超长稳定的混合阳离子钙钛矿太阳能电池性能优化研究

doi:10.15541/jim20230098

无机材料学报 ›› 2023, Vol. 38 ›› Issue (12): 1387-1395.DOI: 10.15541/jim20230098

所属专题：【能源环境】钙钛矿(202312)；【能源环境】太阳能电池(202312)

超长稳定的混合阳离子钙钛矿太阳能电池性能优化研究

马婷婷¹^,²(), 汪志鹏¹^,², 张梅¹^,², 郭敏¹^,²()

1.北京科技大学钢铁冶金新技术国家重点实验室, 北京 100083
2.北京科技大学冶金与生态工程学院, 北京 100083

收稿日期:2023-02-27 修回日期:2023-06-21 出版日期:2023-06-28 网络出版日期:2023-06-28
通讯作者: 郭敏, 教授. E-mail: guomin@ustb.edu.cn
作者简介:马婷婷(1997-), 女, 硕士研究生. E-mail: matingting202202@163.com
基金资助:
国家自然科学基金(52172137);国家自然科学基金(51772023);国家自然科学基金(51572020)

Performance Optimization of Ultra-long Stable Mixed Cation Perovskite Solar Cells

MA Tingting¹^,²(), WANG Zhipeng¹^,², ZHANG Mei¹^,², GUO Min¹^,²()

1. State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
2. School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China

Received:2023-02-27 Revised:2023-06-21 Published:2023-06-28 Online:2023-06-28
Contact: GUO Min, professor. E-mail: guomin@ustb.edu.cn
About author:MA Tingting (1997-), female, Master candidate. E-mail: matingting202202@163.com
Supported by:
National Natural Science Foundation of China(52172137);National Natural Science Foundation of China(51772023);National Natural Science Foundation of China(51572020)

摘要/Abstract

摘要：

钙钛矿太阳能电池(PSCs)发展迅速, 其能量转换效率(PCE)被一再刷新, 但长期稳定性还有待提高。目前大部分高效率钙钛矿太阳能电池在惰性气体环境中完成制备, 成本高且操作空间有限, 不利于产业化应用。本研究成功在空气中制备了具有超长稳定性的混合阳离子钙钛矿太阳能电池, 系统探究了A位阳离子掺杂对钙钛矿微观结构、光电性能以及稳定性的影响。实验结果表明, 掺杂FA⁺和Cs⁺可以提高钙钛矿薄膜质量, 优化钙钛矿/SnO₂的能级排列, 抑制载流子复合, 显著提高器件的光电转换效率、长期以及湿热稳定性。Cs_0.05MA_0.35FA_0.6PbI₃电池的最佳PCE为19.34%, 在(20±5) ℃, 相对湿度<5%的黑暗环境中放置242 d后, 仍保持初始效率的85%。MAPbI₃电池在同样测试条件下放置112 d后, 效率下降为初始值的30%。掺杂FA⁺和Cs⁺也显著提高了电池的抗热和抗湿性。Cs_0.05MA_0.35FA_0.6PbI₃电池分别在(85±5) ℃、相对湿度20%~30%和(20±5) ℃、相对湿度80%~90%的黑暗环境中放置96 h后, PCE分别为初始值的99%和84%, 而MAPbI₃在同样条件下的PCE仅为初始值的70%和56%。本研究为在空气环境制备高效、超长稳定的混合阳离子钙钛矿太阳能电池提供了参考。

关键词: 钙钛矿太阳能电池, 混合阳离子, 长期稳定性, 全空气环境制备

Abstract:

Perovskite solar cells (PSCs) are developing rapidly and their power conversion efficiency (PCE) has been repeatedly refreshed, but their long-term stability still needs to be improved. At present, most of the preparation of high-efficiency PSCs is completed in the inert gas, with high cost and limited operating space, which is not conducive to its industrial application. Here, perovskite solar cells with mixed cation, displaying ultra-long stability, were successfully prepared in the air. Effects of A-site cation doping on the microstructure, optoelectronic properties and stability of the perovskite were systematically investigated. The experimental results show that FA⁺ and Cs⁺ co-doping improves the quality of perovskite films, modulates the energy level arrangement of perovskite/SnO₂, suppresses carrier complexation, and significantly improves the PCE, long-term, wet and thermal stability of the cell. The optimal PCE of Cs_0.05MA_0.35FA_0.6PbI₃ cells is 19.34%, maintaining 85% of the initial efficiency after reserving for 242 d in dark environment at (20±5) ℃ and <5% relative humidity. In contrast, the PCE of the MAPbI₃cell decreased to 30% of the initial value after reserving for 112 d under the same test conditions. FA⁺and Cs⁺ co-doping also significantly improved the thermal and moisture resistance of the cells. Cs_0.05MA_0.35FA_0.6PbI₃ PSCs remain 99% and 84% of initial PCE after aging for 96 h at (85±5) ℃ and 20%-30% relative humidity, (20±5) ℃ and 80%-90% relative humidity in the dark, respectively. In contrast, PCEs of MAPbI₃ PSCs under the same conditions remain only 70% and 56%. This study provides a reference for the preparation of highly efficient and ultra-long stable mixed cation solar cells in the air.

