CN1315139C - Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture - Google Patents
Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture Download PDFInfo
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Abstract
The present invention adopts a way compounding a carbon nanometer tube, and transition metal oxide and/or a conducting polymer. The carbon nanometer tube has good conductivity. A net structure is formed in a composite electrode so as to form an electric charge passage with favorable conductivity. The transition metal oxide and the conducting polymer can form false capacitors so as to obtain high specific capacitance, and thus, the electrode of a superhigh capacity capacitor has high specific capacitance and has high conductivity. In addition, the specific surface area of the carbon nanometer tube in the composite electrode is large so as to form large double electric layer capacitance. The carbon nanometer tube can be used as a nucleation substrate of the transition metal oxide and the conducting polymer in the preparation process, and the transition metal oxide and the conducting polymer with fine crystal grains are favorably obtained. The carbon nanometer tube is compounded with the transition metal oxide and the conducting polymer so as to obtain the superhigh capacity capacitor with favorable forming performance and high mechanical strength.
Description
Technical field:
The present invention relates to a kind of superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, affiliated field is nanometer technology and energy storage field.
Technical background:
Capacitor with super capacity is a kind of novel energy-storing device between storage battery and traditional sucrose capacitor, the traditional sucrose capacitor is to come store charge by polarization of dielectric, comes store charge and capacitor with super capacity is interaction by electrolyte ion and electrode.Compare with the traditional sucrose capacitor, it has very high specific capacitance, and storable energy density is more than 10 times of traditional sucrose capacitor; Compare with storage battery, its power density is high more than 10 times, has that the characteristic of the especially big electric current of abrupt release and charge efficiency are very high, to recycle the life-span long.
Capacitor with super capacity can be used as the power cell of motor vehicle driving power, solve electric motor car developing " bottleneck ", the composite power source motor vehicle that adds capacitor with super capacity with storage battery, storage battery provides required average power under the normal operating condition, and in climbing, start, required accelerating power is provided by the capacitor with super capacity of parallel connection under the on-position, capacitor with super capacity is as " peak power unit ", can alleviate the peak power pressure of storage battery effectively, make the lasting mileage of the each charging of storage battery increase several times, the life-span that recycles of storage battery is prolonged.Capacitor with super capacity also can be applicable to military aspect, and the especially big starting power of MW level is provided as microwave weapon, laser weapon; Also can be used as the stand-by power supply in the electronic equipment, as the uninterruptible power system of television set, Video Camera, PC, mobile phone; The flash of light, the igniter that can be used for industrial equipment are as the initiation power supply of camera, electric welding machine, magnet charger, X-ray machine, fuel cell.
The mode that capacitor with super capacity forms electric capacity has two kinds of electric double layer capacitance and fake capacitances, and electric double layer capacitance is to cause the face-off of electric charge to produce in electrode/electrolyte interface by aligning of electronics and ion.Fake capacitance is that highly reversible redox reaction or adsorption/desorption process take place electroactive material, thereby realize the storage and the release of electric charge and form electric capacity on electrode surface or the body two dimension or accurate two-dimensional space in mutually.The specific capacitance that the fake capacitance mode forms can reach more than 10 times of electric double layer capacitance.The device corresponding with top two kinds of capacitive way is double electric layer capacitor and fake capacitance device.
Usually double electric layer capacitor mainly with active carbon with high specific surface area, activated carbon fiber, carbon aerogels etc. as electrode material, but these material conductivity are relatively poor, capacitor produced equivalent series resistance is big; In addition, it is 2nm or littler micropore that a large amount of apertures are arranged in the active carbon, and electrolyte ion is difficult to enter in these holes, so its specific area utilance is low; And have so-called " dead hole " on the structure, this makes that its frequency response characteristic is poor.In recent years, because the discovery of carbon nano-tube is used carbon nano-tube and caused researcher's attention as the capacitor with super capacity electrode material, carbon nano-tube is the nanoscale tubular material by the curling hollow that forms of single or multiple lift graphite face.Under certain shape and size condition, carbon nano-tube has good electrical conductivity; Carbon nano-tube is interweaved to twine and forms network structure, and mesh size mainly is distributed between the 2-50nm, has huge effective ratio area, is fit to the formation of electric double layer capacitance; Connect mutually between the mesh of carbon nano-tube three-dimensional network, do not have the structural what is called of active carbon " dead hole ".But carbon nano-tube mainly is to form electric double layer capacitance, and specific capacitance is less relatively, is about 100F/g (pressing the single electrode active material calculates).As Ma Renzhi, Wei Bingqing, Xu Cailu, wait on " Chinese science " magazine (E collects, and 2000,30 (2): " based on the ultracapacitor of carbon nano-tube " 112-116) delivered.
