CN102426924A - 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
- Publication number
- CN102426924A CN102426924A CN2011103093470A CN201110309347A CN102426924A CN 102426924 A CN102426924 A CN 102426924A CN 2011103093470 A CN2011103093470 A CN 2011103093470A CN 201110309347 A CN201110309347 A CN 201110309347A CN 102426924 A CN102426924 A CN 102426924A
- Authority
- CN
- China
- Prior art keywords
- carbon
- resin
- composite electrode
- preparation
- carbon composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
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 paper tinsel and preparation method thereof.Particularly, the present invention relates to can be used as the manufacturing approach of a kind of aluminium/carbon composite electrode paper tinsel of used electrode material of devices such as aluminium electrolytic capacitor, ultracapacitor, lithium ion battery or electrode collector material, belong to field of energy source materials.
Background technology
Energy storage device commonly used such as capacitor, battery all have the performance requirement of high power capacity, low internal resistance in order to guarantee its serviceability, to obtain bigger energy reserves and delivery efficiency.The main structure of energy storage device such as capacitor (battery) is anode/dielectric material (electrolyte)/negative electrode/collector electrode.Electrode material has earth shaking influence to capacity, the internal resistance of energy storage device.Make energy storage device obtain high power capacity, electrode material must have bigger 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 that the surface generates insulating oxide aluminium, and negative electrode is electrolyte, inorganic semiconductor, conducting polymer, and the collector electrode that is connected with the negative electrode aluminium foils that enlarged 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, and limited in the degree that guarantees etch raising capacity under the certain mechanical strength, in addition, etch has specific (special) requirements to the impurity content of aluminium foil, thereby its production and processing is had particular restriction.Based on these deficiencies of etch expansion capacity, developed in recent years at aluminium foil surface and applied the method that carbonaceous material improves capacity.The polarizing electrode of double electric layer capacitor is the carbonaceous active material to be coated on aluminium foil collector electrode surface process.The negative material graphite that lithium ion battery is commonly used generally loads on and constitutes electrode on the foil on the matrix.Above application all requires to be coated with the carbon aluminium foil and has low internal resistance and high-specific surface area.For satisfying manufacture craft and stability requirement, be coated with the carbon aluminium foil and also should have higher connecting airtight property simultaneously, in case the blocking layer peels off from electrode.
As the method that on the aluminium foil matrix, applies carbon-coating; The Lv Mingzhe of Japan japan Aluminum Co., Ltd, foot be high kind also to be waited and in patent CN101027736A and CN1777965A, proposes a kind of aluminium foil, carbon-containing bed and aluminium/carbon compound of forming between the two of comprising as vectorial electrode member; Characteristic preparation method is coated in carbonaceous material on the aluminium foil matrix through means such as bonding agent, water, solvents, and the connecting airtight property that generation aluminium/carbide media improves aluminum substrate and carbon-coating is heat-treated at the confined space of hydrocarbonaceous material in dry back, and reduces internal resistance; But must use flammable explosive hydrocarbons in this method heating steps; The hydrocarbons resource-constrained, expensive, the security control in the production process requires high; Equipment and factory building all there are special requirement of explosion proof, have increased production cost greatly.
Pan Yingjun proposes conductive black, dispersant, organic adhesive mixing back adding stirring solvent are evenly processed slurry and be coated in through the pretreated aluminium foil surface of NaOH solution in applying for a patent CN 101923961 A; Put into vacuum furnace then; Heat treatment 1-40h under vacuum degree 10-4 ~ 10-1Pa, temperature 300-660 ℃ condition naturally cools to room temperature and processes aluminium carbon composite insulating foil.This method has overcome Japan aluminium company and has used the restriction of inflammable and explosive atmosphere, and has obtained higher capacity, but this method is conductive agent with the carbon black, because the electric conductivity of carbon black is than graphite difference, so the resistance of its product is higher; And its arts demand carries out preliminary treatment to aluminium foil, and technological process is complicated, and need in vacuum furnace, naturally cool to room temperature after the heat treatment, and is consuming time long, greatly reduces production efficiency.
Nearly rattan respects one, this show of island tree in patent CN 1910711 B through be applied to carbon on the aluminium foil and be heated to the alloying temperature with on form and hang down internal resistance aluminium carbon electrode, comprising following steps: 1, used aluminium foil is carried out plasma pretreatment; 2, be coated in to cover on the aluminium foil and fluoridize aluminium lamination; 3, through vacuum moulding machine, sputter and chemical vapour deposition technique carbon is applied on the aluminium foil; 4, heat the aluminium carbon electrode sheet that has applied carbon-coating and form electrode to aluminium, more than the carbon alloy temperature.But this method will be used high power treatment means such as plasma pretreatment, vacuum moulding machine, sputter and chemical vapour deposition (CVD), apparatus expensive, process control procedure complicacy, and cost is high.
