CN100424796C - Active carbon fibre cloth/sprayed aluminium composite polar plate double-electric layer capacitor and producing method thereof - Google Patents
Active carbon fibre cloth/sprayed aluminium composite polar plate double-electric layer capacitor and producing method thereof Download PDFInfo
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- CN100424796C CN100424796C CNB031242901A CN03124290A CN100424796C CN 100424796 C CN100424796 C CN 100424796C CN B031242901 A CNB031242901 A CN B031242901A CN 03124290 A CN03124290 A CN 03124290A CN 100424796 C CN100424796 C CN 100424796C
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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 discloses an activated carbon fiber cloth/spray coating aluminium compound pole plate electric double-layer capacitor and a preparing method thereof. The preparing method comprises the procedures: 1. activated carbon fiber cloth is obtained; 2. high-purity aluminium wires are melted and sprayed on the surface of the activated carbon fiber cloth in an arc spray coating mode, and the quality of the compound aluminium by the method is 15 to 30% of a compound pole plate; 3. a current collector, a pole plate, a diaphragm, a pole plate, a current collector are orderly stacked for preparing the inner core of the capacitor in a winding or continuous reverse folding mode; 4. an upper end cover is assembled, dewatering treatment is carried out by laser radiation, argon arc welding, or hemming compression and sealing, an organic electrolyte is added to the capacitor, and then a liquid charging hole is sealed. The activated carbon fiber cloth/spray coating aluminium compound pole plate electric double-layer capacitor of the present invention is composed of the pole plates, the current collectors, the diaphragm, the organic electrolyte, a casing, a pole column, a pole ear and the end cover. The quality of the compound aluminium of the prior art accounts for 42 to 53% of the quality of a compound pole plate, but the quality of the compound aluminium of the present invention only accounts for 15 to 30% of the quality of a compound pole plate.
Description
Technical field:
The present invention relates to a kind of capacitor and preparation method thereof, particularly relate to a kind of active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor and preparation method thereof.
Background technology:
Ultracapacitor has than the high energy density more than 10 times of ordinary capacitor, have simultaneously than the high nearly 10 times power density of conventional accumulators, it is the novel electron device that the intermediate application field of this two classes device is replenished or the two performance is strengthened, mainly comprise double electric layer capacitor and pseudo-capacitor type capacitor, the former is an electric double layer effect of utilizing material surface, double electric layer capacitor schematic diagram as shown in Figure 1, by the principle of taking off/adsorb storage/release electric energy of electric charge on its surface, a kind of electronic device of preparation, the present invention is the type capacitor.
The electric double layer principle is very basic theory in the electrochemical field, and it is promptly beginning development 19th century, but utilizes this principle to prepare capacitor, just occurs in the middle and later periods in 20th century.Especially the eighties this device obtain maximum development, " Gold " capacitor with the preparation of Japanese NEC Corporation is a sign especially.Up to entering the nineties, double electric layer capacitor mainly is the small-sized farad level of a preparation device, its life-span is long, self discharge is little and non-maintaining, but its internal resistance is bigger, generally reach more than tens ohm, mainly reach at milliampere and work under the little current conditions with subordinate, substituting battery in computer storage is its typical application occasion.
Since the nineties in last century, the research of high power type ultracapacitor obtains paying attention to, in the latter stage in 20th century, U.S. Maxwell company, Japan Panasonic company, NEC Corporation and Russian ECOND company etc. all development and production have gone out product level ultracapacitor based on electric double layer, the high-energy high power characteristic of this device is along with the appearance of these products, use and also constantly opened up, the particularly propelling of electric automobile research recently, its starting, quicken, occasions such as climbing and brake all can make ultracapacitor be used, so the demand of high power type ultracapacitor is more and more urgent.
Double electric layers supercapacitor early adopts the preparation of active carbon pasty electrode more, United States Patent (USP) U.S.5 as the application of ECOND company, adopting active carbon in 557,497 is that main active material prepares the unit double electric layers supercapacitor, adopts aqueous electrolysis plastidome, and make resulting devices with the mode of unit internal series-connection, the mode that employing adds elevated pressures reduces internal resistance, improves its power-performance, and it exists the unit durable low, energy density is little, problems such as assembling complexity.
United States Patent (USP) U.S.4, suggestion adopts the method for spraying motlten metal to improve contact between electrode and the current collection level in 562,511, reaches the attenuating internal resistance, improves the purpose of power density, does not do more detailed elaboration in its patent.Also have the Auburn University to adopt metallic fiber and activated carbon fiber textile capacitor plate altogether in addition, lower the capacitor internal resistance, this technology is too complicated, is difficult to realize cost degradation.
