CN112533307A - 带有薄膜电极的远红外发热体 - Google Patents
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Abstract
一种带有薄膜电极的远红外发热体,包括电路组件以及发热体组件,电路组件包括变压整流电路;发热体组件由内向外依次包括隔热层、发热层、绝缘层,发热层包括碳制片状电热材料、设置在电热材料两侧的电极,其技术要点是:电热材料由碳纳米管制成的复合纤维纱线纺织而成;绝缘层通过模具预先制成“浮雕结构”;绝缘层上还设有电致变色层,并且电致变色层构成的电阻单元与发热层构成的电阻单元相互并联;电路组件还包括与电致变色层电性连接的PWM调制模块;电极为覆盖在电热材料上的薄膜电极。其具有结构简单紧凑、更轻更薄、使用方便、热转化效率高、环保节能、使用寿命更长等优点。
Description
技术领域
本发明涉及电发热体领域,具体说是一种带有薄膜电极的远红外发热体。其IPC分类号为H05B3/20。
背景技术
现有的远红外发热板画的发热层大多采用碳晶或碳纤维发热纸,其技术方案中由内到外依次设置隔热层、发热层、图片层。发热层采用含有碳纤维的发热纸,发热纸两侧固定铜片作为电极,在铜片之间加载市电即可产生远红外辐射。一方面,由于碳纤维纸的柔韧性相对较差,另一方面,由于碳纤维发热纸的材质特性并不利于油墨的印刷,因此在设置图画层时,通常通过采用另外的画布,以叠加的方式制备而成。但由于该发热层自身材料理化特性的限制,无法简化其整体结构。如果采用叠加画布层的方式,还会影响其散热效果,对产品的悬挂位置和悬挂方式造成了极大限制。
发明内容
本发明的目的是提供一种带有薄膜电极的远红外发热体,从根本上解决了上述问题,其具有结构简单紧凑、更轻更薄、使用方便、热转化效率高、环保节能、使用寿命更长等优点。无需外接电源即可长时间使用,更利于市场推广。
为实现上述目的,本发明提供了如下技术方案:该带有薄膜电极的远红外发热体,包括电路组件以及发热体组件,电路组件包括变压整流电路;发热体组件由内向外依次包括隔热层、发热层、绝缘层,发热层包括碳制片状电热材料、设置在电热材料两侧的电极,其技术要点是:
电热材料由碳纳米管制成的复合纤维纱线纺织而成;
绝缘层通过模具预先制成“浮雕结构”;
绝缘层上还设有电致变色层,并且电致变色层构成的电阻单元与发热层构成的电阻单元相互并联;
电路组件还包括与电致变色层电性连接的PWM调制模块;
电极为覆盖在电热材料上的薄膜电极。
进一步的,“浮雕结构”采用硅胶或塑料或表层带有绝缘膜的金属薄板。
进一步的,电致变色层表面喷涂透明的保护层。
本发明还提供了上述带有薄膜电极的远红外发热体的制备方法,其技术要点是,包括以下步骤:
步骤1,预先设计绝缘层的浮雕结构、电致变色变色位置,并分别制作碳纳米管复合纤维纱线和电致变色层,备用;
步骤2,将碳纳米管复合纤维纱线纺织成发热层织物,将发热层织物与隔热层结合后,裁切至预定尺寸,得到复合结构I;
步骤3,在复合结构I贴合绝缘层的浮雕结构,得到复合结构II;
步骤3-1,制备自修复高分子薄膜:取1.0~22.8重量份的聚二酸和0.5~9.0重量份的二乙烯三胺在氩气气氛下120~160℃搅拌12~36h;产物用50~100重量份的氯仿溶解,再分别以50~100重量份去离子水和20~50重量份的甲醇洗涤,通过旋转蒸发除去溶剂,得到自修复高分子;
