CN106531472A - Preparation method of polypyrrole/graphene/ manganese oxide composite materials - Google Patents
Preparation method of polypyrrole/graphene/ manganese oxide composite materials Download PDFInfo
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- CN106531472A CN106531472A CN201611068192.5A CN201611068192A CN106531472A CN 106531472 A CN106531472 A CN 106531472A CN 201611068192 A CN201611068192 A CN 201611068192A CN 106531472 A CN106531472 A CN 106531472A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 44
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 2
- -1 uniform stirring Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 6
- 229940099596 manganese sulfate Drugs 0.000 abstract description 5
- 239000011702 manganese sulphate Substances 0.000 abstract description 5
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 229920000767 polyaniline Polymers 0.000 description 25
- 239000003643 water by type Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- 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
- H01G11/48—Conductive polymers
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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
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- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses a preparation method of polypyrrole/graphene/ manganese oxide composite materials. The preparation method comprises steps of adsorbing large quantity of graphene oxide on th4e surface of three-dimensional multihole net-shaped polypyrrole by using the static tension force between the positively charged nitrogen on a polypyrrole chain segment and the surface of the graphene oxide, thereby effectively preventing agglomeration of the graphene oxide; then, adding potassium permanganate solution and excessive manganese sulfate solution to the polypyrrole/graphene oxide mixed solution; deposing the generated manganese dioxide on the graphene sheet, wherein the excessive manganese sulfate restores the graphene oxide into the graphene sheet; and deposing the generated manganous-manganic oxide on the graphene sheet, thereby preparing the three-dimensional multihole net-shaped polypyrrole/graphene/ manganese oxide composite materials. The preparation process is simple, green, environmentally friendly and reliable. The prepared composite materials have ordered space structures, high energy density and power density, and excellent circulation performance, are ideal supercapacitor electrode materials and are especially suitable for industrial production.
Description
Technical field
The invention belongs to novel energy field of material technology, more particularly to one kind prepare ultracapacitor with hydro-thermal method and use three
The method of dimension holey polypyrrole/graphene/manganese oxide composite material.
Background technology
Ultracapacitor is as with high-energy-density and power density and outstanding cycle performance etc., conduct is quick
With the primary selection in high-power energy stocking system field.Electrode material in ultracapacitor is risen to the performance of ultracapacitor
To vital effect, therefore, realize that the wide variety of most important thing of ultracapacitor is to prepare and develop high performance electricity
Pole material.
Conducting polymer, transition metal oxide and material with carbon element are three kinds of conventional materials of electrode material for super capacitor.
It is current super electricity to overcome the shortcomings of that using the advantageous characteristic of these three materials homogenous material presence prepares combination electrode material
One of focus of container electrode investigation of materials.Sivakkumar etc. adopts in-situ chemical route synthesizing carbon nanotubes/polypyrrole/dioxy
Change manganese trielement composite material, the material has outstanding cycle performance（S.R. Sivakkumar, et al. Performance
evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical
capacitors[J]. Electrochim. Acta, 2007, 52 (25): 7377-7385).The original position interface such as Wang
Oxidation-reduction method is prepared for layered manganese oxide/electric polypyrrole cladding carbon fibre composite, as in the material, electronics is led
Electricity and component between complete structure and there is good high rate performance and stable cycle performance（J.G. Wang, et al.
Rational synthesis of MnO2/conducting polypyrrole@carbon nanofiber triaxial
nano-cables for high-performance supercapacitors[J]. J. Mater. Chem., 2012,
22(33): 16943-16949.）.Polypyrrole-manganese dioxide-carbon fibre composite that Tao etc. is synthesized using in situ synthesis
There is important application prospect in energy field, the design for energy storage device of future generation provides a kind of new method（J.
Tao, et al. Supercapacitors based on polypyrrole-MnO2-carbon fiber hybrid
structure[J]. Nature, 2013, 3(2286): 1-7.）.The research such as Li finds the ratio CNT-dioxy of synthesis
Change manganese-Pt/Polypyrrole composite material and there is higher specific capacitance, be between the structure and performance for studying polypyrrole-carbon composite
Relation provides important experimental basis（P. Li, et al. Core-double-shell, carbon nanotube@
polypyrrole@MnO2 sponge as freestanding, compressible supercapacitor
electrode[J] ACS Appl. Mater. Interfaces, 2014, 6 (7): 5228-5234.）.
