有机-无机共添加增强柔性钙钛矿太阳能电池机械弯曲及环境稳定性能

doi:10.15541/jim20230532

无机材料学报 ›› 2024, Vol. 39 ›› Issue (5): 477-484.DOI: 10.15541/jim20230532

有机-无机共添加增强柔性钙钛矿太阳能电池机械弯曲及环境稳定性能

陈甜¹(), 罗媛¹, 朱刘²^,³, 郭学益¹, 杨英¹()

1.中南大学冶金与环境学院, 长沙 410083
2.广东先导稀材股份有限公司, 清远 511500
3.广东省高性能薄膜太阳能材料企业重点实验室, 清远 511517

收稿日期:2023-11-16 修回日期:2024-01-20 出版日期:2024-05-20 网络出版日期:2024-02-22
通讯作者: 杨英, 教授. E-mail: muyicaoyang@csu.edu.cn
作者简介:陈甜(1993-), 女, 博士研究生. E-mail: amychen@csu.edu.cn
基金资助:
国家重点研发计划项目(2023YFC3906103);国家自然科学基金(61774169);湖南省自然科学基金-面上项目(2022JJ30757);广东省科技计划(2018B030323010);清远市创新创业科研团队项目(2018001)

Organic-inorganic Co-addition to Improve Mechanical Bending and Environmental Stability of Flexible Perovskite Solar Cells

CHEN Tian¹(), LUO Yuan¹, ZHU Liu²^,³, GUO Xueyi¹, YANG Ying¹()

1. School of Metallurgy and Environment, Central South University, Changsha 410083, China
2. First Rare Materials Co., Ltd., Qingyuan 511500, China
3. Guangdong Provincial Enterprises Key Laboratory of High Performance Thin Film Solar Materials, Qingyuan 511517, China

Received:2023-11-16 Revised:2024-01-20 Published:2024-05-20 Online:2024-02-22
Contact: YANG Ying, professor. E-mail: muyicaoyang@csu.edu.cn
About author:CHEN Tian (1993-), female, PhD candidate. E-mail: amychen@csu.edu.cn
Supported by:
National Key R&D Program of China(2023YFC3906103);National Natural Science Foundation of China(61774169);Natural Science Foundation of Hunan Province(2022JJ30757);Science and Technology Program of Guangdong Province(2018B030323010);Qingyuan Innovation and Entrepreneurship Research Team Project(2018001)

摘要/Abstract

摘要：

近年来, 钙钛矿太阳能电池发展迅速, 其光电转换效率(Power Conversion Efficiency, PCE)已经提高到26.1%, 但是柔性钙钛矿太阳能电池(Flexible Perovskite Solar Cells, F-PSCs)的机械弯曲和环境稳定性仍然是其商业化的主要障碍。本研究通过添加琼脂糖(Agarose, AG)以改善薄膜的质量和结晶性能, 系统探究了AG对钙钛矿的作用机理, 组装成的F-PSCs的PCE和机械弯曲及环境稳定性能。研究发现当AG添加浓度达到最优值3 mmol/L时, 薄膜表面变得更为致密平滑, 钙钛矿结晶度和吸光度增加。此时器件的陷阱态密度降到最低, 电荷传输电阻低至2191 Ω, 光电性能达到最佳, PCE由15.17%提升至17.30%。进一步引入TiO₂纳米颗粒(0.75 mmol/L), 与AG(3 mmol/L)共同作用, 可以提供刚性骨架结构, 增强钙钛矿层的机械性能和环境稳定性。循环弯曲1500次(半径为3 mm)后, AG/TiO₂共添加器件可保持初始PCE的84.73%, 远高于空白器件的9.32%; 在空气中放置49 d后, 该器件仍可保持初始PCE的83.27%, 优于空白器件的62.21%。该研究成果为制备高效且稳定的F-PSCs提供了可能性。

关键词: 柔性钙钛矿太阳能电池, 添加剂工程, 弯曲稳定性, 环境稳定性

Abstract:

Recently, perovskite solar cells have developed marvelously of which power conversion efficiency (PCE) achieved 26.1%, but the mechanical bending and environmental stability of flexible perovskite solar cells (F-PSCs) have remained major obstacles to their commercialization. In this study, the quality and crystallization of perovskite thin films were enhanced by adding agarose (AG). The interaction mechanism, PCE, mechanical bending and environmental stability of the assembled F-PSCs were investigated. It was found that the perovskite films modified by the optimal concentration of AG (3 mmol/L) exhibited denser and smoother morphology, higher crystallinity and absorbance, the lowest defect state density, and lower charge transfer resistance of 2191 Ω. Based on the optimal photoelectric properties, PCE increased from 15.17% to 17.30%. TiO₂ nanoparticles (0.75 mmol/L) were further introduced to form a synergistic interaction with AG (3 mmol/L), which provided a rigid backbone structure, and thus enhanced the mechanical and environmental stability of perovskite layers. After 1500 cycles of bending (3 mm in radius), the AG/TiO₂ co-modified F-PSCs maintained 84.73% of initial PCE, much higher than the blank device (9.32%). After 49 d in the air, the optimal F-PSCs still maintained 83.27% of initial PCE, superior than the blank device (62.21%). This work provides possibility for preparing highly efficient and stable F-PSCs.