Key words: perovskite solar cell, mixed cation, long-term stability, full-air environment preparation

中图分类号:

TQ174

马婷婷, 汪志鹏, 张梅, 郭敏. 超长稳定的混合阳离子钙钛矿太阳能电池性能优化研究[J]. 无机材料学报, 2023, 38(12): 1387-1395.

MA Tingting, WANG Zhipeng, ZHANG Mei, GUO Min. Performance Optimization of Ultra-long Stable Mixed Cation Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2023, 38(12): 1387-1395.

图/表 21

图1 在空气中两步旋涂法制备钙钛矿薄膜及器件制造的流程图

Fig. 1 Flow chart for the preparation of perovskite films and device manufacturing by two-step spin coating in the air

图2 不同样品的晶体结构和微观形貌

Fig. 2 Crystal structures and morphologies of different samples (a) XRD patterns; (b) Locally magnified XRD patterns in the range of 2θ=12.8°-15°; (c, e, g) SEM images and (d, f, h) Statistical distributions of grain diameter for (c, d) MP, (e, f) MFP, and (g, h) CMFP

图3 PSCs的光电性能

Fig. 3 Photovoltaic performances of PSCs Statistical diagram of (a) PCE, (b) Jsc, (c) Voc, and (d) FF; (e) J-V curves; (f) EQE spectra. Colorful figures are available on website

表1 三种钙钛矿太阳能电池的光电性能参数

Table 1 Photovoltaic parameters of three types of perovskite solar cells

Sample	J_sc/(mA•cm^-2)	V_oc/V	FF	PCE/%	PCE_max/%
MP	21.32±0.99	0.95±0.03	0.74±0.02	15.11±0.86	16.31
MFP	22.94±0.98	0.99±0.04	0.76±0.03	17.18±0.61	18.87
CMFP	22.24±0.77	1.03±0.03	0.78±0.02	17.83±0.33	19.34

图4 三种钙钛矿薄膜的光电特性和能级结构

Fig. 4 Photoelectric properties and energy levels of three perovskite films (a) UV-Vis absorption spectra; (b) Tauc plots; (c) PL and (d) TRPL spectra excited from the perovskite layer;(e) Energy level schematics of three samples

图5 PSCs的界面传输和载流子复合特性

Fig. 5 Interface transmission and carrier recombination characteristics of PSCs (a) PL and (b) TRPL spectra excited from FTO layer; (c) Dark-state EIS profiles of the device at 0.8 Vbias with inset showing an equivalent circuit diagram

图6 三种钙钛矿太阳能电池在(20±5) ℃, 相对湿度<5%, 黑暗条件下的长期稳定性

Fig. 6 Long-term stabilities of three perovskite solar cells at (20±5) ℃, relative humidity <5% in the dark

图7 (a) MP、(b) MFP、(c) CMFP钙钛矿太阳能电池在(20±5) ℃, 相对湿度<5%条件下老化前后的暗态EIS图谱

Fig. 7 Dark state EIS profiles of (a) MP, (b) MFP, (c) CMFP PSCs before and after aging at (20±5) ℃ and relative humidity<5%

图8 三种PSCs在(85±5) ℃, 相对湿度20%~30%, 黑暗条件下的热稳定性

Fig. 8 Thermal stability of three PSCs at (85±5) ℃ and relative humidity 20%-30% in the dark

图9 三种PSCs在(20±5) ℃, 相对湿度80%~90%, 黑暗条件下的湿稳定性

Fig. 9 Wet stability of three PSCs at (20±5) ℃ and relative humidity 80%-90% in the dark

图S1 三种钙钛矿薄膜的UPS图谱

Fig. S1 UPS profiles of three perovskite films (a) UPS full spectra; UPS spectra corresponding to the secondary electron cutoff region for (b) MP, (c) MFP, (d) CMFP;(e) UPS valence band spectra; UPS spectra of the valence band top region with respect to the Femi level for (f) MP, (g) MFP, (h) CMFP

