CN101217174A - A repairing method on the photo anode of dye sensitization solar battery - Google Patents

A repairing method on the photo anode of dye sensitization solar battery Download PDF

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Publication number
CN101217174A
CN101217174A CNA2008100520369A CN200810052036A CN101217174A CN 101217174 A CN101217174 A CN 101217174A CN A2008100520369 A CNA2008100520369 A CN A2008100520369A CN 200810052036 A CN200810052036 A CN 200810052036A CN 101217174 A CN101217174 A CN 101217174A
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China
Prior art keywords
light anode
dye
micro
sensitized solar
crack
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CNA2008100520369A
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Chinese (zh)
Inventor
蔡宁
赵颖
张晓丹
熊绍珍
张建军
孙建
魏长春
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Nankai University
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Nankai University
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Priority to CNA2008100520369A priority Critical patent/CN101217174A/en
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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
    • 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

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  • Photovoltaic Devices (AREA)

Abstract

The invention provides a repair method which is simple and can reduce or even eliminate the micro cracks of a photo-anode of a dye-sensitized solar cell. The method is designed against a porous TiO2 electrode which has the micro cracks after sintering, the processing method is that: the electrode is processed in a water solution of titanium salt or titanium butoxide (TiCl4, TiOSO4, Ti(SO4)2, Ti(OC3H7)4, Ti(OC4H9)4) with the concentration of 0 to 0.4M which is easy to be hydrolyzed; the processing conditions are that: the room temperature is 90 DEG C, the time is 0.1 to 48 hours, and then the micro cracks of the electrode can be significantly reduced or even eliminated after the sintering at 400 to 500 DEG C.

