CN106847519B - 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 PDF

Info

Publication number
CN106847519B
CN106847519B CN201710244436.9A CN201710244436A CN106847519B CN 106847519 B CN106847519 B CN 106847519B CN 201710244436 A CN201710244436 A CN 201710244436A CN 106847519 B CN106847519 B CN 106847519B
Authority
CN
China
Prior art keywords
cus
cos
composite structural
nano composite
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201710244436.9A
Other languages
Chinese (zh)
Other versions
CN106847519A (en
Inventor
叶美丹
洪晓丹
刘群
高晓月
贺春锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN201710244436.9A priority Critical patent/CN106847519B/en
Publication of CN106847519A publication Critical patent/CN106847519A/en
Application granted granted Critical
Publication of CN106847519B publication Critical patent/CN106847519B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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.It is assisted by magnetron sputtering, with reference to the method for simple hydrothermal synthesis, prepares the three dimensional composite structure of CuS nanosheet package CoS hollow nanotubes, this kind of structure and morphology rule, and there is big specific surface area.It is applied in quantum dot sensitized solar cell as to electrode material, shows excellent electrocatalysis characteristic.This method has repeatability height, simple operation and other advantages, and combines physics and chemical means, can be mass-produced, a new thinking is provided to prepare new material.

Description

The preparation method of CoS/CuS 3 D stereo nano composite structural materials
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 is because it is with a variety of chemical compositions, various crystal structure, complicated microscopic appearance so that they Possess good physics and chemical characteristic, have good application prospect in field of electronic devices, especially it is as to electrode material Material is applied to quantum dot sensitized solar cell (QDSSCs), thus is 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 in field of photovoltaic devices, just by people probed by the material important as one.CuS With relatively narrow band gap width (1.1-1.4eV), higher absorption coefficient (104cm-1), it is a kind of material of asepsis environment-protecting low consumption Material, and CuS has different microscopic appearances, such as nanometer sheet, nanotube, nanometer rods etc., is a kind of efficient QDSSCs To electrode material.CoS is a kind of promising to electricity because it has good electro catalytic activity in polysulfide electrolyte 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 pass through chemical bath deposition (CBD) method synthesize CoS nanometer sheets and CuS nano wires accumulation structure it is not uniform enough, it is not big enough with the active area of electrolyte contacts, can influence To the catalytic activity of electrode material.Therefore, seek simple environmentally protective method prepare more uniformly, stabilization, tactical rule, Large specific surface area it is most important to the development of quantum dot sensitized solar cell to electrode material.
Invention content
There are rule to electrode material the purpose of the present invention is to provide prepared CoS/CuS three-dimensional manometer composite constructions The features such as microscopic appearance then, bigger serface, excellent catalytic activity, and preparation method it is simple it is controllable, environmentally protective, reappear The preparation method of the high CoS/CuS 3 D stereo nano composite structural materials of property.
The present invention includes 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), vacuum degree 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 For 2cm × 1.5cm；The FTO electro-conductive glass is preferably first sequentially placed into acetone, deionized water, is respectively cleaned by ultrasonic in absolute ethyl alcohol 15min。
In step 2), 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 CuS obtained by step 1) The FTO electro-conductive glass of Seed Layer is placed in the reaction kettle 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, up to the cobalt sulfide hydrate of nano wire pattern after drying；
In step 2) (1) 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；Deionized water flushing can be used in the flushing.
(2) the nine hydrated sodium sulfide aqueous solutions of 0.01M are prepared：The FTO of the cobalt sulfide hydrate of nano wire pattern is conductive Glass is put into the reaction kettle containing reacting solution, after reaction, is cooled to room temperature, and one layer is obtained in FTO conductive glass surfaces Black thin film rinses, up to the cobalt sulfide of hollow Nano tubulose after drying.
In step 2) (2) part, the reaction can react 10h under the conditions of 180 DEG C；The flushing can use deionization Water rinses.
In step 3), it is described prepare CoS/CuS 3 D stereo nano composite structural materials specific method can be：
The cobalt sulfide of hollow Nano tubulose prepared by step 2) is repeated to the magnetron sputtering of step 1), in cobalt sulfide Hollow pipe on obtain the seed of CuS, prepare reacting solution, the reacting solution contains Gerhardite and thiocarbamide, The hollow pipe of the cobalt sulfide with CuS seeds is put into the reaction kettle containing the reacting solution and carries out hydro-thermal reaction Afterwards, it is cooled to room temperature, obtains black thin film, rinse, the three-dimensional manometer that CuS nanosheet package CoS empty nanotubes are obtained after dry is answered Close structure, i.e. CoS/CuS 3 D stereos nano composite structural material；The Gerhardite can be used 0.01M tri- and be hydrated nitre The thiocarbamide of 0.05M can be used in sour copper, the thiocarbamide；The flushing can be rinsed with deionized water；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 assisted by magnetron sputtering, with reference to the method for simple hydrothermal synthesis, prepares CuS nanosheet package CoS The three dimensional composite structure of hollow nanotube, this kind of structure and morphology rule, and with big specific surface area.It is answered as to electrode material For in quantum dot sensitized solar cell, showing excellent electrocatalysis characteristic.This method has repeated high, easy to operate The advantages that, and physics and chemical means are combined, it can be mass-produced, a new think of is provided to prepare new material Road.
