CN104112605A - Electrode plate, manufacturing method thereof, supercapacitor and manufacturing method thereof - Google Patents
Electrode plate, manufacturing method thereof, supercapacitor and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses an electrode plate and a manufacturing method thereof. The manufacturing method includes the following steps that conductive slurry coats one surface of a plain foil, rolling crimping is conducted after the slurry is dried to form a conductive coating, the conductive slurry is formed by mixing metal powder, carbon material powder, dispersing agent, bonding resin and first solvent, high temperature carbonizing is conducted on the plain foil with the formed conductive coating, and the conductive coating is carbonized to form a carbon-covering conductive layer, activated slurry coats the carbon-covering conductive layer, and rolling crimping is conducted after drying to obtain the electrode plate. According to the electrode plate manufacturing method, the bonding resin is carbonized under high temperature processing, the conductive coating is converted to be the carbon-covering conductive layer, the carbon-covering conductive layer is combined with the plain foil through carbon bond-metal, the combination strength is high, and the active layer is closely combined with the plain foil through the carbon-covering conductive layer. A supercapacitor of the electrode plate and a manufacturing method of the supercapacitor are further disclosed.
Description
Technical field
The present invention relates to energy storage device field, particularly relate to a kind of electrode slice and preparation method thereof, adopt ultracapacitor of this electrode slice and preparation method thereof.
Background technology
Ultracapacitor be grew up in the last few years between conventional electrostatic capacitor and chemical power source, energy-storage travelling wave tube in the spy based on Cathode/Solution Interface electrochemical process.Its application contains little of intelligent instrument, electric tool, camera flash-light, street lamp etc., large breaking-closing operating power supply that arrives wind power station, electric automobile, electric locomotive, electroporation equipment, high-voltage switch gear etc., and its application is also continuing expansion, has immeasurable market capacity.
Ultracapacitor is comprised of positive pole, negative pole, electrolyte, barrier film, collector and package casing, and electrode slice is wherein important composition parts.The manufacturing process of super capacitor electrode slice has two kinds, and a kind of is cloth of coating-type, and another kind is diaphragm type.Positive/negative electrode is comprised of positive/negative electrode active material and positive/negative electrode current collecting body, and positive/negative electrode active material comprises by non-porous material with carbon element and porous carbon materials are mixed to the material obtaining.Collector is generally selected the materials such as high-purity aluminum foil, stainless (steel) wire, corrosive aluminum foil and nickel of chemically-resistant and electrochemical corrosion.
The concrete grammar of cloth of coating-type: electrode material is made to slurry, be coated on the collectors such as high-purity aluminum foil or corrosive aluminum foil, dry and make electrode slice.But because adhesion strength between the pole piece of this method and collector is little, in the technical processs such as follow-up roll-in, coiling, there is the phenomenon of dry linting in electrode active material layers, electrode is further processed into after ultracapacitor, product is in large electric current high-frequency charge and discharge process, coating can with collector separated peeling off gradually, the internal resistance of ultracapacitor product is increased gradually, hydraulic performance decline.For this reason, conventionally in active material layer, add more binding agent to improve the adhesion of coating and collector.But along with the increase of consumption of binder, the energy density of ultracapacitor reduces.
The concrete grammar of diaphragm type: by electrode material mixed-powder through roll-in, by semisolid, be shaped to solid-state, to form diaphragm.During use, diaphragm is pressed onto on wire netting or with conducting resinl and is adhered in metal forming, make pole piece.Binding agent mainly adopts polytetrafluoroethylene (PTFE) at present, and PTFE has high expansion coefficient, there will be Swelling in macromolecule electrolyte, thereby causes the problem that the adhesion between electrode material and collector declines.In high low temperature charge and discharge process, the situation that generating electrodes material is peeled off from collection liquid surface, the problem such as cause the stability of ultracapacitor to decline, internal resistance increases, electric leakage rheology is large.
