CN102426924B - High-performance aluminum/carbon composite electrode foil and preparation method thereof - Google Patents
High-performance aluminum/carbon composite electrode foil and preparation method thereof Download PDFInfo
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- CN102426924B CN102426924B CN201110309347.0A CN201110309347A CN102426924B CN 102426924 B CN102426924 B CN 102426924B CN 201110309347 A CN201110309347 A CN 201110309347A CN 102426924 B CN102426924 B CN 102426924B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 68
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011888 foil Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
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- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000005030 aluminium foil Substances 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
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- 230000001070 adhesive effect Effects 0.000 claims description 19
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
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- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 0.000 claims description 2
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- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 claims description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
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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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Abstract
The invention relates to a high-performance aluminum/carbon composite electrode foil and a preparation method thereof. The high-performance aluminum/carbon composite electrode foil comprises a substrate aluminum foil and a carbon-containing layer formed on the surface of the aluminum foil, wherein the carbon-containing layer comprises graphite particles and an amorphous carbon layer, wherein the graphite particles have high electrical conductivity; the amorphous carbon layer is coated on the periphery of the graphite particles and is connected with an aluminum foil substrate to conduct graphite particles; and an interdiffusion layer with a certain depth is formed between the aluminum foil substrate and the carbon-containing layer. The preparation method for the high-performance aluminum/carbon composite electrode foil is characterized by comprising the following steps of: blending graphite powder, organic resin and an active additive in an organic solvent to prepare slurry; coating the slurring on the aluminum foil; and performing heat treatment under the condition of isolating oxygen after drying the slurry. The preparation method is simple in process and low in cost; and the prepared electrode foil has high-temperature stability, extremely low internal resistance, good sealing performance and wide application prospect.
Description
Technical field
The present invention relates to a kind of aluminium/carbon composite electrode foil and preparation method thereof.Particularly, the present invention relates to the manufacture method of a kind of aluminium/carbon composite electrode foil that can be used as the devices such as aluminium electrolytic capacitor, ultracapacitor, lithium ion battery electrode material used or electrode collector material, belong to field of energy source materials.
Background technology
Conventional energy storage device all has the performance requirement of high power capacity, low internal resistance in order to guarantee its serviceability as capacitor, battery, to obtain larger energy reserves and delivery efficiency.Energy storage device as the main structure of capacitor (battery) be anode/dielectric material (electrolyte)/negative electrode/collector electrode.Capacity, the internal resistance of electrode material on energy storage device has earth shaking impact.Make energy storage device obtain high power capacity, electrode material must have larger surface area.The resistance of electrode material is the important composition part of the equivalent series resistance (ESR) of energy storage device simultaneously.
The anode material of aluminium electrolytic capacitor is the formed aluminum foil of Surface Creation insulating oxide aluminium, and negative electrode is electrolyte, inorganic semiconductor, conducting polymer, and the collector electrode being connected with the negative electrode aluminium foils that expanded area that use, are called electrode foil more.The method of traditional expansion electrode foil surface area is that aluminium foil is corroded.But corrosion can reduce the intensity of electrode foil, limited in the degree that guarantees etch raising capacity under certain mechanical strength, in addition, etch has specific (special) requirements to the impurity content of aluminium foil, thereby its production and processing is had to particular restriction.Expand jumbo these deficiencies based on etch, in recent years developed the method that applies carbonaceous material raising capacity at aluminium foil surface.The polarizing electrode of double electric layer capacitor is carbonaceous active material to be coated on to aluminium foil collector electrode surface make.The negative material graphite that lithium ion battery is conventional generally loads on and on foil, on matrix, forms electrode.Above application all requires to be coated with carbon aluminium foil and has low internal resistance and high-specific surface area.For meeting manufacture craft and stability requirement, be coated with carbon aluminium foil and also should there is higher adhesion, in case blocking layer peels off from electrode simultaneously.
As the method that applies carbon-coating on aluminium foil matrix, the Lv Mingzhe of japan Aluminum Co., Ltd of Japan, high being apt to of foot also waited at patent CN101027736A, with in CN1777965A, propose one and comprise aluminium foil, carbon-containing bed and aluminium/carbon compound of forming between the two is as vectorial electrode member, carbonaceous material is passed through bonding agent by feature preparation method, water, the means such as solvent are coated on aluminium foil matrix, after dry, heat-treat the adhesion of generation aluminium/carbide medium raising aluminum substrate and carbon-coating at the confined space of hydrocarbonaceous material, and reduce internal resistance, but must use flammable explosive hydrocarbons in the method heating steps, hydrocarbons resource-constrained, price is high, security control requirements in production process is high, equipment and factory building are had to special requirement of explosion proof, greatly increase production cost.
