CN107731537A - A kind of Co3S4Ultrathin nanometer piece/rGO composite constructions, preparation method and application - Google Patents
A kind of Co3S4Ultrathin nanometer piece/rGO composite constructions, preparation method and application Download PDFInfo
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- CN107731537A CN107731537A CN201710897223.6A CN201710897223A CN107731537A CN 107731537 A CN107731537 A CN 107731537A CN 201710897223 A CN201710897223 A CN 201710897223A CN 107731537 A CN107731537 A CN 107731537A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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- 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 invention discloses a kind of Co3S4Ultrathin nanometer piece/rGO composite constructions, preparation method and application, cobalt chloride hexahydrate is dissolved into solvent and stirred, and adds ammoniacal liquor reaction, then thioacetamide is added to be stirred, room temperature is cooled to after being reacted in autoclave, abandons supernatant, cleaning sample obtains the Co of nanostructured3S4；By graphene oxide ultrasonic dissolution in a solvent, cobalt chloride hexahydrate stirring and dissolving is added, is then slowly added to ammoniacal liquor dropwise, after stirring, add TAA and continue to stir, room temperature is naturally cooled to after then being reacted in autoclave, cleaned respectively with water and ethanol, it is stand-by after product freeze-drying.By adding NH3·H2O introduces NH3Molecule, the pattern of product is adjusted to two-dimensional sheet structure, increases the specific surface area of structure.By introducing GO in building-up process, disperse Co3S4Nanometer chip architecture, avoids the agglomeration of laminated structure, improves Co3S4Catalytic activity, electron transfer capacity and the catalytic stability of nanometer sheet.
Description
Technical field
The present invention relates to a kind of composite Nano functional material, more particularly to a kind of Co3S4Ultrathin nanometer piece/rGO is compound
Structure, preparation method and application.
Background technology
Global energy crisis make it that developing new energy turns into a urgent problem.Photovoltaic technology can will it is clean, can be again
Raw solar energy changes into electric energy, is popular research in recent years.The synthesis technique that is wherein sensitized solar cell is simple, low consumption
Cause the concern of researcher.Sensitization solar battery mainly includes, light anode, light-sensitive material, redox couple and to electrode.
Because Pt is to I3 -Excellent reducing property causes it as good to electrode material.However, the expensive of it causes its big
The production of scale commercial metaplasia is limited.Therefore, find cheap electrode material turns into an important job instead of Pt.
Substantial amounts of research concern transient metal sulfide and metal oxide (M in recent yearsxNy, wherein M=Mo, W, Co；N=
S, O) electrocatalysis characteristic.Wherein Co3S4Nanometer chip architecture, has attracting metallic character, and aboundresources, stability
Good, catalytic performance height, has broad application prospects in electrochemical catalysis field.In order that material shows more excellent electrification
Performance is learned, has Railway Project to need to solve：(1) two-dimensional ultrathin Co is controlled3S4The preparation of structure, two-dimensional nano chip architecture have height
Specific surface area more avtive spots can be provided for catalytic reaction.For stratiform transient metal sulfide such as MoS2、WS2, its
Two-dimensional structure can be easy to be by mechanically pulling off, the mode such as CVD growth, chemical stripping is realized.However, for non-laminar chemical combination
Thing such as Co3S4, due to lacking the intrinsic driving force of inherent growth, in general method does not apply to.Although Co can be synthesized at present3S4
Nanometer sheet, but it is complex, it is necessary to by ion-exchange process from Co3O4Or Co (OH)2Layer structure changes, multistep reaction
Product is caused to be lost, complex process is unfavorable for mass producing；(2) Co is hindered3S4The reunion of nanometer sheet；(3) reduce to greatest extent
Diffusion length；(4) electrical conductance is further increased, by Co3S4Being coupled with conducting material can be reduced to electrode and electrolyte
The charge transfer resistance in section, improve the catalytic capability to electrode.Graphene possesses high electron mobility (~15 000cm2/
V s), good flexibility, it is a kind of excellent to electrode auxiliary material.The big specific surface area of graphene and flexible characteristic can be true
It is conformal into infiltration lane, protect Co3S4The reunion of nanometer sheet.Therefore, it is necessary to which it is simple to develop a kind of preparation technology, it is easy to industry
The Co of metaplasia production3S4The synthetic method of nanometer sheet/graphene composite structure.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Co3S4Ultrathin nanometer piece/rGO composite junctions
Structure, preparation method and application, simple liquid phase hydro-thermal method is employed by controlling the polarity of reaction solution and adjusting NH3Molecule
Amount control atom is self-assembled into Co3S4Laminated structure.
