CN102568842A - Double-sided light-transmission flexible dye sensitized solar cell and special photo anode for the same - Google Patents
Double-sided light-transmission flexible dye sensitized solar cell and special photo anode for the same Download PDFInfo
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- CN102568842A CN102568842A CN2012100305138A CN201210030513A CN102568842A CN 102568842 A CN102568842 A CN 102568842A CN 2012100305138 A CN2012100305138 A CN 2012100305138A CN 201210030513 A CN201210030513 A CN 201210030513A CN 102568842 A CN102568842 A CN 102568842A
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
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- 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
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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
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Abstract
The invention discloses a flexible double-sided light-transmission dye sensitized solar cell and a special photo anode for the solar cell. The dye sensitized solar cell comprises the photo anode, a counter electrode, electrolyte, dye molecules and a transparent flexible substrate, wherein the counter electrode is opposite to the photo anode; the counter electrode and the photo anode are arranged at intervals; the electrolyte is filled between the photo anode and the counter electrode; the dye molecules are adsorbed to the photo anode; the transparent flexible substrate is used for packaging the photo anode, the counter electrode and the electrolyte; the photo anode is a substrate of which the surface is deposited with a zinc oxide nanowire array or an aluminium-doped zinc oxide nanowire array; and the substrate is a metal wire of which the surface is passivated. The dye sensitized solar cell has simple manufacturing flow and low cost. The cell has good photoelectric response in a visible light band. Double-sided light transmission can be realized. The dye sensitized solar cell has good bending performance. The device is ultrathin. The dye sensitized solar cell is very suitable to be used as a sticking membrane, has flexible usages, can be used as the sticking membrane in the aspects of building windows, automobile glass and the like and has very wide application prospect.
Description
Technical field
The present invention relates to a kind of transparent two sides flexible dye-sensitized solar battery and dedicated optical anode thereof.
Background technology
In order to solve energy problem, the exploitation of the novel solar battery cheaper, that performance is higher is continuing carrying out always.Dye solar cell is because its cheap manufacturing cost, high conversion rate and material abundance in the earth's crust of being relied on have obtained great development than advantages such as height in whole world scientific research and practical application.Conventional dyes sensitization battery adopts electrically conducting transparent work electrode substrates such as ITO or FTO mostly, and titanium dioxide absorbs sunlight as the dye sensitization layer.But because it is less to form the distribution of phosphide element in the earth's crust of ITO, also have its suppleness not strong, and face the obstacle of many development.In recent years, the DSSC of flexible substrate is owing to its pliability and be convenient to large tracts of land production and receive increasing concern preferably.
2008, people such as the Zou De of Peking University spring invented a kind of dye-sensitized cell based on metallic fiber.It mainly is configured to form work electrode with thread matrix of conduction and sensitized semiconductor film; The sensitized semiconductor film is served as reasons and is adsorbed the porous membrane structure that the different semiconductor particle of sensitizing dyestuff bulk of molecule constitutes, and sensitized semiconductor film bag is attached to the thread matrix surface of conduction.Use another metal platinum conduct to electrode.Two one metal wires are intertwined, thereby constitute the dye-sensitized cell of wire-shaped.(Xing Fan, Zengze Chu, Fuzhi Wang; Chao Zhang, Lin Chen, Yanwei Tang; And Dechun Zou, Adv.Mater.2008,20; 592) to be work electrode can't guarantee that with contacting of two one metal wires to electrode especially when bending, it is not fine contacting to the problem that exists of this kind technology.And the winding of two metal electrodes will certainly block light effective absorption, can have a strong impact on the photoelectric conversion efficiency of battery like this.A kind of in addition method is to use the titania nanotube of titanium silk outgrowth as work electrode; The metal platinum filament is to electrode; Two one metal wires are encapsulated in the glass tube that is full of electrolyte, but can't realize the flexible requirement of device like this, and be unfavorable for large-scale production.(Liu, Z.; Misra; M.ACS Nano 2010; 4,2196-2200.) occurred the method that titania nanotube that a kind of utilization is coated on titanium silk growth with carbon nano-tube film prepares the single metal wire DSSC outward recently, but this kind method needs annex flow processs such as the extra preparation transfer that carry out CNT and coating; Increased cost of manufacture, and be not very high the raising of efficient.(Sen?Zhang，Chunyan?Ji，ZhuqiangBian，Runhua?Liu，Xinyuan?Xia，Daqin?Yun，Luhui?Zhang，Chunhui?Huang，and?AnyuanCao，Nano?Lett.2011，11，3383-3387)
Summary of the invention
An object of the present invention is to provide light anode of a kind of DSSC and preparation method thereof.
