CN102522213A - Preparation method for dye sensitization solar cell carbon counter electrodes - Google Patents

Preparation method for dye sensitization solar cell carbon counter electrodes Download PDF

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Publication number
CN102522213A
CN102522213A CN2011103955186A CN201110395518A CN102522213A CN 102522213 A CN102522213 A CN 102522213A CN 2011103955186 A CN2011103955186 A CN 2011103955186A CN 201110395518 A CN201110395518 A CN 201110395518A CN 102522213 A CN102522213 A CN 102522213A
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electrode
preparation
carbon
ball milling
solar battery
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CN2011103955186A
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CN102522213B (en
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孙小华
周生刚
李修能
罗志猛
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China Three Gorges University CTGU
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China Three Gorges University CTGU
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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 relates to a preparation method for dye sensitization solar cell carbon counter electrodes. Graphite and carbon black are placed into a ball mill tank containing glycol to be ball milled completely, and then citric acid and acetic acid are added to be ball milled. Finally, diacetone is added to be ball milled to obtain a carbon counter electrode sizing agent. The counter electrode sizing agent is coated on electricity conductive glass evenly in knife coating method, and the carbon counter electrodes are obtained after annealing. The carbon counter electrodes are prepared on the electricity conductive glass by using the knife coating method. The preparation method is simple in manufacture process, good in repeatability and film forming quality and low in manufacture cost, and has great application prospects in battery industrial production.

