CN101562077A - Carbon aerogel composite pair electrode used for dye-sensitized solar cell and preparation method thereof - Google Patents
Carbon aerogel composite pair electrode used for dye-sensitized solar cell and preparation method thereof Download PDFInfo
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- CN101562077A CN101562077A CN 200910043344 CN200910043344A CN101562077A CN 101562077 A CN101562077 A CN 101562077A CN 200910043344 CN200910043344 CN 200910043344 CN 200910043344 A CN200910043344 A CN 200910043344A CN 101562077 A CN101562077 A CN 101562077A
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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
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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
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a carbon aerogel composite pair electrode used for a dye-sensitized solar cell and a preparation method thereof. The carbon aerogel composite pair electrode is formed by coating carbon aerogel compound formed by mixing carbon aerogel (1) and polymer (2) on a conductive substrate (3). The preparation method of the carbon aerogel composite pair electrode comprises the steps: (1) the carbon aerogel is mixed with poly-dioxy ethyl thiophene/poly-p-styrenesulfonic acid water solution to obtain suspending liquid with the concentration of 5-40%, or the carbon aerogel is added into the suspending liquid of polyfluortetraethylene, polyvinylidene fluoride or polyvinylidene fluoride-hexafluoropropylene according to the mass ratio of 5:1-15:1 for ultrasonic dispersion for 10-20min, so that evenly mixed carbon aerogel/ polymer compound can be obtained for standby application; (2) the conductive substrate is cleaned, and the carbon aerogel/ polymer compound is coated on the cleaned conductive substrate and dried, finally, the carbon aerogel composite pair electrode used for the dye-sensitized solar cell can be prepared. The electrode has the characteristics of low cost, high electrical conductivity and catalytic activity as well as being capable of preparing flexible cells and the like, so as to promote the practicability of the dye-sensitized nano-crystalline solar cell.
Description
Technical field
The present invention relates to the compound of a kind of DSSC to electrode and preparation method thereof.
Background technology
From 1991 by Switzerland
The dye sensitization titanium dioxide nano-film solar cell (DSSCs) that professor proposes since have relatively inexpensive, prepare flexible battery, performance up to advantage such as 11% easily, thereby enjoy the attention of scientific research and branch of industry.In order to embody these advantages of dye sensitized nano crystal salar battery, it must satisfy following three requirements to electrode: the one, and material is cheap and easy to get, and the 2nd, the catalytic reduction efficiency height, the 3rd, electrode is had certain flexibility.Yet present high performance DSSCs battery mainly is to adopt the conduct of platinum plating FTO glass to electrode.Although platinum has superior performance to electrode, higher cost has limited its large-scale application, and simultaneously, this class normally adopts the FTO electro-conductive glass as matrix to electrode, is unfavorable for that preparation is flexible to electrode.Therefore, exploitation can replace platinum to electrode, and have cheapness, high-performance, what can prepare the flexible battery feature is one of key content of this research field at present to electrode.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is lower, the simple used by dye sensitization solar battery charcoal-aero gel of preparation technology is compound to electrode, to electrode, be convenient to the practicability of DSSC with its platinum that replaces DSSC.
The present invention realizes as follows: a kind of charcoal-aero gel that is used for DSSC is compound to electrode, by the charcoal-aero gel compound of charcoal-aero gel [1] with polymer [2] blend, is coated in conducting base [3] and goes up and constitute.
The specific area of charcoal-aero gel is between 100～1100m
2/ g, porosity be between 40%～98%, and the aperture is between 2～50nm, fineness 200～400 orders.
Described polymer is poly-dioxoethyl thiophene/poly-p styrene sulfonic acid mixture, polytetrafluoroethylene, Kynoar or the Kynoar-hexafluoropropylene of 1: 6 weight ratio.
Described conducting base is tin indium oxide glass, fluorine-containing tin oxide glass or metallic conduction matrix.
Described metallic conduction matrix is stainless steel thin slice, 100～400 purpose stainless (steel) wires, nickel thin slice or nickel foam.
