CN111537114A - 全纳米纤维电子皮肤及其应用装置 - Google Patents
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Abstract
本发明提供一种全纳米纤维电子皮肤，包括上中下三层纳米纤维膜，分别是接触起电层、中间电极层和底部支撑层，其中，所述接触起电层和底部支撑层均为生物可降解材料的纳米纤维膜；所述中间电极层为具有杀菌功能的纳米纤维膜，与地或者其他导体电连接。该电子皮肤具有多层交错的纳米纤维网络和大量的三维微纳米层次孔，使电子皮肤具有透气性和高输出及高压力灵敏度，同时具有抗菌性。
Description
技术领域
本发明涉及传感器领域，尤其涉及一种全纳米纤维电子皮肤及其应用装置。
背景技术
人体皮肤作为人体最大的器官，不仅具有保护、分泌和呼吸的基本功能，而且是人类感知、与物质世界相互作用和交流的重要体感***。通过模仿自然皮肤的特征和功能，开发仿生电子皮肤已经激起了相当大的兴趣，这些特征和功能在可穿戴的以个人为中心的健康监测、智能假肢、机器人、人机界面和人工智能等领域有着广泛的应用。
电子皮肤基于不同的物理传感机制，如压阻、电容、压电和摩擦电，能够检测和量化环境刺激的多样性，包括温度、湿度、压力、振动和触觉，并将其转化为实时和可视化的电子脉冲。摩擦纳米发电机是一种利用接触起电与静电感应耦合效应，将普遍存在的机械能转化为宝贵电能的新型能量获取技术，具有成本低、结构简单、使用方便、材料选择多样、转换效率高等优点，在可穿戴电源和自供电传感领域具有广阔的应用前景，是能源自主式电子皮肤的理想选择。
柔性、可拉伸性、灵敏性、超适性、机械耐久性是目前电子皮肤最受欢迎的研究方向，也是比较容易实现的。近年来，为了提高电子皮肤的综合性能，电子皮肤的可回收性、自愈性、形状记忆性、电致发光、机械发光等特殊功能逐渐被研究。尽管上述方面不断优化和完善，但电子皮肤的舒适性、安全性和环保性一直被忽视，这在很大程度上阻碍了电子皮肤的实际应用。因此，具有理想的舒适性和实用性的电子皮肤必须具有透气性、生物降解性和抗菌性。透气性是调节热湿平衡，实现人体与外界环境气体交换的重要方式。然而，大多数高性能的电子皮肤都是以膜作为电极或基质，这可能会导致皮肤不适，甚至引发炎症和瘙痒。此外，由于电子皮肤与人体皮肤长期接触，是微生物生长的良好媒介，因此抗菌特性是电子皮肤抑制细菌生长、预防细菌感染的重要性能。此外，大部分材料都不是一次性的，在使用寿命结束时，可能会变成电子垃圾，甚至危害人体或污染环境。
发明内容
本发明的目的是提供一种全纳米纤维电子皮肤，基于摩擦纳米发电机原理，实现了电子皮肤透气性、抗菌性、生物降解性和自供电性的结合，解决了现有电子皮肤的不舒适、细菌感染、环境污染等问题。
为了实现上述目的，本发明提供一种全纳米纤维电子皮肤，包括上中下三层纳米纤维膜，分别是接触起电层、中间电极层和底部支撑层，其中，
所述接触起电层和底部支撑层均为生物可降解材料的纳米纤维膜；
所述中间电极层为具有杀菌功能的纳米纤维膜，与地或者其他导体电连接。
优选的，所述生物可降解材料包括聚乙烯醇、聚乳酸-羟基乙酸共聚物、聚己内酯、聚乳酸、聚羟基乙酸、聚丁二酸酯、聚β-羟基丁酸酯、聚氨酯、纤维素中的一种或几种可用于静电纺丝制备纳米纤维的高分子材料。
优选的，所述中间电极层的材料为银、金、铜纳米线或者掺杂银、金、铜纳米颗粒具有导电功能的纳米线。
优选的，所述接触起电层纤维膜的厚度优选范围为5-120μm；纤维膜中纤维直径范围为580-610nm。
优选的，所述底部支撑层厚度优选范围20-40μm，纤维膜中纤维直径范围为120-150nm。
优选的，所述纳米线的直径范围为150-165。
优选的，所述接触起电层为生物可降解材料聚乳酸-羟基乙酸共聚物，所述中间电极层为银纳米线，所述底部支撑层为生物可降解材料聚乙烯醇。
相应的，本发明还提供一种全纳米纤维电子皮肤的应用装置，包括上述任一项所述的电子皮肤，所述电子皮肤固定在待检测的运动部位，用于检测运动部位的实时运动状态。
优选的，根据上述的应用装置为可穿戴装置。
本发明的技术方案与现有技术相比，有下列优点：