The present invention is achieved by the following technical solutions, a kind of Co of the invention3S4Ultrathin nanometer piece/rGO composite constructions
Preparation method, comprise the following steps：
(1)Co3S4The preparation of nanostructured：
Cobalt chloride hexahydrate is dissolved into solvent and stirred, adds ammoniacal liquor reaction, thioacetamide is then added and is stirred
Mix, room temperature is cooled to after being reacted in autoclave, abandon supernatant, cleaning sample obtains the Co of nanostructured3S4；
(2)Co3S4The preparation of ultrathin nanometer piece/rGO composite constructions：
By graphene oxide ultrasonic dissolution in a solvent, cobalt chloride hexahydrate stirring and dissolving is added, then by ammoniacal liquor dropwise
Be slowly added to, after stirring, add TAA and continue to stir, room temperature is naturally cooled to after then being reacted in autoclave, respectively with water and
Ethanol cleans, stand-by after product freeze-drying.
One of preferred embodiment as the present invention, in the step (1), 300mg cobalt chloride hexahydrate is dissolved in
Add 1~9.6mL ammoniacal liquor in 80mL reaction solution to adjust, the solid-liquid ratio of cobalt chloride hexahydrate and ammoniacal liquor is 300mg:1~
9.6mL。
One of preferred embodiment as the present invention, in the step (2), the solid-liquid ratio of cobalt chloride hexahydrate and ammoniacal liquor is
300mg:1~9.6mL.
One of preferred embodiment as the present invention, the solvent are at least one of water, ethanol and ethylene glycol.
One of preferred embodiment as the present invention, described 150~200 DEG C in autoclave, the reaction time is 22~30h.
A kind of Co3S4The compound that the preparation method of ultrathin nanometer piece/rGO composite constructions is prepared.
A kind of compound described in use prepares method of the solar cell to electrode.
It is a kind of to prepare method of the solar cell to electrode, it is specific as follows：In mass ratio 2.5~4:1 is equipped with compound powder
End and binder combination, it will be transferred to after the molten grinding in ethanol of mixture in the conductive substrates with FTO, in argon after drying
Annealed in gas, then there is the light anode of dyestuff or quantum dot to assemble to form solar cell device with sensitization.
One of preferred embodiment as the present invention, described adhesive is polyethylene glycol powder.
One of preferred embodiment as the present invention, the conductive substrates are glass or PET.
Co3S4Nanometer sheet/rGO composite constructions, has effectively disperseed Co3S4Nanometer chip architecture, improves its stability, base
In the synergy of two kinds of laminated structures, there is provided more avtive spots, show higher catalytic activity and faster electric charge
Transfer ability is a kind of excellent sensitization solar battery to electrode material.
Present invention employs simple liquid phase hydro-thermal method by controlling the polarity of reaction solution and adjusting NH3The amount control of molecule
Atom processed is self-assembled into Co3S4Laminated structure.This growth pattern is still set up under the conditions of existing for graphene oxide.Oxidation
There is substantial amounts of functional group on the surface of graphene, and due to electrostatic interaction, cobalt ions is easily adsorbed onto the surface of graphene oxide,
Co is formed on its surface3S4Layer structure, simultaneously because HTHP, graphene oxide is reduced.
Using the polarity of a variety of chemical reagent regulation and control reaction solutions such as water, ethanol, ethylene glycol, reacted using ammoniacal liquor control
NH in journey3The amount of molecule.The sulfide of Co sources and S sources synthesis cobalt is added, by the polarity and NH that control solution3Amount realize pair
The control of product morphology.