On November 27th, 2013, apply for that disclosed Chinese patent CN103413693A discloses a kind of manufacture method that the invention discloses a kind of ultracapacitor, wherein, in order to improve the cohesive force between corrosive aluminum foil and electrode slurry, adopt and first on corrosive aluminum foil, apply one deck conductive adhesive, the method of electrode coated slurry on conductive adhesive again, what make that electrode slurry can be stable pastes on corrosive aluminum foil, thereby the electrode making can bear 150t to 200t pressure compacting and can not produce electrode slurry pull-up and fall, the problem of distortion, electrode slurry bed of material density reachable to 0.65 is between 0.70.In this invention, the preparation of conductive adhesive layer: Graphene, conductive black, carboxymethyl cellulose and water are mixed, be coated on aluminium foil, hyperthermia drying forms the conductive adhesive layer of 1 μ m to 10 μ m.But, and the temperature and time of not mentioned high temperature drying is, the cost of Graphene is higher.Though this method can reach the effect that conductive adhesive layer is attached to the collection liquid surfaces such as aluminium foil, but its method of adhering to is that electrocondution slurry is coated on to aluminium foil surface, dry and form conductive adhesive layer, only in the mode of binding agent or solvent bonding, the material itself such as Graphene, conductive black that not only makes to form conductive adhesive layer easily comes off, thereby insecure with the adhesion of second layer electrode material layer, easily generating electrodes material layer comes off from conductive adhesive layer surface, affects the performance of ultracapacitor.
In on 04 09th, 2014, authorize disclosed Chinese patent CN102543481B to disclose a kind of manufacture method of ultracapacitor, wherein, in order to solve between collector and electrode slice the problems such as the little and electrode slice internal bond strength of adhesion strength is little, by metal collector surface roughening is processed, active material, electric conducting material, compound binding agent are mixed, be pressed into thickness at the pole piece of 30～100 μ m, pole piece be bonded in to the collection liquid surface that applies one deck conducting resinl, form band electrode.Wherein, as the raw material of collector, be that purity is at least 99.9wt%, the metal aluminum or aluminum alloy of copper content below 0.005wt%.In this technical process, one deck conductive adhesive layer of introducing between active material layer and collector not mentioned concrete material and treatment process.Conventionally, employing be the product of similar EB-012, mainly by graphite, carbon dust, water-base resin and solvent etc., formed, on the low side, the bonding mechanical property of its conductivity is poor.Because compound binding agent easily solidifies, still there is the not strong problem of adhesive force between coating and collector in kind electrode sheet.
Summary of the invention
Based on this, be necessary to provide electrode slice that a kind of adhesive force is stronger and preparation method thereof.
In addition, be also necessary to provide a kind of ultracapacitor that uses this electrode slice and preparation method thereof.
A preparation method for electrode slice, comprises the steps:
A surface-coated electrocondution slurry at light paper tinsel, after dry, form the conductive paste bed of material, then roll-in crimping forms conductive coating, wherein, described electrocondution slurry is that metal dust, material with carbon element powder, dispersant, binding resin and the first solvent form, and the solid content of described electrocondution slurry is 10%～30%;
Under reducibility gas atmosphere or protective gas atmosphere, to being formed with the described smooth paper tinsel of conductive coating, carry out high temperature cabonization processing, described conductive coating carbonization forms covers carbonaceous conductive layer; And
Described covering on carbonaceous conductive layer, apply active slurry, after dry, roll-in crimping forms active layer, obtains described electrode slice, wherein, described active slurry is that active material, conductive agent, binding agent and the second solvent form, and the solid content of described active slurry is 10%～30%.
In one embodiment, in described electrocondution slurry, the mass ratio of described metal dust, described material with carbon element powder, described dispersant and described binding resin is 20～35:20～35:5～25:6～25.
In one embodiment, the particle diameter of described metal dust is 30nm～200 μ m, and the material of described metal dust is selected from least one in aluminium, nickel, silver, titanium, manganese, magnesium, potassium and oxide thereof and hydroxide;
Described material with carbon element powder is selected from least one in graphene powder, conductive black, carbon nano-tube, carbon fiber, acetylene black, active carbon powder and powdered graphite;
Described dispersant is selected from least one in BYK190, BYK182 and BYK162;
Described binding resin is selected from least one in epoxy resin, phenolic resins, acrylonitrile resin, butyral resin, acrylate and polyurethane.
