CN1388540A - Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture - Google Patents
Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture Download PDFInfo
- Publication number
- CN1388540A CN1388540A CN02133455A CN02133455A CN1388540A CN 1388540 A CN1388540 A CN 1388540A CN 02133455 A CN02133455 A CN 02133455A CN 02133455 A CN02133455 A CN 02133455A CN 1388540 A CN1388540 A CN 1388540A
- Authority
- CN
- China
- Prior art keywords
- derivative
- percentage
- weight
- transition metal
- metal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention is the way of compounding carbon nanotube, transition metal oxide and/or conducting polymer. The carbon nanotube has high conductivity and can form netted structure in composite electrode to become well conducting charge passage; and the transition metal oxide and conducting polymer can form false capacitor with high specific capacitance, so that the superhigh capacitance capacitor has both high specific capacitance and high conductivity. At the same time, the carbon nanotube in composite electrode has great specific surface area to result in great capacitance and may be used to form the base for transition metal oxide and conducting polymer with fine crystal particle. The composite of the said three material has good forming performance and high mechanical strength.
Description
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.
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 be at the electrode table and or on the two dimension or accurate two-dimensional space of body in mutually, highly reversible redox reaction or adsorption/desorption process take place in electroactive material, thereby realize the storage and the release of electric charge and form electric capacity.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 or the like " 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.
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 indication transition metal oxide comprises 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 50%-5%, and the percentage by weight of conducting polymer is 40%-5%.Here the indication transition metal oxide comprises 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 50%-5%, and the percentage by weight of active carbon series is 40%-5%.Here the transition metal oxide of indication comprises 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 50%-5%, and the percentage by weight of active carbon series is 40%-5%.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 transition metal oxide is 30%-3%, the percentage by weight of conducting polymer is 30%-5%, and the percentage by weight of active carbon series is 30%-2%.Here the indication transition metal oxide comprises 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.
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 indication transition metal oxide comprises 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 50%-5%, and the percentage by weight of conducting polymer is 40%-5%.Here the indication transition metal oxide comprises 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 50%-5%, and the percentage by weight of active carbon series is 40%-5%.Here the transition metal oxide of indication comprises 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 50%-5%, and the percentage by weight of active carbon series is 40%-5%.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 transition metal oxide is 30%-3%, the percentage by weight of conducting polymer is 30%-5%, and the percentage by weight of active carbon series is 30%-2%.Here the indication transition metal oxide comprises 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.
The advantage of patent of the present invention is: the CNT in the above-mentioned combination electrode can form the good conduction of electric conductivity Network, and wherein transition metal oxide, conducting polymer series can form big specific capacitance. Thereby, Obtain to form simultaneously high-specific capacitance super and the capacitor with super capacity electrode material with good electric conductivity. In addition, in carbon nano-tube combination electrode material, the specific area of CNT itself is big, can form Big electric double layer capacity; In the composite manufacture process, CNT can be used as transiting metal oxidation The forming core substrate of thing, conducting polymer is conducive to obtain the tiny transition metal oxide of crystal grain, conducts electricity and gather Compound; And the mechanical performance complementation of CNT and transition metal oxide, conducting polymer is such as mistake Cross metal oxide and can depend on carbon nano tube network, can obtain preferably processability; The machine of conducting polymer Tool intensity is relatively poor, after conducting polymer and CNT are compound its mechanical strength is obviously improved; And it is active The interpolation of charcoal series can reduce cost. The application of this patent means novel capacitor with super capacity electrode material The appearance of material will advance application and the flow of research of capacitor with super capacity, produce bigger economy and social Benefit. By enforcement of the present invention, can obtain to form simultaneously high-specific capacitance super and have good conduction Property, have the preferably capacitor with super capacity electrode material of processability and mechanical strength, use this electrode Material can be produced capacitor with super capacity.
Claims (6)
1, the present invention relates to a kind of superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, relatively poor transition metal oxide, conducting polymer series, the active carbon series of employing carbon nano-tube that conductivity is good and the conductivity that relates to is mutually 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 indication transition metal oxide comprises 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 its biology that spreads out, 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 50%-5%, and the percentage by weight of conducting polymer is 40%-5%.Here the indication transition metal oxide comprises 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 50%-5%, and the percentage by weight of active carbon series is 40%-5%.Here the transition metal oxide of indication comprises 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 50%-5%, and the percentage by weight of active carbon series is 40%-5%.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 transition metal oxide is 30%-3%, the percentage by weight of conducting polymer is 30%-5%, and the percentage by weight of active carbon series is 30%-2%.Here the indication transition metal oxide comprises 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.
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, superhigh-capacitance capacitor with composite carbon nanotube according to claim 1 and manufacture method thereof can be mixed rare earth element ce or La in the transition metal oxide that it is characterized in that mentioning in the such scheme; Also can not mix Ce or La.
