CN102360957B - 以取向碳纳米管膜为对电极的染料敏化太阳能电池 - Google Patents
以取向碳纳米管膜为对电极的染料敏化太阳能电池 Download PDFInfo
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Abstract
本发明属于太阳能电池制备领域，具体为一种以取向碳纳米管为对电极的染料敏化太阳能电池。本发明以高度取向的碳纳米管薄膜为材料，通过溶剂及热处理使它牢固地连接在FTO玻璃表面形成对电极，并以此对电极来构建染料敏化太阳能电池。该取向碳纳米管薄膜具有很好的催化效应，取代了传统染料敏化太阳能电池中对电极中的铂，从而大大降低了成本，同时它也有很好的柔性及强度，可以构建柔性的太阳能电池。
Description
技术领域
本发明属于太阳能电池技术领域，具体涉及为一种染料敏化太阳能电池。
背景技术
碳纳米管的发现是世界科学史上的一个里程碑。1991年日本Iijima 发现碳纳米管(Carbon Nanotubes , CNTs) 以来[1] , 碳纳米管以其特有的高拉伸强摄氏度、高弹性、从金属到半导体的电学特性、高电流载荷量和高热导体性以及独特的准一维管状分子结构，在未来高科技领域中具有许多潜在的应用价值，成为人们所关注的焦点。
同样，碳纳米管被广泛应用于构建高效的有机太阳能电池[2-11]，比如，碳纳米管在染料敏化太阳能电池中被用来替代铂来催化三碘化物的还原，同时也可以把碳纳米管分散于二氧化钛浆料中来促进电子的扩散[12]，也可以把碳纳米管分散于电解液汇总来促进电子的传输及催化效果[13]。有课题组把碳纳米管分散后旋涂在FTO玻璃表面，形成对电极，得到不错的效果[14]；有课题组通过分散碳纳米管，并使用喷墨打印法形成对电极，也取得不错的效率[15]。但是由于碳纳米管的无规分散降低了电荷的分离和传输，为了进一步提高基于碳纳米管对电极的有机太阳能电池的效率，急需要得到拥有取向碳纳米管薄膜的对电极，从而提高电池的性能。而高度取向的碳纳米管薄膜由于其显著的机械和电学性能[16-23]，被广泛深入的研究，比如它在室温下具有102 S/cm的电导率，因此基于取向碳纳米管薄膜，我们制备了高效率，低成本的染料敏化太阳能电池。
发明内容
本发明的目的在于提供一种效率高、成本低的染料敏化太阳能电池及其制备方法。
本发明提供的染料敏化太阳能电池，是在原有的染料敏化太阳能电池中，用取向碳纳米管薄膜取代金属铂作为对电极而获得。
本发明中，作为对电极的取向碳纳米管薄膜具有很高的取向性（见图1a和图6），即使在很高的倍数下，碳纳米管仍旧具有很好的取向性。单层的碳纳米管薄膜具有很好的透明性（图8），在可见光范围内透光率均大于80%。同时该种碳纳米管薄膜具有很好的柔性（图1c），并且经过多种角度弯曲后，电学性能基本保持不变，误差仅在1%左右，如图1e，f所示。
构建的染料敏化太阳能电池的基本原理图如图2所示，在光照下，染料分子吸收太阳光能量，其电子跃迁至激发态；激发态电子不稳定，电子很快跃迁至较低能级的Ti02导带，此时染料被氧化；注入到Ti02导带的电子富集在导电基底上，并通过导电膜流向外电路对电极（取向碳纳米管薄膜），产生电流；染料分子处于氧化态，从电解质中得到电子并恢复成还原态(基态)得以再生；电解质I3-被来自Ti02导带、通过电极进入外电路、最终到达阴极的电子还原成I-。这样就完成了一个循环。这个激发．氧化．还原的再生循环周而复始的进行，就得到了持续的光电流。
本发明的染料敏化太阳能电池制备方法，具体步骤如下：
（1）对电极的制备，具体步骤如下：
碳纳米管薄膜是通过干仿法直接从阵列中拉出并转移到FTO玻璃（方阻为15欧姆，日本Nippon Sheet Glass公司生产）表面，然后是在附有碳纳米管薄膜的基板表面滴加乙醇并在氩气保护下升温到300-600摄氏度，恒温10-60分钟并退火，实验证明在500度下恒温25--35分钟效果最好，经过以上热处理后碳纳米管薄膜和FTO玻璃之间通过范德华力紧密地连接在一起，形成含有高度取向碳纳米管的对电极。对于柔性电池，碳纳米管薄膜转移到镀有ITO的PEN基板表面，滴加乙醇并在空气中升温到100-200摄氏度，恒温25--35分钟并退火。
（2）工作电极的制备，是在FTO玻璃上使用丝网印刷法印刷上一层4-15微米厚的纳米晶二氧化钛层，实验证明10微米厚的纳米晶二氧化钛层效率最好，然后在450-550摄氏度下煅烧25--35分钟并退火。等工作电极温度降到25-150摄氏度时，把他们转移到0.5mM/L的N719染料溶液（溶剂为乙腈和叔丁醇体积比1：1的混合溶液）中浸泡，实验证明120摄氏度时转移入染料溶液中效率最好，12--18小时后，取出吸附了大量染料的工作电极并用乙腈进行清洗。
