SIOC English
化学学报
高级检索

化学学报 >

0 0

DOI: https://doi.org/10.6023/A26050166

研究论文

钴（Ⅱ/Ⅲ）共掺杂调控钙钛矿缺陷及器件稳定性

  • 唐景航 ,
  • 张林 ,
  • 徐文军 ,
  • 杨英
展开
  • 中南大学 冶金与环境学院 有色金属资源循环利用国家地方联合工程研究中心 有色金属资源循环利用湖南省重点实验室 长沙 410083

收稿日期: 2026-05-18

  网络出版日期: 2026-09-17

基金资助

国家重点研发 (2023YFC3906103) 资助.

收起

Regulation of Perovskite Defects and Device Stability via Co (II/III) Co-Doping

  • Tang Jinghang ,
  • Zhang Lin ,
  • Xu Wenjun ,
  • Yang Ying
Expand
  • School of Metallurgy and Environment, Central South University; National & Regional Joint Engineering Research Center of Nonferrous Metal Resources Recycling;; Hunan Key Laboratory of Nonferrous Metal Resources Recycling, Changsha 410083, China

Received date: 2026-05-18

  Online published: 2026-09-17

Supported by

Nation Key R&D Program of China (Grant Numbers: 2023YFC3906103).

Fold

摘要

钙钛矿太阳电池可通过低成本溶液法制备,且光电性能优异,但薄膜成膜过程中易产生多种铅/碘基缺陷,引发深能级陷阱及离子迁移,导致非辐射复合与结构退化,严重制约器件效率和稳定性。针对现有钝化策略多集中于单一类型缺陷、难以实现铅/碘基缺陷协同钝化的问题,本研究选用FA0.95Cs0.05PbI3钙钛矿体系,创新性地引入Co(acac)2/Co(acac)3作为体相掺杂剂,通过刮涂工艺制备薄膜与器件,系统探究了其对结晶动力学、缺陷化学、电荷传输与器件稳定性的综合影响。研究发现,Co3+通过氧化作用钝化Pb0缺陷,其乙酰丙酮配体同时与不饱和Pb2+配位,增强结构整合;Co2+则与碘空位及活性碘物种相互作用,有效抑制碘迁移与挥发。二者在体系中同步调控铅、碘相关缺陷态。在摩尔分数为0.1%的掺杂浓度下,薄膜结晶质量显著提升,晶粒尺寸增大,缺陷密度降低;相应器件效率达19.52%,Jsc为25.07 mA·cm-2,FF为76.36%。未封装器件在AM 1.5G持续光照400 h后效率保持率达82%,并在热老化与长期储存测试中表现出优越的稳定性。本工作发展了一种钙钛矿太阳电池体相铅碘缺陷同步钝化策略,为构建高效稳定钙钛矿太阳电池提供了新途径。

关键词： 钙钛矿太阳电池; 乙酰丙酮钴（Ⅱ/Ⅲ）; 缺陷钝化; 体相掺杂; 稳定性

本文引用格式

唐景航 , 张林 , 徐文军 , 杨英 . 钴（Ⅱ/Ⅲ）共掺杂调控钙钛矿缺陷及器件稳定性[J]. 化学学报, 0 : 0 . DOI: 10.6023/A26050166

Abstract

Perovskite solar cells (PSCs) possess the advantages of low-cost solution processing and excellent optoelectronic properties. However, various lead- and iodine-related defects are inevitably generated during film formation, which induce deep-level trap states and accelerate ion migration, thereby aggravating non-radiative recombination and structural degradation.These drawbacks severely restrict the power conversion efficiency and long-term stability of PSCs.Most existing passivation strategies focus merely on a single type of defect and cannot realize the synergistic regulation of both lead- and iodine-based defects. To tackle this issue, the FA0.95Cs0.05PbI3 perovskite system was selected, and Co(acac)2/Co(acac)3 was introduced as a bulk dopant. Perovskite films and devices were prepared by blade coating, and the influences of the Co(II/III) acetylacetonates on crystallization kinetics, defect chemistry, charge transport behavior and device durability were systematically explored.Co3+passivates zero-valent lead defects through oxidation, and its acetylacetonate ligands coordinate with undercoordinated Pb2+ to strengthen lattice structural integrity. Meanwhile, Co2+ interacts with iodine vacancies and active iodine species, efficiently inhibiting iodine migration and volatilization. The Co(II/III) acetylacetonates simultaneously modulate lead- and iodine-derived defect states.At an optimal molar fraction of 0.1%, the resulting perovskite film exhibits improved crystallinity, enlarged grain size and reduced defect density. The optimized device delivers a champion efficiency of 19.52%, with a Jsc of 25.07 mA·cm-2 and an FF of 76.36%. Benefiting from the simultaneous modulation effect, the unencapsulated device maintains 82% of the original efficiency after 400 h of continuous AM 1.5G light irradiation, and presents superior resistance to thermal aging and long-term storage.This work develops a bulk lead-iodine defect synchronous passivation strategy for perovskite solar cells, offering a promising route for constructing high-efficiency and ultra-stable perovskite solar cells.

