CN101707140B - Method for preparing platinum counter electrode of dye-sensitized solar cell and platinum counter electrode - Google Patents
Method for preparing platinum counter electrode of dye-sensitized solar cell and platinum counter electrode Download PDFInfo
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- CN101707140B CN101707140B CN2009102259147A CN200910225914A CN101707140B CN 101707140 B CN101707140 B CN 101707140B CN 2009102259147 A CN2009102259147 A CN 2009102259147A CN 200910225914 A CN200910225914 A CN 200910225914A CN 101707140 B CN101707140 B CN 101707140B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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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 discloses a method for preparing a platinum counter electrode of a dye-sensitized solar cell and the platinum counter electrode. The method comprises the following steps of: providing a platinum paste with viscosity suitable for carrying out screen printing; cleaning and drying conductive glass; printing the platinum paste silk screen on a conductive surface of the cleaned ad dried conductive glass by using a screen printer to form a platinum paste coating film; taking the conductive glass with the platinum paste coating film out from the screen printer, and drying the conductive glass; and then sintering the dried conductive glass with a platinum paste coating. The method adopts screen printing technology to prepare the platinum counter electrode; compared with a spinning method with uneven coating, the method has the most obvious characteristic that the method can prepare even platinum counter electrode with large area; and compared with a magnetron sputtering method, the method is simple in operation and suitable for industrial application and can prepare the platinum counter electrode with larger area.
Description
Technical field
The present invention relates to a kind of platinum for preparing DSSC to the method for electrode and thus the platinum of the DSSC prepared of method to electrode, particularly, relate to and utilize screen printing technique, the platinum of preparation large-area dye-sensitized solar battery is to the method for electrode, and thus the platinum of the DSSC prepared of method to electrode.
Background technology
Energy shortage and environmental pollution are the two large problems that the present mankind face.Traditional energy coal, oil and timber can only be kept 50 to 100 years by present depletion rate.In addition, the environmental pollution that is brought is thus also threatening the human earth of depending on for existence.And the mankind in the foreseeable following time, solar energy is as the inexhaustible clear energy sources of the mankind, do not produce any environmental pollution, and be not subjected to the restriction of geographical conditions basically, so the research of solar utilization technique has caused various countries scientists' extensive attention.The utilization of solar energy mainly contains solar cell power generation, and two key issues of exploitation solar cell are exactly: improve conversion efficiency and reduce cost.Because solar battery product silicon solar cell manufacturing cost in the market is too high, is unfavorable for extensive use.And the dye-sensitized nanocrystalline titanium dioxide (TiO that the nineties grows up
2) advantage of solar cell (DSC) is cost and the simple technology and the stable performance of its cheapness, thereby become the very strong competitor of conventional solar cell.Its photoelectric efficiency is stabilized in 10%, and cost of manufacture only is 1/5～1/10 of a silicon solar cell, and the life-span can reach more than 20 years.
DSC mainly forms by the light anode of dye sensitization, electrolyte and to electrode, is plated in the effect that can play catalyst to the platinum on the electrode, helps reducing the loss of electromotive force, has improved the performance of DSC.The method of platinum plating has a lot, yet, many, inhomogeneous with the platinum membrane structure defective of Vacuum Coating method preparation, there is more stain; But the platinum membrane structure that is equipped with the plating legal system evenly, queueing discipline, the few big energy-consuming of defective.The resulting platinum electrode surface of these methods is long-pending all less, the platinum on surface for the catalytic capability of reaction a little less than, cause the entire cell energy efficiency not high.Platinum film with the thermal decomposition method preparation has vesicular texture, thereby bigger specific area arranged, the pt atom that forms bunch can play the effect of catalysis well, when working, electrode can produce bigger exchange current density, the loss of potential that causes is less and more stable, is not vulnerable to corrosion.
Also have report to use the situation of spin-coating method in addition.For example Chinese patent CN101447340 discloses a kind of electrode with large surface area preparation technology who is used for DSSC, its major technique feature is that chloroplatinic acid is dissolved in the isopropyl alcohol, to obtain platinum acid chloride solution is spin-coated on the conductive glass surface, the electro-conductive glass that is coated with metallic gold or platinum grain layer is put into sintering furnace, just can adhere to the less metallic particles of particle diameter at big particle surface, formation has the more gold or the platinum electrode of high surface area.
