CN102456482A - Manufacturing method of electrode structure of base plate - Google Patents
Manufacturing method of electrode structure of base plate Download PDFInfo
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- CN102456482A CN102456482A CN2010105320402A CN201010532040A CN102456482A CN 102456482 A CN102456482 A CN 102456482A CN 2010105320402 A CN2010105320402 A CN 2010105320402A CN 201010532040 A CN201010532040 A CN 201010532040A CN 102456482 A CN102456482 A CN 102456482A
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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
- Y02E10/549—Organic PV 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 a manufacturing method of an electrode structure of a base plate. The manufacturing method of the electrode structure of the base plate comprises the following steps: providing the base plate on which an electrode region defined by a patterned metal layer; coating the patterned metal layer by using a protective glue cover; forming an electrode layer in the electrode region; and implementing a filling step so as to deposit nano oxide on the electrode layer so that the nano oxide is filled in the whole electrode region.
Description
Technical field
The invention relates to the manufacturing approach of electrode of substrate structure, be particularly to promote the method for dye-sensitized solar cells output current and power output.
Background technology
Dye-sensitized solar cells (Dye-Sensitized Solar Cell; Be called for short DSSC) or be called dye sensitization type solar cell; Have that cost is low, efficient is high, making is simple and easy and advantage such as plasticity height, and indoor light source can generate electricity, not receive characteristics such as angle at sunshine.The structure of conventional dyes sensitization solar cell comprises substrate (glass or film substrate), nesa coating, work electrode (containing semiconductor layer and dyestuff), charge transport materials (electrolyte) and is made up of the institutes such as comparative electrode that are coated with nesa coating, platinum catalyst on the substrate.Because the present delivery efficiency of dye-sensitized solar cells secondary module has only 6-8% approximately, and power output is still not high enough.The efficient and the power output that promote the dye-sensitized solar cells secondary module are a big emphasis of developing at present.
When making the secondary module battery of dye-sensitized solar cells, the protection glue that generally can use wire mark method printed silver line and the silver-colored line of protection is on electrically-conductive backing plate.Generally on design and manufacture technology, between work electrode and silver-colored line protection glue, can reserve specific space, but therefore reduce the active area of secondary module work electrode.
In addition, to have fast filming speed, equipment simple and can be deposited on the first-class advantage of object of the different shape with conductivity for electrophoretic deposition.Therefore, in known technology, also be selected the TiO that is used for preparing dye-sensitized solar cells
2Electrode.Broadly electrophoretic deposition is belong to colloid technology a kind of, and the surface state through the control colloidal particle makes its even dispersion suspension in solution; Again two electrodes are immersed in the suspension; And between two electrodes, apply DC electric field, make particle that the surface has electric charge under effect of electric field, towards with itself electrically opposite electrode direction move; Finally be deposited on the substrate, and form a coating.
1763261A number exposure of Chinese patent CN is a kind of to decide current potential mode electrophoretic deposition TiO
2The method of film on the glass electrically-conductive backing plate.Said electrically-conductive backing plate with electrode structure can be applicable to dye-sensitized solar cells.Yet, conventional electrophoretic depositing Ti O
2The method of film has many technical restrictions, for example must prepare TiO to decide voltage system
2Electrode is limited in the cathodic deposition of electrophoresis tank, need contain the salt electrolyte in the electrophoresis liquid, and needs again through 400-500 ℃ or Microwave Treatment electrode, makes merely can't to obtain the electrode quality desired with electrophoretic deposition.
Summary of the invention
The object of the present invention is to provide a kind of manufacturing approach of electrode of substrate structure.
One embodiment of the invention provide a kind of manufacturing approach of electrode of substrate structure; Comprise: a substrate is provided; Have a patterned metal layer above it and define an electrode zone, wherein a protection glue covers this patterned metal layer, and an electrode layer is filled in this electrode zone; And implement a filling steps to deposit a nano-oxide on this electrode layer, make it fill up the entire electrode zone.
Another embodiment of the present invention provides a kind of manufacturing approach of electrode of substrate structure; Comprise: a transparent conductive substrate is provided; It is fixed to have a patterned metal layer above it. and justice goes out an electrode zone; Wherein a protection glue covers this patterned metal layer, and an electrode layer is filled in this electrode zone, wherein this electrode layer comprises a fine grain electrode sublevel and coarse grain footpath electrode sublevel; Implement the gap of nano-oxide particles between this electrode layer and this protection glue in the one first depositing fine-grained footpath of electrophoretic deposition step; And the gap of nano-oxide particles between this electrode layer and this protection glue of implementing one second electrophoretic deposition step deposition coarse grain footpath.
