CN106847519A - The preparation method of CoS/CuS 3 D stereo nano composite structural materials - Google Patents
The preparation method of CoS/CuS 3 D stereo nano composite structural materials Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002071 nanotube Substances 0.000 claims abstract description 46
- 239000011521 glass Substances 0.000 claims abstract description 29
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000003491 array Methods 0.000 claims abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 44
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- IUFLULRFODSQGQ-UHFFFAOYSA-N O.[Co]=S Chemical compound O.[Co]=S IUFLULRFODSQGQ-UHFFFAOYSA-N 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- 239000011165 3D composite Substances 0.000 abstract description 15
- 239000002096 quantum dot Substances 0.000 abstract description 13
- 239000007772 electrode material Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000224 chemical solution deposition Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 15M cobalt chloride hexahydrates Chemical class 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Catalysts (AREA)
Abstract
The preparation method of CoS/CuS 3 D stereo nano composite structural materials, is related to nano composite structural material.Prepare CuS Seed Layers：One layer of CuS Seed Layer is sputtered in FTO conductive glass surfaces by the method for magnetron sputtering C uS targets；Prepare CoS hollow nanotube arrays；Prepare CoS/CuS 3 D stereo nano composite structural materials.Aided in by magnetron sputtering, with reference to the method for simple Hydrothermal Synthesiss, prepare the three dimensional composite structure that CuS nanosheet wraps up CoS hollow nanotubes, this kind of structure and morphology rule, and with big specific surface area.It is applied in quantum dot sensitized solar cell as to electrode material, shows excellent electrocatalysis characteristic.The method has repeatability height, simple operation and other advantages, and combines physics and chemical means, can be mass-produced, and a new thinking is provided to prepare new material.
Description
Technical field
The present invention relates to nano composite structural material, more particularly, to CoS/CuS 3 D stereo nano composite structural materials
Preparation method.
Background technology
Metal sulfide has various chemical compositions, various crystal structure, complicated microscopic appearance because of it so that they
Possess good physics and chemical characteristic, have good application prospect in field of electronic devices, especially it is used as to electrode material
Material is applied to quantum dot sensitized solar cell (QDSSCs), thus is extensively paid close attention to by people.Since 1954 (D.Reynolds,
G.Leies, L.Antes and R.Marburger, Phys.Rev., 1954,96,533.) DC Reynolds discoveries CdS/
Cu2S heterojunction structure solar cells, CuS is just probed into as an important material in field of photovoltaic devices by people.CuS
With narrower band gap width (1.1-1.4eV), absorption coefficient (10 higher4cm-1), it is a kind of material of asepsis environment-protecting low consumption
Material, and CuS has different microscopic appearances, and such as nanometer sheet, nanotube, nanometer rods etc. are a kind of efficient QDSSCs
To electrode material.CoS has good electro catalytic activity because of it in polysulfide electrolyte, is a kind of promising to electricity
Pole material.Zusing Yang etc. (Yang, Z., Chen, C.-Y., Liu, C.-W., Li, C.-L., Chang, H.-T.,
2011.Quantum Dot-Sensitized Solar Cells Featuring CuS/CoS Electrodes Provide
4.1%Efficiency.Advanced Energy Materials 1,259-264.) be prepared for CuS/CoS to electrode material
Material, is effectively improved the efficiency of quantum dot sensitized solar cell.But it is this to be synthesized by chemical bath deposition (CBD) method
CoS nanometer sheets and CuS nano wires pile up structure it is not uniform enough, the active area with electrolyte contacts is not big enough, can influence
To the catalysis activity of electrode material.Therefore, seek simple environmental protection method prepare more uniform, stabilization, tactical rule,
The big development to electrode material to quantum dot sensitized solar cell of specific surface area is most important.
The content of the invention
There are rule to electrode material it is an object of the invention to provide prepared CoS/CuS three-dimensional manometer composite constructions
The features such as microscopic appearance then, bigger serface, excellent catalysis activity, and preparation method simple controllable, environmental protection, reproduction
The preparation method of property CoS/CuS 3 D stereo nano composite structural materials high.