In one embodiment, the thickness of the described conductive paste bed of material is 0.5 μ m～50 μ m, described in cover carbonaceous conductive layer thickness be 0.01 μ m～3 μ m.
In one embodiment, to being formed with the described smooth paper tinsel of conductive coating, carry out in the operation of high temperature cabonization processing, the temperature that described high temperature cabonization is processed is 300 ℃～600 ℃, and the time that described high temperature cabonization is processed is 6h～24h.
In one embodiment, in described active slurry, the mass ratio of described active material, described conductive agent and described binding agent is 80～94:10～2:10～4;
The thickness of described active layer is 50 μ m～200 μ m;
Described active material is selected from least one in active carbon, carbon nano-tube, carbon fiber, Graphene, metal oxide, polyaniline and polypyrrole;
Described conductive agent is acetylene black, conductive black or graphite powder, and the particle diameter of described conductive agent is 0.1 μ m～3 μ m;
Described binding agent is LA132, polytetrafluoroethylene, Kynoar, carboxymethyl cellulose or polyvinyl alcohol.
An electrode slice, adopts the preparation method of above-mentioned electrode slice to prepare.
A ultracapacitor, described ultracapacitor adopts above-mentioned electrode slice.
A preparation method for ultracapacitor, comprises the steps:
Adopt the preparation method of above-mentioned electrode slice to prepare electrode slice;
Described electrode slice is cut into the shape of regulation;
Barrier film and the described electrode slice cutting are made to pocket type electrode, the described electrode slice cutting and described pocket type electrode are stacked to rear soldering polar ear successively, then put into aluminum plastic film and sealing two ends; And
By the described aluminum plastic film of sealing two ends vacuumize 12h～24h at 80 ℃～120 ℃, then under dry protective gas atmosphere, inject electrolyte, finally, by described aluminum plastic film sealing, obtain described ultracapacitor.
In one embodiment, described barrier film is cellulose paper, porous polypropylene, porous Teflon, porous Kynoar or porous polyethylene;
Described electrolyte is the organic solution of the tetraethyl ammonium tetrafluoroborate methyltriethylammonitetrafluoroborate tetrafluoroborate of 0.5mol/L～3mol/L, and the solvent of described electrolyte is propene carbonate or acetonitrile.
Kind electrode piece preparation method, by form the conductive coating that material is the mixture of metal dust, material with carbon element powder, dispersant and binding resin on light paper tinsel, binding resin carbonization under high-temperature process, conductive coating transforms to form and covers carbonaceous conductive layer, cover carbonaceous conductive layer by carbon bond-metal be combined with light paper tinsel thereby bond strength higher, then form active layer covering on carbonaceous conductive layer, active layer is by covering carbonaceous conductive layer and light paper tinsel combines closely.With respect to traditional electrode slice, the adhesive force of the electrode slice that kind electrode piece preparation method makes is stronger.
Accompanying drawing explanation
Fig. 1 is preparation method's the flow chart of the collector of an execution mode;
Fig. 2 is preparation method's the flow chart of the ultracapacitor of an execution mode.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
The preparation method of an execution mode electrode slice as shown in Figure 1, comprises the steps:
S110, at a surface-coated electrocondution slurry of light paper tinsel, form the conductive paste bed of material after dry, then roll-in crimping forms conductive coating.
Light paper tinsel can be aluminium foil, corrosive aluminum foil, Copper Foil, corrosion Copper Foil etc.
Electrocondution slurry can form for metal dust, material with carbon element powder, dispersant, binding resin and the first solvent, and the solid content of electrocondution slurry is 10%～30%.
In electrocondution slurry, the mass ratio of metal dust, material with carbon element powder, dispersant and binding resin is 20～35:20～35:5～25:6～25.
The particle diameter of metal dust is 30nm～200 μ m, and the material of metal dust is selected from least one in aluminium, nickel, silver, titanium, manganese, magnesium, potassium and oxide thereof and hydroxide.
