CN102013341A - Method for preparing DSSC (Dye Sensitized Solar Cell) with double-helix structure - Google Patents

Method for preparing DSSC (Dye Sensitized Solar Cell) with double-helix structure Download PDF

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CN102013341A
CN102013341A CN2010102948513A CN201010294851A CN102013341A CN 102013341 A CN102013341 A CN 102013341A CN 2010102948513 A CN2010102948513 A CN 2010102948513A CN 201010294851 A CN201010294851 A CN 201010294851A CN 102013341 A CN102013341 A CN 102013341A
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preparation
dssc
double
stranded
light anode
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CN102013341B (en
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刘文秀
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Irico Group Corp
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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

Abstract

The invention discloses a method for preparing a DSSC (Dye Sensitized Solar Cell) with a double-helix structure, which comprises the steps of: firstly, preparing a photo anode through preparing a titanium dioxide sol precursor solution and treating by using a helical Ti anode; secondly, preparing a cathode by using helical Ti; and thirdly, carrying out cell assembly sealing on the prepared photo anode and the cathode to prepare the DSSC. The DSSC prepared by using the method has effectively improved long-term stability, can improve the utilization ratio of the light rays by the solar cell, and is beneficial to the development of good low light level, thereby being helpful to promote the industrialized procedure of the DSSC.