The United States Patent (USP) U.S.6 of Maxwell company application, 430, the elaboration that 031 patent document such as grade is detailed the preparation method of its activated carbon fiber ultracapacitor, it has adopted technology such as plasma spraying in activated carbon fiber one side composite layer of aluminum, adopts the method for describing in its file to assemble the single organic electrolyte ultracapacitor of multipole plate then.Compare with this patent, its clad aluminum quality accounts for 42～53% of compound polar plate, and only is 15～30% in this patent; The pole plate of this patent is assembled into single stacked system, and its internal resistance is lower, makes more simple; In addition, the activated carbon fiber that this patent adopts in wide specific area scope, (Maxwell 2500M on the particularly relatively low specific area
2, this patent 1000M
2) still have good energy density and power density, well-known, the activated carbon fiber in this patent scope is easy to low cost and obtains, and its technological requirement harshness of activated carbon with high specific surface area fiber cloth, price is high.
Summary of the invention:
The present invention relates to a kind of electrochemical capacitor in double electrode layer with high-energy-density and power density, more particularly adopt active carbon fiber fabrics, with spraying method molten aluminum is compound in the active carbon fiber fabrics surface, with this electrochemical capacitor in double electrode layer as the pole plate preparation.
The objective of the invention is to improve the shortcoming of prior art, active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor and preparation method thereof is provided.
For achieving the above object, the present invention takes following design: active carbon fiber fabrics/spraying aluminium compound polar plate electric double-layer capacitors prepared method.
A kind of active carbon fiber fabrics/spraying aluminium compound polar plate electric double-layer capacitors prepared method:
Step 4 is clamp-oned inner core in the capacitor casing, and the fit on end cap adopts laser, argon arc welding or crimping compression seal, only stays liquid injection hole to communicate with the external world; The dry state double electric layer capacitor inner core that above-mentioned assembling is finished is put into vacuum drying chamber and is removed water treatment, and temperature is controlled at 30～80 ℃, 2～12 hours time; Take out under dry atmosphere protection afterwards, add organic electrolyte in decompression fluid injection mode, the sealing liquid injection hole becomes the double electric layer capacitor finished product.
A kind of active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor, it is made up of pole plate, collector, barrier film, organic electrolyte, housing, pole, lug, end cap, it is characterized in that: pole plate is made up of the metal aluminium lamination a surface recombination at active carbon fiber fabrics, the inner part aluminium that infiltrates of activated carbon fiber, constitute a conducting matrix grain network configuration, an activated carbon fiber part is contained in it, and the clad aluminum quality is 15～30% of a compound polar plate; The specific area of described active carbon fiber fabrics is greater than 500m
2/ g, thickness are less than 1mm, and surface density is less than 250g/m
2Described pole plate is compounded with metallic aluminium through spraying one side contacts with collector, pole plate is not compounded with metallic aluminium without spraying one side contacts with barrier film, collector, pole plate, barrier film constitute the double electric layer capacitor inner core, described inner core is put into housing, lug is connected with electrode, and end cap is connected with housing, and organic electrolyte is arranged in the housing.
Active carbon fiber fabrics of the present invention/spraying aluminium compound polar plate double electric layer capacitor is made up of pole plate, collector, barrier film, organic electrolyte, housing, pole, lug, end cap, pole plate is made up of the metal aluminium lamination a surface recombination at active carbon fiber fabrics, aluminium content is 15～30% of pole plate quality, and the specific area of described active carbon fiber fabrics is greater than 500m
2/ g, preferred 800～1600m
2/ g, thickness are less than 1mm, and preferably less than 0.5mm, surface density is less than 250g/m
2, preferably less than 150g/m
2The spraying face of described pole plate contacts with collector, and the non-spraying face contacts with barrier film, and collector, pole plate, barrier film constitute the double electric layer capacitor inner core, described inner core is put into housing, lug is connected with electrode, and end cap is connected with housing, and organic electrolyte is arranged in the housing.
Account for 42～53% of compound polar plate with the clad aluminum quality of prior art and compare, this patent only is 15～30%; The pole plate of this patent is assembled into single stacked system, and its internal resistance is lower, makes more simple; In addition, the activated carbon fiber that this patent adopts in wide specific area scope, (Maxwell 2500M on the particularly relatively low specific area
2, this patent 1000M
2) still having good energy density and power density, the activated carbon fiber in this patent scope is easy to low cost and obtains, and its technological requirement harshness of activated carbon with high specific surface area fiber cloth, price is high.