Pan Yingjun proposes after mixing, to add stirring solvent evenly to make slurry conductive black, dispersant, organic adhesive and is coated in through the pretreated aluminium foil surface of NaOH solution applying for a patent in CN 101923961 A, then put into vacuum furnace, heat treatment 1-40h under vacuum degree 10-4 ~ 10-1Pa, temperature 300-660 ℃ condition, naturally cools to room temperature and makes aluminium carbon composite insulating foil.This method has overcome aluminium company of Japan and has used the restriction of inflammable and explosive atmosphere, and has obtained higher capacity, but this method take carbon black as conductive agent, because the electric conductivity of carbon black is poorer than graphite, therefore the resistance of its product is higher; And its technique need to be carried out preliminary treatment to aluminium foil, technological process complexity, and need in vacuum furnace, naturally cool to room temperature after heat treatment, and consuming time long, greatly reduce production efficiency.
Nearly rattan respects one, this show of island set in patent CN 1910711 B by carbon is applied on aluminium foil and be heated to alloying temperature with on form low internal resistance aluminium carbon electrode, comprising following steps: 1, aluminium foil used is carried out to plasma pretreatment; 2, be coated on aluminium foil and cover and fluoridize aluminium lamination; 3, by vacuum moulding machine, sputter and chemical vapour deposition technique, carbon is applied on aluminium foil; 4, the aluminium carbon electrode sheet that heating has applied carbon-coating forms electrode above to aluminium, carbon alloy temperature.But this method will be used the high power treatment means such as plasma pretreatment, vacuum moulding machine, sputter and chemical vapour deposition (CVD), apparatus expensive, process control procedure complexity, cost is high.
Seiji Nonaka, Ibaraki-shi etc. adopt and are pressed into the electrode material of making capacitor with the method for coating combination in U.S. Pat 2002/0080558 A1, and specific practice is as follows: 1) make aluminium foil surface alligatoring by the method for explosion or etching; 2) carbon particle is evenly applied to aluminium foil surface, or by dissolve in volatile solvent (as water, methyl alcohol) be applied to aluminium foil surface after fully disperseing after dry method come uniform, the weight ratio of activated carbon particles and aluminium foil is about 1:2, then by roller press perpendicular to the aluminium foil surface application of force, carbon particle is pressed into and in aluminium foil, makes carbon containing aluminium foil; 3) method that again aluminium foil is imposed to etching or explosion makes carbon particle part be exposed to surface; 4) with activated carbon and binder fiber element, be aided with suitable volatile solvent (as water and methyl alcohol) and make slurry dipping or be applied to aluminium foil surface, after low temperature drying, heat, form an activated carbon layer.But this method complex procedures is various, be difficult to control, the adhesive strength forming by the bonding of carbon particle and carbon-coating is limited, and the coating of last active carbon layer is used bonding agent cellulose can greatly increase the internal resistance of electrode material.
In Japanese Patent Laid-Open 2000-164466 communique, disclose a kind of intermediate coat or noble metal intermediate coat that carbon is set on aluminium foil matrix, the method of carbon coating isoreactivity material layer again, but the carbon intermediate coat of this method or noble metal intermediate layer form by the high energy such as sputter, vapour deposition method, control complicated, with high costs and production efficiency is lower.
In Chinese patent CN1015923962A Ruan hall ripple, old according to equality people, a kind of activated carbon electrodes preparation method who implements rolling process after adding that aluminium foil matrix, graphite electroconductive adhesive layer and active carbon coat are fallen is disclosed, but the graphite electroconductive adhesive layer of this method and active carbon coat all use bonding agent, adhesive strength is limited, and can increase pole piece internal resistance.
The people such as Akihiko Yoshida are dissolved in the aqueous solution of methyl or carboxymethyl cellulose and are made slurry by activated carbon and a kind of auxiliary agent (as acetylene black) that improves conductance in U.S. Pat 5150283 A, then by dipping, the method of coating or printing forms thin film on aluminum substrate surface, after air drying 30min, again with dry 1h left and right at 100 ℃ of near-infrareds, obtain thus the negative electrode of double electric layer capacitor.But only provide adhesive strength and limited by cellulose family bonding agent, the use of cellulose family bonding agent simultaneously can cause larger resistance.
