CN104882285A - Dye-sensitized solar cell counter electrode material and manufacturing method thereof - Google Patents
Dye-sensitized solar cell counter electrode material and manufacturing method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
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- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
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- 229910021389 graphene Inorganic materials 0.000 claims description 46
- 238000002360 preparation method Methods 0.000 claims description 24
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
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- 238000002156 mixing Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 150000004985 diamines Chemical class 0.000 abstract 1
- 238000006385 ozonation reaction Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
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- 239000000463 material Substances 0.000 description 9
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- 239000010970 precious metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 1
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- 229920001940 conductive polymer Polymers 0.000 description 1
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- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
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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
- 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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Abstract
The invention discloses a manufacturing method for a dye-sensitized solar cell counter electrode material. The manufacturing method comprises the following steps: (1) performing ultrasonic dispersion on a grapheme oxide (GO) aqueous solution, and performing ozonation on the grapheme oxide (GO) aqueous solution to obtain a further oxidized grapheme oxide suspension liquid; (2) heating ethidene diamine and the oxidized grapheme oxide suspension liquid obtained in the step (1) in a closed container, heating in a oil bath pan at the temperature of 90-100 DEG C for 5-7 hours, purifying the obtained products to obtain ethidene-diamine-functionalization grapheme (EFG); (3) and mixing the products obtained in the step (2) with right amount of binder, grinding for 20-40 min to obtain a counter electrode slurry, using a knife coating method to coat the slurry on FTO conductive glass, and drying the glass. The manufacturing method for the cell counter electrode material is mild in reaction conditions, low in cost, simple in operation, and easy in commercialized popularization. The dye-sensitized solar cell counter electrode material is relatively high in photoelectric conversion efficiency after being assembled in a dye-sensitized solar cell.
Description
Technical field
The present invention relates to a kind of DSSC to electrode material and preparation method thereof, particularly relate to a kind of for the nonmetal catalyzed material of DSSC to electrode catalyst iodine reduction reaction, belong to photoelectrocatalysis field of new.
Background technology
Energy shortage and environmental pollution are the two large problems of current facing mankind.Traditional energy matchmaker, oil and timber can only maintain 50 to one hundred years by current depletion rate.In addition, environmental pollution brought thus, is also threaten the earth that the mankind depend on for existence.And in the foreseeable future time of the mankind, solar energy is as the inexhaustible clear energy sources of the mankind, do not produce any environmental pollution, and not by the restriction of geographical conditions, therefore solar utilization technique research causes the extensive attention of various countries scientist.
Opto-electronic conversion is one of most important Solar use mode, and this process is realized by solar cell.Solar cell it have efficiently, clean, the advantage of low cost.Difference according to material therefor can be divided into silica-based solar cell, thin-film solar cells and novel solar battery.Wherein DSSC (Dye-sensitized Solar Cells, DSSCs) is a kind of novel solar battery developed in recent years.DSSCs is formed primarily of three parts: the nano porous semiconductor film light anode being adsorbed with dyestuff, and electrolyte is the organic solution containing oxidation-reduction pair, and usually adopts precious metals pt as catalyst to electrode.What wherein mainly play electrode is collect external circuit electronics and catalytic reduction I
3 -effect.Pt is widely used in electrode material as the efficient catalysis material of one, but the reserves of occurring in nature Pt are very limited, and there are some researches show Pt easily corrode by electrolyte solution, this cost just causing DSSCs is higher, is difficult to realize large-scale production.In order to improve the photoelectric conversion efficiency of battery further and reduce production cost, the Pt substitution material of development of new just seems very important.What use at present replaces material to have to electrode: inorganic metal compound, conducting polymer, and material with carbon element.
In many material with carbon elements, Graphene becomes the focus of people's research due to the structure and characteristics of its uniqueness, and it is a kind of two-dimentional monoatomic layer thickness, and the material with carbon element of sp2 hydridization, has the specific area (2630m of super large
2/ g), good conductivity (200000cm
2v
-1s
-1), be therefore suitable for doing electrode material.But single Graphene catalytic performance is poor, the requirement to electrode catalytic materials can not be met completely, its surface characteristic is so regulated by the mode of chemical doping and chemical modification, the electron distributions of modulation graphenic surface, increase the active site of Graphene simultaneously, its catalytic activity can be improved thus widen its application further.
