CN102456482B - Manufacturing method of electrode structure of base plate - Google Patents

Manufacturing method of electrode structure of base plate Download PDF

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Publication number
CN102456482B
CN102456482B CN201010532040.2A CN201010532040A CN102456482B CN 102456482 B CN102456482 B CN 102456482B CN 201010532040 A CN201010532040 A CN 201010532040A CN 102456482 B CN102456482 B CN 102456482B
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electrode
nano
oxide
base plate
oxide particles
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CN102456482A (en
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李坤穆
傅思萍
邱伟豪
洪诠雅
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Industrial Technology Research Institute ITRI
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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
    • 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

The manufacture method of electrode structure of base plate
Technical field
The invention relates to the manufacture method of electrode structure of base plate, 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, efficiency is high, it is simple and easy to make and the advantage such as plasticity is high, and indoor light source can generate electricity, not be subject to sunshine angle the feature such as to affect.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 consists of the institutes such as comparative electrode that are coated with nesa coating, platinum catalyst on substrate.Because the delivery efficiency that dye-sensitized solar cells secondary module is current approximately only has 6-8%, and power output is still not high enough.The efficiency and the power output that promote dye-sensitized solar cells secondary module are a large emphasis of developing at present.
When manufacturing the secondary module battery of dye-sensitized solar cells, generally can use wire mark method printed silver line and protect the protection glue of silver-colored line on electrically-conductive backing plate.Generally, in 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 various shapes with conductivity for electrophoretic deposition.Therefore, in known technology, be also selected to prepare the TiO of dye-sensitized solar cells 2electrode.Broadly electrophoretic deposition is belong to colloid technique a kind of, by controlling the surface state of colloidal particle, make its dispersed being suspended in solution, again two electrodes are immersed in suspension, and apply DC electric field between two electrodes, make the surperficial particle with electric charge under the effect of electric field, towards moving with electrically contrary electrode direction own, finally be deposited on substrate, and form a coating.
No. 1763261A exposure of Chinese patent CN is a kind of to determine current potential mode electrophoretic deposition TiO 2the method of film on glass electrically-conductive backing plate.The described 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 determine voltage system 2electrode, is limited in the cathodic deposition of electrophoresis tank, needs to contain salt electrolyte in electrophoresis liquid, and needs again through 400-500 ℃ or Microwave Treatment electrode, makes with electrophoretic deposition, cannot obtain desired electrode quality merely.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of electrode structure of base plate.
One embodiment of the invention provide a kind of manufacture method of electrode structure of base plate, comprise: a substrate is provided, above it, have a patterned metal layer 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 whole electrode zone.
Another embodiment of the present invention provides a kind of manufacture method of electrode structure of base plate, comprise: a transparent conductive substrate is provided, above it, thering is a patterned metal layer fixed. 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 a coarse grain footpath electrode sublevel; The gap of the nano-oxide particles of implementing the one first depositing fine-grained footpath of electrophoretic deposition step between this electrode layer and this protection glue; And the nano-oxide particles of implementing one second electrophoretic deposition step deposition coarse grain footpath is protected the gap between glue in this electrode layer and this.
Various embodiments of the present invention mainly utilize electrophoretic deposition to fill up space between work electrode and silver-colored line protection glue, promote the active area of work electrode, and as the work electrode of dye-sensitized solar cells to improve output current and the power output of assembly.
For the present invention can be become apparent, special embodiment below, and coordinate appended accompanying drawing, be described in detail below:
Accompanying drawing explanation
Fig. 1 shows the schematic diagram of electrophoretic deposition equipment 10 in embodiments of the invention;
Fig. 2 A and 2B show the manufacture method schematic diagram of electrode structure of base plate according to an embodiment of the invention;
Fig. 3 shows according to the comparative result of the incident wavelength of the electrode structure of base plate of the embodiment of the present invention and incident photon-electronic switch efficiency (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
With each embodiment, describe and be accompanied by below the example of accompanying drawing explanation in detail, 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 expand, and to simplify or convenient sign.Moreover, in accompanying drawing, the part of each assembly will be to describe respectively explanation, it should be noted that, the assembly that does not illustrate in figure or describe, for thering is the form of conventionally knowing known to the knowledgeable in affiliated technical field, in addition, the ad hoc fashion that specific embodiment is only used for disclosing the present invention, 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 silver-colored line protection glue, promote the active area of work electrode, and as the work electrode of dye-sensitized solar cells to improve output current and the power output of assembly.
Fig. 1 shows the schematic diagram of electrophoretic deposition equipment 10 in embodiments of the invention.In Fig. 1, for example, by oxide powder 15 (TiO 2powder) be for example dispersed in, in solvent 18 in electrophoresis solution cell body 12 (IPA, iso-propyl alcohol).By the TiO making 2electrode (is made TiO 2electrode can comprise many modes, electrode wire mark method is for wherein a kind of) as negative electrode 14, using FTO glass as anode 16, the electrophoresis solution configuring is placed between two electrodes, distance is D, see through DC power supply 20 to determine electric current or to determine current potential mode and carry out electrophoretic deposition, generally speaking, be scattered in the TiO in IPA 2particle, because of surface band positive charge, can be deposited on negative electrode 14.Electrophoretic deposition is divided into electrophoresis and two steps of deposition substantially, electrophoresis step is by an extra electric field, making to be suspended in solution particle with electric charge is subject to electric field action and moves, and deposition step be by near particle deposition substrate to substrate, form one deck by the tightly packed coating forming of particle.
Fig. 2 A and 2B show the manufacture method schematic diagram of electrode structure of base plate according to an embodiment of the invention.Refer to Fig. 2 A, first, provide a substrate 102 (for example transparent conductive substrate TCO), above it, there is a patterned metal layer 104 and define an electrode zone A, wherein protection glue 106 overlay pattern metal levels 104.One electrode layer 110 comprises a fine grain electrode sublevel 112 and a coarse grain footpath electrode sublevel 114, is filled in electrode zone A.In order to make technique convenient and smooth, actual electrode layer 110 area B of filling can be less than electrode zone A, make between electrode layer 110 and protection glue 106 reserved specific space.In order to be fully used in these spaces, in embodiments of the present invention, by electrophoresis, carry out depositing Ti O 2in the step of residual area.
