TiO_2/Al_2O_3核壳纳米阵列光阳极对染料敏化太阳能电池光电性能的改善
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摘要
以异丙醇铝为前驱物水解制备了氧化铝溶胶,通过溶胶浸泡Ti O_2纳米管阵列并采用退火处理在纳米管表面引入了具有高介电常数、宽带隙的薄Al_2O_3钝化层,构建了TiO_2/Al_2O_3核壳纳米阵列光阳极并应用于染料敏化太阳能电池(DSSC)。详细研究了不同溶胶浸泡时间和溶胶浓度对阵列光阳极微结构和组装器件光电性能的影响。发现在0.02 mol/L的溶胶中浸泡处理15 min的Ti O_2纳米阵列光阳极组装的电池具有最佳的能量转换效率(η=7.85%),与未经钝化层处理的器件相比电池效率提升了59%。研究表明,纳米阵列光阳极中引入Al_2O_3薄钝化层不仅能提高器件的开路电压,而且有效抑制了载流子与电解液中的I3–离子和染料受主态的复合;适当厚度的Al_2O_3钝化层能让光生载流子有效隧穿到Ti O_2纳米阵列光阳极,因而基于Ti O_2/Al_2O_3核壳纳米阵列光阳极的电池光电性能得到了显著提升。
The alumina sol was firstly prepared by hydrolyzation of aluminum isopropoxide.Ti O_2 nanotube arrays were immersed into alumina sol and followed with annealing treatment to coat a thin layer of high dielectric constant and wide band gap Al_2O_3 blocking layer.The Ti O_2/Al_2O_3 core-shell nanoarrays photoanode was accordingly constructed and applied in dye-sensitized solar cell(DSSC).The influence of sol treatment time and sol concentration on microstructure of photoanodes and photovoltaic performance of assembled solar cells were investigated.It is found that the cell based on the Ti O_2 nanotube arrays treated by immersing into 0.02 mol/L alumina sol for 15 min gives a highest power conversion efficiency of 7.85%,a59%enhancement on power conversion efficiency in comparison with the cell based on Ti O_2 nanotube arrays without sol treatment.The introducing of thin Al_2O_3 blocking layer onto Ti O_2 nanotubes arrays photoanode significantly improves the open circuit voltage of the solar cells and effectively suppresses the recombination between carries and the I_3~–ions in electrolytes or acceptor dye species in DSSC.The Al_2O_3 blocking layer with proper thickness also ensures the photo-excited carriers can effectively tunnel to the Ti O_2 photoanode.Accordingly the photovoltaic performance of solar cell based on Ti O_2/Al_2O_3 core-shell nanoarrays photoanode is significantly improved.
The alumina sol was firstly prepared by hydrolyzation of aluminum isopropoxide.Ti O_2 nanotube arrays were immersed into alumina sol and followed with annealing treatment to coat a thin layer of high dielectric constant and wide band gap Al_2O_3 blocking layer.The Ti O_2/Al_2O_3 core-shell nanoarrays photoanode was accordingly constructed and applied in dye-sensitized solar cell(DSSC).The influence of sol treatment time and sol concentration on microstructure of photoanodes and photovoltaic performance of assembled solar cells were investigated.It is found that the cell based on the Ti O_2 nanotube arrays treated by immersing into 0.02 mol/L alumina sol for 15 min gives a highest power conversion efficiency of 7.85%,a59%enhancement on power conversion efficiency in comparison with the cell based on Ti O_2 nanotube arrays without sol treatment.The introducing of thin Al_2O_3 blocking layer onto Ti O_2 nanotubes arrays photoanode significantly improves the open circuit voltage of the solar cells and effectively suppresses the recombination between carries and the I_3~–ions in electrolytes or acceptor dye species in DSSC.The Al_2O_3 blocking layer with proper thickness also ensures the photo-excited carriers can effectively tunnel to the Ti O_2 photoanode.Accordingly the photovoltaic performance of solar cell based on Ti O_2/Al_2O_3 core-shell nanoarrays photoanode is significantly improved.
引文
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[2]O'REGAN B,GR?TZELI M.kk required to produce one charge-carrier pair,E,(in e V)[J].Nature,1991,353:24.
[3]GR?TZEL M.Perspectives for dye-sensitized nanocrystalline solar cells[J].Prog Photovoltaics:Res Appl,2000,8(1):171-185.
[4]GONG D,GRIMES C A,VARGHESE O K,et al.Titanium oxide nanotube arrays prepared by anodic oxidation[J].J Mater Res,2001,16(12):3331-3334.
[5]PRAKASAM H E,SHANKAR K,PAULOSE M,et al.A new benchmark for Ti O2 nanotube array growth by anodization[J].J Phys Chem C,2007,111(20):7235-7241.