Description

A kind of preparation method of double-stranded DSSC
Technical field
The invention belongs to new material technology and technical field of new energies; Relate in particular to the preparation method of the double-stranded DSSC of a kind of DSSC and photocatalysis association area use.
Background technology
DSSC, the research focus that relies on its low cost, simple and direct preparation process condition and good Environmental compatibility to become area of solar cell.But because the bad and solar cell of its long-time stability is lower to the utilance of light, thereby preparation improves its long-time stability, and improving its utilance to light is its prerequisite of moving towards industrialization [Kuang, D.; Wang, P.; Ito, S.; Zakeeruddin, S.M.; Gra..tzel, M.J.Am.Chem.Soc.2006,128,7732.].
But the DSSC battery all is flat for a long time, and the battery usable floor area is bigger like this, is difficult to bring into play the good advantage of DSSC low light level performance, has limited the breakthrough of its technology and the expansion of application to a great extent.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method of double-stranded DSSC is provided, the double-stranded DSSC of this method preparation can effectively be improved the long-time stability of DSSC battery and the solar cell utilance to light, and helps bringing into play the good characteristics of its low light level.
The objective of the invention is to solve by the following technical programs:
The preparation method of this double-stranded DSSC specifically comprises the steps:
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: titanium source and neutrality or the co-precipitation of basic hydrolysis liquid are reacted in water, obtain white titanium hydroxide precipitation, with after the white titanium hydroxide washing of precipitate under 30～80 ℃, with it according to Ti 4+: organic acid: the mol ratio of hydrogen peroxide is 1: (2～10): (2～10) carry out peptization, obtain the TiO 2 sol precursor liquid behind still aging then 10～15h;
2) with spiral helicine Ti anode through ethanol, acetone respectively after the sonicated, place the TiO 2 sol precursor liquid, taking out behind hydrothermal treatment consists 12～72h under 70～250 ℃ of conditions, behind 200 ℃ of heat treatment 4h, obtain being coated with the preliminary treatment light anode of titanium dioxide then, take out after the preliminary treatment light anode that obtains is soaked into dyestuff 24h, wash out the dyestuff on surface with absolute ethyl alcohol, obtain the light anode;
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, after ethanol, acetone difference sonicated, be impregnated in H 2PtCl 6-6H 2Electroplate in the O solution, sprayed silicon colloidal sol carries out insulation processing after finishing, and obtains negative electrode again behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
The light anode for preparing fills electrolytical glass tube with putting into after negative electrode is connected, and then the glass tube loam cake is tightened and is sealed with fluid sealant.
More than the titanium source of Cai Yonging is one or more in titanyl sulfate, titanium sulfate or the titanium tetrachloride.
Stating basic hydrolysis liquid is NaOH, KOH, NaHCO 3, ammoniacal liquor or NH 4HCO 3
More than the organic acid of Cai Yonging is oxalic acid, citric acid, tartaric acid, benzoic acid, adipic acid or acetic acid.
More than the dyestuff of Cai Yonging is a kind of in N3, N719, the black dyestuff etc.
More than the electrolyte of Cai Yonging is a kind of in liquid electrolyte, the accurate solid-state and solid electrolyte.
More than when the second stepping electroplating, described H 2PtCl 6-6H 2The concentration of O solution is 5 * 10 -3Mol/L; Current density is 15mAcm during plating 2, the reaction time is 60s.
The present invention has following beneficial effect:
Adopt the DSSC of the present invention's preparation, can effectively improve the long-time stability of DSSC battery and solar cell utilance to light, and help bringing into play the good characteristics of its low light level, thereby help to advance the industrialization process of DSSC.In addition, the DSSC of sped structure of the present invention has made full use of three dimensions, gives full play to the advantage of its low light level performance.
Description of drawings
Fig. 1 is the preparation structure chart of battery of the present invention;
Wherein: (a) be the structure of cell metallic electrode; (b) be the schematic diagram that is coated with the preliminary treatment light anode of titanium dioxide; (c) be the light anode after the dye sensitization; (d) be negative electrode Pt electrode; (e) be the battery structure after the encapsulation.
Embodiment
Below in conjunction with embodiment the present invention is done and to describe in further detail:
Embodiment 1
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: at first after the mixed that under 15-20 ℃ by titanium ion concentration is 2mol/L, leave standstill clarification in 12 hours with 0.1mol titanyl sulfate and water, the ammoniacal liquor co-precipitation titration of filtering back and 1mol/L is to the 200ml deionized water, when the pH value equals till 7, the white precipitate that obtains, centrifuge washing is to using Ba (NO 3) 2Solution detects the SO less than remnants 4 2-Till the ion, under 60 ℃, white precipitate is pressed Ti then 4+: oxalic acid: the mol ratio of hydrogen peroxide is to dissolve at 1: 5: 5, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 10 hours and promptly obtains the TiO 2 sol precursor liquid;
2) with spiral helicine Ti anode (shown in Fig. 1 (a)) through ethanol, acetone sonicated three times respectively, place the TiO 2 sol precursor liquid then, in water heating kettle in 90 ℃ of following hydrothermal treatment consists 20h; Behind 200 ℃ of heat treatment 4h, obtain the preliminary treatment light anode that is coated with titanium dioxide shown in Fig. 1 (b) then, then it is soaked into (dye selection N719) in the dyestuff, take out the dyestuff that washes out the surface with absolute ethyl alcohol after soaking 24h, obtain the light anode, shown in Fig. 1 (c);
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, is used ethanol, acetone difference sonicated three times, impregnated in 5 * 10 then -3The H of mol/L 2PtCl 6-6H 2In the O solution, use Keithley-2400 to electroplate as power supply, during plating at 15mAcm 2Sprayed silicon colloidal sol carries out insulation processing after reacting 60s under the current density, obtains the Pt electrode then behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
With the light anode for preparing and negative electrode according to being connected shown in (d) among Fig. 1, and put into the glass tube that fills liquid electrolyte solution, the glass tube loam cake is tightened back the sealing with fluid sealant can obtain the prepared double-stranded DSSC of the present invention, shown in Fig. 1 (e).
Embodiment 2
