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全无机CsPbBr3钙钛矿太阳能电池因其优良的特性而受到广泛关注, 但是钙钛矿层具有带隙宽、结晶性较差、表面缺陷较多和水分稳定性差等缺点, 严重制约了全无机CsPbBr3钙钛矿太阳能电池性能的提高和商业化发展. 本文以无空穴传输层的碳基CsPbBr3钙钛矿太阳能电池作为控制组, 在PbBr2前躯液中引入具有丰富疏水F离子的聚偏氟乙烯(polyvinylidene fluoride, PVDF)作为添加剂, 调节CsPbBr3钙钛矿薄膜的生长过程, 改善晶体结构和薄膜形态, 降低缺陷密度及非辐射复合几率. 结果表明, PVDF处理后钙钛矿器件的光伏性能得到了显著改善, 光电转换效率提高至8.17%. 并且在无封装条件下保存1400 h后, 光电转换效率仍可保持90%以上. 这表明适量添加PVDF可以有效提高CsPbBr3薄膜质量及器件性能. 本工作对进一步拓展CsPbBr3钙钛矿太阳能电池的优化设计思路具有重要意义.
Recently, the power conversion efficiency (PCE) of organic-inorganic hybrid perovskite solar cells has been enhanced rapidly from 3.8% to 25.8%, which is a top research topic in the field of photovoltaic power generation. However, the preparation of the hybrid perovskite solar cells has high environmental requirements, and the absorber layer is easily caused by the environmental influence and decomposition, resulting in the degradation of device performance. The all-inorganic CsPbBr3 perovskite material has good stability, can be prepared directly in air, and is more economical, showing great potential applications. However, the PCE of all-inorganic CsPbBr3 perovskite solar cells is not high, and at this stage, there is still much room for exploring high-quality controllable preparation of CsPbBr3 films. In this paper, we aim to prepare efficient and stable CsPbBr3 perovskite solar cells with additive engineering. Polymer is one of the most effective additives in perovskite solar cells. The use of polymer additive in perovskite layer can improve the shape-form, structure, and band gap of the film, thus improving the quality of perovskite film. Polyvinylidene fluoride (PVDF) is a cheap polymer with hydrophobic F ions and long flexible polymer chains, and can be used to prepare efficient and stable perovskite solar cells. In this paper, CsPbBr3 perovskite films are prepared by multi-part spin-coating method. PVDF with enriched hydrophobic F is added into the PbBr2 precursor solution as an additive to adjust the crystalline quality of the perovskite film, and the effects of PVDF on the growth process and device performance of the perovskite film are systematically studied. The results show that the PVDF can be used as a template to promote the growth of perovskite crystals, improve the crystal structure and film shape, thus reducing the defect density and charge recombination, and increasing the PCE of the device to 8.17%. The original efficiency of more than 90% can be maintained after 1400 h of storage under unencapsulated condition. Finally, high-efficiency, stable and low-cost CsPbBr3 perovskite solar cells are obtained, which is important in further expanding the optimized design ideas of CsPbBr3 perovskite solar cells. The PVDF can form hydrogen bonds with perovskite or interact with lead ions to improve the structural stability of perovskite, and the F ions in PVDF can improve the moisture stability of perovskite layers. -
Keywords:
- CsPbBr3 /
- polyvinylidene fluoride /
- addictive /
- perovskite solar cells
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图 2 不同浓度PVDF处理的PbBr2薄膜的SEM图像 (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL
Fig. 2. SEM images of PbBr2 films treated with different PVDF concentration: (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL.
图 3 不同浓度PVDF处理的CsPbBr3薄膜的SEM图像 (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL
Fig. 3. SEM images of CsPbBr3 films treated with different PVDF concentration: (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL.
图 4 PVDF处理前后CsPbBr3薄膜的AFM图像 (a) 控制组; (b) 0.5 mg/mL PVDF
Fig. 4. AFM images of CsPbBr3 films before and after PVDF treatment: (a) Control; (b) 0.5 mg/mL PVDF.
图 5 PVDF不同添加量所制备的CsPbBr3薄膜的XRD图谱
Fig. 5. XRD patterns of CsPbBr3 films prepared with different amounts of PVDF.