The present invention is comprised the following steps：
1) CuS Seed Layers are prepared：One layer of CuS is sputtered in FTO conductive glass surfaces by the method for magnetron sputtering C uS targets
Seed Layer；
2) CoS hollow nanotube arrays are prepared；
3) CoS/CuS 3 D stereo nano composite structural materials are prepared.
In step 1) in, vacuum needed for the magnetron sputtering can be 1.0 × 103Pa, operating pressure can be 2.5Pa, Ar
Throughput can be 100sccm, and radio-frequency power can be 120W, and sputtering time can be 30min；The size of the FTO electro-conductive glass can
It is 2cm × 1.5cm；The FTO electro-conductive glass is preferably first sequentially placed into acetone, and deionized water is respectively cleaned by ultrasonic in absolute ethyl alcohol
15min。
In step 2) in, it is described prepare CoS hollow nanotube arrays specific method can be：
(1) reacting solution is prepared：The reacting solution contains urea and cobalt chloride hexahydrate, by step 1) gained CuS
The FTO electro-conductive glass of Seed Layer is placed in the reactor for filling the reacting solution, after reaction, is cooled to room temperature, is led in FTO
Electric glass surface obtains one layer of pale pink film, then rinses, and the cobalt sulfide hydrate of nano wire pattern is obtained final product after drying；
In step 2) in (1st) part, the mass percentage concentration of the urea can be 6.25%, and cobalt chloride hexahydrate can be used
0.15M cobalt chloride hexahydrates；The reaction can react 3h under conditions of 90 DEG C；The flushing can use deionized water rinsing.
(2) the nine hydrated sodium sulfide aqueous solution of 0.01M are prepared：The FTO of the cobalt sulfide hydrate of nano wire pattern is conductive
Glass is put into the reactor containing reacting solution, after reaction, is cooled to room temperature, and one layer is obtained in FTO conductive glass surfaces
Black thin film, is rinsed, and the cobalt sulfide of hollow Nano tubulose is obtained final product after drying.
In step 2) in (2nd) part, the reaction can react 10h under the conditions of 180 DEG C；The flushing can use deionization
Water is rinsed.
In step 3) in, it is described prepare CoS/CuS 3 D stereo nano composite structural materials specific method can be：
By step 2) prepared by the cobalt sulfide of hollow Nano tubulose repeat step 1) magnetron sputtering, in cobalt sulfide
Hollow pipe on obtain the seed of CuS, prepare reacting solution, the reacting solution contains Gerhardite and thiocarbamide,
The length is had the hollow pipe of the cobalt sulfide of CuS seeds be put into carries out hydro-thermal reaction in the reactor containing the reacting solution
Afterwards, room temperature is cooled to, black thin film is obtained, is rinsed, the three-dimensional manometer that CuS nanosheet parcel CoS empty nanotubes are obtained after drying is answered
Close structure, i.e. CoS/CuS 3 D stereos nano composite structural material；The Gerhardite can be hydrated nitre using 0.01M tri-
Sour copper, the thiocarbamide can be using the thiocarbamide of 0.05M；The flushing can use deionized water rinsing；The temperature of the hydro-thermal reaction can
It it is 150 DEG C, the time of hydro-thermal reaction can be 2~10h.
The present invention is aided in by magnetron sputtering, with reference to the method for simple Hydrothermal Synthesiss, prepares CuS nanosheet parcel CoS
The three dimensional composite structure of hollow nanotube, this kind of structure and morphology rule, and with big specific surface area.Answered as to electrode material
In for quantum dot sensitized solar cell, excellent electrocatalysis characteristic is shown.The method has repeatability high, simple to operate
The advantages of, and physics and chemical means are combined, and can be mass-produced, provide a new think of to prepare new material
Road.
Brief description of the drawings
Fig. 1 be embodiment 1 in blank FTO glass surfaces SEM (ESEM) front elevation (multiplication factor be 30,000
Times).In Fig. 1, scale is 200nm.
Fig. 2 (scans electricity to pass through magnetically controlled sputter method in embodiment 1 in the FTO glass surfaces SEM for having CuS Seed Layers long
Mirror) front elevation (multiplication factor is 10,000 times).In fig. 2, scale is 1.00 μm.