4, superhigh-capacitance capacitor with composite carbon nanotube according to claim 1 and manufacture method thereof, 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.
5, superhigh-capacitance capacitor with composite carbon nanotube according to claim 1 and manufacture method thereof, it is characterized in that being compressed on nickel foam, graphite flake, nickel sheet, aluminium flake or the copper sheet, make the combination electrode of definite shape with the combination electrode material that stirs.
6, superhigh-capacitance capacitor with composite carbon nanotube according to claim 1 and manufacture method thereof is characterized in that drawing method comprises die pressing, isostatic cool pressing method, hot isostatic pressing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021334552A CN1315139C (en) | 2002-07-12 | 2002-07-12 | Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021334552A CN1315139C (en) | 2002-07-12 | 2002-07-12 | Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1388540A true CN1388540A (en) | 2003-01-01 |
| CN1315139C CN1315139C (en) | 2007-05-09 |
Family
ID=4747201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021334552A Expired - Fee Related CN1315139C (en) | 2002-07-12 | 2002-07-12 | Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1315139C (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005069412A1 (en) * | 2004-01-14 | 2005-07-28 | Kh Chemicals Co., Ltd. | Carbon nanotube or carbon nanofiber electrode comprising sulfur or metal nanoparticles as a binder and process for preparing the same |
| CN1304280C (en) * | 2004-06-25 | 2007-03-14 | 中国科学院上海硅酸盐研究所 | Cobaltosic oxide nano-crystalline coated carbon nano-tube composite powder and preparation method thereof |
| CN100353470C (en) * | 2003-12-05 | 2007-12-05 | 浙江大学 | Natural mineral and nanometer carbon tube compounded super capacitor electrode material and preparing method |
| CN100372035C (en) * | 2003-10-17 | 2008-02-27 | 清华大学 | Polyaniline/carbon nano tube hybrid super capacitor |
| CN100416722C (en) * | 2003-11-20 | 2008-09-03 | 哈尔滨工业大学 | Activated carbon deposited nickel oxide as super capacitor anode material and preparing method |
| US7531267B2 (en) | 2003-06-02 | 2009-05-12 | Kh Chemicals Co., Ltd. | Process for preparing carbon nanotube electrode comprising sulfur or metal nanoparticles as a binder |
| US7532454B2 (en) | 2004-03-09 | 2009-05-12 | Arkema France | Method for making an electrode, resulting electrode and supercapacitor including same |
| CN101302341B (en) * | 2007-05-09 | 2010-11-17 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
| CN101894680A (en) * | 2010-06-23 | 2010-11-24 | 万裕三信电子(东莞)有限公司 | Electrode plate for electric double layer capacitor and preparation method of electric double layer capacitor |
| CN102010577A (en) * | 2010-12-01 | 2011-04-13 | 南昌航空大学 | Method for preparing rare earth-doped ferrite/polythiophene/carbon nano tube microwave absorbent |
| CN101159192B (en) * | 2007-10-29 | 2011-07-13 | 上海中上汽车科技有限公司 | Drawer type super capacitor |
| CN101582302B (en) * | 2008-05-14 | 2011-12-21 | 清华大学 | Carbon nano tube/conductive polymer composite material |
| CN102443167A (en) * | 2010-09-30 | 2012-05-09 | 西门子公司 | Composite material for super capacitor, super capacitor and preparation method thereof |
| CN102585496A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院过程工程研究所 | Carbon-based ternary composite electrode material for super capacitor and preparation method for carbon-based ternary composite electrode material |
| CN101213020B (en) * | 2005-02-07 | 2012-09-26 | 阿肯马法国公司 | Method for synthesis of carbon nanotubes |
| CN101486849B (en) * | 2008-01-18 | 2012-12-05 | 郑州泰达电子材料科技有限公司 | Conductive paint, conductive composition and electronic component using the same |
| CN102924919A (en) * | 2012-10-25 | 2013-02-13 | 无锡市三力胶带厂 | Conductive polymer material |
| WO2013023404A1 (en) * | 2011-08-12 | 2013-02-21 | 清华大学 | Implanted biological electrode and medical assembly including same |
| CN101931043B (en) * | 2009-06-19 | 2013-03-20 | 清华大学 | Thermoelectric conversion material |
| CN101689430B (en) * | 2007-02-16 | 2013-04-17 | Sgl碳股份公司 | Composite comprising carbonized biopolymers and carbon nanotubes |
| CN103493256A (en) * | 2010-12-21 | 2014-01-01 | 拜耳知识产权有限责任公司 | Method for producing powdery polymer/carbon nanotube mixtures |
