CN103903861B - 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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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention 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 is with graphene composite material is to electrode and preparation method thereof and is contaminating
Application in material sensitization solar battery.
Background technology
As energy crisis is increasingly serious with environmental crisis, economic, environmental protection fuel substitute is found extremely urgent.Too
Sunlight as aboundresources, widely distributed, environmental friendliness, the renewable resource of sustainable use and receive significant attention, will too
Sun can be converted into the research boom that the favourable conversion of electric energy has caused solar cell.DSSC is because of its price
Low, packaging technology is simple, and energy consumption is low, and material environment is friendly and electricity conversion is higher (converts under AM1.5 simulated solar irradiations
Rate is worth up to its 12.3%) is gradually being manifested.But the research of DSSC is still in initial stage, mesh
The front cost met and attainable transformation efficiency can not still meet the demand that commercialization is promoted.Therefore, in recent years people are
The preparation cost of DSSC is reduced, and improves its electricity conversion as far as possible, carried out substantial amounts of research
Work.
DSSC is by the light anode (TiO for being adsorbed with dyestuff2), containing oxidation-reduction pair (I-/I3 -)
Electrolyte and catalysis activity it is strong to electrode constitute sandwich battery structure.As the important composition of dye-sensitized cell
Part, the improvement to electrode performance will effectively improve the transformation efficiency of battery.Pt electrodes be it is at present the most frequently used to electrode,
But Pt deposits are rare, expensive, and have corrosion in iodine solution, therefore people continuously attempt to find cheap, reserves
Abundant, electric conductivity is strong, chemical/electrochemical is stable, and catalysis activity can substitute Pt electrodes with the material of Pt phases.At present
That what is studied includes material with carbon element (graphite/carbon is black, porous carbon, CNT, fullerene and Graphene etc.) to electrode electrode material
[CN200610114581.7；CN200710177810.4；CN200710010546.5；CN200810118071.6；
CN200810227107.4；CN201010212640], organic conductive polymer (polythiophene, polypyrrole, polyaniline, gather to benzene,
Polystyrene etc.) to electrode [CN200910043344.X；CN200910072716.1；CN200910072714.2], inorganic nitrogen
Compound (TiN, WN, MoN, Fe2N etc.) to electrode [CN200910068409.6；CN201110004928.8；
Chem.Commun.2009,6720；Angew.Chem.Int.Ed.2010,49,3653], inorganic oxide (NiO, WO3/WO2,
NbO2/Nb2O5) 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,
CuS2, NiS, MoS2, WS2) 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 of some of them material is to electrode.
Catalysis activity is high, and the sulfide of good stability provides one with reduction is embodied as to the research of electrode to electrode cost
The effective approach of bar.Especially there is the sulfide M S of layer structure2(wherein M can be Mo, W and Sn etc.), due to layer with
Weak interaction between layer is easy to either physically or chemically be overcome, and can synthesize which floor or individual layer by multiple means
Sulfide two-dimensional slice.This sulfide thin slice has very high specific surface area and ion transfer efficiency, can be I3 -'s
Reduction provides abundant activated adoption site, therefore is a kind of very promising DSSC to electrode material
Material.Wu et al. [Phys.Chem.Chem.Phys.2011,13,19298] has been respectively synthesized out molybdenum bisuphide and tungsten disulfide is received
To electrode material, bi-material presents the photo-catalysis capability suitable to electrode with Pt to rice thin slice.
But two-dimentional sulfide material is commonly the larger semiconductor of band gap, needs are combined with conductive material and lead improving it
Electric energy power.In recent years, with the continuous progress of research, Graphene industrialization has become possibility, it is meant that Graphene is in the sun
Use in energy battery is not cost prohibitive.Liu et al. [J.Mater.Chem.2012,22,21057] is multiple by high temperature
The method of conjunction has synthesized molybdenum bisuphide graphene composite material, obvious with the photo-catalysis capability of Graphene molybdenum bisuphide after compound
Improve, but the poor controllability due to the method to molybdenum bisuphide structure, it is impossible to effectively synthesize with two-dimensional structure two
Molybdenum sulfide.Accordingly, it is capable to no specific surface area is big, activity the is high two-dimentional sulfide thin slice and it is effectively multiple with Graphene prepared
Close, for its electric conductivity is improved, catalytic capability and stability are most important.