Active carbon fiber fabrics of the present invention has 500m
2The specific area that/g is above, specific area is higher can to reach better capacitive property, but present its manufacture difficulty of the active carbon fiber fabrics of high-specific surface area is bigger, and price is high.In the present invention, can make common active carbon fiber fabrics reach capacitive property preferably, make the capacitor cost be able to maximum reduction.Figure 16 is a double electric layer capacitor constant current charge-discharge curve chart, on the curve characteristic of this figure, can find out that capacitive property of the present invention is superior.
Description of drawings:
Fig. 1, the double electric layer capacitor schematic diagram;
Fig. 2, folding square core arrangement figure;
Fig. 3, button double electric layer capacitor structure chart;
Fig. 4, circular core arrangement figure reels;
Fig. 5, square core arrangement figure reels;
Fig. 6, active carbon fiber fabrics/aluminium compound polar plate structure chart;
Fig. 7, double electric layer capacitor membrane configuration figure;
Fig. 8, the spraying coating process schematic diagram;
Fig. 9, collector-lug johning knot composition;
Fig. 9-1, collector-extreme ear structure figure;
Figure 10, lug-pole johning knot composition;
Figure 10-1, the double electric layer capacitor structure chart;
Figure 11, anti-rotation upper end cover structure chart;
Figure 12, activated carbon fiber cloth is made flow chart;
Figure 13, double electric layer capacitor is made flow chart;
Figure 14, single-ended pole deriving structure figure;
Figure 15, both-end pole deriving structure figure;
Figure 16, double electric layer capacitor constant current charge-discharge curve chart.
Embodiment:
Embodiment 1: make shown in flow chart, Figure 13 double electric layer capacitor making flow chart active carbon fiber fabrics of the present invention/spraying aluminium compound polar plate electric double-layer capacitors prepared method as Figure 12 activated carbon fiber cloth:
Step 4 is clamp-oned inner core in the capacitor casing 5, and fit on end cap 8 adopts laser, argon arc welding or crimping compression seal, only stays liquid injection hole 30 to communicate with the external world; The dry state double electric layer capacitor inner core that above-mentioned assembling is finished is put into vacuum drying chamber and is removed water treatment, and temperature is controlled at 30 ℃, 12 hours time; Afterwards at dry gas (as dry N
2) protection taking-up down, adding organic electrolyte 4 in decompression fluid injection mode, above-mentioned inner core organic electrolyte 4 is as Working electrolyte, and its operating voltage adopts 1.7M Et especially more than 2.3V
4NBF
4/ AN, its moisture of organic electrolyte is not more than 100PPM, preferably is not more than 20PPM.The sealing liquid injection hole becomes the double electric layer capacitor finished product.
Embodiment 2: active carbon fiber fabrics of the present invention/spraying aluminium compound polar plate electric double-layer capacitors prepared method:
Step 4 is clamp-oned inner core 60 in the capacitor casing 5, and fit on end cap 8 adopts laser, argon arc welding or crimping compression seal, only stays liquid injection hole 30 to communicate with the external world; The dry state double electric layer capacitor inner core 60 that above-mentioned assembling is finished is put into vacuum drying chamber and is removed water treatment, and temperature is controlled at 80 ℃, 3 hours time; Afterwards at dry gas (as dry Ar
2) protection takes out down, adds the organic electrolyte 4 of respective quality in decompression fluid injection mode, as Working electrolyte, its operating voltage adopts 1～1.7MEt to above-mentioned inner core 60 especially more than 2.3V with organic electrolyte 4
4NBF
4/ AN, its moisture of organic electrolyte preferably is not more than 10PPM.The sealing liquid injection hole becomes the double electric layer capacitor finished product.
Embodiment 3: active carbon fiber fabrics of the present invention/spraying aluminium compound polar plate electric double-layer capacitors prepared method:
Step 4 is clamp-oned inner core in the capacitor casing 5, and fit on end cap 8 adopts laser, argon arc welding or crimping compression seal, only stays liquid injection hole 30 to communicate with the external world; The dry state double electric layer capacitor inner core that above-mentioned assembling is finished is put into vacuum drying chamber and is removed water treatment, and temperature is controlled at 50 ℃, 8 hours time; Take out down in dry atmosphere (as dry air) protection afterwards, add the organic electrolyte 4 of respective quality in the fluid injection mode that reduces pressure, organic electrolyte 4 its electrolyte are high-purity dry lithium salts, as LiClO
4, LiPF
4, LiPF
6Deng, quaternary amine is as Et
4NBF
4Et (CH
4)
4NBF
4In, or its mixture, organic solvent adopts anhydrous PC, EC, DMC, DEC, EMC, AN, GBL, THF, NMF monomer or its mixture etc., prepares electrolyte with the proportioning of 0.5～2M, and the sealing liquid injection hole becomes the double electric layer capacitor finished product.
