通过调节共轭聚合物侧链实现可绿色溶剂加工的非富勒烯太阳能电池

doi:10.3866/PKU.WHXB201904037

摘要/Abstract

摘要：

有机太阳能电池(OSC)经过长期的发展，其能量转换效率(PCE)已快速推进至14%–16%，基本接近可商业化应用的范围，但在目前所见报道的高效率OSC器件的制备过程中，活性层薄膜的加工大多采用氯苯、二氯苯、氯仿等毒性较高的含卤/芳香性试剂，此类试剂对环境及人类健康的危害非常高。在本工作中，我们基于已报道的高效率给体共轭聚合物PBDB-T，通过扩大共轭侧链结构与增长柔性烷基侧链的方式，合成了新型给体聚合物PBDB-DT。PBDB-DT中较长的柔性烷基侧链保证了其在低毒性溶剂四氢呋喃(THF)溶液中良好的溶解度，同时，扩大的共轭侧链也有效增强了其在THF中的溶液聚集作用，这一特性对于在非富勒烯型OSC器件中获得较好的光伏性能尤其重要。当采用非富勒烯小分子IT-M作为电子受体材料时，以THF为主溶剂加工的基于PBDB-DT:IT-M的OSC器件可以获得10.2%的能量转换效率。

关键词: 共轭聚合物, 非富勒烯受体, 有机太阳能电池, 绿色溶剂, 分子设计

Abstract:

Organic solar cells (OSCs) are a promising next-generation photovoltaic technology that can be used to harvest clean and renewable solar energy. OSCs are typically composed of donor:acceptor blends as photo-active materials. Compared to the conventional inorganic silicon solar cells, OSCs are suitable for large-scale production using roll-to-roll technology, promising low-cost and the potential to avoid environmental pollution. The last few years have witnessed the rapid development of OSCs. The power conversion efficiencies (PCEs) of OSCs have surpassed ~14%–16%, benefiting from the design of novel materials, optimization of blend morphology, and deep understanding of the charge generation mechanism. Currently, the most widely used processing solvents for preparing high-efficient OSCs are chlorinated or aromatic solvents including chlorobenzene, dichlorobenzene, and chloroform, which are highly detrimental to the environment and human health, and may not be utilized for future in industry. Thus, replacing these highly toxic solvents with environmentally friendly alternatives called "green solvents" is an important topic in OSC research. Herein, poly[(2, 6-(4, 8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1, 2-b:4, 5-b′]dithiophene)-co-(1, 3-di(5-thiophene-2-yl)-5, 7-bis(2-ethylhexyl)benzo[1, 2-c:4, 5-c′]dithiophene-4, 8-dione)] (PBDB-T) was used as a reference material to design and synthesize a novel conjugated polymer (PBDB-DT) by extending the alkyl side chains and enlarging the conjugated side groups. The thermal stability of the polymer donor was examined via thermogravimetric analysis, showing that the polymers exhibit very good stability at > 400 ℃. Importantly, PBDB-DT exhibits good solubility in low-toxic solvent tetrahydrofuran (THF) due to its longer alkyl side chains, and shows a strong aggregation effect in THF due to the larger conjugated side groups. A favorable PCE of 10.2% was achieved for the THF-processed PBDB-DT:IT-M based OSC device. In contrast, PBDB-T has limited solubility in THF. The solar cell device based on PBDB-T:IT-M delivered a moderate PCE of 6.41%. The investigation of blend morphology via atomic force microscope suggested that the PBDB-DT:IT-M has a smooth surface, which is favorable for charge generation and transport. These results demonstrate that molecular optimization is a promising strategy to modulate the solubility and achieve high efficiency for organic photovoltaic materials processed using green solvents.

Key words: Conjugated polymer, Non-fullerene acceptor, Organic solar cell, Green solvent, Molecular design

MSC2000:

O646

点击下载补充材料PDF格式文件

吴仪, 孔静宜, 秦云朋, 姚惠峰, 张少青, 侯剑辉. 通过调节共轭聚合物侧链实现可绿色溶剂加工的非富勒烯太阳能电池[J]. 物理化学学报, 2019, 35(12): 1391-1398.

Yi WU, Jingyi KONG, Yunpeng QIN, Huifeng YAO, Shaoqing ZHANG, Jianhui HOU. Realizing Green Solvent Processable Non-fullerene Organic Solar Cells by Modulating the Side Groups of Conjugated Polymers[J]. Acta Physico-Chimica Sinica, 2019, 35(12): 1391-1398.