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: at first with the TiCl of 0.1mol 4NaHCO with the 1mol/L of 400ml 3The white precipitate that obtains in the co-precipitation titration 100ml deionized water, centrifuge washing three times under 50 ℃, is pressed Ti with white precipitate then 4+: citric acid: the mol ratio of hydrogen peroxide is to dissolve at 1: 5: 6, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 15 hours and promptly obtains the TiO 2 sol precursor liquid;
2) with spiral helicine Ti anode through ethanol, acetone sonicated three times respectively, place the TiO 2 sol precursor liquid then, in water heating kettle at 250 ℃ of following hydrothermal treatment consists 8h; Behind 200 ℃ of heat treatment 4h, obtain being coated with the preliminary treatment light anode of titanium dioxide then, then it is soaked into (dye selection is deceived dyestuff) in the dyestuff, take out the dyestuff that washes out the surface with absolute ethyl alcohol behind the immersion 24h, obtain the light anode;
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, is used ethanol, acetone difference sonicated three times, impregnated in 5 * 10 then -3The H of mol/L 2PtCl 6-6H 2In the O solution, use Keithley-2400 to electroplate as power supply, during plating at 15mAcm 2Sprayed silicon colloidal sol carries out insulation processing after reacting 60s under the current density, obtains the Pt electrode then behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
With the light anode for preparing and negative electrode according to being connected shown in (d) among Fig. 1, and put into the glass tube that fills liquid electrolyte solution, then the glass tube loam cake is tightened back the sealing and can be obtained the prepared double-stranded DSSC of the present invention with fluid sealant.
Embodiment 3
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: the white precipitate that obtains in the NaOH co-precipitation titration 200ml deionized water with the 1mol/L of the titanium sulfate of 0.1mol and 400ml at first, centrifuge washing three times under 80 ℃, is pressed Ti with white precipitate then 4+: tartaric acid: the mol ratio of hydrogen peroxide is to dissolve at 1: 10: 10, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol precursor liquid;
2) with spiral helicine Ti anode through ethanol, acetone sonicated three times respectively, place the TiO 2 sol precursor liquid then, in water heating kettle in 160 ℃ of following hydrothermal treatment consists 18h; Behind 200 ℃ of heat treatment 4h, obtain being coated with the preliminary treatment light anode of titanium dioxide then, then it is soaked into (dye selection N719) in the dyestuff, take out the dyestuff that washes out the surface with absolute ethyl alcohol behind the immersion 24h, obtain the light anode;
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, is used ethanol, acetone difference sonicated three times, impregnated in 5 * 10 then -3The H of mol/L 2PtCl 6-6H 2OIn the solution, use Keithley-2400 to electroplate as power supply, during plating at 15mA.cm 2Sprayed silicon colloidal sol carries out insulation processing after reacting 60s under the current density, obtains the Pt electrode then behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
The light anode for preparing and negative electrode are according to being connected shown in (d) among Fig. 1, and put into the glass tube (electrolyte is a solid electrolyte) that fills electrolyte solution, the glass tube loam cake is tightened back the sealing with fluid sealant can obtain the prepared double-stranded DSSC of the present invention.
Embodiment 4
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: at first with the titanium tetrachloride of 0.1mol and the NH of 200ml 4HCO 3The white precipitate that obtains in the shallow lake titration 100ml deionized water, centrifuge washing three times under 50 ℃, is pressed Ti with white precipitate then 4+: benzoic acid: the mol ratio of hydrogen peroxide is to dissolve at 1: 5: 6, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol precursor liquid;
2) with spiral helicine Ti anode through ethanol, acetone sonicated three times respectively, place the TiO 2 sol precursor liquid then, in water heating kettle at 70 ℃ of following hydrothermal treatment consists 72h; Behind 200 ℃ of heat treatment 4h, obtain being coated with the preliminary treatment light anode of titanium dioxide then, then it is soaked into (dye selection N3) in the dyestuff, take out the dyestuff that washes out the surface with absolute ethyl alcohol behind the immersion 24h, obtain the light anode;
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, is used ethanol, acetone difference sonicated three times, impregnated in 5 * 10 then -3The H of mol/L 2PtCl 6-6H 2In the O solution, use Keithley-2400 to electroplate as power supply, during plating at 15mAcm 2Sprayed silicon colloidal sol carries out insulation processing after reacting 60s under the current density, obtains the Pt electrode then behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
With the light anode for preparing and negative electrode according to being connected shown in (d) among Fig. 1, the soldier puts into the glass tube (electrolyte is a quasi-solid electrolyte) that fills electrolyte solution, then the glass tube loam cake is tightened back the sealing with fluid sealant and can be obtained the prepared double-stranded DSSC of the present invention.
Embodiment 5
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: titanyl sulfate and KOH co-precipitation are reacted in water, obtain white titanium hydroxide precipitation, with after the white titanium hydroxide washing of precipitate under 30 ℃, with it according to Ti 4+: adipic acid or acetic acid: the mol ratio of hydrogen peroxide is to carry out peptization at 1: 2: 2, obtains the TiO 2 sol precursor liquid behind the still aging then 13h;
2) with spiral helicine Ti anode through ethanol, acetone respectively after the sonicated, place the TiO 2 sol precursor liquid, taking out behind the hydrothermal treatment consists 12h under 100 ℃ of conditions, behind 200 ℃ of heat treatment 4h, obtain being coated with the preliminary treatment light anode of titanium dioxide then, the preliminary treatment light anode that obtains is soaked into behind the dyestuff 24h takes out (dye selection is deceived dyestuff), wash out the dyestuff on surface with absolute ethyl alcohol, obtain the light anode;
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, after ethanol, acetone difference sonicated, be impregnated in H 2PtCl 6-6H 2Electroplate in the O solution, sprayed silicon colloidal sol carries out insulation processing after finishing, and obtains negative electrode again behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
The light anode for preparing fills electrolytical glass tube (electrolyte is a liquid electrolyte) with putting into after negative electrode is connected, and then the glass tube loam cake is tightened and is sealed with fluid sealant.