Description of the drawings
Fig. 1 be the FTO glass surfaces of blank in embodiment 1 SEM (scanning electron microscope) front elevation (amplification factor be 30,000 Times).In Fig. 1, scale 200nm.
Fig. 2 is in SEM (scanning electricity of the FTO glass surfaces with CuS Seed Layers in embodiment 1 by magnetically controlled sputter method Mirror) front elevation (amplification factor is 10,000 times).In fig. 2, scale is 1.00 μm.
Fig. 3 be embodiment 1 in the FTO glass with CuS Seed Layers 60mL contain 6.25wt% Urea (urea) and 0.15M Co(Cl)2·.12The aqueous solution of O (cobalt chloride hexahydrate), hydrothermal temperature are the cobalt sulfide that reaction 3h is obtained at 90 DEG C SEM (scanning electron microscope) front elevation of hydrate (amplification 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 with cobalt sulfide in embodiment 1 In aqueous solution, hydrothermal temperature is that SEM (scanning electron microscope) front elevation of CoS hollow nanotubes that reaction 10h is obtained 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 embodiment 1 in the CoS hollow nanotubes with CuS seeds 60mL contain 0.01M Gerhardites and The aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature are that the CuS nanosheet that reaction 4h is obtained at 150 DEG C modifies CoS hollow nanotubes SEM (scanning electron microscope) front elevation of three-dimensional manometer composite construction (amplification factor is 1.5 ten thousand times).In Figure 5, scale is 2.00 μ m。
Fig. 6 be embodiment 1 in the CoS hollow nanotubes with CuS seeds 60mL contain 0.01M Gerhardites and The aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature are that the CuS nanosheet that reaction 4h is obtained at 150 DEG C modifies CoS hollow nanotubes SEM (scanning electron microscope) side view of three-dimensional manometer composite construction (amplification factor is 8.00 thousand times).In figure 6, scale is 2.00 μ m。
Fig. 7 be embodiment 1 in the CoS hollow nanotubes with CuS seeds 60mL contain 0.01M Gerhardites and The aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature are that the CuS nanosheet that reaction 4h is obtained at 150 DEG C modifies CoS hollow nanotubes three Tie up TEM (transmission electron microscope) front elevation of nano composite structure (amplification factor is 40,000 times).In the figure 7, scale 100nm.
Fig. 8 is the partial enlarged view of Fig. 7 samples in embodiment 1 (amplification factor is 800,000 times).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 51/nm.
Figure 10 is that the CoS hollow nanotubes with CuS seeds contain 0.01M Gerhardites in 60mL in embodiment 1 With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet that reaction 4h is obtained at 150 DEG C modifies CoS hollow nanotubes 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 For the diffraction maximum of CoS hollow nanotubes, ▲ label 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 is to go out peak position corresponding to the PDF cards of standard CoS.
Figure 11 is to be assembled in embodiment 1 by the use of Fig. 6 samples with reference to tradition Pt and CoS and CuS samples as to electrode material 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), label-◆-for tradition Pt to the J-V curves of electrode ,-▲-is CoS samples J-V curves, the J-V curves of-■-be CuS samples ,-●-J-V curves for being Fig. 6 samples CoS/CuS.
Figure 12 is to become the resistance that Symmetrical cells carry out electrochemical impedance test with three sample assemblies in Figure 11 in embodiment 1 Anti- energy spectrum diagram (i.e. Nquist spectrograms).In fig. 12, abscissa Z ' (Ω), ordinate are-Z " (Ω), label-◆-it is traditional For Pt to the Nquist spectrograms of electrode ,-▲-is the Nquist spectrograms of CoS samples, the Nquist spectrums of-■-be CuS samples Figure ,-●-Nquist spectrograms for being Fig. 6 samples CoS/CuS.
Figure 13 is the cyclic voltammetry curve (i.e. CV curves) that Fig. 6 samples enclose cyclic voltammetries by 500 in embodiment 1. In fig. 13, abscissa is voltage (V), and ordinate is current density (mAcm-2)。
Figure 14 is the Tafel polarization curves measured in embodiment 1 with Fig. 6 sample assemblies as Symmetrical cells.In fig. 14, Abscissa is voltage (V), and ordinate is the logarithm of current density.
Figure 15 is that the CoS hollow nanotubes with CuS seeds contain 0.01M Gerhardites in 60mL in embodiment 2 With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet that do not formed that reaction 1h is obtained at 150 DEG C modifies CoS skies SEM (scanning electron microscope) front elevation of the three dimensional composite structure of heart nanotube (amplification factor is 30,000 times).In fig.15, scale is 200nm。
Figure 16 is that the CoS hollow nanotubes with CuS seeds contain 0.01M Gerhardites in 60mL in embodiment 3 With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet that reaction 2h is obtained at 150 DEG C modifies CoS hollow nanotubes Three dimensional composite structure SEM (scanning electron microscope) front elevation (amplification factor be 1.5 ten thousand times).In figure 16, scale is 2.00 μm.
Figure 17 is that the CoS hollow nanotubes with CuS seeds contain 0.01M Gerhardites in 60mL in embodiment 4 With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet that reaction 6h is obtained at 150 DEG C modifies CoS hollow nanotubes Three dimensional composite structure SEM (scanning electron microscope) front elevation (amplification factor be 1.5 ten thousand times).In fig. 17, scale is 1.00 μm.
