CN101271775B - Platinum alloy electrode and method for producing the same - Google Patents

Platinum alloy electrode and method for producing the same Download PDF

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CN101271775B
CN101271775B CN2008100529594A CN200810052959A CN101271775B CN 101271775 B CN101271775 B CN 101271775B CN 2008100529594 A CN2008100529594 A CN 2008100529594A CN 200810052959 A CN200810052959 A CN 200810052959A CN 101271775 B CN101271775 B CN 101271775B
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platinum alloy
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田建华
赵沧燕
单忠强
刘小东
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Tianjin 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel 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

Abstract

The invention relates to a platinum alloy electrode and a preparation method of the platinum alloy. Mixed water solution of H2PtCl6 and RuCl3 is prepared and is added with (NH4)2HPO4 and Na2HPO4; the mixed solution is heated to a nearly boiling state when smell of ammonia gradually disappears and the color of solution is changed from yellow into colorless, and 5% of NaOH or Na2CO3 saturated watersolution is added and the pH value of the solution is adjusted to 7-8; electrodeposit is carried out by taking ITO conductive glass as a cathode, and the current density is 10-30mAcm<-2>, the electrodeposit time is 1-2 minutes, and the electrolyte temperature is 70-80 DEG C; a deposited Pt-Ru/ITO electrode is cleanly washed by distilled water, dried and kept in a dry environment with normal temperature before the battery is assembled. The dimension of iron particle of the Pt-Ru/ITO of the invention is nano-class, with compact surface structure and uniform distribution; the Pt-Ru/ITO of the invention has good electro-catalytic activity on the electro-chemical deoxidization of I3<->, has more stability performance in DSSC electrolyte compared with a Pt electrode. The platinum alloy electrode of the invention is used as an optical cathode in the dye sensitized solar battery, and the preparation method of the electrode can be applied to the field of fuel battery.

