CN109251457B - 具有荷叶仿生结构的自清洁太阳能电池板薄膜及其制备方法 - Google Patents
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Abstract
本发明公开一种具有荷叶仿生结构的自清洁太阳能电池板薄膜,针对太阳能电池板在室外使用时易积灰进而影响光电转化效率的问题,选择透明性优异的丙烯酸树脂作为基体树脂,通过添加含氟嵌段共聚物作为表面改性剂,另外把蔗糖/聚己内酯两亲性聚合物自组装成的胶束微球分散在基体中形成微米级乳突。同时两亲性聚合物上具有星形多臂状的纳米级绒毛。微米级乳突与纳米级绒毛相结合,构成类似荷叶的微纳二阶结构,这种结构同时具有较大的接触角和较小的滚动角,从而获得优异的自清洁性。该薄膜在基本不影响透光率的同时,大大减少了灰尘等污染物在太阳能电池板上的堆积,提高了光电转化效率,另外其原料成本低,制备方法简单易行。
Description
技术领域
本发明涉及一种功能性纳米仿生复合材料,特别涉及其表面结构及制备方法。
背景技术
环境中的灰尘堆积对光伏组件的光电转换效率有很大影响,这是造成光伏电站发电量下降的关键因素之一。研究表明,若每平方米有4.05g灰尘,光伏太阳能电池板的转化效率将下降40%。同时局部灰尘遮蔽可能会引起热斑效应,造成安全隐患,缩减太阳能电池板的使用寿命。
近年来,有关仿生学的研究受到了世界各国的重视,大自然中许多神奇的现象给了人类灵感与启发,越来越多的发明开始模仿生物体的形态结构,以实现某些特定的功能。荷叶“出淤泥而不染”,具有优异的自清洁性,因此若将具有荷叶效应的薄膜覆盖在太阳能电池板上实现自清洁功能,将大大减少灰尘等污染物在太阳能电池板上的堆积,提高光电转换效率,延长太阳能电池板的使用寿命。
研究表明荷叶效应来自于荷叶表面的蜡状物与一种特殊的微纳二阶结构:荷叶表面有序地分布着微米级的乳突,而每个微米级乳突表面又有纳米级的绒毛。荷叶表面特殊的微纳突出二阶结构和低表面能的蜡状物使得荷叶表面的静止接触角达到160o,且其滚动角只有2o,具有优异的自清洁性。
中国专利申请号CN201710578531.2涉及一种用于网布领域的仿荷叶效应的纳米仿生防水材料,它以聚丙烯、改性封端异氰酸酯为原料,需经螺杆挤出,大长径比喷丝孔,再经集束、上浆液、长牵伸固化等工序制得。该制备方法复杂,对设备的要求高,且上浆过程中会造成较大的溶液污染。
中国专利申请号CN201710619328.5涉及一种超疏水涂料及其制备和施工方法,这种超疏水涂料包括组份A和组份B。首先它把低表面能的颗粒与树脂、固化剂进行混合、稀释,得到组份A;再将经过研磨的、具有纳米孔隙的疏水材料与树脂、固化剂、溶剂进行混合,得到组份B。将上述具有纳米孔隙的超疏水涂料涂装于具有微米级结构的材料之上,获得的涂层在微米级和纳米级疏水结构的双重作用下,实现“荷叶效应”。该制备方法对原料的结构要求苛刻,且制备过程复杂,可操作性不强。
中国专利申请号CN201710354602.0涉及一种对油污形成荷叶效应的聚丙烯复合材料,用于合成这种复合材料的组分包括:聚丙烯、丁腈橡胶、相容剂、氟化物、纳米二氧化硅聚合物复合微粒、复合抗氧剂、复合成核剂。该制备方法需要使用的原料较多,成本也相应较高。
因此针对光伏组件的积灰问题并考虑到以上已有专利的缺点,本发明公开一种具有荷叶仿生结构的自清洁太阳能电池板薄膜及其制备方法。我们将具有类似荷叶乳突结构的蔗糖/聚己内酯两亲性聚合物和低表面能含氟单体加入到丙烯酸类单体的溶液中,进行熔融共聚,从而制备出具有荷叶效应的薄膜,该方法使用的各种原料广泛易得,制备步骤简单,因此成本相对较低。同时,丙烯酸类树脂具有良好的透明性,我们将这种功能性纳米仿生复合薄膜覆盖于光伏组件之上,不仅在一定程度上避免积灰等造成发电量的损失,更减轻了清洁太阳能电池板的工作负担,兼具创新性与实用性。
发明内容
本发明的目的在于颠覆目前传统的太阳能电池板清洁方法,根据光伏组件对透光性的要求,制造一种具有微纳二阶结构的自清洁薄膜,当薄膜覆盖在太阳能电池板表面上时,将大大减少灰尘等污染物在太阳能电池板上的堆积,提高光电转化效率,同时能够避免对太阳能电池板的直接接触式清洗,延长使用寿命。为达到发明目的,采用的技术手段如下。
具有荷叶仿生结构的自清洁太阳能电池板薄膜制备方法,将具有类似荷叶乳突结构的蔗糖/聚己内酯两亲性聚合物和低表面能含氟单体加入到丙烯酸类单体的溶液中,进行熔融共聚;蔗糖/聚己内酯两亲性聚合物自组装成胶束微球分散在基体中形成微米级乳突,该微米级乳突与两亲性聚合物上具有的星形多臂状纳米级绒毛相结合构成类似荷叶的微纳二阶结构;再经模压形成具有较大接触角和较小滚动角且保持较高透光率的目标薄膜;其具体步骤如下:
首先将以丙烯酸类单体为溶剂,加入引发剂、蔗糖/聚己内酯两亲性分子、含氟单体的混合溶液在水浴锅中加热搅拌进行预聚合,待溶液达到凝胶点后,将其放置在空气中冷却至室温,然后将混合溶液倒入模具中,密封,置于温度维持在50-100℃的烘箱内,使其继续发生聚合反应,反应时间为8-36h,待单体聚合完全,将聚合产物取出,再通过模压的方法得到实际应用所需厚度的薄膜产品。
添加的蔗糖/聚己内酯两亲性聚合物分散在基体中,形成微米级乳突,同时两亲性聚合物上有星形多臂状的纳米级绒毛,构成了类似荷叶的微纳二阶结构。另外向其中添加含氟单体,起到降低表面能的作用,提高薄膜的不粘附性。
所述用于制备自清洁薄膜的溶液包括如下部分:用于聚合成基体材料的丙烯酸类单体作为溶剂,以下组分的质量分数相对于溶剂而言,引发剂为0.1-0.5wt%,含氟类单体为1-20%wt,蔗糖/聚己内酯两亲性分子为1-20%wt。制备过程中,首先将该混合溶液在80℃左右的水浴锅中加热搅拌,预聚合30min-60min。待溶液达到凝胶点后,将其放置于空气中冷却至室温,倒入模具中,密封,然后置于50-100℃的烘箱内,继续发生聚合反应。待大于8h后,单体聚合完全,将聚合产物取出。最后采取模压的方法,使聚合产物达到我们实际应用所需的厚度。
所述的用于合成基体材料的丙烯酸类单体,包括丙烯酸或其同系物的酯类,如丙烯酸甲酯、丙烯酸乙酯、2-甲基丙烯酸甲酯、2-甲基丙烯酸乙酯等。
所述的引发剂包括过氧化二苯甲酰(BPO)、过氧化2-乙基已酸叔戊酯(TAPO)、过氧化2-乙基已酸叔丁酯(TBPO)、偶氮二异丁腈(AIBN)等。
所述的含氟单体主要为含氟烯烃,包括四氟乙烯、偏氟乙烯、三氟氯乙烯等。
所述达到溶液凝胶点是指溶液的粘度突然变大,用玻璃棒蘸取少许溶液,可发现有拉丝现象。出现凝胶点后,应立即将其空冷至室温。
所述单体反应完全是指薄膜凝固,即用眼睛观察薄膜中的小气泡不再移动,且不能或较少可以嗅到刺鼻的单体溶液气味。
在具体的实验中,所获的胶束微球的直径为500nm-100μm,纳米级绒毛既有疏水的聚酯聚合物,又有亲水的多糖分子,绒毛的直径为20-40nm,长径比为1:1-10:1;其微纳二阶结构中,每个微米级乳突上存在纳米级绒毛,微米级乳突在每平方厘米的薄膜表面的含量大约为0.01-1mg,纳米级绒毛在每平方厘米的薄膜表面的含量为0.1-1mg。
本发明的另一目的是采用上述方法获得一种具有荷叶仿生结构的自清洁太阳能电池板薄膜,使其接触角大于140度,滚动角小于10度。
具体实施方式
本发明用下面具体实施方式作进一步的详细说明,但本发明所保护的范围并不限于实施例。
实施例1
一种具有荷叶仿生结构的自清洁太阳能电池板薄膜,其基体材料为聚甲基丙烯酸甲酯,用于合成的单体原料为甲基丙烯酸甲酯。以下其他物质的质量比均是相对于此单体而言的。加入0.1-0.5wt%的过氧化二苯甲酰(BPO)作为引发剂;加入1-20wt%的蔗糖/聚己内酯两亲性分子,并使其分散在基体中形成类似荷叶的微纳二阶乳突结构,实现荷叶效应;加入1-20wt%的四氟乙烯单体,以降低薄膜的表面能,提高不粘附性。
其具体步骤为:将上述引发剂、蔗糖/聚己内酯两亲性分子、四氟乙烯单体加入到盛有甲基丙烯酸甲酯的烧瓶中,放入搅拌子,置于水浴锅中加热并搅拌,使其发生预聚反应。待达到凝胶点后,立即将烧瓶从水浴锅中取出,置于空气中冷却至室温。待冷却至室温后,将其倒入模具中,密封。然后将密封好的模具放入烘箱内,继续反应,待单体完全聚合后,打开模具,取出聚合产物。最后采用模压的方法,得到厚度为0.3mm的薄膜。
所述的发生预聚反应时水浴锅的温度为75-85℃;
所述达到凝胶点的时间为开始预聚反应后的30-60min,此时可以看到溶液的粘度突然增大,用玻璃棒蘸取少量溶液不会滴落,而出现拉丝现象;
所述的烘箱温度为50-100℃;
所述继续反应至单体完全聚合的时间为8-36h。
获得具有荷叶仿生结构的自清洁太阳能电池板薄膜,测得其接触角为176度,滚动角为6度。
实施例2
本例与实施例1基本相同,所不同的仅仅是:加入的引发剂为0.1-0.5wt%的偶氮二异丁腈(AIBN)。
获得具有荷叶仿生结构的自清洁太阳能电池板薄膜,测得其接触角为155度,滚动角为8度。
实施例3
本例与实施例1基本相同,所不同的仅仅是:加入的含氟单体为1-20wt%的偏氟乙烯。
获得具有荷叶仿生结构的自清洁太阳能电池板薄膜,测得其接触角为148度,滚动角为8度。
实施例4
本例与实施例1基本相同,所不同的仅仅是:使用模压的方法,将聚合产物模压成厚度为0.1mm的薄膜。
获得具有荷叶仿生结构的自清洁太阳能电池板薄膜,测得其接触角为142度,滚动角为9度。
实施例5
本实施例介绍将目标薄膜贴附在太阳能电池板上的过程:
将具有荷叶仿生结构的自清洁薄膜贴附在太阳能电池板上的具体步骤为:首先,为避免太阳能电池板表面工作温度过高而影响薄膜的贴附效果,应选择在阴天时进行薄膜贴附工作。量取太阳能电池板的长和宽,确定所需薄膜的尺寸大小,在裁取薄膜时应注意比实际太阳能电池板的长、宽多3-5cm。其次,用水冲洗太阳能电池板,并用洁净的擦拭布擦拭干净。将薄膜的一端与太阳能电池板边缘接触,利用静电作用慢慢向另一边缘贴附。待薄膜全部贴附后,用硬质卡片将产生的气泡向边缘挤出,直至气泡消失。最后,将超出太阳能电池板边缘的薄膜进行裁剪,使薄膜尺寸与太阳能电池板相同。
Claims (6)
1.具有荷叶仿生结构的自清洁太阳能电池板薄膜制备方法,将具有类似荷叶乳突结构的蔗糖/聚己内酯两亲性聚合物和低表面能含氟单体加入到丙烯酸类单体的溶液中,进行熔融共聚;蔗糖/聚己内酯两亲性聚合物自组装成胶束微球分散在基体中形成微米级乳突,该微米级乳突与两亲性聚合物上具有的星形多臂状纳米级绒毛相结合构成类似荷叶的微纳二阶结构;再经模压形成具有较大接触角和较小滚动角且保持较高透光率的目标薄膜;其具体步骤如下:
首先将以丙烯酸类单体为溶剂,加入引发剂、蔗糖/聚己内酯两亲性分子、含氟单体的混合溶液在水浴锅中加热并搅拌进行预聚合,待溶液达到凝胶点后,将其放置在空气中冷却至室温,然后将混合溶液倒入模具中,密封,置于温度维持在50-100℃的烘箱内,使其继续发生聚合反应,反应时间为8-36h,待单体聚合完全,将聚合产物取出,再通过模压的方法得到实际应用所需厚度的薄膜产品。
2.根据权利要求1所述的具有荷叶仿生结构的自清洁太阳能电池板薄膜制备方法,其特征在于,所述丙烯酸类单体具体为丙烯酸、丙烯酸甲酯、丙烯酸乙酯、2-甲基丙烯酸甲酯、2-甲基丙烯酸乙酯中的一种,其平均透光率大于97%。
3.根据权利要求1所述的具有荷叶仿生结构的自清洁太阳能电池板薄膜的制备方法,其特征在于,所述的加入的引发剂为过氧化二苯甲酰BPO、过氧化2-乙基已酸叔戊酯TAPO、过氧化2-乙基已酸叔丁酯TBPO、偶氮二异丁腈AIBN中的一种,且其质量分数为丙烯酸类单体的0.1-0.5wt%。
4.根据权利要求1所述的具有荷叶仿生结构的自清洁太阳能电池板薄膜的制备方法,其特征在于,所述的加入的蔗糖/聚己内酯两亲性分子的质量分数为用于合成基体单体的1-20wt%;两亲性聚合物的分子量为40342-160342,是分子量为342.3的蔗糖与分子量为40000的聚己内酯接枝的产物。
5.根据权利要求1所述的具有荷叶仿生结构的自清洁太阳能电池板薄膜的制备方法,其特征在于,所述的加入的含氟单体为四氟乙烯、偏氟乙烯、三氟氯乙烯中的一种,且其质量分数为用于合成基体单体的1-20wt%。
6.根据权利要求1所述的具有荷叶仿生结构的自清洁太阳能电池板薄膜的制备方法,其特征在于,所述的预聚合时水浴锅的温度为75-85℃,预聚合时间为30-60min;所述的到达凝胶点时的表现为,混合溶液的粘度突然增大,用玻璃棒蘸取少量溶液,液滴不能顺利滴落,出现拉丝现象。
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