| CN101874274B (en) * | 2007-11-27 | 2016-06-22 | 玛丽亚·斯特罗姆 | Comprise composite and the method and apparatus of intrinsically conducting polymer |
| CN105895382A (en) * | 2016-03-23 | 2016-08-24 | 中国航空工业集团公司北京航空材料研究院 | Self-supporting flexible composite electrode film, preparation method and application thereof |
| CN106158404A (en) * | 2016-08-12 | 2016-11-23 | 深圳博磊达新能源科技有限公司 | A kind of ternary oxide/conductive agent/carbon/polypyrrole combination electrode material, pole piece and ultracapacitor |
| US10155106B2 (en) | 2012-09-07 | 2018-12-18 | Tsinghua University | Method for making implantable lead |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9928966B2 (en) | 2012-12-28 | 2018-03-27 | Intel Corporation | Nanostructured electrolytic energy storage devices |
| US10319535B2 (en) | 2013-09-27 | 2019-06-11 | Intel Corporation | High voltage high power energy storage devices, systems, and associated methods |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100487069B1 (en) * | 2000-04-12 | 2005-05-03 | 일진나노텍 주식회사 | Supercapacitor using electrode of new material and manufacturing method the same |
| CN1357899A (en) * | 2000-12-13 | 2002-07-10 | 中国科学院成都有机化学研究所 | Application of carbon nanotube as electrode material of super capacitor |
| KR20020051592A (en) * | 2000-12-23 | 2002-06-29 | 오길록 | Triode - type field emission device with carbon nanotube cathode, triode - type RF vacuum device and field emission display using it |
-
2002
- 2002-07-12 CN CNB021334552A patent/CN1315139C/en not_active Expired - Fee Related
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7531267B2 (en) | 2003-06-02 | 2009-05-12 | Kh Chemicals Co., Ltd. | Process for preparing carbon nanotube electrode comprising sulfur or metal nanoparticles as a binder |
| US8278010B2 (en) | 2003-06-02 | 2012-10-02 | Kh Chemicals Co., Ltd. | Carbon nanotube electrode comprising sulfur or metal nanoparticles as a binder and process for preparing the same |
| CN100372035C (en) * | 2003-10-17 | 2008-02-27 | 清华大学 | Polyaniline/carbon nano tube hybrid super capacitor |
| CN100416722C (en) * | 2003-11-20 | 2008-09-03 | 哈尔滨工业大学 | Activated carbon deposited nickel oxide as super capacitor anode material and preparing method |
| CN100353470C (en) * | 2003-12-05 | 2007-12-05 | 浙江大学 | Natural mineral and nanometer carbon tube compounded super capacitor electrode material and preparing method |
| WO2005069412A1 (en) * | 2004-01-14 | 2005-07-28 | Kh Chemicals Co., Ltd. | Carbon nanotube or carbon nanofiber electrode comprising sulfur or metal nanoparticles as a binder and process for preparing the same |
| US7532454B2 (en) | 2004-03-09 | 2009-05-12 | Arkema France | Method for making an electrode, resulting electrode and supercapacitor including same |
| CN1304280C (en) * | 2004-06-25 | 2007-03-14 | 中国科学院上海硅酸盐研究所 | Cobaltosic oxide nano-crystalline coated carbon nano-tube composite powder and preparation method thereof |
| CN101213020B (en) * | 2005-02-07 | 2012-09-26 | 阿肯马法国公司 | Method for synthesis of carbon nanotubes |
| CN101689430B (en) * | 2007-02-16 | 2013-04-17 | Sgl碳股份公司 | Composite comprising carbonized biopolymers and carbon nanotubes |
| CN101302341B (en) * | 2007-05-09 | 2010-11-17 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
| CN101159192B (en) * | 2007-10-29 | 2011-07-13 | 上海中上汽车科技有限公司 | Drawer type super capacitor |
| CN101874274B (en) * | 2007-11-27 | 2016-06-22 | 玛丽亚·斯特罗姆 | Comprise composite and the method and apparatus of intrinsically conducting polymer |
| CN101486849B (en) * | 2008-01-18 | 2012-12-05 | 郑州泰达电子材料科技有限公司 | Conductive paint, conductive composition and electronic component using the same |
| CN101582302B (en) * | 2008-05-14 | 2011-12-21 | 清华大学 | Carbon nano tube/conductive polymer composite material |
| US8802964B2 (en) | 2009-06-19 | 2014-08-12 | Tsinghua University | Method of using thermoelectric device |
| CN101931043B (en) * | 2009-06-19 | 2013-03-20 | 清华大学 | Thermoelectric conversion material |
| US8829327B2 (en) | 2009-06-19 | 2014-09-09 | Tsinghua University | Thermoelectric material and thermoelectric device |
| CN101894680A (en) * | 2010-06-23 | 2010-11-24 | 万裕三信电子(东莞)有限公司 | Electrode plate for electric double layer capacitor and preparation method of electric double layer capacitor |
| CN102443167A (en) * | 2010-09-30 | 2012-05-09 | 西门子公司 | Composite material for super capacitor, super capacitor and preparation method thereof |
