CN103310992A - Photo-anode of dye-sensitized solar cell and preparation method for photo-anode - Google Patents
Photo-anode of dye-sensitized solar cell and preparation method for photo-anode Download PDFInfo
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- CN103310992A CN103310992A CN2013101906841A CN201310190684A CN103310992A CN 103310992 A CN103310992 A CN 103310992A CN 2013101906841 A CN2013101906841 A CN 2013101906841A CN 201310190684 A CN201310190684 A CN 201310190684A CN 103310992 A CN103310992 A CN 103310992A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a photo-anode of a dye-sensitized solar cell. The photo-anode of the dye-sensitized solar cell is characterized by comprising a dye-sensitized semiconductor material and also comprising nanometal particles, small organic molecules and dyes, wherein the nanometal particles are modified to the semiconductor material, and the small organic molecules and the dyes are adsorbed to the surfaces of the nanometal particles. The small organic molecules are adsorbed to empty positions of the surfaces of the nanometal particles. The surfaces of the nanometal particles are treated by the surfaces of the small organic molecules, and therefore, the interface compounding can be effectively restrained, and the device performance is improved. The invention also discloses a method for preparing the photo-anode of the dye-sensitized solar cell. The method comprises the following steps: modifying the semiconductor material of the photo-anode of the dye-sensitized solar cell by the nanometal particles; then, adsorbing the dyes; and finally, adsorbing the small organic molecules at the empty positions of the surfaces of the nanometal particles in the manner of surface treatment of the small organic molecules.
Description
Technical field
The present invention relates to a kind of light anode of DSSC, be specifically related to a kind ofly except the semi-conducting material that comprises dye sensitization, modify the nano-metal particle on semi-conducting material in addition and be adsorbed in organic molecule and the dyestuff on nano-metal particle surface.Belong to the field that suppresses light anodic interface electron recombination in the DSSC.
Background technology
(Dye Sensitized Solar Cell is a kind of novel solar cell that recent two decades gets up based on Nano-technology Development DSSC) to DSSC, because of with low cost, and be described as one of solar cell of commercial application prospect is arranged most.DSSC is mainly formed by electrically conducting transparent substrate, nano-crystal titanium oxide porous membrane, dye sensitization molecule, electrolyte with to electrode, and wherein the suprabasil nano-crystal titanium oxide porous membrane of electrically conducting transparent and N719 dyestuff are conventional light anode materials.The energy flow process of DSSC is as follows: at first chemisorbed transits to excitation state after the dye molecule on titan oxide particles surface is absorbing a photon, produces an electronics and is injected on the conduction band of titanium oxide; Electronics is diffused into rapidly on the electro-conductive glass, is delivered on the electrode by external circuit load then; To the electronics on the electrode through electrolyte diffusion to semiconductor/dyestuff/electrolyte interface, reduce oxidized dyestuff, finish a loop.From above operation principle as can be seen, electric transmission and electron recombination on light anode semiconductor/dyestuff/electrolyte interface are competitive relations, and the electron recombination at minimizing interface has fundamental influence to the performance of DSSC.
The most general mode is to coat one deck inorganic oxide such as aluminium oxide (Al at semiconductor surface at present
2O
3), magnesium oxide (MgO), zirconia (ZrO
2), silica (SiO
2) etc., the protection semiconductor surface, it is compound by electrolyte to prevent injecting semi-conductive photoelectron from dyestuff.Yet this nucleocapsid structure can form the energy barrier between semiconductor and dyestuff, suppressed the injection of light induced electron.Also having a kind of mode is to be adsorbed in semiconductor surface altogether with organic molecule and dyestuff, do not make to be occupied by organic molecule by the semiconductor surface of dye sensitization, thus the electron recombination of prevention semiconductor/electrolyte.But this mode can make dyestuff and organic molecule occupy semiconductor surface with competitive way, is unfavorable for the load of dyestuff, influences the light absorption of device.And adsorb organic micromolecular mode after adopting first sensitizing dyestuff, then most semi-conductive surfaces have been occupied because of dye molecule, can allow the position of organic molecule absorption considerably less, it is very little to make organic molecule reduce the effect of electron recombination of semiconductor/electrolyte interface.
