染料敏化太阳能电池过渡金属化合物对电极制备方法研究进展

doi:10.15541/jim20150283

摘要/Abstract

摘要：

染料敏化太阳能电池(dye-sensitized solar cells, DSSCs)作为制作工艺简易, 成本低廉, 环境友好的新型太阳能电池, 其发展一直备受关注。对电极作为DSSC的核心部件之一, 其制备工艺会直接影响到DSSC的发展和应用。以低成本高性能的催化材料代替传统的贵金属Pt对电极是降低DSSC生产成本的有效途径之一。具有类Pt催化性能的过渡金属化合物(TMCs)由于种类繁多, 制备方式简单多样, 近年来成为DSSC对电极研究中的热点。本文综述了DSSC过渡金属化合物对电极的最新研究进展, 总结概括了过渡金属化合物对电极的制备方法以及性能特点, 并对其发展方向和应用前景进行了分析。

关键词: 染料敏化太阳能电池, 对电极, 过渡金属化合物, 制备方法, 综述

Abstract:

Dye-sensitized solar cells (DSSCs) have attracted extensive attention in recent years due to their simple fabrication, low cost and environmental friendliness. The production process for counter electrode (CE) as one of the key components of DSSC, will significantly affect the DSSCs development and application. Therefore, it is important to develop low cost and high performance catalytic materials instead of noble metal Pt to reduce the production cost of DSSC. Transition metal compounds with Pt-like catalytic activity have become a hot research area for CEs of DSSC in recent years, due to their wide variety and simple preparation. This review briefly addresses recent progresses of transition metal compound CEs of DSSC, focusing on their preparation methods and performance. In addition, the development trends and application prospects of CEs were also discussed.

Key words: dye-sensitized solar cells, counter electrode, transition metal compound, preparation method, review

中图分类号:

TK513

张陈乐, 张培新, 云斯宁, 李永亮, 何挺树. 染料敏化太阳能电池过渡金属化合物对电极制备方法研究进展[J]. 无机材料学报, 2016, 31(2): 113-122.

ZHANG Chen-Le, ZHANG Pei-Xin, YUN Si-Ning, LI Yong-Liang, HE Ting-Shu. Recent Progress on Preparation of Transition Metal Compounds as Counter Electrodes for Dye-sensitized Solar Cells[J]. Journal of Inorganic Materials, 2016, 31(2): 113-122.

图/表 12

图1 使用F127软模板合成有序介孔材料TiN-C的示意图,内嵌图为Pt/FTO和TiN-C/FTO为对电极DSC的电流-电压特性曲线[22]

Fig. 1 Schematic for the synthesis of ordered mesoporous TiN-C nanocomposites, photocurrent-voltage curves of DSCs employing the Pt/FTO, and TiN-C/FTO counter electrodes (insets) [22]

图2 使用“尿素-金属”路线化学合成TMCs的示意图[23]

Fig. 2 Schematic illustration for the chemical synthesis of TMCs by using a urea-metal route[23]

图3 (a~d)分别为TaOX[27]、Ta2O5[28]、VC(N)[18]和VN[26]的SEM照片, 内嵌图为对应样品的TEM照片

Fig. 3 (a-d) SEM and TEM images (inset of c) of the TaOX[27], Ta2O5[28],VC(N)[18] and VN[26]

图4 MS/石墨烯对电极的制备流程[33]

Fig. 4 Overall procedure for the fabrication of MS/graphene composite CEs for DSSCs:(a) Reaction equation of MS precursor preparation; (b) Well dispersed MS precursor solutions in acetone and ethanol solvents; (c) Dielectric SiO2 substrate; (d) Graphene film directly grown on SiO2 substrate; (e) MS NPs loaded on the graphene surface; (f) Application of MS/graphene composite CEs in DSSCs[33]

图5 (a,b)气相沉积在固体DSSC空穴传输层的10 nm厚V2O5的AFM图[34]

Fig. 5 (a-b) AFM images of 10 nm V2O5 deposited on Spiro-OMeTAD at 0.05 nm·s[34]

图6 (a, b)在pH=3.5条件下制备的CoSe电极的SEM照片, (c)电沉积形成的CoSe薄膜的TEM照片和 (d)由HTEM显示的CoSe在(101)的晶格间距大小[43]

Fig. 6 (a-b) Typical SEM images of cobalt selenide electrode prepared at pH=3.5, (c) typical TEM image of the cobalt selenide layers peeled from the electrodeposited films, and (d) HTEM showing (101) lattice fringes of (c)[43]

图7 (a)原位生长技术所制备样品的XRD图谱以及与其相符的(PDF#65-1843)标准XRD图谱, (b)原位生长技术制备的NiSe2纳米颗粒SEM照片[50]

