Nb2O5包覆对TiO2纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响

doi:10.15541/jim20180406

摘要/Abstract

摘要：

采用水热法与旋涂法, 成功制备出基于钛网基底的TiO₂纳米线阵列/Yb-Er-F掺杂TiO₂上转换发光纳米粒子(TNWAs/YEF-TiO₂-UCNPs)复合结构光阳极, 并将其组装成柔性染料敏化太阳能电池(DSSC)。探讨了Yb-Er-F掺杂TiO₂上转换发光纳米粒子的光学性能对复合结构DSSC光电转换性能的影响, 在此基础上系统研究了不同NbCl₅浓度包覆对复合结构形貌和DSSCs性能的影响。结果表明：Yb-Er-F掺杂TiO₂上转换发光纳米粒子的引入可以增大光阳极的入射光利用范围, 但同时也会增加其内部的电子复合。通过Nb₂O₅纳米粒子层的包覆可以在半导体/电解液界面形成能量势垒, 增加复合阻抗R_rec, 抑制电子复合; 提高电子收集效率η_ec和光生电子寿命τ_e, 进一步增大短路电流和开路电位, 最终提高电池的光电转换效率。采用20 mmol/L的NbCl₅乙醇溶液旋涂制备的Nb₂O₅@TNWAs/YEF-TiO₂-UCNPs复合结构柔性DSSC获得了最佳的光电转换效率(6.89%), 比未经包覆的TNWAs/YEF-TiO₂-UCNPs复合结构提升了24.3%。

关键词: Nb₂O₅包覆, Yb-Er-F掺杂TiO₂, 上转换发光纳米粒子, 复合结构, 柔性染料敏化太阳能电池

Abstract:

By using hydrothermal and spin-coating method, Ti mesh supported composite structure, TiO₂ nanowire arrays/Yb-Er-F doped TiO₂ upconversion luminescence nanoparticles (TNWAs/YEF-TiO₂-UCNPs), was synthesized and assembled into flexible dye-sensitized solar cell (DSSC). The effect of YEF-TiO₂-UCNPs optical property on the power conversion efficiency (PCE) of this device was studied. In addition, the influence of NbCl₅ solution coating on morphology and performance of flexible DSSC was also investigated in detail. It is shown that the YEF-TiO₂- UCNPs could expand the range of incident light utilization, in the meantime, however, increase the electron recombination in photoanode. Nb₂O₅ coating layer served as an energy barrier at the semiconductor/electrolyte interface, increased the composite resistance R_rec to inhibit electron recombination, improved the electron collection efficiency η_ec and photogenerated electron lifetime τ_e, then elevated the short circuit current and the open circuit voltage, finally enhanced the performance of DSSC. The Nb₂O₅@TNWAs/YEF-TiO₂-UCNPs composite structured DSSC achieved the best PCE of 6.89% with 20 mmol/L NbCl₅ ethanol solution coating, increased 24.3% compared with the uncoated blank device.

Key words: Nb₂O₅ coating, Yb-Er-F doped TiO₂, upconversion luminescence nanoparticle, composite structure, flexible dye sensitized solar cells

中图分类号:

TB332

吕喜庆, 张环宇, 李瑞, 张梅, 郭敏. Nb₂O₅包覆对TiO₂纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响[J]. 无机材料学报, 2019, 34(6): 590-598.

Xi-Qing LÜ, Huan-Yu ZHANG, Rui LI, Mei ZHANG, Min GUO. Nb₂O₅ Coating on the Performance of Flexible Dye Sensitized Solar Cell Based on TiO₂ Nanoarrays/Upconversion Luminescence Composite Structure[J]. Journal of Inorganic Materials, 2019, 34(6): 590-598.

图/表 12

图1 钛网基底Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构柔性DSSC的制备流程示意图

Fig. 1 Flow chart of the preparation process of flexible DSSC based on Ti mesh supported Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure

图2 YEF-TiO2-UCNPs的(a) XRD图谱和(b)SEM照片; (c) YEF-TiO2-UCNPs和P25的紫外-可见-近红外吸收光谱; (d) YEF-TiO2-UCNPs和YE-TiO2-UCNPs的上转换荧光光谱, 激发波长980 nm

Fig. 2 (a) XRD pattern and (b) SEM image of YEF-TiO2-UCNPs; (c) UV-Vis-NIR absorption spectra of YEF-TiO2-UCNPs and P25; (d) Upconversion fluorescence spectra of YEF-TiO2-UCNPs and YE-TiO2-UCNPs, under 980 nm excitation

图3 YEF-TiO2-UCNPs中Ti, O, F, Er与Yb元素的EDS面扫分布图

Fig. 3 EDS elemental mapping images of Ti, O, F, Er, and Yb in YEF-TiO2-UCNPs

图4 钛网基底TNWAs/YEF-TiO2-UCNPs复合结构的(a)低倍和(b)高倍SEM照片; (c) TNWAs/P25和TNWAs/YEF- TiO2-UCNPs复合结构DSSCs的J-V测试曲线和光伏性能参数

Fig. 4 (a) Low and (b) high magnification SEM images of Ti mesh supported TNWAs/YEF-TiO2-UCNPs composite structure; (c) J-V curves and photovoltaic properties of DSSCs based on Ti mesh supported TNWAs/P25 and TNWAs/YEF-TiO2- UCNPs composite structures

图5 不同NbCl5浓度Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构光阳极的XRD图谱

Fig. 5 XRD patterns of Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure photoanodes prepared with different NbCl5 concentrations

图6 不同NbCl5浓度Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构光阳极的SEM照片 (a) 10 mmol/L; (b) 20 mmol/L; (c) 40 mmol/L; (d) 60 mmol/L

Fig. 6 (a) SEM images of Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure prepared with different NbCl5 concentrations

图7 不同NbCl5浓度的钛网基底Nb2O5@TNWAs/YEF- TiO2-UCNPs复合结构DSSCs的J-V测试曲线

Fig. 7 J-V curves of DSSCs based on Ti mesh supported Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure prepared with different NbCl5 concentrations

表1 不同NbCl5浓度的钛网基底Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构DSSCs的光伏性能参数

Table 1 Photoelectric properties of DSSCs based on Ti mesh supported Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure prepared with different NbCl5 concentrations

NbCl₅ concentration /(mmol?L^-1)	J_sc/ (mA·cm^-2)	V_oc/V	FF	PCE/%
0	12.81	0.74	0.58	5.54
10	13.20	0.76	0.63	6.29
20	13.72	0.78	0.65	6.89
40	8.80	0.71	0.54	3.40
60	5.32	0.68	0.47	1.69

图8 不同NbCl5浓度Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构光阳极脱附染料的吸收光谱图

Fig. 8 UV-Vis absorption spectra of dyes desorbed from corresponding sensitized Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure photoanodes prepared with different NbCl5 concentrations

图9 钛网基底Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构DSSCs中不同物质的能级示意图

Fig. 9 Schematic diagram of the energy levels of materials in the DSSCs based on Ti mesh supported Nb2O5@TNWAs/YEF- TiO2-UCNPs composite structure

图10 不同NbCl5浓度的钛网基底Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构DSSCs的电化学阻抗谱：(a)暗态和(b)光照下的Nyquist 曲线; (c)暗态下的Bode曲线; (d)模拟等效电路图

Fig. 10 EIS plots of DSSCs based on Ti mesh supported Nb2O5@TNWAsYEF-TiO2-UCNPs composite structure prepared with different NbCl5 concentrations: Nyquist plots of DSSCs under (a) dark and (b) illumination; (c) Bode plots of DSSCs under dark; (d) Equivalent circuit of DSSCs

表2 通过等效电路拟合后不同NbCl5浓度的钛网基底Nb2O5@TNWAs/YEF-TiO2-UCNPs复合结构DSSCs的电化学阻抗数据

Table 2 EIS data of DSSCs based on Ti mesh supported Nb2O5@TNWAs/YEF-TiO2-UCNPs composite structure prepared with different NbCl5 concentrations after fitting by equivalent circuit

NbCl₅ concentration /(mmol?L^-1)	R_tr/Ω	R_rec/Ω	η_ec	f_p/Hz	τ_e/ms
0	36.60	101.5	0.73	3.78	42.0
10	24.24	130.2	0.84	3.09	51.3
20	18.25	186.9	0.91	3.06	51.8
40	31.95	89.12	0.73	5.51	28.9
60	34.04	75.56	0.69	6.64	23.9

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Nb₂O₅包覆对TiO₂纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响

Nb₂O₅ Coating on the Performance of Flexible Dye Sensitized Solar Cell Based on TiO₂ Nanoarrays/Upconversion Luminescence Composite Structure

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