Figure 18 is that the CoS hollow nanotubes with CuS seeds contain 0.01M Gerhardites in 60mL in embodiment 5 With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet that reaction 8h is obtained at 150 DEG C modifies CoS hollow nanotubes Three dimensional composite structure SEM (scanning electron microscope) front elevation (amplification factor be 1.5 ten thousand times).In figure 18, scale is 1 μm.
Figure 19 is that the CoS hollow nanotubes with CuS seeds contain 0.01M Gerhardites in 60mL in embodiment 6 With the aqueous solution of the thiocarbamide of 0.05M, hydrothermal temperature is that the CuS nanosheet that reaction 10h is obtained at 150 DEG C modifies CoS hollow Nanos SEM (scanning electron microscope) front elevation of the three dimensional composite structure of pipe (amplification 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 successively in acetone, deionized water, absolute ethyl alcohol and is surpassed respectively Sound cleans 15min, and it is spare to be put in 60 DEG C of oven dryings.Clean FTO electro-conductive glass is put into magnetron sputtering reaction cavity, is treated true Reciprocal of duty cycle reaches 1.0 × 103Pa is passed through argon gas, and operating pressure is made to reach 2.5Pa, and control throughput is 100sccm, adjusts radio frequency Power is to 120W, after pre-sputtering 10min, opens baffle, and CuS, sputtering time 30min are sputtered in FTO conductive glass surfaces.Such as Shown in Fig. 1, clean FTO conductive glass surfaces surround and watch pattern as graininess；As shown in Fig. 2, the FTO tables with 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, which contains the Urea (urea) of 6.25wt%, 0.15M Co (Cl)2·6H2O (six Hydrated cobalt chloride), the obtained FTO electro-conductive glass conduction with CuS Seed Layers of step 1) is placed on containing upper down In the 100mL reaction kettles for stating reaction solution, 3h is reacted at 90 DEG C, is 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 dry.As shown in figure 3, gained The hydrate of the cobalt sulfide arrived is solid nano thread structure, and diameter is about 200nm, and length is about 3 μm.
The nine hydrated sodium sulfide aqueous solutions of 60mL 0.01M are prepared again, by obtained above with cobalt sulfide hydrate FTO electro-conductive glass is put into the 100mL reaction kettles containing reacting solution, is reacted 10h 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, is rinsed with deionized water, it is dry, 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 of CuS nanosheet modification CoS hollow nanotubes is prepared
Cobalt sulfide hollow nanotube prepared by step 2) is repeated to the magnetron sputtering of step 1), in the sky of cobalt sulfide The seed of CuS is obtained on heart pipe.60mL reacting solutions are prepared, which contains 0.01M Gerhardites and 0.05M The above-mentioned cobalt sulfide hollow pipe with CuS seeds is put into the 100mL reaction kettles containing above-mentioned reacting solution by thiocarbamide, 4h is reacted under the conditions of 150 DEG C, after reaction, is cooled to room temperature, obtains the black thin film more darker than step 2), go from Sub- water rinses sample, dry to get the three dimensional composite structure that CoS hollow nanotubes are modified to CuS nanosheet.It as shown in figure 5, can It observes, CuS nanosheet is staggeredly uniformly coated on CoS nanotube surfaces, whole that cylindrical-shaped structure is presented.Shown in fig. 6 section Face figure provides it can also be seen that prepared cylindric CoS/CuS growths interlaced with each other for its catalysis reaction in the electrolytic solution 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 different lattice fringes, passes through measurement, it is known that interplanar distance is 0.568nm and 0.303nm corresponds to the CuS nanosheet of CoS hollow pipes and (102) crystal face respectively.Fig. 9 selective electron diffraction light It is fine that spot further illustrates prepared sample crystallization.Further XRD characterization result figure 10, which more demonstrates, passes through this Kind magnetron sputtering physical means successfully prepare the composite construction of CoS/CuS with hydro-thermal reaction chemical means.
Using above-mentioned sample as quantum dot sensitized solar cell to electrode material, it is assembled into the quantum dot sensitized sun It can battery.Light anode preparation process used is as follows：By 0.5g P25 powder, (i.e. PEG, molal weight are 0.5g polyethylene glycol 20000) it is dissolved into 1mL deionized waters and 1mL absolute ethyl alcohol mixed liquors, slurry is made in stirring 3h.In 2cm × 1.5cm FTO Seamless adhesive tape is sticked to control thicknesses of layers in surface, scratches prepared slurry by the method for blade coating and is 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 carries out TiCl4Processing, will The sample of taking-up is immersed in 0.2M TiCl4In aqueous solution, 40min is reacted at 70 DEG C, then handle in 450 DEG C of air anneals 30min.The deposition that CdS and CdSe is 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 containing 20mM CdCl2, 66mM NH4Cl, 140mM thiocarbamide and 230mM ammonium hydroxide in the aqueous solution that pH value is about 9.50, is put in 10 DEG C of refrigerator and stands 80min, treats after reaction, to take out Sample is simultaneously rinsed with deionized water, obtains the light anode of the CdS quantum dot sensitization of yellow green.B) deposition of CdSe quantum dot：Match Na processed2SeSO30.1M Se powder is dissolved in 0.18M Na by aqueous solution2SO3Solution 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 one water of 0.16M nitrilotriacetic acid trisodium Close object (Na3NTA) the aqueous solution of mixing, with Na2SeSO3Aqueous 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, treats after reaction, to be rinsed with deionized water, in air Naturally dry is to get the light anode being sensitized altogether to CdS/CdSe quantum dots.Electricity used in assembling quantum dot sensitization solar battery Solution liquid is contains 0.5M Na2(the two volume ratio is 3/ for the methanol of S, 0.125M S and 0.2M KCl and the mixed liquor of deionized water 7) it is heat that, heat-sealing film thickness used, which is 60,.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 measured Line) see Figure 11.By table 1 and Figure 11 it is found that 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) for 0.51V, fill factor 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) it improves a lot.
