CN102543477A - Preparation method for metal sulfide catalytic electrode and application thereof - Google Patents
Preparation method for metal sulfide catalytic electrode and application thereof Download PDFInfo
- Publication number
- CN102543477A CN102543477A CN2012100487390A CN201210048739A CN102543477A CN 102543477 A CN102543477 A CN 102543477A CN 2012100487390 A CN2012100487390 A CN 2012100487390A CN 201210048739 A CN201210048739 A CN 201210048739A CN 102543477 A CN102543477 A CN 102543477A
- Authority
- CN
- China
- Prior art keywords
- metal sulfide
- preparation
- catalysis electrode
- metal
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Hybrid Cells (AREA)
Abstract
The invention discloses a preparation method for a metal sulfide catalytic electrode and application thereof. According to the invention, metal element or any one form or more than one form of metal sulfide is resolved in hydrazine together with a sulfur element or together with any one form or more than one form of sulfur ammonium salt or sulfur hydrazonium salt, thereby forming a NH4 or N2H5 kation; the metal and the sulfur element form a precursor solution of an anion; the precursor solution is coated on the transparent conductive substrate; and the obtained transparent conductive substrate adsorbing the precursor is subjected to heating and annealing processing, thereby obtaining the metal sulfide catalytic electrode.
Description
Technical field
The present invention relates to quantum dot sensitized solar cell to the electrode fabrication field, exactly is a kind of preparation method and application thereof of metal sulfide catalysis electrode.
Background technology
Solar cell is one of otherwise effective technique scheme in the various clean energy technologies, and it has great importance for the energy and environment problem that solves in the human development process.Emerged a lot of novel solar cell technology in recent years, inorganic semiconductor sensitization solar cell promptly is the wherein representative of low-cost battery.The quantum dot sensitized solar cell of inorganic semiconductor generally adopts the inorganic semiconductor quantum dot of narrow band gap as photosensitizer, and it is deposited on the oxide semiconductor thin-film electrode of broad stopband, dresses up battery with electrolyte and to the electrode mutual group.
The electrolyte that the quantum dot sensitized solar cell of inorganic semiconductor is commonly used is S
2-/ S
x 2-When solar cell illumination state is worked down, the oxidation state component S in the electrolyte
x 2-Electron gain is reduced into S on to electrode
2-Therefore the electrocatalysis characteristic of electrode there is significant effects to the opto-electronic conversion performance of battery.Pt catalysis electrode commonly used is at S
2-/ S
x 2-Be prone in the electrolyte poison, catalytic activity will greatly reduce.Be applicable to S at present
2-/ S
x 2-The higher electrode of electrolytical catalytic activity is the cuprous sulfide electrode.But this electrode is to utilize copper sheet in concentrated hydrochloric acid, to corrode to vulcanize then to be prepared from, and have problems such as yielding when being assembled into battery, and the battery long-term behaviour is affected also.
The present invention provides a kind of preparation method and application thereof of metal sulfide catalysis electrode in electro-conductive glass or conductive plastics substrate, and it has the advantage that technology is simple and catalytic activity is high.
Summary of the invention
The purpose of this invention is to provide the preparation method and the application thereof of the metal sulfide catalysis electrode that a kind of technology is simple, catalytic activity is high.
The present invention adopts following technical scheme to achieve these goals:
The preparation method of metal sulfide catalysis electrode is characterized in that may further comprise the steps:
(1), reactant A: any one or a few in metal simple-substance or the metal sulfide, reactant A and elemental sulfur are dissolved in the hydrazine, perhaps be dissolved in water or the hydrazine with the ammonium class salt of sulphur or in the hydrazine class salt any one or a few, the formation cation is NH
4 +Or N
2H
5 +, metal combines to form anionic precursor solution with element sulphur;
(2), the described precursor solution of step (1) is coated in the electrically conducting transparent substrate;
(3), heating anneal carried out in the electrically conducting transparent substrate of step (2) gained absorption presoma handle, the control temperature range between 50 ℃-500 ℃, the metal sulfide catalysis electrode;
The preparation method of described metal sulfide catalysis electrode is characterized in that: described elemental metals is selected from any one among Sn, In, Zn, Cu, Ge, Sb, the Mo.
