CN105489384B - A kind of C/Sb2S3Preparation method of the laminated film to electrode material - Google Patents
A kind of C/Sb2S3Preparation method of the laminated film to electrode material Download PDFInfo
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- CN105489384B CN105489384B CN201610013596.8A CN201610013596A CN105489384B CN 105489384 B CN105489384 B CN 105489384B CN 201610013596 A CN201610013596 A CN 201610013596A CN 105489384 B CN105489384 B CN 105489384B
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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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- 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 C/Sb2S3Preparation method of the laminated film to electrode material：A certain amount of antimony trichloride and thiocarbamide are gradually added in dimethylformamide, consistent obtains Sb Tu precursor solutions after stirring a period of time, solution is spin-coated into carbon nano-particles film surface, then puts it into annealing in atmosphere furnace and obtains C/Sb2S3Laminated film.On the other hand, the solvent of Sb Tu precursor solutions is evaporated in atmosphere, annealing obtains Sb2S3Powder.A certain amount of powder is placed in corundum boat, carbon nano-particles film cover is on corundum boat, and constant temperature thermal evaporation 10min ~ 1h, also can obtain C/Sb under atmosphere protection2S3Laminated film.
Description
Technical field
The present invention relates to a kind of C/Sb2S3Laminated film belongs to dye sensitization of solar electricity to the preparation method of electrode material
Pond is to electrode preparation field.
Background technology
DSSC (DSSC) is Switzerland scientist M. since 1991Make a breakthrough with
Come a kind of novel photovoltaic power generating device to grow up (referring to Nature magazines, 1991, volume 353, page 737).It is this
New solar cell is environment-friendly, preparation technology is simple, has outstanding advantage particularly in terms of low cost (referring to J.
Am.Chem.Soc. magazine, 2011, volume 133, page 9304), as long as cost estimation shows the photoelectric transformation efficiency of battery
Reaching 5% just has application value.
As the important component of DSSC, the photoproduction for being mainly used to collect external circuit to electrode is electric
Son simultaneously realizes teriodide (I in electrolyte3 -) reduction, so electric conductivity and electro catalytic activity be influence to electrode material performance
Key factor.Current high performance DSSC is mainly used as to electricity using the electro-conductive glass of plating precious metals pt
Pole, but high cost significantly limit the research and development and extensive use of the extensive device of DSSC.Research and develop low
Cost, efficient non-platinum are always one of the study hotspot in the field to electrode.M. in 2009CoS is applied to dye by group
Expect sensitization solar battery to electrode, and obtain the performance suitable to electrode with Pt (referring to J.Am.Chem.Soc. magazines,
2009, volume 131, page 15976), since then, the cheap research for having attracted researchers dense electrode material without Pt is emerging
Interest.In recent years, inorganic metal compound, including metal carbides, nitride, oxide, sulfide and selenides etc. are to electrode
The research of material is particularly, active.The sulfide Sb of metallic antimony2S3Preferable electrocatalysis characteristic is had shown that in terms of to electrode and is answered
With prospect (referring to J.Phys.Chem.C magazines, 2013, volume 117, page 10285), but the electric conductivity of film is poor
The performance of its catalytic performance is limited, complicated preparation technology also limit its large-scale production and application.On the other hand, base
In the electric conductivity that carbon material (C) is excellent, in recent years, CNT, conductive black, activated carbon and graphite are widely used in dye
Expect sensitization solar battery to (participation J.Phys.Chem.C magazines, 2014, volume 118, page 16727) in electrode.Base
In this point, we devise C/Sb2S3Composite, and C/Sb is prepared by simple solution and thermal evaporation method2S3It is compound
Film, research find that the laminated film has excellent electrocatalysis characteristic, are a kind of cheap, efficient new to electrode material.
The content of the invention
It is an object of the invention to provide a kind of new and effective DSSC to electrode material C/Sb2S3It is multiple
Film and preparation method thereof is closed, the material shows excellent electrocatalysis characteristic in iodine electrolyte, and preparation technology simply may be used
Control, it is expected to substitute precious metals pt to obtain high-performance DSSC.
