CN101714462B - Method for preparing platinum counter electrode of dye sensitization solar battery and platinum counter electrode - Google Patents
Method for preparing platinum counter electrode of dye sensitization solar battery and platinum counter electrode Download PDFInfo
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- CN101714462B CN101714462B CN 200910225913 CN200910225913A CN101714462B CN 101714462 B CN101714462 B CN 101714462B CN 200910225913 CN200910225913 CN 200910225913 CN 200910225913 A CN200910225913 A CN 200910225913A CN 101714462 B CN101714462 B CN 101714462B
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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
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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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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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
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a method for preparing a platinum counter electrode of a dye sensitization solar battery, and a platinum counter electrode. The method comprises the following steps: providing a reverse dip-coating device; cleaning conductive glass; fixing the cleaned conductive glass in the reverse dip-coating device, and pouring a platinum solution or a pulp as the dip-coating liquid to immerse the conductive glass in the dip-coating liquid; completely eluting the dip-coating liquid; and then carrying out heat treatment to obtain a uniform platinum counter electrode. Compared with the prior art, the method has the most obvious characteristic that the large-area uniform platinum counter electrode can be prepared.
Description
Technical field
The present invention relates to platinum that a kind of platinum for preparing DSSC prepares to the method for electrode and by the method to electrode, particularly, relate to and utilize Reversed-dip-coating, prepare the platinum of large-area DSSC to the method for electrode, and the platinum of being prepared by the method is to electrode.
Background technology
Energy shortage and environmental pollution are the two large problems of present facing mankind.Traditional energy of coal, oil and timber can only be kept 50 to 100 years by present depletion rate.In addition, the environmental pollution that brings is thus also threatening the human earth of depending on for existence.And in the foreseeable future time of the mankind, solar energy is as the inexhaustible clear energy sources of the mankind, do not produce any environmental pollution, and basically be not subjected to the restriction of geographical conditions, 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 simple technique 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 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, is conducive to reduce 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 standby platinum membrane structure of legal system is even with electroplating, the queueing discipline big energy-consuming.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 whole energy content of battery efficient not high.And have vesicular texture with the platinum film of thermal decomposition method preparation, thereby larger specific area arranged, the pt atom that forms bunch can play the effect of catalysis well, when working, electrode can produce larger exchange current density, the loss of potential that causes is less and more stable, is difficult for being corroded.
Also have in addition report to use the situation of spin-coating method.For example Chinese patent CN101447340 discloses a kind of preparation technology of the electrode with large surface area for DSSC, its technical characteristics is that chloroplatinic acid is dissolved in the isopropyl alcohol, to obtain platinum acid chloride solution is spin-coated on electro-conductive glass (3) surface, the electro-conductive glass (3) that is coated with metallic gold or platinum grain layer is put into sintering furnace, on large particle surface, just can adhere to the less metallic particles of particle diameter, formation has 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 large, the shortcoming such as the amount of filming is uncontrollable, so its preparation is bad to electrode repeatability, can not obtain stable performance efficiently to electrode.
Czochralski method (perhaps anti-czochralski method) has had widely application on filming technology in addition, it is object to be immersed lift in the liquid, utilize lifting rod band animal body to rise, thereby plate thin film at object, and anti-czochralski method is to utilize the liquid level that lifts liquid to descend to reach the effect of filming.Anti-czochralski method is more easily realized uniform coating when filming for large tracts of land or irregular object, operate simplyr than positive czochralski method, and the area that lifts thing can design as required, is very beneficial for large-scale application.
Summary of the invention
The present invention proposes and instead to lift technology and pyrolytic technique and combine the platinum for preparing DSSC to a kind of method of electrode.
Therefore, the present invention relates to following aspect:
＜1〉a kind of platinum of DSSC for preparing is to the method for electrode, and described method comprises the steps:
A) provide a kind of anti-pulling apparatus;
B) cleaning electro-conductive glass (3);
C) clean electro-conductive glass (3) is fixed in the described anti-pulling apparatus, and pours platinum solution or slurry into as lifting liquid, so that described electro-conductive glass (3) immerses described lifting in the liquid;
D) make and lift liquid and flow out fully;
E) then heat-treat, can obtain uniform platinum to electrode.
＜2〉according to＜1〉described method, at e) described in heat treatment be included under 380-500 ℃ and heat-treat, then heat treatment time 10-30min cools naturally.
＜3〉according to＜1〉or＜2〉described method, described heat treatment is carried out in Muffle furnace.
