CN104377044A - Composite current collector for pseudo type super capacitor and manufacturing method thereof - Google Patents
Composite current collector for pseudo type super capacitor and manufacturing method thereof Download PDFInfo
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- CN104377044A CN104377044A CN201410553104.5A CN201410553104A CN104377044A CN 104377044 A CN104377044 A CN 104377044A CN 201410553104 A CN201410553104 A CN 201410553104A CN 104377044 A CN104377044 A CN 104377044A
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 13
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- 238000005516 engineering process Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
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- 238000006479 redox reaction Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a composite current collector for a pseudo type super capacitor and a manufacturing method of the composite current collector. The composite current collector comprises base materials, the single face or two faces of the base materials are coated with conductive bonding transitional layers, and conductive anti-corrosion layers are adhered to the conductive bonding transitional layers. The composite current collector is resistant to corrosion, high in electrical conductivity, simple in production process and free of solvents, the environmental requirement is met, one-time forming from raw materials to the composite current collector is achieved, the production automation degree is high, and the composite current collector is continuous, efficient and easy to produce in a large scale.
Description
Technical field
The present invention relates to a kind of collector, particularly one counterfeit electric-type ultracapacitor composite current collector and preparation method thereof.
Background technology
Along with global warming, resource shortage, various countries worldwide and area are all at the new environmental type energy of research and development, and ultracapacitor is produced material used and is commonly environmental protection.Ultracapacitor is owing to being with a wide range of applications and huge potential market and become the study hotspot in international energy field.Due to ultracapacitor have that charge/discharge rates is fast, environmentally safe, the advantage such as have extended cycle life, and promises to be novel green energy resource in this century.Just because of many significant advantages of ultracapacitor, at automobile (particularly electric automobile, fuel combination automobile and exceptional load vehicle), electric power, railway, communicate, have huge using value and market potential, thus by countries in the world institute extensive concern in national defence, consumption electronic products etc.Ultracapacitor role in car with mixed energy source is very important.There is a lot of application will use alternative energy source, such as solar energy, wind energy or fuel cell in energy mix technology.But due to the characteristic of energy source itself, the mode determining these generatings often has inhomogeneities, and electric energy exports and easily changes.This just needs to use a kind of buffer to carry out stored energy.In the automobile of above-mentioned use alternative energy source technology, ultracapacitor is a kind of novel critical component.
Adopting in fuel cell-powered automobile, if be combined ultracapacitor, so fuel cell just can meet continued power demand, and is not only that peak value is powered.Except can meeting demand that peak value powers, ultracapacitor also has other elements incomparable response time.The powerful performance of ultracapacitor and fuel cell are combined, the fuel cell system that size is less, weight is lighter, price is cheaper can be obtained.
Ultracapacitor can also with hydrogen fuel cell perfect adaptation, enable the hydrogen fuel cell being in development be applied to multiple field.Such as hydrogen cell automobile, due to much higher when the energy Ratios needed in accelerator at the uniform velocity travels.If do not have energy accumulator, hydrogen fuel cell will do very large, and to meet the highest peak energy demand, its cost is just so great that cannot be stood.By by the stored energy of surplus in energy accumulator, just can provide required peak energy by memory at short notice.
The effect of ultracapacitor in electric motor coach is particularly huge.In view of " visual pollution " and " mobility is poor ", " planning difficulty " Three Difficult Issues of trolley bus overhead wire, trolley bus is caused day by day to meet with unfrequented in China.But because oil is nervous and motor vehicle exhaust emission brings energy crisis and problem of environmental pollution show especially day by day, use automobile also imperfect selection, the awkward condition that to have caused the development of urban public transport to be absorbed in awkward.And the appearance of super capacity public transport electric car, efficiently solve this difficult problem.Ultracapacitor has become and has improved traditional electric car defect, plays the energy storage device of a kind of advanced person of the advantage such as its zero discharge, energy-conservation, low cost, low noise.Super capacity public transport electric car take ultracapacitor as the novel energy-conserving electric car of electrical source of power, and vehicle maintains the advantage of trolley bus, and without any discharge, trackless is wireless simultaneously, meets the needs of modernization environmental protection public transport completely.