Table 1 is the performance parameter with the corresponding batteries of Figure 11 in embodiment 1.Wherein Jsc represents density of photocurrent, unit For mA/cm2；Voc represents photovoltage, unit V；FF represents fill factor；η represents battery efficiency, unit %；Rs, RctFor The parameter that Figure 13 impedance curves are fitted, unit are Ω, wherein RsRepresent battery system resistance, RctIt represents to electricity Pole/electrolyte interface resistance.
Table 1
The cyclic voltammetric (C-V) of Figure 12, which is tested, to be 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 are used as to electrode, and the CoS/CuS of preparation is carried out as working electrode with Chi600e electrochemical workstations Test, electrolyte use and include 0.5M Na2The methanol of S, 0.125M S and 0.2M KCl and mixed liquor (the two of deionized water 3/7) volume ratio is.EIS impedance spectras shown in Figure 13 show that CoS/CuS sandwiches have the resistance of very little, in electricity Electronics can be transmitted faster in solution liquid.The Tafel polarization curves of Figure 14 show that sample has good electrochemical catalysis activity.
Embodiment 2
The step 1) and step 2) in embodiment 1 are repeated, 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, which contains The above-mentioned cobalt sulfide hollow pipe with CuS seeds is put into containing above-mentioned by the thiocarbamide of 0.01M Gerhardites and 0.05M In the 100mL reaction kettles of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 1h after reaction, is cooled to room temperature, obtains The black thin film more darker than step 2), deionized water rinses sample, dry.As shown in figure 15, when the hydro-thermal reaction time by When the 4h of embodiment 1 shortens to 1h, there is no the three dimensional composite structure for forming CuS modification CoS hollow nanotubes, mainly due to anti- Too short between seasonable, CuS fully grows up to the pattern of nanometer sheet not yet.
Embodiment 3
The step 1) and step 2) in embodiment 1 are repeated, 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, which contains The above-mentioned cobalt sulfide hollow pipe with CuS seeds is put into containing above-mentioned by the thiocarbamide of 0.01M Gerhardites and 0.05M In the 100mL reaction kettles of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 2h after reaction, is cooled to room temperature, obtains The black thin film more darker than step 2), deionized water rinses sample, dry.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 of CuS nanosheet modification CoS hollow nanotubes can be equally obtained, Difference lies in the CuS nanosheet obtained at this time 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
The step 1) and step 2) in embodiment 1 are repeated, 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, which contains The above-mentioned cobalt sulfide hollow pipe with CuS seeds is put into containing above-mentioned by the thiocarbamide of 0.01M Gerhardites and 0.05M In the 100mL reaction kettles of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 6h after reaction, is cooled to room temperature, obtains The black thin film more darker than step 2), deionized water rinses sample, dry.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 of CuS nanosheet modification CoS hollow nanotubes can be equally obtained, Difference lies in the CuS nanosheet obtained at this time is thicker relative to embodiment 1, and thickness is about tens nanometers.
Embodiment 5
The step 1) and step 2) in embodiment 1 are repeated, 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, which contains The above-mentioned cobalt sulfide hollow pipe with CuS seeds is put into containing above-mentioned by the thiocarbamide of 0.01M Gerhardites and 0.05M In the 100mL reaction kettles of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 8h after reaction, is cooled to room temperature, obtains The black thin film more darker than step 2), deionized water rinses sample, dry.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 of CuS nanosheet modification CoS hollow nanotubes can be equally obtained, Difference lies in the CuS nanosheet obtained at this time is thicker relative to embodiment 1, and thickness is about 100nm.
Embodiment 6
The step 1) and step 2) in embodiment 1 are repeated, 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, which contains The above-mentioned cobalt sulfide hollow pipe with CuS seeds is put into containing above-mentioned by the thiocarbamide of 0.01M Gerhardites and 0.05M In the 100mL reaction kettles of reacting solution, under the conditions of 150 DEG C, hydro-thermal reaction 10h after reaction, is cooled to room temperature, obtains To the black thin film more darker than step 2), deionized water rinses sample, dry.As shown in figure 19, work as the hydro-thermal reaction time When increasing to 10h by the 4h of embodiment 1, the three-dimensional composite junction of CuS nanosheet modification CoS hollow nanotubes can be equally obtained Structure, difference lies in the CuS nanosheet obtained at this time 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, thickness also thickeies therewith.

