CN1910771A - Carbon nanotube or carbon nanofiber electrode comprising sulfur or metal nanoparticles as a binder and process for preparing the same - Google Patents

Carbon nanotube or carbon nanofiber electrode comprising sulfur or metal nanoparticles as a binder and process for preparing the same Download PDF

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CN1910771A
CN1910771A CNA2005800023708A CN200580002370A CN1910771A CN 1910771 A CN1910771 A CN 1910771A CN A2005800023708 A CNA2005800023708 A CN A2005800023708A CN 200580002370 A CN200580002370 A CN 200580002370A CN 1910771 A CN1910771 A CN 1910771A
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electrode
carbon nano
carbon
fiber
nano
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CN100550485C (en
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金永男
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KH Chemicals Co Ltd
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
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Abstract

The present invention provides an electrode made of carbon nanotubes or carbon nanofibers and a process for preparing the same. The electrode comprising a current collector, sulfur or metal nanoparicles as a binder, and carbon nanotubes or carbon nanofibers is characterized in that the sulfur or metal nanoparticles are bonded, deposited, or fused on the surfaces of the carbon nanotubes or carbon nanofibers so that the carbon nanotubes or carbon nanofibers are bonded to each other and also bonded to the current collector. The electrode prepared according to the present invention exhibits low internal resistance, strong durability and low equivalent series resistance, and therefore the electrode can be effectively used for secondary batteries, supercapacitors or fuel cells.

Description

Comprise carbon nanotube electrode or carbon nano-fiber electrode and preparation technology thereof as the sulfur nano particles or the metal nanoparticle of adhesive
Technical field
The present invention relates to comprise carbon nanotube electrode or carbon nano-fiber electrode and preparation technology thereof as the sulfur nano particles or the metal nanoparticle of adhesive.Particularly, the present invention relates to wherein by utilize sulfur nano particles or metal nanoparticle as adhesive and to the electrode system heating and/or the inside of the electrode material that obtains to comprise carbon nano-tube or carbon nano-fiber of exerting pressure is bonding and electrode material and current-collector (current collector) between bonding carbon nanotube electrode or carbon nano-fiber electrode and preparation technology thereof.The invention still further relates to carbon nanotube electrode or the use of carbon nano-fiber electrode in secondary cell, ultracapacitor or fuel cell.
Background technology
Recently, along with to the transformation of information-intensive society and the appearance of portable electric appts, the concern of energy storing device has been increased.
Utilize the secondary cell (secondary battery) of electrochemical reaction stored energy to have high-energy-density, but its power density is low.Owing to this reason, when secondary cell was applied to require the system of variable power such as motor vehicle or mobile communication equipment etc., it can not produce instantaneous high power, and its useful life and performance reduce, and they also need long charge.Therefore, these feature limits of secondary cell their use.
Simultaneously, capacitor has the useful life and the high power density of short charge, length.But the electrical capacitor of Shi Yonging (electrical capacitor) has very low energy density traditionally, has many restrictions like this when using capacitor as energy storing device.
On the other hand, electrochemical capacitor has the feature between electrical capacitor and secondary cell.They not only have the very short charging interval, and have high power density, thereby can produce high power.They also have high-energy-density, thereby can discharge for a long time.Therefore, they are called as ultracapacitor or ultra-capacitor (hereinafter electrochemical capacitor being called ultracapacitor).
Relying on electric double layer to come the double electric layer capacitor (EDLC) of stored energy is a kind of ultracapacitor, and it comprises electrode, electrolyte and the diffusion barrier of assembling electricity.In these parts, the electrode that require to constitute the most important part of ultracapacitor has such as high electron conductivity, big surface area, electrochemistry inertia and the feature of moulding and processing easily.Therefore, (for example, the conductivity of copper, graphite and semiconductor Germanium is respectively 5.88 * 10 owing to high electron conductivity 5, 1.25 * 10 3With 1.25 * 10 -2S/cm) and good mouldability and machinability, generally with the carbonaceous material of utmost point porous as electrode material.
The carbonaceous material of porous comprises activated carbon, activated carbon fiber, amorphous carbon, carbon aerosol or carbon synthetic.In these material with carbon elements, the material of the most frequent use at present is the material that comprises activated carbon with the fibers form braiding.Although activated carbon and activated carbon fiber have about 1000 to 3000m 2The big surface area of/g, but most surface area is present in its micropore (＜20 ), and these micropores are inoperative for the role as electrode, and its effective hole only accounts for the 20-30% of total surface area.This feature of activated carbon and activated carbon fiber is the shortcoming when utilizing it as electrode material.
Since nineteen ninety has been synthesized carbon nano-tube and carbon nano-fiber first for the initial stage, because its superior characteristic has been made considerable effort and used these material with carbon elements as electrode material.Here carbon nano-fiber (the GNF that mentions, gnf) on shape and diameter, is similar to carbon nano-tube, but refer to diameter is to be up to the non-hollow of hundreds of nanometer, the carbon synthetic of fiber shape, and carbon nano-tube is represented as its title, is the shape of hollow tube.Activated carbon fiber can prepare by spinning (spinning), reaches the length of several microns diameter and hundreds of rice, has the diameter that is up to the hundreds of nanometer and is up to tens microns length and be similar to the carbon nano-fiber that carbon nano-tube synthesized by catalysis.The method that utilization is similar to the synthetic method of carbon nano-tube can form carbon nano-fiber.
Compare with other material with carbon element, carbon nano-tube or carbon nano-fiber have nano level definite pore size distribution, and the accessibility surface area of electrolytic ion is big, and chemical constitution is highly stable.When carbon nano-tube or carbon nano-fiber during as electrode material, the resistance of the electrode of making self is very low.In addition, carbon nano-tube or carbon nano-fiber have up to 1.0 * 10 4The conductance of S/cm, the availability of its particular table area almost reaches 100%, and the peak of its at present known particular table area is about 500m 2/ g.All these features of carbon nano-tube or carbon nano-fiber provide the desired perfect condition of electrode when making high-energy and the ultracapacitor of long life.
And, drawing by research, the carbon nano-tube with fishbone structure shows superior electrical characteristics, has the more edge of many exposures of high capacitance because they comprise than graphite substrate.
On the other hand, as the decision power of ultracapacitor and the key factor of frequency response, relate to the electrolytical resistance in the hole of the resistance of electrode material and electrode possibly.If the size in these holes is little, then along with electrolyte in the hole, electrolytical resistance increases.Therefore, although active carbon material has above-mentioned big surface area, comprise that the ultracapacitor of active carbon material can not be stored lot of energy.And, can only extract the energy of storage with the low frequency that is not more than 100mHz with by dc voltage, because active carbon material has wide pore size distribution.Although these characteristics explain of active carbon material comprise activated carbon why ultracapacitor in current existing sizable improvement, the reason that is not easy to popularize.