Technical scheme comprises the following steps：
Step 1：Carbon nano-particles and carboxymethyl cellulose carboxylic sodium are dispersed in water, after consistent stirring 12-24h
To carbon nano-particles colloidal sol.Colloidal sol is spin-coated to the FTO surfaces of cleaning, by 60~100 DEG C of vacuum drying, obtains C nano grain
Sub- film.
Step 2：A certain amount of antimony trichloride (SbCl is gradually added in dimethylformamide (DMF)3) and thiocarbamide
(Tu), consistent obtains Sb-Tu precursor solutions after stirring a period of time, and solution is spin-coated into the C nano that step 1 obtains
Particle film surface, then put it into atmosphere furnace and make annealing treatment 0.5 at 2~8 DEG C/min of heating rate, 350~450 DEG C
~1 hour, C/Sb is obtained after natural cooling2S3Laminated film.In this step, SbCl3Concentration be 1-2mM, the concentration of thiocarbamide
For 1-3mM, annealing atmosphere N2Atmosphere.
Or step 3：The solvent of Sb-Tu precursor solutions is evaporated in atmosphere, is subsequently placed in atmosphere furnace 400 DEG C
Lower annealing 0.5~1 hour, obtains Sb2S3Powder.A certain amount of powder is placed in corundum boat, C nano particle film (is led
It is electric face-down) cover on corundum boat, the constant temperature thermal evaporation at 2~8 DEG C/min of heating rate, 350~550 DEG C under atmosphere protection
10min~1h, C/Sb is obtained after natural cooling2S3Laminated film.In this step, Sb2S3The dosage of powder is 50-100mg,
Annealing atmosphere is N2Or Ar, 2~8 DEG C/min of tube furnace heating rate, 350~550 DEG C of thermal evaporation temperature, the thermal evaporation time
10min~1h.
The C/Sb that the present invention designs2S3Laminated film can make full use of the excellent electric conductivity of C and Sb2S3Excellent electricity is urged
Change activity, realize both collaboration facilitations.Used thin film preparation process utilizes the loose structure that C films provide, can
To realize C/Sb2S3Uniform compound, the C/Sb being prepared2S3Film has the advantages that homogeneity, favorable repeatability, and
Technique simple and fast.Single Sb is substantially better than to electrode, its performance as DSSC2S3To electrode material.This
The advantage of invention is：
1st, design prepares C/Sb2S3Laminated film, give full play to Sb2S3The excellent conduction of excellent electrocatalysis characteristic and C
Property, and Sb is deposited by solution and thermal evaporation method2S3Film, two kinds of preparation technology simple and fasts, raw material are saved, are prepared into
To laminated film there is good homogeneity and repeatability.
2nd, research shows, C/Sb2S3Film has electrocatalysis characteristic height, good conductivity as a kind of combined counter electrode material
The advantages of.In the case where AM1.5 simulated solar irradiations excite, with solution and the C/Sb of thermal evaporation method preparation2S3Film is used as to electrode point
Highest photoelectric transformation efficiency 6.62% and 6.45% is not realized, it is suitable to the photoelectric transformation efficiency of electrode device with Pt
(6.89%).Therefore, C/Sb2S3Film has excellent to electrode performance, may replace Pt as new and effective dye sensitization too
Positive energy counter electrode of battery material.
Brief description of the drawings
Fig. 1 is the C nano particle film photo and SEM photograph prepared.
Fig. 2 is the Sb-Tu precursor solution photos prepared.
Fig. 3 is the C/Sb of 1 time preparation of example2S3Film SEM photograph.
Fig. 4 is the C/Sb prepared with example 12S3J-V curve of the film as the device obtained to electrode test.
Fig. 5 is Sb-Tu precursor solution solvents to be evaporated and annealed the Sb obtained afterwards2S3The XRD spectrum and standard of powder
PDF card comparison diagrams.
Fig. 6 is Sb2S3The SEM photograph of powder.
Fig. 7 is the C/Sb prepared with example 32S3J-V curve of the film as the device obtained to electrode test.
