CN110724307B - 一种柔性电导率稳定的可再生纤维素导电薄膜制备方法 - Google Patents
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Abstract
一种柔性电导率稳定的可再生纤维素导电薄膜制备方法,涉及一种导电薄膜制备方法,包括以下制备过程:制备水凝胶:将纤维素加入到以上三口烧瓶中,85℃条件下机械搅拌直至纤维素完全溶解,体系变为透明粘稠液体;将PEDOT:PSS/AgNWs负载在水凝胶表面:干燥成膜:将抽滤后的水凝胶取下夹在两个PTFE0.1μm的微孔膜之间,负载约50 N垂直作用力,置于60℃的鼓风干燥箱中处理,既得具有稳定电导率的可再生纤维素膜。制备的CRC薄膜具有更高的导电性。即使在高湿度环境下也具有良好的性能和长期稳定。特别有希望用于下一代电子、光电子、能源存储、软机器人和传感器设备中。
Description
技术领域
本发明涉及一种导电薄膜制备方法,特别是涉及一种柔性电导率稳定的可再生纤维素导电薄膜制备方法。
背景技术
导电膜是具有导电功能的薄膜。导电薄膜的荷电载流子在输运过程中受到表面和界面的散射,当薄膜的厚度可与电子的自由程相比拟时,在表面和界面的影响将变得显著,这个现象称为薄膜的尺寸效应。它等效于载流子的自由程减小,因此与同样材料的块体相比,薄膜的电导率较小。
柔性导电薄膜是显示器、有机薄膜晶体管、光伏器件、和电子外壳等多种柔性电子器件的关键部件之一。近年来,氧化铟锡(ITO)薄膜以其优异的电子性能和光学透明性成为应用最广泛的透明导体。然而,ITO材料的脆性、高成本和铟资源的短缺限制了ITO材料在便携式柔性器件中的大规模应用。为了应对这些挑战,金属纳米材料、导电聚合物、石墨烯、和碳纳米管等替代材料正被开发用于制造柔性导体。银纳米线(AgNWs)具有优良的电学和光学性能,以及丰富的延展性,已被广泛用于制备各种器件的导电柔性薄膜。
大多数导电材料是通过喷涂、刷涂或将AgNWs沉积在聚氨酯(PU)、聚对苯二甲酸乙二醇酯(PET)、聚二甲基硅氧烷(PDMS)和聚对苯二甲酸乙烯等柔性基底上的工艺制备的。然而,AgNWs与衬底界面接触有限且较弱,不利于维持导电网络的长期稳定,当AgNWs受到一定的弯曲变形时,会发生脱落。此外,大气中湿度高或硫化氢含量高,会加速AgNWs的老化速度,导致原有导电性能下降。因此,即使在极端的雨季或恶劣的环境中,保持导体的导电稳定性对于保证器件的正常运行是至关重要的。虽然石墨烯覆盖在AgNWs表面可以提高导体的稳定性,但成本高、界面结合强度弱等问题仍有待控制和改善。设计一种具有生物降解性、完美的机械灵活性、和高导电稳定性仍然是一个具有挑战性的目标。
发明内容
本发明的目的在于提供一种柔性电导率稳定的可再生纤维素导电薄膜制备方法,本发明低AgNWs/PEDOT:PSS负载制备的纤维素可再生薄膜具有更高的导电性,ITO材料的脆性、高成本和铟资源的短缺限制了ITO材料在便携式柔性器件中的应用,可再生纤维素膜的制备有机会替代ITO材料,具有大规模生产的前景。
本发明的目的是通过以下技术方案实现的:
一种柔性电导率稳定的可再生纤维素导电薄膜制备方法,所述方法包括以下制备过程:
步骤一、制备水凝胶:
将纤维素加入到以上三口烧瓶中,85℃条件下机械搅拌直至纤维素完全溶解,体系变为透明粘稠液体;
采用旋转涂布的方法将透明粘稠液体均匀置于抛光的硅片载体,并置入温度85℃,真空度为0.01MPa的真空干燥相中脱气处理,最终既得均匀透明[Bmim]Cl/纤维素体系;
接着放入30℃蒸馏水域中,待水分子完全置换掉[Bmim]Cl离子液体后,均匀透明水凝胶形成;
步骤二、将PEDOT:PSS/AgNWs负载在水凝胶表面:
用直径4.2cm的水凝胶作为过滤器,放置在砂芯过滤装置上;PEDOT:PSS和AgNWs逐滴加入纯化去离子水中;将混合溶液超声处理,然后将混合溶液转移到过滤装置中,通过真空抽滤法过滤去离子水,得到均匀PEDOT:PSS/AgNWs负载在水凝胶表面;
步骤三、干燥成膜:
将抽滤后的水凝胶取下夹在两个PTFE0.1μm的微孔膜之间,负载约50 N垂直作用力,置于60℃的鼓风干燥箱中处理,既得具有稳定电导率的可再生纤维素膜。