Graphene oxide is added in the reaction solution of various polarity, ultrasound is dispersed.After adding Co sources, pass through control
The amount of ammoniacal liquor, form Co and NH3Complex Co [NH3]6 3+.Further add S sources and form small seed crystal, pass through the small seed of HTHP
Crystalline substance is self-assembled into Co3S4Nanometer sheet, simultaneous oxidation graphene are reduced to form Co3S4/ rGO composite constructions.The product of acquisition is cold
It is lyophilized that dry that powder is made is stand-by.
The present invention has advantages below compared with prior art：The preparation method of present invention Co sulfide compared to before, is prepared
Technique is more simple, and it is less expensive to prepare material.The product amount of generation is big, is adapted to large-scale production.Co3S4/ rGO composite constructions
With high catalytic activity and strong charge transport capability, having turns into prospects of the Pt to the substitute of electrode.By simply adjusting
The polarity of the percentage of water saving and alcohol control reaction solution, by adding NH3·H2O introduces NH3Molecule, the pattern of product is adjusted
Two-dimensional sheet structure is saved into, increases the specific surface area of structure.By introducing GO in building-up process, disperse Co3S4Nanometer sheet knot
Structure, the agglomeration of laminated structure is avoided, improves Co3S4Catalytic activity, electron transfer capacity and the catalysis stabilization of nanometer sheet
Property.
Brief description of the drawings
Fig. 1 is the XRD of synthetic product at different conditions；
S1：The product of embodiment 1, S2：The product of embodiment 2, S3：The product of embodiment 3, S4：The product of embodiment 4,
S5：The product of embodiment 5, S6：The product of embodiment 6；
Fig. 2 is the TEM image of product；
S1-S6 in a-f difference corresponding diagrams 1；
Fig. 3 is rGO and Co3S4Nanometer sheet/rGO TEM image；
A is rGO TEM image, and b is Co3S4The TEM image of nanometer sheet/rGO (synthesis condition is similar to sample S1)；
Fig. 4 is cyclic voltammetry curve figure；
A is Co3S4Nanometer sheet/rGO cyclic voltammetry curve (circle of circulation 50), b is Co3S4The cyclic voltammetric of nanometer sheet is bent
Line (circle of circulation 25)；
Fig. 5 is sample S1, sample S5, rGO, Co3S4Nanometer sheet/rGO, impedance diagrams of the Pt to electrode；
Fig. 6 a are Co3S4The schematic diagram of nanometer sheet/rGO- DSSCs, Fig. 6 b are sample S1, sample S5,
RGO, Co3S4Nanometer sheet/rGO, efficiency of the Pt to the DSSC of electrode assembling.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
The present embodiment comprises the following steps：
(1)Co3S4The preparation of nanometer chip architecture：
300mg cobalt chloride hexahydrates (CoCl2·6H2O 80mL water and ethanol (in mass ratio 1) are dissolved into：1) mixture
In, stir 10min.Then, after being slowly added to 4.8mL ammoniacal liquor stirring 30min, 189mg thioacetamides (C is added2H5NS, referred to as
For TAA) stirring 1h.Then 24h is reacted at 180 DEG C in autoclave, naturally cools to room temperature, drawn supernatant liquor, pass through water
With ethanol cleaning sample, finally, freeze-drying obtains the product S1 needed.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 50mg graphene oxides ultrasonic dissolution in the mixture of 80mL water and ethanol (in mass ratio 1：1) in, add
300mg cobalt chloride hexahydrates stirring 10min makes its dissolving, next, 4.8mL ammoniacal liquor is slowly added to dropwise, after stirring 10min,
189mg TAA are added, stir 30min.Then in autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, uses water respectively
Cleaned with ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (in mass ratio 4：1) mixture is dissolved in 1mL ethanol and ground, and passes through knifing
Method is transferred the sample on FTO electro-conductive glass, then it is under Ar gas shieldeds the 60min that annealed at 400 DEG C.And dyestuff then
Light anode, electrolyte after sensitization are assembled into solar cell.