图/表 7

图1

图2

表1

图3

图4

表2

图5

参考文献 45

1	Li Y. Polym. Bull. 2011, 10, 33. doi: 10.14028/j.cnki.1003-3726.2011.10.017
2	Fu Y. ; Wang F. ; Zhang Y. ; Fang X. ; Lai W. ; Huang W. Acta Chim. Sin. 2014, 72, 158. doi: 10.6023/a13111142
3	Yao H. ; Hou J. Acta Polym. Sin. 2016, 11, 1468. doi: 10.11777/j.issn1000-3304.2016.16216
4	Duan C. ; Huang F. ; Cao Y. J. Mater. Chem. 2012, 22, 10416. doi: 10.1039/C2JM30470H
5	Olle I. Adv. Mater. 2018, 30, 1800388. doi: 10.1002/adma.201800388
6	Dou C. ; Liu J. ; Wang L. Sci. China Chem. 2017, 60, 450. doi: 10.1007/s11426-016-0503-x
7	Fan H. ; Zhu X. Sci. China Chem. 2015, 58, 922. doi: 10.1007/s11426-015-5418-6
8	Jia, B.; Wu, Y.; Zhao, F.; Yan, C.; Zhu, S.; Cheng, P.; Mai, J.; Lau, T. K.; Lu, X.; Su, C. J.; et al. Sci. China Chem. 2017, 60, 257. doi: 10.1007/s11426-016-0336-6
9	Kan B. ; Feng H. ; Yao H. ; Chang M. ; Wan X. ; Li C. ; Hou J. ; Chen Y. Sci. China Chem. 2018, 61, 1307. doi: 10.1007/s11426-018-9334-9
10	Fan Q. ; Su W. ; Wang Y. ; Guo B. ; Jiang Y. ; Guo X. ; Liu F. ; Russell T. P. ; Zhang M. ; Li Y. Sci. China Chem. 2018, 61, 531. doi: 10.1007/s11426-017-9199-1
11	Heeger A. J. Adv. Mater. 2014, 26, 10. doi: 10.1002/adma.201304373
12	Li G. ; Zhu R. ; Yang Y. Nat. Photonics 2012, 6, 153. doi: 10.1038/nphoton.2012.11
13	Chen J. D. ; Cui C. ; Li Y. Q. ; Zhou L. ; Ou Q. D. ; Li C. ; Li Y. ; Tang J. X. Adv. Mater. 2015, 27, 1035. doi: 10.1002/adma.201404535
14	Zhang S. Q. ; Ye L. ; Zhao W. C. ; Yang B. ; Wang Q. ; Hou J. H. Sci. China Chem. 2015, 58, 248. doi: 10.1007/s11426-014-5273-x
15	Liu Y. ; Zhao J. ; Li Z. ; Mu C. ; Ma W. ; Hu H. ; Jiang K. ; Lin H. ; Ade H. ; Yan H. Nat. Commun. 2014, 5, 5293. doi: 10.1038/ncomms6293
16	He Z. ; Xiao B. ; Liu F. ; Wu H. ; Yang Y. ; Xiao S. ; Wang C. ; Russell T. P. ; Cao Y. Nat. Photonics 2015, 9, 174. doi: 10.1038/nphoton.2015.6
17	He Z. ; Zhong C. ; Su S. ; Xu M. ; Wu H. ; Cao Y. Nat. Photonics 2012, 6, 591. doi: 10.1038/NPHOTON.2012.190
18	Li, M.; Gao, K.; Wan, X.; Zhang, Q.; Kan, B.; Xia, R.; Liu, F.; Yang, X.; Feng, H.; Ni, W.; et al. Nat. Photonics 2016, 11, 85. doi: 10.1038/nphoton.2016.240
19	Ouyang X. ; Peng R. ; Ai L. ; Zhang X. ; Ge Z. Nat. Photonics 2015, 9, 520. doi: 10.1038/nphoton.2015.126
20	Zhao J. ; Li Y. ; Yang G. ; Jiang K. ; Lin H. ; Ade H. ; Ma W. ; Yan H. Nat. Energy 2016, 1, 15027. doi: 10.1038/nenergy.2015.27
21	Deng, D.; Zhang, Y.; Zhang, J.; Wang, Z.; Zhu, L.; Fang, J.; Xia, B.; Wang, Z.; Lu, K.; Ma, W.; et al. Nat. Commun. 2016, 7, 13740. doi: 10.1038/ncomms13740
22	Zhang H. ; Yao H. ; Hou J. ; Zhu J. ; Zhang J. ; Li W. ; Yu R. ; Gao B. ; Zhang S. ; Hou J. Adv. Mater. 2018, 30, e1800613. doi: 10.1002/adma.201800613
23	Yuan, J.; Zhang, Y.; Zhou, L.; Zhang, G.; Yip, H. L.; Lau, T. K.; Lu, X.; Zhu, C.; Peng, H.; Johnson, P. A.; et al. Joule 2019, 3, 1140. doi: 10.1016/j.joule.2019.01.004