Fig. 3 be the FTO glass Urea (urea) that contains 6.25wt% in 60mL that length has CuS Seed Layers in embodiment 1 and
0.15M Co(Cl)2·.12The aqueous solution of O (cobalt chloride hexahydrate), hydrothermal temperature is that the cobalt sulfide that 3h is obtained is reacted at 90 DEG C
SEM (ESEM) front elevation of hydrate (multiplication factor is 10,000 times).In figure 3, scale is 1.00 μm.
Fig. 4 is nine hydrated sodium sulfides of the FTO glass in 60mL 0.01M of the hydrate that length has cobalt sulfide in embodiment 1
In the aqueous solution, hydrothermal temperature is that SEM (ESEM) front elevation that the CoS hollow nanotubes that 10h is obtained are reacted at 180 DEG C (is put
Big multiple is 1.5 ten thousand times).In fig. 4, scale is 1.00 μm.
Fig. 5 be in embodiment 1 length have the CoS hollow nanotubes of CuS seeds 60mL contain 0.01M Gerhardites and
The aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes that 4h is obtained are reacted at 150 DEG C
SEM (ESEM) front elevation of three-dimensional manometer composite construction (multiplication factor is 1.5 ten thousand times).In Figure 5, scale is 2.00 μ
m。
Fig. 6 be in embodiment 1 length have the CoS hollow nanotubes of CuS seeds 60mL contain 0.01M Gerhardites and
The aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes that 4h is obtained are reacted at 150 DEG C
SEM (ESEM) side view of three-dimensional manometer composite construction (multiplication factor is 8.00 thousand times).In figure 6, scale is 2.00 μ
m。
Fig. 7 be in embodiment 1 length have the CoS hollow nanotubes of CuS seeds 60mL contain 0.01M Gerhardites and
The aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes three that 4h is obtained are reacted at 150 DEG C
Tie up TEM (transmission electron microscope) front elevation of nano composite structure (multiplication factor is 40,000 times).In the figure 7, scale is 100nm.
Fig. 8 is the partial enlarged drawing (multiplication factor is 800,000 times) of Fig. 7 samples in embodiment 1.In fig. 8, scale is
5nm。
Fig. 9 is the TEM electronic diffraction ring figures of Fig. 7 samples in embodiment 1.In fig .9, scale is 51/nm.
Figure 10 contains 0.01M Gerhardites for the CoS hollow nanotubes that length in embodiment 1 has CuS seeds in 60mL
With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes that 4h is obtained are reacted at 150 DEG C
X-ray diffraction (XRD) characterization result of three dimensional composite structure material.In Fig. 10, abscissa is 2 times of angle of diffraction (°), indulges and sits
It is designated as the relative intensity (a.u.) of diffraction maximum；◆ sign flag is the diffraction maximum of FTO electro-conductive glass substrates, ● sign flag
It is the diffraction maximum of CoS hollow nanotubes, ▲ mark is the diffraction maximum of CuS nanosheet, and upper strata vertical line is the PDF cards of standard CuS
Go out peak position corresponding to piece, lower floor's vertical line goes out peak position corresponding to the PDF cards of standard CoS.
Figure 11 is to be assembled as to electrode material with reference to tradition Pt and CoS and CuS samples with Fig. 6 samples in embodiment 1
Into the current density voltage curve (i.e. J-V curves) of quantum dot sensitized solar cell.In fig. 11, abscissa is voltage
(V), ordinate is current density (mAcm-2), mark-◆-be tradition Pt to the J-V curves of electrode ,-▲-be CoS samples
J-V curves ,-■-be the J-V curves of CuS samples ,-●-for Fig. 6 samples CoS/CuS J-V curves.
Figure 12 is the resistance for carrying out electrochemical impedance test in embodiment 1 as Symmetrical cells with three sample assemblies in Figure 11
Anti- energy spectrum diagram (i.e. Nquist spectrograms).In fig. 12, abscissa is Z ' (Ω), and ordinate is-Z " (Ω), mark-◆-it is tradition
Pt to the Nquist spectrograms of electrode ,-▲-be the Nquist spectrograms of CoS samples ,-■-be CuS samples Nquist spectrums
Figure ,-●-it is the Nquist spectrograms of Fig. 6 samples CoS/CuS.
