CN115490632A - 一种螺型空穴传输材料及其制备方法与应用 - Google Patents
一种螺型空穴传输材料及其制备方法与应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于太阳能电池技术领域,具体涉及一种空穴传输材料及其制备方法与应用。
背景技术
近几年来,以有机-无机杂化钙钛矿材料为“光吸收剂”的钙钛矿太阳能电池取得了飞速的发展,其最近的验证效率已经突破25%,可以媲美传统硅基太阳能电池。钙钛矿太阳能电池中除了活性层钙钛矿之外,空穴传输材料对其效率与稳定性的影响也是至关重要的,其能级结构、空穴迁移率、薄膜形貌与界面属性等都对空穴的提取、转移、传输以及激子的复合产生重要影响,从而影响最终器件的性能表现。
目前,在正置钙钛矿电池中,使用最广泛且普适性最强的空穴传输材料为Spiro-OMeTAD。但是,其合成提纯较为困难、造价成本较高,且本征空穴迁移率较低,需掺杂剂才能提高空穴传输层的电导率,而掺杂剂的引入会降低器件的寿命。因此,设计开发具有能级匹配且空穴迁移率高的空穴传输材料对提升钙钛矿太阳能电池的效率与稳定性有着重要的意义。
发明内容
针对现有技术的不足,本发明的目的在于提供一种空穴传输材料及其制备方法与应用,所述空穴传输材料具有优良的溶解性,可调控的能级、空穴迁移率与薄膜形貌以及相对于传统空穴传输材料Spiro-OMeTAD更为优越的空穴传输性能和界面特性,可应用于钙钛矿太阳能电池中。
为达到此发明目的,本发明采用以下技术方案:
第一方面,本发明提供一种螺型空穴传输材料,所述空穴传输材料具有如式Ⅰ所示结构:
式I;
其中,D1基团和D2基团为给体单元基团。
优选地,所述的给体单元基团D1选自如下结构所示的给体单元基团中的任意一种:
其中,R基团独立地选自氢、甲基、甲氧基、2-甲氧基乙氧基、甲硫基、叔丁基或乙烯基,N上的虚线表示基团连接位置。
优选地,所述的给体单元基团D2选自如下结构所示的给体单元基团中的任意一种且不与D1基团相同:
其中,R基团独立地选自氢、甲基、甲氧基、2-甲氧基乙氧基、甲硫基、叔丁基或乙烯基,N上的虚线表示基团连接位置。
优选地,所述空穴传输材料选自如下所示化合物中的任意一种:
第二方面,本发明提供了一种如第一方面所述的空穴界面材料的制备方法,所述制备方法包括以下步骤:
(1)化合物A与化合物B进行偶联反应,得到化合物C,反应式如下:
(2)化合物C和化合物E进行偶联反应,得到式I所示化合物,反应式如下:
其中,给体单元基团D1选自如下结构所示的给体单元基团中的任意一种:
其中,所述的给体单元基团D2选自如下结构所示的给体单元基团中的任意一种且不与D1相同:
优选地,步骤(1)中所述钯催化剂为Pd(OAc)2;
优选地,步骤(1)中化合物A与化合物B的摩尔质量比为1:2;
优选地,步骤(1)所述偶联反应的溶剂为甲苯;
优选地,步骤(1)所述偶联反应的温度为90-100℃,例如可以是90℃、100℃;
优选地,步骤(1)所述偶联反应的时间为20-24 h,例如可以是20 h、21 h、22 h、23h、24 h;
优选地,步骤(2)所述偶联反应的催化剂为Pd(OAc)2;
优选地,步骤(2)中化合物C与化合物E的摩尔质量比为1:(2.1-2.4),例如可以是1:2.1、1:2.2、1:2.3、1:2.4;
优选地,步骤(2)所述偶联反应的溶剂为甲苯;
优选地,步骤(2)所述偶联反应的温度为100-120℃,例如可以是100℃、110℃、120℃;
优选地,步骤(2)所述偶联反应的时间为20-24 h,例如可以是20 h、21 h、22 h、23h、24 h。
第三方面,本发明提供一种如第一方面所述的空穴传输材料在制备太阳能电池材料中的应用;
优选地,所述太阳能电池为钙钛矿太阳能电池。