24	Che X. ; Li Y. ; Qu Y. ; Forrest S. R. Nat. Energy 2018, 3, 422. doi: 10.1038/s41560-018-0134-z
25	Bin, H.; Gao, L.; Zhang, Z. G.; Yang, Y.; Zhang, Y.; Zhang, C.; Chen, S.; Xue, L.; Yang, C.; Xiao, M.; et al. Nat. Commun. 2016, 7, 13651. doi: 10.1038/ncomms13651
26	Meng, L.; Zhang, Y.; Wan, X.; Li, C.; Zhang, X.; Wang, Y.; Ke, X.; Xiao, Z.; Ding, L.; Xia, R.; et al. Science 2018, 361, 1094. doi: 10.1126/science.aat2612
27	Cui, Y.; Yao, H.; Hong, L.; Zhang, T.; Xu, Y.; Xian, K.; Gao, B.; Qin, J.; Zhang, J.; Wei, Z.; et al. Adv. Mater. 2019, 0, 1808356. doi: 10.1002/adma.201808356
28	Duan, C.; Cai, W.; Hsu, B. B. Y.; Zhong, C.; Zhang, K.; Liu, C.; Hu, Z.; Huang, F.; Bazan, G. C.; Heeger, A. J.; et al. Energy Environ. Sci. 2013, 6, 3022. doi: 10.1039/C3EE41838C
29	Xu X. ; Yu T. ; Bi Z. ; Ma W. ; Li Y. ; Peng Q. Adv. Mater. 2018, 30, 1703973. doi: 10.1002/adma.201703973
30	Fan B. ; Ying L. ; Wang Z. ; He B. ; Jiang X. F. ; Huang F. ; Cao Y. Energy Environ. Sci. 2017, 10, 1243. doi: 10.1039/C7EE00619E
31	Li Z. ; Ying L. ; Zhu P. ; Zhong W. ; Li N. ; Liu F. ; Huang F. ; Cao Y. Energy Environ. Sci. 2019, 12, 157. doi: 10.1039/C8EE02863J
32	Zhang S. ; Ye L. ; Zhang H. ; Hou J. Mater. Today 2016, 19, 533. doi: 10.1016/j.mattod.2016.02.019
33	Chen Y. ; Zhang S. ; Wu Y. ; Hou J. Adv. Mater. 2014, 26, 2744. doi: 10.1002/adma.201304825
34	Hou J. ; Inganäs O. ; Friend R. H. ; Gao F. Nat. Mater. 2018, 17, 119. doi: 10.1038/nmat5063
35	Fan Q. ; Zhu Q. ; Xu Z. ; Su W. ; Chen J. ; Wu J. ; Guo X. ; Ma W. ; Zhang M. ; Li Y. Nano Energy 2018, 48, 413. doi: 10.1016/j.nanoen.2018.04.002
36	Fan Q. ; Su W. ; Guo X. ; Guo B. ; Li W. ; Zhang Y. ; Wang K. ; Zhang M. ; Li Y. Adv. Energy Mater. 2016, 6, 1600430. doi: 10.1002/aenm.201600430
37	Yu R. ; Zhang S. ; Yao H. ; Guo B. ; Li S. ; Zhang H. ; Zhang M. ; Hou J. Adv. Mater. 2017, 29, 1700437. doi: 10.1002/adma.201700437
38	Huang F. ; Wu H. ; Wang D. ; Yang W. ; Cao Y. Chem. Mater. 2004, 16, 708. doi: 10.1021/cm034650o
39	Yang T. B. ; Wang M. ; Duan C. H. ; Hu X. W. ; Huang L. ; Peng J. B. ; Huang F. ; Gong X. Energy Environ. Sci. 2012, 5, 8208. doi: 10.1039/C2ee22296e
40	Li W. ; Zhang S. ; Zhang H. ; Hou J. Org. Electron. 2017, 44, 42. doi: 10.1016/j.orgel.2017.01.036
41	Zhang J. ; Tan H. S. ; Guo X. ; Facchetti A. ; Yan H. Nat. Energy 2018, 3, 720. doi: 10.1038/s41560-018-0181-5
42	Zhao W. ; Qian D. ; Zhang S. ; Li S. ; Inganas O. ; Gao F. ; Hou J. Adv. Mater. 2016, 28, 4734. doi: 10.1002/adma.201600281
43	Zhang S. ; Hou J. Acta Phys. -Chim. Sin. 2017, 33, 2327. doi: 10.3866/PKU.WHXB201706161
	张少青; 侯剑辉. 物理化学学报, 2017, 33, 2327. doi: 10.3866/PKU.WHXB201706161
44	Xu Y. ; Yao H. ; Hou J. Chin. J. Chem. 2019, 37, 207. doi: 10.1002/cjoc.201800471
45	Zhang S. ; Ye L. ; Wang Q. ; Li Z. ; Guo X. ; Huo L. ; Fan H. ; Hou J. J. Phys. Chem. C 2013, 117, 9550. doi: 10.1021/jp312450p

