CN108305792A - A kind of preparation method of sulfide composite nano film - Google Patents
A kind of preparation method of sulfide composite nano film Download PDFInfo
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- CN108305792A CN108305792A CN201810078681.1A CN201810078681A CN108305792A CN 108305792 A CN108305792 A CN 108305792A CN 201810078681 A CN201810078681 A CN 201810078681A CN 108305792 A CN108305792 A CN 108305792A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of preparation method of sulfide composite nano film, is related to capacitor composite material.Prepare Co9S8Nano whiskers array；Prepare Co9S8CuS three-dimensional manometer composite constructions；Prepare Co9S8‑MoS2Three-dimensional manometer composite construction；Prepare Co9S8‑NiS2Three-dimensional manometer composite construction.By the proportioning of the metal salt and thiocarbamide of different concentration and ratio, reaction time and temperature are controlled by the method for simple hydrothermal synthesis, Co is prepared on carbon cloth9S8‑The three-dimensional manometers composite construction such as CuS prepares various metals sulfide nanostructure package Co9S8The three dimensional composite structure of nano whiskers array, such structure and morphology rule, and there is larger specific surface area, uniform and stable electric property is applied in ultracapacitor as working electrode material, shows excellent electric property.This method has repeatability height, simple operation and other advantages, can be mass-produced.
Description
Technical field
The present invention relates to capacitor composite materials, more particularly, to a kind of preparation side of sulfide composite nano film
Method.
Background technology
Ultracapacitor is a kind of novel energy storage device, with good cycling stability, power density height, Applicable temperature
The advantages that range is wide, but the energy density of presently used low dimensional material electrodes is relatively low, limits its application, it is super to improve
The performance of grade capacitor, the synthesis and design of three-dimensional material are most important.
Transient metal sulfide has 3d valence electron shell structurres, there is various crystal structure and excellent physical chemistry
Can, it is one of the Main way of materials science field development, is had a wide range of applications in light, electricity, catalysis etc..(Pranav
Kulkarni,S.K.Nataraj,R.Geetha Balakrishna,D.H.Nagaraju and
M.V.Reddy.Nanostructured binary and ternary metal sulfides:synthesis methods
and their application in energy conversion and storage
Devices.J.Mater.Chem.A, 2017,5,22040-22094.) such as CuS, NiS2、MoS2A variety of nanostructures are all had,
It is used widely in terms of the electronic devices such as energy storage as modified new material so as to be used for embedded host.
Carbon cloth has reticular structure, excellent electric conductivity and flexibility, is often used as substrate support active material
Electrode is prepared, the material of gained can be directly used as the working electrode of ultracapacitor, it is not necessary that any adhesive is added, to
Internal resistance and quality are effectively reduced, so that the performance of material is effectively improved, plays an important roll to preparing flexible electronic device.
(La Li,Zheng Lou,Di Chen,Kai Jiang,Wei Han,and Guozhen Shen.Recent Advances
in Flexible/Stretchable Supercapacitors for Wearable Electronics.Small 2017,
1702829)
But current electronic device device is limited to the selection of material structure and performance, there is various limitations and lacks
It falls into.Therefore, it seeks a kind of simple pervasive and environmentally protective method and prepares more uniform, stabilization, tactical rule, specific surface area
Big and light weight composite material is most important to the development of electronic device.
Invention content
The purpose of the present invention is to provide gather around well-regulated microscopic appearance, larger specific surface area and uniform and stable electrical property
A kind of preparation method of sulfide composite nano film of energy.
