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传统的高效率钙钛矿太阳能电池, 需要在具有氮气保护的严苛条件下方可实现. 高湿度(55%)空气环境中, 大面积钙钛矿成膜工艺开发及器件结构优化对模组器件效率和稳定性的提高至关重要. 本工作采用一种真空抽气萃取方法在空气中实现了高质量钙钛矿薄膜的制备, 并研究了双端可低温光聚合单体分子对钙钛矿薄膜内封装的可行性. 研究发现, 当抽气时间为60 s, 在空气中可以形成均匀、致密的钙钛矿薄膜. 通过调控单体分子浓度, 能够在内封装的同时, 实现对钙钛矿表面缺陷的钝化, 当浓度为1 mg/mL时, 对应钙钛矿薄膜的形貌及荧光强度达到最优. 最终, 基于聚合物内封装修饰的刚性和柔性模组(有效面积: 18 cm2)器件分别实现了19.51%和18.17%的室外光电转化效率(34.5%和30.2%的室内弱光转化效率). 此外, 聚合物内封装提升器件湿度稳定性及抑制铅泄漏的同时, 也显著提升了柔性模组的耐弯折稳定性. 聚合物内封装技术为未来大面积模组器件的发展及进一步产业应用提供了新的方向和可能.The preparation of traditional organic-inorganic lead-halogen hybrid perovskite solar cells often requires strict nitrogen glove box conditions, thus hindering their industrial scalability. This study develops a large-area perovskite film formation process and designs a novel device structure to achieve a dual enhancement of module device efficiency and stability in a high humidity air environment (55%). High-quality perovskite thin films are successfully prepared by vacuum extraction in ambient air, followed by a double-end low-temperature photopolymerization process utilizing acrylate monomer molecules for inner encapsulation modification of the freshly formed perovskite thin films. The influences of these techniques on the photoelectric characteristics of perovskite thin films and devices are investigated. The results indicate that uniform and dense perovskite films can be achieved in ambient air with a pumping time of 60 s. By adjusting the concentration of ethylene glycol dimethacrylate monomer molecules used in the low-temperature photopolymerization process, the surface defects on the perovskite film can be effectively controlled. The optimal concentration of 1 mg/mL results in perovskite film with optimal morphology and fluorescence intensity. Furthermore, rigid module device and flexible module device (effective area: 18 cm²), based on the polymer inner encapsulation, demonstrate outstanding outdoor photoelectric conversion efficiencies of 19.51% and 18.17%, respectively (with the highest indoor low-light conversion efficiencies of 34.5% and 30.2%, respectively). Notably, the untreated flexible device exhibits a significant decline in photoelectric conversion efficiency, falling below 50% of the initial value after one month of exposure to air. In contrast, device incorporating the polymer inner encapsulation layer maintains over 90% of their original efficiency, highlighting their excellent humidity resistance stability. Moreover, the polymer encapsulation layer also greatly improves the bending stability of the flexible device. This research paves the way for industrial-scale producing perovskite solar cells and addressing the challenges associated with humidity and large-area fabrication. The findings contribute to advancing perovskite solar cell technology and offering a pathway for high-efficiency and stable devices suitable for practical applications.
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Keywords:
- perovskite solar cell /
- module /
- low temperature photopolymerization /
- polymer internal encapsulation
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图 1 (a) SEM截面形貌图; (b) DEGDMA单体在钙钛矿薄膜上的光聚合过程
Fig. 1. (a) SEM morphology of the cross-section for device; (b) polymerization process of DEGDMA on the perovskite fIlm after light-initiated process.
图 2 空气中真空萃取制备的钙钛矿薄膜的表面SEM和AFM形貌图 (a), (e) 0 mg/mL; (b), (f) 1.0 mg/mL; (c), (g) 2.0 mg/mL; (d), (h) 5.0 mg/mL
Fig. 2. SEM and AFM morphologies of perovskite films prepared by vacuuming in air with different weight concentrations: (a), (e) 0 mg/mL; (b), (f) 1.0 mg/mL; (c), (g) 2.0 mg/mL; (d), (h) 5.0 mg/mL.
图 3 大气环境中真空抽气法制备的钙钛矿薄膜PEGDMA处理前后的(a) XRD图和接触角, 以及(b) Pb元素的XPS特征峰
Fig. 3. Perovskite films prepared in atmospheric environment with and without PEGDMA: (a) XRD patterns and contact angles; (b) XPS characteristic peak of Pb.
图 4 PEGDMA聚合物夹层处理前后钙钛矿表面的(a) 吸收光谱及(b) 荧光发射光谱; (c) 单电子器件电流-电压曲线及(d)标准器件电化学阻抗谱
Fig. 4. (a) Absorption spectrum and (b) fluorescence emission spectrum of perovskite films with polymer layer modified; (c) dark J-V curves of electron-only devices and (d) Nyquist plots of devices.
图 5 (a) 钙钛矿模组实物图及(b)激光刻蚀结构图
Fig. 5. (a) Photo and (b) cross section structure of laser etching for the perovskite module.
图 6 (a)刚性和(b)柔性钙钛矿模组器件的室外J-V曲线图
Fig. 6. The J-V curves of rigid (a) and flexible (b) perovskite module with or without PEGDMA.
图 7 (a)室内LED白光的光谱曲线及(b)刚性和(c)柔性钙钛矿模组器件的室内弱光J-V曲线
Fig. 7. (a) Illumination spectra of white LED and J-V curves of (b) rigid and (c) flexible perovskite module with or without PEGDMA under white LED.
图 8 柔性PEN导电层方阻随退火时间(150 ℃)的变化曲
Fig. 8. Curve of square resistance for flexible PEN with annealing time (150 ℃).
