CN111363146A - Preparation method of polyaniline/capacitance carbon-based composite material, product and application thereof - Google Patents

Preparation method of polyaniline/capacitance carbon-based composite material, product and application thereof Download PDF

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CN111363146A
CN111363146A CN202010191354.4A CN202010191354A CN111363146A CN 111363146 A CN111363146 A CN 111363146A CN 202010191354 A CN202010191354 A CN 202010191354A CN 111363146 A CN111363146 A CN 111363146A
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polyaniline
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CN111363146B (en
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李振湖
刘双翼
刘瑶
曲超
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Chongqing Zhongke Chaorong Technology Co ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H—ELECTRICITY
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    • 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
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Abstract

The invention relates to a preparation method of a polyaniline/capacitance carbon-based composite material, and a product and application thereof, and belongs to the field of composite material preparation. According to the invention, the carbon material, the aniline and the peroxide are reacted in the acid solution, a one-step in-situ doping polymerization mode is mainly adopted, the preparation method is simple and normal temperature, no dispersing agent or surfactant is required to be added, and compared with the prior art, the flow is greatly shortened and the cost is reduced. The polyaniline/capacitor carbon-based composite material prepared by the invention combines the characteristics of capacitor carbon and polyaniline, can be used as a positive electrode material or a negative electrode material of a super capacitor, widens the condition that the polyaniline is used under the positive potential acidic condition to be used under the negative potential (-1-0V) and alkaline (KOH, NaOH, LiOH and the like), and shows high capacity (>350F/g), good rate characteristic and cycling stability (the capacity retention ratio of the material is still more than 80% at 8000 cycles under the current density of 4A/g).

Description

Preparation method of polyaniline/capacitance carbon-based composite material, product and application thereof
Technical Field
The invention belongs to the field of composite material preparation, and particularly relates to a preparation method of a polyaniline/capacitor carbon-based composite material, and a product and application thereof.
Background
The super capacitor is a novel energy device, has the performance between that of a traditional capacitor and a battery, and has the advantages of higher power, wider service temperature range, long cycle life and the like. The super capacitor gradually shows great application value and market potential in various fields, such as new energy automobiles, power storage, railway transportation, communication, national defense, electronic products and the like, and is widely applied. And the development of electrode materials which are the most core for limiting the development of supercapacitors has been hindered. Most of the existing supercapacitor products are activated carbon materials based on an electric double layer capacitance electricity storage mechanism, and due to the fact that the energy density of the carbon materials is low, modification researches on the basis of the carbon materials do not obviously improve the power density and the energy density of the materials.
Polyaniline is a common conductive polymer, raw materials are easy to obtain, the preparation method is simple, charges are stored based on a pseudo-capacitor of an oxidation-reduction reaction in an electrode electrochemical capacitor, the conductivity and the energy density are high, but the volume change of the material is caused by the doping/dedoping of ions in the oxidation reaction process, so that the expansion/contraction of the surface of an electrode is caused, the surface of the electrode is cracked, the performance of the electrode material is reduced, the cycle life is shortened, and the stability is poor.
Therefore, the carbon material is compounded with polyaniline, the polyaniline increases the capacity of the material, the carbon material can buffer the volume change of the polyaniline, the polyaniline composite material is a high-performance new material with research value, such as conductive polyaniline/carbon nano tube, polyaniline/graphene and other composite materials, and the electrochemical performance is improved to a great extent. Although the carbon nano tube material has large specific surface area, excellent conductivity and obviously improved performance of the composite material, the preparation cost of the carbon nano tube is higher, so that the application of the carbon nano tube is greatly limited; compared with graphene, the activated carbon is lower in price, simple and mature in production process, large in specific surface area and more suitable for commercialization due to the cost advantage, and has higher economic value. The Tonwei new material technology development company Limited in Zhang hong City mentions a preparation method of polyaniline/activated carbon compound in patent CN107481867A, but the initiator adopts a common method of dropwise adding, is relatively complicated, is more difficult to control the operation, is easy to initiate the secondary agglomeration of polyaniline to form irregular morphology, and the resistivity of the prepared compound is 2 omega/cm and is relatively large; the patent CN102649843A by Girale et al, Lin chemical industry research institute of China forestry science research institute, mentions a preparation method of polyaniline/activated carbon composite added with methyl orange, the addition of methyl orange can be used as dopant acid, and simultaneously generates electrostatic interaction with aniline monomer, thus strengthening the interaction between polyaniline and activated carbon and improving the degree of polymerization, but the performance of the electrode material of the composite obtained in the patent is only 150F/g when the charge and discharge performance is poor at 1A/g; the patent CN102134318A of Beijing chemical university Chenghong et al invented a bamboo charcoal/activated carbon composite material, well balanced the stability of bamboo charcoal and the good pseudocapacitance performance of polyaniline, the cost of bamboo charcoal is relatively low, although the bamboo charcoal shows better than the performance of single carbon material or polyaniline, but also has the problems of poor performance, poor stability, short cycle life, complex experimental process, etc. In addition, carbon-based polyaniline composite materials in the existing reports are almost applied to water-based acidic and positive electrode window supercapacitors, and are rarely applied to alkaline electrolyte and negative voltage windows.