The present invention includes the following steps：
1) Co is prepared9S8Nano whiskers array；
In step 1), the preparation Co9S8The specific method of nano whiskers array can be：Carbon cloth after cleaning is placed in
Ultrasound in the reaction kettle of reacting solution A is filled, reaction postcooling obtains one layer of pale pink film to room temperature in carbon cloth surfaces,
It is dry after flushing, obtain Co9S8The hydrate of nano whiskers array places into the reaction kettle of Sodium Sulphate Nine Hydroxide aqueous solution, then instead
It answers postcooling to room temperature, one layer of black thin film is obtained in carbon cloth surfaces, then dried to get Co after rinsing9S8Nano whiskers array；
The cleaning, which can be sequentially placed into acetone, deionized water, absolute ethyl alcohol, is respectively cleaned by ultrasonic 15min；The carbon cloth size can be 2cm
×3cm；Urea, 0.15M cobalt chloride hexahydrates containing mass ratio for 6.25% can be used in the reacting solution A；The ultrasound
Time can be 30min, the condition of the reaction can be to react 3h under conditions of 90 DEG C；Deionized water can be used in the flushing
It rinses；0.01M Sodium Sulphate Nine Hydroxide aqueous solutions can be used in the Sodium Sulphate Nine Hydroxide aqueous solution；The condition reacted again can be
10h is reacted under the conditions of 180 DEG C；Deionized water flushing can be used in described rinse again；
2) Co is prepared9S8- CuS three-dimensional manometer composite constructions；
In step 2), the preparation Co9S8The specific method of-CuS three-dimensional manometer composite constructions can be：Step 1) is made
Standby Co9S8Nano whiskers array is put into hydro-thermal reaction in the reaction kettle containing reacting solution B, is cooled to room temperature, it is thin to obtain black
Film is dried after flushing and wraps up Co to get CuS nanosheet9S8The Co of nanoneedle9S8- CuS three-dimensional manometer composite constructions；The reaction
Aqueous solution B contains 0.01M Gerhardites and the thiocarbamide of 0.05M, and the temperature of the hydro-thermal reaction is 150 DEG C, hydro-thermal reaction
Time 2h.
3) Co is prepared9S8-MoS2Three-dimensional manometer composite construction；
In step 3), the preparation Co9S8-MoS2The specific method of three-dimensional manometer composite construction can be：By step 1)
Co9S8Nano whiskers array is put into the reaction kettle containing reacting solution C after hydro-thermal reaction, is cooled to room temperature, it is thin to obtain black
Film is dried after flushing to get MoS2Nanometer sheet wraps up Co9S8The Co of nanoneedle9S8-MoS2Three-dimensional manometer composite construction；It is described anti-
Aqueous solution C is answered to contain the thiocarbamide of bis- molybdic acid hydrate sodium and 50mg of 25mg；The temperature of the hydro-thermal reaction can be 200 DEG C, and hydro-thermal is anti-
The time answered can be for 24 hours.
4) Co is prepared9S8-NiS2Three-dimensional manometer composite construction.
In step 4), the preparation Co9S8-NiS2The specific method of three-dimensional manometer composite construction can be：It will be in step 1)
Co9S8Nano whiskers array is put into the reaction kettle containing reacting solution D after hydro-thermal reaction, is cooled to room temperature, is obtained black
Film, it is dry after flushing, obtain NiS2Nano particle wraps up Co9S8The Co of nanoneedle9S8-NiS2Three-dimensional manometer composite construction, i.e. sulphur
Compound composite nano film；The reacting solution D contains 0.015M Nickel dichloride hexahydrates and the thiocarbamide of 0.15M；The hydro-thermal
The temperature of reaction is 180 DEG C, and the time of hydro-thermal reaction is 2h.
The present invention passes through the method for simple hydrothermal synthesis by the proportioning of the metal salt and thiocarbamide of different concentration and ratio
Reaction time and temperature are controlled, Co is prepared on carbon cloth9S8-CuS、Co9S8/MoS2、Co9S8-NiS2Equal three-dimensional manometers composite junction
Structure prepares various metals sulfide nanostructure package Co9S8The three dimensional composite structure of nano whiskers array, the class formation shape
Looks rule, and there is larger specific surface area, uniform and stable electric property is applied to super as working electrode material
In capacitor, excellent electric property is shown.This method has repeatability high, and simple operation and other advantages can be mass-produced,
Preparation for sulfide three-dimensional composite material provides a kind of universal method while providing one to prepare advanced composite material (ACM)
New thinking.