A large amount of production experience prove, ordinary electrode bonding agent is as butadiene-styrene rubber, cellulose family bonding agent, very large to the Resistance Influence of pole piece, under lower addition, as 3-8%, can make resistance significantly increase, thereby limit its consumption, therefore the getable adhesive strength of pole piece institute that uses ordinary electrode bonding agent to make is limited, resistance is also larger, and non-refractory.
Above-mentioned various technology, no matter be the pole piece obtaining by bonding agent, intermediate layer or roll-in, all can not obtain the unification of specific area, adhesive strength and low internal resistance.
Summary of the invention
The object of the invention is to address the above problem, what a kind of safe and reliable, economical and efficient was provided prepares high power capacity, high-adhesive-strength, low internal resistance and resistant to elevated temperatures high-performance aluminum/carbon composite electrode foil and preparation method thereof.
A kind of high-performance aluminum/carbon composite electrode foil of the present invention, its composition comprises matrix aluminium foil and is formed at the carbon-containing bed of aluminium foil surface, the carbon-containing bed amorphous carbon layer that comprises the graphite granule that conductivity is higher and be coated on graphite granule around and play connection function.The high-performance aluminum/carbon composite electrode foil that the present invention makes does not rely on the bonding carbon-coating of bonding agent, but rely on the generated in-situ amorphous carbon layer of electrically conductive graphite particle surface that electrically conductive graphite particle and aluminium foil matrix are linked into an integrated entity, the graphite of crystalline state is connected phase combination with amorphous carbon makes pole piece obtain conductivity, adhesive strength and the unification with organic bath compatibility, has overcome the bad drawback of single graphite and organic bath compatibility and the defect of conductivity and stability deficiency during as electric conducting material with unformed carbon black.Meanwhile, have the phase diffusion layer of certain depth between carbon-containing bed and aluminium foil matrix, this that is to say to have the carbon concentration higher than aluminium foil matrix inside with the carbon-containing bed aluminium foil surface contacting, have one from surface the carbon diffusion layer to inner stairway degression.Equally, also there is the aluminium element concentration higher than remainder on the carbon-containing bed surface contacting with aluminium foil, has an aluminium diffusion layer successively decreasing towards outer step from interface.Also the be improved to some extent effect of aluminium foil matrix and carbon-containing bed adhesion of the existence of this phase diffusion layer.In addition, the generated in-situ amorphous carbon layer of electrically conductive graphite particle surface has porous and scramble network form, can increase carbon-containing bed surface area.
A kind of high-performance aluminum/carbon composite insulating foil of the present invention and preparation method thereof, its master operation is that graphite powder, organic resin and active additive are mixed and made into slurry in organic solvent, be coated on aluminium foil, after being dried, under the condition of starvation, heat-treat, make aluminium/carbon composite insulating foil.Be mixed with slurry process and be organic resin is dissolved in and under stirring condition, progressively adds active additive after organic solvent and graphite powder obtains slurry.
Described preferably spherical graphite of graphite powder of the present invention, more preferably spherical graphite particle diameter is between 0.1-30 μ m.The carbon black higher with respect to amorphous degree, crystal structure of graphite is complete stable, conductivity is fabulous, with play that the amorphous carbon layer of connection function is composite obtains conductivity, adhesive strength and the unification with organic bath compatibility, overcome the bad drawback of single graphite and organic bath compatibility and the defect of conductivity and stability deficiency during as electric conducting material with unformed carbon black.Graphite powder in the present invention also can use in active carbon, carbon nano-tube, carbon fiber, carbonaceous mesophase spherules one or more mixture replace.
The preferred organic resin of organic resin of the present invention comprises any one or a few the mixture in aethylis carbamas resin, the fine resin of propylene, polyamide acetic acid second resin, epoxy resin, furane resins, phenolic resins, alkene ester resin, vinyl chloride resin, chloroethylene copolymer resin, vinyl chloride vinyl acetate copolymerization resin, polyvinyl butyral resin, polyurethane resin, urea resin, vinyl acetate and relevant modified resin thereof, and the content preferable range of bonding agent is total material 1wt%-80wt% of (not comprising solvent).
