CN101189373A - Improved ozonolysis of carbon nanotubes - Google Patents

Abstract

Methods of treating single walled and multiwalled carbon nanotubes with ozone are provided. The carbon nanotubes are treated by contacting the carbon nanotubes with ozone at a temperature range between 0 DEG C and 100 DEG C to yield functionalized nanotubes which are greater in weight than the untreated carbon nonotubes. The carbon nonotubes treated according to methods of the invention can be used to prepare complex structures such as three dimensional networks or rigid porous structures which can be utilized to form electordes for fabrication of improved electrochemical capacitors. Useful catalyst supports are prepared by contacting carbon nanotube structures such as carbon nanotube aggregates, three dimensional network or rigid porous structures with ozone in the temperature range between 0 DEG C and 100 DEG C.

Description

Improved CNT ozone decomposes

Background of invention

Invention field

The present invention relates to method with the surface of ozone treatment single wall and multi-walled carbon nano-tubes.The present invention also comprises the method and its method of use of the aggregation of the nanotube for preparing ozone treatment.The invention still further relates to the labyrinth that preparation is made up of the CNT of this ozone treatment connected to one another such as the method for three-dimensional network or rigid porous structure.The present invention also comprises by the method for preparing catalyst carrier with aggregation, three-dimensional network or the rigid porous structure of ozone treatment.

Description of Related Art

CNT

The present invention is in the submicron graphite carbon filament often is called the scope of nanotube.Carbon filament is a diameter less than 1.0 μ, preferably less than 0.5 μ with even be more preferably less than the vermiform carbon deposits of 0.2 μ.CNT can be (promptly the having only a single graphite linings on the nanometer tubular axis) of many walls (promptly having an above graphite linings on the nanometer tubular axis) or single wall.Other CNT type has also been described below.

Can instruct the CNT of processing to be different from commercial available continuous carbon fibre according to the application.(L/D) is at least 10 with aspect ratio ⁴With often 10 ⁶Or these above fibers compare, and carbon filament has big but inevitable limited aspect ratio ideally.The diameter of continuous fibers also is far longer than the diameter of fibril, always＞1.0 μ and be generally 5-7 μ.

CNT is different from commercial available continuous carbon fibre as reinforcing material physically and chemically, also is different from other carbon form such as standard graphite and carbon black.Standard graphite is because its structure and experiencing is oxidized to almost completely saturated.In addition, carbon black is for having the amorphous carbon of the spheric granules form of graphene structure usually, and carbon-coating is round unordered nuclear.Difference makes graphite and carbon black become the indication of the difference of carbon nanotube chemical.

CNT exists with various forms, and prepares by the catalytic decomposition of various carbonaceous gass at the place, metal surface.From electron microscope this vermiform carbon deposits appears just observing almost.(Baker and Harris, Chemistry and Physics of Carbon, Walkerand Thrower ed, 14 volumes, 1978,83 pages; Rodriguez, N., J.Mater.Research, 8 volumes, 3233 pages (1993)).

In 1976, Endo etc. (referring to Oberlin, A.and Endo, M., J.of Crystal Growth, Vol.32 (1976) 335-349), is incorporated herein by reference here, has illustrated the basic mechanism of this carbon filament growth.See that they originate from metal catalyst particles, in the presence of gas containing hydrocarbon, the carbon supersaturation becomes.Cylindric orderly graphite core is extruded, and according to Endo etc., it becomes the skin that scribbles pyrolytic deposition graphite immediately.These fibrils with pyrolysis external coating generally have 0.1 μ of surpassing, the diameter of more general 0.2-0.5 μ.

Nineteen eighty-three, the United States Patent (USP) 4663230 of Tennent has been described not to be had Continuous Heat method carbon external coating and has the outer field carbon filament of a plurality of graphite that is basically parallel to the fibril axle, and this paper is incorporated herein by reference.Thereby they are characterised in that the c-axle with them, and these are basically perpendicular to their cylinder axis perpendicular to the tangent line of graphite flex layers.They have diameter that is not more than 0.1 μ and the length over diameter ratio that is at least 5 usually.Ideally, they do not have Continuous Heat method carbon external coating substantially, i.e. the carbon of the pyrolytic deposition that is obtained by the thermal cracking of the gas feed that is used to prepare them.Therefore, the invention of Tennent provides and has obtained less diameter fibril and be generally

The method of (0.0035-0.070 μ) and orderly " growth attitude " graphite surface.Grown and had the not too fibrous carbon of perfect structure, and do not had the RESEARCH OF PYROCARBON skin.

The United States Patent (USP) 5171560 of Tennent etc. has been described does not have hot method external coating and has the graphite linings that is basically parallel to the fibril axle to make described layer stretch out the carbon filament of the distance of at least two fibril diameters in the projection of described fibril axle that this paper is incorporated herein by reference.Usually, this fibril is the graphite nanotubes with substantially cylindrical of constant substantially diameter, and comprises that the c-axle is basically perpendicular to the cylindrical graphite linings of their cylinder axis.They do not have the carbon of pyrolytic deposition substantially, have less than the diameter of 0.1 μ with greater than 5 length over diameter ratio.These fibrils can be by method oxidation of the present invention.

When the projection of graphite linings on the nanometer tubular axis stretch out less than two nanotube diameters apart from the time, the carbon face of graphite nanotubes presents the fishbone outward appearance on cross section.These are named as the fishbone fiber.The United States Patent (USP) 4855091 of Geus provides preparation not have the process of the fishbone fibril of pyrolysis external coating substantially, and this paper is incorporated herein by reference.These CNTs also are used in the enforcement of the present invention.

In pyrocarbon electric arc, grow pattern and be similar to CNT (Iijima, the Nature of above-mentioned catalytic growth fibril 354, 56,1991).It is generally acknowledged (Weaver, Science now 265, 1994; De Heer, Walt A., " Nano tubes and the Pursuit ofApplication ", MRS Bulletin, in April, 2004, this paper introduces both as a reference) nanofiber of these electric arcs growth has the identical pattern of fibril with the early stage catalytic growth of Tennent.The carbon nano-fiber of electric arc growth is called " flat to pipe " usually by colloquiolly, also use in the present invention.

For example, at " Single-shell carbon nanotubes of 1-nm diameter ", S Iijima and T Ichihashi Nature, vol.363, p.603 (1993) and " Cobalt-catalysed growth of carbon nanotubes with single-atomic-layer walls ", D S Bethune, C H Kiang, M S DeVries, G Gorman, R Savoy and R Beyers Nature, vol.363, p.605 disclose useful Single Walled Carbon Nanotube and their method of preparation in (1993), this paper introduces these two pieces of articles as a reference.

Also disclose Single Walled Carbon Nanotube in the United States Patent (USP) 6221330 of Moy etc., this paper introduces its disclosure as a reference.Moy discloses the method by one or more gaseous carbon compound production hollow Single Walled Carbon Nanotube of catalytic decomposition, at first form the gas phase mixture carbon unstripped gas that comprises one or more gaseous carbon compounds, every kind of gaseous carbon compound all has 1 to 6 carbon atom and unique H, O, N, S or Cl as hetero atom, unstripped gas randomly is mixed with hydrogen and also can forms the gas phase containing metal compound that is used as the containing metal catalyst of decomposition catalyst under the reaction condition unstable under the described decomposition reaction condition; Under the decomposition reaction condition, carry out described decomposition reaction then, produce described nanotube thus.This invention relates to gas-phase reaction, and wherein gas phase containing metal compound is introduced in the reactant mixture that also comprises gaseous carbon source.Carbon source is generally the C with hetero atom H, O, N, S or Cl ₁-C ₆Compound randomly is mixed with hydrogen.Carbon monoxide or carbon monoxide and hydrogen are preferred carbon raw materials.Increase reaction zone temperature and be considered to cause that to about 400 ℃ of-1300 ℃ of pressure gas phase containing metal compound decomposition becomes the containing metal catalyst with the about 100p.s.i.g of about 0-.Decomposition can be arrived the middle species of atom metal or part decomposition.Containing metal catalyst (1) catalysis CO decomposes and (2) catalysis SWNT forms.

Aerosol technology is used in the invention of United States Patent (USP) 6221330 in some embodiments, and wherein the aerosol of metallic catalyst is introduced in the reactant mixture.The advantage that produces the aerosol method of SWNT is to produce the catalyst granules of uniform-dimension and yardstick, and this method can effective and continuous commerce or industrial production.Aforesaid arc discharge and laser deposition method can not be amplified to this commerce or industrial production economically.The example that is used in the containing metal compound in this invention comprises metal carbonyl, metal acetyl acetonate and can introduce and be decomposed to form other material of unsupported metallic catalyst as steam under decomposition condition.Catalytically-active metals comprises Fe, Co, Mn, Ni and Mo.Molybdenum carbonyl and carbonyl iron are preferred containing metal compound, and they can be decomposed to form gas phase catalyst under reaction condition.The solid form of these metal carbonyls can be transported to pretreatment zone, and they are evaporated there, thereby becomes the vapor precursor of catalyst.Discovery can use two kinds of methods to form SWNT on unsupported catalyst.

First method is directly to inject volatile catalyst.Directly method for implanting is described in the United States Patent (USP) 6696387, and this paper is incorporated herein by reference.The direct injection of discovery volatile catalyst precursor can be used hexacarbonylmolybdenum [Mo (CO) ₆] and cobalt octacarbonyl [CO ₂(CO) ₈] can cause the formation of SWNT.Two kinds of materials at room temperature all are solid, but is heat-staple at distillation-molybdenum compound under environment or the near-ambient temperature under at least 150 ℃, cobalt compound is with decomposition distil (" Organic Syntheses via Metal Carbonyls ", Vol.1, I.Wender and P.Pino, eds., Interscience Publishers, New York, 1968, p.40).

The second method of describing in the United States Patent (USP) 6221330 uses evaporimeter to introduce containing metal compound (seeing the Fig. 1 in the United States Patent (USP) 6221330).In a kind of preferred embodiment of invention, the evaporimeter 10 that shows among the Fig. 2 in United States Patent (USP) 6221330 comprises from its bottom about 1 " sealing 24 the quartzy thermocouple sheath 20 that has form second compartment.This compartment has two 1/4 " hole 26, they be open and be exposed to reactant gas.Catalyst is placed in this compartment, uses evaporimeter stove 32 to evaporate under any required temperature then.Use first thermocouple, 22 these stoves of control.Containing metal compound preferable alloy carbonyl compound is evaporated reactant gas CO or CO/H being lower than under the temperature of its decomposition point ₂Purge precursor in reaction zone 34, it is controlled separately by the reaction zone stove 38 and second thermocouple 42.Although the applicant does not wish to be limited to specific operation principle, think that under temperature of reactor the containing metal compound is partly resolved into middle species or resolves into metallic atom fully.Species and/or metallic atom are agglomerated into the big aggregate particle as actual catalyst in the middle of these.Particle grows into suitable dimensions then and comes the decomposition of not only catalysis CO but also promote the SWNT growth.Among Fig. 1 in United States Patent (USP) 6221330, collection catalyst particle and the carbon form that obtains on quartzy tampon 36.The speed of growth of particle depends on the concentration of the middle species of gas phase containing metal.This concentration is by the vapour pressure in the evaporimeter (with therefore temperature) decision.If concentration is too high, then germination is too fast, the structure (for example MWNT, amorphous carbon, onion etc.) except that SWNT of will growing.The full content that this paper introduces United States Patent (USP) 6221330 comprises that the embodiment that wherein describes as a reference.