Description of the drawings
Fig. 1 is the Co that carbon cloth surfaces are generated by hydro-thermal reaction in embodiment 19S8SEM (the scanning electricity of nano whiskers array
Mirror) front elevation (amplification factor is 10,000 times).In Fig. 1, scale is 1 μm.
Fig. 2 is the Co generated by hydro-thermal reaction in carbon cloth surfaces in embodiment 19S8SEM (the scannings of nano whiskers array
Electronic Speculum) front elevation (amplification factor is 20,000 times).In fig. 2, scale 200nm.
Fig. 3 is the Co in embodiment 19S8Sample measures different scanning speed in the electrolyte of 3M KOH with three-electrode system
CV curves under degree.In figure 3, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label for：-■-
The CV curves under the sweep speed of 5mV/s ,-●-be the CV curves under the sweep speed of 10mV/s ,-▲-be
CV curves under the sweep speed of 20mV/s ,-▼-they are the CV curves under the sweep speed of 40mV/s ,-◆-it is in 50mV/s
Sweep speed under CV curves.
Fig. 4 is the Co in embodiment 19S8It is close that sample measures different electric currents in the electrolyte of 3M KOH with three-electrode system
Charging and discharging curve under degree.In Fig. 4, abscissa is the time (s), and ordinate is voltage (V)；Each label for：- ■-be
1mA*cm-2Sweep speed under charging and discharging curve ,-●-be in 2mA*cm-2Sweep speed under charging and discharging curve ,-▲-
It is in 5mA*cm-2Sweep speed under charging and discharging curve ,-▼-is in 8mA*cm-2Sweep speed under charge and discharge it is bent
Line ,-◆-it is in 10mA*cm-2Sweep speed under charging and discharging curve.
Fig. 5 is in embodiment 2 in carbon cloth surfaces Co9S860mL 0.01M tri- are added on the basis of nano whiskers array to be hydrated
The aqueous solution of the thiocarbamide of copper nitrate and 0.05M, hydrothermal temperature are that the CuS nanosheet that reaction 2h is obtained at 150 DEG C modifies Co9S8It receives
The SEM (scanning electron microscope) of the three-dimensional manometer composite construction of the needle-shaped array of rice (amplification factor is 10,000 times).In Figure 5, scale is 1 μ
m。
Fig. 6 is in embodiment 2 in carbon cloth surfaces Co9S860mL 0.01M tri- are added on the basis of nano whiskers array to be hydrated
The aqueous solution of the thiocarbamide of copper nitrate and 0.05M, hydrothermal temperature are that the CuS nanosheet that reaction 2h is obtained at 150 DEG C modifies Co9S8It receives
The SEM (scanning electron microscope) of the three-dimensional manometer composite construction of the needle-shaped array of rice (amplification factor is 20,000 times).In figure 6, scale is
200nm。
Fig. 7 is in embodiment 2 in carbon cloth surfaces Co9S860mL 0.01M tri- are added on the basis of nano whiskers array to be hydrated
The aqueous solution of the thiocarbamide of copper nitrate and 0.05M, hydrothermal temperature are that the CuS nanosheet that reaction 2h is obtained at 150 DEG C modifies Co9S8It receives
The XRD characterization result of the three-dimensional manometer composite construction of the needle-shaped array of rice.In the figure 7, abscissa is 2 times of angle of diffraction (°), indulges and sits
It is designated as the relative intensity (a.u.) of diffraction maximum；Each label for：◆ the diffraction maximum of the carbon cloth substrate of sign flag, -- sign flag
For Co9S8The XRD spectrum of-CuS；Vertical line is to go out peak position corresponding to the PDF cards of standard CuS.
Fig. 8 is the Co in embodiment 29S8- CuS samples measure difference with three-electrode system in the electrolyte of 3M KOH and sweep
Retouch the CV curves under speed.In fig. 8, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label for：-
■-is the CV curves under the sweep speed of 5mV/s ,-●-be the CV curves under the sweep speed of 10mV/s ,-▲-be
CV curves under the sweep speed of 20mV/s ,-▼-they are the CV curves under the sweep speed of 40mV/s ,-◆-it is in 50mV/s
Sweep speed under CV curves.