Figure 13 be embodiment 1 in Fig. 6 samples by 500 circle cyclic voltammetries cyclic voltammetry curves (i.e. CV curves).
In fig. 13, abscissa is voltage (V), and ordinate is current density (mAcm-2)。
Figure 14 is the Tafel polarization curves measured as Symmetrical cells with Fig. 6 sample assemblies in embodiment 1.In fig. 14,
Abscissa is voltage (V), and ordinate is the logarithm value of current density.
Figure 15 contains 0.01M Gerhardites for the CoS hollow nanotubes that length in embodiment 2 has CuS seeds in 60mL
With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature be react that 1h obtains at 150 DEG C not form CuS nanosheet modification CoS empty
SEM (ESEM) front elevation of the three dimensional composite structure of heart nanotube (multiplication factor is 30,000 times).In fig .15, scale is
200nm。
Figure 16 contains 0.01M Gerhardites for the CoS hollow nanotubes that length in embodiment 3 has CuS seeds in 60mL
With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes that 2h is obtained are reacted at 150 DEG C
Three dimensional composite structure SEM (ESEM) front elevation (multiplication factor be 1.5 ten thousand times).In figure 16, scale is 2.00 μm.
Figure 17 contains 0.01M Gerhardites for the CoS hollow nanotubes that length in embodiment 4 has CuS seeds in 60mL
With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes that 6h is obtained are reacted at 150 DEG C
Three dimensional composite structure SEM (ESEM) front elevation (multiplication factor be 1.5 ten thousand times).In fig. 17, scale is 1.00 μm.
Figure 18 contains 0.01M Gerhardites for the CoS hollow nanotubes that length in embodiment 5 has CuS seeds in 60mL
With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow nanotubes that 8h is obtained are reacted at 150 DEG C
Three dimensional composite structure SEM (ESEM) front elevation (multiplication factor be 1.5 ten thousand times).In figure 18, scale is 1 μm.
Figure 19 contains 0.01M Gerhardites for the CoS hollow nanotubes that length in embodiment 6 has CuS seeds in 60mL
With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet modification CoS hollow Nanos that 10h is obtained are reacted at 150 DEG C
SEM (ESEM) front elevation of the three dimensional composite structure of pipe (multiplication factor is 10,000 times).In Figure 19, scale is 1 μm.
Specific embodiment
Embodiment 1
1) magnetron sputtering method prepares CuS Seed Layers
The FTO electro-conductive glass of 2cm × 1.5cm sputtering methods is put in acetone, deionized water, absolute ethyl alcohol successively and is surpassed respectively
Sound cleans 15min, is put in 60 DEG C of oven dryings standby.Clean FTO electro-conductive glass is put into magnetron sputtering reaction cavity, treats true
Reciprocal of duty cycle reaches 1.0 × 103Pa, is passed through argon gas, operating pressure is reached 2.5Pa, controls throughput for 100sccm, adjusts radio frequency
Power after pre-sputtering 10min, opens baffle plate to 120W, and CuS is sputtered in FTO conductive glass surfaces, and sputtering time is 30min.Such as
Shown in Fig. 1, clean FTO conductive glass surfaces surround and watch pattern for graininess；As shown in Fig. 2 length has the FTO tables of CuS Seed Layers
Face can be observed one layer of dark little particle and be attached to FTO particle surfaces, make FTO surfaces more coarse, be the growth of next step
The hydrate of cobalt sulfide provides advantage.
2) cobalt sulfide hollow nanotube array is prepared
60mL reacting solutions are prepared, the solution contains the Urea (urea) of 6.25wt%, 0.15M Co (Cl)2·6H2O (six
Hydrated cobalt chloride), by step 1) obtained by the length FTO electro-conductive glass conductions that have CuS Seed Layers face down and be placed on containing upper
State in the 100mL reactors of reaction solution, 3h is reacted at 90 DEG C, be cooled to room temperature, one layer of light powder is obtained in FTO conductive glass surfaces
Color film, with deionized water lavage specimens product, obtains the hydrate of the cobalt sulfide of nano wire pattern after drying.As shown in figure 3, gained
To the hydrate of cobalt sulfide be solid nano thread structure, diameter is about 200nm, and length is about 3 μm.