＜4〉according to＜1〉described method, comprise also that repetition is counter to lift-heat treated step c) to e) repeatedly, can obtain the large tracts of land platinum of required year platinum amount to electrode.
＜5〉according to＜3〉described method, wherein said repeatedly is 2-3 time.
＜6〉according to＜1〉described method, described cleaning electro-conductive glass (3) comprising: clean in ultrasonic cleaning tank with washing agent, ethanol, acetone respectively, use alcohol flushing after taking out, dry stand-by.
＜7〉according to＜1〉described method, described platinum solution or slurry are platinum acid chloride solution or slurry.
＜8〉according to＜7〉described method, wherein the concentration at described platinum acid chloride solution or slurry is 5-20mM.
＜9〉according to＜7〉described method, described platinum acid chloride solution obtains by chloroplatinic acid is dissolved in the alcoholic solution.
＜10〉according to＜7〉described method, described chloroplatinic acid slurry is to obtain by following step:
Under stirring condition, be in the alcoholic solution of chloroplatinic acid of 5-20mM to 100-500mL concentration, 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;
Then carry out the first ultrasonic processing;
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 the alcoholic solution of 10-20 quality %, continues to stir 1-5min;
Then carry out the second ultrasonic processing, and
Randomly part removes solvent, to obtain required chloroplatinic acid slurry viscosity.
＜11〉according to＜1〉described method, in described steps d) in, the speed that lifts the liquid outflow is controlled in 0.4-3mm/s.
＜12〉according to＜1〉described method, described anti-pulling apparatus has the container (1) of a constant volume, wherein said container (1) is connected with the container (2) of another lower position by conduit (4), and described conduit (4) coupling has valve (5).
＜13〉according to＜12〉described method, step a) in, the container with certain volume that provides can also be in bottom opening.
＜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 25cm to the area of electrode
2-300cm
2
With the method for the standby large-area dye-sensitized solar battery platinum of reverse dip-coating legal system to electrode, compared with prior art, the most obvious feature is that method of the present invention can prepare uniform platinum to electrode, and all there is the inhomogeneous shortcoming of coating in the platinum of existing method preparation to electrode.
In addition, the present invention can prepare different large-area platinum as required to electrode, can be controlled by the size that lifts liquid container, and the spin coating method preparation is limited to electrode area, because being subjected to the size of spin coating rotating disk container controls, and the spin coating rotating disk can not be done too greatly, otherwise can inhale the thing of incessantly being filmed.
Description of drawings
Fig. 1 is the schematic diagram of a kind of embodiment of anti-pulling apparatus used in the present invention.
Embodiment
The invention provides a kind of platinum of DSSC for preparing to the method for electrode, described method comprises the steps: a) to provide a kind of anti-pulling apparatus particularly; B) cleaning is as the electro-conductive glass 3 of substrate; C) clean electro-conductive glass 3 is fixed in the described anti-pulling apparatus, and pour the chloroplatinic acid slurry of certain density platinum acid chloride solution or viscosity into as lifting liquid, so that described electro-conductive glass 3 immerses the described certain hour in the liquid that lifts, described certain hour is generally 1-3min so that 3 substrates of described electro-conductive glass fully contact and the liquid level calmness that lifts liquid is limited with lifting liquid; D) can utilize siphon principle or Action of Gravity Field to extract to lift liquid, after lifting liquid and flowing out fully, take out glass and will lift liquid and dry; E) then heat-treat, that is, naturally cool after can under 380-500 ℃, heat-treating 10-30min, can obtain uniform platinum to electrode.Usually, the temperature of heat-treating is higher, and the time of then heat-treating is shorter.And, if heat treatment temperature is lower than 380 ℃, be unfavorable for chloroplatinic acid to the conversion of platinum, on the contrary, the too high platinum that may make again of temperature forms spongy platinum, adds and considers economic reason, and therefore, the upper limit of heat treatment temperature is selected 500 ℃.In experimentation, the inventor has chosen following several groups of heat-treat conditions and has all obtained good result: 380 ℃, and 30min; 400 ℃, 15min; 450 ℃, 10min; 500 ℃, 10min.Preferably at 400 ℃ of lower heat treatment 15min.
In the present invention, described anti-pulling apparatus refers to utilize the liquid level decline that lifts liquid to reach the device of the effect of filming.A concrete example of anti-pulling apparatus is: can utilize siphon principle or Action of Gravity Field to extract and lift liquid, lift liquid and descend to reach the device of effect of filming thereby make.