图 9 柔性钙钛矿模组的器件湿度稳定性(a)和耐弯折稳定性(b)
Fig. 9. Humidity (a) and bending stability (b) of flexible perovskite module.
图 10 钙钛矿模组器件的水侵蚀研究及铅泄漏评估
Fig. 10. Water erosion study and lead leakage assessment of perovskite module.
表 1 聚合物层修饰的刚性和柔性模组器件室外光电参数比较
Table 1. Comparison of optoelectronic parameters of polymer layer modified rigid and flexible perovskite module devices.
器件 JSC/(mA·cm–2) VOC/V FF/% PCE/% Glass/ITO-控制组 (in air) 3.84 6.62 73.6 18.71 Glass/ITO-PEGDMA (in air) 3.94 6.70 73.9 19.51 Glass/ITO-PEGDMA (in N2) 4.02 6.65 73.3 19.59 PEN/ITO-控制组 (in air) 3.81 6.51 65.6 16.26 PEN/ITO-PEGDMA (in air) 3.83 6.60 71.9 18.17 PEN/ITO-PEGDMA (in N2) 3.89 6.63 71.3 18.39 
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[1] Brenner T M, Egger D A, Kronik L, Hodes G, Cahen D 2016 Nat. Rev. Mater. 1 15007
Google Scholar
[2] Wolf S D, Holovsky J, Moon S J, Löper P, Niesen B, Ledinsky M, Haug F J, Yum J H, Ballif C 2014 J. Phys. Chem. Lett. 5 1035
Google Scholar
[3] Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J P, Leijtens T, Herz L, Petrozza A, Snaith H J 2013 Science 342 341
Google Scholar
[4] Xing G C, Mathews N, Sun S Y, Lim S S, Lam Y M, Grätzel M, Mhaisalkar S, Sum T C 2013 Science 342 344
Google Scholar
[5] Leijtens T, Lim J, Teuscher J, Park T, Snaith H 2013 Adv. Mater. 25 3227
Google Scholar
[6] https://www.nrel.gov/pv/interactive-cell-efficiency.html
[7] Ding Y, Ding B, Kanda H, Usiobo O J, Gallet T, Yang Z H, Liu Y, Huang H, Sheng J, Liu C, Yang Y, Queloz V I E, Zhang X F, Audinot J N, Redinger A, Dang W, Mosconic E, Luo W, Angelis F D, Wang M K, Dörflinger P, Armer M, Schmid V, Wang R, Brooks K G, Wu J H, Dyakonov V, Yang G J, Dai S Y, Dyson P J, Nazeeruddin M K 2022 Nat. Nanotechnol. 17 598
Google Scholar
[8] Rana P J S, Febriansyah B, Koh T M, Muhammad B T, Salim T, Hooper T J N, Kanwat A, Ghosh B, Kajal P, Lew J H, Aw Y C, Yantara N, Bruno A, Pullarkat S A, Ager J W, Leong W L, Mhaisalkar S G, Mathews N 2022 Adv. Funct. Mater. 32 2113026
Google Scholar
[9] Wang Y, Yang H, Zhang K, Tao M Q, Li M Z, Song Y L 2022 ACS Energy Lett. 7 3646
Google Scholar
[10] Zhang K, Wang Y, Tao M Q, Guo L T, Yang Y R, Shao J Y, Zhang Y Y, Wang F Y, Song Y L 2023 Adv. Mater. 35 2211593
Google Scholar
[11] Brooks K G, Nazeeruddin M K 2021 Adv. Energy Mater. 11 2101149
Google Scholar
[12] Castriotta L A, Zendehdel M, Nia N Y, Leonardi E, Löfffer M, Paci B, Generosi A, Rellinghaus B, Carlo A D 2022 Adv. Energy Mater. 12 2103420
Google Scholar
[13] Babayigit A, Haen J D, Boyen H G, Conings B 2018 Joule 2 1205
Google Scholar
[14] Konstantakou M, Perganti D, Falaras P, Stergiopoulos T 2017 Crystals 7 291
Google Scholar
[15] Gu L, Wang S, Fang X, Liu D, Xu Y, Yuan N, Ding J 2020 ACS Appl. Mater. Interfaces 12 33870
Google Scholar
[16] Jang G, Kwon H C, Ma S, Yun S C, Yang H, Moon J 2019 Adv. Energy Mater. 9 1901719
Google Scholar
[17] Gu L L, Fei F, Xu Y B, Wang S B, Yuan N Y, Ding J N 2022 ACS Appl. Mater. Interfaces 14 2949
Google Scholar
[18] Li H Y, Bu T L, Li J, Lin Z P, Pan J Y, Li Q H, Zhang X L, Ku Z L, Cheng Y B, Huang F Z 2021 ACS Appl. Mater. Interfaces 13 18724
Google Scholar
[19] Vesce L, Stefanelli M, Herterich J P, Castriotta L A, Kohlstädt M, Würfel U, Carlo A D 2021 Solar RRL 5 2100073
Google Scholar
[20] Xu J, Dong H, Xi J, Yang Y, Yu Y, Ma L, Chen J B, Jiao B, Hou X, Li J R, Wu Z X 2020 Nano Energy 75 104940
Google Scholar
[21] Xu J, Xi J, Dong H, Ahn N, Zhu Z L, Chen J B, Li P Z, Zhu X Y, Dai J F, Hu Z Y, Jiao B, Hou X, Li J R, Wu Z X 2021 Nano Energy 88 106286
Google Scholar
[22] Zhu X Y, Dong H, Chen J B, Xu J, Li Z J, Yuan F, Dai J F, Jiao B, Hou X, Xi J, Wu Z X 2022 Adv. Funct. Mater. 32 2202408
Google Scholar
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