CN103903861A - Counter electrode made of metal sulfide and graphene composite materials and preparation method and application of counter electrode - Google Patents
Counter electrode made of metal sulfide and graphene composite materials and preparation method and application of counter electrode Download PDFInfo
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Abstract
The invention relates to a counter electrode made of two-dimensional metal sulfide and graphene composite materials, a preparation method of the counter electrode and application of the counter electrode in dye sensitization solar cells. Metal sulfide and graphene composites are loaded on a conductive substrate for preparation. The metal sulfide and graphene composites are dissolved in a solution and are deposited to form a film after being filtered, compressed film plating is carried out on the conductive substrate, drying is carried out, and then the obtained counter electrode is cooled to be at a room temperature, wherein the mass ratio of the metal sulfide to graphene is 20:1 to 20, and the mass ratio of sulfide to tert-butyllithium is 1:5 to 50. Binding agents do not need to be added, and accordingly high-temperature impurity removing is not needed, and the appearance and the structure of the materials can be well maintained. Compared with the material of a Pt counter electrode, the materials are richly reserved in nature, and industrial production can be carried out on a large scale. Compared with materials of other counter electrodes, the materials are easy and convenient to prepare and excellent in catalytic performance, and accordingly the two-dimensional metal sulfide and graphene composite materials have wide application prospects in the field of the dye sensitization solar cells.
Description
Technical field
The present invention relates to a kind of two-dimensional metallic sulfide and graphene composite material to electrode and preparation method thereof and the application in DSSC.
Background technology
Increasingly serious along with energy crisis and environmental crisis, the fuel substitute of finding economy, environmental protection is extremely urgent.Sunlight is as the renewable resource of aboundresources, widely distributed, environmental friendliness, sustainable use and be subject to extensive concern, and the favourable conversion converting solar energy into electrical energy has caused the research boom of solar cell.DSSC because of its price low, packaging technology is simple, energy consumption is low, material environment close friend and electricity conversion higher (under AM1.5 simulated solar irradiation, conversion ratio can reach 12.3%) are manifesting its value gradually.But the research of DSSC is still in initial stage, the cost that can meet at present and attainable transformation efficiency still can not meet the demand that commercialization is promoted.Therefore, people are the preparation cost of reduction DSSC in recent years, and improve as far as possible its electricity conversion, have carried out a large amount of research work.
DSSC is had the light anode (TiO of dyestuff by absorption
2), contain oxidation-reduction pair (I
-/ I
3 -) electrolyte and the strong battery structure to electrode composition sandwich of catalytic activity.As the important component part of dye-sensitized cell, will effectively improve the transformation efficiency of battery to the improvement of electrode performance.Pt electrode is at present the most frequently used to electrode, but Pt deposit is rare, expensive, and have corrosion in iodine solution, therefore people constantly attempt finding that cheap, reserves are abundant, conductivity is strong, chemical/electrochemical is stable, and catalytic activity can substitute Pt electrode with the material of Pt phase.That has studied at present comprises that to electrode material material with carbon element (graphite/carbon is black, porous carbon, carbon nano-tube, fullerene and Graphene etc.) is to electrode [CN200610114581.7; CN200710177810.4; CN200710010546.5; CN200810118071.6; CN200810227107.4; CN201010212640], and organic conductive polymer (polythiophene, polypyrrole, polyaniline, poly-to benzene, polystyrene etc.) to electrode [CN200910043344.X; CN200910072716.1; CN200910072714.2], inorganic nitride (TiN, WN, MoN, Fe
2n etc.) to electrode [CN200910068409.6; CN201110004928.8; Chem.Commun.2009,6720; Angew.Chem.Int.Ed.2010,49,3653], inorganic oxide (NiO, WO
3/ WO
2, NbO
2/ Nb
2o
5) to electrode [Chem.Commun.2011,47,4535; Chem.Commun.2011,47,11489; Electrochem.Commun.2012,24,69], inorganic carbide (MoC, VC, TiC, ZrC etc.) is to electrode [Chem.Commun.2010,46,8600; Angew.Chem.Int.Ed.2011,50,3520], inorganic sulphide (CoS, CuS
2, NiS, MoS
2, WS
2deng) to electrode [J.Am.Chem.Soc.2009,131,15976; Energy Environ.Sci.2011,4,2630; Angew.Chem.Int.Ed.2011,50,11739; Aust.J.Chem.2012,65,1342; J.Mater.Chem.2012,22,18572], and the composite material of some of them material is to electrode.
