CN103400700A - Dye-sensitized solar cell based on binary low-platinum alloy counter electrode and preparation method and applications thereof - Google Patents
Dye-sensitized solar cell based on binary low-platinum alloy counter electrode and preparation method and applications thereof Download PDFInfo
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- CN103400700A CN103400700A CN201310342851XA CN201310342851A CN103400700A CN 103400700 A CN103400700 A CN 103400700A CN 201310342851X A CN201310342851X A CN 201310342851XA CN 201310342851 A CN201310342851 A CN 201310342851A CN 103400700 A CN103400700 A CN 103400700A
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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
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Abstract
The invention provides a dye-sensitized solar cell based on a binary low-platinum alloy counter electrode and a preparation method and applications thereof. Specifically, alloy forms the alloy counter electrode on an FTO (Fluorine-doped Tin Oxide) or ITO (Indium Tin Oxide) conductive glass substrate through electrochemical deposition. The dye-sensitized solar cell fully utilizes the low cost, high conductivity, stability and good electro-catalytic performance of the alloy, conducts a reasonable element proportioning design, optimizes the formation of the platinum alloy counter electrode, and increases the electro-catalytic performance of the platinum alloy counter electrode. The binary low-platinum alloy counter electrode has high electrode stability, good conductivity and good electro-catalytic performance. The preparation method is simple and easy and has low cost and a large improved space. The assembled dye-sensitized solar cell has high photoelectric conversion efficiency and good reducibility of electrolyte.
Description
Technical field
The invention belongs to new material technology and technical field of new energies, be specifically related to based on the low platinum alloy of binary DSSC of electrode and its preparation method and application.
Background technology
DSSC is a kind of by the nanocrystalline smooth anode of poriferous titanium dioxide, sensitizing dyestuff, I
-/ I
3 -Electrolyte and to what electrode formed, solar energy can be changed into the electrochemical appliance of electric energy.
Dye sensitized nano crystal salar battery is a kind of model electrochemical solar cell of developing in 90 generations of twentieth century, has the characteristics such as cost is low, preparation technology is easy, good stability, environmental friendliness, has a good application prospect.Yet the platinum of dye sensitized nano crystal salar battery use at present is higher to the electrode price, is unfavorable for the business application of this solar cell.
Summary of the invention
The object of the present invention is to provide based on the low platinum alloy of binary DSSC of electrode and its preparation method and application, the present invention can obtain that cost is low, good stability, the low platinum alloy of binary that catalytic performance is good be to electrode, make it can replace in dye sensitized nano crystal salar battery platinum commonly used to electrode, promote the practical of dye sensitized nano crystal salar battery, accelerate the industrialization process of dye sensitized nano crystal salar battery, have important practical value and economic worth.
For achieving the above object, the present invention is achieved by the following technical solutions:
, based on the preparation method of low platinum alloy to the DSSC of electrode, comprise the following steps:
(1), compound concentration is the aqueous metal salt of 1 ~ 5 mol/L, concentration is that 1 ~ 8 mmol/L chloroplatinic acid aqueous solution and concentration are the hydrochloride aqueous solution of 1 ~ 2 mol/L;
(2), by volume be aqueous metal salt: chloroplatinic acid aqueous solution: hydrochloride aqueous solution: water=1 ~ 10:1 ~ 5:1 ~ 5:10 ~ 100 are mixed with uniform reaction solution;
(3), put into the FTO that cleans up or ITO electro-conductive glass matrix in the reaction solution in step (2) as work electrode, take the Ag/AgCl electrode as reference electrode, take the Pt electrode as electrode assembling is become three-electrode system, adopt electrochemical deposition method to hang down platinum alloy to electrode in the uniform binary of electro-conductive glass matrix surface deposition, with this alloy to electrode through washing, drying, obtain the low platinum alloy of dry binary to electrode;
(4), prepare colloidal tio 2, colloidal tio 2 is applied on FTO or ITO electro-conductive glass matrix, controlling thickness is 5～15 μ m, through 450 ° of C calcinings, prepares porous titanium dioxide thin-film;
(5), will form the dye sensitization titanium dioxide photo anode in the dyestuff of titanium deoxid film immersion 0.2～0.5 mmol/L of step (4) preparation;
(6), with the dye sensitization titanium dioxide photo anode combination of the alloy of step (3) preparation to electrode and step (5) preparation, and add liquid electrolyte assembling DSSC in centre.
Further, the metal in described step (1) is a kind of in iron, nickel or cobalt.
Further, the slaine in described step (1) is metal villaumite or nitrate.
Further, the electrochemical deposition method that adopts in described step (3) is constant voltage method, galvanostatic method or cyclic voltammetry.
Further, in described step (4), colloidal tio 2 forms by conventional Sol-Hydrothermal legal system is standby.
Further, the dyestuff in described step (5) is N719 or N3 dyestuff.
Further, the liquid electrolyte in described step (6) is comprised of the acetonitrile solution of 0.01 ~ 0.06 mol/L iodine, 0.08 ~ 0.12 mol/L lithium iodide, 0.4 ~ 0.8 mol/L tetrabutylammonium iodide and 0.4 ~ 0.6 mol/L 4-tert .-butylpyridine.
The present invention also provide utilize that described preparation method makes based on the DSSC of the low platinum alloy of binary to electrode.
Further, the open circuit voltage of described DSSC is that 700～800 mV, short circuit current are 16～22 mAcm
-2, fill factor, curve factor is 0.6～0.7, photoelectric conversion efficiency is 7.5～11%.
The present invention also provide described based on the low platinum alloy of binary to the DSSC of electrode in the application as in battery component and power station.
Compared with prior art, advantage of the present invention and technique effect are: the present invention takes full advantage of low cost, high conductivity and the stability of alloy and good electrocatalysis, and carry out rational element proportion design, and optimize the composition of low platinum alloy to electrode, improve its electrocatalysis characteristic.The low platinum alloy of binary of the present invention is high to electrode stability, conductivity good, electro catalytic activity is superior, the preparation method is simple and easy to do, with low cost, room for improvement is large, and the photoelectric conversion efficiency of the DSSC of assembling is high, electrolytical Well-recovered.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
Of the present inventionly based on the preparation method of the low platinum alloy of binary to the DSSC of electrode, comprise the following steps:
1, the preparation of reaction solution: compound concentration is the aqueous metal salt of 1 ~ 5 mol/L, concentration is the chloroplatinic acid aqueous solution of 1 ~ 8 mmol/L, concentration is 1 ~ 2 mol/L hydrochloride aqueous solution, described aqueous metal salt is a kind of in molysite, nickel salt or cobalt salt, and described slaine is metal villaumite or nitrate.
2, be by volume described aqueous metal salt: chloroplatinic acid aqueous solution: hydrochloride aqueous solution: the ratio of water=1 ~ 10:1 ~ 5:1 ~ 5:10 ~ 100 is mixed with uniform reaction solution.
3, put into the FTO that cleans up or ITO electro-conductive glass matrix in the reaction solution in step (2) as work electrode, take the Ag/AgCl electrode as reference electrode, take platinum electrode as electrode assembling is become three-electrode system, adopt the electrochemical deposition techniques such as potentiostatic method, galvanostatic method, cyclic voltammetry, in the uniform binary of pretreated electro-conductive glass matrix surface deposition, hang down platinum alloy to electrode.With the low platinum alloy of this binary to electrode through washing, drying, finally be prepared into the low platinum alloy of dry binary to electrode.
4, the preparation of titanium deoxid film: the standby colloidal tio 2 of conventional Sol-Hydrothermal legal system is applied on FTO or ITO electro-conductive glass matrix, and controlling thickness is 5 ~ 10 μ m,, through 450 ℃ of calcining 30 min, prepares the titanium dioxide nanocrystalline film.
5, the preparation of dye sensitization titanium dioxide photo anode: 24 H-shapeds in the N719 dyestuff (or N3 dyestuff) of titanium deoxid film immersion 0.3 mmol/L of step (4) preparation are become the dye sensitization titanium dioxide photo anode.
6, the assembling of DSSC: the low platinum alloy of binary of step 3 and step 5 preparation is made up electrode and dye sensitization titanium dioxide photo anode, and in centre, add liquid electrolyte to be assembled into DSSC.Described liquid electrolyte is comprised of the acetonitrile solution of 0.01 ~ 0.06 mol/L iodine, 0.08 ~ 0.12 mol/L lithium iodide, 0.4 ~ 0.8 mol/L tetrabutylammonium iodide and 0.4 ~ 0.6 mol/L 4-tert .-butylpyridine.
By said method, can obtain open circuit voltage is 700～800 mV, and short circuit current is 16～22 mAcm
-2, fill factor, curve factor is 0.6～0.7, photoelectric conversion efficiency is that the low platinum alloy of 7.5～11% binary is to the two-sided DSSC of electrode base.DSSC of the present invention can be used as battery component and power plant application.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment, the present invention is had been described in detail, for the person of ordinary skill of the art, still can modify to the technical scheme that previous embodiment is put down in writing, perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of the present invention's technical scheme required for protection.
Claims (10)
1., based on the preparation method of low platinum alloy to the DSSC of electrode, it is characterized in that comprising the following steps:
(1), compound concentration is the aqueous metal salt of 1 ~ 5 mol/L, concentration is that 1 ~ 8 mmol/L chloroplatinic acid aqueous solution and concentration are the hydrochloride aqueous solution of 1 ~ 2 mol/L;
(2), by volume be aqueous metal salt: chloroplatinic acid aqueous solution: hydrochloride aqueous solution: water=1 ~ 10:1 ~ 5:1 ~ 5:10 ~ 100 are mixed with uniform reaction solution;
(3), put into the FTO that cleans up or ITO electro-conductive glass matrix in the reaction solution in step (2) as work electrode, take the Ag/AgCl electrode as reference electrode, take the Pt electrode as electrode assembling is become three-electrode system, adopt electrochemical deposition method to hang down platinum alloy to electrode in the uniform binary of electro-conductive glass matrix surface deposition, with this alloy to electrode through washing, drying, obtain the low platinum alloy of dry binary to electrode;
(4), prepare colloidal tio 2, colloidal tio 2 is applied on FTO or ITO electro-conductive glass matrix, controlling thickness is 5～15 μ m, through 450 ° of C calcinings, prepares porous titanium dioxide thin-film;
(5), will form the dye sensitization titanium dioxide photo anode in the dyestuff of titanium deoxid film immersion 0.2～0.5 mmol/L of step (4) preparation;
(6), with the dye sensitization titanium dioxide photo anode combination of the alloy of step (3) preparation to electrode and step (5) preparation, and add liquid electrolyte assembling DSSC in centre.
2. according to claim 1 based on the preparation method of low platinum bianry alloy to the DSSC of electrode, it is characterized in that: the metal in described step (1) aqueous metal salt is a kind of in iron, nickel or cobalt.
3. according to claim 1 based on the preparation method of low platinum bianry alloy to the DSSC of electrode, it is characterized in that: the slaine in described step (1) is metal villaumite or nitrate.
4. according to claim 1 based on the preparation method of the low platinum alloy of binary to the DSSC of electrode, it is characterized in that: the electrochemical deposition method that adopts in described step (3) is constant voltage method, galvanostatic method or cyclic voltammetry.
5. according to claim 1 based on the preparation method of the low platinum alloy of binary to the DSSC of electrode, it is characterized in that: in described step (4), colloidal tio 2 forms by the Sol-Hydrothermal legal system is standby.
6. according to claim 1 based on the preparation method of the low platinum alloy of binary to the DSSC of electrode, it is characterized in that: the dyestuff in described step (5) is N719 or N3 dyestuff.
7. according to claim 1 based on the preparation method of the low platinum alloy of binary to the DSSC of electrode, it is characterized in that: the liquid electrolyte in described step (6) is comprised of the acetonitrile solution of 0.01 ~ 0.06 mol/L iodine, 0.08 ~ 0.12 mol/L lithium iodide, 0.4 ~ 0.8 mol/L tetrabutylammonium iodide and 0.4 ~ 0.6 mol/L 4-tert .-butylpyridine.
8. what according to claim 1 ~ 7 described preparation methods of any one made hangs down the DSSC of platinum alloy to electrode based on binary.
9. according to claim 8 based on the DSSC of the low platinum alloy of binary to electrode, it is characterized in that: the open circuit voltage of described DSSC is that 700～800 mV, short circuit current are that 16～22 mAcm-2, fill factor, curve factor are 0.6～0.7, photoelectric conversion efficiency is 7.5～11%.
According to claim 8 based on the low platinum alloy of binary to the DSSC of electrode in the application as in battery component and power station.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895377A (en) * | 2016-06-07 | 2016-08-24 | 中国海洋大学 | All-weather solar cell capable of realizing power generation at night, and preparation method and application for all-weather solar cell |
| CN106057473A (en) * | 2016-07-29 | 2016-10-26 | 中国海洋大学 | All-weather mesoporous sensitized solar cell based on graphene quantum dots and preparation method and application thereof |
| CN106158391A (en) * | 2016-08-19 | 2016-11-23 | 中国海洋大学 | A kind of DSSC of round-the-clock generating and its preparation method and application |
| CN106206032A (en) * | 2016-06-24 | 2016-12-07 | 中国海洋大学 | Graphene quantum dot prepared by a kind of natural macromolecular and the application in preparing quantum dot sensitization solar battery thereof |
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| CN1770401A (en) * | 2005-09-30 | 2006-05-10 | 清华大学 | Process for preparing mesoporous metal counter electrode for dye-sensitized solar cell |
| JP5216411B2 (en) * | 2008-05-13 | 2013-06-19 | 株式会社フジクラ | Photoelectric conversion element |
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Patent Citations (2)
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|---|---|---|---|---|
| CN1770401A (en) * | 2005-09-30 | 2006-05-10 | 清华大学 | Process for preparing mesoporous metal counter electrode for dye-sensitized solar cell |
| JP5216411B2 (en) * | 2008-05-13 | 2013-06-19 | 株式会社フジクラ | Photoelectric conversion element |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895377A (en) * | 2016-06-07 | 2016-08-24 | 中国海洋大学 | All-weather solar cell capable of realizing power generation at night, and preparation method and application for all-weather solar cell |
| CN105895377B (en) * | 2016-06-07 | 2018-06-22 | 中国海洋大学 | A kind of all-weather solar battery that can be generated electricity at night and its preparation method and application |
| CN106206032A (en) * | 2016-06-24 | 2016-12-07 | 中国海洋大学 | Graphene quantum dot prepared by a kind of natural macromolecular and the application in preparing quantum dot sensitization solar battery thereof |
| CN106057473A (en) * | 2016-07-29 | 2016-10-26 | 中国海洋大学 | All-weather mesoporous sensitized solar cell based on graphene quantum dots and preparation method and application thereof |
| CN106158391A (en) * | 2016-08-19 | 2016-11-23 | 中国海洋大学 | A kind of DSSC of round-the-clock generating and its preparation method and application |
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