CN114085361A - 一种三苯胺联萘酚共聚物及其在太阳能电池中的应用 - Google Patents
一种三苯胺联萘酚共聚物及其在太阳能电池中的应用 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种三苯胺联萘酚共聚物及其在太阳能电池中的应用,属于钙钛矿太阳能电池技术领域。
背景技术
将清洁和可持续的太阳能转化为电能是解决化石能源短缺和环境污染问题的重要途经之一。近年来,有机-无机杂化钙钛矿太阳能电池(Perovskite solar cells,PSCs)成为新能源领域的研究热点。PSCs基于有机金属卤化物钙钛矿(ABX3,如CH3NH3PbI3)光活性层材料,可溶液加工的工艺简单且光电转换效率(PCE)高,目前PCE已经超过了25%,具有良好的商业化前景。空穴传输材料(Hole Transporting Material,HTM)有助于钙钛矿太阳能电池结构的界面调节,对于减少电荷复合,加速空穴传输起到关键性的作用,能够有效地提高钙钛矿太阳能电池的PCE。然而,PSC仍面临着对水、空气、热、光等的一系列的稳定性问题,这些问题均与钙钛矿的结构和晶格缺陷密切相关,根据钙钛矿薄膜缺陷的特性,修补钙钛矿薄膜的缺陷可在提高效率的同时提高器件的稳定性。开发具有保护钙钛矿层功能的空穴传输材料是提高钙钛矿太阳能电池器件性能的重要手段。
现有技术中,钙钛矿太阳能电池中最广泛使用的有机空穴传输材料主要为2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(Spiro-OMeTAD)。但是Spiro-OMeTAD化学结构复杂、合成路线长、价格昂贵,同时该材料空穴迀移率较低。通常需要采用双(三氟甲基磺酰亚胺)锂(LiTFSI)、叔丁基吡啶(TBP)等进行p型掺杂来提高空穴迀移率,但这类掺杂会导致电池器件性能不稳定。
参考文献:
1)Park,N-G.Perovskite Solar Cells:An Emerging Photovoltaic Technology[J].Mater.Today 2015,18,65-72;
2)National Renewable Energy Laboratory.(NREL)Best Research-CellEfficiencies,https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.20200104.pdf.
3)Hawash,Z.;Ono,L.K.;Qi Y.B.Recent Advances in Spiro-MeOTAD HoleTransport Material and Its Applications in Organic–Inorganic HalidePerovskite Solar Cells[J].Adv.Mater.Interfaces 2018,5,1700623.
4)Boyd,C.C.;Cheacharoen,R;Leijtens,T.;McGehee M.D.UnderstandingDegradation Mechanisms and Improving Stability of Perovskite Photovoltaics[J].Chem.Rev.2019,119,3418-3451.
5)黄飞洪,宋金魁,廖沛哲,王鸣魁钙钛矿太阳能电池的稳定性[J].科学通报2017,62,4256-4269.
发明内容
本发明针对现有技术存在的不足,提供一种三苯胺联萘酚共聚物及其在钙钛矿太阳能电池中的应用,提高钙钛矿太阳能电池器件的稳定性。
本发明解决上述技术问题的技术方案如下:一种三苯胺联萘酚共聚物,所述三苯胺联萘酚共聚物的结构式为如下式I或式II中的任意一个:
优选的,所述三苯胺联萘酚共聚物的结构式I由化合物式III反应制得,所述三苯胺联萘酚共聚物的结构式II由化合物式IV反应制得,式III和式IV的结构式如下:
优选的,所述三苯胺联萘酚共聚物为如下结构式中的任意一个:
所述三苯胺联萘酚共聚物的下结构式最优选为I-1、II-1:
本发明还公开了所述三苯胺联萘酚共聚物的应用:
所述三苯胺联萘酚共聚物应用于钙钛矿太阳能电池。
进一步的,所述钙钛矿太阳能电池包括空穴传输层,所述三苯胺联萘酚共聚物作为钙钛矿太阳能电池的空穴传输层材料应用;所述空穴传输层的厚度优选为20~100nm。
本发明的有益效果是:
与现有技术相比,本发明提供的三苯胺联萘酚共聚物将具有空间构型的三苯胺和联萘酚交替连接,使得该材料能在空间上有较好的重叠性,有效延伸π共轭中心核,通过引入对二甲氧基(或烷基)二苯氨基等电子给体,以提高空穴迁移率,为PSCs提供足够的载流子;再引入带有孤对电子的氮、氧来钝化钙钛矿层,修补钙钛矿薄膜的缺陷,抑制钙钛矿分解,提高钙钛矿太阳能电池器件的稳定性。实验结果表明,采用本发明所述的三苯胺联萘酚共聚物作为空穴传输层制备的钙钛矿太阳能电池器件具有19.5%~21.2%的能量转换效率,同时,制备得到的钙钛矿太阳能电池器件具有优秀的稳定性。