图 6 PVDF不同添加量所制备的CsPbBr3薄膜 (a) XPS全谱图; (b)—(d)分别对应Cs 3d, Pb 4f及Br 3d的高分辨率XPS图谱
Fig. 6. XPS spectra of CsPbBr3 films prepared with different amounts of PVDF: (a) XPS full spectrum; (b)–(d) correspond to the high-resolution XPS spectra of Cs 3d, Pb 4f and Br 3d, respectively.
图 7 控制组和0.5 mg PVDF处理的CsPbBr3薄膜的FTIR光谱
Fig. 7. FTIR spectra of control and 0.5 mg PVDF-treated perovskite films.
图 8 PVDF处理前后CsPbBr3薄膜的水接触角θca (a) 控制组, θca = 57.30°; (b) 0.5 mg PVDF, θca = 66.31°
Fig. 8. Water contact angle θca of CsPbBr3 films before and after PVDF treatment: (a) Control, θca = 57.30°; (b) 0.5 mg PVDF, θca = 66.31°.
图 9 PVDF制备CsPbBr3钙钛矿晶体 (a) 生长过程; (b) 作用机理; (c) 器件结构示意图
Fig. 9. CsPbBr3 perovskite crystal prepared by PVDF: (a) Schematic growth process; (b) mechanism of action; (c) structural schematic of the device.
图 10 PVDF不同添加量所制备的CsPbBr3薄膜 (a) UV-vis光谱图; (b) 稳态PL光谱图
Fig. 10. CsPbBr3 films prepared with different amounts of PVDF: (a) UV-vis spectra; (b) steady-state PL spectra.
图 11 PVDF不同添加量所制备的CsPbBr3 PSCs的J-V曲线图
Fig. 11. J-V curves of CsPbBr3 PSCs prepared with different amounts of PVDF.
图 12 PVDF不同添加量所制备的CsPbBr3-PSCs的各特性的箱试图(每组准备了26个电池装置) (a) FF; (b) VOC; (c) Jsc; (d) PCE
Fig. 12. Box attempts of different characteristics for CsPbBr3 PSCs prepared with different amounts of PVDF (26 cell devices were prepared for each group): (a) FF; (b) VOC; (c) Jsc; (d) PCE.
图 13 PVDF不同添加量所制备的CsPbBr3 PSCs的瞬态VOC测量光谱
Fig. 13. Transient VOC spectrogram of CsPbBr3 PSCs prepared with different amounts of PVDF.
图 14 PVDF不同添加量所制备的CsPbBr3-PSCs在空气中的稳定性
Fig. 14. Stability of CsPbBr3-PSCs prepared with different amounts of PVDF in air.
表 1 PVDF不同添加量所制备的CsPbBr3 PSCs的光伏参数
Table 1. Photovoltaic parameters of CsPbBr3 PSCs prepared with different amounts of PVDF.
器件薄膜类型 开路电压
VOC/V短路电流
Jsc/(mA·cm–2)光电转换效
率PCE/%填充因子
FF/%Control 1.34 6.77 6.81 75 0.3 mg PVDF 1.36 7.03 7.12 74 0.5 mg PVDF 1.31 8.26 8.17 76 1.0 mg PVDF 1.33 7.39 7.40 75 
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[1] Wang D, Li W J, Du Z B, Li G D, Sun W H, Wu J H, Lan Z 2020 ACS Appl. Mater. Interfaces 12 10579
Google Scholar
[2] Liu G C, Liu Z H, Wang L, Xie X Y 2021 Chem. Phys. 542 111061
Google Scholar
[3] Jin I S, Park S H, Kim K S, Jung J W 2020 J. Alloys Compd. 847 156512
Google Scholar
[4] Wan X J, Yu Z, Tian W M, Huang F Z, Jin S Y, Yang X C, Cheng Y B, Hagfeldt A, Sun L C 2020 J. Energy Chem. 46 8
Google Scholar
[5] Fu Y J, Sun Y P, Tang H, Wang L Y, Yu H Z, Cao D R 2021 Dye. Pigment. 191 109339
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[6] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
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