Claims (7)

1. the preparation method of a double-stranded DSSC is characterized in that, comprises the steps:
The first step: the preparation of light anode
1) preparation of TiO 2 sol precursor liquid: titanium source and neutrality or the co-precipitation of basic hydrolysis liquid are reacted in water, obtain white titanium hydroxide precipitation, with after the white titanium hydroxide washing of precipitate under 30～80 ℃, with it according to Ti 4+: organic acid: the mol ratio of hydrogen peroxide is 1: (2～10): (2～10) carry out peptization, obtain the TiO 2 sol precursor liquid behind still aging then 10～15h;
2) with spiral helicine Ti anode through ethanol, acetone respectively after the sonicated, place the TiO 2 sol precursor liquid, taking out behind hydrothermal treatment consists 12～72h under 70～250 ℃ of conditions, behind 200 ℃ of heat treatment 4h, obtain being coated with the preliminary treatment light anode of titanium dioxide then, take out after the preliminary treatment light anode that obtains is soaked into dyestuff 24h, wash out the dyestuff on surface with absolute ethyl alcohol, obtain the light anode;
Second step: the preparation of negative electrode
Spiral helicine Ti after sand papering, after ethanol, acetone difference sonicated, be impregnated in H 2PtCl 6-6H 2Electroplate in the O solution, sprayed silicon colloidal sol carries out insulation processing after finishing, and obtains negative electrode again behind 150 ℃ of processing 30min;
The 3rd step: the assembling of battery
The light anode for preparing fills electrolytical glass tube with putting into after negative electrode is connected, and then the glass tube loam cake is tightened and is sealed with fluid sealant.
2. the preparation method of double-stranded DSSC according to claim 1 is characterized in that, described titanium source is one or more in titanyl sulfate, titanium sulfate or the titanium tetrachloride.
3. the preparation method of double-stranded DSSC according to claim 1 is characterized in that, described basic hydrolysis liquid is NaOH, KOH, NaHCO 3, ammoniacal liquor or NH 4HCO 3
4. the preparation method of double-stranded DSSC according to claim 1 is characterized in that, described organic acid is oxalic acid, citric acid, tartaric acid, benzoic acid, adipic acid or acetic acid.
5. the preparation method of double-stranded DSSC according to claim 1 is characterized in that, described dyestuff is a kind of in N3, N719 or the black dyestuff.
6. the preparation method of double-stranded DSSC according to claim 1 is characterized in that, described electrolyte is a kind of in liquid electrolyte, the accurate solid-state and solid electrolyte.
7. the preparation method of double-stranded DSSC according to claim 1 is characterized in that, when the second stepping electroplating, and described H 2PtCl 6-6H 2The concentration of O solution is 5 * 10 -3Mol/L; Current density is 15mAcm during plating 2, the reaction time is 60s.
CN2010102948513A 2010-09-28 2010-09-28 Method for preparing DSSC (Dye Sensitized Solar Cell) with double-helix structure Expired - Fee Related CN102013341B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102360961A (en) * 2011-08-23 2012-02-22 奇瑞汽车股份有限公司 Preparation method and modification process of sizing agent of scattering layer of dye-sensitized solar cell
CN102983010A (en) * 2012-11-29 2013-03-20 深圳清华大学研究院 TiO2 nano-tube array for dye-sensitized solar cell and preparation method thereof
CN107151804A (en) * 2017-05-09 2017-09-12 中国人民解放军92609部队 A kind of double spiral electrode component and the electrolytic cell with double spiral electrode component
CN114835209A (en) * 2022-04-26 2022-08-02 北京交通大学 Electrochemical membrane contact ozone catalytic device based on titanium fiber electrode and water treatment method

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102360961A (en) * 2011-08-23 2012-02-22 奇瑞汽车股份有限公司 Preparation method and modification process of sizing agent of scattering layer of dye-sensitized solar cell
CN102360961B (en) * 2011-08-23 2013-01-30 奇瑞汽车股份有限公司 Preparation method and modification process of sizing agent of scattering layer of dye-sensitized solar cell
CN102983010A (en) * 2012-11-29 2013-03-20 深圳清华大学研究院 TiO2 nano-tube array for dye-sensitized solar cell and preparation method thereof
CN102983010B (en) * 2012-11-29 2016-12-21 深圳清华大学研究院 A kind of TiO for DSSC2nano-tube array and preparation method thereof
CN107151804A (en) * 2017-05-09 2017-09-12 中国人民解放军92609部队 A kind of double spiral electrode component and the electrolytic cell with double spiral electrode component
CN114835209A (en) * 2022-04-26 2022-08-02 北京交通大学 Electrochemical membrane contact ozone catalytic device based on titanium fiber electrode and water treatment method
CN114835209B (en) * 2022-04-26 2024-04-09 北京交通大学 Electrochemical membrane contact ozone catalytic device based on titanium fiber electrode and water treatment method

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