CN113233968A - 一种聚合物太阳能电池活性层添加剂及其制备方法 - Google Patents
一种聚合物太阳能电池活性层添加剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚合物太阳能电池活性层添加剂及其制备方法，将4‑氟苯甲醛、4‑氯苯甲醛或4‑溴苯甲醛与1,3‑茚满二酮在乙醇溶液中混合，加入哌啶搅拌混合均匀，升温至60‑70℃反应回流3‑5小时；冷却至室温过滤沉淀物，并用乙醇洗涤；以二氯甲烷作为洗脱液使用硅胶柱层析法进一步纯化残余物，得到黄色固体。在活性层溶液中添加少量本发明固体添加剂，旋涂成膜，经相应的退火处理后即可得到具备良好微纳形貌的活性层薄膜，器件的光电转换效率与液体添加剂的效果无异。应用于PM6:Y6‑BO和PM6:Y7‑BO二元异质结聚合物太阳能电池活性层体系不仅保持着高效率，而且兼具了优异的运行稳定性。
Description
技术领域
本发明属于聚合物太阳能电池技术领域，具体涉及聚合物太阳能电池添加剂及其制备方法。
背景技术
人类频繁的社会活动加剧了不可再生资源的消耗，也带来了冰川融化、海平面上升、土地荒漠化等问题，这些问题造成的社会损失不可估量。在太阳能、风能、地热能、潮汐能、生物质能等可再生能源中，太阳能来源广泛、清洁安全、使用可靠、垂手可得，是最为理想的能源之一。太阳能电池利用光伏效应把太阳能转变为电能，转换过程中不会产生任何有害的副产物，是一种高效利用太阳能的方式。根据不同的光活性半导体材料，太阳能电池可划分为硅基太阳能电池、染料敏化太阳能电池、量子点太阳能电池、钙钛矿太阳能电池和聚合物太阳能电池等。相比于其他太阳能电池，聚合物太阳能电池质量轻、柔性好、可采用溶液法加工，通过化学改性能调控材料的结构以改善器件的光电性能，这些特点，均使得聚合物太阳能电池成为研究热点。如今，单结聚合物太阳能电池的最高转换效率高于18％，已超过叠层有机太阳能电池(17.3％)。然而，聚合物太阳能电池要走向商业化，不仅需要高效率，还要保证优良的运行稳定性。
PBDB-T-2F(PM6):BTP-BO-4F(Y6-BO)和PM6:BTP-BO-4Cl(Y7-BO)是两种高效率的二元异质结聚合物太阳能电池活性层体系，具有很大的应用潜力。但其缺点在于使用了稳定性较差的液体添加剂1,8-二碘辛烷(DIO)，在后续的存储和运行过程中，残留的DIO缓慢挥发，会损害器件的长期稳定性。
发明内容
本发明的目的是在太阳能电池活性层体系中引入一种新型分子结构固体添加剂，在保持高光电转换效率的同时，也达到了优良的运行稳定性；本发明另一目的在于提供一种稳定高效的二元异质结聚合物太阳能电池。
为达到上述目的，采用技术方案如下：
一种聚合物太阳能电池活性层添加剂，具有以下分子结构：
上述聚合物太阳能电池活性层添加剂的制备方法，包括以下步骤：
将4-氟苯甲醛、4-氯苯甲醛或4-溴苯甲醛与1,3-茚满二酮在乙醇溶液中混合，加入哌啶搅拌混合均匀，升温至60-70℃反应回流3-5小时；冷却至室温过滤沉淀物，并用乙醇洗涤；以二氯甲烷作为洗脱液使用硅胶柱层析法进一步纯化残余物，得到黄色固体。
按上述方案，4-氟苯甲醛、4-氯苯甲醛或4-溴苯甲醛与1,3-茚满二酮的摩尔比为1:1。
一种聚合物太阳能电池，包括透明导电基底、电子传输层、光活性层、空穴传输层和金属电极；其中所述光活性层中添加了上述添加剂。
按上述方案，所述光活性层中给体材料为PM6；受体材料为Y6-BO或Y7-BO。
按上述方案，所述添加剂在光活性层中的添加量相对于受体的质量占比25wt％。
其中，给体材料PM6、受体材料Y6-BO、Y7-BO以及氟、氯取代的添加剂分子式如下：
本发明聚合物太阳能电池活性层添加剂的分子反应方程式如下：
相对于现有技术，本发明有益效果如下：
本发明卤化的固体添加剂合成路线简洁，结构由茚酮单元和卤素原子组成，在氯仿、氯苯、邻二氯苯等常用溶剂中均具有良好的溶解性，且挥发性很强，110℃退火10分钟即可被完全除去。同时其高度的分子平面性有利于提供电子受体分子之间π-π堆叠的桥梁，控制分子的聚集态。
在活性层溶液中添加少量本发明固体添加剂，旋涂成膜，经相应的退火处理后即可得到具备良好微纳形貌的活性层薄膜，器件的光电转换效率与液体添加剂的效果无异。应用于PM6:Y6-BO和PM6:Y7-BO二元异质结聚合物太阳能电池活性层体系不仅保持着高效率，而且兼具了优异的运行稳定性。
电子给体材料PM6的光学吸收谱带分别与Y6-BO和Y7-BO互补，从500nm至850nm处宽阔的吸收范围使器件的短路电流较高，制备的聚合物太阳能电池具有良好的光电转换效率，这为得到高效稳定的电池提供了效率基础。
附图说明
图1：实施例1所得产品核磁共振氢谱图；
图2：实施例1所得产品核磁共振碳谱图；
图3：实施例2所得产品核磁共振氢谱图；
图4：实施例2所得产品核磁共振碳谱图；
图5：实施例3所得产品核磁共振氢谱图；
图6：实施例3所得产品核磁共振碳谱图；
图7：PM6:Y6-BO和PM6:Y7-BO聚合物太阳能电池光伏性能参数变化图。
具体实施方式
以下实施例进一步阐释本发明的技术方案，但不作为对本发明保护范围的限制。
实施例1：
X为F的固体添加剂INB-F的具体制备方法如下：
将4-氟苯甲醛(1.24g，10mmol)和1,3-茚满二酮(1.46g，10mmol)在乙醇溶液(50mL)中混合，加入哌啶(85.15mg，1mmol)搅拌混合均匀，升温至60-70℃反应回流3-5小时；冷却至室温过滤沉淀物，并用乙醇洗涤；以二氯甲烷作为洗脱液使用硅胶柱层析法进一步纯化残余物，得到黄色固体(1.38g，55％)。
本实施例所得产品核磁共振核磁共振氢谱图见图1所示，1H NMR(500MHz,CDCl3)δ8.57–8.44(m,2H),7.97(s,2H),7.80(s,3H),7.16(t,J＝8.1Hz,2H).19F NMR(471MHz,CDCl3)δ-103.4(s)。
本实施例所得产品核磁共振碳谱图见图2所示，13C NMR(126MHz,CDCl3)δ190.2(s),189.2(s),166.7(s),164.6(s),145.5(s),142.5(s),140.1(s),137.0(d,J＝9.3Hz),135.5(s),135.3(s),129.6(d,J＝3.1Hz),128.7(s),123.4(d,J＝2.4Hz),116.2(s),116.1(s)。
实施例2：
X为Cl的固体添加剂INB-Cl的具体制备方法如下：
将4-氯苯甲醛(1.4g，10mmol)和1,3-茚满二酮(1.46g，10mmol)在乙醇溶液(50mL)中混合，加入哌啶(85.15mg，1mmol)搅拌混合均匀，升温至60-70℃反应回流3-5小时；冷却至室温过滤沉淀物，并用乙醇洗涤；以二氯甲烷作为洗脱液使用硅胶柱层析法进一步纯化残余物，得到黄色固体(1.22g，43.8％)。
本实施例所得产品核磁共振氢谱图见图3所示，1H NMR(500MHz,CDCl3)δ8.41(d,J＝8.5Hz,2H),8.01(d,J＝5.3Hz,2H),7.82(t,J＝4.3Hz,3H),7.47(d,J＝8.5Hz,2H)。
本实施例所得产品核磁共振碳谱图见图4所示，13C NMR(126MHz,CDCl3)δ198.6(s),192.1(s),170.1(s),168.3(s),150.1(s),143.1(s),142.1(s),137.7(d,J＝9.3Hz),136.7(s),136.4(s),130.5(d,J＝3.1Hz),129.6(s),128.1(d,J＝2.4Hz),118.3(s),117.1(s)。
实施例3
X为Br的固体添加剂INB-Br的具体制备方法如下：
将4-溴苯甲醛(1.84g，10mmol)和1,3-茚满二酮(1.46g，10mmol)在乙醇溶液(50mL)中混合，加入哌啶(85.15mg，1mmol)搅拌混合均匀，升温至60-70℃反应回流3-5小时；冷却至室温过滤沉淀物，并用乙醇洗涤；以二氯甲烷作为洗脱液使用硅胶柱层析法进一步纯化残余物，得到黄色固体(0.84g，53.6％)。
本实施例所得产品核磁共振氢谱图见图5所示，1H NMR(500MHz,CDCl3)δ8.33(d,J＝8.5Hz,2H),8.02(dd,J＝5.8,4.3Hz,2H),7.85-7.79(m,3H),7.64(d,J＝8.5Hz,2H)。
本实施例所得产品核磁共振碳谱图见图6所示，13C NMR(126MHz,CDCl3)δ187.5(s),186.8(s),142.7(s),140.8(s),136.2(s),136.1(s),135.5(s),125.4(s),123.9(d,J＝18.2Hz)。
实施例4
制备一种兼具高的光电转换效率和良好的运行稳定性的二元体系异质结构聚合物太阳能电池，其结构为ITO/ZnO/PM6:Y6-BO/MoO3/Au或ITO/ZnO/PM6:Y7-BO/MoO3/Au，具体实施过程如下：
光活性层的制备步骤为：以1:1.2的质量比将PM6:Y6-BO或PM6:Y7-BO溶于氯仿溶液中，加入25wt.％(相对于Y6-BO/Y7-BO的质量)的INB-F或INB-Cl固体添加剂，搅拌均匀的溶液旋涂于电子传输层ZnO上，在110℃下退火10分钟，得到厚度约为100nm的活性层薄膜。
该聚合物太阳能电池其余部分的制备过程与一般电池无异，依次在透明导电基底氧化铟锡(ITO)玻璃上沉积电子传输层氧化锌(ZnO)、光活性层PM6:Y6-BO或PM6:Y7-BO、空穴传输层氧化钼(MoO3)、金(Au)电极。得到的聚合物太阳能电池在标准模拟太阳光谱下进行光电转换效率和运行稳定性测试，PM6:Y6-BO电池的光伏性能参数见表1，PM6:Y7-BO电池的光伏性能参数见表2。
表1
对于PM6:Y6-BO器件来说，不加任何添加剂的参比电池，最高的光电转换效率(PCEmax)仅有15.1％(平均效率PCEave为14.6±0.4％)，填充因子FF、短路电流JSC、开路电压VOC分别为68.6％、25.3mA cm-2、0.84V。相比之下，活性层中加入DIO后，器件的JSC和VOC几乎没有改变，分别为25.5mA cm-2、0.84V，最终的PCEmax达到16.3％(PCEave为16.1±0.2％)。固体添加剂INB-F和INB-Cl加入PM6:Y6-BO混合溶液中调节活性层的成膜过程，并在蒸镀空穴传输层和电极之前经过110℃退火10分钟被除去。该方法制备的器件，尽管VOC稍有降低，但FF分别能提升至76.3％和74.5％，JSC提升至26.2和26.7mA cm-2，最终器件的最大效率各自达到16.7％和16.3％。
表2
对于PM6:Y7-BO体系，添加剂的效果是类似的，DIO处理的器件PCEmax从没有任何添加剂的15.3％增大到16.5％；而固体添加剂INB-F和INB-Cl尽管让VOC略微降低，器件的FF和JSC却大幅提升，最终分别使PM6:Y7-BO器件的效率提升至16.3％和16.8％。以上结果说明，INB-F和INB-Cl固体添加剂，在优化器件的光伏性能上，优于液体添加剂DIO。
对器件的运行稳定性测试，用环氧树脂和载玻片封装电池，在20℃室温大气环境和标准光强(白色LED光源)下照射1000小时，期间连续运行，每隔10分钟测试一次，实时观察各光伏参数的变化。图7展示了归一化的PM6:Y6-BO体系的太阳能电池运行稳定性变化，表1的最后一列标出了几种电池的T80参数(电池损失原始效率的20％所用的时间)，显然，加入了DIO的器件稳定性最差，运行初始就经历了快速的老化过程，效率呈指数衰减，T80仅为6.6h。运行1000小时后效率骤降，仅为初始效率的20％以下，甚至低于参比器件：仍能保持40％的效率(T80＝66.2h)。薄膜中残留的DIO缓慢挥发，对器件的长期稳定性造成不良影响。而对于加入了INB-Cl的电池，JSC和FF的衰减趋势缓和，T80为120h，在运行1000小时后，电池保持了约50％的效率。INB-F能获得最稳定的太阳能电池，它的PCE和VOC衰减速度最慢，T80为523小时，电池运行1000小时后仍能维持初始效率的60％。固体添加剂INB-F和INB-Cl对PM6:Y7-BO体系太阳能电池运行稳定性的影响与PM6:Y6-BO相似。
本实施例的结果充分说明，本发明制备的固体添加剂提供了一种简单有效的方法，能同时提升聚合物太阳能电池的光电转换效率和运行稳定性。
Claims (6)
1.一种聚合物太阳能电池活性层添加剂，其特征在于具有以下分子结构：
2.权利要求1所述聚合物太阳能电池活性层添加剂的制备方法，其特征在于包括以下步骤：
将4-氟苯甲醛、4-氯苯甲醛或4-溴苯甲醛与1,3-茚满二酮在乙醇溶液中混合，加入哌啶搅拌混合均匀，升温至60-70℃反应回流3-5小时；冷却至室温过滤沉淀物，并用乙醇洗涤；以二氯甲烷作为洗脱液使用硅胶柱层析法进一步纯化残余物，得到黄色固体。
3.如权利要求2所述聚合物太阳能电池活性层添加剂的制备方法，其特征在于4-氟苯甲醛、4-氯苯甲醛或4-溴苯甲醛与1,3-茚满二酮的摩尔比为1:1。
4.一种聚合物太阳能电池，包括透明导电基底、电子传输层、光活性层、空穴传输层和金属电极；其特征在于所述光活性层中添加了权利要求1所述的添加剂。
5.如权利要求4所述聚合物太阳能电池，其特征在于所述光活性层中给体材料为PM6；受体材料为Y6-BO或Y7-BO。
6.如权利要求4所述聚合物太阳能电池，其特征在于所述添加剂在光活性层中的添加量相对于受体的质量占比25wt％。
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