CN104882285B - DSSC is to electrode material and preparation method thereof - Google Patents
DSSC is to electrode material and preparation method thereof Download PDFInfo
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- CN104882285B CN104882285B CN201510299457.1A CN201510299457A CN104882285B CN 104882285 B CN104882285 B CN 104882285B CN 201510299457 A CN201510299457 A CN 201510299457A CN 104882285 B CN104882285 B CN 104882285B
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- graphene
- ethylenediamine
- graphene oxide
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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
Preparation method the invention discloses DSSC to electrode material, the preparation method comprise the following steps：(1) by graphene oxide (GO) aqueous solution ultrasonic disperse, ozone oxidation is then carried out, the graphene oxide suspension further aoxidized；(2) graphene oxide suspension that heating ethylenediamine and step (1) obtain in a closed container, 90 100 DEG C of 5 7h of heating, products therefrom is purified to obtain the graphene (EFG) of ethylenediamine functionalization in oil bath pan；(3) product obtained by step (2) processing is mixed with appropriate binding agent, 20 40min of grinding are obtained to electrode slurry, and slurry is coated on FTO electro-conductive glass using knife coating, is then dried.Preparation method reaction condition of the present invention to electrode material is gentle, and cost is cheap, and easy to operate to be easy to commercialization popularization, electricity conversion is higher after being assembled into DSSC.
Description
Technical field
The present invention relates to a kind of DSSC to electrode material and preparation method thereof, more particularly to a kind of pin
Nonmetal catalyzed material to DSSC to electrode catalyst iodine reduction reaction, belong to photoelectrocatalysis new material neck
Domain.
Background technology
Energy shortage and the two large problems that environmental pollution is current facing mankind.Traditional energy matchmaker, oil and timber are pressed
Current depletion rate can only maintain 50 to 100 years.In addition, thus caused environmental pollution, also threatens the mankind
The earth depended on for existence.And in the foreseeable future time of the mankind, solar energy is inexhaustible as the mankind
Clear energy sources, any environmental pollution is not produced, and do not limited by geographical conditions, therefore solar utilization technique research is drawn
The extensive attention of scientists from all over the world is played.
Opto-electronic conversion is one of most important Solar use mode, and this process is realized by solar cell
's.Its advantage with efficient, cleaning, low cost of solar cell.The silicon substrate sun can be divided into according to the difference of material therefor
Can battery, thin-film solar cells and novel solar battery.Wherein DSSC (Dye-sensitized
Solar Cells, DSSCs) it is a kind of novel solar battery developed in recent years.DSSCs is mainly made up of three parts：
The nano porous semiconductor film light anode of dyestuff is adsorbed with, electrolyte is the organic solution containing oxidation-reduction pair, and
To electrode generally use precious metals pt as catalyst.Wherein electrode is primarily served is to collect external circuit electronics and catalysis
Reduce I3 -Effect.Pt is widely used in electrode material as a kind of efficient catalysis material, but Pt in nature
Reserves be very limited amount of, and there are some researches show Pt is easily corroded by electrolyte solution, this has resulted in DSSCs cost
It is higher, it is difficult to realize large-scale production.In order to further improve the photoelectric transformation efficiency of battery and reduce production cost, open
The Pt alternative materials for sending out new just seem particularly significant.Have used at present to electrode instead of material：Inorganic metal compound,
Conducting polymer, and carbon material.
The focus that graphene is studied due to its unique structure and characteristic as people in many carbon materials, it is one
The two-dimentional monoatomic layer thickness of kind, the carbon material of sp2 hydridization, there is the specific surface area (2630m of super large2/ g), good conduction
Property (200000cm2V-1s-1), therefore suitably do electrode material., can not be complete but single graphene catalytic performance is poor
Meet the requirement to electrode catalytic materialses, then its surface characteristic is adjusted by way of chemical doping and chemical modification,
The electronics distribution of modulation graphenic surface, while increases the active site of graphene, can improve its catalytic activity from
And further widen its application field.