本发明提出了一种全纳米纤维组成的电子皮肤，结合透气性、抗菌性、可降解性及自供电等性能为一体，丰富电子皮肤的功能和应用范围。该电子皮肤包括上中下三层纳米纤维膜，分别是上层接触起电层，中间电极层和底部支撑层。该电子皮肤利用纳米摩擦发电的原理，当电子皮肤受力时，在接触与分离的过程中，起电层与电极层产生电输出。本发明的电子皮肤结构简单，便于制作，功能多样，应用前景广泛。
所述上层起电层和底部支撑层均为生物可降解材料通过静电纺丝技术得到的纳米纤维膜，以提高电子皮肤生物可降解性。所述中间电极层通过银纳米线真空过滤在底层上成纳米纤维膜。银纳米线本身具有优异的广谱抗菌性，赋予了电子皮肤抗菌性。
该电子皮肤具有多层交错的纳米纤维网络和大量的三维微纳米层次孔，为接触起电和压力传感提供了高比表面积，并为热-湿传递提供了多个纤维间毛细管通道，使电子皮肤具有透气性和高输出及高压力灵敏度。
本发明的电子皮肤应用装置，包括上述技术方案中的电子皮肤。该应用装置可以实现自供电，可以作为人体全身生理和运动监测传感装置。且具有透气性、抗菌性和可降解性等多功能特性，在个人健康监控，病人康复，运动表现监控，娱乐活动人体运动追踪等方面具有很好的应用前景。
附图说明
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：
图1为本发明全纳米纤维电子皮肤的结构示意图；
图2为本发明全纳米纤维电子皮肤的平面俯视示意图；
图3为全纳米纤维电子皮肤工作原理示意图；
图4为具体全纳米纤维电子皮肤的输出电压、电流和电量曲线；
图5为具体全纳米纤维电子皮肤不同压力下的输出电压曲线；
图6为具体全纳米纤维电子皮肤不同压强下的透气性测试结果；
图7为本发明全纳米纤维电子皮肤抗菌性能测试结果；
图8为本发明全纳米纤维电子皮肤不同纤维膜的降解性能测试结果；
图9为本发明全纳米纤维电子皮肤监测人体手指和手肘不同运动角度下的运动信号。
具体实施方式
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明提供的全纳米纤维电子皮肤典型结构参见图1和图2，该电子皮肤包括上中下三层纳米纤维膜，分别是上层的接触起电层1，中间电极层2和底部支撑层3。该电子皮肤利用摩擦纳米发电机的原理，工作模式为单电极工作模式。当外界物体，比如人体皮肤，与接触起电层1进行一次接触和分离，会在中间电极层2和与之连接的地或者其他导体之间产生一个交流电信号，连续进行这种接触和分离会产生连续的交流电流，从而该电子皮肤将机械能转变为电能。接触起电层1和底部支撑层3均为生物可降解材料通过静电纺丝技术得到的纳米纤维膜。所述中间电极层2采用具有杀菌功能的导电纤维膜。
在具体制备过程中可以通过银纳米线真空过滤在底部支撑层3上形成银纳米纤维膜作为中间电极层2，将铜箔4贴于银纳米线表面作为引出电极，然后通过静电纺丝的方法，将接触起电层1覆盖在带有中间电极层2的底部支撑层3上。
接触起电层1和底部支撑层3采用的所述生物可降解材料可以包括聚乙烯醇、聚乳酸-羟基乙酸共聚物、聚己内酯、聚乳酸、聚羟基乙酸、聚丁二酸酯、聚β-羟基丁酸酯、聚氨酯、纤维素等可用于静电纺丝制备纳米纤维的高分子材料。
所述中间电极层2的材料可以包括银、金、铜等纳米线、或掺杂这些纳米颗粒具有导电功能的纳米线。
下面以一个具体的电子皮肤为例，详细描述本发明的全纳米纤维电子皮肤的性能和结构。根据电子皮肤的结构特点，其中生物可降解材料聚乳酸-羟基乙酸共聚物(PLGA)为接触起电层，银纳米线(Ag NWs)为中间电极层，生物可降解材料聚乙烯醇(PVA)为底部支撑层。
本发明的电子皮肤制备过程如下：
(1)静电纺丝方法制备底部支撑层纤维膜。PVA静电纺丝的最佳浓度为10wt％，电压为25kV，流速0.5mL/h，PVA纳米纤维直径范围120-150nm，厚度优选范围20-40μm。
(2)在底部支撑层上制备中间电极层。Ag NWs的直径范围为150-165nm，长度为120μm。使用真空抽滤的方法，沉积在底部支撑层上，然后使用铜箔(优选宽度0.5cm)贴于银纳米线表面作为引出电极与外接地或者其他导体连接，用于测量电信号输出。
(3)静电纺丝法制备接触起电层纤维膜。PLGA静电纺丝的最佳浓度为8.5wt％，电压为15kV，流速为0.45mL/h，PLGA纳米纤维直径约为580-610nm。接触起电层的纤维膜厚度可根据纺丝时间的长短调节，但是太薄了膜容易破坏，使中间电极层外漏；太厚了会影响透气性和起电性能，厚度优选范围为5-120μm。
