CN105261489B - A kind of PPy/MoS2/Ni3S2The preparation method and application of composite - Google Patents
A kind of PPy/MoS2/Ni3S2The preparation method and application of composite Download PDFInfo
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- CN105261489B CN105261489B CN201510752176.7A CN201510752176A CN105261489B CN 105261489 B CN105261489 B CN 105261489B CN 201510752176 A CN201510752176 A CN 201510752176A CN 105261489 B CN105261489 B CN 105261489B
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- nickel foam
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- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 46
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 206
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 70
- 239000006260 foam Substances 0.000 claims abstract description 56
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 27
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229920000128 polypyrrole Polymers 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 46
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000005215 recombination Methods 0.000 claims description 4
- 230000006798 recombination Effects 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 65
- 229910021641 deionized water Inorganic materials 0.000 description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 44
- 238000001035 drying Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 thio sulphur Chemical compound 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of PPy/MoS2/Ni3S2The preparation method and application of composite.The present invention forms a strata pyrroles by the way that in hydrochloric acid solution or hypo solution, pyrrole monomer polymerize on the surface of nickel foam in the foam nickel surface that cleans up, then by itself and MoO3, thiocarbamide the aqueous solution carry out chemical liquid deposition reaction, so as to obtain the PPy/MoS of wire2/Ni3S2Composite.Its preparation technology is simple, with low cost, and the one-dimensional appearance structure with overlength, superior performance, is provided simultaneously with that specific capacitance is big, the performance of good cycling stability, can be used as the electrode material of ultracapacitor.
Description
Technical field
Composite technology of preparing and electrochemistry crossing domain of the present invention, and in particular to a kind of PPy/MoS2/Ni3S2It is compound
The preparation method and application of material.
Background technology
In the sulfide of transition metal, because it has unique physics and chemical property, thus in catalysis, electrification
The field such as and gas sensor has a wide range of applications, so as to cause the high interest of people.Conducting polymer is due to it
High-energy-density, low cost, be readily synthesized, good heat endurance and it is environment-friendly the features such as, be also research focus.But
It is that the composite of transient metal sulfide and conducting polymer few is reported.
The content of the invention
The invention provides a kind of PPy/MoS2/Ni3S2The preparation method of composite, the present invention utilizes liquid phase synthesizing method
Prepare PPy/ MoS2/Ni3S2Composite.Its preparation technology is simple, with low cost, and the one-dimensional pattern knot with overlength
Structure, superior performance.
Present invention also offers PPy/MoS2/Ni3S2Composite as electrode material for super capacitor application.
The technical scheme that the present invention takes is：
A kind of PPy/MoS2/Ni3S2Composite, the composite is by pyrrole monomer in hydrochloric acid solution or thio sulphur
Surface in acid sodium solution in nickel foam polymerize, in foam nickel surface one strata pyrroles of formation, then by itself and MoO3, thiocarbamide
The aqueous solution of composition carries out chemical liquid deposition reaction and is made.
The invention also discloses a kind of PPy/MoS2/Ni3S2The preparation method of composite, the preparation method include with
Lower step：
(a) nickel foam is cleaned；
(b) nickel foam and pyrroles's stirring reaction in reaction solution after cleaning, clean, dry, obtaining surface recombination has poly-
The nickel foam of pyrroles；
(c) surface recombination is had to nickel foam, the MoO of polypyrrole3, thiocarbamide react in aqueous, clean, dry, you can
PPy/ MoS are made2/Ni3S2Composite.
Reaction time in the step (b) is 8~16 hours.
Reaction solution in the step (b) is the thiosulfuric acid that PH is less than that 7 hydrochloric acid solution or concentration are 1.6~1.7g/L
Sodium solution.
In the step (b), the mass concentration of pyrroles is 10~20mg/ml, the top surface area of nickel foam and reaction solution
The ratio between volume is 6cm2：(25~90) ml.
Reaction temperature in the step (c) is 155-170 DEG C, and the time is 10-12h；Preferably reaction temperature is 160
DEG C, time 11.5h.