The nine hydrated sodium sulfide aqueous solution of 60mL 0.01M are prepared again, and length obtained above is had into cobalt sulfide hydrate
FTO electro-conductive glass is put into the 100mL reactors containing reacting solution, and 10h is reacted under the conditions of 180 DEG C, is cooled to room temperature,
One layer of black thin film is obtained in FTO conductive glass surfaces, with deionized water rinsing, is dried, obtain cobalt sulfide hollow nanotube battle array
Row.As shown in figure 4, prepared cobalt sulfide is hollow nano-tube array, in the radial uniform growth in FTO surfaces.
3) three dimensional composite structure that CuS nanosheet modifies CoS hollow nanotubes is prepared
By step 2) prepared by cobalt sulfide hollow nanotube repeat step 1) magnetron sputtering, in the sky of cobalt sulfide
The seed of CuS is obtained on heart pipe.60mL reacting solutions are prepared, the aqueous solution contains 0.01M Gerhardites and 0.05M
Thiocarbamide, the cobalt sulfide hollow pipe that above-mentioned length has CuS seeds is put into the 100mL reactors containing above-mentioned reacting solution,
React 4h under the conditions of 150 DEG C, after reaction terminates, be cooled to room temperature, obtain than step 2) darker black thin film, go from
Sub- water rinses sample, dries, that is, obtain the three dimensional composite structure that CuS nanosheet modifies CoS hollow nanotubes.As shown in figure 5, can
It was observed that, CuS nanosheet is interlocked and is uniformly coated on CoS nanotube surfaces, overall that cylindrical-shaped structure is presented.Cutting shown in Fig. 6
Face figure it can also be seen that prepared cylindric CoS/CuS growths interlaced with each other, for its catalytic reaction in the electrolytic solution is provided
Larger effective active area.The TEM image of Fig. 7, matches with the SEM image of Fig. 5, can be observed to be laminated around hollow pipe
It is dispersed with the structure of nanometer sheet.Fig. 8 is evident that two kinds of different lattice fringes, by measurement, it is known that interplanar distance is
0.568nm and 0.303nm correspond to the CuS nanosheet of CoS hollow pipes and (102) crystal face respectively.Fig. 9 SEAD light
It is fine that spot further illustrates prepared sample crystallization.Further XRD characterization results Figure 10 is more demonstrated by this
Plant the composite construction that magnetron sputtering physical means successfully prepare CoS/CuS with hydro-thermal reaction chemical means.
Using above-mentioned sample as quantum dot sensitized solar cell to electrode material, be assembled into the quantum dot sensitized sun
Can battery.Light anode preparation process used is as follows：By 0.5g P25 powder, (i.e. PEG, molal weight is 0.5g polyethylene glycol
20000) it is dissolved into 1mL deionized waters and 1mL absolute ethyl alcohol mixed liquors, stirring 3h is made slurry.In 2cm × 1.5cm FTO
Surface sticks seamless adhesive tape to control thicknesses of layers, and the slurry that will be prepared by the method for scratching is scratched and formed on FTO surfaces
20 μm of film layer, and make annealing treatment 30min in 450 DEG C of air；When sample is cooled to room temperature, then carry out TiCl4Treatment, will
The sample of taking-up is immersed in 0.2M TiCl4In the aqueous solution, 40min is reacted at 70 DEG C, then in 450 DEG C of air anneal treatment
30min.The deposition that CdS and CdSe are sensitized quantum dot altogether is realized by the method for chemical bath deposition (CBD)：A) CdS quantum
The deposition of point：By the TiO of above-mentioned preparation2Light anode material is immersed in and contains 20mM CdCl2, 66mM NH4Cl, 140mM thiocarbamide and
230mM ammoniacal liquor, pH value is about in 9.50 aqueous solution, is put in 10 DEG C of refrigerator and stands 80min, after question response terminates, takes out
Sample simultaneously uses deionized water rinsing, obtains the light anode of the CdS quantum dot sensitization of yellow green.B) deposition of CdSe quantum dot：Match somebody with somebody