The preparation method of described metal sulfide catalysis electrode is characterized in that: described metal sulfide is selected from SnS
2, In
2S
3, ZnS
2, Cu
2S, GeS
2, Sb
2S
3, MoS
2, CuInS
2In any one.
The preparation method of described metal sulfide catalysis electrode is characterized in that: described precursor solution is coated to and adopts curtain coating in the electrically conducting transparent substrate, drip be coated with, spin coating, dipping lift, the method for silk screen printing or inkjet printing.
The preparation method of described metal sulfide catalysis electrode is characterized in that described electrically conducting transparent substrate is electro-conductive glass or conductive plastic film.
The application of described metal sulfide catalysis electrode; It is characterized in that: the application of described metal sulfide catalysis electrode on quantum dot sensitized solar cell is assembled into quantum dot sensitized solar cell with metal sulfide catalysis electrode and quantum dot sensitized electrode, electrolyte.
Advantage of the present invention:
Metal sulfide catalysis electrode raw material of the present invention source is abundant, avoids the use of noble metal platinum, greatly reduces cost;
Metal sulfuration catalysis electrode of the present invention is used for quantum dot sensitized solar cell and has advantages of high catalytic activity, can obtain higher photoelectricity conversion performance;
The present invention is a kind of preparation method based on solution, is easy to mass preparation, has industrial prospect.
Description of drawings
Fig. 1 is a preparation flow sketch map of the present invention.
Fig. 2 is quantum dot sensitized solar battery structure sketch map.
The Cu of Fig. 3 for using this method to obtain
2S is total to sensitization titanium dioxide solar cell i-v curve comparison diagram to electrode with the CdS and the CdSe that use Pt to electrode.
Embodiment
Introduce exemplifying embodiment of the present invention below, but the present invention is limited to embodiment absolutely not:
Embodiment 1:Cu
2The preparation of S catalysis electrode
Get 1mmol cuprous sulfide powder, the 2mmol sublimed sulfur joins in the hydrazine, at room temperature stirs, and obtains lurid N
4H
9Cu
7S
4Precursor solution; It is on glass that this precursor solution is sprayed to FTO with spraying process, and 120 degree annealing obtain Cu under argon gas atmosphere
2S is to electrode.
Embodiment 2:Cu
2The S catalysis electrode is applied to quantum dot sensitized solar cell
Get 1mmol cuprous sulfide powder, the 2mmol sublimed sulfur joins in the hydrazine, at room temperature stirs, and obtains lurid N
4H
9Cu
7S
4Precursor solution; It is on glass that this precursor solution is sprayed to FTO with spraying process, and 120 degree annealing obtain Cu under argon gas atmosphere
2S is to electrode; This is total to sensitization TiO 2 nanocrystal porous film electrode, many sulphur electrolyte (1M Na to electrode and cadmium sulfide cadmium selenide
2S, 1M S, 0.1M NaOH) the quantum dot sensitized solar cell of assembling acquisition.
Claims (6)
1. the preparation method of a metal sulfide catalysis electrode is characterized in that may further comprise the steps:
(1), reactant A: any one or a few in metal simple-substance or the metal sulfide, reactant A and elemental sulfur are dissolved in the hydrazine, perhaps any one or a few in the ammonium class salt of sulphur or the hydrazine class salt is dissolved in water or the hydrazine, the formation cation is NH
4 +Or N
2H
5 +, metal combines to form anionic precursor solution with element sulphur;
(2), the described precursor solution of step (1) is coated in the electrically conducting transparent substrate;
(3), heating anneal carried out in the electrically conducting transparent substrate of step (2) gained absorption presoma handle, the control temperature range between 50 ℃-500 ℃, the metal sulfide catalysis electrode.