[6]MACAK J M,TSUCHIYA H,TAVEIRA L,et al.Smooth anodic Ti O2 nanotubes[J].Angew Chem Int Ed,2005,44(45):7463-7465.
[7]SHANKAR K,MOR G K,PRAKASAM H E,et al.Highly-ordered Ti O2 nanotube arrays up to 220μm in length:use in water photoelectrolysis and dye-sensitized solar cells[J].Nanotechnology,2007,18(6):065707.
[8]WANG D,YU B,WANG C,et al.A novel protocol toward perfect alignment of anodized Ti O2 nanotubes[J].Adv Mater,2009,21(19):1964-1967.
[9]CHEN Q,XU D.Large-scale,noncurling,and free-standing crystallized Ti O2 nanotube arrays for dye-sensitized solar cells[J].J Phys Chem C,2009,113(15):6310-6314.
[10]LEI B X,LIAO J Y,ZHANG R,et al.Ordered crystalline Ti O2 nanotube arrays on transparent FTO glass for efficient dye-sensitized solar cells[J].J Phys Chem C,2010,114(35):15228-15233.
[11]ZHU K,NEALE N R,MIEDANER A,et al.Enhanced charge-collection efficiencies and light scattering in dye-sensitized solar cells using oriented Ti O2 nanotubes arrays[J].Nano Lett,2007,7(1):69-74.
[12]ZHANG Q,CAO G.Nanostructured photoelectrodes for dye-sensitized solar cells[J].Nano Today,2011,6(1):91-109.
[13]GANAPATHY V,KARUNAGARAN B,RHEE S W.Improved performance of dye-sensitized solar cells with Ti O2/alumina core–shell formation using atomic layer deposition[J].J Power Sources,2010,195(15):5138-5143.
[14]PALOMARES E,CLIFFORD J N,HAQUE S A,et al.Control of charge recombination dynamics in dye sensitized solar cells by the use of conformally deposited metal oxide blocking layers[J].J Am Chem Soc,2003,125(2):475-482.
[15]RAMASAMY P,KANG M S,CHA H J,et al.Highly efficient dye-sensitized solar cells based on Hf O2 modified Ti O2 electrodes[J].Mater Res Bull,2013,48(1):79-83.
[16]CHEN J G,CHEN C Y,WU C G,et al.An efficient flexible dye-sensitized solar cell with a photoanode consisting of Ti O2 nanoparticle-filled and Sr O-coated Ti O2 nanotube arrays[J].J Mater Chem,2010,20(34):7201-7207.
[17]ZHANG Q,CAO G.Nanostructured photoelectrodes for dye-sensitized solar cells[J].Nano Today,2011,6(1):91-109.
[18]KANG S H,KIM J Y,KIM Y,et al.Surface modification of stretched Ti O2 nanotubes for solid-state dye-sensitized solar cells[J].J Phys Chem C,2007,111(26):9614-9623.
[19]ZHANG J,LI S,DING H,et al.Transfer and assembly of large area Ti O2 nanotube arrays onto conductive glass for dye sensitized solar cells[J].J Power Sources,2014,247:807-812.
[20]谭毅,阳方玉,程义,等.氧化铝、氧化钛多孔膜的阳极氧化制备与微结构比较[J].电子元件与材料,2017(8):39-44.
[21]阳方玉,丁浩,杜伟,等.阳极氧化制备新颖的Ti O2多孔纳米结构膜及其形成机理与应用[J].中国科学:技术科学,2017(7):727-737.
[22]ZHANG J,LI Q,LI S,et al.An efficient photoanode consisting of Ti O2 nanoparticle-filled Ti O2 nanotube arrays for dye sensitized solar cells[J].J Power Sources,2014,268:941-949.
[23]GHOSH A K,FISHMAN C,FENG T.Sn O2/Si solar cells—heterostructure or Schottky-barrier or MIS-type device[J].J Appl Phys,1978,49(6):3490-3498.
[24]FABREGAT-SANTIAGO F,BISQUERT J,GARCIABELMONTE G,et al.Influence of electrolyte in transport and recombination in dye-sensitized solar cells studied by impedance spectroscopy[J].Solar Energy Mater Solar Cells,2005,87(1):117-131.
[25]KOWALCZYK S P,MCFEELY F R,LEY L,et al.The electronic structure of Sr Ti O3 and some simple related oxides(Mg O,Al2O3,Sr O,Ti O2)[J].Solid State Commun,1977,23(3):161-169.
[26]SONG L,DU P,SHAO X,et al.Effects of hydrochloric acid treatment of Ti O2 nanoparticles/nanofibers bilayer film on the photovoltaic properties of dye-sensitized solar cells[J].Mater Res Bull,2013,48(3):978-982.
[27]HSU C P,LEE K M,HUANG J T W,et al.EIS analysis on low temperature fabrication of Ti O2 porous films for dye-sensitized solar cells[J].Electrochim Acta,2008,53(25):7514-7522.