CN100389472C - Method for producing mixed type super capacitor - Google Patents
Method for producing mixed type super capacitor Download PDFInfo
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- CN100389472C CN100389472C CNB031151051A CN03115105A CN100389472C CN 100389472 C CN100389472 C CN 100389472C CN B031151051 A CNB031151051 A CN B031151051A CN 03115105 A CN03115105 A CN 03115105A CN 100389472 C CN100389472 C CN 100389472C
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- capacitor
- super capacitor
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- negative pole
- positive pole
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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
Abstract
The present invention relates to a method for producing a mixed type super capacitor, which comprises a manufacturing method of a super capacitor positive pole and a super capacitor negative pole. The present invention is characterized in that materials of the capacitor positive pole and the capacitor negative pole can be regulated to paste with water and absolute ethyl alcohol, then material can be pressed on a roller mill into the capacitor positive plate and the capacitor negative plate through drying, and finally, the single side or the two sides of the pole plate can be stuck on a foam nickel current collector; the paste can be spread on the foam nickel current collector to make the super capacitor positive pole and the super capacitor negative pole. A capacitor cell is assembled by the crossed superposition of the positive pole, the negative pole and a diaphragm, or by the winding molding of the positive pole, the negative pole and the diaphragm on a winding machine. The capacitor cell can be sealed after being perfused, so a mixed type super capacitor monomer is obtained. A mixed type super capacitor final product is obtained by connecting a plurality of monomer super capacitors in series or in parallel for combination. The present invention has the characteristics that preparation flow is simple, operation is easy, product performance is good, cost is low, uniformity is good, mechanized large scale production can be achieved easily, etc.
Description
Technical field
The present invention relates to a kind of hybrid super capacitor manufacture method with electric double layer capacitance, more specifically relate to porous carbon materials and make the hybrid super capacitor of negative pole and commercially available ordinary hydrogen nickel oxide material work positive pole manufacture method, energy technology and the association area thereof of (also claiming " asymmetric ultracapacitor ").
Background technology
Ultracapacitor (Supercapacitor or Ultracapacitor), it is a kind of novel energy-storing device that develops rapidly in the 60 to 70's of last century, it carries out the energy storage according to electrochemical principle and discharges, therefore cry again usually " electrochemical capacitor (Electrochemical Capacitor, EC) ".It is in order to remedy the special device that battery is developed in the deficiency aspect the high energy pulse power at first, as big power drive is provided for laser, therefore has saying of " power memory ".Since this device be proved to be afterwards aspect the store energy density and storage battery have comparativity, therefore by with the in addition commercialization rapidly of the developed country headed by the U.S., the Japan, be widely used in various electronic components, as the back-up source (Back-up Power) of electromagnetically operated valve, computer storage, the uninterrupted power supply of communication system (Uninterrupted Power Sources, UPS), electronic toy or the like.Ultracapacitor has been taken into account the advantage separately of battery and traditional capacitor as a kind of novel energy-storing device---when having higher power density, also have suitable energy density simultaneously.Simultaneously, because it recycles the characteristics of life-span very big (about 10,0000 times), cleanliness without any pollution, be considered to one of final selection of electric car power supply.According to the difference of the principle of store energy, ultra-capacitor is divided into electric double layer ultra-capacitor, metal oxide pseudo-capacitance ultra-capacitor and conducting polymer ultra-capacitor.The electric double layer ultra-capacitor is to utilize electric double layer solid or that the liquid interface forms to have differential capacitance (10～40 μ F/cm