New-energy automobile is the field that Global Auto industry is paid close attention to, and super capacitor is its vitals.
Ultracapacitor is mainly divided into electric double layer type ultracapacitor and oxidation-reduction type ultracapacitor.Utilize the super capacitor energy density of electric double layer capacitance too little.The fake capacitance ultracapacitor being obtained high power capacity by the electrochemical process of material surface is also rely on electrochemical process energy storage in essence, similar in essence to storage battery (such as lithium ion battery), so can be considered high specific power and long-life storage battery based on the ultracapacitor of fake capacitance.The generation form of current existing fake capacitance has: the surface chemistry adsorption desorption of (1) electrode and deficient electromotive force deposition; (2) electrode surface sull is as the redox reaction of RuO2, IrO2, Cr3O4; (3) doping and dedoping of conducting polymer; (4) surface of lithium ion embeds-deviates from.But the problems such as existing all types of fake capacitance ultracapacitor exists cycle life difference respectively, expensive, still can not meet practical requirement.
Obtaining the mode of fake capacitance based on thin liquid layer redox couple, is a kind of ultracapacitor of novel function admirable.This Novel super capacitor utilizes the redox couple in liquid phase (solution) to award nucleophobic Faradaic processes on inert solid electrode, and its active material is oxidation-reduction pair solvable in the thin liquid layer in inert electrode surface.Before and after discharge and recharge there is not chemical change and physical change in electrode solid phase.On the one hand, this ultracapacitor not only has the feature of conventional Super capacitor high-specific-power, long circulation life and high security, has more competitiveness in price simultaneously; On the other hand, owing to adopting liquid phase energy storage mode to have higher specific capacity, because of and than existing ultra-capacitor, there is higher specific energy.
The feature of this Novel super capacitor shows as high power high current charge-discharge, therefore requires the electric current that the current collector material with high electrical conductivity produces for collecting redox reaction.In addition, some high concentration redox couple electrolyte have highly acid, Strong oxdiative reproducibility at present, the metal material such as Cu that general conductance is high is not also suitable for highly acid, strong oxidizing property electrolyte, and corrosion resistant electric conducting material is if the conductivity of the material such as graphite cake or conductive plastics is well below metal material, the needs of Novel super capacitor high current charge-discharge can not be met.The collector of electrode plays a supportive role to electrode and CURRENT DISTRIBUTION effect, is the important component part of electrode.In chemical power source use procedure, the corrosion of electrolyte to collector is one of reason of chemical power source inefficacy.Therefore current collector material that is corrosion-resistant, high conductivity is developed most important for this Novel super capacitor.
Chinese patent CN101192669A adopts between the conductive film that to be clipped in by the metal foil scribbling conducting resinl and to be folded in half into " V " type, by the method for hot pressing compound or the vacuum coated method at metal collector Surface coating one deck anti-corrosion electric conducting thin-film material, pad pasting process discontinuousization, production efficiency is not high.
Summary of the invention
The object of the present invention is to provide a kind of counterfeit electric-type ultracapacitor composite current collector that is corrosion-resistant, high conductivity.
Another object of the present invention is the preparation method providing a kind of counterfeit electric-type ultracapacitor composite current collector, simple, and energy continuous prodution, production efficiency is high.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of counterfeit electric-type ultracapacitor composite current collector, comprise base material, the one side of described base material or dual coating have conductive bond transition zone, conductive bond transition zone are bonded with conduction anticorrosive coat.
The material that base material is good conductivity, intensity is high; The coating that conductive bond transition zone is good conductivity, adhesion strength is high; Conduction anticorrosive coat is the thin layer of good conductivity, resistance to strong acid, powerful oxidation corrosion resistance reproducibility.