（3）最后工作电极和对电极通过一个环形衬底进行封装，封装压力为0.1-0.5MPa，温度为110-140摄氏度，电解液是通过对电极上的小孔中注入。最后使用微型盖玻片和衬底封住小孔，得到完整的电池。
以铂，取向碳纳米管薄膜和无规分散碳纳米管为对电极的太阳能电池的性能变化见图3所示，三种电池的开路电压基本没有变化，而取向碳纳米管电极制备的电池的短路电流和填充因子具有相同的表现，相比于铂电极略差，但是比无规分散碳纳米管的电池高。因此，最后得到的光电转化效率比铂电极略低，而优于无规分散碳纳米管电极的电池。
为了进一步了解取向碳纳米管作为对电极电池的短路电流和填充影子不如铂电极的原因，我们做了电化学阻抗谱测试，如图4所示，我们可以看到，由于对应于对电极上的传荷电阻，取向碳纳米管电极大于铂电极，因此导致了串联电阻的增加，因此导致了电池的短路电流和填充因子的下降。
同时，多层的取向碳纳米管薄膜也进一步进行了研究，从图5中看到，从单层到9层取向碳纳米管薄膜作为对电极，但是电池的各种参数基本没有发生明显的变化，这说明，单层的碳纳米管已经足够催化染料敏化电池中电解液的氧化还原反应。
最后我们也利用取向碳纳米管的柔性，制备了柔性太阳能电池，光学照片如图9所示，得到的电池效率为1.22%。
本发明中，使用的碳纳米管阵列的制备步骤为（常规方法）[24]：
合成碳纳米管阵列的催化剂采用结构形式为Si/SiO2/Al2O3/Fe的复合材料，其中Al2O3位于硅片和Fe的中间，作为缓冲层，Fe作为催化剂的活性成份，它们分别通过电子束蒸发镀膜仪在硅片（Si）上沉积一层纳米厚度的薄膜制备获得。其中，SiO2层厚度为300-1000 μm，Al2O3层厚度为10-30 nm，Fe层厚度为0.5-1.5 nm。采用化学气相沉积法，以Si/SiO2/Al2O3/Fe为催化剂，用乙烯做碳源，氩气和氢气作为载气，在有氧化层Si基片上合成高摄氏度取向的碳纳米管阵列；其中乙烯流量为190-290 sccm，氩气流量为400-620 sccm，氢气流量为20-48 sccm，在管式炉中生长5-200 min。
附图说明
图1，基于取向碳纳米管薄膜的染料敏化太阳能电池的原理示意图。
图2，a碳纳米管薄膜的扫描电镜图，b为单根碳纳米管的扫描电镜图，c为碳纳米管薄膜覆盖于写有fudan university字样的纸张上，说明碳纳米管薄膜具有很好的透明性。d为碳纳米管薄膜附在PET塑料进行弯曲，说明碳纳米管薄膜具有很好的柔性。e为碳纳米管薄膜通过垂直碳纳米管取向方向弯曲后的电导率变化。f为碳纳米管薄膜通过平行碳纳米管取向方向弯曲后的电导率变化。
图3，以铂电极，取向碳纳米管电极和无规分散碳纳米管电极作为对电极所构建的染料敏化太阳能电池在一个太阳光下测得的JV曲线。
图4，以铂电极，取向碳纳米管电极作为对电极所构建的染料敏化太阳能电池在一个太阳光下测得的交流阻抗谱。
图5，以不同层数取向碳纳米管电极作为对电极所构建的染料敏化太阳能电池的参数的变化。a为开路电压，b为短路电流，c为填充因子，d为光电转化效率。
图6，取向碳纳米管薄膜的高倍扫描电镜图。
图7，取向碳纳米管薄膜的拉曼图。
图8，取向碳纳米管薄膜的透光率图。
图9，取向碳纳米管薄膜作为对电极做成的柔性染料敏化太阳能电池在在一个太阳光下测得的JV曲线。
表1，以铂电极，取向碳纳米管电极和无规分散碳纳米管电极作为对电极所构建的染料敏化太阳能电池在一个太阳光下测得的电池性能的各种具体参数。
具体实施方式
制备的具体过程如下：
第一，取向碳纳米管阵列的合成。
垂直生长的碳纳米管阵列以Fe(1nm)/Al2O3(10nm)/SiO2/Si作为催化剂在管式炉的石英管中使用典型的化学气相沉积法来合成。催化剂中Al2O3位于硅片和Fe的中间，作为缓冲层，Fe作为催化剂，它们分别通过电子束蒸发镀膜仪在硅片上沉积一层纳米厚摄氏度的膜制备的。采用化学气相沉积法，用乙烯做碳源，氩气和氢气作为载气，在有氧化层Si基片上合成高摄氏度取向的碳纳米管阵列。合成的细节和纤维中碳管的自组装可参考已有文献报道。
第二，基于碳纳米管薄膜的燃料敏化太阳能电池的制备。
碳纳米管薄膜是通过干仿法直接从阵列中拉出并转移到FTO玻璃表面，然后是在附有碳纳米管薄膜的基板表面滴加乙醇并在氩气保护下升温到500摄氏度，恒温30分钟并退火，经过以上热处理后碳纳米管薄膜和FTO玻璃之间通过范德华力紧密地连接在一起，形成含有高度取向碳纳米管的对电极。对于柔性电池，碳纳米管薄膜转移到镀有ITO的PEN基板表面，滴加乙醇并在空气中升温到150摄氏度，恒温30分钟并退火。