Catalytic activity is high, the sulfide of good stability to the research of electrode be embodied as reduce provide an effective approach to electrode cost.Especially there is the sulfide M S2 (wherein M can be Mo, W and Sn etc.) of layer structure, because weak interaction is between layers easy to be overcome by physics or chemical method, can synthesize by multiple means the sulfide two-dimensional slices of which floor or individual layer.This sulfide thin slice has very high specific area and ion transport efficiency, can be I
3 -reduction abundant activated adoption site is provided, be therefore that the very promising DSSC of one is to electrode material.The people such as Wu [Phys.Chem.Chem.Phys.2011,13,19298] have synthesized respectively molybdenum bisuphide and Wolfram disulfide nano thin slice to electrode material, and bi-material presents the photo-catalysis capability suitable to electrode with Pt.
But two-dimentional sulfide material is commonly the semiconductor that band gap is larger, need to compound its conductive capability that improves of electric conducting material.In recent years, along with the continuous progress of research, Graphene industrialization has become possibility, means that the use of Graphene in solar cell do not limited by cost.The people such as Liu [J.Mater.Chem.2012,22,21057] synthesized molybdenum bisuphide graphene composite material by the compound method of high temperature, obviously improve with the photo-catalysis capability of the compound rear molybdenum bisuphide of Graphene, but due to the poor controllability of the method to molybdenum bisuphide structure, can not effectively synthesize the molybdenum bisuphide with two-dimensional structure.Therefore, can prepare large, the active high two-dimentional sulfide thin slice of specific area and by effectively compound to its and Graphene, for its conductivity of raising, catalytic capability and stability are most important.
Summary of the invention
The object of the present invention is to provide a kind of two-dimensional metallic sulfide and graphene composite material to electrode and its preparation method and application.Prepare metal sulfide and the Graphene combined counter electrode material with two-dimensional structure by effective and feasible method.By synthetic two-dimensional metallic sulfide nanometer sheet further compound with Graphene, obtain having the composite material of large specific area and good conductive ability, meanwhile by the method for film formation at low temp, make material pattern avoid the destruction of high temperature sintering, and then the catalytic performance of optimization DSSC to electrode, thereby obtain that cost is low, catalytic activity is high, the DSSC of stable in properties, promote the development of DSSC to industrialization promotion.The present invention, without adding binding agent, does not therefore need high temperature removal of impurities, can keep well the morphology of material.To compared with electrode, the type material is abundant at nature reserves, can realize mass industrialized production with Pt.With other semiconductors of the same type to compared with electrode material, two-dimensional metallic sulfide Graphene is easy to electrode preparation method, catalytic performance is excellent, and therefore this two-dimensional metallic sulfide graphene composite material has wide practical use in field of dye-sensitized solar cells.
Two-dimensional metallic sulfide provided by the present invention and graphene composite material load to metal sulfide and graphene complex in conductive substrates and prepare electrode, detailed process is that synthetic metal sulfide and graphene complex are scattered in solution, by filter deposition film forming, again by pressurizeing plated film in conductive substrates, after conductive substrates after plated film is dry, naturally cool to room temperature, obtain the metal sulfide Graphene of DSSC to electrode.
Two-dimensional metallic sulfide provided by the invention and graphene composite material comprise the following steps the preparation method of electrode:
1) under inert atmosphere protection, inject tert-butyl lithium solution by metering after metal sulfide is mixed with graphene uniform, mix, under normal temperature condition, stir 12-48h.
2) product is filtered, and obtains the metal sulfide graphene powder after lithiumation.
3) the sulfide graphene powder obtaining after lithiumation is distributed in a large amount of water, and at the ultrasonic 1-10h of normal temperature, after leaving standstill 12-72h, get the product after upper strata suspension is peeled off, filter, at vacuum, argon gas or nitrogen atmosphere 30-80 ℃ in dry 1-4h, naturally cool to room temperature, obtain two-dimensional metallic sulfide graphene complex;
4) the two-dimensional metallic sulfide graphene complex obtaining is distributed in a large amount of dispersion liquids, and at the ultrasonic 1-5h of normal temperature, through filtering coating, be pressurized to again in conductive substrates, at 30-80 ℃, in dry 1-4h, naturally cool to room temperature, obtain metal sulfide Graphene to electrode.
