CN110600612B - 基于自组装工程的p-i-n型钙钛矿电池空穴传输层 - Google Patents
基于自组装工程的p-i-n型钙钛矿电池空穴传输层 Download PDFInfo
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Abstract
Description
技术领域
本发明属于能源材料领域,具体涉及一种p-i-n型钙钛矿电池空穴传输层的制备及其用途。
背景技术
当今社会,人类生产活动对能源的消耗与日俱增,煤、石油和天然气等不可再生能源逐渐枯竭,开发和利用可再生能源对人类社会的可持续发展具有十分重大的战略意义。其中太阳能是一种应用前景广阔的可再生能源。相比于传统的硅电池,钙钛矿太阳能电池由于其低廉的成本,简单的溶液加工过程和优异的光电转化效率得的各国科研人员和工商界人士的广泛关注,展现出极其光明的商业化价值(Science 2018,361,1214)。
p-i-n型钙钛矿电池具有结构简单,迟滞效应小,不需掺杂长期稳定性好等优点,在未来的实际应用中具有很大竞争力。其中,空穴传输层对p-i-n型电池的钙钛矿活性层形貌和电池性能具有很大影响。除了高光电转化效率和长期工作稳定性,为了满足商业化的需求,钙钛矿电池还必须要能够实现模块化制备。使用有机小分子自组装制备p-i-n型钙钛矿电池空穴传输层被证明是一种成本低廉,材料利用率高的方法(Energy Environ.Sci.,2019,12,230-237)。但是有机分子的疏水性阻碍连续大面积钙钛矿薄膜的制备(Adv.Mater.2017,29,1606363)。因此,解决钙钛矿前驱体在自组装空穴传输层上的不浸润性问题有利于低成本,低能耗钙钛矿电池的大面积制备,推进该技术的商业化。
发明内容
本发明首要目的在于,提供一种p-i-n型钙钛矿电池的空穴传输层,
本发明另一目的在于,提供一种上述空穴传输层材料的制备方法;
本发明再一目的在于,提供一种上述空穴传输层的用途。
相对于现有p-i-n型钙钛矿电池的有机空穴传输层,该类空穴传输层能够实现在大面积基底上的均匀制备并与钙钛前驱体溶液具有良好的亲和性,同时材料利用率高,极大地降低了光电器件中空穴传输层的成本;
本发明的目的通过下述方案实现:
一类基于自组装工程制备空穴传输层,该空穴传输层及自组装分子具有疏水性的式(5)和亲水性的式(9)所示结构的分子结构式合成:
式中:R1为氢,甲基或烷氧基,R2为1~3碳链,R3为卤素原子,n1和n2为0~4。
本发明还提供一种制备本发明所述的自组装分子的方法,其合成步骤如下:
1)
2)
所述方法的主要步骤是:
1)自组装空穴传输材料以取代的溴代三苯胺式(1)所示化合物为起始原料,与二溴代吩噻嗪经Suzuki偶联反应得式(3)所示化合物,然后由式(3)所示化合物与式(4)进行亲核取代反应得式(5)所示化合物;
2)自组装亲水性分子以式(6)和式(7)所示化合物直接生成有机铵盐式(8),再经水解得到终产物式(9)。
附图说明
图1为自组装空穴传输材料在二氯甲烷溶液(支持电解质为0.1M的四丁基六氟磷酸铵)中的循环伏安曲线图;
图2为自组装空穴传输材料与亲水性分子共吸附空穴传输层接触角变化(溶剂为二氯甲烷和异丙醇(V:V=1:1),空穴传输材料浓度保持为0.5mM不变,亲水性分子浓度从0(0%)到0.25mM(50%));