Described preferably four gas phthalic anhydrides, hexahydrophthalic anhydride, 2-ethyl-4 methylimidazole, 2 of crosslinking agent class of active additive of the present invention, 5-dimethyl-2,5 di-t-butyl hexane peroxides, benzoyl peroxide, tetramethylethylenediamine, with one or more the mixture in titanate coupling agent, silane coupler and the aluminate coupling agent of coupling agent type, more preferably the additive of different efficacies between rise synergistic composite.Can all can there is bonding with the inorganic functional group on the large molecule of organic resin, matrix aluminium foil and carbon materials surface in the active additive in the present invention simultaneously, can effectively improve the interface between carbon materials, aluminium foil matrix and organic resin, interfacial adhesion strength is obviously promoted, it also has the effect of surfactant simultaneously, and the mixing that is conducive to slurry disperses.Through experimental exploration, preferable amount is total material 0.5wt%-15wt% of (not comprising solvent).
Organic solvent of the present invention is any one in propylene glycol monomethyl ether, propene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, vinylene carbonate, ethylene isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, methyl ethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1-METHYLPYRROLIDONE and several mixtures preferably, add the amount of solvent to regulate the solid content of slurry at 5wt%-80wt% by adjusting, thereby regulate carbon-coating coating thickness.
The preferred cathode aluminum foil of aluminium foil matrix of the present invention, preferably the purity of aluminium foil is 90-100%, before applying, can use the well-known method alligatoring such as sandblast, corrosion, more preferably before applying, generate one deck passivating film as application bottom by chemical conversion process such as phosphatization, chromium phosphatizations.
In preparation method of the present invention, coating method is not particularly limited, can on aluminium foil single or double, applies carbon-coating by methods such as dipping, blade coating, printing, printings.
Not limiting mode of dry run in technical process of the present invention, only needs all solvents remove, and can pass through oven for drying, also can naturally dry or air-dry.
In the present invention, in the preparation method of high-performance aluminum/carbon composite insulating foil, the atmosphere that heat treated atmosphere is starvation, can be N
2, Ar
2etc. atmosphere of inert gases, can be also vacuum, or reducing atmosphere.Wherein reducing atmosphere can be by directly passing into the reducibility gas such as CO, H2, water-gas, or in inert atmosphere, place the material with carbon elements such as carbon black, activated carbon, graphite, carbonaceous mesophase spherules, carbon nano-tube, carbon fiber and obtain.Preferably 400-620 ℃ of the heat treated temperature of carbon, heat treatment time is preferably between 0.5-48h.This heat treatment mainly reduces pole piece sheet resistance by carbonization organic resin, the graphite granule high with degree of graphitization with generated in-situ amorphous carbon network after the well-mixed organic resin carbonization of powdered graphite is connected closely simultaneously, makes pole piece obtain lower internal resistance in the higher adhesive strength of maintenance.
The preparation method of of the present invention provided a kind of high-performance aluminum/carbon composite electrode foil, can be before heat treatment or the after-applied suitable rolling process of heat treatment, to obtain higher adhesive strength.
The preparation method of high-performance aluminum/carbon composite insulating foil of the present invention compares with prior art, has the following advantages:
(1) high-performance aluminum/carbon composite insulating foil that prepared by the present invention has overcome the problem that sheet resistance is high, adhesive strength is limited that existing most of product causes because relying on bonding agent, has low sheet resistance and high adhesiveness simultaneously.
(2) without using hydrocarbons, preparation technology is simply controlled, safe and reliable, economical and efficient, and equipment investment is few, and raw material is cheap and easy to get, has cost advantage.
In sum, the invention provides a kind of simple, economic, preparation method of high-performance aluminum/carbon composite electrode foil reliably, be applicable to industrialization and produce, there is great application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope image in the present invention aluminium/carbon composite insulating foil front of preparing.
Fig. 2 is the scanning electron microscope image of aluminium/carbon composite insulating foil section of preparing of the present invention.
