高效CdS量子点敏化B/S共掺杂纳米TiO2太阳能电池的制备及光电性能研究

doi:10.15541/jim20150518

无机材料学报 ›› 2016, Vol. 31 ›› Issue (6): 627-633.DOI: 10.15541/jim20150518

高效CdS量子点敏化B/S共掺杂纳米TiO₂太阳能电池的制备及光电性能研究

李玲¹, 肖俊莹¹, 崔米豆¹, 太优一², 庞永文¹, 韩松¹, 李晓苇¹

(1. 河北大学物理科学与技术学院, 河北省光电信息材料重点实验室, 保定 071002; 2. 四川大学材料科学与工程学院, 成都 610064)

收稿日期:2015-10-23 修回日期:2015-12-01 出版日期:2016-06-20 网络出版日期:2016-05-19
作者简介:李玲(1980–), 女, 副教授. E-mail: lilinghbu@163.com
基金资助:
国家自然科学基金(21201053);高等学校博士学科点专项科研基金新教师类资助课题(20121301120005);河北省自然科学基金(F2014201078, 2015201050);河北省应用基础研究计划重点基础研究项目(14964306D);河北省教育厅基金(ZD2016055, QN2014057);河北省大学创新创业训练计划项目(2015066, 2015161, 201510075047, 026);河北大学学生综合素质培养项目(2015zh0442;2015zh0443);河北大学杰出青年基金(2015JQ02)

Boron and Sulfur Co-doped TiO₂ Nanofilm as High Efficiency CdS Quantum-dot-sensitized Solar Cells

LI Ling¹, XIAO Jun-Ying¹, CUI Mi-Dou¹, TAI You-Yi², PANG Yong-Wen¹, HAN Song¹, LI Xiao-Wei¹

(1. Hebei Key Lab of Optic-electronic Information and Materials, College of Physics Science and Technology, Hebei University, Baoding 071002, China; College of Materials and Engineering, Sichuan University, Chengdu 610064, China)

Received:2015-10-23 Revised:2015-12-01 Published:2016-06-20 Online:2016-05-19
About author:LI Ling. E-mail: lilinghbu@163.com
Supported by:
National Natural Science Foundation of China (21201053);Specialized Research Fund for the Doctoral Program of Higher Education (20121301120005);Fund in Hebei Province Natural Science (F2014201078, 2015201050);Applied Basic Research Plan Key Basic Research Project in Hebei Province(14964306D);Youth Fund in Hebei Province Department of Education China (ZD2016055, QN2014057);College Students' Innovative Entrepreneurial Training Program in Hebei Province(2015066;2015161;201510075047, 026);Students' Comprehensive Quality Training Program in Hebei University (2015zh0442;2015zh0443);Outstanding Youth Fund of Hebei University(2015JQ02)

摘要/Abstract

摘要：

采用水热法制备硼硫(B/S)共掺杂纳米二氧化钛(B-S-TiO₂), 并配制成浆料, 利用丝网印刷技术在FTO导电玻璃上制备B-S-TiO₂薄膜; 用化学浴沉积(CBD)法制备了CdS量子点敏化B-S-TiO₂薄膜电极, 并用X射线衍射(XRD)、电子显微镜(TEM)、元素分析能谱(EDS)和紫外-可见光谱对其进行表征分析; 结果显示: B/S共掺杂不会改变TiO₂的晶型, 掺杂后的TiO₂吸收边带发生明显红移, 吸收强度显著增强; 同样用化学浴沉积的方法制备NiS工作电极, 用改性的聚硫化物((CH₃)₄N)₂S/((CH₃)₄N)₂S_n)电解液, 组装CdS量子点敏化硼硫(B/S)共掺杂纳米二氧化钛(B-S-TiO₂)太阳能电池, 并测试电池光电性能。测试结果表明, 在AM1.5G的照射下, 电池的能量转化效率(η)由3.21%增大到3.69%, 提高了14.9%, 电池获得高达 (V_oc)1.218 V的开路电压和3.42 mA/cm²的短路光电流(J_sc), 以及高达88.7%的填充因子(ff)。

