CN1189391C - Manufacturing method of carbon nano tube paper - Google Patents
Manufacturing method of carbon nano tube paper Download PDFInfo
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- CN1189391C CN1189391C CNB031500528A CN03150052A CN1189391C CN 1189391 C CN1189391 C CN 1189391C CN B031500528 A CNB031500528 A CN B031500528A CN 03150052 A CN03150052 A CN 03150052A CN 1189391 C CN1189391 C CN 1189391C
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 129
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000012065 filter cake Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 230000009514 concussion Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 230000010355 oscillation Effects 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002071 nanotube Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002238 carbon nanotube film Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- UUZZMWZGAZGXSF-UHFFFAOYSA-N peroxynitric acid Chemical compound OON(=O)=O UUZZMWZGAZGXSF-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a preparation method of carbon nanotube paper. In the method, firstly, carbon nanotubes are poured into acid, heating or continuous heating reflux, or/and ultrasonic oscillation, or/and stir are carried out until the carbon nanotubes are sufficiently dispersed and impurities are removed; then, water dilution and filtration are carried out, and a filter cake is for standby after being washed by water; the carbon nanotubes are dispersed in water and are uniformly dispersed in the water by ultrasound or stir to form a solution in which the carbon nanotubes are uniformly dispersed; finally, the solution of the carbon nanotubes is dried on a carrier form the carbon nanotube paper. The carbon nanotube paper has the advantages of regular structure, uniform height, high purity, high conductivity and enough mechanical strength, the thickness, the shape and the size of the carbon nanotube paper can be controlled, and various kinds of carbon nanotube paper meeting the requirements of people can be prepared. The carbon nanotube paper can be used as nanofilter membranes, and can also be used as electrode materials in super capacitors, lithium batteries and electrochemically synthetic or electrolytic processes.
Description
Technical field
The present invention relates to the forming technique of carbon nanotube, relate in particular to a kind of preparation method of carbon nanotube paper.
Background technology
Nanotechnology is the commanding elevation of 21 century development in science and technology, is the dominant technology of the new Industrial Revolution.In November, 1991, the Electronic Speculum expert Iijima of Japanese NEC has at first found carbon nanotube under high resolution transmission electron microscopy (HRTEM), caused people's extensive concern.The one dimension carbon material that carbon nanotube is made up of the hexagonal mesh of similar graphite, pipe is to be made of single or multiple lift, and between tens nanometers, length can reach several microns to diameter in several nanometers, its lamellar spacing is 0.34nm, and is bigger slightly than the lamellar spacing (0.335nm) of graphite.Carbon nanotube is concentrated the nano-grade size that distributes, high effective ratio area, good electrical conductivity and excellent chemical stability owing to having, thereby has application very widely.
Though the carbon nanotube excellent performance has widely and uses, carbon nanotube is a particulate state or Powdered generally speaking, and this application for people has caused a lot of inconvenience.In order to make flaky material, often need to adopt the high temperature compacting or add binding agent.As Ma Renzhi, Wei Bingqing, (E collects Xu Cailu etc., 2000 on " Chinese science " magazine, the 30th the 2nd phase of volume, the 112-116 page or leaf) " based on the ultracapacitor of carbon nanotube " delivered is before carbon nanotube uses, through the peroxy-nitric acid purification process, promptly remove metal catalyst through 20% nitric acid dousing 24h, with two kinds of methods carbon nanotube is made flaky material then, a kind of is under argon shield, and the pressure that adopts 25MPa is in the moulding of 2000 ℃ of hot pressing pure nano-carbon tubes; Another kind is that carbon nanotube and 20% resol are mixed, at low temperature (100 ℃) and certain pressure compacted under, then in nitrogen atmosphere in 800 ℃ of charings, the charing rear electrode carries out chemical after-treatment in concentrated nitric acid solution manages.Though the first method preparation is pure nano-carbon tube, manufacture craft is cumbersome.Though second method does not need high temperature, but can not get pure carbon nanometer.Wang Xiaofeng etc. on " Chinese Journal of Inorganic Chemistry " magazine (2003, the 19th the 2nd phase of volume, the 137-141 page or leaf) " development of nickel oxide/carbon nanotube hybrid supercapacitor " delivered, take by weighing an amount of carbon nanotube, it is wetting with it to add small quantity of deionized water, add an amount of ptfe emulsion and fully stirring subsequently, carbon nanotube and