Described sulfide and the mass ratio of tert-butyl lithium are: 1: 5-50.
Described inert gas can be argon gas, nitrogen etc.
Described metal sulfide and the mass ratio of Graphene are: 20: 1-20.
Described metal sulfide is: MoS
2, WS
2or SnS
2.
Described dispersion liquid can be water, ethanol, or the mixture that mixes with arbitrary proportion with ethanol of water.
Step 3) sulfide graphene powder after lithiumation and the mass ratio of water: 1: 200-20000.
Step 4) described dispersion liquid is water, ethanol, or the miscible fluid of both arbitrary proportions.
Step 4) described two-dimensional metallic sulfide graphene complex and the mass ratio of dispersion liquid: 1: 100-10000.
Described conductive substrates is electro-conductive glass or metal (copper, aluminium etc.).
The present invention is the TiO with N-719 dye sensitization
2film is as light anode.The electrolyte adopting is by 0.05 mole of I
2, 0.1 mole of LiI, 0.6 mole 1, it is formulated that 2-dimethyl-3-propylimidazolium iodide (DMPII) and 0.5 mole of 4-tert-butylpyridine are dissolved in acetonitrile (acetonitrile).Adopt the two-dimensional metallic sulfide Graphene prepared of the present invention to electrode, jointly form simulated battery system with the light anode of dye sensitization and electrolyte and test.
The present invention, by the advantage in conjunction with two-dimensional metallic sulfide and Graphene, makes material present good conductivity and catalytic capability.Test result shows, two-dimensional metallic sulfide Graphene to electrode material can present with Pt to electrode suitable be even better than electricity conversion and the fill factor, curve factor of Pt to electrode.Therefore, two-dimensional metallic sulfide graphene composite material can be good at realizing the raising to electrode material catalytic performance, because its preparation technology is simple, cost is low, this type of composite material can become good Pt metal substitute material, and can be generalized in large batch of suitability for industrialized production.Two-dimensional metallic sulfide graphene composite material not only synthetic technology is simple but also have high catalytic capability and stability, and therefore this type of material has higher commercial value and wide application prospect in DSSC.
Accompanying drawing explanation
The XRD figure of Fig. 1 molybdenum bisuphide and graphene composite material (MoS2/rGO) and the standard x RD figure of MoS2.
Scanning electron microscope (SEM) photograph (c), the transmission electron microscope picture (d) of scanning (a), transmission (b) Electronic Speculum figure and the molybdenum bisuphide graphene composite material of Fig. 2 Graphene.
Fig. 3 molybdenum bisuphide and the graphene composite material current density voltage curve to electrode.
Fig. 4 molybdenum bisuphide and the graphene composite material power density-voltage curve to electrode.
Embodiment
Below in conjunction with example, the invention will be further described, but be not limited to this.
Embodiment 1: the preparation of two-dimentional molybdenum bisuphide Graphene to electrode
1) two-dimentional molybdenum bisuphide Graphene is synthetic: by 0.25g molybdenum disulfide powder (Tianjin recovery fine chemistry industry research institute, AR) (be prepared from according to the Hummer method of modifying with 0.05g graphene powder, commercially available graphene powder all can) be put in round-bottomed flask, under argon gas atmosphere protection, inject 10mL tert-butyl lithium, and stir 24h, the molybdenum bisuphide obtaining after filtration after lithiumation [is shown in Angew.Chem.2010,122,4153; Angew.Chem.2013,125,4254] Graphene mixture.Molybdenum bisuphide Graphene mixture after lithiumation is scattered in 500mL distilled water, ultrasonic 3h, obtain the mixing suspension that contains molybdenum bisuphide and Graphene, after solution left standstill 24h, getting upper strata suspension solution filter also cleans with a large amount of distilled water, 60 ℃ of dry 2h of vacuum, obtain molybdenum bisuphide graphene complex.