Above-mentioned spin coating proceeding exists and films inhomogeneously, and chloroplatinic acid waste is many, consume big, shortcoming such as the amount of filming is uncontrollable, thus its preparation is bad to electrode repeatability, can not obtain stable performance, efficiently to electrode.Spin coating is limited to the size of electrode in addition, is not suitable for preparing larger area to electrode, and large-scale preparation.
In addition, adopt silk screen printing to prepare the existing a lot of reports of method of dye-sensitized solar cell anode, obtained good application, electrode is reported rarely silk screen printing is easy and simple to handle, helped large-scale application and adopt the method to prepare platinum.
Summary of the invention
Therefore, the present invention proposes a kind of screen printing technique that utilizes and prepare the method for the platinum of large-area dye-sensitized solar battery electrode, it is a kind of when can solve in the prior art the problems referred to above that purpose is to provide, and the platinum that obtains large-area DSSC is to electrode.
Therefore, the present invention relates to following aspect:
＜1〉a kind of screen printing technique that adopts prepares the method for the platinum of DSSC to electrode, and described method comprises the steps:
A) provide platinum slurry with the viscosity that is suitable for carrying out silk screen printing;
B) electro-conductive glass is cleaned and dry;
C) utilize screen process press, the silk screen printing of described platinum slurry is filmed to form the platinum slurry on the conducting surface of the electro-conductive glass through cleaning and drying;
D) take out the electro-conductive glass that has the platinum slurry coating from screen process press, dry;
E) then, the electro-conductive glass that has the platinum slurry coating with oven dry carries out sintering.
＜2〉sintering basis＜1〉described method, wherein e) comprises: at 380-500 ℃ of following sintering 10-30min.
＜3〉according to basis＜1〉or＜2〉described method, wherein said sintering carries out in Muffle furnace or tube furnace.
＜4〉according to＜1〉described method, also be included in step (e) afterwards, (c)-(e) repeats repeatedly successively with step, with the platinum that obtains required year platinum amount to electrode.
＜5〉according to＜1〉described method, wherein said platinum slurry is the chloroplatinic acid slurry.
＜6〉according to＜3〉described method, wherein said chloroplatinic acid platinum slurry can provide as follows:
Under stirring condition, to 100-500mL concentration is in the alcoholic solution of chloroplatinic acid of 5-20mM, adding is stirred 1-5min by one or more compounds in terpinol, kerosene, higher boiling point paraffin oil and the ethyl cellosolve acetate of being selected from of the described chloroplatinic acid slurry of 100g 38.34-70g;
Carry out first sonicated then;
Under stirring condition, add the ethyl cellulose by the 4.15-20g of the described chloroplatinic acid slurry of 100g again, described ethyl cellulose adds with the form of 10-20 quality % alcoholic solution, continues to stir 1-5min;
Carry out second sonicated then, and
Part removes solvent, with the viscosity that obtains to be suitable for carrying out silk screen printing.
＜7〉according to＜6〉described method, the content of platinum is 0.49-13.3g/100g chloroplatinic acid slurry in the wherein said platinum slurry.
＜8〉according to＜6〉described method, wherein said part removes solvent and comprises and carry out decompression distillation.
＜9〉according to＜6〉described method, the viscosity of wherein said platinum slurry is 4-50Pas.
＜10〉according to＜9〉described method, the viscosity of wherein said chloroplatinic acid slurry is 15-50Pa.s.
＜11〉according to＜1〉described method, wherein said cleaning comprises: clean described electro-conductive glass 10-30min with washing agent, 0.1MHCl-ethanolic solution, acetone in ultrasonic cleaning tank respectively, use alcohol flushing again after described electro-conductive glass is taken out.
＜12〉according to＜1〉described method, wherein said electro-conductive glass has 5cm
2-500cm
2Area.
＜13〉according to＜1〉described method, wherein said silk screen printing also comprises hand-printing and or prints automatically and carry out blade coating.
＜14〉a kind of by＜1〉platinum of the DSSC that obtains of described method is to electrode.
