CN1995143A - Method for preparing composite electrode material for super capacitor - Google Patents
Method for preparing composite electrode material for super capacitor Download PDFInfo
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- CN1995143A CN1995143A CN 200610105268 CN200610105268A CN1995143A CN 1995143 A CN1995143 A CN 1995143A CN 200610105268 CN200610105268 CN 200610105268 CN 200610105268 A CN200610105268 A CN 200610105268A CN 1995143 A CN1995143 A CN 1995143A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- 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
Abstract
The invention discloses a making method of super capacitance composite electrode material, which is characterized by the following: compounding conductive macromolecule and functional carbon nanometer pipe; cutting carbon nanometer pipe in the condensed sulfuric acid or nitrite acid through ultrasonic vibration; making the hollow structure of carbon nanometer pipe adsorb bulk compaction and bulking due to discharge; improving conductivity and reducing resistant of carbon nanometer pipe.
Description
Technical field
The present invention relates to a kind of novel electron material preparation method, particularly relate to the preparation method of composite electrode material for super capacitor.
Technical background
Ultracapacitor has than battery and has higher power density, has higher energy density than traditional capacitor, not only can provide peak power with supporting use of battery to power truck etc., even can be separately for power tool or power truck provide power, to reduce the negative impact that burning provides energy that ecology is brought based on the petrochemical industry resource.
Electrode materials is the deciding factor of ultracapacitor performance, and people have more high-energy-density and the more electrode materials of high power density in exploitation always.Owing to there is the different states of oxidation, conducting polymer (polypyrrole, polyaniline, Polythiophene, polyhenylene, and their derivative equiconjugate superpolymer) can be used as the electrode materials of oxidation-reduction type ultracapacitor.Compare with the electrode materials (carbon material and metal oxide) of the common ultracapacitor of other two class, conducting polymer composite (being also referred to as conduction high polymer) is than carbon material (gac, carbon fiber and carbon nanotube) have higher specific storage and specific energy density, have lower cost than metal oxide (as ruthenium oxide).Therefore, conducting polymer is a kind of electrode material for super capacitor that has very much practical value.
Yet, conductive high molecular electrode material is followed dedoping when discharge, just mix ion is deviate to enter electrolytic solution in the polymkeric substance grid, this can cause the volumetric shrinkage of polymkeric substance, influence to ion at when charging embedded polymer thing grid and reduce the capacity of polymkeric substance, and cyclical stability that can the impact polymer electrode.Polymkeric substance specific conductivity when discharge condition (dedoping state) can sharply descend, and also will increase the internal resistance of electrical condenser greatly.
Summary of the invention
The object of the present invention is to provide a kind of volumetric properties and cyclical stability that can strengthen conducting polymer, the volume change that causes polymkeric substance when reducing to discharge and recharge further improves the preparation method of composite electrode material for super capacitor of the cycle performance of composite electrode material.
For achieving the above object, the technical solution used in the present invention is: at first carbon nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 20 ℃～80 ℃ sonic oscillations 1～60 hour, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.01mol/L～0.6mol/L that next adding conductive high polymer monomer in the diluting soln of A solution or A makes conductive high polymer monomer concentration; And then add to support ionogen and make that to support electrolytical concentration be that 0mol/L～0.3mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 0.1～10mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
Carbon nanotube of the present invention is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; Conductive high polymer monomer is pyrroles, aniline, thiophene or their derivative methylpyrrole, ethene dioxythiophene; The support ionogen is muriate, perchlorate or nitrate.
The present invention utilizes the high conductivity and the hollow structure of carbon nanotube, strengthens the volumetric properties and the cyclical stability of conducting polymer by preparation conducting polymer and carbon mano-tube composite.Because carbon nanotube is reunited easily, is difficult to disperse in solution.Therefore at first carbon nanotube is carried out cutting and functionalization is ionization, be beneficial to the conducting polymer and the carbon mano-tube composite of preparation even structure so that better be dispersed in the polymeric solution, the prior advantage of another of Chu Liing is to obtain carbon nano tube-doped conducting polymer like this, the volume change that causes polymkeric substance when reducing to discharge and recharge can further improve the cycle performance of composite electrode material thus.
Description of drawings
Fig. 1 is the electromicroscopic photograph of polypyrrole/functionalized carbon nano-tube mixture;
Fig. 2 (, a), (b) He (c) be respectively polypyrrole film, the cyclic voltammetry curve of polypyrrole/carbon nanotube and polypyrrole/functionalized carbon nano-tube, wherein X-coordinate is a current potential, ordinate zou is an electric current;
Fig. 3 is polypyrrole film (1), polypyrrole/carbon nanotube (2) and the specific storage of polypyrrole/functionalized carbon nano-tube (3) when different scanning rates, and wherein X-coordinate is a scanning speed, ordinate zou is a specific storage.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1: at first Single Walled Carbon Nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 20 ℃ of sonic oscillations 60 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.01mol/L that next adding conductive high polymer monomer pyrroles in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding muriate, to make muriatic concentration be that 0.05mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 0.1mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
Embodiment 2: at first multi-walled carbon nano-tubes is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 50 ℃ of sonic oscillations 30 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is that 0.05mol/L makes solution B that next adding conductive high polymer monomer aniline in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; At last working electrode and counter electrode are placed solution B, on working electrode, apply 5mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
Embodiment 3: at first Single Walled Carbon Nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 80 ℃ of sonic oscillations 1 hour, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.2mol/L that next adding conductive high polymer monomer thiophene in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding nitrate, to make nitrate concentration be that 0.1mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 8mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
Embodiment 4: at first multi-walled carbon nano-tubes is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 40 ℃ of sonic oscillations 40 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.6mol/L that next adding conductive high polymer monomer methylpyrrole in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding muriate, to make muriatic concentration be that 0.2mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 10mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
Embodiment 5: at first Single Walled Carbon Nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 60 ℃ of sonic oscillations 20 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.4mol/L that next adding conductive high polymer monomer ethene dioxythiophene in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding nitrate, to make the concentration of nitrate be that 0.3mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 2mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
Referring to Fig. 1, granular material is a polypyrrole among the figure, and thinner rod shape thing is that (diameter is 10～20nm) to carbon nanotube, and thicker rod shape thing is the polypyrrole coated carbon nanotube.
Referring to Fig. 2 (a), (b) and (c) be respectively polypyrrole film, the cyclic voltammetry curve of polypyrrole/carbon nanotube and polypyrrole/functionalized carbon nano-tube, as can be seen from the figure, when polypyrrole film was 10mV/s in scanning speed, the polypyrrole film electrode showed comparatively ideal ultracapacitor cyclic voltammetry curve (near rectangle), but along with the increase of scanning speed, polypyrrole film just shows the cyclic voltammetry curve of resistance gradually, shown in Fig. 2 (a); Polypyrrole/carbon nanotube (not functionalization) shows the electrochemistry capacitance performance more excellent than polypyrrole film when rapid scanning, shown in Fig. 2 (b).This is because in this matrix material, and carbon nanotube not only can be contributed the electric double layer capacitance amount, and its hollow structure can absorb volumetric shrinkage and the expansion that causes when macromolecular material discharges and recharges, so mixture has ion transport characteristic faster.Yet polypyrrole/functionalized carbon nano-tube shows ion transport characteristic faster, shows the volumetric properties of better ultracapacitor during for 200mV/s in scanning speed, shown in Fig. 2 (c).Ionized carbon nanotube can mix to conducting polymer, because the volume of carbon nanotube is bigger, be not easy to deviate from from polymkeric substance when discharge, so the negative charge on the polymer chain will be compensated by the positively charged ion that enters in the solution.Negatively charged ion is deviate from polymer phase than bringing two benefits to I haven't seen you for ages when this and discharge, once being not deviate from the volume change that can not cause polymkeric substance and increase when charging difficulty of entering of ion owing to negatively charged ion, the 2nd, cationic volume is less than negatively charged ion, positively charged ion enter deviate from than negatively charged ion easier.And, functionalized carbon nanotube has dispersed preferably in solution, thereby can prepare the mixture of even structure, therefore, polymkeric substance/Ionized carbon mano-tube composite has than polymkeric substance/unionization carbon mano-tube composite charge-discharge characteristic faster.The specific storage of these three kinds of materials when different scanning rates as shown in Figure 3, when scanning speed was 10mV/s, the specific storage of two kinds of polypyrrole/carbon mano-tube composites all surpassed 200F/g, but the specific storage of polypyrrole/functionalized carbon nano-tube mixture is higher.When scanning speed is 200mV/s, it is 13.6% of 10mV/s that the specific storage instrument of polypyrrole film has scanning speed, it is 71.1% of 10mV/s that the specific storage of polypyrrole/carbon nanotube (not functionalization) mixture still has scanning speed, is 89.8% of 10mV/s and polypyrrole/functionalized carbon nano-tube mixture still has scanning speed.Therefore, the conducting polymer that makes/functionalized carbon nano-tube electrode materials has high conductivity, height ratio capacity and super-quick charging discharge capability.This composite materials can make high-energy-density, high-specific-power and long-life ultracapacitor.
Claims (9)
1, the preparation method of composite electrode material for super capacitor is characterized in that:
1) at first carbon nanotube is added in the mixing solutions that volume ratio is 3: 1 98% the vitriol oil and 68% concentrated nitric acid 20 ℃～80 ℃ sonic oscillations 1～60 hour, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid;
Secondly 2) adding conductive high polymer monomer in the diluting soln of A solution or A, to make conductive high polymer monomer concentration be 0.01mol/L～0.6mol/L; And then add to support ionogen and make that to support electrolytical concentration be that 0mol/L～0.3mol/L makes solution B;
3) at last working electrode and counter electrode are placed solution B, on working electrode, apply 0.1～10mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
2, the preparation method of composite electrode material for super capacitor according to claim 1 is characterized in that: said carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
3, the preparation method of composite electrode material for super capacitor according to claim 1 is characterized in that: said conductive high polymer monomer is pyrroles, aniline, thiophene or their derivative methylpyrrole, ethene dioxythiophene.
4, the preparation method of composite electrode material for super capacitor according to claim 1 is characterized in that: said support ionogen is muriate, perchlorate or nitrate.
5, the preparation method of composite electrode material for super capacitor according to claim 1, it is characterized in that: at first Single Walled Carbon Nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 20 ℃ of sonic oscillations 60 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.01mol/L that next adding conductive high polymer monomer pyrroles in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding muriate, to make muriatic concentration be that 0.05mol/L makes solution B; At last working electrode and counter electrode are placed solution B, two apply 0.1mA/cm on working electrode
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
6, the preparation method of composite electrode material for super capacitor according to claim 1, it is characterized in that: at first multi-walled carbon nano-tubes is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 50 ℃ of sonic oscillations 30 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is that 0.05mol/L makes solution B that next adding conductive high polymer monomer aniline in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; At last working electrode and counter electrode are placed solution B, on working electrode, apply 5mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
7, the preparation method of composite electrode material for super capacitor according to claim 1, it is characterized in that: at first Single Walled Carbon Nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 80 ℃ of sonic oscillations 1 hour, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.2mol/L that next adding conductive high polymer monomer thiophene in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding nitrate, to make nitrate concentration be that 0.1mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 8mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
8, the preparation method of composite electrode material for super capacitor according to claim 1, it is characterized in that: at first multi-walled carbon nano-tubes is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 40 ℃ of sonic oscillations 40 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.6mol/L that next adding conductive high polymer monomer methylpyrrole in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding muriate, to make muriatic concentration be that 0.2mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 10mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
9, the preparation method of composite electrode material for super capacitor according to claim 1, it is characterized in that: at first Single Walled Carbon Nanotube is added volume ratio and be in the mixing solutions of 3: 1 98% the vitriol oil and 68% concentrated nitric acid 60 ℃ of sonic oscillations 20 hours, dilute the concentrated acid solution of carbon nanotubes then, adopt filtration method or centrifugal separation to remove the dispersion liquid A that obtains being rich in functionalized carbon nano-tube behind sulfuric acid and the nitric acid; It is 0.4mol/L that next adding conductive high polymer monomer ethene dioxythiophene in the diluting soln of A solution or A makes the concentration of conductive high polymer monomer; And then adding nitrate, to make the concentration of nitrate be that 0.3mol/L makes solution B; At last working electrode and counter electrode are placed solution B, on working electrode, apply 2mA/cm
2Current density is carried out electrochemical polymerization, can obtain the composite membrane of layer of even conducting polymer and carbon nanotube after polymerization is finished on working electrode, and the thickness of this composite membrane can be that the polymerization electric current multiply by polymerization time and controls by the polymerization electric weight.
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| CN102020845A (en) * | 2010-11-25 | 2011-04-20 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| US8187887B2 (en) | 2009-10-06 | 2012-05-29 | Massachusetts Institute Of Technology | Method and apparatus for determining radiation |
| US8212132B2 (en) | 2007-03-07 | 2012-07-03 | Massachusetts Institute Of Technology | Functionalization of nanoscale articles including nanotubes and fullerenes |
| US8456073B2 (en) | 2009-05-29 | 2013-06-04 | Massachusetts Institute Of Technology | Field emission devices including nanotubes or other nanoscale articles |
| US8476510B2 (en) | 2010-11-03 | 2013-07-02 | Massachusetts Institute Of Technology | Compositions comprising and methods for forming functionalized carbon-based nanostructures |
| US8735313B2 (en) | 2008-12-12 | 2014-05-27 | Massachusetts Institute Of Technology | High charge density structures, including carbon-based nanostructures and applications thereof |
| US8951473B2 (en) | 2008-03-04 | 2015-02-10 | Massachusetts Institute Of Technology | Devices and methods for determination of species including chemical warfare agents |
| CN109243861A (en) * | 2018-09-26 | 2019-01-18 | 南京科莱菲恩新材料科技有限公司 | The method for improving performance of the supercapacitor |
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| CN1133219C (en) * | 1999-12-17 | 2003-12-31 | 南京大学 | High-strength macroreluctance conductive polymerized film and its preparation method |
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| US8212132B2 (en) | 2007-03-07 | 2012-07-03 | Massachusetts Institute Of Technology | Functionalization of nanoscale articles including nanotubes and fullerenes |
| US9267908B2 (en) | 2008-03-04 | 2016-02-23 | Massachusetts Institute Of Technology | Devices and methods for determination of species including chemical warfare agents |
| US8951473B2 (en) | 2008-03-04 | 2015-02-10 | Massachusetts Institute Of Technology | Devices and methods for determination of species including chemical warfare agents |
| US9114377B2 (en) | 2008-12-12 | 2015-08-25 | Massachusetts Institute Of Technology | High charge density structures, including carbon-based nanostructures and applications thereof |
| US8735313B2 (en) | 2008-12-12 | 2014-05-27 | Massachusetts Institute Of Technology | High charge density structures, including carbon-based nanostructures and applications thereof |
| US8456073B2 (en) | 2009-05-29 | 2013-06-04 | Massachusetts Institute Of Technology | Field emission devices including nanotubes or other nanoscale articles |
| US8426208B2 (en) | 2009-10-06 | 2013-04-23 | Massachusetts Institute Of Technology | Method and apparatus for determining radiation |
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| CN102020845A (en) * | 2010-11-25 | 2011-04-20 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| CN102020845B (en) * | 2010-11-25 | 2012-05-23 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| US11505467B2 (en) | 2017-11-06 | 2022-11-22 | Massachusetts Institute Of Technology | High functionalization density graphene |
| CN109243861A (en) * | 2018-09-26 | 2019-01-18 | 南京科莱菲恩新材料科技有限公司 | The method for improving performance of the supercapacitor |
| CN113643908A (en) * | 2021-06-25 | 2021-11-12 | 浙江工业大学 | One kind (Ni, Co)3S4CNT material and preparation method and application thereof |
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