Material	λ_onse/nm	λ_peak/nm	E_HOMO/eV	E_LUMO/eV	ε/(mol⁻¹∙L∙cm⁻¹))	μ_h/(cm²∙V⁻¹∙s⁻¹)	μ_e/(cm²∙V⁻¹∙s⁻¹)
PBDB-T	676	620	−5.30	−3.48	4.64 × 10⁴	3.43 × 10⁻⁶	3.21 × 10⁻⁶
PBDB-DT	686	622	−5.36	−3.53	5.42 × 10⁴	4.53× 10⁻⁶	4.33× 10⁻⁶

Active layer	Additive	V_oc/V	J_sc/(mA∙cm⁻²)	FF/%	PCE/%
PBDB-DT:IT-M	0.5% DIO	0.92	18.02	62.29	10.20
PBDB-T:IT-M	0.5% DIO	0.90	13.06	54.00	6.41

[1]	张美琪, 马云龙, 郑庆东. 含萘并二噻吩小分子受体材料的带隙调控及其在非富勒烯太阳能电池中的应用[J]. 物理化学学报, 2019, 35(5): 503 -508 .
[2]	邓祎华, 彭爱东, 吴筱曦, 陈华杰, 黄辉. 有机太阳能电池中基于苝二酰亚胺结构小分子受体进展[J]. 物理化学学报, 2019, 35(5): 461 -471 .
[3]	章中强, 张书华, 刘志玺, 张志国, 李永舫, 李昌治, 陈红征. 骨架非稠合的电子受体在聚合物太阳能电池中的应用[J]. 物理化学学报, 2019, 35(4): 394 -400 .
[4]	薛佩瑶,张俊祥,辛景明,RECHJeromy,李腾飞,孟凯鑫,王嘉宇,马伟,尤为,MARDER Seth R.,韩平畴,占肖卫. 第三组份端基对有机太阳能电池性能的影响[J]. 物理化学学报, 2019, 35(3): 275 -283 .
[5]	刘方彬,刘俊,王利祥. 带有噻吩侧基的有机硼小分子电子受体光伏材料[J]. 物理化学学报, 2019, 35(3): 251 -256 .
[6]	杨阳,蒋秀,占肖卫,陈兴国. 以绕丹宁和噻唑烷-2, 4-二酮为端基的不对称结构有机受体分子的设计合成与构性关系探讨[J]. 物理化学学报, 2019, 35(3): 257 -267 .
[7]	许青青,常春梅,李万宾,郭冰,国霞,张茂杰. 基于一种新型聚噻吩衍生物为给体的非富勒烯聚合物太阳能电池[J]. 物理化学学报, 2019, 35(3): 268 -274 .
[8]	贾国骁,张少青,杨丽燕,何畅,范慧俐,侯剑辉. A-D-A型小分子电子给体光伏材料的端基修饰及其光伏性能[J]. 物理化学学报, 2019, 35(1): 76 -83 .
[9]	何畅,侯剑辉. 基于非富勒烯受体的溶液加工型全小分子太阳能电池研究进展[J]. 物理化学学报, 2018, 34(11): 1202 -1210 .
[10]	杜惟实,吕耀康,蔡志威,张诚. 基于三维多孔石墨烯/含钛共轭聚合物复合多孔薄膜的柔性全固态超级电容器[J]. 物理化学学报, 2017, 33(9): 1828 -1837 .
[11]	张少青,侯剑辉. 面向非富勒烯型有机光伏电池的聚合物给体材料设计[J]. 物理化学学报, 2017, 33(12): 2327 -2338 .
[12]	刘继翀,唐峰,叶枫叶,陈琪,陈立桅. 利用扫描开尔文探针显微镜观察薄膜光电器件能级排布[J]. 物理化学学报, 2017, 33(10): 1934 -1943 .
[13]	刘艳苹,吴义室,付红兵. 单重态激子裂分的研究进展[J]. 物理化学学报, 2016, 32(8): 1880 -1893 .
[14]	胡彬,王培,吕晓静,王萍静,戴玉玉,欧阳密. 单体摩尔比对共聚物电化学及电致变色性质的影响[J]. 物理化学学报, 2016, 32(4): 961 -968 .
[15]	周晓,孙敏强,王庚超. 石墨烯负载新型π-共轭聚合物纳米复合电极材料的合成及其超级电容特性[J]. 物理化学学报, 2016, 32(4): 975 -982 .