Shown in Fig. 1 is the schematic diagram of a kind of embodiment of employed anti-pulling apparatus among the present invention, wherein, the 1st, the container with a constant volume, can hold in the container 1 and lift liquid, 3 is electro-conductive glass 3, described container 1 is connected with the container 2 of another lower position by conduit 4, and described conduit 4 couplings have valve 5.The another embodiment of employed anti-pulling apparatus is to have the hole in the bottom of described container 1, lifts liquid to utilize Action of Gravity Field to extract.
In the present invention, the employed liquid that lifts is platinum solution or slurry.In this article, preferably platinum acid chloride solution or slurry of described platinum solution or slurry.
Described platinum acid chloride solution is commercially available chloroplatinic acid to be dissolved in be configured to certain density solution in the alcoholic solution and obtain.
And described chloroplatinic acid slurry is to obtain by following step: under stirring condition, be in the alcoholic solution of chloroplatinic acid of 5-20mM to 100-500mL concentration, 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; Then carry out the first ultrasonic processing; 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 the alcoholic solution of 10-20 quality %, continues to stir 1-5min; Then carry out the second ultrasonic processing, and randomly part removes solvent, to obtain required platinum concentration.The described example that partly removes solvent comprises and carries out decompression distillation.The wherein said first ultrasonic processing and the described second ultrasonic processing can be identical or different.Described ultrasonic processing is included under the ultrasonic power of 400-800W, ultrasonic processing 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 " refers to that boiling range is at 150-170 ℃ higher boiling point paraffin oil.
In this article, term " kerosene " refers to 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 etc.
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 the solvent in the chloroplatinic acid slurry is measured when measuring solvent.
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 add 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 affect the platinum of DSSC to the performance of electrode, on the contrary, use be added with that the platinum slurry of these materials prepares 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 (conventional to electrode) and table 2 (anti-czochralski method 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 electro-conductive glass 3.The electro-conductive glass 3 of certain area is cleaned in ultrasonic cleaning tank with washing agent, ethanol, acetone respectively, and ultrasonic power is 300-500W, uses alcohol flushing after taking out, and dries stand-by.Wherein the cleaning sequence of ethanol and acetone can exchange.
The washed electro-conductive glass 3 that dries is fixed on has the lifting in the liquid container 1 (as shown in Figure 1) an of constant volume, pour the 20mM platinum acid chloride solution or the conduct of chloroplatinic acid slurry that prepare in advance into and lift liquid, electro-conductive glass 3 immersions are lifted 1min in the liquid, utilize siphon principle or Action of Gravity Field to extract and lift liquid or slurry, perhaps in the container lower openings, utilize gravity to make and lift liquid in the container 2 of conduit 4 inflow lower positions, flow velocity is by valve 5 controls, and pull rate is controlled at 0.4-3mm/s.After lifting liquid and flowing out fully, take out glass and will lift liquid and naturally dry.Then put into Muffle furnace, heat-treat under 380-500 ℃, this is because the chloroplatinic acid pyrolysis becomes the temperature of platinum to need about 400 ℃.Heat treatment time can be 1-3min, then naturally cools, and the uniform platinum that can obtain to film is to electrode.If need the more platinum of plating, lift more than can repeating-the step c of sintering) to e) repeatedly, preferred 1-2 time, can obtain the large tracts of land platinum of required year platinum amount to electrode.
For detect adopt the reverse dip-coating preparation platinum to the prepared battery efficiency of electrode, also detected the resulting platinum of drop-coating to the efficient of the prepared battery of electrode as a comparison, the result is as shown in table 2.
The method of testing of battery efficiency is as follows: at first with TiO
2Slurry (Dalian HeptaChroma SolarTech Co., Ltd.) silk screen printing is on the electro-conductive glass 3 that ethanol cleans up, at 500 ℃ of lower 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, then with what prepare among the present invention the electrodes conduct cover is lived the light anode, 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 irradiation 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).
Wherein, the drop-coating preparation is as follows to electrode method: the 5mM platinum acid chloride solution of 20ul is dripped on the electro-conductive glass 3 that area is 1.5cm * 2cm, treat that it dries, put into 400 ℃ of Muffle furnaces and burn 15min, can make electrode.
