CN108010728A - The preparation method of polyaniline nano linear array/graphene film/manganese oxide composite material - Google Patents
The preparation method of polyaniline nano linear array/graphene film/manganese oxide composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 43
- 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 41
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011572 manganese Substances 0.000 claims abstract description 14
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000746 purification Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 21
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 16
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 229940099596 manganese sulfate Drugs 0.000 abstract description 3
- 239000011702 manganese sulphate Substances 0.000 abstract description 3
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 abstract description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000012695 Interfacial polymerization Methods 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010399 three-hybrid screening Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- 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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Abstract
The invention discloses a kind of preparation method of polyaniline nano linear array/graphene film/manganese oxide composite material.Using graphene oxide three-dimensional structure as skeleton, using the electrostatic tension between the epoxy bond on the nitrogen and surface of graphene oxide of positively charged on Oligoanilines polyaniline nano linear array is grown in surface of graphene oxide, liquor potassic permanganate and excessive manganese sulfate solution are added into polyaniline nano-line/graphene oxide liquid mixture, generation manganese dioxide is deposited on above graphene oxide sheet；At the same time, Mn (II) ion of excessive positively charged is entered between electronegative graphene oxide layer, and redox reaction occurs with graphene oxide and generates Mn (III) ion, graphene oxide is reduced to graphene at the same time, then the nano manganic manganous oxide particle generated by hydro-thermal method is deposited between the graphene layer after reduction, finally prepares polyaniline nano linear array/graphene film/manganese oxide composite material.
Description
Technical field
The invention belongs to technical field of energy material, more particularly to one kind prepares super electricity with interfacial polymerization and hydro-thermal method
The method of container polyaniline nano linear array/graphene film/manganese oxide composite material.
Background technology
Ultracapacitor is quick due to being used as with high-energy-density and power density and outstanding cycle performance etc.
With the primary selection in high-power energy stocking system field.Electrode material in ultracapacitor plays the performance of ultracapacitor
To vital effect, therefore, it is to prepare and develop high performance electricity to realize the widely applied most important thing of ultracapacitor
Pole material.
Conducting polymer, transition metal oxide and carbon material are the common three kinds of materials of electrode material for super capacitor.
It is current super electricity to overcome deficiency existing for homogenous material to prepare combination electrode material using the advantageous characteristic of these three materials
One of hot spot of container electrode investigation of materials.Razak et al. has synthesized the ternary of polyaniline, multi-walled carbon nanotube and manganese dioxide
Composite material is simultaneously characterized and analyzed to its structure.The material has high thermal stability, good cycle performance and low electricity
Conductance（S.I.A. Razak, et al. MnO2-filled multiwalled carbon nanotube/polyaniline
nanocomposites: effect of loading on the conduction properties and its
percolation threshold[J]. Nano, 2011, 6(1): 81-91）.Li et al. uses simple wet chemistry method with poly-
Aniline, multi-walled carbon nanotube and manganese dioxide prepare the trielement composite material of coaxial configuration for raw material, can effectively improve titanium dioxide
The electrochemical utilization rate of manganese and reduce the contact resistance between each component and obtain good chemical property（Q. Li, et
al. Synthesis and electrochemical performance of multi-walled carbon
nanotube/Polyaniline/MnO2 ternary coaxial nanostructures for supercapacitors
[J]. J. Power Sources, 2011, 196(1): 565-572.).Meng etc. is prepared poly- using a step interfacial polymerization
Aniline/manganese dioxide composite material, the material have good cyclical stability and high capacitance（F. Meng, et al.
Controllable synthesis of MnO2/polyaniline nanocomposite and its
electrochemical capacitive property[J]. Nanoscale Res. Lett., 2013, 8(1):
179.）.Han etc. prepares ternary composite electrode material by raw material of manganese dioxide nano-rod, polyaniline and graphene oxide, for length
The preparation in service life, high performance metal-oxide based super capacitor electrode material provides a kind of effective method（G. Han,
et al. MnO2 nanorods intercalating graphene oxide/Polyaniline ternary
composites for robust high-performance supercapacitors[J]. Nature, 2014, 4
(4824):1-7.）.Applicant seminar uses interfacial polymerization one-step synthesis manganese dioxide/polyaniline/graphene three
Hybrid material is tieed up, important experimental basis is provided for the industrialized production of high-performance super capacitor electrode material（X. Fan,
et al. Preparation of 3D MnO2/polyaniline/graphene hybrid material via
interfacial polymerization as high-performance supercapacitor electrode[J].
Chin. J. Chem. 2016, 34(8): 839-846.）.
Therefore high-performance super capacitor electrode material is prepared for it in electrochemical energy storage using simple synthetic technology
The application in field is of great significance.The present invention using three-dimensional graphene oxide, aniline, manganese sulfate and potassium permanganate as raw material,
Polyaniline nano linear array/graphene film/manganese oxide composite material is prepared using interfacial polymerization and hydro-thermal method.Gained is compound
Material has regular space arrangement, good dispersiveness, high-energy-density and power density, outstanding cycle performance, is one
The preferable electrode material for super capacitor of kind, is especially suitable for industrialized production.
The content of the invention
The object of the present invention is to provide a kind of system of polyaniline nano linear array/graphene film/manganese oxide composite material
Preparation Method.
Thinking of the present invention：Using graphene oxide three-dimensional structure as skeleton, nitrogen and oxidation using positively charged on Oligoanilines
The electrostatic tension between epoxy bond on graphene surface grows polyaniline nano linear array in surface of graphene oxide, effectively
Prevent the reunion of graphene oxide；Liquor potassic permanganate and excessive manganese sulfate solution are added to polyaniline nano-line/oxidation
In graphene mixed liquor, the manganese dioxide of generation is deposited on above graphene oxide sheet；Meanwhile the Mn (II) of excessive positively charged
Ion is entered between electronegative graphene oxide layer, and redox reaction occurs with graphene oxide and generates Mn (III)
Ion, while graphene oxide is reduced to graphene, the nano manganic manganous oxide particle then generated by hydro-thermal method deposits
Between graphene layer after reduction（The effective reunion for preventing graphene）, finally prepare polyaniline nano linear array/
Graphene film/manganese oxide composite material.
Concretely comprise the following steps：
（1）Three-dimensional graphene oxide is dissolved in deionized water, three-dimensional graphene oxide solution is made in 10 min of ultrasound, is
Water phase.
（2）Aniline after purification is dissolved in chloroform oil phase is made, with step（1）Obtained water mixes, using boundary
Face polymerization, reacts 24 h at 0 ~ 5 DEG C, and oil-water interfaces blackish green product occur, after filtered, washing, done at 60 DEG C
Dry 12 h, that is, be made graphene oxide/polyaniline nano-line composite material.
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is filled
Divide stirring is lower to add KMnO4Solution and MnSO4Solution, is transferred in autoclave after being ultrasonically treated 5 min, anti-at 180 DEG C
4 h are answered, room temperature is subsequently cooled to and mixed solution is made.
（4）To step（3）NaOH solution is added in obtained mixed solution, after being ultrasonically treated 5 min, is reacted at 180 DEG C
2 h, after cooled to room temperature, products therefrom is dried after being washed with deionized to neutrality, that is, polyaniline nano is made
Linear array/graphene film/manganese oxide composite material.
The mass ratio of aniline and three-dimensional graphene oxide after the purification is 0.1 ~ 4:1；The MnSO4With the thing of NaOH
The ratio between amount of matter is 3:5；The MnSO4With KMnO4The ratio between the amount of material be 9:1；The Mn oxide and three-dimensional graphite oxide
The mass ratio of alkene is 0.05 ~ 0.5:1, the ratio between amount of material of manganese dioxide and mangano-manganic oxide is 1 in the Mn oxide:1.
The method of the present invention preparation process is simple, reliable, environmentally protective, and there is obtained composite material regular space to tie
Structure, high-energy-density and power density, and outstanding cycle performance, are a kind of preferable electrode material for super capacitor, especially
It is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is obtained polyaniline nano linear array/graphene film/manganese oxide composite material in the embodiment of the present invention 15
Scanning electron microscope (SEM) photograph.
Embodiment
Embodiment 1：
（1）0.5 g three-dimensional graphene oxides are dissolved in 100 mL deionized waters, three-dimensional graphite oxide is made in 10 min of ultrasound
Alkene solution, is water phase.
（2）Aniline after 0.05 g is purified, which is dissolved in 50 mL chloroforms, is made oil phase, with step（1）Obtained water phase
Mixing, using interfacial polymerization, reacts 24 h at 3 DEG C, and substantial amounts of blackish green product occur in oil-water interfaces, filtered, wash
After washing, dry 12 h, that is, be made graphene oxide/polyaniline nano-line composite material at 60 DEG C.
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is filled
Divide stirring is lower to add MnSO4Solution（Containing 0.0430 g MnSO4）And KMnO4Solution（Containing 0.005 g KMnO4）, it is ultrasonically treated 5
It is transferred to after min in autoclave, 4 h is reacted at 180 DEG C, is subsequently cooled to room temperature and mixed solution is made.
（4）To step（3）NaOH solution is added in obtained mixed solution（Containing 0.0190 g NaOH）, it is ultrasonically treated 5
After min, 2 h are reacted at 180 DEG C, after cooled to room temperature, products therefrom is done after being washed with deionized to neutrality
It is dry, that is, polyaniline nano linear array/graphene film/manganese oxide composite material is made.In the Mn oxide manganese dioxide and
The ratio between amount of material of mangano-manganic oxide is 1:1.
Embodiment 2：
（1）0.5 g three-dimensional graphene oxides are dissolved in 100 mL deionized waters, three-dimensional graphite oxide is made in 10 min of ultrasound
Alkene solution, is water phase.
（2）Aniline after 0.05 g is purified, which is dissolved in 50 mL chloroforms, is made oil phase, with step（1）Obtained water phase
Mixing, using interfacial polymerization, reacts 24 h at 3 DEG C, and substantial amounts of blackish green product occur in oil-water interfaces, filtered, wash
After washing, dry 12 h, that is, be made graphene oxide/polyaniline nano-line composite material at 60 DEG C.
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is filled
Divide stirring is lower to add MnSO4Solution（Containing 0.0861 g MnSO4）And KMnO4Solution（Containing 0.01 g KMnO4）, it is ultrasonically treated 5
It is transferred to after min in autoclave, 4 h is reacted at 180 DEG C, is subsequently cooled to room temperature and mixed solution is made.
（4）To step（3）NaOH solution is added in obtained mixed solution（Containing 0.0380 g NaOH）, it is ultrasonically treated 5
After min, 2 h are reacted at 180 DEG C, after cooled to room temperature, products therefrom is done after being washed with deionized to neutrality
It is dry, that is, polyaniline nano linear array/graphene film/manganese oxide composite material is made.In the Mn oxide manganese dioxide and
The ratio between amount of material of mangano-manganic oxide is 1:1.
Embodiment 3：
（1）0.5 g three-dimensional graphene oxides are dissolved in 100 mL deionized waters, three-dimensional graphite oxide is made in 10 min of ultrasound
Alkene solution, is water phase.
（2）Aniline after 0.05 g is purified, which is dissolved in 50 mL chloroforms, is made oil phase, with step（1）Obtained water phase
Mixing, using interfacial polymerization, reacts 24 h at 3 DEG C, and substantial amounts of blackish green product occur in oil-water interfaces, filtered, wash
After washing, dry 12 h, that is, be made graphene oxide/polyaniline nano-line composite material at 60 DEG C.
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is filled
Divide stirring is lower to add MnSO4Solution（Containing 0.1722 g MnSO4）And KMnO4Solution（Containing 0.02 g KMnO4）, it is ultrasonically treated 5
It is transferred to after min in autoclave, 4 h is reacted at 180 DEG C, is subsequently cooled to room temperature and mixed solution is made.
（4）To step（3）NaOH solution is added in obtained mixed solution（Containing 0.0760 g NaOH）, it is ultrasonically treated 5
After min, 2 h are reacted at 180 DEG C, after cooled to room temperature, products therefrom is done after being washed with deionized to neutrality
It is dry, that is, polyaniline nano linear array/graphene film/manganese oxide composite material is made.In the Mn oxide manganese dioxide and
The ratio between amount of material of mangano-manganic oxide is 1:1.
Embodiment 4：
（1）0.5 g three-dimensional graphene oxides are dissolved in 100 mL deionized waters, three-dimensional graphite oxide is made in 10 min of ultrasound
Alkene solution, is water phase.
（2）Aniline after 0.05 g is purified, which is dissolved in 50 mL chloroforms, is made oil phase, with step（1）Obtained water phase
Mixing, using interfacial polymerization, reacts 24 h at 3 DEG C, and substantial amounts of blackish green product occur in oil-water interfaces, filtered, wash
After washing, dry 12 h, that is, be made graphene oxide/polyaniline nano-line composite material at 60 DEG C.
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is filled
Divide stirring is lower to add MnSO4Solution（Containing 0.2152 g MnSO4）And KMnO4Solution（Containing 0.025 g KMnO4）, it is ultrasonically treated 5
It is transferred to after min in autoclave, 4 h is reacted at 180 DEG C, is subsequently cooled to room temperature and mixed solution is made.