Embodiment 4: shown in Fig. 8 spraying coating process schematic diagram, in the above embodiments 1 or 2 or 3, selectively active carbon fiber sheet 83 requires complete nothing damaged, and its thickness is 0.5mm or less than 0.5mm, surface density 120～250g/m
2, preferred 120～200g/m
2Step; on the constant tilt flat board 80 with (ventilating cabinets) in the smooth protective cover 81 that is positioned over forced-ventilated wind of active carbon fiber fabrics 83; active carbon fiber fabrics 83 each edge are fixed on dull and stereotyped 80 with the smooth press strip 82 of wide 5cm, and it is compound that aluminium is carried out in present embodiment employing electric arc spraying.
The compressed air pressure that spraying work is adopted is 4～7MPa, preferred 5.5～6.5MPa, and the compressed air of drawing from air compressor passes through dried.Sprayed on material adopts high-purity aluminium wire 85, and aluminium wire 85 diameters are 2mm, around rolling up on the spraying equipment wire feed rolls.In distance active carbon fiber fabrics 83 (30～60) cm distance, preferred 40～50cm, spray gun 84 send compressed air, and the aluminium particulate of fusion or semi-molten shape is sprayed in the starting the arc towards active carbon fiber fabrics 83 then.With active carbon fiber fabrics 83 surface aluminium coating particulates and form even continuous structure and exceed fully.
The clad aluminum amount is 15～30% of a whole compound polar plate, preferred 20～25%.
Embodiment 5: the monomer electric double-layer capacitors prepared
As shown in figure 10, the utility model active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor is made up of pole plate 1, collector 2, barrier film 3, organic electrolyte 4, housing 5, pole 6, lug 7, end cap 8, collector 2 adopts aluminum foil material, also can adopt nickel foil; The step that cuts is arranged, and aluminum foil current collector 2 is cut into wide rectangular of 10cm, the concordant no burr in edge, and it is equidistant that its width is 10mm with the thick matter lug 7 of ultrasonic spot welding, and thickness is greater than 0.1mm, and it is 20 that one pole collector 2 is drawn lug quantity.Another type is on the wide aluminum foil current collector 2 of 15cm, on one side keeps 40 above quantity through cutting at it, and width is drawn lug 7 certainly greater than 10mm's.
Kraft capacitor paper barrier film 3 is that 11cm is wide rectangular, on the length than collector 10cm more than 2.Check barrier film, require no any breakage, no trachoma, pollution-free, neat in edge.Compound polar plate is cut into wide rectangular of 10cm, requires neat in edge, do not have any overlap, length and collector 2 are isometric.Pole plate 1 is made up of the metal aluminium lamination a surface recombination at active carbon fiber fabrics 83, the inner part aluminium that infiltrates of activated carbon fiber, constitute a conducting matrix grain network configuration, an activated carbon fiber part is contained in it, the clad aluminum quality that adopts this mode is 15～30% of a compound polar plate; The specific area of described active carbon fiber fabrics 83 is greater than 500m
2/ g, preferred 800～1600m
2/ g, thickness are less than 1mm, and preferably less than 0.5mm, surface density is less than 250g/m
2, preferably less than 150g/m
2The described metal aluminium lamination that is compounded with may instead be and is compounded with the metal nickel dam.Active carbon fiber fabrics 83 can adopt the activated carbon fiber felt; The spraying face 11 of described pole plate 1 contacts with collector 2, non-spraying face 12 contacts with barrier film 3, collector 2, pole plate 1, barrier film 3, pole plate 1, collector 2 in proper order superpose, pole plate clad aluminum face 11 contacts with aluminium foil 2, the light face contacts with barrier film 3, aluminium foil draw lug 7 towards unanimity, guarantee the lug 7 no any contacts between the two poles of the earth simultaneously.The list of forming double electric layer capacitor with constantly folded inverted structure is the double electric layer capacitor inner core to pole plate folded form inner core 60, as shown in Figure 2, then on hydraulic press with the inner core compacting, preparation double electric layer capacitor inner core.With PTFE film uniform winding inner core, make inner core 60 and housing 5 insulation afterwards.