Na processed2SeSO3The aqueous solution, 0.18M Na are dissolved in by 0.1M Se powder2SO3Solution, after stirring 7h at 70 DEG C, stops heating, treats
Solution is cooled to room temperature, filters unreacted Se powder；Prepare 0.08M Cd (NO3)2With the water of 0.16M NTA trisodium one
Compound (Na3NTA) the aqueous solution of mixing, with Na2SeSO3The aqueous solution mixes in equal volume, the light that above-mentioned CdS quantum dot is sensitized
Anode is dipped into mixed liquor, and 30h is stood in 10 DEG C of refrigerator, after question response terminates, with deionized water rinsing, in atmosphere
Naturally dry, that is, obtain the light anode that CdS/CdSe quantum dots are sensitized altogether.Electricity used by assembling quantum dot sensitization solar battery
Solution liquid is to contain 0.5M Na2(both volume ratios are 3/ for the methyl alcohol of S, 0.125M S and 0.2M KCl and the mixed liquor of deionized water
7), the film thickness that seals used is for 60 is heat.Packaged cell active area is about 0.14cm2, test condition is simulated solar
Light (i.e. AM1.5,100mWcm-2) performance parameter of battery is listed in table 1, (J-V is bent for the Cell current density-voltage curve for measuring
Line) see Figure 11.From table 1 and Figure 11, the battery efficiency to electrode based on CoS/CuS composite constructions reaches
4.44%, short-circuit current density (JSC) it is 20.20mAcm-2, open-circuit voltage (VOC) it is 0.51V, fill factor, curve factor is 0.43；Phase
Than in traditional Pt electrodes (PCE：1.96%, JSC：11.45mA·cm-2, VOC：0.47V, FF：0.36)CoS(PCE：1.96%,
JSC：16.80mA·cm-2, VOC：0.48V, FF：0.46) with CuS samples (PCE：3.83%, JSC：16.37mA·cm-2, VOC：
0.51V, FF：0.46) improve a lot.
Table 1 is the performance parameter of battery corresponding with Figure 11 in embodiment 1.Wherein Jsc represents density of photocurrent, unit
It is mA/cm2；Voc represents photovoltage, and unit is V；FF represents fill factor, curve factor；η represents battery efficiency, and unit is %；Rs, RctFor
The parameter that the fitting of Figure 13 impedance curves is obtained, unit is Ω, wherein RsRepresent battery system resistance, RctRepresent to electricity
Pole/electrolyte interface resistance.
Table 1
The cyclic voltammetric (C-V) of Figure 12 is tested and shown after being tested by 500 circles, prepared CoS/CuS composite constructions
Material still has good catalytic performance, and its catalytic in the electrolytic solution is not degenerated significantly, illustrates prepared
Sample has good stability.Cyclic voltammetric (C-V) test condition be：Three-electrode system, using saturated calomel electrode as
Reference electrode, platinum electrode is carried out as working electrode as the CoS/CuS to electrode, preparation with Chi600e electrochemical workstations
Test, electrolyte is used comprising 0.5M Na2The methyl alcohol of S, 0.125M S and 0.2M KCl and mixed liquor (both of deionized water
3/7) volume ratio is.EIS impedance spectras display CoS/CuS sandwiches shown in Figure 13 have the resistance of very little, in electricity
Electronics can be faster transmitted in solution liquid.The Tafel polarization curves of Figure 14 show that sample has good electrochemical catalysis activity.
Embodiment 2
Repeat the step 1 in embodiment 1) and step 2), prepared cobalt sulfide hollow nanotube is repeated into step
1) magnetron sputtering, obtains the seed of CuS on the hollow pipe of cobalt sulfide.60mL reacting solutions are prepared, the aqueous solution contains
The thiocarbamide of 0.01M Gerhardites and 0.05M, the cobalt sulfide hollow pipe that above-mentioned length has CuS seeds is put into containing above-mentioned
In the 100mL reactors of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 1h after reaction terminates, is cooled to room temperature, obtains
Than step 2) darker black thin film, deionized water rinsing sample dries.As shown in figure 15, when the hydro-thermal reaction time by
When the 4h of embodiment 1 shortens to 1h, the three dimensional composite structure that CuS modifies CoS hollow nanotubes is not formed, mainly due to anti-
Too short between seasonable, CuS does not grow up to the pattern of nanometer sheet fully also.
Embodiment 3
Repeat the step 1 in embodiment 1) and step 2), prepared cobalt sulfide hollow nanotube is repeated into step
1) magnetron sputtering, obtains the seed of CuS on the hollow pipe of cobalt sulfide.60mL reacting solutions are prepared, the aqueous solution contains
The thiocarbamide of 0.01M Gerhardites and 0.05M, the cobalt sulfide hollow pipe that above-mentioned length has CuS seeds is put into containing above-mentioned
In the 100mL reactors of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 2h after reaction terminates, is cooled to room temperature, obtains
Than step 2) darker black thin film, deionized water rinsing sample dries.As shown in figure 16, when the hydro-thermal reaction time by
When the 4h of embodiment 1 shortens to 2h, the three dimensional composite structure that CuS nanosheet modifies CoS hollow nanotubes can be equally obtained, its
Difference is that the CuS nanosheet for now obtaining is very thin, and thickness is about more than ten nm.It can thus be seen that within a short period of time, although
The CuS nanosheet that can be formed, but its very thin thickness, electrocatalysis characteristic are weaker with respect to embodiment 1.
Embodiment 4
Repeat the step 1 in embodiment 1) and step 2), prepared cobalt sulfide hollow nanotube is repeated into step
1) magnetron sputtering, obtains the seed of CuS on the hollow pipe of cobalt sulfide.60mL reacting solutions are prepared, the aqueous solution contains
The thiocarbamide of 0.01M Gerhardites and 0.05M, the cobalt sulfide hollow pipe that above-mentioned length has CuS seeds is put into containing above-mentioned
In the 100mL reactors of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 6h after reaction terminates, is cooled to room temperature, obtains
Than step 2) darker black thin film, deionized water rinsing sample dries.As shown in figure 17, when the hydro-thermal reaction time by
When the 4h of embodiment 1 increases to 6h, the three dimensional composite structure that CuS nanosheet modifies CoS hollow nanotubes can be equally obtained, its
Difference is that the CuS nanosheet for now obtaining is thicker relative to embodiment 1, and thickness is about tens nanometers.
Embodiment 5
Repeat the step 1 in embodiment 1) and step 2), prepared cobalt sulfide hollow nanotube is repeated into step
1) magnetron sputtering, obtains the seed of CuS on the hollow pipe of cobalt sulfide.60mL reacting solutions are prepared, the aqueous solution contains
The thiocarbamide of 0.01M Gerhardites and 0.05M, the cobalt sulfide hollow pipe that above-mentioned length has CuS seeds is put into containing above-mentioned
In the 100mL reactors of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 8h after reaction terminates, is cooled to room temperature, obtains
Than step 2) darker black thin film, deionized water rinsing sample dries.As shown in figure 18, when the hydro-thermal reaction time by
When the 4h of embodiment 1 increases to 8h, the three dimensional composite structure that CuS nanosheet modifies CoS hollow nanotubes can be equally obtained, its
Difference is that the CuS nanosheet for now obtaining is thicker relative to embodiment 1, and thickness is about 100nm.
Embodiment 6
Repeat the step 1 in embodiment 1) and step 2), prepared cobalt sulfide hollow nanotube is repeated into step
1) magnetron sputtering, obtains the seed of CuS on the hollow pipe of cobalt sulfide.60mL reacting solutions are prepared, the aqueous solution contains
The thiocarbamide of 0.01M Gerhardites and 0.05M, the cobalt sulfide hollow pipe that above-mentioned length has CuS seeds is put into containing above-mentioned
In the 100mL reactors of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 10h after reaction terminates, is cooled to room temperature, obtains
To than step 2) darker black thin film, deionized water rinsing sample dries.As shown in figure 19, the hydro-thermal reaction time is worked as
When increasing to 10h by the 4h of embodiment 1, the three-dimensional composite junction that CuS nanosheet modifies CoS hollow nanotubes can be equally obtained
Structure, its difference is that the CuS nanosheet for now obtaining is very thick relative to embodiment 1, and thickness is up to 200nm.Thus we can
Know, with the lengthening of hydro-thermal time, the CuS nanosheet meeting continued propagation of the hollow pipe surfaces of CoS, its thickness also thickeies therewith.