Nano-metal particle has the surface plasma body resonant vibration effect, and the defective of semiconductor surface of contact is with it had passivation, and it is compound to be conducive to reduce semiconductor/electrolytical interface.In addition, the surface plasma body resonant vibration effect of metallic particles can increase the light absorption of dyestuff, thereby improves device performance.And nano-metal particle directly contacts with electrolyte, and the electronics that injects nano-metal particle is fallen by electrolyte is compound.Before; there is the researcher that titanium oxide or silica are coated on the metallic particles; to reduce the compound of metallic particles/electrolyte interface; but this protected mode can spatially will be kept apart between metallic particles/semiconductor, the metallic particles/dyestuff, is unfavorable for the performance of the surface plasma body resonant vibration effect of metallic particles.
The present invention adopts the semi-conducting material of the containing metal particle of organic molecule surface treatment dye sensitization, make organic molecule occupy the vacant locations of surface of metal particles, metallic particles and electrolyte are kept apart, and the interface of reducing between metallic particles/electrolyte is compound.This processing mode can spatially will not kept apart between metallic particles/semiconductor, the metallic particles/dyestuff, can negative effect not arranged to the surface plasma body resonant vibration effect of metallic particles.Decorated nanometer metallic particles on the dye sensitization light anode of routine, and at surface of metal particles absorption organic molecule, it is compound effectively to reduce the interface, thereby improves device performance.
Summary of the invention
The purpose of this invention is to provide light anode of a kind of DSSC and preparation method thereof, with nano-metal particle and be adsorbed in the organic molecule of surface of metal particles, suppress the electron recombination of light anodic interface.
The technical scheme that the present invention adopts for achieving the above object is:
A kind of light anode of DSSC, it is characterized in that: it comprises outside the semi-conducting material of dye sensitization, also comprises organic molecule and the dyestuff modifying the nano-metal particle on described semi-conducting material and be adsorbed in described nano-metal particle surface.Described organic molecule is adsorbed in the vacant locations place on described nano-metal particle surface.
Modify nano-metal particle at the semiconductor surface of dye-sensitized solar cell anode, absorbing dye adsorbs organic molecule with organic molecule surface-treated mode in the surface of metal particles vacant locations at last more then.
Described semi-conducting material is titanium oxide TiO
2Or zinc oxide ZnO.The semi-conducting material of described dye-sensitized solar cell anode can be TiO
2Also can be ZnO, its structure can be that porous nanocrystalline also can be nanometer stick array, and sample can be bought the product of commercial production, also can be with reference to the preparation of disclosed method (Ceramics International38 (8): 6461-6467; Applied Physics Letters100 (12); Nanotechnology22 (11): 7; Applied Physics a-Materials Science﹠amp; Processing109 (3): 655-663; Electrochimica Acta56 (5): 1960-1966).
The size of described nano-metal particle is less than or equals 10nm, and this nano-metal particle is golden Au nano particle, platinum Pt nano particle, silver-colored Ag nano particle, or the alloy nanoparticle of two or more noble metal.Wherein alloy nanoparticle mainly is made up of Au, Pt, Ag.Described organic molecule is the thiophenol that contains the mercaptan of alkyl chain or contain aromatic group.The described alkyl chain that contains the mercaptan of alkyl chain is 6-18 carbon atom.Described dyestuff is the N719 dyestuff, adsorbs in the N719 dye solution dye sensitization of the tert-butyl alcohol and second cyanogen to form.The N719 dyestuff is conventional light anode material.