Then, refer to Fig. 2 B, implement a filling steps to deposit a nano oxide layer 120 on this electrode layer 110, make it fill up whole electrode zone.Filling steps comprises implements an electrodeposition process, for example electrophoretic deposition.The composition of described electrode layer 110 and nano-oxide 120 can be identical also can be not identical.Described nano-oxide 120 can comprise titanium oxide (TiOx), titanium dioxide, zinc oxide, tin oxide, silica, other applicable oxide semiconductor material or aforesaid combination.In one embodiment, the thickness of electrode through electrophoretic deposition is about 0.1 μ m between 50 μ m.The particle size of the nano-oxide of electrophoretic deposition can be selected and be about 5nm between 400nm.
In another embodiment, implement the nano-oxide particles 122 in the one first depositing fine-grained footpath of electrophoretic deposition step and protect the gap between glue in this electrode layer and this, wherein the particle size range of the nano-oxide particles of this fine grain can be about 5nm to 50nm; And the gap of the nano-oxide particles 124 in enforcement one second electrophoretic deposition step deposition coarse grain footpath between this electrode layer and this protection glue, 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, the nano-oxide particles in coarse grain footpath contributes to the scattering of incident photon, and then increases the absorption efficiency of photon.In another embodiment, the blending at random of the nano-oxide of electrophoretic deposition, also can control the deposition that distributes.For example, the first nano-oxide in depositing fine-grained footpath, then deposit the nano-oxide in coarse grain footpath.
The electrophoretic deposition step that the embodiment of above-mentioned exposure is used, except filling up the hole in scattering layer prepared by wire mark, also can be deposited on void area between work electrode and protection glue, approximately can promote active area 20%.Further can pass through Multiple depositions process, change different Ti O 2particle diameter and kenel deposit, to deposit the TiO of different distributions kenel 2electrode, to increase incident light utilization, promotes output current.
[first implements example]
Below hereby especially with several enforcement examples, particular instantiation technological means of the present invention is with spiritual:
Step 1. preparation work electrode: prepare titanium dioxide electrodes layer (18 microns of thickness), patterning silver line and protect the glass cement of silver-colored line to transparent conductive substrate (FTO/glass) in wire mark mode, sending into high temperature furnace and carry out sintering 30 minutes in 500 ℃.
Step 2. is prepared electrode: in wire mark mode, prepare platinum to electrode, patterning silver line and protect the glass cement of silver-colored line to transparent conductive substrate (FTO/glass), sending into high temperature furnace and carry out sintering 30 minutes in 500 ℃.
Step 3. adds the titanic oxide nano powder of 1.25 grams (purchased from Degussa company, product type P90, particle diameter 15～20nm) in the IPA solution of 500 milliliters, stirs 6 hours, makes titanium dioxide nano-particle dispersed.
Step 4. is soaked the electrode base board preparing in step 1 solution that is placed in step 3, the negative pole of power supply unit (Keithley 2400) is connected with substrate, and positive pole is connected approximately 1 centimetre of positive and negative polarities distance with bottom conductive substrate.
Step 5. power supply unit is set as determining 100 milliamperes, electric current, and on the work electrode of preparing in step 1 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 again the titanium dioxide that 4 minutes particle diameters are about 100nm.
After step 6. electrophoresis, be statically placed at 25 ℃ of room temperatures after 3 hours, enter in high temperature furnace and carry out double sintering with 500 ℃.
Step 7. is soaked in 3 * 10 by the electrode in step 5 -4in the N719 dye solution of M, under room temperature, soak after 24 hours, standing after cleaning with acetone.
Step 8. is bonding by the work electrode after electrode and step 7 absorbing dye is carried out organizing with thermoplastic plastic in step 2, and will contain I -/ I 3 -electrolyte inject between two electrodes and encapsulation after, carry out battery efficiency test.
Experimental result under each condition, as shown in Table 1.
Table one, electrophoresis time are on battery performance performance impact
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 in wire mark mode 2particle diameter 50-100nm, 18 microns of thickness), patterning silver line and protect the glass cement of silver-colored line to transparent conductive substrate (FTO/glass), send into high temperature furnace and carry out sintering 30 minutes in 500 ℃.
Step 2. is prepared electrode: in wire mark mode, prepare platinum to electrode, patterning silver line and protect the glass cement of silver-colored line to transparent conductive substrate (FTO/glass), sending into high temperature furnace and carry out sintering 30 minutes in 500 ℃.
Step 3. adds the titanic oxide nano powder of 1.25 grams (purchased from Degussa company, product type P90, particle diameter 15～20nm) in the IPA solution of 500 milliliters, stirs 6 hours, makes titanium dioxide nano-particle dispersed.
Step 4. is soaked the electrode base board preparing in step 1 solution that is placed in step 3, the negative pole of power supply unit (Keithley 2400) is connected with substrate, and positive pole is connected approximately 1 centimetre of positive and negative polarities distance with bottom conductive substrate.
Step 5. power supply unit is set as determining 100 milliamperes, electric current, and on the electrode of preparing in step 1 with electrophoretic deposition 100nm titanium dioxide, sedimentation time is 1 minute.
After step 6. electrophoresis, be statically placed at 25 ℃ of room temperatures after 3 hours, enter in high temperature furnace and carry out double sintering with 500 ℃.
Step 7. is soaked in 3 * 10 by the electrode in step 5 -4in the N719 dye solution of M, under room temperature, soak after 24 hours, standing after cleaning with acetone.
Step 8. is bonding by the work electrode after electrode and step 7 absorbing dye is carried out organizing with thermoplastic plastic in step 2, and will contain I -/ I 3 -electrolyte inject between two electrodes and encapsulation after.
According to the embodiment of the present invention, more only by wire mark printing, form the work electrode (omitting abovementioned steps 3. to 6.) of dye-sensitized solar cells and incident wavelength and incident photon-electronic switch efficiency (the incident photon-to-electron conversion efficiency that process electrophoretic deposition is filled up the work electrode that forms dye-sensitized solar cells, IPCE), as shown in Figure 3, electrophoresis step also can promote battery for the utilance of the light of longer wavelength (500-750nm) to its comparative result.
The embodiment of above-mentioned exposure can utilize electrophoretic deposition to fill up space between work electrode and 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 output current and the power output of assembly.For example electrophoretic deposition step can be filled up TiO effectively 2space between electrode and silver-colored line protection glue; promote active area approximately 20% (with the battery experiment of 0.5cm * 4cm); and the output current that obviously promotes battery (rises to 35.8mA from 31.6mA; promote approximately 13%) and power output (13.28mW rises to 15.32mW, promotes approximately 15%).
Though the present invention discloses as above with various embodiment; so it is not in order to limit scope of the present invention; under any, in technical field, have and conventionally know the knowledgeable; send out in spirit and scope not departing from the present invention; when doing a little change and retouching, so the scope that protection scope of the present invention ought define depending on appending claims is as the criterion.