Description

A kind of platinum alloy electrode and preparation method thereof
Technical field
The present invention relates to a kind of platinum alloy electrode and preparation method thereof, be applied to the DSSC technical field especially.This electrode preparation method also can be applicable to fuel cell field.
Background technology
Solar energy is a kind of inexhaustible, nexhaustible clear energy sources, is the energy that the mankind is full of glamour.Utilize solar cell that solar energy directly is converted to electric energy is pursuing one's goal of scientists always.
(Dye-Sensitized Solar Cells DSSC) is a class novel solar battery to DSSC.Early 1990s, engineering institutes such as Lausanne, SUI height The Alow cost that professor and his research group deliver, high efficiency solar cell based on dye-sensitized colloidal TiO 2Film.Nature, 1991,353:737Regan B O,
Figure S2008100529594D00012
M, et al. adopts the nanoporous TiO of high-specific surface area 2Film is done semi-conducting electrode, makes sensitizing dyestuff with the organic complex of transition metal Ru or Os, with (I 3 -/ I -) solution is that electrolyte is developed a kind of nanocrystalline DSSC, its photoelectric conversion efficiency reaches more than 7% (brought up to 10 ~ 11% again) afterwards, had started the research and development upsurge of efficient DSSC thus.1997, this
Figure S2008100529594D00013
Battery has been applied to electrochromic device: as Brian A Gregg.Photoelectrochromic cells and their applications.Endeavour, 1997,21 (2): 52～55, with Bechinger C, Gregg B A.Development of a self-powered electrochromic device forlight modulation without external power supply.Solar Energy Materials and SolarCells, 1998,54:405～410 are described; People estimate that in several years of future, this solar cell will enter the practical stage.At present, the electricity conversion of DSSC can be stabilized in more than 10%, and the life-span can reach 15～20 years.
DSSC compares with traditional solar cell, and the most noticeable is its huge price advantage that has, and its manufacturing cost only is 1/5～1/10 of a silicon solar cell.The potential application prospect of DSSC is very wide, because DSSC transparency height can be selected characteristics such as color according to used dyestuff difference, can consider its superiority on design surface.In addition, because that DSSC relies on temperature and incident angle of light is little, making it may be as the commercialization wall material of building or with smart window and use etc.
On the DSSC electrode (photocathode) is generally used precious metals pt, main cause is its high catalytic activity and relatively low overpotential.Chen Jinmao etc. 2005,50 (1) deliver about receiving platinum in the crystal sensitized solar battery in Science Bulletin and modify a kind of new preparation method to electrode, have prepared nano level Pt electrode with self-assembly method on the FTO conducting surface, and its particle diameter is about 15nm; Fang Xiaomings etc. 2006,27 (2) are delivered the novel to electrode research of dye sensitization nano-film solar cell at solar energy journal, adopt sputtering method to form the Pt thin layer on different matrix such as electro-conductive glass; Adopt infusion process on electro-conductive glass, to deposit preparation DSSC and report is also arranged with the Pt electrode.But Pt is higher to the cost of electrode itself, also has problems to wait to solve on performance, such as the dissolving of Pt and poisoning problem.
Summary of the invention
The objective of the invention is to solve the deficiencies in the prior art, propose a kind of PtRu that is used for DSSC electrode and the electro-deposition method for preparing this electrode.
Platinum alloy electrode of the present invention is that deposition PtRu is an electrode on electro-conductive glass.
The preparation method of platinum alloy electrode of the present invention, its step is as follows:
(1) preparation H 2PtCl 6And RuCl 3Mixed aqueous solution, H in the mixed solution 2PtCl 6Concentration is 9 * 10 -4～2.0 * 10 -3MolL -1, RuCl 3Concentration is 1.5 * 10 -3～3.5 * 10 -3MolL -1
(2) with solid (NH 4) 2HPO 4With solid Na 2HPO 4Join successively in the above-mentioned mixed solution, stir under the room temperature.(NH 4) 2HPO 4And Na 2HPO 4Addition be respectively 5～6g/L and 15～20g/L;
(3) above-mentioned mixed liquor is heated to nearly fluidized state, fades away to the smell of ammonia, solution is transformed into colourless by yellow, add 5%NaOH or Na 2CO 3Saturated aqueous solution adjust pH to 7～8;
(4) described step (3) gained solution adding distil water being diluted to original volume of step (1) mixed liquor, is that negative electrode carries out electro-deposition with the ITO electro-conductive glass, current density 10～30mAcm -2, electrodeposition time 1～2 minute, 70～80 ℃ of electrolyte temperatures;
(5) described step (4) deposition PtRu/ITO electrode is clean with distilled water flushing, to dry, normal temperature is kept in the dry environment before the assemble.
Before described ITO electro-conductive glass uses with 0.5% ~ 2%NaOH aqueous solution soaking more than 2 hours, then successively with distilled water, acetone, secondary deionized water, absolute ethyl alcohol cleaning, dry up be placed in distilled water standby;
Platinum alloy electrode of the present invention uses as photocathode in DSSC, and this electrode preparation method also can be applicable to fuel cell field.
The metal particle size of Pt-Ru/ITO electrode of the present invention is a nanoscale, the surface texture densification, and also it is comparatively even to distribute.To I 3 -Electrochemical reduction have good electro catalytic activity, more stable than the Pt electrode performance in DSSC electrolyte.
Description of drawings
Fig. 1 (a): the SEM photo of embodiment 1Pt-Ru/ITO electrode;
Fig. 1 (b) embodiment 1EDS resolution chart;
Fig. 2 (a): the SEM photo of embodiment 2Pt-Ru/ITO electrode;
Fig. 2 (b) embodiment 2EDS resolution chart.
Embodiment
Embodiment 1:
(1) preparation 100ml H 2PtCl 6And RuCl 3Mixed aqueous solution, H 2PtCl 6Concentration is 1.93 * 10 -3MolL -1, RuCl 3Concentration is 2.7 * 10 -3MolL -1
(2) with 0.5g solid (NH 4) 2HPO 4With 1.5g solid Na 2HPO 4Join successively in the above-mentioned mixed solution, stir under the room temperature;
(3) above-mentioned mixed liquor is heated to nearly fluidized state, fades away to the smell of ammonia, solution is transformed into colourless by yellow, add 5%NaOH (or Na 2CO 3Saturated aqueous solution) solution adjust pH to 8.
(4) described step (3) gained solution being diluted to 100ml, is that negative electrode carries out electro-deposition with the ITO electro-conductive glass.Current density 25mAcm -2, electrodeposition time 1.5 minutes, 70 ℃ of electrolyte temperatures;
(5) in the described step (4), with 0.5%NaOH aqueous solution soaking 5 hours, clean with distilled water, acetone, secondary deionized water, absolute ethyl alcohol successively then before commodity ITO electro-conductive glass uses, dry up be placed in distilled water standby;
(6) described step (4) deposition PtRu/ITO electrode is clean with distilled water flushing, to dry, normal temperature is kept in the dry environment before the assemble.
Adopt the XL30ESEM type environmental scanning electron microscope of Dutch phlilps company, multiplication factor is ten thousand times of 1-10, and accelerating voltage 0.2-30KV adopts the computer acquisition image; This apparatus preparation Britain ISIS300 of OXFORD company type gamma ray spectrometer transmission electron microscope can carry out the EDS analytical test.
Implementation result is seen accompanying drawing 1 (a) (b), and the Pt-Ru atomic ratio is 76.4/23.6.
Embodiment 2:
(1) preparation 100ml H 2PtCl 6And RuCl 3Mixed aqueous solution, H 2PtCl 6Concentration is 0.9 * 10 -3MolL -1, RuCl 3Concentration is 1.5 * 10 -3MolL -1
(2) with 0.6g solid (NH 4) 2HPO 4With 2.0g solid Na 2HPO 4Join successively in the above-mentioned mixed solution, stir under the room temperature;
(3) above-mentioned mixed liquor is heated to nearly fluidized state, fades away to the smell of ammonia, solution is transformed into colourless by yellow, add Na 2CO 3Saturated aqueous solution solution adjust pH to 7.
(4) described step (3) gained solution being diluted to 100ml, is that negative electrode carries out electro-deposition with the ITO electro-conductive glass.Current density 15mAcm -2, electrodeposition time 2.0 minutes, 80 ℃ of electrolyte temperatures;
(5) in the described step (4), with 1%NaOH aqueous solution soaking 3 hours, clean with distilled water, acetone, secondary deionized water, absolute ethyl alcohol successively then before commodity ITO electro-conductive glass uses, dry up be placed in distilled water standby;
(6) described step (4) deposition PtRu/ITO electrode is clean with distilled water flushing, to dry, normal temperature is kept in the dry environment before the assemble.
Implementation result is seen accompanying drawing 2 (a) (b), and the Pt-Ru atomic ratio is 90.2/9.8.
Embodiment 3
(1) preparation 100ml H 2PtCl 6And RuCl 3Mixed aqueous solution, H 2PtCl 6Concentration is 2 * 10 -3MolL -1, RuCl 3Concentration is 3.5 * 10 -3MolL -1
(2) with 0.55g solid (NH 4) 2HPO 4With 1.7g solid Na 2HPO 4Join successively in the above-mentioned mixed solution, stir under the room temperature;
(3) above-mentioned mixed liquor is heated to nearly fluidized state, fades away to the smell of ammonia, solution is transformed into colourless by yellow, add Na 2CO 3Saturated aqueous solution solution adjust pH to 7.5.
(4) described step (3) gained solution being diluted to 100ml, is that negative electrode carries out electro-deposition with the ITO electro-conductive glass.Current density 30mAcm -2, electrodeposition time 1.0 minutes, 75 ℃ of electrolyte temperatures;
(5) in the described step (4), with 2%NaOH aqueous solution soaking 2 hours, clean with distilled water, acetone, secondary deionized water, absolute ethyl alcohol successively then before commodity ITO electro-conductive glass uses, dry up be placed in distilled water standby;
(6) described step (4) deposition PtRu/ITO electrode is clean with distilled water flushing, to dry, normal temperature is kept in the dry environment before the assemble.
The present invention open and the platinum alloy electrode that is used for DSSC and the preparation method that propose, those skilled in the art can be by using for reference this paper content, and the appropriate change raw material is formed with link such as proportioning and is realized.Product of the present invention and method are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.