Embodiment
Below by embodiment, the present invention is described in detail, example below just meets several examples of the technology of the present invention content, do not illustrate that the present invention only limits to the content described in following example, the technical staff in the industry all belongs to content of the present invention according to the product of the claims in the present invention item manufacture.
embodiment 1by Kynoar 1 weight portion, powdered graphite 98.5 weight portions that average grain diameter is 25 microns, silane coupler 0.5 weight portion is dispersed in solvent (1-METHYLPYRROLIDONE), obtain the slurry of solid content 5%, by this slurry by immersion coating in the corrosive aluminum foil two sides of thickness 50 μ m, dry after carbon-coating one side thickness be 50 microns.By this pole piece at N
2in atmosphere, at 350 ℃, keep 48h.
embodiment 2by ptfe emulsion (water serial emulsion of polytetrafluoroethylene content 50%) 6 weight portions, powdered graphite 96 weight portions that average grain diameter is 15 microns, titanate coupling agent 1 weight portion is dispersed in solvent (dimethyl carbonate), obtain solid content 10%, slurry, by this slurry by immersion coating in the corrosive aluminum foil two sides of thickness 50 μ m, dry after carbon-coating one side thickness be 35 microns.By this pole piece at N
2in atmosphere, at 380 ℃, keep 40h.
embodiment 3by graphite 94.5 weight portions and titanate coupling agent 0.5 weight portion of 20 microns of epoxy resin 5 weight portions, average grain diameter, in solvent (propylene glycol monomethyl ether), evenly mix and disperse, obtain the slurry of solid content 20%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by knife coating, dry rear carbon-coating one side thickness is 45 microns.By this pole piece at N
2in atmosphere, at 400 ℃, keep 36h.
embodiment 4by carbonaceous mesophase spherules 79 weight portions and titanate coupling agent 0.6 weight portion and four gas phthalic anhydride 0.4 weight portions of 10 microns of polyvinyl butyral resin 20 weight portions, average grain diameter, in solvent (gamma-butyrolacton), evenly mix and disperse, obtain the slurry of solid content 30%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 24 μ m by print process, dry rear carbon-coating one side thickness is 25 microns.By this pole piece at N
2in atmosphere, at 600 ℃, keep 1h.
embodiment 5by 5 microns of carbonaceous mesophase spherules 69 weight portions, the average lengths of 10 microns of polyvinyl butyral resin 20 weight portions, average grain diameter, 1 micron of diameter carbon nano-tube 10 weight portions and aluminate coupling agent 0.6 weight portion and 2-ethyl-4 methylimidazole 0.4 weight portion, in solvent (gamma-butyrolacton), evenly mix and disperse, obtain the slurry of solid content 40%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by print process, dry rear carbon-coating one side thickness is 25 microns.By this pole piece at N
2in atmosphere, at 600 ℃, keep 1h.
embodiment 6by vinyl chloride-based resin 30 weight portions, active carbon 68 weight portions and aluminate coupling agent 2 weight portions, in solvent (propene carbonate), evenly mix and disperse, obtain the slurry of solid content 50%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by coating machine, dry rear carbon-coating one side thickness is 13 microns.By this pole piece at Ar
2in atmosphere, at 550 ℃, keep 10h.
embodiment 7by 56 parts of graphite weight and titanate esters 3 weight portions, 2 of 7 microns of epoxy resin 40 weight portions, average grain diameter, 5-dimethyl-2,5 di-t-butyl hexane peroxide 1 weight portions, in solvent (propene carbonate), evenly mix and disperse, obtain the slurry of solid content 60%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by coating machine, dry rear carbon-coating one side thickness is 15 microns.This pole piece is kept to 24h in vacuum atmosphere at 450 ℃.
embodiment 8by graphite 53 weight portions of 7 microns of epoxy resin 20 weight portions, phenolic resins resin 20 weight portions, average grain diameter and titanate coupling agent 6 weight portions, hexahydrophthalic anhydride 1 weight portion, in solvent (dimethyl carbonate), evenly mix and disperse, obtain the slurry of solid content 70%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m, dry rear carbon-coating one side thickness is 15 microns.This pole piece is kept to 24h in vacuum atmosphere at 450 ℃.
embodiment 9by carbon fiber 40 weight portions of polyamide 50 weight portions, average length 8 μ m, diameter 2 μ m and aluminate coupling agent 6 weight portions, silane coupler 4 weight portions, in solvent (propene carbonate), evenly mix and disperse, obtain the slurry of solid content 80%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by print process, dry rear carbon-coating one side thickness is 13 microns.This pole piece is kept to 14h in CO atmosphere at 520 ℃.
embodiment 10by carbon fiber 40 weight portions of 7 microns of polyamide 50 weight portions, average length and silane coupler 8 weight portions, benzoyl peroxide 2 weight portions, in solvent (propene carbonate), evenly mix and disperse, obtain the slurry of solid content 80%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by printing, this etched foil had carried out the processing of chromium phosphatization before applying, and dry rear carbon-coating one side thickness is 13 microns.By this pole piece at H
2in atmosphere, at 520 ℃, keep 14h.
embodiment 11by polyester resin adhesive 60 weight portions, 7 microns of average lengths, 1 micron of diameter carbon nano-tube 27 weight portions and aluminate coupling agent 9 weight portions and silane coupler 4 weight portions, in solvent (1-METHYLPYRROLIDONE), evenly mix and disperse, obtain the slurry of solid content 5%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by inkjet printing, dry rear carbon-coating one side thickness is 13 microns.By this pole piece in the space that is equipped with activated carbon, Ar
2in atmosphere, at 550 ℃, keep 10h.
embodiment 12by graphite 5 weight portions of 0.5 micron of vinylacetate resin 80 weight portion, average grain diameter and titanate coupling agent 10 weight portions, tetramethylethylenediamine 3 weight portions, 2-ethyl-4 methylimidazole 2 weight portions, in solvent (methyl acetic acid ester and vinylene carbonate are pressed 2:1 volume ratio and mixed), evenly mix and disperse, obtain the slurry of solid content 10%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by inkjet printing, dry rear carbon-coating one side thickness is 10 microns.By this pole piece at Ar
2in atmosphere, at 620 ℃, keep 0.5h.
comparative example 1by vinyl chloride-based resin 30 weight portions, active carbon 68 amounts part and aluminate coupling agent 2 weight portions, in solvent (toluene), evenly mix and disperse, obtain the slurry of solid content 40%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by coating machine, dry rear carbon-coating one side thickness is 13 microns.
comparative example 2by epoxy resin 20 weight portions, phenolic resins resin 20 weight portions, carbon black 60 weight portions, in solvent (dimethyl carbonate), evenly mix and disperse, obtain the slurry of solid content 60%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by printing, dry rear carbon-coating one side thickness is 15 microns.This pole piece is kept to 24h in vacuum atmosphere at 450 ℃.
comparative example 3by carbon fiber 40 weight portions and aluminate coupling agent 10 weight portions of 7 microns of polyamide 50 weight portions, average length, in solvent (propene carbonate), evenly mix and disperse, obtain the slurry of solid content 20%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by infusion process, dry rear carbon-coating one side thickness is 13 microns.By this pole piece in air atmosphere, keep 14h at 520 ℃.
comparative example 4carbon black 20 weight portions of 0.1 micron of sodium carboxymethylcellulose 2 weight portion, butadiene-styrene rubber 8 weight portions, active carbon 70 weight portions, average grain diameter are evenly mixed and disperseed in solvent (water), obtain the slurry of solid content 50%, this slurry is coated on to the corrosive aluminum foil two sides of thickness 50 μ m by coating machine, dry rear carbon-coating one side thickness is 40 microns.
Adhesive strength, sheet resistance and the volumetric properties of measuring as follows above-described embodiment 1-12, comparative example 1-4, measurement result is as shown in table 1.
(1) adhesive strength
Measure the adhesive strength of pole piece by adhesive tape method.On the pole piece of wide 45mm, long 60mm, paste the adhesive tape of the long 70mm of wide 50mm, the adhesive tape of then tearing, is calculated as follows adhesive strength:
Adhesive strength=(bonding rear residual carbon-coating weight/bonding front carbon-coating weight) × 100%
(2) sheet resistance
Utilize sheet resistance characterization of surfaces resistance characteristic.Sheet resistance is exactly square resistance, refer to a foursquare thin film of conductive material while arriving the resistance between " it ", square resistance has a characteristic, the square resistance while arriving that is arbitrary size is all the same, no matter the length of side is 1 meter or 0.1 meter, their sheet resistance is all the same, and sheet resistance is only relevant with the factor such as the character of conducting film own like this.The DMR-1C type sheet resistance instrument that adopts Nanjing Da Ming Instrument Ltd. to produce carries out sheet resistance test to sample, to characterize sample surfaces resistance characteristic.
(3) capacitive property
Pole piece is made to solid aluminum electrolytic capacitor, obtain the specific volume performance of pole piece by measuring the electric capacity of this capacitor divided by pole piece area.
Table 1
Result by table 1 learns, embodiment 1-12 demonstrates higher capacitance, lower internal resistance and higher adhesive strength with respect to aluminium/carbon composite electrode foil of comparative example 1-4.