Therefore, use carbon nano-tube or carbon nano-fiber to make and to make the ultracapacitor that to handle high-frequency energy as electrode material.This feature of carbon nano-tube or carbon nano-fiber proves that these carbon nanomaterials are better than any other carbonaceous material, is the only material of the electrode of ultracapacitor.
In addition, one of the problem that will consider when manufacturing is used for the carbon electrode of ultracapacitor is to reduce the internal resistance of electrode.The internal resistance of electrode causes the loss of energy, thereby has reduced the performance of ultracapacitor.
Usually, can provide by following formula 1 from the maximum power density that ultracapacitor obtains;
[formula 1]
P max＝V i 2/4R
V wherein iIt is initial voltage, R is equivalent series resistance (ESR) [B.E.Conway, Electrochemical Supercapacitors:Scientific Fundamentals andTechnological Applications, Kluwer Academic/Plenum Publishers, New York 1999, Ch.15].
Therefore, the internal resistance of electrode self is the key factor of power density that decision comprises the ultracapacitor of carbon electrode.The internal resistance of carbon electrode self comprises: (i) form the contact resistance between the carbon particle of electrode, the (ii) resistance between electrolyte and the electrode material, and the (iii) contact resistance between electrode and the current-collector.In these resistance, in making the process of electrode, can improve contact resistance between the carbon particle and the contact resistance between electrode and the current-collector.
At first, various types of electrodes and manufacture method thereof have been proposed, to improve the contact resistance between the carbon particle that forms electrode.
Improvement for the internal resistance of electrode, when electrode material is traditional carbonaceous material (as activated carbon or activated carbon fiber), in the practice, made the electrode of compression-type, adhesive type, matrix (matrix) type, monolithic (monolith) type, fabric (cloth) type or film (film) type.
Compression-type prepares by under pressure the electrode material of carbon particle being exerted pressure, thereby has improved the contact between the carbon particle, and compression-type mainly uses with the material with carbon element of other type.Adhesive type prepares by utilizing the adhesive as PTFE (polytetrafluoroethylene), thereby has improved the contact characteristic between the carbon particle.By active carbon particle is mixed with polymer nature, make this mixture carbonization then and form matrix type.Although the adhesive in the adhesive type self can not be used as electrode, the polymer in the matrix type can be used as electrode, also can obtain bonding between the carbon particle.Monolithic type comprises carbon aerosol, carbon foam or the like.Because these materials are full units of porous, has continuous carbon trunk (backbone), so do not need to consider the contact in the carbon electrode material.Membranous type comprises non-porous material with carbon element, and electrolyte is not included in the electrode, but only is included in the diffusion barrier.Amorphous carbon can be used for membranous type.The textile type that is made of activated carbon fiber is most widely used type when making carbon electrode.
For the self-resistance that improves the electrode that comprises active carbon particle of broad research so far or improve electrolyte and electrode between contact resistance, carried out the electrode of the above-mentioned type and the trial of manufacture method thereof.
Introduce example below as the method for the contact resistance in the material with carbon element that reduces to form electrode.
People such as Kurabayashi are at United States Patent (USP) the 5th, 099, disclose the method for making double electric layer capacitor in No. 398.In this patent, electrode comprises the porous sintered body of the small active carbon particle through connecting, and current-collector is the form by the conducting film of making such as the mixture of powders of the electric conducting material of carbon and synthetic resin or rubber.For current-collector is adhered to electrode,, electrode is pressed to the dissolved surface of current-collector by the surface dissolution of organic solvent with current-collector.When solvent evaporation, electrode is glued fast to current-collector, has therefore made to have the low electrode that electrically contacts resistance between electrode and the current-collector.
People such as Kurabayashi are at United States Patent (USP) the 5th, 072, disclose the another kind of method of making double electric layer capacitor in No. 336.In this patent, in order to reduce the resistance that electrically contacts between electrode and the current-collector, by from forming conductive metal film on each surface of each electrode or current-collector, electrode is contacted with current-collector such as the evaporation of metal of gold (Au), silver (Ag), nickel (Ni), platinum (Pt) or copper (Cu).In addition, they are at United States Patent (USP) the 5th, 142, and the 451 and the 5th, 121, disclose in No. 301 and utilized various adhesives between electrode and current-collector, to carry out bonding method in the mode that is similar to said method.
People such as Nishino are at United States Patent (USP) the 4th, 562, disclose a kind of method of the lip-deep metal level of carbon fiber or active carbon electrode as current-collector that be formed on of utilizing in No. 511.This patent has considered to form on the surface of electrode the whole bag of tricks of metal level, as the use of plasma spraying, arc spraying, vacuum moulding machine, sputter, non-electrolyte plating and electrically-conducting paint.
At United States Patent (USP) the 5th, 102,745,5,304,330 and 5,080, in No. 963, people such as Tatarchuk disclose by being heated to the fusing point of metallic fiber, carry out bonding method between the electrode of metallic fiber form and current-collector.Adhesion technique between the carbon fiber that uses in metallic fiber that uses in the following execution current-collector and the electrode.The stainless steel fibre of the about 2 μ m of diameter and diameter are that carbon fiber and the length of 1～5 μ m is that cellulose and the water of 5mm mixes equably by stirring, filtration then, thereby be formed for the composite fibre synthetic of electrode.This fiber synthetic is pressed into thin slice in mould.Zhi Bei thin slice stands high temperature and pressure then like this, with at its place, crosspoint binder fibre, makes the electrode of the internal resistance with improvement like this.These patents have also been described the additional fibers as adhesive, to help bonding between the above-mentioned fiber.This additional fibers comprises metal, pottery, carbon or its any combination.
People such as Farahmandi are at United States Patent (USP) the 5th, 777, and 428 and 6,059, the electrode that comprises the activated carbon that is woven into fabric is disclosed in No. 847.Particularly, use aluminium foil, make electrode by the impregnated absorbent carbon fabric of aluminium that utilizes fusing as current-collector.In this patent, carry out the diffusion-bonded technology by the temperature below 600 ℃ (corresponding to fusing points of aluminium) aluminium foil is attached to aluminium/carbon synthetic electrode, to avoid forming the aluminium carbide that meeting significantly reduces electrode performance by the reaction between carbon and the aluminium.
People such as Zuckerbrod are at United States Patent (USP) the 4th, 448, disclose a kind of electrode by utilizing adhesive that activated carbon and stainless powder are prepared in No. 856.The density of each powder is limited to 25～450 μ m, with these powder coated on nickel wire line or sheet metal as current-collector, thereby make electrode.