Key words： Perovskite solar cells; Co(II)/Co(III) acetylacetonate; defect passivation; bulk doping; stability

参考文献

[1] Shen X.; Lin X.; Su H.; Zhang Z.; Wu T.; Zhang J.; Peng Y.; Zhang Y.; Zhang S.; Zhou Z.; et al.Nano-Micro Letters.2026,18,1.
[2] Wang J.; Bi L.; Fu Q.; Jen, A. K. Y.Adv. Energy Mater.2024,14,35.
[3] Min J.; Choi Y.; Kim D.; Park, T.Adv. Energy Mater.2023,14,6.
[4] Ren J.; Liu T.; He B.; Wu G.; Gu H.; Wang B.; Li J.; Mao Y.; Chen S.; Xing G.Small.2022,18,47.
[5] Zhao P.; Kim B. J.; Jung, H. S.Materials Today Energy.2018,7,267-286.
[6] Li Y.; Li Z.; Liu F.; Wei J.Surface Innovations.2021,10,1,3-20.
[7] Xia J.; Liang C.; Gu H.; Mei S.; Li S.; Zhang N.; Chen S.; Cai Y.; Xing, G.Energy & Environmental Materials.2021,6,1.
[8] Aydin E.; De Bastiani M.; De Wolf, S.Advanced Materials.2019,31,25.
[9] Li C.; Li H.; Zhu Z.; Cui N.; Tan Z. a.; Yang R.Solar RRL.2020,5,1.
[10] Gozukara Karabag Z.; Karabag A.; Gunes U.; Gao X.-X.; Syzgantseva O. A.; Syzgantseva M. A.; Varlioglu Yaylali F.; Shibayama N.; Kanda H.; Rafieh A. I.; et al.Adv. Energy Mater.2023,13,2302038.
[11] Feng X.; Li X.; Li Z.; Xue Y.; Chen X.; Sun X.; Tang J.; Liu S.; Wang Z.; Xie Y.; et al.ACS Applied Materials & Interfaces.2025,17,25883-25893.
[12] Wang,J.Y.;Guo,H.H.;Yin,X.Y.;Zhang,Y.Z.;WANG,W.;Zhao,C.R.;Chen,J.;Wen,J.;Sun,W.H.Acta Chim.Sin2026,84(2):231-239.(in Chinese).(汪佳艳,郭焕焕,殷逍遥,张昀照,王威,赵晨瑞,陈洁,文洁,孙伟海,化学学报,2026,84(2):231-239.)
[13] Liu,B.B.;Chen,Y.;Jia,T.C.;Chen,C.;Wu,Z.H.;Liu,Y.H.;Zhai,Y.H.;Ma,T.S.;Wang,C.L.Acta Phys.-Chim.Sin.2026,42(1):41-51.(in Chinese)(刘彬彬, 陈杨, 贾天赐, 陈辰, 吴章豪, 刘毓辉, 翟宇航, 马天舒, 王长擂. 物理化学学报, 2026,42(1): 41-51.)
[14] Li W.; Zhu A.; Gu H.; Wang B.; Wang G.; Li S.; Chen S.; Liao J.; Xing, G.Chemical Engineering Journal.2023,471,144561.
[15] Guo,Z.W.;Jiang,Y.;Zeng,T.;Chen Y.X.Acta Ceram.Sin.2026,47(3):547-558. (in Chinese).(郭章旺,江炀,曾涛,陈云霞,陶瓷学报,2026,47(3):547-558.)
[16] Wang L.; Zhou H.; Hu J.; Huang B.; Sun M.; Dong B.; Zheng G.; Huang Y.; Chen Y.; Li L.Science.2019,363,265-270.
[17] Yarranton J. T.; McCusker, J. K.Journal of the American Chemical Society.2022,144,12488-12500.
[18] Nohenschwander U.Ph.D. Dissertation. ETH Zurich, Zurich, Switzerland, 2011.
[19] Li N.; Shi L.; Wang X.; Guo F.; Yan, C.Int J Anal Chem.2011,2011,130102.
[20] Sadeek, S. A. J.Argent. Chem. Soc.2005,93, 165-176.
[21] Hashem H. A.; Refat M. S.Surface Review and Letters. 2006,13,439-449.