The content of the invention
It is an object of the invention to provide a kind of two-dimensional metallic sulfide and graphene composite material are to electrode and its preparation
Methods and applications.Metal sulfide with two-dimensional structure and Graphene combined counter electrode are prepared by effective and feasible method
Material.By synthesizing two-dimensional metallic sulfide nanometer sheet and further compound with Graphene, obtain with big specific surface area with
The composite of good conductive ability, at the same time by the method for film formation at low temp, makes material morphology avoid high temperature sintering and quilt
Destruction, and then optimize catalytic performance of the DSSC to electrode, so as to obtain low cost, catalysis activity height, property
The stable DSSC of matter, promotes development of the DSSC to industrialization promotion.Nothing of the present invention
Binding agent need to be added, therefore is not required to high temperature removal of impurities, can well keep the pattern and structure of material.Compared with Pt is to electrode,
The type material is in nature rich reserves, it is possible to achieve mass industrialized production.With other same type semiconductors to electrode
Material is compared, and two-dimensional metallic sulfide Graphene is easy to electrode preparation method, catalytic performance is excellent, therefore the two-dimensional metallic sulphur
Compound 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 are by metal sulfide and stone to electrode
Black alkene compound loads to what is prepared in conductive substrates, and detailed process is to be combined the metal sulfide of synthesis and Graphene
Thing is scattered in solution, by filter deposition film forming, then by pressurizeing plated film in conductive substrates, by the conductive substrates after plated film
After drying, room temperature is naturally cooled to, obtain the metal sulfide Graphene of DSSC to electrode.
The two-dimensional metallic sulfide that the present invention is provided includes following step with graphene composite material to the preparation method of electrode
Suddenly：
1) injection tert-butyl lithium is molten under inert atmosphere protection after metal sulfide is mixed with graphene uniform by metering
In liquid, mixing stirs 12-48h under normal temperature condition.
2) product is filtered, and obtains the metal sulfide graphene powder after lithiumation.
3) the sulfide graphene powder obtained after lithiumation is distributed in substantial amounts of water, and in normal temperature ultrasound 1-10h, it is quiet
Put and the product after upper strata suspension is peeled off is taken after 12-72h, filter, do at 30-80 DEG C of vacuum, argon gas or nitrogen atmosphere
Dry 1-4h, naturally cools to room temperature, obtains two-dimensional metallic sulfide graphene complex；
4) the two-dimensional metallic sulfide graphene complex for obtaining is distributed in substantial amounts of dispersion liquid, and in normal temperature ultrasound
1-5h, through filtering coating, then is pressurized in conductive substrates, and at 30-80 DEG C 1-4h is dried, and naturally cools to room temperature,
Metal sulfide Graphene is obtained to electrode.
Described sulfide is with the mass ratio of tert-butyl lithium：1∶5-50.
Described inert gas can be argon gas, nitrogen etc..
Described metal sulfide is with the mass ratio of Graphene：20∶1-20.
Described metal sulfide is：MoS2、WS2Or SnS2。
Described dispersion liquid can be water, ethanol, or the mixture that water is mixed with ethanol with arbitrary proportion.
Step 3) sulfide graphene powder after lithiumation and water mass ratio：1∶200-20000.
Step 4) described in dispersion liquid be water, the miscible fluid of the arbitrary proportion of ethanol, or both.
Step 4) described in two-dimensional metallic sulfide graphene complex and dispersion liquid mass ratio：1∶100-10000.
Described conductive substrates are electro-conductive glass or metal (copper, aluminium etc.).
The present invention is with the TiO of N-719 dye sensitizations2Film is used as light anode.Using electrolyte be by 0.05 mole of I2、
0.1 mole of LiI, 0.6 mole of 1,2-dimethyl-3-propylimidazolium iodide (DMPII) and 0.5 mole of 4-
Tert-butyl pyridine are dissolved in acetonitrile (acetonitrile) and are formulated.The two dimension prepared using the present invention
Metal sulfide Graphene collectively constitutes simulated battery system and is surveyed to electrode with the light anode and electrolyte of dye sensitization
Examination.
The present invention is by the advantage with reference to two-dimensional metallic sulfide and Graphene so that material presents good electric conductivity
And catalytic capability.Test result shows that two-dimensional metallic sulfide Graphene can present with Pt to electrode phase to electrode material
When even better than electricity conversions and fill factor, curve factor of the Pt to electrode.Therefore, two-dimensional metallic sulfide Graphene composite wood
Material can be good at realizing the raising to electrode material catalytic performance, because of its preparation process is simple, low cost, such composite
Good Pt metal substitute materials can be become, and can be generalized in large batch of industrialized production.Two-dimensional metallic sulfide
Not only synthetic technology is simple but also with high catalytic capability and stability for graphene composite material, therefore such material is in dyestuff
There is higher commercial value and wide application prospect in sensitization solar battery.