Various embodiments of the present invention mainly utilize electrophoretic deposition to fill up space between work electrode and the silver-colored line protection glue, promote the active area of work electrode, and as the work electrode of dye-sensitized solar cells to improve the output current and the power output of assembly.
For making the present invention can be more obviously understandable, hereinafter is special lifts embodiment, and cooperates appended accompanying drawing, elaborates as follows:
Description of drawings
Fig. 1 shows the sketch map of electrophoretic deposition equipment 10 in the embodiments of the invention;
Fig. 2 A and 2B show the manufacturing approach sketch map of electrode of substrate structure according to an embodiment of the invention;
Fig. 3 shows according to the incident wavelength of the electrode of substrate structure of the embodiment of the invention and the comparative result of incident photon-electronic switch efficient (IPCE).
[primary clustering symbol description]
10～electrophoretic deposition equipment;
12～electrophoresis solution cell body;
14～negative electrode;
15～charged oxide powder;
16～anode;
18～solvent;
20～DC power supply;
The interelectrode distance of D～two;
102～substrate;
104～patterned metal layer;
106～protection glue;
110～electrode layer;
112～fine grain electrode sublevel;
114～coarse grain footpath electrode sublevel;
120～electrophoretic deposition nano oxide layer;
The nano-oxide particles of 122～fine grain;
The nano-oxide particles in 124～coarse grain footpath;
A～electrode zone;
The electrode layer area of B～actual print.
Embodiment
Below specify and be accompanied by the example of description of drawings with each embodiment, as reference frame of the present invention.In accompanying drawing or specification description, similar or identical part is all used identical figure number.And in the accompanying drawings, the shape of embodiment or thickness can enlarge, and to simplify or convenient the sign.Moreover; The part of each assembly will be it should be noted that the assembly that does not illustrate among the figure or describe to describe explanation respectively in the accompanying drawing; For having the form that common knowledge the knowledgeable is known in the affiliated technical field; In addition, certain embodiments is merely and discloses the ad hoc fashion that the present invention uses, and it is not in order to limit the present invention.
Various embodiments of the present invention mainly utilize electrophoretic deposition to fill up space between work electrode and the silver-colored line protection glue, promote the active area of work electrode, and as the work electrode of dye-sensitized solar cells to improve the output current and the power output of assembly.
Fig. 1 shows the sketch map of electrophoretic deposition equipment 10 in the embodiments of the invention.In Fig. 1, with oxide powder 15 (TiO for example
2Powder) is dispersed in the solvent 18 in the electrophoresis solution cell body 12 (for example IPA, iso-propyl alcohol).With the TiO that makes
2Electrode (is made TiO
2Electrode can comprise many modes; Electrode wire mark method is for wherein a kind of) as negative electrode 14, as anode 16, the electrophoresis solution that configures places between two electrodes with FTO glass; Distance is D; See through DC power supply 20 to decide electric current or to decide the current potential mode and carry out electrophoretic deposition, generally speaking, be scattered in the TiO among the IPA
2Particle is positively charged because of the surface, can be deposited on the negative electrode 14.Electrophoretic deposition is divided into electrophoresis basically and deposits two steps; Electrophoresis step is promptly through an extra electric field; Make and be suspended in the particle that has electric charge in the solution and receive electric field action and move; And deposition step is that near the particle the substrate is deposited on the substrate, forms one deck by the tightly packed coating that forms of particle.
Fig. 2 A and 2B show the manufacturing approach sketch map of electrode of substrate structure according to an embodiment of the invention.See also Fig. 2 A, at first, a substrate 102 (for example transparent conductive substrate TCO) is provided, have a patterned metal layer 104 above it and define an electrode zone A, wherein a protection glue 106 overlay pattern metal levels 104.One electrode layer 110 comprises a fine grain electrode sublevel 112 and coarse grain footpath electrode sublevel 114, is filled in the electrode zone A.In order to make technology convenient and smooth, actual electrode layer 110 area B of filling can make between electrode layer 110 and the protection glue 106 less than electrode zone A, reserve specific space.In order to be fully used in these spaces, in embodiments of the present invention, come depositing Ti O through electrophoresis
2Step in residual area.