Fig. 9 is the Co in embodiment 29S8- CuS samples measure different electricity in the electrolyte of 3M KOH with three-electrode system
Charging and discharging curve under current density.In fig.9, abscissa is the time (s), and ordinate is voltage (V).Each label for：- ■-is
In 1mA*cm-2Sweep speed under charging and discharging curve ,-●-be in 2mA*cm-2Sweep speed under charging and discharging curve ,-
▲-is in 5mA*cm-2Sweep speed under charging and discharging curve ,-▼-is in 8mA*cm-2Sweep speed under charge and discharge it is bent
Line ,-◆-it is in 10mA*cm-2Sweep speed under charging and discharging curve.
Figure 10 is in embodiment 3 in carbon cloth surfaces Co9S860mL 25mg bis- are added on the basis of nano whiskers array to be hydrated
The aqueous solution of the thiocarbamide of sodium molybdate and 50mg, hydrothermal temperature are to react the MoS obtained for 24 hours at 200 DEG C2Nanometer sheet modifies Co9S8It receives
The SEM (scanning electron microscope) of the three-dimensional manometer composite construction of the needle-shaped array of rice (amplification factor is 10,000 times).In Fig. 10, scale 1
μm。
Figure 11 is in embodiment 3 in carbon cloth surfaces Co9S860mL 25mg bis- are added on the basis of nano whiskers array to be hydrated
The aqueous solution of the thiocarbamide of sodium molybdate and 50mg, hydrothermal temperature are to react the MoS obtained for 24 hours at 200 DEG C2Nanometer sheet modifies Co9S8It receives
The SEM (scanning electron microscope) of the three-dimensional manometer composite construction of the needle-shaped array of rice (amplification factor is 20,000 times).In fig. 11, scale is
200nm。
Figure 12 is in embodiment 3 in carbon cloth surfaces Co9S860mL 25mg bis- are added on the basis of nano whiskers array to be hydrated
The aqueous solution of the thiocarbamide of sodium molybdate and 50mg, hydrothermal temperature are to react the MoS obtained for 24 hours at 200 DEG C2Nanometer sheet modifies Co9S8It receives
The XRD characterization result of the three-dimensional manometer composite construction of the needle-shaped array of rice.In fig. 12, abscissa is 2 times of angle of diffraction (°), is indulged
Coordinate is the relative intensity (a.u.) of diffraction maximum；Each label for：◆ the diffraction maximum of the carbon cloth substrate of label, -- label is
Co9S8-MoS2XRD spectrum；Vertical line is standard MoS2PDF cards corresponding to go out peak position.
Figure 13 is the Co in embodiment 39S8-MoS2Sample measures difference in the electrolyte of 3M KOH with three-electrode system
CV curves under sweep speed.In fig. 13, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label
For：- ■-is the CV curves under the sweep speed of 5mV/s ,-●-it is the CV curves under the sweep speed of 10mV/s ,-▲-
The CV curves under the sweep speed of 20mV/s ,-▼-is the CV curves under the sweep speed of 40mV/s ,-◆-be
CV curves under the sweep speed of 50mV/s.
Figure 14 is the Co in embodiment 39S8-MoS2Sample measures difference in the electrolyte of 3M KOH with three-electrode system
Charging and discharging curve under current density.In fig. 14, abscissa is the time (s), and ordinate is voltage (V)；Each label for：-■-
It is in 1mA*cm-2Sweep speed under charging and discharging curve ,-●-be in 2mA*cm-2Sweep speed under charge and discharge it is bent
Line ,-▲-is in 5mA*cm-2Sweep speed under charging and discharging curve ,-▼-is in 8mA*cm-2Sweep speed under charge and discharge
Electric curve ,-◆-it is in 10mA*cm-2Sweep speed under charging and discharging curve.