Description of the drawings
Fig. 1 molybdenum bisuphide and graphene composite material (MoS2/ rGO) XRD and MoS2Standard x RD figure.
The scanning (a) of Fig. 2 Graphenes and transmission electron microscope (b) figure and the ESEM of molybdenum bisuphide graphene composite material
Figure (c), transmission electron microscope picture (d).
Fig. 3 molybdenum bisuphide and current density voltage curve of the graphene composite material to electrode.
Fig. 4 molybdenum bisuphide and power density-voltage curve of the graphene composite material to electrode.
Specific embodiment
With reference to example, the invention will be further described, but not limited to this.
Embodiment 1：Preparation of the two-dimentional molybdenum bisuphide Graphene to electrode
1) synthesis of two-dimentional molybdenum bisuphide Graphene：By 0.25g molybdenum disulfide powders, (fine chemistry industry research is recovered in Tianjin
Institute, AR) it is put in 0.05g graphene powders (being prepared from according to the Hummer methods of modification, commercially available graphene powder)
In round-bottomed flask, 10mL tert-butyl lithiums are injected under argon gas atmosphere protection, and stir 24h, two sulphur after lithiumation are obtained after filtration
Change molybdenum [see Angew.Chem.2010,122,4153；Angew.Chem.2013,125,4254] Graphene mixture.By lithiumation
Molybdenum bisuphide Graphene mixture afterwards is scattered in 500mL distilled water, ultrasonic 3h, is obtained containing molybdenum bisuphide and Graphene
Mixing suspension, after solution left standstill 24h, takes upper strata suspension liquor and filters and cleaned with a large amount of distilled water, and vacuum 60C is dried
2h, obtains molybdenum bisuphide graphene complex.
2) 0.05g molybdenum bisuphide graphene complexes are taken and is scattered in ultrasound 2h in distilled water, be filled into miillpore filter (mixing
Fibre resin, 0.45 μm of aperture) on, (normal temperature force pressurization) is then pressurizeed in the conductive substrates (SnO of doping fluorine2It is transparent
Electro-conductive glass, FTO) on, 1.5h is dried at 60 DEG C, to 5～10 μm of electrode film thickness, obtain molybdenum bisuphide Graphene composite wood
Material is to electrode.
3) electrolyte is by 0.05 mole of I2, 0.1 mole of LiI, 0.6 mole 1,2-dimethyl-3-
Propylimidazolium iodide (DMPII) and 0.5 mole of 4-tert-butyl pyridine are dissolved in acetonitrile
(acetonitrile) it is formulated.
By above-mentioned to electrode, N-719 dye sensitization TiO2Light anode and the composition simulation dye sensitization of said ratio electrolyte
Solar cell, in the 100mW cm of simulated solar light source Global AM 1.5-2Irradiation under the conditions of survey its photovoltaic curve.
Fig. 1 is molybdenum bisuphide/graphene complex (MoS that embodiment 1 is obtained2/ rGO, rGO graphene oxide) sample
The compares figure of XRD and molybdenum bisuphide standard spectrogram, the as seen from the figure MoS in embodiment 12Fall within hexagonal crystal system (JCPDS
No.9-312), because the molybdenum bisuphide thickness after stripping is reduced, (002) peak value is made substantially to weaken.
Fig. 2 (a) and (b) are the scanning electron microscope (SEM) photographs and transmission electron microscope picture of the Graphene used in embodiment 1, can by figure
Know two-dimensional sheet structure of the prepared Graphene for thin layer, this structure is by with higher specific surface area.Fig. 2 (c), (d)
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of molybdenum bisuphide graphene complex synthesized by example 1, by Fig. 2 (c) it can be seen that
The molybdenum bisuphide graphene complex for synthesizing presents laminated structure, with very high specific surface area, can and solar-electricity
Electrolyte in pond is sufficiently contacted, and is I3 -/I-Conversion reaction abundant reaction site is provided.It can be seen that two from Fig. 2 (d)
Molybdenum bisuphide in molybdenum sulfide graphene complex has been stripped into the structure that individual layer is piled up to few layer.Due to being catalyzed I3 -Reduction
Reaction occur on the surface of molybdenum bisuphide, therefore this laminate structure more effectively land productivity can improve the catalysis of molybdenum bisuphide and imitate
Rate.At the same time, due to molybdenum bisuphide and the effective contact of Graphene, material can be made to present conductive capability well, is entered
And the reduction reaction carried out for electrode surface provides effective electric transmission.
Fig. 3 is current density voltage curve of the molybdenum bisuphide graphene composite material that synthesizes of example 1 to electrode, multiple
Condensation material has the Current density-voltage comparable with Pt electrodes special electrode material as DSSC
Levy, molybdenum bisuphide graphene complex even shows the short-circuit current density higher to electrode than Pt to electrode.Fig. 4 gives
Power density-voltage curve of the molybdenum bisuphide graphene composite material that example 1 synthesizes to electrode.As shown in Figure 4, curing
Molybdenum graphene complex be to accessible phototranstormation efficiency during electrode be 5.66% its counted fill factor, curve factor be 0.57, it is identical
Under the conditions of as control Pt as to accessible phototranstormation efficiency during electrode for 5.58% fill factor, curve factor be 0.56. because
This, by compare as can be seen that it is synthesized go out sulfide-Graphene to electrode material, due to its well electric conductivity and
Big specific surface area provides effectively catalysis auxiliary for the conversion of the redox couple in electrolyte, so as to present well
Light changing effect, and can mutually be equal to the measurement result of Pt electrodes.
The present invention need not add binding agent, therefore be not required to high temperature removal of impurities, can well keep the pattern and structure of material.
Compared with Pt is to electrode, the type material is in nature rich reserves, it is possible to achieve mass industrialized production.It is similar with other
Type semiconductor is compared to electrode material, and two-dimensional metallic sulfide Graphene is easy to electrode preparation method, catalytic performance is excellent, because
This two-dimensional metallic sulfide graphene composite material has wide practical use in field of dye-sensitized solar cells.
Claims (6)
1. a kind of two-dimensional metallic sulfide and preparation method of the graphene composite material to electrode, it is characterised in that including following step
Suddenly：
1) inject in tert .-butyllithium solution under inert atmosphere protection after metal sulfide is mixed with graphene uniform by metering,
Mixing, under normal temperature condition 12-48h is stirred；
2) product is filtered, and obtains the metal sulfide graphene powder after lithiumation；
3) the metal sulfide graphene powder obtained after lithiumation is distributed in substantial amounts of water, and in normal temperature ultrasound 1-10h, it is quiet
Put and the product after upper strata suspension is peeled off is taken after 12-72h, filter, do at 30-80 DEG C of vacuum, argon gas or nitrogen atmosphere
Dry 1-4h, naturally cools to room temperature, obtains two-dimensional metallic sulfide graphene complex；
4) the two-dimensional metallic sulfide graphene complex for obtaining is distributed in substantial amounts of dispersion liquid, and in normal temperature ultrasound 1-
5h, through filtering coating, then is pressurized in conductive substrates, and at 30-80 DEG C 1-4h is dried, and naturally cools to room temperature, is obtained
To metal sulfide Graphene to electrode；
Described metal sulfide is with the mass ratio of Graphene：20∶1-20；The mass ratio of described sulfide and tert-butyl lithium
For：1∶5-50；
Described metal sulfide is MoS2。
2. method according to claim 1, it is characterised in that described conductive substrates are electro-conductive glass or metallic copper, aluminium.
3. method according to claim 1, it is characterised in that described inert gas is argon gas, nitrogen.
4. method according to claim 1, it is characterised in that described dispersion liquid be water, ethanol, or water with ethanol to appoint
The mixture of meaning ratio mixing.
5. method according to claim 1, it is characterised in that step 3) two-dimensional metallic sulfide graphene powder and water
Mass ratio：1∶200-20000.
6. method according to claim 5, it is characterised in that step 4) described in two-dimensional metallic sulfide Graphene be combined
The mass ratio of thing and dispersion liquid：1∶100-10000.
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| CN105280900A (en) * | 2015-09-22 | 2016-01-27 | 复旦大学 | Tungsten disulfide/graphene nanobelt composite material and preparation method thereof |
| KR101844345B1 (en) * | 2015-10-13 | 2018-04-03 | 한국세라믹기술원 | Preparation Method of Hybrid Materials composed of Two-Dimensional Plate materials |
| CN105336508A (en) * | 2015-11-06 | 2016-02-17 | 东华大学 | Preparation method of flexible transparent molybdenum disulfide film electrode |
| CN105374573A (en) * | 2015-12-21 | 2016-03-02 | 哈尔滨工业大学 | Preparation method of sulfur-doped graphene-based super capacitor electrode material |
| CN105719845B (en) * | 2015-12-22 | 2018-02-13 | 信阳师范学院 | A kind of electrode material for super capacitor tungsten sulfide charcoal-aero gel and preparation method thereof |
| 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 |
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| 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 |
| CN109174128B (en) * | 2018-09-13 | 2020-06-19 | 浙江大学 | Modification method of tungsten disulfide and application thereof |
| 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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