P5/HCl协同作用对低温烧结FDSSC光阳极性能调控研究

doi:10.16553/j.cnki.issn1000-985x.2025.0125

摘要/Abstract

摘要： 针对导电高分子基底在柔性染料敏化太阳能电池（FDSSC）中因低温耐受性差（<150 ℃）导致TiO₂薄膜界面结合力不足的问题，本研究首次提出三步化学烧结法在导电高分子基底上制备TiO₂薄膜，并调节P25-P100 TiO₂浆料与P5/HCl粘结剂的比例。结合XRD晶体结构分析，SEM、TEM形貌表征，柔性膜弯折测试，电化学工作站FDSSC光电性能测试，探讨不同配比与弯曲半径对FDSSC综合性能的影响。研究表明，当P25-P100浆料与P5/HCl粘结剂比例为4:1时，制备出团聚现象和裂缝缺陷较少的TiO₂薄膜，电池的光电转换效率（PCE）达5.17%，较对照组提升109.3%，同时降低电子传输阻抗（R_ct2）并延长电子传输寿命（τ_n）；通过研究不同弯曲半径（R=250~100 mm）下的应变规律与光电性能表明，材料应变在弯曲半径250~100 mm呈现“先增后缓”的趋势，且临界转变发生在175~100 mm，当R=100 mm时电池仍保持2.34%的PCE（原始状态45.3%保留率）。本研究为FDSSC光电-机械性能优化提供了新思路。

关键词: 柔性; 染料敏化太阳能电池; 三步化学烧结法; 弯折测试; TiO₂

Abstract: Aiming at the issue of insufficient interfacial adhesion of the TiO₂ film caused by the poor low-temperature tolerance （<150 ℃） of conductive polymer substrates in flexible dye-sensitized solar cells （FDSSC）， a three-step chemical sintering method was proposed for the first time to prepare TiO₂ film on conductive polymer substrat， Meanwhile， the ratio of P25-P100 TiO₂ slurry to P5/HCl binder was adjusted. Combined with XRD crystal structure analysis， SEM and TEM morphology characterization， flexible film bending test， and photoelectric performance test of FDSSC by electrochemical workstation， the influence of different ratio and bending radius on the comprehensive performance of FDSSC was discussed. The results show that when the ratio of P25-P100 slurry to P5/HCl binder is 4:1， a TiO₂ film with fewer agglomeration and crack defects is prepared. The photoelectric conversion efficiency （PCE） of the battery reaches 5.17%， which is 109.3% higher than that of the control group， while reducing the electron transmission impedance （R_ct2） and prolonging the electron transmission life （τ_n）. By studying the strain law and photoelectric properties under different bending radius （R=250~100 mm）， it is shown that the strain of the material shows a trend of “first increase and then slow” in the range of bending radius 250~100 mm， and the critical transition occurs between 175~100 mm.When R=100 mm， the battery still maintains 2.34% PCE （45.3% retention rate of the original state）.This study provides a new idea for the optimization of photoelectric-mechanical properties of FDSSC.

Key words: flexible; dye-sensitized solar cell; three-step chemical sintering method; bending test; TiO₂

中图分类号:

TM914.4

程鹏元, 沈民伟, 张成龙, 于立冉, 余子聪, 王璟. P5/HCl协同作用对低温烧结FDSSC光阳极性能调控研究[J]. 人工晶体学报, 2025, 54(11): 2002-2014.

CHENG Pengyuan, SHEN Minwei, ZHANG Chenglong, YU Liran, YU Zicong, WANG Jing. Synergistic Effect of P5/HCl on the Performance Regulation of FDSSC Photoanode Sintered at Low Temperature[J]. Journal of Synthetic Crystals, 2025, 54(11): 2002-2014.

图/表 25

图1 FDSSC基本结构

Fig.1 Basic structure of FDSSC

图2 实验所用关键材料的化学组成与实物特征

Fig.2 Chemical composition and physical characteristics of the key materials used in the experiment

图3 TiO2薄膜制备工艺流程图

Fig.3 Preparation process of TiO2 thin film

图4 TiO2薄膜弯折测试示意图

Fig.4 Bending test diagram of TiO2 thin film

表1 TiO2薄膜弯折设置参数

Table 1 TiO2 film bending setting parameters

Length of the film/cm	Expansion amount/cm	R/mm
10	2	250
10	3.5	175
10	5	100

图5 不同配比TiO2浆料XRD图谱

Fig.5 XRD patterns of TiO2 slurry with different proportions

图6 TiO2薄膜的SEM照片与二值化图

Fig.6 SEM image and binary image of TiO2 thin film

表2 不同比例下TiO2薄膜裂缝平均宽度

Table 2 Average crack width of TiO2 thin films with different proportions

Sample	Pristine	5:1	4:1	3:1
Crack width/μm	3.242	2.935	2.589	3.086

图7 TiO2薄膜中颗粒间连接机理图

Fig.7 Interparticle bonding mechanism in TiO2 film

图8 基于4:1比例TiO2颗粒微观形貌表征

Fig.8 Characterization of the microstructure of TiO2 particles based on 4:1 ratio