关键词: CdS量子点敏化太阳能电池, B/S共掺杂TiO2, 化学浴沉积(CBD), NiS对电极, 多硫电解液

Abstract:

B and S co-doped TiO₂ was prepared by a typical hydrothermal synthesis. Then the obtained B-S-TiO₂ was dissolved in organic solvent to form paste and then coated on FTO conducting glass by screen printing to prepare nanofilm. The CdS/B-S-TiO₂ composite electrodes was obtained by chemical bath deposition (CBD) using B-S-TiO₂ nanofilm and CdS quantum dots (QDs). The obtained samples were characterized by EDS, XRD, TEM and UV-Vis. The results show that B and S do not change the structure of anatase TiO₂. Noticeable shifts of absorbance edge towards longer wavelength were observed and the absorbance intensity of the B-S-TiO₂ nanofilm increases significantly. Furthermore, NiS was prepared as counter electrode by CBD and a modified polysulfide redox couple, ((CH₃)₄N)₂S/((CH₃)₄N)₂S_n, was employed as electrolyte to assemble CdS quantum-dots (QDs)-sensitized solar cells. The measurements show that the cells have an enhanced energy conversion efficiency under AM 1.5 G illuminations which increased from 3.21% to 3.69%, about 14.9% increment, with a significantly high open voltage (V_oc) of 1.218 V, a high filled factor (ff) of 88.7%, and a short-circuit photocurrent (J_sc) of 3.42 mA/cm².

Key words: CdS quantum dots sensitized solar cells, B/S co-doped TiO2, chemical bath deposition (CBD), NiS counter electrode, ((CH3)4N)2S/((CH3)4N)2Sn electrolyte

中图分类号:

O613

李玲, 肖俊莹, 崔米豆, 太优一, 庞永文, 韩松, 李晓苇. 高效CdS量子点敏化B/S共掺杂纳米TiO₂太阳能电池的制备及光电性能研究[J]. 无机材料学报, 2016, 31(6): 627-633.

LI Ling, XIAO Jun-Ying, CUI Mi-Dou, TAI You-Yi, PANG Yong-Wen, HAN Song, LI Xiao-Wei. Boron and Sulfur Co-doped TiO₂ Nanofilm as High Efficiency CdS Quantum-dot-sensitized Solar Cells[J]. Journal of Inorganic Materials, 2016, 31(6): 627-633.

图/表 10

方案1 CdS QD 敏化B/S共掺杂TiO2太阳能电池的结构原理图

Scheme 1 Schematic presentation of the CdS QD sensitized B/S co-doped TiO2 solar cell structure

表1 不同CdS量子点沉积层数下基于纯TiO2电池的J-V曲线参数

Table 1 Parameter of J-V curve in different amounts of CdS quantum deposition layer with pure TiO2

Sample	V_oc/V	J_sc/(mA·cm^-2)	ff	E_ff
TiO₂/TGA/CdS-1	1.102	1.46	75.1%	1.21%
TiO₂/TGA/CdS-2	1.204	2.25	77.7%	2.10%
TiO₂/TGA/CdS-3	1.217	2.96	89.1%	3.21%
TiO₂/TGA/CdS-4	1.207	1.33	68.2%	1.09%
TiO₂/TGA/CdS-5	1.122	2.09	42.3%	0.99%

表2 不同CdS量子点沉积层数下基于B/S-TiO2电池的J-V曲线参数

Table 2 Parameter of J-V curve in different amount of CdS quantum deposition layer with B/S-TiO2

Sample	V_oc/V	J_sc/(mA·cm^-2)	ff	E_ff
B/S/TiO₂/TGA/CdS/1	1.211	1.17	67.8%	0.96%
B/S/TiO₂/TGA/CdS/2	1.225	2.55	83.8%	2.62 %
TiO₂/TGA/CdS-3	1.217	2.96	89.1%	3.21%
B/S/TiO₂/TGA/CdS/3	1.218	3.42	88.7%	3.69 %
B/S/TiO₂/TGA/CdS/4	1.112	1.25	80.9%	1.12%
B/S/TiO₂/TGA/CdS/5	1.211	1.48	48.2%	0.86%