Then, see also Fig. 2 B, implement a filling steps, make it fill up the entire electrode zone to deposit a nano oxide layer 120 on this electrode layer 110.Filling steps comprises implements an electrodeposition process, for example electrophoretic deposition.The composition of said electrode layer 110 and nano-oxide 120 can be identical also can be inequality.Said nano-oxide 120 can comprise titanium oxide (TiOx), titanium dioxide, zinc oxide, tin oxide, silica, other oxide semiconductor material or aforesaid combination that is fit to.In one embodiment, the thickness of electrode through electrophoretic deposition is about 0.1 μ m between the 50 μ m.The size of the nano-oxide of electrophoretic deposition can be selected for use and be about 5nm between the 400nm.
In another embodiment, implement the gap of nano-oxide particles 122 between this electrode layer and this protection glue in the one first depositing fine-grained footpath of electrophoretic deposition step, wherein the particle size range of the nano-oxide particles of this fine grain can be about 5nm to 50nm; And the gap of nano-oxide particles 124 between this electrode layer and this protection glue of implementing one second electrophoretic deposition step deposition coarse grain footpath, wherein the particle size range of the nano-oxide particles in this coarse grain footpath can be about 50nm to 400nm.It should be noted that the nano-oxide particles in coarse grain footpath helps the scattering of incident photon, and then increase the absorption efficiency of photon.In another embodiment, the blending at random of the nano-oxide of electrophoretic deposition also can be controlled the deposition that distributes.For example, the nano-oxide in depositing fine-grained footpath deposits coarse grain nano-oxide directly more earlier.
The employed electrophoretic deposition step of the embodiment of above-mentioned exposure the hole in the scattering layer that can fill up the wire mark preparation, also can be deposited on void area between work electrode and the protection glue, can promote active area 20% approximately.Further can pass through repeatedly deposition process, change different Ti O
2Particle diameter and kenel deposit, to deposit the TiO of different distributions kenel
2Electrode to increase the incident light utilization, promotes output current.
[first implements example]
Below implement example with several especially now, concrete illustration technological means of the present invention and spirit:
Step 1. preparation work electrode: after preparing titanium dioxide electrodes layer (18 microns of thickness), patterning silver line and protect glass cement to the transparent conductive substrate (FTO/glass) of silver-colored line with the wire mark mode, send into high temperature furnace and carried out sintering 30 minutes in 500 ℃.
Step 2. prepares electrode: prepare platinum to electrode, patterning silver line and after protecting glass cement to the transparent conductive substrate (FTO/glass) of silver-colored line with the wire mark mode, send into high temperature furnace and carried out sintering 30 minutes in 500 ℃.
(available from Degussa company, product type P90, particle diameter 15～20nm) add in 500 milliliters the IPA solution step 3., stir 6 hours, and titanium dioxide nano-particle is evenly disperseed with the titanic oxide nano powder of 1.25 grams.
Step 4. is soaked the solution that places step 3 with the electrode base board for preparing in the step 1, the negative pole of power supply unit (Keithley 2400) is connected with substrate, and anodally is connected with the bottom conductive substrate, and positive and negative polarities are apart from about 1 centimetre.
Step 5. power supply unit is set at decides 100 milliamperes in electric current, and on the work electrode that in step 1, prepares with different time electrophoretic deposition titanium dioxide, and sedimentation time can 1 minute, 3 minutes, 5 minutes and 7 minutes.In addition, can optionally deposit the titanium dioxide that 4 minutes particle diameters are about 100nm again.
After step 6. electrophoresis finishes, be statically placed in 25 ℃ of room temperatures after following 3 hours, get in the high temperature furnace and carry out double sintering with 500 ℃.
Step 7. is soaked in 3 * 10 with the electrode in the step 5
-4In the N719 dye solution of M, after soaking 24 hours under the room temperature, to leave standstill after the acetone.
Step 8. is bonding with the work electrode behind electrode and step 7 absorbing dye is carried out organizing with thermoplastic plastic in the step 2, and will contain I
-/ I
3 -Electrolyte inject between two electrodes and encapsulation after, carry out the battery efficiency test.
Experimental result under each condition is shown in table one.
