CN102543466B - Counter electrode material for dye sensitization solar battery and preparation method and application thereof - Google Patents
Counter electrode material for dye sensitization solar battery and preparation method and application thereof Download PDFInfo
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- CN102543466B CN102543466B CN2011104492529A CN201110449252A CN102543466B CN 102543466 B CN102543466 B CN 102543466B CN 2011104492529 A CN2011104492529 A CN 2011104492529A CN 201110449252 A CN201110449252 A CN 201110449252A CN 102543466 B CN102543466 B CN 102543466B
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- 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
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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
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Abstract
The invention discloses a counter electrode material for a dye sensitization solar battery and a preparation method and application thereof. The preparation method of the electrode material is considering phenolic resin generated by metal chloride, phenols materials and aldehydes materials as a carbon source, enabling a template agent to be triblock polymers, mixing, blending and firing. The novel material can serve as an electrode material for the dye sensitization solar battery. Experiments indicate that the dye sensitization solar battery of an electrode made of the material can obtain high light current, open-circuit voltage and photoelectric conversion efficiency, can replace traditional electrodes made of platinum materials. The material is low in price, preparation process of the electrodes and the batteries is simple, the problem of expensive platinum electrodes and resource shortage and the like are solved, and the counter electrode material has wide application prospects.
Description
Technical field
The invention belongs to new material and technical field of green regenerative energy sources, be specifically related to a kind of preparation to electrode material for DSSC and application.
Background technology
1991, professor Graetzel of engineering college of Swiss Confederation invented DSSC (Dye-sensitized Solar Cell is called for short DSC).Because it is with low cost, manufacture craft is simple, and efficiency is higher, and environmental friendliness just causes worldwide research boom once coming out.DSC mainly is comprised of three parts, that is: the light anode, normally adsorb the nano-crystalline titanium dioxide film that dyestuff is arranged; To electrode, platinum electrode normally; Comprise in addition I
3 -/ I
-The electrolyte of oxidation-reduction pair.Its principle is: dyestuff absorbs a photon, dyestuff is from the ground state transition to excitation state, dyestuff excitation state is unstable, produce a light induced electron and dyestuff cation, light induced electron can be injected into rapidly the conduction band of titanium dioxide and the loose structure by titanium dioxide reaches conductive substrates, and the external circuit of then flowing through reaches electrode.On to electrode, I
3 -The electron reduction of the external circuit of being flowed through is I
-, in titanium dioxide porous membrane, the dyestuff cation is by I
-Reduction, realize the regeneration of dyestuff, completes whole circuit cycles.This shows to electrode it is the important component part of DSC, is mainly to do electrode with platinum (Pt) at present., although the platinum electrode superior performance is still expensive, and the reserves of platinum are very limited, therefore be badly in need of finding the substitution material of platinum.
Summary of the invention
For the problems referred to above, the invention discloses a kind of for DSSC to electrode material, its preparation method and with it as to electrode material, replacing platinum to be applied to the application of DSSC.The present invention to the preparation method of electrode material is: with metal chloride, the phenolic resins that aldehydes matter and aldehyde material generate is carbon source, and template is triblock polymer, through the process of mixing, stirring, sintering, is prepared from.The electrode of this material preparation that can replace platinum is the oxidation-reduction pair in related electrolyte in can the catalysis DSSC, as I
3-/I-, Br
3-/Br-and other organic oxidation reduction electricity are right, and the metal organic complex oxidation-reduction pair, can obtain very high photoelectric current and open circuit voltage and photoelectric conversion efficiency.
The present invention prepares by following method, and concrete steps comprise:
(a) by template: aldehydes matter: acetic acid: metal chloride: the mass ratio of aldehyde material is 2.5: 1.65: 0.25～1.0: 0.45～1.8: 1.35～5.4 to take each raw material;
(b) ratio of template in 2.5g/30mL is dissolved in ethanol, stirs until dissolve fully;
(c) in the mixed liquor of step (b) acquisition, add aldehydes matter and acetic acid, stir 30min;
(d) in the mixed liquor of step (c) acquisition, add metal chloride, stir 30min;
(e) in the mixed liquor of step (d) acquisition, add aldehyde material, obtain colloidal liquid after stirring 30min, then through oversintering, make;
Wherein:
Template is triblock polymer P123 or F127;
Aldehydes matter is a kind of in resorcinol, phloroglucin, phenol;
Metal chloride is following a kind of: divanadyl tetrachloride, titanium tetrachloride, zirconium chloride, columbium pentachloride, chromium trichloride, molybdenum pentachloride, tungsten hexachloride;
Aldehyde material is formaldehyde or acetaldehyde.
Preferably, the template in said method is triblock polymer F127.
Preferably, the metal chloride in said method is divanadyl tetrachloride.
Preferably, the aldehydes matter in said method is resorcinol.
Preferably, the aldehyde material in said method is formaldehyde.
Preferably, the condition of the sintering in said method is, in 80 ℃ of placements 3 days, at 1100 ℃ of sintering 5h.
Other one side of the present invention is: utilize said method preparation a kind of for DSSC to electrode material.
Of the present inventionly be on the one hand again: utilize the said method preparation mesoporous carbon-loaded to electrode material as the application of DSSC to electrode.
Vanadium carbide (hereinafter to be referred as the VC-MC) material of the mesoporous carbon-loaded by the preparation of the described method of embodiment in the present invention, can be used as electrode material is used for DSSC, experiment shows, can obtain very high photoelectric current and open circuit voltage and photoelectric conversion efficiency take this kind material as the DSSC to electrode, can replace the electrode of tradition with the alloy platinum material preparation, because material therefor is cheap and simple to the manufacture craft of electrode and battery, solved the problems such as the expensive and shortage of resources of platinum electrode, had broad application prospects.
Beneficial effect of the present invention:
Utilizing synthetic technology provided by the invention can prepare a series of low costs can replace platinum to be used for the metal carbides of the mesoporous carbon-loaded of DSSC.The present invention is cheap and simple to the manufacture craft of electrode and battery due to material therefor, has solved the problems such as the expensive and shortage of resources of platinum electrode.
Description of drawings
The XRD spectra of accompanying drawing 1 mesoporous carbon-loaded vanadium carbide;
It is the scanning electron microscope (SEM) photograph of mesoporous carbon-loaded vanadium carbide as Fig. 2;
Accompanying drawing 3 be the DSSC that electrode and traditional platinum prepared electrode with invention mesoporous carbon-loaded vanadium carbide Performance Ratio.
Embodiment
Describe specific embodiments of the invention in detail below in conjunction with technical scheme and accompanying drawing.Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
F127：Polyethylene-polypropylene?glycol，Sigma-aldrich，USA.
FTO electro-conductive glass: F-doped tin oxide conductive glass, 15 Ω/, Pilkington, USA.
Embodiment 1
(1) preparation of mesoporous carbon-loaded vanadium carbide
The triblock polymer F127 of 2.5g is dissolved in 30mL ethanol, stirs until dissolve fully.Add the 1.65g resorcinol, 0.5g acetic acid, stir 30min.Add 0.9g divanadyl tetrachloride (VOCl
3), stir 30min.Add 2.7g formaldehyde, stir 30min.With the gained colloidal liquid, placed 3 days under 80 ℃ of conditions,, then at 1100 ℃ of sintering 5h, both obtain the vanadium carbide of mesoporous carbon-loaded.
(2) sign of the vanadium carbide of mesoporous carbon-loaded
The vanadium carbide of mesoporous carbon-loaded: at normal temperatures and pressures, it is black, and the powder of metallic luster is arranged.
As shown in Figure 1, the diffraction maximum correspondence of 23.6 ° of appearance mesoporous carbon to X-ray diffraction (XRD).Other 5 diffraction maximums (37.28 °, 43.38 °, 63.14 °, 75.80 °, 79.86 °, 73-0476, PDF 2 database) corresponding vanadium carbide.
Fig. 2 is the scanning electron microscope (SEM) photograph of the vanadium carbide of mesoporous carbon-loaded.As shown in FIG., the mesh structural porous structure of gray be mesoporous carbon, and the white cube that is embedded in wherein is the vanadium carbide particle.In conjunction with the XRD data, the vanadium carbide of successfully preparing mesoporous carbon-loaded is described.
(3) to the preparation of electrode
(1) utilize the preparation of vanadium carbide (hereinafter to be referred as the VC-MC) conduct of the synthetic mesoporous carbon-loaded of said method to electrode: get the VC-MC of 500mg, add in the isopropyl alcohol of 4mL, ultrasonic dispersion 30min makes slurry.Slurry with preparation, uniformly spray on tin indium oxide (FTO) electro-conductive glass that fluorine mixes with spray gun, and film thickness monitoring is at 0.2～200 μ m, and under nitrogen atmosphere, 500 ℃ of sintering 30 minutes, make VC-MC to electrode.
(2) preparation of Pt to electrode: with spraying process, the aqueous isopropanol of the chloroplatinic acid of 0.5wt% is coated on the FTO electro-conductive glass uniformly, under air atmosphere, 380 ℃ were burnt electrode 30 minutes, make Pt to electrode in tube furnace.
Embodiment 2
(1) preparation is based on VC-MC and the Pt DSSC to electrode
(1) making of light anode: on the FTO electro-conductive glass, with knife coating, titania slurry is prepared into TiO
2Film, 500 ℃ of sintering 30 minutes, be cooled to 80 ℃, in concentration, is 5x10
-4Soaked 16 hours in the ruthenium dye N719 of M, be made into the light anode;
(2) electrolyte is for containing I
3 -/ I
-Acetonitrile solution; Namely contain the 0.1M lithium iodide, 0.3M 1,2-dimethyl-3-propyl group-imidazoles iodine, 0.05M iodine, and the acetonitrile solution of 0.5M tert .-butylpyridine.
(3) be that the VC-MC that makes in embodiment 1 or Pt are to electrode to electrode;
(4) with the light anode of above-mentioned making, electrode is assembled,, with the encapsulation of sarin film, then, at intermediate course, injecting electrolyte, be assembled into the DSSC battery.
(2) test of solar cell photoelectric conversion efficiency
As shown in Figure 3, round dot and side point are respectively the mesoporous carbon-loaded vanadium carbide to electrode and the platinum current-voltage curve to the solar cell of electrode fabrication, electrochemical workstation is Keithley 2601, USA, the sunlight analog light source is PEC-L15, Peccell, Japan, the intensity of light source is AM 1.5, I=100mW cm
-2The I-V curve of Fang Dian representative take Pt as the DSSC to electrode, the I-V curve of round dot representative take VC-MC as the DSSC to electrode.As shown in table 1, the open circuit voltage take VC-MC as the battery to electrode and fill factor, curve factor all than corresponding with the height of Pt to the battery of electrode.Cause 7.63% the surpassing with Pt 7.50% of the battery of electrode of photoelectric conversion efficiency take VC-MC as the battery to electrode.This shows that VC-MC is that a kind of very potential platinum electrode of costliness that can substitute is as the material of DSSC to electrode.
Table 1: the opto-electronic conversion parameter of DSSC
Inventive concept disclosed according to this paper embodiment, those skilled in the art can obtain corresponding technology enlightenment, utilize synthetic method disclosed herein, prepare titanium carbide, zirconium carbide, niobium carbide, chromium carbide, molybdenum carbide, tungsten carbide synthetic of mesoporous carbon-loaded, thereby explore cheap and can effectively replace the new material of platinum electrode.
Claims (2)
1. preparation method to electrode material who is used for DSSC, it is characterized in that: concrete steps are as follows,
(a) by template: aldehydes matter: acetic acid: metal chloride: the mass ratio of aldehyde material is that 2.5:1.65:0.25 ~ 1.0:0.45 ~ 1.8:1.35 ~ 5.4 take each raw material;
(b) ratio of template in 2.5g/30mL is dissolved in ethanol, stirs until dissolve fully;
(c) in the mixed liquor of step (b) acquisition, add aldehydes matter and acetic acid, stir 30 min;
(d) in the mixed liquor of step (c) acquisition, add metal chloride, stir 30 min;
(e) in the mixed liquor of step (d) acquisition, add aldehyde material, obtain colloidal liquid after stirring 30 min, then through oversintering, make;
Wherein:
Template is triblock polymer P123 or F127;
Aldehydes matter is a kind of in resorcinol, phloroglucin, phenol;
Metal chloride is following a kind of: divanadyl tetrachloride, titanium tetrachloride, zirconium chloride, columbium pentachloride, chromium trichloride, molybdenum pentachloride, tungsten hexachloride;
Aldehyde material is formaldehyde or acetaldehyde.
2. method according to claim 1, it is characterized in that: template is triblock polymer F127.
3. method according to claim 1 and 2, it is characterized in that: metal chloride is divanadyl tetrachloride.
4. method according to claim 3, it is characterized in that: aldehydes matter is resorcinol.
5. according to claim 1 or 4 described methods, it is characterized in that: aldehyde material is formaldehyde.
6. method according to claim 5 is characterized in that: the condition of sintering is, places 3 days in 80 ℃, at 1100 ℃ of sintering 5h.
The method of claim 1 preparation a kind of for DSSC to electrode material.
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