In a preferred embodiment, the particle diameter of metal dust is 100nm～50 μ m.
Material with carbon element powder is selected from least one in graphene powder, conductive black, carbon nano-tube, carbon fiber, acetylene black, active carbon powder and powdered graphite.
Dispersant is selected from least one in BYK190, BYK182 and BYK162.
Binding resin is selected from least one in epoxy resin, phenolic resins, acrylonitrile resin, butyral resin, acrylate and polyurethane.
The thickness of the conductive paste bed of material is 0.5 μ m～50 μ m.
The first solvent is selected from least one in ethanol, butanone, acetone, toluene and ethyl acetate.
In S110, dry condition can be for ventilating and dry at 80 ℃～150 ℃.
In S110, the pressure selection 10t～20t of roll-in crimping.
S120, under reducibility gas atmosphere or protective gas atmosphere, the light paper tinsel that is formed with conductive coating that S110 is obtained carries out high temperature cabonization processing, conductive coating carbonization forms covers carbonaceous conductive layer.
Reducibility gas is selected from least one in methane, ethane, butane and hydrogen.
Protective gas is nitrogen, helium, neon, argon gas or Krypton.
The thickness that covers carbonaceous conductive layer is 0.01 μ m～3 μ m.
In high temperature cabonization processing procedure, can select normal pressure, decompression or pressurization.
The temperature that high temperature cabonization is processed is 300 ℃～600 ℃, and the time that high temperature cabonization is processed is 6h～24h.
At one, preferably in embodiment, the temperature that high temperature cabonization is processed is 500 ℃～600 ℃, and the time that high temperature cabonization is processed is 6h～10h.
S130, covering on carbonaceous conductive layer of obtaining at S120 apply active slurry, dry after roll-in crimping form active layer, obtain electrode slice.
Active slurry is that active material, conductive agent, binding agent and the second solvent form, and the solid content of active slurry is 10%～30%.
The thickness that covers carbonaceous conductive layer is 0.01 μ m～3 μ m.
In active slurry, the mass ratio of active material, conductive agent and binding agent is 80～94:10～2:10～4.
The thickness of active layer is 50 μ m～200 μ m.
Active material is selected from least one in active carbon, carbon nano-tube, carbon fiber, Graphene, metal oxide, polyaniline and polypyrrole.
Conductive agent is acetylene black, conductive black or graphite powder, and the particle diameter of conductive agent is 0.1 μ m～3 μ m.
Binding agent is acrylonitrile multiple copolymer (LA132), polytetrafluoroethylene, Kynoar, carboxymethyl cellulose or polyvinyl alcohol.
The second solvent is selected from least one in water, ethanol, butanone, acetone, toluene and ethyl acetate.
In S130, dry condition can be for ventilating and dry at 80 ℃～160 ℃.
In S130, the pressure selection 10t～20t of roll-in crimping.
Kind electrode piece preparation method, by form the conductive coating that material is the mixture of metal dust, material with carbon element powder, dispersant and binding resin on light paper tinsel, binding resin carbonization under high-temperature process, conductive coating transforms to form and covers carbonaceous conductive layer, cover carbonaceous conductive layer by carbon bond-metal be combined with light paper tinsel thereby bond strength higher, then form active layer covering on carbonaceous conductive layer, active layer is by covering carbonaceous conductive layer and light paper tinsel combines closely.With respect to traditional electrode slice, the adhesive force of the electrode slice that kind electrode piece preparation method makes is stronger.
In addition, kind electrode sheet good conductivity, the electrode mechanical strength of making is large, is easy to serialization and produces.
The invention also discloses a kind of electrode slice, adopt the preparation method of above-mentioned electrode slice to prepare.
The electrode slice preparing comprises the light paper tinsel that stacks gradually, covers carbonaceous conductive layer and active layer.Cover that carbonaceous conductive layer is combined with light paper tinsel by carbon bond-metal thereby bond strength is higher, active layer is by covering carbonaceous conductive layer and light paper tinsel combines closely.With respect to traditional electrode slice, the adhesive force of electrode slice is stronger.