Key words: flexible perovskite solar cell, additive engineering, bending stability, environmental stability

中图分类号:

O646

陈甜, 罗媛, 朱刘, 郭学益, 杨英. 有机-无机共添加增强柔性钙钛矿太阳能电池机械弯曲及环境稳定性能[J]. 无机材料学报, 2024, 39(5): 477-484.

CHEN Tian, LUO Yuan, ZHU Liu, GUO Xueyi, YANG Ying. Organic-inorganic Co-addition to Improve Mechanical Bending and Environmental Stability of Flexible Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2024, 39(5): 477-484.

图/表 10

图1 在ITO-PEN/SnO2上沉积的xAG-P (x=0, 3, 6, 9, 12)薄膜的形貌、晶体结构和光学特性

Fig. 1 Morphologies, crystal structure and optical properties of xAG-P (x=0, 3, 6, 9, 12) films deposited on ITO-PEN/SnO2 (a-e) SEM images; (f) XRD patterns; (g) UV-Vis absorption spectra; (h) Tauc plots; (i) Photoluminescence emission Colorful figures are available on website

图2 xAG-P (x=0, 3, 6, 9, 12)薄膜的(a) C1s, (b) Pb4f, (c) I3d, (d) N1s, (e) O1s XPS光谱图和(f) AG, 0AG-P, 3AG-P薄膜的FT-IR光谱图

Fig. 2 (a) C1s, (b) Pb4f, (c) I3d, (d) N1s, and (e) O1s XPS spectra of xAG-P (x=0, 3, 6, 9, 12) films, and (f) FT-IR spectra of AG, 0AG-P, and 3AG-P films

图3 xAG-PSC (x=0, 3, 6, 9, 12)的光伏性能和稳定性

Fig. 3 Photovoltaic performance and stability of xAG-PSC (x=0, 3, 6, 9, 12) (a) J-V curves; (b) External quantum efficiency (EQE) curves; (c) I-V plots based on space charges limit current model; (d) Nyquist plots; (e) Bending stability; (f) Environmental stability Colorful figures are available on website

图4 在ITO-PEN/SnO2上沉积的3AG-yTiO2-P (y=0, 0.75, 1.50, 2.25, 3.00)薄膜的形貌、晶体结构和光学特性

Fig. 4 Morphologies, crystal structure, and optical properties of 3AG-yTiO2-P (y=0, 0.75, 1.50, 2.25, 3.00) films deposited on ITO-PEN /SnO2 (a-e) SEM images; (f) XRD patterns; (g) UV-Vis absorption spectra; (h) Photoluminescence emission spectra; (i) FT-IR spectra of TiO2, AG, AG-TiO2, 0AG-P, 3AG-P, and 3AG-0.75TiO2-P films Colorful figures are available on website

图5 3AG-yTiO2-PSC (y=0, 0.75, 1.50, 2.25, 3.00)的(a)弯曲稳定性和(b)环境稳定性

Fig. 5 (a) Bending stability and (b) environmental stability of 3AG-yTiO2-PSC (y=0, 0.75, 1.50, 2.25, 3.00) Colorful figures are available on website

表S1 不同浓度琼脂糖改性MAPbI3薄膜的XRD特征峰半峰宽信息/(°)

Table S1 FWHM of XRD peaks of MAPbI3 films modified with different agarose concentrations/(°)

Sample	FWHM₍₁₁₀₎	FWHM₍₂₂₀₎	FWHM₍₃₁₀₎	FWHM₍₃₂₁₎
0AG-P	0.220	0.183	0.196	0.271
3AG-P	0.165	0.136	0.149	0.257
6AG-P	0.210	0.146	0.156	0.261
9AG-P	0.208	0.199	0.156	0.260
12AG-P	0.239	0.221	0.223	0.276

表S2 AG、0AG-P和3AG-P主要官能团的FT-IR伸缩振动峰位信息

Table S2 Stretching vibration peaks corresponding to the main functional groups of AG, 0AG-P abd 3AG-P