Seiji Nonaka, Ibaraki-shi etc. adopt in U.S. Pat 2002/0080558 A1 and are pressed into the electrode material that the method that combines with coating is made capacitor, and specific practice is following: 1) method with explosion or etching makes the aluminium foil surface alligatoring; 2) carbon particle evenly is applied to aluminium foil surface; Or through dissolve in the volatile solvent (like water, methyl alcohol) be applied to aluminium foil surface after fully disperseing after dry method be uniformly distributed with; The weight ratio of activated carbon particles and aluminium foil is about 1:2; Pass through roller press then perpendicular to the aluminium foil surface application of force, carbon particle is pressed into processes the carbon containing aluminium foil in the aluminium foil; 3) method that once more aluminium foil is imposed etching or explosion makes carbon particle partly be exposed to the surface; 4) plain with activated carbon and binder fiber, be aided with suitable volatile solvent (like water and methyl alcohol) and process the slurry dipping or be applied to aluminium foil surface, heat after the low temperature drying, form an activated carbon layer.But this method complex procedures is various, is difficult to control, and the adhesive strength that the bonding through carbon particle and carbon-coating forms is limited, and the coating of last active carbon layer use bonding agent cellulose can increase the internal resistance of electrode material greatly.
Japanese Patent Laid is opened and disclosed a kind of intermediate coat or noble metal intermediate coat that carbon is set in the 2000-164466 communique on the aluminium foil matrix; The method of carbon coated isoreactivity material layer again; But the carbon intermediate coat or the noble metal intermediate layer of this method form through high energy methods such as sputter, vapour depositions; Control is complicated, and is with high costs and production efficiency is lower.
Ruan hall ripple, old photograph equality people disclose a kind of activated carbon electrodes preparation method who adds back execution rolling process that aluminium foil matrix, graphite electroconductive adhesive layer and active carbon coat are fallen in Chinese patent CN1015923962A; But the graphite electroconductive adhesive layer of this method and active carbon coat all use bonding agent; Adhesive strength is limited, and can increase the pole piece internal resistance.
People such as Akihiko Yoshida are dissolved in the aqueous solution of methyl or carboxymethyl cellulose through activated carbon and a kind of auxiliary agent (like acetylene black) that improves conductance in U.S. Pat 5150283 A and process slurry; Then through dipping; Coating or method of printing form thin film on the aluminum substrate surface; Again with about 100 ℃ of following dry 1h of near-infrared, obtain the negative electrode of double electric layer capacitor thus behind the air drying 30min.But only through the cellulose family bonding agent adhesive strength and limited is provided, the use of cellulose family bonding agent simultaneously can cause bigger resistance.
A large amount of production experience prove, ordinary electrode bonding agent such as butadiene-styrene rubber, cellulose family bonding agent are very big to the resistance influence of pole piece; Under lower addition,, resistance is significantly risen like 3-8%; Thereby limited its consumption; So the getable adhesive strength of pole piece institute of using the ordinary electrode bonding agent to make is limited, resistance is also bigger, and non-refractory.
Above-mentioned various technology no matter be the pole piece that obtains through 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 objective of the invention is to address the above problem, preparation high power capacity, high-adhesive-strength, low internal resistance and resistant to elevated temperatures high-performance aluminum/carbon composite electrode paper tinsel of a kind of safe and reliable, economical and efficient and preparation method thereof are provided.
A kind of high-performance aluminum of the present invention/carbon composite electrode paper tinsel, its composition comprise the matrix aluminium foil and be formed at the carbon-containing bed of aluminium foil surface, carbon-containing bedly comprises the higher graphite granule of conductivity and be coated on around the graphite granule and play the amorphous carbon layer of interconnect function.The high-performance aluminum that the present invention processes/carbon composite electrode paper tinsel 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 with amorphous carbon combination make pole piece obtain conductivity, adhesive strength and with the unification of organic bath compatibility, overcome the bad drawback of single graphite and organic bath compatibility and conductivity and stable defect of insufficient during as electric conducting material with unformed carbon black.Simultaneously, have the phase diffusion layer of certain depth between the carbon-containing bed and aluminium foil matrix, this that is to say, has with the carbon-containing bed aluminium foil surface that contacts to be higher than the inner carbon concentration of aluminium foil matrix, have one from the surface carbon diffusion layer to inner stairway degression.Equally, also there is the aluminium element concentration that is higher than remainder on the carbon-containing bed surface that contacts with aluminium foil, has an aluminium diffusion layer that successively decreases towards outer step from the 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 of the present invention/carbon composite insulating foil 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 the aluminium foil, heat-treat under the condition of starvation dry back, processes aluminium/carbon composite insulating foil.Be mixed with the slurry process and be organic resin is dissolved in and under stirring condition, progressively add active additive behind the organic solvent and graphite powder obtains slurry.