2) thereby (30～300F/g) principle is carried out store energy to cause considerable integrating capacitor to make the material (such as porous activated carbon, carbon cloth, carbon nanometer tube etc.) of high-specific surface area.Because its thermal energy storage process belongs to static focus, belongs to physics electric capacity on the principle, (500～3000W/kg), still the energy density of this capacitor is lower, generally between 1～5Wh/kg therefore to have high power density.And for metal oxide pseudo-capacitance ultra-capacitor (as nickel oxide, ruthenium-oxide ultra-capacitor) with conducting polymer ultra-capacitor (as polyaniline, polypyridine etc.), situation is just opposite, because this capacitor of two types carries out the energy storage according to the Faradic electricity charge transfer reaction, therefore its energy storage characteristics are similar with battery, promptly have high energy density and have lower power density.On present ultra-capacitor market, adopt material with carbon element to be lopsided situation, and that interest rate is occupied in metal oxide ultra-capacitor and conducting polymer ultra-capacitor market is minimum as the ultra-capacitor of electrode.To develop electric vehicle and push agenda (China has also set up 863 electric motor car special projects) to along with countries in the world, high-energy, high power energy storage device have become one of technology of most critical.Not enough and the employing material with carbon element of storage battery power output is had to the hybrid super capacitor of sight trend of purchasing metal oxide and electric double layer ultra-capacitor composition the people of making on the low side aspect the energy density as the symmetric form electric double layer ultra-capacitor of electrode.This hybrid super capacitor is when guaranteeing that enough power output is arranged, and the energy density of capacitor has lifting to a certain degree.CN for example
1369886A and CN 1345074A disclose MnO respectively
2/ C and RuO
2The preparation method of/C hydridization ultra-capacitor.The MnO of the former preparation
2Bigger than electric capacity, but weak point is MnO
2Need the laboratory synthetic, cost is higher; The latter prepares ultra-capacitor by chemical synthesis, but this method does not provide relevant performance parameter, as if ruthenium costs an arm and a leg and is difficult to become the first-selection of hydridization ultra-capacitor simultaneously.And for example, CN 1348596A has announced the preparation method of nickel oxide and carbon hydridization electrochemical capacitance, and in this patent, the designer is coated with on collector such as precious metal elements such as silver, gold in order to improve the power output of capacitor.Though this method can significantly improve the power output of capacitor, manufacturing process is more loaded down with trivial details, and cost also is the obstacle that limits its further commercial applications in addition.
Summary of the invention
The objective of the invention is to overcome the shortcomings and deficiencies in the existing ultracapacitor manufacturing technology, a kind of hybrid super capacitor and manufacture method thereof with electric double layer capacitance is provided.Compared with prior art, it is simple that manufacture method provided by the invention has a preparation flow, processing ease, and the properties of product height, with low cost, homogeneity is good, and mechanization large-scale production is characteristics such as realization easily.
The present invention realizes by following technical scheme: the manufacture method that comprises ultracapacitor positive pole and negative pole, it is characterized in that: with capacitor anode and negative material water and absolute ethyl alcohol furnishing slurry, after the drying material is pressed into capacitance cathode sheet and negative plate on roll forming machine, at last this pole piece single or double is attached on the nickel foam collector; Perhaps above-mentioned slurry is applied on the nickel foam collector, make the positive pole and the negative pole of ultracapacitor, positive pole, negative pole and barrier film are intersected stack or be assembled into capacitor cell behind coiling and molding on the up-coiler, and sealed behind the perfusion electrolyte, obtain the hybrid super capacitor monomer, a plurality of monomer ultracapacitors are gone here and there or combination in parallel, just obtain the hybrid super capacitor finished product.
The capacitor anode material is made up of nickel hydroxide, anodal conductive agent, adhesive, and nickel hydroxide is a major ingredient, and anodal conductive agent, adhesive are auxiliary materials, auxiliary material content with good conductivity, bonding be not separated into suitable; The capacitor anode major ingredient can be in active carbon, carbon cloth, carbon nano-tube, carbon nano-fiber, carbon and carbon complex, charcoal aerosol and the network configuration material with carbon element one or more, and the negative pole auxiliary material is cathode conductive agent, adhesive.