Description

The restorative procedure of dye-sensitized solar cells light anode micro-crack
[technical field]
The present invention relates to dye-sensitized solar cells and make the field, relate in particular to a kind of restorative procedure of dye-sensitized solar cells light anode micro-crack.
[background technology]
Because ecological deterioration and energy crisis, solar cell had been subjected to global extensive concern in recent years.Dye-sensitized solar cells (Dye-Sensitized Solar Cell, DSC) be a kind of novel solar cell that got up based on Nano-technology Development in nearest 20 years, this battery cost is low, manufacturing process is simple, the energy recovery time short (less than 1 year), the relative transformation efficiency height of the low light level, though its stability and transformation efficiency were still waiting to improve in present stage, this battery still is considered to have most a class solar cell of application prospect.
Dye-sensitized solar cells mainly by conductive substrates, adsorbed the nano porous semiconductor film of dye sensitizing agent (as TiO 2Nano thin-film), electrolyte, electrode is formed.Operation principle is: dye molecule absorbs behind the sunlight from the ground state transition to excitation state; The electronics of excitation state is injected into rapidly in the conduction band of Nano semiconductor, diffuses to conductive substrates subsequently, is transferred to electrode through external loop; The dyestuff that is in oxidation state is reduced the electrolyte reducing/regenerating of attitude; The electrolyte of oxidation state is reduced in that electrode is accepted electronics, thereby has finished a cyclic process of electron transport.Nano titanium dioxide porous film plays the effect of absorbing dye, transmission light induced electron in whole process, be the key link in the charge transport circulation.In addition, the position of its Fermi level and electrolytical redox potential are determining the open circuit voltage of battery jointly.Therefore, nano titanium dioxide porous film is the important component part of dye-sensitized solar cells.
At present, the preparation process of nano titanium dioxide porous film is generally among the DSC: nano-titanium dioxide powder and an amount of organic additive are mixed and made into uniform TiO 2Slurry adopts blade coating or screen printing technique with TiO usually 2Slurry coating is in the conductive substrates surface, through obtaining porous TiO behind 400～500 ℃ of sintering 2Film.Organic additive generally accounts for more than 50% of slurry cumulative volume, and it not only can increase the porosity of film, improves nano-TiO 2The dispersiveness of powder, and can increase TiO 2The adhesive force of film and substrate is TiO 2The important component part of slurry.But,, make the film behind the sintering crackle occur easily because a large amount of organic additives can discharge in high-temperature sintering process.In cracks, exposed conductive substrates contacts with electrolyte easily, increases the generation probability of dark current.In addition, the appearance of crackle also will cause TiO on the unit are 2The reduction of distributed mass, the adsorbance of minimizing dyestuff, unfavorable to the raising of battery efficiency.
Therefore, guaranteeing TiO 2When electrode had enough porositys, how reducing the electrode crackle was an important channel of improving battery efficiency.In the investigation process of document, the researcher adopts the method that reduces the light anode thickness to avoid the generation of crackle usually, does not retrieve the report about electrode crackle processing method aspect at present.The present invention proposes the new method that a kind of simple electrode crackle is repaired, use this method can effectively alleviate even eliminate the micro-crack of electrode, thereby improve battery efficiency.
[summary of the invention]
Purpose of the present invention is intended to overcome the deficiencies in the prior art, and a kind of restorative procedure that is used for dye-sensitized solar cells light anode micro-crack is provided.Simple, the easy row of this method, the dye-sensitized solar cells efficient after the reparation of light anode obviously improves, and can promote the development of dye cell.
The restorative procedure that is used for dye-sensitized solar cells light anode micro-crack provided by the invention, it is characterized in that described method be the light anode that will have micro-crack to place hydrolyzable concentration be that the titanium salt of 0～0.4M or the aqueous solution of titanium alkoxide are handled, finish through 400～500 ℃ of sintering again.The micro-flaw of electrode is obviously alleviated even disappear.
The processing method of smooth anode provided by the invention, operation is simple, and strong with preparation technology's compatibility of DSC battery, obvious to the repairing effect of electrode, can obviously improve battery efficiency.
[description of drawings]
Fig. 1 is the forward and backward microphoto of embodiment 1 heat treatment;
Fig. 2 is the forward and backward microphotos of embodiment 2 heat treatments;
Fig. 3 is the forward and backward microphotos of embodiment 3 heat treatments.
Be described in detail with reference to accompanying drawing below in conjunction with embodiments of the invention.
[embodiment]
The present invention is to have the porous TiO of micro-crack among the DSC 2The light anode is a process object, and the titanium salt of employing or titanium alkoxide are: TiCl 4, TiOSO 4, Ti (SO 4) 2, Ti (OC 3H 7) 4Or Ti (OC 4H 9) 4In the aqueous solution of any one or a few mixing be treatment media, the concentration of this aqueous solution is 0～0.4M, temperature is room temperature～90 ℃, the electrode processing time is 0.1～48 hour.Then, the electrode after handling can be obtained required light anode in 30 minutes at 400～500 ℃ of following sintering.The TiO that this method of process was handled 2The micro-crack of light anode can significantly improve even eliminate, and the electricity conversion of DSC can be improved.
The concrete preparation process of the method for the invention comprises:
(1) at first adopts light microscope observation TiO 2The light anode will have the electrode of micro-crack to select, as process object;
(2) select TiCl 4, TiOSO 4, Ti (SO 4) 2Or Ti (OC 3H 7) 4In any one or a few, disposing an amount of concentration is the aqueous solution of 0～0.4M;
(3) the pending TiO that will select 2The light anode is put in the aqueous solution for preparing, and makes liquid level be higher than electrode surface;
(4) aqueous solution that the light anode will be housed is heated to room temperature～90 ℃, and keeps under this temperature 0.1～48 hour;
(5) with TiO 2The light anode takes out from the aqueous solution, after the drying, puts into heat-treatment furnace under the room temperature, at 400～500 ℃ of insulations 30 minutes, the TiO that can obtain handling well behind the natural cooling 2The light anode.
Embodiment 1:
The TiCl of configuration 0.04M 4Aqueous solution 200ml places beaker, puts into pending light anode, beaker is placed on the magnetic stirring apparatus again, regulates temperature control handle to 70 ℃, keeps 1 hour after temperature.Then, close heater, take out the light anode, air drying 5 minutes.At last, at 450 ℃ of following heat treatments 30 minutes, the TiO that can obtain handling well behind the natural cooling 2The light anode.
The forward and backward microphoto of heat treatment is shown in Fig. 1 (a) and (b).
Embodiment 2:
The TiCl of configuration 0.1M 4Aqueous solution 200ml places beaker, puts into pending light anode, beaker is placed the waters pot again, regulates temperature control handle to 55 ℃, keeps 10 hours after temperature.Then, close heater, take out the light anode, air drying 5 minutes.At last, at 500 ℃ of following heat treatments 30 minutes, the TiO that can obtain handling well behind the natural cooling 2The light anode.
The forward and backward microphoto of heat treatment is shown in Fig. 2 (a) and (b).
Embodiment 3:
Ti (the OC of configuration 0.2M 3H 7) 4Aqueous solution 100ml places beaker, puts into pending light anode, again beaker is placed thermostatic drying chamber, regulates temperature control handle to 80 ℃, keeps 20 hours after temperature.Then, powered-down took out the light anode, air drying 5 minutes.At last, at 480 ℃ of following heat treatments 30 minutes, the TiO that can obtain handling well behind the natural cooling 2The light anode.
The forward and backward microphoto of heat treatment is shown in Fig. 3 (a) and (b).