The content of the invention
In order to solve the above problems, a kind of reaction condition of present invention offer is gentle, and cost is cheap, easy to operate, is easy to business
Industryization is promoted, the higher preparation method to electrode material (ethylenediamine functionalization graphene) of photoelectric transformation efficiency.Present invention side
Under relatively mild experiment condition, using the epoxy-functional and ethylenediamine of surface of graphene oxide open loop nucleophilic displacement of fluorine occurs for method
Reaction has synthesized the graphene of this ethylenediamine functionalization.The graphene photoelectric transformation efficiency of ethylenediamine functionalization reaches
7.39%, close to the electricity conversion of the Pt with the conditions of, a kind of efficient non-metal base can be used as to be applied to electrode material
Precious metals pt is replaced in DSSC.
The present invention is achieved through the following technical solutions：
DSSC comprises the following steps to the preparation method of electrode material：
(1) by graphene oxide (GO) aqueous solution ultrasonic disperse, ozone oxidation is then carried out, is further aoxidized
Graphene oxide suspension；
(2) graphene oxide suspension that heating ethylenediamine and step (1) obtain in a closed container, in oil bath pan
Middle 90-100 DEG C of heating 5-7h, products therefrom is separated, washed, is dried, obtains the graphene (EFG) of ethylenediamine functionalization；
(3) product obtained by step (2) processing is mixed with appropriate binding agent, grinding 20-40min is obtained to electricity
Pole slurry, slurry is coated on FTO electro-conductive glass using knife coating, is then dried.
Preferably, the graphene oxide water solution concentration in the 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 the step (1) is air.
Preferably, the mass ratio of graphene oxide and ethylenediamine is 1 in the step (2):0.5-3.
Preferably, what the washing process in the step (2) was is washed with deionized 7-8 times；In the step (2)
Drying process is freeze-drying 22-26h.
Preferably, 90-100 DEG C of oil bath pan temperature control in the step (2), heat time 5-7h.
Preferably, the drying process in the step (3) is in tube furnace, under nitrogen protection, with 2 DEG C of min-1Liter
Warm speed rises to 400-600 DEG C, maintains 20-40min.
Preferably, the dosage of binding agent is the graphene of ethylenediamine functionalization and the quality of binding agent in the step (3)
Than for 1:12-14.
Preferably, in the step (3), the blade coating thickness of slurry is 10-11 μm.The blade coating thickness of slurry is 10-11 μm
The DSSC to electrode assembling optoelectronic transformation efficiency it is higher, but the blade coating thickness of slurry is not limited to 10-11 μ
m。
In the step of preparation method of the present invention (1), the optimal time of ozone oxidation is 8-12min, experimental result table
The electricity conversion of bright final product is higher, and this is due to the lifting of graphene oxide degree of oxidation, graphene sheet layer
On epoxy-functional increase, be advantageous to the further reaction with ethylenediamine；However as the further lifting of degree of oxidation, stone
Black alkene piece is broken, can influence the electric conductivity of lamella.
The another object that the present invention solves is to provide DSSC that above-mentioned preparation method obtains to electrode.
Ethylamino- is introduced in the graphene for the ethylenediamine functionalization that preparation method of the present invention is prepared, is changed
The distribution of charges of graphenic surface, the energy of ionization value of graphene is reduced, be easy to provide electronics under electrochemical environment, so as to
Promote to I on electrode3 -Reduction reaction, improve the catalytic performance to electrode.Therefore the photoelectricity to electrode that prepared by the present invention
Conversion efficiency is higher, close to the photoelectric transformation efficiency of the Pt with the conditions of, can be used as a kind of efficient non-metal base to electrode material
Applied to replacing precious metals pt in DSSC.
The beneficial effect of invention
Preparation method reaction condition of the present invention to electrode material is gentle, and cost is cheap, easy to operate to be easy to business
Change and promote, be assembled into that the electricity conversion of DSSC is higher, the photoelectricity close to the platinum electrode with the conditions of turns
Change efficiency, stability is good, is a kind of replacement material of the DSSC non-metal base to electrode for having development potentiality
Material.
Brief description of the drawings
The width of accompanying drawing 5 of the present invention,
Fig. 1 is the graphene of ethylenediamine functionalization and the contrast infrared spectrum of graphene oxide prepared by embodiment 1；
Fig. 2 is the graphene of ethylenediamine functionalization and the contrast Raman spectrogram of graphene oxide prepared by embodiment 1；
Fig. 3 is the graphene of ethylenediamine functionalization and the contrast X-ray diffraction of graphene oxide prepared by embodiment 1
Figure；
Fig. 4 be embodiment 1, embodiment 6 and embodiment 7 prepare to electrode assembling into DSSC
J-V curves；
Fig. 5 be embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 prepare to electrode assembling into dyestuff
The J-V curves of sensitization solar battery.