The United States Patent (USP) 5424054 of Bethune etc. has been described by making the description of carbon steam contact Co catalysts manufacture order wall carbon nano tube, and this paper is incorporated herein by reference.Produce carbon steam by the electric arc heated solid carbon, solid carbon can be amorphous carbon, graphite, activated carbon or decolorizing carbon or their mixture.Other technology of carbon heating has been discussed, as LASER HEATING, electron beam heating and RF eddy-current heating.

Smalley (Guo, T., Nikoleev, P., Thess, A., Colbert, D.T., and Smally, R.E., Chem.Phys.Lett.243:1-12 (1995)) method of manufacture order wall carbon nano tube described, wherein evaporate graphite rod and transition metal simultaneously with high-temperature laser, this paper is incorporated herein by reference.

Smalley (Thess, A., Lee, R., Nikolaev, P., Dai, H., Petit, P., Robert, J., Xu, C, Lee, Y.H., Kim, S.G., Rinzler, A.G., Colbert, D.T., Scuseria, G.E., Tonarek, D., Fischer, J.E., and Smalley, R.E., Science, 273:483-487 (1996)) method of manufacture order wall carbon nano tube has also been described, by laser evaporation, this paper is incorporated herein by reference the graphite rod that wherein comprises a small amount of transition metal in about 1200 ℃ baking oven.Report can be to surpass 70% productive rate manufacture order wall carbon nano tube.

The metal supported catalyst that is used to form SWNT also is known.Smalley (Dai., H., Rinzler, A.G., Nikolaev, P., Thess, A., Colbert, D.T., and Smalley, R.E., Chem.Phys.Lett.260:471-475 (1996)) load C o, the Ni and the Mo catalyst that are used for being given birth to by CO long multi-wall nanotube and single-walled nanotube described, with the mechanism that is their formation suggestion, this paper is incorporated herein by reference.

The United States Patent (USP) 6761870 of Smalley etc. (also for WO 00/26138) discloses supply and has been preheated high pressure (for example 30 atmospheric pressure) CO of (for example to about 1000 ℃) and the catalyst precarsor gas among the CO under remaining below the catalyst precursors decompose temperature (Fe (CO) for example ₅) to the method for Mixed Zone, this paper is incorporated herein by reference.In this Mixed Zone, catalyst precarsor is rapidly heated to according to record can cause following temperature: (1) precursors decompose, (2) form suitably the active catalytic metals cluster and bunch upward favourable SWNT growth of (3) catalyst of size.

Other method that produces CNT is disclosed in " Controlledproduction of single-wall carbon nanotubes by catalyticdecomposition of CO onbimetallic Co-Mo catalysts " such as Resasco, ChemicalPhysics Letters, in the United States Patent (USP) 6333016 of 317 (2000) 497-503 and Resasco, this paper introduces the two as a reference.By being contacted with the metal catalytic particle, carbonaceous gas produces CNT therein.

The aggregation of CNT and aggregation

The CNT that produces can be discrete nanotube, nanotube aggregation or both forms.

Nanotube is prepared to and has various patterns the aggregation of (measuring by ESEM), and wherein they tangle at random each other and form nanotube entanglement ball like Bird's Nest (" BN "); Or be prepared into the aggregation of forming by carbon nano-tube bundle straight or slight curvature or kink, wherein CNT has essentially identical relative orientation, and have combed yarn (" CY ") outward appearance, for example the longitudinal axis of each nanotube (no matter independent bending or kinking) with intrafascicular around extend on the identical direction of nanotube; Or be prepared into the aggregation of forming by nanotube bundle straight or slight curvature or kink, the nanotube loosely formation structure of " opening net " of tangling each other wherein.In opening web frame, nanotube entanglement degree is greater than viewed in combed yarn aggregation (wherein independent nanotube has essentially identical relative orientation) but less than Bird's Nest.Other useful aggregate structure comprises cotton candy (" CC ") structure.

Pattern by selecting catalyst carrier control aggregation.Ball type carrier is growing nano-tube on all directions, causes forming the Bird's Nest aggregation.Use has the preparing carriers combed yarn of one or more scissile plane surfaces and opens the net aggregation, and carrier for example is deposited on has one or more easy cleaved surfaces and surface area is iron or ferrous metal catalyst granules on the carrier material of at least 1 meters squared per gram.People's such as Moy the exercise question of submitting to June 6 nineteen ninety-five has been described for " ImprovedMethods and Catalysts for the Manufacture of Carbon Fibrils " United States Patent (USP) 6143689 and has been prepared into the have various patterns nanotube of aggregation of (measuring by ESEM), and this paper is incorporated herein by reference.

The more details that form about the CNT aggregation can find in following discloses: the United States Patent (USP) 5165909 of Tnenent; The United States Patent (USP) 5456897 of Moy etc.; Snyder etc., the United States Patent (USP) 5707916 that on May 1st, 1991 submitted to, with PCT application US 89/00322 (" Carbon the Fibrils ") WO89/07163 that submitted on January 28th, 1989, with people such as Moy, the United States Patent (USP) 5456897 that on August 2nd, 1994 submitted to, with PCT application US90/05498 (" the Battery ") WO91/05089 that submits to September 27 nineteen ninety, United States Patent (USP) 5456897 that United States Patent (USP) of submitting on June 7th, 1996 with Mandeville etc. 5500200 and Moy etc. submitted on August 2nd, 1994 and the United States Patent (USP) of submitting on October 11st, 1,994 5569635, they all are transferred to the assignee identical with the present invention, and this paper is incorporated herein by reference.

Filtering nanotube then by dispersing Nano carbon tubes in water or organic media forms clump bunch or aggregation and prepares nanotube clump bunch or aggregation.By being prepared as follows clump bunch: for example form the gel or the paste of nanotube in organic solvent such as the propane at fluid, heat gel then or stick with paste the temperature that surpasses the medium critical-temperature, from the container of the process of carrying out, remove supercritical fluid, shift out at last the porous that obtains from or plug.Exercise question referring to Tennent etc. is the U.S. Patent application 08/428496 of " Three-Dimensional Macroscopic Assemblages of Randomly OrientedCarbon Fibrils and Composites Containing Same ", it is used as United States Patent (USP) 5691054 on November 25th, 1997 and authorizes, and this paper is incorporated herein by reference.

The oxidation of CNT

Although found many purposes of CNT and CNT aggregation, described in above-cited patent and patent application, but the front has found still can develop multiple difference and important purposes, if carry out functionalized with containing the oxygen part to nanotube surface.A kind of method that is used for functionalized carbon nanotubes is by utilizing the oxidation reaction of liquid oxidizer such as nitric acid or hydrogen peroxide.Unique material that oxidation allows functionalized nanotube and various substrate interaction formation to have special performance is formed and is allowed carbon nano tube structure to form based on the connection between the functionalized position on the carbon nano tube surface.

But a kind of common harmful side effect is to have destroyed CNT or carbon nano tube structure itself simultaneously.Therefore, not only the intensity of CNT or carbon nano tube structure and integrality reduce, but also how much contain the boundary that the oxygen part has qualification on CNT or the carbon nano tube structure for deposition.Thereby, needing improving one's methods of a kind of functionalized carbon nanotubes, it can produce less destruction to CNT or carbon nano tube structure, produces the higher oxygen part concentration that contains simultaneously on carbon nano tube surface.

Summary of the invention

The invention provides in the method that is enough to form under the condition of the big functionalized nanotube of the original CNT of weight ratio in 0 ℃-100 ℃ temperature range with ozone treatment single wall or multi-walled carbon nano-tubes.Preferably, make nanotube under room temperature or about room temperature, contact ozone.More preferably, nanotube is being contacted between 0 ℃ and 60 ℃ and most preferably in the temperature range between 20 ℃ and 50 ℃ with ozone.

Can make ozone contact CNT by gaseous state or liquid medium.Want processed CNT to can be single form or be the carbon nano tube structure form, as have similar cotton candy, Bird's Nest, combed yarn or open the aggregation of the macro morphology of mesh-shaped.Other carbon nano tube structure comprises clump bunch (mat), aggregation, three-dimensional network, rigid porous structure etc.Preferred multi-walled carbon nano-tubes has and is not more than 1 micron diameter, and preferred Single Walled Carbon Nanotube has the diameter less than 5nm.

The CNT of ozone treatment can further carry out the after-treatment step, thus the nanotube of ozone treatment contain oxygen part and suitable reactant reaction to increase at least one secondary group to the surface of the nanotube of handling.

The CNT of ozone treatment also is used for the raw material for preparing carbon nano tube network, rigid porous structure or use as the electrode that electrochemical capacitor uses.

Preferably by in 0 ℃-100 ℃ temperature range, preparing catalyst carrier with ozone contact or processing CNT aggregation, three-dimensional network or rigid porous structure.Preferably, make aggregation, three-dimensional network or rigid porous structure under room temperature or about room temperature, contact ozone.More preferably, aggregation, three-dimensional network or rigid porous structure are being contacted between 0 ℃ and 60 ℃ and most preferably in the temperature range between 20 ℃ and 50 ℃ with ozone.Use the functionalized catalyst support structures of ozone to show higher acidometric titration degree, therefore make higher catalyst loading become initial carrier structure and the integrality that may and keep them preferably.

The electrochemical capacitor of the electrode assembling of being made by the CNT of ozone treatment of the present invention shows the electrochemical properties of enhancing, as than electric capacity.

In a word, the present invention includes a kind of carbon nano tube structure, it comprises a large amount of CNTs that tangle each other, and described structure shows the acidometric titration degree of 1-2meq/g when titration.Carbon nano tube structure can be the CNT aggregate form with the macro morphology that is similar to the shape that is selected from cotton candy, Bird's Nest, combed yarn and opens the net aggregation.Carbon nano tube structure also can be three-dimensional network, CNT clump bunch or aggregation, rigid porous structure or any other carbon nano tube structure.

The present invention show when also being included in titration 1.6 and 2.2meq/g between or greater than the CNT of 2meq/g or the acidometric titration degree between 2.5-3.5meq/g.In addition, the present invention includes the CNT of ozone treatment, compare with the acidometric titration degree of the CNT of non-ozone treatment, it shows when titration increases 1.5meq/g at least or the acidometric titration degree between 2meq/g or 1.5meq/g and the 3meq/g at least.

To determine other improvement that surpasses prior art provided by the invention by the following description of having narrated the preferred embodiment of the invention.The scope that description does not limit the present invention in any way, but the work example of the preferred embodiment of the invention only is provided.Scope of the present invention will be pointed out in accessory claim.

