CN1300812C - Manufacture of high-capacity electrochemical capacitor - Google Patents
Manufacture of high-capacity electrochemical capacitor Download PDFInfo
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- CN1300812C CN1300812C CNB01132080XA CN01132080A CN1300812C CN 1300812 C CN1300812 C CN 1300812C CN B01132080X A CNB01132080X A CN B01132080XA CN 01132080 A CN01132080 A CN 01132080A CN 1300812 C CN1300812 C CN 1300812C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a manufacture method of an electrochemical super capacitor with high capacity, which belongs to the field of an electrochemical capacitor. The present invention is characterized in that materials formed by compounding oxides or hydroxides of ruthenium and activated carbon with high specific surface area serve as a positive electrode and a negative electrode of the electrochemical capacitor or the compounded materials serving as the positive electrode and the negative electrode are made of porous carbon materials with high specific surface area. Two composing modes of the positive electrode and the negative electrode both take aqueous alkali or acid solution as electrolytes. Insulated polymer is taken as a diaphragm between the positive electrode and the negative electrode to assemble electrochemical capacitors with different shapes and purposes. The manufacture method provided by the present invention is simple, the price of the present invention is cheaper than that of an electrochemical capacitor made of the oxides of the ruthenium, and the capacity is far larger than that of an electrochemical capacitor made of pure activated carbon materials.
Description
Technical field
The present invention relates to a kind of preparation method of high-capacity electrochemical capacitor, more specifically relate to composite material that it forms by the oxide of ruthenium or hydroxide and porous activated carbon prepares the high electrochemical capacitor of a kind of capacity as electrode in electrochemical capacitor preparation method, belong to the electrochemical capacitor field.
Background technology
Electrochemical capacitor has obtained people with its outstanding effect and advantage and has approved widely in electronics industry.Compare with traditional capacitor, electrochemical capacitor has high capacitance, limited frequency response, high equivalent series resistance (ESR), the electric capacity relevant with voltage and the relevant self discharge speed with voltage.Electrochemical capacitor is to be used for providing bigger excitation energy for high-energy laser at first.The model electrochemical capacitor can also replace nickel-cadmium cell and the lithium battery uninterrupted power supply (ups) Unity as computer and communication system.Large-scale electrochemical capacitor is used on the electric automobile to provide heavy-current discharge under situations such as startup, braking, and the high power that has effectively solved storage battery discharges and recharges problem, has prolonged the working life of storage battery.Therefore, electrochemical capacitor has a wide range of applications at numerous areas.
Be different from traditional capacitor, the high power capacity of electrochemical capacitor forms by adopting the large tracts of land porous electrode and storing energy between the diffuse double layer.This bilayer can be separated matter at electrode-electric and form naturally at the interface when having voltage between the electrode, its thickness generally has only the diameter of a hydrone, has formed minimum effective " plate separation " thus.In addition, under many circumstances, energy stored increases by so-called " pseudo-capacitance " or " pseudocapacity " basically, and this kind effect also occurs in electrode-electric and separates matter at the interface.Electric double layer capacitance is generally 16-40 microfarad/square centimeter, and passes through the highest 100 microfarads/more than the square centimeter of can reaching of capacitance that " pseudo-capacitance " form.Adsorption desorption or fast electrochemical redox reaction (there is not tangible phase change in active material) take place near electrode place or its, and this capacitance can further increase.The capacitance of this increase is called " pseudo-capacitance ", and resulting device is by popular the becoming of people " ultra-capacitor " or " ultracapacitor ", and it is the pseudocapacity of reflection faraday signal, has the specific capacity higher than pure electric double layer capacitance.
Double layer capacitor is based on high surface area electrode material activity charcoal, and this kind material provides high surface A, and " effectively double-deck " thickness d is reduced to the atomic diameter scale, has therefore formed high capacitance.Beck has delivered the patent of first piece of relevant double electric layer capacitor early than the sixties.But the real rise of electrochemical capacitor research is to be widely used as the computer uninterrupted power supply and after the early 1990s, American National Ministry of Energy proposed electrochemical capacitor is applied to the huge plan of electric automobile at it.