The method of above-mentioned manufacturing activated carbon or active carbon fiber electrode has been represented the various technologies that reduce the resistance between active carbon electrode material and the current-collector.Because activated carbon can be made into the form of fiber, thereby can consider activated carbon treatment is become the whole bag of tricks of electrode.But, can not make fibers form to carbon nano-tube or carbon nano-fiber, this has produced restriction to making carbon nanotube electrode or carbon nano-fiber electrode.Method in common is by the mixture of carbon nano-tube or carbon nano-fiber and adhesive being exerted pressure, making the carbon nanotube electrode or the carbon nano-fiber electrode of dish type.
People such as Niu [" High Power E1ectrochemical Capacitors Based onCarbon Nanotube Electrodes ", Applied Physics Letter, 70, pp.1480-1482 (1997)] preparation of carbon nanotube electrode has been proposed, wherein utilize the oxidation processes of nitric acid and replace the function group (functional group) of about 10% on the carbon nano tube surface.Compare with the electrode that does not have to handle, surface treated electrode shows the performance of improvement.Particularly, they have proved and have not used adhesive to improve resistance between the carbon nano-tube by exerting pressure simply, and can prepare this electrode with having no problem.
People such as Ma [" Study of Electrochemical Capacitors Utilizing CarbonNanotube Electrodes ", Journal of Power Sources, 84, pp.126-129 (1999)] utilize phenolic resins (PF) powder to prepare carbon nanotube electrode as adhesive.Particularly, they have proposed to make the following technology of carbon nanotube electrode: the molded mixture of carbon nano-tube and PF powder (electrode (a)); Heat treatment makes this molded mixture carbonization (electrode (b)); Electrode (b) is immersed in the hot mixt of the concentrated sulfuric acid and nitric acid, then washing and dry (electrode (c)).According to results of comparative experiment, electrode (a) shows the highest internal resistance, and this is because adhesive makes the performance degradation of electrode.Therefore, must carry out carbonization technique.It is the highest utilizing the performance of the electrode (c) of carbonization and nitric acid treatment, and is second high with the performance of the electrode (b) of carbonization treatment only.
People such as An [" Supercapacitors Using Single-Walled Carbon NanotubeElectrodes ", Advanced Materials, 13, pp.479-500 (2001)] by carbonization prepares carbon nanotube electrode with exerting pressure then as the mixture of the polyvinylidene chloride (PVdC) of adhesive to carbon nano-tube.Particularly, in order to improve carbon nano-tube and as the contact resistance between the nickel foil of current-collector, they utilize the nickel foil of flat nickel foil, polishing and nickel foam to make electrode as current-collector respectively.Measure according to the ESR to these electrodes, the nickel foil of polishing and the ESR of nickel foam respectively are reduced to the half-sum 1/4th of the ESR of flat nickel foil.
People such as Emmenegger [" Carbon Nanotube Synthesized on MetallicSubstrates ", Applied Surface Science 162-163, pp451-456 (2000)] prepare at the electrode that can be used as the last carbon nano-tube that generates of the substrate of current-collector (aluminium or silicon).Substrates coated has metal, can generate carbon nano-tube on metal.Then, be coated with synthesize nano carbon periosteum on the substrate of metal, thereby making electrode by the chemical vapor deposition (CVD) method.Wished that this electrode has the internal resistance of reduction,, also had big surface area because it is to make from the carbon nano-tube film that is deposited on the proper alignment (well-aligned) on the current-collector.But the electrode for preparing in this mode has some shortcomings, separates from current-collector easily as carbon nano-tube, and this is because a little less than the bonding force between them; With compare by the electrode of making that carbon nano-tube is exerted pressure, this electrode has low-density carbon nano-tube; And the carbon nano-tube that on current-collector, is difficult to synthetic height crystalization.
Shown in the The above results of former research,, then can improve the performance of carbon nanotube electrode if reduce contact resistance between carbon nano-tube and the current-collector effectively.According to above-mentioned patent and document, can consider to use organic bond as utilizing the whole bag of tricks to handle the universal method that carbon nano-tube is made electrode.Although utilize the technology of this adhesive easy, exist the shortcoming that internal resistance is increased owing to organic bond.
Equally, PF, the PVdC and the PTFE that are used as adhesive have good affinity to carbon nano-tube, thereby when being mixed together and handling with carbon nano-tube, the most surfaces of these adhesive coverage carbon nano-tube.Therefore, carry out under the situation of carbonization after adding these organic bonds, the whole surface of carbon nanotube electrode is surrounded by the thermal decomposition of organic bond carbon that obtain, that resistance is higher.
Summary of the invention
The invention provides carbon nanotube electrode or carbon nano-fiber electrode, this carbon nanotube electrode or carbon nano-fiber electrode comprise current-collector, such as the adhesive of sulfur nano particles or metal nanoparticle and as the carbon nano-tube or the carbon nano-fiber of electrode material, wherein sulfur nano particles or metal nanoparticle, make carbon nano-tube or carbon nano-fiber be bonded to each other and are attached to current-collector on the surface of carbon nano-tube or carbon nano-fiber in conjunction with, deposition or fusion.
Owing to find can be applicable to secondary cell, the electrode of being made by carbon nano-tube or carbon nano-fiber in ultracapacitor or the fuel cell can be prepared by a kind of like this method, the present inventor has finished the present invention, in the method, by utilizing sulfur nano particles, metal nanoparticle or metallic compound nano particle are as adhesive and by to electrode system heating and/or bonding between the electrode material inside of realizing comprising carbon nano-tube or carbon nano-fiber and electrode material and the current-collector of exerting pressure, thereby reduced the internal resistance of electrode, make electrode produce strong durability, the contact resistance of adhesive interface is minimized, and therefore reduce equivalent series resistance (ESR).
Therefore according to the present invention, can provide have strong durability, low contact resistance and carbon nanotube electrode or the carbon nano-fiber electrode of very low ESR (equivalent series resistance), wherein by utilizing sulfur nano particles, metal nanoparticle or metallic compound nano particle as adhesive and by to the electrode system heating and/or bonding between the electrode material inside that obtains to comprise carbon nano-tube or carbon nano-fiber and electrode material and the current-collector of exerting pressure.
Description of drawings
Fig. 1 is according to the present invention, uses by deposition on carbon nano-tube and heat-treats prepared electrode then as the copper nano-particle of adhesive, the Ragon curve chart that obtains in test 1.