＜15〉basis＜14〉described platinum is to electrode, and described platinum is 2500mm to the area of electrode
2-30000mm
2
The present invention adopts screen printing technique to prepare platinum to electrode, compare with the coating of spin-coating method is inhomogeneous, obvious characteristics is that the present invention can prepare uniform large-area platinum to electrode, compare with magnetically controlled sputter method, the present invention is simple to operate, be suitable for commercial Application, the platinum electrode area that can prepare is bigger.
Embodiment
The invention provides a kind of screen printing technique that adopts and prepare the method for the platinum of DSSC to electrode, a specific embodiments of described method comprises the steps:
A) provide platinum slurry with the viscosity that is suitable for carrying out silk screen printing; B) electro-conductive glass is cleaned and dry; C) utilize screen process press, the silk screen printing of described platinum slurry is filmed to form the platinum slurry on the conducting surface of the electro-conductive glass through cleaning and drying; D) have the electro-conductive glass of platinum slurry coating from the screen process press taking-up, and after leaving standstill 1-5 minute, dry; E) then, the electro-conductive glass that has the platinum slurry coating of drying is carried out sintering, usually at 380-500 ℃ of following sintering 10-30min.
In the present invention, described platinum slurry has no particular limits, as long as its viscosity satisfies general silk screen printing.The general required slurry viscosity of silk screen printing is 4-60Pas.In this article, the preferred chloroplatinic acid slurry of described platinum slurry.
Because the platinum acid chloride solution that obtains of the prior art itself is rarer, generally be unsuitable for being directly used in printing, and viscosity is little, the platinum amount that coating is got on is less, and what make is not good to electrode performance, and a year platinum amount can't accurately be controlled the properties of product instability.In addition, form by powder preparation the required sintering temperature 800-1200 of platinum slurry ℃, and the melt temperature of substrate of glass is 600 ℃, therefore this platinum slurry is unsuitable for the sintering of substrate of glass.For this reason, it is 4-50Pas that the present invention also provides a kind of preparation viscosity at this, the method of the platinum slurry of preferred 15-50Pas, this preparation method comprises the steps: under stirring condition, to 100-500mL concentration is in the alcoholic solution of chloroplatinic acid of 5-20mM, adding is stirred 1-5min by one or more compounds in terpinol, kerosene, higher boiling point paraffin oil and the ethyl cellosolve acetate of being selected from of the described chloroplatinic acid slurry of 100g 38.34-70g; Carry out first sonicated then; Under stirring condition, add the ethyl cellulose by the 4.15-20g of the described chloroplatinic acid slurry of 100g again, described ethyl cellulose adds with the form of 10-20 quality % alcoholic solution, continues to stir 1-5min; Carry out second sonicated then, and part removes solvent, with the viscosity that obtains to be suitable for carrying out silk screen printing, wherein said part removes solvent and comprises and carry out decompression distillation.The viscosity of the platinum slurry of preparing like this is 4-50Pas, preferred 15-50Pas, and platinum content is a 0.49-13.3g/100g chloroplatinic acid slurry.Wherein said first sonicated and described second sonicated can be identical or different.Described sonicated is included under the ultrasonic power of 400-800W, sonicated 1-6 second, and 1-2 second intermittently, and repeat 20-40 time.
In the above-mentioned method for preparing the chloroplatinic acid slurry, described one or more compounds are preferably terpinol.Described solvent can be methyl alcohol, isopropyl alcohol, absolute ethyl alcohol equal solvent.Terpinol, kerosene, higher boiling point paraffin oil and ethyl cellosolve acetate have no particular limits, and can directly use commercially available terpinol, kerosene, higher boiling point paraffin oil and ethyl cellosolve acetate.
In this article, term " higher boiling point paraffin oil " is meant that boiling range is at 150-170 ℃ higher boiling point paraffin oil.
In this article, term " kerosene " is meant that boiling point is at 160-200 ℃ kerosene.
In this article, described ethyl cellosolve acetate can be ethyl cellosolve methyl acetate, ethyl cellosolve ethyl acetate, ethyl cellosolve propyl acetate, ethyl cellosolve isopropyl acetate or the like.