图1 (a)纯TiO2和(b)0.5%B/S 掺杂TiO2的XRD图谱

Fig. 1 XRD patterns of pure TiO2 (a) and 0.5%B/S-doped TiO2 (b)

图2 B/S/TiO2样品的XPS图谱

Fig. 2 XPS spectra of B/S/TiO2

图3 B/S共掺杂TiO2薄膜吸附CdS QD的TEM照片

Fig. 3 TEM image of CdS QD sensitized B/S co-doped TiO2 film

图4 (a)纯TiO2薄膜, (b)B/S共掺杂TiO2/TGA/CdS-1 薄膜, (c) B/S共掺杂TiO2/TGA/CdS-3 薄膜和(d) B/S共掺杂TiO2/ TGA/CdS-5的紫外-可见吸收光谱

Fig. 4 UV-vis absorption spectra of (a) pure TiO2 film, (b) B/S doped TiO2/TGA/CdS-1 film, (c) B/S doped TiO2/TGA/ CdS-3 film, and (d) B/S doped TiO2/TGA/CdS-5 film

图5 TiO2与B-S-TiO2电池的J-V特性

Fig. 5 J-V characteristics of the B-S-TiO2/TGA/CdS-3 cell and TiO2/TGA/CdS-3 cell

图6 TiO2与B-S-TiO2电池的光电转换效率(IPCE)光谱

Fig. 6 Incident photon-to-current conversion efficiency (IPCE) of the cell based on TiO2/TGA/CdS-3 electrode and B-S-TiO2/ TGA/CdS-3 electrode

图7 NiS和Pt对电极的电化学阻抗谱(EIS)

Fig. 7 Electrochemical impedance spectra for NiS and Pt counter electrodes with the same B-S-TiO2/TGA/CdS-3 film

