CN108305792B - 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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Abstract
A kind of preparation method of sulfide composite nano film, is related to capacitor composite material.Prepare Co9S8Nano whiskers array；Prepare Co9S8- CuS three-dimensional manometer composite construction；Prepare Co9S8‑MoS2Three-dimensional manometer composite construction；Prepare Co9S8‑NiS2Three-dimensional manometer composite construction.By the metal salt of different concentration and ratio and the proportion of thiocarbamide, 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 biggish specific surface area, uniform and stable electric property is applied in supercapacitor 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 technique
Supercapacitor 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 lower, 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 structurre, there is the crystal structure and excellent physical chemistry of multiplicity
Can, be one of the Main way of materials science field development, light, electricity, in terms of have a wide range of applications.(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,
So as to be used to be embedded in host, as modified new material, it is used widely in terms of the electronic devices such as energy storage.
Carbon cloth has reticular structure, excellent electric conductivity and flexibility, is often used as substrate support active material
Electrode is prepared, resulting material can be directly used as the working electrode of supercapacitor, it is not necessary that any adhesive is added, thus
Internal resistance and quality is effectively reduced, is effectively improved the performance of material, plays a significant role to flexible electronic device is prepared.
(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, stable, tactical rule, specific surface area
Big and light weight composite material is most important to the development of electronic device.
Summary of the invention
The purpose of the present invention is to provide gather around well-regulated microscopic appearance, biggish specific surface area and uniform and stable electrical property
A kind of preparation method of sulfide composite nano film of energy.
The present invention the following steps are included:
1) Co is prepared9S8Nano whiskers array；
In step 1), the preparation Co9S8The specific method of nano whiskers array can are as follows: is placed in the carbon cloth after cleaning
Ultrasound in the reaction kettle of reacting solution A is filled, is cooled to room temperature after reaction, obtains one layer of pale pink film 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
Should after be cooled to room temperature, obtain one layer of black thin film in carbon cloth surfaces, then dry to get Co after rinsing9S8Nano whiskers array；
The cleaning can be sequentially placed into acetone, deionized water, respectively be cleaned by ultrasonic 15min in dehydrated alcohol；The carbon cloth size can be 2cm
×3cm；Urea, 0.15M cobalt chloride hexahydrate 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 solution 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 construction；
In step 2), the preparation Co9S8The specific method of-CuS three-dimensional manometer composite construction can are as follows: makes step 1)
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 construction；The reaction
Aqueous solution B contains 0.01M Gerhardite 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 are as follows: 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 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 are as follows: 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 hexahydrate 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 metal salt of different concentration and ratio and the proportion of thiocarbamide
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 biggish 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.
Detailed description of the invention
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 in carbon cloth surfaces by hydro-thermal reaction in embodiment 19S8SEM (the scanning 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 with three-electrode system in the electrolyte of 3M KOH
CV curve under degree.In Fig. 3, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label are as follows:-■-
The CV curve under the scanning speed of 5mV/s ,-●-be the CV curve under the scanning speed of 10mV/s ,-▲-be
CV curve under the scanning speed of 20mV/s ,-▼-they are the CV curves under the scanning speed of 40mV/s ,-◆-it is in 50mV/s
Scanning speed under CV curve.
Fig. 4 is the Co in embodiment 19S8It is close that sample measures different electric currents with three-electrode system in the electrolyte of 3M KOH
Charging and discharging curve under degree.In Fig. 4, abscissa is the time (s), and ordinate is voltage (V)；Each label are as follows:-■-be
1mA*cm-2Scanning speed under charging and discharging curve ,-●-be in 2mA*cm-2Scanning speed under charging and discharging curve ,-▲-
It is in 5mA*cm-2Scanning speed under charging and discharging curve ,-▼-is in 8mA*cm-2Scanning speed under charge and discharge it is bent
Line ,-◆-it is in 10mA*cm-2Scanning speed under charging and discharging curve.
Fig. 5 is in embodiment 2 in carbon cloth surfaces Co9S860mL 0.01M tri- is 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 Fig. 5, scale is 1 μ
m。
Fig. 6 is in embodiment 2 in carbon cloth surfaces Co9S860mL 0.01M tri- is 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 Fig. 6, scale is
200nm。
Fig. 7 is in embodiment 2 in carbon cloth surfaces Co9S860mL 0.01M tri- is 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 Fig. 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 are as follows: ◆ 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 card of standard CuS.
Fig. 8 is the Co in embodiment 29S8- CuS sample measures difference with three-electrode system in the electrolyte of 3M KOH and sweeps
Retouch the CV curve under speed.In fig. 8, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label are as follows:-
■-is the CV curve under the scanning speed of 5mV/s ,-●-be the CV curve under the scanning speed of 10mV/s ,-▲-be
CV curve under the scanning speed of 20mV/s ,-▼-they are the CV curves under the scanning speed of 40mV/s ,-◆-it is in 50mV/s
Scanning speed under CV curve.
Fig. 9 is the Co in embodiment 29S8- CuS sample measures different electricity with three-electrode system in the electrolyte of 3M KOH
Charging and discharging curve under current density.In Fig. 9, abscissa is the time (s), and ordinate is voltage (V).Each label are as follows:-■-is
In 1mA*cm-2Scanning speed under charging and discharging curve ,-●-be in 2mA*cm-2Scanning speed under charging and discharging curve ,-
▲-is in 5mA*cm-2Scanning speed under charging and discharging curve ,-▼-is in 8mA*cm-2Scanning speed under charge and discharge it is bent
Line ,-◆-it is in 10mA*cm-2Scanning speed under charging and discharging curve.
Figure 10 is in embodiment 3 in carbon cloth surfaces Co9S860mL 25mg bis- is 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 Figure 10, scale 1
μm。
Figure 11 is in embodiment 3 in carbon cloth surfaces Co9S860mL 25mg bis- is 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 Figure 11, scale is
200nm。
Figure 12 is in embodiment 3 in carbon cloth surfaces Co9S860mL 25mg bis- is 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 Figure 12, abscissa is 2 times of angle of diffraction (°), is indulged
Coordinate is the relative intensity (a.u.) of diffraction maximum；Each label are as follows: ◆ the diffraction maximum of the carbon cloth substrate of label, -- label is
Co9S8-MoS2XRD spectrum；Vertical line is standard MoS2PDF card corresponding to go out peak position.
Figure 13 is the Co in embodiment 39S8-MoS2Sample measures difference with three-electrode system in the electrolyte of 3M KOH
CV curve under scanning speed.In Figure 13, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label
Are as follows:-■-is the CV curve under the scanning speed of 5mV/s ,-●-it is the CV curve under the scanning speed of 10mV/s ,-▲-
The CV curve under the scanning speed of 20mV/s ,-▼-is the CV curve under the scanning speed of 40mV/s ,-◆-be
CV curve under the scanning speed of 50mV/s.
Figure 14 is the Co in embodiment 39S8-MoS2Sample measures difference with three-electrode system in the electrolyte of 3M KOH
Charging and discharging curve under current density.In Figure 14, abscissa is the time (s), and ordinate is voltage (V)；Each label are as follows:-■-
It is in 1mA*cm-2Scanning speed under charging and discharging curve ,-●-be in 2mA*cm-2Scanning speed under charge and discharge it is bent
Line ,-▲-is in 5mA*cm-2Scanning speed under charging and discharging curve ,-▼-is in 8mA*cm-2Scanning speed under charge and discharge
Electric curve ,-◆-it is in 10mA*cm-2Scanning 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 Figure 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 Figure 17, abscissa is 2 times of angle of diffraction (°),
Ordinate is the relative intensity (a.u.) of diffraction maximum；Each label are as follows: ◆ the diffraction maximum of the carbon cloth substrate of label, -- sign flag
For Co9S8-NiS2XRD spectrum；Vertical line is standard NiS2PDF card corresponding to go out peak position.
Figure 18 is the Co in embodiment 49S8-NiS2Sample measures difference with three-electrode system in the electrolyte of 3M KOH
CV curve under scanning speed.In Figure 18, abscissa is voltage (V), and ordinate is current density (mAcm-2)；Each label
Are as follows:-■-is the CV curve under the scanning speed of 5mV/s ,-●-it is the CV curve under the scanning speed of 10mV/s ,-▲-
The CV curve under the scanning speed of 20mV/s ,-▼-is the CV curve under the scanning speed of 40mV/s ,-◆-be
CV curve under the scanning speed of 50mV/s
Figure 19 is the Co in embodiment 49S8-NiS2Sample measures difference with three-electrode system in the electrolyte of 3M KOH
Charging and discharging curve under current density.In Figure 19, abscissa is the time (s), and ordinate is voltage (V)；Each label are as follows:-■-
It is in 1mA*cm-2Scanning speed under charging and discharging curve ,-●-be in 2mA*cm-2Scanning speed under charge and discharge it is bent
Line ,-▲-is in 5mA*cm-2Scanning speed under charging and discharging curve ,-▼-is in 8mA*cm-2Scanning speed under charge and discharge
Electric curve ,-◆-it is in 10mA*cm-2Scanning speed under charging and discharging curve.