电池的工作电极是在FTO玻璃上使用丝网印刷法印刷上一层10微米厚的纳米晶二氧化钛层，然后在500摄氏度下煅烧30分钟并退火。然后在二氧化钛表面用50 mM/L的TiCl4水溶液在70摄氏度下处理30分钟，然后在空气中450摄氏度煅烧30分钟并退火，对二氧化钛层表面形貌进行优化。等工作电极温度降到120摄氏度时，把他们转移到0.5mM/L的N719染料溶液中浸泡，16小时后，取出吸附了大量染料的工作电极并用乙腈进行清洗。
最后工作电极和对电极通过一个环形衬底进行封装，封装压力为0.2MPa，温度为125摄氏度，电解液是通过对电极上的小孔中注入。最后使用微型盖玻片和衬底封住小孔，得到完整的电池。
碳纳米管的结构是通过透射电子电镜(TEM, JEOL JEM-2100F operated at 200 kV)来表征的，取向碳纳米管薄膜的结构是通过扫描电子显微镜(SEM, Hitachi FE-SEM S-4800 operated at 1 kV)来表征的。太阳能电池的J-V曲线是通过在一个太阳光的强度下测得，所用太阳能模拟器是Oriel-94023型，带有Keithley 2400源表，和1000WXe灯。电池的交流阻抗谱是在一个太阳光下通过CHI 660a（中国上海）型电化学工作站测得。拉曼光谱是在Renishaw inVia Reflex仪器上测得，激发波长为514.5 nm，室温下激光的能量为20 mW。取向碳纳米管薄膜的透光率是在Shimadz UV-3150上测得。
表1
| CE | Voc (V) | Isc (mA/cm2) | FF | η(%) |
| Pt | 0.67 | 12.49 | 0.63 | 5.27 |
| CNT sheet | 0.67 | 10.80 | 0.57 | 4.18 |
| Random CNT | 0.67 | 7.17 | 0.54 | 2.58 |
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Claims (3)
1.一种以取向碳纳米管为对电极的染料敏化太阳能电池的制备方法，其特征在于具体步骤如下：
（1）制备对电极，碳纳米管薄膜通过干仿法直接从阵列中拉出并转移到FTO玻璃表面，然后是在附有碳纳米管薄膜的基板表面滴加乙醇并在氩气保护下升温到300-600摄氏度，恒温10-60分钟并退火，使碳纳米管薄膜和FTO玻璃之间通过范德华力紧密地连接在一起，形成含有高度取向碳纳米管的对电极；
对于柔性电池，碳纳米管薄膜转移到镀有ITO的PEN基板表面，滴加乙醇并在空气中升温到100-200摄氏度，恒温25--35分钟并退火，得到含有高度取向碳纳米管的对电极；
（2）制备工作电极，在FTO玻璃上使用丝网印刷法印刷上一层4-15微米厚的纳米晶二氧化钛层，然后在450-550摄氏度下煅烧25--35分钟并退火；温度降到25-150度时，把他们转移到0.5mM/L的N719染料溶液中浸泡12--18小时，取出，得到吸附了大量染料的工作电极，并用乙腈进行清洗；
（3）最后工作电极和对电极通过一个环形衬底进行封装，封装压力为0.1-0.5MPa，温度为110-140摄氏度，通过对电极上的小孔注入电解液；最后使用微型盖玻片和衬底封住小孔，得到完整的电池。
2.根据权利要求1所述的染料敏化太阳能电池的制备方法，其特征在于使用的碳纳米管薄膜的制备步骤为：
催化剂采用结构形式为Si/SiO2/Al2O3/Fe的复合材料，其中Al2O3位于硅片和Fe的中间，作为缓冲层，Fe作为催化剂的活性成份，它们分别通过电子束蒸发镀膜仪在硅片上沉积一层纳米厚度的薄膜制备获得；其中，SiO2层厚度为300-1000 μm，Al2O3层厚度为10-30 nm，Fe层厚度为0.5-1.5 nm；采用化学气相沉积法，以Si/SiO2/Al2O3/Fe为催化剂，用乙烯做碳源，氩气和氢气作为载气，在有氧化层Si基片上合成高度取向的碳纳米管阵列；其中乙烯流量为190-290 sccm，氩气流量为400-620 sccm，氢气流量为20-48 sccm，在管式炉中生长5-200 min。
3.一种如权利要求1所述制备方法制备得到的以取向碳纳米管为对电极的染料敏化太阳能电池。
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