In this article, chloroplatinic acid is a kind of compound, and the conversion relation of wherein said platinum content and described chloroplatinic acid content is as follows:
The amount (g) * 0.38 of the amount of platinum (g)=chloroplatinic acid
In the present invention, described viscosity is to use brookfield dvII rotation viscometer under the condition of 1r/min rotating speed and 25 ℃, and serves as to measure when measuring solvent with the solvent in the chloroplatinic acid slurry.
It is worthy of note, in this article, one or more compounds in terpinol, kerosene, higher boiling point paraffin oil and the ethyl cellosolve acetate of being selected from that added are in order to improve the viscosity of slurry, and the same ethyl cellulose that adds also is in order to improve the viscosity of slurry.The adding of these materials does not influence the performance of the platinum of DSSC to electrode, opposite use that the platinum pulp preparation that is added with these materials goes out to the prepared DSSC of electrode and conventional method (for example spin-coating method) electrode is also slightly improved on performance, for example referring to the data of table 1 (routine is to electrode) and table 2 (silk screen printing prepares electrode):
Table 1
| Short circuit current Isc (mA/cm 2) | Open circuit voltage Voc (V) | Fill factor, curve factor FF | Electricity conversion η (%) |
| 16.05 | 0.714 | 0.63 | 7.2 |
In the present invention, employed substrate to electrode is an electro-conductive glass, and usually, electro-conductive glass has 5cm
2-500cm
2Area.Electro-conductive glass is cleaned 10-30min with washing agent, 0.1M HCl-ethanolic solution, acetone respectively in ultrasonic cleaning tank, take out the back and use alcohol flushing, dry stand-by.Wherein, the use of 0.1M HCl-ethanolic solution, acetone order can be exchanged.Ultrasonic power is 300-500W.
At step c-e) in, the silk screen that the washed electro-conductive glass conducting surface that dries is placed on screen process press up is the location down, but and the silk screen printing area be 200 * 300mm
2, go up in right amount at the above-mentioned platinum slurry of preparing at the scraper plate place of silk screen, silk screen is put down, start the screen process press blade coating, perhaps carry out blade coating by hand, then silk screen is mentioned, the glass of blade coating spreading mass is taken out, place 1-5min, put into baking oven, take out 60-150 ℃ of oven dry down.Put into Muffle furnace or tube furnace again at 380-500 ℃ of following sintering 10-30min, promptly obtain platinum electrode.Usually, the temperature of heat-treating is high more, and the time of then heat-treating is short more.And, if sintering temperature is lower than 380 ℃, be unfavorable for the conversion of chloroplatinic acid to platinum, on the contrary, the too high platinum that may make again of temperature forms spongy platinum, adds and considers economic reasons, and therefore, the upper limit of sintering is selected 500 ℃.In experimentation, the inventor has chosen following several groups of sintering conditions and has all obtained good result: 380 ℃, and 30min; 400 ℃, 15min; 450 ℃, 10min; 500 ℃, 10min.Preferably at 400 ℃ of following sintering 15min.
If will plate more platinum, can repeat repeatedly silk screen printing, promptly step c) is to e) process, the platinum that can obtain required year platinum amount is to electrode.Described repeatedly is more than 2 times, and preferred 2-3 time.
In the present invention, adopt screen printing mode that platinum is coated in the electro-conductive glass substrate, the chloroplatinic acid consumption is few, and carrying the platinum amount can quantitatively control, and the platinum of available energy stability and high efficiency is to electrode.Silk screen print method can prepare 5-500cm in addition
2Large-area platinum to electrode, be very suitable for large-scale preparation, for industrial production lays the first stone.