第四方面,本发明提供一种空穴传输层,所述空穴传输层包括如第一方面所述的空穴传输材料。
第五方面,本发明提供一种钙钛矿太阳能电池,所述钙钛矿太阳能电池包括如第四方面所述的空穴传输层。
优选地,所述钙钛矿太阳能电池由上到下依次包括:阳极电极层、空穴传输层、钙钛矿活性层、电子传输层和阴极电极层。
优选地,所述阳极电极层为银电极。
优选地,所述阳极电机层的厚度为100-150 nm,例如可以是100 nm、110 nm、120nm、130 nm、140 nm、150 nm。
优选地,所述空穴传输层的厚度为80-120 nm,例如可以是80 nm、90 nm、100 nm、110 nm、120 nm。
优选地,所述钙钛矿活性层为CH3NH3PbI3,其厚度为400-600 nm,例如可以是400nm、420 nm、440 nm、460 nm、480 nm、500 nm、520 nm、540 nm、560 nm、580 nm、600 nm。
优选地,所述电子传输层为TiO2电子传输层。
优选地,所述电子传输层的厚度为40-60 nm,例如可以是40 nm、50 nm、60 nm。
优选地,所述阴极电极为ITO导电玻璃。
优选地,所述阴极电极的厚度为150-180 nm,例如可以是150 nm、160 nm、170 nm、180 nm。
相对于现有技术,本发明具有以下有益效果:
本发明所述空穴传输材料具有优良的溶解性,可调控的能级、空穴迁移率与薄膜形貌以及相对于传统空穴传输材料Spiro-OMeTAD更为优越的空穴传输性能和界面特性,可应用于钙钛矿太阳能电池中。
附图说明
图1是实施例1-5提供的空穴传输材料的电化学性能测试对比图。
图2为实施例1-5提供的空穴传输材料的紫外可见吸收光谱对比图。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
本实施例提供一种空穴传输材料,具有如式Ⅰ-1所示结构:
式Ⅰ-1
空穴传输材料Ⅰ-1的合成路线:
(1)中间体化合物1的合成:
将2,7-二溴-2’,7’-二碘螺二芴(150 mg, 0.2 mmol),双(4-甲氧基苯基)胺(92mg, 0.4 mmol),Pd(OAc)2(1 mg, 0.004 mmol),三叔丁基膦(20 μL, 0.008 mmol),叔丁醇钠(58 mg, 0.6 mmol),置于双口瓶中;抽冲氩气三次后,加入甲苯5 mL;反应在氩气保护下进行;90℃下反应24 h后,待反应完成后将反应体系冷却至室温,旋出溶剂,粗产物过柱纯化,可得到中间体化合物1,质量为101 mg,产率55%。
1H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 8.0Hz, 2H), 7.56 (d, J = 8.1 Hz, 2H), 6.85-6.83 (m, 10H), 6.76-6.74 (m, 10H),3.67 (s, 12H);
高分辨质谱: C53H40Br2N2O4 计算值:926.1355, 实测值:926.1359 [M+]。
(2)空穴传输材料Ⅰ-1的合成:
将步骤(1)制得的中间体化合物1(60 mg, 0.064 mmol),3,6-二甲氧基咔唑(36mg, 0.1536 mmol),Pd(OAc)2(0.32 mg, 0.00128 mmol),三叔丁基膦(6.4 μL, 0.00256mmol),叔丁醇钠(18 mg, 0.192 mmol),置于双口瓶中;抽冲氩气三次后,加入甲苯4 mL;反应在氩气保护下进行;回流反应24 h后,待反应完成后将反应体系冷却至室温,旋出溶剂,粗产物过柱纯化,可得到空穴传输材料I-1,质量为60 mg,产率77%。