取0.1~1重量份上述自修复高分子溶解于1~10重量份三氯甲烷获得均一溶液,将此溶液滴加于清洁玻璃片上,室温下挥发溶剂0.5~2h,50~80℃烘干15~30min,蒸干溶剂,获得自修复高分子薄膜;
步骤3-2,制备取向碳纳米管阵列:通过化学气相沉积法合成可纺的碳纳米管阵列,化学气相沉积得到可纺的碳纳米管阵列;
催化剂为等质量的平均粒度1~2nmFe和平均粒度8~12nmAl2O3的混合物;
碳源为乙烯;
气相载体为等体积氩气和氢气的混合气体;
步骤3-3,制备可拼接电极:将取向碳纳米管薄膜直接从碳纳米管阵列中拉出,正交铺排于自修复聚合物薄膜表面组成复合膜,并将多块复合膜拼接,得到取向碳纳米管/自修复聚合物的平面电极;
步骤4,在复合结构II的绝缘层上粘贴电致变色层,组装电路组件并通电测试,测试通过后,在电致变色层表面喷涂透明的抗氧化保护薄层,通风处晾干固化即得成品。
进一步的,上述步骤1中发热层的碳纳米管复合纤维纱线的制备方法包括以下步骤:
步骤1.1,将涤纶纱线浸入3wt%的NaOH溶液中,90~110℃浸泡2~5min后取出洗涤4~6次,晾干后得到涤纶纱线基材;
步骤1.2,将质量比20:1:4的碳纳米管、3-黄丙基十四烷基二甲甜菜碱、聚氧乙烯十二烷基磺酸醚依次加入定量的去离子水中,随后倒入超声波清洗器中,30~50℃、40~60Hz下振荡35~45min至分散均匀,得到碳纳米管悬浮液;
步骤1.3,将涤纶纱线基材浸入碳纳米管悬浮液中,30~50℃浸染3~7min,得到复合涤纶纱线I;
步骤1.4,将复合涤纶纱线I置于干燥炉中,110~130℃干燥2~4min,取出后浸入70~90℃的等质量比的水性聚氨酯和丁腈橡胶的水溶液中,得到复合涤纶纱线II;
步骤1.5,将复合涤纶纱线II置入固化炉中,50~70℃固化成型2~4min,得到发热层复合纤维纱线。
本发明的有益效果:将碳纤维与涤纶织物完美结合,避免了现有碳晶发热体理化性质差的问题,兼具涤纶纤维和碳纤维发热体的优点。碳纳米管的引入不仅提升了纤维的导电性,还利于聚吡咯在纤维表面形成致密层,从而进一步提升修饰后织物的电性能。
棉纤维表面进行MWCNTs沉积之前,将MWCNTs采用H2SO4/HNO3(3:1)进行表面改性处理以引入羧基、羟基等亲水性功能基团。纤维表面沉积MWCNTs层后,采用界面聚合的方式进行PPy层构筑。MWCNTs表面活性基团可与PPy单元形成氢键,同时由于MWCNTs天然的芳香性,还可以与PPy产生π键相互作用,使得纤维表面沉积的PPy层更为致密。
纤维织物展现出优异的机械稳定性,在扭曲、弯曲、折叠等循环测试中仍保持良好的电性能。采用碱减法对涤纶纱线进行界面处理,提高了涤纶纱线限位的复合牢度,更易印染。采用碳纳米管涂覆涤纶纱线纤维制备高导热、热柔性发热丝,降低了发热丝的制备难度、缩短了制备周期;与金属发热丝相比,手感轻薄、透气性强、耐折性好;与非金属复合加热材料,如碳纤维及聚合物混合的制备方法相比,工艺简单,过程可控,且制备的复合织物既具有碳纳米管的导电性能,又能保持基体织物的机械性能。
图像层由耐热颜料印刷,耐热颜料例如有机颜料,通过印刷的方式可实现高效批量化生产。相较于现有的碳纤维/碳晶发热体(工作温度95~150℃),在本发明发热层两端施加3.5V~7.5V电压时,工作温度通常在20~75℃,而耐热颜料可在该温度范围内保持稳定,不会发生褪色、变色、分解等现象。另外,即使考虑到发热层热量的积聚效应,在最高工作温度的基础上增加20%~40%,现有的颜料完全可满足需求。