Description

A kind of dye sensitizing solar battery carbon is to the preparation method of electrode
Technical field
The invention belongs to the research field of DSSC to electrode, be specifically related to the expensive platinum of a kind of replacement to electrode, the carbon pastes for preparing citric acid-glycol system with ball milling is as the method that electrode is used among the DSSC.
Background technology
Electrode is also referred to as negative electrode, its effect be electronics that external circuit is arrived fast, pass to the oxidation-reduction electrolyte to low-loss, it is reduced on to electrode.This just requires should have advantages of high catalytic activity to electrode.Because platinum is to I -/ I 3-Redox reaction show extraordinary catalytic activity, so platinum has obtained widely using in the laboratory to electrode.But in practical application,, significantly increased the battery cost, be not suitable for being used in the DSSC commercial production because Pt is very expensive.
In order to reduce in the DSSC the cost of electrode, people expect to develop function admirable, cheap cathode material replaces noble metal platinum.Material with carbon element is with its cheapness, high conductivity, to I 2Corrosion resistance and to I 3 -The high reaction activity of reduction becomes the most attractive substitution material, obtains extensive concern.People such as Kiyoaki Imoto are (referring to Kiyoaki Imotoa; Kohshin Takahashi; Kazuhiko Murata Solar Energy Materials & Solar Cells 79 (2003) 459 – 469) adding 0.4g carbon black (specific area is 68m2/g) in the 2g active carbon adds in the mixed liquor of 16ml distilled water and 8ml ethanol; Add the 0.24g carboxymethyl cellulose again, heat 1h down at 180 ℃.Obtain the photoelectric conversion efficiency of 3.9% (active area 0.05cm-2).People such as Jikun Chen (referring to Jikun Chen, Kexin Li, Yanhong Luo; Xiaozhi Guo; Dongmei Li, Minghui Deng, Shuqing Huang; Qingbo Meng, CARBON 47 (2009) 2704 – 2708) add 0.1g carbon black (specific area is 77m2/g) in the 0.4g active carbon and join 4g terpinol and 0.1 g nano SnO 2(particle diameter 10nm) ball milling 5h.Use knife coating to be evenly coated on the electro-conductive glass,, obtain 6.17% transformation efficiency in the specified temp calcining.Compare with the Pt electrode, the catalytic activity of carbon electrode is lower slightly, and contact resistance is bigger, causes the photoelectric conversion efficiency of battery to descend to some extent.In addition, in the preparation process of carbon to electrode, avoiding phenomenons such as electrode film ftracture, comes off also is urgent problem.This method that just need find material with carbon element more suitably and more suitably make electrode improves the performance of carbon electrode with this, and further improves the overall conversion efficiency of battery.
Summary of the invention
To the problem that exists in the prior art, the purpose of this invention is to provide a kind of production cost that reduces DSSC, and make dye sensitizing solar battery carbon that battery obtains higher phototranstormation efficiency electrode.
The objective of the invention is to realize like this: a kind of dye sensitizing solar battery carbon is put into the abundant ball milling of the ball grinder that ethylene glycol is housed to the preparation method of electrode with graphite and carbon black, adds citric acid and acetic acid ball milling again; Add the acetylacetone,2,4-pentanedione ball milling at last, obtain carbon electrode slurry; Knife coating just is evenly coated on the electro-conductive glass electrode slurry, obtains carbon after the annealing to electrode.
The mass ratio of carbon black and graphite is 1: (1.5 ~ 3.5).
When carrying out the multistep ball milling, (graphite+carbon black): ethylene glycol: citric acid: acetic acid: the mass ratio of acetylacetone,2,4-pentanedione is 1 ~ 4:5 ~ 8:2.50 ~ 7.50:0.23 ~ 1.42:0.05 ~ 1:0.26 ~ 1.02.The time that adding ethylene glycol carries out ball grinder is 3-8 hour.The time that adds citric acid and acetic acid ball milling is 3 ~ 12 hours.The time that adds the acetylacetone,2,4-pentanedione ball milling is 2-8 hour.Annealing conditions is 450 ℃-500 ℃ of temperature, time 0.2-1 hour.
Dye sensitizing solar battery carbon provided by the invention utilizes knife coating on electro-conductive glass, to prepare carbon to electrode to the preparation method of electrode.This method manufacture craft is simple, good reproducibility, and quality of forming film is good, and cost of manufacture is low, in the DSSC suitability for industrialized production, has great application prospect.
Embodiment
Embodiment 1The mass ratio of carbon black and graphite be 1:3 to electrode
Prepare carbon to electrode with ball milling, coating, sintering.Graphite and carbon black (mass ratio of graphite and carbon black is 3:1) are put into the ball grinder fully ball milling 3-8 hour that ethylene glycol is housed, add citric acid and acetic acid ball milling 3 ~ 12h again; Added the acetylacetone,2,4-pentanedione ball milling at last 2-8 hour, and obtained carbon electrode slurry.
Aforesaid carbon is to the preparing electrode paste method, and graphite+carbon black: ethylene glycol: citric acid: acetic acid: SnO2: the mass ratio of acetylacetone,2,4-pentanedione is 1 ~ 4:5 ~ 8:2.50 ~ 7.50:0.05 ~ 1:0.26 ~ 1.02, carries out the multistep ball milling.
Obtain carbon to electrode slurry after, use knife coating to be evenly coated on the electro-conductive glass to electrode slurry, obtained carbon to electrode in 0.2-1 hour 450 ℃-500 ℃ annealing.
Material sensitization solar battery light anode prepares the titanium dioxide nanocrystalline film through cladding process, titania slurry make by hydro-thermal is synthetic (referring to S. Ito, T. Murakami; P. Comte, P. Liska, C. Gr tzel; M. Nazeeruddin; M. Gr tzel, Thin Solid Films, 516 (2008) 4613-4619.).
With N719 sensitization battery light anode; And dripping redox electrolytes matter on this electrode, redox electrolytes plasmogamy ratio is: 0.1M 1-propy-3-methylimidazolium iodide (1-propyl group-3-methylimidazole iodine), 0.05M LiI; 0.1M GNCS, 0.03M I 2, 0.5M 4- TerT-butylpridine (4-tert .-butylpyridine), solvent are the mixed solution (volume ratio is 1:1) of propene carbonate and acetonitrile.The carbon of adding a cover the present invention's preparation is assembled into DSSC to electrode, test performance.
At room temperature, and use 1000W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0.25cm that battery receives illuminating area 2Measuring light electric energy conversion efficient is 5.99% under the condition, and using Pt is 6.60% to the transformation efficiency of the solar cell of electrode, and the former is equivalent to 90.7% of latter's transformation efficiency.
Embodiment 2The mass ratio of carbon black and graphite be 1:2 to electrode
Prepare carbon to electrode with ball milling, coating, sintering.Graphite and carbon black (mass ratio of graphite and carbon black is 2:1) are put into the ball grinder fully ball milling 3-8 hour that ethylene glycol is housed, add citric acid and acetic acid ball milling 3 ~ 12h again; Added the acetylacetone,2,4-pentanedione ball milling at last 2-8 hour, and obtained carbon electrode slurry.
Aforesaid carbon is to the preparing electrode paste method, and graphite+carbon black: ethylene glycol: citric acid: acetic acid: SnO2: the mass ratio of acetylacetone,2,4-pentanedione is 1 ~ 4:5 ~ 8:2.50 ~ 7.50:0.05 ~ 1:0.26 ~ 1.02, carries out the multistep ball milling.
Obtain carbon to electrode slurry after, use knife coating to be evenly coated on the electro-conductive glass to electrode slurry, obtained carbon to electrode in 0.2-1 hour 450 ℃-500 ℃ annealing.
Material sensitization solar battery light anode prepares the titanium dioxide nanocrystalline film through cladding process, titania slurry make by hydro-thermal is synthetic (referring to S. Ito, T. Murakami; P. Comte, P. Liska, C. Gr tzel; M. Nazeeruddin; M. Gr tzel, Thin Solid Films, 516 (2008) 4613-4619.).
With N719 sensitization battery light anode; And dripping redox electrolytes matter on this electrode, redox electrolytes plasmogamy ratio is: 0.1M 1-propy-3-methylimidazolium iodide (1-propyl group-3-methylimidazole iodine), 0.05M LiI; 0.1M GNCS, 0.03M I 2, 0.5M 4- TerT-butylpridine (4-tert .-butylpyridine), solvent are the mixed solution (volume ratio is 1:1) of propene carbonate and acetonitrile.The carbon of adding a cover the present invention's preparation is assembled into DSSC to electrode, test performance.
At room temperature, and use 1000W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0.25cm that battery receives illuminating area 2Measuring light electric energy conversion efficient is 6.138% under the condition, and using Pt is 6.60% to the transformation efficiency of the solar cell of electrode, and the former is equivalent to 93% of latter's transformation efficiency.