A kind of preparation is characterized in that according to the method for the light anode of described DSSC it may further comprise the steps:
1) preparation semiconductor material thin film;
2) adopt the mode of original position photo catalytic reduction or ion sputtering to finish the load of nano-metal particle on described semi-conducting material;
3) with step 2) resulting load has the semi-conducting material of nano-metal particle to be immersed in the N719 dye solution of the tert-butyl alcohol and second cyanogen to carry out dye sensitization, use alcohol flushing then; Wherein, the volume ratio of the described tert-butyl alcohol and second cyanogen is 1:1, and concentration is 0.3mM;
4) semi-conducting material that contains nano-metal particle after the resulting dye sensitization of step 3) be impregnated in the second cyanogen solution of organic molecule 2-24 hour, at last with alcohol flushing, dry, namely obtain the light anode of needed DSSC; Wherein, described organic molecule is the thiophenol that contains the mercaptan of alkyl chain (6-18 carbon atom) or contain aromatic group.
The general mode of described ion sputtering is under the function of current, in the Ar atmosphere, with the sputter on semiconductor material thin film of Emitech K575X ion sputtering instrument.The general mode of described original position photo catalytic reduction, the ethanol that semiconductor material thin film is dipped in respective substance (gold chloride, chlorine silver acid etc.) mutually in, then with alcohol flushing, dry, use UV-irradiation at last.
Adopt the advantage of the prepared dye-sensitized solar cell anode of the present invention to be:
1, the present invention adopts nano-metal particle to modify the defective that dye-sensitized solar cell anode can the passivated semiconductor surface, is conducive to accelerate electronics in semi-conductive transmission, reduces the probability of electron recombination;
2, the present invention adopts nano-metal particle to modify the light absorption that dye-sensitized solar cell anode can increase dyestuff, improves device performance;
3, the absorption of organic molecule of the present invention is after dye sensitization, can the load of dyestuff not had a negative impact;
4, nano-metal particle and electrolyte can be effectively isolated in the protection of the fence type of the organic molecule of the surface of metal particles among the present invention, to reduce the electron recombination of metallic particles/electrolyte interface;
5, the organic molecule among the present invention is handled not isolating metal particle/semiconductor, metallic particles/dyestuff, effectively the surface plasma body resonant vibration effect of protective money metal particles spatially;
6, reaction condition of the present invention is gentle simple, does not need expensive equipment and raw material, the control that is conducive to produce and popularization.
Below in conjunction with embodiment, the present invention is further described.
Embodiment
Embodiment 1:
A kind of light anode of DSSC, it comprises outside the semi-conducting material of dye sensitization, also comprises organic molecule and the dyestuff modifying the nano-metal particle on described semi-conducting material and be adsorbed in described nano-metal particle surface.Described organic molecule is adsorbed in the vacant locations place on described nano-metal particle surface.
Modify nano-metal particle at the semiconductor surface of dye-sensitized solar cell anode, absorbing dye adsorbs organic molecule with organic molecule surface-treated mode in the surface of metal particles vacant locations at last more then.
Described semi-conducting material is titanium oxide TiO
2Or zinc oxide ZnO.The semi-conducting material of described dye-sensitized solar cell anode can be TiO
2Also can be ZnO, its structure can be that porous nanocrystalline also can be nanometer stick array, and sample can be bought the product of commercial production, also can be with reference to disclosed method preparation.As: Degussa (Degussa) P25TiO that buys commercial production
2Nanocrystalline, also can be with reference to the preparation of disclosed method as chemical liquid phase reaction growing ZnO nanorod (Ceramics International38 (8): 6461-6467), Hydrothermal Growth ZnO nanometer rods (Journal of Physical Chemistry C117 (20): 1197-1203), metallochemistry vapour deposition process growth TiO
2Nanometer rods (Applied Physics Letters100 (12): 123108), nanocrystalline (the International Journal of Hydrogen Energy37 (6): 4863-4870) etc. of Prepared by Sol Gel Method ZnO.
The size of described nano-metal particle is less than or equals 10nm, and this nano-metal particle is golden Au nano particle, platinum Pt nano particle, silver-colored Ag nano particle, or the alloy nanoparticle of two or more noble metal.Wherein alloy nanoparticle mainly is made up of Au, Pt, Ag.Described organic molecule is the thiophenol that contains the mercaptan of alkyl chain or contain aromatic group.The described alkyl chain that contains the mercaptan of alkyl chain is 6-18 carbon atom.Described dyestuff is the N719 dyestuff, adsorbs on it through the semi-conducting material sensitization in the N719 solution of the tert-butyl alcohol and second cyanogen.The N719 dyestuff is conventional light anode material.