The platinum of table 2 reverse dip-coating and drop-coating preparation is to the battery efficiency of electrode
As can be seen from Table 2, the preparation of anti-czochralski method electrode is made battery after, the efficient that electrode is made behind the battery that its efficient and drop-coating prepare is basically identical, this explanation can adopt this method to prepare platinum to electrode.
In addition, it is worthy of note, the platinum of the present invention's preparation has the platinum amount of carrying an of the best to electrode, be generally 5-6ug/cm
2, this can accurately be controlled by the concentration that lifts liquid, and therefore lifting in the liquid concentration of chloroplatinic acid, to be controlled at 5-20mM be good.
Use anti-czochralski method to prepare platinum electrode, carrying the platinum amount can control well by lifting liquid, and the use of chloroplatinic acid can not cause waste.And in spin-coating method, in the time of spin coating, a lot of chloroplatinic acids have all been got rid of away, cause very large waste, therefore anti-czochralski method has been saved raw material than spin-coating method, in addition, the anti-liquid that lifts that flows in the lower container in position 2 can reuse after recycling, thereby provides cost savings; And, lift the preparation technology that films and can obtain than the more uniform platinum of spin-coating method electrode (vision observation); The platinum that lifts the coating method preparation can by lift liquid container control, use the container that lifts of different sizes, thereby can prepare different large-area platinum to electrode electrode area.
The platinum that platinum by preparation DSSC of the present invention can obtain a kind of large-area DSSC to the method for electrode is to electrode, and described large tracts of land for example is 5 * 5cm
2-15 * 20cm
2
Embodiment
Embodiment 1
The electro-conductive glass 3 (Japanese Nippon Sheet Glass company) that is purchased of 10cm * 20cm * 0.22cm is cleaned 10min with washing agent, ethanol, acetone respectively in power 300W ultrasonic cleaning tank, uses alcohol flushing after taking out, dry stand-by.
The washed electro-conductive glass 3 stuck-at-１ cm (wide) that dry * 22cm (length) * 12cm (height) is lifted in the liquid container 1 (as shown in Figure 1), pour the 20mM platinum acid chloride solution for preparing in advance into.Being prepared as follows of described platinum acid chloride solution: commercially available 1.2948g chloroplatinic acid (analyze pure, Beijing Chemical Plant) is dissolved in the 125ml isopropyl alcohol (analyze pure, Beijing Chemical Plant), prepare 20mM (mM/l) platinum acid chloride solution.Electro-conductive glass 3 is immersed 1min in the platinum acid chloride solutions, utilize siphon principle to extract and lift liquid, allow the liquid level that lifts liquid descend with the speed of 1mm/s, flow in the container 2 of lower position.After lifting liquid and flowing out fully, take out this electro-conductive glass 3, will lift liquid and dry, then put into Muffle furnace, at 400 ℃ of lower insulation 15min, then naturally cool, can obtain the large-area platinum of 10cm * 20cm of required year platinum amount to electrode.The results are shown in the table 2.
Embodiment 2
The electro-conductive glass 3 (Japanese Nippon Sheet Glass company) that is purchased of 10cm * 10cm * 0.22mm is cleaned 10min with washing agent, ethanol, acetone respectively in power 500W ultrasonic cleaning tank, uses alcohol flushing after taking out, dry stand-by.
The washed electro-conductive glass 3 stuck-at-１ cm (wide) that dry * 22cm (length) * 12cm (height) is lifted in the liquid container 1 (as shown in Figure 1), pour the 10mM platinum acid chloride solution for preparing in advance into.Being prepared as follows of described platinum acid chloride solution: commercially available 0.6474g chloroplatinic acid (analyze pure, Beijing Chemical Plant) is dissolved in the 125ml isopropyl alcohol (analyze pure, Beijing Chemical Plant), prepares the 10mM platinum acid chloride solution.Electro-conductive glass 3 is immersed 1min in the platinum acid chloride solutions, utilize siphon principle to extract and lift liquid, allow the liquid level that lifts liquid descend with the speed of 2mm/s, flow in the container 2 of lower position.After lifting liquid and flowing out fully, take out this electro-conductive glass 3, will lift liquid and dry, then put into Muffle furnace, at 400 ℃ of lower insulation 15min, then naturally cool, can obtain the large-area platinum of 10cm * 10cm of required year platinum amount to electrode.The results are shown in the table 2.