1H NMR (400 MHz, DMSO-d 6): δ 8.16 (d, J = 8.1 Hz, 2H), 7.83 (d, J =2.4 Hz, 4H), 7.63-7.60 (m, 4H), 7.13 (d, J = 8.9 Hz, 4H), 7.01 (dd, J = 8.9,2.4 Hz, 4H), 6.89-6.85 (m, 10H), 6.79 (dd, J = 8.4, 2.1 Hz, 2H), 6.73 (d, J =9.0 Hz, 8H), 6.32 (d, J = 2.1 Hz, 2H), 3.88 (s, 12H), 3.65 (s, 12H);
元素分析计算值:C, 79.65; H, 5.28; N, 4.59, 实测值:C, 79.95; H, 5.16;N, 4.78。
实施例2
本实施例提供一种空穴传输材料,具有如式Ⅰ-2所示结构:
式Ⅰ-2
空穴界面材料Ⅰ-2的合成路线:
空穴传输材料Ⅰ-2的合成
1H NMR (400 MHz, THF-d 8) δ 8.03 (dd, J = 8.1, 1.2 Hz, 2H), 6.85 (d, J= 1.9 Hz, 2H), 6.82 – 6.70 (m, 12H), 6.68 – 6.61 (m, 10H), 6.57 (dq, J = 6.9,3.1 Hz, 14H), 5.89 – 5.79 (m, 4H), 3.64 (d, J = 1.2 Hz, 12H);
元素分析计算值:C, 81.61; H, 4.98; N, 4.94, 实测值:C, 81.88; H, 4.77;N, 4.70。
MALDI-TOF质谱:C77H56N4O6分析值:1132.4,实测值:1132.4[M+]。
实施例3
本实施例提供一种空穴传输材料,具有如式Ⅰ-3所示结构:
式Ⅰ-3
空穴界面材料Ⅰ-3的合成路线:
空穴传输材料Ⅰ-3的合成
1H NMR (400MHz, CD2Cl2): δ 8.05 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 9.4Hz, 4H), 7.05-6.99 (m, 10H), 6.92-6.85 (m, 14H), 6.72 (br, 10H), 6.20 (d, J =8.0 Hz, 4H), 3.77 (s, 12H);
元素分析计算值:C, 79.36; H, 4.84; N, 4.81; S, 5.50 实测值:C, 79.27;H, 4.95; N, 4.61; S, 5.32。
MALDI-TOF质谱:C77H56N4O4S2分析值:1164.3,实测值:1164.4[M+]。
实施例4
本实施例提供一种空穴传输材料,具有如式Ⅰ-4所示结构:
式Ⅰ-4
空穴界面材料Ⅰ-4的合成路线:
空穴传输材料Ⅰ-4的合成
1H NMR (400 MHz, THF-d 8) δ 7.97 (d, J = 8.0 Hz, 2H), 6.93 – 6.85 (m,7H), 6.83 – 6.69 (m, 18H), 6.60 (dd, J = 13.3, 8.7 Hz, 10H), 6.54 – 6.48 (m,3H), 6.38 (d, J = 8.2 Hz, 5H), 3.64 (s, 12H);
元素分析计算值:C, 73.44; H, 4.48; N, 4.45, 实测值:C, 73.72; H, 4.69;N, 4.23。
MALDI-TOF质谱:C77H56N4O4Se2分析值:1260.2,实测值:1260.3[M+]。
实施例5
本实施例提供一种空穴传输材料,具有如式Ⅰ-5所示结构:
式Ⅰ-5
空穴界面材料Ⅰ-5的合成路线:
空穴传输材料Ⅰ-5的合成