Composite current collector of the present invention is for highly acid, strong oxidizing property electrolyte and designing; the present invention utilizes the coated high conductivity base material of conduction anticorrosive coat to protect; conduction anticorrosive coat adopts high conductive material to mix with macromolecular material; then by extruding formation conductive film through T-shaped die head after plastic extruder fusion plastification; this conductive film with uniform temperature directly fit to be coated with conductive bond transition zone base material on, thus obtain composite current collector.
Conduction anticorrosive coat, highly acid can be stoped, strong oxidizing property electrolyte directly contacts with base material, require existing good conductivity, there is electrochemicaUy inert again, it has chemical stability to electrode activity solution, the compactness of conduction anticorrosive coat wants enough, to stop acidity, strong oxidizing property active electrolyte to the corrosion of base material.
As preferably, the one in metal forming, wire netting, metal grid, Metal-Piercing net, woven wire cloth selected by described base material, and its thickness is 0.01mm-2mm.Metal is generally copper or aluminium.
As preferably, by weight, described conductive bond transition zone is mixed by 20-30 weight portion conductive component, 20-40 weight portion adhesion component, 40-60 parts by weight solvent and 2-8 weight portion auxiliary agent.
As preferably, described conductive component is selected from one or more in active carbon, activated carbon fiber, chopped carbon fiber, carbon fiber powder, carbon nano-tube, graphite, acetylene black, Graphene, Fullerene C20, carbon black; Described adhesion component is selected from one or more in epoxy resin, phenolic resins, polyurethane; Described solvent is selected from one or more in benzene,toluene,xylene, carrene, NMP, polystyrolsulfon acid; Described auxiliary agent comprises dispersant, levelling agent, thickener, lubricant and antioxidant.
The Main Function of conductive bond transition zone is the bonding being conducive to conduction anticorrosive coat and base material.In conductive bond transition zone, the content of adhesion component is less, and density is low, can form good roughness after conductive component mixes with adhesion component, and the stickup being convenient to conduction anticorrosive coat combines.The adhesion component of conductive bond transition zone is thermosetting resin, energy rapid solidification, and forms the high polymer with three-dimensional network-like structure after solidification, has excellent adhesion strength with the surface of metal and non-metallic substrate.
The selection of conductive component, not only conducts electricity very well, and can coordinate with adhesion component and form good roughness, and the stickup of anticorrosive coat of being convenient to conduct electricity combines.
As preferably, by weight percentage, described conduction anticorrosive coat is mixed by the conductive agent of 30-90% and the anticorrosion binding agent of 10-70%.The conduction anticorrosive coat density that the proportioning controlling conductive agent and anticorrosion binding agent is formed like this is high, and antiseptic property is good.
As preferably, described conductive agent is selected from one or more in active carbon, activated carbon fiber, chopped carbon fiber, carbon fiber powder, carbon nano-tube, graphite, acetylene black, Graphene, Fullerene C20, carbon black, polyaniline, polypyrrole, PEDOT; Described anticorrosion binding agent is selected from one or more in ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polymethyl methacrylate, polystyrene.
Anticorrosion binding agent is thermoplastic resin, cheap, easily processes, and these anticorrosion binder component antiseptic property itself is also better.
As preferably, described conductive bond transition region thickness is 2-50 micron, and described conduction anticorrosive coat thickness is 50-200 micron.
A preparation method for counterfeit electric-type ultracapacitor composite current collector,
(1) each for conductive bond transition zone component is mixed formation slurry, adjustment slurry viscosity is 2000-8000mPa.S, substrate surface is coated to by the mode of transfer coated, blade coating, extrusion coated or silk screen printing, dry 5-20min at 40-200 DEG C, obtains the conductive bond transition zone that thickness is 2-50 micron;
(2) each for conduction anticorrosive coat component is mixed, by extruding the anticorrosion film of conduction forming thickness 50-200 micron after plastic extruder 130-300 DEG C fusion plastification through T-shaped die head, the anticorrosion film of this conduction directly fits on conductive bond transition zone and also adopts heating twin rollers thermal-adhering, machines conduction anticorrosive coat.