Embodiment：
Example 1
Carbon nano-particles and carboxymethyl cellulose carboxylic sodium are dispersed in water and obtain carbon nano-particles colloidal sol, colloidal sol is spin-coated to
The SnO2 of fluorine transparent conductive glass surface is adulterated, by 60~100 DEG C of vacuum drying, obtains carbon nano-particles film；
1mM SbCl are gradually added in DMF3With 2mM Tu, consistent obtains Sb-Tu forerunner after stirring a period of time
Liquid solution, solution is spin-coated to C nano particle film surface, then puts it into N2In atmosphere furnace 2~8 DEG C of heating rate/
Min, make annealing treatment 0.5 hour at 350~450 DEG C, wait natural cooling, that is, obtain C/Sb2S3Laminated film.
Fig. 1 is the C nano particle film photo and SEM photograph prepared.Fig. 2 is the Sb-Tu presomas prepared under the example
Solution thereon, found out by picture, good homogeneity, the transparency is presented in the solution, can be deposited 7-10 days in air, has very
Good stability.Fig. 3 is the C/Sb prepared under the example2S3Film SEM photograph, it can be seen that the laminated film is more
Pore structure, and there is good homogeneity.Fig. 4 is the C/Sb to be prepared under the example2S3Film is as obtaining to electrode test
The J-V curves of device, it can be calculated that the photoelectric transformation efficiency of device is 6.62% from figure, the light with Pt to electrode device
Photoelectric transformation efficiency is quite (6.89%), it was demonstrated that the C/Sb2S3Film is excellent to electrode performance, is expected to substitute Pt as new
Efficient DSSC is to electrode material.
Carbon nano-particles and carboxymethyl cellulose carboxylic sodium are dispersed in water and obtain carbon nano-particles colloidal sol by example 2, by colloidal sol
The SnO2 of doping fluorine transparent conductive glass surface is spin-coated to, by 60~100 DEG C of vacuum drying, it is thin to obtain carbon nano-particles
Film；
1-2mM SbCl are gradually added in DMF3With 2-3mM Tu, consistent obtains Sb-Tu after stirring a period of time
Precursor solution, solution is spin-coated to C nano particle film surface, then puts it into N2In heating rate 5 in atmosphere furnace
DEG C/min, make annealing treatment 0.5 hour at 400 DEG C, natural cooling is waited, that is, obtains C/Sb2S3Laminated film.
Carbon nano-particles and carboxymethyl cellulose carboxylic sodium are dispersed in water and obtain carbon nano-particles colloidal sol by example 3, by colloidal sol
The SnO2 of doping fluorine transparent conductive glass surface is spin-coated to, by 60~100 DEG C of vacuum drying, it is thin to obtain carbon nano-particles
Film；
1mM SbCl are gradually added in DMF3With 2mM Tu, consistent obtains Sb-Tu forerunner after stirring a period of time
Liquid solution, its solvent is evaporated in atmosphere, is subsequently placed in atmosphere furnace at 400 DEG C and makes annealing treatment 0.5~1 hour, obtain
Sb2S3Powder.100mg powders are placed in corundum boat, C nano particle film (conductive face-down) is covered on corundum boat, atmosphere
Under protection at 8 DEG C/min of heating rate, 350~550 DEG C constant temperature thermal evaporation 30min, wait natural cooling, you can obtain C/
Sb2S3Laminated film.
Fig. 5 and 6 is Sb-Tu precursor solution solvents to be evaporated and annealed the Sb obtained afterwards2S3The XRD spectrum of powder with
Standard PDF cards comparison diagram and SEM photograph.Comparing result shows that the powder that we obtain is pure phase Sb2S3, and be bar-shaped shape
Looks, a diameter of 3 μm or so of rod.Fig. 7 is the C/Sb to be prepared under the example2S3Film is as the device obtained to electrode test
J-V curves, it can be calculated that the photoelectric transformation efficiency of device is 6.45% from figure, the photoelectricity of electrode device is turned with Pt
Change efficiency quite (6.89%), it was demonstrated that the C/Sb2S3Film is excellent to electrode performance, is expected to substitute Pt as new and effective
DSSC to electrode material.