Summary of the invention
In order to solve the problem, the invention provides a kind of reaction condition gentle, with low cost, easy and simple to handle, be easy to commercialization and promote, the preparation method to electrode material (ethylenediamine functionalization graphene) that photoelectric conversion efficiency is higher.The inventive method, under relatively mild experiment condition, utilizes the epoxy-functional of surface of graphene oxide and ethylenediamine generation open loop nucleophilic substitution to synthesize the Graphene of this ethylenediamine functionalization.The Graphene photoelectric conversion efficiency of ethylenediamine functionalization reaches 7.39%, close to the electricity conversion of Pt under condition, can be used as a kind of non-metal base efficiently and is applied in DSSC electrode material and replaces precious metals pt.
The present invention is achieved through the following technical solutions:
DSSC is the preparation method to electrode material comprise the following steps:
(1) by graphene oxide (GO) aqueous solution ultrasonic disperse, then carried out ozone oxidation, obtained the graphene oxide suspension of oxidation further;
(2) in a closed container, heat the graphene oxide suspension that ethylenediamine and step (1) obtain, 90-100 DEG C of heating 5-7h in oil bath pan, by products therefrom separation, washing, drying, obtain the Graphene (EFG) of ethylenediamine functionalization;
(3) mix processing through step (2) product obtained with appropriate binding agent, grinding 20-40min obtains electrode slurry, adopts knife coating to be coated in by slurry on FTO electro-conductive glass, then carries out drying.
Preferably, the graphene oxide water solution concentration in described step (1) is 0.5-1.5mg/mL, and ultrasonic time is 0.5-1.5h.
Preferably, the ozone oxidation source of the gas in described step (1) is air.
Preferably, in described step (2), the mass ratio of graphene oxide and ethylenediamine is 1:0.5-3.
Preferably, what the washing process in described step (2) was spends deionized water 7-8 time; Dry run in described step (2) is freeze drying 22-26h.
Preferably, oil bath pan temperature control 90-100 DEG C in described step (2), heating time is 5-7h.
Preferably, the dry run in described step (3) is in tube furnace, under nitrogen protection, with 2 DEG C of min
-1heating rate rise to 400-600 DEG C, maintain 20-40min.
Preferably, in described step (3), the consumption of binding agent is that the Graphene of ethylenediamine functionalization and the mass ratio of binding agent are 1:12-14.
Preferably, in described step (3), the blade coating thickness of slurry is 10-11 μm.The blade coating thickness of slurry is that the optoelectronic transformation efficiency of the DSSC to electrode assembling of 10-11 μm is higher, but the blade coating thickness of slurry is not limited to 10-11 μm.
In the step (1) of preparation method of the present invention, the optimal time of ozone oxidation is 8-12min, experimental result shows that the electricity conversion of end product is higher, this is due to the lifting along with graphene oxide degree of oxidation, epoxy-functional on graphene sheet layer increases, and is conducive to the further reaction with ethylenediamine; But along with the further lifting of degree of oxidation, graphene film is broken, can affect the electric conductivity of lamella.
Another object that the present invention solves is to provide DSSC that above-mentioned preparation method obtains to electrode.
Introduce ethylamino-in the Graphene of the ethylenediamine functionalization that preparation method of the present invention prepares, change the CHARGE DISTRIBUTION of graphenic surface, reduce the energy of ionization value of Graphene, be easy to provide electronics under electrochemical environment, thus promote I on electrode
3 -reduction reaction, improve the catalytic performance to electrode.What therefore prepared by the present invention is higher to the photoelectric conversion efficiency of electrode, close to the photoelectric conversion efficiency of Pt under condition, can be used as a kind of non-metal base efficiently and is applied in DSSC electrode material and replaces precious metals pt.
The beneficial effect of the invention
Preparation method's reaction condition to electrode material of the present invention is gentle, with low cost, easy and simple to handle be easy to commercialization promote, the electricity conversion being assembled into DSSC is higher, close to the electricity conversion with platinum electrode under condition, stability is good, and being a kind ofly has the DSSC non-metal base of development potentiality to the substitution material of electrode.