附图说明
图1为实施例中所述钙钛矿太阳能电池器件的结构示意图;
图2基于I-1和II-1空穴传输层材料的钙钛矿太阳能电池器件的J-V曲线;
图3基于I-1和Spiro-OMeTAD的钙钛矿太阳能电池器件60℃黑暗条件下的稳定性比较。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似改进,因此本发明不受下面公开的具体实施例的限制。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。
三苯胺联萘酚共聚物结构式为:
在本发明中,所述烃基可为直链烃基也可为支链烃基,并无特殊的限制。
所述烷氧基可为直链的烷氧基也可为支链烷氧基,并无特殊的限制。
本发明提供的三苯胺联萘酚类共聚物的制备方法,包括分别将式III和式IV所示的化合物反应,分别得到式I和式II所示的三苯胺联萘酚共聚物;
在本发明中,所述烃基可为直链烃基也可为支链烃基,并无特殊的限制。
所述烷氧基可为直链的烷氧基也可为支链烷氧基,并无特殊的限制。
本发明的三苯胺联萘酚共聚物作为钙钛矿太阳能电池的空穴传输层材料,还可以抑制钙钛矿分解保护钙钛矿层,提高钙钛矿层的稳定性从而提高器件的稳定性。
本发明还提供了一种钙钛矿太阳能电池,包括上述技术方案所述制备的三苯胺联萘酚共聚物。
按照本发明,所述钙钛矿太阳能电池包括空穴传输层;所述空穴传输层包括上述技术方案所述的三苯胺联萘酚共聚物。
实施例中,所述钙钛矿太阳能电池的器件结构参见图1,自下而上依次包括玻璃基底、透明氧化物电极、电子传输层、钙钛矿光活性层、空穴传输层与金属电极。
其中,所述基底为本领域技术人员熟知的基底即可,并无特殊的限制,优选为玻璃、石英、柔性PET或PEN。
所述的透明氧化物电极为本领域技术人员熟知的透明氧化物电极即可,并无特殊限制,本发明中优选为氟掺氧化锡(FTO)或氧化铟锡(ITO)。
所述的电子传输层为本领域技术人员熟知的电子传输层即可,并无特殊的限制,本发明中优选为TiO2、PC61BM、PC71BM或ZnO。
所述的光活性层为本领域技术人员熟知的光活性层即可,并无特殊的限制,化学结构式为Csx(FA0.83MA0.17)(1-x)Pb(Br0.17I0.83)3,其中(0<x<0.1)。
所述钙钛矿电池的制备方法为本领域技术人员熟知的制备方法即可,并无特殊的限制,以电子传输层为TiO2为例本发明优选按照以下方法进行:
将表面刻蚀有图案的基底清洗,烘干,再用紫外臭氧机处理;将处理后的基底置于40mM的TiCl4-盐酸水溶液中,在70℃下水解1.5h,并用去离子水、乙醇冲洗;接着,在基底上旋涂TiO2的乙醇溶液,于热板上120℃退火10min后,在空气流中450℃煅烧30min,其中TiO2浆料和乙醇的质量比为1:3.5,旋涂条件4000r,20s;然后在TiO2衬底上旋涂LiTFSI的乙腈溶液,浓度0.1M,旋涂条件3000r,30s,之后在空气流中450℃煅烧30min;然后,一步法旋涂钙钛矿前驱溶液制备钙钛矿薄膜,100℃退火30min,旋涂条件:1000r,10s,6000r,30s,其中在第二阶段旋涂最后5s的时候用150uL的氯苯洗涤旋转中的衬底。最后,在钙钛矿表面旋涂空穴传输材料,溶液配方:60mM本发明上述的三苯胺联萘酚共聚物溶解于氯苯溶液中,旋涂条件:6000r,30s。最后,真空蒸镀上金属电极电极,得到钙钛矿太阳能电池器件。
实施例中优选采用空间电荷限制电流方法对制备得到的三苯胺联萘酚共聚物的空穴迀移率进行测定。
以下实施例将有助于理解本发明,但不限于本发明的内容:
以下实施例中,所用起始原料和常用化学试剂均为市售获得;化合物1~7参考陈荣业著《有机合成工艺优化》(化学工业出版社2006北京)和文献(N.Lv,M.L.Xie,W.B.Gu,etal.Org.Lett.2013,15,10,2382-2385;C.H.Chen,M.K.Leung,Tetrahedron2011,67,3924-3935;Z.H.Li,M.S.Wong,Org.Lett.2006,8,1499-1502)分别按实施例中所示合成方法和路线得到。
实施例1以三苯胺联萘酚共聚物I-1为代表的合成操作如下:
在250mL圆底烧瓶中加入化合物1(2.03g,5.60mmol)、化合物2(2.48g,5.60mmol)、Pd(PPh3)4(1.21g,1.00mmol)、K2CO3(7.79g,56.40mmol)、H2O(20mL)和甲苯(80mL)。通氮气,回流搅拌反应两天后,冷却至室温,倾倒入200ml甲醇中快速搅拌析出固体,过滤出的固体在索氏提取器中用甲醇、氯仿抽提,剩余的固体聚合物真空干燥至恒重,得到2.75g化合物III-1,收率为86.1%。GPC:Mn=23.2K;Mw/Mn=2.0;Anal.Calcd for C39H27NO3(%):C,84.00;H,4.88;N,2.51.Found(%):C,83.88;H,4.52;N,2.59.
