CN109727779A - A kind of doping type graphene quantum dot and compound complete graphene-based to electrode and its preparation method and application of modified graphene - Google Patents
A kind of doping type graphene quantum dot and compound complete graphene-based to electrode and its preparation method and application of modified graphene Download PDFInfo
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Classifications
-
- 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
Abstract
The present invention provides a kind of doping type graphene quantum dots and compound complete graphene-based to electrode and its preparation method and application of modified graphene.The method comprises the steps of firstly, preparing doping type graphene quantum dots, and it is compound obtained to electrode with modified graphene, finally will carry out cell package to electrode and titanium dioxide photo anode, measure higher battery efficiency.The preparation method of doping type graphene quantum dot provided by the invention and modified graphene combined counter electrode material, does not need expensive experimental facilities, and the utilization rate of material is high；Prepared is graphene-based to electrode even compact, and homogeneity is good.The present invention advantageously reduces cost, saves material, and can be adapted for industrialized production, has good market application prospect.
Description
Technical field
The invention belongs to dye-sensitized solar cells technical fields, and in particular to a kind of doping type graphene quantum dot with
Compound complete graphene-based to electrode and its preparation method and application of modified graphene.
Background technique
With the continuous development of human society, the continuous burning of fossil feedstock, while the mankind are also considerably increased to the energy
Demand.A series of energy crises such as the deposit of the non-renewable energy resources thus caused reduces, environmental pollution, and air deteriorates are asked
Topic.Therefore, developing a kind of renewable, environmental-friendly new energy becomes current major issue.Currently, there are many new energy
Studied to utilize, most widely used includes solar energy, biological energy source, tide energy, wind energy, ocean energy and nuclear energy etc., wherein the sun
It can be a kind of inexhaustible, environmentally friendly green energy resource, the extensive favor by people.People include the sun to the utilization of solar energy
Can photoelectric conversion, photothermal conversion and photochemistry utilize, wherein being too using the device that photoelectric conversion this characteristic is prepared
Positive energy battery, it can directly convert light energy into electric energy and be exported, while because its is cheap, environmental-friendly, structure is simple
The easily advantages such as realization, are the research hotspots of current energy field.Since dye-sensitized solar cells comes out for the first time since 1991,
Because it is with simple packaging technology, the features such as low cost, flexibility, can apply different from traditional silica-based solar cell
Application field.
Dye-sensitized solar cells structure is typical " sandwich " structure, mainly by light anode, electrolyte, to electrode
Three parts composition, wherein being the important component of dye-sensitized solar cells to electrode, it is in the entire dye sensitization sun
The important function for being catalyzed reduction-oxidation state electrolyte can be played in cell operations, specifically can behave as from light anode through outer
The electronics that circuit transmission comes is returned to on electrode.Under the action of elctro-catalyst, the electrolyte in oxidant is to electrode
Receive electronics and is reduced this process.Therefore for the selection to electrode material, electro catalytic activity, conductive capability, chemistry is surely
Qualitative etc. performance largely will affect the photovoltaic performance of battery.Nowadays Pt is most extensive to application of electrode, due to
It is with good electric conductivity and electro catalytic activity, but alloy platinum material is expensive, at high cost, is also easy to by iodine system electrolyte corrosion
Generate PtI4Or H2A series of problems, such as PtI6, causes dye-sensitized solar cells to be unfavorable for being mass produced.Therefore seek
A kind of substitution platinum becomes a kind of new dye sensitization solar battery this research and becomes important current to electrode material
Business.
Graphene is a kind of single layer of carbon atom material, is the two-dimensional structure material of carbon, in the form of sheets structure, has good lead
Electrical property, development is complete graphene-based to electrode, and the cost of solar battery can be greatly lowered.Doped graphene quantum dot has
Good electrocatalysis characteristic, and be easily dispersed in the tridimensional network of modified graphene, make to possess more electrode material
Active site has better electro catalytic activity.
Summary of the invention
For above-mentioned present Research, the present invention provides a kind of doping type graphene quantum dot and modified graphene are compound
It is complete graphene-based to electrode and its preparation method and application, the doping type graphene quantum dot and modified graphene are compound
Material price is cheap, and production method is easy, and utilization rate is high.
For achieving the above object, the present invention, which discloses, adopts the following technical scheme that
The present invention provides a kind of doping type graphene quantum dots and the compound complete graphene-based system to electrode of modified graphene
Preparation Method, comprising the following steps:
(1) doping type graphene quantum dot is prepared using carbon source and doped source, carries out washing centrifugation with ethyl alcohol later, and with dialysis
Bag is dialysed；Dialyzate is finally placed in doping type graphene quantum dot obtained by drying in baking oven；
(2) appropriate modified graphene powder dispersion is taken in organic solvent, and ultrasonic disperse obtains graphene solution, is denoted as molten
Liquid A；It takes the graphene quantum dot of doping type to mix with organic solvent simultaneously, is denoted as solution B；
(3) solution A is mixed with solution B, and adhesive mixing ultrasound is added, obtained to electrode slurry, and in substrate
Coating filmform；
(4) coated conductive substrates are placed in tube furnace, are heat-treated, obtain doping type graphene quantum dot and modification
Reduced graphene is compound to electrode.