2. the preparation method of metal sulfide catalysis electrode according to claim 1 is characterized in that: described elemental metals is selected from any one among Sn, In, Zn, Cu, Ge, Sb, the Mo.
3. the preparation method of metal sulfide catalysis electrode according to claim 1 is characterized in that: described metal sulfide is selected from SnS
2, In
2S
3, ZnS
2, Cu
2S, GeS
2, Sb
2S
3, MoS
2, CuInS
2In any one.
4. the preparation method of metal sulfide catalysis electrode according to claim 1 is characterized in that: described precursor solution is coated to and adopts curtain coating in the electrically conducting transparent substrate, drip be coated with, spin coating, dipping lift, the method for silk screen printing or inkjet printing.
5. the preparation method of metal sulfide catalysis electrode according to claim 1 is characterized in that described electrically conducting transparent substrate is electro-conductive glass or conductive plastic film, and the control temperature range is between 80 ℃-120 ℃.
6. the application of a metal sulfide catalysis electrode as claimed in claim 1; It is characterized in that: the application of described metal sulfide catalysis electrode on quantum dot sensitized solar cell is assembled into quantum dot sensitized solar cell with metal sulfide catalysis electrode and quantum dot sensitized electrode, electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100487390A CN102543477A (en) | 2012-02-29 | 2012-02-29 | Preparation method for metal sulfide catalytic electrode and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100487390A CN102543477A (en) | 2012-02-29 | 2012-02-29 | Preparation method for metal sulfide catalytic electrode and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102543477A true CN102543477A (en) | 2012-07-04 |
Family
ID=46350119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100487390A Pending CN102543477A (en) | 2012-02-29 | 2012-02-29 | Preparation method for metal sulfide catalytic electrode and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102543477A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117173A (en) * | 2013-03-11 | 2013-05-22 | 武汉大学 | Double-side light entering quantum dot sensitization solar cell and preparation method thereof |
| CN103227054A (en) * | 2012-12-18 | 2013-07-31 | 南开大学 | Antimony sulfide counter electrode of dye-sensitized solar cell and a preparation method of antimony sulfide counter electrode |
| CN105023757A (en) * | 2015-07-10 | 2015-11-04 | 三峡大学 | Tin-doped Sb2S3 thin film material and preparation method thereof |
| CN105271411A (en) * | 2015-11-04 | 2016-01-27 | 太原理工大学 | Preparation method for molybdenum disulfide quantum dot |
| CN105489384A (en) * | 2016-01-11 | 2016-04-13 | 三峡大学 | Preparation method of C/Sb<2>S<3> composite thin-film counter electrode material |
| CN107262116A (en) * | 2017-05-31 | 2017-10-20 | 武汉理工大学 | A kind of hierarchy MoS2/Cu2S composites and preparation method thereof |
| CN107673395A (en) * | 2016-08-02 | 2018-02-09 | 中国科学院大连化学物理研究所 | A kind of thermoelectric material for vulcanizing indium doping cuprous sulfide and preparation method thereof |
| CN107785173A (en) * | 2016-08-30 | 2018-03-09 | 东北师范大学 | It is a kind of be applied to low light condition under quantum dot sensitized solar cell to electrode material and preparation method thereof |
| CN109574096A (en) * | 2018-10-31 | 2019-04-05 | 南京邮电大学 | A kind of preparation method and application of metal sulfide |
| CN110246698A (en) * | 2019-06-21 | 2019-09-17 | 南京邮电大学 | A kind of metal sulfide film method for cooking based on reuse precursor liquid |
| CN110265223A (en) * | 2019-06-06 | 2019-09-20 | 河南大学 | A kind of molybdenum indium sulphur is to electrode and the method for preparing dye-sensitized solar cells using it |
| CN114031108A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Composite sulfide and preparation method and application thereof |
| WO2024103645A1 (en) * | 2022-11-17 | 2024-05-23 | 碳能科技（北京）有限公司 | In-situ regeneration method for electrochemical co2 reduction catalytic electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011194A (en) * | 2010-10-11 | 2011-04-13 | 中国科学院青岛生物能源与过程研究所 | Photovoltaic semiconductor nanocrystalline and preparation method and application thereof |
| CN102360962A (en) * | 2011-09-30 | 2012-02-22 | 中国科学院等离子体物理研究所 | Preparation method of quantum dot sensitized solar cell |
-
2012
- 2012-02-29 CN CN2012100487390A patent/CN102543477A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011194A (en) * | 2010-10-11 | 2011-04-13 | 中国科学院青岛生物能源与过程研究所 | Photovoltaic semiconductor nanocrystalline and preparation method and application thereof |
| CN102360962A (en) * | 2011-09-30 | 2012-02-22 | 中国科学院等离子体物理研究所 | Preparation method of quantum dot sensitized solar cell |
Non-Patent Citations (3)
| Title |
|---|
| DAVID B.MITZI: "N4H9Cu7S4: A Hydrazinium-Based Salt with a Layered Cu7S4-Framework", 《INORG.CHEM》 * |
| MINGHUI DENG等: "Screen-printed Cu2S-based Counter Electrode for Quantum-dot-sensitized Solar Cell", 《CHEM. LETT.》 * |
| MINGXING WU等: "Economical and effective sulfide catalysts for dye-sensitized solar cells as counter electrodes", 《PHYS. CHEM.》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103227054A (en) * | 2012-12-18 | 2013-07-31 | 南开大学 | Antimony sulfide counter electrode of dye-sensitized solar cell and a preparation method of antimony sulfide counter electrode |
| CN103227054B (en) * | 2012-12-18 | 2015-10-14 | 南开大学 | The antimony trisulfide of DSSC is to electrode and preparation method thereof |
| CN103117173A (en) * | 2013-03-11 | 2013-05-22 | 武汉大学 | Double-side light entering quantum dot sensitization solar cell and preparation method thereof |
| CN103117173B (en) * | 2013-03-11 | 2016-02-10 | 武汉大学 | Can two-sided enter the quantum dot sensitized solar cell and preparation method thereof of light |
| CN105023757A (en) * | 2015-07-10 | 2015-11-04 | 三峡大学 | Tin-doped Sb2S3 thin film material and preparation method thereof |
| CN105023757B (en) * | 2015-07-10 | 2018-04-20 | 三峡大学 | A kind of tin dope Sb2S3 thin-film materials and preparation method thereof |
| CN105271411A (en) * | 2015-11-04 | 2016-01-27 | 太原理工大学 | Preparation method for molybdenum disulfide quantum dot |
| CN105489384B (en) * | 2016-01-11 | 2018-04-10 | 三峡大学 | A kind of C/Sb2S3Preparation method of the laminated film to electrode material |
| CN105489384A (en) * | 2016-01-11 | 2016-04-13 | 三峡大学 | Preparation method of C/Sb<2>S<3> composite thin-film counter electrode material |
| CN107673395A (en) * | 2016-08-02 | 2018-02-09 | 中国科学院大连化学物理研究所 | A kind of thermoelectric material for vulcanizing indium doping cuprous sulfide and preparation method thereof |
| CN107785173A (en) * | 2016-08-30 | 2018-03-09 | 东北师范大学 | It is a kind of be applied to low light condition under quantum dot sensitized solar cell to electrode material and preparation method thereof |
| CN107262116A (en) * | 2017-05-31 | 2017-10-20 | 武汉理工大学 | A kind of hierarchy MoS2/Cu2S composites and preparation method thereof |
| CN107262116B (en) * | 2017-05-31 | 2020-08-04 | 武汉理工大学 | Hierarchical structure MoS2/Cu2S composite material and preparation method thereof |
| CN109574096A (en) * | 2018-10-31 | 2019-04-05 | 南京邮电大学 | A kind of preparation method and application of metal sulfide |
| CN109574096B (en) * | 2018-10-31 | 2021-07-30 | 南京邮电大学 | Preparation method and application of metal sulfide |
| CN110265223A (en) * | 2019-06-06 | 2019-09-20 | 河南大学 | A kind of molybdenum indium sulphur is to electrode and the method for preparing dye-sensitized solar cells using it |
| CN110246698A (en) * | 2019-06-21 | 2019-09-17 | 南京邮电大学 | A kind of metal sulfide film method for cooking based on reuse precursor liquid |
| CN114031108A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Composite sulfide and preparation method and application thereof |
| CN114031108B (en) * | 2021-11-02 | 2024-04-26 | 远景动力技术(江苏)有限公司 | Composite sulfide and preparation method and application thereof |
| WO2024103645A1 (en) * | 2022-11-17 | 2024-05-23 | 碳能科技（北京）有限公司 | In-situ regeneration method for electrochemical co2 reduction catalytic electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102543477A (en) | Preparation method for metal sulfide catalytic electrode and application thereof | |
| Luo et al. | Solution transformation of Cu2O into CuInS2 for solar water splitting | |
| DeAngelis et al. | Antimony (III) sulfide thin films as a photoanode material in photocatalytic water splitting | |
| Mali et al. | Enhanced photoelectrochemical solar water splitting using a platinum-decorated CIGS/CdS/ZnO photocathode | |
| Steinhagen et al. | Synthesis of Cu2ZnSnS4 nanocrystals for use in low-cost photovoltaics | |
| Yang et al. | Upscaling solution‐processed perovskite photovoltaics | |
| Ge et al. | Employing overlayers to improve the performance of Cu2BaSnS4 thin film based photoelectrochemical water reduction devices | |
| Norako et al. | Synthesis and characterization of wurtzite-phase copper tin selenide nanocrystals | |
| Todorov et al. | CuInS2 films for photovoltaic applications deposited by a low-cost method | |
| van Embden et al. | Solution-processed CuSbS2 thin films and superstrate solar cells with CdS/In2S3 buffer layers | |
| JP5928612B2 (en) | Compound semiconductor solar cell | |
| CN105731820A (en) | Solvothermal preparation method of in-situ molybdenum disulfide electrode | |
| Guan et al. | Aging precursor solution in high humidity remarkably promoted grain growth in Cu2ZnSnS4 films | |
| CN102360962B (en) | Preparation method of quantum dot sensitized solar cell | |
| Chen et al. | Synthesis and Photoelectrochemical Properties of (Cu2Sn) x Zn3 (1–x) S3 Nanocrystal Films | |
| CN104934539A (en) | Solar cell adopting metal transparent electrode and preparation of solar cell | |
| Halder et al. | Cation exchange in Zn–Ag–In–Se core/alloyed shell quantum dots and their applications in photovoltaics and water photolysis | |
| CN103219159A (en) | CuxS (x=1-2) counter electrode preparation method for quantum dot sensitization solar batteries | |
| Park et al. | Effective formation of WO3 nanoparticle/Bi2S3 nanowire composite for improved photoelectrochemical performance | |
| Kim et al. | Toward robust photoelectrochemical operation of cuprous oxide nanowire photocathodes using a strategically designed solution-processed titanium oxide passivation coating | |
| JP2008287900A (en) | Photoelectric transfer element and manufacturing method therefor, and solar cell using the element | |
| Patil et al. | Optoelectronic and photovoltaic properties of the Cu2ZnSnS4 photocathode by a temperature-dependent facile hydrothermal route | |
| JP5815848B2 (en) | Method for manufacturing photoelectric conversion device | |
| CN101958352A (en) | Solar cell and manufacture method thereof | |
| JP2013089690A (en) | Method for manufacturing quantum dot sensitized type solar battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |