基于二氧化钛纳米管的染料敏化电池光阳极研究

doi:10.3724/SP.J.1077.2013.12368

摘要/Abstract

摘要：

本文报道了一种基于二氧化钛(TiO₂)纳米管的染料敏化太阳能电池。用二次阳极氧化法在钛箔上生长出高度有序的TiO₂纳米管薄膜, 然后将完整剥落的纳米管薄膜结合TiO₂纳米颗粒的浆料转移到掺杂氟的SnO₂透明导电玻璃(FTO)基底上, 从而获得一种特殊的染料敏化光阳极。对比了不同长度的TiO₂纳米管的电池性能, 发现经TiCl₄处理长度为32.8 μm的TiO₂纳米管对应的电池表现较好的光电转换效率, 达到4.15%。通过X射线衍射分析了高温退火对纳米管晶化结构的影响。电化学阻抗谱分析表明: 光电子传输对光阳极纳米管层厚依赖性强, 随着纳米管长度的增长, 界面电阻呈明显的减小, 这一结果对于理解和进一步改善染料敏化电池光阳极内部电子输运过程具有重要意义。

关键词: 二次阳极氧化法, TiO₂纳米管, 正入射, 染料敏化太阳能电池

Abstract:

A front-illuminated TiO₂ nanotube-based dye-sensitized solar-cell (DSC) was presented. Highly ordered TiO₂ nanotube membranes were fabricated by two-step anodic oxidation of Ti foil, and then they were transferred to fluorine-doped tin oxide glass substrates to produce a special kind of photoanode. A series of comparison were made between DSCs with different length of nanotubes. Front-illuminated DSC with 32.8 μm nanotube membrane showed an efficiency of 4.15% with TiCl₄ treatment. The crystal phase evolution of the TiO₂ nanotubes was researched using X-Ray Diffraction (XRD). Electrochemical Impedance Spectra (EIS) results indicated that the electron transportation efficiency had a strong dependence on the thickness of photoanode, and interfacial resistances decreased with the increasing of nanotubes length. These results could help us to understand the mechanism of the electron transportation and further improve the photoanode of DSCs.

Key words: two-step anodization, TiO₂ nanotubes, front illumination, dye-sensitized solar cells

中图分类号:

TM914

罗华明, 刘志勇, 白传易, 鲁玉明, 蔡传兵. 基于二氧化钛纳米管的染料敏化电池光阳极研究[J]. 无机材料学报, 2013, 28(5): 521-526.

LUO Hua-Ming, LIU Zhi-Yong, BAI Chuan-Yi, LU Yu-Ming, CAI Chuan-Bing. TiO₂ Nanotube Based Dye-sensitized Photoanode[J]. Journal of Inorganic Materials, 2013, 28(5): 521-526.

图/表 7

图1 不同阳极氧化时间制备的TiO2纳米管的SEM照片

Fig. 1 SEM images of TiO2 nanotubes prepared for different anodic oxidation time

图2 从Ti箔上剥落的不同厚度的TiO2纳米管薄膜照片

Fig. 2 Detached TiO2 nanotubes with different thicknesses

图3 (a)钛箔, (b,c) 500℃退火前后的TiO2纳米管, (d)剥落的TiO2纳米管和(e)与FTO基底结合的TiO2纳米管的XRD图谱

Fig. 3 XRD patterns of (a) Ti foil, (b, c) unannealed and 500℃annealed TiO2 nanotube on Ti foil, (d) detached TiO2 nanotubes and (e) TiO2 nanotubes on FTO substrate

图4 TiO2纳米管阵列与纳米颗粒相结合后电极的SEM照片

Fig. 4 SEM image of the electrode combined TiO2 nanotubes with nanoparticles

图5 染料敏化太阳能电池光电转化效率I-V曲线表1 染料敏化太阳能电池光电转化参数

Fig. 5 The I-V curves of dye-sensitized solar cells

Table 1 Photovoltaic properties of dye-sensitized solar cells

Sample	R_ct/Ω	J_sc/(mA∙cm^-2)	V_oc/V	η/%	FF/%
dsc-NP	89.4	4.50	0.643	2.02	69.8
dsc-16.8 μm	78.5	4.01	0.639	1.81	70.7
dsc-21.6 μm	75.3	4.69	0.608	1.99	69.7
dsc-32.8 μm	32.7	5.08	0.609	2.09	67.6
dsc-32.8-treated	57.8	9.19	0.698	4.15	64.5

图6 不同纳米结构染料敏化太阳电池的电化学阻抗谱

Fig. 6 Electrochemical impedance spectra of dye-sensitized solar cells with different structures

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