Therefore, the platinum by above-mentioned DSSC of the present invention can obtain a kind of 2500mm of having to the method for electrode
2-30000mm
2The platinum of large-area DSSC to electrode, described large tracts of land for example is 100 * 100mm
2
Embodiment
Embodiment 1
At first, preparation viscosity is suitable for the platinum slurry of silk screen printing.Detailed process is as follows: the commercially available analytically pure ethyl cellulose of 3g is under agitation slowly added in the 30g absolute ethyl alcohol, make ethyl cellulose-ethanolic solution of 10%.Then, commercially available analytically pure chloroplatinic acid 2.5895g is dissolved in the ethanolic solution of 500ml, the platinum acid chloride solution of preparation 10mM (mM/liter), under the magneton stirring condition, it is (commercially available to add the 10g terpinol, the Beijing Chemical Plant, together, analyze pure down), stir 1min, carry out ultrasonic, ultrasound condition is power 400w, ultrasonic 2 seconds, and intermittently 2 seconds, ultrasonic 30 times altogether, ethyl cellulose (Beijing Chemical Plant the analyzes pure)-ethanolic solution that adds 30g previously prepared 10% again under the magneton stirring condition continues to stir 1min, carry out ultrasonic 30 times according to above-mentioned condition then, at 40 ℃ of following decompression distillation 30min, vacuum gauge pressure is-0.09Pa to make required chloroplatinic acid slurry again, final slurry viscosity is 30Pas, and platinum content is about 6.3%.
Then, with 150 * 200mm
2Electro-conductive glass (Japanese Nippon Sheet Glass company) in power 300W ultrasonic cleaning tank, clean 15min with washing agent, 0.1M HCl-ethanolic solution, acetone respectively, take out the back and use alcohol flushing, dry stand-by.
(but the silk screen printing area is 200 * 300mm to the silk screen that the washed electro-conductive glass conducting surface that dries is placed on screen process press (wc-260B, Rong Long Industrial Co., Ltd produces) up in the location down
2), the scraper plate place of silk screen on the platinum slurry of about 20g, silk screen is put down, start the screen process press blade coating, then silk screen is mentioned, the glass of blade coating spreading mass is taken out, place 3min, put into baking oven, take out 80 ℃ of oven dry down, put into Muffle furnace or tube furnace again at 400 ℃ of following sintering 15min, can obtain 150 * 200mm
2Platinum to electrode.Gained is as shown in table 2 to the DSSC performance of electrode preparation.
Method of testing is as follows: at first with TiO
2Slurry (Dalian HeptaChroma SolarTech Co., Ltd.) uses silk screen printing on the ethanol clean conductive glass, at 500 ℃ of following sintering 1h, be cooled to 80 ℃ with stove, N719 dyestuff (Dalian HeptaChroma SolarTech Co., Ltd.) ethanolic solution of putting into 0.5mM soaks 24h, taking-up cleans up with ethanol, dry, be the light anode, with ready-made the electrodes conduct cover is lived the light anode then, respectively expose a part of glass at two, as derived current usefulness, clamp both sides with clip again and fix, expose TiO
2, splash into several electrolyte solutions (Dalian HeptaChroma SolarTech Co., Ltd.) in the side, with solar simulator irradiates light anode (light intensity 100mw/cm
2), the product maximum of calculating electric current and voltage is its maximum power Pmax, photoelectric conversion efficiency η=Pmax/TiO
2Area; Fill factor, curve factor FF=Pmax/ (short circuit current Isc * open circuit voltage Voc).
Table 2
| Short circuit current Isc (mA/cm 2) | Open circuit voltage Voc (V) | Fill factor, curve factor FF | Electricity conversion η (%) |
| 17.1 | 0.723 | 0.62 | 7.66 |
Embodiment 2
At first, preparation viscosity is suitable for the platinum slurry of silk screen printing.Detailed process is as follows: at first, 3g (Beijing Chemical Plant, below identical) ethyl cellulose is under agitation slowly added in the 27g absolute ethyl alcohol, make ethyl cellulose-ethanolic solution of 10%.
Then, with the commercially available (Beijing Chemical Plant of 2.5895g, below identical) analytically pure chloroplatinic acid is dissolved in the ethanolic solution of 500ml, the platinum acid chloride solution of preparation 10mM, under the magneton stirring condition, add 10g terpinol (Beijing Chemical Plant analyzes pure), stir 1min, carry out first sonicated, ultrasound condition is power 400w, ultrasonic 2 seconds, intermittently 2 seconds, ultrasonic 30 times altogether, ethyl cellulose-ethanolic solution of adding 20g previously prepared 10% under the magneton stirring condition continues to stir 1min again, carry out second sonicated according to above-mentioned condition then, ultrasonic 30 times.
Again at 40 ℃ of following decompression distillation 30min, vacuum gauge pressure is-0.09Pa, and can make final slurry viscosity is the chloroplatinic acid slurry of 20Pas, and platinum content is about 6.7g/100g chloroplatinic acid slurry.
