CN113461911A - 一类离子共轭聚电解质材料的合成方法及其在钙钛矿太阳能电池中的应用 - Google Patents
一类离子共轭聚电解质材料的合成方法及其在钙钛矿太阳能电池中的应用 Download PDFInfo
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- CN113461911A CN113461911A CN202110562664.7A CN202110562664A CN113461911A CN 113461911 A CN113461911 A CN 113461911A CN 202110562664 A CN202110562664 A CN 202110562664A CN 113461911 A CN113461911 A CN 113461911A
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- conjugated polyelectrolyte
- perovskite
- fluorenyl
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Abstract
本专利主要是将一类芴基离子共轭聚电解质材料，作为界面材料，用于正置结构钙钛矿太阳能电池钙钛矿与空穴传输层之间；修饰后的钙钛矿层质量得到显著提高，晶界减少，表面均匀、规整，对水、氧的稳定性明显改善；制备的钙钛矿层太阳能电池具有优异的光电转换效率与稳定性。展示出该类材料在钙钛矿太阳能电池领域中潜在而广泛的应用前景；
Description
技术领域
本发明涉及一类芴基离子共轭聚电解质材料的化学结构设计、合成及其作为钙钛矿太阳能电池界面材料的应用。
背景技术
太阳能电池是一种将太阳能转化为电能的器件装置，是未来人类获取能源不可或缺的重要组成部分。太阳能电池根据发展阶段可分为第一代硅太阳能电池(SC)，其主要技术结构为以硅为基体材料的太阳能电池，包括单晶硅、多晶硅太阳能电池。由CdTe、CIGS和非晶硅制成的第二代薄膜太阳能电池，其层厚度范围从几纳米到几十微米，与第一代晶体硅太阳能电池相比，第二代薄膜太阳能电池具有更加低廉的成本，但功率转换效率(PCE)较低。正在发展的第三代太阳能电池，包括有机、染料敏化、聚合物、铜锌锡硫(CZTS)、纳米晶体、微晶、量子点和钙钛矿太阳能电池等多个种类。在过去的几十年中，太阳能电池技术在快速地进步，其中钙钛矿太阳能电池发展最快，现如今其光电转化效率已经突破23％，叠层钙钛矿太阳能电池的效率已经突破25％。钙钛矿太阳能电池吸光层主要是由有机-无机铅或卤化锡组成，工作原理涉及到钙钛矿层对光子的吸收及激子的产生过程，电子、空穴分别向传输层的注入及传输过程，与电极的收集过程。在平面型太阳能电池的制备过程中，界面存在缺陷，导致载流子被捕获或者发生复合。这些缺陷存在于钙钛矿层、载流子传输层和电极之间的界面上，所以对器件界面进行改性可有效减少缺陷、促进载流子传输、降低载流子复合，最终可提高器件的光电转换效率和稳定性。
离子共轭聚电解质材料具有丰富的电学性能，可用于界面能级的调控及晶体表面质量的提高。
发明内容
1.本发明的特征是提供一类芴基离子共轭聚电解质，其结构如下所示：
式中R为1～16烷基直链与支链。
R为
芴基离子共轭聚电解质材料为FF-BOC，其结构式为：
2.本发明的另一特征是提供用于上述芴基离子共轭聚电解质材料的合成方法。
3.本发明的另一特征是芴基离子共轭聚电解质作为钙钛矿太阳能电池界面材料的应用。
附图说明
结合如下附图及详细描述将会更清楚地理解本发明的上述和其它特征及优点，其中：
图1化合物1的核磁共振氢谱图；
图2化合物2的核磁共振氢谱图；
图3化合物3的核磁共振氢谱图；
图4化合物4的核磁共振氢谱图；
图5化合物5的核磁共振氢谱图；
图6化合物6的核磁共振氢谱图；
图7钙矿太阳能电池结构示意图；
图8钙钛矿太阳能电池短路电流密度JSC(mA/cm2)-开路电压VOC(V)曲线图