参考文献 50

[1]	O'REGAN B, GRAETZEL M, O'REGAN B, et al. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films.Nature, 1991, 353(6346): 737-740.
[2]	LEE Y L, LO Y S.Highly efficient quantum-dot-sensitized solar cell based on co-sensitization of CdS/CdSe.Advanced Functional Materials, 2009, 19(4): 604-609.
[3]	JIN Z, ZHANG X, LI Y, et al.5.1% Apparent quantum efficiency for stable hydrogen generation over eosin-sensitized CuO/TiO2 photocatalyst under visible light irradiation.Catalysis Communications, 2007, 8(8): 1267-1273.
[4]	XIAOBO C, CLEMENS B.The electronic origin of the visible- light absorption properties of C-, N- and S-doped TiO2 nanomaterials.Journal of the American Chemical Society, 2008, 130(15): 5018.
[5]	ZHAO Y, QIU X, BURDA C.The effects of sintering on the photocatalytic activity of N-doped TiO2 nanoparticles.Chemistry of Materials, 2008, 20(8): 2629-2636.
[6]	CHEN X, SHEN S, GUO L, et al.Semiconductor-based photocatalytic hydrogen generation.Chemical Reviews, 2010, 110(11): 6503-6570.
[7]	SANG L X, ZHANG Z Y, BAI G M, et al.A photoelectrochemical investigation of the hydrogen-evolving doped TiO2 nanotube arrays electrode.International Journal of Hydrogen Energy, 2012, 37(1): 854-859.
[8]	ASAHI R, MORIKAWA T, OHWAKI T, et al.Visible-light photocatalysis in nitrogen-doped titanium oxides.Science, 2001, 293(5528): 269-271.
[9]	YANG K, DAI Y, HUANG B.Understanding photocatalytic activity of S- and P-doped TiO2 under visible light from first-principles.J. Phys. Chem. C, 2007, 111(51): 18985-18994.
[10]	CHI B, ZHAO L, JIN T.One-Step Template-free route for synthesis of mesoporous N-doped titania spheres.Journal of Physical Chemistry C, 2007, 111(17): 6189-6193.
[11]	SHAO G.Red shift in manganese- and iron-doped TiO2: A DFT+U analysis.J. Phys. Chem. C, 2009, 113(16): 6800-6808.
[12]	JIA L, WU C, LI Y, et al. Enhanced visible-light photocatalytic activity of anatase TiO2 through N and S codoping. Applied Physics Letters, 2011, 98(21): 211903-1-3.
[13]	KARUNAKARAN C, GOMATHISANKAR P, VIJAYABALAN A, et al.Visible light photocatalytic disinfection of bacteria by Cd-TiO2 .Catalysis Communications, 2011, 12(9): 826-829.
[14]	JIA L, WU C, HAN S, et al.Theoretical study on the electronic and optical properties of (N, Fe)-codoped anatase TiO2 photocatalyst.Journal of Alloys & Compounds, 2011, 509(20): 6067-6071.
[15]	RENGIFO-HERRERA J A, PIERZCHAŁA K, SIENKIEWICZ A, et al. Synthesis, characterization, and photocatalytic activities of nanoparticulate N, S-codoped TiO2 having different surface-to- volume ratios.The Journal of Physical Chemistry C, 2010, 114(6): 2717-2723.
[16]	NAIK B, PARIDA K M, GOPINATH C S.Facile synthesis of N- and S-incorporated nanocrystalline TiO2 and direct solar-light- driven photocatalytic activity.J. Phys. Chem. C, 2010, 114(45): 19473-19482.
[17]	XU J H, LI J, DAI W L, et al.Simple fabrication of twist-like helix N,S-codoped titania photocatalyst with visible-light response.Applied Catalysis B Environmental, 2008, 79(1): 72-80.
[18]	RENGIFO-HERRERA J A, PULGARIN C. Photocatalytic activity of N, S co-doped and N-doped commercial anatase TiO2 powders towards phenol oxidation and E. coli inactivation under simulated solar light irradiation.Solar Energy, 2010, 84(1): 37-43.
[19]	LIU G, ZHAO Y, SUN C, et al.Synergistic effects of B/N doping on the visible-light photocatalytic activity of mesoporous TiO2 .Angew. Chem. Int. Ed, 2008, 47(24): 4516-4520.
[20]	EYCHMÜLLER A, HÄSSELBARTH A, KATSIKAS L, et al. Fluorescence mechanism of highly monodisperse Q-sized CdS colloids. Journal of Luminescence, 1991, 48-49(91): 745-749.
[21]	HOTCHANDANI S, KAMAT P V.Charge-transfer processes in coupled semiconductor systems. Photochemistry and photoelectrochemistry of the colloidal cadmium sulfide-zinc oxide system.J. Phys. Chem., 1992, 96(16): 6834-6839.
[22]	TOYODA T, SAIKUSA K, SHEN Q.Photoacoustic and photocurrent ptudies of highly porous TiO2 electrodes sensitized by quantum-sized CdS.Japanese Journal of Applied Physics, 1999, 38(5S): 3185-3186.
[23]	LIN S C, LEE Y L, CHANG C H, et al. Quantum-dot-sensitized solar cells: assembly of CdS-quantum-dots coupling techniques of self-assembled monolayer and chemical bath deposition. Applied Physics Letters, 2007, 90(14): 143517-1-3.
[24]	CHANG C H, LEE Y L. Chemical bath deposition of CdS quantum dots onto mesoscopic TiO2 films for application in quantum- dot-sensitized solar cells . Applied Physics Letters, 2007, 91(5): 053503-1-3.
