方法将步骤(6)中的纳米纤维纱线编织成聚偏氟乙烯纳米纤维织物和尼龙66纳米纤维织物两种织物层,两层织物中间利用超细透明的尼龙线(0.08mm)进行连接如图1所示,所述组装后纳米纤维发电机织物的层数为2层,经密90根/5cm,纬密90根/5cm。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (7)
1.一种可穿戴织物纳米发电机的制备方法,其特征在于按以下步骤进行:
(1)利用化学电镀的方式对纯棉纱添加镀层制得导电纱线;
(2)将聚偏氟乙烯颗粒加入到N,N二甲基甲酰胺溶液中加热于20℃-80℃的条件下搅拌2h-15h得到质量分数为5%-30%的聚偏氟乙烯纺丝液,所述聚偏氟乙烯的分子量规格为60万-100万;
(3)将尼龙66颗粒加入到甲酸溶液中常温搅拌3h-20h得到质量分数为10%-30%的尼龙66纺丝液;
(4)以步骤(1)制得的导电纱线为导电芯纱材料,将步骤(2)所得聚偏氟乙烯纺丝液、步骤(3)所得尼龙66纺丝液分别作为外层纺丝溶液,利用静电纺丝装置分别进行同轴静电纺丝,得到捻度为30捻/10cm-60捻/10cm的聚偏氟乙烯纳米纤维纱线和尼龙66纳米纤维纱线;
(5)利用机织的方法将步骤(4)中的纳米纤维纱线编织成聚偏氟乙烯纳米纤维织物和尼龙66纳米纤维织物两种织物层,两层织物中间利用超细透明的尼龙线进行连接得到可穿戴织物纳米发电机,组装后的纳米发电机的织物的层数≥2,织物层经密10-150根/5cm,纬密10-150根/5cm;
所述的可穿戴织物纳米发电机,利用化学电镀的方式对纯棉纱添加镀层制得导电纱线,将制得的导电纱线利用共轭静电纺进行纳米纤维的包覆制得包芯纱线,利用机织的方法将得到的两种包芯纱各自单独编织形成纳米纤维单层织物,后利用超细透明尼龙将两织物层进行连接,给两层留出相应空气层,最终获得可穿戴织物纳米发电机。
2.根据权利要求1所述的可穿戴织物纳米发电机的制备方法,其特征在于:所述纳米纤维由高分子聚合物构成,纳米纤维的直径为100-900nm。
3.根据权利要求1所述的可穿戴织物纳米发电机的制备方法,其特征在于:所述包芯纱线的直径为150-1000μm。
4.根据权利要求1所述的可穿戴织物纳米发电机的制备方法,其特征在于:组装后的纳米发电机的织物的层数≥2,其中单层织物结构为平纹组织、凹凸组织、蜂窝组织的一种或几种。
5.根据权利要求1所述的可穿戴织物纳米发电机的制备方法,其特征在于:所述可穿戴织物纳米发电机长度≥5 mm,宽度≥5 mm,厚度≥1 mm。
6.根据权利要求1所述的可穿戴织物纳米发电机的制备方法,其特征在于:所述步骤(1)中利用化学电镀的方式对纯棉纱添加镀层制得导电纤维的方法如下:将纯棉股纱进行碱性溶液中进行碱处理、敏化、活化为下一步镀铜/镍做准备;利用化学镀铜液进行棉纱镀铜1-10min,利用化学镀镍液棉纱棉纱镀镍1h-5h,为棉纱添加导电性能。
7.根据权利要求1所述的可穿戴织物纳米发电机的制备方法,其特征在于:所述步骤(4)中PVDF纺丝溶液流量为0.3ml/h-0.9ml/h,尼龙纺丝液流量为0.1ml/h-0.3ml/h;纺丝电压为10 kV -30 kV,纺丝温度为20℃-40℃,喇叭转速50-180 r/min,卷绕速度10-50 r/min。
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