Sample	ν_C−O−C/cm⁻¹	ν_O−H/cm⁻¹	ν_N−H/cm⁻¹
AG	1076	3444
0AG-P			1452
3AG-P			1454

表S3 不同浓度琼脂糖改性MAPbI3薄膜的F-PSCs光电性能参数

Table S3 Photoelectric performance parameters of F-PSCs based on MAPbI3 films with different agarose concentrations

Sample	J_sc/(mA·cm^-2)	V_oc/V	FF/%	PCE/%
0AG-PSC	19.66	1.09	70.58	15.17
3AG-PSC	22.89	1.06	71.12	17.30
6AG-PSC	20.17	1.06	64.18	13.65
9AG-PSC	18.31	1.03	68.45	12.86
12AG-PSC	17.53	1.00	64.35	11.20

表S4 不同浓度TiO2改性MAPbI3薄膜的XRD特征峰半峰宽信息/(°)

Table S4 FWHM of XRD peaks of MAPbI3 films modified with different concentrations of TiO2/(°)

Sample	FWHM₍₁₁₀₎	FWHM₍₂₂₀₎	FWHM₍₃₁₀₎	FWHM₍₃₂₁₎
3AG-0TiO₂-P	0.165	0.136	0.149	0.257
3AG-0.75TiO₂-P	0.188	0.183	0.196	0.255
3AG-1.50TiO₂-P	0.169	0.193	0.189	0.263
3AG-2.25TiO₂-P	0.146	0.169	0.174	0.254
3AG-3.00TiO₂-P	0.161	0.179	0.189	0.246

表S5 TiO2, AG, TiO2-AG, 0AG-P, 3AG-P 和 3AG-0.75TiO2-P主要官能团的FT-IR伸缩振动峰位信息

Table S5 Stretching vibration peaks corresponding to the main functional groups of TiO2, AG, TiO2-AG 0AG-P, 3AG-P and 3AG-0.75TiO2-P

Sample	ν_C−O−C/cm⁻¹	ν_O−H/cm⁻¹	ν_C−H/cm⁻¹	ν_N−H/cm⁻¹
TiO₂		3415
AG	1076	3444
TiO₂-AG	1099	3448
0AG-P			2871	1452
3AG-P			2873	1454
3AG-0.75TiO₂-P			2873	1456