A kind of preparation is according to the method for the light anode of described DSSC, and it may further comprise the steps:
1) preparation semiconductor material thin film;
2) adopt the mode of original position photo catalytic reduction or ion sputtering to finish the load of nano-metal particle on described semi-conducting material;
3) with step 2) resulting load has the semi-conducting material of nano-metal particle to be immersed in the N719 dye solution of the tert-butyl alcohol and second cyanogen to carry out dye sensitization, use alcohol flushing then; Wherein, the volume ratio of the described tert-butyl alcohol and second cyanogen is 1:1, and concentration is 0.3mM;
4) semi-conducting material that contains nano-metal particle after the resulting dye sensitization of step 3) be impregnated in the second cyanogen solution of organic molecule 2-24 hour, at last with alcohol flushing, dry, namely obtain the light anode of needed DSSC; Wherein, described organic molecule is the thiophenol that contains the mercaptan of alkyl chain (6-18 carbon atom) or contain aromatic group.
The general mode of described ion sputtering is under the function of current, in the Ar atmosphere, with the sputter on semiconductor material thin film of Emitech K575X ion sputtering instrument.The general mode of described original position photo catalytic reduction, the ethanol that semiconductor material thin film is dipped in respective substance (gold chloride, chlorine silver acid etc.) mutually in, then with alcohol flushing, dry, use UV-irradiation at last.
Embodiment 2:
Present embodiment provides a kind of light anode of DSSC, and its material and preparation method are substantially the same manner as Example 1, and its difference is:
Described semi-conducting material is the ZnO nanometer stick array, and its nanometer rods length is about 1 μ m.
Described nano-metal particle is the Pt nano particle.The preparation method of described Pt nano particle adopts ion sputtering, and the size of Pt nano particle is about 8nm.Described dyestuff is the N719 dyestuff.Described organic molecule is positive stearylmercaptan.
The preparation method of the light anode of above-mentioned DSSC, it may further comprise the steps:
1) with hydro thermal method growing ZnO nanorod arrays on electro-conductive glass, forms the ZnO nano-rod film then;
2) under the 150mA electric current, use ion sputtering instrument sputter 3s on the ZnO nano-rod film in the Ar atmosphere, thereby obtain being carried on the Pt nano particle on the ZnO nanometer rods;
3) with step 2) sample be immersed in the N719 dye solution of the tert-butyl alcohol of 0.3mM and second cyanogen (1:1 volume ratio) 30 minutes, use alcohol flushing then;
4) protect with the noresidue adhesive tape around the sample with step 3); and impregnated in the second cyanogen solution of positive stearylmercaptan of 0.1mM 2 hours; at last with alcohol flushing, the band that dries, removes photoresist, the Pt nano particle that obtained load and adsorbed the ZnO nanometer rods light anode of positive stearylmercaptan molecule.
Embodiment 3: present embodiment provides a kind of light anode of DSSC, its material and preparation method and embodiment 1,2 basic identical, and its difference is:
The semiconductor of described dye-sensitized solar cell anode is TiO
2Nanometer stick array, its nanometer rods length is about 1 μ m.
Described nano-metal particle is the Ag nano particle.The preparation method of described Ag nano particle adopts ion sputtering, and the size of Ag nano particle is about 5nm.
Described organic molecule is positive lauryl mercaptan.
The preparation method of the light anode of above-mentioned DSSC, it may further comprise the steps:
1) use hydro thermal method at electro-conductive glass (FTO) growth TiO
2Nanometer stick array;
2) under the 150mA electric current, use ion sputtering instrument at TiO in the Ar atmosphere
2Sputter 3s on the nano-rod film, thus obtain being carried on TiO
2Ag nano particle on the nanometer rods;
3) with step 2) sample be immersed in the N719 dye solution of the tert-butyl alcohol of 0.3mM and second cyanogen (1:1 volume ratio) 24 hours, use alcohol flushing then;
4) protect with the noresidue adhesive tape around the sample with step 3); and impregnated in the second cyanogen solution of positive lauryl mercaptan of 0.1mM 12 hours; at last with alcohol flushing, the band that dries, removes photoresist, the Ag nano particle that obtained load and adsorbed the TiO of positive lauryl mercaptan molecule
2Nanometer rods light anode.