On base material, coated with conductive bonding transition zone has the maturation process of large-scale industrial application, conduction anticorrosive coat forms certain thickness conductive film by extruding through T-shaped die head after plastic extruder fusion plastification, this conductive film with uniform temperature directly fits on base material, thus obtain composite current collector, be easy to the realization of large-scale industrial production.
The advantage of such preparation technology is adopted to be: simple, continuous, efficient.
As preferably, the binding temperature of thermal-adhering controls as 80-200 DEG C.
A counterfeit electric-type ultracapacitor prepared by composite current collector of the present invention, comprises the basic structural unit that at least one is made up of positive pole composite current collector, positive electrode, barrier film, negative electrode and negative pole composite current collector.
The invention has the beneficial effects as follows: composite current collector of the present invention is corrosion-resistant, conductivity is high, production technology is simple, does not need solvent, meet environmental requirement, realize the one-shot forming of raw material → composite current collector, production automation degree is high, continuously, efficiently, large-scale production is easy to.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of the counterfeit electric-type ultracapacitor that composite current collector of the present invention is assembled into.
Fig. 2 is the another kind of structural representation of the counterfeit electric-type ultracapacitor that composite current collector of the present invention is assembled into.
Fig. 3 is the process chart of composite current collecting preparation of the present invention.
In figure: 1, base material, 2, conductive bond transition zone, 3, conduction anticorrosive coat, 4, positive electrode, 5, barrier film, 6, negative electrode, 7, external lug, 8, aluminum plastic film, 9, plastic extruder, 10, heating twin rollers, 11, conduct electricity anticorrosion film.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1:
A kind of counterfeit electric-type ultracapacitor composite current collector, comprise base material 1, Copper Foil selected by base material 1, its thickness is 0.01mm, the one side of described base material 1 is coated with conductive bond transition zone 2, conductive bond transition zone 2 thickness is 2 microns, conductive bond transition zone 2 is bonded with conduction anticorrosive coat 3, and conduction anticorrosive coat 3 thickness is 50 microns (see accompanying drawings 1).
Preparation method:
(1) each for conductive bond transition zone component is mixed formation slurry, adjustment slurry viscosity is 8000mPa.S, is coated to substrate surface by the mode of transfer coated, dry 20min at 40 DEG C, obtains the conductive bond transition zone that thickness is 2 microns.
By weight, each amounts of components of conductive bond transition zone be 20 weight portion conductive components (active carbon), 20 weight portion adhesion components (polyurethane resin), 40 parts by weight solvent (benzene) and 2 weight portion auxiliary agents (being mixed according to the weight ratio of 1:1:1:1:1 by dispersant (polyethylene glycol), levelling agent (BYK-333), thickener (CMC), lubricant (calcium stearate) and antioxidant (antioxidant 1010)).
(2) each for conduction anticorrosive coat component is mixed, after 130 DEG C of fusion plastifications, extruded the anticorrosion film 11 of conduction forming thickness 50 microns through T-shaped die head by plastic extruder 9, the anticorrosion film of this conduction directly fits on conductive bond transition zone and also adopts heating twin rollers 10 thermal-adhering, the binding temperature of thermal-adhering controls to be 80 DEG C, machines conduction anticorrosive coat (see accompanying drawing 3).
By weight percentage, each amounts of components of described conduction anticorrosive coat is the conductive agent (active carbon) of 30% and the anticorrosion binding agent (polyethylene and polystyrene are according to the mixture of the mass ratio of 1:1) of 70%.
Embodiment 2:
A kind of counterfeit electric-type ultracapacitor composite current collector, comprise base material 1, aluminium sheet grid selected by base material 1, its thickness is 2mm, the one side of described base material 1 is coated with conductive bond transition zone 2, conductive bond transition zone 2 thickness is 50 microns, conductive bond transition zone 2 is bonded with conduction anticorrosive coat 3, and conduction anticorrosive coat 3 thickness is 200 microns (see accompanying drawings 1).