| CN102010577A (en) * | 2010-12-01 | 2011-04-13 | 南昌航空大学 | Method for preparing rare earth-doped ferrite/polythiophene/carbon nano tube microwave absorbent |
| CN102010577B (en) * | 2010-12-01 | 2012-05-02 | 南昌航空大学 | Method for preparing rare earth-doped ferrite/polythiophene/carbon nano tube microwave absorbent |
| CN103493256A (en) * | 2010-12-21 | 2014-01-01 | 拜耳知识产权有限责任公司 | Method for producing powdery polymer/carbon nanotube mixtures |
| CN102585496B (en) * | 2011-01-11 | 2014-02-26 | 中国科学院过程工程研究所 | Carbon-based ternary composite electrode material for super capacitor and preparation method for carbon-based ternary composite electrode material |
| CN102585496A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院过程工程研究所 | Carbon-based ternary composite electrode material for super capacitor and preparation method for carbon-based ternary composite electrode material |
| WO2013023404A1 (en) * | 2011-08-12 | 2013-02-21 | 清华大学 | Implanted biological electrode and medical assembly including same |
| US10080890B2 (en) | 2011-08-12 | 2018-09-25 | Tsinghua University | Implantable biological electrode and medical assembly including the same |
| US10155106B2 (en) | 2012-09-07 | 2018-12-18 | Tsinghua University | Method for making implantable lead |
| CN102924919A (en) * | 2012-10-25 | 2013-02-13 | 无锡市三力胶带厂 | Conductive polymer material |
| CN105895382A (en) * | 2016-03-23 | 2016-08-24 | 中国航空工业集团公司北京航空材料研究院 | Self-supporting flexible composite electrode film, preparation method and application thereof |
| CN106158404A (en) * | 2016-08-12 | 2016-11-23 | 深圳博磊达新能源科技有限公司 | A kind of ternary oxide/conductive agent/carbon/polypyrrole combination electrode material, pole piece and ultracapacitor |
| CN106158404B (en) * | 2016-08-12 | 2018-02-16 | 深圳博磊达新能源科技有限公司 | A kind of ternary oxide/conductive agent/carbon/polypyrrole combination electrode material, pole piece and ultracapacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1315139C (en) | 2007-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1315139C (en) | Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture | |
| Cui et al. | Preparation and properties of Co 3 O 4 nanorods as supercapacitor material | |
| Cao et al. | Lignin-based multi-channels carbon nanofibers@ SnO2 nanocomposites for high-performance supercapacitors | |
| Gu et al. | Morphology control of nanoscale metal-organic frameworks for high-performance supercapacitors | |
| JPWO2013073526A1 (en) | Electrode for electricity storage device, electricity storage device, and method for producing electrode for electricity storage device | |
| US20110286147A1 (en) | Electrode material and capacitor | |
| JP2007115721A (en) | Lithium ion capacitor | |
| JPWO2005096333A1 (en) | Organic electrolyte capacitor using mesopore carbon material for negative electrode | |
| Ye et al. | Facile synthesis of hierarchical CuO nanoflower for supercapacitor electrodes | |
| WO2012050104A1 (en) | Conductive polymer/porous carbon material composite and electrode material using same | |
| CN103011143A (en) | Graphene and fabrication method thereof and super capacitor | |
| CN104715934A (en) | Hybrid super capacitor and manufacturing method thereof | |
| Aristote et al. | General overview of sodium, potassium, and zinc-ion capacitors | |
| CN102820136A (en) | High-energy-density supercapacitor | |
| Lokhande et al. | Inorganic electrolytes in supercapacitor | |
| JP3591055B2 (en) | Electric double layer capacitor, method of manufacturing the same, and method of manufacturing electrodes therefor | |
| CN101393800B (en) | Electrode material for super capacitor and preparing method thereof | |
| CN105632776A (en) | Asymmetric super capacitor with super long cycle stability and preparation method thereof | |
| CN101740230B (en) | Carbon compound cathode material for ultracapacitor battery | |
| JP2007019108A (en) | Lithium ion capacitor | |
| CN102093712A (en) | Preparation method of composite super capacitor electrode material | |
| JP2007067088A (en) | Lithium ion capacitor | |
| CN101004973A (en) | Mixed super capacitor | |
| CN106169377A (en) | Carbon nano-tube network/Ni (OH)2/ PPY combination electrode, preparation method and application | |
| CN103086350B (en) | Mesoporous carbon electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |