CN103280326A - Solar cell based on natural organic dye and TiO2 nano array - Google Patents

Solar cell based on natural organic dye and TiO2 nano array Download PDF

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Publication number
CN103280326A
CN103280326A CN2013102241544A CN201310224154A CN103280326A CN 103280326 A CN103280326 A CN 103280326A CN 2013102241544 A CN2013102241544 A CN 2013102241544A CN 201310224154 A CN201310224154 A CN 201310224154A CN 103280326 A CN103280326 A CN 103280326A
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solar cell
tio
electrode
organic dye
array
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陈延学
李逸坦
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Shandong University
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Shandong University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention aims at a serious electronic dissipation process brought by a multihole thin film solar cell at present. Natural organic dye is utilized to be combined with a TiO2 monocrystal nano array to assemble a natural organic dye-sensitized solar cell of a novel structure. The invention provides a method including that a water hot method is used for manufacturing 3D nanostructured materials and radix ophiopogonis fruits and purple sweet potatoes are fully utilized to serve as novel sensitized materials to be used in the sensitized solar cell. Therefore, a possibility is provided for the natural organic dye to replace existing artificial organic dye to serve as sensitizer of the solar cell.

Description

Based on natural organic dyestuff and TiO 2The solar cell of nano-array
Technical field
The present invention relates to utilize natural organic dyestuff and in conjunction with TiO 2The natural organic dye sensitized solar cell of nanometer monocrystalline array assembling new structure belongs to solar cell and makes the field.
Background technology
China's total energy consumption rapid growth since new century, huge total energy consumption have brought heavy pressure for " energy security supply system " and " environmental protection work " of China.Nearly 90% is traditional fossil energy in China's energy consumption structure, a large amount of greenhouse gas, poisonous and harmful substance and dust have been discharged, so that when this year, the Winter-Spring replaced, the serious haze weather that the nationwide continues the several months had had a strong impact on the healthy of people and life order.Government has successively put into effect " plan of solar energy roof " and " golden sun engineering ", nearest " 12 planning " has proposed to adjust the policy of optimizing energy resource structure, make up the strategic system of the modern energy industry of safety, stable, economic, cleaning, the solar energy resources clean environment firendly, reserves are big, time is permanent, occupies a position of strategic importance therein.Solar cell power generation is the main mode that solar energy resources utilizes, but China's solar cell research and development at present and innovation ability weakness, photovoltaic industry is not set up comprehensive research and development and innovation system as yet, and crucial production equipment and production line be main dependence on import also.
Traditional monocrystalline silicon, polysilicon solar cell are expensive, are difficult to popularize.In emerging solar cell, quantum dot sensitized solar energy has caused the extensive concern in the world with the advantage that its battery life is long, the energy recovery cycle is short, cost is low, be easy to make.
At present, experimental group both domestic and external, all in the research of carrying out sensitization solar battery, but these researchs all concentrate on artificial synthetic dyestuffs and inorganic semiconductor material.Though these materials can obtain comparatively desirable photoelectric efficiency, its production cost is extremely high, is example with N719, and the market price of present this dyestuff is about 15000 yuan/g.There is the shortcoming of the deficiency of stability in this based sensitisers simultaneously, makes it also to be difficult to far away be applied to produce.Aspect novel sensitization solar battery, the experimental group that has has been put into sight on the natural organic dyestuff that is easy to obtain.This kind natural dye is with low cost, is easy to obtain, and has application prospect well as the byproduct of a lot of agricultural productions.
The research of DSSC mainly concentrates on the porous membrane solar cell, and the electronics dissipation process that its porous electrode brings becomes the bottleneck of further raising photoelectric properties.Hope is by seeking the substrate of efficient stable, and the sensitizer of economic environmental protection improves the photoelectric properties of sensitization solar battery.All research at present all concentrates on natural organic dyestuff and poriferous titanium dioxide nano thin-film is combined, both at home and abroad also not with its relevant report that combines with the titanium dioxide single crystalline nano-array.
Summary of the invention
The present invention with purple potato and the tuber of dwarf lilyturf fruit extract be applied to TiO 2The nanometer monocrystalline array, the natural organic dye sensitized solar cell of assembling new structure improves Solar cell performance.This battery energy-conserving and environment-protective, with low cost.With respect to traditional film sensitization solar battery, this TiO 2The nanometer monocrystalline array substrate has reduced the electronics dissipation process, improves photoelectric efficiency.This kind solar cell is carried out the test of photoelectric properties, obtained photoelectric efficiency and be respectively 1.2% and 1.15% solar cell.
The technical solution used in the present invention is as follows:
A kind of method for preparing sensitization solar battery is characterized in that: electrode is by with TiO 2Sensitization obtains the nanometer monocrystalline array in the sensitizer that is obtained by natural dye, and its step comprises:
(1) preparation TiO 2The nanometer monocrystalline array;
(2) from crops, extract natural dye liquor, prepare natural organic sensitizer;
(3) with TiO 2Nano-array immerses in the sensitizer of previous step acquisition, makes the light anode;
(4) respectively with the anode of ZnO nanometer monocrystalline array as battery, that the Pt magnetron sputtering is on glass as negative electrode at FTO, encapsulant is attached on the Pt electrode, Pt electrode and sample conductive side inwardly are sealed, injection polysulphide polymer electrolyte between the electrode.
Preferably, described crops are fruit and the purple potato tuber of dwarf lilyturf.