Embodiment 4: present embodiment provides a kind of light anode of DSSC, its material and preparation method and embodiment 1,2,3 basic identical, and its difference is:
The semiconductor of described dye-sensitized solar cell anode is the ZnO nano-crystal film, its nanocrystalline being of a size of about 10-25 μ m.
Described nano-metal particle is the Au nano particle.The preparation method of described Au nano particle adopts the light-catalysed method of original position, and the size of Au nano particle is about 3-8nm.
Described organic molecule is toluene-.
The preparation method of the light anode of above-mentioned DSSC, it may further comprise the steps:
1) method with silk screen printing is coated in the nanocrystalline slurry of ZnO on the electro-conductive glass, obtains the ZnO nano-crystal film;
2) the ZnO nano-crystal film is dipped in 2mM gold chloride ethanol mutually in after 5 minutes, with alcohol flushing, dry, used the 325nm UV-irradiation at last 40 minutes; Repeat above-mentioned steps, obtain containing the ZnO nano-crystal film of Au nano particle;
3) with step 2) sample be immersed in the N719 dye solution of the tert-butyl alcohol of 0.3mM and second cyanogen (1:1 volume ratio) 30 minutes, use alcohol flushing then;
4) protect with the noresidue adhesive tape around the sample with step 3); and impregnated in the second cyanogen solution of toluene-of 0.1mM 24 hours; at last with alcohol flushing, the band that dries, removes photoresist, the Au nano particle that obtained load and adsorbed the nanocrystalline smooth anode of ZnO of toluene-molecule.
Embodiment 5: present embodiment provides a kind of light anode of DSSC, its material and preparation method and embodiment 1,2,3,4 basic identical, and its difference is:
The semiconductor of described dye-sensitized solar cell anode is TiO
2Nano-crystal film, its nanocrystalline being of a size of about 10-25 μ m.
Described nano-metal particle is the Au-Ag alloy nanoparticle.The preparation method of described Au-Ag alloy nanoparticle adopts the light-catalysed method of original position, and the Au-Ag alloy nanoparticle is of a size of 4-10nm.
Described organic molecule is different spicy thioalcohol.
The preparation method of the light anode of above-mentioned DSSC, it may further comprise the steps:
1) use the method for silk screen printing with TiO
2Nanocrystalline slurry is coated on the electro-conductive glass, obtains TiO
2Nano-crystal film;
2) 2.1) with TiO
2Nano-crystal film be dipped in 2mM gold chloride ethanol mutually in after 5 minutes, with alcohol flushing, dry, used the 325nm UV-irradiation at last 40 minutes; 2.2) with step 2.1) and in sample be dipped in 2mM chlorine silver acid ethanol mutually in after 5 minutes, with alcohol flushing, dry, used the 325nm UV-irradiation at last 40 minutes, namely obtain containing the TiO of Au-Ag alloy nanoparticle
2Nano-crystal film;
3) with step 2) sample be immersed in the N719 dye solution of the tert-butyl alcohol of 0.3mM and second cyanogen (1:1 volume ratio) 24 hours, use alcohol flushing then;
4) protect with the noresidue adhesive tape around the sample with step 3); and impregnated in the second cyanogen solution of different spicy thioalcohol of 0.1mM 2 hours; at last with alcohol flushing, the band that dries, removes photoresist, the Au-Ag alloy nanoparticle that obtained load and adsorbed the micromolecular TiO of different spicy thioalcohol
2Nanocrystalline smooth anode.
Adopt the advantage of the prepared dye-sensitized solar cell anode of the present invention to be:
1, the present invention adopts nano-metal particle to modify the defective that dye-sensitized solar cell anode can the passivated semiconductor surface, is conducive to accelerate electronics in semi-conductive transmission, reduces the probability of electron recombination; 2, the present invention adopts nano-metal particle to modify the light absorption that dye-sensitized solar cell anode can increase dyestuff, improves device performance; 3, the absorption of organic molecule of the present invention is after dye sensitization, can the load of dyestuff not had a negative impact; 4, nano-metal particle and electrolyte can be effectively isolated in the protection of the fence type of the organic molecule of the surface of metal particles among the present invention, to reduce the electron recombination of metallic particles/electrolyte interface; 5, the organic molecule among the present invention is handled not isolating metal particle/semiconductor, metallic particles/dyestuff, effectively the surface plasma body resonant vibration effect of protective money metal particles spatially; 6, reaction condition of the present invention is gentle simple, does not need expensive equipment and raw material, the control that is conducive to produce and popularization.
But the above only is preferable possible embodiments of the present invention, is not in order to limit to claim of the present invention, so the equivalent structure that all utilizations specification of the present invention and accompanying drawing content are done changes, all to be included in protection scope of the present invention.
Claims (10)
1. the light anode of a DSSC, it is characterized in that: it comprises the semi-conducting material of dye sensitization, also comprises organic molecule and the dyestuff modifying the nano-metal particle on described semi-conducting material and be adsorbed in described nano-metal particle surface.
2. dye-sensitized solar cell anode according to claim 1, it is characterized in that: described organic molecule is adsorbed in the vacant locations place on described nano-metal particle surface.
3. dye-sensitized solar cell anode according to claim 1, it is characterized in that: described semi-conducting material is titanium oxide TiO
2Or zinc oxide ZnO.
4. the light anode of DSSC according to claim 1, it is characterized in that: the size of described nano-metal particle is less than or equals 10nm, this nano-metal particle is golden Au nano particle, platinum Pt nano particle, silver-colored Ag nano particle, or the alloy nanoparticle of two or more this metal.
5. the light anode of DSSC according to claim 1, it is characterized in that: described organic molecule is the thiophenol that contains the mercaptan of alkyl chain or contain aromatic group.
6. dye-sensitized solar cell anode according to claim 5, it is characterized in that: the described alkyl chain that contains the mercaptan of alkyl chain is 6-18 carbon atom.
7. the light anode of DSSC according to claim 1, it is characterized in that: described dyestuff is N719.
8. method for preparing according to the light anode of the described DSSC of one of claim 1 to 7 is characterized in that it may further comprise the steps:
1) preparation semiconductor material thin film;
2) adopt the mode of original position photo catalytic reduction or ion sputtering to finish the load of nano-metal particle on described semi-conducting material;
3) with step 2) resulting load has the semi-conducting material of nano-metal particle to be immersed in the N719 dye solution of the tert-butyl alcohol and second cyanogen to carry out dye sensitization, use alcohol flushing then;
4) semi-conducting material that contains nano-metal particle after the resulting dye sensitization of step 3) be impregnated in the second cyanogen solution of organic molecule 2-24 hour, at last with alcohol flushing, dry, namely obtain the light anode of needed DSSC.
9. the method for the light anode of DSSC according to claim 8 is characterized in that: step 2) described in the volume ratio of the tert-butyl alcohol and second cyanogen be 1:1, concentration is 0.3mM.
10. the method for the light anode of DSSC according to claim 8, it is characterized in that: the organic molecule in the described step 4) is the thiophenol that contains the mercaptan of alkyl chain or contain aromatic group.
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| CN105537620A (en) * | 2016-01-05 | 2016-05-04 | 河南师范大学 | Universal preparation method of Au-modified oxide semiconductor |
| CN108447693A (en) * | 2018-03-01 | 2018-08-24 | 深圳市创艺工业技术有限公司 | Utilize the drawing and pulling type solar collecting device of dye cell |
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| CN105280388A (en) * | 2015-10-14 | 2016-01-27 | 上海大学 | Composite electrode for dye-sensitized solar cell and preparation method of composite electrode |
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