Embodiment 2
The present embodiment comprises the following steps：
(1)Co3S4The preparation of nanometer chip architecture：
300mg cobalt chloride hexahydrates (CoCl2·6H2O 80mL water and ethanol (in mass ratio 1) are dissolved into：1) mixture
In, stir 20min.Then, after being slowly added to 9.6mL ammoniacal liquor stirring 20min, 189mg thioacetamides (C is added2H5NS) stir
1h.Then 24h is reacted at 180 DEG C in autoclave, naturally cools to room temperature, draw supernatant liquor, cleaned by water and ethanol
Sample, finally, freeze-drying obtain the product S2 needed.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 50mg graphene oxides ultrasonic dissolution in the mixture of 80mL water and ethanol (in mass ratio 1：1) in, add
300mg cobalt chloride hexahydrates stirring 10min makes its dissolving, next, 9.6mL ammoniacal liquor is slowly added to dropwise, after stirring 10min,
189mg TAA are added, stir 30min.Then in autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, uses water respectively
Cleaned with ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (in mass ratio 3：1) mixture is dissolved in 1mL ethanol and ground, and passes through knifing
Method is transferred the sample on FTO electro-conductive glass, then it is under Ar gas shieldeds the 60min that annealed at 400 DEG C.And dyestuff then
Light anode, electrolyte after sensitization are assembled into solar cell.
Embodiment 3
(1)Co3S4The preparation of nanometer chip architecture：
300mg cobalt chloride hexahydrates (CoCl2·6H2O) it is dissolved into 80mL water, stirs 10min.Then, it is slowly added to
After 4.8mL ammoniacal liquor stirring 30min, 189mg thioacetamides (C is added2H5NS 1h) is stirred.Then it is anti-at 180 DEG C in autoclave
24h is answered, naturally cools to room temperature, draws supernatant liquor, by water and ethanol cleaning sample, finally, freeze-drying is needed
Product S3.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 50mg graphene oxides ultrasonic dissolution in 80mL water, adding 300mg cobalt chloride hexahydrates stirring 10min makes it
Dissolving, next, 4.8mL ammoniacal liquor is slowly added to dropwise, after stirring 10min, 189mg TAA are added, stir 30min.Then exist
In autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, is cleaned respectively with water and ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (3：1) mixture is dissolved in 1mL ethanol and ground, by scraping embrane method by sample
It is transferred on FTO electro-conductive glass, then it is under Ar gas shieldeds the 60min that annealed at 400 DEG C.Then with after dye sensitization
Light anode, electrolyte are assembled into solar cell.
Embodiment 4
(1)Co3S4The preparation of nanostructured：
300mg cobalt chloride hexahydrates (CoCl2·6H2O) it is dissolved into 80mL ethanol, stirs 10min.Then, it is slowly added to
After 4.8mL ammoniacal liquor stirring 30min, 189mg thioacetamides (C is added2H5NS 1h) is stirred.Then it is anti-at 180 DEG C in autoclave
24h is answered, naturally cools to room temperature, draws supernatant liquor, by water and ethanol cleaning sample, finally, freeze-drying is needed
Product S4.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 50mg graphene oxides ultrasonic dissolution in the mixture of 80mL water and ethanol (in mass ratio 4：1) in, add
300mg cobalt chloride hexahydrates stirring 10min makes its dissolving, next, 4.8mL ammoniacal liquor is slowly added to dropwise, after stirring 10min,
189mg TAA are added, stir 30min.Then in autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, uses water respectively
Cleaned with ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (in mass ratio 3：1) mixture is dissolved in 1mL ethanol and ground, and passes through knifing
Method is transferred the sample on FTO electro-conductive glass, then it is under Ar gas shieldeds the 60min that annealed at 400 DEG C.And dyestuff then
Light anode, electrolyte after sensitization are assembled into solar cell.