Embodiment
Following nonlimiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
(1) 0.1g graphene oxides (GO) powder is taken to be dissolved in 100mL deionized waters, ultrasonic disperse 1h, then in air
As under gas source condition, being carried out ozone oxidation, oxidization time 10min, you can the graphite oxide further aoxidized
Alkene suspension；
(2) graphene oxide that heating ethylenediamine (120 μ L) and above-mentioned steps (1) obtain in a closed container suspends
Liquid (90mL, 1mg/mL), 95 DEG C of heating 6h in oil bath pan, by products therefrom deionized water, the filtering that aperture is 0.45 μm
Film is filtered by vacuum, and is washed 7-8 times, is freeze-dried 24h, you can obtain the graphene of the ethylenediamine functionalization of black powder
(EFG) (its phenogram as shown in Figure 1, Figure 2, shown in Fig. 3 and table 1)；
(3) obtained product will be handled by step (2), and (terpinol, dosage are to be dripped per 6mg products with appropriate binding agent
Add two drop binding agents) mixing, grind 30min and obtain to electrode slurry, slurry is coated on FTO electro-conductive glass using knife coating,
Thickness is 10-11 μm, then the FTO electro-conductive glass for being covered with slurry is put into tube furnace, under nitrogen protection, with 2 DEG C of min-1
Heating rate rise to 500 DEG C, maintain 30min.DSSC is made to electrode.
Table 1 is the graphene of ethylenediamine functionalization and the contrast element analyze data of graphene oxide prepared by step (2).
Table 1
Embodiment 2
Condition and step the difference is that only, without this step of ozone oxidation in step (1) with embodiment 1.
Embodiment 3
Condition and step the difference is that only, the ozone oxidation in step (1) is as gas in air with embodiment 1
Under the conditions of source, oxidization time 30min.
Embodiment 4
Condition and step the difference is that only, the ozone oxidation in step (1) is as gas in air with embodiment 1
Under the conditions of source, oxidization time 60min.
Embodiment 5
Condition and step the difference is that only, the ozone oxidation in step (1) is as gas in oxygen with embodiment 1
Under the conditions of source, oxidization time 10min.
Embodiment 6
Graphene oxide powder is put into tube furnace, under nitrogen protection, it is black that 800 DEG C of calcining 1h obtain graphene (G)
Color powder, DSSC is then made to electrode, it is to electrode preparation method with embodiment 1 (3).
Embodiment 7
Platinum electrode (Pt) uses Pt pairs of the DHS-ED03 models of Dalian HeptaChroma SolarTech Co., Ltd.'s purchase
Electrode, made using Pt slurries (PtSP), the thickness of platinum is about 200nm.
Effect example --- to electrode photoelectric performance test
Embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 prepare to electrode
DSSC is assembled into as follows.
DSSC assembling process is as follows：
1. it is about 20-30nm TiO by granular size2Slurry is printed onto on FTO electro-conductive glass, and its effective area is
4mm × 4mm, thickness are about 14-16 μm；Then 325 DEG C of temperature control, 375 DEG C, 450 DEG C, 500 DEG C of roastings successively in Muffle furnace by it
15min, 15min, 25min, 30min are burnt, after being cooled to room temperature, is soaked in the N719 dye solutions that concentration is 0.5mM,
Taken out after 20h, you can obtain light anode；
2. soak the TiO after dyestuff2Light anode is dried up with alcohol flushing, then with embodiment 1, embodiment 2, embodiment 3,
Embodiment 4, embodiment 5, embodiment 6 and embodiment 7 are obtained to be assembled into battery to electrode and hot melt adhesive film with hot press, electricity
Solving matter, (solvent is acetonitrile, and solute is 0.06M anhydrous LiI, 0.03M I2, 0.5M tert .-butylpyridines and 0.1M isothiocyanic acids
Guanidine) rushed under vacuumized conditions between two electrode slices.
The model PEC-L15, Peccell, Yokohama, Japan of solar simulator used by this experiment.Electrification
Work station is Keithley 2601, Cleveland, OH.Potential scan scope is 0mV~800mV.And tested in identical
Under the conditions of, photoelectric properties test is carried out to the battery assembled.