In the step (c), MoO3, thiocarbamide mass concentration be respectively 1.0~1.5mg/mL, 2.0~2.5mg/mL；Bubble
The ratio between the top surface area of foam nickel and the volume of the aqueous solution are 6cm2：(25~40) ml；Preferably, MoO3, thiocarbamide mass concentration point
Wei not 1.3~1.5mg/mL, 2.0~2.2 mg/mL；The ratio between the top surface area of nickel foam and the volume of the aqueous solution are 6cm2：
30ml。
The PPy/MoS2/Ni3S2Composite is linear nano structure.
Present invention also offers the PPy/MoS prepared by the preparation method2/Ni3S2Composite is used as super electricity
The application of container electrode material.PPy/MoS2/Ni3S2Composite possesses that specific capacitance is big, the performance of good cycling stability, can use
Make the electrode material of ultracapacitor.
The present invention is by the way that in hydrochloric acid solution or hypo solution, pyrrole monomer occurs poly- on the surface of nickel foam
Close, in the foam nickel surface one strata pyrroles of formation cleaned up, then by itself and MoO3, thiocarbamide the aqueous solution carry out chemical liquid phase
Deposition reaction, so as to obtain the PPy/ MoS of wire2/Ni3S2Composite.
PPy/MoS disclosed by the invention2/Ni3S2The preparation method of composite, be it is a kind of it is simple to operate, with low cost,
Mild condition, the chemical liquid deposition of environmental protection.Any stabilizer, template or table need not be added during the course of the reaction
Face activating agent, the convenient post-treatment of product, it is easy to which size and pattern to material regulate and control, are adapted to large-scale production.
PPy/MoS disclosed by the invention2/Ni3S2PPy/MoS made from the preparation method of composite2/Ni3S2Composite wood
Material is the electrode material of the ultracapacitor of excellent performance, under 1A/g current densities, PPy/MoS2/Ni3S2The ratio of composite
Electric capacity can reach 2213.2F/g；After 3000 cycle charge-discharges, PPy/MoS2/Ni3S2The electric capacity of composite still with just
Beginning electric capacity is identical, illustrates PPy/MoS2/Ni3S2Composite has good stability.
Brief description of the drawings
The PPy/MoS that Fig. 1 is prepared for implementation 12/Ni3S2SEM (SEM) figure of composite；
The PPy/MoS that Fig. 2 is prepared for implementation 12/Ni3S2Transmission electron microscope (TEM) figure of composite；
The PPy/MoS that Fig. 3 is prepared for implementation 12/Ni3S2X-ray power spectrum (EDX) figure of composite；
The PPy/MoS that Fig. 4 is prepared for implementation 12/Ni3S2X-ray photoelectron spectroscopy (XPS) figure of composite；
The PPy/MoS that Fig. 5 is prepared for implementation 12/Ni3S2X-ray diffraction pattern (XRD) figure of composite；
Fig. 6 is to implement 1 PPy/MoS prepared2/Ni3S2Composite exchanges resistance before discharge and recharge with after 100 circle circulations
Anti- curve；
Fig. 7 is to implement 1 PPy/MoS prepared2/Ni3S2The cyclic voltammetry curve of composite；
The PPy/MoS that Fig. 8 is prepared for implementation 12/Ni3S2Constant current charge-discharge of the composite under different current densities is bent
Line；
Fig. 9 is to implement 1 PPy/MoS prepared2/Ni3S2Composite circulation-specific capacitance when current density is 4A/g is bent
Line.
Embodiment
Nickel foam, pyrroles used in the present invention, MoO3, thiocarbamide can be from the market sale producer be directly commercially available.
Embodiment 1
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 15min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 250mL beakers, adds the hydrochloric acid solution 90ml that PH is 3, stirring is added
1mL pyrroles, persistently stirs 12h, is rinsed respectively with deionized water and absolute ethyl alcohol after the completion of reaction, and 60 DEG C of drying, polypyrrole is multiple
Condensation material one；
(c) MoO is sequentially added in a kettle.3After 40mg, thiocarbamide 60mg, 30mL deionized water stirring 15min, add
Composite one made from step (b), 12h is reacted at 160 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 2
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 100mL beakers, adds the hydrochloric acid solution 65ml that PH is 4, stirring is added
1mL pyrroles, persistently stirs 14h, takes out nickel sheet and is rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain composite
One.
(c) MoO is sequentially added in a kettle.3After 43mg, thiocarbamide 65mg, 30mL deionized water stirring 15min, add
Composite one made from step (b), 11.5h is reacted at 160 DEG C.Cooling uses deionized water and absolute ethyl alcohol respectively after taking out
Washing 3 times, 60 DEG C of drying.