The accompanying drawing summary

Fig. 1 is to the curve in reaction time based on fibril weight in the result's of embodiment 2 the ozone treatment.

Fig. 2 has shown the some oxygen 1s spectrum according to the various fibril samples of embodiment 5.

Fig. 3 illustrates the electron micrograph according to the fibril of the ozone treatment of embodiment 6.

Fig. 4 A and 4B for diagram with before the ozone treatment and after the TEM microphoto of fibril.

DESCRIPTION OF THE PREFERRED

Definition

Term " nanotube ", " nanofiber " and " fibril " are used in reference to single wall or multi-walled carbon nano-tubes interchangeably.Each refers to that all advantageous cross sections (for example have limit have angle fiber) or diameter (for example circular) are less than 1 micron (for many walls nanotube) or less than the narrow structure of 5nm (for single-walled nanotube).Term " nanotube " also comprises " flat to pipe " and fishbone fibril.

" many walls " used herein nanotube refers to as the graphite nanotubes of the substantially cylindrical with constant substantially diameter and comprises that the c-axle is basically perpendicular to the cylindrical graphite flake of cylinder axis or the CNT of layer, those as describing in the United States Patent (USP) 5171560 of for example Tennent etc.

" Single Walled Carbon Nanotube " used herein is meant as the graphite nanotubes of the substantially cylindrical with constant substantially diameter and comprises that the c-axle is basically perpendicular to their the single cylindrical graphite flake of cylinder axis or the CNT of layer, those as describing in the United States Patent (USP) 6221330 of for example Moy etc.

Term " functional group " is meant the compound that connects them or the atomic radical of peculiar chemistry of material and physical property.

" functionalized " surface is meant and absorbs on it or the chemical carbon surface that connects chemical group.

" graphenic " carbon is connected to three carbon forms on other carbon atom separately for carbon atom in the basic plane layer that forms the hexagon condensed ring.Layer is for having only the thin slice of several rings on diameter, or they can be band, and a plurality of rings are long singly to have only several ring widthes.

" graphite " carbon is made up of parallel to each other substantially and the graphenic layer that is no more than 3.6 dusts of being separated by.

Term " aggregation " is meant the fine and close microscopic particles structure that comprises the entanglement CNT.

Term " micropore " is meant the hole of diameter less than 2 nanometers.

Term " mesopore " is meant that cross section is greater than 2 nanometers and less than the hole of 50 nanometers.

Term " surface area " is meant the total surface area by the material of BET commercial measurement.

Term " accessible surface long-pending " is meant not the surface area owing to micropore (being diameter or the cross section hole less than 2nm).

Term " isotropism " is meant that all measured values of physical property in structural plane or the volume and direction of measurement have nothing to do, and are steady state value.The measurement that it should be understood that this inventive non-solid compositions must be carried out on the representative sample of structure, so that consider the mean value of void space.

Compare with the CNT of " ozone treatment ", when using term " to be untreated ", aggregation or any other carbon nano tube structure mean that CNT, aggregation or structure do not use ozone treatment specially.It is not precluded within ozone treatment advance CNT, aggregation or the structure of its non-ozone treatment of Xingqi.

Method with the ozone treatment CNT

In the present invention, according to a preferred embodiment, by CNT being handled surface nature and the characteristic that changes CNT with ozone.It is functionalized that a kind of desired result of handling fibril according to a kind of preferred embodiment is that the surface of fibril is contained the oxygen part.

In addition, the nanotube of the ozone treatment that obtains can easily be dispersed in the organic and inorganic solvent, especially in water.The nanotube of ozone treatment can be placed in the matrix of other material such as plastics, or is made into to be used in the structure in catalysis, chromatogram, filtration system, electrode, the capacitor etc.In addition, the nanotube of ozone treatment also can be used for forming other useful CNT of discussing in the following paragraph.

In preferred embodiments, CNT is the substantially cylindrical graphitic carbon fibril with constant substantially diameter, and does not have the carbon of pyrolytic deposition substantially.Nanotube comprise length over diameter than greater than 5 and nanotube on the projection of graphite linings extend those of at least two nanotube diameter distances.

Being used for the single wall of the inventive method and multi-walled carbon nano-tubes has described in greater detail under in front the title " CNT ".In a kind of preferred embodiment, according to the patent 5171560 of Tennent etc. or United States Patent (USP) 6696387 many walls of preparation nanotubes of Moy, this paper introduces both as a reference.Multi-walled carbon nano-tubes preferably has and is not more than 1 micron diameter, more preferably no more than 0.2 micron.Even the multi-walled carbon nano-tubes of diameter between 2 and 100 nanometers more preferably, comprise two end points; Most preferably between 3.5 and 75 nanometers.

Perhaps, press the preferred Single Walled Carbon Nanotube of United States Patent (USP) 6211330 disclosed preparations of Moy etc., this paper is incorporated herein by reference.Single Walled Carbon Nanotube preferably has the diameter that is not more than 5 nanometers, more preferably between 0.6 and 5 nanometers.

The ozone that is used for handling CNT can or be dissolved in aqueous solvent such as the ozone form of water is carried with gaseous ozone, liquid ozone.Gas ozoniferous can randomly dilute with gas such as oxygen, air, nitrogen, inert gas and their mixture.Can use any routine or commercial available ozone generator to produce ozone or gas ozoniferous.In order to produce ozone or gas ozoniferous, gas such as air or purity oxygen can be supplied to ozone generator.Use air as unstripped gas often also comprise can with medium such as water reaction form nitric acid nitrogen oxide contain ozone gas.Contain in the ozone gas this extra nitrogen oxide or nitric acid accessory substance and may influence the required functionalized of CNT.On the other hand, use purity oxygen generation to be contained the gas of purer ozone as unstripped gas, without any or the much smaller meeting of the amount of having influence CNT required functionalized extra accessory substance such as nitrogen oxide.

In one embodiment, can ozone be incorporated in the CNT with the speed of 250mg/hr.Preferably, the speed with 200-300mg/hr is incorporated into CNT with ozone.Those skilled in the art can recognize, the actual flow velocity of gas ozoniferous will depend on the quantity of the CNT of ozone quantity in the gas and processing.

Can use known popular response device, process or method to introduce ozone, comprise by vertical type reactor as passing through to use riser reactor, packed bed, fluid bed etc. to CNT.Also can use non-vertical type or horizontal reactor.For example, can be by distributor with ozone supply to reactor or the rotary drum reactor of rolling, the container that wherein holds CNT is rotated with the CNT that distributes more equably to the exposure of ozone with produce the more even functionalized of CNT.

In preferred embodiments, under 0 ℃-100 ℃ temperature, use the ozone treatment CNT.Preferably, under room temperature or about room temperature, nanotube is contacted with ozone.More preferably, between 0 ℃ and 60 ℃ and most preferably, in the temperature range between 20 ℃ and 50 ℃ nanotube is contacted with ozone.

In exemplary, this ozone decomposable process under preferred temperature can carry out more than 24 hours.Preferably, allow reaction to continue 3-8 hour, or 10-45 hour, more preferably 15-25 hour.Those skilled in the art can recognize the carbon filament that the size that depends on factor such as reactor the running time of this process and temperature, needs are handled quantity, speed that ozone is introduced in fibril, introduce ozone to the mode (for example in gaseous state or liquid medium) of fibril, required acidity etc.

The CNT of handling according to this preferred embodiment produces a large amount of unexpected benefits.

Find that unexpectedly weightening finish rather than weightless takes place the CNT of the ozone treatment of preferred embodiment, weightlessness reckons with the oxidizer treatment CNT time.Weightening finish can be preferably greater than 5% greater than 1%.In one embodiment, the CNT of the ozone treatment of preferred embodiment shows the 5-20% weightening finish, more preferably 10-15% weightening finish.

Do not wish to be subjected to any theory constraint, think the surface treatment (thereby causing functional group to connect, form, replace or deposit on the surface of CNT and aggregation) that this total body weight gains is attributable to ozone preferentially carries out carbon nano tube surface in described temperature range, rather than more commonly when carrying out under higher temperature open, peel off or shorten reaction (thereby causing minimum immeasurablel or visible carbonaceous amount to be lost) with other oxidant (for example nitric acid-degraded aggregation forms the weathering Cable Structure).On more atomic energy level, ozone treatment under the moderate temperature according to a preferred embodiment is considered to be undertaken by addition reaction, by addition reaction, ozone forms five yuan " ozonide " ring with two key surface carbon atoms, and it resolves into COOH and C=O then.Therefore this result is wonderful, because ozone is strong oxidizer under higher temperature, and is expected to open, peel off to aggressiveness as nitric acid with other strong oxidizer or shortens CNT.The mechanism description that ozone decomposes is at Murray, Robert W, and in " The Mechanism ofOzonolysis ", Accounts of Chemical Research, the 1st volume, 313-320 page or leaf (October nineteen sixty-eight), this paper is incorporated herein by reference.

Consistent with weightening finish, also find can be created in the ozone treatment CNT according to a preferred embodiment the CNT of the functional group's (especially acidic-group) that has the quantity bigger on the nanotube surface unexpectedly than the processing of other oxidant of use.(therefore, in specification and claims, term " functionalized " nanotube can exchange with " CNT of ozone treatment " and use, wherein the nanotube ozone treatment).Specifically, and compare, can reach higher acidometric titration degree (promptly having more acidic-group) with the CNT of ozone treatment with the nanotube of other oxidant such as nitric acid and hydrogen peroxide treatment.Can use the method for describing among the application to measure the acidometric titration degree as the method for description under title " is measured the method for titer " in the embodiment part.

The CNT of the ozone treatment of preferred embodiment can reach the acidometric titration degree greater than 2meq/g, preferably in the scope of 1.6-2.2meq/g.Perhaps, the CNT of ozone treatment can reach 0.0040-0.0080meq/m ²Acidometric titration degree in the scope.Because acidometric titration degree measured value is to indicate as the acid amount of reactions such as COOH, phenol OH, lactone with the oxygen part that contains that deposits on the CNT, therefore the too high acidometric titration degree that reaches confirms ozone and the reaction of carbon nano tube surface sidewall in the preferred embodiment method, and is not only end cap.

Find that also according to preferred embodiment, ozone can be used for further processing and used other oxidant oxidation or functionalized CNT.For example, especially can at first use conventional method to come purified mixture (promptly removing amorphous carbon) by oxidation with list or the multi-walled carbon nano-tubes mixture that nitric acid oxidation comprises amorphous carbon.The CNT that contains functionalized these oxidations of oxygen part subsequently with some, and the low acidometric titration degree when therefore producing titration.When further handling the CNT of these oxidations with ozone according to a preferred embodiment, the CNT of ozone treatment is dissolved, and showing at least during titration, 1.5meq/g increases with the acidometric titration degree that is preferably greater than 2meq/g.For example, the increase of acidometric titration degree can be between 1.5meq/g and 3meq/g, or between 2meq/g and 2.5meq/g.(with do not compare with the CNT of the preparation of oxidizer treatment in advance, these acidometric titration degree increases also are applicable to the CNT of ozone treatment).The CNT of final ozone treatment self can show when titration greater than 2.5meq/g or the acidometric titration degree between 2.5meq/g and 3.5meq/g.