Preparation method:
(1) each for conductive bond transition zone component is mixed formation slurry, adjustment slurry viscosity is 2000mPa.S, is coated to substrate surface by the mode of blade coating, dry 5min at 200 DEG C, obtains the conductive bond transition zone that thickness is 50 microns.
By weight, the each amounts of components of conductive bond transition zone is 30 weight portion conductive components (carbon fiber powder and carbon nano-tube are according to the mixtures of the mass ratio of 1:1), 40 weight portion adhesion components (epoxy resin and phenolic resins are according to the mixture of the mass ratio of 1:1), 60 parts by weight solvent (toluene and dimethylbenzene are according to the mixture of the mass ratio of 1:1) and 8 weight portion auxiliary agents are (by dispersant (polyethylene glycol), levelling agent (BYK-333), thickener (CMC), lubricant (calcium stearate) and antioxidant (antioxidant 1010) mix according to the weight ratio of 1:1:1:1:1).
(2) each for conduction anticorrosive coat component is mixed, by extruding the anticorrosion film of conduction forming thickness 200 microns after plastic extruder 300 DEG C of fusion plastifications through T-shaped die head, the anticorrosion film of this conduction directly fits on conductive bond transition zone and also adopts heating twin rollers thermal-adhering, the binding temperature of thermal-adhering controls to be 200 DEG C, machines conduction anticorrosive coat.
By weight percentage, each amounts of components of described conduction anticorrosive coat is the conductive agent (polyaniline and polypyrrole are according to the mixture of the mass ratio of 1:1) of 90% and the anticorrosion binding agent (ethylene-vinyl acetate copolymer) of 10%.
Embodiment 3:
A kind of counterfeit electric-type ultracapacitor composite current collector, comprise base material 1, Copper Foil selected by base material 1, its thickness is 0.5mm, the one side of described base material 1 is coated with conductive bond transition zone 2, conductive bond transition zone 2 thickness is 10 microns, conductive bond transition zone 2 is bonded with conduction anticorrosive coat 3, and conduction anticorrosive coat 3 thickness is 100 microns (see accompanying drawings 1).
Preparation method:
(1) each for conductive bond transition zone component is mixed formation slurry, adjustment slurry viscosity is 5000mPa.S, is coated to substrate surface by the mode of silk screen printing, dry 10min at 100 DEG C, obtains the conductive bond transition zone that thickness is 10 microns.
By weight, each amounts of components of conductive bond transition zone be 25 weight portion conductive components (Graphene), 30 weight portion adhesion components (phenolic resins), 50 parts by weight solvent (polystyrolsulfon acid) and 5 weight portion auxiliary agents (being mixed according to the weight ratio of 1:1:1:1:1 by dispersant (polyethylene glycol), levelling agent (BYK-333), thickener (CMC), lubricant (calcium stearate) and antioxidant (antioxidant 1010)).
(2) each for conduction anticorrosive coat component is mixed, by extruding the anticorrosion film of conduction forming thickness 100 microns after plastic extruder 200 DEG C of fusion plastifications through T-shaped die head, the anticorrosion film of this conduction directly fits on conductive bond transition zone and also adopts heating twin rollers thermal-adhering, the binding temperature of thermal-adhering controls to be 120 DEG C, machines conduction anticorrosive coat.
By weight percentage, each amounts of components of described conduction anticorrosive coat is the conductive agent (carbon nano-tube) of 50% and the anticorrosion binding agent (polymethyl methacrylate) of 50%.
By the graphite felt (porosity 80%) of thickness 1mm as positive electrode 4 and negative electrode 6, be assembled into capacitance core with composite current collector of the present invention and barrier film 5,2M VOSO
4/ (VO
2)
2sO
4+ 1MH
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1M H
2sO
4as electrolyte liquid, both positive and negative polarity reserves lug, by the external external lug 7 with heat-seal adhesive of switching weldering, encapsulates to obtain the counterfeit electric-type ultracapacitor of one chip (see accompanying drawing 1) with aluminum plastic film 8.