Embodiment
In a preferred embodiment of the invention, as the sulfur nano particles of adhesive or the amount of metal nanoparticle, by weight, in 0.01 times to 3 times scope of the amount of carbon nano-tube or carbon nano-fiber.
In another preferred embodiment of the present invention, the metal that constitutes metal nanoparticle can be selected from such group, this group comprises alkali metal, alkaline-earth metal, representative metal and transition metal, metal nanoparticle also can comprise the material of selecting from such group, this group comprises metal itself, metal sulfide, metal carbides, metal oxide and metal nitride.
When using sulphur as adhesive, by adding the sulphur particle or can being deposited on sulphur on the surface of carbon nano-tube by the sulfuration of the whole bag of tricks for bonding between the carbon nano-tube.
In the preferred embodiment of another one of the present invention, the average particle size of sulfur nano particles or metal nanoparticle is 1 μ m or littler.In the present invention, under the situation of deterioration effect of the present invention not, adhesive can comprise sulfur nano particles or the metal nanoparticle of size greater than 1 μ m, amount with respect to carbon nano-tube or carbon nano-fiber, by weight, its amount be 50% or below, be preferably 30% or below, more preferably be 10% or below, further preferably be 5% or following and also further preferably be 1% or below.
In another preferred embodiment of the present invention, the current-collector that is used for carbon nanotube electrode or carbon nano-fiber electrode can comprise the metal material as main component, and can have the shape of selecting from plane, netted and foam.
In another one preferred embodiment of the present invention, by from 1 to 500atm, be preferably under 1 to 100atm pressure the mixture of carbon nano-tube or carbon nano-fiber and sulfur nano particles or metal nanoparticle is exerted pressure, or by (being preferably M.P. ± 200 ℃ at the fusing point (M.P.) ± 500 of metal or metallic compound ℃, more preferably be M.P. ± 100 ℃) scope in temperature under this mixture is heat-treated, with sulfur nano particles or metal nanoparticle chemical bond or physical deposition or fusion on carbon nano-tube or carbon nano-fiber.
Another object of the present invention provides the technology of preparation carbon nanotube electrode or carbon nano-fiber electrode, this technology comprises following step: (1) is by mixing carbon nano-tube or carbon nano-fiber mutually with adhesive such as sulfur nano particles or metal nanoparticle, or by deposition sulfur nano particles or metal nanoparticle on carbon nano-tube or carbon nano-fiber, and the preparation electrode material; (2) prepare electrode material by first electrode material being exerted pressure through pressurized; (3) exerting pressure or heat treatment through the electrode material of pressurized to being placed on previous on the current-collector subsequently, therefore making carbon nano-tube or carbon nano-fiber is bonded to each other and make carbon nano-tube or carbon nano-fiber be adhered to this current-collector simultaneously.
In a preferred embodiment of the invention, by on current-collector, scattering electrode material equably, pressurization first then, or by under 1 to 500atm pressure, simultaneously electrode material being scattered and the above-mentioned steps (2) of pressurization execution first.
In another preferred embodiment of the present invention, in step (3), under 1 to 500atm pressure, metal nanoparticle is exerted pressure, or in inert gas, heat-treat under the temperature in fusing point ± 50～500 ℃ scope of metal that uses or metallic compound.
In another one preferred embodiment of the present invention, can utilize the method that is similar to rubber vulcanization process that sulphur is added in carbon nano-tube or the carbon nano-fiber, thereby between carbon nano-tube or carbon nano-fiber, carry out bonding.
In another one preferred embodiment of the present invention, in above-mentioned steps (1), can carry out mixing of carbon nano-tube or carbon nano-fiber and sulfur nano particles or metal nanoparticle or carbon nano-tube or carbon nano-fiber are carried out applying of sulfur nano particles or metal nanoparticle by the method for selecting from following a group, this group comprises physical mixed, Microwave Hybrid, solvent and scatter sulfur nano particles or metal nanoparticle equably on the surface of carbon nano-tube or carbon nano-fiber.
The method that utilization is selected from following one group can be carried out the said method that scatters sulfur nano particles or metal nanoparticle on the surface of carbon nano-tube or carbon nano-fiber equably, and this group comprises catalyst soakage method (back is with optional oxidation or reduction), precipitation (precipitation), chemical vapor deposition (CVD), electro-deposition, plasma spraying and sputter.
Simultaneously, in the present invention, when the nano particle that forms when metallic compound is deposited on carbon nano-tube or carbon nano-fiber surperficial, this metallic compound first the pressurization before and afterwards, or before secondary pressurization/heat treatment and afterwards, can partially or even wholly be converted into metal, metal sulfide, metal carbides or metal nitride.After this transformed, the conductivity of nano particle strengthened, because the ductility and the pliability of metal, its machinability also strengthens, and had therefore increased the effect as the metal nanoparticle of adhesive.But, have only in case of necessity just reducing metal compound, because can have the activity of enhancing in some cases as the metal of lithium.Utilize the conventional method of using in the relevant technologies can carry out the transformation of metallic compound, for example in hydrogen, reduce, utilize H 2S carries out presulfurization etc.
In another one preferred embodiment of the present invention, under pressure, carry out pressurization first, utilize this pressure can make carbon nano-tube or carbon nano-fiber the shape of dish or film.This pressure generally arrives in the scope of 100atm 1.
In another one preferred embodiment of the present invention, pressurization in step (3) and heat treatment can be carried out simultaneously or order is carried out.
In another one preferred embodiment of the present invention, heat treatment in step (3) can utilize the heating means of selecting from following a group to carry out, and this group comprises heating power heating (thermalheating), chemical vapour deposition (CVD), plasma heating, RF (radio frequency) heating and microwave heating.
The present invention also provides the double electric layer capacitor, secondary cell or the fuel cell that comprise carbon nanotube electrode or carbon nano-fiber electrode according to the foregoing description.
In the present invention, current-collector comprises sheet metal, metallic mesh or metal foam, and electrode material comprises carbonaceous material, particularly carbon nano-tube or carbon nano-fiber.
As mentioned above, carbon nano-tube or carbon nano-fiber have superior characteristic as electrode material, but still have problem to be solved efficiently when carbon nanotube electrode or carbon nano-fiber electrode in actual fabrication.For activated carbon, because activated carbon can be made into fiber, so use not so difficult as electrode material it.In addition, if activated carbon is woven into fibers form with metallic fiber, then solved the problem that is adhered to current-collector to a certain extent.But diameter has only the hundreds of nanometer, and in fact length has only from the carbon nano-tube of several to dozens of microns can not be woven into fibers form.
Therefore, for making electrode, require carbon nano-tube or carbon nano-fiber bonded to each other and bonding with current-collector.Therefore, when carbon nano-tube or carbon nano-fiber during, need utilize adhesive to handle these carbon nanomaterials as electrode material.