Therefore high-performance super capacitor electrode material is prepared for which is in electrochemical energy storage using simple synthetic technology
The application in field is significant.The present invention is with three-dimensional graphene oxide, three-dimensional porous netted polypyrrole, manganese sulfate and height
Potassium manganate is raw material, prepares three-dimensional porous netted polypyrrole/graphene/manganese oxide composite material using hydro-thermal method.
The content of the invention
It is an object of the invention to provide a kind of preparation method of polypyrrole/graphene/manganese oxide composite material.
Thinking of the present invention：Using between the epoxy bond on the nitrogen and surface of graphene oxide of positively charged on polypyrrole segment
Electrostatic tension effectively prevents the group of graphene oxide in the substantial amounts of graphene oxide of three-dimensional porous netted polypyrrole adsorption
It is poly-, it is subsequently adding the manganese sulfate solution of liquor potassic permanganate and excess in polypyrrole/graphene oxide liquid mixture, the two of generation
On graphene film, graphene oxide is reduced to graphene film to manganese-oxide deposition by excessive manganese sulfate, while generate four
Mn 3 O is deposited on graphene film and prepares three-dimensional porous netted polypyrrole/graphene/Mn oxide（Manganese dioxide and four oxygen
Change three manganese）Composite.
Concretely comprise the following steps：
(1) graphene oxide is dissolved in deionized water, ultrasonic 10 min is obtained graphene oxide solution.
(2) three-dimensional porous polypyrrole is added in graphene oxide solution obtained in step (1), be sufficiently stirred for lower addition
KMnO4Solution and MnSO48 h are reacted under solution, uniform stirring, mixed solution is obtained.
(3) NaOH solution is added in mixed solution obtained in step (2), be transferred to high pressure anti-after ultrasonically treated 5 min
In answering kettle, 4 h at 185 DEG C, are reacted, after naturally cooling to room temperature, products therefrom deionized water is cleaned and done to neutrality
It is dry, that is, polypyrrole/graphene/manganese oxide composite material is obtained.
The three-dimensional porous polypyrrole is 0.1 ~ 4 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material
Amount ratio be 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the matter of the Mn oxide and graphene oxide
Amount is than being 0.05 ~ 0.5:1.
The inventive method preparation process is simple, environmental protection, reliability, and obtained composite has regular space knot
Structure, high-energy-density and power density, outstanding cycle performance, are a kind of preferable electrode material for super capacitor, especially fit
Close industrialized production.
Description of the drawings
Fig. 1 is the ESEM of obtained polypyrrole/graphene/manganese oxide composite material in the embodiment of the present invention 18
Figure.
Specific embodiment
Embodiment 1：
(1) 0.5 g graphene oxides are dissolved in 100 mL deionized waters, ultrasonic 10 min is obtained graphene oxide solution.
(2) the three-dimensional porous polypyrroles of 0.05 g are added in graphene oxide solution obtained in step (1), is sufficiently stirred for down
Add KMnO4Solution（Containing 0.005 g KMnO4）And MnSO4Solution（Containing 0.0430 g MnSO4）, 8 h are reacted under uniform stirring,
Prepared mixed solution.
(3) NaOH solution is added in mixed solution obtained in step (2)（Containing 0.0190 g NaOH）, ultrasonically treated 5
It is transferred to after min in autoclave, at 185 DEG C, reacts 4 h, after naturally cooling to room temperature, products therefrom deionized water is clear
It is dried after being washed till neutrality, that is, polypyrrole/graphene/manganese oxide composite material is obtained.
The three-dimensional porous polypyrrole is 0.1 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material
The ratio of amount is 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the quality of the Mn oxide and graphene oxide
Than for 0.05:1.
Embodiment 2：
(1) 0.5 g graphene oxides are dissolved in 100 mL deionized waters, ultrasonic 10 min is obtained graphene oxide solution.
(2) the three-dimensional porous polypyrroles of 0.05 g are added in graphene oxide solution obtained in step (1), is sufficiently stirred for down
Add KMnO4Solution（Containing 0.01 g KMnO4）And MnSO4Solution（Containing 0.0861 g MnSO4）, 8 h are reacted under uniform stirring,
Prepared mixed solution.
(3) NaOH solution is added in mixed solution obtained in step (2)（Containing 0.0380 g NaOH）, ultrasonically treated 5
It is transferred to after min in autoclave, at 185 DEG C, reacts 4 h, after naturally cooling to room temperature, products therefrom deionized water is clear
It is dried after being washed till neutrality, that is, polypyrrole/graphene/manganese oxide composite material is obtained.
The three-dimensional porous polypyrrole is 0.1 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material
The ratio of amount is 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the quality of the Mn oxide and graphene oxide
Than for 0.1:1.
