CN102779655A - Method for CoS counter electrode preparation based on soft chemical method - Google Patents

Method for CoS counter electrode preparation based on soft chemical method Download PDF

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Publication number
CN102779655A
CN102779655A CN2012102538217A CN201210253821A CN102779655A CN 102779655 A CN102779655 A CN 102779655A CN 2012102538217 A CN2012102538217 A CN 2012102538217A CN 201210253821 A CN201210253821 A CN 201210253821A CN 102779655 A CN102779655 A CN 102779655A
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fto substrate
cos
fto
cobalt salt
salt solution
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CN2012102538217A
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CN102779655B (en
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徐国平
叶长辉
季书林
缪春辉
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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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 discloses a method for CoS counter electrode preparation based on a soft chemical method. The method includes: cleaning an FTO (fluorine-doped tin oxide) substrate and drying; preparing cobalt salt solution and sodium sulfide solution; fixing the cleaned FTO substrate on a spin coater, taking a drop of the prepared cobalt salt solution to uniformly distribute the same on the FTO substrate, performing spin coating, transferring the FTO substrate coated with the cobalt salt solution to a heating plate for roasting, and cooling the FTO substrate in air; placing the cooled FTO substrate into the pre-prepared sodium sulfide for vulcanization, and transferring to the heating plate for roasting until black CoS particles are deposited on the surface of the FTO substrate; and obtaining porous CoS counter electrodes uniformly distributed on the surface of the FTO substrate by means of multiple circulations, wherein the cooled CoS can be directly used for counter electrodes of solar cells. The method for CoS counter electrode preparation based on a soft chemical method is simple in operation, low in cost, environment-friendly, free of pollution and high vacuum, low in requirement on equipment and applicable to mass production.