Claims (7)

1. a dye sensitizing solar battery carbon is characterized in that the preparation method of electrode: graphite and carbon black are put into the abundant ball milling of ball grinder that ethylene glycol is housed, add citric acid and acetic acid ball milling again; Add the acetylacetone,2,4-pentanedione ball milling at last, obtain carbon electrode slurry; Knife coating just is evenly coated on the electro-conductive glass electrode slurry, obtains carbon after the annealing to electrode.
2. dye sensitizing solar battery carbon according to claim 1 is characterized in that the preparation method of electrode: the mass ratio of carbon black and graphite is 1: (1.5 ~ 3.5).
3. dye sensitizing solar battery carbon according to claim 1 and 2 is to the preparation method of electrode; It is characterized in that: when carrying out the multistep ball milling, (graphite+carbon black): ethylene glycol: citric acid: acetic acid: the mass ratio of acetylacetone,2,4-pentanedione is 1 ~ 4:5 ~ 8:2.50 ~ 7.50:0.23 ~ 1.42:0.05 ~ 1:0.26 ~ 1.02.
4. dye sensitizing solar battery carbon according to claim 1 is characterized in that the preparation method of electrode: the time that adding ethylene glycol carries out ball grinder is 3-8 hour.
5. dye sensitizing solar battery carbon according to claim 1 is characterized in that the preparation method of electrode: the time that adds citric acid and acetic acid ball milling is 3 ~ 12 hours.
6. dye sensitizing solar battery carbon according to claim 1 is characterized in that the preparation method of electrode: the time that adds the acetylacetone,2,4-pentanedione ball milling is 2-8 hour.
7. dye sensitizing solar battery carbon according to claim 1 is characterized in that the preparation method of electrode: annealing conditions is 450 ℃-500 ℃ of temperature, time 0.2-1 hour.
CN2011103955186A 2011-12-03 2011-12-03 Preparation method for dye sensitization solar cell carbon counter electrodes Expired - Fee Related CN102522213B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104240962A (en) * 2014-08-29 2014-12-24 电子科技大学成都研究院 Dye-sensitized solar cell and manufacturing method thereof
CN107195385A (en) * 2017-05-16 2017-09-22 华中科技大学 A kind of conductive carbon pastes, its preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100790405B1 (en) * 2006-07-19 2008-01-02 한국전기연구원 Structure of dye-sensitized solar cell and its manufacturing method
US20080087322A1 (en) * 2006-10-13 2008-04-17 Korea Institute Of Science And Technology Counter electrode having carbon material layer for dye-sensitized photovoltaic cell and method of preparing the same
CN101388294A (en) * 2008-08-07 2009-03-18 中国科学院物理研究所 Full carbon counter electrode dye-sensitized solar cell and preparing method
CN101872655A (en) * 2010-05-21 2010-10-27 武汉大学 Method for preparing nanocrystalline porous thick film by one-time sintering

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100790405B1 (en) * 2006-07-19 2008-01-02 한국전기연구원 Structure of dye-sensitized solar cell and its manufacturing method
US20080087322A1 (en) * 2006-10-13 2008-04-17 Korea Institute Of Science And Technology Counter electrode having carbon material layer for dye-sensitized photovoltaic cell and method of preparing the same
CN101388294A (en) * 2008-08-07 2009-03-18 中国科学院物理研究所 Full carbon counter electrode dye-sensitized solar cell and preparing method
CN101872655A (en) * 2010-05-21 2010-10-27 武汉大学 Method for preparing nanocrystalline porous thick film by one-time sintering

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T. DENARO ET.AL: "Investigation of low cost carbonaceous materials for application as counter electrode in dye-sensitized solar cells", 《J APPL ELECTROCHEM》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104240962A (en) * 2014-08-29 2014-12-24 电子科技大学成都研究院 Dye-sensitized solar cell and manufacturing method thereof
CN107195385A (en) * 2017-05-16 2017-09-22 华中科技大学 A kind of conductive carbon pastes, its preparation method and application
CN107195385B (en) * 2017-05-16 2019-03-08 华中科技大学 A kind of conductive carbon pastes, preparation method and application

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