CN103400700B - DSSC based on the low platinum alloy of binary to electrode and its preparation method and application - Google Patents
DSSC based on the low platinum alloy of binary to electrode and its preparation method and application Download PDFInfo
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- CN103400700B CN103400700B CN201310342851.XA CN201310342851A CN103400700B CN 103400700 B CN103400700 B CN 103400700B CN 201310342851 A CN201310342851 A CN 201310342851A CN 103400700 B CN103400700 B CN 103400700B
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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
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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
- 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
Abstract
The invention provides DSSC to electrode and its preparation method and application based on the low platinum alloy of binary, specifically alloy is formed to alloy to electrode by being electrochemically-deposited on FTO or ITO electro-conductive glass matrix, the present invention makes full use of low cost, high conductivity and the stability of alloy and good electrocatalysis, and carry out rational element proportion design, 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, electrical conductivity good, electro catalytic activity is superior, preparation method is simple and easy to do, with low cost, room for improvement is large, and the photoelectric transformation efficiency of the DSSC of assembling is high, electrolytical Well-recovered.
Description
Technical field
The invention belongs to new material technology and technical field of new energies, be specifically related to DSSC to electrode and its preparation method and application based on the low platinum alloy of binary.
Background technology
DSSC is a kind of by the nanocrystalline smooth anode of poriferous titanium dioxide, sensitizing dyestuff, I-/I3 -Electrolyte and the electrochemical appliance that solar energy can be changed into electric energy to electrode composition.
Dye sensitized nano crystal salar battery is a kind of model electrochemical solar cell of developing in 90 generations of twentieth century, has the features such as cost is low, preparation technology is easy, good stability, environmental friendliness, has a good application prospect. But the platinum that dye sensitized nano crystal salar battery uses is at present higher to electrode price, be unfavorable for the business application of this solar cell.
Summary of the invention
The object of the present invention is to provide DSSC to electrode and its preparation method and application based on the low platinum alloy of binary, 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 conventional platinum to electrode, promote the practical of dye sensitized nano crystal salar battery, the industrialization process that accelerates dye sensitized nano crystal salar battery, has important practical value and economic worth.
For achieving the above object, the present invention is achieved by the following technical solutions:
The preparation method of the DSSC based on low platinum alloy to electrode, comprises the following steps:
(1), the compound concentration aqueous metal salt that is 1 ~ 5mol/L, concentration is the hydrochloride aqueous solution that 1 ~ 8mmol/L chloroplatinic acid aqueous solution and concentration are 1 ~ 2mol/L;
(2) be aqueous metal salt, by volume: chloroplatinic acid aqueous solution: hydrochloride aqueous solution: water=1 ~ 10:1 ~ 5:1 ~ 5:10 ~ 100, are mixed with uniform reaction solution;
(3), in the reaction solution in step (2), put into the FTO that cleans up or ITO electro-conductive glass matrix as working electrode, taking Ag/AgCl electrode as reference electrode, taking Pt electrode as electrode assembling is become to three-electrode system, adopt electrochemical deposition method to deposit the low platinum alloy of uniform binary to electrode at electro-conductive glass matrix surface, by this alloy to electrode through washing, dry, 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, prepares porous titanium dioxide thin-film through 450 ° of C calcining;
(5) in the dyestuff of the titanium deoxid film immersion 0.2～0.5mmol/L, being prepared by step (4), form dye sensitization titanium dioxide photo anode;
(6), alloy prepared by step (3) dye sensitization titanium dioxide photo anode combination prepared by electrode and step (5), and add liquid electrolyte assembling DSSC in centre.
Further, the metal in described step (1) is the one in iron, nickel or cobalt.
Further, the slaine in described step (1) is metal villaumite or nitrate.
Further, the electrochemical deposition method adopting in described step (3) is constant voltage method, galvanostatic method or cyclic voltammetry.
Further, in described step (4), colloidal tio 2 is prepared from by conventional Sol-Hydrothermal method.
Further, the dyestuff in described step (5) is N719 or N3 dyestuff.
Further, the liquid electrolyte in described step (6) is made up of the acetonitrile solution of 0.01 ~ 0.06mol/L iodine, 0.08 ~ 0.12mol/L lithium iodide, 0.4 ~ 0.8mol/L tetrabutylammonium iodide and 0.4 ~ 0.6mol/L4-tert .-butylpyridine.
The present invention also provides the DSSC to electrode based on the low platinum alloy of binary that utilizes described preparation method to make.
Further, the open-circuit voltage of described DSSC is that 700～800mV, short circuit current are 16～22mAcm-2, fill factor, curve factor is 0.6～0.7, photoelectric transformation 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 makes full use 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, electrical conductivity good, electro catalytic activity is superior, preparation method is simple and easy to do, with low cost, room for improvement is large, and the photoelectric transformation efficiency of the DSSC of assembling is high, electrolytical Well-recovered.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical scheme of the present invention is described in further detail.