Claims (8)

  1. The preparation method of 1.CoS/CuS 3 D stereo nano composite structural materials, it is characterised in that include 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, specific method is：
    (1) reacting solution is prepared：The reacting solution contains urea and cobalt chloride hexahydrate, by CuS seeds obtained by step 1) The FTO electro-conductive glass of layer is placed in the reaction kettle 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, up to the cobalt sulfide hydrate of nano wire pattern after drying；
    (2) the nine hydrated sodium sulfide aqueous solutions 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 reaction kettle containing nine hydrated sodium sulfide solution, after reaction, is cooled to room temperature, one is obtained in FTO conductive glass surfaces Layer black thin film, is rinsed, up to the cobalt sulfide of hollow Nano tubulose after drying；
    3) CoS/CuS 3 D stereo nano composite structural materials are prepared, specific method is：
    The cobalt sulfide of hollow Nano tubulose prepared by step 2) is repeated to the magnetron sputtering of step 1), in the sky of cobalt sulfide The seed of CuS is obtained on heart pipe, prepares reacting solution, the reacting solution contains Gerhardite and thiocarbamide, by institute The hollow pipe for stating the cobalt sulfide with CuS seeds is put into the reaction kettle containing the reacting solution after progress hydro-thermal reaction, It is cooled to room temperature, obtains black thin film, rinse, the three-dimensional manometer composite junction of CuS nanosheet package CoS empty nanotubes is obtained after dry Structure, i.e. CoS/CuS 3 D stereos nano composite structural material.
  2. 2. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described in claim 1, it is characterised in that in step It is rapid 1) in, vacuum degree needed for the magnetron sputtering be 1.0 × 103Pa, operating pressure 2.5Pa, Ar throughput are 100sccm, Radio-frequency power is 120W, sputtering time 30min.
  3. 3. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described 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 is respectively cleaned by ultrasonic 15min in absolute ethyl alcohol.
  4. 4. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described in claim 1, it is characterised in that in step In rapid 2) (1) part, the mass percentage concentration of the urea is 6.25%, and the concentration of cobalt chloride hexahydrate is 0.15M.
  5. 5. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described in claim 1, it is characterised in that in step In rapid 2) (1) part, the reaction is to react 3h under conditions of 90 DEG C；Described rinse is rinsed using deionized water.
  6. 6. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described in claim 1, it is characterised in that in step In rapid 2) (2) part, the reaction is to react 10h under the conditions of 180 DEG C；The flushing is rinsed with deionized water.
  7. 7. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described in claim 1, it is characterised in that in step It is rapid 3) in, the concentration of the Gerhardite is 0.01M, and the concentration of the thiocarbamide is 0.05M；The flushing deionized water It rinses.
  8. 8. the preparation method of CoS/CuS 3 D stereos nano composite structural material as described in claim 1, it is characterised in that in step It is rapid 3) in, the temperature of the hydro-thermal reaction is 150 DEG C, and the time of hydro-thermal reaction is 2~10h.
CN201710244436.9A 2017-04-14 2017-04-14 The preparation method of CoS/CuS 3 D stereo nano composite structural materials Expired - Fee Related CN106847519B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710244436.9A CN106847519B (en) 2017-04-14 2017-04-14 The preparation method of CoS/CuS 3 D stereo nano composite structural materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710244436.9A CN106847519B (en) 2017-04-14 2017-04-14 The preparation method of CoS/CuS 3 D stereo nano composite structural materials