In addition, and compare, in described temperature range, use the ozone treatment CNT also to cause more high efficiency surface acidity group to produce (higher percentage) with the CNT of nitric acid or hydrogen peroxide oxidation.CNT with ozone treatment in described temperature range has than those the high oxygen contents with nitric acid or hydrogen peroxide oxidation.The surface of the CNT of the ozone treatment of preferred embodiment can have the oxygen content greater than 4% (for example 4-10%), is preferably greater than 6% (for example 6-10%).The preferred functional group that is produced by ozone treatment comprises carboxyl, acid anhydride and ketone.

Find that further compare with other oxidant, the ozone treatment of CNT according to a preferred embodiment also causes the less destruction to CNT itself.Those that show among experimental data and ESEM microphoto such as Fig. 4 A and the B have disclosed the minimum or otherwise immeasurability or the visible carbonaceous amount loss of the CNT self of ozone treatment.

Except oneself surface and structural benefit on one's body of CNT (is more functional group, less carbon destroys) outside, using another benefit of preferred ozone treatment to be can be in lower temperature range as at room temperature carry out energy and the cost savings that ozone Oxidation Treatment provided.Therefore, compare, needn't need extra firing equipment with other oxidizing process.

Carbon nano tube structure-the general introduction of ozone treatment

Also find when with any carbon nano tube structure of ozone treatment (for example the fibril aggregation, clump bunch, aggregation, three-dimensional network, rigid porous structure etc.) time all these benefits all be suitable for.The structure of ozone treatment is kept perfectly, although the surface oxidation degree height, all above-mentioned weightening finishes, oxygen content and acidometric titration degree characteristic also all are suitable for.

In addition, described in paragraph subsequently, also be given similar benefit by the carbon nano tube structure of the made of carbon nanotubes of these ozone oxidation.

Carbon nano tube structure include but not limited to following these: aggregation, aggregation, network and rigid porous structure.

A. aggregation is the fine and close micro-grain structure of entanglement CNT, and similar Bird's Nest, cotton candy, combed yarn or open the pattern of net.

B. the carbon nano tube structure (for example United States Patent (USP) 5691054, this paper be incorporated herein by reference) of aggregation for having relative homogeneity matter along the ideal three-dimensional axle of the one dimension of three-dimensional set thing, preferred two peacekeepings.Usually, ressemble their formation aggregations then by disaggregation CNT aggregate structure and form aggregation.

C. by the connection molecule of use between the functionalized group on the carbon nano tube surface single functionalized carbon nanotubes is connected together the network of formation.(for example PCT/US97/03553 or WO97/32571, this paper is incorporated herein by reference).

D. by not using the connection molecule that single functionalized carbon nanotubes is connected together or forming rigid porous structure by using adhesive that the CNT aggregate structure is bonded together.(for example United States Patent (USP) 6099965, and this paper is incorporated herein by reference).

In preferred embodiments, the carbon nano tube structure of ozone treatment can prepare by above described in " with the method for ozone treatment CNT " this structure being carried out ozone treatment then by at first forming each self-structure.Perhaps, the carbon nano tube structure of ozone treatment can be prepared by the CNT of ozone treatment itself.

Method with ozone treatment CNT aggregation

Also find, can form improved CNT aggregation with ozone treatment according to a preferred embodiment.As previously mentioned, aggregation is the fine and close micro-grain structure of entanglement CNT, and can use any process of introducing for above-mentioned in " CNT aggregation and aggregation " paragraph or document at exercise question to prepare.Preferred aggregation has the diameter less than 50 microns.

Consistent with the non-destructive processing of CNT discussed above, further find, can form the aggregation of improved CNT by the CNT of described ozone treatment.Perhaps, can carry out the aggregation that ozone treatment forms improved CNT to untreated aggregation according to a preferred embodiment.

When the CNT by ozone treatment forms the aggregation of CNT, at first single CNT is carried out the CNT that ozone treatment forms ozone treatment by disclosed in the earlier paragraphs " with the method for ozone treatment CNT ".Using exercise question then is as the CNT aggregation that the CNT of ozone treatment is formed ozone treatment with reference to disclosed any method in the document of introducing in the earlier paragraphs of " CNT aggregation and aggregation ".

Perhaps, if formed the aggregation of untreatment carbon nanotube, then can carry out ozone treatment to these untreated aggregations according to same way as and the condition described in the earlier paragraphs " with the method for ozone treatment CNT ".

In any embodiment, find that the CNT aggregation of ozone treatment all has the similar benefit of CNT of a large amount of and ozone treatment.For example, compare with the aggregation that is untreated of CNT, the aggregation of ozone treatment shows unexpected weightening finish.Compare with the aggregation that is untreated of CNT, the weight increase of the CNT aggregation of ozone treatment can be greater than 1%, and is preferably greater than 5%.In one embodiment, the CNT aggregation of the ozone treatment of preferred embodiment shows the 5-20% weightening finish, more preferably 10-15% weightening finish.

In addition, find unexpectedly also that ozone treatment according to a preferred embodiment can be created in the CNT of the functional group's (especially acidic-group) that has the quantity bigger than the processing of using other oxidant on the nanotube surface.Specifically, and compare with those of other oxidant such as nitric acid and hydrogen peroxide treatment, the CNT aggregation of ozone treatment can reach higher acidometric titration degree (promptly having more acidic-group).The CNT aggregation of ozone treatment can reach the acidometric titration degree between the 1meq/g-2meq/g.

Even the CNT aggregation of more surprisingly finding ozone treatment kept the structure of the original aggregation that is untreated substantially, reaches the acidometric titration degree between the 1meq/g-2meq/g simultaneously.The non-destruction of ozone when using according to a preferred embodiment reconfirmed in this basic maintenance of structure.The CNT aggregation of handling with other oxidant such as nitric acid can not reach this high acidometric titration degree, because reaction will be opened, peels off and be shortened to these oxidants on CNT, thereby causes aggregate structure to untie and separate.

Experiment further confirms, and compares with the CNT of nitric acid or hydrogen peroxide oxidation, uses ozone treatment CNT aggregation to cause the more effective generation of surface acidity group (higher percentage) in described temperature range.The CNT aggregation of ozone treatment has than those the high oxygen contents with nitric acid or hydrogen peroxide oxidation.The surface of the CNT aggregation of ozone treatment can have the oxygen content greater than 4% (for example 4-10%), is preferably greater than 6% (for example 6-10%).Experiment shows that also the preferred functional group that comes from ozone treatment is carboxyl, acid anhydride and ketone.

Method with other carbon nano tube structure of ozone treatment

The earlier paragraphs that with exercise question is " with the method for ozone treatment CNT aggregation " is consistent, can be formed other improved carbon nano tube structure by the CNT of ozone treatment.Perhaps, can carry out ozone treatment to untreated carbon nano tube structure according to a preferred embodiment.Ozone treatment can be carried out in gas phase or liquid phase.

The CNT of ozone treatment also can be used for functionalized high-quality extrudate by using the small amounts of water soluble adhesive to form.In extrudate preparation, the functionalized surfaces of nanotube can improve adhesive in the mix stages disperse with the heating steps that reduces subsequently in the separating of adhesive.

The method for preparing carbon nano tube network comprise with the ozone treatment CNT be enough to the functionalized carbon nanotubes surface a period of time, make the CNT contact of ozone treatment be fit to increase secondary functional group to contact with the crosslinking agent that can effectively produce carbon nano tube network with the nanotube that further makes secondary treatment to the reactant of carbon nano tube surface.Preferred cross-linking agents is polyalcohol, polyamines or polycarboxylic acids.Useful polyalcohol is a glycol, and useful polyamines is a diamines.

In aspect of invention, make the nanotube of ozone treatment stand to promote that crosslinked condition obtains carbon nano tube network then by the CNT of at first using ozone (perhaps, can use liquid phase ozone) oxidation production attitude.For example, the nanotube of heating ozone treatment causes making the nanotube of ozone treatment crosslinked together in 180 ℃-650 ℃ temperature range, reduced ozone treatment nanotube contain the oxygen part.

The present invention comprises that also the nanotube by the ozone treatment that connects preferred embodiment forms three-dimensional network.These associations comprise at least two surface-modified nano pipes that connect with one or more attachments that contain straight key or chemical part.These networks comprise having the porous media that obviously evenly equates hole dimension.They are used as absorbent, catalyst carrier and separating medium.

(the porous 3-dimension network or the structure in hole＞2nm) are particularly useful as catalyst or chromosorb to have mesopore and macropore.Because nanotube can disperseed on indivedual bases, therefore come the sample of stable fine dispersion can make up this carrier by crosslinked.The nanotube of ozone treatment is desirable for this application, because they can easily be dispersed in water or the polarizable medium, the oxygen that contains that exists on the oxidation nanometer pipe partly provides crosslinking points.In addition, contain the point that the oxygen part also provides supported catalyst or chromatogram position.Final result is that its total surface area can be the approaching rigidity 3-dimension structure in the secondary group position of supported active agent.

Although the space between these nanotubes all is being irregular aspect the size and dimension two, they can be regarded as the hole and be characterised in that the method that is used to characterize porous media.Can disperse concentration and level and crosslinker concentration and chain length to control the size in space in this network by nanotube.This material can be used as the structure catalyst carrier and can be designed to get rid of or comprise the molecule of specific dimensions.Except conventional Industrial Catalysis, they have the special applications as the biocatalyst macropore carrier.

The typical case of these carriers in catalysis uses the highly porous carrier comprise that their are used as the metallic catalyst that obtains by dipping such as noble metal hydrogenation catalyst.In addition, make and to carry out homogeneous reaction in non-homogeneous mode to the ability on the carrier by the secondary group utilization constraint effect fixed member catalyst that combines with the very high porosity of structure.The molecular catalyst of constraint dangles in continuous liquid phase substantially, is similar to homogeneous reactor, wherein can utilize the advantage of distinctive selectivity of homogeneous reaction and speed aspect.But, be bound to solid carrier and allow easily to separate and reclaim active material, in many cases, be unusual expensive catalysts.

By connecting suitable optical siomerism catalyst or selectivity substrate to carrier, these stable rigid structures also allow to carry out up to now the very reaction of difficulty, as asymmetric syntheses or affinity chromatography.The rigidity network also can be used as the skeleton in the molecular recognition usefulness bionic system.This type systematic is described in United States Patent (USP) 5110833 and the International Patent Application WO 93/19844.The suitable selection of crosslinking agent and complexing agent allows the stable of particular molecule framework.