Figure 15 is in embodiment 4 in carbon cloth surfaces Co9S8Six water of 60mL 0.015M is added on the basis of nano whiskers array
The aqueous solution of nickel chloride and the thiocarbamide of 0.15M is closed, hydrothermal temperature is the NiS that reaction 2h is obtained at 180 DEG C2Nanometer sheet modifies Co9S8
The SEM (scanning electron microscope) of the three-dimensional manometer composite construction of nano whiskers array (amplification factor is 10,000 times).In fig.15, scale
It is 1 μm.
Figure 16 is in embodiment 4 in carbon cloth surfaces Co9S8Six water of 60mL 0.015M is added on the basis of nano whiskers array
The aqueous solution of nickel chloride and the thiocarbamide of 0.15M is closed, hydrothermal temperature is the NiS that reaction 2h is obtained at 180 DEG C2Nanometer sheet modifies Co9S8
The SEM (scanning electron microscope) of the three-dimensional manometer composite construction of nano whiskers array (amplification factor is 20,000 times).In figure 16, scale
For 200nm.
Figure 17 is in embodiment 4 in carbon cloth surfaces Co9S8Six water of 60mL 0.015M is added on the basis of nano whiskers array
The aqueous solution of nickel chloride and the thiocarbamide of 0.15M is closed, hydrothermal temperature is the NiS that reaction 2h is obtained at 180 DEG C2Nanometer sheet modifies Co9S8
The XRD characterization result of the three-dimensional manometer composite construction of nano whiskers array.In fig. 17, abscissa is 2 times of angle of diffraction (°),
Ordinate is the relative intensity (a.u.) of diffraction maximum；Each label for：◆ the diffraction maximum of the carbon cloth substrate of label, -- sign flag
For Co9S8-NiS2XRD spectrum；Vertical line is standard NiS2PDF cards corresponding to go out peak position.
Figure 18 is the Co in embodiment 49S8-NiS2Sample measures difference in the electrolyte of 3M KOH with three-electrode system
CV curves under sweep speed.In figure 18, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label
For：- ■-is the CV curves under the sweep speed of 5mV/s ,-●-it is the CV curves under the sweep speed of 10mV/s ,-▲-
The CV curves under the sweep speed of 20mV/s ,-▼-is the CV curves under the sweep speed of 40mV/s ,-◆-be
CV curves under the sweep speed of 50mV/s
Figure 19 is the Co in embodiment 49S8-NiS2Sample measures difference in the electrolyte of 3M KOH with three-electrode system
Charging and discharging curve under current density.In Figure 19, abscissa is the time (s), and ordinate is voltage (V)；Each label for：-■-
It is in 1mA*cm-2Sweep speed under charging and discharging curve ,-●-be in 2mA*cm-2Sweep speed under charge and discharge it is bent
Line ,-▲-is in 5mA*cm-2Sweep speed under charging and discharging curve ,-▼-is in 8mA*cm-2Sweep speed under charge and discharge
Electric curve ,-◆-it is in 10mA*cm-2Sweep speed under charging and discharging curve.
Specific implementation mode
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
Embodiment 1
1) Co is prepared9S8Nano whiskers array
60mL reacting solutions are prepared, which contains the Urea (urea) of 6.25wt%, 0.15M Co (Cl)2·6H2O (six
Hydrated cobalt chloride), the carbon cloth that step 1) is cleaned ultrasound 30min in above-mentioned reacting solution keeps its surface and solution complete
Full connected is subsequently placed in the 100mL reaction kettles containing above-mentioned reaction solution, is reacted 3h under the conditions of 90 DEG C, is cooled to room temperature,
One layer of pale pink film is obtained in carbon cloth surfaces, with deionized water lavage specimens product, the Co of nanoneedle pattern is obtained after dry9S8It receives
The hydrate of the needle-shaped array of rice.
The Sodium Sulphate Nine Hydroxide aqueous solution for preparing 60mL 0.01M, by Co obtained above9S8The hydration of nano whiskers array
Object 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, in carbon cloth table
Face obtains one layer of black thin film, is rinsed with deionized water, dry, obtains Co9S8Nano whiskers array.As shown in Figure 1, 2, made
Standby Co9S8For array-like structure, in the radial uniform growth of carbon cloth surfaces, diameter is about 200nm, and length is about 3 μ
m。
2) sample of preparation is subjected to cyclic voltammetric (CV) and charge-discharge test.
Cyclic voltammetric (CV) testing process is as follows:It is tested with Chi600e electrochemical workstations, prepares 3M KOH conducts
Electrolyte, three-electrode system, wherein platinum electrode are to electrode, and Hg/HgO electrodes are reference electrode, the sample Co of preparation9S8For work
Make electrode.Select different sweep speeds to be tested under CV test patterns, respectively 50mV/s, 40mV/s, 20mV/s,
10mV/s and 5mV/s, as shown in Figure 3.It can be seen that CV curves are the fullest under the test condition of 50mV/s, redox
Current density corresponding to peak is also bigger.With the reduction of sweep speed, curve narrows, and oxidation peak moves to left, and reduction peak moves to right, right
The current density answered also becomes smaller.
Charge-discharge test flow is as follows：It is tested with Chi600e electrochemical workstations, prepares 3M KOH as electrolysis
Liquid, three-electrode system, wherein platinum electrode are to electrode, and Hg/HgO electrodes are reference electrode, the sample Co of preparation9S8For work electricity
Pole.Different charging and discharging currents density is selected to be tested under charge-discharge test pattern, respectively 10mA*cm-2、8mA*cm-2、5mA*cm-2、2mA*cm-2And 1mA*cm-2.As shown in figure 4, in 10mA*cm-2Test condition under the charge and discharge time quickly,
And with the reduction of charging and discharging currents density, the charge and discharge time is constantly elongated, in 1mA*cm-2Under conditions of discharge time be about
150s。
Embodiment 2
Repeat the 1 of embodiment 1) step, 60mL reacting solutions are prepared, which contains 0.01M Gerhardites
With the thiocarbamide of 0.05M, by above-mentioned with Co9S8It is anti-that the carbon cloth of nanometer needle construction is put into the 100mL containing above-mentioned reacting solution
It answers in kettle, reacts 2h under the conditions of 150 DEG C, after reaction, be cooled to room temperature, obtain more darker than embodiment a sample
Black thin film, deionized water rinses sample, dry to modify Co to get to CuS nanosheet9S8The three dimensional composite structure of nano whiskers.
As shown in Figure 5,6, it can be seen that CuS nanosheet is evenly distributed on Co9S8Array surrounding, length are about 300nm.Such as Fig. 7 institutes
Show, further XRD characterization is it can also be seen that the diffraction maximum of sample is matched with the standard PDF cards of CuS.
Repeat the 2 of embodiment 1) step, as shown in figure 8, it can be seen that Co from cyclic voltammetry curve9S8The CV of-CuS is bent
The corresponding current density of redox peaks of line is much larger than single Co9S8Structure.As shown in figure 9, from charge-discharge performance test
As can be seen that it is in 1mA*cm-2Under conditions of discharge time be about 200s, also superior to the performance of single structure.
Embodiment 3
Repeat embodiment 1 1) step, prepare 60mL reacting solutions, the aqueous solution contain bis- molybdic acid hydrate sodium of 25mg and
The thiocarbamide of 50mg, by above-mentioned with Co9S8The carbon cloth of nanometer needle construction is put into the reactions of the 100mL containing above-mentioned reacting solution
In kettle, reacts for 24 hours under the conditions of 200 DEG C, after reaction, be cooled to room temperature, obtain more darker than embodiment a sample
Black thin film, deionized water rinse sample, dry to get to MoS2Nanometer sheet modifies Co9S8The three-dimensional composite junction of nano whiskers
Structure.As shown in FIG. 10 and 11, MoS2Nanometer sheet is uniformly evenly distributed on Co9S8Array surrounding, length are about 50nm.Such as figure
Shown in 12, further XRD characterization it can also be seen that sample diffraction maximum and MoS2Standard PDF cards matching.