1H NMR (400 MHz, THF-d 8) δ 8.22 (d, J = 8.0 Hz, 2H), 8.03 (dd, J =7.8, 1.6 Hz, 4H), 7.44 (dd, J = 8.1, 1.7 Hz, 4H), 7.37 (ddd, J = 8.7, 7.2,1.7 Hz, 4H), 7.27 – 7.18 (m, 4H), 7.02 (d, J = 1.9 Hz, 2H), 6.84 – 6.76 (m,8H), 6.74 (dd, J = 8.3, 2.1 Hz, 2H), 6.70 – 6.62 (m, 8H), 6.61 – 6.52 (m,6H), 3.67 (s, 12H);
元素分析计算值:C, 75.23 H, 4.59; N, 4.56; S, 5.22 实测值:C, 75.17; H,4.50; N, 4.48; S, 5.16。
MALDI-TOF质谱:C77H56N4O8S2分析值:1228.3,实测值:1228.4[M+]。
实施例6
本实施例提供一种空穴传输材料,具有如式Ⅰ-6所示结构:
式Ⅰ-6
空穴界面材料Ⅰ-6的合成路线:
空穴传输材料Ⅰ-6的合成
1H NMR (400 MHz, THF-d 8) δ 7.78 (d, J = 8.5 Hz, 4H), 7.64 (d, J = 8.2Hz, 2H), 7.39 – 7.24 (m, 8H), 7.23 – 7.16 (m, 2H), 7.11 (dd, J = 7.4, 1.2 Hz,2H), 6.88 – 6.81 (m, 8H), 6.80 – 6.60 (m, 18H), 6.60 – 6.44 (m, 7H), 3.68 (s,12H), 3.62 (d, J = 1.1 Hz, 6H);
MALDI-TOF质谱:C87H68N4O6分析值:1264.5,实测值:1264.5[M+]。
实施例7
本实施例提供一种空穴传输材料,具有如式Ⅰ-7所示结构:
式Ⅰ-7
空穴界面材料Ⅰ-7的合成路线:
(1)中间体化合物2的合成
将2,7-二溴-2’,7’-二碘螺二芴(150 mg, 0.2 mmol),3,6-二甲氧基-9H-咔唑(91mg, 0.4 mmol),Pd(OAc)2(1 mg, 0.004 mmol),三叔丁基膦(20 μL, 0.008 mmol),叔丁醇钠(58 mg, 0.6 mmol),置于双口瓶中;抽冲氩气三次后,加入甲苯5 mL;反应在氩气保护下进行;90℃下反应24 h后,待反应完成后将反应体系冷却至室温,旋出溶剂,粗产物过柱纯化,可得到中间体化合物2,质量为140 mg,产率77%。
1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.1 Hz, 2H), 7.64 (dd, J = 8.1,1.9 Hz, 2H), 7.59 (d, J = 8.2 Hz, 2H), 7.50-7.47 (m, 6H), 7.17 (s, 2H), 7.15(s, 2H), 7.08 (d, J = 1.8 Hz, 2H), 6.97 (d, J = 2.5 Hz, 2H), 6.95 (d, J = 2.5Hz, 2H), 6.92 (d, J = 1.9 Hz, 2H), 3.90 (s, 12H);
(2)空穴传输材料Ⅰ-7的合成
空穴传输材料Ⅰ-7步骤(2)合成方法同空穴传输材料I-1的合成,空穴传输材料Ⅰ-7产率42%。
1H NMR (400 MHz, THF-d 8) δ 7.92 (dd, J = 9.3, 4.5 Hz, 2H), 7.72 (dd, J= 16.5, 8.4 Hz, 5H), 7.63 – 7.55 (m, 6H), 7.52 – 7.46 (m, 2H), 7.41 (d, J =8.3 Hz, 2H), 7.26 (t, J = 7.8 Hz, 2H), 7.19 (d, J = 9.0 Hz, 6H), 7.12 – 7.07(m, 2H), 7.06 – 6.95 (m, 9H), 6.81 – 6.74 (m, 4H), 6.66 (dd, J = 8.3, 2.2 Hz,2H), 6.58 (dd, J = 8.5, 1.8 Hz, 6H), 3.86 (s, 12H), 3.59 (d, J = 1.5 Hz, 6H);