The method of the rigid porous structure of preparation ozone treatment

By at first pressing the nanotube of top described preparation ozone treatment, they are dispersed in form suspension in the medium, separating medium formation loose structure prepares rigid porous structure from suspension, wherein the nanotube of ozone treatment is further interconnected and is formed rigid porous structure, be the method for more specifically describing in the United States Patent (USP) 6099965 of " Rigid Porous CarbonStructure; Methods of Making; Methods of Using and ProductsContaining Same " according to the exercise question of submitting on May 15th, 1997 all, this paper is incorporated herein by reference.

Hard high porosity structure can be formed by CNT or nanotube aggregation.In order to increase the stability of nano tube structure, also can be at the gap of structure deposited polymer.This can be by with the dilute solution saturated set compound of low-molecular weight polymer cement (promptly less than about 1000MW) and solvent is evaporated realize.Capillary force arrives the nanotube gap with concentrated polymer.It should be understood that rigidity and integrality, only need to engage a fraction of nanotube space in order to improve structure greatly.

Nanotube can be made peace to be evenly distributed in the total or for being interconnected and be formed the aggregate particle form of structure by one.When needs the former the time, fully the dispersing nanometer pipe forms the dispersion of independent nanotube in medium.When the needs latter, the nanotube aggregation is dispersed in and forms slurries in the medium, and described aggregate particle connects together with cement and forms described structure.

The medium that uses can be selected from water and organic solvent.Preferably, medium comprises the dispersant that is selected from alcohol, glycerine, surfactant, polyethylene glycol, polymine and the polypropylene glycol.

Should select to satisfy following medium: (1) makes cement finely divided in aggregation; The aggregation internal structure is collapsed when (2) also preventing that as the template agent mixture is dry.

A kind of preferred embodiment use be dissolved in as the water of decentralized medium or the polyethylene glycol in the alcohol (PEG) but but and the combination of glycerine and char-forming material as hanging down MW phenolic resins or other carbonized polymers or carbohydrate (starch or sugar).In case the preparation rigid porous structure can be used ozone treatment then according to a preferred embodiment, for example, is used to prepare electrochemical capacitor.

In other words, preferred embodiment comprises the method that forms catalyst carrier, comprise step: form the rigid porous structure comprise CNT, and in 0 ℃-100 ℃ temperature range, make described rigid porous structure contact ozone with being enough to form under the condition of weight greater than the functionalized rigid porous structure of described rigid porous structure.

In another embodiment, if use the CNT of ozone treatment or aggregation to form rigid porous structure, use the ozone treatment nanotube before then in being distributed to medium according to a preferred embodiment, and form rigid structure by the adhesion certainly bonding in the nanotube gap.Structure can be removed deoxidation by pyrolysis subsequently.Useful pyrolysis temperature range is about 200 ℃-Yue 2000 ℃, preferred 200 ℃-Yue 900 ℃.

According to another embodiment, nanotube is dispersed in the described suspension with cement, and the cement described nanotube that bonds forms described rigid structure.Preferably, cement comprises carbon, even more preferably cement is selected from the material that only stays carbon when pyrolysis.Therefore, the structure of utilizing this joint to form can be changed into carbon with cement by pyrolysis subsequently.Other method and the details that form rigid porous structure are present in the United States Patent (USP) 6099965, and this paper is incorporated herein by reference.

Preferably, cement is selected from acrylate copolymer, carboxylic acid polyalcohol, cellulose, carbohydrate, polyethylene, polystyrene, nylon, polyurethane, polyester, polyamide, polyvinyl acetate/polyvinyl alcohol emulsion or resin, amino resins, epoxy resin and phenolic resins.

According to another embodiment of the present invention, separating step comprises filtering suspension liquid or evaporative medium from described suspension.

According to going back an embodiment, suspension comprises step for comprising the gel or the paste of nanotube in fluid, separating:

(a) heating gel or stick with paste the temperature that surpasses the fluid critical-temperature in pressure vessel;

(b) from pressure vessel, remove supercritical fluid; With

(c) from pressure vessel, shift out structure.

The homogeneous slurry dispersion of the nanotube aggregation in the solvent/dispersant mixture that can use Waring blender or kneader to be implemented in to comprise cement is not destroyed aggregation.The nanotube aggregation is caught resin particle and is kept them to distribute.

These mixtures can be used as maybe can be filtered removes enough solvents obtain having high nanotube content filter cake of (5-20% dry weight base).Filter cake can be by moulding, extrude or granulation.The shape of moulding is enough stable, thereby further drying can be carried out under the form destruction situation not having.Remove when desolvating, dispersant molecule is concentrated with cement particles, and accumulates in the nanotube aggregation and the nanotube intersection point place of aggregation outer edge.When further drying of mixture quilt and final carbonization, nanotube bundle that aggregation is interior and aggregation originally are engaged to together in the contact point place.Because aggregate structure does not destroy, thereby form the low-density particles of hard relatively very porous.By same way as and condition described in " with the method for ozone treatment CNT " rigid porous structure that obtains is carried out ozone treatment then.

As mentioned above, also the nanotube formation rigid porous structure that uses ozone treatment under the cement situation can be with or without.CNT becomes from adhesion after by ozone oxidation.By high degree of dispersion oxidation nanometer pipe (as separate bunches), filter and dry will be stone fine and close clump of bunch foamed.Dry clump bunch has the density of 1-1.2g/cc, depends on oxygen content, and enough firmly to grinding and classification by sieving.The surface area of measuring is about 275m ²/ g.

The nanotube of ozone treatment also can be used in combination with cement.The nanotube of ozone treatment is good raw material, because they have the tie point that clings cement and template agent.The latter is used for keeping their internal structure when particle or clump are bunch dry, thereby has prevented the high porosity and the low-density of original nanotube aggregation.By with material such as polyethyleneimine: amine cellulose (PEI unit) the nanotube pulp of ozone treatment being obtained good dispersion, this moment, alkaline imine formed the strong electrostatic interaction with carboxylic acid functionalized fibril.Filtering mixt forms clump bunch.The pyrolysis clump bunch changes into carbon with the PEI unit under greater than 650 ℃ temperature in inert atmosphere, and it is used to fuse the nanotube aggregation to becoming hard structure together.The result is the pure substantially carbon structure of rigidity, and if desired, available then ozone is further handled once more.

Also can be before structure forms additive package and nanotube dispersion in structure, introduce solid constituent.Can make the content of other solid in the stem structure high to 50 parts of solids of every part of nanotube.

According to a kind of preferred embodiment, in high shear mixer such as Waring mixer under high shear the dispersing nanometer pipe.Dispersion can roughly comprise the 0.01-10% nanotube in water, ethanol, mineral solvent wet goods.This process is fully opened nanotube bundle, i.e. the tight winding bundle of nanotube, and filtering and dry back dispersing nanometer pipe forms self-supporting clump bunch.Applying of high shear mixing spends several hrs possibly.But the clump of preparation bunch has aggregation by this method.

If follow sonicated after the high shear process, then disperse to be improved.Be diluted to 0.1% or below help sonicated.Therefore, for example available Bronson Sonifier Probe (450 watts of power supplys) sonicated 200cc 0.1% fibril 5 minutes or disperse to come up further to improve.

In order to obtain the highest degree of scatter, promptly do not have or do not have in fact the dispersion of nanotube aggregation, must be in compatible liquid for example for example in adding the water that concentration is about 0.5% surfactant such as Triton X-100, carry out sonicated 0.1% time under the 0.001%-0.01% concentration in ethanol or under higher concentration under the low-down concentration.The clump that forms subsequently bunch can entry have or do not have surfactant ground to wash vacuum filtration then substantially by adding continuously.The clump that forms like this bunch can be used ozone treatment then according to a preferred embodiment.

Before clump bunch formation, can in the nanotube dispersion of ozone treatment, add granular solids such as MnO ₂(for battery) and Al ₂O ₃(for high temperature gasket), every part of nanotube adds 50 parts of solids at most.

Also can be on clump bunch in the forming process or clump bunch in introduce and strengthen net and scrim.Example has polypropylene net and nickel foam sieve.

Catalyst carrier

Carbon nano tube structure such as CNT aggregation, three-dimensional network or rigid porous structure useful as catalysts carrier include but not limited to the catalyst catalyst carrier that energy catalyzed carbon nanotube forms.In these were selected, rigid porous structure provided the preferred compositions of size, intensity and surface area as catalyst carrier.

Therefore, preferred embodiment comprises by come functionalized carbon nanotubes structure such as aggregation, rigid porous structure or three-dimensional network to form catalyst carrier with ozone treatment.Can prepare aggregation by any method previously discussed, comprise the United States Patent (USP) 5165909 of following middle those disclosed: Tennent; The United States Patent (USP) 5456897 of Moy etc.; Snyder etc., the United States Patent (USP) 5707916 that on May 1st, 1991 submitted to, with PCT application US89/00322 (" Carbon the Fibrils ") WO89/07163 that submitted on January 28th, 1989, with people such as Moy, the United States Patent (USP) 5456897 that on August 2nd, 1994 submitted to, with PCT application US90/05498 (" the Battery ") WO91/05089 that submits to September 27 nineteen ninety, United States Patent (USP) 5456897 that United States Patent (USP) of submitting on June 7th, 1996 with Mandeville etc. 5500200 and Moy etc. submitted on August 2nd, 1994 and the United States Patent (USP) of submitting on October 11st, 1,994 5569635, this paper all is incorporated herein by reference.

Can use aforesaid any method to prepare rigid porous structure, be included in those disclosed in the United States Patent (USP) 6432866 of Tennent etc., this paper is incorporated herein by reference.In a word, rigid porous structure as describe in top or the United States Patent (USP) 6432866 those heat them then by the oxidation nanometer pipe and cause crosslinked preparation between the nanotube, or prepare by mixing nanotube and cement and heating the carbonization cement.Three-dimensional network can use that disclosed any method prepares in the United States Patent (USP) 5968650 of Tennent etc., and this paper is incorporated herein by reference.

An importance of catalyst carrier is that carrier must hold onto catalyst in catalytic reaction process, no matter be by chemical bond, adhere to or can make catalyst be retained in originally on one's body other power of carrier.In order to promote the stable and fully combination between catalyst and the carrier, preferred vector this in catalyst will in conjunction with or reacted surface on comprise a large amount of functional groups so that between catalyst and carrier, set up required combination.

Another importance of catalyst carrier is that carrier should be able to keep its structure and do not destroy or divide in course of reaction.

In preferred embodiments, by between 0 ℃ and 100 ℃, preferably between 0 ℃ and 60 ℃, most preferably form catalyst carrier with ozone treatment or contact carbon nano tube structure such as CNT aggregation, three-dimensional network or rigid porous structure between 20 ℃-50 ℃ or in the temperature range under the about room temperature.Ozone is especially preferred because its dissolved increase functional group to carbon nano tube structure, can not weaken or destroy with these structure controls to together crosslinked, engage or other power or key (promptly not having observable structural change).

Other strong oxidizer such as nitric acid also can be used for increasing functional group to the surface of these structures, still, find more possible hydrolytic crosslinking key of nitric acid or dissolving engagement keys or reduce other key, thereby weaken the integrality of initial carrier structure.On the contrary, weak oxidant such as hydrogen peroxide when can not weakening the carrier structure integrality, can not cause enough functional groups to be added on the carrier surface (promptly low acidometric titration degree) yet and commercial practical use is arranged.

