CN110656339B - Method for preparing large-area photoelectrode with patterned metal electrode - Google Patents
Method for preparing large-area photoelectrode with patterned metal electrode Download PDFInfo
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- CN110656339B CN110656339B CN201910940470.9A CN201910940470A CN110656339B CN 110656339 B CN110656339 B CN 110656339B CN 201910940470 A CN201910940470 A CN 201910940470A CN 110656339 B CN110656339 B CN 110656339B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 238000005289 physical deposition Methods 0.000 claims abstract description 7
- 238000000059 patterning Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002390 adhesive tape Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
A method for preparing a large-area photoelectrode with a patterned metal electrode belongs to the technical field of photoelectrocatalysis. The method comprises patterning photoelectrode by physical or chemical method to expose substrate to obtain channel for depositing metal electrode; and then, depositing conductive metal on the metal electrode channel by using a physical deposition method to serve as a metal electrode, leading out an electrode lead, and packaging the obtained metal electrode and the electrode lead to obtain the large-area photoelectrode with the patterned metal electrode. The preparation method is simple, can effectively overcome the technical defects of resistance increase and performance reduction of the photoelectrode along with the increase of the base area of the photoelectrode, and is particularly suitable for preparing the large-area photoelectrode. The current density of the large-area photoelectrode prepared by the method can reach 2.6mA/cm under the voltage of 1.23V2The maximum fill factor of the corresponding current curve is 36%, this performance is associated with a small area photoelectrode (<1cm2) The performance of (A) is equivalent.
Description
Technical Field
The invention relates to a preparation method of a large-area photoelectrode, in particular to a method for preparing a large-area photoelectrode with a patterned metal electrode, and belongs to the technical field of photoelectrocatalysis.
Background
The photoelectrocatalysis decomposition of water to produce hydrogen and oxygen is one of new energy technologies with application prospects. Electrodes for photoelectrocatalysis are commonly referred to as photoelectrodes and include photocathodes and photoanodes. To push the photoelectrocatalysis further to the application, the preparation area is more than 8 x 8cm2The large-area photoelectrode has important practical significance. However, the substrate of the photoelectrode is typically fluorine-doped tin oxide transparent conductive glass (FTO), indium tin oxide transparent conductive glass (ITO), or aluminum-doped zinc oxide transparent conductive glass (AZO). As the size of the conductive glass increases, the resistance of the conductive glass increases, and the voltage loss applied to the conductive glass increases, so that the current loss generated by the photoelectrode increases, and is particularly reflected in the fill factor loss of the current curve. Therefore, there is a need to provide a method to improve the conductivity of large area conductive glass, thereby improving the performance of large area photoelectrodes.
Disclosure of Invention
The invention aims to provide a method for preparing a large-area photoelectrode with a patterned metal electrode, which not only has simple preparation method, but also can effectively overcome the technical defect that the performance of the photoelectrode is reduced due to the increase of the resistance of the photoelectrode along with the increase of the substrate area of the photoelectrode.
The invention is realized by the following technical scheme:
a method of making a large area photoelectrode having a patterned metal electrode, the method comprising the steps of:
1) patterning the photoelectrode by physical or chemical means, exposing the substrate to obtain channels for depositing metal electrodes;
2) depositing a conductive metal on the metal electrode channel as a metal electrode by using a physical deposition method; and (4) after the electrode lead is led out, packaging the obtained metal electrode and the electrode lead to obtain the large-area photoelectrode with the patterned metal electrode.
In the above technical solution of the present invention, the metal electrode channel is in a finger-shaped structure or a rib-shaped structure.
Preferably, the conductive metal deposited in step 2) is gold, silver, copper or a copper alloy; the physical deposition method is a sputtering, evaporation or printing method.
Preferably, the substrate in step 1) is fluorine-doped tin oxide transparent conductive glass, indium tin oxide transparent conductive glass or aluminum-doped zinc oxide transparent conductive glass; the material for packaging the metal electrode and the electrode lead in the step 2) adopts waterproof insulating adhesive tape or waterproof insulating glue.