Publications (2)

Publication Number Publication Date
CN106847519A CN106847519A (en) 2017-06-13
CN106847519B true CN106847519B (en) 2018-06-26

Family

ID=59147671

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710244436.9A Expired - Fee Related CN106847519B (en) 2017-04-14 2017-04-14 The preparation method of CoS/CuS 3 D stereo nano composite structural materials

Country Status (1)

Country Link
CN (1) CN106847519B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109100055A (en) * 2018-08-27 2018-12-28 厦门大学 A kind of preparation method of sulphide-oxide composite Nano pressure sensor

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110282663B (en) * 2019-08-06 2020-06-02 厦门大学 Method for preparing nano materials with different dimensions based on same metal iron ions
CN111321424B (en) * 2020-03-04 2022-04-19 太原理工大学 Preparation method of self-supporting high-density copper-cobalt-selenium nanotube electrode
CN112174190B (en) * 2020-09-07 2022-10-04 湖北大学 Preparation method of copper sulfide composite material
CN112466668B (en) * 2020-12-04 2022-06-10 福州大学 Tungsten sulfide-doped cobalt sulfide copper counter electrode catalyst with hollow nanotube structure and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2230702A1 (en) * 2009-03-19 2010-09-22 Ecole Polytechnique Fédérale de Lausanne (EPFL) Modified surface
CN103117173B (en) * 2013-03-11 2016-02-10 武汉大学 Can two-sided enter the quantum dot sensitized solar cell and preparation method thereof of light