图3为钙钛矿在图2所对应基底薄膜照片;
图4为钙钛矿膜在ITO和含有共吸附空穴传输层(含30%自组装亲水性分子)ITO(以下称ITO/c-SA)上的荧光强度图;
图5为钙钛矿膜在ITO和ITO/c-SA上的寿命图;
图6为以ITO和ITO/c-SA基底的钙钛矿太阳能电池的I-V曲线图;
图7为钙钛矿模块图片(6×6cm-2,左)和基于ITO与ITO/c-SA基底的钙钛矿太阳能模块的I-V曲线图;
图8为5a的核磁氢谱;
图9为5a的高分辨质谱;
图10为9a的核磁氢谱;
图11为9a的高分辨质谱;
图12为基于自组装工程的p-i-n型钙钛矿电池空穴传输层示意图。
具体实施方式
一种制备本发明所述的自组装空穴传输材料和亲水性分子的方法,包括如下步骤:
a)以式(1)和式(2)为原料使用Suzuki偶联反应得到中间体式(3);
b)将中间体式(3)和式(4)置于KOH的DMSO溶液中,加热(100℃)反应,直接得式(5)所示自组装空穴传输材料终产物;
c)以式(6)和式(7)所示化合物在甲醇溶液中常温条件下直接生成有机铵盐式(8),再经水解得到自组装亲水性终产物式(9)。
本发明所述的自组装空穴传输材料和亲水性分子,可经自组装工程形成钙钛矿太阳能电池的空穴传输层。此类空穴传输层具有良好的可扩展性、与钙钛矿前驱体溶液的亲和性以及电荷提取能力,分别对此类空穴传输材料的循环伏安特性、空穴传输层对钙钛矿膜的覆盖率影响以及对钙钛矿层的空穴提取能力进行了表征,结果如附图1~5所示,所说的钙钛矿太阳能电池包括:以导电ITO玻璃作为光阴极,自组装空穴传输材料和亲水性分子作为空穴传输层,有机无机杂化钙钛矿作为光活性层,PCBM为电子传输层,BCP为空穴阻挡层,金或银等金属作为对电极的叠层结构。
下面通过实施例对本发明作进一步的阐述,目的在于更好理解本发明的内容。因此,所举之例并不限制本发明的保护范围:
实施例1
(1)将1a(0.85g,2.2mmol)溶于15mL无水四氢呋喃(THF),注入干燥的schlenk管中,降温至-78℃,注入正丁基锂的正己烷溶液(1.5mL,3.6mmol),保持低温1h,注入硼酸三甲酯(0.4mL,3.6mmol),保持低温反应1h后过夜搅拌,直接进行下一步Suzuki反应。向100mL三口瓶中加入二溴代吩噻嗪(0.355g,1mmol)、四三苯基膦合钯(0.4g,0.105mmol)、四氢呋喃(20mL)和2M碳酸钾水溶液(8mL),氮气保护下升温至回流后,注入之前制备溶液,85℃回流反应10h。冷却至室温,旋干溶剂后加水,用CH2Cl2萃取,有机相旋干后柱层析(200~300目硅胶,DCM:PE=3:1),得到淡黄色固体约500mg,产率62%。
1H NMR(400MHz,DMSO-d6,δ,ppm):8.72(s,1H),7.40(d,J=8.72Hz,4H),7.22(d,J=8.32Hz,2H),7.14(s,2H),7.02(d,J=8.96Hz,8H),6.91(d,J=9.00Hz,8H),6.79(d,J=8.68Hz,4H),6.71(d,J=8.24Hz,2H),3.74(s,12H).HRMS-ESI(m/z):[M+H]+calcd.for(C52H44N3O4S)806.3053,found:806.3047.