[25]	LIU D, KAMAT P V.Photoelectrochemical behavior of thin cadmium selenide and coupled titania/cadmium selenide semiconductor films .J. Phys. Chem., 1993, 97(41): 10769-10773.
[26]	NASR C, KAMAT P V, HOTCHANDANI S.Photoelectro chemical behavior of coupled SnO2 & CdSe nanocrystalline semiconductor films .Journal of Electroanalytical Chemistry, 1997, 420(1): 201-207.
[27]	RINCÓN M E, JIMÉNEZ A, ORIHUELA A, et al. Thermal treatment effects in the photovoltaic conversion of spray-painted TiO2 coatings sensitized by chemically deposited CdSe thin films.Solar Energy Materials & Solar Cells, 2001, 70(2): 163-173.
[28]	PLASS R, PELET S, KRUEGER J, et al.Quantum dot sensitization of organic-inorganic hybrid solar cells.J. Phys. Chem. B, 2002, 106(31): 7578-7580.
[29]	YU P, KAI Z, NORMAN A G, et al.Nanocrystalline TiO2 solar cells sensitized with InAs quantum dots .J. Phys. Chem. B, 2006, 110(50): 25451-25454.
[30]	ZABAN A, MIĆIĆ O I, GREGG B A, et al. Photosensitization of nanoporous TiO2 electrodes with InP quantum dots.Langmuir, 1998, 14(12): 3153-3156.
[31]	SUN B, HAO Y Z, LI W, et al.Research progress in nanocrystalline solar cell.Journal of Hebei University of Science and Technology, 2002, 23(2): 22-30.
[32]	WU W J, HAO Y Z.The study on sensitization and mechanism of the nanocrystalline photoelectron chemical cells.Journal of Hebei University of Science and Technology, 2004, 25(2): 4-9.
[33]	LEE M M, JOL T, TSUTOMU M, et al.Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites.Science, 2012, 338(6107): 643-647.
[34]	MINGZHEN L, JOHNSTON M B, SNAITH H J.Efficient planar heterojunction perovskite solar cells by vapour deposition.Nature, 2013, 501(7467): 395-398.
[35]	JULIAN B, NORMAN P, SOO-JIN M, et al.Sequential deposition as a route to high-performance perovskite-sensitized solar cells.Nature, 2013, 499(7458): 316-319.
[36]	ZHOU H, CHEN Q, LI G, et al.Interface engineering of highly efficient perovskite solar cells.Science, 2014, 345(6196): 542-546.
[37]	PARK N G.Organometal perovskite light absorbers toward a 20% efficiency low-cost solid-state mesoscopic solar cell.Journal of Physical Chemistry Letters, 2013, 4(15): 2423-2429.
[38]	EDRI E, KIRMAYER S, CAHEN D, et al.High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite.Journal of Physical Chemistry Letters, 2013, 4(6): 897-902.
[39]	PAN Z, MoRA-SERÓ I, SHEN Q, et al. High-efficiency “green” quantum dot solar cells.Journal of the American Chemical Society, 2014, 136(25): 9203-9210.
[40]	ZHAO K, PAN Z, MORA-SERO I, et al.Boosting power conversion efficiencies of quantum dot sensitized solar cells beyond 8% by recombination control.Journal of the American Chemical Society, 2015, 137: 5602-5609.
[41]	LÓPEZ-LUKE T, WOLCOTT A, XU L P, et al. Nitrogen-doped and CdSe quantum-dot-sensitized nanocrystalline TiO2 films for solar energy conversion applications.J. Phys. Chem. C, 2008, 112(4): 1282-1292.
[42]	LING L, XICHUAN Y, JIAJIA G, et al.Highly efficient CdS quantum dot-sensitized solar cells based on a modified polysulfide electrolyte.Journal of the American Chemical Society, 2011, 133(22): 8458-8460.
[43]	MINGKUI W, ANGHEL A M, BENO, T M, et al.CoS supersedes Pt as efficient electrocatalyst for triiodide reduction in dye-sensitized solar cells.Journal of the American Chemical Society, 2009, 131(44): 15976-15977.
[44]	LU N, QUAN X, LI J Y, et al.Fabrication of boron-doped TiO2 nanotube array electrode and investigation of its photoelectrochemical capability.J. Phys. Chem. C, 2007, 111(32): 11836-11842.
[45]	LIU G, ZHAO Y M, SUN C H, et al.Synergistic effects of B/N doping on the visible-light photocatalytic activity of mesoporous TiO2.Angew. Chem. Int. Ed., 2008, 47(24): 4516-4520.
[46]	CHEN D M, YANG D, WANG Q, et al.Effects of boron doping on photocatalytic activity and microstructure of titanium dioxide nanoparticles. Ind. Eng.Chem. Res., 2006, 45(12): 4110-4116.
[47]	UMEBAYASHI T, YAMAKI T, ITOH H, et al.Band gap narrowing of titanium dioxide by sulfur doping.Phys. Lett., 2002, 81(3): 454-456.
[48]	GONBEAU D, GUIMON C, PFISTER-GUILLOUZO G, et al.XPS study of thin films of titanium oxysulfides.Surface Science, 1991, 254(91): 81-89.
[49]	LI X W, CHEN R X, CUI T, et al.Preparation and photocatalytic properties of PbS quantum dots sensitized B/S/TiO2 composite nanotube.Journal of materials science & Engineering, 2015, 33(5): 630-634.
[50]	TIAN H, YANG X, CHEN R, et al.Effect of different dye baths and dye-structures on the performance of dye-sensitized solar cells based on triphenylamine dyes.J. Phys. Chem. C, 2008, 112(29): 11023-11033.