Embodiment 3
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 250mL beakers, adds the hydrochloric acid solution 50ml that PH is 5, stirring is added
1mL pyrroles, persistently stirs 13h, takes out nickel sheet and is rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain composite
One.
(c) MoO is sequentially added in a kettle.3After 38.5mg, thiocarbamide 62mg, 30mL deionized water stirring 20min, plus
Enter composite one made from step (b), 12h is reacted at 160 DEG C.Cooling uses deionized water and absolute ethyl alcohol respectively after taking out
Washing 3 times, 60 DEG C of drying.
Embodiment 4
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 100mL beakers, adds the hydrochloric acid solution 30ml that PH is 1.5, stirring adds
Enter 0.6mL pyrroles, persistently stir 8h, take out nickel sheet and rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain composite wood
Material one.
(c) MoO is sequentially added in a kettle.3After 40mg, thiocarbamide 66mg, 30mL deionized water stirring 20min, add
Composite one made from step (b), 10h is reacted at 160 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 5
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 15min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 200mL beakers, adds the hydrochloric acid solution 85ml that PH is 6.5, stirring adds
Enter 0.85mL pyrroles, persistently stir 16h, take out nickel sheet and rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain compound
Material one.
(c) MoO is sequentially added in a kettle.3After 42mg, thiocarbamide 61mg, 30mL deionized water stirring 20min, add
Composite one made from step (b), 11h is reacted at 160 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 6
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 15min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 100mL beakers, adds the hydrochloric acid solution 40ml that PH is 2.5, stirring adds
Enter 0.8mL pyrroles, persistently stir 10h, take out nickel sheet and rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain compound
Material one.
(c) MoO is sequentially added in a kettle.3After 42mg, thiocarbamide 61mg, 30mL deionized water stirring 20min, add
Composite one made from step (b), 11h is reacted at 160 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 7
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 15min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 100mL beakers, adds the hydrochloric acid solution 20ml that PH is 0..5, stirring
0.2mL pyrroles is added, 8h is persistently stirred, nickel sheet is taken out and is rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain compound
Material one.
(c) MoO is sequentially added in a kettle.3After 39mg, thiocarbamide 62.5mg, 30mL deionized water stirring 20min, plus
Enter composite one made from step (b), 11h is reacted at 160 DEG C.Cooling uses deionized water and absolute ethyl alcohol respectively after taking out
Washing 3 times, 60 DEG C of drying.
Embodiment 8
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 15min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 250mL beakers, adds the hydrochloric acid solution 90ml that PH is 3, stirring is added
1mL pyrroles, persistently stirs 12h, is rinsed respectively with deionized water and absolute ethyl alcohol after the completion of reaction, and 60 DEG C of drying, polypyrrole is multiple
Condensation material one；
(c) MoO is sequentially added in a kettle.3After 25mg, thiocarbamide 50mg, 25mL deionized water stirring 15min, add
Composite one made from step (b), 12h is reacted at 155 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 9
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 100mL beakers, adds the hydrochloric acid solution 65ml that PH is 4, stirring is added
1mL pyrroles, persistently stirs 14h, takes out nickel sheet and is rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain composite
One.
(c) MoO is sequentially added in a kettle.3After 52.5mg, thiocarbamide 80.5mg, 35mL deionized water stirring 15min,
Composite one made from adding step (b), 11.5h is reacted at 165 DEG C.Cooling uses deionized water and nothing respectively after taking out
Water-ethanol is washed 3 times, 60 DEG C of drying.
Embodiment 10
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam after cleaning is positioned in 250mL beakers, adds the hydrochloric acid solution 50ml that PH is 5, stirring is added
1mL pyrroles, persistently stirs 13h, takes out nickel sheet and is rinsed respectively with deionized water and absolute ethyl alcohol, 60 DEG C of drying obtain composite
One.
(c) MoO is sequentially added in a kettle.3After 52mg, thiocarbamide 80mg, 40mL deionized water stirring 20min, add
Composite one made from step (b), 12h is reacted at 170 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 11
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam is put into 100ml beakers, adds deionized water 30mL, sodium thiosulfate 0.05g, stirring is added
Pyrroles 0.3mL, and nickel foam in step 1, persistently stir 15h.Take out nickel sheet to be rinsed with deionized water and absolute ethyl alcohol respectively, 60
DEG C drying.