At first be to be the positive pole that raw material is made super capacitor, need only pass through simple activation processing, just can obtain the very high positive electrode of energy density, thereby reduce the cost of manufacture of product significantly with common commercially available nickel hydroxide; Secondly one or several of hundred million porous active material with carbon elements are that super capacitor one side has the feature of electric double layer capacitance for the negative pole of raw material making super capacitor, to improve the operating voltage of capacitor.And then improve its energy density, improve the power characteristic of capacitor.Because the technology with the making electric double layer of material with carbon element is quite ripe, so the negative pole cost of manufacture is also quite low.Positive pole, barrier film, negative pole are intersected stack assembling car coiling and molding willingly or on up-coiler be assembled into capacitor cell, and sealed after pouring into certain electrolyte, the nickel hydroxide negative pole is the ultracapacitor monomer of material with carbon element thereby obtain just very.A plurality of monomer ultracapacitors are gone here and there or combination in parallel, just obtain different application occasion ultracapacitor product.
Be described in further detail the bright ultracapacitor cell manufacturing method for anode of this law below:
1. nickel hydroxide active material is equipped with binding agent, conductive agent, furnishing slurry in water and pure mixed liquor, under 80～120 ℃ temperature, dried by the fire 2～6 hours then, then above-mentioned material is pressed into the electrode slice of 0.1～0.5mm on roll forming machine, at last this pole piece is overlayed on commercially available race fan nickel collector, constitute the positive pole of hybrid super electric capacity.According to the requirement of energy density and power density, can adopt the method for nickel foam collector single face or two-sided compressing tablet.
2. another kind of method: nickel hydroxide active material is equipped with binding agent, conductive agent, furnishing slurry in water and pure mixed liquor, be coated in commercially available nickel foam collector single face or two-sided on, under 80～120 ℃ temperature, dry, then above-mentioned material is pressed into the positive pole of hybrid super electric capacity on roll forming machine.
Described adhesive can be selected a kind of in ptfe emulsion, Kynoar emulsion, sodium carboxymethylcellulose; Cathode conductive agent can be selected a kind of in electrically conductive graphite, conductive acetylene are deceived; Anodal conductive agent is an extra-fine nickel powder; Electrolyte is potassium hydroxide electrolyte, and concentration is at 6mol/L～600mol/L.
The ultracapacitor cell method for manufacturing negative pole:
The manufacture method of electric double layer negative pole and anodal manufacture method are basic identical, and difference is that the thickness of electrode slice is between 0.2～0.8mm.
The moulding of ultracapacitor cell:
Positive pole, negative pole, barrier film are assembled into the monolithic capacitor unit, and are sealed behind the perfusion electrolyte, obtain the hybrid super capacitor monomer.According to the requirement of energy density and power density, the assembly unit method can be selected lamination or winding process equally.
The super capacitor product:
Above-mentioned electric capacity monomer according to string or combination in parallel, can be obtained different application and requires elegant hybrid super electric capacity product.
According to method vegetation provided by the invention for the hybrid super capacitor of electric double layer capacitance have that technology is simple, with low cost, energy density and power density be all than the much higher novel ultracapacitor of simple active carbon electric double layer symmetry ultracapacitor.
Embodiment
Embodiment 1 accurately takes by weighing the nickel hydroxide of a certain amount of activated processing, be equipped with conductive agent---extra-fine nickel powder, at first carry out mechanical mixture, treat that even back is 1: 1 water and an absolute ethyl alcohol furnishing suspension with volume ratio, dropwise joins an amount of 60wt% polytetrafluoroethylene in the above-mentioned system under ultrasonic concussion condition.Treat that suspension becomes when having the certain viscosity slurry, in drying box, dried by the fire 2-6 hour with about 80～120 ℃.The material of above-mentioned baking is pricked the electrode anode that is pressed into 0.2mm on the film machine, be attached on the commercially available nickel foam collector this pole piece is two-sided at last, constituting the positive pole of hybrid super capacitor.
Perhaps accurately take by weighing a certain amount of nickel hydroxide of crossing through activation processing, be equipped with conductive agent---extra-fine nickel powder, at first carry out mechanical mixture, treat that even back is that 1: 1 water and absolute ethyl alcohol furnishing suspension and an amount of 60wt% polytetrafluoroethylene mix stirring and make slurry with volume ratio, be coated on the commercially available nickel foam collection liquid surface, under 80～120 ℃ temperature, dry, then above-mentioned material is pressed into the positive pole of hybrid super capacitor on roll forming machine.