Further: the doped source in the step (1) is the one or more of S, N, P or B, the doping type graphene
Quantum dot the preparation method comprises the following steps: by carbon source and doped source according to mass ratio be reacted after 1-20:1 is mixed by solvent-thermal method, it is molten
Agent gel reaction, hydro-thermal reaction or coprecipitation are made.
Further: organic solvent is ethyl alcohol, isopropanol, ethyl acetate, N, N- dimethyl formyl in the step (2)
One or more of amine, acetonitrile, toluene, ether, acetone, butanone or N-Methyl pyrrolidone.
Further: the mass ratio of solution A and solution B is 2.5-20:1 in the step (3).
Further: adhesive is acrylate, polyurethane, epoxy resin, cellulose, phenolic aldehyde tree in the step (3)
One of rouge or Lauxite.
Further: the temperature being heat-treated in the step (4) is 250-800 DEG C.
Further: conductive substrates are to adulterate the SnO of fluorine in the step (4)2Transparent conducting glass, indium tin oxide transparent
Electropane, flexibility PET conductive film, copper sheet, aluminium flake, gold plaque or silver strip.
The present invention also provides utilize doping type graphene quantum dot and modified graphene made from the preparation method
Compound is complete graphene-based to electrode.
The present invention also provides the complete graphene-based applications to electrode in preparation dye-sensitized solar cells.
It is further: the modified graphene and N doping type graphene quantum dot mass ratio electrode is formed for 10:1
Battery performance it is excellent.
Compared with prior art, advantages of the present invention and have the technical effect that the present invention has studied different preparation methods to complete
The influence of graphene-based composite material catalytic performance, and provide the doping type graphene quantum dot and modified graphene is compound
Material does the application that dye-sensitized solar cells is used for electrode.The present invention is by a kind of modification that solvent-thermal method is prepared
Graphene, and by doping type graphene quantum dot and both material ultrasonic disperses of modified graphene, and will using polyurethane
Its composite material is combined together, and by the effect of ultra-violet curing, what composite material can consolidate is bonded in FTO electro-conductive glass substrate
On, then composite material is obtained to electrode by heat-treating methods.The present invention is done using graphene-based composite material to electrode,
Since it has many advantages, such as good electrocatalysis characteristic, catalytic activity, it is most important that no pollution to the environment, and battery performance
Platinum is apparently higher than to electrode, therefore becomes a kind of potential dye-sensitized solar cells to electrode material, is had good
Market application prospect.
Detailed description of the invention
Fig. 1 is the N doping type graphene quantum dot of modified graphene Yu different quality ratio, pair obtained through Overheating Treatment
Battery efficiency value corresponding to electrode.
Fig. 2 is the graphene quantum dot of modified graphene and N doping to electrode material, corresponds to material under different calcination temperatures
The battery efficiency value of material.
Fig. 3 is that the graphene quantum dot mass ratio of modified graphene and N doping is 10:1, and under argon hydrogen mixed atmosphere
The battery performance parameter to electrode that 450 DEG C of heat treatment obtains.
Specific embodiment
Technical solution of the present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
The present embodiment sulphur, nitrogen-doped graphene quantum dot and the compound complete graphene-based preparation to electrode of reductive modification graphene
Method the following steps are included:
(1) sulphur, N doping type graphene quantum dot are prepared by hydrothermal synthesis method: takes 1.26 g citric acids and 1.38 g sulphur
Urea is scattered in 30ml deionized water and stirs 1h, this solution is transferred in 100 ml polytetrafluoroethyllining linings later,
180 DEG C of hydro-thermal reaction 6h；Washing centrifugation is carried out with ethyl alcohol later；Precipitating is finally placed in sulphur obtained by drying in 60 DEG C of baking ovens, nitrogen
Doping type graphene quantum dot；
(2) it prepares modified graphene powder: adding graphene oxide into ethyl alcohol and stir to get mixture A, the oxidation stone
The mass ratio of black alkene and ethyl alcohol is 1:10-100, and is warming up to 60 DEG C；It is 1:1- according to the mass ratio of silane coupling agent and ethyl alcohol
After 20 are sufficiently mixed the two, mixture B is obtained；Mixture B is slowly added dropwise in mixture A, following reaction is mixed
Object C；The two is mixed for 1:20-100 with the mass ratio of mixture C according to hydrazine hydrate, is reacted 2-15 hours, by second alcohol and water
After cleaning, finally it is freeze-dried to obtain modified graphene powder.
