CN106183142B - 一种基于石墨烯纤维无纺布的自热膜 - Google Patents
一种基于石墨烯纤维无纺布的自热膜 Download PDFInfo
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Abstract
本发明公开了一种基于石墨烯纤维无纺布的自热膜及其制备方法。该自热膜由光伏薄膜作为能量层提供电压和电流,并利用石墨烯纤维无纺布的电致发热效应构成发热层,能量层与发热层中间由隔热材料隔开。由于石墨烯纤维无纺布具有高的导电率和相对较低的密度,因此能够在较低的工作电压下获得较大的发热温度和较高的升温、降温速率。同时,石墨烯纤维无纺布具有高柔性和结构稳定性,该自热膜在弯曲状态下依然能够表现出稳定的发热行为,因此这种基于石墨烯纤维无纺布的自热膜可用于新型清洁能源的可穿戴式发热器件。
Description
技术领域
本发明涉及电热膜,尤其涉及一种基于石墨烯纤维无纺布作为发热元件的自热膜。
背景技术
电致发热是电流通过导体时使导体产生热量的现象,从而将电能转化成导体的内能。电流所产生的热量遵循焦耳定律,即热量与电流的平方、电阻值和通电时间成正比(Q=I2Rt)。在纯电阻电路中,热量与施加的电压的平方成正比,与导体的电阻值成反比(Q=(U2/R)t)。由碳材料制成的电致发热材料具有电热转换效率高,使用寿命长等优异性能,并且能够发出对人体有益的远红外线辐射。因此与传统的金属等电热材料相比,呈现出较为明显的优势。
石墨烯作为近年来备受关注的碳纳米材料,可由石墨为原料通过化学剥离法大量制备,其宏观组装体如薄膜等还原后的导电性较高,将其用作电热材料时具有均匀的温度分布,加之石墨烯薄膜良好的柔性,因此是一种理想的电致发热材料,可应用于玻璃除雾、机翼除冰等用途(Nano Lett.,2011,11(12):5154-5158;Chem.Mater.,2014,26(23):6786-6795)。其在可穿戴柔性电热膜方面的应用同样具有较大的潜力,相关器件的制备有待开发。
发明内容
本发明针对目前石墨烯电热薄膜材料工作电压高、发热速度慢、饱和温度低等不足提出一种基于石墨烯纤维无纺布的自热膜,石墨烯纤维无纺布作为该自热膜的发热层材料具有导电率高、密度低的优势,因此可在较低的工作电压下快速发热,达到高的饱和温度。同时,将柔性的光伏薄膜作为能量层与石墨烯纤维无纺布发热层整合,能够得到柔性的自发热膜,在弯曲时发热性能不发生变化。
本发明通过以下技术方案实现:一种基于石墨烯纤维无纺布的自热膜,所述自热膜包括能量层和发热层,以及位于能量层和发热层之间的隔离层,所述能量层的两极分别与发热层的两端相连,形成闭合回路;所述能量层由柔性光伏薄膜构成,所述发热层由石墨烯纤维无纺布构成。
进一步地,所述能量层的一端与发热层的一端通过开关相连。
进一步地,所述隔离层由热隔离材料构成。
进一步地,所述石墨烯纤维无纺布由直径为1~1000μm的石墨烯纤维相互搭接形成网络结构,网格节点处的石墨烯纤维之间相互融合,所述石墨烯纤维由石墨烯片沿轴向定向排列而成。
进一步地,所述石墨烯纤维无纺布通过以下方法制备得到:
(1)配置浓度为1~15mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.01~10mL/min挤出速度通过直径为10~1000μm的纺丝管进入乙酸乙酯凝固液中,凝固液中浸泡30~200min后凝固成丝,真空抽滤收集,室温放置5-30h,60℃真空干燥,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇的混合液(水:乙醇的体积比=3:1~1:3)中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布还原,得到石墨烯纤维无纺布。
进一步地,凝固液置于可旋转的容器中,通过控制容器的旋转速度与纺丝液挤出速度的比值,使得石墨烯纤维的长度在2mm以上。
进一步地,收集石墨烯短纤维的滤网为孔径在0.2~100μm范围的微孔滤膜、纱网或不锈钢金属网。