The light anode of DSSC provided by the present invention, it is the substrate of surface deposition zinc oxide nano-wire array or aluminum doped zinc oxide nano-wire array, said substrate is the wire of surface passivation.
Wherein, said wire comprises simple metal silk or stainless steel wire.Said simple metal silk specifically can be processed by following any one metal: gold, silver, copper, iron, tungsten and aluminium.The diameter of said metal material silk is 10-500 μ m.
Prepare the method for the light anode of above-mentioned DSSC, comprise the steps:
1) the metal material silk is carried out surface passivation and handle, obtain the wire of surface passivation;
2) adopt chemical vapour deposition technique depositing zinc oxide nano-wire array or aluminum doped zinc oxide nano-wire array on the wire of said surface passivation, obtain the light anode of said DSSC.
Above-mentioned steps 1) it is following in wire to be carried out the method that surface passivation handles: the mixed solution of wire being put into the concentrated sulfuric acid and hydrogen peroxide solution promptly got in 70-95 ℃ of immersion in 10-60 minute; The said concentrated sulfuric acid is the sulfuric acid solution of mass fraction 98%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide solution is 4 in the said mixed liquor: 1-6: 1.
Above-mentioned steps 2) on the wire of surface passivation the concrete grammar of deposition of aluminum doped zinc oxide nano-wire array following: the mixed-powder of zinc powder and alchlor is put into tube furnace according to 3: 1 ratio of mass ratio is heated to 600-800 ℃; The argon gas of feeding 100sccm is a reacting gas as the oxygen of carrier gas, 2-8sccm; The metal material silk places gas downstream, deposits 4-10 minute and promptly gets.
A further object of the present invention provides DSSC of a kind of flexibility and transparent two sides and preparation method thereof.
DSSC provided by the present invention, it comprise light anode that the present invention prepares, with said smooth anode relatively and place at interval to electrode, be filled into said smooth anode and to the electrolyte between the electrode, be adsorbed in the dye molecule of said smooth anode and be used to encapsulate said smooth anode, to electrode and electrolytical transparent flexible substrate.
Light anode in the above-mentioned DSSC usually with to electrode gap relatively and be arranged in parallel, its spacing can be 10-50 μ m.
Said electrode specifically can be the wire of platinum filament or surperficial platinum plating, its diameter can be 10-500 μ m.
Conventional transparent flexible substrate all can be used as encapsulating material of the present invention, specifically can be PET (PET) or dimethyl silicone polymer (PDMS).The thickness of said transparent flexible substrate can be 30-100 μ m.
Said dye molecule and electrolyte are dye molecule and electrolyte commonly used in the existing DSSC.
The preparation method of DSSC described in the present invention comprises the steps:
1) place dye molecule solution to soak on smooth anode provided by the invention, the abundant absorbing dye molecule of zinc oxide nano-wire array that zinc oxide nano-wire array or aluminium in the light anode are mixed;
2) the light anode that takes out after handling is rinsed the dye molecule of its surface physics absorption well with absolute ethyl alcohol;
3) light anode that dye sensitization is good and to electrode package between double-deck transparent flexible substrate, said smooth anode with electrode is placed relatively and at interval;
4) the electrolyte filling is rushed between the double-deck transparent flexible substrate, obtained said DSSC.
