CN102436934B - Composite nanometer carbon paper and preparation method thereof - Google Patents
Composite nanometer carbon paper and preparation method thereof Download PDFInfo
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- CN102436934B CN102436934B CN201110271170.XA CN201110271170A CN102436934B CN 102436934 B CN102436934 B CN 102436934B CN 201110271170 A CN201110271170 A CN 201110271170A CN 102436934 B CN102436934 B CN 102436934B
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Abstract
The invention discloses composite nanometer carbon paper and a preparation method thereof. The nanometer carbon paper uses carbon nanometer paper as a framework network, MnO2 metallic oxides are deposited on the surface, the outer layer is covered with grapheme, and the composite nanometer carbon paper belongs to a flexible composite film material. The preparation method of the composite nanometer carbon paper comprises the steps that carbon nanometer tubes are dispersed in a solvent, then, the suction filtering is carried out to obtain carbon nanometer tube paper, next, the carbon nanometer tube paper is used as a carrier for depositing the MnO2 metallic oxides on the surface, and finally, the grapheme is adhered on the product surface to obtain target products. The electrical conductivity, the heavy current charging and discharging capability, the specific capacitance and the cycle life of the composite nanometer carbon paper are respectively and obviously enhanced through being compared with those of the carbon nanometer tube-MnO2, the problems that in the existing super capacitor, the metallic oxides easily fall off from the surface of the carbon nanometer tubes, the electrical conductivity of the metallic oxides is poor, and the like are solved, the composite nanometer carbon paper also has the characteristics of light weight and flexibility of materials and high efficiency, simultaneously, the preparation process is simple, the operation is easy, the controllability is good, and in addition, the cost is low. The composite nanometer carbon paper and the preparation method have wide application prospects in fields of new energy sources, advanced chemical engineering, electronic devices, film preparation and the like.
Description
Technical field
The present invention be more particularly directed to a kind of by carbon nano-tube, MnO
2sandwich type composite nanometer carbon paper being compounded to form with Graphene and preparation method thereof, belongs to nano-carbon material preparing technical field.
Background technology
Ultracapacitor, especially light flexible capacitor are the focuses of current energy field research, and its electrode material is divided into material with carbon element, transition metal oxide material and conducting polymer materials.As electrode, material with carbon element has high power density and long cycle life; Metal oxide and conducting polymer have high specific capacitance, but power density is not high.In addition, in work, come off because change in volume easily causes active material, make the cycle life of material not high.
For overcoming the deficiency of conventional art, researchers develop the scheme of materials such as adopting carbon nanotube dust and metal oxide formation composite material, it can produce the effect that the capacitive property of metal oxide is significantly improved, but the composite material of preparation can not meet the efficient requirement of material light flexible, maximum operating currenbt is little, power density is still very low, can not meet the requirement of the large current work of ultracapacitor high power, and the conductivity away from the metal oxide of carbon nano-tube in composite material is still very poor, in addition, metal oxide is ubiquitous also fails well to be solved because of the active material phenomenon that the cycle life that causes reduces that comes off.
Summary of the invention
The object of the present invention is to provide a kind of by carbon nano-tube, MnO
2with grapheme material form, there is composite nanometer carbon paper of sandwich structure and preparation method thereof, to overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of composite nanometer carbon paper, is characterized in that, described nanometer carbon paper has composite sandwich, and it comprises:
The back bone network being formed by the carbon nanotube paper with macroscopical nonwoven fabrics form;
Be deposited on the MnO of the carbon nano tube surface that forms carbon nanotube paper
2metal oxide layer;
And, be covered in the graphene layer on described back bone network;
In described nanometer carbon paper, the content of grapheme material is below 10wt%, MnO
2the content of metal oxide is below 50wt%.
Further say, described carbon nanotube paper has by the disordered carbon nanotube porous network structure forming that interweaves, and in described porous network structure, also infiltrates grapheme material.
Described MnO
2metal oxide layer is continuous rete or the discrete MnO that is modified at carbon nano tube surface that is wrapped in carbon nano tube surface
2granuloplastic discontinuous rete.
Described graphene layer is by any one or two or more being combined to form in graphene oxide, reduced graphene and pure Graphene.
The preparation method of composite nanometer carbon paper, is characterized in that as mentioned above, and the method is:
First get carbon nano-tube and make carbon nano-tube suspended dispersed liquid, and filter formation carbon nanotube paper, thereafter, in carbon nanotube paper, deposit MnO
2thereby, form MnO in carbon nano tube surface
2metal oxide layer, last, on carbon nanotube paper, cover grapheme material, obtain target product.