Table one, electrophoresis time are to battery performance performance influence
Condition: dyestuff/electrolyte: N719/0.6M PMII+0.1M LiI+0.05M I2+0.5M TBP in acetonitrile, the silver-colored line height of patterning: 10 μ m.
[second implements example]
Step 1. preparation work electrode: prepare titanium dioxide electrodes layer (TiO with the wire mark mode
2Particle diameter 50-100nm, 18 microns of thickness), patterning silver line and protect glass cement to the transparent conductive substrate (FTO/glass) of silver-colored line after, send into high temperature furnace and carried out sintering 30 minutes in 500 ℃.
Step 2. prepares electrode: prepare platinum to electrode, patterning silver line and after protecting glass cement to the transparent conductive substrate (FTO/glass) of silver-colored line with the wire mark mode, send into high temperature furnace and carried out sintering 30 minutes in 500 ℃.
(available from Degussa company, product type P90, particle diameter 15～20nm) add in 500 milliliters the IPA solution step 3., stir 6 hours, and titanium dioxide nano-particle is evenly disperseed with the titanic oxide nano powder of 1.25 grams.
Step 4. is soaked the solution that places step 3 with the electrode base board for preparing in the step 1, the negative pole of power supply unit (Keithley 2400) is connected with substrate, and anodally is connected with the bottom conductive substrate, and positive and negative polarities are apart from about 1 centimetre.
Step 5. power supply unit is set at decides 100 milliamperes in electric current, and on the electrode that in step 1, prepares with electrophoretic deposition 100nm titanium dioxide, sedimentation time is 1 minute.
After step 6. electrophoresis finishes, be statically placed in 25 ℃ of room temperatures after following 3 hours, get in the high temperature furnace and carry out double sintering with 500 ℃.
Step 7. is soaked in 3 * 10 with the electrode in the step 5
-4In the N719 dye solution of M, after soaking 24 hours under the room temperature, to leave standstill after the acetone.
Step 8. is bonding with the work electrode behind electrode and step 7 absorbing dye is carried out organizing with thermoplastic plastic in the step 2, and will contain I
-/ I
3 -Electrolyte inject between two electrodes and encapsulation after.
According to the embodiment of the invention; More only form the work electrode (omitting abovementioned steps 3. to 6.) of dye-sensitized solar cells and incident wavelength and incident photon-electronic switch efficient (the incident photon-to-electron conversion efficiency that the process electrophoretic deposition is filled up the work electrode that forms dye-sensitized solar cells through the wire mark printing; IPCE); Its comparative result is as shown in Figure 3, and electrophoresis step also can promote the utilance of battery for the light of longer wavelength (500-750nm).
The embodiment of above-mentioned exposure electrophoretic deposition capable of using is filled up space between work electrode and the silver-colored line protection glue, to promote TiO
2The active area of electrode, and as the work electrode of dye-sensitized solar cells to improve the output current and the power output of assembly.For example electrophoretic deposition step can be filled up TiO effectively
2Space between electrode and the silver-colored line protection glue; Promote about 20% (with the battery experiment of 0.5cm * 4cm) of active area; And obviously promote the output current (rise to 35.8mA from 31.6mA, promote about 13%) and power output (13.28mW rises to 15.32mW, promotes about 15%) of battery.
Though the present invention discloses as above with various embodiment; So it is not in order to limit scope of the present invention; Has common knowledge the knowledgeable in the technical field under any; Send out in spirit and the scope not breaking away from the present invention, when can doing a little change and retouching, so protection scope of the present invention ought be looked the scope that appending claims defines and is as the criterion.
Claims (11)
1. the manufacturing approach of an electrode of substrate structure is characterized in that, comprising:
One substrate is provided, has a patterned metal layer above it and define an electrode zone, wherein a protection glue covers this patterned metal layer, and an electrode layer is prepared in this electrode zone; And
Implement a filling steps to deposit a nano-oxide, make it fill up the entire electrode zone in this electrode zone.
2. the manufacturing approach of electrode of substrate structure according to claim 1 is characterized in that, this filling steps comprises implements an electrodeposition process.
3. the manufacturing approach of electrode of substrate structure according to claim 2 is characterized in that, this electrodeposition process comprises implements an electrophoretic deposition, to deposit the gap of this nano-oxide particles between this electrode layer and this protection glue.