As a result show, as shown in figure 4, quick for the dyestuff to electrode assembling prepared by embodiment 1, embodiment 6 and embodiment 7
Change the J-V curves of solar cell.EFG (air 10min), G and Pt is wherein marked to represent embodiment 1, embodiment 6 and reality respectively
Apply example 7 preparation to electrode assembling into DSSC.It is indicated above that the graphene of ethylenediamine functionalization with it is pure
Graphene is compared, and photoelectric transformation efficiency is significantly improved, and is due to that the introducing of ethylamino- changes the electricity of graphenic surface
Lotus is distributed, and reduces the energy of ionization value of graphene, is easy to provide electronics under electrochemical environment, so as to promote to I on electrode3 -
Reduction reaction, improve the catalytic performance to electrode.Table 2 is the corresponding photovoltaic parameter of above-mentioned three kinds of batteries.
Table 2
As shown in figure 5, be embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 prepare to electrode assembling
DSSC J-V curves.Wherein mark EFG (air 10min), EFG (not aoxidizing), EFG (air
30min), EFG (air 60min) and EFG (oxygen 10min) represents embodiment 1, embodiment 2, embodiment 3, embodiment 4 respectively
With embodiment 5 prepare to electrode assembling into DSSC.As seen from Figure 5, EFG (air 10min)
Electricity conversion it is higher because with the lifting of graphene oxide degree of oxidation, the epoxy official on graphene sheet layer
Increase can be rolled into a ball, is advantageous to the further reaction with ethylenediamine；However as the further lifting of degree of oxidation, graphene film is beaten
It is broken, the electric conductivity of lamella can be influenceed.Table 3 is the corresponding photovoltaic parameter of above-mentioned four kinds of batteries.Table 3
Claims (8)
1. the graphene of ethylenediamine functionalization is used as application of the DSSC to electrode material,
The DSSC comprises the following steps to the preparation method of electrode material：
（1）By graphene oxide water solution ultrasonic disperse, ozone oxidation is then carried out, the oxidation stone further aoxidized
Black alkene suspension；
（2）Ethylenediamine and step are heated in a closed container（1）Obtained graphene oxide suspension, in oil bath pan
90-100 DEG C of heating 5-7h, products therefrom is separated, washed, is dried, obtains the graphene of ethylenediamine functionalization；
（3）Step will be passed through（2）The graphene for handling obtained ethylenediamine functionalization is mixed with binding agent, and grinding 20-40min is obtained
To electrode slurry, slurry is coated on FTO electro-conductive glass using knife coating, is then dried；
The step（1）In ozone oxidation source of the gas be air, the time of ozone oxidation is 8-12min.
2. application according to claim 1, it is characterised in that：The step（1）In graphene oxide water solution concentration
For 0.5-1.5mg/mL, ultrasonic time 0.5-1.5h.
3. application according to claim 1, it is characterised in that：The step（2）The matter of middle graphene oxide and ethylenediamine
Amount is than being 1:0.5-3.
4. application according to claim 1, it is characterised in that：The step（2）In washing process to use deionized water
Washing 7-8 times；The step（2）In drying process for freeze-drying 22-26h.
5. application according to claim 1, it is characterised in that：The step（3）In drying process be in tube furnace
Carry out.
6. application according to claim 1, it is characterised in that：The step（3）In drying process be nitrogen protect
Under, with 2 DEG C of min-1Heating rate rise to 400-600 DEG C, maintain 20-40min.
7. application according to claim 1, it is characterised in that：The step（3）In, the graphene of ethylenediamine functionalization with
The mass ratio of binding agent is 1:12-14.
8. application according to claim 1, it is characterised in that：The step（3）The blade coating thickness of middle slurry is 10-11 μ
m。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347143A (en) * | 2011-07-11 | 2012-02-08 | 中国科学院上海硅酸盐研究所 | Graphene composite porous counter electrode, preparation method and application thereof |
| CN102849731A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nitrogen-doped graphene hydrogel, preparation method and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347143A (en) * | 2011-07-11 | 2012-02-08 | 中国科学院上海硅酸盐研究所 | Graphene composite porous counter electrode, preparation method and application thereof |
| CN102849731A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nitrogen-doped graphene hydrogel, preparation method and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| 氧化石墨的表面功能化及其应用;马慧玲;《北京化工大学博士研究生学位论文》;20130607;第46-47页 * |
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