Therefore, the development of the polyaniline/capacitance carbon-based composite material with universality, high efficiency, economy and excellent performance is the key point of the development of the conductive polyaniline composite material.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a polyaniline/capacitor carbon-based composite material; the second purpose of the invention is to provide a polyaniline/capacitance carbon-based composite material; the invention also aims to provide application of the polyaniline/capacitance carbon-based composite material in a super capacitor.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a polyaniline/capacitance carbon-based composite material comprises the following steps:
(1) adding a carbon material into an alcohol-water solution for uniform dispersion, carrying out hydrothermal reaction at 120-200 ℃ for 5-240 min, cooling to normal temperature after the reaction is finished, centrifuging, and drying to obtain a composite carbon-based material precursor;
(2) sequentially adding the composite carbon-based material precursor and aniline in the step (1) into an acid solution, and ultrasonically stirring and dispersing to form a uniformly dispersed mixed acid solution;
(3) dissolving a peroxide into an acid solution, and uniformly stirring to obtain a peroxide acid solution;
(4) at room temperature, rapidly pouring the acid solution of the over oxidant in the step (3) into the stirred mixed acid solution, and stirring for polymerization reaction;
(5) and after the reaction is finished, obtaining a mixed solution, and sequentially performing centrifugation, washing and drying to obtain the polyaniline/capacitance carbon composite material.
Preferably, the carbon material in step (1) is any one or more of graphene, carbon tubes or activated carbon.
Preferably, the mass ratio of the graphene to the carbon tubes to the activated carbon in the carbon material is 0.5-10: 99-80.
Preferably, the mass-to-volume ratio of the carbon material to the alcohol-water solution in the step (1) is 0.1:1 to 30:1, g: L.
Preferably, the volume ratio of the alcohol to the water in the alcohol-water solution in the step (1) is 1: 10-8: 1.
Preferably, the alcohol is any one of ethanol, isopropanol, butanol, ethylene glycol or glycerol.
Preferably, the mass ratio of the composite carbon-based material precursor to the aniline in the step (2) is 1: 0.1-1: 100.
Preferably, the molar volume ratio of the aniline to the acid solution in the step (2) is 0.05-10: 1, mol: L.
Preferably, the molar volume ratio of the hyperoxidant to the acid solution in the step (3) is 1: 20-1: 500, and mol: L.
Preferably, the per-oxidant in step (3) is any one or more of ammonium persulfate, lithium perchlorate, ferric chloride or potassium permanganate.
Preferably, the molar ratio of the aniline in the mixed acid solution in the step (4) to the peroxide in the peroxide agent acid solution is 1: 1-1: 10.
Preferably, the concentration of the acid solution is 0.1-6 mol/L.
Preferably, the acid in the acid solution is HCl or H2SO4Or H3PO4。
Preferably, the stirring and dispersing time in the step (2) is 10-240 min.
Preferably, the polymerization reaction in the step (4) has a reaction temperature of 0-60 ℃ and a reaction time of 0.5-24 h.
2. The polyaniline/capacitance carbon-based composite material prepared by the preparation method.
3. The polyaniline/capacitance carbon-based composite material is applied to a super capacitor.
Preferably, the application specifically comprises: and the polyaniline/capacitance carbon-based composite material is used as a positive electrode material or a negative electrode material of the super capacitor under the conditions of a negative voltage window and alkalinity.
The invention has the beneficial effects that:
1. the invention discloses a preparation method of polyaniline/capacitance carbon-based composite material, which mainly adopts a one-step in-situ doping polymerization mode, has simple preparation method and normal temperature, does not need to add a dispersant or a surfactant, greatly shortens the flow and reduces the cost compared with the prior art, and mainly shows the following points: (1) the method comprises the following steps of uniformly dispersing capacitive carbon and a polyaniline material by adopting a one-step in-situ doping polymerization mode, polymerizing aniline on the surface of the capacitive carbon by taking the capacitive carbon as a site, and uniformly dispersing; (2) the initiator oxide is poured quickly, and compared with dropwise addition of other polymerization reactions, the preparation method is simpler, the operation is simpler, and the application potential is higher; (3) the one-step in-situ doping reaction is carried out at room temperature, and the operation condition is easier to realize and more controllable.