Preferably, described encapsulant is the encapsulant that comprises the 60 μ m in 3 * 3mm aperture.
Preferably, described electrolyte is stirred under 80 ℃ of conditions by the NaOH of the vulcanized sodium of 1 mole every liter sulphur and 1 mole every liter and 0.1 mole every liter and made in 2 hours.
Description of drawings
Fig. 1 is the schematic diagram of the scanning electron microscopy of single crystal titanium dioxide nano-array;
Fig. 2 be purple potato and the tuber of dwarf lilyturf fruit extracting solution optical absorption spectra;
Fig. 3 is based on TiO 2The organic dye sensitized solar cell of nano-array with based on TiO 2The photoelectric curve of the organic dye sensitized solar cell of nano thin-film relatively.
Embodiment
Method of the present invention specifically may further comprise the steps:
(1) preparation of substrate
Get the deionized water of 50mL, 40mL concentrated hydrochloric acid (36-38%(weight) hydrochloric acid, traditional Chinese medicines) and 350 μ L titanium tetrachloride (titanium tetrachloride, 99.9%, Aladdin) wiring solution-formings, the synthetic TiO of conduct under hydrothermal condition 2The raw material of the excellent array of rice.In the process of obtain solution, in the end a step adds titanium tetrachloride.The FTO ultrasonic wave was cleaned 10 minutes, be positioned in the polytetrafluoroethylcontainer container FTO is angled then, conductive side down.Solution is injected, under 180 ℃, carry out 2 hours synthetic reaction.After synthetic, autoclave is cooled to room temperature, and FTO is taken out, thoroughly wash with deionized water, and at open air drying.Nano thin-film utilizes the flow casting molding technology that nano thin-film is grown on the FTO.Then, TiO 2Film was annealed 30 minutes in the Oxygen Flow of 500 ° of C, then at room temperature was statically placed in the TiCl of 0.02M 4In the aqueous solution 6 hours.
(2) natural organic sensitizer obtains
The tuber of dwarf lilyturf, fruit was not usually because there being using value to go out of use; Purple potato is planted on a large scale as common crops.With the tuber of dwarf lilyturf fruit and purple potato mix with deionized water respectively to squeeze and obtain natural dye liquor, place 4 ℃ refrigerator to store dye liquor, avoid exposing in the sun.
(3) preparation of electrode
In the environment of dark, with TiO 2Nano-array and TiO 2Film immerses in the dye liquor and to make the light anode in 8 hours.Respectively the assembling of 4 kinds of nanostructures is the anode of battery, magnetron sputtering at the thick Pt electrode of FTO about 20nm on glass as negative electrode.The 60 μ m encapsulants that will comprise 3 * 3mm aperture are attached on the Pt electrode.Pt electrode and sample conductive side inwardly are sealed.Injection polysulphide polymer electrolyte between the electrode.Electrolyte is stirred under 80 ℃ of conditions by the NaOH of the vulcanized sodium of 1 mole every liter sulphur and 1 mole every liter and 0.1 mole every liter and made in 2 hours.
Utilize scanning electron microscopy to observe the nanostructure characteristic of sample, and use x-ray diffractometer (XD-3, PG Instr Ltd.) (λ=0.154nm) checks their crystal structure with the sweep speed of 2 ° of per minutes, as shown in Figure 1 with the CuK alpha ray.The voltage and current of X-ray tube is separately positioned on 40KV and 30mA.Use ultraviolet-visible spectrophotometer (TU-1900, PG Instr Ltd.) test to obtain the transmitted spectrum of sample.
Use Keithley2400 digital source and the solar simulator with AM1.5 to illuminate solar cell, test is the photoelectric current-voltage relationship under 1 the solar illumination (100mWcm-2) in the luminous intensity of using solar simulator (model 94022A, Newport) to produce.
The tuber of dwarf lilyturf, the optical absorption spectra of fruit and purple potato extract drew, and wave-length coverage is indicated in Fig. 2 at the corresponding absorption spectra curve between the 400-800nm.The tuber of dwarf lilyturf, the absorption spectra of fruit showed that wavelength an absworption peak occurred at 550nm, and showing has good absorptivity in visible-range.Same, the absorption spectra of purple potato shows a slight absworption peak in close scope.Fig. 2 shows these two kinds of dyestuffs good absorptivity in visible-range, and this is conducive to the assembling of solar cell and the raising of photoelectric efficiency.
Based on TiO 2Nano-array and TiO 2The photoelectric curve of the organic dye sensitized solar cell of nano thin-film as shown in Figure 3.A1, A2 are based on TiO 2The photoelectric curve of the organic dye sensitized solar cell of nano-array, B1, B2 are based on TiO 2The photoelectric curve of the organic dye sensitized solar cell of nano thin-film.Compared to based on TiO 2Film is with the organic dye sensitized TiO that the tuber of dwarf lilyturf, fruit extracted 2The solar cell of nano-array has better performance aspect photoelectric efficiency.Short circuit current is by 2.7mA/cm 2Be increased to 5.2mA/cm 2Open circuit voltage is increased to 0.42V by 0.37V; Photoelectric efficiency is 1.2%, and 155% lifting is arranged.In the solar cell of purple potato extract sensitization, short circuit current is increased to 5mA/cm by 3.5mA/cm2 2Open circuit voltage is increased to 0.47V by 0.39V; Photoelectric efficiency is 1.15%, and 91% lifting is arranged.
Natural organic dyestuff and TiO 2Nano array structure excellent performance on photoelectric property can be summed up as following reason: (1) TiO 2Band gap filled by natural organic dyestuff, cause higher current density; (2) TiO of direct growth on the FTO electro-conductive glass 2Nanometer stick array has been avoided TiO 2The film particle frequency hopping phenomenon on the polycrystalline crystal boundary that mostly occurs; (3) TiO 2Nanometer rods can form an open relatively structure, has improved and porous TiO 2The diffusion problem that oxidation-reduction pair in the optical-fiber network is relevant.
The present invention prove with the hydro-thermal method make the 3D nano structural material and take full advantage of the tuber of dwarf lilyturf fruit and purple potato be used for the possibility of sensitization solar battery as new sensitizing dyestuff.The tuber of dwarf lilyturf fruit extract more stable than purple potato, may for replacing existing artificial organic dyestuff to provide.
Though above-mentionedly by reference to the accompanying drawings the specific embodiment of the present invention is described; but be not the restriction to the invention protection range; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various modifications that creative work can make or distortion still in protection scope of the present invention.

Claims (4)

1. method for preparing sensitization solar battery is characterized in that: electrode is by with TiO 2Sensitization obtains the nanometer monocrystalline array in the sensitizer that is obtained by natural dye, and its step comprises:
(1) preparation TiO 2The nanometer monocrystalline array;
(2) from crops, extract natural dye liquor, prepare natural organic sensitizer;
(3) with TiO 2Nano-array immerses in the sensitizer of previous step acquisition, makes the light anode;
(4) respectively with the anode of ZnO nanometer monocrystalline array as battery, that the Pt magnetron sputtering is on glass as negative electrode at FTO, encapsulant is attached on the Pt electrode, Pt electrode and sample conductive side inwardly are sealed, injection polysulphide polymer electrolyte between the electrode.
2. the method for preparing sensitization solar battery as claimed in claim 1 is characterized in that: described crops are fruit and the purple potato tuber of dwarf lilyturf.
3. the method for preparing sensitization solar battery as claimed in claim 1 is characterized in that: described encapsulant is the encapsulant of the 60 μ m that comprise 3 * 3mm aperture.
4. the method for preparing sensitization solar battery as claimed in claim 1 is characterized in that: described electrolyte is stirred under 80 ℃ of conditions by the NaOH of the vulcanized sodium of 1 mole every liter sulphur and 1 mole every liter and 0.1 mole every liter and made in 2 hours.
CN2013102241544A 2013-06-06 2013-06-06 Solar cell based on natural organic dye and TiO2 nano array Pending CN103280326A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100006134A1 (en) * 2004-03-19 2010-01-14 Nippon Oil Corporation Nanotube-shaped titania and process for producing the same
CN102157265A (en) * 2011-03-21 2011-08-17 中国科学院半导体研究所 Composite electrode of dye sensitized solar cell and preparation method thereof
US20120125439A1 (en) * 2008-10-16 2012-05-24 Consiglio Nazionale Delle Ricerche Photoelectrochemical Solar Cell Comprising Sensitizing Anthocyanin And Betalain Dyes Of Vegetal Or Synthetic Origin, Or Mixtures Thereof
CN102832051A (en) * 2012-10-07 2012-12-19 复旦大学 Preparation method for photoanode of dye-sensitized solar battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100006134A1 (en) * 2004-03-19 2010-01-14 Nippon Oil Corporation Nanotube-shaped titania and process for producing the same
US20120125439A1 (en) * 2008-10-16 2012-05-24 Consiglio Nazionale Delle Ricerche Photoelectrochemical Solar Cell Comprising Sensitizing Anthocyanin And Betalain Dyes Of Vegetal Or Synthetic Origin, Or Mixtures Thereof
CN102157265A (en) * 2011-03-21 2011-08-17 中国科学院半导体研究所 Composite electrode of dye sensitized solar cell and preparation method thereof
CN102832051A (en) * 2012-10-07 2012-12-19 复旦大学 Preparation method for photoanode of dye-sensitized solar battery

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Application publication date: 20130904