Fig. 7 (a) XRD patterns and the corresponding simulated XRD data for NiSe2 (PDF #65-1843), and (b) typical SEM image of the NiSe2 particles[50]

图8 (a)以I-/I3-为电解质CoTe、NiTe2和 Pt对电极的电池C-V曲线, (b) CoTe、NiTe2和 Pt对电极的对称薄层电池的EIS图, (c) CoTe、NiTe2和 Pt对电极的对称薄层电池的塔菲尔极化曲线, (d) CoTe、NiTe2和 Pt对电极的染料敏化太阳能电池的J-V曲线[59]

Fig. 8 (a) Cyclic voltammograms of the triiodide/iodide redox couple for CoTe, NiTe2 and Pt CEs, (b) nyquist plots of EIS for the symmetrical cells, (c) tafel polarization curves of the symmetrical cells, and (d) J-V curves of the DSCs based on CoTe, NiTe2, and Pt CEs[59]

图9 (a) TiC-C纳米丝的SEM照片(a中内嵌图为EDS能谱图), (b) TEM照片(b中内嵌图为高倍TEM照片); (c) TiC/C-Pt纳米材料的SEM照片(c中内嵌图为EDS能谱), 和(d) TEM照片(d中内嵌图为高倍TEM照片)[60]

Fig. 9 (a) SEM image with EDS spectrum (inset); (b) TEM image with high magnification TEM image (inset) acquired from electrospun TiC/C nano-felt; (c) SEM image with EDS spectrum (inset), and (d) TEM image with high magnifycation TEM image (inset) acquired from electrospun TiC/C nano-felt after surface-decoration with Pt NPs[60]

图10 在U=0.61V(vs SHE), 由第一性原理计算出的对电极Pt(111)、 Fe2O3(104)和Fe2O3(012)催化反应的能量图[61]

Fig. 10 Energy profiles of the whole CE reaction on Pt(111), Fe2O3(104) and Fe2O3(012), respectively, which were calculated at U=0.61 V(vs SHE)[61]

图11 (a)d轨道上Pt和Hf原子的DOS图, (b)不同时间下Pt 和 HfO2原子表面上I与I3, S原子在T2染料环境的距离变化图[21]

Fig. 11 (a) The projected density of state (DOS) on the d orbital of Pt and Hf atoms, and (b) the atomic distance variation with respect to time for I atoms in I3 and S atoms in T2 on Pt and HfO2[21]

表1 使用不同衬底、染料、电解质以及对电极催化剂组装的染料敏化太阳能电池光电性能

Table 1 Photovoltaic parameters of dye-sensitized solar cells with different substrates, redox couples, dyes, and CE catalysts

CE catalysts	Substrate	Redox couples	Dye	J_sc/ (mA·cm^-2)	V_oc/V	FF	PCE/%	Ref
C_0.85Se	FTO	I^-/I₃^-	N719	16.98	0.738	0.75	9.40	[49]
TiC	FTO	Co²⁺/Co³⁺	N719	9.77	0.640	0.66	4.13	[63]
Carbon/SnO₂/TiO₂	FTO	I^-/I₃^-	N3	12.98	0.740	0.64	6.15	[66]
NiO-Pt	FTO	I^-/I₃^-	Ru535	0.30	0.530	0.63	2.80	[71]
Co₉S₈	Mo	I^-/I₃^-	N719	13.98	0.720	0.69	6.91	[32]
TiN	Ti	I^-/I₃^-	N719	15.78	0.760	0.64	7.73	[67]
TiN/PEDOT-PSS	Ti	I^-/I₃^-	CYC-B1	14.20	0.68	0.69	6.67	[69]
NiS	Ni	I^-/I₃^-	N719	16.26	0.800	0.66	8.55	[45]
TiC	BG/CC	I^-/I₃^-	N719	12.98	0.790	0.56	5.71	[68]
TiC	PI/CC	I^-/I₃^-	N719	12.32	0.770	0.41	3.90	[68]
FeS₂	ITO/PEN	I^-/I₃^-	N719	15.14	0.710	0.68	7.31	[31]
CoS	ITO/PEN	I^-/I₃^-	Z907	11.91	0.750	0.73	6.50	[41]
TiO₂-C	FTO	I^-/I₃^-	Z907	12.53	0.700	0.57	5.50	[70]
CoS	ITO/PEN	T₂/T^-	Z907	14.60	0.643	0.49	4.60	[65]
TiN-C	FTO	T₂/T^-	N719	14.36	0.697	0.67	6.71	[22]
Ta₃N₅/Graphene	FTO	Co²⁺/Co³⁺	FNE29	13.53	0.837	0.69	7.85	[64]

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