2. The polyaniline/capacitance carbon-based composite material prepared by the invention comprises polyaniline-activated carbon, polyaniline-graphene, polyaniline-carbon tube, aniline-graphene-activated carbon, aniline-graphene-carbon tube-activated carbon and other components, combines the characteristics of capacitance carbon and polyaniline, the polyaniline/carbon composite material has better application prospect and economic benefit in the field of super capacitors, can be used as a positive material or a negative material of a super capacitor, widens the condition that polyaniline is used under the positive potential acidic condition to be used under the negative potential (-1-0V) and alkaline (KOH, NaOH, LiOH and the like), and shows high capacity (>350F/g), good rate characteristic and cycling stability (the capacity retention ratio of the material is still more than 80% after 8000 cycles of cycling under the current density of 4A/g).
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
fig. 1 is an SEM image of the polyaniline-graphene-activated carbon composite prepared in example 4;
fig. 2 is a cyclic voltammetry test graph of the polyaniline-graphene-activated carbon composite material prepared in example 4;
fig. 3 is a charge-discharge test curve diagram of the polyaniline-graphene-activated carbon composite material prepared in example 4;
fig. 4 is a graph showing the cycle performance and the charge/discharge efficiency at a current density of 4A/g of the polyaniline-graphene-activated carbon composite material prepared in example 4;
FIG. 5 is a graph of a charge and discharge test curve of the composite material prepared in examples 1-3 under negative potential (-1-0V).
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
(1) Adding carbon material graphene into a glycerol-water solution (wherein the volume ratio of glycerol to water is 1:10) according to the mass volume ratio of 0.1:1 and g: L, uniformly dispersing, carrying out hydrothermal reaction at 120 ℃ for 240min, cooling to normal temperature after the reaction is finished, centrifuging, and drying to obtain a composite carbon-based material precursor;
(2) sequentially adding H with the concentration of 0.1mol/L into the composite carbon-based material precursor prepared in the step (1) and aniline (wherein the mass ratio of the composite carbon-based material precursor to the aniline is 1:0.1)3PO4Ultrasonically stirring and dispersing in a solution (wherein the molar volume ratio of aniline to acid solution is 0.05:1, mol: L) for 240min to form a uniformly dispersed mixed acid solution;
(3) ammonium persulfate is dissolved into H with the concentration of 0.1mol/L according to the molar volume ratio of 1:20(mol: L)3PO4Stirring the solution uniformly to obtain a peroxide acid solution;
(4) at room temperature, quickly pouring the acid solution of the peroxidating agent in the step (3) into the mixed acid solution under stirring (wherein the molar ratio of aniline in the mixed acid solution to ammonium persulfate in the acid solution of the peroxidating agent is 1:1), and stirring for carrying out polymerization reaction at 60 ℃ for 0.5 h;
(5) and after the reaction is finished, obtaining a mixed solution, and sequentially performing centrifugation, washing and drying to obtain the polyaniline-graphene composite material.
Example 2
(1) Adding carbon tubes into an isopropanol-water solution (wherein the volume ratio of isopropanol to water is 4:1) according to the mass volume ratio of 10:1 and g: L, uniformly dispersing, carrying out hydrothermal reaction at 100 ℃ for 60min, cooling to normal temperature after the reaction is finished, centrifuging, and drying to obtain a composite carbon-based material precursor;
(2) sequentially adding H with the concentration of 3mol/L into the composite carbon-based material precursor prepared in the step (1) and aniline (wherein the mass ratio of the composite carbon-based material precursor to the aniline is 1:1)2SO4Solution (in which aniline and H2SO4The molar volume ratio of the solution is 1:1, mol: L) for 60min by ultrasonic stirring and dispersing to form a uniformly dispersed mixed acid solution;
(3) dissolving the lithium perchlorate serving as a per oxidant into H with the concentration of 3mol/L according to the molar volume ratio of 1:100(mol: L)2SO4Stirring the solution uniformly to obtain a peroxide acid solution;
(4) at room temperature, quickly pouring the acid solution of the peroxide agent obtained in the step (3) into the stirred mixed acid solution (wherein the molar ratio of aniline in the mixed acid solution to lithium perchlorate serving as the peroxide agent in the acid solution of the peroxide agent is 1:5), and stirring the mixture to perform polymerization reaction for 12 hours at the temperature of 30 ℃;
(5) and after the reaction is finished, obtaining a mixed solution, and sequentially performing centrifugation, washing and drying to obtain the polyaniline-carbon tube composite material.