Therefore, in order to obtain having the catalyst support structures of enough structural intergrities and enough functional group, preferably, carbon nano tube structure such as CNT aggregation, three-dimensional network or rigid porous structure prepare catalyst support structures by being contacted with ozone as preferred oxidant, because with compare with other oxidant, ozone can produce the catalyst carrier of functional group with higher concentration (be higher acidometric titration degree and therefore catalyst confining force preferably) and stronger structural intergrity.

Preferred catalyst carrier shows the carbon nano tube structure greater than the ozone treatment of the acidometric titration degree of 1meq/g such as 1-2meq/g when being included in titration.Compare with original untreatment carbon nano tube structure, the carbon nano tube structure of these ozone treatment does not also show observable structural change.The carbon nano tube structure of ozone treatment also shows the weightening finish greater than 1%, the weightening finish of preferred 5-20%, the more preferably weightening finish of 10-15%.Previously described other acidometric titration degree, oxygen content and weightening finish feature also are applicable to the functionalized structure as catalyst carrier.

Electrochemical capacitor

Carbon nanotube conducting.The exercise question of submitting on May 15th, 1997 electrode and their application in electrochemical capacitor for having described to comprise CNT and/or functionalized carbon nanotubes in the United States Patent (USP) 6031711 of " GraphiticNanofibers in Electrochemical Capacitors ", this paper is incorporated herein by reference.

Be disclosed in Chumming Niu etc. " High Power Electrochemical Capacitors basedon Carbon Nanotube Electrodes " based on the more details of the electrochemical capacitor of the CNT of catalytic growth, Applied Physics Letters70 (11), the 1480-1482 page or leaf, on March 17th, 1997, this paper is incorporated herein by reference.

The quality of plate electrode depends on the microstructure of electrode, the density of electrode, the functional group of electrode surface and the mechanical integrity of electrode structure.

The microstructure of electrode just hole dimension and Size Distribution has determined electrolytical ion resistance in the electrode.(bore dia＜2nm) the middle surface area that exists is considered to form bilayer (2) to micropore.On the other hand, distribution hole dimension, composite holes geometry (dead end hole, ceasma, cylindrical hole etc.) and surface nature produce the distribution time constant usually.Have only and utilize different rates can very little get the energy of storing in the electrode with distribution time constant.Utilize kind electrode can not realize the repid discharge that pulse power is required.

Its volume electric capacity of density decision of electrode.Density is impracticable for practical devices less than the electrode of 0.4g/cc.Simply, low density electrodes will absorb too many electrolyte, and this will reduce the volume and weight electric capacity of device.

The surface of CNT relates to the electrolytical wettability of electrode pair.The surface of the CNT of the catalytic growth of production attitude is hydrophobic.By preparing the hydrophobic surface properties of the CNT of attitude or the CNT that the CNT aggregation can change the preparation attitude to hydrophily with ozone treatment according to a preferred embodiment.In addition, increase electric capacity by on carbon nano tube surface, further connecting oxidizing reducing group.

At last, the structural intergrity of electrode is vital for the repeatability and the long-time stability of device.Entanglement by CNT in the electrode and the combination degree between the CNT determine to introduce the mechanical strength of electrodes of CNT.High entanglement and CNT combination degree also improve electrical conductivity, and this power-performance to electrode is most important.Ratio electric capacity (D.C. electric capacity) by the electrode of the fibril of gas phase treatment preparation is about 40F/g.

One aspect of the present invention relates to made of carbon nanotubes electrode and the electrochemical capacitor by ozone treatment.Put it briefly, the single wall or the multi-walled carbon nano-tubes that can be used for preparing electrode of the present invention of surface oxidation is provided with the CNT of ozone treatment preparation according to a preferred embodiment.

In another aspect of the present invention, can further handle the nanotube of ozone treatment, form the nanotube that has secondary group in its surface and also be used to prepare electrode of the present invention with the reactant of the partial reaction that exists on suitable and the oxidation nanometer pipe.

The simple filtration of the slurries of the nanotube by ozone treatment is come assembling electrode.By quantity of material and the geometry control thickness that uses, suppose and rule of thumb expect density.Has necessary adjustment thickness to obtain the self-supporting felt.

Advantageously characterize electrode by cyclic voltammetry, conductance and DC capacitance measurement.

Embodiment

The following examples are used to provide further understanding of the present invention, but the effective range that is not meant to limit the present invention in any manner.

Measure the method for titer

As primary problem, can make and realize acidometric titration degree mensuration in various manners.In one embodiment, the 0.10g fibril is transferred among the WaringLaboratory Blender that comprises the 350-400CC deionized water.Down mixing fibril 10-15 minute at a slow speed, appearing as even black up to whole fibrils of aqueous phase.In the blender that comprises thin fibril slurries, add 10CC standard 0.10N sodium hydroxide solution, and mixed once more 4-5 minute.Slurries are transferred in the beaker that comprises stirring rod and pH electrode then.During the hydrochloric acid solution that adds concentration known then gradually comes and the fibril slurries to pH 7.0.Record is used for the hydrochloric acid volume of fibril slurries and uses in the meq/g of fibril calculates.It (is meq/m that the result that titer is measured can be expressed as the every nanotube weight of milliequivalent (being meq/g) or the every nanotube surface of milliequivalent long-pending ²).

Embodiment 1

By can be with the ozoniferous Del Industry of the speed of 250mg/hr, San LuisObispo, the air purge device that CA makes produces ozone.Make flow velocity 1-inch (OD) reactor tube by with dry preparation attitude fibril fill of the mixture of ozone and air (0.29% ozone) then with 1200mL/min.The weight of the preceding and back fibril of record ozone treatment.Reaction was at room temperature carried out 3-45 hour.

In independent experiment, restrain the fibril that is equipped with attitude with 20 and be put in the flask that comprises 500mL 30% or 60% nitric acid.Heating reaction flask then kept 4-6 hour under 95-120 ℃ reflux temperature.After stopping reaction, the cooling fibril filters, and washes with water up to neutrality to room temperature.In another independent experiment, 20 fibrils that restrain to be equipped with attitude are put into to comprise 376.2 gram mol ratios be 1: 2 30%H ₂O ₂Flask in.Temperature is located near 35 ℃, but it is raised to reflux temperature fast.Use water-bath to keep reaction temperature under 30 ℃.After the reaction in 2 hours, filter slurries, and washing, up to removing whole remaining H ₂O ₂

Below the results are shown in:

Changes in weight in the table 2 fibril oxidizing process

Sample number into spectrum	Oxidant	Weight (g)	Running time (hr)	Changes in weight (%)
					1	O 3/ air	3	20	+13.9
2	O 3/ air	3	20	+8.0
					3	O 3/ air	10	45	+10.4
4	O 3/ air	9	45	+10.2
					5	O 3/ air	3	25	+12.1
6	30％HNO 3	20	6	-6.4
					7	60％HNO 3	20	4	-15.3
8	30％H 2O 2	20	2	-1.7

Test data confirms, compares with other oxidant such as nitric acid or hydrogen peroxide, at room temperature uses the ozone oxidation CNT to cause wonderful final products weight differential.That is to say that compare with the CNT through other oxidation processes, at room temperature the CNT through ozone treatment has disclosed tangible weightening finish, rather than weightless.Consider that ozone is strong oxidizer, this is wonderful.

For using nitric acid as oxidant, nitric acid intensity and reaction condition influence weightless degree.Weightless owing to oxidation of coal formation CO or CO ₂, they are overflowed from reaction system.

Embodiment 2

The fibril that 3 grams are done is put in the vertical type reactor, and makes ozone-containing air at room temperature by them.Regular off-response device is per hour measured the gross weight that fibril adds reactor tube on electric balance.After removing the reactor metering, obtain the relation of the weightening finish of fibril then to the reaction time.

The result of this measurement is presented among Fig. 7, and Fig. 7 has shown that example weight increases and stablized after about 15 hour reaction time in course of reaction.

Embodiment 3

By titrimetry according to the various oxidation fibrils of the method among the embodiment 1 preparation such as sample 1-3 and 5-7 to determine their acidic-group relative populations.Every kind of sample of 0.25 gram is put in the flask that comprises the 300mL deionized water, with 0.1N NaOH titration slurries.Convert the consumption of NaOH the quantity of all surfaces acidic-group to, represent with meq/g.

Table 3 is by titrimetry surface acidity group

As shown in table 3, compare with other oxidant such as nitric acid or hydrogen peroxide, when with ozone oxidation at room temperature, can deposit more acidic-group on carbon nano tube surface.In other words, at room temperature handle CNT with ozone generation is had the titer higher than the nanotube that obtains with other oxidizer treatment (being the indication of acidic-group).

In addition, promptly use the CNT of nitric acid treatment can reach by the titer in the minimum titer scope of ozone treatment generation, the nanotube of this nitric acid treatment also is not suitable for application-specific, because it is significantly weightless to follow this titer scope to exist.

Table 3 further confirms, and compares with those of weak acid such as hydrogen peroxide or dilution nitric acid, and the ozone treatment under the room temperature produces significantly the CNT than peracidity.

Embodiment 4

In order to compare the destructiveness that oxidation processes is carried out carbon nano tube surface, use the surface area of the fibril of Autosorb-1 apparatus measures processing.For the fibril of room temperature ozone oxidation, the average BET surface area under-196 ℃ is all at 240-250m ²In the scope of/g, this is in close proximity to the untreated fibril of preparation attitude.On the other hand, use the average BET surface area (measuring down) of the oxidation fibril of nitric acid treatment from 250m at 196 ℃ ²/ g is increased to 341m ²/ g.

Sample	Preparation attitude (surface area)	(surface area) of ozone treatment	(surface area) of 60% nitric acid treatment	Titer (meq/m 2Surface area)
					9	240m 2/g	247m 2/g		0.0055
10	240m 2/g		323m 2/g	0.0029
					11	240m 2/g		404m 2/g	0.0028

This surface area increase be considered to since the layer peel off or opening of nanotube causes.Therefore, in the ozone treatment process at room temperature, on carbon nano tube surface, produce minimum or immeasurablel destruction.

Embodiment 5

Use XPS (x-ray photoelectron spectroscopy) sign and use the fibril surface of the fibril aggregation of nitric acid, hydrogen peroxide, gaseous ozone (all as previously mentioned) and liquid ozone (as mentioned below) processing, compare with the untreated fibril aggregation of blank.

Measure three groups of characteristics: the atomic concentration of surperficial oxygen; Carbon degree of functionality and oxygen degree of functionality.

The surface composition and the carbon degree of functionality of table 4A and the different fibrils of B

(table 4A)

(table 4B)

According to expectation, blank fibril has the oxygen of minimum number from the teeth outwards, and this forms when being exposed to air usually after production.Table 4A confirms that further oxidation produces the group of polyoxyization more to the fibril surface because for the fibril of useful oxidizer treatment, all increased oxygen content.Table 4A and 4B confirm, at room temperature show the highest oxygen content in the CNT that gaseous ozone is handled.