Particularly, in the method, be that by carbon nanotube dispersed, the mode in solvent forms carbon nano-tube suspended dispersed liquid in employing;
More than described solvent is at least selected from any one in water, ethanol, isopropyl alcohol, DMF, 1-METHYLPYRROLIDONE, ethyl acetate and chloroform equal solvent;
More than described process for dispersing is at least selected from any one of high speed shear, grinding, ball milling and ultra-sonic dispersion method.
Preferably, in described solvent, also can contain dispersant, described dispersant is at least selected from polymer, any one in lauryl sodium sulfate, neopelex, softex kw, Tween-80 and Qu Latong-100 or the two or more combinations such as polyvinyl alcohol, polyvinylpyrrolidone, cellulose.
In the method, be to adopt without press filtration or the preparation of vacuum filtration method to form carbon nanotube paper, and the thickness of described carbon nanotube paper is 1 μ m-1mm.
Thereby in the method, at least adopt any one realization in following manner in carbon nanotube paper, to deposit MnO
2:
(1) MnO
2mechanical mixture with carbon nano-tube;
(2) constant current electro-deposition;
(3) cyclic voltammetric electro-deposition;
(4) constant voltage electro-deposition;
(5) electrophoretic deposition;
(6) chemical reaction deposit MnO
2, described chemical reaction comprises Hydrothermal Synthesis MnO
2reaction.
Thereby in the method, at least adopt any one realization in following manner depositing MnO
2carbon nanotube paper on cover grapheme material:
(1) CVD growing graphene material on carbon nanotube paper;
(2) carbon nanotube paper is infiltrated in graphene dispersing solution;
(3) at carbon nanotube paper surface-coated graphene dispersing solution.
The present invention is take carbon nano-tube as back bone network, and by its surface deposition MnO
2metal oxide, outer parcel Graphene, thus obtaining the flexible compound membrane material with sandwich structure, this thickness of composite material can regulate and control at several microns to thousands of microns, can self-supporting, do not need to rely on other substrates.
More specifically say, the one-dimentional structure that the present invention makes full use of carbon nano-tube forms porous network, possesses the characteristic such as high-specific surface area, high conduction, has given full play to MnO
2faraday's electric capacity characteristic that metal oxide is good, and, by adopting Graphene to improve package structure conductivity and capacitance behavior activity, also obtain outstanding electrochemical capacitor performance.
The invention solves the problems such as metal oxide in ultracapacitor work easily comes off in carbon nano tube surface, and metal conductive oxide is poor, and by regulating the content of Graphene in composite material, also can control conductivity of composite material and electrolyte soaks into MnO
2(Graphene is unfavorable for the raising of material conductivity to energy equilibrium of forces very little, the too high MnO that is unfavorable for of content
2capacitive property performance), and can stop the problem that specific area that graphene sheet layer there will be when thicker declines.
Summarize it, compared with prior art, advantage of the present invention is at least:
(1) provide a kind of novel flexible composite film material, its conductivity, large current density ability, specific capacitance, cycle life are compared with carbon nano-tube-MnO
2all there is obvious enhancing, fully having solved metal oxide in existing ultracapacitor work easily comes off in carbon nano tube surface, the poor problem of metal conductive oxide, take into account the efficient feature of material light flexible simultaneously, had important application prospect in fields such as new forms of energy (rechargeable battery, ultracapacitor), advanced chemical industry, electronic device, film preparations;
(2) prepare the technique of aforementioned novel flexible composite film material simple, easy operating, controllability is good, and with low cost, is suitable for large-scale industrial and produces.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of composite nanometer carbon paper of the present invention;
Fig. 2 a is the stereoscan photograph of the carbon nanotube paper that obtains in the embodiment of the present invention 1;
Fig. 2 b is the carbon nano-tube-MnO that obtains in the embodiment of the present invention 1
2the stereoscan photograph of paper;
Fig. 2 c is the target product graphene/carbon nanotube-MnO that obtains in the embodiment of the present invention 1
2the stereoscan photograph of/Graphene sandwich structure composite nanometer carbon paper;
Fig. 3 a be when in the embodiment of the present invention 1, composite nanometer carbon paper is as electrode of super capacitor than electric capacity the change curve with charging and discharging currents density;
Fig. 3 b is cycle life curve when composite nanometer carbon paper is as electrode of super capacitor in the embodiment of the present invention 1 (three-electrode system test, charging and discharging currents density: 1A/g);
Fig. 4 is the carbon nano-tube-MnO that obtains in the embodiment of the present invention 2
2the electromicroscopic photograph of extrusion coating paper.
Embodiment
For many defects of the prior art, this case inventor, through long-term theory research and practice in a large number, has proposed self-supporting graphene/carbon nanotube-MnO of the present invention
2/ Graphene sandwich structure composite nanometer carbon paper, this self-supporting composite nanometer carbon paper has following characteristic:
I, be made up of three-decker, skin is Graphene, and internal layer is surface deposition MnO
2carbon nano-tube, in fact, because carbon nanometer paper is by the disordered carbon nanotube porous network structure forming that interweaves, so also there is part grapheme material to infiltrate among this porous network structure;
II, thickness at several microns to thousands of microns and can control as required thickness;
III, area are greater than 10 cm
2, and can control as required;
Carbon nano-tube, MnO in IV, material
2, Graphene content controlled, comparatively preferably, Graphene accounts for nano-sized carbon paper weight percentage 0～10%, MnO
2account for nano-sized carbon paper weight percentage 0～50%;
V, material have suitable flexibility;
VI, can self-supporting, do not need to rely on other substrates;
VII, use common experimental provision and method to complete.
Aforementioned carbon nano-tube can adopt any one method in chemical vapour deposition technique, catalyse pyrolysis, arc discharge, template or laser evaporation method etc. to make, and described carbon nano-tube be in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or carbon nano-fiber any one or multiple.In addition, described carbon nano-tube can be the modified carbon nano-tube that has the groups such as carboxyl, amino, hydroxyl, fluorine or acid amides, also can be without modification.
Aforementioned Graphene can be prepared from by any one method in chemical oxidization method, chemical vapour deposition (CVD), combustion method etc., and described Graphene be in graphene oxide, reduced graphene, pure Graphene any one or multiple.
Aforementioned MnO
2oxide can be to be wrapped in the continuous rete of carbon nano tube surface or the granuloplastic discontinuous layer structure of discrete modification.
Further, consult Fig. 1, this self-supporting graphene/carbon nanotube-MnO
2/ Graphene sandwich structure composite nanometer carbon paper is prepared by the following method:
A. prepare carbon nanotube paper: carbon nanotube dust is sneaked in solvent, through disperseing to make dispersion liquid relatively uniformly, wherein carbon nano-tube needn't realize single dispersion, dispersion liquid is carried out to suction filtration (certainly with pumping and filtering device, also can be without press filtration or vacuum filtration), remove the impurity such as residual dispersant (certainly, also can not use dispersant) with clear water washing afterwards, the carbon nanotube paper thickness of acquisition can be controlled in several microns to several millimeters;
B. deposit MnO
2: take carbon nanotube paper as carrier, surface deposition MnO
2, the method for deposition can be simple mechanical mixture, can be chemical reaction, can be also electro-deposition etc.;
C. surface attachment Graphene: will deposit MnO
2carbon nanotube paper surface attachment Graphene, the method for adhering to can be infiltrate, graphene coated solution, can be also to adopt the method such as CVD surface direct growth Graphene.
The optional water of aforementioned solvents, ethanol, isopropyl alcohol, N, any one in dinethylformamide (DMF), 1-METHYLPYRROLIDONE (NMP), ethyl acetate, chloroform equal solvent, and be not limited to this, and high speed shear, grinding, ball milling, the process for dispersing such as ultrasonic any one can be selected and be not limited to the method for disperseing, carbon nano-tube wherein can be scattered in solution with single form, also can become large stretch of reunion to be distributed in solution.
If employing dispersant, dispersant can be selected but be not limited to the polymer such as polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), cellulose, any one of the surfactants such as lauryl sodium sulfate (SDS), neopelex (SDBS), softex kw (CTAB), Tween-80, Qu Latong-100 or multiple.
Below in conjunction with accompanying drawing and some preferred embodiments, technical scheme of the present invention is elaborated.
embodiment 1take the carbon nano-tube of 500 mg after hydrochloric acid purifying, be scattered in 1L deionized water, dispersant is polyvinylpyrrolidone, by high-shear impeller stirred for several minute, forms pulpous state distribute to carbon nano-tube in dispersion liquid, cellulose filter paper is layered on to the Buchner funnel bottom that diameter is 25 cm, use vacuum pump suction filtration, make carbon nano-tube uniform deposition on filter paper, when half-dried, carbon nanotube paper is separated with filter paper, obtain carbon nanotube paper, its thickness is approximately 65 um.Circular carbon nanotube paper is spent to direction lead-in conductors along four 90, central angle, make electrode, this electrode is immersed to the mixed solution number minute of 0.8mol/L sulfuric acid and 0.6mol/L manganese sulfate monohydrate, electrolyte and carbon nanotube paper are fully infiltrated, then carry out anode constant current electrochemical deposition, depositing current density is 5mA/cm
2, depositing temperature 0
oc, temperature is controlled with condensation ice bag, and sedimentation time is 20min, is 40cm to electrode
2graphite flake.Electrode is taken out, in deionized water, clean taking-up in several minutes, immerse in the graphene aqueous solution of 0.05mg/ml.Infiltrate after 3.5 hours and take out, after being dried, obtain target product in baking oven, its performance is as shown in Fig. 3 a and 2b.
The carbon nanotube paper that obtains, carbon nano-tube-MnO in table 1 embodiment 1
2, graphene/carbon nanotube-MnO
2the variation of/Graphene sandwich structure composite nanometer carbon paper (three's structure is as shown in Fig. 2 a-2c) three's conductivity
| Sample | Carbon nanotube paper | Carbon nano-tube-MnO 2 | Sandwich composite nanometer carbon paper |
| Conductivity (S.m -1) | 4.2×10 3 | 2.0×10 3 | 3.6×10 3 |
embodiment 2take the carbon nano-tube of 120mg after hydrochloric acid purifying, be scattered in 1L deionized water, dispersant, for going to La Tong-100, by high-shear impeller stirred for several minute, forms pulpous state and distributes in dispersion liquid to carbon nano-tube, cellulose filter paper is layered on to Buchner funnel bottom, use vacuum pump suction filtration, make carbon nano-tube uniform deposition on filter paper, when half-dried, carbon nanotube paper is separated with filter paper, the carbon nanotube paper that acquisition diameter is 6cm, its thickness is approximately 60 um.By circular carbon nanotube paper lead-in conductor, make electrode, this electrode is immersed to the mixed solution number minute of 1mol/L sodium acetate and 0.5mol/L manganese acetate, electrolyte and carbon nanotube paper are fully infiltrated, then carry out cyclic voltammetric electrochemical deposition, potential region is 0～1.2V, sweep speed: 100mv/s, sedimentation time is 10min, depositing temperature: room temperature is 8cm to electrode
2graphite, reference electrode is saturated calomel.Electrode is taken out, in deionized water, clean taking-up in several minutes, immerse in the graphene aqueous solution of 0.1mg/ml.Infiltrate after 1.5 hours and take out, after being dried, obtain target product in baking oven, as shown in Figure 4, its electric property is close with embodiment 1 for its structure.
embodiment 3take the carbon nano-tube of 500 mg after hydrochloric acid purifying, be scattered in 1L deionized water, dispersant is neopelex (SDBS), by high-shear impeller stirred for several minute, forms pulpous state distribute to carbon nano-tube in dispersion liquid, cellulose filter paper is layered on to the Buchner funnel bottom that diameter is 25 cm, use vacuum pump suction filtration, make carbon nano-tube uniform deposition on filter paper, when half-dried, carbon nanotube paper is separated with filter paper, obtain carbon nanotube paper, its thickness is approximately 65 um.Circular carbon nanotube paper is spent to direction lead-in conductors along four 90, central angle, make electrode, this electrode is immersed to the mixed solution number minute of 0.8mol/L sulfuric acid and 0.6mol/L manganese sulfate monohydrate, electrolyte and carbon nanotube paper are fully infiltrated, then carry out anode constant voltage electrochemical deposition, sedimentation potential is 2.5V, and depositing temperature is room temperature, sedimentation time is 20min, is 40cm to electrode
2graphite flake.Electrode is taken out, clean taking-up in several minutes in deionized water, immerse in the graphene aqueous solution of 0.05mg/ml, infiltrate after 5 hours and take out, after being dried, obtain target product in baking oven, its structure and electric property are close with embodiment 1,2.
embodiment 4take the carbon nano-tube of 120 mg after hydrochloric acid purifying, be scattered in 0.5L deionized water, dispersant is polyvinylpyrrolidone, with ultrasonic dispersion 1 hour, forms pulpous state distribute to carbon nano-tube in dispersion liquid, cellulose filter paper is layered on to Buchner funnel bottom, use vacuum pump suction filtration, make carbon nano-tube uniform deposition on filter paper, when half-dried, carbon nanotube paper is separated with filter paper, obtaining diameter is 6cm carbon nanotube paper, and its thickness is approximately 65 um.By circular carbon nanotube paper lead-in conductor, make electrode, the mixed solution that this electrode is immersed to 0.8mol/L sulfuric acid and 0.6mol/L manganese sulfate monohydrate carries out anode constant current electrochemical deposition, and depositing current density is 5mA/cm
2, sedimentation time 5min.Electrode is taken out, and the mixed solution of putting into 1mol/L sodium acetate and 0.5mol/L manganese acetate carries out cyclic voltammetric electro-deposition, and potential region is 0～1.2V, sweep speed: 100mv/s, and sedimentation time is 3min, is 8cm to electrode
2graphite flake, reference electrode is saturated calomel.Take out electrode cleans several minutes in deionized water.Immerse in the graphene aqueous solution of 0.05mg/ml.Infiltrate after 3.5 hours and take out, after being dried, obtain target product in baking oven, its structure and electric property are close with embodiment 1,2.
More than explanation, and the embodiment shown on drawing, can not resolve the design philosophy surely of the present invention that is limited.In technical field of the present invention, holding the identical the knowledgeable of knowing can change technical thought of the present invention with various form improvement, such improvement and change are interpreted as belonging in protection scope of the present invention.
Claims (8)
1. a composite nanometer carbon paper, is characterized in that, described nanometer carbon paper has composite sandwich, and it comprises:
The back bone network being formed by the carbon nanotube paper with macroscopical nonwoven fabrics form;
Be deposited on the MnO of the carbon nano tube surface that forms carbon nanotube paper
2metal oxide layer;
And, be wrapped in the graphene layer on described back bone network;
In described nanometer carbon paper, the content of grapheme material is below 10wt%, MnO
2the content of metal oxide is below 50wt%.
2. composite nanometer carbon paper according to claim 1, is characterized in that, described MnO
2metal oxide layer is continuous rete or the discrete MnO that is modified at carbon nano tube surface that is wrapped in carbon nano tube surface
2granuloplastic discontinuous rete.
3. composite nanometer carbon paper according to claim 1, is characterized in that, described graphene layer is by any one or two or more being combined to form in graphene oxide, reduced graphene and pure Graphene.
4. the preparation method of composite nanometer carbon paper as claimed in claim 1, is characterized in that, the method is:
First get carbon nano-tube and make carbon nano-tube suspended dispersed liquid, and filter formation carbon nanotube paper, thereafter, in carbon nanotube paper, deposit MnO
2thereby, form MnO in carbon nano tube surface
2metal oxide layer, last, on carbon nanotube paper, wrap up grapheme material, obtain target product;
The method of wherein, wrapping up grapheme material on carbon nanotube paper at least adopts any one in following manner:
(1) CVD growing graphene material on carbon nanotube paper;
(2) carbon nanotube paper is infiltrated in graphene dispersing solution;
(3) at carbon nanotube paper surface-coated graphene dispersing solution.
5. the preparation method of composite nanometer carbon paper according to claim 4, is characterized in that, is to adopt that the mode in solvent forms carbon nano-tube suspended dispersed liquid by carbon nanotube dispersed in the method;
More than described solvent is at least selected from any one in water, ethanol, isopropyl alcohol, DMF, 1-METHYLPYRROLIDONE, ethyl acetate and chloroform solvent.
6. the preparation method of composite nanometer carbon paper according to claim 5, it is characterized in that, in described solvent, also contain dispersant, described dispersant is at least selected from any one or the two or more combinations in polyvinyl alcohol, polyvinylpyrrolidone, cellulose, lauryl sodium sulfate, neopelex, softex kw, Tween-80 and Qu Latong-100.
7. the preparation method of composite nanometer carbon paper according to claim 4, is characterized in that, be to adopt without press filtration or the preparation of vacuum filtration method to form carbon nanotube paper, and the thickness of described carbon nanotube paper is 1 μ m-1mm in the method.
8. the preparation method of composite nanometer carbon paper according to claim 4, is characterized in that, deposits MnO thereby at least adopted any one in following manner to realize in the method in carbon nanotube paper
2:
(1) MnO
2mechanical mixture with carbon nano-tube;
(2) constant current electro-deposition;
(3) cyclic voltammetric electro-deposition;
(4) constant voltage electro-deposition;
(5) electrophoretic deposition;
(6) chemical reaction deposit MnO
2, described chemical reaction comprises Hydrothermal Synthesis MnO
2reaction.
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| 章仁毅等.基于碳纳米管的超级电容器研究进展.《应用化学》.2011,第28卷(第5期),第489-499页 1.3，2.2，4. |
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