Described inner core 60 is put into housing 5, and lug 7 is connected with pole 6, and end cap 8 is connected with housing 5, and organic electrolyte 4 is arranged in the housing 5, and housing 5 is connected with pressure-relief valve or explosion-proof valve 50.
Preparation double electric layer capacitor inner core 60.Shown in Fig. 9, Figure 10-1, each utmost point is drawn lug 7, and ultra-sonic welded 27 is in two pole bottom surfaces 90 respectively, and as shown in figure 15, at housing 5 two ends, slot milling is avoided direct contact between the lug of the two poles of the earth respectively in pole 6 positions.
Embodiment 6: shown in Fig. 9-1, active carbon fiber fabrics of the present invention/spraying aluminium compound polar plate double electric layer capacitor is made up of pole plate 1, collector 2, barrier film 3, organic electrolyte 4, housing 5, pole 6, lug 7, end cap 8, be used in the identical compound polar plate material of above-mentioned capacitor as this type capacitor plate 1, its pole plate 1 width 4cm.Collector 2 aluminium foil width are 4cm, adopt ultra-sonic welded lug 7 and collector 2, shown in Fig. 9-1; Lug 7 adopts draws from collector 2 length 1/2 position, and the lug width is 4mm, with collector 2, pole plate 1, barrier film 3, pole plate 1, collector 2, pole plate 1, barrier film 3, pole plate 1, as shown in Figure 5; Or collector 2, pole plate 1, barrier film 3, pole plate 1, collector 2, barrier film 40 order laminations, as Fig. 4; On up-coiler circular roll pin, this lamination consolidation is constituted circular double electric layer capacitor inner core, make another convoluted inner core of double electric layer capacitor with winding method with winding method.Insulating spacer is a polypropylene, and polyethylene or its compound, inner core are put into circular aluminum enclosure 5, and explosion-proof groove is carved with in the aluminum hull bottom, forms the sealing groove at aluminum hull upper end edging then, and employing as above-mentioned drying mode make inner core reach the bone dry state.Housing 5 has vacuum to soak the organic electrolyte 4 that stagnates, and organic electrolyte 4 is identical with above-mentioned capacitor.Aluminium matter pole on ultra-sonic welded or riveted joint lug 7 and the composite decking.On pressure closing machine by mold pressing make the aluminum hull upper limb mutually in fastening on end cap 8, reach complete sealing state.Obtain the double electric layer capacitor of medium-sized capacity.This type capacitor is little owing to its housing quality, its energy density height.Its pole plate area is little simultaneously, and leakage current is corresponding to be reduced.
Embodiment 7: the utility model active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor is made up of pole plate 1, collector 2, barrier film 3, organic electrolyte 4, housing 5, pole 6, lug 7, end cap 8, pole 6 also can adopt aluminium pole or nickel pole or stainless steel pole, or the compound pole of aluminium or nickel and other metals, but itself and electrolyte contact jaw are aluminium matter or nickel matter.Be used in the identical compound polar plate material of above-mentioned capacitor as this type capacitor plate 1, its pole plate 1 width 4cm.Collector 2 aluminium foil width are 4cm, adopt ultra-sonic welded lug 7 and collector 2, and lug 7 adopts draws from collector 2 length 1/2 position, and lug 7 width are 4mm.
Embodiment 8: as shown in figure 11, and small-sized Wound square electric double-layer capacitors prepared; Active carbon fiber fabrics of the present invention/spraying aluminium compound polar plate double electric layer capacitor is made up of pole plate 1, collector 2, barrier film 3, organic electrolyte 4, housing 5, pole 6, lug 7, end cap 8, nut 32, pressure-relief valve or explosion-proof valve 50, liquid injection hole 30.Housing 5 is connected with pressure-relief valve or explosion-proof valve 50 and liquid injection hole 30.Pole 6 has endoporus spiral shell button; Described housing 5 is rectangle or circle, and material is aluminium or stainless steel, and end cap 8 is phenolic resins-rubber composite.End cap 8 prevents rotation hole 31, pole 6 be connected with end cap 8 adopt to cooperate abnormally-structured-prevent that rotation hole 31 from preventing to rotate, combine end face etc. as rectangle end face, circular arc with straight line, be not limited in this.When end cap 8 is metal, fill insulant 33 between pole 6 and the housing 5, as polytetrafluoroethylene, PVC, pottery, rubber etc. are not only for therewith.
The mode identical with monomer double electric layer capacitor inner core reeled, but adopts rectangle volume pin, rolls out the ellipse that is shaped as afterwards.Coiling is put into corresponding rectangular mould compacting with inner core after finishing, and obtains the capacitor inner core of rectangle.