In the present invention, because sulfur nano particles or metal nanoparticle be as adhesive, so compare with utilizing conventional electrodes organic or that contain carbon binder, above-mentioned carbon nanotube electrode or carbon nano-fiber electrode have the following advantages.
At first, when sulfur nano particles or metal nanoparticle as adhesive between carbon nano-tube or carbon nano-fiber, to carry out when bonding because there is internal resistance hardly in these adhesives, this is with organic or to contain carbon binder different.
Secondly, as the sulfur nano particles of adhesive or metal nanoparticle and carbon nano-tube or carbon nano-fiber physical mixed together, or deposition in its surface, heat-treat subsequently, thereby realize bonding between carbon nano-tube or the carbon nano-fiber, and the Inherent advantage of deterioration carbon nano-tube or carbon nano-fiber not, this is different from the adhesive that the whole surface by coated carbon nanotube or carbon nano-fiber causes the routine of such deterioration to be used.
Next, as organic or contain aspect the durability that the shortcoming of carbon binder pointed out, utilizing sulfur nano particles or metal nanoparticle is very favorable as adhesive bonding, and this is because these adhesives are to select from the sulphur that can resist electrolytical corrosion or metal.
In addition, organic bond is subjected to reacting with corrosive electrolyte easily, or is dissolved in the electrolyte, then can be not like this as the sulfur nano particles or the metal nanoparticle of adhesive.
Therefore, above-mentioned advantage makes and can effectively utilize carbon nanotube electrode among the present invention or carbon nano-fiber electrode as the negative electrode in the secondary cell.When long-time use secondary cell, its useful life or performance reduce, and this mainly is that this causes internal short-circuit or causes that by the blocking electrode inner surface accessibility surface area reduces owing to formed the precipitated solid material during charging.This problem is called as " negative electrode obstruction ", by utilize do not have a micropore and can address this problem by the carbon nanotube electrode that structure constituted that causes being easy to the quality transmission or carbon nano-fiber electrode.Particularly, prepared according to the methods of the invention carbon nanotube electrode or carbon nano-fiber electrode have very low internal resistance and favorable durability, can show good performance as the negative electrode of secondary cell.
In addition, have very low internal resistance and help the structure that reacting gas spreads according to carbon nanotube electrode of the present invention or carbon nano-fiber electrode, the electrode of the battery that therefore acts as a fuel is compared with traditional carbon electrode, shows superior performance.
In the present invention, use sulfur nano particles, metal nanoparticle or metallic compound nano particle as adhesive, sulfuration process or the pressing technology of utilization under the temperature of the fusing point of metal nanoparticle or higher temperature stably is bonded to each other carbon nano-tube.Because utilizing does not have the stable metal of resistance that carbon nano-tube is bonded to each other substantially, and utilize organically or carbon adhesive and the electrode made is compared, the carbon nanotube electrode of gained has the internal resistance that greatly improved and good durability.
In addition, in the present invention, current-collector and electrode material are not physically combinations, but utilize the energy combination, so that directly combine between current-collector and the electrode material, therefore the ESR of electrode is minimized, and electrode efficiently is provided.
Preparation according to carbon nanotube electrode of the present invention or carbon nano-fiber electrode will more specifically be described below.As mentioned above, the present invention also provides preparation to have the technology of the carbon nanotube electrode or the carbon nano-fiber electrode of low internal resistance, particularly, this technology may further comprise the steps: sulfur nano particles or metal nanoparticle as adhesive are mixed with carbon nano-tube or carbon nano-fiber, or utilize various deposition processs deposit binder on the surface of carbon nano-tube or carbon nano-fiber, pressurize then and/or heat treatment.
Above-mentioned pressurization and heat treatment can sequentially or simultaneously be carried out.Particularly, the mixture of carbon nano-tube or carbon nano-fiber and nano particle adhesive is exerted pressure, heat treatment is then perhaps exerted pressure to mixture and heat treatment is carried out simultaneously.In addition, by pressurization sequentially and heat treatment or pressurization and heat treatment simultaneously, can obtain said mixture bonding to current-collector.
According to a preferred embodiment of the invention, for simplifying above-mentioned technology, by the distribution carbon nano-tube or the carbon nano-fiber that deposit or mix with sulfur nano particles or metal nanoparticle equably on current-collector, pressurization and heat treatment simultaneously can be made carbon nanotube electrode or carbon nano-fiber electrode subsequently.
In the technology of preparation carbon nanotube electrode according to the present invention or carbon nano-fiber electrode, importantly carbon nano-tube or carbon nano-fiber are mixed equably with the sulfur nano particles or the metal nanoparticle that are used as adhesive, but mix their qualification particularly of method.As the method for mixing, that mentions has physical mixed, ultrasonic mixing, usually disperses to remove then solvent or the like in solvent.
In description of the invention, " metal " speech specifically be not limited to literal on, its expression has any material of conductivity.For example, its expression is except nonmetal (element in periodic table among the VIII of family, the F among the VII of family, Cl, Br and I, O among the VI of family, the N among the V of family, the H among the I of family) and the semimetal (B among the IIIB of family, C among the IV of family, Si and Ge, the Se among the V of family, Te and Po) outside any element.Particularly, " metal " speech does not have concrete qualification in the present invention, comprise representative metal as alkali metal, alkaline-earth metal, transition metal and have conductivity with can by mix with carbon nano-tube or carbon nano-fiber or be deposited on these carbon nanomaterials, pressurization and heat treatment and other any metal of carbon nano-tube or carbon nano-fiber ability bonded to each other then.
In the present invention, metal nanoparticle can not only comprise metal itself, and comprises the metallic compound as metal oxide, metal sulfide, metal nitride, metal carbides etc.Therefore, in an embodiment of the present invention, " metal nanoparticle " speech not only comprises metal nanoparticle, and comprises the nano particle of metallic compound.
In the present invention, " nano particle " vocabulary shows that the average diameter that constitutes respective substance is 1 μ m or littler, is preferably from 10 to 500nm with more preferably for from 10 to 100nm particle.In addition, preferably, the particle size distribution of metal nanoparticle is 50% or more, is preferably 70% or more, further preferably be 90% or more particle have 1 μ m or littler diameter.
According to the present invention, the size distribution that the particle of respective material also represented to constitute in " nano particle " speech comprises that size is nano level particle, and can comprise substantially that average diameter is the particle of several to dozens of microns, if they can provide bonding as the carbon nano-tube or the microcosmic between the carbon nano-fiber of electrode material.