Claims (2)

1. a platinum alloy electrode that is used for DSSC is characterized in that deposition PtRu is an electrode on electro-conductive glass;
Preparation process is as follows:
(1) preparation H 2PtCl 6And RuCl 3Mixed aqueous solution, H in the mixed solution 2PtCl 6Concentration is 9 * 10 -4～2.0 * 10 -3MolL -1, RuCl 3Concentration is 1.5 * 10 -3～3.5 * 10 -3MolL -1
(2) with solid (NH 4) 2HPO 4With solid Na 2HPO 4Join successively in the above-mentioned mixed solution, stir (NH under the room temperature 4) 2HPO 4And Na 2HPO 4Addition be respectively 5～6g/L and 15～20g/L;
(3) above-mentioned mixed liquor is heated to nearly fluidized state, fades away to the smell of ammonia, solution is transformed into colourless by yellow, add 5%NaOH or Na 2CO 3Saturated aqueous solution adjust pH to 7～8;
(4) described step (3) gained solution adding distil water being diluted to original volume of step (1) mixed liquor, is that negative electrode carries out electro-deposition with the ITO electro-conductive glass, current density 10～30mAcm -2, electrodeposition time 1～2 minute, 70～80 ℃ of electrolyte temperatures;
(5) described step (4) deposition PtRu/ITO electrode is clean with distilled water flushing, to dry, normal temperature is kept in the dry environment before the assemble.
2. the platinum alloy electrode that is used for DSSC as claimed in claim 1, it is characterized in that described ITO electro-conductive glass use before with 0.5%～2%NaOH aqueous solution soaking more than 2 hours, clean with distilled water, acetone, secondary deionized water, absolute ethyl alcohol successively then, be kept at after drying up in the distilled water, directly take out during electro-deposition and use.
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NO20081386L (en) * 2008-03-14 2009-09-15 Rec Solar As Method for texturing silicon surfaces and wafers thereof
CN101515505B (en) * 2009-03-31 2011-04-13 彩虹集团公司 Method for preparing platinum electrode of dye sensitized solar cell
CN103088377B (en) * 2013-01-05 2016-07-06 上海交通大学 The preparation method of Pt/ITO electrode
CN106430090A (en) * 2016-10-17 2017-02-22 南昌航空大学 Rare earth doped TiO2 hybrid solar cell

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN2365760Y (en) * 1999-01-14 2000-02-23 北京大学 Solar battery
US6602630B1 (en) * 2000-03-14 2003-08-05 The Electrosynthesis Company, Inc. Membrane electrode assemblies for electrochemical cells
CN1512599A (en) * 2002-12-30 2004-07-14 中国科学院化学研究所 Method for preparing platinum catalytic electrode

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN2365760Y (en) * 1999-01-14 2000-02-23 北京大学 Solar battery
US6602630B1 (en) * 2000-03-14 2003-08-05 The Electrosynthesis Company, Inc. Membrane electrode assemblies for electrochemical cells
CN1512599A (en) * 2002-12-30 2004-07-14 中国科学院化学研究所 Method for preparing platinum catalytic electrode

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