tetrafluoroethylene mass ratio are 95/5.With slurry 60 ℃ of bakings to the half-dried attitude shape in that to be pressed into thickness on the twin rollers be the film about 0.2mm and cut thereon that to obtain diameter be the 2cm electrode slice.Electrode slice is rolled on the nickel foam collector, and pressure-controlling is at 12-15MPa.This method is made binding agent with an amount of tetrafluoroethylene, is pressed into carbon nano-tube film, can not get pure carbon nanotube.Wear dawn, the Chinese patent " multilayer carbon nanotube films " of Huang Shaoming application (open day: 2002.05.15, publication number: 1349478), the method of the nano-tube film that a kind of arrangement for preparing no matrix that proposes is good, this method comprises: (a) in the presence of the catalyzer that is fit to nanotube formation, by the pyrolysis carbon nanotube that synthetic one deck is arranged on silica glass matrix of carbonaceous material; And (b) in nanotube/matrix interface etching silica glass matrix, so that peel off the good nanotube layer of described arrangement from matrix.This method needs catalyzer and silica glass matrix, need be in nanotube/matrix interface etching silica glass matrix, so that peel off the good nanotube layer of described arrangement from matrix.The Chinese patent of applications such as Wei Fei " a kind of method of utilizing external force to crush, wash and purify slender carbon nanotube " (open day 2002.10.16 publication number 1374250), be a kind of method of utilizing external force to crush, wash and purify slender carbon nanotube, do not form carbon nanotube paper.Chunming Niu, Deng at " Appl.Phys.Lett. " (Vol.70, No.11, " the Highpower electrochemical capacitors based on carbon nanotube electrodes " that delivers on 1840-1842), use the nitric acid treatment carbon nanotube, filtration and washing after the drying, adds the carbon nanotube after the 0.2g processing in the 200mL water, refilter, after the drying, heat cross-linking has formed uniform inflexible thin electrode.But this method adopts filtering method to form carbon nano-tube sheets, and in the reality, the diameter of carbon nanotube is nano level, this requires the aperture of filter membrane very little (such filter membrane cost is also than higher), and when filtering, can lose a part of carbon nanotube, especially when the carbon nanotube sheet material that forms as thin as a wafer, the quality of carbon nanotube is difficult to control on its thickness and the unit surface.Since be subjected to the restriction of filtration unit, the size and dimension of thin electrode, and shape also is restricted.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of carbon nanotube paper, this method is simple to operate, need not binding agent, and the thickness of carbon nanotube paper, shape and size can control, and can make the various carbon nanotube paper that meet people's needs.This carbon nanotube paper have compound with regular structure, highly evenly, high purity, high conductivity and enough physical strengths.
Technical scheme of the present invention is as follows: a kind of preparation method of carbon nanotube paper, this method comprises the steps:
A. purifying carbon nanometre tube: carbon nanotube is poured in the acid, in room temperature to 200 ℃ heating or reflux down continuously, or/and ultrasonic concussion, or/and stir, fully disperse and remove impurity, dilute with water then up to carbon nanotube, filter, it is standby to wash the gained filter cake with water clean back;
B. dispersing Nano carbon tubes: the clean filter cake of gained among the step a is put into water, and ultrasonic concussion or stirring form homodisperse carbon nano-tube solution;
C. form carbon nanotube paper: homodisperse carbon nano-tube solution is poured on carries out drying on the carrier, form carbon nanotube paper.
Sulfuric acid, nitric acid, hydrochloric acid or their mixture are adopted in acid described in the present invention.
The container that carrier described in the present invention adopts plastics, stone, stainless steel, aluminium foil or glass material to make.
The present invention forms carbon nanotube paper with carbon nanotube, is convenient to people and uses carbon nanotube, has expanded the range of application of carbon nanotube; This method not only technology is simple, need not binding agent, also need not pressurization and high temperature, can obtain under normal pressure and lower temperature; And the carbon nanotube paper of making has compound with regular structure, and quality is even, purity height, the high and enough physical strengths of specific conductivity.Because it can form uniform nano aperture, can be used as nanofiltration membrane, also can in ultracapacitor, lithium cell, electrochemical synthesis or electrolytic process, be used as electrode materials.Can make ultra-capacitor have higher specific storage, specific energy, specific power, good environmental stability, and increase the service life greatly.The thickness of this film, shape and size can be controlled, and can make the carbon nanotube paper of the needs that meet people.
Description of drawings
Fig. 1 is the structure of primary carbon nanotube.
Fig. 2 is the structure of the carbon nanotube paper that forms on plastic carrier.
Fig. 3 is the infrared spectrum of primary carbon nanotube.
Fig. 4 is the infrared spectrum of carbon nanotube paper.
Fig. 5 is the structure of the carbon nanotube paper that forms on stainless steel carrier.
Fig. 6 is the structure of the carbon nanotube paper that forms on the stone matter carrier.
Fig. 7 is the structure of the carbon nanotube paper that forms on glass carrier.
Fig. 8 is the structure of the carbon nanotube paper that forms on aluminium carrier.
Embodiment
The invention will be described further below by embodiment.
The used carbon nanotube of the present invention can be to use any method, as laser bombardment method, chemical vapor deposition method, electric glow discharge method, direct current arc electric discharge, gaseous combustion method, catalyzer high temperature pyrolytic cracking (HTP) etc., the carbon nanotube of preparation.Because the carbon nanotube of different methods preparation, the kind of impurity such as its structure, composition and catalyzer is also different with content, in order to remove impurity, and even carbon nanotube is disperseed, the composition of the consumption of its required acid and acid also will be done suitable adjustment, till the abundant dispersion that reaches carbon nanotube.If, can repeatedly handle, till carbon nanotube is fully disperseed and removing impurity for the first time carbon nanotube fully being disperseed in afterwards to the carbon nanotube purifying treatment with acid.
Embodiment 1
Take by weighing the 1g carbon nanotube, pour in the mixed solution (volume ratio of the vitriol oil and concentrated nitric acid 3: 1) of the 1000ml vitriol oil and concentrated nitric acid, under 70 ℃, ultrasonic concussion, and stir, react after 24 hours, with deionized water dilution, filter, with filter cake with deionized water wash clean after, ultrasonic filter cake is dispersed in the deionized water, forms carbon nano-tube solution; Carbon nano-tube solution is poured in the smooth plastic containers in bottom, at room temperature dry, form carbon nanotube paper.Gained carbon nanotube paper, its thickness are 50 μ m, have higher specific conductivity, and its square resistance is 13 Ω/1cm, and far above the specific conductivity of carbon fiber paper (its thickness is 500 μ m), the square resistance of carbon fiber paper is 35 Ω/1cm.Fig. 1 is the structure of primary carbon nanotube, and Fig. 2 is the structure of the carbon nanotube paper that forms on plastic carrier.Compare with primary carbon nanotube, carbon nanotube paper has compound with regular structure, highly even, and has enough mechanical strengths, owing to do not add any binding agent, so gained carbon nanotube paper has high purity, the infrared spectrum of carbon nanotube paper has also confirmed this point.Fig. 3 is the infrared spectrum of primary carbon nanotube, and Fig. 4 is the infrared spectrum of carbon nanotube paper, and therefrom carbon nanotube paper has high purity as can be seen.
Owing to form carbon nanotube paper,, can make the carbon nanotube paper of the needs that meet people so the thickness of carbon nanotube paper, shape and size can be controlled by dry.
Embodiment 2
Take by weighing the 1g carbon nanotube, pour in the mixed solution (volume ratio of the vitriol oil and concentrated nitric acid 3: 1) of the 1000ml vitriol oil and concentrated nitric acid, under 70 ℃, ultrasonic concussion, and stir, react after 24 hours, dilute with deionized water then, filter, with filter cake with deionized water wash clean after, ultrasonic filter cake is disperseed in the deionized water, form carbon nano-tube solution, carbon nano-tube solution is poured in the smooth stainless steel vessel in bottom, at room temperature dry, form carbon nanotube paper.Gained carbon nanotube paper, its thickness are 70 μ m, have higher specific conductivity, and its square resistance is 10 Ω/1cm, and far above the specific conductivity of carbon fiber paper (its thickness is 500 μ m), the square resistance of carbon fiber paper is 35 Ω/1cm.Fig. 5 is the structure of the carbon nanotube paper that forms on stainless steel carrier.Compare with primary carbon nanotube, carbon nanotube paper has compound with regular structure, height advantage of uniform.
Embodiment 3. takes by weighing the 1g carbon nanotube, pour in the mixed solution (volume ratio of the vitriol oil and concentrated nitric acid 3: 1) of the 100ml vitriol oil and concentrated nitric acid, and stir, reaction is after 48 hours under the room temperature, dilute with deionized water then, filter, with filter cake with deionized water wash clean after, ultrasonic filter cake is disperseed in the deionized water, form carbon nano-tube solution, carbon nano-tube solution is poured in the smooth stone matter container in bottom, at room temperature dry, form carbon nanotube paper.Gained carbon nanotube paper, its thickness are 500 μ m, have higher specific conductivity, and its square resistance is 17 Ω/1cm, and far above the specific conductivity of carbon fiber paper (its thickness is 500 μ m), the square resistance of carbon fiber paper is 35 Ω/1cm.Fig. 6 is the structure of the carbon nanotube paper that forms on stone matter carrier.Compare with primary carbon nanotube, carbon nanotube paper has compound with regular structure, height advantage of uniform.
Embodiment 4. takes by weighing the 1g carbon nanotube, pour in the mixed solution (volume ratio of the vitriol oil and concentrated nitric acid 3: 1) of the 100ml vitriol oil and concentrated nitric acid, and stir, reaction is diluted with deionized water after 48 hours then under the room temperature, filter, with filter cake with deionized water wash clean after, ultrasonic filter cake is disperseed in the deionized water, form carbon nano-tube solution, pour carbon nano-tube solution in the smooth Glass Containers in bottom drying, under 100 degree, form carbon nanotube paper.Gained carbon nanotube paper, its thickness are 430 μ m, have higher specific conductivity, and its square resistance is 13 Ω/1cm, and far above the specific conductivity of carbon fiber paper (its thickness is 500 μ m), the square resistance of carbon fiber paper is 35 Ω/1cm.Fig. 7 is the structure of the carbon nanotube paper that forms on glass carrier.Compare with primary carbon nanotube, carbon nanotube paper has compound with regular structure, height advantage of uniform.
Embodiment 5. takes by weighing the 1g carbon nanotube, pours the 100ml vitriol oil into, ultrasonic concussion 2 hours, constant temperature is about 200 ℃, continuous backflow heating 13 hours, filter with the deionized water dilution cooling back, with filter cake with deionized water wash clean after, ultrasonic filter cake is disperseed in the deionized water, form carbon nano-tube solution, carbon nano-tube solution is poured in the smooth aluminum container in bottom, at room temperature dry, form carbon nanotube paper.Gained carbon nanotube paper, its thickness are 100 μ m, have higher specific conductivity, and its square resistance is 19 Ω/1cm, and far above the specific conductivity of carbon fiber paper (its thickness is 500 μ m), the square resistance of carbon fiber paper is 35 Ω/1cm.Fig. 8 is the structure of the carbon nanotube paper that forms on aluminium carrier.Compare with primary carbon nanotube, carbon nanotube paper has compound with regular structure, height advantage of uniform.
Claims (1)
1. the preparation method of a carbon nanotube paper is characterized in that this method comprises the steps:
A. purifying carbon nanometre tube: carbon nanotube is poured in sulfuric acid, nitric acid, hydrochloric acid or their mixture, in room temperature to 200 ℃ heating or reflux down continuously, or/and ultrasonic concussion, or/and stir, fully disperse and remove impurity up to carbon nanotube, dilute with water filters then, and it is standby to wash the gained filter cake with water clean back;
B. dispersing Nano carbon tubes: the clean filter cake of gained among the step a is put into water, and ultrasonic concussion or stirring form homodisperse carbon nano-tube solution;
C. form carbon nanotube paper: homodisperse carbon nano-tube solution is poured on carries out drying on the carrier, form carbon nanotube paper, described carrier is the smooth container made from plastics, stone material, stainless steel, aluminium or glass material in bottom.
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