This inner core is clamp-oned in the rectangular housing 5, and soldering polar ear and extraction electrode (can draw as the utmost point wherein with housing) adopt the laser welding top end cover, only reserve liquid injection hole and communicate with the external world.After the drying, the vacuum fluid injection seals liquid injection hole 30 then, obtains the small rectangular double electric layer capacitor.
Embodiment 9: as shown in Figure 9, aluminium foil adopts the ultrasonic spot welding lug or from the collector 2 of lead-out mode as this capacitor, for reducing the overall volume and the quality of capacitor, aluminum foil current collector should be thin as far as possible, as 0.02mm or thinner, the quantity of lug 7 should decide according to the ability that capacitor bears maximum current.According to the housing 5 of capacity requirement design, the shape of rectangle, circle and button is arranged usually, Fig. 2,3,4,5.Pressure-relief valve or explosion-proof valve/groove 50 are arranged on the housing 5, reach under the stable condition in internal pressure and open, guarantee the fail safe under abuse condition.A plurality of lugs 7 that inner core is drawn are by positive and negative combination in parallel, are connected on a large scale in the mode of large power supersonic welding 60 and draw on the pole 6, as shown in figure 10.Forbid taking place mutually between the two poles of the earth lug, the pole electronic conduction.Inner core is clamp-oned in the capacitor casing 5, fit on end cap 8, adopt laser, argon arc welding or crimping compression seal, only stay liquid injection hole 30 to communicate with the external world, pole 6 is drawn and also can be adopted the one pole post to draw, with metal shell 5 is that a utmost point is drawn, and pole 6 is drawn and adopted the single-ended bipolar post of housing 5 to draw, or the both-end pole of housing 5 is drawn.
The dry state double electric layer capacitor inner core that above-mentioned assembling is finished is put into vacuum drying chamber and is removed water treatment, and temperature is controlled at 30～80 ℃, 2～12 hours time.Afterwards in dry atmosphere (as dry N
2, Ar
2, air etc.) air conservation takes out down, adds the organic electrolyte of respective quality in decompression fluid injection mode, the sealing liquid injection hole becomes the double electric layer capacitor finished product
The barrier film of this capacitor adopts electrolyte resistance materials such as porous PP film, in order to reduce the barrier film internal resistance to greatest extent, this barrier film should be selected the porous thin gauge film, in addition, diaphragm material should have intensity preferably, to guarantee not take place the two poles of the earth that pole plate causes piercing through of barrier film isolating under certain pressure electronic conduction takes place.
The just folding inner core of finishing is very fluffy, need be with certain pressure with the inner core compacting, and the inner core compacting all is very favourable to improving capacitor volume specific energy and power.Inner core after the compacting is under identical active carbon fiber fabrics raw material and identical electrolyte situation, and condenser capacity can be designed shell dimension by the area decision of giving fixed plate easily according to inner core.
The case material of this double electric layer capacitor should be selected the material of electrolyte resistance for use, it has good gas and liquid isolation simultaneously, and prevent to infiltrate, guarantee the isolation fully of capacitor internal atmosphere and external environment, also should possess intensity preferably, aluminium or stainless steel are the materials that satisfies above-mentioned requirements, are applied in the present invention.
The electrolyte of organic electrolyte adopts dry lithium salts, as LiClO
4, LiPF
6, LiPF
4Deng, quaternary amine is as Et
4NBF
4In, or its mixture, organic solvent adopts anhydrous PC, EC, DMC, DEC, EMC, AN, GBL, THF, NMF monomer or its mixture etc., prepares electrolyte with the proportioning of 0.5～2M, particularly adopts 1～1.7M Et
4NBF
4/ AN seals stand-by.
Claims (21)
1. active carbon fiber fabrics/spraying aluminium compound polar plate electric double-layer capacitors prepared method is characterized in that:
Step 1 is a base material with viscose glue or propionitrile, after the fiber wire drawing, be woven into fiber cloth, fiber cloth is become carbon fiber sheet after the charing under 400～600 ℃ of temperature, afterwards under catalyst action, in 600～1000 ℃, water vapour atmosphere, activate and obtain active carbon fiber fabrics;
Step 2 is protected the edge of active carbon fiber fabrics, at 4～8Kg/cm
2Compressed air under, the aluminium wire fusion is ejected into the surface of active carbon fiber fabrics in the mode of electric arc spraying, coating thickness reaches the surface and just forms the continuous aluminium face of thin layer and constitute compound polar plate, after spraying aluminium is compound, part aluminium is also infiltrated in activated carbon fiber inside, constitute a conducting matrix grain network configuration, an activated carbon fiber part is contained in it, the clad aluminum quality that adopts this mode is 15～30% of a compound polar plate;
Step 3, aluminium foil adopts the ultrasonic spot welding lug or makes collector from lead-out mode, and barrier film adopts electrolyte resistance material kraft capacitor paper barrier film or porous PP film, with collector, pole plate, barrier film, pole plate, collector order lamination, collector and pole plate size match, barrier film is greater than pole plate; With reel or constantly folded inverted mode prepare the capacitor inner core, folding finishing after the capacitor inner core, at its whole outer surface coated insulation material, with certain pressure with the inner core compacting;
Step 4 is clamp-oned inner core in the capacitor casing, and the fit on end cap adopts laser, argon arc welding or crimping compression seal, only stays liquid injection hole to communicate with the external world; The dry state double electric layer capacitor inner core that above-mentioned assembling is finished is put into vacuum drying chamber and is removed water treatment, and temperature is controlled at 30～80 ℃, 2～12 hours time; Take out under dry atmosphere protection afterwards, add organic electrolyte in decompression fluid injection mode, the sealing liquid injection hole becomes the double electric layer capacitor finished product.
2. active carbon fiber fabrics according to claim 1/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: it is compound that the mode of above-mentioned electric arc spraying adopts plasma spraying to carry out aluminium, with collector, pole plate, barrier film, pole plate, collector, pole plate, barrier film, pole plate or collector, pole plate, barrier film, pole plate, collector, barrier film order laminated construction, on up-coiler circular roll pin, this lamination consolidation is constituted circular double electric layer capacitor inner core with winding method.
3. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: the step that cuts is arranged, it is rectangular cutting aluminum foil current collector, cut kraft capacitor paper barrier film length greater than collector, it is rectangular cutting compound polar plate, and length and collector are isometric.
4. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: it is characterized in that: the specific area of described active carbon fiber fabrics is 800～1600m
2/ g, thickness are less than 0.5mm, and surface density is less than 150g/m
2
5. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: described organic electrolyte is as Working electrolyte, and its operating voltage is more than 2.3V.
6. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method is characterized in that: described organic electrolyte adopts 1～1.7MEt
4NBF
4/ AN, its moisture of organic electrolyte is not more than 100PPM.
7. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: its moisture of organic electrolyte is not more than 20PPM.
8. active carbon fiber fabrics according to claim 4/spraying aluminium compound polar plate electric double-layer capacitors prepared method is characterized in that: described active carbon fiber fabrics adopts the activated carbon fiber felt.
9. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method is characterized in that: described active carbon fiber fabrics adopts the activated carbon fiber felt.
10. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: its electrolyte of organic electrolyte is dry lithium salts, and the proportioning that this electrolyte and organic solvent mix with 0.5～2M prepares electrolyte.
11. active carbon fiber fabrics according to claim 8/spraying aluminium compound polar plate electric double-layer capacitors prepared method, it is characterized in that: its electrolyte of organic electrolyte is dry lithium salts, and the proportioning that this electrolyte and organic solvent mix with 0.5～2M prepares electrolyte.
12. active carbon fiber fabrics according to claim 1 and 2/spraying aluminium compound polar plate electric double-layer capacitors prepared method is characterized in that: lug adopts the thick type aluminium foil of ultra-sonic welded, and lug is connected employing large tracts of land ultra-sonic welded and connects with pole.
13. active carbon fiber fabrics according to claim 8/spraying aluminium compound polar plate electric double-layer capacitors prepared method is characterized in that: lug adopts the thick type aluminium foil of ultra-sonic welded, and lug is connected employing large tracts of land ultra-sonic welded and connects with pole.
14. active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor, it is made up of pole plate, collector, barrier film, organic electrolyte, housing, pole, lug, end cap, it is characterized in that: pole plate is made up of the metal aluminium lamination a surface recombination at active carbon fiber fabrics, the inner part aluminium that infiltrates of activated carbon fiber, constitute a conducting matrix grain network configuration, an activated carbon fiber part is contained in it, and the clad aluminum quality is 15～30% of a compound polar plate; The specific area of described active carbon fiber fabrics is greater than 500m
2/ g, thickness are less than 1mm, and surface density is less than 250g/m
2Described pole plate is compounded with metallic aluminium through spraying one side contacts with collector, pole plate is not compounded with metallic aluminium without spraying one side contacts with barrier film, collector, pole plate, barrier film constitute the double electric layer capacitor inner core, described inner core is put into housing, lug is connected with pole plate, and end cap is connected with housing, and organic electrolyte is arranged in the housing.