(c) MoO is sequentially added in a kettle.3After 45mg, thiocarbamide 63.5mg, 30mL deionized water stirring 15min, plus
Enter composite one made from step (b), 12h is reacted at 160 DEG C.Cooling uses deionized water and absolute ethyl alcohol respectively after taking out
Washing 3 times, 60 DEG C of drying.
Embodiment 12
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam is put into 100ml beakers, adds deionized water 50mL, sodium thiosulfate 0.08g, stirring is added
Pyrroles 0.5mL, and nickel foam in step 1, persistently stir 10h.Take out nickel sheet to be rinsed with deionized water and absolute ethyl alcohol respectively, 60
DEG C drying.
(c) MoO is sequentially added in a kettle.3After 40mg, thiocarbamide 60mg, 30mL deionized water stirring 15min, add
Composite one made from step (b), 12h is reacted at 160 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 13
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam is put into 100ml beakers, adds deionized water 80mL, sodium thiosulfate 0.13g, stirring is added
Pyrroles 1mL, and nickel foam in step 1, persistently stir 8h.Take out nickel sheet to be rinsed with deionized water and absolute ethyl alcohol respectively, 60 DEG C
Drying.
(c) MoO is sequentially added in a kettle.3After 45mg, thiocarbamide 63.5mg, 30mL deionized water stirring 15min, plus
Enter composite one made from step (b), 12h is reacted at 160 DEG C.Cooling uses deionized water and absolute ethyl alcohol respectively after taking out
Washing 3 times, 60 DEG C of drying.
Embodiment 14
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam is put into 100ml beakers, adds deionized water 20mL, sodium thiosulfate 0.032g, stirring is added
Pyrroles 0.4mL, and nickel foam in step 1, persistently stir 15h.Take out nickel sheet to be rinsed with deionized water and absolute ethyl alcohol respectively, 60
DEG C drying.
(c) MoO is sequentially added in a kettle.3After 45mg, thiocarbamide 80mg, 40mL deionized water stirring 15min, add
Composite one made from step (b), 12h is reacted at 170 DEG C.Cooling is washed with deionized water and absolute ethyl alcohol respectively after taking out
Wash 3 times, 60 DEG C of drying.
Embodiment 15
A kind of PPy/MoS2/Ni3S2The preparation method of composite, comprises the following steps：
(a) nickel foam (2 × 3cm) is successively cleaned by ultrasonic 10min with absolute ethyl alcohol and deionized water；
(b) nickel foam is put into 100ml beakers, adds deionized water 90mL, sodium thiosulfate 0.15g, stirring is added
Pyrroles 0.9mL, and nickel foam in step 1, persistently stir 15h.Take out nickel sheet to be rinsed with deionized water and absolute ethyl alcohol respectively, 60
DEG C drying.
(c) MoO is sequentially added in a kettle.3After 37.5mg, thiocarbamide 50mg, 25mL deionized water stirring 15min, plus
Enter composite one made from step (b), 10h is reacted at 170 DEG C.Cooling uses deionized water and absolute ethyl alcohol respectively after taking out
Washing 3 times, 60 DEG C of drying.
Embodiment 16
PPy/MoS2/Ni3S2The sign of composite：
(1) morphology analysis is carried out to the products therefrom of embodiment 1 with SEM (SEM), as a result as shown in figure 1,
Show the nanostructured that prepared sample is wire.
(2) the products therefrom composition of embodiment 1 is analyzed with X-ray energy spectrum (EDX), as a result as shown in Figure 2.Show
MoS in the sample2, Ni3S2, pyrroles can couple well.
(3) gained of embodiment 1 is analyzed product elemental chemical valence with x-ray photoelectron power spectrum (XPS), as a result such as
Fig. 3, the chemical valence of molybdenum element is+4, and corresponding compound should be MoS2；The chemical valence of nickel element is+2, and corresponding compound should
For Ni3S2；The functional group of pyrroles can also be detected well.So the compound that can draw the gained of embodiment 1 is PPy/
MoS2/Ni3S2Composite.