图9 基于不同配比P5/HCl-P25-P100 TiO2光阳极FDSSC的J-V曲线

Fig.9 J-V curves of P5/HCl-P25-P100 TiO2 photoanode FDSSC with different ratios

表3 FDSSC光电转换参数

Table 3 FDSSC photoelectric conversion parameters

Sample	V_oc/V	J_sc/（mA·cm^-2）	FF	PCE/%
Pristine	0.833	9.715	0.305	2.47
5:1	0.749	12.640	0.355	3.36
4:1	0.785	15.923	0.413	5.17
3:1	0.763	8.660	0.280	1.85

图10 基于P5/HCl-P25-P100 TiO2光阳极FDSSC光电转换模型示意图

Fig.10 Based on the FDSSC photoelectric conversion model of P5/HCl-P25-P100 TiO2 photoanode

图11 FDSSC器件电化学阻抗谱

Fig.11 Electrochemical impedance spectroscopy of FDSSC device

图12 基于P5/HCl-P25-P100 TiO2光阳极FDSSC的Nyquist图（a）和Bode图（b）

Fig.12 Nyquist plots （a） and Bode plots （b） of FDSSC based on P5/HCl-P25-P100 TiO2 photoanode

表4 不同比例光阳极FDSSC的电化学阻抗谱参数

Table 4 Electrochemical impedance spectroscopy parameters of photoanode FDSSC with different proportions

Sample	R_ct2/Ω	τ_n/ms
Pristine	13.25	43.6
5:1	8.65	46.4
4:1	6.97	51.7
3:1	17.49	42.4

图13 不同弯曲半径下的TiO2薄膜的SEM照片与二值化图

Fig.13 SEM and binary images of TiO2 thin films with different bending radius

表5 不同弯曲半径下对TiO2薄膜裂缝影响参数

Table 5 Influence parameters of TiO2 thin film crack under different bending radius

Sample	m_0.5/μm	u/μm	∣u-m_0.5∣/μm	Crack percentage/%
Pristine	3.143	4.01	0.867	1.22
R=250 mm	3.514	4.67	1.156	2.21
R=175 mm	4.006	5.22	1.214	3.01
R=100 mm	4.969	5.37	0.401	3.68

图14 不同弯曲半径下裂缝量化趋势图

Fig.14 Crack quantitative trend diagram under different bending radius

图15 不同弯曲半径下TiO2薄膜裂缝宽度频数分布图

Fig.15 Frequency distribution of crack width of TiO2 thin films with different bending radius

表6 不同弯曲半径下对TiO2薄膜裂缝宽度频数分布曲线参数

Table 6 Parameters of crack width frequency distribution curve of TiO2 thin film under different bending radius

Sample	u_g/μm	u_g error/μm	u/μm	∣u-u_g∣/μm	W₅₀/μm	R²
Pristine	2.346 59	0.151 81	4.01	1.663 41	2.55	0.992 1
R=250 mm	3.213 57	0.530 27	4.67	1.456 43	3.15	0.945 88
R=175 mm	2.746 7	0.920 51	5.22	2.473 3	5.22	0.926 73
R=100 mm	3.757 41	0.119 63	5.37	1.612 59	5.37	0.911 53

图16 不同弯曲条件下FDSSC的J-V性能分析

Fig.16 J-V performance analysis of FDSSC under different bending conditions

表7 弯折后FDSSC光电转换参数

Table 7 Photoelectric conversion parameters of FDSSC after bending

Sample	V_oc/V	J_sc/（mA·cm^-2）	FF	PCE/%
Pristine	0.785	15.923	0.413	5.17
R=250 mm	0.741	14.57	0.352	3.80
R=175 mm	0.714	10.94	0.352	2.76
R=100 mm	0.671	10.101	0.345	2.34

图17 不同弯曲条件下FDSSC的Nyquist图（a）和Bode图（b）

Fig.17 Nyquist diagram （a） and Bode diagram （b） of FDSSC under different bending conditions

表8 不同弯曲条件下FDSSC的电化学阻抗谱图参数

Table 8 Electrochemical impedance spectroscopy parameters of FDSSC under different bending conditions

Sample	R_ct2/Ω	τ_n/ms
Pristine	6.97	51.7
R=250 mm	8.03	42.4
R=175 mm	9.59	41.6
R=100 mm	17.83	39.8

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