所述的一种柔性电导率稳定的可再生纤维素导电薄膜制备方法,所述柔性电导率稳定的可再生纤维素导电薄膜应用于应变传感器和微型超级电容器中。
本发明的优点与效果是:
本发明采用界面工程的方法,研制出一种柔性、透明、稳定的导电薄膜。与其他常规制备方法相比,低AgNWs负载制备的CRC薄膜具有更高的导电性。改进的性能归功于PEDOT:PSS与AgNWs的桥接作用以及由此形成的均匀导电网络。配位络合与H键的协同作用使CRC膜具有较强的界面稳定性和抗氧化性能。即使经过500轮弯曲(角度可达180°)、400多轮粘贴剥落、浸泡在水中30天、高温高湿60天(90%RH,65℃)等处理后,CRC薄膜仍然保持着较高的导电性和良好的柔韧性,没有发生明显的降解。并对该薄膜作为电子皮肤传感器和微型超级电容器(MSC)储能装置的实际应用进行了说明,该薄膜即使在高湿度环境下也具有良好的性能和长期稳定。CRC薄膜特别有希望用于下一代电子、光电子、能源存储、软机器人和传感器设备中。
本发明提高柔性导体的导电稳定性对便携式电子器件的工作性能和使用寿命具有积极的影响。然而,由于导电网络在大变形或高湿度条件下的损伤,设计一种兼具导电稳定性和良好柔韧性能的材料仍然不是一件容易的事情。本发明通过开发一种界面工程策略来克服这一挑战,用于构建柔性、透明、电导率稳定的薄膜。在配位络合和氢键的协同作用下,银纳米线(AgNWs)被再生纤维素薄膜(作为柔性衬底)和PEDOT:PSS纳米片(作为导电桥梁和覆盖层)夹覆。所得到的薄膜具有健壮的接口体系结构和显著的稳定性能。即使受到条件如暴露于相对湿度90%和温度65℃的环境中为期60天,重复弯曲500次,表面粘贴超过400次或在水中浸泡30天,薄膜仍表现出高稳定性的电导率的11.3Ωsq-1。利用这种导体,展示了一种灵活、透明、生物相容性强的应变电传感器和微型超级电容器,该器件以可再生材料为基础,具有很高的工作稳定性,具有大规模生产的前景。
本发明所提供的方法具有成本低、产品性能环保、改性效果显著的优点。
附图说明
图1为CRC膜光学照片;(透明性与柔韧性)
图2为CRC膜SEM图像;
图3为不同AgNWs负载量的CRC膜的拉伸应力-应变曲线;
图4为不同AgNWs负载量的CRC膜的透光率;
图5为不同AgNWs负载量的CRC膜含的电阻;
图6为本发明与两种传统制膜方法在相同条件下180°弯曲500次电阻变化情况;
图7为本发明与两种传统制膜方法在相同条件下水环境浸泡30天电阻变化情况;
图8为本发明与两种传统制膜方法在相同条件下胶带剥离后电阻变化情况;
图9为具有良好透明性和灵活性的CRC薄膜应变传感器的光学图像;
图10为传感器对不同压力响应的电流波形;
图11为将传感器置于RH 90%和t25℃环境中30天后对压力响应电流波形;
图12为CRC膜作为集流体在微型电容器中的应用;
图13为在6m KOH电解质浸润的微型电容器交流电行为;
图14为扫描速率为50 - 800mv /s时的循环伏安曲线。
具体实施方式
下面结合附图所示实施例对本发明进行详细说明。
本发明采用界面工程的方法,研制出一种柔性、透明、稳定的导电薄膜。与其他常规制备方法相比,虽然低AgNWs负载量但制备的导电薄膜具有更高的导电性。
本发明采用绿色环保溶剂置换方法制备导电膜基材水凝胶。本发明采用简单的绿色溶剂置换方法制备高性能的纤维素膜。首先,采用旋转涂布方法将1丁基3甲基咪唑氯([Bmim]Cl)/纤维素体系均匀置于抛光硅片载体上;然后采用溶剂置换方法将其放入蒸馏水池中,直至转化为透明水凝胶材料;
本发明配位络合与H键的协同作用使薄膜具有较强的界面稳定性和抗氧化性能。配位键,又称配位共价键,是一种特殊的共价键。当共价键中共用的电子对是由其中一原子独自供应,另一原子提供空轨道时,就形成配位键。成键的两原子间共享的两个电子不是由两原子各提供一个,而是来自一个原子。
络合反应也称配位反应,络合是电子对给予体与电子接受体,互相作用而形成各种络合物的过程。给予体有原子或离子,不论构成单质或化合物,凡能提供电子对的物质,接受体有金属离子和有机化合物。分子或者离子与金属离子结合,形成很稳定的新的离子的过程。
氢键,氢原子与电负性大的原子X以共价键结合,若与电负性大、半径小的原子Y(OF N等)接近,在X与Y之间以氢为媒介,生成X-H…Y形式的一种特殊的分子间或分子内相互作用。[X与Y可以是同一种类分子,如水分子之间的氢键;也可以是不同种类分子,如一水合氨分子(NH3·H2O)之间的氢键]。