A kind of compound preparation method to electrode of charcoal-aero gel who is used for DSSC, realize through the following steps:
(1) charcoal-aero gel and poly-dioxoethyl thiophene/poly-p styrene sulfonic acid aqueous solution being become mass percentage concentration is 5%～40% suspension, or be that 5: 1～15: 1 ratio joins in the suspension of polytetrafluoroethylene, Kynoar or Kynoar-hexafluoropropylene with mass ratio with charcoal-aero gel, ultrasonic dispersion 10～20min, charcoal-aero gel/the polymer complex that obtains mixing, standby;
(2) clean conducting base, charcoal-aero gel/polymer complex is coated on the conducting base that has cleaned up, the charcoal-aero gel that promptly obtains being used for DSSC after the drying is compound to electrode.
The dioxoethyl thiophene/when gathering the aqueous solution of p styrene sulfonic acid mixture, the concentration of the charcoal-aero gel suspension of being prepared is 5%～40% in order to gather when polymer; Obtain charcoal-aero gel/polymer suspension compound, charcoal-aero gel/polymer suspension the compound for preparing is dripped on conducting base, and it is even with the sol evenning machine spin coating, the spin coating rotating speed is 500～3000 commentaries on classics/min, time is 30s, be placed in the baking oven in 100～150 ℃ of baking 20～60min down, the charcoal-aero gel that promptly obtains being used for DSSC after the cooling is compound to electrode.
When polymer is polytetrafluoroethylene, Kynoar or Kynoar-hexafluoropropylene, charcoal-aero gel is that 5: 1～15: 1 ratio joins in the polymer suspension with mass ratio, the adding volume ratio is 1%～10% ethanol or N-N-methyl-2-2-pyrrolidone N-, obtains charcoal-aero gel/polymer pasty state compound; On conducting base, be placed under vacuum drying oven or the room temperature dry then charcoal-aero gel/polymer pasty state compound blade coating; Compressing tablet is carried out in dry back under 10MPa～20MPa, the charcoal-aero gel that obtains being used for DSSC is compound to electrode.
The present invention has following technique effect, the charcoal-aero gel that is used for DSSC of the present invention's preparation is compound to electrode, employing helps the charcoal-aero gel of central hole structure of ion transfer as the catalytic reduction material of main part, thereby has high performance catalytic reduction I
3 -Ability.This charcoal-aero gel is compound not only to have the low characteristics of cost to electrode, and preparation technology is simple, stability is high, conductivity is high, it is flexible to advantages such as electrodes to prepare, after being applied to dye sensitized nano crystal salar battery, solved the platinum problem high that DSSC is generally used, be convenient to the practicability of DSSC the electrode cost.
Description of drawings
Fig. 1 is a structural representation of the present invention; Among the figure: 1, charcoal-aero gel particle, 2, polymer, 3, conducting base.
Fig. 2 is the I-V curve of charcoal-aero gel of the present invention/PTFE/ stainless (steel) wire to electrode.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.
Embodiment 1: the sheet that ito glass is cut into 1cm * 1.5cm size, use liquid detergent, distilled water, absolute ethyl alcohol, the ultrasonic 15min of isopropyl alcohol then successively, clean up the back it is carried out oxygen plasma treatment, processing time is 5min, power is 20～50W, the main effect of handling is to reduce the mean roughness of conductive glass surface film and peak-paddy roughness, and its evenness is improved; And increase the surface energy of electro-conductive glass, reduce its contact angle, the conductive film wettability of the surface energy and the absorption property of electro-conductive glass are improved.With charcoal-aero gel and the poly-dioxoethyl thiophene/poly-p styrene sulfonic acid aqueous solution (PEDOT: PSS, Bayer, Baytron 4083) be mixed with the suspension (mass percent concentration is between 5%～40%) of variable concentrations, joining suspension rotary speed with 500～3000 commentaries on classics/min on sol evenning machine is spun on above the electro-conductive glass, the spin coating time is 30s, in 150 ℃ of baking ovens, dry by the fire 30min after the spin coating, obtain after the drying having catalytic activity to electrode.
Embodiment 2: stainless steel substrates (or nickel sheet) is cut into the sheet of 1cm * 1.5cm size, cleans up with absolute ethyl alcohol, and stand-by; With charcoal-aero gel and poly-dioxoethyl thiophene/poly-p styrene sulfonic acid aqueous solution (PEDOT: PSS) be mixed with the suspension (concentration is between 5%～40%) of variable concentrations, joining suspension rotary speed with 500～3000 commentaries on classics/min on sol evenning machine is spun on above the electro-conductive glass, the spin coating time is 30s, in 150 ℃ of baking ovens, dry by the fire 30min after the spin coating, obtain after the drying having catalytic activity to electrode.
Embodiment 3: stainless steel substrates (or nickel sheet) is cut into the sheet of 1cm * 1.5cm size, cleans up with absolute ethyl alcohol, and stand-by; Is that 9: 1 ratio is mixed with the water slurry of polytetrafluoroethylene (mass fraction is 60%) with charcoal-aero gel with mass ratio, the absolute ethyl alcohol of adding 5%, ultrasonic 15min, allow it fully mix, with glass bar it evenly is applied on the stainless steel substrates of above-mentioned processing then, smearing the back that finishes dries by the fire 24～48h and makes its sufficiently dry about 45 ℃ in vacuum drying chamber, after the oven dry, press stainless steel substrates with tablet press machine with the pressure of 20MPa, make that material is more uniform to be attached on the slice, thin piece, the flexible charcoal-aero gel that obtains having catalytic activity is compound to electrode.
Embodiment 4: changes the stainless steel substrates of the 3rd embodiment into stainless (steel) wire, and is cut into the sheet of 1cm * 1.5cm size equally, clean up with acetone, and stand-by; Is that 9: 1 ratio is mixed with the water slurry of polytetrafluoroethylene (mass fraction is 60%) with charcoal-aero gel with mass ratio, the absolute ethyl alcohol of adding 5%, because stainless (steel) wire has pore space structure, so the absolute ethyl alcohol that is added, can make like this that material can better stick on the stainless (steel) wire than lacking among first embodiment.With the ultrasonic 15min of mixture, allow it fully mix, with glass bar it evenly is applied on the stainless (steel) wire of above-mentioned processing then, smear the back that finishes and in vacuum drying chamber, dry by the fire 24～48h about 45 ℃, make its sufficiently dry, after the oven dry, press stainless (steel) wire with the pressure of 20MPa with tablet press machine, make that material is more uniform to be attached on the slice, thin piece, the flexible charcoal-aero gel that obtains having catalytic activity is compound to electrode.
Embodiment 5: changes the stainless (steel) wire of the 4th embodiment into nickel foam, also is cut into the nickel sheet of 1cm * 1.5cm size, clean up with ethanol, and stand-by; Is that 9: 1 ratio is mixed with the water slurry of polytetrafluoroethylene (mass fraction is 60%) with charcoal-aero gel with mass ratio, the absolute ethyl alcohol of adding 10%, because the nickel sheet is relatively thick, so use the method for soaking rather than smearing that material is fully sticked on the nickel sheet, so the absolute ethyl alcohol that adds more than embodiment 4.With the ultrasonic 15min of gained mixture, after fully mixing, the nickel sheet put in the mixture to soak about 20s take out, be placed on 50 ℃ of drying 24～48h in the vacuum drying chamber, after the oven dry, same press the nickel sheet with tablet press machine with the pressure of 20MPa, the flexible charcoal-aero gel that obtains having catalytic activity is compound to electrode.
More than be 5 embodiment of the present invention, charcoal-aero gel with the present invention's preparation is compound to electrode, because charcoal-aero gel itself has certain suction-operated to electrolyte, therefore, when the assembling DSSC, be necessary earlier electrolyte solution to be dripped compound to electrode surface, make that charcoal-aero gel is compound to reach saturated substantially to electrode adsorbing electrolyte solution at charcoal-aero gel, and then the assembling solar battery device.