Accompanying drawing explanation
Accompanying drawing 5 width of the present invention,
Fig. 1 is the Graphene of ethylenediamine functionalization and the contrast infrared spectrum of graphene oxide of embodiment 1 preparation;
Fig. 2 is the Graphene of ethylenediamine functionalization and the contrast Raman spectrogram of graphene oxide of embodiment 1 preparation;
Fig. 3 is the Graphene of ethylenediamine functionalization and the contrast X-ray diffractogram of graphene oxide of embodiment 1 preparation;
Fig. 4 is the J-V curve to the DSSC that electrode assembling becomes prepared by embodiment 1, embodiment 6 and embodiment 7;
Fig. 5 is the J-V curve to the DSSC that electrode assembling becomes prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5.
Embodiment
Following nonlimiting examples 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.
Embodiment 1
(1) getting 0.1g graphene oxide (GO) powder is dissolved in 100mL deionized water, ultrasonic disperse 1h, then at air as under gas source condition, carried out ozone oxidation, oxidization time is 10min, can obtain the graphene oxide suspension of oxidation further;
(2) in a closed container, heat the graphene oxide suspension (90mL that ethylenediamine (120 μ L) and above-mentioned steps (1) obtain, 1mg/mL), 95 DEG C of heating 6h in oil bath pan, it is the filter membrane vacuum filtration of 0.45 μm by products therefrom deionized water, aperture, wash 7-8 time, freeze drying 24h, can obtain the Graphene (EFG) (its phenogram as shown in Figure 1, Figure 2, Fig. 3 and table 1 shown in) of the ethylenediamine functionalization of black powder;
(3) will process through step (2) product and appropriate binding agent (terpinol that obtain; consumption is that every 6mg product drips two binding agents) mixing; grinding 30min obtains electrode slurry; knife coating is adopted to be coated in by slurry on FTO electro-conductive glass; thickness is 10-11 μm; then the FTO electro-conductive glass being covered with slurry is put into tube furnace, under nitrogen protection, with 2 DEG C of min
-1heating rate rise to 500 DEG C, maintain 30min.Obtained DSSC is to electrode.
Table 1 is that the Graphene of ethylenediamine functionalization prepared by step (2) and the contrast element of graphene oxide analyze data.
Table 1
Embodiment 2
Condition and step are with embodiment 1, and difference is only, do not carry out this step of ozone oxidation in step (1).
Embodiment 3
Condition and step are with embodiment 1, and difference is only, the ozone oxidation in step (1) is at air as under gas source condition, and oxidization time is 30min.
Embodiment 4
Condition and step are with embodiment 1, and difference is only, the ozone oxidation in step (1) is at air as under gas source condition, and oxidization time is 60min.
Embodiment 5
Condition and step are with embodiment 1, and difference is only, the ozone oxidation in step (1) is at oxygen as under gas source condition, and oxidization time is 10min.
Embodiment 6
Graphene oxide powder is put into tube furnace; under nitrogen protection; 800 DEG C calcining 1h obtain Graphene (G) black powder, then by its obtained DSSC to electrode, its to electrode preparation method with embodiment 1 (3).
Embodiment 7
The DHS-ED03 model Pt that platinum electrode (Pt) adopts Dalian HeptaChroma SolarTech Co., Ltd. to buy is to electrode, and use Pt slurry (PtSP) to make, the thickness of platinum is approximately 200nm.
Effect example---to electrode photoelectric performance test
Prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 is assembled into DSSC as follows to electrode.
DSSC assembling process is as follows:
1. granular size is approximately the TiO of 20-30nm
2slurry is printed onto on FTO electro-conductive glass, and its effective area is 4mm × 4mm, and thickness is about 14-16 μm; Then by its temperature control 325 DEG C, 375 DEG C, 450 DEG C, 500 DEG C roastings 15min, 15min, 25min, 30min successively in Muffle furnace, after being cooled to room temperature, being soaked in concentration is in the N719 dye solution of 0.5mM, takes out, can obtain light anode after 20h;
2. soak the TiO after dyestuff
2light anode alcohol flushing dries up, what then obtain with embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 is assembled into battery to electrode and hot melt adhesive film hot press, (solvent is acetonitrile to electrolyte, and solute is the I of anhydrous LiI, 0.03M of 0.06M
2, 0.5M tert .-butylpyridine and 0.1M guanidinium isothiocyanate) rush between two electrode slices under vacuumized conditions.