图S2 在85 ℃, 相对湿度20%~30%条件下, 三种钙钛矿薄膜随时间变化的XRD图谱

Fig. S2 XRD patterns of three perovskite thin films over time at 85 ℃, 20%-30% RH (a) MP; (b) MFP; (c) CMFP

图S3 在(20±5) ℃, 相对湿度80%~90%条件下三种钙钛矿薄膜随时间变化的XRD图谱

Fig. S3 XRD patterns of three perovskite thin films over time at (20±5) ℃, 80%-90% RH (a) MP; (b) MFP; (c) CMFP

表S1 三种性能最佳的PSCs的性能参数(图3(e)和图S1)

Table S1 Performance parameters of three best performing PSCs (Fig. 3 (e) and Fig. S1)

Sample	J_sc/(mA•cm^-2)	V_oc/V	FF	PCE_max/%	Intergrated current density/(mA•cm^-2)
MP	22.87	0.97	0.74	16.34	21.87
MFP	23.48	1.05	0.76	18.66	22.71
CMFP	23.30	1.06	0.78	19.34	22.37

表S2 从钙钛矿一侧激发瞬态光谱(图4(d))的拟合结果

Table S2 Fitting results of transient spectra (Fig. 4(d)) excited from the perovskite side

Sample	τ₁/ns	τ₂/ns	B₁	B₂	τ_mean/ns
MP	33.64	96.21	0.45	0.55	68.05
MFP	31.70	81.41	0.68	0.32	47.61
CMFP	26.51	77.12	0.22	0.78	65.99

表S3 由 UPS图谱(图S1)计算得到的三种钙钛矿薄膜的EVB和ECB

Table S3 EVB and ECB of three perovskite films calculated from UPS profiles (Fig. S1)

Sample	Ф/eV	$E_{\text{VB}}^{\text{F}}$/eV	E_VB/eV	E_g/eV	E_CB/eV
MP	3.74	1.59	-5.33	1.61	-3.72
MFP	4.02	1.49	-5.51	1.55	-3.96
CMFP	3.93	1.47	-5.40	1.55	-3.85

表S4 从FTO一侧激发瞬态光谱(图5(b))的拟合结果

Table S4 Fitting results of transient spectra (Fig. 5(b)) excited from the FTO side

Sample	${{\tau }_{1}}^{\prime }$/ns	${{\tau }_{2}}^{\prime }$/ns	${{B}_{1}}^{\prime }$	${{B}_{2}}^{\prime }$
MP	75.22	422.18	0.47	0.53
MFP	35.4	21.42	0.38	0.62
CMFP	8.21	34.52	0.76	0.24

表S5 EIS(图7)数据的拟合结果

Table S5 Fitting results of EIS (Fig. 7) data

Long-term stability		R_s/(Ω·cm²)	R_rec/(Ω·cm²)	R_nrec
Before testing	MP	32.40	4932	—
	MFP	27.18	7261	—
	CMFP	21.84	10890	—
After testing	MP	47.99	1462	0.30
	MFP	39.88	5430	0.75
	CMFP	34.16	9173	0.84

表S6 三种PSCs经长期稳定性测试后的J-V相对参数值

Table S6 Relative J-V values of three PSCs after long-term stability testing

Sample	FF_n	V_noc	J_nsc	PCE_n
MP	0.54	0.85	0.63	0.30
MFP	0.90	0.94	0.92	0.81
CMFP	0.88	0.96	0.90	0.85

表S7 三种PSCs经热稳定性测试后的J-V相对数值

Table S7 Relative J-V values of three PSCs after thermal stability testing

Sample	FF_n	V_noc	J_nsc	PCE_n
MP	0.81	0.89	0.87	0.70
MFP	0.94	0.94	0.92	0.93
CMFP	0.95	0.96	0.95	0.99

表S8 三种PSCs经湿稳定性测试后的J-V相对数值

Table S8 Relative J-V values of three PSCs after wet stability testing

Sample	FF_n	V_noc	J_nsc	PCE_n
MP	0.72	0.86	0.88	0.56
MFP	0.89	0.92	0.90	0.78
CMFP	0.91	0.96	0.92	0.84

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超长稳定的混合阳离子钙钛矿太阳能电池性能优化研究

Performance Optimization of Ultra-long Stable Mixed Cation Perovskite Solar Cells

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