进一步地,还原方法为使用氢碘酸、水合肼、维他命C、硼氢化钠等化学还原剂进行还原或100~3000℃热还原。
本发明与现有技术相比,具有的优势如下:
(1)基于溶液法连续纺丝得到的石墨烯纤维无纺布制备工艺简单,易于得到大面积的面状电热材料。
(2)制得的自热膜可在远低于人体安全电压的范围内高效率工作,升温和降温速率快,饱和温度高。
(3)制得的自热膜柔性好,在弯曲状态下发热性能不改变。
(4)光伏薄膜使用清洁能源,使自热膜器件工作时更节能环保。
附图说明
图1是自热膜器件的示意图,光伏薄膜为能量层,石墨烯纤维无纺布为发热层,中间为隔热材料构成的隔离层。能量层的两极与发热层的两端相连,在一端设有开关。
图2为发热层的扫描电镜图。
具体实施方式
本发明公开了一种基于石墨烯纤维无纺布的自热膜,包括能量层和发热层,以及位于能量层和发热层之间的隔离层,所述能量层的两极分别与发热层的两端相连,形成闭合回路;所述能量层由柔性光伏薄膜构成,所述发热层由石墨烯纤维无纺布构成。石墨烯纤维无纺布的纤维之间相互融合,接触电阻较低,因此无纺布整体的导电性和导热性都较高,同时,石墨烯纤维无纺布是一种多孔的二维薄膜状材料,其密度与之前的石墨烯薄膜和石墨烯纸相比相对较低。将其用作电致发热材料,该电热织物在较低的工作电压下即可达到快速的电热响应和高的饱和温度。另一方面,石墨烯纤维无纺布具有较好的柔性和结构稳定性,在弯曲状态下不发生结构破坏和由此而导致的电阻变化,因此该电热织物在自然状态和弯曲状态下的发热行为相同。
为搭建仅由石墨烯构成的网络结构的无纺布,本发明通过将湿纺得到的氧化石墨烯纤维组成的薄膜重新分散、沉积,得到纤维搭接、形状平整的氧化石墨烯无纺布结构,重新分散、沉积(即步骤3)使步骤2得到的团聚的石墨烯纤维重新分散在溶液中,同时纤维含有的溶剂量大大减少,从而显著降低氧化石墨烯纤维在干燥过程中的体积收缩,使得氧化石墨烯纤维无纺布的结构能够保持,解决了湿纺纤维溶剂脱除过程中由于严重的体积收缩而无法成型为无纺布的技术问题,最终得到的石墨烯纤维无纺布显现出密度低,孔隙率高,比表面积大的特点。此外,重新分散后的氧化石墨烯纤维呈低程度的溶胀状态,纤维表面结构疏松,因此沉积时在相互搭接的节点处会发生融合,纤维之间不再是较弱的摩擦力,能提供更多的强π-π相互作用。同时,纤维融合后形成整体式的传导网络,避免了传导过程中在纤维搭接处跃迁所导致的能量损耗,因此具有更好的导电导热性能。
本发明进一步将石墨烯纤维无纺布用作发热层,并由现有的柔性的光伏薄膜提供能量,中间添加隔热材料,得到了具有柔性和优良发热效率的自热膜。
下面通过实施例对本发明进行具体描述,本实施例只用于对本发明做进一步的说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整,均属于本发明的保护范围。
实施例1:
(1)配置浓度为5mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.04mL/min挤出速度通过直径为130μm的纺丝管进入乙酸乙酯旋转凝固液中,凝固液中浸泡30min后凝固成长度在2mm以上的氧化石墨烯短纤维,真空抽滤收集,室温放置10h,60℃真空干燥3h,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇按表1所示的体积比组成的混合液中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布经3000℃热还原得到石墨烯纤维无纺布。得到的无纺布的性质如表1所示。
表1水和乙醇体积比对制备石墨烯纤维无纺布的影响
(5)以水和乙醇按体积比3:1组成的混合液条件下获得的产物作为发热层,将其裁成条状,两端刷涂导电银胶并粘贴导电铜箔作为电极。
(6)将封装在聚合物薄膜中的1.5V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关,由此得到柔性自热膜。
经过以上步骤,得到的自热膜发热温度为40℃,通电时升温速率20℃s-1,断电时降温速率10℃s-1。自热膜弯曲时发热温度和速率不变。
实施例2:
(1)配置浓度为5mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.06mL/min挤出速度通过直径为200μm的纺丝管进入乙酸乙酯旋转凝固液中,凝固液中浸泡30min后真空抽滤收集,室温放置10h,60℃真空干燥3h,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇按体积比3:1的混合液中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布经3000℃热还原得到石墨烯纤维无纺布,如图2所示。
(5)将步骤4得到的石墨烯纤维无纺布裁成条状,两端刷涂导电银胶并粘贴导电铜箔作为电极。
(6)将封装在聚合物薄膜中的2V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关,由此得到柔性自热膜。
经过以上步骤,得到的自热膜发热温度为45℃。自热膜弯曲时发热温度和速率不变。
实施例3:
步骤1-5同实施例1。
(6)将封装在聚合物薄膜中的2V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关,由此得到柔性自热膜。
经过以上步骤,得到的自热膜发热温度为50℃,通电时升温速率55℃s-1,断电时降温速率58℃s-1。自热膜弯曲时发热温度和速率不变。
实施例4:
步骤1-5同实施例1。
(6)将3V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关。
经过以上步骤,得到的自热膜发热温度为79℃,通电时升温速率135℃s-1,断电时降温速率134℃s-1。
Claims (7)
1.一种基于石墨烯纤维无纺布的自热膜,其特征在于,所述自热膜包括能量层和发热层,以及位于能量层和发热层之间的隔离层,所述能量层的两极分别与发热层的两端相连,形成闭合回路;所述能量层由柔性光伏薄膜构成,所述发热层由石墨烯纤维无纺布构成;所述石墨烯纤维无纺布由直径为1~1000μm的石墨烯纤维相互搭接形成网络结构,网格节点处的石墨烯纤维之间相互融合,所述石墨烯纤维由石墨烯片沿轴向定向排列而成。
2.根据权利要求1所述的自热膜,其特征在于,所述能量层的一端与发热层的一端通过开关相连。
3.根据权利要求1所述的自热膜,其特征在于,所述隔离层由热隔离材料构成。
4.根据权利要求1所述的自热膜,其特征在于,所述石墨烯纤维无纺布通过以下方法制备得到:
(1)配置浓度为1~15 mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液;
(2)使纺丝液以0.01~10 mL/min挤出速度通过直径为10~1000 μm的纺丝管进入乙酸乙酯凝固液中,凝固液中浸泡30~200 min后凝固成丝,真空抽滤收集,室温放置5-30 h,60 °C真空干燥,得到氧化石墨烯纤维组成的薄膜;
(3)将步骤2得到的薄膜在水和乙醇按照体积比=3:1~1:3组成的混合液中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80 °C干燥;
(4)将干燥后的氧化石墨烯纤维无纺布还原,得到石墨烯纤维无纺布。
5. 根据权利要求4所述的自热膜,其特征在于,凝固液置于可旋转的容器中,通过控制容器的旋转速度与纺丝液挤出速度的比值,使得氧化石墨烯纤维的长度在2 mm以上。
6. 根据权利要求4所述的自热膜,其特征在于,收集氧化石墨烯纤维的滤网为孔径在0.2~100 μm范围的微孔滤膜、纱网或不锈钢金属网。
7. 根据权利要求4所述的自热膜,其特征在于,还原方法为使用氢碘酸、水合肼、维他命C、硼氢化钠进行还原或100~3000 °C热还原。
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