（4）To step（3）NaOH solution is added in obtained mixed solution（Containing 0.0950 g NaOH）, it is ultrasonically treated 5
After min, 2 h are reacted at 180 DEG C, after cooled to room temperature, products therefrom is done after being washed with deionized to neutrality
It is dry, that is, polyaniline nano linear array/graphene film/manganese oxide composite material is made.In the Mn oxide manganese dioxide and
The ratio between amount of material of mangano-manganic oxide is 1:1.
Embodiment 5：
（1）0.5 g three-dimensional graphene oxides are dissolved in 100 mL deionized waters, three-dimensional graphite oxide is made in 10 min of ultrasound
Alkene solution, is water phase.
（2）Aniline after 0.05 g is purified, which is dissolved in 50 mL chloroforms, is made oil phase, with step（1）Obtained water phase
Mixing, using interfacial polymerization, reacts 24 h at 3 DEG C, and substantial amounts of blackish green product occur in oil-water interfaces, filtered, wash
After washing, dry 12 h, that is, be made graphene oxide/polyaniline nano-line composite material at 60 DEG C.
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is filled
Divide stirring is lower to add MnSO4Solution（Containing 0.4304 g MnSO4）And KMnO4Solution（Containing 0.05 g KMnO4）, it is ultrasonically treated 5
It is transferred to after min in autoclave, 4 h is reacted at 180 DEG C, is subsequently cooled to room temperature and mixed solution is made.
（4）To step（3）NaOH solution is added in obtained mixed solution（Containing 0.1900 g NaOH）, it is ultrasonically treated 5
After min, 2 h are reacted at 180 DEG C, after cooled to room temperature, products therefrom is done after being washed with deionized to neutrality
It is dry, that is, polyaniline nano linear array/graphene film/manganese oxide composite material is made.In the Mn oxide manganese dioxide and
The ratio between amount of material of mangano-manganic oxide is 1:1.
Embodiment 6：
The step of repeating embodiment 1, only changes the step（2）The addition of aniline after middle purification is 0.125 g.
Embodiment 7：
The step of repeating embodiment 1, only changes the step（2）The addition of aniline after middle purification is 0.25 g.
Embodiment 8：
The step of repeating embodiment 1, only changes the step（2）The addition of aniline after middle purification is 0.5 g.
Embodiment 9：
The step of repeating embodiment 1, only changes the step（2）The addition of aniline after middle purification is 1 g.
Embodiment 10：
The step of repeating embodiment 1, only changes the step（2）The addition of aniline after middle purification is 2 g.
Embodiment 11：
The step of repeating embodiment 2, only changes the step（2）The addition of aniline after middle purification is 0.125 g.
Embodiment 12：
The step of repeating embodiment 2, only changes the step（2）The addition of aniline after middle purification is 0.25 g.
Embodiment 13：
The step of repeating embodiment 2, only changes the step（2）The addition of aniline after middle purification is 0.5 g.
Embodiment 14：
The step of repeating embodiment 2, only changes the step（2）The addition of aniline after middle purification is 1 g.
Embodiment 15：
The step of repeating embodiment 2, only changes the step（2）The addition of aniline after middle purification is 2 g.
Embodiment 16：
The step of repeating embodiment 3, only changes the step（2）The addition of aniline after middle purification is 0.125 g.
Embodiment 17：
The step of repeating embodiment 3, only changes the step（2）The addition of aniline after middle purification is 0.25 g.
Embodiment 18：
The step of repeating embodiment 3, only changes the step（2）The addition of aniline after middle purification is 0.5 g.
Embodiment 19：
The step of repeating embodiment 3, only changes the step（2）The addition of aniline after middle purification is 1 g.
Embodiment 20：
The step of repeating embodiment 3, only changes the step（2）The addition of aniline after middle purification is 2 g.
Embodiment 21：
The step of repeating embodiment 4, only changes the step（2）The addition of aniline after middle purification is 0.125 g.
Embodiment 22：
The step of repeating embodiment 4, only changes the step（2）The addition of aniline after middle purification is 0.25 g.
Embodiment 23：
The step of repeating embodiment 4, only changes the step（2）The addition of aniline after middle purification is 0.5 g.
Embodiment 24：
The step of repeating embodiment 4, only changes the step（2）The addition of aniline after middle purification is 1 g.
