CN103956429B - 智能太阳能电池 - Google Patents
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Abstract
本发明公开了一种智能太阳能电池,是以光伏变色材料作为吸光材料的有机薄膜太阳能电池。所述光伏变色材料在同一个分子中既具有光致变色基团又具有光伏功能基团,在光照下不仅能够变色,而且能够产生激子。该智能太阳能电池在太阳光照射下,会从透明变为深色,自动调节透射光强,从而增大对阳光的吸收,提高光电转化效率。该智能太阳能电池非常适合用作玻璃贴膜,成为智能光响应效果的光伏玻璃。
Description
技术领域
本发明涉及有机薄膜太阳能电池,特别涉及具有光响应功能的有机薄膜太阳能电池。
背景技术
有机薄膜太阳能电池由于其低成本、柔软、轻便易携,以及适合大面积生产等特性,正在逐渐进入日常生活中。有机薄膜太阳能电池可以应用于移动终端设备,手表、计算器等便携设备,光伏玻璃和柔性可卷曲物品等,为其提供电能。
传统有机薄膜太阳能电池的材料大可以分成这样几类:有机小分子材料,如富勒烯、并五苯、酞菁、卟啉等;有机大分子材料,如富勒烯、聚噻吩、PPV、聚芴及他们的衍生物;D-A体系;有机无机杂化体系等。
从结构上来看,有机薄膜电池结构有以下几种:异质结电池、染料敏化电池、量子点电池等等。以异质结电池为例,器件结构一般是在玻璃衬底上依次层叠透明导电氧化物层、阳极缓冲层、有源层、阴极缓冲层以及金属电极层,其中有源层由有机给体材料和有机受体材料两种物质混合形成,或者是由受体在上、给体在下的两层结构组成。有源层中的两种有机材料由于对电子亲和力的不同,电子会在光激发下从给体转移到受体,电子和空穴在分离后再分别运动到电极上,就产生了电流。
另一方面,有机光致变色材料也是发展较快的一种有机材料。有机光致变色指的是一种化合物在受到一定波长的光照射时,发生特定的化学反应,产物由于结构的改变导致其吸收光谱发生明显的颜色改变,而在另一波长的光照或热或无光的条件下,又能恢复到原来的结构形式的一种可逆的变化。
有机光致变色材料主要有这样几类:螺吡喃、螺噁嗪、苯并吡喃、俘精酸酐、偶氮化合物、二芳基乙烯、苯胺衍生物等等。广泛应用在印刷、包装、防伪、国防、光信息记录等方面。
发明内容
基于上述两种功能的材料(光伏材料和有机光致变色材料)和已有的有机薄膜电池结构,本发明的目的是提供一种新的太阳能电池——智能太阳能电池。这种电池是一种具有光强响应功能的有机薄膜太阳能电池:随着光强的变强,电池的阻光率会有明显的提高,颜色发生变化,同时光电转化效率也会提高。智能电池非常适合用作玻璃贴膜,成为智能光响应效果的光伏玻璃。
为实现上述目的,本发明首先提供一种有机材料,这种有机材料在光照下能够变色,而且能够产生激子,在本发明中称作光伏变色材料。这种光伏变色材料可以是设计合成的新材料,也可以是已有的具有此类性质的材料。
进一步的,本发明将上述光伏变色材料作为吸光材料应用于有机薄膜太阳能电池,从而提供一种光致变色有机太阳能电池,在本发明中称为智能太阳能电池。这种有机薄膜太阳能电池,在阳光变强时会由无色变成深色,从而自动调节透射光强。
在本发明的光伏变色材料中,既有光致变色基团,又有光伏基团。我们可以通过化学手段将光致变色基团和光伏基团连接起来,合成新的分子,从而得到所述的光伏变色材料。如果以A代表光致变色基团,B代表光伏基团,本发明的光伏变色材料就是将A和B通过化学键连接成的新分子。本领域技术人员根据现有技术,对不同的基团选择不同的连接方法,于此不再赘述。
常见的A有螺吡喃衍生物、螺噁嗪衍生物、苯并吡喃衍生物、俘精酸酐衍生物、二芳基乙烯衍生物、偶氮苯衍生物、苯胺衍生物等等。常见的B有聚噻吩衍生物、PPV衍生物等聚合物基团,还有C60/C70衍生物等大分子,以及卟啉衍生物、酞菁衍生物等敏化电池常用染料,上述的具有较大共轭体系的基团都是有潜力的光伏基团。
表1.常见的光致变色基团(A)和光伏基团(B)
表1列出了一些常见光致变色基团(A)和光伏基团(B)的结构式,通过本领域的公知技术可以将上述A基团和B基团进行连接,得到本发明的光伏变色材料。例如:在有机变色材料二噻吩乙烯(式I)上修饰具有光伏给体效应的聚噻吩(式II,其中n为大于0的自然数),得到式III所示的具有光伏给体效应基团的有机光致变色材料,即光伏变色材料。式III化合物两端的噻吩链可以继续加长或再修饰以其他共轭结构,以调节光伏和变色性质。
此外,若已有的光致变色材料已经具有一定的光伏效果,也可以直接作为本发明智能太阳能电池的吸光材料。
本发明所提供的智能太阳能电池是有机薄膜太阳能电池,其结构是根据吸光材料的性质决定的。常见的有异质结电池、染料敏化电池、量子点电池等等。
以染料敏化电池为例,它的结构包括透明导电衬底和层叠于衬底上的多孔层,吸附于多孔层上的染料吸光层,电解质和对电极,所述染料为光伏变色材料。所述透明导电衬底一般是FTO玻璃。多孔层材料一般是TiO2,所述吸光层的染料为光伏变色材料,电解质是离子溶液,对电极可以是沉积在透明玻璃上的Pt导电层。
以异质结电池为例,其结构包括衬底和层叠于衬底上的半透明阳极导电层、阳极缓冲层、有源层、阴极缓冲层和半透明阴极导电层,其中所述有源层中的给体材料为具有光伏给体效应基团的有机光致变色材料(光伏变色材料),而受体材料可以采用传统的受体材料,如PCBM、C60等。在异质结电池结构中还可以设置光学填充层和折射率匹配层,它们的存在是为了优化器件的结构,增加器件效率,它们的厚度可以根据各层的材料和厚度,通过光学传输矩阵模型仿真模拟计算得到的。光学填充层的位置是可以变化的,器件中还可以有多个光学填充层,一般填充在有源层的一侧或两侧。折射率匹配层则设置在半透明阴极导电层之上。
本发明提出的智能太阳能电池是一种具有光响应功能的有机薄膜太阳能电池,兼具光致变色和光伏两种功能。在染料敏化电池结构中,用光伏变色材料做吸光材料;在异质结电池结构中,用经过光伏给体效应基团修饰的光致变色材料替代传统的给体材料。并且,光致变色和光伏这两种功能的叠加并不是通过将光致变色材料和有机光伏材料简单混合在一起来实现的,而是经过分子层面的修饰,使光伏功能和光致变色功能集中在一个分子上。这种有机材料的分子结构中既有光致变色基团,同时也具有光伏功能基团,因此能够兼具上述两种功能,在光照下能够变色,并且还能够产生激子。
利用这种双功能有机材料制备的太阳能电池,既有光致变色功能,又有光伏功能,我们称之为智能太阳能电池。智能太阳能电池在太阳光照射下,会从透明变为深色,从而增大对阳光的吸收。
附图说明
图1是实施例1制备的智能太阳能电池的结构示意图。
图2是实施例1制备的智能太阳能电池的伏安曲线。
图3是实施例1制备的智能太阳能电池在不同光强条件下的吸收光谱。
图4是实施例2制备的智能太阳能电池的结构示意图。
具体实施方式
下面结合附图,通过实施例进一步说明本发明,但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下,对本发明器件结构、制作步骤或条件所做的修改或替换,均属于本发明的范围。
实施例1
在本实施例中,选用式1所示的光伏变色材料吲哚啉螺苯并噻喃衍生物(简称式1染料),基于图1所示的染料敏化电池结构来制作本发明的智能太阳能电池。
其中,式1染料是通过下述方法制备得到的(参考文献:四川大学学报自然科学版Vol 29No.3,1992):
吲哚啉螺苯并噻喃衍生物(c产物,即式1染料)的制备:将式a所示吲哚盐(CAS138559-05-4)(0.005mol)和式b所示的硫代水杨醛(CAS 29199-11-9)(0.0055mol)溶解在20ml乙醇中,加入六氢吡啶0.5ml,回流3小时,浓缩,冷却,重结晶。
通过下述步骤制备智能太阳能电池:
1.二氧化钛光电极的制备:二氧化钛光电极是沉积有多孔TiO2层的FTO导电玻璃,对应图1中第一玻璃衬底101、FTO透明电极102和多孔TiO2层103这三部分。通常的制备方法是在干净的FTO导电玻璃上旋涂TiO2纳米颗粒的浆料,再经过500℃的烧结形成的。TiO2光电极可以很方便地在市场上买到。
2.铂对电极的制备。铂对电极是沉积有Pt层的玻璃衬底,对应图1中的Pt对电极105和第二玻璃衬底106两部分。通常的制备方法是在干净的玻璃片上,用磁控溅射方法沉积一层金属Pt,厚度2~100nm不等。铂对电极可以很方便地在市场上买到。
3.二氧化钛光电极的染料敏化。将二氧化钛光电极进行500℃的退火,趁热(80℃)浸泡在式1染料的乙腈溶液中,式1染料的浓度是0.3mmol/L,避光浸泡30min后取出,再用乙腈润洗,室温下静置干燥。
4.电解质的制备。采用离子液体为电解质,具体是含有0.6mol/L BMII、0.03mol/L I2、0.10mol/L异硫氰酸胍、0.5mol/L 4-叔丁基吡啶的乙腈溶液。
5.电池的组装。将步骤3得到的吸附好染料的二氧化钛光电极与铂对电极用热封装膜粘合在一起。使用抽真空技术将步骤4制备的电解质注入电池内部。具体方法是将滴上电解质溶液的电池放在真空室内抽真空,然后将真空室恢复到大气压,这样,由于电池内外的压力差,电解质溶液104被吸入到电池内部。最后再用紫外固化胶水把小孔封住。
(一)电池电学性质的表征
在国际标准光照条件AM1.5下(即100mW/cm2太阳光照射),本实施例制备的电池的伏安曲线如图2所示,其电学性质列于表2:
表2:国际标准光照条件AM1.5下电池的电学性质
效率(%) | 开路电压(mV) | 短路电流(mA/cm2) | 填充因子 | |
origin(紫外照射前) | 0.16 | 400 | 0.686 | 0.59 |
UV(紫外照射后) | 0.20 | 401 | 0.775 | 0.63 |
dark(避光放置) | 0.16 | 365 | 0.846 | 0.52 |
通过图2和表2可以说明,紫外照射前,电池有0.16%的光电转化效率。在紫外照射后,效率提升到0.20%,提高了25%,电池具有光响应效果。在暗处放置一段时间之后,电池又恢复到了0.16%的效率,表明电池的光响应过程是可重复的。
(二)电池光学性质的表征
本实施例制备的电池在不同光强条件下有不同的吸收曲线,如图3所示,电池的颜色是随着光强变化的。
图3表明,在光照条件发生变化的时候,电池的吸收是不同的,其中dark:电池在暗处放置一段时间,测量到的吸收曲线;sunlight:电池在阳光下放置一段时间后,测量到的吸收曲线。吸收系数的计算公式是A=-lgT,其中T是透射率。
实施例2
根据下述步骤制备图4所示的智能太阳能电池:
1.在玻璃衬底201上用磁控溅射的方式沉积10~30nm厚的Ag层,形成半透明阳极导电层202;
2.将PEDOT∶PSS溶液旋涂在Ag薄膜上,经过热退火,形成10nm左右厚的薄层,作为阳极缓冲层203;
3.将光伏变色材料与受体PCBM的混合溶液,旋涂在PEDOT∶PSS层上,经过热退火过程,形成有源层薄膜204,这一层厚度一般是30~100nm;
其中光伏变色材料是如下式2所示的化合物:
4.在有源层204上溅射ITO作为光学填充层205,该层的厚度一般为0~100nm;
5.在光学填充层205上蒸镀LiF作为阴极缓冲层206,厚度在1nm左右;
6.在阴极缓冲层206上蒸镀Ag作为半透明阴极导电层207,厚度在10~20nm左右;
7.最后在半透明阴极导电层207上蒸镀MoO3作为折射率匹配层208,该层的厚度一般为0~100nm。
Claims (3)
1.一种有机薄膜太阳能电池,该电池是光致变色有机太阳能电池,其吸光材料为在同一个分子中既具有光致变色基团又具有光伏功能基团的光伏变色材料,其特征在于,该电池为染料敏化电池结构,包括透明导电衬底和层叠于衬底上的多孔层,吸附于多孔层上的染料吸光层,电解质和对电极,其中所述染料为所述光伏变色材料,为式1所示的化合物:
2.一种有机薄膜太阳能电池,该电池是光致变色有机太阳能电池,其吸光材料为在同一个分子中既具有光致变色基团又具有光伏功能基团的光伏变色材料,其特征在于,该电池为异质结电池结构,包括衬底和层叠于衬底上的半透明阳极导电层、阳极缓冲层、有源层、阴极缓冲层和半透明阴极导电层,所述有源层中的给体材料为修饰有光伏给体效应基团的有机光致变色材料,所述光伏给体效应基团是聚噻吩基团,如式II所示:
式II中,n为大于0的自然数。
3.根据权利要求2所述的有机薄膜太阳能电池,其特征在于,所述具有光伏给体效应基团的有机光致变色材料是如下式III所示的化合物:
式III中,n为大于0的自然数。
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