由于采用复合纤维织物替代了电极结构,突破了锂电池厚度与工艺难度相关性的限制,通过同一工艺条件即可制得更薄的带有电源的复合发热结构,进而提高了产品的适用范围,且外形更为简洁美观。螺旋纤维锂电池无需弹性基底即可实现拉伸性能,减轻了器件的重量和体积,提高了器件的比容量和能量密度。具有良好的柔韧性,易于编织、抗拉伸,耐久度更高。
将发热层上的绝缘层设置成浮雕效果,并在浮雕图层上粘贴电致变色层,可配合图像的内容进行局部颜色变化。具体而言,在电致变色层的输入端上连接PWM调制模块(现有技术中,如智能设备上的呼吸灯,本发明中仅采用其调压功能),根据脉冲序列的周期为2560ms,即约2.5s;经积分模块积分运算后可输出2.5s周期近似正弦的驱动功率,驱动改变电致变色层两端的电压,使其循环变色,通过电致变色层的不同种类颜色、同种类颜色不同深浅度的交替变化。从而产生意想不到的视觉效果,例如枫叶图像,可通过电致变色实现绿、黄、红颜色的转化,以呈现不同季节。例如,风吹过大树,树叶在深绿与浅绿色之间交替变化。又如,瀑布水流、泛光湖面等蓝色、白色交替的水流效果。
附图说明
图1为本发明其中一种实施例的剖视结构示意图。
图2为本发明另一种实施例的剖视结构示意图。
附图标记说明:
1 隔热层
2 发热层
3 绝缘层
4 电致变色层
5 薄膜电极
具体实施方式
以下结合图1~2,通过具体实施例详细说明本发明的内容。
实施例1
该带有薄膜电极的远红外发热体,包括电路组件以及发热体组件,电路组件(图中未示出)包括变压整流电路、与电致变色层电性连接的PWM调制模块;发热体组件由内向外依次包括隔热层1、发热层2、绝缘层3,隔热层1优选采用具有防止热量散失及单面反射热辐射的功能,例如在泡沫材料或纤维材料等表面粘贴铝箔或金属聚氨酯(隔热材料属于本领域的公知常识,本实施例仅以常见的隔热材料方案举例),发热层2包括碳制片状电热材料、设置在电热材料两侧的电极。例如,采用现有的铜电极,将铜片粘接或缝合在发热层两端,也可直接将电热材料两端加厚作为电极使用。进一步优选的,电极采用覆盖在电热材料上的薄膜电极。
电热材料由碳纳米管制成的复合纤维纱线纺织而成;绝缘层可采用硅胶或塑料或表层带有绝缘膜的金属薄板,通过模具预先制成“浮雕结构”。具体而言,当采用硅胶时,通过灌模工艺获得所需形状的硅胶绝缘层;当采用塑料时,通过金属模具注塑工艺获得所需的绝缘层;当采用金属薄板时,通过冲压工艺获得所需的金属板形状,而后在表面喷涂绝缘漆或贴塑料膜。绝缘层上还设有电致变色层4,并且电致变色层4构成的电阻单元与发热层构成的电阻单元相互并联,电致变色层4表面喷涂透明的保护层,如透明绝缘漆(如市售的“凡立水”)。
通常情况下,电致变色层采用的复合物具有以下性质,当两端电压差为0V时,呈现第一种颜色;当两端电压差达到临界值时,正负极呈现不同的颜色。对于其中几种主要的复合物在通断电流状态下所呈现的不同颜色如下表所示。
上述远红外发射体的制备方法优选采用以下制备方法。
步骤1,预先选定印刷的图案、尺寸、图像上的变色位置,并分别制作发热层复合纤维纱线和电致变色层,备用;
发热层的碳纳米管复合纤维纱线的制备方法包括以下步骤:
步骤1.1,将涤纶纱线浸入3wt%的NaOH溶液中,90~110℃浸泡2~5min后取出洗涤4~6次,晾干后得到涤纶纱线基材;
步骤1.2,将质量比20:1:4的碳纳米管、3-黄丙基十四烷基二甲甜菜碱、聚氧乙烯十二烷基磺酸醚依次加入定量的去离子水中,随后倒入超声波清洗器中,30~50℃、40~60Hz下振荡35~45min至分散均匀,得到碳纳米管悬浮液;
步骤1.3,将涤纶纱线基材浸入碳纳米管悬浮液中,30~50℃浸染3~7min,得到复合涤纶纱线I;
步骤1.4,将复合涤纶纱线I置于干燥炉中,110~130℃干燥2~4min,取出后浸入70~90℃的等质量比的水性聚氨酯和丁腈橡胶的水溶液中,得到复合涤纶纱线II;
步骤1.5,将复合涤纶纱线II置入固化炉中,50~70℃固化成型2~4min,得到发热层复合纤维纱线。
步骤2,将发热层复合纤维纱线纺织成发热层织物,将发热层织物与隔热层结合后,裁切至预定尺寸,得到复合结构I;
步骤3,将复合结构I作为画布印刷所需的图画,得到复合结构II;
步骤4,在复合结构II上依次粘贴薄膜电极和电源,得到成品。
以下以碳纳米管/聚苯胺复合物和碳纳米管/钨酸钠复合物的制备过程为例,当采用其他成分时,碳纳米管/非金属复合物的制备过程参考1.1,碳纳米管/金属复合物的制备过程参考1.2。
碳纳米管/聚苯胺复合物的制备:
步骤1,聚二甲硅氧烷及固化剂以质量比5:1混合倒入培养皿中脱气,10℃固化0.5h,取出,裁切成特定大小,制得薄膜基底;
步骤2,取碳纳米管溶于无水乙醇中,在室温下置于超声波清洗器中分散1h,即得碳纳米管溶液;
步骤3,在薄膜基底上旋涂碳纳米管溶液,待分散剂自然挥发干燥后,进行二次旋涂,干燥后进行三次旋涂,即得碳纳米管薄膜;
步骤4,在碳纳米管薄膜上电沉积聚苯胺;
步骤5,在步骤4所得的复合结构表面覆绝缘膜;
步骤6,撤去聚二甲基硅氧烷薄膜,得到碳纳米管/聚苯胺复合物。
碳纳米管/钨酸钠复合物的制备:
步骤1~3同1.1中碳纳米管/聚苯胺复合物的制备的步骤1~3;
步骤4,向钨酸钠溶液中加入适量的双氧水和0.1M硫酸,将碳纳米管薄膜作为负极,以铂片作为正极,在恒电流下沉积100s,得到WO3薄膜;
步骤5,在步骤4所得的复合结构表面覆绝缘膜;
步骤6,撤去聚二甲基硅氧烷薄膜,得到碳纳米管/钨酸钠复合物。
实施例2
本实施例为小试制备螺旋纤维锂电池的过程,包括以下步骤:
步骤1,制备凝胶电解液:
步骤101,将等质量的聚(偏二氟乙烯-co-六氟丙烯)与N-甲基吡咯烷酮混合,搅拌均匀后得到溶液A;
步骤102,将等质量比的高氯酸锂与碳酸二乙酯混合,搅拌均匀后得到溶液B;
步骤103,将2-羟基-2-甲基-1-苯基-1-丙酮加入到100倍其重量的乙氧基化三羟甲基丙烷三丙烯酸酯中,搅拌均匀后得到溶液C;
步骤104,将等质量的溶液A、溶液B和溶液混合,搅拌均匀后即得凝胶电解液;
步骤2,将连有细铜丝集流体的锂丝全部浸入到凝胶电解液中5~10s后取出,紫外光照5~20s,使凝胶电解液前驱体固化;
步骤3,重复步骤2,直至锂丝被凝胶电解液完全包覆;
步骤4,在经步骤3得到的锂丝上缠绕厚度为100μm的作为碳纳米管空气电极的取向碳纳米管薄膜,得到复合结构;
步骤5,在步骤4得到的复合结构上覆绝缘膜,然后加捻形成螺旋形,得到螺旋纤维锂电池。
实施例3
本实施例为小试制备薄膜电极的过程,包括以下步骤:
步骤1,制备自修复高分子薄膜:取1.0~22.8g聚二酸和0.5~9.0g二乙烯三胺在氩气气氛下120~160℃搅拌12~36h;产物用50~100ml氯仿溶解,再分别以50~100ml去离子水和20~50ml甲醇洗涤,通过旋转蒸发除去溶剂,得到自修复高分子;