Double-faced flexible DSSC sample provided by the present invention open circuit voltage 0.5V under 1.5AM illumination, short-circuit current density 18mA/cm
2, spectral response range is from 450nm to 700nm.
The dedicated optical anode of novel two-sided printing opacity flexible dye-sensitized solar battery provided by the invention; Its preparation method is easy; The zinc powder that adopts the nature enrichment can be realized the preparation of zinc oxide nano-wire array as raw material on various wires, greatly reduce cost of manufacture.Adopt the transparent flexible substrate to encapsulate to said smooth anode with to electrode, realized real flexibility function, photovoltaic performance does not obviously descend under the bending situation.Owing to unique preparation process, very easily realize the large-scale industrial production of volume to volume.The device transparent two sides, device is ultra-thin, is suitable as very much pad pasting and uses, and usage is flexible, can be at construction window, aspects such as vehicle glass are used as pad pasting, and application prospect is very wide.
Transparent two sides flexible dye-sensitized solar battery provided by the invention is compared with the existing DSSC that coats titania slurry or nanotube outward based on wire, has following outstanding advantage:
1) the present invention is utilized in wire (like stainless steel) and goes up the light anode of the zinc oxide nano-wire array of deposition as dye-sensitized cell, has expanded the specific area of light anode greatly.Because it is regular that nano-wire array is arranged, and in extremely wide spectral region, shows extremely low reflectivity.Zinc oxide is compared with the titanium dioxide photo anode that adopts at present extensively, has higher electron mobility and low recombination rate, and growing and preparing on various wire-shaped substrates easily, obtains the good nano-wire array of crystal mass, and applicability is wider, more is prone to realize.Be different from titania slurry commonly used at present or nanotube as the light anode, still do not have bibliographical information at present;
2) the present invention is encapsulated in the substrate of transparent flexible with work electrode with to the wire of electrode, has realized truly the transparent flexible dye-sensitized cell.Can be used as individual devices uses.Because the bright speciality of its full impregnated can realize unique two-sided absorption light.Help more in architectural use, realize the outer luminous energy of absorption chamber on daytime, the interior luminous energy of absorption chamber at night.
3) speed of depositing zinc oxide nano-wire array of the present invention is fast, and because the carrier of deposition is a stainless steel micron silk, helps using volume to volume technology to carry out a large amount of fast production.Because the basic construction unit of battery is wire and metal platinum filament, can simple realization plane net trellis solar cell, thus raising utilizes the efficient of solar energy greatly.
4) double-faced flexible DSSC of the present invention has extremely thin thickness, can be used as adhering film to glass and is convenient to use, and can be used as building or automobile adhesive film, is convenient to popularize the application of solar cell in old local-style dwelling houses.
5) the inventive method is simple, and cost is low, and repeatability is fine.
Description of drawings
Fig. 1 is the device architecture sketch map of novel two-sided printing opacity flexible dye-sensitized solar battery provided by the invention.
Fig. 2 is the photo in kind of the novel two-sided printing opacity flexible dye-sensitized solar battery of the present invention.
Fig. 3 is at the electron scanning micrograph of the intact zinc oxide nano-wire array (left side) of stainless steel wire surface deposition with zinc oxide nano-wire array (right side).
Fig. 4 is after zinc oxide nano-wire array is carried out dye sensitization, the transmission electron microscope photo of the single zinc oxide nanowire of taking-up, and wherein a left side is a macrograph, the right side is the high power photo.
Fig. 5 is the external quantum efficiency response curve of the transparent two sides flexible dye-sensitized solar battery of the present invention's preparation.
Fig. 6 is transparent two sides flexible dye-sensitized solar battery current/voltage response curve under 1.5AM illumination of the present invention's preparation.
Fig. 7 is its bending performance of displaying for the transparent two sides flexible dye-sensitized solar battery of the present invention's preparation.
Fig. 8 for the transparent two sides flexible dye-sensitized solar battery of the present invention preparation at the two-sided photovoltaic performance that adds under the light.
Embodiment
The present invention will be described through specific embodiment below, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is conventional method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
Embodiment 1, preparation double-faced flexible DSSC
1) metal platinum filament (diameter is 40 microns) and stainless steel wire (diameter is 50 microns) being put into the concentrated sulfuric acid (mass fraction 98%) and hydrogen peroxide solution volume ratio is that 4: 1 mixed solution soaked 30 minutes in 95 ℃; Remove surface organic matter; Use deionized water rinsing again three times, obtain the metal platinum filament of surface passivation and the stainless steel wire of surface passivation.
2) at the surperficial method deposition of aluminum doped zinc oxide nano-wire array that adopts chemical vapour deposition (CVD) of the stainless steel wire of surface passivation; Concrete grammar is: the mixed-powder (mass ratio 3: 1) of zinc powder and alchlor is put into tube furnace be heated to 700 ℃ of argon gas that feed 100sccm as carrier gas, the oxygen of 8sccm is reacting gas, and stainless steel wire is in gas downstream, and sedimentation time is 5 minutes.
3) stainless steel wire with deposition of aluminum doped zinc oxide nano-wire array soaked 10 minutes under 50 ℃ of conditions in N719 ethanolic solution (0.5mM), made the abundant absorbing dye molecule of aluminum doped zinc oxide nano-wire array;
4) taking out stainless steel wire rinses the dye molecule of its surface physics absorption well with absolute ethyl alcohol;
5) the stainless steel wire that deposits the aluminum doped zinc oxide nano-wire array that dye sensitization is good parallel with the platinum filament of surface passivation near; Spacing is 10 microns; (300LSE 3M) is encapsulated between double-deck transparent PET (PET) plastics of 80 micron thick with double faced adhesive tape;
6) irritate the acetonitrile solution of 0.5M lithium iodide, 0.5M iodine, 0.05M lithium perchlorate and 0.5M tetra-tert pyridine as electrolyte and rush between the double-layer PET film, thereby realized the assembling and the sealing-in of entire cell.
The electron scanning micrograph of the zinc oxide nano-wire array that zinc oxide nano-wire array that the stainless steel wire surface deposition aluminium that above-mentioned steps 2) obtains mixes and aluminium mix is as shown in Figure 3.Can be known that by Fig. 3 the aluminum doped zinc oxide nano-wire array has been realized perfect all standing on the stainless steel wire surface, the length of aluminum doped zinc oxide nano-wire is 2.4 μ m, and the aluminium-doped zinc oxide resilient coating is 1.3 μ m.
After zinc oxide nano-wire array carried out dye sensitization, the transmission electron microscope photo of the single zinc oxide nanowire of taking-up was as shown in Figure 4.Can be known that by Fig. 4 zinc oxide nanowire has perfect monocrystalline property, and dye molecule is even in the zinc oxide nanowire surface distributed, thickness is 2nm.
Photoelectric properties to prepared transparent two sides flexible dye-sensitized solar battery are tested; Fig. 5 is to use the external quantum efficiency response curve of the DSSC of internal quantum efficiency test macro (chin or cheek light scientific & technical corporation) measurement; By Fig. 5 can know the absorption region of DSSC be 450nm to 650nm, absworption peak is near 525nm.
Fig. 6 is DSSC current/voltage response curve under 1.5AM illumination, can know that by Fig. 6 DSSC open circuit voltage under 1.5AM illumination is 0.545V, short-circuit current density 6.3mA/cm
2
Fig. 7 is the photovoltaic performance under the DSSC bending; Can know by Fig. 7; DSSC device of the present invention performance under different bending degrees is not affected basically, or even bend 107 degree time device photovoltaic performance all do not change.
Fig. 8 is that DSSC is at the two-sided photovoltaic performance that adds under the light.Add light from front and back, device can be made essentially identical response.When the two sides received illumination simultaneously, the open circuit voltage of device was constant, and short circuit current has increased twice.
Claims (10)
1. the light anode of a DSSC, it is characterized in that: said smooth anode is the substrate of surface deposition zinc oxide nano-wire array or aluminum doped zinc oxide nano-wire array, said substrate is the wire of surface passivation.
2. the light anode of DSSC according to claim 1, it is characterized by: said wire is simple metal silk or stainless steel wire; Said simple metal silk is processed by following any one metal: gold, silver, copper, iron, tungsten and aluminium; The diameter of said metal material silk is 10-500 μ m.
3. the method for the light anode of preparation claim 1 or 2 said DSSCs comprises the steps: 1) the metal material silk is carried out the surface passivation processing, obtain the wire of surface passivation;
2) adopt chemical vapour deposition technique depositing zinc oxide nano-wire array or aluminum doped zinc oxide nano-wire array on the wire of said surface passivation, obtain the light anode of said DSSC.
4. method according to claim 3 is characterized in that: it is following in the step 1) wire to be carried out the method that surface passivation handles: the mixed solution of the metal material silk being put into the concentrated sulfuric acid and hydrogen peroxide solution promptly got in 70-95 ℃ of immersion in 10-60 minute; The said concentrated sulfuric acid is the sulfuric acid solution of mass fraction 98%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide solution is 4 in the said mixed liquor: 1-6: 1.
5. according to claim 3 or 4 described methods; It is characterized in that: step 2) on the wire of surface passivation the method for deposition of aluminum doped zinc oxide nano-wire array following: the mixed-powder of zinc powder and alchlor is put into tube furnace according to 3: 1 ratio of mass ratio is heated to 600-800 ℃; The argon gas of feeding 100sccm is a reacting gas as the oxygen of carrier gas, 2-8sccm; The metal material silk places gas downstream, deposits 4-10 minute and promptly gets.
6. DSSC, it comprise claim 1 or 2 described smooth anodes, with said smooth anode relatively and place at interval to electrode, be filled into said smooth anode and to the electrolyte between the electrode, be adsorbed in the dye molecule of said smooth anode and be used to encapsulate said smooth anode, to electrode and electrolytical transparent flexible substrate.
7. DSSC according to claim 6 is characterized in that: said smooth anode with to electrode gap relatively and be arranged in parallel, spacing is 10-50 μ m; Said is the wire of platinum filament or surperficial platinum plating to electrode, and its diameter is 10-500 μ m.
8. according to claim 6 or 7 described DSSCs, it is characterized in that: said transparent flexible substrate is PET or dimethyl silicone polymer, and the thickness of said transparent flexible substrate is 30-100 μ m.
9. prepare the method for each said DSSC among the claim 6-8, comprise the steps:
1) places dye molecule solution to soak claim 1 or 2 said smooth anodes, make zinc oxide nano-wire array or the abundant absorbing dye molecule of aluminum doped zinc oxide nano-wire array in the light anode;
2) the light anode that takes out after handling is rinsed the dye molecule of its surface physics absorption well with absolute ethyl alcohol;
3) light anode that dye sensitization is good and to electrode package between double-deck transparent flexible substrate, said smooth anode with electrode is placed relatively and at interval;
4) the electrolyte filling is rushed between the double-deck transparent flexible substrate, obtained said DSSC.
10. method according to claim 9 is characterized in that: be platinum filament or surperficial platinum plating wire to electrode described in the step 3), its diameter is 10-500 μ m;
Said to the said smooth anode of electrode with the electrode gap opposing parallel is arranged, spacing is 10-500 μ m;
The substrate of transparent flexible described in the step 4) is PET or dimethyl silicone polymer, and the thickness of said transparent flexible substrate is 30-100 μ m.
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| CN103093963A (en) * | 2013-01-28 | 2013-05-08 | 北京大学 | Flexible and light dye-sensitized solar cell with double faces specular |
| CN105355437A (en) * | 2015-11-21 | 2016-02-24 | 河南师范大学 | Preparation method of flexible sensitized solar cell counter electrode |
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