Table 4B has also shown the classification of these oxidation content on the fibril surface, and confirms that different oxidants produces the different functional groups of varying number.For example, utilize H ₂O ₂The processing CNT of handling forms more-OH base, and nitric acid produces more-COOH as the whole functional groups percentage increase that produces.At room temperature the fibril of handling with gaseous ozone produces maximum-COOH increases.

For the information of determining the fibril surface functional group the further analysis of oxygen content is presented among table 4C and Fig. 8.Fig. 8 has shown the oxygen spectrum of 1s location.Initial data is represented with the point of drawing, and the fitting data and the signal that deconvolutes are represented with solid line.The peak at 531eV, 533eV and 535eV place is assigned to C-O, C=O and H ₂The O conformation.Data among Fig. 8 gather among below the table 4C:

Table 4C oxygen degree of functionality is analyzed

As show shown in the 4C, the oxygen groups of blank fibril is generally singly-bound " O-" conformation.Through H ₂O ₂The fibril of oxidation produces the oxygen groups of more-OH and C=O form.But, owing to singly-bound-O conformation is still occupied an leading position, so this soluble low titer result who uses the nanotube of hydrogen peroxide treatment.

On the other hand, nitric acid or ozone oxidation produce the CNT of surperficial oxygen groups from main singly-bound-O Conformation Transition to main two keys=O conformation.In addition, the fibril through the gas phase ozone treatment also produces less moisture.

Embodiment 6

Use SEM to check the fibril of ozone treatment under the room temperature.The analysis of fibril aggregate structure as shown in Figure 9 under ESEM confirms that the fibril aggregate structure at room temperature is kept perfectly after the ozone treatment.

Embodiment 7

According to following test untreated fibril aggregation is described, with the fibril aggregation of nitric acid oxidation with the difference between the fibril aggregation of ozone oxidation.Prepare three groups of fibril aggregations by identical mode.First group of fibril aggregation keeps being untreated after preparation.At room temperature handle second group of fibril aggregation with nitric acid subsequently.At room temperature handle the 3rd group of fibril aggregation with ozone subsequently.Three groups of fibril aggregations are dispersed in the water, and observe following difference:

The fibril aggregation	Hydrophobic to hydrophilic	Wetting characteristics	The structure retentivity
				Be untreated	Hydrophobic	Nonwetting	Keep structure
Use nitric acid oxidation	Hydrophilic	Wetting	Division
				Use ozone oxidation	Hydrophilic	Wetting	Keep structure

Therefore, the fibril aggregation with ozone treatment has different with untreated fibril aggregation (being hydrophobic and nonwetting to hydrophilic and wetting) and different with the fibril aggregation with strong oxidizer such as nitric acid treatment (promptly keeping structure to division).

Embodiment 8

Use the process of describing among the embodiment 1 to carry out following experiment, except application of heat device such as heating are taken on 1 inch reactor tube.In room temperature with carry out the ozone treatment of dried fibril aggregation slightly under the high-temperature.Obtain following data.

These test confirmation, and condition such as temperature and reaction time can influence the ozone treatment to CNT that obtains at last.The reaction of carrying out under the temperature between 0 ℃ and 100 ℃ causes enriching effective generation of surface functional group, and does not destroy fibril aggregation quality.More substantial reaction between ozone and the carbon be can cause 100 ℃ or bigger time long period of experiments of carrying out, CO and CO formed ₂, cause the mass loss of fibril aggregation.

Embodiment 9

At room temperature 1 fibril that restrains the nitric acid treatment that shows 0.93meq/g titer is carried out 5 hours ozone treatment.Processing according to identical process described in the embodiment 1.The material list that obtains reveals 10.6% weightening finish, and its titer is enhanced 1.84meq/g.This titer level is unexpected and wonderful, because can not obtain with nitric acid oxidation, and does not destroy substantially and the depolymerization carbon nano tube structure.

Embodiment 10

With nitric acid the impure mixture of Single Walled Carbon Nanotube and amorphous carbon is carried out selective oxidation and handle, to reduce cigarette ash and amorphous carbon.Gained oxidation mixture by the electron micrograph analysis is that about 20-50% is impure, and shows the acidometric titration degree of 0.9meq/g when titration.Use the process of describing among the embodiment 1, at room temperature oxidation mixture is carried out about 5 hours ozone treatment.The mixture of ozone treatment shows the acidometric titration degree of 2.86meq/g when titration.

Embodiment 11

The fibril of ozone treatment mixed with water further to form solids content be 15～25% slurries, extrude by 1/8 inch mould then.Obtain columniform oxidation fibril extrudate, and following dry 12 hours at 180 ℃.Extrudate looks very strong, is similar to those that produce with the fibril of nitric acid oxidation.Think that abundant surface functional group may the crosslinked rigid porous structure that is self-assembled into.The fibril of preparation attitude can not form this structure when having suitable jointing material.

Embodiment 12

The 20 CC nanotubes that restrain to be equipped with attitude are placed in the Waring blender, will be in the aqueous solution comprise 10% polymer for example 60 gram cements of polyacrylic acid (MW=15000) join in the CNT, and blend mixture is up to evenly.Make the material that obtains by 1/8 via the Brabender extruder then " mould (tie), dry then and in argon gas the temperature lower calcination between 300 and 600 ℃.Use among the embodiment 1 extrudate 20 hours that the process described obtains with ozone treatment then.After the ozone treatment, extrudate shows 0.79～0.93 acidometric titration degree.

Embodiment 13

10 fibrils that restrain to be equipped with attitude are placed in the cyclohexane in the reaction flask.Under strong agitation, make gas ozoniferous feed slurries then.Make to be reflected at and carried out under the environmental condition 8-10 hour.After the reaction, filter fibril, washing is also dry.Suitable liquid medium can be but is not limited to water, saturated alcohols, saturated hydrocarbons or cyclic hydrocarbon etc.Also can under the high-temperature of super critical condition and pressure, react.

Embodiment 14

1/16 inch CNT extrudate is put in the rotary drum reactor.Speed with 1L/min and 2.5L/min will be incorporated in the rotary drum reactor by the ozone gas that contains that the pure oxygen gas charging that enters ozone generator produces by distributor.In selected time titration from two samples of each reactor with degree of functionality uniformity relatively.Obtain following result:

Running time (hr)	Ozone flow velocity (L/min)	Titer-sample 1 (meq/g)	Titer-sample 2 (meq/g)
				3	1	0.23	0.19
8	1	0.29	0.26
				24	1	0.44	0.49
48	1	0.69	0.63

Running time (hr)	Ozone flow velocity (L/min)	Titer-sample 1 (meq/g)	Titer-sample 2 (meq/g)
				3	2.5	0.08	0.18
8	2.5	0.21	0.29
				24	2.5	0.40	0.41

Term that uses and expression are as descriptive rather than restricted term, do not plan when using this class term or expressing, to get rid of any equivalent as its a part of feature that shows and describe, it should be understood that within the scope of the invention various variations all are possible.

Claims (102)

1. the method for a functionalized carbon nanotubes comprises step:

CNT is contacted with ozone in 0 ℃-100 ℃ temperature range being enough to form under the condition of the big functionalized nanotube of the described CNT of weight ratio.

2. the process of claim 1 wherein that described temperature range is 0 ℃-60 ℃.

3. the process of claim 1 wherein that described temperature range is 20 ℃-50 ℃.

4. the process of claim 1 wherein that described CNT is a diameter less than 0.1 micron multi-walled carbon nano-tubes.

5. the process of claim 1 wherein that described CNT is the Single Walled Carbon Nanotube of diameter less than 5 nanometers.

6. the process of claim 1 wherein that the surface of described functionalized nanotube has the oxygen content greater than 4%.

7. the process of claim 1 wherein that the surface of described functionalized nanotube has the oxygen content greater than 6%.

8. the process of claim 1 wherein that described functionalized nanotube shows the acidometric titration degree greater than 2meq/g when titration.

9. the process of claim 1 wherein that described functionalized nanotube shows the acidometric titration degree of 1.6-2.2meq/g when titration.

10. the process of claim 1 wherein that described functionalized nanotube shows the acidometric titration degree of 2.5-3.5meq/g when titration.

11. the process of claim 1 wherein that described functionalized nanotube shows the big acidometric titration degree of 1.5meq/g at least of acidometric titration degree than described CNT when titration.

12. the process of claim 1 wherein that described functionalized nanotube shows the big acidometric titration degree of 2meq/g at least of acidometric titration degree than described CNT when titration.

13. the process of claim 1 wherein that described functionalized nanotube shows the acidometric titration degree than the big 1.5meq/g-3meq/g of described CNT when titration.

14. the process of claim 1 wherein that described functionalized carbon nanotubes compares the weightening finish that shows greater than 5% with described CNT.

15. the process of claim 1 wherein that described functionalized carbon nanotubes compares the weightening finish that shows 5%-20% with described CNT.

16. the process of claim 1 wherein that described functionalized carbon nanotubes compares the weightening finish that shows 10%-15% with described CNT.

17. the method for claim 1 comprises that also the reactant of the partial reaction of using suitable and described functionalized carbon nanotubes is handled described functionalized carbon nanotubes, thereby increases secondary at least group to the surface of described functionalized nanotube.

18. the method for claim 17, the secondary group of wherein said increase is selected from alkyl or aryl silane, and wherein said alkyl has C ₁-C ₁₈, described aryl has C ₁-C ₁₈, C ₁-C ₁₈Alkyl or C ₁-C ₁₈Aralkyl, C ₁-C ₁₈Hydroxyl and C ₁-C ₁₈Amido.

19. the method for claim 17, the secondary group of wherein said increase is a fluorine carbon.

20. the method for claim 1 also comprises:

Disperse described functionalized carbon nanotubes in liquid medium, to form mixture;

Filter the residue of described medium collection functionalized carbon nanotubes; With

Dry described residue forms clump bunch.

21. the method for claim 20 also comprises and heats described clump bunch to 200 ℃-900 ℃ temperature range.

22. the method for claim 20 also comprises forming electrode with described clump bunch.

23. the process of claim 1 wherein that described CNT is the aggregate form with the macro morphology that is similar to the shape that is selected from cotton candy, Bird's Nest, combed yarn and opens the net aggregation.

24. the method for claim 23, wherein said aggregation has the average diameter less than 50 microns.

25. a method that produces carbon nano tube network comprises step:

(a) CNT is contacted being enough to form under the condition of the big functionalized nanotube of the described CNT of weight ratio in 0 ℃-100 ℃ temperature range with ozone;

(b) make described functionalized nanotube stand to be enough to cause crosslinked condition.

26. the method for claim 25, wherein said temperature range are 0 ℃-60 ℃.

27. the method for claim 25, wherein said temperature range are 20 ℃-50 ℃.