Claims (5)

1. a manufacture method for electrode structure of base plate, is characterized in that, comprising:
One substrate is provided, has a patterned metal layer and define an electrode zone above it, wherein a protection glue covers this patterned metal layer, and electrode layer preparation is in this electrode zone; And
Implement a filling steps with electrophoretic deposition one nano-oxide the gap between this electrode layer and this protection glue, make it fill up whole electrode zone, wherein this nano-oxide comprises titanium oxide, zinc oxide, tin oxide or silica.
2. the manufacture method of electrode structure of base plate according to claim 1, is characterized in that, this filling steps comprises:
Implement one first electrophoretic deposition, with the nano-oxide particles in depositing fine-grained footpath, in this gap, the particle size of the nano-oxide particles of this fine grain is to 50nm between 5nm; And
Implement one second electrophoretic deposition, with the nano-oxide particles that deposits coarse grain footpath, in this gap, the particle size of the nano-oxide particles in this coarse grain footpath is to 400nm between 50nm.
3. the manufacture method of electrode structure of base plate 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 ℃.
4. a manufacture method for electrode structure of base plate, is characterized in that, comprising:
One transparent conductive substrate is provided, has a patterned metal layer and define an electrode zone above it, wherein a protection glue covers this patterned metal layer, and an electrode layer is formed in this electrode zone;
The gap of the nano-oxide particles of implementing the one first depositing fine-grained footpath of electrophoretic deposition step between this electrode layer and this protection glue, the particle size of the nano-oxide particles of this fine grain is to 50nm between 5nm; And
The gap of the nano-oxide particles of implementing one second electrophoretic deposition step deposition coarse grain footpath between this electrode layer and this protection glue, the particle size of the nano-oxide particles in this coarse grain footpath is to arrive 400nm between 50nm;
Wherein, this nano-oxide comprises titanium oxide, zinc oxide, tin oxide or silica.
5. the manufacture method of electrode structure of base plate according to claim 4, 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 ℃.
CN201010532040.2A 2010-10-27 2010-10-27 Manufacturing method of electrode structure of base plate Active CN102456482B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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