With 100 * 100mm
2Electro-conductive glass (Japanese Nippon Sheet Glass company) in the ultrasonic cleaning tank of power 300W, clean 30min with washing agent, 0.1M HCl-ethanolic solution, acetone respectively, take out the back and use alcohol flushing, dry stand-by.
(but the silk screen printing area is 200 * 300mm to the silk screen that the washed electro-conductive glass conducting surface that dries is placed on screen process press (wc-260B, Rong Long Industrial Co., Ltd produces) up in the location down
2), the scraper plate place of silk screen on the platinum slurry of about 10g, silk screen is put down, start the screen process press blade coating, then silk screen is mentioned, the glass of blade coating spreading mass is taken out, place 5min, put into baking oven 100 ℃ of oven dry down, take out, put into Muffle furnace or tube furnace again at 400 ℃ of following sintering 15min.Gained is to the DSSC performance such as the table 3 of electrode preparation:
Method of testing is with the method for testing among the embodiment 1.
Table 3
| Short circuit current Isc (mA/cm 2) | Open circuit voltage Voc (V) | Fill factor, curve factor FF | Electricity conversion η (%) |
| 16.5 | 0.753 | 0.63 | 7.57 |
Embodiment 3
At first, the commercially available analytically pure ethyl cellulose of 3g is under agitation slowly joined in the 27g absolute ethyl alcohol, make ethyl cellulose-ethanolic solution of 10%.
Then, the commercially available analytically pure chloroplatinic acid of 5.179g is dissolved in the ethanolic solution of 500ml, the platinum acid chloride solution of preparation 20mM under the magneton stirring condition, adds 10g terpinol (Beijing Chemical Plant, analyze pure), stir 2min, carry out first sonicated, ultrasound condition is power 800w, ultrasonic 6 seconds, intermittently 2 seconds, ultrasonic 40 times altogether, 10% the ethyl cellulose-ethanolic solution that adds under the magneton stirring condition then that 30g prepares in advance, continue to stir 2min, carry out second sonicated again, ultrasound condition is power 600w, ultrasonic 3 seconds, intermittently 1 second, ultrasonic 30 times altogether.Then, at 40 ℃ of following decompression distillation 60min, vacuum gauge pressure is-0.09Pa, and can make final slurry viscosity is the chloroplatinic acid slurry of 30Pas, and wherein platinum content is about 10.8g/100g chloroplatinic acid slurry.
With 50 * 100mm
2Electro-conductive glass (Japanese Nippon Sheet Glass company) in the ultrasonic cleaning tank of power 300W, clean 30min with washing agent, 0.1M HCl-ethanolic solution, acetone respectively, take out the back and use alcohol flushing, dry stand-by.
(but the silk screen printing area is 200 * 300mm to the silk screen that the washed electro-conductive glass conducting surface that dries is placed on screen process press (wc-260B, Rong Long Industrial Co., Ltd produces) up in the location down
2), the scraper plate place of silk screen on the platinum slurry of about 8g, silk screen is put down, start the screen process press blade coating, then silk screen is mentioned, the glass of blade coating spreading mass is taken out, place 5min, put into baking oven 100 ℃ of oven dry down, take out, put into Muffle furnace or tube furnace again at 450 ℃ of following sintering 10min.Gained is to the DSSC performance such as the table 4 of electrode preparation:
Method of testing is with the method for testing among the embodiment 1.
Table 4
| Short circuit current Isc (mA/cm 2) | Open circuit voltage Voc (V) | Fill factor, curve factor FF | Electricity conversion η (%) |
| 16.7 | 0.734 | 0.63 | 7.72 |
Industrial applicability
Adopt screen printing technique to prepare platinum to electrode, compared with prior art, the most obvious feature is that the present invention can prepare uniform platinum to electrode, and existing method prepares platinum to the electrode complex operation, and applies inhomogeneous. The present invention can prepare required large-area to electrode as required, and existing method preparation is limited to electrode area. In addition, operation is very easy to electrode for the present invention's preparation, is conducive to large-scale industrial production platinum to electrode.
Because silk screen print method is very widely used a kind of method, also do not see it is used for preparing platinum to the concrete report of electrode that therefore this technology will have very widely application prospect at present.