Preparation comprises any conventional method that nano particle can be provided as the method for the nano particle of adhesive, as mechanical lapping, co-precipitation, spraying, colloidal sol and gel (sol-gel) method, electrolysis, emulsion process, inversed phase emulsification (reversed-phase emulsion) or the like, and there is no particular limitation.
In addition, method at depositing nano particle on the surface of carbon nano-tube or carbon nano-fiber comprises any method that can deposit as the nano particle of adhesive on these carbon nanomaterials, as be used for dipping, precipitation, colloidal sol and the gel method of catalyst deposit, the CVD method that is for general on the metal deposition on the substrate, sputter, evaporation etc., and there is no particular limitation.
In the present invention, can utilize traditionally the technology of using to carry out the technology that the electrode material to the mixture that comprises carbon nano-tube or carbon nano-fiber and sulfur nano particles or metal nanoparticle pressurizes, this mixture as electrode material can (for example arrive under the pressure of 500atm) pressurization first 1 under the pressure of any value, electrode material is made desirable Any shape, for example make dish type.
Subsequently 1 under the pressure of 500atm to the electrode material pressurization of such preparation, and/or can be melted or be at the nano particle of sulfur nano particles, metal nanoparticle or metallic compound under the temperature of similar state and heat-treat, be deposited on sulfur nano particles on carbon nano-tube or the carbon nano-fiber or metal nanoparticle like this and obtain level and smooth bonding between the three-dimensional joint between these carbon nanomaterials or fusion and electrode material and current-collector.
Can comprise any heating means that can heat sulphur, metallic element or metallic compound to being deposited on the sulfur nano particles on carbon nano-tube or the carbon nano-fiber or the heat treatment method of metal nanoparticle, as heating power heating, chemical vapour deposition technique, plasma heating, radio frequency heating or microwave heating, and there is no particular limitation.
According to metal species as adhesive, can change above-mentioned heat treated temperature and time, these temperature and times have no particular limits, as long as heat treated state can be realized joint or fusion between carbon nano-tube or the carbon nano-fiber by for example fusing or softening physics and/or chemical change.Treatment temperature (is preferably fusing point ± 200 ℃ of sulfur nano particles or metal nanoparticle specifically in fusing point ± 500 of sulfur nano particles or metal nanoparticle ℃, more preferably being fusing point ± 100 ℃ of sulfur nano particles or metal nanoparticle, further preferably is fusing point ± 50 ℃ of sulfur nano particles or metal nanoparticle) scope in.When carrying out pressurization and heat treatment simultaneously, according to the pressure may command treatment temperature of pressurization, for example this temperature can reduce along with the increase of pressure.
In addition, by heat treatment, the surface of current-collector can be melted or be in similar state, therefore current-collector is adhered to electrode.
The present invention will more specifically be described with reference to following example.But it should be understood that these examples that the invention is not restricted to describe below.
The preparation of carbon nanotube electrode or carbon nano-fiber electrode
Example 1
This example shown is utilized the preparation of copper (Cu) nano particle as the carbon nanotube electrode or the carbon nano-fiber electrode of adhesive, and wherein the Cu nano particle reduces these nano particles then by deposited copper compound nano particle on carbon nano-tube and prepares.
Carbon nano-tube (CNT) as electrode material is by synthetic average diameter with 1nm and the 210m of catalysis evaporation 2The single wall face nanotube (SWCNT) of the surface area of/g (KH ChemicalsCo., Ltd.).
Utilize infusion process with 8: 2 (CNT: weight ratio Cu), copper compound Cu (NO 3) 2Be deposited on the carbon nano-tube.110 ℃ dry one day of the carbon nano-tube that deposits the copper compound nano particle, then in hydrogen 400 ℃ of reduction two hours.Under the pressure of 10atm these so preparation depositions the carbon nano-tube of Cu nano particle make plate-like.
The thickness that the carbon nano-tube dish that has deposited the Cu nano particle is placed on as current-collector is on the nickel foil of 75 μ m, keeps ten minutes at 900 ℃ then, exerts pressure under the pressure of 10atm in nitrogen simultaneously.The thickness of Zhi Bei electrode is 150～300 μ m in this example.
Example 2
As the deposition of preparation in the example 1 powder of carbon nano-tube of Cu nano particle be dispersed on the nickel foil as current-collector, remain on 1100 ℃ then, in nitrogen, exert pressure simultaneously, thereby generate electrode.Applied pressure is 10atm, and the time of pressurization is 5 minutes.
Example 3
This example shown is utilized the preparation of Cu nano particle as the carbon nanotube electrode of adhesive, wherein prepares the Cu nano particle by inversed phase emulsification.
(KH Chemicals Co. Ltd.), mixes with the Cu nano particle by stirring that (CNT on the weight: Cu=8: 2), wherein can alternatively prepare the Cu nano particle, its average diameter is 30nm to the SWCNT that use is used in example 1 in nitrogen.Then, by exerting pressure under the pressure of 10atm, this mixture forms plate-like.
The deposition of above-mentioned preparation the thickness that is placed on as current-collector of the carbon nano-tube dish of Cu nano particle be on the nickel foil of 75 μ m, kept ten minutes at 1000 ℃ then, in nitrogen, under the pressure of 20atm, exert pressure simultaneously, therefore generate electrode.
Example 4
This example shown is used the preparation of cobalt (Co) nano particle as the carbon nanotube electrode of adhesive, and this reduces these nano particles then by deposit cobalt compound on carbon nano-tube and prepares.
Utilize infusion process, with 8: 2 (CNT: weight ratio Co), cobalt compound Co (NO 3) 2Be deposited on example 1 in use same SWCNT (KH Chemicals Co., Ltd.) on.110 ℃ dry one day of the carbon nano-tube that deposits the cobalt compound nano particle, then in hydrogen 400 ℃ of reduction two hours.Following of the pressure of 10atm like this preparation deposition the carbon nano-tube of Co nano particle make plate-like.
The thickness that the carbon nano-tube dish that has deposited the Co nano particle is placed on as current-collector is on the nickel foil of 75 μ m, keeps ten minutes at 1200 ℃ then, exerts pressure under the pressure of 10atm in nitrogen simultaneously, therefore generates electrode.
Example 5
This example shown is used CoS 2Nano particle is as the preparation of the carbon nanotube electrode of adhesive, and this is to utilize H then by deposit cobalt compound on carbon nano-tube 2S carries out presulfurization to the cobalt compound nano particle and prepares.
Utilize infusion process, with 8: 2 (CNT: weight ratio Co), cobalt compound Co (NO 3) 2Deposition and the same SWCNT that in example 1, uses (KH Chemicals Co., Ltd.) on.110 ℃ dry one day of the carbon nano-tube that deposits the cobalt compound nano particle, then in the mist of hydrogen and hydrogen sulfide 400 ℃ of presulfurizations two hours.Following of the pressure of 10atm like this preparation deposition CoS 2The carbon nano-tube of nano particle is made plate-like.
The thickness that the carbon nano-tube dish that has deposited the Co nano particle is placed on as current-collector is on the nickel foil of 75 μ m, keeps ten minutes at 700 ℃ then, exerts pressure under the pressure of 10atm in nitrogen simultaneously, therefore generates electrode.
Example 6
This example shown is by the preparation of sputter utilization as the carbon nanotube electrode that is deposited on the Cu nano particle on the carbon nano-tube of adhesive.
By exerting pressure under the pressure of 5atm, (KHChemicals Co. Ltd.) is made into the plate-like that thickness is 100～300 μ m with the identical SWCNT that uses in the example 1.
The carbon nano-tube dish of preparation is like this put in the sputter device (film former), and the sputter device is pumped into and is approximately 10 then -6The vacuum of Torr.Subsequently, by flowing into Ar gas, the pressure in the sputter device is controlled at 2 * 10 -2Torr.Form the Ar plasma by applying dc voltage, then the copper target sputter of metal 5 minutes.Copper is removed this dish by after sputtering sedimentation is on the carbon nano-tube dish from the sputter device, clays into power then.Mix the powder that obtains equably, under the pressure of 5atm, be pressed into plate-like once more.The dish of preparation is like this put into the sputter device again, as mentioned above sputter copper.
The circulation of sputter-grinding-pressurization is repeated 20 times, has deposited the powder of the carbon nano-tube of Cu nano particle with formation, under the pressure of 10atm this powder is pressed into dish at last.
The deposition of above preparation the thickness that is placed on as current-collector of the carbon nano-tube dish of Cu particle be on the nickel foil of 75 μ m, kept ten minutes at 1000 ℃ then, in nitrogen, under the pressure of 10atm, exert pressure simultaneously, therefore generate electrode.
Example 7
This is the example for preparing the carbon nanotube electrode that is used for fuel cell by deposition Pt on the carbon nano-tube dish of preparation in example 1.
The carbon nano-tube dish of preparation in the example 1 is immersed H 2PtCl 6In the aqueous solution, then should dish 110 ℃ of dryings.400 ℃ by flowing through this dish of hydrogen reducing two hours, therefore be formed for the carbon nanotube electrode of fuel cell.
Example 8
This is to utilize the Pt nano particle to prepare the example of the carbon nanotube electrode that is used for fuel cell as adhesive, wherein the nano particle of platinum compounds is deposited on the carbon nano-tube, then reduction.
Utilize infusion process, platinum compounds H 2PtCl 6Be deposited on as the SWCNT that uses in the example 1 (with CNT: Pt=95: 5 weight ratio).Subsequently, at 110 ℃ dry one day of the carbon nano-tube that deposits the platinum compounds nano particle, then by flowing into 400 ℃ hydrogen reducing two hours.The deposition of so preparation the thickness that is placed on as current-collector of the carbon nano-tube of Pt nano particle be on the nickel foil of 75 μ m, kept ten minutes at 1500 ℃ then, in nitrogen, under the pressure of 10atm, exert pressure simultaneously, therefore generate electrode.
Example 9
This example shown is utilized the preparation of atomic sulfur as the carbon nanotube electrode of adhesive.
(CNT: weight ratio S) was mixed with atomic sulfur with 95: 5 as the sort of carbon nano-tube used in the example 1.Be different from other metal-to-metal adhesive, can utilize a spot of sulphur to prepare electrode, this be because sulphur can by and carbon nano-tube react and chemically bonding between adjacent carbon nano-tube.So process quilt is called sulfuration.The material of the carbon nano-tube of the above-mentioned preparation that physically mixes with sulphur is applied in pressure under 10atm, then 200 ℃ of sulfurations 30 minutes, therefore generate electrode.
The test of electrode performance
Carry out the performance test of the electrode of all above-mentioned preparations as described below.
Use the 7M KOH aqueous solution as electrolyte of electrodes.It is 1.5 centimetres that in the electrode of above-mentioned preparation each all is made into diameter.The spacer of electrode is polymeric barrier films (CelgardInc.).Two gaps between electrodes remain 300 μ m.The resistance coefficient of electrode is measured by Van derPauw method.
Test 1
Utilize Van der Pauw method, the resistance coefficient of the electrode of preparation is 9.1m Ω cm in the example 1 of measurement.According to complex plane impedance diagram (complex plane impedance plot), the equivalent series resistance (ESR) of the unit cell (unit cell) that obtains by extrapolation is 35m Ω.The electric capacity that utilizes dc voltage to measure in the mode that applies constant current is 175F/g.After being charged to 1V, utilize variation from 1 to 50mA electric current, measure energy density and power density.As what calculate by the weight of whole electrodes, power density is 15kW/kg, and energy density is 5.8Wh/kg.The Ragon figure of electrode is illustrated among Fig. 1 in the unit cell.
Test 2
The resistance coefficient of the electrode of preparation is measured as 10m Ω cm in the example 2.The equivalent series resistance (ESR) of the unit cell that obtains by extrapolation from the complex plane impedance diagram is 41m Ω.
Test 3
The resistance coefficient of the electrode of preparation is measured as 25m Ω cm in the example 3.The ESR of the unit cell that obtains by extrapolation from the complex plane impedance diagram is 151m Ω.
Test 4
The resistance coefficient of the electrode of preparation is measured as 15m Ω cm in the example 4.The ESR of the unit cell that obtains by extrapolation from the complex plane impedance diagram is 91m Ω.
Test 5
The resistance coefficient of the electrode of preparation is measured as 27m Ω cm in the example 5.The ESR of the unit cell that obtains by extrapolation from the complex plane impedance diagram is 95m Ω.
Test 6
The resistance coefficient of the electrode of preparation is measured as 14.4m Ω cm in the example 6.The ESR of the unit cell that obtains by extrapolation from the complex plane impedance diagram is 88m Ω.
Test 7
The resistance coefficient of the electrode for preparing in the example 9 of utilizing Van der Pauw method to measure is 13m Ω cm.The ESR of the unit cell that obtains by extrapolation from the complex plane impedance diagram is 102m Ω.Utilizing the electric capacity of the electrode that dc voltage measures in the mode that applies constant current is 155F/g.After being charged to 1V, utilize variation, the energy density of measurement electrode and power density from 1 to 50mA electric current.As what calculate by the weight of whole electrodes, power density is 12.5kW/kg, and energy density is 4Wh/kg.
Can find that from The above results according to an embodiment of the invention utilizing sulfur nano particles or metal nanoparticle to prepare electrode as adhesive is very useful technology for the internal resistance that reduces electrode.
Therefore, electrode prepared in accordance with the present invention has the internal resistance that is lower than the internal resistance value of reporting in the past, this proved for make carbon nano-tube bonded to each other for, compare with traditional handicraft (for example utilize the bonding or surface treatment of organic bond after bonding), using sulfur nano particles or metal nanoparticle is better technology as adhesive.
And the electrostatic capacitance of electrode prepared in accordance with the present invention is 175F/g.This value approaches the theoretical value of conventional obtainable electrostatic capacitance in the electrode that carbon nano-tube forms, the maximum electrostatic capacitance of the 180F/g that also approaches so far to be reported.
In addition, as test shown in 1 the result, the ESR of electrode is very little, makes the power density of electrode show as very high.Therefore, can find, very little according to the variation of the energy density of power density, as shown in Figure 1.
Therefore, that can expect is carbon nanotube electrode prepared in accordance with the present invention or carbon nano-fiber Electrode has low internal resistance, strong durability and very low ESR, so this electrode is as secondary electric The electrode of pond, ultracapacitor or fuel cell is very useful. What also can expect is, with biography The electrode that system uses is compared, and such electrode prepared in accordance with the present invention can be made more high performance Stable electric equipment.

Claims (22)

1. electrode of being made by carbon nano-tube or carbon nano-fiber comprises:
Current-collector,
Carbon nano-tube or carbon nano-fiber and
As the sulfur nano particles or the metal nanoparticle of adhesive,
Wherein said sulfur nano particles or metal nanoparticle combination, deposition or fusion make described carbon nano-tube or carbon nano-fiber be bonded to each other, and combine with described current-collector on the surface of described carbon nano-tube or carbon nano-fiber.
2. electrode according to claim 1, wherein as the sulfur nano particles of adhesive or the amount of metal nanoparticle, by weight, in 0.01 times to 3 times scope of the amount of carbon nano-tube or carbon nano-fiber.
3. electrode according to claim 1, the metal that wherein forms described metal nanoparticle is selected from following group, and this group comprises alkali metal, alkaline-earth metal, representative metal and transition metal.
4. according to any described electrode in the claim 1 to 3, wherein said metal nanoparticle comprises the material of selecting from such group, and this group comprises metal itself, metal sulfide, metal carbides, metal oxide and metal nitride.
5. according to any described electrode in the claim 1 to 3, wherein said sulfur nano particles or metal nanoparticle have 1 μ m or littler average particle size.
6. electrode according to claim 1, wherein said current-collector comprises the metal material as main composition, and has the shape of selecting from plane, netted and foam.
7. electrode according to claim 1, electrode material comprising described sulfur nano particles or metal nanoparticle is characterised in that, by exerting pressure under 1 to 500atm the pressure or in inert gas, heat-treating under by the temperature in sulphur, metal or metallic compound fusing point ± 500 ℃ scope, with described sulfur nano particles or metal nanoparticle chemically in conjunction with or physically deposition or fusion on carbon nano-tube or carbon nano-fiber.
8. technology for preparing carbon nanotube electrode or carbon nano-fiber electrode, this technology comprises following step:
(1) by carbon nano-tube or carbon nano-fiber are mixed mutually with adhesive such as sulfur nano particles or metal nanoparticle, or by deposition sulfur nano particles or metal nanoparticle on carbon nano-tube or carbon nano-fiber, and the preparation electrode material;
(2), described electrode material prepares electrode material by being exerted pressure first through pressurized; With
(3) exerting pressure or heat treatment through the electrode material of pressurized to being placed on previous on the current-collector subsequently, thereby making carbon nano-tube or carbon nano-fiber is bonded to each other and make carbon nano-tube or carbon nano-fiber be adhered to this current-collector simultaneously.
9. technology according to claim 8 wherein in described step (2), is scattered electrode material equably on current-collector, exert pressure then, or scatter simultaneously and exert pressure.
10. wherein in described step (2), under 1 to 500atm pressure, the electrode material that comprises described sulfur nano particles or metal nanoparticle is exerted pressure according to Claim 8 or 9 described technologies.
11. according to Claim 8 or 9 described technologies, wherein, in described step (3), to comprising the electrode material of described sulfur nano particles or metal nanoparticle, under 1 to 500atm pressure, exerting pressure or inert gas, heat-treating under the temperature in metal or metallic compound fusing point ± 500 ℃ scope.
12. according to Claim 8 or 9 described technologies, wherein in described step (1), method execution carbon nano-tube that utilization is selected from following group or carbon nano-fiber mix with sulfur nano particles or metal nanoparticle, and this group comprises physical mixed, ultrasonic mixing, solvent and scatter sulfur nano particles or metal nanoparticle equably on the surface of carbon nano-tube or carbon nano-fiber.
13. technology according to claim 12, wherein utilize the method for from following group, selecting to carry out the described method of on the surface of carbon nano-tube or carbon nano-fiber, scattering sulfur nano particles or metal nanoparticle equably, this group comprises catalyst soakage, precipitation, chemical vapor deposition (CVD), electro-deposition, plasma spraying and sputter, wherein carries out oxidation or reduction after the catalyst soakage alternatively.
14. according to Claim 8 or 9 described technologies, wherein in described step (2), exert pressure first the electrode material of dish or film shape is provided.
15. according to Claim 8 or 9 described technologies, wherein in described step (3), exert pressure and heat treatment is carried out simultaneously or order is carried out.
16. according to Claim 8 or 9 described technologies, wherein in described step (3), described heat treatment has utilized the heating means of selecting from following group to carry out, and this group comprises heating power heating, chemical vapour deposition (CVD), plasma heating, RF (radio frequency) heating and microwave heating.
17. a double electric layer capacitor comprises carbon nanotube electrode or carbon nano-fiber electrode according to claim 1.
18. a double electric layer capacitor comprises according to Claim 8 or 9 technology and the carbon nanotube electrode or the carbon nano-fiber electrode that prepare.
19. a secondary cell comprises carbon nanotube electrode or carbon nano-fiber electrode according to claim 1.
20. a secondary cell comprises according to Claim 8 or 9 technology and the carbon nanotube electrode or the carbon nano-fiber electrode that prepare.
21. a fuel cell comprises carbon nanotube electrode or carbon nano-fiber electrode according to claim 1.
22. a fuel cell comprises according to Claim 8 or 9 technology and the carbon nanotube electrode or the carbon nano-fiber electrode that prepare.
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