取0.1~1g上述自修复高分子溶解于1~10ml三氯甲烷获得均一溶液,将此溶液滴加于清洁玻璃片上,室温下挥发溶剂0.5~2h,50~80℃烘干15~30min,蒸干溶剂,获得自修复高分子薄膜;
步骤2,制备取向碳纳米管阵列:通过化学气相沉积法合成可纺的碳纳米管阵列,化学气相沉积得到可纺的碳纳米管阵列;
催化剂为等质量的平均粒度1~2nmFe和平均粒度8~12nmAl2O3的混合物;
碳源为乙烯;
气相载体为等体积氩气和氢气的混合气体;
步骤3,制备可拼接电极:将取向碳纳米管薄膜直接从碳纳米管阵列中拉出,正交铺排于自修复聚合物薄膜表面组成复合膜,并将多块复合膜拼接,得到取向碳纳米管/自修复聚合物的平面电极。
实施例4
区别于实施例1,其主要用于制备具有特定图像而非重复色彩单元的情况。其主要层结构包括内到外依次设置隔热层1、发热层2、绝缘层3。
该方案的制备过程包括以下步骤:
步骤1,预先选定印刷的图案、尺寸、图像上的变色位置,并分别制作发热层复合纤维纱线和电致变色层,备用;
步骤2,将发热层复合纤维纱线纺织成发热层织物,将发热层织物与隔热层结合后,裁切至预定尺寸,得到复合结构I;
步骤4,将复合结构I作为画布印刷所需的图像,得到复合结构II;
步骤5,在复合结构II上依次粘贴薄膜电极和电源,得到成品。
实施例5
与实施例4相似,为提高图像的观赏性,使图像中的特定部分具有颜色可变的性质,在实施例4的基础上增加了电致变色层。其主要层结构包括内到外依次设置隔热层1、发热层2、绝缘层3、电致变色层4。
该方案的制备过程包括以下步骤:
步骤1,预先选定印刷的图案、尺寸、图像上的变色位置,并分别制作发热层复合纤维纱线和电致变色层,备用;
步骤2,将发热层复合纤维纱线纺织成发热层织物,将发热层织物与隔热层结合后,裁切至预定尺寸,得到复合结构I;
步骤3,在复合结构I的相应位置上粘贴电致变色层,得到复合结构II;
步骤4,将复合结构II作为画布印刷所需的图像,得到复合结构III;
步骤5,在复合结构III上依次粘贴薄膜电极和电源,得到复合结构IV。
实施例6
与实施例5相似,为进一步提高图像的观赏性,在平面图像的基础上粘贴浮雕,并可在浮雕上粘贴电致变色层,由内到外依次设置隔热层1、发热层2、绝缘层3、电致变色层4、保护层。
该方案的制备过程包括以下步骤:
步骤1,将隔热层与发热层复合,得到复合结构I;
步骤2,在复合结构I的相应位置粘贴电致变色层,得到复合结构II,电致变色层采用具有可逆电致变色性质的复合纤维制成;
步骤3,将复合结构II作为画布印刷所需的图像,得到复合结构III;
步骤4,在复合结构III的相应位置上粘贴浮雕图层,在所需的浮雕图层上粘贴电致变色层,得到复合结构IV,电致变色层采用具有可逆电致变色性质的复合纤维制成;
步骤5,在复合结构IV上依次粘贴薄膜电极和电源,得到复合结构V;
步骤6,在复合结构V上覆膜绝缘层,即得成品。
本发明中的复合纤维结构,均可通过扫描电子显微镜(SEM,Hitachi FE-SEMS-4800 Operated at 1kV) 来表征。其电化学性能可通过Arbin多通道电化学测试仪(Arbin,MSTAT-5V/10mA/16Ch)测试。其拉伸性能可在拉力测试机(HY-0350)上完成。
Claims (5)
1.一种带有薄膜电极的远红外发热体,包括电路组件以及发热体组件,电路组件包括变压整流电路;发热体组件由内向外依次包括隔热层、发热层、绝缘层,发热层包括碳制片状电热材料、设置在电热材料两侧的电极,其特征在于:
电热材料由碳纳米管制成的复合纤维纱线纺织而成;
绝缘层通过模具预先制成“浮雕结构”;
绝缘层上还设有电致变色层,并且电致变色层构成的电阻单元与发热层构成的电阻单元相互并联;
电路组件还包括与电致变色层电性连接的PWM调制模块;
电极为覆盖在电热材料上的薄膜电极。
2.根据权利要求1所述的带有薄膜电极的远红外发热体,其特征在于:“浮雕结构”采用硅胶或塑料或表层带有绝缘膜的金属薄板。
3.根据权利要求1或2所述的带有薄膜电极的远红外发热体,其特征在于:电致变色层表面喷涂透明的保护层。
4.一种权利要求1所述带有薄膜电极的远红外发热体的制备方法,其特征在于,包括以下步骤:
步骤1,预先设计绝缘层的浮雕结构、电致变色变色位置,并分别制作碳纳米管复合纤维纱线和电致变色层,备用;
步骤2,将碳纳米管复合纤维纱线纺织成发热层织物,将发热层织物与隔热层结合后,裁切至预定尺寸,得到复合结构I;
步骤3,在复合结构I贴合绝缘层的浮雕结构,得到复合结构II;
步骤3-1,制备自修复高分子薄膜:取1.0~22.8重量份的聚二酸和0.5~9.0重量份的二乙烯三胺在氩气气氛下120~160℃搅拌12~36h;产物用50~100重量份的氯仿溶解,再分别以50~100重量份去离子水和20~50重量份的甲醇洗涤,通过旋转蒸发除去溶剂,得到自修复高分子;
取0.1~1重量份上述自修复高分子溶解于1~10重量份三氯甲烷获得均一溶液,将此溶液滴加于清洁玻璃片上,室温下挥发溶剂0.5~2h,50~80℃烘干15~30min,蒸干溶剂,获得自修复高分子薄膜;
步骤3-2,制备取向碳纳米管阵列:通过化学气相沉积法合成可纺的碳纳米管阵列,化学气相沉积得到可纺的碳纳米管阵列;
催化剂为等质量的平均粒度1~2nmFe和平均粒度8~12nmAl2O3的混合物;
碳源为乙烯;
气相载体为等体积氩气和氢气的混合气体;
步骤3-3,制备可拼接电极:将取向碳纳米管薄膜直接从碳纳米管阵列中拉出,正交铺排于自修复聚合物薄膜表面组成复合膜,并将多块复合膜拼接,得到取向碳纳米管/自修复聚合物的平面电极;
步骤4,在复合结构II的绝缘层上粘贴电致变色层,组装电路组件并通电测试,测试通过后,在电致变色层表面喷涂透明的抗氧化保护薄层,通风处晾干固化即得成品。
5.根据权利要求4所述的制备方法,其特征在于,步骤1中发热层的碳纳米管复合纤维纱线的制备方法包括以下步骤:
步骤1-1 ,将涤纶纱线浸入3wt%的NaOH溶液中,90~110℃浸泡2~5min后取出洗涤4~6次,晾干后得到涤纶纱线基材;
步骤1-2,将质量比20:1:4的碳纳米管、3-黄丙基十四烷基二甲甜菜碱、聚氧乙烯十二烷基磺酸醚依次加入定量的去离子水中,随后倒入超声波清洗器中,30~50℃、40~60Hz下振荡35~45min至分散均匀,得到碳纳米管悬浮液;
步骤1-3,将涤纶纱线基材浸入碳纳米管悬浮液中,30~50℃浸染3~7min,得到复合涤纶纱线I;
步骤1-4,将复合涤纶纱线I置于干燥炉中,110~130℃干燥2~4min,取出后浸入70~90℃的等质量比的水性聚氨酯和丁腈橡胶的水溶液中,得到复合涤纶纱线II;
步骤1-5,将复合涤纶纱线II置入固化炉中,50~70℃固化成型2~4min,得到发热层复合纤维纱线。
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