2) get 0.05g molybdenum bisuphide graphene complex and be scattered in ultrasonic 2h in distilled water, be filled into miillpore filter (composite fibre resin, aperture 0.45 μ is m) upper, and then pressurizeed (pressurization of the normal temperature application of force) is at the conductive substrates (SnO of doped with fluorine
2transparent conducting glass, FTO) upper, at 60 ℃ of dry 1.5h, to electrode film thickness 5～10 μ m, obtain molybdenum bisuphide graphene composite material to electrode.
3) electrolyte by 0.05 mole of I2,0.1 mole of LiI, 0.6 mole 1, it is formulated that 2-dimethyl-3-propylimidazolium iodide (DMPll) and 0.5 mole of 4-tert-butyl pyridine are dissolved in acetonitrile (acetonitrile).
By above-mentioned to electrode, N-719 dye sensitization TiO
2light anode and said ratio electrolyte composition simulation DSSC, at the 100mW cm of simulated solar light source Global AM1.5
-2illuminate condition under survey its photovoltaic curve.
Fig. 1 is molybdenum bisuphide/graphene complex (MoS that embodiment 1 obtains
2/ rGO, rGO is graphene oxide) the XRD figure of sample and the figure that contrasts of molybdenum bisuphide standard spectrogram, MoS2 in embodiment 1 also belongs to hexagonal crystal system (JCPDS No.9-312) as seen from the figure, due to the molybdenum bisuphide thickness reduction after peeling off, (002) peak value is obviously weakened.
Fig. 2 (a) and (b) be scanning electron microscope (SEM) photograph and the transmission electron microscope picture of the Graphene that uses in embodiment 1, the two-dimensional sheet structure that prepared Graphene is thin layer as seen from the figure, this structure will have higher specific area.Fig. 2 (c), (d) are scanning electron microscope (SEM) photograph and the transmission electron microscope pictures of the molybdenum bisuphide graphene complex of example 1 synthesized, can find out that by Fig. 2 (c) the molybdenum bisuphide graphene complex synthesizing presents laminated structure, there is very high specific area, can contact fully with the electrolyte in solar cell, be I
3 -/ I
-conversion reaction abundant reaction site is provided.From Fig. 2 (d), can see that the molybdenum bisuphide in molybdenum bisuphide graphene complex is stripped from into the structure of individual layer to few layer of accumulation.Due to catalysis I
3 -the reaction of reduction occurs in the surface of molybdenum bisuphide, and therefore this laminate structure can more effectively improve the catalytic efficiency of molybdenum bisuphide.Meanwhile, because molybdenum bisuphide contacts with the effective of Graphene, can make material present conductive capability well, and then the reduction reaction of carrying out for electrode surface provide effective electric transmission.
Fig. 3 is the current density voltage curve of the molybdenum bisuphide graphene composite material that synthesizes of example 1 to electrode, composite material has the current density-voltage characteristic comparable with Pt electrode as DSSC to electrode material, and molybdenum bisuphide graphene complex even shows the short-circuit current density higher to electrode than Pt to electrode.Fig. 4 has provided molybdenum bisuphide graphene composite material that example 1 the synthesizes power density-voltage curve to electrode.As shown in Figure 4, molybdenum bisuphide graphene complex be during to electrode accessible phototranstormation efficiency be 5.66% its calculate fill factor, curve factor be 0.57, under the same terms Pt in contrast accessible phototranstormation efficiency when to electrode be 5.58% and fill factor, curve factor be 0.56. therefore, by relatively finding out, sulfide-Graphene that synthesized goes out is to electrode material, due to it, electric conductivity and large specific area provide effective catalysis auxiliary for the conversion of the redox couple in electrolyte well, thereby present good flash of light preceding an earthquake changing effect, and can be equal to mutually with the measurement result of Pt electrode.
The present invention, without adding binding agent, does not therefore need high temperature removal of impurities, can keep well the morphology of material.To compared with electrode, the type material is abundant at nature reserves, can realize mass industrialized production with Pt.With other semiconductors of the same type to compared with electrode material, two-dimensional metallic sulfide Graphene is easy to electrode preparation method, catalytic performance is excellent, and therefore this two-dimensional metallic sulfide graphene composite material has wide practical use in field of dye-sensitized solar cells.
Claims (10)
1. a two-dimensional metallic sulfide and graphene composite material are to electrode, it is characterized in that it loads to metal sulfide and graphene complex in conductive substrates and prepare, detailed process is that metal sulfide and graphene complex are scattered in solution, by filter deposition film forming, again by pressurizeing plated film in conductive substrates, after conductive substrates after plated film is dry, naturally cool to room temperature, obtain the metal sulfide Graphene of DSSC to electrode.