Example 3
(1) Adding activated carbon into an ethylene glycol-water solution (wherein the volume ratio of ethylene glycol to water is 8:1) according to the mass-volume ratio of 30:1, g: L, uniformly dispersing, carrying out hydrothermal reaction at 200 ℃ for 5min, cooling to normal temperature after the reaction is finished, centrifuging, and drying to obtain a composite carbon-based material precursor;
(2) sequentially adding the composite carbon-based material precursor prepared in the step (1) and aniline (wherein the mass ratio of the composite carbon-based material precursor to the aniline is 1:100) into a 6mol/L HCl solution (wherein the molar volume ratio of the aniline to the HCl solution is 10:1, and the mol: L) for ultrasonic stirring and dispersing for 10min to form a uniformly dispersed mixed acid solution;
(3) dissolving a peroxidation agent ferric chloride into a 6mol/L HCl solution according to a molar volume ratio of 1:500(mol: L) and uniformly stirring to obtain a peroxidation agent acid solution;
(4) at room temperature, quickly pouring the acid solution of the peroxidating agent in the step (3) into the stirred mixed acid solution (wherein the molar ratio of aniline in the mixed acid solution to ferric chloride serving as a peroxidating agent in the acid solution of the peroxidating agent is 1:10), and stirring for carrying out polymerization reaction at 0 ℃ for 24 hours;
(5) and after the reaction is finished, obtaining a mixed solution, and sequentially carrying out centrifugation, washing and drying to obtain the polyaniline-activated carbon composite material.
Example 4
(1) Adding a carbon material consisting of activated carbon and graphene with equal mass into an ethanol-water solution (wherein the volume ratio of alcohol to water is 2:1) according to the mass-volume ratio of 10:1, g: L, uniformly dispersing, carrying out hydrothermal reaction at 200 ℃ for 5min, cooling to normal temperature after the reaction is finished, centrifuging, and drying to obtain a composite carbon-based material precursor;
(2) sequentially adding the composite carbon-based material precursor prepared in the step (1) and aniline (the mass ratio of the composite carbon-based material precursor to the aniline is 10:7) into an HCl solution with the concentration of 0.8mol/L (wherein the molar volume ratio of the aniline to the HCl solution is 0.05:1, and the mol: L) to be ultrasonically stirred and dispersed for 140min to form a uniformly dispersed mixed acid solution;
(3) dissolving a peroxygen ammonium persulfate into an HCl solution with the concentration of 0.8mol/L according to the molar volume ratio of 1:50(mol: L), and uniformly stirring to obtain a peroxygen acid solution;
(4) at room temperature, quickly pouring the acid solution of the peroxidating agent in the step (3) into the stirred mixed acid solution (wherein the molar ratio of aniline in the mixed acid solution to ammonium persulfate serving as the peroxidating agent in the acid solution of the peroxidating agent is 7:6), and stirring for carrying out polymerization reaction for 1h at 20 ℃;
(5) and after the reaction is finished, obtaining a mixed solution, and sequentially performing centrifugation, washing and drying at 80 ℃ to obtain the polyaniline-graphene-activated carbon composite material.
The polyaniline-graphene-activated carbon composite material prepared in example 4 is characterized by a Scanning Electron Microscope (SEM), and the morphology result is shown in fig. 1. The obtained polyaniline-graphene-activated carbon composite material is made into electrode plates with required sizes, and then cyclic voltammetry tests and different constant current charge and discharge tests with different sweep rates are carried out, and the results are shown in fig. 2 and fig. 3. From the test results, the composite material prepared in the embodiment 4 of the invention shows obvious pseudocapacitance characteristics, which indicates that polyaniline exists in the composite, wherein fig. 2 is a CV curve with a sweep rate of 1-10 mV/s at a negative potential (-1-0V), wherein a pair of significant redox peaks are caused by redox reaction of polyaniline, and CV curves with different sweep rates keep good similarity; fig. 3 is a charge and discharge test curve at a negative potential (-1-0V), and compared with an individual activated carbon or polyaniline material, the platform of the composite material has a greatly increased capacity (the capacity can reach 355F/g), and the voltage drop is also relatively small (only 30mV), which indicates that the polyaniline-graphene-activated carbon composite material prepared in example 4 has good electrode conductivity. The result of the cycle performance test of the composite material is shown in fig. 4, and it can be seen from fig. 4 that the material has good cycle performance (the capacity retention rate of the material is still above 82% at 8000 cycles under 4A/g current density and negative potential (-1-0V)) and charge-discharge stability (the charge-discharge efficiency is 100%).