(2)在100mL三口烧瓶中,加入3a(150mg,0.19mM),KOH(280mg,0.5M),10mL DMSO,4a(0.14g,0.57mmol),加热到100℃,氮气保护反应10h。后处理:先用盐酸中和,然后使用CH2Cl2萃取,合并有机相后使用Na2SO4,干燥,柱层析(200~300目硅胶,DCM:MeOH=20:1)分离,得到黄色固体终产物(0.14g,79%)。使用核磁氢谱和高分辨质谱对5a进行表征(附图8,9)
1H NMR(400MHz,DMSO-d6,δ,ppm)11.97(s,1H),7.46(d,J=8.4Hz,4H),7.41(d,J=8.6Hz,2H),7.36(s,2H),7.04(d,J=8.9Hz,10H),7.92(d,J=8.9Hz,8H),6.80(d,J=8.6Hz,4H),3.75(s,12H),3.88(s,2H),2.18(t,J=7.2Hz,2H),1.52-1.37(m,4H),1.33-1.24(m,4H).HRMS-ESI(m/z):[M+H]+calcd.for(C59H56N3O6S)934.3890,found:934.3908.
实施例2
向100mL单口烧瓶中依次加入化合物(6a)(0.45g,4.4mmol),7-溴庚酸乙酯(1.0g,4.2mmol)和乙腈(5mL)。油浴加热至75℃搅拌反应30h,旋干溶剂,使用NaOH的水溶液85℃水解。乙醇,丙酮重结晶得白色针状固体化合物(9a)0.98g,产率78%。使用核磁氢谱和高分辨质谱对5a进行表征(附图10,11)
1H NMR(400MHz,D2O,δ,ppm)3.14(q,J=7.2Hz,6H),3.02(t,J=8.6Hz,2H),2.64(t,J=7.3Hz,2H),1.58-1.45(m,4H),1.26-1.25(m,4H),1.14-1.10(m,9H).HRMS-ESI(m/z):[M]+calcd.for(C13H28NO2 +)230.2120,found:230.2124.
其他分子如A1等结构式,可以依照上述类似步骤获取,在此不做赘述。
实施例3
首先对5a的光化学性质进行表征,循环伏安测试表明其最高电子占用轨道能级(HOMO)为-5.20eV与钙钛矿的价带能级相匹配(图1)。
以式(5)和式(9)化合物使用自组装方法制备空穴传输层,在制作电池之前先对混合溶剂中两者混合的比例进行了优化。当式(9)化合物的含量由0%增加到50%,可以明显看出该空穴产生的疏水性的到明显改善(图2),有利于钙钛膜的制备。图3是在不同含量的式(9)化合物自组装薄膜上制备钙钛矿的图片。
以含30%式(9)化合物的自组装膜为例,记为c-SA。稳态荧光测(图4)表明,该空穴传输层的能够有效的提取界面电荷,荧光寿命(图5)同时也证明了这一点。最后将其应用于p-i-n钙钛矿太阳能电池器件,其结构示意图如图12所示,包括如下步骤:
A)自组装空穴传输层的制备:将清洗干净的ITO玻璃放置于式(5)和式(9)化合物的混合溶液中(二氯甲烷:异丙醇=1:1),35℃浸泡8小时,使用乙醇冲洗后吹干,转移到手套箱中,120℃加热20分钟后冷却到室温待用;
B)钙钛矿层的制备:将PbI2(1.2M)和MAI(1.2M)溶于DMF和DMSO的混合溶液中(DMF和DMSO体积比为1:4),50℃搅拌12小时形成钙钛矿前驱体溶液,再以氯苯为反溶剂,通过“一步法”在自组装空穴传输层上沉积一层钙钛矿膜;
C)电子传输层和空穴阻挡层的制备:使用氯苯配制[6,6]-phenyl-C61-butyricacid methyl ester(PCBM)溶液(20mg mL-1),50℃搅拌过夜,然后将此溶液旋涂于钙钛矿层上,空穴阻挡层由旋涂浴灵铜(BCP)的饱和溶液得到;