2. two-dimensional metallic sulfide according to claim 1 and graphene composite material, to electrode, is characterized in that described metal sulfide and the mass ratio of Graphene are: 20: 1-20: described sulfide and the mass ratio of tert-butyl lithium are: 1: 5-50.
3. two-dimensional metallic sulfide according to claim 1 and graphene composite material, to electrode, is characterized in that described metal sulfide is: MoS
2, WS
2or SnS
2.
4. two-dimensional metallic sulfide according to claim 1 and graphene composite material be to electrode, it is characterized in that described conductive substrates is electro-conductive glass or metallic copper, aluminium.
5. two-dimensional metallic sulfide claimed in claim 1 and the preparation method of graphene composite material to electrode, is characterized in that comprising the following steps:
1) under inert atmosphere protection, inject tert-butyl lithium solution by metering after metal sulfide is mixed with graphene uniform, mixing is stirred 12-48h under normal temperature condition;
2) product is filtered, and obtains the metal sulfide graphene powder after lithiumation;
3) the metal sulfide graphene powder obtaining after lithiumation is distributed in a large amount of water, and at the ultrasonic 1-10h of normal temperature, after leaving standstill 12-72h, get the product after upper strata suspension is peeled off, filter, dry 1-4h at vacuum, argon gas or nitrogen atmosphere 30-80 ℃, naturally cool to room temperature, obtain two-dimensional metallic sulfide graphene complex;
4) the two-dimensional metallic sulfide graphene complex obtaining is distributed in a large amount of dispersion liquids, and at the ultrasonic 1-5h of normal temperature, through filtering coating, be pressurized to again in conductive substrates, at 30-80 ℃, dry 1-4h, naturally cools to room temperature, obtains metal sulfide Graphene to electrode.
6. method according to claim 5, is characterized in that described sulfide and the mass ratio of tert-butyl lithium are: 1: 5-50.
7. method according to claim 5, is characterized in that described inert gas is argon gas, nitrogen.
8. method according to claim 5, is characterized in that described dispersion liquid is water, ethanol, or the mixture that mixes with arbitrary proportion with ethanol of water.
9. method according to claim 5, is characterized in that step 3) mass ratio of two-dimensional metallic sulfide graphene powder and water: 1: 200-20000.
10. method according to claim 5, is characterized in that step 4) described two-dimensional metallic sulfide graphene complex and the mass ratio of dispersion liquid: 1: 100-10000.
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| CN105719845A (en) * | 2015-12-22 | 2016-06-29 | 信阳师范学院 | Supercapacitor electrode material tungsten sulfide-carbon aerogel and preparation method thereof |
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| CN106356202A (en) * | 2016-09-28 | 2017-01-25 | 上海电力学院 | Graphene/tungsten disulfide film flexible super capacitor and manufacturing method and application thereof |
| CN106299315B (en) * | 2016-10-14 | 2018-08-14 | 黑龙江科技大学 | The method for preparing three-dimensional combination electrode material using laminated metal sulfide of the growth in three-dimensional graphene framework with hierarchical structure |
| CN106299315A (en) * | 2016-10-14 | 2017-01-04 | 黑龙江科技大学 | The laminated metal sulfide utilizing growth in three-dimensional graphene framework to have hierarchy prepares the method for three-dimensional combination electrode material |
| CN107799314A (en) * | 2017-10-10 | 2018-03-13 | 浙江理工大学 | Molybdenum disulfide/titanium carbide/carbon composite nano-fiber film and its preparation method and application |
| CN107799314B (en) * | 2017-10-10 | 2023-06-06 | 浙江理工大学 | Molybdenum disulfide/titanium carbide/carbon composite nanofiber membrane and preparation method thereof |
| CN109174128A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | A kind of method of modifying of tungsten disulfide and its application |
| CN110534257A (en) * | 2019-08-19 | 2019-12-03 | 北京理工大学 | A kind of accurate production method of microelectrode of thermo-labile dimensional thinlayer material |
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| CN113426468A (en) * | 2021-06-23 | 2021-09-24 | 山东华素制药有限公司 | Wastewater treatment material and preparation method thereof |
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