CN102351167A - Carbon nanotube ultrathin film with stable electrochemical property and preparation method thereof - Google Patents
Carbon nanotube ultrathin film with stable electrochemical property and preparation method thereof Download PDFInfo
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- CN102351167A CN102351167A CN2011101882424A CN201110188242A CN102351167A CN 102351167 A CN102351167 A CN 102351167A CN 2011101882424 A CN2011101882424 A CN 2011101882424A CN 201110188242 A CN201110188242 A CN 201110188242A CN 102351167 A CN102351167 A CN 102351167A
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Abstract
The invention relates to the technical field of carbon nanotube thin film preparation, in particular to a carbon nanotube ultrathin film with stable electrochemical property and a preparation method thereof. The invention aims to overcome the defect that irreversible oxidation reaction is easy to perform under current catalysis in the prior art. The preparation method for the carbon nanotube ultrathin film with the stable electrochemical property comprises the following steps of: 1, preparing a carbon nanotube ultrathin film layer which is formed on a solid substrate by a solution of soluble carboxyl carbon nanotubes through a chemical self-assembly method; and 2, terminating, namely performing grafting chemical reaction of the carbon nanotube ultrathin film layer on the solid substrate and conductive molecules in a chemical coupling or electrochemical oxidation polymerization mode to obtain the carbon nanotube ultrathin film.
Description
Technical field
The present invention relates to carbon nano-tube film manufacturing technology field, specifically is carbon nanotube ultrathin membrane of a kind of stable electrochemical property and preparation method thereof.
Background technology
(Carbon nanotubes is a kind of new carbon of being found by the Iijima of Japanese NEC Corporation in 1991 CNT) to carbon nanotube, has excellent electricity, heat, mechanical property.Typical carbon nanotube is prone to assemble bunchy in solution, is dissolved in any solvent hardly, big limitations CNTs application in every respect.In recent years, through the package action of tensio-active agent, the different solvents that CNTs is dispersed in of success comprises in the water; In addition, after chemical reaction is modified with various functionalized, and decapacitation obtains outside the dispersion liquid of CNTs, also provides possible for the assembling of CNTs and surface reaction.Owing to have good electronic conductance property, chemical stability; And unique physical and chemical performance such as high specific surface area, the CNT film has represented fine application prospect in fields such as chemical catalysis, intelligent response, fuel cell, secondary cell and ultracapacitors.
The preparation of CNT film can be divided into solution casting method usually, layer-layer absorption self-assembly method, and electrochemical deposition method is self-assembled into embrane method (SAM) and LB technology etc.Owing to have the good environmental stability and the higher degree of order; The self-assembling ultrathin film that chemical bond is constructed has obtained extensive studies in recent years; The solution that the steps include: solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method; The solution of solubility carboxyl carbon nanotube is the solution of solubility carboxyl Single Walled Carbon Nanotube, the solution of solubility carboxyl double-walled carbon nano-tube or the solution of solubility carboxyl multi-walled carbon nano-tubes; Fixing base is that indium tin oxide target (ITO) or silicon chip constitute, and handles through aminosiloxane in advance; The film thickness that makes is at 1 ~ 100nm.Yet, when utilizing chemical bond to prepare the carbon nanotube assembling film, need to use the carbon nanotube of carboxylic acid group's modification, because the reaction limit usually causes the inner residual a large amount of free carboxylate radical of assembling film as motivating force.When using as electrochemical device, under the catalysis of electric current, these are present in the lip-deep free active group of CNT and are prone to the irreversible oxidizing reaction of generation, thereby device performance is seriously descended.Therefore in order to obtain carbon nano-tube film, must carry out inerting to the remaining carboxylate radical in its inside and handle with good electric chemical stability.Because the indissoluble characteristic of carbon nanotube causes very difficulty is handled in the inerting of its carboxylate radical, to obtain simultaneously with carboxylate radical between rely on firm chemical bond to link to each other modifier also very difficult.
Summary of the invention
The objective of the invention is carbon nanotube ultrathin membrane that will provide a kind of stable electrochemical property and preparation method thereof, to overcome the shortcoming that is prone under electric current catalysis, take place irreversible oxidizing reaction that prior art exists.