高效CdS量子点敏化B/S共掺杂纳米TiO₂太阳能电池的制备及光电性能研究

Boron and Sulfur Co-doped TiO₂ Nanofilm as High Efficiency CdS Quantum-dot-sensitized Solar Cells

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 50

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王红宁, 黄丽, 清江, 马腾洲, 黄维秋, 陈若愚. 有机-无机氧化硅空心球的合成及VOCs吸附应用[J]. 无机材料学报, 2022, 37(9): 991-1000.
[2]	许伟佳, 邱大平, 刘诗强, 李敏, 杨儒. 用于高性能超级电容器电极的栓皮栎基多孔活性炭的制备[J]. 无机材料学报, 2019, 34(6): 625-632.
[3]	王勇, 于云, 冯爱虎, 江峰, 胡学兵, 宋力昕. Nafion改性多级孔径石墨烯气凝胶制备与性能研究[J]. 无机材料学报, 2018, 33(4): 469-474.
[4]	鄢波, 彭泽洋, 吕斌, 刘薇. 圆偏振光诱导CdTe量子点再生长及其对光致发光的影响[J]. 无机材料学报, 2017, 32(12): 1321-1326.
[5]	余正发, 王旭珍, 侯亚男, 赵宗彬, 李芮, 邱介山. 熔盐法制备氮掺杂多孔炭及其催化脱硫性能[J]. 无机材料学报, 2017, 32(7): 770-776.
[6]	白雪君, 刘婵, 侯敏, 王彪, 曹辉, 付俊杰. 锂离子电池硅/碳纳米管/石墨烯自支撑负极材料研究[J]. 无机材料学报, 2017, 32(7): 705-712.
[7]	胡枫香, 李玲, 林奎, 崔兰, 石彩静, Sayyar Ali Shah, 崔屾. 氮掺杂空心碳球的制备及其光学性质研究[J]. 无机材料学报, 2016, 31(8): 827-833.
[8]	孙晓丹, 刘中群, 颜昊. 石墨烯量子点的制备及其生物应用[J]. 无机材料学报, 2016, 31(4): 337-344.
[9]	闻海萌, 宋军, 王重庆, 周瑜, 王军. 海绵辅助离子液体干胶法合成ZSM-22分子筛大颗粒[J]. 无机材料学报, 2015, 30(6): 615-620.
[10]	黄燕华, 韩响, 陈慧鑫, 陈松岩, 杨勇. 锂离子电池多孔硅/碳复合负极材料的研究[J]. 无机材料学报, 2015, 30(4): 351-356.
[11]	陈爱兵, 于奕峰, 臧文伟, 齐国禄, 于运红, 李月彤. 掺氮多孔碳在二氧化碳吸附分离中的应用[J]. 无机材料学报, 2015, 30(1): 9-16.
[12]	赵新红, 李晓斌, 陈静, 祁永东, 问娟娟, 季东. 具有特殊形貌的多级孔SAPO-5分子筛的常压合成[J]. 无机材料学报, 2014, 29(8): 821-826.
[13]	李建林, 陈彬彬, 章文, 王连军, 江莞. 陶瓷/石墨烯块体复合材料的研究进展[J]. 无机材料学报, 2014, 29(3): 225-236.
[14]	李剑文, 周爱军, 刘兴泉, 李晶泽. 化学蚀刻法制备纳米硅线作为高能锂离子电池的负极[J]. 无机材料学报, 2013, 28(11): 1207-1212.
[15]	于晓磊, 杨军, 冯雪娇, 高鹏飞, 王久林, 努丽燕娜. 多孔硅/碳复合负极材料的制备及电化学性能[J]. 无机材料学报, 2013, 28(9): 937-942.