MALDI-TOF质谱:C87H64N4O6分析值:1260.4,实测值:1260.5[M+]。
对实施例1~5提供的空穴传输材料进行电化学性能测试,方法如下:
由CHI760电化学工作站测试其电化学性能;
图1为实施例1-5提供的空穴传输材料的电化学性能测试对比图,本发明所述空穴传输材料均呈现出明显的氧化还原峰,由氧化还原起始峰位计算各空穴传输材料的HOMO能级,具体测试结果如表1所示:
表1
由上述测试数据可知,实施例1-5提供的空穴传输材料HOMO能级为-5.11~-5.16eV,说明本发明所述空穴传输材料具有与钙钛矿价带较为匹配的能级,利于钙钛矿电池器件中空穴的提取与转移。
对实施例1~5提供的空穴传输材料进行紫外可见吸收光谱测试,方法如下:
由Shimadzu UV-3600紫外可见吸收光谱仪测试其性能;
图2为实施例1-5提供的空穴传输材料的紫外可见吸收光谱对比图,本发明所述空穴传输材料主要在320nm,380nm左右呈现出明显的吸收峰。在可见光波长未出现吸收峰,说明在可见光范围内未出现吸收峰,说明由本发明所述空穴传输材料可以避免对可见光的吸收,利于提高钙钛矿活性层的光吸收,从而提高短路电流。
申请人声明,本发明通过上述实施例来说明本发明所述的空穴传输材料及其制备方法和应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用原料的等效替换及辅助成分的添加,具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
6.根据权利要求4所述的制备方法,其特征在于,步骤(1)所述偶联反应的催化剂为钯催化剂;
优选地,所述钯催化剂为Pd(OAc)2;
优选地,步骤(1)中化合物A与化合物B的摩尔质量比为1:2;
优选地,步骤(1)所述偶联反应的溶剂为甲苯;
优选地,步骤(1)所述偶联反应的温度为90-100℃;
优选地,步骤(1)所述偶联反应的时间为12 h;
优选地,步骤(2)所述偶联反应的催化剂为Pd(OAc)2;
优选地,步骤(2)中化合物C与化合物E的摩尔质量比为1:(2.1-2.4);
优选地,步骤(2)所述偶联反应的溶剂为甲苯;
优选地,步骤(2)所述偶联反应的温度为100-120℃;
优选地,步骤(2)所述偶联反应的时间为20-28 h。
7.权利要求1-3任一项所述的空穴传输材料在制备太阳能电池材料中的应用;
优选地,所述太阳能电池为钙钛矿太阳能电池。
8.一种空穴传输层,其特征在于,所述空穴传输层包括权利要求1-3任一项所述的空穴传输材料。
9.一种钙钛矿太阳能电池,其特征在于,所述钙钛矿太阳能电池包括权利要求8所述的空穴传输层。
10.根据权利要求9所述的钙钛矿太阳能电池,其特征在于,所述钙钛矿太阳能电池由上到下依次包括:阳极电极层、权利要求8所述的空穴传输层、钙钛矿活性层、电子传输层和阴极电极层;
优选地,所述阳极电极层为银电极;
优选地,所述阳极电极层的厚度为100-150 nm;
优选地,所述空穴传输层的厚度为80-120 nm;
优选地,所述钙钛矿活性层为CH3NH3PbI3,其厚度为400-600 nm;
优选地,所述电子传输层为TiO2电子传输层;
优选地,所述电子传输层的厚度为40-60 nm;
优选地,所述阴极电极为ITO导电玻璃;
优选地,所述阴极电极的厚度为150-180 nm。
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