Claims (5)

1. the restorative procedure of a dye-sensitized solar cells light anode micro-crack, it is characterized in that described method be the light anode that will have micro-crack to place hydrolyzable concentration be that the titanium salt of 0～0.4M or the aqueous solution of titanium alkoxide are handled, finish through 400～500 ℃ of sintering again.
2. the restorative procedure of dye-sensitized solar cells light anode micro-crack according to claim 1 is characterized in that described light anode with micro-crack is porous TiO 2The light anode.
3. the restorative procedure of dye-sensitized solar cells light anode micro-crack according to claim 1 and 2 is characterized in that described titanium salt or titanium alkoxide are TiCl 4, TiOSO 4, Ti (SO 4) 2, Ti (OC 3H 7) 4Or Ti (OC 4H 9) 4In any one or a few.
4. the restorative procedure of dye-sensitized solar cells light anode micro-crack according to claim 1 and 2 is characterized in that described treatment temperature is room temperature～90 ℃, and the processing time is 0.1～48 hour.
5. the restorative procedure of dye-sensitized solar cells light anode micro-crack according to claim 3 is characterized in that described treatment temperature is room temperature～90 ℃, and the processing time is 0.1～48 hour.
CNA2008100520369A 2008-01-09 2008-01-09 A repairing method on the photo anode of dye sensitization solar battery Pending CN101217174A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101958370A (en) * 2009-05-19 2011-01-26 肖特太阳能股份公司 Be used on semiconductor device, making the method for electric contact
CN104756262A (en) * 2012-09-14 2015-07-01 原子能和代替能源委员会 Device and method for restoring silicon-based photovoltaic solar cells using an ultrasound transducer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101958370A (en) * 2009-05-19 2011-01-26 肖特太阳能股份公司 Be used on semiconductor device, making the method for electric contact
CN101958370B (en) * 2009-05-19 2014-09-17 肖特太阳能股份公司 Method for producing electric contacts on a semiconductor component
CN104756262A (en) * 2012-09-14 2015-07-01 原子能和代替能源委员会 Device and method for restoring silicon-based photovoltaic solar cells using an ultrasound transducer
CN104756262B (en) * 2012-09-14 2017-03-08 原子能和代替能源委员会 Repair the apparatus and method of silicon-based photovoltaic solaode using ultrasonic transducer

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Open date: 20080709