[22] Wu W. C.; Feng H. Q.; Wu K. Z.Science Press: Beijing, 1991; pp. 77-83, 125-131, 179-185.(in Chinese)(吴维昌, 冯洪清, 吴开治, 科学出版社,北京, 1991.77-83, 125-131, 179-185).
[23] VASVÁRI G, HAJDU I P, GÁL D.J. Chem. Soc., Dalton Trans., 1974,5: 465-470.
[24] Zhang Y.; Yu, H.Chemical Engineering Journal.2026,531,173913.
[25] Jubu P. R.; Obaseki O. S.; Nathan-Abutu A.; Yam F. K.; Yusof Y.; Ochang, M. B.Results in Optics.2022,9,100273.
[26] Rietwyk K. J.; Lin X.; Tan B.; Warnakula T.; Holzhey P.; Zhao B.; Deng S.; Surmiak M. A.; Jasieniak J.; Bach, U.Adv. Energy Mater.2023,13,9,15.
[27] van Franeker J. J.; Hendriks K. H.; Bruijnaers B. J.; Verhoeven M. W. G. M.; Wienk M. M.; Janssen, R. A. J.Adv. Energy Mater.2017,7,1601822.
[28] Wang Z.Y.; Xiang W.C.; Shi C.; Xiao S.P.; Wu R.; Yu X.L.; Ma L.; Qin Z.L.; Lei H.W.; Chen X.B.; Fang G.J.; Qin, P.L. ACS Appl. Mater. Interfaces.2023,15,49739-49748
[29] Li C.; Zhang N.; Gao, P.Materials Chemistry Frontiers.2023,7,3797-3802.
[30] Jiang H.; Yang R.; Zhu Z.; Sun C.; Jin Y.; Zheng L.; Shen L.; Tian C.; Xie L.; Yang J.; et al.Advanced Science.2025,12,2416634.
[31] Li C.; Song Z.; Zhao D.; Xiao C.; Subedi B.; Shrestha N.; Junda M. M.; Wang C.; Jiang C.-S.; Al-Jassim M.; et al.Adv. Energy Mater.2019,9,1803135.
[32] Jiménez-Tejada J. A.; García-Rosell M.; Almora O.; López-Varo P.Solar Energy.2025,287,113187.
[33] Caprioglio P.; Wolff C. M.; Sandberg O. J.; Armin A.; Rech B.; Albrecht S.; Neher D.; Stolterfoht, M.Adv. Energy Mater.2020,10,27,2000502.
[34] Wu F.; Mabrouk S.; Han M.; Tong Y.; Zhang T.; Zhang Y.; Bobba R. S.; Qiao, Q.Journal of Energy Chemistry.2022,76,414-420.
[35] Wang,H.;Zheng,D.X.;Jiang,X.;Cao,Y.X.;Du,M.Y.;Wang,K.;Liu,S.Z.;Zhang C.F.Acta Phys.Sin.2024,73(7):078401. (in Chinese).(王辉,郑德旭,姜箫,曹越先,杜敏永,王开,刘生忠,张春福,物理学报,2024,73(7):078401.)
[36] Swift M. W.; Lyons, J. L.J. Mater. Chem. A.2021,9,7491-7495.
[37] Li B. e.; Liu C.; Zhang X.Nanomaterials.2024,14,17,1406.
[38] Wang J.; Hu S.; Chen Z.; Yuan Z.; Zhao P.; Dasgupta A.; Yang F.; Yao J.; Truong M. A.; Kusch G.; et al.Energy & Environmental Science.2025,18,7680-7694.
[39] Wu X.; Wang S.; Zhang J.; Shiu H.-W.; Hsu Y.-J.; Yan H.; Zhu J.; Lu X.Nano Energy.2023,117,108907.
[40] Wang H.; Li Q.; Zhu Y.; Sui X.; Fan X.; Lin M.; Shi Y.; Zheng Y.; Yuan H.; Zhou Y.; et al.Energy & Environmental Science.2025,18,2254-2263.
[41] Zhou J.; Liu Z.; Yu P.; Tong G.; Chen R.; Ono L. K.; Chen R.; Wang H.; Ren F.; Liu S.; et al.Nature Communications.2023,14,6120.
Options
文章导航

/

〈 〉