For overcoming the problem that prior art exists, the present invention provides a kind of preparation method of carbon nanotube ultrathin membrane of stable electrochemical property, comprises the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2, termination process: the ultra-thin rete of the carbon nanotube on solid substrate carries out the grafting chemical reaction through the mode of chemical coupling or electrochemically oxidative polymerization with the electroconductibility molecule, gets the carbon nanotube ultrathin membrane.
Above-mentioned electroconductibility molecule is electrically conductive polyaniline, oligomer of phenylamine, electric polypyrrole or conductive polythiophene.
Above-mentioned chemical coupling mode is: the substrate immersion of having assembled the ultra-thin rete of carbon nanotube in conductive polymer solution; Make above the remaining carboxyl to form, wash the particle of physical adsorption then with the organic solvent N-Methyl pyrrolidone with the joining conducting polymer of firm chemical bond.
Above-mentioned electrochemically oxidative polymerization mode is: the substrate immersion of having assembled the ultra-thin rete of carbon nanotube in conductive high polymer monomer solution; Apply from-2 ~+sweep voltage of 2V is so that form conducting polymer above the remaining carboxyl, and the particle that washes physical adsorption with the organic solvent N-Methyl pyrrolidone is promptly realized carbon nanotube ultrathin membrane of the present invention at last.
A kind of carbon nanotube ultrathin membrane of the stable electrochemical property that obtains by above-mentioned preparation method.
Compared with prior art, advantage of the present invention is:
1, the carbon nanotube ultrathin membrane of this method manufacturing links to each other with substrate with firm chemical bond; And remaining carboxylic acid group also is connected with the electroconductibility molecule with firm chemical bond; Stable physical property; Electric conductivity is about 1.0 S/cm; Film thickness is even; Favorable dispersity (like Fig. 1) has extremely strong electrochemical stability, can under the sour environment of aerobic, demonstrate stable redox chemical property.
2, to have technology simple for this method, and the characteristics of processing ease are not subjected to the influence of substrate surface shape.
3, because carbon nano-tube film provided by the invention has excellent electrochemical redox stability; Can improve the performance and the work-ing life thereof of device greatly; Be suitable as fields such as all kinds of photoelectric devices, ultracapacitor, secondary cell, therefore widened the use range of carbon nano-tube film in all kinds of light, electrochemical device.
Description of drawings:
Fig. 1 is the characteristic atomic power flying-spot microscope figure of the present invention's carbon nanotube ultrathin membrane of making stable electrochemical property;
Fig. 2 is the H of the carbon nano-tube film that provides respectively of prior art and embodiment 1 at 1.0M
2SO
4Electrochemical property test curve comparison diagram in the solution.
Fig. 3 is the H of the carbon nano-tube film that provides respectively of prior art and embodiment 3 at 1.0M
2SO
4Electrochemical property test curve comparison diagram in the solution.
Embodiment:
To combine accompanying drawing and embodiment that the present invention is elaborated below.
Embodiment 1: a kind of carbon nanotube ultrathin membrane of stable electrochemical property, obtain by following preparation method, comprise the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2, termination process: the N that the substrate of having assembled the ultra-thin rete of carbon nanotube is immersed in 0.1mmol/L earlier; N'-dicyclohexylcarbodiimide/N; Stop 30min in the dinethylformamide solution; Be immersed in polyaniline/N of 0.1mol/L again; Stop 2hr in the dinethylformamide solution; Form conducting polymer above making remaining carboxyl; Then earlier with a large amount of N; Dinethylformamide cleans; Wash the particle of physical adsorption again with the organic solvent N-Methyl pyrrolidone, get the carbon nanotube ultrathin membrane.
Referring to Fig. 1, the carbon nanotube ultrathin membrane of the present invention's preparation links to each other with substrate with firm chemical bond, and remaining carboxylic acid group also is connected with the electroconductibility molecule with firm chemical bond; Stable physical property; Electric conductivity is about 1.0 S/cm, and film thickness is even, favorable dispersity.
Referring to Fig. 2 a; Carbon nano-tube film to not passing through termination process is tested; Can find out; Under the catalysis of electric current; (Fig. 2 a) to have tangible irreversible oxidation current peak without the end capped carbon nano-tube film of electroconductive molecule; This is because the free carboxy that is present on the carbon nano tube surface takes place due to the irreversible oxidizing reaction, shows that the electrochemical redox stability of film is not high.
Referring to Fig. 2 b, get the carbon nano-tube film of embodiment 1 and test, can find out that the electrochemical redox stability of carbon nano-tube film in acidic medium significantly improves.The specific conductivity of the carbon nano-tube film that four probe method records is 1.0 S/cm.
Embodiment 2: a kind of carbon nanotube ultrathin membrane of stable electrochemical property, obtain by following preparation method, comprise the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2, termination process: the N that the substrate of having assembled the ultra-thin rete of CNT is immersed in 0.1mmol/L earlier; N'- dicyclohexylcarbodiimide/N; Stop 30min in the dinethylformamide solution; Be immersed in p-phenylenediamine (PPD)/N of 0.1mol/L again; Stop 2hr in the dinethylformamide solution; Be immersed at last in the acidic aqueous solution of oligomer of phenylamine of 1.0mol/L; Apply from-2 ~+scanning voltage of 2V is so that form conducting polymer above the remaining carboxyl, and the particle that washes physical absorption with organic solvent N- methyl pyrrolidone is promptly realized CNT ultrathin membrane of the present invention at last.
Embodiment 3: a kind of carbon nanotube ultrathin membrane of stable electrochemical property, obtain by following preparation method, comprise the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2, termination process: the substrate immersion of having assembled the ultra-thin rete of CNT at the N that the substrate of having assembled the ultra-thin rete of CNT is immersed in 0.1mmol/L earlier; N'- dicyclohexylcarbodiimide/N; Stop 30min in the dinethylformamide solution; Be immersed in 2- amino-pyrroles/N of 0.1mol/L again; Stop 2hr in the dinethylformamide solution; Be immersed at last in pyrroles's acidic aqueous solution of 1.0mol/L; Apply from-2 ~+scanning voltage of 2V is so that form conducting polymer above the remaining carboxyl, and the particle that washes physical absorption with organic solvent N- methyl pyrrolidone is promptly realized CNT ultrathin membrane of the present invention at last.
Referring to Fig. 3 b, get the carbon nano-tube film of embodiment 3 and test, can find out that the electrochemical redox stability of carbon nano-tube film in acidic medium significantly improves.
Embodiment 4: a kind of carbon nanotube ultrathin membrane of stable electrochemical property, obtain by following preparation method, comprise the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2, termination process: the substrate immersion of having assembled the ultra-thin rete of CNT at the N that the substrate of having assembled the ultra-thin rete of CNT is immersed in 0.1mmol/L earlier; N'- dicyclohexylcarbodiimide/N; Stop 30min in the dinethylformamide solution; Be immersed in 3- aminothiophene/N of 0.1mol/L again; Stop 2hr in the dinethylformamide solution; Be immersed at last in the thiophene acidic aqueous solution of 1.0mol/L; Apply from-2 ~+scanning voltage of 2V is so that form conducting polymer above the remaining carboxyl, and the particle that washes physical absorption with organic solvent N- methyl pyrrolidone is promptly realized CNT ultrathin membrane of the present invention at last.
Embodiment 5: a kind of carbon nanotube ultrathin membrane of stable electrochemical property, obtain by following preparation method, comprise the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2; Termination process: the N that the substrate of having assembled the ultra-thin rete of carbon nanotube is immersed in 0.1mmol/L earlier; N'-dicyclohexylcarbodiimide/N; Stop 30min in the dinethylformamide solution; Be immersed in 3-aminothiophene/N of 0.1mol/L again; Stop 2hr in the dinethylformamide solution; Be immersed at last in thiophene/chloroformic solution of the 1.0mmol/L that contains iron trichloride; So that form conducting polymer above the remaining carboxyl, the particle that washes physical adsorption with the organic solvent N-Methyl pyrrolidone is promptly realized carbon nanotube ultrathin membrane of the present invention at last.
The performance test methods of above-mentioned product is following:
Three electrode modes are adopted in test to the chemical property of carbon nanotube ultrathin membrane, and the carbon nano-tube film that obtains with embodiment one is a tested object.Carbon nano-tube film is as working electrode, and platinum electrode is as counter electrode, and the Ag/AgCl electrode is as reference electrode, the H of 1.0M
2SO
4Solution is as supporting electrolyte, and voltage scan range is-0.1 ~ 0.9V.
Claims (5)
1. the preparation method of the carbon nanotube ultrathin membrane of a stable electrochemical property comprises the steps:
Step 1, the ultra-thin rete of preparation carbon nanotube: the solution of solubility carboxyl carbon nanotube forms on solid substrate through chemical self-assembly method;
Step 2, termination process: the ultra-thin rete of the carbon nanotube on solid substrate carries out the grafting chemical reaction through the mode of chemical coupling or electrochemically oxidative polymerization with the electroconductibility molecule, gets the carbon nanotube ultrathin membrane.
2. the preparation method of the carbon nanotube ultrathin membrane of stable electrochemical property as claimed in claim 1; It is characterized in that: said electroconductibility molecule is electrically conductive polyaniline, oligomer of phenylamine, electric polypyrrole or conductive polythiophene, is not having significant difference aspect the chemical property of stable carbon nano-tube.
3. the preparation method of the carbon nanotube ultrathin membrane of stable electrochemical property as claimed in claim 1 or 2; It is characterized in that: said chemical coupling mode is: the substrate immersion of having assembled the ultra-thin rete of carbon nanotube in conductive polymer solution; Make above the remaining carboxyl to form, wash the particle of physical adsorption then with the organic solvent N-Methyl pyrrolidone with the joining conducting polymer of firm chemical bond.
4. the preparation method of the carbon nanotube ultrathin membrane of stable electrochemical property as claimed in claim 1 or 2; It is characterized in that: said electrochemically oxidative polymerization mode is: the substrate immersion of having assembled the ultra-thin rete of carbon nanotube in conductive high polymer monomer solution; Apply from-2 ~+sweep voltage of 2V is so that form conducting polymer above the remaining carboxyl, and the particle that washes physical adsorption with the organic solvent N-Methyl pyrrolidone is promptly realized carbon nanotube ultrathin membrane of the present invention at last.
5. the carbon nanotube ultrathin membrane of the stable electrochemical property that preparation method as claimed in claim 1 makes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103086362A (en) * | 2012-12-11 | 2013-05-08 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
| CN103346021A (en) * | 2013-06-27 | 2013-10-09 | 中国铝业股份有限公司 | Mixed type electrochemical capacitor |
| CN103897183A (en) * | 2014-04-02 | 2014-07-02 | 电子科技大学 | Binary carbon material-conductive polymer composite nano gas-sensitive thin film and preparation method thereof |
| CN109056036A (en) * | 2018-07-23 | 2018-12-21 | 北京工业大学 | The preparation method of carbon naotube-polyaniline electrochromism laminated film |
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| CN101924184A (en) * | 2010-07-09 | 2010-12-22 | 电子科技大学 | Organic thin film solar cell and preparation method thereof |
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| CN101924184A (en) * | 2010-07-09 | 2010-12-22 | 电子科技大学 | Organic thin film solar cell and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086362A (en) * | 2012-12-11 | 2013-05-08 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
| CN103086362B (en) * | 2012-12-11 | 2014-10-15 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
| CN103346021A (en) * | 2013-06-27 | 2013-10-09 | 中国铝业股份有限公司 | Mixed type electrochemical capacitor |
| CN103897183A (en) * | 2014-04-02 | 2014-07-02 | 电子科技大学 | Binary carbon material-conductive polymer composite nano gas-sensitive thin film and preparation method thereof |
| CN103897183B (en) * | 2014-04-02 | 2016-04-06 | 电子科技大学 | Binary carbon material-conductive composite nano-polymers air-sensitive film and preparation method thereof |
| CN109056036A (en) * | 2018-07-23 | 2018-12-21 | 北京工业大学 | The preparation method of carbon naotube-polyaniline electrochromism laminated film |
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Application publication date: 20120215 |