Embodiment 25：
The step of repeating embodiment 4, only changes the step（2）The addition of aniline after middle purification is 2 g.
Embodiment 26：
The step of repeating embodiment 5, only changes the step（2）The addition of aniline after middle purification is 0.125 g.
Embodiment 27：
The step of repeating embodiment 5, only changes the step（2）The addition of aniline after middle purification is 0.25 g.
Embodiment 28：
The step of repeating embodiment 5, only changes the step（2）The addition of aniline after middle purification is 0.5 g.
Embodiment 29：
The step of repeating embodiment 5, only changes the step（2）The addition of aniline after middle purification is 1 g.
Embodiment 30：
The step of repeating embodiment 5, only changes the step（2）The addition of aniline after middle purification is 2 g.
Claims (1)
1. a kind of preparation method of polyaniline nano linear array/graphene film/manganese oxide composite material, it is characterised in that specific
Step is：
（1）Three-dimensional graphene oxide is dissolved in deionized water, three-dimensional graphene oxide solution is made in 10 min of ultrasound, is
Water phase；
（2）Aniline after purification is dissolved in chloroform oil phase is made, with step（1）Obtained water mixes, and is gathered using interface
It is legal, 24 h are reacted at 0 ~ 5 DEG C, blackish green product occur in oil-water interfaces, after filtered, washing, dry 12 at 60 DEG C
H, that is, be made graphene oxide/polyaniline nano-line composite material；
（3）Take step（2）Obtained graphene oxide/polyaniline nano-line composite material dissolving in deionized water, is fully stirred
Mix lower addition KMnO4Solution and MnSO4Solution, is transferred in autoclave after being ultrasonically treated 5 min, reacts 4 at 180 DEG C
H, is subsequently cooled to room temperature and mixed solution is made；
（4）To step（3）NaOH solution is added in obtained mixed solution, after being ultrasonically treated 5 min, 2 h are reacted at 180 DEG C,
After cooled to room temperature, products therefrom is dried after being washed with deionized to neutrality, that is, polyaniline nano linear array is made
Row/graphene film/manganese oxide composite material；
The mass ratio of aniline and three-dimensional graphene oxide after the purification is 0.1 ~ 4:1；The material of the MnSO4 and NaOH
The ratio between amount is 3:5；The ratio between amount of material of the MnSO4 and KMnO4 is 9:1；The Mn oxide and three-dimensional graphene oxide
Mass ratio be 0.05 ~ 0.5:1, the ratio between amount of material of manganese dioxide and mangano-manganic oxide is 1 in the Mn oxide:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110136974A (en) * | 2019-04-23 | 2019-08-16 | 太仓萃励新能源科技有限公司 | A kind of MnO2The synthetic method of-PANi-RGO ternary electrochemical capacitance material |
| CN111416096A (en) * | 2020-03-24 | 2020-07-14 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465121A (en) * | 2014-11-28 | 2015-03-25 | 天津大学 | Graphene oxide-polyaniline composite electrode material with three-dimensional structure and manufacturing method thereof |
| CN104559176A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material |
| CN106409526A (en) * | 2016-11-24 | 2017-02-15 | 桂林理工大学 | Preparation method of sulfonated graphene oxide/manganese dioxide/polyaniline composite material |
| CN106558420A (en) * | 2016-11-29 | 2017-04-05 | 桂林理工大学 | A kind of preparation method of polyaniline/Graphene/manganese oxide composite material |
-
2017
- 2017-11-20 CN CN201711158596.8A patent/CN108010728A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104465121A (en) * | 2014-11-28 | 2015-03-25 | 天津大学 | Graphene oxide-polyaniline composite electrode material with three-dimensional structure and manufacturing method thereof |
| CN104559176A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material |
| CN106409526A (en) * | 2016-11-24 | 2017-02-15 | 桂林理工大学 | Preparation method of sulfonated graphene oxide/manganese dioxide/polyaniline composite material |
| CN106558420A (en) * | 2016-11-29 | 2017-04-05 | 桂林理工大学 | A kind of preparation method of polyaniline/Graphene/manganese oxide composite material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110136974A (en) * | 2019-04-23 | 2019-08-16 | 太仓萃励新能源科技有限公司 | A kind of MnO2The synthetic method of-PANi-RGO ternary electrochemical capacitance material |
| CN111416096A (en) * | 2020-03-24 | 2020-07-14 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
| CN111416096B (en) * | 2020-03-24 | 2023-03-10 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
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