Preferably, the patterning of the photoelectrode in step 1) is performed by the following method: and (3) physically polishing the optical electrode by using sand paper with the mesh number of 2000-12000, or wiping the optical electrode by using a cotton stick stained with a chemical reagent which does not corrode the substrate.
The invention has the following advantages and prominent technical effects: the method is simple to operate and is suitable for manufacturing the large-area photoelectrode. ② the belt chart obtained by the method of the inventionThe large-area photoelectrode with the patterned metal electrode effectively overcomes the technical defect that the performance of the photoelectrode is reduced due to the increase of the resistance of the photoelectrode caused by the increase of the area of the substrate. Thirdly, the current density of the large-area photoelectrode prepared by the invention can reach 2.6mA/cm under the voltage of 1.23V2The maximum fill factor of the corresponding current curve is 36%, this performance is associated with a small area photoelectrode (<1cm2) The performance of (A) is equivalent. The high-performance large-area photoelectrode prepared by the method is expected to promote the practical application of photoelectrocatalysis water decomposition.
Drawings
FIG. 1 is a photomicrograph of a bismuth vanadate photoelectrode having a finger-like metal electrode prepared in accordance with the present invention.
Fig. 2 is a macroscopic photograph of a bismuth vanadate photoelectrode having a rib-like metal electrode prepared according to the present invention.
Fig. 3 is a performance curve of a bismuth vanadate photoelectrode with a spareribs-shaped metal electrode prepared according to the present invention.
Detailed Description
The invention provides a method for preparing a large-area photoelectrode with a patterned metal electrode, which comprises the following steps:
1) patterning the photoelectrode by a physical or chemical method, for example, physically polishing the photoelectrode by using sand paper with a mesh number of 2000-12000, or wiping the photoelectrode by using a cotton stick stained with a chemical reagent which does not corrode a substrate, so as to expose the substrate to obtain a channel for depositing the metal electrode, wherein the shape of the electrode channel is a finger-shaped structure or a sparerib-shaped structure; the substrate is typically fluorine-doped tin oxide transparent conductive glass, indium tin oxide transparent conductive glass, or aluminum-doped zinc oxide transparent conductive glass; the photo-electrode is patterned into a finger-like structure or a rib-like structure.
2) Depositing a conductive metal on the metal electrode channel as a metal electrode by using a physical deposition method; the physical deposition method can adopt a sputtering, evaporation or printing method; the conductive metal is preferably gold, silver, copper or copper alloy.
3) And leading out an electrode lead on the metal electrode, packaging the obtained metal electrode and the electrode lead, wherein the material for packaging the metal electrode and the electrode lead can adopt waterproof insulating adhesive tape or waterproof insulating glue, and obtaining the large-area photoelectrode with the patterned metal electrode after packaging.
The preparation method and the practical effect of the invention are further explained in the following by combining the drawings and the specific embodiments, so that the purpose and the technical scheme of the invention are more clearly understood. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
1) fixing a mask plate with a finger-shaped structure on a bismuth vanadate photoelectrode (8 x 9 cm) with FTO as a substrate2) A surface of (a);
2) polishing the photo-electrode by using 4000-mesh plastic film abrasive paper according to the shape of the mask plate until a clean conductive glass substrate is exposed;
3) removing the mask plate, cleaning the patterned photoelectrode with deionized water, drying, and continuously fixing the mask plate on the surface of the photoelectrode in situ;
4) depositing pure silver metal on the electrode channel obtained by polishing in the step 2) by using a thermal evaporation method to obtain a metal electrode with a finger-shaped structure;
5) after the tin is melted by a welding gun, welding a copper wire on a bus of the metal electrode;
6) cutting the polyimide adhesive tape into strips with the width of 1.5-2.5 mm, adhering the polyimide adhesive tape to the surface of the sub-wire of the metal electrode, and completely covering the metal electrode sub-wire;
7) the metal electrode bus and the copper wire above the bus are covered with acrylic resin to obtain a bismuth vanadate photoelectrode with a finger-shaped metal electrode, as shown in fig. 1.
Example 2:
the procedure of example 1 was repeated by replacing the mask blank for the finger-like structure in example 1 with the mask blank for the rib-like structure, thereby obtaining a photoelectrode (8X 9 cm) having a metal electrode of rib-like shape2) As in fig. 2.