Embodiment 1
It is of the present invention that based on the low platinum alloy of binary, the preparation method of the DSSC to electrode comprises the following steps:
1, the preparation of reaction solution: the aqueous metal salt that compound concentration is 1 ~ 5mol/L, concentration is the chloroplatinic acid aqueous solution of 1 ~ 8mmol/L, concentration is 1 ~ 2mol/L hydrochloride aqueous solution, described aqueous metal salt is the one 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, in the reaction solution in step (2), put into the FTO that cleans up or ITO electro-conductive glass matrix as working electrode, taking Ag/AgCl electrode as reference electrode, taking platinum electrode as electrode assembling is become to three-electrode system, adopt the electrochemical deposition techniques such as potentiostatic method, galvanostatic method, cyclic voltammetry, deposit the low platinum alloy of uniform binary to electrode at pretreated electro-conductive glass matrix surface. By low this binary platinum alloy to electrode through washing, dry, be finally 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 DEG C of calcining 30min, prepares titanium dioxide nanocrystalline film.
5, the preparation of dye sensitization titanium dioxide photo anode: the middle 24h of N719 dyestuff (or N3 dyestuff) that titanium deoxid film prepared by step (4) immerses 0.3mmol/L forms dye sensitization titanium dioxide photo anode.
6, the assembling of DSSC: the low platinum alloy of binary prepared by step 3 and step 5 is to electrode and the combination of dye sensitization titanium dioxide photo anode, and add liquid electrolyte to be assembled into DSSC in centre. Described liquid electrolyte is made up of the acetonitrile solution of 0.01 ~ 0.06mol/L iodine, 0.08 ~ 0.12mol/L lithium iodide, 0.4 ~ 0.8mol/L tetrabutylammonium iodide and 0.4 ~ 0.6mol/L4-tert .-butylpyridine.
By said method, can obtain open-circuit voltage is 700～800mV, and short circuit current is 16～22mAcm-2, fill factor, curve factor is 0.6～0.7, the low platinum alloy of binary that photoelectric transformation efficiency is 7.5～11% 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 the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these amendments or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (8)
1. the preparation method of the DSSC to electrode based on the low platinum alloy of binary, is characterized in that comprising the following steps:
(1), the compound concentration aqueous metal salt that is 1 ~ 5mol/L, concentration is the hydrochloride aqueous solution that 1 ~ 8mmol/L chloroplatinic acid aqueous solution and concentration are 1 ~ 2mol/L; Metal in described aqueous metal salt is the one in iron, nickel or cobalt, and described slaine is metal villaumite or nitrate;
(2) be aqueous metal salt, by volume: chloroplatinic acid aqueous solution: hydrochloride aqueous solution: water=1 ~ 10:1 ~ 5:1 ~ 5:10 ~ 100, are mixed with uniform reaction solution;
(3), in the reaction solution in step (2), put into the FTO that cleans up or ITO electro-conductive glass matrix as working electrode, taking Ag/AgCl electrode as reference electrode, taking Pt electrode as electrode assembling is become to three-electrode system, adopt electrochemical deposition method to deposit the low platinum alloy of uniform binary to electrode at electro-conductive glass matrix surface, by this alloy to electrode through washing, dry, 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, prepares porous titanium dioxide thin-film through 450 ° of C calcining;
(5) in the dyestuff of the titanium deoxid film immersion 0.2～0.5mmol/L, being prepared by step (4), form dye sensitization titanium dioxide photo anode;
(6), alloy prepared by step (3) dye sensitization titanium dioxide photo anode combination prepared by electrode and step (5), and add liquid electrolyte assembling DSSC in centre.
According to claim 1 based on the low platinum alloy of binary the preparation method of the DSSC to electrode, it is characterized in that: the electrochemical deposition method adopting in described step (3) is constant voltage method, galvanostatic method or cyclic voltammetry.
According to claim 1 based on the low platinum alloy of binary the preparation method of the DSSC to electrode, it is characterized in that: in described step (4), colloidal tio 2 is prepared from by Sol-Hydrothermal method.
According to claim 1 based on the low platinum alloy of binary the preparation method of the DSSC to electrode, it is characterized in that: the dyestuff in described step (5) is N719 or N3 dyestuff.
According to claim 1 based on the low platinum alloy of binary the preparation method of the DSSC to electrode, it is characterized in that: the liquid electrolyte in described step (6) is made up of the acetonitrile solution of 0.01 ~ 0.06mol/L iodine, 0.08 ~ 0.12mol/L lithium iodide, 0.4 ~ 0.8mol/L tetrabutylammonium iodide and 0.4 ~ 0.6mol/L4-tert .-butylpyridine.
6. the DSSC to electrode based on the low platinum alloy of binary making according to the preparation method described in claim 1 ~ 5 any one.
According to claim 6 based on the low platinum alloy of binary the DSSC to electrode, it is characterized in that: the open-circuit voltage of described DSSC is that 700～800mV, short circuit current are 16～22mAcm-2, fill factor, curve factor is 0.6～0.7, photoelectric transformation efficiency is 7.5～11%.
According to claim 6 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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| 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 |
| CN106057473B (en) * | 2016-07-29 | 2018-04-10 | 中国海洋大学 | A kind of round-the-clock mesoporous sensitization solar battery based on graphene quantum dot and its preparation method and application |
| CN106158391B (en) * | 2016-08-19 | 2018-04-13 | 中国海洋大学 | A kind of dye-sensitized solar cells of round-the-clock power generation and its preparation method and application |
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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Ni1-xPtx (x=0-0.08) films as the photocathode of dye-sensitized solar cells with high efficiency;Peng Shengjie, et al,;《Nano Research》;20090326;第2卷;摘要 * |
| 染料敏化太阳能电池微铂对电极的制备与性能;马换梅;《中国优秀硕士学位论文全文库》;20130531(第5期);第19页12-21行，第20页第19-25行，第28页第1-5行 * |
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