Description

Prepare the method for CoS based on softening method to electrode
Technical field
The present invention relates to a kind of preparation method of solar cell material, relate in particular to and a kind ofly prepare the method for CoS electrode based on softening method.
Background technology
The mankind earnestly explore new technology and new forms of energy when recognizing increasingly serious energy demand and environmental problem, and solar energy is the most direct energy in the Nature, and are inexhaustible.Be conversion of solar energy that heat energy and electric energy are the two big approach that utilize solar energy so.Constantly the photochemistry solar cell of development such as dye-sensitized cell (Dye Sensitized Solar Cell (DSSC)) and quantum dot sensitized battery (Quantum dot sensitized Solar Cell (QDSC)) are to be conversion of solar energy the mainstream technology of electric energy in the third generation solar cell in recent years.Wherein to how improving the solar cell photoelectric conversion efficiency promptly to make full use of solar energy more be the target that numerous researchers lay siege to always, and restrict a key factor that these two kinds of batteries raise the efficiency be battery to electrode.
There is following defective in Pt of the prior art (platinum) to electrode: the firstth, and cost is high; The Pt resource-constrained; The secondth, Pt is easy to generate overpotential to electrode; Influence the open circuit voltage that transports (electron lifetime is short) and battery of electric charge, the 3rd is that Pt is poor to electrode pair polysulfide electrolyte catalytic activity low electric conductivity.
Summary of the invention
But what the purpose of this invention is to provide a kind of cheapness, simple and easy scale prepares the method for CoS to electrode based on softening method.
The objective of the invention is to realize through following technical scheme:
Of the present inventionly prepare the method for CoS, comprise step electrode based on softening method:
The FTO preliminary treatment of A, commercialization: the FTO substrate is cleaned up, and in drying;
B, preparation cobalt salt solution and sodium sulfide solution;
C, spin coating cation Co 2+: the FTO substrate with wash clean is fixed on above the spin coating appearance earlier, the cobalt salt solution for preparing is got one be evenly distributed on the FTO substrate, carries out spin coating, and the FTO substrate-transfer that then will scribble cobalt salt solution is toasted to heating plate, is allowed to condition in the air then and cools off;
D, sulfuration: the FTO substrate after will cooling off is inserted in the vulcanized sodium for preparing in advance again and is vulcanized, and then transfers on the heating plate and toast, and the CoS particle deposition that black is arranged is to the FTO substrate surface;
Said step C and D constitute a growth circulation, obtain at the equally distributed porous C oS of FTO substrate surface electrode through a plurality of circulations;
CoS after E, the cooling can be directly as solar cell to electrode.
Technical scheme by the invention described above provides can find out, provided by the inventionly prepares the method for CoS to electrode based on softening method, because with slaine cation Co 2+Be dissolved in ethanolic solution, with sulfide anion S 2-Be dissolved in first alcohol and water (V: V=1: 1) mixed solution; Under air ambient, on the FTO substrate, directly can react generate solar cell with efficient electro catalytic activity to electrode CoS; Simple to operate, cost is low, environment friendly and pollution-free, need not high vacuum, low for equipment requirements, can be used for large-scale production.
Embodiment
To do to describe in detail further to the embodiment of the invention below.
The present invention is based on softening method and prepare the method for CoS to electrode, its preferable embodiment comprises step:
The FTO preliminary treatment of A, commercialization: the FTO substrate is cleaned up, and dry;
B, preparation cobalt salt solution and sodium sulfide solution;
C, spin coating cation Co 2+: the FTO substrate with wash clean is fixed on above the spin coating appearance earlier, the cobalt salt solution for preparing is got one be evenly distributed on the FTO substrate, carries out spin coating, and the FTO substrate-transfer that then will scribble cobalt salt solution is toasted to heating plate, is allowed to condition in the air then and cools off;
D, sulfuration: the FTO substrate after will cooling off is inserted in the vulcanized sodium for preparing in advance again and is vulcanized, and then transfers on the heating plate and toast, and the CoS particle deposition that black is arranged is to the FTO substrate surface;
Said step C and D constitute a growth circulation, obtain at the equally distributed porous C oS of FTO substrate surface electrode through a plurality of circulations;
CoS after E, the cooling can be directly as solar cell to electrode.
In the said steps A: with FTO base each ultrasonic 30min in acetone, absolute ethyl alcohol, deionized water successively, use washed with de-ionized water then, and at air drying.
Among the said step B: as solvent, prepare the cobalt salt solution of 0.05M with ethanol, and with the sodium sulfide solution of 1: 1 first alcohol and water of volume ratio as solvent preparation 0.05M;
Among the said step C: the FTO substrate with wash clean is fixed on above the spin coating appearance earlier; The cobalt salt solution for preparing is got one to be evenly distributed on the FTO substrate; Then with the rotating speed spin coating 1min of 1600rpm; The FTO substrate-transfer that then will scribble cobalt salt solution is to heating plate, and 120 ℃ of baking 1min are allowed to condition in the air then and cool off;
Among the said step D: the FTO substrate after will cooling off is inserted in the vulcanized sodium for preparing in advance again and is vulcanized 1min, and then transfers to above the heating plate, 120 ℃ of baking 2min, and the CoS particle deposition that black is arranged is to the FTO substrate surface;
The present invention adopts the CoS that has synthesized the photochemistry solar cell with efficient electro catalytic activity based on softening ie in solution method to electrode (counter electrode (CE)), with slaine cation Co 2+Be dissolved in ethanolic solution, with sulfide anion S 2-Be dissolved in first alcohol and water (V: V=1: 1) mixed solution.Under air ambient, on the FTO substrate, directly can react generate solar cell with efficient electro catalytic activity to electrode CoS.This method is simple to operate, and cost is low, and is environment friendly and pollution-free, need not high vacuum, low for equipment requirements, can be used for large-scale production.Utilize the softening ie in solution method growing technology of learning, the CoS that uses nontoxic, cheap liquid phase method to prepare to have efficient electro catalytic activity is to electrode.This CoS is the nanostructure of porous to electrode, has the big characteristics of specific area, and is evenly distributed on the FTO substrate, fast growth, short instant effect of cycle.
Characteristics of the present invention have following some:
Use rich abundant cobalt salt of resource and common vulcanized sodium to do presoma, use common methyl alcohol, ethanol and deionized water to make solvent, greatly reduce cost;
Through the way of spin coating heating, the CoS of preparation combines closely with substrate FTO, difficult drop-off, thus guaranteed the stability of electrode itself;
The CoS of preparation be the porous membrane of densification, and specific area is big, thereby has guaranteed that CoS has very high electro catalytic activity to electrode as battery;
The preparation process is simple to operation, need not complex conditions such as high vacuum high temperature, under atmospheric environment, gets final product;
Manufacturing cycle is short, fast growth, and energy consumption is low, and promptly system is promptly used;
Production cost is low, and the preparation method is simple, easy to be controlled, and need not the experimental facilities of expensive.
Specific embodiment:
Device therefor: spin coating appearance, heating plate;
Concrete steps:
1, earlier with acetone, ethanol, use deionized water ultrasonic cleaning commercialization FTO (30mm*14mm) again, then with the FTO of cleaning at air drying.
2, take by weighing the cobalt salt solution of quantitative cobalt salt (cobalt nitrate, cobalt chloride, cobalt acetate etc.) preparation 0.05M, make solvent, take by weighing quantitative vulcanized sodium preparation 0.05M sulfide solution, make solvent with first alcohol and water (volume ratio 1: 1) with ethanol.Each stirs 30min.
3, spin coating: the FTO of cleaning is fixed on above the spin coating appearance; Get an amount of cobalt salt solution with dropper and be evenly distributed on the FTO substrate, then with the rotating speed spin coating 1min of 1600rpm, then with substrate-transfer above heating plate; 120 ℃ of baking 1min cool off in air under air ambient.Baking for the first time guarantees that the cobalt salt cation combines closely with substrate
4, sulfuration: the FTO substrate after will cooling off is inserted in the sodium sulfide solution for preparing in advance and is vulcanized 1min; In methanol solution, wash remaining unreacted ion then; Transfer to then above the heating plate, 120 ℃ of baking 2min cool off in air under air ambient.Just have the CoS of black to be deposited on the FTO surface this moment.
5, step 3 and 4 constitutes a growth circulation, just can obtain the CoS film with the compact porous of substrate through circulation (general 2 to 3 times) repeatedly.
6, characterize this CoS through means such as SEM, EDS, CV (cyclic voltammetry), EIS (electrochemical impedance spectroscopy) and solar cell I-V tests electrode is had electrocatalysis characteristic efficiently.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.