Embodiment 5
(1)Co3S4The preparation of nanostructured：
300mg cobalt chloride hexahydrates (CoCl2·6H2O) it is dissolved into 80mL water, stirs 10min.Add the thio second of 189mg
Acid amides (C2H5NS 1h) is stirred.Then 24h is reacted at 180 DEG C in autoclave, naturally cools to room temperature, draw supernatant liquor, led to
Water and ethanol cleaning sample are crossed, finally, freeze-drying obtains the product S5 needed.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 50mg graphene oxides ultrasonic dissolution in 80mL water, adding 300mg cobalt chloride hexahydrates stirring 10min makes it
Dissolving, next, 4.8mL ammoniacal liquor is slowly added to dropwise, after stirring 10min, 189mg TAA are added, stir 30min.Then exist
In autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, is cleaned respectively with water and ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (in mass ratio 3：1) mixture is dissolved in 1mL ethanol and ground, and passes through knifing
Method is transferred the sample on FTO electro-conductive glass, then it is under Ar gas shieldeds the 60min that annealed at 400 DEG C.And dyestuff then
Light anode, electrolyte after sensitization are assembled into solar cell.
Embodiment 6
(1)Co3S4The preparation of nanostructured：
300mg cobalt chloride hexahydrates (CoCl2·6H2O) it is dissolved into 80mL ethanol, stirs 10min.It is thio to add 189mg
Acetamide (C2H5NS 1h) is stirred.Then 24h is reacted at 180 DEG C in autoclave, naturally cools to room temperature, draw supernatant liquor,
By water and ethanol cleaning sample, finally, freeze-drying obtains the product S6 needed.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 50mg graphene oxides ultrasonic dissolution in 80mL water, adding 300mg cobalt chloride hexahydrates stirring 10min makes it
Dissolving, next, 4.8mL ammoniacal liquor is slowly added to dropwise, after stirring 10min, 189mg TAA are added, stir 30min.Then exist
In autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, is cleaned respectively with water and ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (in mass ratio 3：1) mixture is dissolved in 1mL ethanol and ground, and passes through knifing
Method is transferred the sample on FTO electro-conductive glass, then it is under Ar gas shieldeds the 60min that annealed at 400 DEG C.And dyestuff then
Light anode, electrolyte after sensitization are assembled into solar cell.
Embodiment 7
(1)Co3S4The preparation of nanometer chip architecture：
600mg cobalt chloride hexahydrates (CoCl2·6H2O 80mL water and ethanol (in mass ratio 1) are dissolved into：1) mixture
In, stir 10min.Then, after being slowly added to 9.6mL ammoniacal liquor stirring 30min, 378mg thioacetamides (C is added2H5NS) stir
1h.Then 24h is reacted at 180 DEG C in autoclave, naturally cools to room temperature, draw supernatant liquor, cleaned by water and ethanol
Sample, finally, freeze-drying obtain the product needed.
(2)Co3S4The preparation of nanometer sheet/rGO composite constructions：
By 100mg graphene oxides ultrasonic dissolution in the mixture of 80mL water and ethanol (in mass ratio 1：1) in, add
600mg cobalt chloride hexahydrates stirring 30min makes its dissolving, next, 9.6mL ammoniacal liquor is slowly added to dropwise, after stirring 30min,
378mg TAA are added, stir 60min.Then in autoclave, 24h is reacted at 180 DEG C, room temperature is naturally cooled to, uses water respectively
Cleaned with ethanol, it is stand-by after product freeze-drying.
(3) solar cell is prepared to electrode：
40mg sample powder and polyethylene glycol (in mass ratio 3：1) mixture is dissolved in 1mL ethanol and ground, and passes through knifing
Method is transferred the sample on PET-ITO conductive films, then it is under Ar gas shieldeds the 60min that annealed at 150 DEG C.Then and
Light anode, electrolyte after dye sensitization are assembled into solar cell.
The Co that embodiment 1~6 is generated3S4Nanometer chip architecture carries out XRD detections, as a result as shown in figure 1, can be seen in figure
The product for going out containing water in reaction solution and being generated in the case of adding ammoniacal liquor is purer Emission in Cubic Co3S4, otherwise in product
Will be with CoS1.097Presence.
Above-mentioned product is subjected to TEM detections, as a result as shown in Fig. 2 as can be seen from the figure containing in reaction solution
The water and product generated in the case of adding ammoniacal liquor is laminated structure, further by controlling the amount of alcohol to adjust the pole of reaction solution
Property and the amount of ammoniacal liquor can optimize the quality of laminated structure.