28. the method for claim 25 is enough to wherein to cause that crosslinked described condition is included in the described functionalized nanotube of heating in 200 ℃-600 ℃ the inherent air of temperature range.

29. the method for claim 25 is enough to wherein to cause that crosslinked described condition is included in the described functionalized nanotube of heating in 200 ℃-2000 ℃ the inherent inert atmosphere of temperature range.

30. a method that produces the functionalized carbon nanotubes network comprises step:

(a) CNT is contacted being enough to form under the condition of the big functionalized nanotube of the described CNT of weight ratio in 0 ℃-100 ℃ temperature range with ozone;

(b) use the reactant of the partial reaction of suitable and described functionalized carbon nanotubes to handle described functionalized nanotube, thereby secondary at least group is increased on the surface of described functionalized nanotube;

(c) further make the described nanotube that has secondary group contact the crosslinking agent of effective quantity.

31. the method for claim 30, wherein said temperature range are 0 ℃-60 ℃.

32. the method for claim 30, wherein said temperature range are 20 ℃-50 ℃.

33. the method for claim 30, wherein said crosslinking agent is selected from polyalcohol or polyamines.

34. the method for claim 30, wherein said polyalcohol are glycol, described polyamines is a diamines.

35. a method for preparing rigid porous structure comprises step:

(a) CNT is contacted being enough to form under the condition of the big functionalized nanotube of the described CNT of weight ratio in 0 ℃-100 ℃ temperature range with ozone;

(b) in medium, disperse described functionalized nanotube to form suspension; With

(c) separate the loose structure that described medium forms the functionalized nanotube that tangles from described suspension, the wherein said nanotube formation rigid porous structure that interconnected.

36. the method for claim 35, wherein said temperature range are 0 ℃-60 ℃.

37. the method for claim 35, wherein said temperature range are 20 ℃-50 ℃.

38. the method for claim 35, wherein said CNT are the aggregate form with the macro morphology that is similar to the shape that is selected from cotton candy, Bird's Nest, combed yarn and opens the net aggregation.

39. the method for claim 35 also is included in the described suspension of heating in the inherent air of about 200 ℃-Yue 600 ℃ temperature range, forms described rigid porous structure thus.

40. the method for claim 35 also is included in the described suspension of heating in the inherent inert gas of about 200 ℃-Yue 2000 ℃ temperature range, forms described rigid porous structure thus.

41. the method for claim 35, wherein said medium are water or organic solvent.

42. the method for claim 35, wherein said medium comprises the dispersant that is selected from alcohol, glycerine, surfactant, polyethylene glycol, polymine and the polypropylene glycol.

43. the method for claim 35, wherein said suspension also comprises the cement that is selected from cellulose, carbohydrate, polyethylene, polystyrene, nylon, polyurethane, polyester, polyamide and the phenolic resins.

44. the method for claim 35 also comprises step:

(a) described rigid porous structure is formed the clump bunch; With

(b) form electrode with described clump bunch.

45. an electrochemical capacitor has at least one electrode, described electrode comprises the functionalized carbon nanotubes by the method preparation of claim 1.

46. an electrochemical capacitor has at least one electrode, the method preparation of described electrode by may further comprise the steps:

(a) the CNT aggregation is contacted under the condition of the aggregation that is enough to form the big functionalized nanotube of the described CNT of weight ratio in 0 ℃-100 ℃ temperature range with ozone;

(b) the described functionalized nanotube aggregation for preparing in the dispersion steps (a) in liquid medium forms slurries;

(c) filter and dry described slurries form functionalized carbon nanotubes clump bunch; With

(d) make described clump bunch of condition that stands to be enough to cause that described functionalized carbon nanotubes is crosslinked.

47. the method for claim 46, wherein the described temperature range in the step (a) is 0 ℃-60 ℃.

48. the method for claim 46, wherein the described temperature range in the step (a) is 20 ℃-50 ℃.

49. the electrochemical capacitor of claim 46, wherein the described condition of step (d) comprises described clump bunch is heated to 180 ℃ of temperature in-350 ℃ of scopes.

50. an electrochemical capacitor has at least one electrode, electrode forms by the method that may further comprise the steps:

(a) aggregation of dispersing Nano carbon tubes forms slurries in liquid medium;

(b) filter and dry described slurries form CNT clump bunch;

(c) be enough to form under the condition of the described CNT clump of weight ratio bunch big functionalized nanotube clump bunch in 0 ℃-100 ℃ temperature range with the described clump of ozone treatment bunch.

51. the CNT of ozone treatment, it shows the acidometric titration degree greater than 2meq/g when titration.

52. the CNT of ozone treatment, it shows the acidometric titration degree of 1.6-2.2meq/g when titration.

53. the CNT of ozone treatment, it shows the acidometric titration degree of 2.5-3.5meq/g when titration.

54. the carbon nano tube structure of ozone treatment, it shows the acidometric titration degree greater than 1meq/g when titration, and the carbon nano tube structure of described ozone treatment comprises a large amount of CNTs that tangle each other.

55. the carbon nano tube structure of the ozone treatment of claim 54, wherein said structure are the CNT aggregate form with the macro morphology that is similar to the shape that is selected from cotton candy, Bird's Nest, combed yarn and opens the net aggregation.

56. the carbon nano tube structure of the ozone treatment of claim 54, it has kept original untreated carbon nano tube structure substantially.

57. the carbon nano tube structure of the ozone treatment of claim 54, it shows the acidometric titration degree of 1-2meq/g when titration.

58. a method that forms catalyst carrier comprises step:

Form the CNT aggregation; With

Described aggregation is contacted with ozone in 0 ℃-100 ℃ temperature range being enough to form under the condition of the big functionalized poly collective of the described aggregation of weight ratio;

59. the method for claim 58, wherein said temperature range are 0 ℃-60 ℃.

60. the method for claim 58, wherein said temperature range are 20 ℃-50 ℃.

61. the method for claim 58, wherein said CNT are diameter less than 0.1 micron multi-walled carbon nano-tubes.

62. the method for claim 58, wherein said CNT are the Single Walled Carbon Nanotube of diameter less than 5 nanometers.

63. the method for claim 58, the surface of wherein said functionalized poly collective has the oxygen content greater than 4%.

64. the method for claim 58, the surface of wherein said functionalized poly collective has the oxygen content greater than 6%.

65. the method for claim 58, wherein said functionalized poly collective shows the acidometric titration degree of 1-2meq/g when titration, and keeps the structure of described aggregation.

66. the method for claim 58, wherein said functionalized poly collective shows the acidometric titration degree of 1-2meq/g when titration.

67. the method for claim 58, wherein said functionalized poly collective compares the weightening finish that shows greater than 5% with described aggregation.

68. the method for claim 58, wherein said functionalized poly collective compares the weightening finish that shows 5%-20% with described aggregation.

69. the method for claim 58, wherein said functionalized poly collective compares the weightening finish that shows 10%-15% with described aggregation.

70. pass through the catalyst carrier that the method for claim 58 forms.

71. pass through the catalyst carrier that the method for claim 58 forms, wherein functionalized poly collective shows the acidometric titration degree of 1-2meq/g when titration.

72. pass through the catalyst carrier that the method for claim 58 forms, wherein functionalized poly collective shows the acidometric titration degree greater than 1meq/g when titration, and keeps the structure of described aggregation.

73. a method that forms catalyst carrier comprises step:

Form carbon nano tube network; With

Described network is contacted with ozone in 0 ℃-100 ℃ temperature range being enough to form under the condition of the big functionalized network of the described network of weight ratio;

74. the method for claim 73, wherein said temperature range are 0 ℃-60 ℃.

75. the method for claim 73, wherein said temperature range are 20 ℃-50 ℃.

76. the method for claim 73, wherein said CNT are diameter less than 0.1 micron multi-walled carbon nano-tubes.

77. the method for claim 73, wherein said CNT are the Single Walled Carbon Nanotube of diameter less than 5 nanometers.

78. the method for claim 73, the surface of wherein said functionalized network has the oxygen content greater than 4%.

79. the method for claim 73, the surface of wherein said functionalized network has the oxygen content greater than 6%.

80. the method for claim 73, wherein said functionalized network shows the acidometric titration degree greater than 1meq/g when titration, and keeps the structure of described network.

81. the method for claim 73, wherein said functionalized network shows the acidometric titration degree of 1-2meq/g when titration.

82. the method for claim 73, wherein said functionalized network is compared the weightening finish that shows greater than 5% with described network.

83. the method for claim 73, wherein said functionalized network is compared the weightening finish that shows 5%-20% with described network.

84. the method for claim 73, wherein said functionalized network is compared the weightening finish that shows 10%-15% with described network.

85. pass through the catalyst carrier that the method for claim 73 forms.

86. pass through the catalyst carrier that the method for claim 73 forms, wherein functionalized network shows the acidometric titration degree of 1-2meq/g when titration.

87. pass through the catalyst carrier that the method for claim 73 forms, wherein functionalized network shows the acidometric titration degree greater than 1meq/g when titration, and keeps the structure of described network.

88. a method that forms catalyst carrier comprises step:

Formation comprises the rigid porous structure of CNT; With

Described rigid porous structure is contacted with ozone in 0 ℃-100 ℃ temperature range being enough to form under the condition of the big functionalized rigid porous structure of the described rigid porous structure of weight ratio;

89. the method for claim 88, wherein said temperature range are 0 ℃-60 ℃.

90. the method for claim 88, wherein said temperature range are 20 ℃-50 ℃.

91. the method for claim 88, wherein said CNT are diameter less than 0.1 micron multi-walled carbon nano-tubes.

92. the method for claim 88, wherein said CNT are the Single Walled Carbon Nanotube of diameter less than 5 nanometers.

93. the method for claim 88, the surface of wherein said functionalized rigid porous structure has the oxygen content greater than 4%.

94. the method for claim 88, the surface of wherein said functionalized rigid porous structure has the oxygen content greater than 6%.

95. the method for claim 88, wherein said functionalized rigid porous structure shows the acidometric titration degree greater than 1meq/g when titration, and keeps the structure of described rigid porous structure.

96. the method for claim 88, wherein said functionalized rigid porous structure shows the acidometric titration degree of 1-2meq/g when titration.

97. the method for claim 88, wherein said functionalized rigid porous structure is compared the weightening finish that shows greater than 5% with described rigid porous structure.

98. the method for claim 88, wherein said functionalized rigid porous structure is compared the weightening finish that shows 5%-20% with described rigid porous structure.

99. the method for claim 88, wherein said functionalized rigid porous structure is compared the weightening finish that shows 10%-15% with described rigid porous structure.

100. pass through the catalyst carrier that the method for claim 88 forms.

101. pass through the catalyst carrier that the method for claim 88 forms, wherein functionalized rigid porous structure shows the acidometric titration degree of 1-2meq/g when titration.

102. pass through the catalyst carrier that the method for claim 88 forms, wherein functionalized rigid porous structure shows the acidometric titration degree greater than 1meq/g when titration, and keeps the structure of described rigid porous structure.

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