The invention also discloses a kind of ultracapacitor, adopt above-mentioned electrode slice.
The preparation method of the ultracapacitor of an execution mode as shown in Figure 2, comprises the steps:
S210, adopt the preparation method of above-mentioned electrode slice to prepare electrode slice, and the electrode slice obtaining is cut into the shape of regulation.
In S210, can electrode slice be cut into rectangle, strip with banding machine and pole piece die-cutting machine.
S220, the electrode slice cutting that barrier film and S210 are obtained are made pocket type electrode, and the electrode slice cutting and pocket type electrode that S210 is obtained stack rear soldering polar ear successively, then put into aluminum plastic film and sealing two ends.
In S220, on employing closedtop machine, by tab and aluminum plastic film heat-sealing, make aluminum plastic film sealing two ends.
Aluminum plastic film vacuumize 12h～24h at 80 ℃～120 ℃ of S230, sealing two ends that S220 is obtained then injects electrolyte under dry protective gas atmosphere, finally, by aluminum plastic film sealing, obtains ultracapacitor.
Preferably, the vacuum drying temperature of aluminum plastic film is 100 ℃.
Barrier film can be cellulose paper, porous polypropylene, porous Teflon, porous Kynoar or porous polyethylene.
Electrolyte is the organic solution of the tetraethyl ammonium tetrafluoroborate methyltriethylammonitetrafluoroborate tetrafluoroborate of 0.5mol/L～3mol/L, and the solvent of electrolyte is propene carbonate or acetonitrile.
This ultracapacitor internal resistance is low, has good capability retention and cycle life, and under 1A electric current, carrying out capability retention after charge-discharge test 20,000 times is 91%.
Be specific embodiment below.
Embodiment 1
The aluminium powder, conductive black, BYK190 and the epoxy resin that by particle diameter, are 5 μ m are after 25:35:15:25 mixes according to mass ratio, with ethanol, are that to be mixed with solid content be 10% electrocondution slurry to solvent.
Utilizing intaglio press is on the corrosive aluminum foil of 30 μ m at thickness by electrocondution slurry gravure, and after drying at 100 ℃, forming thickness is the conductive paste bed of material of 50 μ m.To be formed with corrosive aluminum foil roll-in on the roll squeezer of 10t of the conductive paste bed of material, put at 500 ℃ of the high temperature process furnances of nitrogen high vacuum and process 10h after completing, obtain being formed with the corrosive aluminum foil that covers carbonaceous conductive layer after cooling, the thickness that covers carbonaceous conductive layer is 3 μ m.
Active carbon and acetylene black is even in plough coulter type stirrer for mixing, LA132 (as binding agent) is added to stirring and dissolving in suitable quantity of water simultaneously, binding agent slurry is slowly added in the stirring that powder is housed and to continue to stir, make solid content and be 30% active slurry.Wherein, the mass ratio of active carbon, acetylene black and LA132 is 85:10:5.
On coating machine, the active slurry mixing is evenly coated in and is covered on carbonaceous conductive layer, after drying, roll-in crimping formation thickness is the active layer of 120 μ m, obtains required electrode slice.
The present embodiment makes is formed with the corrosive aluminum foil that covers carbonaceous conductive layer and has high conduction performance, and sheet resistance is less than 80m Ω; Strong adhesion, there is not peeling phenomenon in 1min in HCl solution; Adopt the test of 3M Scotch adhesive tape delamination, coating is intact.
Embodiment 2
The nickel powder that is 30nm by particle diameter, graphene powder, BYK182 and phenolic resins are after 28:32:22:18 mixes according to mass ratio, with butanone, are that to be mixed with solid content be 10% electrocondution slurry to solvent.
Utilizing intaglio press is on the aluminium foil of 30 μ m at thickness by electrocondution slurry gravure, and after drying at 80 ℃, forming thickness is the conductive paste bed of material of 0.5 μ m.To be formed with aluminium foil roll-in on the roll squeezer of 20t of the conductive paste bed of material, put at 300 ℃ of the high temperature process furnances of helium high vacuum and process 24h after completing, obtain being formed with the corrosive aluminum foil that covers carbonaceous conductive layer after cooling, the thickness that covers carbonaceous conductive layer is 0.01 μ m.