And the fake capacitance device is often with metal oxide RuO
2Be electrode material, RuO
2The conductance height, the specific capacitance height of gained capacitor with super capacity, but RuO
2Cost an arm and a leg, seek cheap alternative RuO
2Electrode material cause researcher's interest.As: Wang Xiaofeng etc. " research of nickel oxide ultra-capacitor " that delivers (2001,25 (3)) on " power technology " magazine.Oxide (NiO with nickel
x) be electrode material, but the oxide (NiO of nickel
x) conductivity is relatively poor, the equivalent series resistance of gained capacitor with super capacity is big.In addition, the processability of transition metal oxide is poor.Another kind of fake capacitance device electrode material is a conducting polymer, comprises polyaniline (PAN) and derivative thereof, polythiophene (PTH) and derivative thereof, polypyrrole (PPY) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof; Thereby the capacitor with super capacity based on conducting polymer can form the bigger specific capacitance of fake capacitance acquisition, but the conductivity of conducting polymer is also poor.In addition, the mechanical strength of conducting polymer is low.
The performance of electrode material decision capacitor with super capacity, carbon nano-tube can reach higher conductivity in the electrode material above-mentioned, but it mainly is to form electric double layer capacitance, specific capacitance is less relatively.And transition metal oxide and conducting polymer can form fake capacitance, obtain higher specific capacitance, but conductivity are relatively poor.This means that present capacitor with super capacity electrode material is being difficult to take into account aspect high specific capacitance amount and the high conductivity.In addition, the transition metal oxide processability is poor, and the conducting polymer mechanical strength is low, and this all will influence the performance of capacitor with super capacity.
" carbon-doped nanometer tube capacity with very high capacitance " of people such as Fu Xutao application, number of patent application is: 00136008.6 patent of invention is compound with active carbon (or activated carbon fiber) and carbon nano-tube, as the capacitor with super capacity electrode material, but no transition metal oxide or conducting polymer in this material, be difficult to form fake capacitance, the ratio electric capacity of gained is little." the using the ultracapacitor and the manufacture method of the electrode of new material " of people such as Li Yongxi application, number of patent application is: 01109703.5 patent of invention with carbon nano-tube or nickel-plating carbon nanotube as vast capacity ion-conductance container electrode material, but no transition metal oxide or conducting polymer in this material are difficult to form fake capacitance; In addition, this material cost is too high.And separate sparkling and crystal-clear " electrochemical super-capacitor and the manufacture method " that waits people's application, number of patent application is: 00119499.2 patent of invention is the positive electrode of vast capacity ion-conductance container with the oxide or the hydroxide of nickel, with porous large tracts of land charcoal is negative material, but the oxide of nickel or the poorly conductive of hydroxide, the equivalent series resistance of gained capacitor with super capacity is big.
Summary of the invention:
The purpose of patent of the present invention is in order to obtain simultaneously to form the high specific capacitance amount, have good electrical conductivity, to have the capacitor with super capacity electrode material of good processability and mechanical performance and the electrode that makes thus, and then makes specific capacitance height, capacitor with super capacity that equivalent series resistance is low.