Carbon nano-particles and carboxymethyl cellulose carboxylic sodium are dispersed in water and obtain carbon nano-particles colloidal sol by example 4, by colloidal sol
The SnO2 of doping fluorine transparent conductive glass surface is spin-coated to, by 60~100 DEG C of vacuum drying, it is thin to obtain carbon nano-particles
Film；1mM SbCl are gradually added in DMF3With 2mM Tu, it is molten that consistent obtains Sb-Tu presomas after stirring a period of time
Liquid, its solvent is evaporated in atmosphere, is subsequently placed in atmosphere furnace at 400 DEG C and makes annealing treatment 0.5~1 hour, obtain Sb2S3Powder
Body.50-100mg powders are placed in corundum boat, C nano particle film (conductive face-down) is covered on corundum boat, and atmosphere is protected
Under shield at 8 DEG C/min of heating rate, 500 DEG C constant temperature thermal evaporation 10min-1h, wait natural cooling, you can obtain C/Sb2S3It is multiple
Close film.
Claims (4)
- A kind of 1. DSSC C/Sb2S3Preparation method of the laminated film to electrode material, it is characterised in that bag Include following steps：（1）Carbon nano-particles and carboxymethyl cellulose carboxylic sodium are dispersed in water and obtain carbon nano-particles colloidal sol, by colloidal sol It is spin-coated to the SnO of doping fluorine2Transparent conducting glass FTO surfaces, by 60 ~ 100oC is dried in vacuo, and it is thin to obtain carbon nano-particles Film；（2）Antimony trichloride SbCl is gradually added in dimethylformamide DMF3Obtained with thiocarbamide Tu, consistent stirring 10-30min To Sb-Tu precursor solutions, precursor solution is coated on to be put into nitrogen atmosphere stove after carbon nano-particles film surface risen Warm speed is 2 ~ 8oUnder C/min, 350oC~450oMade annealing treatment 0.5 ~ 1 hour under C, C/Sb is obtained after natural cooling2S3THIN COMPOSITE Film.
- 2. the C/Sb described in claim 12S3Preparation method of the laminated film to electrode material, it is characterised in that antimony trichloride with The mol ratio of thiocarbamide is 1-2:1-3.
- 3. the C/Sb described in claim 12S3Preparation method of the laminated film to electrode material, it is characterised in that step（2）In The solvent of Sb-Tu precursor solutions is evaporated in atmosphere, is subsequently placed in 350 in atmosphere furnaceoC~450o0.5 ~ 1 is made annealing treatment under C Hour, obtain Sb2S3Powder, powder is placed in corundum boat, carbon nano-particles film cover is on corundum boat, under atmosphere protection In heating rate 2 ~ 8oC/min、350~550oConstant temperature thermal evaporation 10min ~ 1h under C, C/Sb is obtained after natural cooling2S3THIN COMPOSITE Film.
- 4. the C/Sb described in claim 32S3Preparation method of the laminated film to electrode material, it is characterised in that carbon nano-particles During film cover is on the corundum boat, it is conductive down.
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| CN106277051A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院合肥物质科学研究院 | A kind of crystallinity Sb2s3the solution preparation for processing of thin film |
| CN106927512B (en) * | 2017-03-22 | 2018-07-06 | 三峡大学 | A kind of preparation method and application of nickel antimony sulphur film |
| CN109037034B (en) * | 2018-07-26 | 2021-02-12 | 深圳清华大学研究院 | Antimony selenide thin film, preparation method thereof and solar cell applying antimony selenide thin film |
| CN111508716B (en) * | 2020-04-03 | 2021-06-18 | 三峡大学 | Ni3Bi2S2Preparation method of/N-C electrocatalytic material |
| CN112885711A (en) * | 2021-01-18 | 2021-06-01 | 中国科学院合肥物质科学研究院 | Compact Sb2S3Preparation method of thin film and solar cell based on thin film |
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