Repeat the 2 of embodiment 1) step, as shown in figure 13, it can be seen that Co from cyclic voltammetry curve9S8-MoS2CV
The corresponding current density of redox peaks of curve is much larger than single Co9S8Structure.As shown in figure 14, it is surveyed from charge-discharge performance
As can be seen that it is in 1mA*cm in examination-2Under conditions of discharge time be about 200s, also superior to the performance of single structure.
Embodiment 4
Repeat the 1 of embodiment 1) step, 60mL reacting solutions are prepared, which contains 0.015M Nickel dichloride hexahydrates
With the thiocarbamide of 0.15M, by above-mentioned with Co9S8It is anti-that the carbon cloth of nanometer needle construction is put into the 100mL containing above-mentioned reacting solution
It answers in kettle, reacts 2h under the conditions of 180 DEG C, after reaction, be cooled to room temperature, obtain more darker than embodiment a sample
Black thin film, deionized water rinse sample, dry to get to NiS2Nano-particle modified Co9S8The three-dimensional composite junction of nano whiskers
Structure.As shown in figs, NiS2Nanometer sheet is uniformly evenly distributed on Co9S8Array surrounding, size are about 100nm.Such as figure
Shown in 17, further XRD characterization it can also be seen that sample diffraction maximum and NiS2Standard PDF cards matching.
Repeat the 2 of embodiment 1) step, as shown in figure 18, it can be seen that Co from cyclic voltammetry curve9S8-NiS2CV
The corresponding current density of redox peaks of curve is not only much larger than single Co9S8Structure, and it is higher than Co9S8- CuS and
Co9S8-MoS2.As shown in figure 19, as can be seen that it is in 1mA*cm from charge-discharge performance test-2Under conditions of discharge time
About 500s, performance is best in the composite material of preparation.
The present invention passes through the method for simple hydrothermal synthesis by the proportioning of the metal salt and sulphur source of different concentration and ratio
Reaction time and temperature are controlled, various metals sulfide nanostructure package Co is prepared in carbon cloth substrate9S8Nano whiskers battle array
The three dimensional composite structure of row, such structure and morphology rule, and there is big specific surface area, as working electrode material application
In ultracapacitor, excellent electric property is shown, wherein with Co9S8-NiS2Performance is especially prominent.The present invention has weight
Renaturation height, simple operation and other advantages, can be mass-produced, a kind of pervasive side is provided for the preparation of sulfide three-dimensional composite material
Method provides a new thinking to prepare advanced composite material (ACM) and device simultaneously.
Claims (10)
1. a kind of preparation method of sulfide composite nano film, it is characterised in that include the following steps：
1) Co is prepared9S8Nano whiskers array；
2) Co is prepared9S8- CuS three-dimensional manometer composite constructions；
3) Co is prepared9S8-MoS2Three-dimensional manometer composite construction；
4) Co is prepared9S8-NiS2Three-dimensional manometer composite construction.
2. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 1), institute
It states and prepares Co9S8The specific method of nano whiskers array is：Carbon cloth after cleaning is placed in the reaction kettle for filling reacting solution A
Middle ultrasound, reaction postcooling obtains one layer of pale pink film to room temperature in carbon cloth surfaces, dry after flushing, obtains Co9S8Nanoneedle
The hydrate of shape array places into the reaction kettle of Sodium Sulphate Nine Hydroxide aqueous solution, then reacts postcooling to room temperature, in carbon cloth table
Face obtains one layer of black thin film, then is dried to get Co after rinsing9S8Nano whiskers array.
3. a kind of preparation method of sulfide composite nano film as claimed in claim 2, it is characterised in that the cleaning is successively
It is put into acetone, deionized water, absolute ethyl alcohol and is respectively cleaned by ultrasonic 15min；The carbon cloth size can be 2cm × 3cm；The reaction
Urea, 0.15M cobalt chloride hexahydrates containing mass ratio for 6.25% can be used in water solution A；The time of the ultrasound can be
30min, the condition of the reaction can be to react 3h under conditions of 90 DEG C；Deionized water flushing can be used in the flushing.