Embodiment 3：
(1) 0.5 g graphene oxides are dissolved in 100 mL deionized waters, ultrasonic 10 min is obtained graphene oxide solution.
(2) the three-dimensional porous polypyrroles of 0.05 g are added in graphene oxide solution obtained in step (1), is sufficiently stirred for down
Add KMnO4Solution（Containing 0.02 g KMnO4）And MnSO4Solution（Containing 0.1722 g MnSO4）, 8 h are reacted under uniform stirring,
Prepared mixed solution.
(3) NaOH solution is added in mixed solution obtained in step (2)（Containing 0.0760 g NaOH）, ultrasonically treated 5
It is transferred to after min in autoclave, at 185 DEG C, reacts 4 h, after naturally cooling to room temperature, products therefrom deionized water is clear
It is dried after being washed till neutrality, that is, polypyrrole/graphene/manganese oxide composite material is obtained.
The three-dimensional porous polypyrrole is 0.1 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material
The ratio of amount is 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the quality of the Mn oxide and graphene oxide
Than for 0.2:1.
Embodiment 4：
(1) 0.5 g graphene oxides are dissolved in 100 mL deionized waters, ultrasonic 10 min is obtained graphene oxide solution.
(2) the three-dimensional porous polypyrroles of 0.05 g are added in graphene oxide solution obtained in step (1), is sufficiently stirred for down
Add KMnO4Solution（Containing 0.025 g KMnO4）And MnSO4Solution（Containing 0.2152 g MnSO4）, 8 h are reacted under uniform stirring,
Prepared mixed solution.
(3) NaOH solution is added in mixed solution obtained in step (2)（Containing 0.0950 g NaOH）, ultrasonically treated 5
It is transferred to after min in autoclave, at 185 DEG C, reacts 4 h, after naturally cooling to room temperature, products therefrom deionized water is clear
It is dried after being washed till neutrality, that is, polypyrrole/graphene/manganese oxide composite material is obtained.
The three-dimensional porous polypyrrole is 0.1 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material
The ratio of amount is 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the quality of the Mn oxide and graphene oxide
Than for 0.25:1.
Embodiment 5：
(1) 0.5 g graphene oxides are dissolved in 100 mL deionized waters, ultrasonic 10 min is obtained graphene oxide solution.
(2) the three-dimensional porous polypyrroles of 0.05 g are added in graphene oxide solution obtained in step (1), is sufficiently stirred for down
Add KMnO4Solution（Containing 0.05 g KMnO4）And MnSO4Solution（Containing 0.4304 g MnSO4）, 8 h are reacted under uniform stirring,
Prepared mixed solution.
(3) NaOH solution is added in mixed solution obtained in step (2)（Containing 0.1900 g NaOH）, ultrasonically treated 5
It is transferred to after min in autoclave, at 185 DEG C, reacts 4 h, after naturally cooling to room temperature, products therefrom deionized water is clear
It is dried after being washed till neutrality, that is, polypyrrole/graphene/manganese oxide composite material is obtained.
The three-dimensional porous polypyrrole is 0.1 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material
The ratio of amount is 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the quality of the Mn oxide and graphene oxide
Than for 0.5:1.
Embodiment 6：
The step of repeating embodiment 1, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.125 g.
Embodiment 7：
The step of repeating embodiment 1, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.25 g.
Embodiment 8：
The step of repeating embodiment 1, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.5 g.
Embodiment 9：
The step of repeating embodiment 1, the addition for only changing three-dimensional porous polyaniline in step (2) are 1 g.
Embodiment 10：
The step of repeating embodiment 1, the addition for only changing three-dimensional porous polyaniline in step (2) are 2 g.
Embodiment 11：
The step of repeating embodiment 2, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.125 g.
Embodiment 12：
The step of repeating embodiment 2, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.25 g.
Embodiment 13：
The step of repeating embodiment 2, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.5 g.
Embodiment 14：
The step of repeating embodiment 2, the addition for only changing three-dimensional porous polyaniline in step (2) are 1 g.
Embodiment 15：
The step of repeating embodiment 2, the addition for only changing three-dimensional porous polyaniline in step (2) are 2 g.
Embodiment 16：
The step of repeating embodiment 3, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.125 g.
Embodiment 17：
The step of repeating embodiment 3, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.25 g.
Embodiment 18：
The step of repeating embodiment 3, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.5 g.
Embodiment 19：
The step of repeating embodiment 3, the addition for only changing three-dimensional porous polyaniline in step (2) are 1 g.