The principle of patent of the present invention is: intend to adopt carbon nano-tube and transition metal oxide and (or) conducting polymer mutually compound by way of, carbon nano-tube has good electrical conductivity in the gained combination electrode, and transition metal oxide and conducting polymer can form higher specific capacitance.Carbon nano-tube forms network structure in combination electrode, become the good electric charge path of conductivity; And transition metal oxide, conducting polymer can form fake capacitance, obtain higher specific capacitance, and this makes the capacitor with super capacity electrode can form the high specific capacitance amount, have a high conductivity again.In addition, in carbon nano-tube combination electrode material, the specific area of carbon nano-tube itself is big, can form bigger electric double layer capacity; In the preparation process of composite material, carbon nano-tube can be used as the forming core substrate of transition metal oxide, conducting polymer, helps obtaining the tiny transition metal oxide of crystal grain, conducting polymer; And the mechanical performance complementation of carbon nano-tube and transition metal oxide, conducting polymer can be attached on the carbon nano tube network as transition metal oxide, thereby obtains processability preferably; The mechanical strength of conducting polymer is relatively poor, after conducting polymer and carbon nano-tube are compound its mechanical strength is obviously improved.And moulding performance and mechanical strength also are very important concerning electrode material.
The technical scheme of the key technical problem of patent of the present invention is achieved in that patent of the present invention adopts carbon nano-tube that conductivity is good and the relatively poor serial composite methods mutually of transition metal oxide, conducting polymer series, active carbon of other conductivity that relates to, thereby obtains forming simultaneously high specific capacitance amount and the capacitor with super capacity electrode material with good electrical conductivity.Concrete compound scheme has following 6 kinds:
(1) carbon nano-tube and transition metal oxide are compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of transition metal oxide is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x).
(2) carbon nano-tube and conducting polymer series are compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of conducting polymer is 90%-10%; The conducting polymer series here comprises polyaniline (PAN) and derivative, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof.
(3) carbon nano-tube and transition metal oxide, conducting polymer are simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of conducting polymer is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x); Here the conducting polymer series of indication comprises polyaniline (PAN) and derivative, polypyrrole (PPY) and derivative thereof, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof.
(4) carbon nano-tube and transition metal oxide, active carbon series is simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x); Here the active carbon series of indication comprises active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
(5) carbon nano-tube and conducting polymer series, active carbon series is simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of conducting polymer is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the conducting polymer series of indication comprises polyaniline (PAN) and derivative, polypyrrole (PPY) and derivative thereof, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof; Here the active carbon series of indication comprises active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
(6) carbon nano-tube and transition metal oxide, conducting polymer, active carbon series are simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of active carbon series is 90%-10%, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of conducting polymer is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x); Here the conducting polymer series of indication comprises polyaniline (PAN) and derivative, polypyrrole (PPY) and derivative thereof, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof; Here the active carbon series of indication comprises active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
The carbon nano-tube of being mentioned in above-mentioned 6 kinds of compound schemes need be carried out oxidation processes before compound, oxidation processes is carried out in air or liquid medium, and oxidation temperature is 80-120 ℃, and oxidation treatment time is 2-10 hour.Can mix rare earth element ce or La in the transition metal oxide of mentioning in the such scheme; Also can not mix Ce or La.By compound scheme batching, fully grind then, add the binding agent that percentage by weight is 1%-20% more therein, binding agent comprises ptfe emulsion, carboxymethyl cellulose, polyvinyl alcohol.Be compressed on nickel foam, graphite flake, nickel sheet, aluminium flake or the copper sheet with the combination electrode material that stirs, make the combination electrode of definite shape.Drawing method comprises common die pressing, isostatic cool pressing method, hot isostatic pressing method.Two identical carbon nano-tube combination electrodes are separated with the barrier film that an electrolyte ion can pass through, and barrier film is all-glass paper or polymer film.Pack into then in the shell.Electrolyte solution reinjects, the carbonic allyl ester solution of electrolyte solution available hydrogen aqueous solution of sodium oxide, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, aqueous sulfuric acid, aqueous solution of nitric acid, lithium perchlorate, the carbonic allyl ester solution of tetraethylammonium tetrafluoroborate, or its mixed liquor.Promptly get capacitor with super capacity after the encapsulation.