The TiO of DSSC
2Porous electrode, dye sensitizing agent and electrolyte solution all use and well known to a person skilled in the art material and preparation method.Wherein, TiO
2Porous electrode is with P25 type TiO
2At the FTO TiO that is prepared into one deck densification on glass
2Film; Dye sensitizing agent adopts N719; Electrolyte solution adopts and contains the KI of 0.5M and the I of 0.05M
2Liquid electrolyte or gel-form solid polymer electrolyte;
Charcoal-aero gel flexibility with example 4 preparations prepares battery device to electrode and platinum under the same conditions to electrode respectively, and its test result is shown in Fig. 2, is listed in table 1.
Table 1
Claims (8)
1, a kind of charcoal-aero gel that is used for DSSC is compound to electrode, it is characterized in that: by the charcoal-aero gel compound of charcoal-aero gel [1] with polymer [2] blend, be coated in conducting base [3] and go up and constitute.
2, a kind of charcoal-aero gel that is used for DSSC according to claim 1 is compound to electrode, and it is characterized in that: the specific area of charcoal-aero gel is between 100～1100m
2/ g, porosity be between 40%～98%, and the aperture is between 2～50nm, fineness 200～400 orders.
3, compound according to the described a kind of charcoal-aero gel that is used for DSSC of claim 1 to electrode, it is characterized in that: described polymer is poly-dioxoethyl thiophene/poly-p styrene sulfonic acid mixture, polytetrafluoroethylene, Kynoar or the Kynoar-hexafluoropropylene of 1: 6 weight ratio.
4, compound to electrode according to the described a kind of charcoal-aero gel that is used for DSSC of claim 1, it is characterized in that: described conducting base is tin indium oxide glass, fluorine-containing tin oxide glass or metallic conduction matrix.
5, compound to electrode according to the described a kind of charcoal-aero gel that is used for DSSC of claim 4, it is characterized in that: described metallic conduction matrix is stainless steel thin slice, 100～400 purpose stainless (steel) wires, nickel thin slice or nickel foam.
6,, realize through the following steps according to the described a kind of compound preparation method of charcoal-aero gel who is used for DSSC of claim 1 to electrode:
(1) charcoal-aero gel and poly-dioxoethyl thiophene/poly-p styrene sulfonic acid aqueous solution to be become mass percentage concentration be 5%～40% suspension or be that 5: 1～15: 1 ratio joins in the suspension of polytetrafluoroethylene, Kynoar or Kynoar-hexafluoropropylene with charcoal-aero gel with mass ratio, ultrasonic dispersion 10～20min, charcoal-aero gel/the polymer complex that obtains mixing, standby;
(2) clean conducting base, charcoal-aero gel/polymer complex is coated on the conducting base that has cleaned up, the charcoal-aero gel that promptly obtains being used for DSSC after the drying is compound to electrode.
7, according to the described a kind of compound preparation method of charcoal-aero gel who is used for DSSC of claim 6 to electrode, it is characterized in that: the dioxoethyl thiophene/when gathering the aqueous solution of p styrene sulfonic acid mixture, the mass percentage concentration of the charcoal-aero gel suspension of being prepared is 5%～40% in order to gather when polymer; Obtain charcoal-aero gel/polymer suspension compound, charcoal-aero gel/polymer suspension the compound for preparing is dripped on conducting base, and it is even with the sol evenning machine spin coating, the spin coating rotating speed is 500～3000 commentaries on classics/min, time is 30s, be placed in the baking oven in 100～150 ℃ of baking 20～60min down, the charcoal-aero gel that promptly obtains being used for DSSC after the cooling is compound to electrode.
8, according to the described a kind of compound preparation method of charcoal-aero gel who is used for DSSC of claim 6 to electrode, it is characterized in that: polymer is polytetrafluoroethylene, Kynoar or Kynoar-hexafluoropropylene, charcoal-aero gel is that 5: 1～15: 1 ratio joins in the polymer suspension with mass ratio, the adding volume ratio is 1%～10% ethanol or N-N-methyl-2-2-pyrrolidone N-, obtains charcoal-aero gel/polymer pasty state compound; On conducting base, be placed under vacuum drying oven or the room temperature dry then charcoal-aero gel/polymer pasty state compound blade coating; Compressing tablet is carried out in dry back under 10MPa～20MPa, the charcoal-aero gel that obtains being used for DSSC is compound to electrode.
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