The same charge and discharge tests were performed on the composite materials prepared in examples 1 to 3 at negative potential (-1-0V), and the results are shown in fig. 5, which illustrates that the composite materials prepared in examples 1 to 3 all exhibit significant pseudocapacitance characteristics, good electrode conductivity, good cycle performance and charge and discharge stability.
In conclusion, the polyaniline/capacitor carbon-based composite material prepared by the invention combines the characteristics of capacitor carbon and polyaniline, has better application prospect and economic benefit in the field of super capacitors, can be used as a positive electrode material or a negative electrode material of a super capacitor, widens the condition that polyaniline is used under the positive potential acidic condition to the condition that the polyaniline can be used under the negative potential (-1-0V) and alkaline (KOH, NaOH, LiOH and the like), and shows high capacity (>350F/g), good rate characteristic and cycling stability (the capacity retention ratio of the material is still more than 80% after the material is cycled for 8000 turns under the current density of 4A/g).
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.

Claims (10)

1. A preparation method of a polyaniline/capacitance carbon-based composite material is characterized by comprising the following steps:
(1) adding a carbon material into an alcohol-water solution for uniform dispersion, carrying out hydrothermal reaction at 120-200 ℃ for 5-240 min, cooling to normal temperature after the reaction is finished, centrifuging, and drying to obtain a composite carbon-based material precursor, wherein the carbon material is any one or more of graphene, a carbon tube or activated carbon;
(2) sequentially adding the composite carbon-based material precursor and aniline in the step (1) into an acid solution, and ultrasonically stirring and dispersing to form a uniformly dispersed mixed acid solution;
(3) dissolving a peroxide into an acid solution, and uniformly stirring to obtain a peroxide acid solution;
(4) at room temperature, rapidly pouring the acid solution of the over oxidant in the step (3) into the stirred mixed acid solution, and stirring for polymerization reaction;
(5) and after the reaction is finished, obtaining a mixed solution, and sequentially performing centrifugation, washing and drying to obtain the polyaniline/capacitance carbon composite material.
2. The method according to claim 1, wherein the mass-to-volume ratio of the carbon material to the alcohol-water solution in step (1) is 0.1:1 to 30:1, g: L, the volume ratio of the alcohol to water in the alcohol-water solution is 1:10 to 8:1, and the alcohol is any one of ethanol, isopropanol, butanol, ethylene glycol, and glycerol.
3. The method according to claim 1, wherein the mass ratio of the carbon-based material precursor to the aniline in the step (2) is 1:0.1 to 1:100, and the molar volume ratio of the aniline to the acid solution is 0.05 to 10:1, mol: L.
4. The preparation method according to claim 1, wherein the molar volume ratio of the hyperoxidant to the acid solution in the step (3) is 1: 20-1: 500, mol: L, and the hyperoxidant is any one or more of ammonium persulfate, lithium perchlorate, ferric chloride and potassium permanganate.
5. The preparation method according to claim 1, wherein the molar ratio of the aniline in the mixed acid solution in the step (4) to the peroxide in the peroxide acid solution is 1:1 to 1: 10.
6. The method according to any one of claims 3 to 5, wherein the concentration of the acid solution is 0.1 to 6mol/L, and the acid in the acid solution is HCl or H2SO4Or H3PO4。
7. The method according to claim 1, wherein the stirring and dispersing time in the step (2) is 10 to 240 min.
8. The method according to claim 1, wherein the polymerization in the step (4) is carried out at a reaction temperature of 0 to 60 ℃ for a reaction time of 0.5 to 24 hours.
9. The polyaniline/capacitance carbon-based composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the polyaniline/capacitive carbon-based composite material of claim 9 in a supercapacitor.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201120109A (en) * 2009-12-14 2011-06-16 Chung Shan Inst Of Science Polymer/carbon nanotube composite film with high gas permeability resistance and manufacturing method thereof
CN103413689A (en) * 2013-07-19 2013-11-27 北京科技大学 Method for preparing graphene aerogel and graphene/ metallic oxide aerogel
CN107417910A (en) * 2017-06-14 2017-12-01 福州大学 The preparation method and application of carbon nanohorn/grapheme/polyaniline composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201120109A (en) * 2009-12-14 2011-06-16 Chung Shan Inst Of Science Polymer/carbon nanotube composite film with high gas permeability resistance and manufacturing method thereof
CN103413689A (en) * 2013-07-19 2013-11-27 北京科技大学 Method for preparing graphene aerogel and graphene/ metallic oxide aerogel
CN107417910A (en) * 2017-06-14 2017-12-01 福州大学 The preparation method and application of carbon nanohorn/grapheme/polyaniline composite material

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