The general stored energy of chemical power source equals to change relevant electric charge with electrochemical redox and multiply by potential difference between the battery electrode.Discharge and recharge the variation that often relates to the active material phase in the course of reaction.Thereby, although energy density is higher relatively, discharges and recharges reaction speed and compare relatively slow with electrochemical capacitor.Compare with battery, electrochemical capacitor have do not need repairing, longer cycle life, safe in utilization, do not have advantages such as memory effect.The more important thing is that electrochemical capacitor has the performance that the big electric current of high power that battery do not have discharges and recharges continuously, has promoted this class high power devices and Products Development.Therefore, electrochemical capacitor is a kind of extremely attractive energy storage device.
The energy storage system that is used for electric motor car requires to possess high energy density so that enough driving scopes to be provided.It must have higher power density to satisfy the acceleration performance demands of electric automobile.It must have sufficiently long discharge and recharge the life-span and also must have the user the price that rises that can bear.The plurality of advantages of electrochemical capacitor energy storage system makes it have the potentiality of application in fields such as electric vehicle power sources.Electrochemical capacitor is necessary in the hybrid electric vehicle composite power source, electrochemical capacitor can be provided for electric automobile and quicken fast, the power increment that the heavy load operation is required can't this maximum commercialization technical barrier of high power discharge thereby solved batteries of electric automobile.Battery and electric capacity form parallel circuits, when automobile overflows row still by the battery normal power supply, begin worker's work at next capacitors of relative abominable service condition such as automobile starting, acceleration, climbing and brakings, the use of capacitor has effectively solved the heavy-current discharge problem of battery, and compares a kind of battery with effect of the same race of design and want worthwhile many on cost.
At present technology is comparatively ripe is to be the electrochemical double layer electric capacity (i.e. the positive and negative pole material of this capacitor all be made up of active carbon class material symmetry electric capacity) of electrode material with the porous active carbon, yet, generally be difficult in practice reach according to the materials theory capacitance that calculates to the thickness of the mensuration of surface area and electrode couple layer, the surface area of material is big more, gap between the capacity of Theoretical Calculation and actual measurement is big more, because " micropore " that the surface of material with carbon element exists electrolyte to be difficult to flood, people can't utilize the surface area of activated carbon fully.Therefore, it is little to improve the leeway of material capacity by the surface area that improves material.Contact resistance between active carbon particle has limited Electric double-layer capacitor with higher power density output.The striving direction that promotes the development of electrochemical capacitor store energy should be placed on how to make full use of material " pseudo-capacitance " with on the capacity characteristic that significantly improves material.
It is transition metal oxide class material such as ru oxide (RuO that material people with higher faraday " pseudo-capacitance " study more
2XH
2O) as U.S5621609A, disclosed anodal and negative pole by the ruthenium-oxide that contains moisture with have the carbon black or the carbon fiber formation of good porous permeability performance, with the sulfuric acid solution of various concentration as electrolyte.Though RuO
2XH
2O possesses gratifying capacity (hundreds of farad/gram active material), but its fancy price has limited its further business-like application.
Summary of the invention
The object of the invention is to overcome shortcoming of the prior art: be electrode material with the porous active carbon, can't make full use of its surface area, can't increase substantially the energy intensity of material, though and ru oxide has gratifying capacity costs an arm and a leg.Thereby a kind of high-capacity electrochemical capacitor is provided, reduces the capacitor cost simultaneously.