15. a kind of active carbon fiber fabrics according to claim 14/spraying aluminium compound polar plate double electric layer capacitor is characterized in that: the specific area 800～1600m of described active carbon fiber fabrics
2/ g, thickness are less than 0.5mm, and surface density is less than 150g/m
2
16. according to claim 14 or 15 described a kind of active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor, it is characterized in that: superpose in proper order collector, pole plate, barrier film, pole plate, collector, form the list of double electric layer capacitor to pole plate folded form inner core with constantly folded inverted structure.
17. according to claim 14 or 15 described a kind of active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor, it is characterized in that:, on up-coiler circular roll pin, this lamination consolidation is constituted circular double electric layer capacitor inner core with winding method with collector, pole plate, barrier film, pole plate, collector, pole plate, barrier film, pole plate or collector, pole plate, barrier film, pole plate, collector, barrier film order laminated construction.
18. a kind of active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor according to claim 1 or 2 described method preparations, it is characterized in that: described housing is rectangle or circle, material is aluminium or stainless steel, end cap is that phenolic resins-rubber composite or end cap are metal, pole is connected the employing cooperation with end cap abnormally-structured, and pole has endoporus spiral shell button.
19. a kind of active carbon fiber fabrics according to claim 18/spraying aluminium compound polar plate double electric layer capacitor, it is characterized in that: fill insulant between pole and the housing, pole is drawn and is adopted the single-ended bipolar post of housing to draw, or the both-end pole of housing draws, or housing is the utmost point and the one pole post is drawn for another utmost point.
20. a kind of active carbon fiber fabrics/spraying aluminium compound polar plate double electric layer capacitor according to claim 1 or 2 described method preparations, it is characterized in that: pole adopts the compound pole of aluminium pole or stainless steel pole or aluminium and other metals, but itself and electrolyte contact jaw are aluminium matter, pole is connected the employing cooperation with end cap abnormally-structured, and end cap prevents rotation hole.
21. a kind of active carbon fiber fabrics according to claim 20/spraying aluminium compound polar plate double electric layer capacitor, it is characterized in that: housing is connected with liquid injection hole, relief valve or explosion-proof valve.
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| CNB031242901A CN100424796C (en) | 2003-05-08 | 2003-05-08 | Active carbon fibre cloth/sprayed aluminium composite polar plate double-electric layer capacitor and producing method thereof |
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|---|---|---|---|
| CNB031242901A CN100424796C (en) | 2003-05-08 | 2003-05-08 | Active carbon fibre cloth/sprayed aluminium composite polar plate double-electric layer capacitor and producing method thereof |
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| CN101562078B (en) * | 2009-05-15 | 2012-08-22 | 深圳清华大学研究院 | Super-capacitor and preparation method thereof |
| CN101901696A (en) * | 2009-05-26 | 2010-12-01 | 上海空间电源研究所 | Super-capacitor serving as primary power source of launch vehicle |
| CN101656155B (en) * | 2009-09-22 | 2012-02-22 | 南京双登科技发展研究院有限公司 | Method for making high-capacity organic ultracapacitor in flexible package |
| CN101840789A (en) * | 2010-04-14 | 2010-09-22 | 上海奥威科技开发有限公司 | Electrochemical electric container sealing device |
| CN101864635B (en) * | 2010-05-25 | 2012-05-23 | 大连理工大学 | Method for manufacturing high-strength viscose-based active carbon fiber fabrics |
| 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 |
| KR102434695B1 (en) * | 2015-02-24 | 2022-08-22 | 삼성전자주식회사 | Stretchable supercapacitor and method of manufacturing the same |
| CN104867695A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Light-metal-doped straw based carbon electrode material and preparation method thereof |
| CN106298265A (en) * | 2015-06-10 | 2017-01-04 | 辽宁立德电力工程设计有限公司 | Ultracapacitor composite and preparation method thereof |
| CN107546035A (en) * | 2017-09-11 | 2018-01-05 | 北京三雄科技公司 | High-precision Vacuum printing capacitor and its application |
| CN109175383B (en) * | 2018-08-28 | 2020-10-23 | 鑫威铝业（漳州）有限公司 | Preparation process of solar cell aluminum alloy bracket |
| CN110579296B (en) * | 2019-09-30 | 2020-08-04 | 西安交通大学 | Double electric layer capacitance type flexible pressure sensor with enhanced inclined structure and manufacturing method thereof |
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