参考文献 31

[1]	The National Renewable Energy Laboratory. Best research-cell efficiency chart. (2023-07-10)[2024-01-17]. https://www.nrel.gov/pv/cell-efficiency.html.
[2]	FANG W, SHEN L, LI H, et al. Effect of film formation processes of NiO_x mesoporous layer on performance of perovskite solar cells with carbon electrodes. J. Inorg. Mater., 2023, 38(9): 1103.
[3]	LUO Q, MA H, HOU Q, et al. All-carbon-electrode-based endurable flexible perovskite solar cells. Adv. Funct. Mater., 2018, 28(11): 1706777.
[4]	WEI J, GUO F, WANG X, et al. SnO₂-in-polymer matrix for high-efficiency perovskite solar cells with improved reproducibility and stability. Adv. Mater., 2018, 30(52): 1805153.
[5]	LI M, ZHOU J, TAN L, et al. Multifunctional succinate additive for flexible perovskite solar cells with more than 23% power- conversion efficiency. The Innovation, 2022, 3(6): 100310.
[6]	ZHU C T, YANG Y, LIN F Y, et al. Electrodeposited transparent PEDOT for inverted perovskite solar cells: improved charge transport and catalytic performances. Rare Metals, 2021, 40(9): 2402.
[7]	YANG Y, CHEN T, PAN D, et al. MAPbI₃/agarose photoactive composite for highly stable unencapsulated perovskite solar cells in humid environment. Nano Energy, 2020, 67: 104246.
[8]	BI D, YI C, LUO J, et al. Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%. Nat. Energy, 2016, 1(10): 16142.
[9]	YAO Z, QU D, GUO Y, et al. Grain boundary regulation of flexible perovskite solar cells via a polymer alloy additive. Org. Electron., 2019, 70: 205.
[10]	LIU C, SUN J, JIANG X F, et al. A universal tactic of using Lewis-base polymer-CNTs composites as additives for high performance cm²-sized and flexible perovskite solar cells. Science China Chemistry, 2021, 64(2): 281.
[11]	WANG P C, GOVINDAN V, CHIANG C H, et al. Room- temperature-processed fullerene/TiO₂ nanocomposite electron transporting layer for high-efficiency rigid and flexible planar perovskite solar cells. Solar RRL, 2020, 4(10): 2000247.
[12]	CHANG C Y, CHU C Y, HUANG Y C, et al. Tuning perovskite morphology by polymer additive for high efficiency solar cell. ACS Appl. Mater. Interfaces, 2015, 7(8): 4955.
[13]	GAO L L, LIANG L S, SONG X X, et al. Preparation of flexible perovskite solar cells by a gas pump drying method on a plastic substrate. J. Mater. Chem. A, 2016, 4(10): 3704.
[14]	ZHOU X, ZHANG Y, KONG W, et al. Crystallization manipulation and morphology evolution for highly efficient perovskite solar cell fabrication via hydration water induced intermediate phase formation under heat assisted spin-coating. J. Mater. Chem. A, 2018, 6(7): 3012.
[15]	ZONG Y, ZHOU Y, ZHANG Y, et al. Continuous grain-boundary functionalization for high-efficiency perovskite solar cells with exceptional stability. Chem, 2018, 4(6): 1404.
[16]	ZHAO Z, XU W, PAN G, et al. Enhancing the exciton emission of CsPbCl₃ perovskite quantum dots by incorporation of Rb⁺ions. Mater. Res. Bull, 2019, 112: 142.
[17]	MEI H, WU Y, WANG C, et al. Synergistic engineering of bromine and cetyltrimethylammonium chloride molecules enabling efficient and stable flexible perovskite solar cells. J. Mater. Chem. A, 2020, 8(37): 19425.
[18]	SUN Q, FASSL P, BECKER‐KOCH D, et al. Role of microstructure in oxygen induced photodegradation of methylammonium lead triiodide perovskite films. Adv. Energy. Mater, 2017, 7(20): 1700977.
[19]	LI Y, LU K, LING X, et al. High performance planar-heterojunction perovskite solar cells using amino-based fulleropyrrolidine as the electron transporting material. J. Mater. Chem. A, 2016, 4(26): 10130.
[20]	YANG J, HONG Q, YUAN Z, et al. Unraveling photostability of mixed cation perovskite films in extreme environment. Adv. Opt. Mater., 2018, 6(20): 1800262.
[21]	LI M, YANG Y G, WANG Z K, et al. Perovskite grains embraced in a soft fullerene network make highly efficient flexible solar cells with superior mechanical stability. Adv. Mater., 2019, 31(25): 1901519.
[22]	ZHANG F, XIAO C X, CHEN X H, et al. Self-seeding growth for perovskite solar cells with enhanced stability. Joule, 2019, 3(6): 1452. DOI
[23]	THIESBRUMMEL J, PEÑA-CAMARGO F, BRINKMANN K O, et al. Understanding and minimizing V_OC losses in all-perovskite tandem photovoltaics. Adv. Energy Mater, 2023, 13(3): 2202674.
[24]	WANG C, SONG Z, ZHAO D, et al. Improving performance and stability of planar perovskite solar cells through grain boundary passivation with block copolymers. Solar RRL, 2019, 3(9): 1900078.
[25]	NGUYEN B P, KIM G Y, JO W, et al. Trapping charges at grain boundaries and degradation of CH₃NH₃Pb(I_1-_xBr_x)₃ perovskite solar cells. Nanotechnology, 2017, 28(31): 315402.
[26]	WALI Q, IQBAL Y, PAL B, et al. Tin oxide as an emerging electron transport medium in perovskite solar cells. Sol. Energy Mater. Sol. Cells, 2018, 179: 102.
[27]	LEIJTENS T, EPERON G E, BARKER A J, et al. Carrier trapping and recombination: the role of defect physics in enhancing the open circuit voltage of metal halide perovskite solar cells. Energy Environ. Sci., 2016, 9(11): 3472.
[28]	HUANG Z, HU X, LIU C, et al. Nucleation and crystallization control via polyurethane to enhance the bendability of perovskite solar cells with excellent device performance. Adv. Funct. Mater., 2017, 27(41): 1703061.
[29]	CAPIGLIA C, MUSTARELLI P, QUARTARONE E, et al. Effects of nanoscale SiO₂ on the thermal and transport properties of solvent-free, poly(ethylene oxide) (PEO)-based polymer electrolytes. Solid State Ionics, 1999, 118(1/2): 73.
[30]	SCROSATI B, CROCE F, PERSI L. Impedance spectroscopy study of PEO-based nanocomposite polymer electrolytes. J. Electrochem. Soc., 2000, 147(5): 1718.
[31]	HAN H, LIU W, ZHANG J, et al. A hybrid poly(ethylene oxide)/poly(vinylidene fluoride)/TiO₂ nanoparticle solid‐state redox electrolyte for dye-sensitized nanocrystalline solar cells. Adv. Funct. Mater., 2005, 15(12): 1940.

有机-无机共添加增强柔性钙钛矿太阳能电池机械弯曲及环境稳定性能

Organic-inorganic Co-addition to Improve Mechanical Bending and Environmental Stability of Flexible Perovskite Solar Cells

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