Claims (2)

1. one kind prepares the method for CoS to electrode based on softening method, it is characterized in that, comprises step:
The FTO preliminary treatment of A, commercialization: the FTO substrate is cleaned up, and dry;
B, preparation cobalt salt solution and sodium sulfide solution;
C, spin coating cation Co 2+: the FTO substrate with wash clean is fixed on above the spin coating appearance earlier, the cobalt salt solution for preparing is got one be evenly distributed on the FTO substrate, carries out spin coating, and the FTO substrate-transfer that then will scribble cobalt salt solution is toasted to heating plate, is allowed to condition in the air then and cools off;
D, sulfuration: the FTO substrate after will cooling off is inserted in the vulcanized sodium for preparing in advance again and is vulcanized, and then transfers on the heating plate and toast, and the CoS particle deposition that black is arranged is to the FTO substrate surface;
Said step C and D constitute a growth circulation, obtain at the equally distributed porous C oS of FTO substrate surface electrode through a plurality of circulations;
CoS after E, the cooling can be directly as solar cell to electrode.
2. according to claim 1ly prepare the method for CoS, it is characterized in that electrode based on softening method:
In the said steps A: with FTO base each ultrasonic 30min in acetone, absolute ethyl alcohol, deionized water successively, use washed with de-ionized water then, and at air drying.
Among the said step B: as solvent, prepare the cobalt salt solution of 0.05M with ethanol, and with the sodium sulfide solution of 1: 1 first alcohol and water of volume ratio as solvent preparation 0.05M;
Among the said step C: the FTO substrate with wash clean is fixed on above the spin coating appearance earlier; The cobalt salt solution for preparing is got one to be evenly distributed on the FTO substrate; Then with the rotating speed spin coating 1min of 1600rpm; The FTO substrate-transfer that then will scribble cobalt salt solution is to heating plate, and 120 ℃ of baking 1min are allowed to condition in the air then and cool off;
Among the said step D: the FTO substrate after will cooling off is inserted in the vulcanized sodium for preparing in advance again and is vulcanized 1min, and then transfers to above the heating plate, 120 ℃ of baking 2min, and the CoS particle deposition that black is arranged is to the FTO substrate surface.
CN201210253821.7A 2012-07-19 2012-07-19 Method for CoS counter electrode preparation based on soft chemical method Active CN102779655B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721108A (en) * 2018-12-06 2019-05-07 盐城工学院 A kind of porous cobalt sulfide nano flower and its preparation method and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515285A (en) * 2011-11-23 2012-06-27 陕西科技大学 Preparation method of cobalt sulfide nanocrystalline

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515285A (en) * 2011-11-23 2012-06-27 陕西科技大学 Preparation method of cobalt sulfide nanocrystalline

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MINGKUI WANG ET AL.: "CoS Supersedes Pt as Efficient Electrocatalyst for Triiodide Reduction in Dye-Sensitized Solar Cells", 《J.AM.CHEM.SOC.》, 21 October 2009 (2009-10-21), pages 2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721108A (en) * 2018-12-06 2019-05-07 盐城工学院 A kind of porous cobalt sulfide nano flower and its preparation method and application
CN109721108B (en) * 2018-12-06 2021-12-31 盐城工学院 Porous cobalt sulfide nanoflower and preparation method and application thereof

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