(4) implement 1 products therefrom with X-ray diffraction (XRD) detection, as a result marked as shown in figure 4, obtaining collection of illustrative plates with JCPDS
Ni corresponding to quasi- card NO.44-14183S2Diffraction maximum and the MoS corresponding to JCPDS standard cards NO.37-14922Spread out
Peak is penetrated to fit like a glove.The diffraction maximum for being PPy in the diffraction maximum of 17 degree or so appearance, this XRD can be very good to prove the material
For PPy/MoS2/Ni3S2Composite.
Embodiment 17
A kind of PPy/MoS2/Ni3S2Composite as electrode material for super capacitor application.
Test instrument is CHI660E electrochemical workstations, the manufacture of Shanghai Chen Hua Instrument Ltd. below.
Test below and use three-electrode system, wherein, PPy/MoS prepared by embodiment 12/Ni3S2Composite, cuts
Into 1cm × 1cm sizes, working electrode is used as；Using platinum electrode and saturated calomel electrode (SCE) as to electrode and ginseng
Compare electrode；Electrolyte is used as using 3M NaOH solutions.
(1) electrochemical impedance spectroscopy is tested
PPy/MoS is drawn by electrochemical impedance spectroscopy2/Ni3S2Composite electrode 100 circles before and after discharge and recharge fill
Ac impedance spectroscopy after electric discharge, as shown in fig. 6,0 represents PPy/MoS2/Ni3S2Friendship before composite electrode discharge and recharge
Flow impedance curve, 100 represent PPy/ MoS2/Ni3S2AC impedance curve when the circle charge and discharge cycles of nano line electrode 100.
Ac impedance spectroscopy is divided into high frequency region part and low frequency range part, by the arc and low frequency range of one section of semicircle of high frequency region
A skew lines composition.It is PPy/MoS in the intersection point of high frequency region impedance spectrum and real axis2/Ni3S2The internal resistance of composite electrode,
Include the contact resistance of active material resistance in itself, the resistance of electrolyte and active material and electrolyte.Can be with high frequency region
It was found that PPy/MoS2/Ni3S2Curve approximation when composite electrode is before discharge and recharge and after 100 cycle charge-discharges,
Electrode material of the curve of high frequency region before discharge and recharge and after cycle charge-discharge closer to excellent ultracapacitor,
It has been indicated above PPy/MoS2/Ni3S2Nano line electrode can as ultracapacitor electrode material.
(2) cyclic voltammetry (CV) is tested
Respectively with 10mV s-1、20mV s-1、50mV s-1With 100mV s-1Sweep speed be scanned, draw embodiment
PPy/ MoS in 12/Ni3S2The cyclic voltammetry curve of composite as shown in fig. 7, the curve potential range for 0v~
0.5V。
(3) chronoptentiometry (CP) is tested
Respectively in 1A g-1、2Ag-1、3Ag-1With 4A g-1Lower progress constant current charge-discharge detection, draws the PPy/ in embodiment 1
MoS2/Ni3S2Constant current charge-discharge curve of the composite under different current densities, as shown in Figure 8.Wherein, the vertical seat of the curve
Mark is that voltage range is 0~0.5V.The specific capacitance discharge and recharge under different current densities is calculated by following equation.Pass through charge and discharge
Electrograph calculates specific capacitance, i.e. PPy/MoS2/Ni3S2Nano wire in 1A g-1Specific capacitance is 2213.2F g under current density-1, say
Bright PPy/MoS2/Ni3S2Nano wire has the performance of excellent storage electricity.Wherein, electric capacity calculation formula is：Cm=C/m=
(It)/(△ Vm), I are size of current, and t is discharge time, and △ V are voltage difference, and m is the matter of sample on working electrode piece
Amount.
(4) constant current charge-discharge is detected
In 4A g-1Constant current charge-discharge 3000 times under current density, obtain the PPy/MoS in embodiment 12/Ni3S2Composite wood
Material circulation-specific capacitance curve when current density is 4A/g, as a result as shown in figure 9, can by termination capacity and initial capacity contrast
Know, it is identical with initial capacitance after 3000 cycle charge-discharges, illustrate PPy/MoS2/Ni3S2Nano wire has excellent stabilization
Property.