The model of the solar simulator that this experiment adopts is PEC-L15, Peccell, Yokohama, Japan.Electrochemical workstation is Keithley 2601, Cleveland, OH.Potential scan scope is 0mV ~ 800mV.And under identical experiment condition, photoelectric properties test is carried out to assembled battery.
Result shows, and as shown in Figure 4, is the J-V curve of the DSSC to electrode assembling of embodiment 1, embodiment 6 and embodiment 7 preparation.Wherein mark EFG (air 10min), G with Pt represent the DSSC become electrode assembling prepared by embodiment 1, embodiment 6 and embodiment 7 respectively.Show thus, the Graphene of ethylenediamine functionalization is compared with pure Graphene, photoelectric conversion efficiency is significantly improved, because the introducing of ethylamino-changes the CHARGE DISTRIBUTION of graphenic surface, reduce the energy of ionization value of Graphene, be easy to provide electronics under electrochemical environment, thus promote I on electrode
3 -reduction reaction, improve the catalytic performance to electrode.Table 2 is above-mentioned three kinds of corresponding photovoltaic parameters of battery.
Table 2
As shown in Figure 5, be the J-V curve of the DSSC to electrode assembling of embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 preparation.Wherein mark EFG (air 10min), EFG (not being oxidized), EFG (air 30min), EFG (air 60min) and EFG (oxygen 10min) and represent the DSSC that electrode assembling is become prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 respectively.As seen from Figure 5, the electricity conversion of EFG (air 10min) is higher, this is because along with the lifting of graphene oxide degree of oxidation, the epoxy-functional on graphene sheet layer increases, and is conducive to the further reaction with ethylenediamine; But along with the further lifting of degree of oxidation, graphene film is broken, can affect the electric conductivity of lamella.Table 3 is above-mentioned four kinds of corresponding photovoltaic parameters of battery.Table 3
Claims (10)
1. DSSC is to the preparation method of electrode material, it is characterized in that: described preparation method comprises the following steps:
(1) by graphene oxide water solution ultrasonic disperse, then carried out ozone oxidation, obtained the graphene oxide suspension of oxidation further;
(2) in a closed container, heat the graphene oxide suspension that ethylenediamine and step (1) obtain, 90-100 DEG C of heating 5-7h in oil bath pan, products therefrom be separated, washing, dry, obtain the Graphene of ethylenediamine functionalization;
(3) Graphene that will process through step (2) the ethylenediamine functionalization obtained mixes with binding agent, and grinding 20-40min obtains electrode slurry, adopts knife coating to be coated in by slurry on FTO electro-conductive glass, then carries out drying.
2. preparation method according to claim 1, is characterized in that: the graphene oxide water solution concentration in described step (1) is 0.5-1.5mg/mL, and ultrasonic time is 0.5-1.5h.
3. preparation method according to claim 1, is characterized in that: the ozone oxidation source of the gas in described step (1) is air.
4. preparation method according to claim 1, is characterized in that: in described step (2), the mass ratio of graphene oxide and ethylenediamine is 1:0.5-3.
5. preparation method according to claim 1, is characterized in that: what the washing process in described step (2) was spends deionized water 7-8 time; Dry run in described step (2) is freeze drying 22-26h.
6. preparation method according to claim 1, is characterized in that: the dry run in described step (3) for carry out in tube furnace.
7. preparation method according to claim 1, is characterized in that: the dry run in described step (3) is under nitrogen protection, with 2 DEG C of min
-1heating rate rise to 400-600 DEG C, maintain 20-40min.
8. preparation method according to claim 1, is characterized in that: in described step (3), and the Graphene of ethylenediamine functionalization and the mass ratio of binding agent are 1:12-14.
9. preparation method according to claim 1, is characterized in that: in described step (3), the blade coating thickness of slurry is 10-11 μm.
10. DSSC is to electrode material, it is characterized in that: described to electrode material by described in claim 1-9 any one claim method prepare.
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| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
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