化合物I-1的合成:
在100mL圆底烧瓶中加入化合物III-1(2.75g)、二碘甲烷(3.45g)、K2CO3(3.31g)和丙酮(60mL)。通氮气,在90℃下搅拌12h后,冷却至室温,倾倒入200ml甲醇-水(1:1)中快速搅拌析出固体,过滤出的固体在索氏提取器中用甲醇、氯仿抽提,剩余的固体聚合物真空干燥至恒重,得到2.26g化合物I-1,收率为80.5%。GPC:Mn=23.3K;Mw/Mn=2.0.Anal.Calcdfor C40H27NO3(%):C,84.34;H,4.78;N,2.46.Found(%):C,84.28;H,4.12;N,2.56.
实施例2以三苯胺联萘酚共聚物II-1为代表的合成操作如下:
在250mL圆底烧瓶中加入化合物3(2.20g,5.6mmol)、化合物2(2.48g,5.6mmol)、Pd(PPh3)4(1.21g,1.00mmol)、K2CO3(7.79g,56.4mmol)、H2O(20mL)和甲苯(100mL)。通氮气,回流搅拌反应两天后,冷却至室温,倾倒入200ml甲醇中快速搅拌析出固体,过滤出的固体在索氏提取器中用甲醇、氯仿抽提,剩余的固体聚合物真空干燥至恒重,得到2.68g化合物IV-1,收率为79.5%。GPC:Mn=23.1K;Mw/Mn=2.0;Anal.Calcd for C40H29NO4(%):C,81.75;H,4.97;N,2.38.Found(%):C,81.17;H,5.02;N,2.69.
化合物II-1的合成:
在100mL圆底烧瓶中加入化合物IV-1(2.68g)、二碘甲烷(3.45g)、K2CO3(3.31g)和丙酮(60mL)。通氮气,在90℃下搅拌12h后,冷却至室温,倾倒入200ml甲醇-水(1:1)中快速搅拌析出固体,过滤出的固体在索氏提取器中用甲醇、氯仿抽提,剩余的固体聚合物真空干燥至恒重,得到2.23g化合物II-1,收率为80.2%。GPC:Mn=23.2K;Mw/Mn=2.0.Anal.Calcdfor C41H29NO4(%):C,82.12;H,4.87;N,2.34.Found(%):C,81.78;H,4.12;N,2.55.
实施例3三苯胺联萘酚共聚物I-2的合成操作
参照实施例1中合成化合物I-1的操作,可合成I-2,合成路线如下:
合成所得I-2GPC:Mn=23.1K;Mw/Mn=2.0.Anal.Calcd for C45H37NO3(%):C,84.48;H,5.83;N,2.19.Found(%):C,81.78;H,5.12;N,2.55.
实施例4三苯胺联萘酚共聚物I-3的合成操作
参照实施例1中合成化合物I-1的操作,可合成I-3,合成路线如下:
合成所得I-3GPC:Mn=22.3K;Mw/Mn=2.1.Anal.Calcd for C51H49NO3(%):C,84.61;H,6.82;N,1.93.Found(%):C,83.88;H,6.15;N,2.33.
实施例5三苯胺联萘酚共聚物II-2的合成
参照实施例2中合成化合物II-1的操作,可合成II-2,合成路线如下:
合成所得II-2GPC:Mn=22.8K;Mw/Mn=2.0.Anal.Calcd for C51H49NO4(%):C,82.78;H,6.67;N,1.89.Found(%):C,82.17;H,6.06;N,2.53.
实施例6三苯胺联萘酚共聚物II-3的合成
参照实施例2中合成化合物II-1的操作,可合成II-3,合成路线如下:
合成所得II-3GPC:Mn=21.3K;Mw/Mn=2.0.Anal.Calcd for C63H73NO4(%):C,83.31;H,8.10;N,1.54.Found(%):C,82.35;H,7.09;N,2.35.
实施例7钙钛矿太阳能电池器件的制备:
依次用洗涤剂、去离子水、丙酮、乙醇和异丙醇在超声仪中清洗FTO玻璃基底,每次10分钟。将0.6mL二(乙酰丙酮基)钛酸二异丙酯和0.4mL乙酰丙酮溶于9mL无水乙醇中配成前躯体溶液,再在450℃下,以氧气为载气将制得的前驱体溶液通过喷雾热解法沉积在FTO(透明氧化物电极)上,形成30nm厚的致密TiO2层(电子传输层)。将市售的TiO2糊剂(30NR-D)和无水乙醇按质量比为1:6稀释,然后以2000rpm s-1的转速旋涂10s使得介孔TiO2沉积在基底上,形成200nm厚的介孔TiO2层(电子传输层)。再在80℃下干燥10min,然后将TiO2薄膜在450℃干燥空气流动下热退火30min,再进行紫外-臭氧处理30min。用DMSO/DMF(体积比为1:4)的混合溶液溶解1.30M PbI2、1.19M FAI,0.14M PbBr2和0.14M MABr以及0.07M CsI制备得到(FAPbI3)0.875(MAPbBr3)0.075(CsPbI3)0.05(PbI2)0.03的钙钛矿前驱体溶液,然后在相对湿度小于2%的干燥空气流动下的手套箱中进行钙钛矿光活性层的制备,连续两步以200rpm s-1的转速旋凃10s和以2000rpm s-1的转速旋凃30s,将钙钛矿前躯体溶液沉积在电子传输层上。在程序结束前的前15s,将150μL的氯苯滴在正在旋转的吸光层上,然后将钙钛矿光活性层在120℃下热退火1h,完成钙钛矿光活性层的制备。
空穴传输层的制备也是在相对湿度小于2%的干燥空气流动下的手套箱中进行的,将上述的三苯胺联萘酚共聚物型空穴传输材料分别掺杂0.5当量的HTFSI(二(三氟甲基磺酰)酰胺)和3.3当量的tBP(叔丁基吡啶)并配成30mM氯苯溶液。然后以4000rpm s-1的转速旋涂20s,将其沉积在退火后的钙钛矿光活性层上,最后真空蒸镀一层120nm厚的金电极(金属电极)后完成钙钛矿太阳能电池器件的制作。
实施例8钙钛矿太阳能电池器件参数和稳定性测试
以三苯胺联萘酚共聚物为空穴传输层的钙钛矿电池器件的光伏性能参数如表1所示。基于I-1空穴传输层的钙钛矿太阳能电池器件的光电转换效率分别为21.2%,高于以Spiro-OMeTAD为空穴传输层的钙钛矿电池器件的20.9%的光电转换效率,基于II-1空穴传输层的钙钛矿太阳能电池器件的光电转换效率较低,为19.5%。
表1分别以三苯胺联萘酚共聚物和Spiro-OMeTAD为空穴传输层的钙钛矿电池器件的光伏性能参数
如图3所示,基于I-1和Spiro-OMeTAD空穴传输层的封装的钙钛矿太阳能电池器件在经过60℃、1000h的黑暗条件下的老化后,PCE保有率分别为92.9%和87.1%。说明基于I-1的钙钛矿太阳能电池器件稳定性较好。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (5)
4.一种根据权利要求1-3任意一项所述的一种三苯胺联萘酚共聚物的应用,其特征在于,所述三苯胺联萘酚共聚物应用于钙钛矿太阳能电池。
5.根据权利要求4所述的一种三苯胺联萘酚共聚物的应用,其特征在于,所述钙钛矿太阳能电池包括空穴传输层,所述三苯胺联萘酚共聚物作为钙钛矿太阳能电池的空穴传输层材料应用。
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US20170194103A1 (en) * | 2015-11-16 | 2017-07-06 | Pusan National University Industry-University Cooperation Foundation | Novel triphenylamine derivatives and photovoltaic device including the same |
CN110372524A (zh) * | 2019-06-26 | 2019-10-25 | 天津理工大学 | 一种以联二萘胺为母核的三苯胺类有机空穴传输材料及其的合成及其用途 |
CN110982515A (zh) * | 2019-11-18 | 2020-04-10 | 浙江大学 | 一种三苯胺修饰联萘衍生物的用途 |
CN112126057A (zh) * | 2020-09-24 | 2020-12-25 | 天津理工大学 | 一种联二萘基有机聚合物空穴传输材料及其合成方法和应用 |
CN112778518A (zh) * | 2020-12-30 | 2021-05-11 | 天津理工大学 | 一种酰胺桥联有机聚合物空穴传输材料及其合成方法和应用 |
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