Above-mentioned reference embodiment is to PPy/MoS2/Ni3S2The detailed description that the preparation method and application of composite is carried out,
It is illustrative rather than limited, several embodiments can be included according to limited scope, therefore do not departing from this hair
Changing and modifications under bright general plotting, should belong within protection scope of the present invention.
Claims (9)
1. a kind of PPy/MoS2/Ni3S2The preparation method of composite, it is characterised in that the preparation method includes following step
Suddenly：
(a) nickel foam is cleaned；
(b) nickel foam and pyrroles's stirring reaction in reaction solution after cleaning, clean, dry, obtaining surface recombination has polypyrrole
Nickel foam；
(c) surface recombination is had to nickel foam, the MoO of polypyrrole3, thiocarbamide react in aqueous, clean, dry, you can be made
PPy/MoS2/Ni3S2Composite；
Reaction time in the step (b) is 8~16 hours.
2. preparation method according to claim 1, it is characterised in that：Reaction solution in the step (b) is less than 7 for PH
Hydrochloric acid solution or the hypo solution that concentration is 1.6~1.7g/L.
3. preparation method according to claim 1, it is characterised in that：In the step (b), the mass concentration of pyrroles is 10
~20mg/ml, the ratio between the top surface area of nickel foam and the volume of reaction solution are 6cm2：(25~90) ml.
4. preparation method according to claim 1, it is characterised in that the reaction temperature in the step (c) is 155-170
DEG C, the time is 10-12h.
5. the preparation method according to claim 1 or 4, it is characterised in that the reaction temperature in the step (c) is 160
DEG C, the time is 11.5h.
6. preparation method according to claim 1, it is characterised in that in the step (c), MoO3, thiocarbamide mass concentration
Respectively 1.0~1.5mg/mL, 2.0~2.5mg/mL；The ratio between the top surface area of nickel foam and the volume of the aqueous solution are 6cm2：
(25~40) ml.
7. preparation method according to claim 6, it is characterised in that：In the step (c), MoO3, thiocarbamide mass concentration
Respectively 1.3~1.5mg/mL, 2.0~2.2mg/mL；The ratio between the top surface area of nickel foam and the volume of the aqueous solution are 6cm2：
30ml。
8. preparation method according to claim 1, it is characterised in that the PPy/MoS2/Ni3S2Composite is line style
Nanostructured.
9. the PPy/MoS that the preparation method according to claim 1-8 any one is prepared2/Ni3S2Composite is made
For the application of electrode material for super capacitor.
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| CN106057498B (en) * | 2016-06-15 | 2018-09-04 | 齐鲁工业大学 | A kind of preparation method and application of molybdenum disulfide/polypyrrole electrode material for super capacitor |
| CN106501455B (en) * | 2016-11-03 | 2019-05-28 | 山东师范大学 | A kind of preparation method of the highly sensitive stretchable biosensor in situ detection |
| CN107086132B (en) * | 2017-04-26 | 2019-07-19 | 安徽师范大学 | Flower-shaped three nickel nano film of vanadic anhydride/curing and its preparation method and application |
| CN107968208B (en) * | 2017-12-01 | 2020-09-25 | 吉林大学 | Nano lamellar structure of trinickel disulfide/molybdenum disulfide composite material and preparation method thereof |
| CN108155028B (en) * | 2017-12-29 | 2020-03-17 | 安徽大学 | Preparation method of flower-like molybdenum disulfide high-performance supercapacitor electrode |
| CN109455774B (en) * | 2018-12-27 | 2020-03-13 | 西安交通大学 | Ni-Fe-OH/MoS2/Ni3S2Composite nano sheet/carbon fiber cloth, preparation method and application |
| CN110075873B (en) * | 2019-04-29 | 2021-11-23 | 苏州大学 | Layered self-assembled Fe-MoS2/Ni3S2/NF composite nano material and preparation method and application thereof |
| CN111540609B (en) * | 2020-05-07 | 2021-04-30 | 电子科技大学 | Crystalline-amorphous MoO for super capacitor3@Ni3S2Method for producing a material |
| CN113058622A (en) * | 2021-03-26 | 2021-07-02 | 安徽大学 | Nickel sulfide/molybdenum disulfide composite nano array for photoelectrocatalysis killing of drug-resistant bacteria and preparation method thereof |
| WO2024083850A1 (en) | 2022-10-18 | 2024-04-25 | ETH Zürich | Electrocatalyst |
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