Claims (12)
1. method for preparing the platinum of DSSC to electrode, described method comprises the steps:
A) provide that to have the viscosity that is suitable for carrying out silk screen printing be the chloroplatinic acid slurry of 4-50Pas;
B) electro-conductive glass is cleaned and dry;
C) utilize screen process press, the silk screen printing of described chloroplatinic acid slurry is filmed to form the chloroplatinic acid slurry on the conducting surface of the electro-conductive glass through cleaning and drying;
D) have the electro-conductive glass that the chloroplatinic acid slurry is filmed from the screen process press taking-up, dry;
E) then, the electro-conductive glass that has the chloroplatinic acid slurry coating of drying is carried out sintering,
Wherein said chloroplatinic acid slurry provides as follows:
Under stirring condition, to 100-500mL concentration is in the alcoholic solution of chloroplatinic acid of 5-20mM, adding is stirred 1-5min by one or more compounds in terpinol, kerosene, higher boiling point paraffin oil and the ethyl cellosolve acetate of being selected from of the described chloroplatinic acid slurry of 100g 38.34-70g;
Carry out first sonicated then;
Under stirring condition, add the ethyl cellulose by the 4.15-20g of the described chloroplatinic acid slurry of 100g again, described ethyl cellulose adds with the form of 10-20 quality % alcoholic solution, continues to stir 1-5min;
Carry out second sonicated then, and
Part removes solvent, with the viscosity that obtains to be suitable for carrying out silk screen printing.
2. method according to claim 1, wherein e) described in sintering comprise: at 380-500 ℃ of following sintering 10-30min.
3. method according to claim 1 and 2, wherein said sintering carries out in Muffle furnace or tube furnace.
4. method according to claim 1 also is included in step (e) afterwards, with step (c)-(e) repeat 2-3 time successively, with the platinum that obtains required year platinum amount to electrode.
5. method according to claim 1, the platinum content of wherein said chloroplatinic acid slurry are 0.49-13.3g/100g chloroplatinic acid slurry.
6. method according to claim 1, wherein said part remove solvent and comprise and carry out decompression distillation.
7. method according to claim 1, the viscosity of wherein said chloroplatinic acid slurry are 15-50Pas.
8. method according to claim 1, wherein said cleaning comprises: clean described electro-conductive glass 10-30min with washing agent, 0.1M HCl-ethanolic solution, acetone in ultrasonic cleaning tank respectively, use alcohol flushing again after described electro-conductive glass is taken out.
9. method according to claim 1, wherein said electro-conductive glass has 5cm
2-500cm
2Area.
10. method according to claim 1, wherein said silk screen printing also comprise hand-printing or print automatically and carry out blade coating.
11. the platinum of a DSSC that obtains by the described method of claim 1 is to electrode.
12. platinum according to claim 11 is to electrode, described platinum is 2500mm to the area of electrode
2-30000mm
2
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| CN101373670A (en) * | 2008-10-09 | 2009-02-25 | 彩虹集团公司 | Method for preparing porous platinum electrode of solar cell |
| CN101373668A (en) * | 2008-10-09 | 2009-02-25 | 彩虹集团公司 | Encapsulation method for dye sensitization solar cell |
| CN101447339A (en) * | 2008-12-11 | 2009-06-03 | 彩虹集团公司 | Method for preparing solar battery photo-anode substrate |
| CN101515505A (en) * | 2009-03-31 | 2009-08-26 | 彩虹集团公司 | Method for preparing platinum electrode of dye sensitized solar cell |
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| CN101373670A (en) * | 2008-10-09 | 2009-02-25 | 彩虹集团公司 | Method for preparing porous platinum electrode of solar cell |
| CN101373668A (en) * | 2008-10-09 | 2009-02-25 | 彩虹集团公司 | Encapsulation method for dye sensitization solar cell |
| CN101447339A (en) * | 2008-12-11 | 2009-06-03 | 彩虹集团公司 | Method for preparing solar battery photo-anode substrate |
| CN101515505A (en) * | 2009-03-31 | 2009-08-26 | 彩虹集团公司 | Method for preparing platinum electrode of dye sensitized solar cell |
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