图3为上述制备的全纳米纤维电子皮肤的工作原理示意图。基于摩擦纳米发电机单电极模式的工作原理，当外物(图中接触材料)和电子皮肤的接触起电层(PLGA)接触时，存在完全接触-分离-完全分离-接触的过程，由于摩擦起电和静电感应效应，会在中间电极层(AgNWs)与地之间发生电荷转移，从而产生交流电输出。图4为使用0.1mm厚度的聚四氟乙烯(PTFE)作为接触接触材料，电子皮肤在不同频率下的输出性能。相关测试表明，可以达到最大95V开路电压，1.5μA短路电流，30nC电荷转移量以及130mW m-2功率密度。压力灵敏度可达到0.011kPa-1，如图5所示。
图6为不同压强下电子皮肤的透气性测试结果，一般的牛仔布透气性为10mm s-1,结果表明在该电子皮肤的透气性远远高于牛仔布。原因在于结构中多层交错的纳米纤维网络和大量的三维微纳米层次孔增强了透气性。
图7为电子皮肤抗菌性能测试结果。选用金黄色葡萄球菌作为革兰氏阳性代表细菌，大肠杆菌作为革兰氏阴性代表细菌进行抗菌试验，通过菌落计数法对比加入电子皮肤共培养前后细菌的数量，计算抗菌效率。相关实验结果表明，银纳米线对于金黄色葡萄球菌和大肠杆菌均有明显抗菌性，其抗菌效率分别为87％和54％。需要说明的是通过增加银纳米线的浓度可以提高抗菌效率，同时银纳米线具有广谱抗菌性，对于多种细菌、真菌和病毒均有较好的抗菌性，因此也拓宽了电子皮肤的抗菌应用范围。
图8为不同的纳米纤维膜在放置于PBS溶液中一定时间内的降解情况，其中PVA在3天后基本完全降解，PLGA在21天后开始降解，不同的材料降解的速度不一样，因此可以通过改变材料的种类和调节不同材料的重量比例来获得不同的降解周期。
本发明还提供全纳米纤维电子皮肤的应用装置，可以将电子皮肤固定在待检测的运动部位，当待检测部位运动时，电子皮肤会产生电信号输出，可以检测运动部位的实时运动状态，并且该应用装置不需要外接电源，实现自驱动进行检测。例如可以通过借助创可贴将电子皮肤固定在人体的监测部位形成可穿戴装置，可输出人体眨眼、皱眉、脉搏、呼吸、说话、手指、手肘、膝盖、脚踝等关节运动电信号特征，从而快速实现人体全身生理和运动实时监测，使该电子皮肤在个人健康监控、病人康复、运动表现监控、娱乐活动如人体运动追踪等领域具有很大的前景。图9为该电子皮肤用于监测人体手指和手肘不同运动角度下的运动信号。相应的，该应用装置除了可以应用在人体可穿戴方面，也可以在机器人、机械运动等领域，对运动部位进行检测。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。
Claims (9)
1.一种全纳米纤维电子皮肤，其特征在于，包括上中下三层纳米纤维膜，分别是接触起电层、中间电极层和底部支撑层，其中，
所述接触起电层和底部支撑层均为生物可降解材料的纳米纤维膜；
所述中间电极层为具有杀菌功能的纳米纤维膜，与地或者其他导体电连接。
2.根据权利要求1所述的电子皮肤，其特征在于，所述生物可降解材料包括聚乙烯醇、聚乳酸-羟基乙酸共聚物、聚己内酯、聚乳酸、聚羟基乙酸、聚丁二酸酯、聚β-羟基丁酸酯、聚氨酯、纤维素中的一种或几种可用于静电纺丝制备纳米纤维的高分子材料。
3.根据权利要求1或2所述的电子皮肤，其特征在于，所述中间电极层的材料为银、金、铜纳米线或者掺杂银、金、铜纳米颗粒具有导电功能的纳米线。
4.根据权利要求1至3任一项所述的电子皮肤，其特征在于，所述接触起电层纤维膜的厚度优选范围为5-120μm；纤维膜中纤维直径范围为580-610nm。
5.根据权利要求1至4任一项所述的电子皮肤，其特征在于，所述底部支撑层厚度优选范围20-40μm，纤维膜中纤维直径范围为120-150nm。
6.根据权利要求3所述的电子皮肤，其特征在于，所述纳米线的直径范围为150-165。
7.根据权利要求1至4任一项所述的电子皮肤，其特征在于，所述接触起电层为生物可降解材料聚乳酸-羟基乙酸共聚物，所述中间电极层为银纳米线，所述底部支撑层为生物可降解材料聚乙烯醇。
8.一种全纳米纤维电子皮肤的应用装置，其特征在于，包括权利要求1-7任一项所述的电子皮肤，所述电子皮肤固定在待检测的运动部位，用于检测运动部位的实时运动状态。
9.根据权利要求8所述的应用装置为可穿戴装置。
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