Carbon nano-tube and conductive black is even in high speed dispersion stirrer for mixing, Kynoar is added to stirring and dissolving in proper amount of acetone simultaneously, Kynoar slurry is slowly added in the stirring that powder is housed and to continue to stir, make solid content and be 10% active slurry.Wherein, the mass ratio of carbon nano-tube, conductive black and Kynoar is 90:5:5.
On coating machine, the active slurry mixing is evenly coated in and is covered on carbonaceous conductive layer, after drying, roll-in crimping formation thickness is the active layer of 50 μ m, obtains required electrode slice.
Embodiment 3
The nickel powder, carbon fiber, BYK162 and the acrylate that by particle diameter, are 200 μ m are after 32:25:18:25 mixes according to mass ratio, with toluene, are that to be mixed with solid content be 30% electrocondution slurry to solvent.
Utilizing intaglio press is on the Copper Foil of 30 μ m at thickness by electrocondution slurry gravure, and after drying at 80 ℃, forming thickness is the conductive paste bed of material of 0.5 μ m.To be formed with Copper Foil roll-in on the roll squeezer of 15t of the conductive paste bed of material, put at 600 ℃ of the high temperature process furnances of methane high vacuum and process 6h after completing, obtain being formed with the corrosive aluminum foil that covers carbonaceous conductive layer after cooling, the thickness that covers carbonaceous conductive layer is 3 μ m.
Polyaniline and graphite powder is even in stirrer for mixing, polyvinyl alcohol is added to stirring and dissolving in appropriate ethyl acetate simultaneously, polyvinyl alcohol pulp is slowly added in the stirring that powder is housed and to continue to stir, make solid content and be 20% active slurry.Wherein, the mass ratio of polyaniline, graphite powder and polyvinyl alcohol is 80:6:14.
On coating machine, the active slurry mixing is evenly coated in and is covered on carbonaceous conductive layer, after drying, roll-in crimping formation thickness is the active layer of 200 μ m, obtains required electrode slice.
Embodiment 4
The electrode slice that embodiment 1 is made is cut into rectangular sheet according to required specification, and makes pocket type electrode slice on pocket type diaphragm machine, and the electrode slice of pocket type electrode slice and pocket type processing is stacked successively, and soldering polar ear, puts into aluminum plastic film sealing two ends.Put it into 24h in 120 ℃ of vacuum drying chambers.Under dry protective atmosphere, inject electrolyte, the carbonic allyl ester solution of the tetraethyl ammonium tetrafluoroborate that electrolyte is 1mol/L, envelope makes ultracapacitor eventually.
The internal resistance of the ultracapacitor that embodiment 4 makes is low, and under 1A electric current, 20,000 capability retentions of charge-discharge test are 91%.
Embodiment 5
Other conditions are with embodiment 4, and difference is to take that nickel powder and al powder mixt that particle diameter is 100nm replace the aluminium powder in embodiment 4, with carbon nano-tube, replaces the conductive black in embodiment 4.
Low 5% left and right of ultracapacitor that the internal resistance of the ultracapacitor that embodiment 5 makes makes than embodiment 4, cycle performance is than high 7% left and right in embodiment 1.
Embodiment 6
Other conditions are with embodiment 4, and difference is to replace the epoxy resin in embodiment with phenolic resins, and the nitrogen atmosphere with in the mixing reducing atmosphere replacement embodiment 4 of methane and hydrogen, adopts the mode of spraying to replace the gravure in embodiment 4.
The ultracapacitor that the internal resistance of the ultracapacitor that embodiment 6 makes makes than embodiment 4 is low by 3%, and cycle performance is higher by 4% than embodiment's 1.
Embodiment 7
Other conditions are with embodiment 4, and difference is to replace the shallow corrosive aluminum foil in embodiment 4 with aluminium foil.
High 2% left and right of ultracapacitor that the internal resistance of the ultracapacitor that embodiment 7 makes makes than embodiment 4.
Embodiment 8
Other conditions are with embodiment 4, and difference is to take that the mixture (mass ratio is 1:2) of Graphene and active carbon replaces executes the active carbon in example 4.
Low 12% left and right of ultracapacitor that the internal resistance of the ultracapacitor that embodiment 8 makes makes than embodiment 4, high 5% left and right in Capacity Ratio embodiment 1.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for electrode slice, is characterized in that, comprises the steps:
A surface-coated electrocondution slurry at light paper tinsel, after dry, form the conductive paste bed of material, then roll-in crimping forms conductive coating, wherein, described electrocondution slurry is that metal dust, material with carbon element powder, dispersant, binding resin and the first solvent form, and the solid content of described electrocondution slurry is 10%～30%;
Under reducibility gas atmosphere or protective gas atmosphere, to being formed with the described smooth paper tinsel of conductive coating, carry out high temperature cabonization processing, described conductive coating carbonization forms covers carbonaceous conductive layer; And
Described covering on carbonaceous conductive layer, apply active slurry, after dry, roll-in crimping forms active layer, obtains described electrode slice, wherein, described active slurry is that active material, conductive agent, binding agent and the second solvent form, and the solid content of described active slurry is 10%～30%.
2. the preparation method of electrode slice according to claim 1, is characterized in that, in described electrocondution slurry, the mass ratio of described metal dust, described material with carbon element powder, described dispersant and described binding resin is 20～35:20～35:5～25:6～25.
3. the preparation method of electrode slice according to claim 1, it is characterized in that, the particle diameter of described metal dust is 30nm～200 μ m, and the material of described metal dust is selected from least one in aluminium, nickel, silver, titanium, manganese, magnesium, potassium and oxide thereof and hydroxide;
Described material with carbon element powder is selected from least one in graphene powder, conductive black, carbon nano-tube, carbon fiber, acetylene black, active carbon powder and powdered graphite;
Described dispersant is selected from least one in BYK190, BYK182 and BYK162;
Described binding resin is selected from least one in epoxy resin, phenolic resins, acrylonitrile resin, butyral resin, acrylate and polyurethane.
4. the preparation method of electrode slice according to claim 1, is characterized in that, the thickness of the described conductive paste bed of material is 0.5 μ m～50 μ m, described in cover carbonaceous conductive layer thickness be 0.01 μ m～3 μ m.
5. the preparation method of electrode slice according to claim 1, it is characterized in that, to being formed with the described smooth paper tinsel of conductive coating, carry out in the operation of high temperature cabonization processing, the temperature that described high temperature cabonization is processed is 300 ℃～600 ℃, and the time that described high temperature cabonization is processed is 6h～24h.
6. the preparation method of electrode slice according to claim 1, is characterized in that, in described active slurry, the mass ratio of described active material, described conductive agent and described binding agent is 80～94:10～2:10～4;
The thickness of described active layer is 50 μ m～200 μ m;
Described active material is selected from least one in active carbon, carbon nano-tube, carbon fiber, Graphene, metal oxide, polyaniline and polypyrrole;
Described conductive agent is acetylene black, conductive black or graphite powder, and the particle diameter of described conductive agent is 0.1 μ m～3 μ m;
Described binding agent is acrylonitrile multiple copolymer, polytetrafluoroethylene, Kynoar, carboxymethyl cellulose or polyvinyl alcohol.
7. an electrode slice, is characterized in that, described electrode slice adopts the preparation method of the electrode slice described in any one in claim 1～6 to prepare.
8. a ultracapacitor, is characterized in that, described ultracapacitor adopts electrode slice claimed in claim 7.
9. a preparation method for ultracapacitor, is characterized in that, comprises the steps:
Adopt the preparation method of the electrode slice described in any one in claim 1～6 to prepare electrode slice;
Described electrode slice is cut into the shape of regulation;
Barrier film and the described electrode slice cutting are made to pocket type electrode, the described electrode slice cutting and described pocket type electrode are stacked to rear soldering polar ear successively, then put into aluminum plastic film and sealing two ends; And
By the described aluminum plastic film of sealing two ends vacuumize 12h～24h at 80 ℃～120 ℃, then under dry protective gas atmosphere, inject electrolyte, finally, by described aluminum plastic film sealing, obtain described ultracapacitor.