纤维素的丰富性、可再生性和环境可持续发展性使其在储能、热电装置、有机光电子和柔性电子等方面具有潜在的用途。纤维素分子链间氢键的解离使纤维素容易溶解在离子液体(IL)中。通过简单的相转换方法,可以获得柔性、韧性好的水凝胶材料。本发明中,水凝胶可以作为一种基材,无需用胶粘连AgNWs。
聚(3,4 -乙烯二氧噻吩)-聚苯乙烯磺酸盐(PEDOT:PSS)是一种具有内在柔性和溶液可加工性的导电聚合物,是一种极具应用前景的柔性导体。在AgNWs的上表面,PEDOT:PSS液体沉积并覆盖AgNWs。在60℃24 h干燥过程中,水凝胶和PEDOT:PSS之间形成复杂的界面连接,AgNWs被封装在水凝胶和PEDOT:PSS之间,三者紧密结合,这种结构具有较强的界面粘结强度和良好的导电性稳定性。得到了一种导电可再生纤维素膜(CRC膜),它灵活可任意折叠,且电导率稳定。
实施例1
步骤一、制备水凝胶
将1.55g纤维素(3wt.%)加入到以上三口烧瓶中,85℃条件下机械搅拌直至纤维素完全溶解,体系变为透明粘稠液体,时间约为1.5h。
采用旋转涂布的方法将透明粘稠液体均匀置于抛光的硅片载体,并置入温度85℃,真空度为0.01MPa的真空干燥相中脱气处理约12h,最终既得均匀透明[Bmim]Cl/纤维素体系。
接着放入30℃蒸馏水域中,待水分子完全置换掉[Bmim]Cl离子液体后(约60min),均匀透明水凝胶形成。
步骤二、将PEDOT:PSS/AgNWs负载在水凝胶表面
用直径4.2cm的水凝胶作为过滤器,放置在砂芯过滤装置上。PEDOT:PSS(2.4mg)和AgNWs(1.2mg)逐滴加入30g纯化去离子水中。将混合溶液超声处理30min,然后将3g混合溶液转移到过滤装置中,通过真空抽滤法过滤去离子水,得到均匀PEDOT:PSS/AgNWs负载在水凝胶表面。
步骤三、干燥成膜
将抽滤后的水凝胶取下夹在两个PTFE0.1μm的微孔膜之间,负载约50 N垂直作用力,置于60℃的鼓风干燥箱中处理12h,既得具有稳定电导率的可再生纤维素膜。
性能测试:
采用场发射扫描电子显微镜(SEM)和Tecnai G2透射电镜(TEM)观察可再生纤维素膜的微观结构;采用高灵敏度万能力学试验机测试可再生纤维素膜机械拉伸力学性能;采用TU-1901分光光度计测定了薄膜的透光率;采用手持四探针M-6测试仪测量薄膜的片材电阻值;采用CHI 700E电化学工作站对微型电容器的循环伏安和恒流充放电电化学性能进行了研究。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (2)
1.一种柔性电导率稳定的可再生纤维素透明导电薄膜制备方法,其特征在于,所述方法包括以下制备过程:
步骤一、制备水凝胶:
将纤维素和[Bmim]Cl离子液体加入到三口烧瓶中,85℃条件下机械搅拌直至纤维素完全溶解,体系变为透明粘稠液体;
采用旋转涂布的方法将透明粘稠液体均匀置于抛光的硅片载体,并置入温度85℃,真空度为0.01MPa的真空干燥箱中脱气处理,最终即得均匀透明[Bmim]Cl/纤维素体系;
接着放入30℃蒸馏水浴中,待水分子完全置换掉[Bmim]Cl离子液体后,均匀透明水凝胶形成;
步骤二、通过配位络合与氢键的协同作用将PEDOT:PSS/AgNWs负载在水凝胶表面:
用直径4.2cm的水凝胶作为过滤器,放置在砂芯过滤装置上;PEDOT:PSS和AgNWs逐滴加入纯化去离子水中;将混合溶液超声处理,然后将混合溶液转移到过滤装置中,通过真空抽滤法过滤去离子水,得到均匀PEDOT:PSS/AgNWs负载在水凝胶表面;
步骤三、干燥成膜:
将抽滤后的水凝胶取下夹在两个PTFE0.1μm的微孔膜之间,负载约50 N垂直作用力,置于60℃的鼓风干燥箱中处理,即得具有稳定电导率的可再生纤维素膜。
2.根据权利要求1所述的一种柔性电导率稳定的可再生纤维素透明导电薄膜制备方法,其特征在于,所述柔性电导率稳定的可再生纤维素导电薄膜应用于应变传感器、微型超级电容器。
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