Specific embodiment
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
Embodiment 1
1) Co is prepared9S8Nano whiskers array
60mL reacting solution is 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 kettle 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, obtains the Co of nanoneedle pattern 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 kettle 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: being tested with Chi600e electrochemical workstation, prepares 3M KOH conduct
Electrolyte, three-electrode system, wherein platinum electrode is to electrode, and Hg/HgO electrode is reference electrode, the sample Co of preparation9S8For work
Make electrode.Select different scanning speeds to be tested under CV test pattern, respectively 50mV/s, 40mV/s, 20mV/s,
10mV/s and 5mV/s, as shown in Figure 3.It can be seen that CV curve is the fullest under the test condition of 50mV/s, redox
Current density corresponding to peak is also bigger.With the reduction of scanning 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 process is as follows: being tested with Chi600e electrochemical workstation, prepares 3M KOH as electrolysis
Liquid, three-electrode system, wherein platinum electrode is to electrode, and Hg/HgO electrode is 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 mode, 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 solution is prepared, which contains 0.01M Gerhardite
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 institute
Show, further XRD characterization is it can also be seen that the diffraction maximum of sample is matched with the standard PDF card 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 the 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 solution, 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 reaction 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 MoS is arrived2Nanometer 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 card 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 the 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 solution is prepared, which contains 0.015M Nickel dichloride hexahydrate
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 NiS is arrived2Nano-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 card 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 the 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 metal salt of different concentration and ratio and the proportion of sulphur source
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 column, such structure and morphology rule, and there is big specific surface area, as working electrode material application
In supercapacitor, 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, provide a kind of pervasive side for the preparation of sulfide three-dimensional composite material
Method provides a new thinking simultaneously to prepare advanced composite material (ACM) and device.
Claims (6)
1. a kind of preparation method of sulfide composite nano film, it is characterised in that the following steps are included:
1) Co is prepared9S8Nano whiskers array, method particularly includes: the carbon cloth after cleaning is placed in the reaction for filling reacting solution A
It is ultrasonic in kettle, it is cooled to room temperature after reaction, obtains one layer of pale pink film in carbon cloth surfaces, it is dry after flushing, obtain Co9S8Nanometer
The hydrate of needle-shaped array places into the reaction kettle of Sodium Sulphate Nine Hydroxide aqueous solution, then is cooled to room temperature after reacting, in carbon cloth
Surface obtains one layer of black thin film, then dries after rinsing to get Co9S8Nano whiskers array；The reacting solution A, which is used, to be contained
Having mass ratio is 6.25% urea and 0.15M cobalt chloride hexahydrate；
2) Co is prepared9S8- CuS three-dimensional manometer composite construction, method particularly includes: the Co for preparing step 1)9S8Nano whiskers array
Be put into hydro-thermal reaction in the reaction kettle containing reacting solution B, be cooled to room temperature, obtain black thin film, after flushing dry to get
CuS nanosheet wraps up Co9S8The Co of nanoneedle9S8- CuS three-dimensional manometer composite construction；The reacting solution B contains 0.01M tri-
The thiocarbamide of nitric hydrate copper and 0.05M；
3) Co is prepared9S8-MoS2Three-dimensional manometer composite construction, method particularly includes: by the Co of step 1)9S8Nano whiskers array is put into
It in reaction kettle containing reacting solution C after hydro-thermal reaction, is cooled to room temperature, obtains black thin film, dry after flushing to get MoS2
Nanometer sheet wraps up Co9S8The Co of nanoneedle9S8-MoS2Three-dimensional manometer composite construction；The reacting solution C contains the hydration of 25mg bis-
The thiocarbamide of sodium molybdate and 50mg；
4) Co is prepared9S8-NiS2Three-dimensional manometer composite construction, method particularly includes: by the Co in step 1)9S8Nano whiskers array is put
Enter in the reaction kettle containing reacting solution D after hydro-thermal reaction, is cooled to room temperature, obtains black thin film, it is dry after flushing, it obtains
NiS2Nano particle wraps up Co9S8The Co of nanoneedle9S8-NiS2Three-dimensional manometer composite construction, i.e. sulfide composite nano film；Institute
It states reacting solution D and contains 0.015M Nickel dichloride hexahydrate and the thiocarbamide of 0.15M.
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
Cleaning is stated to be sequentially placed into acetone, deionized water, be respectively cleaned by ultrasonic 15min in dehydrated alcohol；The carbon cloth is having a size of 2cm × 3cm；
The time of the ultrasound is 30min, and the condition of the reaction is to react 3h under conditions of 90 DEG C；The flushing using go from
Sub- water rinses.
3. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 1), institute
Sodium Sulphate Nine Hydroxide aqueous solution is stated using 0.01M Sodium Sulphate Nine Hydroxide aqueous solution；Under the conditions of the condition reacted again is 180 DEG C
React 10h；Described rinse again is rinsed using deionized water.
4. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 2), institute
The temperature for stating hydro-thermal reaction is 150 DEG C, the time 2h of hydro-thermal reaction.
5. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 3), institute
The temperature for stating hydro-thermal reaction is 200 DEG C, and the time of hydro-thermal reaction is for 24 hours.
6. a kind of preparation method of sulfide composite nano film as described in claim 1, it is characterised in that in step 4), institute
The temperature for stating hydro-thermal reaction is 180 DEG C, and the time of hydro-thermal reaction is 2h.
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| CN108821348B (en) * | 2018-09-17 | 2021-02-19 | 陕西科技大学 | Cobalt sulfide nanosheet material and preparation method thereof |
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| CN110391089A (en) * | 2019-08-27 | 2019-10-29 | 信阳学院 | A kind of MoS2@CoS2The preparation method of composite material |
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