10. the preparation method of ultracapacitor according to claim 9, is characterized in that, described barrier film is cellulose paper, porous polypropylene, porous Teflon, porous Kynoar or porous polyethylene;
Described electrolyte is the organic solution of the tetraethyl ammonium tetrafluoroborate methyltriethylammonitetrafluoroborate tetrafluoroborate of 0.5mol/L～3mol/L, and the solvent of described electrolyte is propene carbonate or acetonitrile.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104867695A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Light-metal-doped straw based carbon electrode material and preparation method thereof |
| CN106498465A (en) * | 2016-11-18 | 2017-03-15 | 珠海特普力高精细化工有限公司 | A kind of water-soluble conducting carbon nano-metal slurry and electrical-conductive nanometer metal carbon film bushing pipe |
| CN106502020A (en) * | 2017-01-13 | 2017-03-15 | 合肥微晶材料科技有限公司 | A kind of controllable conductivity light modulation structure and preparation method thereof |
| CN107268025A (en) * | 2017-07-21 | 2017-10-20 | 刘秋雷 | One kind electrolyzes table salt water electrode |
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| CN104867695A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Light-metal-doped straw based carbon electrode material and preparation method thereof |
| CN108779363A (en) * | 2016-03-29 | 2018-11-09 | 拓自达电线株式会社 | Conductive coating paint and used the conductive coating paint barrier enclosure body manufacturing method |
| CN106498465B (en) * | 2016-11-18 | 2019-02-01 | 珠海特普力高精细化工有限公司 | A kind of water-soluble conducting carbon nano-metal slurry and electrical-conductive nanometer metal carbon film bushing pipe |
| CN106498465A (en) * | 2016-11-18 | 2017-03-15 | 珠海特普力高精细化工有限公司 | A kind of water-soluble conducting carbon nano-metal slurry and electrical-conductive nanometer metal carbon film bushing pipe |
| CN106502020A (en) * | 2017-01-13 | 2017-03-15 | 合肥微晶材料科技有限公司 | A kind of controllable conductivity light modulation structure and preparation method thereof |
| CN106502020B (en) * | 2017-01-13 | 2019-06-21 | 合肥微晶材料科技有限公司 | A kind of controllable conductivity light modulation structure and preparation method thereof |
| CN107268025A (en) * | 2017-07-21 | 2017-10-20 | 刘秋雷 | One kind electrolyzes table salt water electrode |
| CN108099358A (en) * | 2017-12-28 | 2018-06-01 | 广州云普电子科技有限公司 | A kind of copper-clad plate processing method that can improve electric property |
| CN108099358B (en) * | 2017-12-28 | 2020-11-24 | 广州云普电子科技有限公司 | Copper-clad plate processing method capable of improving electrical performance |
| CN108987666A (en) * | 2018-06-29 | 2018-12-11 | 成都三乙医疗科技有限公司 | A kind of battery electrode piece preparation method |
| CN108878175A (en) * | 2018-06-29 | 2018-11-23 | 成都三乙医疗科技有限公司 | A kind of super capacitor electrode slice preparation method |
| CN110165143A (en) * | 2019-05-24 | 2019-08-23 | 东莞市安德丰电池有限公司 | A kind of lithium battery electrode plate and the preparation method and application thereof |
| CN110739436A (en) * | 2019-10-28 | 2020-01-31 | 昆山宝创新能源科技有限公司 | Graphene-silver composite tab, preparation method thereof and lithium battery pole piece |
| CN112121306A (en) * | 2020-06-05 | 2020-12-25 | 未来穿戴技术有限公司 | Electrode sheet manufacturing method, electrode sheet, and neck massager |
| CN112121306B (en) * | 2020-06-05 | 2024-04-19 | 未来穿戴技术有限公司 | Electrode plate manufacturing method, electrode plate and neck massager |
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