The manufacture method of negative pole is with anodal identical, and only negative active core-shell material is that specific area is greater than 2000m
2The active carbon of/g, conductive agent are graphite powder.At last positive pole, negative pole, barrier film are assembled into capacitor cell behind coiling and molding on the up-coiler, and are sealed behind the potassium hydroxide electrolyte of perfusion 6mol/L, the nickel hydroxide negative pole is the ultracapacitor monomer of material with carbon element thereby obtain just very.A plurality of monomer ultracapacitors are gone here and there or combination in parallel, just obtain the super capacitor electrode Rongcheng product of applied voltage.
Embodiment 2
Other condition is identical with embodiment 1, and difference is that the electrochemical capacitance unit has adopted the process of lamination.The energy density of the ultracapacitor cell that is prepared into is 98% of embodiment 1.
Embodiment 3
The manufacture method of positive and negative electrode is with 1, and difference is: the conductive agent that (1) negative pole adopts is 320 order graphite powders; (2) binding agent is a Kynoar; (3) the two-sided pole piece that overlayed of nickel foam collector.Compare with embodiment 1, the energy storage capacity of monomer capacitor cell has risen 8%.
Embodiment 4
Other condition is identical with embodiment 1, and only with the activated carbon negative electrode in the carbon cloth alternate embodiment 1 (thereby can omit some operations), the energy density of the hybrid super capacitor that finally obtains and power density and embodiment 1 are than high by about 2%.
Embodiment 5
Other condition is identical with embodiment 1, and only with the activated carbon negative electrode in the composite material alternate embodiment 1 of active carbon and CNT (carbon nano-tube), the energy density of the hybrid super capacitor that finally obtains and power density and embodiment 1 are than high by about 3%.
Need to prove; the cited embodiment of the present invention is not limited only to above-mentioned nickel hydroxide and active carbon, nickel hydroxide and carbon cloth, nickel hydroxide and (active carbon+carbon nano-tube); other nickel hydroxides and electric double layer capacitance ultracapacitor; such as the military negative pole applications of the present invention such as composite carbon negative electrode of one or more formations of nickel hydroxide and carbon nano-tube, nickel hydroxide and petroleum coke and these materials, therefore all at the row of patent protection right.
Claims (5)
1. hybrid super capacitor manufacture method, the manufacture method that comprises ultracapacitor positive pole and negative pole, it is characterized in that: with capacitor anode and negative material water and absolute ethyl alcohol furnishing slurry, the material that forms after the slurry drying is pressed into capacitance cathode sheet and negative plate on roll forming machine, at last this pole piece single or double is attached on the nickel foam collector, makes the positive pole and the negative pole of ultracapacitor; Perhaps above-mentioned slurry is applied on the nickel foam collector, after the drying compacting, make ultracapacitor positive pole and negative pole, then positive pole, negative pole and barrier film are intersected stack or behind coiling and molding on the up-coiler, be assembled into capacitor cell, and sealed behind the perfusion electrolyte, obtain the hybrid super capacitor monomer, a plurality of monomer ultracapacitors are gone here and there or combination in parallel after, just obtain the hybrid super capacitor finished product.
2. hybrid super capacitor manufacture method according to claim 1, it is characterized in that: the capacitor anode material is made up of nickel hydroxide, anodal conductive agent, adhesive, nickel hydroxide is a major ingredient, anodal conductive agent, adhesive are auxiliary materials, the capacitor anode major ingredient is one or more in active carbon, carbon cloth, carbon nano-tube, carbon nano-fiber, carbon and carbon complex, charcoal aerosol and the network configuration material with carbon element, and the negative pole auxiliary material is cathode conductive agent, adhesive.
3. hybrid super capacitor manufacture method according to claim 2 is characterized in that: described adhesive is selected a kind of in ptfe emulsion, Kynoar emulsion, sodium carboxymethylcellulose.
4. hybrid super capacitor manufacture method according to claim 2 is characterized in that: described cathode conductive agent is selected a kind of in electrically conductive graphite, conductive acetylene are deceived, and anodal conductive agent is an extra-fine nickel powder.
5. hybrid super capacitor manufacture method according to claim 4 is characterized in that: described electrolyte is potassium hydroxide electrolyte, and concentration is at 6mol/L～600mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031151051A CN100389472C (en) | 2003-01-23 | 2003-01-23 | Method for producing mixed type super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031151051A CN100389472C (en) | 2003-01-23 | 2003-01-23 | Method for producing mixed type super capacitor |
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| Publication Number | Publication Date |
|---|---|
| CN1519870A CN1519870A (en) | 2004-08-11 |
| CN100389472C true CN100389472C (en) | 2008-05-21 |
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| CNB031151051A Expired - Fee Related CN100389472C (en) | 2003-01-23 | 2003-01-23 | Method for producing mixed type super capacitor |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101162650B (en) * | 2007-05-29 | 2010-06-30 | 中南大学 | Flexible thin film type solid-state super capacitor and its manufacture process |
| CN101847513B (en) * | 2010-02-26 | 2013-08-07 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
| CN102856537A (en) * | 2012-09-17 | 2013-01-02 | 福建卫东投资集团有限公司 | Preparation method of metal hydride nickel accumulator plate |
| CN103198929B (en) * | 2013-03-06 | 2016-12-28 | 长春吉大科诺科技有限责任公司 | A kind of super capacitor electrode sheet and preparation method thereof |
| CN103258657A (en) * | 2013-05-22 | 2013-08-21 | 南京双登科技发展研究院有限公司 | Manufacturing method for organic mixed type capacitor electrode |
| CN104599848A (en) * | 2013-10-30 | 2015-05-06 | 张彩欣 | Hybrid capacitor and manufacturing method thereof |
| CN104599849A (en) * | 2013-10-30 | 2015-05-06 | 张彩欣 | Hybrid capacitor and manufacturing method thereof |
| WO2015119211A1 (en) * | 2014-02-06 | 2015-08-13 | 独立行政法人科学技術振興機構 | Sheet for pressure sensor, pressure sensor, and method for producing sheet for pressure sensor |
| CN107564736B (en) * | 2017-07-31 | 2018-10-26 | 西北工业大学 | The preparation method of all solid state asymmetric capacitor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH065467A (en) * | 1992-06-24 | 1994-01-14 | Nec Corp | Electric double layer capacitor |
| US5963417A (en) * | 1995-11-09 | 1999-10-05 | Wisconsin Alumni Research Foundation | Electrochemical capacitor |
| CN1345075A (en) * | 2001-11-02 | 2002-04-17 | 中国科学院上海冶金研究所 | Manufacture of high-voltage electrochemical capacitor |
| CN1369886A (en) * | 2002-03-06 | 2002-09-18 | 哈尔滨工程大学 | Electrochemical capacitor |
-
2003
- 2003-01-23 CN CNB031151051A patent/CN100389472C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH065467A (en) * | 1992-06-24 | 1994-01-14 | Nec Corp | Electric double layer capacitor |
| US5963417A (en) * | 1995-11-09 | 1999-10-05 | Wisconsin Alumni Research Foundation | Electrochemical capacitor |
| CN1345075A (en) * | 2001-11-02 | 2002-04-17 | 中国科学院上海冶金研究所 | Manufacture of high-voltage electrochemical capacitor |
| CN1369886A (en) * | 2002-03-06 | 2002-09-18 | 哈尔滨工程大学 | Electrochemical capacitor |
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| CN1519870A (en) | 2004-08-11 |
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Denomination of invention: Method for producing mixed type super capacitor Effective date of registration: 20140724 Granted publication date: 20080521 Pledgee: Pudong Shanghai technology financing Company limited by guarantee Pledgor: Shanghai Aowei Technology Development Co., Ltd. Registration number: 2014310000054 |
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