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109100055A (en) * 2018-08-27 2018-12-28 厦门大学 A kind of preparation method of sulphide-oxide composite Nano pressure sensor

Also Published As

Publication number Publication date
CN106847519A (en) 2017-06-13

Similar Documents

Publication Publication Date Title
CN106847519B (en) The preparation method of CoS/CuS 3 D stereo nano composite structural materials
Kumar et al. Zinc oxide nanostructure-based dye-sensitized solar cells
Xu et al. Co-Fe-MoSx hollow nanoboxes as high-performance counter electrode catalysts for Pt-free dye-sensitized solar cells
Gopi et al. ZnO nanorods decorated with metal sulfides as stable and efficient counter-electrode materials for high-efficiency quantum dot-sensitized solar cells
Ye et al. In situ growth of CuS and Cu 1.8 S nanosheet arrays as efficient counter electrodes for quantum dot-sensitized solar cells
Chen et al. Rational design and fabrication of skeletal Cu7S4 nanocages for efficient counter electrode in quantum dot-sensitized solar cells
Sun et al. Morphology-tunable synthesis of ZnO nanoforest and its photoelectrochemical performance
Li et al. Carbon quantum dots decorated Cu 2 S nanowire arrays for enhanced photoelectrochemical performance
Ren et al. Photoelectrochemical water splitting strongly enhanced in fast-grown ZnO nanotree and nanocluster structures
Zhu et al. Controllable synthesis of ZnO nanograss with different morphologies and enhanced performance in dye-sensitized solar cells
Zhou et al. Copper selenide (Cu 3 Se 2 and Cu 2− x Se) thin films: electrochemical deposition and electrocatalytic application in quantum dot-sensitized solar cells
Mao et al. Synthesis and photoelectrochemical cell properties of vertically grown α-Fe 2 O 3 nanorod arrays on a gold nanorod substrate
Chen et al. In situ synthesis of two-dimensional leaf-like Cu 2 ZnSnS 4 plate arrays as a Pt-free counter electrode for efficient dye-sensitized solar cells
Yao et al. Chemical bath deposition synthesis of TiO2/Cu2O core/shell nanowire arrays with enhanced photoelectrochemical water splitting for H2 evolution and photostability
Wang et al. Recent advances in counter electrodes of quantum dot-sensitized solar cells
Wu et al. Co/Se and Ni/Se nanocomposite films prepared by magnetron sputtering as counter electrodes for dye-sensitized solar cells
Yao et al. In situ fabrication of Co0. 85Se and Ni0. 85Se hierarchical thin films as high-performance counter electrode for dye-sensitized solar cells
Guo et al. Hierarchical TiO 2–CuInS 2 core–shell nanoarrays for photoelectrochemical water splitting
Kim et al. Cost-effective and morphology controllable PVP based highly efficient CuS counter electrodes for high-efficiency quantum dot-sensitized solar cells
Chen et al. Size-controllable synthesis of NiCoSe 2 microspheres as a counter electrode for dye-sensitized solar cells
Goh et al. Low temperature grown ZnO@ TiO2 core shell nanorod arrays for dye sensitized solar cell application
Lu et al. Electrodeposition of hierarchical ZnO nanorod arrays on flexible stainless steel mesh for dye-sensitized solar cell
Jo et al. Enhanced electrocatalytic activity and electrochemical stability of Cu2S/PbS counter electrode for quantum-dot-sensitized solar cells
Rao et al. A hydrothermal reaction combined with a post anion-exchange reaction of hierarchically nanostructured NiCo 2 S 4 for high-performance QDSSCs and supercapacitors
Rao et al. Enhancing the photovoltaic performance and stability of QDSSCs using surface reinforced Pt nanostructures with controllable morphology and superior electrocatalysis via cost-effective chemical bath deposition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180626

Termination date: 20190414

CF01 Termination of patent right due to non-payment of annual fee