The present invention is by following two scheme implementations, and the one, the material that the active carbon material of the oxide of ruthenium or hydroxide and high-specific surface area is compound is as the electrochemical capacitor positive and negative electrode, to improve the energy density of electrochemical capacitor; Another scheme then is as negative pole with porous height ratio table specific area material with carbon element, with the compound material of the active carbon material of the oxide of ruthenium or hydroxide and high-specific surface area as positive pole, with the operating voltage that improves electrochemical capacitor and then improve its energy density.Using aqueous slkali or the acid solution electrolyte as electrochemical capacitor in two schemes, is finally to be assembled into the electrochemical capacitor of difformity and different purposes by the insulating properties polymer of ion between positive pole and the negative pole.
Discuss it below respectively
Scheme 1
(1) chooses 100 milliliters of the aqueous solution of the halogen of ruthenium of 0.05-0.5M or sulfate, the mixture that adds 2g activated carbon, nano-scale carbon fiber, CNT (carbon nano-tube), carbon aerosol or any two kinds of compositions between them, the mass ratio of two kinds of compositions is 1: 1 in the mixture, and its specific area is 900-2000m
2/ g, fully stirred 3-5 hour, dropwise add KOH or the NaOH solution of 0.3M afterwards and continue stirring, when solution PH reaches 7, stop to add aqueous slkali, and continue to stir 5 hours, mixed liquor is filtered, the distilled water washing and filtering is dried under 80 ℃ of conditions, grinds 10 minutes in agate grinds in the back of dehydration below 150 ℃;
(2) take by weighing the part material of preparation according to the method described above, add account for total weight 10-30wt% as conductive agent, graphite, carbon black, nickel powder, add account for total weight 5-10wt% as adhesive, as polytetrafluoroethylene, poly-inclined to one side tetrafluoroethene, be coated in nickel foam as collector, punching nickel-clad steel plate-, on the aluminium foil, Copper Foil,, make the positive and negative electrode of capacitor through operations such as compacting, oven dry, sections.
(3) choose strong alkaline substance (as LiOH, KOH, NaOH etc.) or highly acid material (as H
2SO
4Deng) be dissolved in ionic solvent (as water) or nonionic solvent (as ethanol, propene carbonate etc.) as electrolyte.Choose possess the ion guide general character the insulating properties material as barrier film (as all-glass paper, polymer film etc.).With positive pole, negative pole, electrolyte, the electrochemical capacitor of barrier film assembling becoming with difformity and purposes.
Scheme 2
(1) chooses 100 milliliters of the aqueous solution of the halogen of ruthenium of 0.05M-0.5M or sulfate, add active carbon, nano-scale carbon fiber, CNT (carbon nano-tube), carbon aerosol or the mixture of any two kinds of compositions between them, the mass ratio of two kinds of compositions is 1: 1 in the mixture, and its specific area is 900-2000m
2/ g fully stirred 3-5 hour, dropwise add KOH or the NaOH solution of 0.3M and continue stirring, when solution acidity PH reaches 7, stop to add aqueous slkali and continue and stirred 5 hours, to mix liquid filters, washing leaching cake, and filter cake dried under 80 ℃ of conditions, after dehydration below 150 ℃, in agate mortar, ground 10 minutes, take by weighing the part material of preparation according to the method described above then, add the graphite that accounts for total weight 10-30wt% as conductive agent, carbon black, nickel powder adds the polytetrafluoroethylene as adhesive that accounts for total weight 5-10wt%, poly-inclined to one side tetrafluoroethene is coated in as the nickel foam on the collector, the punching nickel-clad steel plate, aluminium foil, on the Copper Foil, through compacting, oven dry, slicing process is made the positive pole of capacitor;
(2) choosing its specific area is 900-2000m
2/ g active carbon, nano-scale carbon fiber, CNT (carbon nano-tube), carbon aerosol or the mixture of any two kinds of compositions between them, the mass ratio of two kinds of compositions in the mixture is 1: 1, add the graphite as conductive agent, carbon black, the nickel powder that account for total weight 10-30wt% and account for the polytetrafluoroethylene of total weight 5-10wt%, poly-inclined to one side tetrafluoroethene as adhesive as adding, be coated on nickel foam as collector, punching nickel-clad steel plate, aluminium foil, the Copper Foil, through compacting, oven dry, slicing process, make the negative pole of capacitor.
(3) choose strong alkaline substance, as LiOH, KOH, NaOH etc., or the highly acid material is (as H
2SO
4Deng) be dissolved in ionic solvent (as water) or nonionic solvent, as ethanol, propene carbonate etc., as electrolyte.Choose possess the ion guide general character the insulating properties material as barrier film, as all-glass paper, polymer film etc., with positive pole, negative pole, electrolyte, the electrochemical capacitor of barrier film assembling becoming with difformity and purposes.
It is simple to have preparation one technology according to the electrochemical capacitor of method provided by the invention preparation, and price is that the electrochemistry device of electrode is cheap and capacitance is far longer than the electrochemical capacitor that simple absorbent charcoal material is formed with the oxide of ruthenium.
Embodiment
According to such scheme, further specify substantive distinguishing features of the present invention and marked improvement below, but the present invention is confined to embodiment by no means.
Embodiment 1
Choose 100 milliliters of the muriatic aqueous solution of the ruthenium of 0.1M concentration, add the activated carbon of the bigger serface of 2g porous, its specific area 1500m
2/ g, fully stir more than 4 hours, dropwise add the KOH solution of 0.3M and continue stirring, when solution acidity PH reaches 7, stop to add aqueous slkali and continue and stirred 5 hours, will mix liquid and filter, washing leaching cake, and filter cake dried under 80 ℃ of conditions, after dehydration below 150 ℃, in agate mortar, ground 10 minutes.
Take by weighing the part material of preparation according to the method described above, add the graphite agent of 20Wt%, add 8% polytetrafluoroethylene adhesive, be suppressed into electrode diaphragm,, make the positive and negative electrode of capacitor through operations such as compacting, oven dry, sections.
The electrode diaphragm of two above-mentioned identical components is placed on the all-glass paper both sides of the ion guide general character, forms sandwich, through compacting, operations such as section are cut into different shapes as required.Choose strong alkaline substance, be dissolved in the water ion solvent as electrolyte as LiOH.The electrode for preparing, the electrolyte assembling becomes the capacitor of difformity and different purposes.
Embodiment 2
Choose the some milliliters of the aqueous solution of certain density 0.25M ruthenium sulfate, the specific area that adds the bigger serface of 2g porous is respectively 1000m
2/ g and 1800m
2The mixture of/g nano-scale carbon fiber and carbon aerosol, both mass ratioes are 1: 1.Fully stir more than 5 hours, dropwise add the NaOH solution of 0.3M and continue stirring, when solution acidity PH reaches 7, stop to add aqueous slkali and continue and stirred 5 hours, to mix liquid and filter, washing leaching cake, and filter cake dried under 80 ℃ of conditions, after dehydration below 150 ℃, in agate mortar, ground 10 minutes.
Take by weighing the part material of preparation according to the method described above, add the nickel powder conductive agent of 15Wt%, add the polytetrafluoroethylene adhesive of 5Wt%, be coated on the nickel foam collector,, make the both positive and negative polarity of capacitor through operations such as compacting, oven dry, sections.
Choose strong alkaline substance, be dissolved in ethanol as electrolyte as NaOH.Choose polymer film as barrier film, with positive pole, negative pole, electrolyte, the electrochemical capacitor of barrier film assembling becoming with difformity and purposes.
Embodiment 3
Choose activated carbon, its specific area is 2000m
2/ g adds the 12Wt% carbon black and does conductive agent, and adding the poly-inclined to one side tetrafluoroethene of 8%Wt% is bonding agent, is coated on the Copper Foil collector, through operations such as compacting, oven dry, sections, makes the negative pole of capacitor.
The positive pole of capacitor, electrolyte and barrier film all constitute high-capacity electrochemical capacitor with the negative pole that embodiment 2 and present embodiment are made.
Claims (2)
1, a kind of manufacture method of high-capacity electrochemical capacitor, it is characterized in that with the positive and negative electrode of the compound material of the activated carbon of the oxide of ruthenium or hydroxide and high specific area as electrochemical capacitor, with aqueous slkali or acid solution as electrolyte, be barrier film with the insulating properties polymer between positive and negative electrode, be assembled into the electrochemical capacitor of difformity and purposes, the concrete preparation method of positive and negative electrode is
(1) chooses 100 milliliters of the aqueous solution of the halogen of ruthenium of 0.05-0.5M or sulfate, add the mixture of 2g activated carbon, nano-scale carbon fiber, carbon pipe nanometer, carbon aerosol or any two kinds of compositions between them, the mass ratio of two kinds of compositions is that 1: 1 specific area is 900-2000m in the mixture
2/ g, fully stir 3-5 hour after, dropwise add the KOH of 0.3M or NaOH solution again and continue and stir; When the pH value of solution equals 7, stop to add aqueous slkali, and continue to stir 5 hours, mixed liquor is filtered, through the distilled water washing and filtering, under 80 ℃ of conditions, dry, ground 10 minutes in agate grinds in the back of dehydration below 150 ℃;
(2) take by weighing the part material of preparation according to the method described above, adding accounts for the graphite as conductive agent, carbon black or the nickel powder of total weight 10-30% and polytetrafluoroethylene or the poly-inclined to one side tetrafluoroethene as adhesive that adding accounts for total weight 5-10%, be coated on nickel foam, punching nickel-clad steel plate, aluminium foil or the Copper Foil as collector, through compacting, oven dry, slicing process, make the positive and negative electrode of capacitor.
2, a kind of manufacture method of high-capacity electrochemical capacitor is characterized in that with the positive pole of the compound material of the active carbon material of the halogen of ruthenium or sulfate and high-specific surface area as electrochemical capacitor, with porous bigger serface material with carbon element as negative pole; With aqueous slkali or acid solution as electrolyte; Be barrier film by the insulating properties polymer between positive and negative electrode, be assembled into the electrochemical capacitor of difformity and purposes, the concrete preparation method of positive and negative electrode is
(1) chooses 100 milliliters of the aqueous solution of the halogen of ruthenium of 0.05M-0.5M or sulfate, add active carbon, the nano-scale carbon fiber, CNT (carbon nano-tube), the carbon aerosol or the mixture of any two kinds of compositions between them, the mass ratio of two kinds of compositions is 1: 1 in the mixture, fully stir after 3-5 hour, dropwise add KOH or the NaOH solution of 0.3M again and continue stirring, when the pH value of solution equals 7, stop to add aqueous slkali and continue and stirred 5 hours, mixed liquor is filtered, washing leaching cake, and filter cake dried under 80 ℃ of conditions, after dehydration below 150 ℃, in agate mortar, ground 10 minutes, take by weighing the part material of preparation according to the method described above then, add the graphite that accounts for total weight 10-30% as conductive agent, carbon black or nickel powder and adding account for polytetrafluoroethylene or the poly-inclined to one side tetrafluoroethene as adhesive of total weight 5-10wt%, are coated in as the nickel foam on the collector, the punching nickel-clad steel plate, aluminium foil, on the Copper Foil, through compacting, oven dry, slicing process is made the positive pole of capacitor;
(2) choosing its specific area is 900-2000m
2/ g active carbon, nano-scale carbon fiber, CNT (carbon nano-tube), carbon aerosol or the mixture of any two kinds of compositions between them, the mass ratio of two kinds of compositions in the mixture is 1: 1, add the graphite as conductive agent, carbon black or the nickel powder that account for total weight 10-30%, add polytetrafluoroethylene or the poly-inclined to one side tetrafluoroethene that account for total weight 5-10% as adhesive, be coated on nickel foam as collector, punching nickel-clad steel plate, aluminium foil, the Copper Foil, through compacting, oven dry, slicing process, make the negative pole of capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01132080XA CN1300812C (en) | 2001-10-31 | 2001-10-31 | Manufacture of high-capacity electrochemical capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01132080XA CN1300812C (en) | 2001-10-31 | 2001-10-31 | Manufacture of high-capacity electrochemical capacitor |
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| CN1345074A CN1345074A (en) | 2002-04-17 |
| CN1300812C true CN1300812C (en) | 2007-02-14 |
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| CNB01132080XA Expired - Fee Related CN1300812C (en) | 2001-10-31 | 2001-10-31 | Manufacture of high-capacity electrochemical capacitor |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4765077B2 (en) * | 2004-06-11 | 2011-09-07 | 国立大学法人東京農工大学 | Ruthenium oxide encapsulated nanocarbon composite structure |
| CN100368079C (en) * | 2006-02-23 | 2008-02-13 | 华南理工大学 | Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide |
| CN101038816B (en) * | 2007-04-20 | 2010-06-02 | 哈尔滨工程大学 | Method for preparing porous carbon/nano metal oxide composite material |
| RU2419907C1 (en) * | 2010-04-23 | 2011-05-27 | ЮГ Инвестмент Лтд. | Multiple-element electrochemical capacitor and its manufacturing method |
| CN101950673A (en) * | 2010-07-29 | 2011-01-19 | 南京双登科技发展研究院有限公司 | High-multiplying-power super capacitor |
| CN102938324A (en) * | 2011-08-15 | 2013-02-20 | 海洋王照明科技股份有限公司 | Super mixed capacitor and preparation method thereof |
| CN105869913B (en) * | 2016-04-06 | 2018-07-20 | 江苏中天科技股份有限公司 | A kind of ultracapacitor and preparation method thereof |
| CN106952745B (en) * | 2017-03-14 | 2018-09-11 | 苏州海凌达电子科技有限公司 | A kind of preparation method of ultracapacitor ruthenium-oxide based combined electrode material |
| CN107658146A (en) * | 2017-10-17 | 2018-02-02 | 天津工业大学 | A kind of ultracapacitor aqueous alkaline electrolyte method of modifying |
| CN112466677A (en) * | 2020-10-13 | 2021-03-09 | 暨南大学 | Zinc ion hybrid capacitor based on ruthenium oxide/carbon material composite positive electrode and construction method thereof |
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| US5631609A (en) * | 1995-02-15 | 1997-05-20 | Seiko Epson Corporation | Piezoelectric oscillator, voltage-controlled oscillator and production method thereof |
| JPH11354389A (en) * | 1998-06-03 | 1999-12-24 | Nissan Motor Co Ltd | Electrochemical capacitor |
| JP2000036441A (en) * | 1998-07-17 | 2000-02-02 | Fuji Electric Co Ltd | Electrical energy storage device and manufacture thereof |
| WO2000033336A1 (en) * | 1998-11-27 | 2000-06-08 | Sergey Nikolaevich Razumov | Asymmetric electrochemical capacitor |
-
2001
- 2001-10-31 CN CNB01132080XA patent/CN1300812C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5631609A (en) * | 1995-02-15 | 1997-05-20 | Seiko Epson Corporation | Piezoelectric oscillator, voltage-controlled oscillator and production method thereof |
| JPH11354389A (en) * | 1998-06-03 | 1999-12-24 | Nissan Motor Co Ltd | Electrochemical capacitor |
| JP2000036441A (en) * | 1998-07-17 | 2000-02-02 | Fuji Electric Co Ltd | Electrical energy storage device and manufacture thereof |
| WO2000033336A1 (en) * | 1998-11-27 | 2000-06-08 | Sergey Nikolaevich Razumov | Asymmetric electrochemical capacitor |
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| CN1345074A (en) | 2002-04-17 |
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