CN1315139C - Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture - Google Patents

Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture Download PDF

Info

Publication number
CN1315139C
CN1315139C CNB021334552A CN02133455A CN1315139C CN 1315139 C CN1315139 C CN 1315139C CN B021334552 A CNB021334552 A CN B021334552A CN 02133455 A CN02133455 A CN 02133455A CN 1315139 C CN1315139 C CN 1315139C
Authority
CN
China
Prior art keywords
derivative
percentage
transition metal
tube
weight
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.)
Expired - Fee Related
Application number
CNB021334552A
Other languages
Chinese (zh)
Other versions
CN1388540A (en
Inventor
梁逵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN POLYTECHINCAL COLLEGE
Original Assignee
SICHUAN POLYTECHINCAL COLLEGE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SICHUAN POLYTECHINCAL COLLEGE filed Critical SICHUAN POLYTECHINCAL COLLEGE
Priority to CNB021334552A priority Critical patent/CN1315139C/en
Publication of CN1388540A publication Critical patent/CN1388540A/en
Application granted granted Critical
Publication of CN1315139C publication Critical patent/CN1315139C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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

Superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof
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.
CNB021334552A 2002-07-12 2002-07-12 Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture Expired - Fee Related CN1315139C (en)

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 CN1388540A (en) 2003-01-01
CN1315139C true 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 (2)

* Cited by examiner, † Cited by third party
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

Families Citing this family (25)

* Cited by examiner, † Cited by third party
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
KR100584671B1 (en) * 2004-01-14 2006-05-30 (주)케이에이치 케미컬 Process for the preparation of carbon nanotube or carbon nanofiber electrodes by using sulfur or metal nanoparticle as a binder and electrode prepared thereby
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
FR2867600B1 (en) 2004-03-09 2006-06-23 Arkema METHOD OF MANUFACTURING ELECTRODE, ELECTRODE OBTAINED AND SUPERCONDENSOR COMPRISING 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
FR2881734B1 (en) * 2005-02-07 2009-02-20 Arkema Sa PROCESS FOR THE SYNTHESIS OF CARBON NANOTUBES
ATE466370T1 (en) * 2007-02-16 2010-05-15 Sgl Carbon Se COMPOSITE WITH CARBONIZED BIOPOLYMERS AND CARBON NANOTUBE
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
RU2490738C2 (en) * 2007-11-27 2013-08-20 Мария СТРЕММЕ Composite materials containing internally conducting polymer and method and apparatus
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
CN101931043B (en) * 2009-06-19 2013-03-20 清华大学 Thermoelectric conversion material
CN101894680B (en) * 2010-06-23 2012-08-29 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
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
US20140001416A1 (en) * 2010-12-21 2014-01-02 Bayer Intellectual Property Gmbh 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
CN102327668B (en) 2011-08-12 2014-01-22 清华大学 Implanted bioelectrode and medical assembly comprising same
CN102824689B (en) 2012-09-07 2014-12-24 清华大学 Implanted electrode and preparation method thereof and medical assembly comprising implanted electrode
CN102924919A (en) * 2012-10-25 2013-02-13 无锡市三力胶带厂 Conductive polymer material
CN105895382B (en) * 2016-03-23 2018-04-03 中国航空工业集团公司北京航空材料研究院 A kind of self-supporting flexible compound electrode film and its production and use
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317809A (en) * 2000-04-12 2001-10-17 李永熙 Super-grade capacitor for electrode of using new material and its mfg. method
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
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317809A (en) * 2000-04-12 2001-10-17 李永熙 Super-grade capacitor for electrode of using new material and its mfg. method
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

Cited By (2)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN1388540A (en) 2003-01-01

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
JP4924966B2 (en) Lithium ion capacitor
Gu et al. Morphology control of nanoscale metal-organic frameworks for high-performance supercapacitors
WO2013073526A1 (en) Electrode for electricity storage devices, electricity storage device, and method for producing electrode for electricity storage devices
US20110286147A1 (en) Electrode material and capacitor
CN101165827A (en) Mixed electrochemical capacitor and its manufacture method
JPWO2006118120A1 (en) Negative electrode active material for electricity storage devices
Wang et al. Design and construction of three-dimensional graphene/conducting polymer for supercapacitors
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
JP2007180431A (en) Lithium ion capacitor
CN103011143A (en) Graphene and fabrication method thereof and super capacitor
Lokhande et al. Inorganic electrolytes in supercapacitor
CN103050293A (en) Hard-carbon-based chemical power supply with long service life
CN105632776A (en) Asymmetric super capacitor with super long cycle stability and preparation method thereof
CN101740230B (en) Carbon compound cathode material for ultracapacitor battery
JP3591055B2 (en) Electric double layer capacitor, method of manufacturing the same, and method of manufacturing electrodes therefor
Isah Advanced materials for energy storage devices
Aristote et al. General overview of sodium, potassium, and zinc-ion capacitors
CN101393800B (en) Electrode material for super capacitor and preparing method thereof
CN102093712A (en) Preparation method of composite super capacitor electrode material
JP2007067088A (en) Lithium ion capacitor
CN101004973A (en) Mixed super capacitor

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