The product generated under the conditions of S1 is subjected to TEM detections, as a result as shown in Figure 3.
By Co3S4Nanometer sheet/rGO composite construction and Co3S4Nanometer sheet is detected by cyclic voltammetry, as a result such as
Shown in Fig. 4.
By sample S1, sample S5, rGO, Co3S4Nanometer sheet/rGO, carry out testing impedances of the Pt to electrode, as a result such as Fig. 5 institutes
Show.
It will be detected using solar cell produced by the present invention as shown in fig. 6, sample S1 dye sensitization of solar is electric
The efficiency in pond shows the excellent electrochemical properties of laminated structure more than sample S5.Co3S4Nanometer sheet/rGO dye-sensitized solar cells
Efficiency show graphene and Co more than sample S13S4The synergy of nanometer sheet can further improve both performances.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. Co3S4The preparation method of ultrathin nanometer piece/rGO composite constructions, it is characterised in that comprise the following steps：(1)Co3S4The preparation of nanostructured：Cobalt chloride hexahydrate is dissolved into solvent and stirred, adds ammoniacal liquor reaction, thioacetamide is then added and is stirred, Room temperature is cooled to after being reacted in autoclave, abandons supernatant, cleaning sample obtains the Co of nanostructured3S4；(2)Co3S4The preparation of ultrathin nanometer piece/rGO composite constructions：By graphene oxide ultrasonic dissolution in a solvent, cobalt chloride hexahydrate stirring and dissolving is added, it is then that ammoniacal liquor is slow dropwise Add, after stirring, add TAA and continue to stir, room temperature is naturally cooled to after then being reacted in autoclave, respectively with water and ethanol Cleaning, it is stand-by after product freeze-drying.
- A kind of 2. Co according to claim 13S4The preparation method of ultrathin nanometer piece/rGO composite constructions, it is characterised in that In the step (1), 300mg cobalt chloride hexahydrate is dissolved in 80mL reaction solution and adds 1~9.6mL ammoniacal liquor tune The solid-liquid ratio of section, cobalt chloride hexahydrate and ammoniacal liquor is 300mg:1~9.6mL.
- A kind of 3. Co according to claim 13S4The preparation method of ultrathin nanometer piece/rGO composite constructions, it is characterised in that In the step (2), the solid-liquid ratio of cobalt chloride hexahydrate and ammoniacal liquor is 300mg:1~9.6mL.
- A kind of 4. Co according to claim 13S4The preparation method of ultrathin nanometer piece/rGO composite constructions, it is characterised in that The solvent is at least one of water, ethanol and ethylene glycol.
- A kind of 5. Co according to claim 13S4The preparation method of ultrathin nanometer piece/rGO composite constructions, it is characterised in that It is described 150~200 DEG C in autoclave, the reaction time is 22~30h.
- A kind of 6. Co as claimed in claim 13S4The preparation method of ultrathin nanometer piece/rGO composite constructions is prepared compound Thing.
- 7. a kind of prepare method of the solar cell to electrode using compound as claimed in claim 6.
- 8. a kind of method of the solar cell to electrode is prepared according to claim 7, it is characterised in that specific as follows： In mass ratio 2.5~4:1 is equipped with composite powder and binder combination, will be transferred to tool after the molten grinding in ethanol of mixture Have in FTO conductive substrates, annealed after drying in argon gas, then there is the light anode of dyestuff or quantum dot to assemble to be formed with sensitization Solar cell device.
- 9. a kind of method of the solar cell to electrode is prepared according to claim 8, it is characterised in that described adhesive For polyethylene glycol powder.
- 10. a kind of method of the solar cell to electrode is prepared according to claim 8, it is characterised in that the conduction Substrate is glass or PET.
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| CN114613608B (en) * | 2022-03-06 | 2023-12-29 | 光萤新能源(杭州)有限公司 | Hollow Co rich in sulfur vacancy 3 S 4 RGO composite material and preparation method and application thereof |
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