The advantage of patent of the present invention is: the carbon nano-tube in the above-mentioned combination electrode can form conductivity favorable conductive network, and wherein transition metal oxide, conducting polymer series can form big specific capacitance.Thereby, obtain the capacitor with super capacity electrode material that can form the high specific capacitance amount simultaneously and have good electrical conductivity.In addition, in carbon nano-tube combination electrode material, the specific area of carbon nano-tube itself is big, can form bigger electric double layer capacity; In the preparation process of composite material, carbon nano-tube can be used as the forming core substrate of transition metal oxide, conducting polymer, helps obtaining the tiny transition metal oxide of crystal grain, conducting polymer; And the mechanical performance complementation of carbon nano-tube and transition metal oxide, conducting polymer can be depended on carbon nano tube network as transition metal oxide, can obtain processability preferably; The mechanical strength of conducting polymer is relatively poor, after conducting polymer and carbon nano-tube are compound its mechanical strength is obviously improved; And the interpolation of active carbon series can reduce cost.The application of this patent means the appearance of novel capacitor with super capacity electrode material, with advancing the application and the flow of research of capacitor with super capacity, produces bigger economic and social benefit.By enforcement of the present invention, can obtain forming simultaneously the high specific capacitance amount and have good electrical conductivity, have the capacitor with super capacity electrode material of processability and mechanical strength preferably, use this electrode material can produce capacitor with super capacity.
Embodiment:
Embodiment: the present invention relates to existing capacitor with super capacity electrode material and can be divided into two classes, a class is the good carbon nano-tube of conductivity, and another kind of is the relatively poor transition metal oxide of conductivity, active carbon series and conducting polymer series.The present invention adopts carbon nano-tube and relatively poor transition metal oxide, active carbon series, the mutually compound way of conducting polymer series of other conductivity that relates to that conductivity is good, thereby obtains forming simultaneously high specific capacitance amount and the capacitor with super capacity electrode material with good electrical conductivity.Concrete compound scheme has following 6 kinds:
(1) carbon nano-tube and transition metal oxide are compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of transition metal oxide is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x).
(2) carbon nano-tube and conducting polymer series are compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of conducting polymer is 90%-10%; The conducting polymer series here comprises polyaniline (PAN) and derivative, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof.
(3) carbon nano-tube and transition metal oxide, conducting polymer are simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of conducting polymer is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x); Here the conducting polymer series of indication comprises polyaniline (PAN) and derivative, polypyrrole (PPY) and derivative thereof, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof.
(4) carbon nano-tube and transition metal oxide, active carbon series is simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x); Here the active carbon series of indication comprises active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
(5) carbon nano-tube and conducting polymer series, active carbon series is simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of conducting polymer is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the conducting polymer series of indication comprises polyaniline (PAN) and derivative, polypyrrole (PPY) and derivative thereof, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof; Here the active carbon series of indication comprises active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
(6) carbon nano-tube and transition metal oxide, conducting polymer, active carbon series are simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of active carbon series is 90%-10%, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of conducting polymer is 90%-10%; Here the transition metal oxide of indication is the oxide (NiO of nickel
x), the oxide (CoO of cobalt
x); Here the conducting polymer series of indication comprises polyaniline (PAN) and derivative, polypyrrole (PPY) and derivative thereof, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and derivative, coalescence benzene (PAS) and derivative thereof; Here the active carbon series of indication comprises active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
The carbon nano-tube of being mentioned in above-mentioned 6 kinds of compound schemes need be carried out oxidation processes before compound, oxidation processes is carried out in air or liquid medium, and oxidation temperature is 80-120 ℃, and oxidation treatment time is 2-10 hour.Can mix rare earth element ce or La in the transition metal oxide of mentioning in the such scheme; Also can not mix Ce or La.By compound scheme batching, fully grind then, add the binding agent that percentage by weight is 1%-20% more therein, binding agent comprises ptfe emulsion, carboxymethyl cellulose, polyvinyl alcohol.Be compressed on nickel foam, graphite flake, nickel sheet, aluminium flake or the copper sheet with the combination electrode material that stirs, make the combination electrode of definite shape.Drawing method comprises common die pressing, isostatic cool pressing method, hot isostatic pressing method.Two identical carbon nano-tube combination electrodes are separated with the barrier film that an electrolyte ion can pass through, and barrier film is all-glass paper or polymer film.Pack into then in the shell.The electrolyte solution that reinjects, the carbonic allyl ester solution of electrolyte solution available hydrogen aqueous solution of sodium oxide, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, aqueous sulfuric acid, aqueous solution of nitric acid, lithium perchlorate, the carbonic allyl ester solution of tetraethylammonium tetrafluoroborate or its mixed liquor.Promptly get capacitor with super capacity after the encapsulation.
