CN105280388A - Composite electrode for dye-sensitized solar cell and preparation method of composite electrode - Google Patents
Composite electrode for dye-sensitized solar cell and preparation method of composite electrode Download PDFInfo
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- CN105280388A CN105280388A CN201510659914.3A CN201510659914A CN105280388A CN 105280388 A CN105280388 A CN 105280388A CN 201510659914 A CN201510659914 A CN 201510659914A CN 105280388 A CN105280388 A CN 105280388A
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- electrode
- combination electrode
- solar battery
- dye
- dye sensitization
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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
- 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 composite electrode for a dye-sensitized solar cell and a preparation method of the composite electrode. Under a normal temperature condition, the method uses a pulse current to directly deposit precious metal nanocrystals on a thin film of a disordered nanometer mesoporous structure. The particle size range and the load capacity of the precious metal nanocrystals can be effectively controlled according to the pulse current, connection time, disconnection time and deposition loop number which are selected during deposition. With the method, the precious metal nanocrystals are embedded in the nanometer mesoporous structure evenly and can be separately used as a photoanode or a cathode of a dye-sensitized solar cell. The photoelectric conversion efficiency of dye-sensitized solar energy cells is improved. The method is simple and easy for operation. The composite electrode has good chemical stability and can be used at a low cost and in a large scale.
Description
Technical field
The present invention relates to a kind of used by dye sensitization solar battery combination electrode and preparation method thereof, combination electrode prepared by the method may be used for light anode and the negative electrode of DSSC, belongs to DSSC technical field.
Background technology
In today that energy crisis is day by day serious, the sustainable development of utilization to the mankind of the sustainable energies such as solar energy is had great importance.DSSC (DyeSensitizedSolarCell, DSSC) be a kind of novel solar cell got up based on Nano-technology Development from the nineties in last century, be described as most one of solar cell having commercial application prospect because abundant raw materials, cost are low, technology is relatively simple.DSSC mainly comprises the light anode, dye sensitization molecule, the electrolyte and to electrode that are made up of the brilliant film of electrically conducting transparent substrate and TiOx nano.The working mechanism of DSSC is that dye sensitization molecule absorption light produces light induced electron and is injected into fast in titanium dioxide porous film, dyestuff self becomes oxidation state, electronics in titanium dioxide is diffused into rapidly on electro-conductive glass, then by external circuit dynamic changes process to on electrode; Simultaneously the dyestuff of titanium dioxide can I in electrolyte
3 -reduction, I
3 -be oxidized to I
-diffusing to electrode, is I by arriving the electron reduction on electrode
3 -, complete a loop.Therefore, when dyestuff and electrolyte are determined, how effectively to optimize light anode and have important effect to the efficiency of electrode pair raising dye sensitization of solar.
Current is add a small amount of noble metal nano particles in the slurry in one of method optimizing light anode, nano-metal particle has the function storing electric charge, can make contiguous titanium dioxide semiconductor Fermi level moves, be conducive to reducing semiconductor/electrolytical Interface composites.In addition, the surface plasma body resonant vibration effect between metallic particles and dyestuff can increase the absorption of dyestuff to light, thus improves the electricity conversion of DSSC.But this method building-up process is very complicated, and easily reunites in sintering process, affects general effect.
For in the catalytic performance research improved electrode, it is found that Pt still applies at most at present, stability is best, the material that electrocatalysis characteristic is higher.But how increasing attachment site and the catalysis area of Pt further, is improve the difficult problem to needing in electrode catalyst activity to tackle.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, provides a kind of used by dye sensitization solar battery combination electrode.
Two of object of the present invention is the preparation method providing this combination electrode, the method under normal temperature condition on nano-porous film direct electro-deposition go out the metallic nano crystals such as gold, silver, form noble metal nanocrystalline and be embedded in the method for the combination electrode in nano-porous film.
The embedding of noble metal can adjust the metal oxides such as titanium dioxide conduction band positions, make it negative to move, effectively can inhibit the compound of electron-hole pair, and can utilize and strengthen dyestuff to the absorption of light by surface plasma body resonant vibration (SPR) effect of gold nanocrystals, improve the utilance to light, thus improve the electricity conversion of DSSC, avoid the impact of the metal nanoparticle reunion that high temperature sintering in conventional method causes, can successfully as the optoelectronic pole of DSSC.In addition, at nano-porous film substrates Pt nanocrystal, formed noble metal nanocrystalline nanoporous composite construction also can as DSSC to electrode, considerably increase the roughness on its surface, increase attachment site and the catalysis area of Pt, and then improve the photoelectric conversion efficiency of DSSC.
The present invention for achieving the above object and adopt technical scheme as follows:
A kind of used by dye sensitization solar battery combination electrode, it is characterized in that this combination electrode goes out noble metal nanocrystalline at the surface deposition of unordered mesoporous nano film, the mass ratio of this unordered mesoporous nano film and noble metal nanocrystalline is:.
The aperture of above-mentioned unordered mesoporous nano film is 6 ~ 50nm.
The material of above-mentioned unordered mesoporous nano film is by TiO
2, ZnO and SnO
2in at least one; Or the TiO of F, W, N, Nb element doping
2, ZnO or SnO
2in at least one.
The particle size range of above-mentioned nano particle is 15 ~ 30nm.
Above-mentioned noble metal nanocrystalline is two or more in Au, Pt and Ag.
Above-mentioned noble metal nanocrystalline particle size range is 1 ~ 20nm.
Prepare a method for above-mentioned used by dye sensitization solar battery combination electrode, it is characterized in that the concrete steps of the method are:
A. by inorganic acid and precious metal salt soluble in water, wherein the concentration of inorganic acid is 0.5 ~ 5mM, and the concentration of precious metal salt is 1 ~ 10mM;
B. with the aqueous solution of step a gained for electrodeposit liquid, system used is three-electrode system, wherein the electro-conductive glass of the unordered mesoporous nano film of load is work electrode, Pt is reference electrode to electrode, Ag/AgCl, adopt waveform to be the pulse current of square wave, wherein said current density range is 20 ~ 1000mA/cm
2, sedimentation time is 0.001 ~ 0.3 second, and intermittent time scope is 1 ~ 14 second; Use water and ethanol purge respectively subsequently, dry, namely obtain used by dye sensitization solar battery combination electrode.
8. method according to claim 7, is characterized in that described inorganic acid is hydrochloric acid, inorganic acid or nitric acid.
Above-mentioned slaine is chloride, nitrate or organic metal salt.
The present invention has the following advantages and beneficial effect:
1, the combination electrode that the gold prepared of the present invention or silver-colored noble metal nanocrystalline are evenly inlayed in unordered mesoporous nano film is applied in dye-sensitized solar cell anode, not only effectively can suppress the compound of electronics but also the absorption of dyestuff to light can be improved, thus the open circuit voltage of raising battery and short circuit current are to improve the photoelectric conversion efficiency of DSSC;
2, the nanocrystalline combination electrode evenly inlayed in unordered mesoporous nano film of platinum noble metals that prepared by the present invention is applied in DSSC to electrode, considerably increase the roughness on its surface, increase attachment site and the catalysis area of Pt, and then improve the photoelectric conversion efficiency of DSSC.
3, present invention process is simple, and reaction condition is gentle, does not need expensive equipment and raw material, is conducive to commercial introduction.
Below in conjunction with accompanying drawing and embodiment, the present invention is further described.
Accompanying drawing explanation
Fig. 1 is that the scanning electron microscope (SEM) photograph of composite light anode for dye-sensitized solar cell in the present invention is schemed with the mapping of correspondence, as can be seen from the figure, golden nanometer particle is embedded in the surface of titanium dioxide porous film and duct and the Elemental redistribution of Ti, O, Au element in complex light anode.
Fig. 2 forms the J-V curve corresponding to DSSC respectively for the gold in the present invention and titanium dioxide complex light anode and pure titanium dioxide, as can be seen from the figure, the battery that the electricity conversion of battery that gold and titanium dioxide complex light anode form forms apparently higher than pure titanium dioxide.
Embodiment
embodiment 1:
The preparation method of composite light anode for dye-sensitized solar cell, realizes as follows:
(1) prepare the aqueous solution of inorganic acid and gold chloride, in the described aqueous solution, the concentration of sulfuric acid is 5mM, and the concentration of chlorauric acid solution is 1M.
(2) aqueous solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein titanium dioxide porous film is work electrode, Pt is reference electrode to electrode, Ag/AgCl, and adopt waveform to be the pulse current of square wave, wherein said current density is 200mA/cm
2, sedimentation time is 0.1 second, and the intermittent time is 3 seconds, and periodicity is 1.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain gold and be embedded in combination electrode in titanium dioxide porous film.
Through the light anode of the combination electrode utilizing electrodeposition process to be deposited on by gold nanocrystals the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC, by this electrode and platinum of the same area to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 2:
The preparation method of composite light anode for dye-sensitized solar cell, its step is substantially identical with enforcement 1, and its difference is:
(1) prepare the aqueous solution of inorganic acid and gold chloride, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of chlorauric acid solution is 1M.
(2) aqueous solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein titanium dioxide porous film is work electrode, Pt is reference electrode to electrode, Ag/AgCl, and adopt waveform to be the pulse current of square wave, wherein said current density is 500mA/cm
2, sedimentation time is 0.01 second, and the intermittent time is 3 seconds, and number of deposition cycles is 2.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain gold and be embedded in combination electrode in titanium dioxide porous film.
Through the light anode of the combination electrode utilizing electrodeposition process to be deposited on by gold nanocrystals the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC, by this electrode and platinum of the same area to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 3:
The preparation method of composite light anode for dye-sensitized solar cell, its step is substantially identical with enforcement 1,2, and its difference is:
(1) prepare the aqueous solution of inorganic acid and gold chloride, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of chlorauric acid solution is 1M.
(2) aqueous solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein titanium dioxide porous film is work electrode, Pt is reference electrode to electrode, Ag/AgCl, and adopt waveform to be the pulse current of square wave, wherein said current density is 300mA/cm
2, sedimentation time is 0.001 second, and the intermittent time is 3 seconds, and number of deposition cycles is 1.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain gold and be embedded in combination electrode in titanium dioxide porous film.
Through the light anode of the combination electrode utilizing electrodeposition process to be deposited on by gold nanocrystals the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC, by this electrode and platinum of the same area to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 4:
The preparation method of composite light anode for dye-sensitized solar cell, its step is substantially identical with enforcement 1,2,3, and its difference is:
(1) prepare the aqueous solution of inorganic acid and gold chloride, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of chlorauric acid solution is 1M.
(2) aqueous solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein tin dioxide porous film is work electrode, Pt is reference electrode to electrode, Ag/AgCl, and adopt waveform to be the pulse current of square wave, wherein said current density is 700mA/cm
2, sedimentation time is 0.1 second, and the intermittent time is 6 seconds, and number of deposition cycles is 1.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain gold and be embedded in combination electrode in tin dioxide porous film.
Through the light anode of the combination electrode utilizing electrodeposition process to be deposited on by gold nanocrystals the unordered mesopore film of tin ash is formed of the present invention as DSSC, by this electrode and platinum of the same area to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 5:
The preparation method of composite light anode for dye-sensitized solar cell, its step is substantially identical with enforcement 1,2,3,4, and its difference is:
(1) prepare the aqueous solution of inorganic acid and gold chloride, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of chlorauric acid solution is 1M.
(1) aqueous solution prepared with step (2) is for electrodeposit liquid, and system used is three-electrode system, and wherein titanium dioxide porous film is work electrode, Pt is reference electrode to electrode, Ag/AgCl, adopts multi-ladder current method electro-deposition gold nanoparticles; Wherein said current density is 900mA/cm
2, sedimentation time is 0.3 second, and the intermittent time is 3 seconds, and number of deposition cycles is 1.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain gold and be embedded in combination electrode in titanium dioxide porous film.
Through the light anode of the combination electrode utilizing electrodeposition process to be deposited on by gold nanocrystals the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC, by this electrode and platinum of the same area to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 6:
The preparation method of composite light anode for dye-sensitized solar cell, its step is substantially identical with enforcement 1,2,3,4,5, and its difference is:
(1) prepare the aqueous solution of inorganic acid and gold chloride, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of chlorauric acid solution is 1M.
(3) aqueous solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein titanium dioxide porous film is work electrode, Pt is reference electrode to electrode, Ag/AgCl, and adopt waveform to be the pulse current of square wave, wherein said current density is 700mA/cm
2, sedimentation time is 0.02 second, and the intermittent time is 4 seconds, and number of deposition cycles is 1.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain gold and be embedded in combination electrode in titanium dioxide porous film.
Through the light anode of the combination electrode utilizing electrodeposition process to be deposited on by gold nanocrystals the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC, by this electrode and platinum of the same area to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 7:
The preparation method of DSSC combined counter electrode pole, its step is substantially identical with enforcement 1,2,3,4,5,6, and its difference is:
(1) prepare the aqueous solution of inorganic acid and chloroplatinic acid, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of platinum acid chloride solution is 1M.
(2) alcoholic solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein electrically conducting transparent substrate be work electrode, Pt to electrode, Ag/AgCl is reference electrode, adopt waveform to be the pulse current of square wave, wherein said current density is 30mA/cm
2, sedimentation time is 0.05 second, and the intermittent time is 2 seconds, and deposition cycle issue is 10.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain platinum and be embedded in combination electrode in titanium dioxide porous film.
Through the combination electrode utilizing electrodeposition process to be deposited on by Pt nanocrystal the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC to electrode, by this electrode together with pure titinium dioxide film light anode assembling of the same area, middle perfusion electrolyte, can obtain DSSC.
embodiment 8:
The preparation method of DSSC combined counter electrode pole, its step is substantially identical with enforcement 1,2,3,4,5,6,7, and its difference is:
(1) prepare the aqueous solution of inorganic acid and chloroplatinic acid, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of platinum acid chloride solution is 1M.
(2) alcoholic solution prepared with step (2) of the preparation of Pt/ titanium dioxide combination electrode is for electrodeposit liquid, system used is three-electrode system, wherein electrically conducting transparent substrate be work electrode, Pt to electrode, Ag/AgCl is reference electrode, adopts multi-ladder current method electrodeposition Pt nano particle; Wherein said current density is 50mA/cm
2, sedimentation time is 0.04 second, and the intermittent time is 5 seconds number of deposition cycles is 20.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain platinum and be embedded in combination electrode in titanium dioxide porous film.
Through the combination electrode utilizing electrodeposition process to be deposited on by Pt nanocrystal the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC to electrode, by this electrode together with pure titinium dioxide film light anode assembling of the same area, middle perfusion electrolyte, can obtain DSSC.
embodiment 9:
The preparation method of DSSC combined counter electrode pole, its step with enforcement 1,2,3,4,5,6,7,8, substantially identical, its difference is:
(1) prepare the aqueous solution of inorganic acid and chloroplatinic acid, in the described aqueous solution, the concentration of sulfuric acid is 10mM, and the concentration of platinum acid chloride solution is 1M.
(2) alcoholic solution prepared with step (1) is for electrodeposit liquid, system used is three-electrode system, wherein electrically conducting transparent substrate be work electrode, Pt to electrode, Ag/AgCl be reference electrode adopt waveform be the pulse current of square wave, wherein said current density is 35mA/cm
2, sedimentation time is 0.1 second, and the intermittent time is 8 seconds, and number of deposition cycles is 30.Use water and ethanol purge respectively subsequently, under vacuo 100 DEG C of dryings 10 hours.Namely obtain platinum and be embedded in combination electrode in titanium dioxide porous film.
Through the combination electrode utilizing electrodeposition process to be deposited on by Pt nanocrystal the unordered mesopore film of titanium dioxide is formed of the present invention as DSSC to electrode, by this electrode together with pure titinium dioxide film light anode assembling of the same area, middle perfusion electrolyte, can obtain DSSC.
Claims (9)
1. a used by dye sensitization solar battery combination electrode, it is characterized in that this combination electrode goes out noble metal nanocrystalline at the surface deposition of unordered mesoporous nano film, the mass ratio of this unordered mesoporous nano film and noble metal nanocrystalline is: 0.01% ~ 0.5%.
2. used by dye sensitization solar battery combination electrode according to claim 1, is characterized in that the aperture of described unordered mesoporous nano film is 6 ~ 50nm.
3. used by dye sensitization solar battery combination electrode according to claim 2, is characterized in that the material of described unordered mesoporous nano film is by TiO
2, ZnO and SnO
2in one; Or the TiO of F, W, N, Nb element doping
2, ZnO or SnO
2in at least one.
4. used by dye sensitization solar battery combination electrode according to claim 3, is characterized in that the particle size range of described nano particle is 15 ~ 30nm.
5. used by dye sensitization solar battery combination electrode according to claim 1, is characterized in that described noble metal nanocrystalline is two or more in Au, Pt and Ag.
6. used by dye sensitization solar battery combination electrode according to claim 5, is characterized in that described noble metal nanocrystalline particle size range is 1 ~ 20nm.
7. prepare a method for the used by dye sensitization solar battery combination electrode according to any one of claim 1 ~ 6, it is characterized in that the concrete steps of the method are:
A. by inorganic acid and precious metal salt soluble in water, wherein the concentration of inorganic acid is 0.5 ~ 5mM, and the concentration of precious metal salt is 1 ~ 10mM;
B. with the aqueous solution of step a gained for electrodeposit liquid, system used is three-electrode system, wherein the electro-conductive glass of the unordered mesoporous nano film of load is work electrode, Pt is reference electrode to electrode, Ag/AgCl, adopt waveform to be the pulse current of square wave, wherein said current density range is 20 ~ 1000mA/cm
2, sedimentation time is 0.001 ~ 0.3 second, and intermittent time scope is 1 ~ 14 second; Use water and ethanol purge respectively subsequently, dry, namely obtain used by dye sensitization solar battery combination electrode.
8. method according to claim 7, is characterized in that described inorganic acid is hydrochloric acid, inorganic acid or nitric acid.
9. method according to claim 7, is characterized in that described slaine is chloride, nitrate or organic metal salt.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103310992A (en) * | 2013-05-21 | 2013-09-18 | 东莞上海大学纳米技术研究院 | Photo-anode of dye-sensitized solar cell and preparation method for photo-anode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103310992A (en) * | 2013-05-21 | 2013-09-18 | 东莞上海大学纳米技术研究院 | Photo-anode of dye-sensitized solar cell and preparation method for photo-anode |
Non-Patent Citations (1)
| Title |
|---|
| XINNING LUAN等: "Plasmon-enhanced Performance of Dye-sensitized Solar Cells Based on Electrodeposited Ag Nanoparticles", 《J. MATER. SCI. TECHNOL.》 * |
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