By using threeAn electrode system (reference electrode is silver and silver chloride, counter electrode is platinum electrode, and working electrode is the photoelectrode) is under simulated sunlight of AM 1.5G (100 mW/cm)2) The photoelectrode was subjected to a linear voltage sweep in an open reactor containing 0.4M sodium sulfite and 0.1M potassium borate solution to obtain a current density curve of the photoelectrode and a corresponding fill factor curve, as shown in fig. 3. The current density of the resulting photoelectrode at a voltage of 1.23V (relative to a standard hydrogen electrode) was 2.6mA/cm2The maximum fill factor of the current curve is 36%. Thus a high performance large area photoelectrode with a patterned metal electrode is obtained by the present invention.
Claims (6)
1. A method of making a large area photoelectrode having a patterned metal electrode, the method comprising the steps of:
1) patterning the photoelectrode by physical or chemical means: physically polishing the optical electrode by using sand paper with the mesh number of 2000-12000, or wiping the optical electrode by using a cotton stick stained with a chemical reagent which does not corrode a substrate; exposing the substrate to obtain a channel for depositing a metal electrode;
2) depositing a conductive metal on the metal electrode channel as a metal electrode by using a physical deposition method; and (4) after the electrode lead is led out, packaging the obtained metal electrode and the electrode lead to obtain the large-area photoelectrode with the patterned metal electrode.
2. The method of claim 1, wherein the metal electrode channel in step 1) is in the shape of a finger-like structure or a rib-like structure.
3. The method of claim 1, wherein the conductive metal deposited in step 2) is gold, silver, copper or a copper alloy.
4. A method according to claim 1, 2 or 3, wherein the physical deposition method in step 2) is a sputtering, evaporation or printing method.
5. The method according to claim 1, 2 or 3, wherein the substrate in step 1) is a fluorine-doped tin oxide transparent conductive glass, an indium tin oxide transparent conductive glass or an aluminum-doped zinc oxide transparent conductive glass.
6. The method as claimed in claim 1, 2 or 3, wherein the material for encapsulating the metal electrodes and the electrode leads in step 2) is waterproof insulating adhesive tape or waterproof insulating glue.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910940470.9A CN110656339B (en) | 2019-09-30 | 2019-09-30 | Method for preparing large-area photoelectrode with patterned metal electrode |
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| CN201910940470.9A CN110656339B (en) | 2019-09-30 | 2019-09-30 | Method for preparing large-area photoelectrode with patterned metal electrode |
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| CN110656339A CN110656339A (en) | 2020-01-07 |
| CN110656339B true CN110656339B (en) | 2021-02-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510769A (en) * | 2002-12-20 | 2004-07-07 | ͨ�õ�����˾ | Large organic device and manufactring method thereof |
| JP2006286434A (en) * | 2005-04-01 | 2006-10-19 | Kansai Pipe Kogyo Kk | Electrode base for dye-sensitized solar cell, optical electrode and counter electrode for dye-sensitized solar cell, and dye-sensitized solar cell |
| CN101447339A (en) * | 2008-12-11 | 2009-06-03 | 彩虹集团公司 | Method for preparing solar battery photo-anode substrate |
| CN102522215A (en) * | 2011-12-09 | 2012-06-27 | 北京化工大学 | Sensitized cell large-area preparation method based on light scattering zinc-base film |
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2019
- 2019-09-30 CN CN201910940470.9A patent/CN110656339B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510769A (en) * | 2002-12-20 | 2004-07-07 | ͨ�õ�����˾ | Large organic device and manufactring method thereof |
| JP2006286434A (en) * | 2005-04-01 | 2006-10-19 | Kansai Pipe Kogyo Kk | Electrode base for dye-sensitized solar cell, optical electrode and counter electrode for dye-sensitized solar cell, and dye-sensitized solar cell |
| CN101447339A (en) * | 2008-12-11 | 2009-06-03 | 彩虹集团公司 | Method for preparing solar battery photo-anode substrate |
| CN102522215A (en) * | 2011-12-09 | 2012-06-27 | 北京化工大学 | Sensitized cell large-area preparation method based on light scattering zinc-base film |
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