Described graphite powder of the present invention is spherical graphite preferably, and more preferably the spherical graphite particle diameter is between 0.1-30 μ m.With respect to the higher carbon black of amorphous degree; Crystal structure of graphite is complete stable; Conductivity is fabulous; With the amorphous carbon layer that plays interconnect function composite obtain conductivity, adhesive strength and with the unification of organic bath compatibility, overcome the bad drawback of single graphite and organic bath compatibility and conductivity and stable defect of insufficient during as electric conducting material with unformed carbon black.Graphite powder among the present invention also can use one or more the mixture in active carbon, CNT, carbon fiber, the carbonaceous mesophase spherules to 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 combined polymerization resin, polyvinyl butyral resin, polyurethane resin, urea resin, vinyl acetate and the relevant modified resin thereof, and the content preferable range of bonding agent is total material 1wt%-80wt% of (not comprising solvent).
Described active additive of the present invention is four gas phthalic anhydrides, hexahydrophthalic anhydride, 2-ethyl-4 methylimidazole, 2 of crosslinking agent class preferably; 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.Bonding can all can take place with the surperficial inorganic functional group of the big molecule of organic resin, matrix aluminium foil and carbon materials in active additive among the present invention simultaneously; Can effectively improve the interface between carbon materials, aluminium foil matrix and the organic resin; Interfacial adhesion strength is obviously promoted; It also has influence of surfactant simultaneously, helps the mixed and dispersed of slurry.Explore through test, preferable amount is total material 0.5wt%-15wt% of (not comprising solvent).
Organic solvent of the present invention is the mixture of 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, the N-methyl pyrrolidone and several kinds preferably; Regulate solid content of slurry at 5wt%-80wt% through regulating the amount that adds solvent, thereby regulate the carbon-coating coating thickness.
The preferred cathode aluminum foil of aluminium foil matrix of the present invention; The purity of preferred aluminium foil is 90-100%; Before applying, can use well-known method alligatoring such as sandblast, corrosion, more preferably before applying, generate one deck passivating film as the application bottom through chemical conversion process such as phosphatization, chromium phosphatizations.
Among the preparation method of the present invention, coating method is not had special qualification, can on the aluminium foil single or double, apply carbon-coating through methods such as dipping, blade coating, printing, printings.
Dry run in the technical process of the present invention is limiting mode not, only needs all solvents are removed to get final product, and can pass through oven for drying, also can dry naturally or air-dry.
Among the preparation method of high-performance aluminum among the present invention/carbon composite insulating foil, heat treated atmosphere is the atmosphere of starvation, can be N
2, Ar
2Etc. atmosphere of inert gases, also can be vacuum, perhaps reducing atmosphere.Wherein reducing atmosphere can be through direct reducibility gas such as feeding CO, H2, water-gas, or in inert atmosphere, place material with carbon elements such as carbon black, activated carbon, graphite, carbonaceous mesophase spherules, CNT, 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 the pole piece sheet resistance through the carbonization organic resin; Simultaneously with the well-mixed organic resin carbonization of powdered graphite after generated in-situ amorphous carbon network be connected closely with the high graphite granule of degree of graphitization, make pole piece in the higher adhesive strength of maintenance, obtain lower internal resistance.
The preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel that provides of the present invention 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 of the present invention/carbon composite insulating foil compares with prior art, has the following advantages:
(1) high-performance aluminum/carbon composite insulating foil of the present invention's preparation has overcome high, the limited problem of adhesive strength of sheet resistance that existing most of product causes because of relying on bonding agent, has low sheet resistance and high adhesiveness simultaneously.
(2) need not to use hydrocarbons, preparation technology's simple controllable, safe and reliable, economical and efficient, equipment investment is few, and low in raw material cost is easy to get, and has cost advantage.
In sum, the present invention provides the preparation method of a kind of simple, economic, reliable high-performance aluminum/carbon composite electrode paper tinsel, is fit to industrialization production, has great application prospect.
Description of drawings
Fig. 1 is the positive scanning electron microscope image of the aluminium/carbon composite insulating foil of the present invention's preparation.
Fig. 2 is the scanning electron microscope image of the aluminium/carbon composite insulating foil section of the present invention's preparation.
Embodiment
Through embodiment the present invention is elaborated below; Following Example just meets several instances of technology contents of the present invention; Do not explain that the present invention only limits to the described content of following instance, the technical staff in the industry all belongs to content of the present invention according to the product of claim item of the present invention manufacturing.
Embodiment 1With Kynoar 1 weight portion; Powdered graphite 98.5 weight portions that average grain diameter is 25 microns; Silane coupler 0.5 weight portion evenly disperses in solvent (N-methyl pyrrolidone); Obtain the slurry of solid content 5%, this slurry is passed through immersion coating in the corrosive aluminum foil two sides of thickness 50 μ m, dry back carbon-coating single face thickness is 50 microns.With this pole piece at N
2Keep 48h down at 350 ℃ in the atmosphere.
Embodiment 2With 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 evenly disperses in solvent (dimethyl carbonate), obtains solid content 10%, slurry; This slurry is passed through immersion coating in the corrosive aluminum foil two sides of thickness 50 μ m, and dry back carbon-coating single face thickness is 35 microns.With this pole piece at N
2Keep 40h down at 380 ℃ in the atmosphere.
Embodiment 3Graphite 94.5 weight portions and titanate coupling agent 0.5 weight portion with 20 microns of epoxy resin 5 weight portions, average grain diameter; Even mixed and dispersed in solvent (propylene glycol monomethyl ether); Obtain the slurry of solid content 20%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through knife coating, and dry back carbon-coating single face thickness is 45 microns.With this pole piece at N
2Keep 36h down at 400 ℃ in the atmosphere.
Embodiment 4Carbonaceous mesophase spherules 79 weight portions and titanate coupling agent 0.6 weight portion and four gas phthalic anhydrides, 0.4 weight portion with 10 microns of polyvinyl butyral resin 20 weight portions, average grain diameter; Even mixed and dispersed in solvent (gamma-butyrolacton); Obtain the slurry of solid content 30%; This slurry is coated on the corrosive aluminum foil two sides of thickness 24 μ m through print process, and dry back carbon-coating single face thickness is 25 microns.With this pole piece at N
2Keep 1h down at 600 ℃ in the atmosphere.
Embodiment 5With 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 CNT 10 weight portions and aluminate coupling agent 0.6 weight portion and 2-ethyl-4 methylimidazole 0.4 weight portion; Even mixed and dispersed in solvent (gamma-butyrolacton); Obtain the slurry of solid content 40%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through print process, and dry back carbon-coating single face thickness is 25 microns.With this pole piece at N
2Keep 1h down at 600 ℃ in the atmosphere.
Embodiment 6With vinyl chloride-based resin 30 weight portions, active carbon 68 weight portions and aluminate coupling agent 2 weight portions; Even mixed and dispersed in solvent (propene carbonate); Obtain the slurry of solid content 50%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through coating machine, and dry back carbon-coating single face thickness is 13 microns.With this pole piece at Ar
2Keep 10h down at 550 ℃ in the atmosphere.
Embodiment 756 parts of graphite weight and titanate esters 3 weight portions, 2 with 7 microns of epoxy resin 40 weight portions, average grain diameter; 5-dimethyl-2; 5 di-t-butyl hexane peroxides, 1 weight portion, even mixed and dispersed in solvent (propene carbonate) obtains the slurry of solid content 60%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through coating machine, and dry back carbon-coating single face thickness is 15 microns.This pole piece is kept 24h down at 450 ℃ in vacuum atmosphere.
Embodiment 8With 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; Even mixed and dispersed in solvent (dimethyl carbonate); Obtain the slurry of solid content 70%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m, and dry back carbon-coating single face thickness is 15 microns.This pole piece is kept 24h down at 450 ℃ in vacuum atmosphere.
Embodiment 9With 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; Even mixed and dispersed in solvent (propene carbonate); Obtain the slurry of solid content 80%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through print process, and dry back carbon-coating single face thickness is 13 microns.This pole piece is kept 14h down at 520 ℃ in CO atmosphere.
Embodiment 10With 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; Even mixed and dispersed in solvent (propene carbonate); Obtain the slurry of solid content 80%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through printing, and this etched foil had carried out the chromium phosphatization before applying handles, and dry back carbon-coating single face thickness is 13 microns.With this pole piece at H
2Keep 14h down at 520 ℃ in the atmosphere.
Embodiment 11With polyester resin adhesive 60 weight portions, 7 microns of average lengths, 1 micron of diameter CNT 27 weight portions and aluminate coupling agent 9 weight portions and silane coupler 4 weight portions; Even mixed and dispersed in solvent (N-methyl pyrrolidone); Obtain the slurry of solid content 5%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through inkjet printing, and dry back carbon-coating single face thickness is 13 microns.With this pole piece in being equipped with the space of activated carbon, Ar
2Keep 10h down at 550 ℃ in the atmosphere.
Embodiment 12With 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; Even mixed and dispersed in solvent (methyl acetic acid ester and vinylene carbonate are pressed the 2:1 volume ratio and mixed); Obtain the slurry of solid content 10%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through inkjet printing, and dry back carbon-coating single face thickness is 10 microns.With this pole piece at Ar
2Keep 0.5h down at 620 ℃ in the atmosphere.
Comparative Examples 1With vinyl chloride-based resin 30 weight portions, active carbon 68 amount part and aluminate coupling agent 2 weight portions; Even mixed and dispersed in solvent (toluene); Obtain the slurry of solid content 40%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through coating machine, and dry back carbon-coating single face thickness is 13 microns.
Comparative Examples 2With epoxy resin 20 weight portions, phenolic resins resin 20 weight portions, carbon black 60 weight portions; Even mixed and dispersed in solvent (dimethyl carbonate); Obtain the slurry of solid content 60%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through printing, and dry back carbon-coating single face thickness is 15 microns.This pole piece is kept 24h down at 450 ℃ in vacuum atmosphere.
Comparative Examples 3Carbon fiber 40 weight portions and aluminate coupling agent 10 weight portions with 7 microns of polyamide 50 weight portions, average length; Even mixed and dispersed in solvent (propene carbonate); Obtain the slurry of solid content 20%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through infusion process, and dry back carbon-coating single face thickness is 13 microns.With this pole piece in air atmosphere, 520 ℃ keep down 14h.