Claims (10)
- The preparation method of 1.CoS/CuS 3 D stereo nano composite structural materials, it is characterised in that comprise the following steps：1) CuS Seed Layers are prepared：One layer of CuS seed is sputtered in FTO conductive glass surfaces by the method for magnetron sputtering C uS targets Layer；2) CoS hollow nanotube arrays are prepared；3) CoS/CuS 3 D stereo nano composite structural materials are prepared.
- 2. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 1, it is characterised in that in step It is rapid 1) in, vacuum needed for the magnetron sputtering be 1.0 × 103Pa, operating pressure is 2.5Pa, and Ar throughputs are 100sccm, Radio-frequency power is 120W, and sputtering time is 30min.
- 3. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 1, it is characterised in that in step It is rapid 1) in, the size of the FTO electro-conductive glass is 2cm × 1.5cm；The FTO electro-conductive glass is first sequentially placed into acetone, deionization Water, it is each in absolute ethyl alcohol to be cleaned by ultrasonic 15min.
- 4. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 1, it is characterised in that in step It is rapid 2) in, it is described prepare CoS hollow nanotube arrays specific method be：(1) reacting solution is prepared：The reacting solution contains urea and cobalt chloride hexahydrate, by step 1) gained CuS seeds The FTO electro-conductive glass of layer is placed in the reactor for filling the reacting solution, after reaction, is cooled to room temperature, in FTO conduction glass Glass surface obtains one layer of pale pink film, then rinses, and the cobalt sulfide hydrate of nano wire pattern is obtained final product after drying；(2) the nine hydrated sodium sulfide aqueous solution of 0.01M are prepared：By the FTO electro-conductive glass of the cobalt sulfide hydrate of nano wire pattern It is put into the reactor containing reacting solution, after reaction, is cooled to room temperature, one layer of black is obtained in FTO conductive glass surfaces Film, is rinsed, and the cobalt sulfide of hollow Nano tubulose is obtained final product after drying.
- 5. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 4, it is characterised in that in step In rapid 2) (1st) part, the mass percentage concentration of the urea is 6.25%, and cobalt chloride hexahydrate uses the chloride hydrates of 0.15M six Cobalt.
- 6. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 4, it is characterised in that in step In rapid 2) (1st) part, the reaction is to react 3h under conditions of 90 DEG C；The flushing uses deionized water rinsing.
- 7. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 4, it is characterised in that in step In rapid 2) (2nd) part, the reaction is to react 10h under the conditions of 180 DEG C；The flushing deionized water rinsing.
- 8. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 1, it is characterised in that in step It is rapid 3) in, it is described prepare CoS/CuS 3 D stereo nano composite structural materials specific method be：By step 2) prepared by the cobalt sulfide of hollow Nano tubulose repeat step 1) magnetron sputtering, in the sky of cobalt sulfide The seed of CuS is obtained on heart pipe, reacting solution is prepared, the reacting solution contains Gerhardite and thiocarbamide, by institute The hollow pipe that stating length has the cobalt sulfide of CuS seeds is put into after carrying out hydro-thermal reaction in the reactor containing the reacting solution, Room temperature is cooled to, black thin film is obtained, rinsed, the three-dimensional manometer composite junction that CuS nanosheet wraps up CoS empty nanotubes is obtained after drying Structure, i.e. CoS/CuS 3 D stereos nano composite structural material.
- 9. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 1, it is characterised in that in step It is rapid 3) in, the Gerhardite use 0.01M Gerhardites, the thiocarbamide using 0.05M thiocarbamide；The flushing Use deionized water rinsing.
- 10. the preparation method of CoS/CuS 3 D stereos nano composite structural material as claimed in claim 1, it is characterised in that Step 3) in, the temperature of the hydro-thermal reaction is 150 DEG C, and the time of hydro-thermal reaction is 2~10h.
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