Embodiment 3
At first prepare the chloroplatinic acid slurry: 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, adds 10g terpinol (Beijing Chemical Plant, analyze pure), stir 1min, carry out the first ultrasonic processing, ultrasound condition is power 400w, ultrasonic 2 seconds, intermittently 2 seconds, be total to ultrasonic 30 times, under the magneton stirring condition, add again ethyl cellulose-ethanolic solution of 20g previously prepared 10%, continue to stir 1min, then carry out the second ultrasonic processing according to above-mentioned condition, ultrasonic 30 times, decompression distillation.Can obtain viscosity is 5pa.s, and every 100g chloroplatinic acid slurry contains 3.0g platinum, and is stand-by.
The electro-conductive glass 3 (Japanese Nippon Sheet Glass company) that is purchased of 15cm * 20cm * 0.22mm is cleaned 15min with washing agent, ethanol, acetone respectively in the 300W ultrasonic cleaning tank, uses alcohol flushing after taking out, dry stand-by.
The washed electro-conductive glass 3 stuck-at-１ cm (wide) that dry * 22cm (length) * 17cm (height) is lifted in the liquid container (as shown in Figure 1), and to wherein pouring the chloroplatinic acid slurry for preparing in advance into.
Described glass is immersed 1min in the chloroplatinic acid slurry, utilize siphon principle to extract slurry, allow the liquid level of slurry descend with the speed of 0.4mm/s, flow in the container 2 of lower position.After lifting liquid and flowing out fully, take out glass and will lift liquid and dry.Then put into Muffle furnace, at 450 ℃ of lower insulation 10min, then naturally cool.Counter lifting more than the repetition-heat treated process 2 times can obtain the large-area platinum of 15cm * 20cm of required year platinum amount to electrode, and gained platinum is shown in the table 2 performance that electrode is prepared into after the battery.
Industrial applicability
It is very extensive to the scope of application of the method for electrode that this anti-czochralski method prepares the platinum of large-area dye-sensitized solar battery, under the condition that lifts the concentration range that is usually satisfying a best in filming, can obtain surface uniform better performance to electrode.
Claims (11)
1. one kind prepares the platinum of DSSC to the method for electrode, and described method comprises the steps:
A) provide a kind of anti-pulling apparatus;
B) cleaning electro-conductive glass (3);
C) clean electro-conductive glass (3) is fixed in the described anti-pulling apparatus, and pours the chloroplatinic acid slurry into as lifting liquid, so that described electro-conductive glass (3) immerses described lifting in the liquid;
D) make and lift liquid and flow out fully;
E) then heat-treat, can obtain uniform platinum to electrode,
Wherein said chloroplatinic acid slurry is to obtain by following step:
Under stirring condition, be in the alcoholic solution of chloroplatinic acid of 5-20mM to 100-500mL concentration, 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;
Then carry out the first ultrasonic processing;
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 the alcoholic solution of 10-20 quality %, continues to stir 1-5min;
Then carry out the second ultrasonic processing, decompression distillation, and
Solvent is partly removed, to obtain required chloroplatinic acid slurry viscosity.
2. method according to claim 1 is at e) described in heat treatment be included under 380-500 ℃ and heat-treat, then heat treatment time 10-30min cools naturally.
3. method according to claim 1 and 2, described heat treatment is carried out in Muffle furnace.
4. method according to claim 1 comprises also that repetition is counter to lift-heat treated step c) to e) 2-3 time, can obtain the large tracts of land platinum of required year platinum amount to electrode.
5. method according to claim 1, described cleaning electro-conductive glass (3) comprising: clean in ultrasonic cleaning tank with washing agent, ethanol, acetone respectively, uses alcohol flushing after taking out, dry stand-by.
6. method according to claim 1, wherein said chloroplatinic acid slurry viscosity is 5pa.s.
7. method according to claim 1 is in described steps d) in, lift the speed that liquid flows out and be controlled in 0.4-3mm/s.
8. method according to claim 1, described anti-pulling apparatus has the container (1) of a constant volume, wherein said container (1) is connected with the container (2) of another lower position by conduit (4), and described conduit (4) coupling has valve (5).
9. method according to claim 8, step a) in, the container with a constant volume that provides can also be in bottom opening.
10. the platinum of a DSSC that obtains by method claimed in claim 1 is to electrode.
11. platinum according to claim 10 is to electrode, described platinum is 25cm to the area of electrode
2-300cm
2
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| CN1698974A (en) * | 2004-05-17 | 2005-11-23 | 电子科技大学 | Reversed dip coating device |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1698974A (en) * | 2004-05-17 | 2005-11-23 | 电子科技大学 | Reversed dip coating device |
| 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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