Modified graphene powder is dispersed in n,N-Dimethylformamide, and ultrasonic disperse 6h graphene derived above is molten
Liquid is denoted as solution A；It takes the sulphur, N doping type graphene quantum dot to mix with n,N-Dimethylformamide simultaneously, is denoted as solution
B；
(3) it is that 10:1 is mixed, and 0.125g polyurethane mixing ultrasound is added with mass ratio with B solution by above-mentioned A, is eventually adding
0.025 g photoinitiator, obtains to electrode slurry, and be kept in dark place；
(4) then electrode slurry will be uniformly coated on Indium-tin Oxide Transparent Conductive Film glass, and irradiated under ultraviolet light
25 min；
(5) coated FTO electro-conductive glass is placed in tube furnace again, under argon hydrogen mixed atmosphere, heat is carried out at a temperature of 450 DEG C
It is compound to electrode to obtain sulphur, N doping type graphene quantum dot and reductive modification graphene for processing.
Embodiment 2
The present embodiment is with nitrogen-doped graphene quantum dot and the compound complete graphene-based preparation to electrode of reductive modification graphene
Method the following steps are included:
(1) N doping type graphene quantum dot is prepared by hydrothermal synthesis method: takes 1 g citric acid and 0.2 g urea, is scattered in
In 25ml deionized water and 30min is stirred, this solution is transferred in 100ml polytetrafluoroethyllining lining later, in 180 DEG C of hydro-thermals
React 6h；Washing centrifugation is carried out with ethyl alcohol later, and is dialysed with bag filter；Finally dialyzate is placed in 60 DEG C of baking ovens
N doping type graphene quantum dot obtained by drying；
(2) the preparation method is the same as that of Example 1 for modified graphene powder, and the modified graphene powder is dispersed in N, N- dimethyl
In formamide, and ultrasonic disperse 6h graphene solution derived above, it is denoted as solution A；N doping type graphene quantum dot is taken simultaneously
It is mixed with n,N-Dimethylformamide, is denoted as solution B；
(3) it is that 10:1 is mixed, and 0.125 g polyurethane mixing ultrasound is added with mass ratio with B solution by above-mentioned A, is eventually adding
0.025g photoinitiator, obtains to electrode slurry, and is kept in dark place；
(4) then electrode slurry will be uniformly coated on Indium-tin Oxide Transparent Conductive Film glass, and irradiated under ultraviolet light
25 min；
(5) coated FTO electro-conductive glass is placed in tube furnace again, under argon hydrogen mixed atmosphere, heat is carried out at a temperature of 450 DEG C
Processing, obtains nitrogen-doped graphene quantum dot and reductive modification graphene is compound to electrode material.
Experimental result is as shown in Figure 1, from figure 1 it appears that the present invention has chosen modified graphene and N doping type stone
Black alkene quantum dot mass ratio is respectively 2.5:1,5:1,10:1,20:1 to electrode material, 450 DEG C of heat under argon hydrogen mixed atmosphere
Carry out battery assembly after processing, the efficiency value of test dye sensitization solar battery is respectively 6.06%, 6.92%, 10.03%,
5.66%, therefore doping ratio is the best to electrode material performance of 10:1.
Figure it is seen that the graphene quantum dot mass ratio of modified graphene and N doping is 10:1, and mixed in argon hydrogen
Close that different temperatures heat treatment under atmosphere obtains to electrode material, wherein calcination temperature be respectively 300 DEG C, 350 DEG C, 400 DEG C,
450℃,500℃.Can be obtained by cell testing results, corresponding battery efficiency value is respectively 3.69%, 4.89%, 7.83%,
10.28%, 5.82%, so the battery performance that calcination temperature is 450 DEG C is most excellent.
From figure 3, it can be seen that the graphene quantum dot mass ratio of modified graphene and N doping is 10:1, mixed in argon hydrogen
Lower 450 DEG C of atmosphere are heat-treated the best to electrode performance of acquisition, and doing in dye-sensitized solar cells can to electrode efficiency
Reach 10.03%, fill factor 0.59, battery performance is excellent.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although referring to aforementioned reality
Applying example, invention is explained in detail, for those of ordinary skill in the art, still can be to aforementioned implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these are modified or replace
It changes, the spirit and scope for claimed technical solution of the invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of doping type graphene quantum dot and the compound complete graphene-based preparation method to electrode of modified graphene, special
Sign be the following steps are included:
(1) doping type graphene quantum dot is prepared using carbon source and doped source, carries out washing centrifugation with ethyl alcohol later, and with dialysis
Bag is dialysed；Dialyzate is finally placed in doping type graphene quantum dot obtained by drying in baking oven；
(2) appropriate modified graphene powder dispersion is taken in organic solvent, and ultrasonic disperse obtains graphene solution, is denoted as molten
Liquid A；It takes the graphene quantum dot of doping type to mix with organic solvent simultaneously, is denoted as solution B；
(3) solution A is mixed with solution B, and adhesive mixing ultrasound is added, obtained to electrode slurry, and in substrate
Coating filmform；
(4) coated conductive substrates are placed in tube furnace, are heat-treated, obtain doping type graphene quantum dot and modification
Reduced graphene is compound to electrode.