Claims (7)
1. the preparation method of a high-performance aluminum/carbon composite electrode foil, the composition of high-performance aluminum/carbon composite electrode foil comprises matrix aluminium foil and is formed at the carbon-containing bed of aluminium foil surface, the carbon-containing bed graphite granule that comprises that conductivity is higher is connected the agraphitic carbon network of effect mutually with being coated on graphite granule around and plaing, and carbon-containing bed and interface aluminium foil exists phase counterdiffusion; Described aluminium foil comprises corroding electrode aluminium foil and non-corrosive electrode aluminium foil, and aluminium foil purity is between 90wt%-100wt%; Described graphite granule comprises natural flake graphite and spherical graphite, between graphite particle diameter 0.1-30 μ m; The preparation method's of high-performance aluminum/carbon composite electrode foil feature operation is graphite powder, organic resin and active additive to be mixed and made into slurry in organic solvent be coated on aluminium foil, after dry, under inertia or reducing atmosphere, heat-treat, make aluminium/carbon composite electrode foil; The addition of described organic resin accounts for the 60-80wt% of total material, and described total material does not comprise solvent; Described organic resin comprises one or more in vinyl chloride vinyl acetate copolymerization resin, urea resin, aethylis carbamas resin, epoxy resin, furane resins, phenolic resins, polytetrafluoroethylene, Kynoar, polyamide acetic acid second resin, polyvinyl butyral resin, polyurethane resin, acrylic resin, alkene ester resin, vinyl chloride resin, chloroethylene copolymer resin, acrylonitrile resin, vinylacetate and relevant modified resin thereof; Described active additive comprises the mixture of coupling agent or coupling agent and crosslinking agent, described coupling agent comprises one or more in titanate coupling agent, silane coupler and aluminate coupling agent, described crosslinking agent comprises tetrabydrophthalic anhydride, hexahydrophthalic anhydride, 2-ethyl-4 methylimidazole, 2,5-dimethyl-2,5 di-t-butyl hexane peroxides, benzoyl peroxide, tetramethylethylenediamine, the content of described active additive accounts for the 0.5wt%-15wt% of total material, and described total material does not comprise solvent; Described heat treated temperature range is 400-620 ℃, and time range is 0.5-48 hour.
2. the preparation method of a kind of high-performance aluminum/carbon composite electrode foil as claimed in claim 1, described one or more replacements in active carbon, carbon nano-tube, carbon fiber, carbonaceous mesophase spherules for graphite powder.
3. the preparation method of a kind of high-performance aluminum/carbon composite electrode foil as claimed in claim 1, described organic solvent is any one or a few in propylene glycol monomethyl ether, propene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, vinylene carbonate, ethylene isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, methyl ethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1-METHYLPYRROLIDONE.
4. the preparation method of a kind of high-performance aluminum/carbon composite electrode foil as claimed in claim 1, described coating method comprises and on aluminium foil single or double, applies carbon-containing bed by dipping, blade coating, printing and printing type.
5. the preparation method of a kind of high-performance aluminum/carbon composite electrode foil as claimed in claim 1, adds rolling process before described heat treatment or after heat treatment, further to improve coated adhesive intensity.
6. the high-performance aluminum/carbon composite electrode foil that as claimed in claim 1 prepared by high-performance aluminum/carbon composite electrode foil preparation method, its composition comprises matrix aluminium foil and is formed at the carbon-containing bed of aluminium foil surface, the carbon-containing bed graphite granule that comprises that conductivity is higher is connected the agraphitic carbon network of effect mutually with being coated on graphite granule around and plaing, and carbon-containing bed and interface aluminium foil exists phase counterdiffusion; Described aluminium foil comprises corroding electrode aluminium foil and non-corrosive electrode aluminium foil, and aluminium foil purity is between 90wt%-100wt%; Described graphite granule comprises natural flake graphite and spherical graphite, between graphite particle diameter 0.1-30 μ m.
7. a kind of high-performance aluminum/carbon composite electrode foil as claimed in claim 6, described one or more replacements in active carbon, carbon nano-tube, carbon fiber, carbonaceous mesophase spherules for graphite granule.
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Application publication date: 20120425 Assignee: Jiangsu Rong Sheng Electronics Co., Ltd. Assignor: Li Jian|Yao Jianjun Contract record no.: 2016320010010 Denomination of invention: High-performance aluminum/carbon composite electrode foil and preparation method thereof Granted publication date: 20140514 License type: Exclusive License Record date: 20160302 |
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