具体实施方式
下面对本发明的优选实施案例进行详细阐述，以使本发明的优点和特征能更易于被本领域技术人员理解，以芴基离子共轭聚电解质FF-BOC为例说明材料的化学合成。
实施案例1：
芴基离子共轭聚电解质FF-BOC的合成：
反应方程式如下：
化合物1的合成
将10g芴和0.15g的FeCl3溶解在50mL氯仿中，将溶液温度降至0℃，然后滴加6.46mL的Br2；滴加完成后缓慢升至室温，继续搅拌2h。后处理：用饱和亚硫酸氢钠水溶液中和所得混合物，并用20mL二氯甲烷萃取三次。合并有机相用无水硫酸钠干燥，减压下蒸发除去溶剂。不需要进一步纯化，获得白色固体化合物，收率为95％。1H NMR(400MHz，CDCl3)δ(ppm)：7.67(s，2H)，7.61(d，2H)，7.50(d，2H)，3.88(s，2H)。
化合物2的合成
将6g的化合物1、5.16g丙烯酸甲酯、600mg四丁基溴化铵和30mL甲苯添加到三颈烧瓶中，在搅拌下加入12mL的50％的NaOH水溶液，然后使反应在室温下进行过夜。第二天，将甲苯层转移至烧瓶中，用两份甲苯萃取水层。合并有机相，用MgSO4干燥，在低真空下蒸发除去溶剂。所得粗品经硅胶柱色谱法纯化，用石油醚为洗脱剂，获得的纯产物为白色固体，产率90％。1H NMR(400MHz，DMSO-d6)δ(ppm)：7.83(d，2H)，7.78(s，2H)，7.58(d，2H)，3.36(s，6H)，2.40(t，4H)，1.42(t，4H)。
化合物3合成
将4g的化合物2加到70mL的1，4-二氧六环中，加入42mL的0.5mol/L的KOH水溶液，然后在70℃下回流24小时。冷却到室温，将溶液在低真空下旋转蒸发以除去过量的1，4-二氧六环。加入1mol/L的HCl溶液将PH值调节至约2，得到白色沉淀，将其过滤用大量水洗涤，获得白色粉末状固体，产率80％。1H NMR(400MHz，DMSO-d6)δ(ppm)：7.83(d，2H)，7.81(s，2H)，7.58(d，2H)，3.34(t，4H)，1.31(t，4H)。
化合物4合成
向三颈烧瓶中加入6g的化合物3和60mL的THF，再加入56mL的1.0M硼烷-四氢呋喃络合物；在20℃搅拌反应2小时，将反应混合物倒入水中以淬灭反应并形成沉淀。加入50mL乙酸乙酯，沉淀物溶解，分层收集有机相；再用乙酸乙酯从水相萃取两次，合并的有机相用MgSO4干燥，低压蒸馏除去溶剂，获得的固体用氯仿重结晶，得到浅黄色针状晶体，产率85％。1H NMR(400MHz，DMSO-d6)δ(ppm)：7.81(d，2H)，7.68(s，2H)，7.54(d，2H)，4.23(t，2H)，3.12(q，4H)，2.01(m，4H)，0.61(m，4H)。
化合物5合成
在氮气气氛下，将0.5g化合物4、0.65g的对甲苯磺酰氯和5mL二氯甲烷加入三口烧瓶中，将冷却至0℃，加入0.39mL的吡啶；自然升至室温，搅拌反应过夜。反应结束后加15mL水淬灭，用15mL的二氯甲烷萃取三次，有机相经无水MgSO4干燥后减压蒸发除去溶剂得到粗品。用二氯甲烷作为洗脱剂将粗品通过硅胶柱色谱法纯化，得到固体粉末产品，产率为47.9％。1H NMR(400MHz，CDCl3)δ(ppm)：7.69(d，4H)，7.47(t，4H)，7.35(s，2H)，7.32(d，4H)，3.74(t，4H)，2.44(s，6H)，1.94(m，4H)，0.88(m，4H)。
化合物6合成
在氮气气氛下，将0.6g丝氨酸与0.3g的化合物5溶解在60mL的DMF中，加入0.105g的K2CO3，在35℃下反应30小时。后处理：在反应混合物中加入150mL的2M HCl进行淬灭，用3×50mL乙醚萃取；将合并的有机层用1M HCl(2×50mL)和水(2×50mL)依次洗涤，用MgSO4干燥，在低压下蒸馏除去有机溶剂。将收集的固体粗品经硅胶色谱柱纯化，用乙酸乙酯和石油醚的混合溶剂为洗脱剂，获得白色产物，产率75％。1H NMR(400MHz，DMSO-d6)δ(ppm)：7.82(d，2H)，7.72(s，2H)，7.55(d，2H)，6.85(d，2H)，4.84(t，2H)，3.94(m，2H)，3.78(m，4H)，3.57(t，4H)，2.06(t，4H)，1.34(s，18H)，0.78(m，4H)。
芴基离子共轭聚电解质FF-BOC的合成：
取化合物6和9，9-二辛基芴-2，7-双(硼酸频哪醇酯)加入三口烧瓶中，迅速加入四(三苯基膦)钯催化剂，在氮气气氛下，加入除氧后的5mL甲苯溶液、5mL四氢呋喃及2M的碳酸钠水溶液。反应在氮气保护、85℃温度下搅拌回流72h。后处理：将反应体系冷却至室温，立即向混合物中加入50mL的乙腈，过滤收集沉淀。在Soxhlet装置中使用丙酮将所得固体物质洗涤24h，除去低聚物、单体及残留催化剂。最终得到聚合物FF-BOC。其中FF-BOC的重均分子量(Mw)为18007g/mol。
实施案例2：
钙钛矿太阳能电池的制备与表征：
(1)使用稀盐酸和锌粉将1.5cm x 1.5cm的ITO基片进行刻蚀，之后用棉球擦，用水冲洗干净，去离子水、丙酮、异丙醇各超声15min清洗，用氮气吹干，UV-O3中照射20min。
(2)标准器件ITO/SnO2/MAPbI3/Spiro-OMeTAD/Au的制备：
先将SnO2旋涂到处理过的ITO基片上，在100-150℃的条件下退火10-40min；将配置好的PbI2与MAI的DMSO/DMF的混合溶液旋涂到SnO2薄膜上面，在80-130℃的条件下退火10-20min；最后以4000rpm、30s旋涂Spiro-OMeTAD，蒸镀Au薄膜80nm。
(3)FF-BOC作为界面传输材料的电池ITO/SnO2/MAPbI3/FF-BOC/Spiro-OMeTAD/Au制备：
步骤同以上(1)与(2)，不同之处在于引入FF-BOC用于修饰钙钛矿层与Spiro-OMeTAD层之间的界面，FF-BOC层制备条件4000rpm、30s旋涂FF-BOC，130℃退火10min。
(4)电池性能测试：
使用Keithley2400对器件进行性能测试：在模拟AM 1.5G太阳光照射条件下(光强度为100mW/cm2)可获得光电流-电压曲线，扫描电压范围是1.2V→-1.2V。
FF-BOC作为界面传输层，具有高空穴迁移率、良好的界面相容性与疏水性；修饰后的钙钛矿层质量得到显著提高，晶界减少，表面均匀、规整，对水、氧的稳定性明显改善；电池光电转换效率从19％提高到22％，在湿度为25-40％的大气环境下，未封装电池60天后，光电转换效率没有降低。
Claims (4)
1.一类芴基离子共轭聚电解质，其特征在于：芴基离子共轭聚电解质材料结构通式如下：
其中，式中R为1～16烷基直链与支链。
2.根据权利要求1所述芴基离子共轭聚电解质材料的合成方法，其特征在于：芴经溴化得到芴的二溴化物；该二溴化物反应生成侧链含有酯基的芴衍生物，在碱的作用下脱掉甲氧基得到侧链含有酸根的芴衍生物；将酸根还原得到羟基，该羟基经对-甲苯磺酰基的活化，与氨基酸在碱的作用下反应，在侧链上引入氨基酸基团；用BOC基团对氨基进行保护，然后与9，9-二辛基芴-2，7-双(硼酸频哪醇酯)在钯催化剂作用下聚合得到共轭聚电解质材料。
3.一类芴基离子共轭聚电解质作为界面材料应用于钙钛矿太阳能电池，其特征在于：先将SnO2溶液旋涂到处理过的导电玻璃ITO基片上，在100-150℃的条件下退火10-40min；然后将钙钛矿溶液旋涂到ITO/SnO2基片上，在80-130℃的条件下退火10-20min；再将配好的芴基离子共轭聚电解质溶液引入到钙钛矿层上，而后将Spiro-OMeTAD溶液旋涂到界面层上；最后转置于真空蒸镀仓内，蒸镀80nm的Au电极。
4.根据权利要求3所述芴基离子共轭聚电解质用于钙钛矿层与空穴传输层之间的界面层，其特征在于：修饰后的钙钛矿层质量得到显著提高，制备的钙钛矿层太阳能电池的性能具有优异的光电转换效率与稳定性。
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