2. preparation method according to claim 1, it is characterised in that: doped source in the step (1) be S, N, P or
The one or more of B, the doping type graphene quantum dot the preparation method comprises the following steps: according to mass ratio being 1- by carbon source and doped source
It is made after 20:1 mixing by solvent-thermal method reaction, sol gel reaction, hydro-thermal reaction or coprecipitation.
3. preparation method according to claim 1, it is characterised in that: organic solvent is ethyl alcohol, different in the step (2)
One in propyl alcohol, ethyl acetate, n,N-Dimethylformamide, acetonitrile, toluene, ether, acetone, butanone or N-Methyl pyrrolidone
Kind is several.
4. preparation method according to claim 1, it is characterised in that: the matter of solution A and solution B in the step (3)
Amount is than being 2.5-20:1.
5. preparation method according to claim 1, it is characterised in that: in the step (3) adhesive be acrylate,
One of polyurethane, epoxy resin, cellulose, phenolic resin or Lauxite.
6. preparation method according to claim 1, it is characterised in that: the temperature of heat treatment is in the step (4)
250-800℃。
7. preparation method according to claim 1, it is characterised in that: conductive substrates are doping fluorine in the step (4)
SnO2Transparent conducting glass, Indium-tin Oxide Transparent Conductive Film glass, flexibility PET conductive film, copper sheet, aluminium flake, gold plaque or silver
Piece.
8. doping type graphene quantum dot made from the described in any item preparation methods of claim 1-7 and modified graphene are compound
It is complete graphene-based to electrode.
9. the complete graphene-based application to electrode in preparation dye-sensitized solar cells according to any one of claims 8.
10. the complete graphene-based application to electrode in preparation dye-sensitized solar cells according to claim 9,
Be characterized in that: the modified graphene is 10:1 to the cell performance of electrode composition with N doping type graphene quantum dot mass ratio
It can be excellent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110010265A (en) * | 2019-05-24 | 2019-07-12 | 浙江王点科技有限公司 | A kind of graphene quantum dot electrocondution slurry and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102543476A (en) * | 2012-02-24 | 2012-07-04 | 电子科技大学 | Graphene counter electrode for dye-sensitized solar cell and manufacturing method of graphene counter electrode |
| KR20130123477A (en) * | 2012-05-03 | 2013-11-13 | 한국에너지기술연구원 | Method of manufacturing coating agent of dye-sensitive solar cell surface, coating agent thereof and dye-sensitive solar cell coated with coating agent |
| CN105206352A (en) * | 2015-10-16 | 2015-12-30 | 青岛科技大学 | Graphene transparent conductive film and preparation method thereof |
| CN105964286A (en) * | 2016-05-18 | 2016-09-28 | 江苏理工学院 | Nitrogen-doped graphene quantum dot and graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
-
2018
- 2018-12-12 CN CN201811517201.3A patent/CN109727779A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102543476A (en) * | 2012-02-24 | 2012-07-04 | 电子科技大学 | Graphene counter electrode for dye-sensitized solar cell and manufacturing method of graphene counter electrode |
| KR20130123477A (en) * | 2012-05-03 | 2013-11-13 | 한국에너지기술연구원 | Method of manufacturing coating agent of dye-sensitive solar cell surface, coating agent thereof and dye-sensitive solar cell coated with coating agent |
| CN105206352A (en) * | 2015-10-16 | 2015-12-30 | 青岛科技大学 | Graphene transparent conductive film and preparation method thereof |
| CN105964286A (en) * | 2016-05-18 | 2016-09-28 | 江苏理工学院 | Nitrogen-doped graphene quantum dot and graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| QUANHONG CHANG,ET AL.: ""Hybrid Graphene Quantum Dots@Graphene Foam Nanosheets for Dye-Sensitized Solar Cell Electrodes"", 《ENERGY TECHNOL.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110010265A (en) * | 2019-05-24 | 2019-07-12 | 浙江王点科技有限公司 | A kind of graphene quantum dot electrocondution slurry and preparation method |
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