4. a kind of preparation method of sulfide composite nano film as claimed in claim 2, it is characterised in that the nine hydrations sulphur
Change sodium water solution and uses 0.01M Sodium Sulphate Nine Hydroxide aqueous solutions；The condition reacted again reacts 10h under the conditions of being 180 DEG C；Institute
It states to rinse again and be rinsed using deionized water.
5. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 2), institute
It states and prepares Co9S8The specific method of-CuS three-dimensional manometer composite constructions is：Co prepared by step 1)9S8Nano whiskers array is put
Enter hydro-thermal reaction in the reaction kettle containing reacting solution B, be cooled to room temperature, obtain black thin film, is dried to get CuS after flushing
Nanometer sheet wraps up Co9S8The Co of nanoneedle9S8- CuS three-dimensional manometer composite constructions.
6. a kind of preparation method of sulfide composite nano film as claimed in claim 5, it is characterised in that the reaction is water-soluble
Liquid B contains 0.01M Gerhardites and the thiocarbamide of 0.05M, and the temperature of the hydro-thermal reaction is 150 DEG C, hydro-thermal reaction when
Between 2h.
7. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 3), institute
It states and prepares Co9S8-MoS2The specific method of three-dimensional manometer composite construction is：By the Co of step 1)9S8Nano whiskers array, which is put into, to be contained
Have in the reaction kettle of reacting solution C after hydro-thermal reaction, be cooled to room temperature, obtain black thin film, is dried to get MoS after flushing2It receives
Rice piece wraps up Co9S8The Co of nanoneedle9S8-MoS2Three-dimensional manometer composite construction.
8. a kind of preparation method of sulfide composite nano film as claimed in claim 7, it is characterised in that the reaction is water-soluble
Liquid C contains the thiocarbamide of bis- molybdic acid hydrate sodium and 50mg of 25mg；The temperature of the hydro-thermal reaction is 200 DEG C, the time of hydro-thermal reaction
For for 24 hours.
9. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 4), institute
It states and prepares Co9S8-NiS2The specific method of three-dimensional manometer composite construction is：By the Co in step 1)9S8Nano whiskers array is put into
It in reaction kettle containing reacting solution D after hydro-thermal reaction, is cooled to room temperature, obtains black thin film, it is dry after flushing, obtain NiS2
Nano particle wraps up Co9S8The Co of nanoneedle9S8-NiS2Three-dimensional manometer composite construction, i.e. sulfide composite nano film.
10. a kind of preparation method of sulfide composite nano film as claimed in claim 9, it is characterised in that the reaction is water-soluble
Liquid D contains 0.015M Nickel dichloride hexahydrates and the thiocarbamide of 0.15M；The temperature of the hydro-thermal reaction be 180 DEG C, hydro-thermal reaction when
Between be 2h.
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| CN111362320A (en) * | 2020-03-13 | 2020-07-03 | 江西师范大学 | Loaded nickel sulfide nanorod material and preparation method and application thereof |
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| CN112110489A (en) * | 2020-09-24 | 2020-12-22 | 西北大学 | Micro-spherical CuS-MoS2Method for preparing composite material |
| CN112110489B (en) * | 2020-09-24 | 2021-09-03 | 西北大学 | Micro-spherical CuS-MoS2Method for preparing composite material |
| CN113223869A (en) * | 2021-04-15 | 2021-08-06 | 山东科技大学 | Three-dimensional porous nanoflower-like NiS2Preparation and application of/carbon cloth composite material |
| CN113223869B (en) * | 2021-04-15 | 2023-03-03 | 山东科技大学 | Three-dimensional porous nanoflower-like NiS 2 Preparation and application of/carbon cloth composite material |
| CN114496593A (en) * | 2021-12-28 | 2022-05-13 | 哈尔滨工程大学 | Preparation method of PANI array/CuS @ fCC composite electrode material |
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