Embodiment 4:
A kind of counterfeit electric-type ultracapacitor composite current collector, comprise base material 1, Copper Foil selected by base material 1, its thickness is 0.5mm, the dual coating of described base material 1 has conductive bond transition zone 2, conductive bond transition zone 2 thickness is 10 microns, two-layer conductive bond transition zone 2 is all bonded with conduction anticorrosive coat 3, and conduction anticorrosive coat 3 thickness is 100 microns (see accompanying drawings 2).
Preparation method:
(1) each for conductive bond transition zone component is mixed formation slurry, adjustment slurry viscosity is 5000mPa.S, is coated to substrate surface by the mode of silk screen printing, dry 10min at 100 DEG C, obtains the conductive bond transition zone that thickness is 10 microns.
By weight, each amounts of components of conductive bond transition zone be 25 weight portion conductive components (Graphene), 30 weight portion adhesion components (phenolic resins), 50 parts by weight solvent (polystyrolsulfon acid) and 5 weight portion auxiliary agents (being mixed according to the weight ratio of 1:1:1:1:1 by dispersant (polyethylene glycol), levelling agent (BYK-333), thickener (CMC), lubricant (calcium stearate) and antioxidant (antioxidant 1010)).
(2) each for conduction anticorrosive coat component is mixed, by extruding the anticorrosion film of conduction forming thickness 100 microns after plastic extruder 200 DEG C of fusion plastifications through T-shaped die head, the anticorrosion film of this conduction directly fits on conductive bond transition zone and also adopts heating twin rollers thermal-adhering, the binding temperature of thermal-adhering controls to be 120 DEG C, machines conduction anticorrosive coat.
By weight percentage, each amounts of components of described conduction anticorrosive coat is the conductive agent (carbon nano-tube) of 50% and the anticorrosion binding agent (polymethyl methacrylate) of 50%.
By the graphite felt (porosity 80%) of thickness 1mm as positive electrode 4 and negative electrode 6, with composite current collector of the present invention and barrier film 5, dress up shunt capacitance core by stack of laminations, 2M VOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1M H
2sO
4as electrolyte liquid, both positive and negative polarity reserves lug, by the external external lug 7 with heat-seal adhesive of switching weldering, encapsulates to obtain multi-electrode counterfeit electric-type ultracapacitor (see accompanying drawing 2) in parallel with aluminum plastic film 8.
Composite current collector antiseptic property test of the present invention:
Drop on the conduction anticorrosive coat of composite current collector with the salpeter solution of 2mol/L, after the week, the constant indigo plant of nitric acid drop, antiseptic property is better.
Conducting performance test: the sheet resistance adopting four probe method to record conduction anticorrosive coat is 10
2~ 10
5Ω/square.
Conduction anticorrosive coat conductivity test: with the anticorrosion film of the conduction of a wide 1cm (conduction anticorrosive coat), draw the contact point of two lines as universal instrument two test pencils at the 1cm place that is separated by.Then the anticorrosion film that will conduct electricity leads to 100mA constant-current source, and surveying its voltage with universal instrument is U, by
calculate resistance, then by
d is thickness, unit m) calculate the anticorrosion film conductivity of conduction, ρ=0.7-1.0 Ω .m.
Adopt the composite current collector of the present invention of 5cm × 9cm to assemble the ultracapacitor list battery core that capacity is 75mAh, internal resistance is 20 ~ 40m Ω.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (10)
1. a counterfeit electric-type ultracapacitor composite current collector, comprises base material, it is characterized in that: the one side of described base material or dual coating have conductive bond transition zone, conductive bond transition zone is bonded with conduction anticorrosive coat.