D)在空穴阻挡层上真空蒸镀100nm的银作为对电极。
将此钙钛矿太阳能电池,放置于AM1.5的模拟太阳光下测量其电流密度-电压曲线(测试仪器为(Keithley 2400数字源表(美国Keithley公司))。电池的开路电压为1.039V,短路电流为21.80mA cm-2,填充因子为0.77,光电转化效率为17.49%。其光电流和光电压曲线见图6。而不含有该空穴传输层在相同条件下制备的电池,其光电转化效率要低,具体参数如下,开路电压为0.96V,短路电流为16.26mA cm-2,填充因子为0.57,光电转化效率为8.93%。更进一步,我们将该空穴传输层用于小型模块组件中,面积为36cm-2。相比于不含有空穴传输层的模块而言,含有该自组装空穴传输层的模块效率由5.3%提高到12.7%。模块图片及光伏曲线见图7。
Claims (6)
1.一种基于自组装工程的p-i-n型钙钛矿电池空穴传输层,该空穴传输层及自组装分子具有疏水性的式(5)和亲水性的式(9)所示结构的分子结构式合成:
式中:R1为氢,甲基或C1-C6烷氧基,R2为1~3碳链,R3为卤素原子,n1为0~4;n2为0~4;
该疏水性的式(5)和亲水性的式(9)的合成方法是:
1)
2)
1)自组装空穴传输材料以取代的溴代三苯胺式(1)所示化合物为起始原料,与二溴代吩噻嗪经Suzuki偶联反应得式(3)所示化合物,然后由式(3)所示化合物与式(4)进行亲核取代反应得式(5)所示化合物;
2)自组装亲水性分子以式(6)和式(7)所示化合物直接生成有机铵盐式(8),再经水解得到式(9);
3)自组装空穴传输层的制备:将清洗干净的ITO玻璃放置于式(5)和式(9)化合物的二氯甲烷:异丙醇=1:1混合溶液中,35℃浸泡8小时,使用乙醇冲洗后吹干,转移到手套箱中,120℃加热20分钟后冷却到室温待用;
4)钙钛矿层的制备:将1.2mol PbI2和1.2mol MAI溶于DMF和DMSO的混合溶液中,DMF和DMSO体积比为1∶4,50℃搅拌12小时形成钙钛矿前驱体溶液,再以氯苯为反溶剂,通过一步法在自组装空穴传输层上沉积一层钙钛矿膜。
2.如权利要求1所述的基于自组装工程的p-i-n型钙钛矿电池空穴传输层,其特征在于,R3为氯,溴或碘离子。
3.如权利要求1所述的基于自组装工程的p-i-n型钙钛矿电池空穴传输层,其特征在于,所述亲水性的式(9)中亲水性基团为卤化铵。
4.如权利要求3所述的基于自组装工程的p-i-n型钙钛矿电池空穴传输层,其特征在于,所述卤化胺为氯化铵或溴化铵。
5.如权利要求1~4中任意一项所述的空穴传输层在制备p-i-n型钙钛矿太阳能电池中的应用。
6.一种制备权利要求1所述基于自组装工程的p-i-n型钙钛矿电池空穴传输层的方法,其合成步骤如下:
1)
2)
1)自组装空穴传输材料以取代的溴代三苯胺式(1)所示化合物为起始原料,与二溴代吩噻嗪经Suzuki偶联反应得式(3)所示化合物,然后由式(3)所示化合物与式(4)进行亲核取代反应得式(5)所示化合物;
2)自组装亲水性分子以式(6)和式(7)所示化合物直接生成有机铵盐式(8),再经水解得到式(9);
3)自组装空穴传输层的制备:将清洗干净的ITO玻璃放置于式(5)和式(9)化合物的二氯甲烷:异丙醇=1∶1混合溶液中,35℃浸泡8小时,使用乙醇冲洗后吹干,转移到手套箱中,120℃加热20分钟后冷却到室温待用;
4)钙钛矿层的制备:将1.2mol PbI2和1.2mol MAI溶于DMF和DMSO的混合溶液中,DMF和DMSO体积比为1∶4,50℃搅拌12小时形成钙钛矿前驱体溶液,再以氯苯为反溶剂,通过一步法在自组装空穴传输层上沉积一层钙钛矿膜。
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