Embodiment 20：
The step of repeating embodiment 3, the addition for only changing three-dimensional porous polyaniline in step (2) are 2 g.
Embodiment 21：
The step of repeating embodiment 4, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.125 g.
Embodiment 22：
The step of repeating embodiment 4, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.25 g.
Embodiment 23：
The step of repeating embodiment 4, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.5 g.
Embodiment 24：
The step of repeating embodiment 4, the addition for only changing three-dimensional porous polyaniline in step (2) are 1 g.
Embodiment 25：
The step of repeating embodiment 4, the addition for only changing three-dimensional porous polyaniline in step (2) are 2 g.
Embodiment 26：
The step of repeating embodiment 5, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.125 g.
Embodiment 27：
The step of repeating embodiment 5, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.25 g.
Embodiment 28：
The step of repeating embodiment 5, the addition for only changing three-dimensional porous polyaniline in step (2) are 0.5 g.
Embodiment 29：
The step of repeating embodiment 5, the addition for only changing three-dimensional porous polyaniline in step (2) are 1 g.
Embodiment 30：
The step of repeating embodiment 5, the addition for only changing three-dimensional porous polyaniline in step (2) are 2 g.
Claims (1)
1. a kind of preparation method of polypyrrole/graphene/manganese oxide composite material, it is characterised in that concretely comprise the following steps：
(1) graphene oxide is dissolved in deionized water, ultrasonic 10 min is obtained graphene oxide solution；
(2) three-dimensional porous polypyrrole is added in graphene oxide solution obtained in step (1), be sufficiently stirred for lower addition KMnO4It is molten
Liquid and MnSO48 h are reacted under solution, uniform stirring, mixed solution is obtained；
(3) NaOH solution is added in mixed solution obtained in step (2), be transferred to autoclave after ultrasonically treated 5 min
In, 4 h are reacted at 185 DEG C, after naturally cooling to room temperature, products therefrom deionized water is cleaned and is dried to neutrality, i.e.,
Prepared polypyrrole/graphene/manganese oxide composite material；
The three-dimensional porous polypyrrole is 0.1 ~ 4 with the mass ratio of graphene oxide:1, the MnSO4With KMnO4Material amount
Ratio be 9:1, the MnSO4Ratio with the amount of the material of NaOH is 3:5, the mass ratio of the Mn oxide and graphene oxide
For 0.05 ~ 0.5:1.
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| CN201611068192.5A CN106531472B (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of polypyrrole/graphene/manganese oxide composite material |
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| CN201611068192.5A CN106531472B (en) | 2016-11-29 | 2016-11-29 | A kind of preparation method of polypyrrole/graphene/manganese oxide composite material |
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| CN107913668A (en) * | 2017-10-25 | 2018-04-17 | 浙江工商大学 | A kind of nanocomposite with absorption and catalytic degradation and its preparation method and application |
| CN107913667A (en) * | 2017-10-25 | 2018-04-17 | 浙江工商大学 | A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application |
| CN107913667B (en) * | 2017-10-25 | 2020-10-13 | 浙江工商大学 | Magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite and preparation and application thereof |
| CN107913668B (en) * | 2017-10-25 | 2020-10-13 | 浙江工商大学 | Nano composite material with adsorption and catalytic degradation functions and preparation method and application thereof |
| CN108010752A (en) * | 2017-11-20 | 2018-05-08 | 桂林理工大学 | The preparation method of polypyrrole nano line array/graphene film/manganese oxide composite material |
| CN109037565A (en) * | 2018-09-17 | 2018-12-18 | 宁德卓高新材料科技有限公司 | Composite diaphragm, preparation method and the lithium-sulfur cell comprising it |
| CN109622056A (en) * | 2018-12-29 | 2019-04-16 | 武汉大学 | A kind of composite efficient visible-light photocatalyst and its preparation method and application |
| CN109622056B (en) * | 2018-12-29 | 2020-10-30 | 武汉大学 | Composite efficient visible light photocatalyst and preparation method and application thereof |
| CN114050279A (en) * | 2021-10-26 | 2022-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of composite catalyst |
| CN115465924A (en) * | 2022-09-19 | 2022-12-13 | 西安泰金工业电化学技术有限公司 | PPy/GO/MnO 2 Nano composite electrode, preparation method and application |
| CN115465924B (en) * | 2022-09-19 | 2024-03-26 | 西安泰金新能科技股份有限公司 | PPy/GO/MnO 2 Nano composite electrode, preparation method and application |
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