Comparative Examples 4With carbon 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 even mixed and dispersed in solvent (water); Obtain the slurry of solid content 50%; This slurry is coated on the corrosive aluminum foil two sides of thickness 50 μ m through coating machine, and dry back carbon-coating single face thickness is 40 microns.
Measure adhesive strength, sheet resistance and the volumetric properties of the foregoing description 1-12, Comparative Examples 1-4 as follows, measurement result is as shown in table 1.
(1) adhesive strength
Measure the adhesive strength of pole piece through the 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 tearing then is calculated as follows adhesive strength:
Adhesive strength=(the residual carbon-coating weight in bonding back/bonding preceding carbon-coating weight) * 100%
(2) sheet resistance
The resistance of utilization side characterizes the sheet resistance characteristic.Side's resistance is exactly a square resistance; Refer to a foursquare thin film of conductive material while arriving the resistance between " it "; Square resistance has a characteristic, and promptly the square resistance while arriving of size all is the same arbitrarily, no matter the length of side is 1 meter or 0.1 meter; Their side's resistance all is the same, and this sample prescription resistance is only relevant with the factors such as character of conducting film own.The DMR-1C type side resistance appearance that adopts Nanjing Da Ming Instr Ltd. to produce is tested the resistance of the sample side of carrying out, to characterize the sample surfaces resistance characteristic.
(3) capacitive property
Pole piece is processed solid aluminum electrolytic capacitor, obtain the specific volume performance of pole piece through the electric capacity of measuring this capacitor divided by the 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 paper tinsel of Comparative Examples 1-4.
Claims (11)
1. high-performance aluminum/carbon composite electrode paper tinsel; Its composition comprises the matrix aluminium foil and is formed at the carbon-containing bed of aluminium foil surface; Carbon-containing bed comprise the higher graphite granule of conductivity and be coated on around the graphite granule and play be connected the agraphitic carbon network that acts on mutually, there are the counterdiffusion mutually of certain depth in carbon-containing bed and the interface of aluminium foil; The preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel; Its characteristic operation is graphite powder, organic resin and active additive to be mixed and made into slurry be coated on the aluminium foil in organic solvent; Heat-treat under the atmosphere of starvation dry back, processes aluminium/carbon composite electrode paper tinsel.
2. according to claim 1, a kind of high-performance aluminum/carbon composite electrode paper tinsel, described aluminium foil comprise corroding electrode aluminium foil and non-corrosive electrode aluminium foil, and aluminium foil purity is between 90wt%-100wt%.
3. according to claim 1, the preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel, described graphite powder comprises natural flake graphite and spherical graphite, between the graphite particle diameter 0.1-30 μ m.
4. according to claim 1, described graphite powder can use one or more the mixture in active carbon, CNT, carbon fiber, the carbonaceous mesophase spherules to replace.
5. according to claim 1; The preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel; Described organic resin comprises one or more the mixture in vinyl chloride vinyl acetate combined polymerization 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, the fine resin of propylene, vinyl acetate and the relevant modified resin thereof, and the organic resin content of adding accounts for total material 1wt%-80wt% of (not comprising solvent).
6. the four gas phthalic anhydrides, hexahydrophthalic anhydride, 2-ethyl-4 methylimidazole, 2 that comprise the crosslinking agent class like claims 1 described active additive; 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, the content of the active additive of adding accounts for total material 0.5wt%-15wt% of (not comprising solvent).
7. according to claim 1; The preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel, described organic solvent is any one or a few the mixture 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, the N-methyl pyrrolidone.
8. according to claim 1, the preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel, described coating method comprises and on the aluminium foil single or double, applies carbon-containing bed through modes such as dipping, blade coating, printing and printings.
9. according to claim 1, the preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel, described drying mode comprises that nature dries, all methods that can organic solvent all be removed such as oven for drying, drier.
10. according to claim 1; The preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel, described heat treatment process is characterized in that the heat treatment atmosphere is inert atmosphere, vacuum atmosphere or reducing atmosphere; Heat-treatment temperature range is 400-620 ℃, and the heat treatment time scope is 0.5-48h.
11. according to claim 1, the preparation method of a kind of high-performance aluminum/carbon composite electrode paper tinsel can add rolling process before heat treatment or after the heat treatment, with further raising coated adhesive intensity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110309347.0A CN102426924B (en) | 2011-10-13 | 2011-10-13 | High-performance aluminum/carbon composite electrode foil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110309347.0A CN102426924B (en) | 2011-10-13 | 2011-10-13 | High-performance aluminum/carbon composite electrode foil and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102426924A true CN102426924A (en) | 2012-04-25 |
| CN102426924B CN102426924B (en) | 2014-05-14 |
Family
ID=45960893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110309347.0A Active CN102426924B (en) | 2011-10-13 | 2011-10-13 | High-performance aluminum/carbon composite electrode foil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102426924B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718291A (en) * | 2012-06-15 | 2012-10-10 | 吉林省华通制药设备有限公司 | Ion exchange resin modified polyvinylidene fluoride (PVDF) charcoal electrode and preparation method thereof |
| CN102983307A (en) * | 2012-12-10 | 2013-03-20 | 天津巴莫科技股份有限公司 | Preparation method for graphite negative electrode of lithium ion battery |
| CN103275627A (en) * | 2013-05-23 | 2013-09-04 | 安徽溢彩玻璃器皿有限公司 | Heat transfer printing adhesive for metal shell and preparation method thereof |
| CN103545532A (en) * | 2013-10-18 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method of carbon film aluminum mesh for current collector |
| CN103614672A (en) * | 2013-12-09 | 2014-03-05 | 国家电网公司 | Preparation method of carbon nano tube-reinforced aluminum base composite material |
| CN105161698A (en) * | 2015-08-06 | 2015-12-16 | 苏州第一元素纳米技术有限公司 | Fabrication method for aluminum/carbon composite electrode |
| CN105461022A (en) * | 2014-09-12 | 2016-04-06 | 南京大学 | Flake graphite doped binary carbon material composite electrode, and preparation thereof, and applications of flake graphite doped binary carbon material composite electrode in electroadsorption desalination |
| CN106299524A (en) * | 2016-08-24 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | A kind of it is prone to carbon coated collector that powder separates and application and recovery method with foil |
| CN107039636A (en) * | 2017-03-30 | 2017-08-11 | 湖北金泉新材料有限责任公司 | Anode pole piece preparation method, anode pole piece, preparation method of lithium ion battery |
| CN108172321A (en) * | 2017-12-19 | 2018-06-15 | 宇东箔材科技南通有限公司 | A kind of solid capacitor carbon foil and preparation method thereof |
| CN108492988A (en) * | 2018-03-22 | 2018-09-04 | 全椒金富康电子有限公司 | A kind of solid-state capacitor cathode carbon foil and preparation method thereof and a kind of solid-state capacitor and preparation method thereof |
| CN110071291A (en) * | 2019-03-19 | 2019-07-30 | 长沙市秒冲电池技术与材料研究所 | Power battery, negative electrode tab, cathode composite foil and preparation method thereof |
| CN110098059A (en) * | 2019-04-01 | 2019-08-06 | 扬州宏远电子股份有限公司 | Long-life high stability solid state electrode foil and its production method |
| CN110357092A (en) * | 2019-06-06 | 2019-10-22 | 宁波中车新能源科技有限公司 | A kind of activated carbon for super capacitors and its preparation method and application |
| CN111029529A (en) * | 2019-12-24 | 2020-04-17 | 北京汽车集团越野车有限公司 | Preparation method of positive electrode material structure, battery positive electrode, battery and automobile |
| CN111640913A (en) * | 2019-03-01 | 2020-09-08 | 宁德时代新能源科技股份有限公司 | Negative plate and secondary battery |
| CN112670090A (en) * | 2020-12-24 | 2021-04-16 | 电子科技大学 | Electrode plate and preparation method and application thereof |
| CN112670091A (en) * | 2020-12-24 | 2021-04-16 | 电子科技大学 | Aluminum/carbon composite cathode foil for solid aluminum capacitor and preparation method thereof |
| CN113140733A (en) * | 2021-03-29 | 2021-07-20 | 南通耐维特电源有限公司 | Preparation process of lithium battery based on carbon-coated aluminum foil |
| CN113178335A (en) * | 2019-03-20 | 2021-07-27 | 安徽纳诺箔材有限公司 | High specific volume, ultra-thin type negative electrode foil and liquid aluminum electrolytic capacitor |
| CN113178334A (en) * | 2019-03-20 | 2021-07-27 | 安徽纳诺箔材有限公司 | High specific volume, low resistance, ultra-thin type negative electrode foil and solid-state aluminum electrolytic capacitor |
| WO2023097594A1 (en) * | 2021-12-02 | 2023-06-08 | Guangdong Haozhi Technology Co. Limited | Modified current collector for secondary battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020080558A1 (en) * | 1998-01-23 | 2002-06-27 | Seiji Nonaka | Electrode metal material, capacitor and battery formed of the material and method of producing the material and the capacitor and battery |
| CN1905100A (en) * | 2006-08-16 | 2007-01-31 | 锦州富辰超级电容器有限责任公司 | Method for making electrode of ultra-capacitor |
| CN101283420A (en) * | 2005-10-11 | 2008-10-08 | 昭和电工株式会社 | Electricity collection body for electric double layer capacitor, electrode for electric double layer capacitor, and electric double layer capacitor as well as manufacturing method thereof |
| CN101901694A (en) * | 2010-06-23 | 2010-12-01 | 万星光电子(东莞)有限公司 | Super capacitor electrode slice |
| CN101923961A (en) * | 2010-07-27 | 2010-12-22 | 武汉科技大学 | Carbon/aluminum composite cathode foil for solid aluminum electrolytic capacitor and preparation method thereof |
-
2011
- 2011-10-13 CN CN201110309347.0A patent/CN102426924B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020080558A1 (en) * | 1998-01-23 | 2002-06-27 | Seiji Nonaka | Electrode metal material, capacitor and battery formed of the material and method of producing the material and the capacitor and battery |
| CN101283420A (en) * | 2005-10-11 | 2008-10-08 | 昭和电工株式会社 | Electricity collection body for electric double layer capacitor, electrode for electric double layer capacitor, and electric double layer capacitor as well as manufacturing method thereof |
| CN1905100A (en) * | 2006-08-16 | 2007-01-31 | 锦州富辰超级电容器有限责任公司 | Method for making electrode of ultra-capacitor |
| CN101901694A (en) * | 2010-06-23 | 2010-12-01 | 万星光电子(东莞)有限公司 | Super capacitor electrode slice |
| CN101923961A (en) * | 2010-07-27 | 2010-12-22 | 武汉科技大学 | Carbon/aluminum composite cathode foil for solid aluminum electrolytic capacitor and preparation method thereof |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718291A (en) * | 2012-06-15 | 2012-10-10 | 吉林省华通制药设备有限公司 | Ion exchange resin modified polyvinylidene fluoride (PVDF) charcoal electrode and preparation method thereof |
| CN102983307A (en) * | 2012-12-10 | 2013-03-20 | 天津巴莫科技股份有限公司 | Preparation method for graphite negative electrode of lithium ion battery |
| CN103275627A (en) * | 2013-05-23 | 2013-09-04 | 安徽溢彩玻璃器皿有限公司 | Heat transfer printing adhesive for metal shell and preparation method thereof |
| CN103275627B (en) * | 2013-05-23 | 2014-11-12 | 安徽溢彩玻璃器皿有限公司 | Heat transfer printing adhesive for metal shell and preparation method thereof |
| CN103545532A (en) * | 2013-10-18 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method of carbon film aluminum mesh for current collector |
| CN103614672A (en) * | 2013-12-09 | 2014-03-05 | 国家电网公司 | Preparation method of carbon nano tube-reinforced aluminum base composite material |
| CN105461022A (en) * | 2014-09-12 | 2016-04-06 | 南京大学 | Flake graphite doped binary carbon material composite electrode, and preparation thereof, and applications of flake graphite doped binary carbon material composite electrode in electroadsorption desalination |
| CN105161698A (en) * | 2015-08-06 | 2015-12-16 | 苏州第一元素纳米技术有限公司 | Fabrication method for aluminum/carbon composite electrode |
| CN106299524A (en) * | 2016-08-24 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | A kind of it is prone to carbon coated collector that powder separates and application and recovery method with foil |
| CN107039636A (en) * | 2017-03-30 | 2017-08-11 | 湖北金泉新材料有限责任公司 | Anode pole piece preparation method, anode pole piece, preparation method of lithium ion battery |
| CN108172321A (en) * | 2017-12-19 | 2018-06-15 | 宇东箔材科技南通有限公司 | A kind of solid capacitor carbon foil and preparation method thereof |
| CN108492988A (en) * | 2018-03-22 | 2018-09-04 | 全椒金富康电子有限公司 | A kind of solid-state capacitor cathode carbon foil and preparation method thereof and a kind of solid-state capacitor and preparation method thereof |
| CN108492988B (en) * | 2018-03-22 | 2020-05-05 | 全椒金富康电子有限公司 | Solid-state capacitor cathode carbon foil and preparation method thereof, and solid-state capacitor and preparation method thereof |
| CN111640913A (en) * | 2019-03-01 | 2020-09-08 | 宁德时代新能源科技股份有限公司 | Negative plate and secondary battery |
| CN111640913B (en) * | 2019-03-01 | 2021-08-06 | 宁德时代新能源科技股份有限公司 | Negative plate and secondary battery |
| CN110071291A (en) * | 2019-03-19 | 2019-07-30 | 长沙市秒冲电池技术与材料研究所 | Power battery, negative electrode tab, cathode composite foil and preparation method thereof |
| CN113178335A (en) * | 2019-03-20 | 2021-07-27 | 安徽纳诺箔材有限公司 | High specific volume, ultra-thin type negative electrode foil and liquid aluminum electrolytic capacitor |
| CN113178334B (en) * | 2019-03-20 | 2023-01-06 | 安徽纳诺箔材有限公司 | High specific volume negative electrode foil and polymer solid-state aluminum electrolytic capacitor |
| CN113178334A (en) * | 2019-03-20 | 2021-07-27 | 安徽纳诺箔材有限公司 | High specific volume, low resistance, ultra-thin type negative electrode foil and solid-state aluminum electrolytic capacitor |
| CN110098059A (en) * | 2019-04-01 | 2019-08-06 | 扬州宏远电子股份有限公司 | Long-life high stability solid state electrode foil and its production method |
| CN110098059B (en) * | 2019-04-01 | 2020-05-05 | 扬州宏远电子股份有限公司 | Long-life high-stability solid-state electrode foil and production method thereof |
| CN110357092A (en) * | 2019-06-06 | 2019-10-22 | 宁波中车新能源科技有限公司 | A kind of activated carbon for super capacitors and its preparation method and application |
| CN111029529A (en) * | 2019-12-24 | 2020-04-17 | 北京汽车集团越野车有限公司 | Preparation method of positive electrode material structure, battery positive electrode, battery and automobile |
| CN112670091A (en) * | 2020-12-24 | 2021-04-16 | 电子科技大学 | Aluminum/carbon composite cathode foil for solid aluminum capacitor and preparation method thereof |
| CN112670090A (en) * | 2020-12-24 | 2021-04-16 | 电子科技大学 | Electrode plate and preparation method and application thereof |
| CN112670091B (en) * | 2020-12-24 | 2022-02-25 | 电子科技大学 | Aluminum/carbon composite cathode foil for solid aluminum capacitor and preparation method thereof |
| CN113140733A (en) * | 2021-03-29 | 2021-07-20 | 南通耐维特电源有限公司 | Preparation process of lithium battery based on carbon-coated aluminum foil |
| WO2023097594A1 (en) * | 2021-12-02 | 2023-06-08 | Guangdong Haozhi Technology Co. Limited | Modified current collector for secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102426924B (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102426924B (en) | High-performance aluminum/carbon composite electrode foil and preparation method thereof | |
| Murali et al. | A review on MXenes: new-generation 2D materials for supercapacitors | |
| Gao et al. | Several economical and eco-friendly bio-carbon electrodes for highly efficient perovskite solar cells | |
| Lee et al. | Performance enhancement of a lithium ion battery by incorporation of a graphene/polyvinylidene fluoride conductive adhesive layer between the current collector and the active material layer | |
| EP2675004A1 (en) | Current collector | |
| CN104192836B (en) | The solution hot preparation method of self-supporting porous graphene base film | |
| CN101923961B (en) | Carbon/aluminum composite cathode foil for solid aluminum electrolytic capacitor and preparation method thereof | |
| CN110670107B (en) | Titanium carbide nanosheet/carbon nanotube electromagnetic shielding film and preparation method thereof | |
| JP2015167127A (en) | Negative electrode material for lithium secondary battery and manufacturing method therefor, negative electrode active material composition for lithium secondary battery using negative electrode material, negative electrode for lithium secondary battery and lithium secondary battery | |
| CN109456645B (en) | Surfactant-free graphene composite conductive ink | |
| Wang et al. | A MXene‐coated activated carbon cloth for flexible solid‐state supercapacitor | |
| CN111484271B (en) | Method for preparing graphene composite conductive slurry by microwave-ultrasonic and obtained product | |
| CN109082050B (en) | Preparation method of CQDs @ PVP/PVDF composite dielectric film | |
| CN112967889B (en) | Lignin-based high-area-ratio-capacitance super-capacitor material and preparation method and application thereof | |
| CN110098443B (en) | Method for coating waste lithium battery negative electrode material with carbon | |
| CN109360962B (en) | High-stability silicon-carbon negative electrode material for lithium battery and preparation method thereof | |
| CN105186004A (en) | Copper current collector for lithium-ion battery anodes as well as preparation method and application of copper current collector | |
| CN103839683A (en) | Graphene electrode plate and preparation method thereof | |
| Shrestha et al. | Electrophoretic deposition of activated carbon YP-50 with ethyl cellulose binders for supercapacitor electrodes | |
| Zheng et al. | Fabrication and characterization of a multi-walled carbon nanotube-based counter electrode for dye-sensitized solar cells | |
| CN106206051A (en) | A kind of Graphene modified activated carbon and application thereof | |
| Tu et al. | Three-dimensional MXene/BCN microflowers for wearable all-solid-state microsupercapacitors | |
| CN108198701A (en) | A kind of cobaltosic oxide/carbon composite electrode material, preparation method and applications | |
| CN109509570B (en) | Preparation method of surface-modified graphene modified carbon electrode | |
| Li et al. | Hydrothermal fabrication of reduced graphene oxide/activated carbon/MnO 2 hybrids with excellent electrochemical performance for supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170215 Address after: 410205 Changsha hi tech Industrial Development Zone, Hunan agricultural extension building No. 202 Patentee after: Hunan Province Zhengyuan Energy Storage Materials and Device Institute Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932, Department of materials science and Engineering School of Central South University Patentee before: Li Jian Patentee before: Yao Jianjun |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170914 Address after: 226361 Jiangsu province Nantong city Nantong high tech Zone to the North West of Qingdao Road, Bihualu Jubao Industrial Park standard plant Patentee after: Yu Tung foil technology Nantong Co., Ltd. Address before: 410205 Changsha hi tech Industrial Development Zone, Hunan agricultural extension building No. 202 Patentee before: Hunan Province Zhengyuan Energy Storage Materials and Device Institute |