4. the manufacturing approach of electrode of substrate structure according to claim 1 is characterized in that, this nano-oxide comprises titanium oxide, titanium dioxide, zinc oxide, tin oxide or silica.
5. the manufacturing approach of electrode of substrate structure according to claim 1 is characterized in that, this filling steps comprises:
Implement one first electrophoretic deposition, with the gap of nano-oxide particles between this electrode layer and this protection glue in depositing fine-grained footpath; And
Implement one second electrophoretic deposition, with the gap of nano-oxide particles between this electrode layer and this protection glue in deposition coarse grain footpath.
6. the manufacturing approach of electrode of substrate structure according to claim 5; It is characterized in that; The size of the nano-oxide particles of this fine grain is to arrive 50nm between 5nm, and the size of the nano-oxide particles in this coarse grain footpath is to 400nm between 50nm.
7. the manufacturing approach of electrode of substrate structure according to claim 1 is characterized in that, also comprises a drying steps and a calcining step, and wherein the temperature of this calcining step is between 100～550 ℃.
8. the manufacturing approach of an electrode of substrate structure is characterized in that, comprising:
One transparent conductive substrate is provided, has a patterned metal layer above it and define an electrode zone, wherein a protection glue covers this patterned metal layer, and an electrode layer is formed in this electrode zone;
Implement the gap of nano-oxide particles between this electrode layer and this protection glue in the one first depositing fine-grained footpath of electrophoretic deposition step; And
Implement the gap of nano-oxide particles between this electrode layer and this protection glue in one second electrophoretic deposition step deposition coarse grain footpath.
9. the manufacturing approach of electrode of substrate structure according to claim 8 is characterized in that, this nano-oxide comprises titanium oxide, titanium dioxide, zinc oxide, tin oxide or silica.
10. the manufacturing approach of electrode of substrate structure according to claim 8; It is characterized in that; The size of the nano-oxide particles of this fine grain is to arrive 50nm between 5nm, and the size of the nano-oxide particles in this coarse grain footpath is to 400nm between 50nm.
11. the manufacturing approach of electrode of substrate structure according to claim 8 is characterized in that, also comprises a drying steps and a calcining step, wherein the temperature of this calcining step is between 100～550 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4971633A (en) * | 1989-09-26 | 1990-11-20 | The United States Of America As Represented By The Department Of Energy | Photovoltaic cell assembly |
| CN101373794A (en) * | 2007-08-22 | 2009-02-25 | 中国科学院化学研究所 | Dye sensitization nano-crystal thin-film solar cell photoelectric pole and preparation method thereof |
| TW200932958A (en) * | 2008-01-30 | 2009-08-01 | Univ Nat Taipei Technology | Manufacturing method of the nanoscale TiO2 multilayer films electrode by means of electrophoresis deposition applying to dye-sensitized solar cell |
| CN201302932Y (en) * | 2008-12-10 | 2009-09-02 | 大连七色光太阳能科技开发有限公司 | Electrode structure of dye-sensitized solar cell |
| CN101665973A (en) * | 2009-09-29 | 2010-03-10 | 黑龙江大学 | Method for preparing nanocrystal ternary titanium dioxide porous electrode by auxiliary crystallization in electrophoretic deposition high-voltage electric field |
-
2010
- 2010-10-27 CN CN201010532040.2A patent/CN102456482B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4971633A (en) * | 1989-09-26 | 1990-11-20 | The United States Of America As Represented By The Department Of Energy | Photovoltaic cell assembly |
| CN101373794A (en) * | 2007-08-22 | 2009-02-25 | 中国科学院化学研究所 | Dye sensitization nano-crystal thin-film solar cell photoelectric pole and preparation method thereof |
| TW200932958A (en) * | 2008-01-30 | 2009-08-01 | Univ Nat Taipei Technology | Manufacturing method of the nanoscale TiO2 multilayer films electrode by means of electrophoresis deposition applying to dye-sensitized solar cell |
| CN201302932Y (en) * | 2008-12-10 | 2009-09-02 | 大连七色光太阳能科技开发有限公司 | Electrode structure of dye-sensitized solar cell |
| CN101665973A (en) * | 2009-09-29 | 2010-03-10 | 黑龙江大学 | Method for preparing nanocrystal ternary titanium dioxide porous electrode by auxiliary crystallization in electrophoretic deposition high-voltage electric field |
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