Claims (5)
1, the present invention relates to a kind of superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, in carbon nano-tube that employing is good with conductivity and transition metal oxide, electroconductive oxide and the active carbon series one or more are compound, it is characterized in that concrete compound scheme has following 6 kinds:
(1) carbon nano-tube and transition metal oxide are compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of transition metal oxide is 90%-10%; Here the transition metal oxide of indication is the oxide NiO of nickel
x, cobalt oxide CoO
x
(2) carbon nano-tube and electroconductive oxide are compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of electroconductive oxide is 90%-10%; Here the electroconductive oxide of indication is polyaniline (PAN) and derivative, polythiophene (PTH) and derivative thereof, poly-to benzene (PPP) and its biology that spreads out, coalescence benzene (PAS) and derivative thereof.
(3) carbon nano-tube and transition metal oxide, electroconductive oxide are simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of electroconductive oxide is 90%-10%; Here the transition metal oxide of indication is the oxide NiO of nickel
x, cobalt oxide CoO
xHere the electroconductive oxide of indication is polyaniline PAN and derivative, polypyrrole PPY and derivative thereof, polythiophene PTH and derivative thereof, poly-to benzene PPP and derivative, coalescence benzene PAS and derivative thereof.
(4) carbon nano-tube and transition metal oxide, active carbon series is simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the transition metal oxide of indication is the oxide NiO of nickel
x, cobalt oxide CoO
xHere the active carbon series of indication is active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
(5) carbon nano-tube and electroconductive oxide, active carbon series is simultaneously compound, and the percentage by weight of carbon nano-tube is 10%-90% in this composite material, and the percentage by weight of electric polymer is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the electroconductive oxide of indication is polyaniline PAN and derivative, polypyrrole PPY and derivative thereof, polythiophene PTH and derivative thereof, poly-to benzene PPP and derivative, coalescence benzene PAS and derivative thereof; Here the active carbon series of indication is active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
(6) carbon nano-tube and transition metal oxide, electroconductive oxide, active carbon series are simultaneously compound, the percentage by weight of carbon nano-tube is 10%-90% in this composite material, the percentage by weight of transition metal oxide is 90%-10%, the percentage by weight of conducting polymer is 90%-10%, and the percentage by weight of active carbon series is 90%-10%; Here the transition metal oxide of indication is the oxide NiO of nickel
x, cobalt oxide CoO
xHere the electroconductive oxide of indication is polyaniline PAN and derivative, polypyrrole PPY and derivative thereof, polythiophene PTH and derivative thereof, poly-to benzene PPP and derivative, coalescence benzene PAS and derivative thereof; Here the active carbon series of indication is active carbon, activated carbon fiber, active carbon fiber fabrics and carbon aerogels.
2, superhigh-capacitance capacitor with composite carbon nanotube according to claim 1 and manufacture method thereof, it is characterized in that the carbon nano-tube of being mentioned in above-mentioned 6 kinds of compound schemes need carry out oxidation processes before compound, oxidation processes is carried out in air or liquid medium, oxidation temperature is 80-120 ℃, and oxidation treatment time is 2-10 hour.
3, compound scheme according to claim 1, it is characterized in that by compound scheme batching, fully grind, add the binding agent that percentage by weight is 1%-20% more therein, binding agent comprises ptfe emulsion, carboxymethyl cellulose, polyvinyl alcohol.
4, the combination electrode material of compound scheme preparation according to claim 1 is characterized in that being compressed on nickel foam, graphite flake, nickel sheet, aluminium flake or the copper sheet with the combination electrode material that stirs, and makes the combination electrode of definite shape.
5, drawing method according to claim 4 is characterized in that drawing method comprises die pressing, isostatic cool pressing method, hot isostatic pressing method.
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US9928966B2 (en) | 2012-12-28 | 2018-03-27 | Intel Corporation | Nanostructured electrolytic energy storage devices |
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