2. counterfeit electric-type ultracapacitor composite current collector according to claim 1, is characterized in that: the one in metal forming, wire netting, metal grid, Metal-Piercing net, woven wire cloth selected by described base material, and its thickness is 0.01mm-2mm.
3. counterfeit electric-type ultracapacitor composite current collector according to claim 1 and 2, it is characterized in that: by weight, described conductive bond transition zone is mixed by 20-30 weight portion conductive component, 20-40 weight portion adhesion component, 40-60 parts by weight solvent and 2-8 weight portion auxiliary agent.
4. counterfeit electric-type ultracapacitor composite current collector according to claim 3, is characterized in that: described conductive component is selected from one or more in active carbon, activated carbon fiber, chopped carbon fiber, carbon fiber powder, carbon nano-tube, graphite, acetylene black, Graphene, Fullerene C20, carbon black; Described adhesion component is selected from one or more in epoxy resin, phenolic resins, polyurethane; Described solvent is selected from one or more in benzene,toluene,xylene, carrene, NMP, polystyrolsulfon acid; Described auxiliary agent comprises dispersant, levelling agent, thickener, lubricant and antioxidant.
5. counterfeit electric-type ultracapacitor composite current collector according to claim 1 and 2, is characterized in that: by weight percentage, and described conduction anticorrosive coat is mixed by the conductive agent of 30-90% and the anticorrosion binding agent of 10-70%.
6. counterfeit electric-type ultracapacitor composite current collector according to claim 5, is characterized in that: described conductive agent is selected from one or more in active carbon, activated carbon fiber, chopped carbon fiber, carbon fiber powder, carbon nano-tube, graphite, acetylene black, Graphene, Fullerene C20, carbon black, polyaniline, polypyrrole, PEDOT; Described anticorrosion binding agent is selected from one or more in ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polymethyl methacrylate, polystyrene.
7. counterfeit electric-type ultracapacitor composite current collector according to claim 1 and 2, is characterized in that: described conductive bond transition region thickness is 2-50 micron, and described conduction anticorrosive coat thickness is 50-200 micron.
8. the preparation method of counterfeit electric-type ultracapacitor composite current collector as claimed in claim 1, is characterized in that:
(1) each for conductive bond transition zone component is mixed formation slurry, adjustment slurry viscosity is 2000-8000mPa.S, substrate surface is coated to by the mode of transfer coated, blade coating, extrusion coated or silk screen printing, dry 5-20min at 40-200 DEG C, obtains the conductive bond transition zone that thickness is 2-50 micron;
(2) each for conduction anticorrosive coat component is mixed, by extruding the anticorrosion film of conduction forming thickness 50-200 micron after plastic extruder 130-300 DEG C fusion plastification through T-shaped die head, the anticorrosion film of this conduction directly fits on conductive bond transition zone and also adopts heating twin rollers thermal-adhering, machines conduction anticorrosive coat.
9. preparation method according to claim 8, is characterized in that: the binding temperature of thermal-adhering controls as 80-200 DEG C.
10. the counterfeit electric-type ultracapacitor adopting composite current collector according to claim 1 to prepare, is characterized in that: comprise the basic structural unit that at least one is made up of positive pole composite current collector, positive electrode, barrier film, negative electrode and negative pole composite current collector.
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| CN104882614A (en) * | 2015-04-28 | 2015-09-02 | 超威电源有限公司 | Lead-acid battery plate with high energy density |
| CN105609703A (en) * | 2015-12-25 | 2016-05-25 | 超威电源有限公司 | Integrated electrode and fabrication method |
| CN111313030A (en) * | 2020-03-02 | 2020-06-19 | 太仓中科赛诺新能源科技有限公司 | Corrosion-resistant composite current collector of water-based battery and preparation method of corrosion-resistant composite current collector |
| CN111334026A (en) * | 2020-03-12 | 2020-06-26 | 周洪光 | PU conductive and heating carbon film and preparation method thereof |
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| CN104377044B (en) | 2017-06-30 |
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