CN102543481B - Manufacture method of super capacitor - Google Patents
Manufacture method of super capacitor Download PDFInfo
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- CN102543481B CN102543481B CN201110450262.4A CN201110450262A CN102543481B CN 102543481 B CN102543481 B CN 102543481B CN 201110450262 A CN201110450262 A CN 201110450262A CN 102543481 B CN102543481 B CN 102543481B
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- collector electrode
- electrode
- pole piece
- ultracapacitor
- fuse
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
A manufacture method of a super capacitor belongs to the technical field of new energy accumulation and includes conducting roughness processing on the surface of a metal collector, evenly mixing active materials, conductive materials and composite adhesive, pressing the mixture into a pole piece with the thickness between 30 micrometer to 100 micrometer, bonding the pole piece to the surface of the collector to form a belt pole, cutting the belt pole into two poles identical in size, enabling the two poles to be riveted with a wire, adding a pole separation film with the thickness between 10 micrometer to 15 micrometer, winding the film to form a core, drying the core for 8 to 72 hours under the temperature of 100 DEG C to 150 DEG C in vacuum mode, immersing the core in organic electrolyte, electrifying the electrolyte for 10 hours through 2.7V direct current voltage under 50 DEG C temperature, and packaging the core in a round aluminum casing to obtain a product of the super capacitor. The composite adhesive is a mixture of a substance with [NH-R-CO-R-CO]x formula and teflon. Poles manufactured by the composite adhesive are flexible, high in mechanical strength, easy to produce continuously in large scale and substantially longer in service life.
Description
Technical field
The invention belongs to new forms of energy energy storage technology field, relate to ultracapacitor, be specifically related to the manufacture method of ultracapacitor.
Background technology
Two piths of ultracapacitor are electrode and electrolyte, and its energy storage principle is to put aside electric charge, storage power at electrode and electrolyte interface formation electric double layer.In order to improve energy density, the active material of electrode is selected active carbon, carbon black, carbon nano-tube, Graphene, expanded graphite, metal oxide and conducting polymer etc. conventionally, for ultracapacitor long-life high efficiency is discharged and recharged, collector electrode is generally selected the materials such as rafifinal, stainless steel and nickel of chemically-resistant and electrochemical corrosion, also the Low ESR such as binding metal and graphite coating on collector electrode conventionally.Electrolyte has water-soluble electrolyte and organic electrolyte, wherein the operating voltage of organic electrolyte is high, the energy of storage is many, but because having moisture, capacitor unit inside exists, ultracapacitor causes that water decomposition will make ultracapacitor performance degradation when charging, therefore use the ultracapacitor of organic electrolyte fully to dewater to electrode, conventionally take high-temperature vacuum to dewater.Active carbon in electrode, carbon black, carbon nano-tube, Graphene, expanded graphite, metal oxide and conducting polymer isoreactivity material, be generally Powdered, mix with rubber-like binding agent and water, active material and electric conducting material are dispersed in rubber-like binding agent and water, make slurry, form pole piece, be applied on collector electrode, the dry electrode of making, but a little less than the cohesive force due to this method, pole piece and inter-collector adhesion strength are little, electrode is further processed into after ultracapacitor, product is in large electric current high-frequency charge and discharge process, pole piece can with collector electrode separated peeling off gradually, make ultracapacitor product obtain major cycle.
Summary of the invention
The problem existing for current ultracapacitor production technology, the invention provides a kind of manufacture method of ultracapacitor, solves between collector electrode and pole piece the problems such as the little and pole piece internal bond strength of adhesion strength is little.
In the present invention, pole piece consists of active material, electric conducting material and compound binding agent, pole piece and metal collector form one, form the electrode of ultracapacitor, electrode is processed into after certain size, lead-in wire in connection, in the middle of two electrodes, add the fuse that is wound into certain size every utmost point film, vacuumize, add organic electrolyte after encapsulation make ultracapacitor.
(1) prepare collector electrode: choose feed metal aluminum or aluminum alloy, after surperficial AC corrosion roughening is processed, as collector electrode;
(2) prepare pole piece: active material and electric conducting material are mixed, compoiste adhering agent solution is joined in the above-mentioned material mixing and is uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 0.5-3%, active material is 80-94.5%, and electric conducting material is 5-10%, then said mixture is pressed into the pole piece that thickness is 30-100 μ m; Described compoiste adhering agent solution is to have the material of general formula (1) structure and the compound binding agent that polytetrafluoroethylene forms, be dissolved in water, ethanol, isopropyl alcohol or acetone solvent and be uniformly dispersed, the solution forming, material 30-55% by weight general formula (1), polytetrafluoroethylene is 45-70%, and the structure of matter of general formula (1) is:
[NH-R-CO-R-CO]
x （1）
x=1-1000，R:C
nH
2n ，n=1-10
(3) prepare electrode: by collector electrode surface-coated one deck conducting resinl, pole piece is sticked to the one or both sides of collector electrode, form electrode;
(4) prepare fuse: by after two measure-alike electrode connecting lead wires, sandwich therebetween 10-50 μ m thick every utmost point film, being wound into diameter is that Φ 3-Φ 65mm is highly the fuse of 5-165mm, then vacuumize 8-72 hour at 100-150 ℃;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, and the 10h that then switches under 50 ℃ of additional 2.7V direct voltages, is finally packaged in circular aluminum hull, obtains ultracapacitor product.
The wherein said raw material as collector electrode is that purity is at least 99.9wt%, the metal aluminum or aluminum alloy of copper content below 0.005wt%.Collector electrode requires rough surface, is in order to contact well with pole piece.
In pole piece of the present invention, compoiste adhering agent content is 0.5-3%,, all the other are active material and electric conducting material, wherein compoiste adhering agent content is 0.5% and just can reaches the intensity of required pole piece with superior pole piece, but compound binding agent too high levels, it is large that pole piece resistance becomes, and is preferably 1.5-3%.
Described active material is selected the inactive active carbon of chemical property, carbon black, carbon nano-tube, Graphene or expanded graphite, adopt one or more composition wherein, when selecting with more than one compositions, each component is mixed with arbitrary proportion, and wherein the specific area of activated carbon is 800-3000m
2/ g, carbon black specific surface is 100-600 m
2/ g, the specific area of carbon nano-tube is 200-600m
2/ g, the specific area of Graphene is 500-1500 m
2/ g, expanded graphite specific area is 100-300m
2/ g.
Described electric conducting material is graphite, carbon black or acetylene black, and granularity is 0.1-2 μ m.
Described conducting resinl is graphite conductive adhesive, cupric powder conductive adhesive or sliver-powder conducting glue.
Described is cellulose paper, porous polypropylene, porous Teflon, porous Kynoar, porous polyethylene, the laminating film of porous polypropylene polyethylene or porous polyimide every utmost point film, requirement is 60-95% every the porosity of utmost point film, thickness 10-100 μ m, aperture 0.05-0.2 μ m.
Described organic electrolyte is the salt R that contains dissociative
1r
2r
3r
4nY or R
1r
2r
3r
4nPY is dissolved in and forms in organic solvent, R
1r
2r
3r
4for alkyl, identical or not identical, Y is BF
4 -, PF
6 -clO
4 -or CF
3sO
3 -anion, described organic solvent is propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, sulfolane, acetonitrile or oxolane, or more than one mixed solvents that are mixed to form according to arbitrary proportion wherein.
Compared with prior art, feature of the present invention and beneficial effect are:
One or more compositions when existing electrode of super capacitor is made in common employing polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, Kynoar are as binding agent, a little less than adopting the electrode plates mechanical strength of these binding agents making, be unfavorable for serialization industrial production; Core content of the present invention is to adopt [NH-R-CO-R-CO]
xwith polytetrafluoroethylene compound binding agent, the electrode of making is soft, mechanical strength is large, is easy to serialization and produces; To ultracapacitor of the present invention, in ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is under the condition of 100A, to discharge and recharge cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times, and this illustrates that ultracapacitor of the present invention has good capacity stability and higher cycle life, can store higher energy, there is larger power.
Embodiment
Raw material that the present invention adopts: the material of general formula (1) is from the research institute that becomes more meticulous of Bohai University, and all the other products are commercially available prod.
Embodiment 1
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general structure (1):
[NH-R-CO-R-CO]
x （1）
X=100 wherein, R:C
2h
4, n=2
In compound binding agent, in mass ratio, the material of general formula (1) is 30% to each constituent content, polytetrafluoroethylene 70%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 30 μ m, and roughness is the collector electrode of one-sided thickness 3 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in isopropyl alcohol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 2%, active material is 92%, and electric conducting material is 6%, then said mixture is rolled into the pole piece that thickness is 50 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to the surface of collector electrode both sides, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 30 μ m thick every utmost point film, every utmost point film, adopting cellulose paper, is 80% every the porosity of utmost point film, and thickness is 50 μ m, aperture is 0.2 μ m, being wound into diameter is Φ 35mm, is highly the fuse of 100mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V400F.
Described collector electrode adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
Described active material is the active carbon of stable electrochemical property, and specific area is 1800m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NBF
4the solution that mixes according to volume ratio 1:1:1:1:1:1 of propene carbonate, ethylene carbonate, butylene carbonate fat, dimethyl carbonate, carbonic acid diethyl ester and methyl ethyl carbonate fat.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 50A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 93%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 86% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 2
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general structure (1):
[NH-R-CO-R-CO]
x （1）
X=200 wherein, R:C
3h
6, n=3
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 35%, polytetrafluoroethylene 65%.
(1) prepare collector electrode: aluminum alloy surface is carried out to AC corrosion thickness roughening and process, obtaining thickness is 30 μ m, and roughness is the collector electrode of one-sided 3 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in isopropyl alcohol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 2%, active material is 91%, and electric conducting material is 7%, then said mixture is rolled into the pole piece that thickness is 50 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck cupric powder conductive adhesive, pole piece is sticked to the surface of collector electrode one side, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 30 μ m thick every utmost point film, every utmost point film, adopt cellulose paper, porosity every utmost point film is 80%, and aperture is 0.2 μ m, and being wound into diameter is Φ 20mm, be highly the fuse of 40mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V90F.
Described collector electrode adopts purity more than 99.9wt%, the aluminium alloy of copper content below 0.005wt%.
Described active material is the active carbon of stable electrochemical property, and specific area is 1800m
2/ g.
The electric conducting material of selecting is acetylene black, and granularity is 1 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NBF
4ethylene carbonate and the solution that mixes according to volume ratio 1:1 of acetonitrile.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 20A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 93%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 87% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 3
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
[NH-R-CO-R-CO]
x （1）
X=300 wherein, R:C
4h
8, n=4
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 40%, polytetrafluoroethylene 60%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided thickness 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in ethanol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 1.5%, active material is 92.5%, and electric conducting material is 6%, then said mixture is rolled into the pole piece that thickness is 70 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck sliver-powder conducting glue, pole piece is sticked to the both side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 20 μ m thick every utmost point film, every utmost point film, adopt cellulose paper, porosity every utmost point film is 80%, and aperture is 0.1 μ m, and being wound into diameter is Φ 50mm, be highly the fuse of 100mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V1500F.
The collector electrode of the present embodiment adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
The active material that the present embodiment is selected is the active carbon of stable electrochemical property, and specific area is 1800m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NClO
44butylene carbonate lipoprotein solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 20A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 4
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
[NH-R-CO-R-CO]
x （1）
X=400 wherein, R:C
4h
8, n=4
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 40%, polytetrafluoroethylene 60%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided thickness 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in ethanol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 6%, active material is 88%, and electric conducting material is 6%, and then said mixture being rolled into thickness with roller machine is 120 μ m pole pieces;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to a side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 20 μ m thick every utmost point film, every utmost point film, adopt porous polypropylene, porosity every utmost point film is 80%, and aperture is 0.1 μ m, and being wound into diameter is Φ 35mm, be highly the fuse of 100mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V1000F.
Described collector electrode adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
Described active material is the active carbon of stable electrochemical property and the mixture of carbon nano-tube, and active carbon and carbon nano-tube mass ratio are 8:2, and active carbon specific area is 1800 m
2/ g, specific surface area of carbon nanotube is 400m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NBF
4dimethyl carbonate solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 100A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 5
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
[NH-R-CO-R-CO]
x （1）
X=500 wherein, R:C
5h
10, n=5
In compoiste adhering agent solution, each constituent content is in mass ratio: the material of general formula (1) is 45%, polytetrafluoroethylene 55%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in ethanol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 1.5%, active material is 90.5%, and electric conducting material is 8%, then said mixture is rolled into the pole piece that thickness is 80 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to the both side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 30 μ m thick every utmost point film, every utmost point film, adopt porous Teflon, porosity every utmost point film is 70%, and aperture is 0.2 μ m, and being wound into diameter is Φ 35mm, be highly the fuse of 60mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V350F.
The collector electrode of the present embodiment adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
The active material that the present embodiment is selected is the active carbon of stable electrochemical property and the mixture of carbon nano-tube, and active carbon and carbon nano-tube mass ratio are 8:2, and active carbon specific area is 2000 m
2/ g, specific surface area of carbon nanotube is 400m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
3h
8) NPF
6methyl ethyl carbonate lipoprotein solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 50A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 6
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
[NH-R-CO-R-CO]
x （1）
X=600 wherein, R:C
6h
12, n=6
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 90%, polytetrafluoroethylene 10%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided thickness 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in ethanol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 2%, active material is 90%, and electric conducting material is 8%, then said mixture is rolled into the pole piece that thickness is 80 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to a side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 20 μ m thick every utmost point film, every utmost point film, adopt porous Kynoar, porosity every utmost point film is 80%, and aperture is 0.2 μ m, and being wound into diameter is Φ 25mm, be highly the fuse of 100mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V800F.
Described collector electrode adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
Described active material is the active carbon of stable electrochemical property and the mixture of carbon nano-tube, and active carbon and carbon nano-tube mass ratio are 8:2, and active carbon specific area is 2000 m
2/ g, specific surface area of carbon nanotube is 400m
2/ g.
The electric conducting material of selecting is acetylene black, and granularity is 0.1 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NCF
3sO
3sulfolane solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 20A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 7
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
[NH-R-CO-R-CO]
x （1）
X=700 wherein, R:C
7h
14, n=7
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 55%, polytetrafluoroethylene 45%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in ethanol and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 4%, active material is 88%, and electric conducting material is 8%, then said mixture is rolled into the pole piece that thickness is 80 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to the both side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 20 μ m thick every utmost point film, every utmost point film, adopt porous polyethylene, porosity every utmost point film is 80%, and aperture is 0.2 μ m, and being wound into diameter is Φ 30mm, be highly the fuse of 100mm, by the vacuumize 48 hours at 120 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V800F.
Described collector electrode adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
Described active material is the carbon nano-tube of stable electrochemical property and the mixture of Graphene, and mass ratio is 4:6, and the specific area of carbon nano-tube is 200 m
2/ g, the specific area of Graphene is 1500 m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NBF
4carbon acetonitrile solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 20A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 8
The compound binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
[NH-R-CO-R-CO]
x （1）
X800 wherein, R:C
8h
16, n=8
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 35%, polytetrafluoroethylene 65%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in water and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 4%, active material is 88%, and electric conducting material is 8%, then said mixture is rolled into the pole piece that thickness is 80 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to the both side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 20 μ m thick every utmost point film, every utmost point film, adopt porous polypropylene polyethylene composite film, porosity every utmost point film is 60%, and aperture is 0.2 μ m, and being wound into diameter is Φ 30mm, be highly the fuse of 100mm, by the vacuumize 8 hours at 150 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V1200F.
Described collector electrode adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
Described active material is the mixture of active carbon, carbon black and the expanded graphite of stable electrochemical property, and its mass ratio is 1:2:7, and active carbon specific area is 3000m
2/ g, the specific area of carbon black is 600 m
2/ g, the specific area of expanded graphite is 100 m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NBF
4tetrahydrofuran solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 100A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Embodiment 9
The binding agent that the present embodiment adopts is mixed by material and the polytetrafluoroethylene with following general formula (1) structure:
R[NH-R-CO-R-CO]
x （1）
X=900 wherein, R:C
9h
18, n=9
In compound binding agent, each constituent content is in mass ratio: the material of general formula (1) is 45%, polytetrafluoroethylene 55%.
(1) prepare collector electrode: the processing of AC corrosion roughening is carried out in metallic aluminium surface, and obtaining thickness is 20 μ m, and roughness is the collector electrode of one-sided 2 μ m;
(2) prepare pole piece: active material and electric conducting material are mixed, compound binding agent is dissolved in acetone and is uniformly dispersed, form compoiste adhering agent solution, join in the above-mentioned material mixing and be uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 3%, active material is 87%, and electric conducting material is 10%, then said mixture is rolled into the pole piece that thickness is 100 μ m with roller machine;
(3) prepare electrode: by collector electrode surface-coated one deck graphite conductive adhesive, pole piece is sticked to the both side surface of collector electrode, form band electrode;
(4) prepare fuse: above-mentioned electrode is cut into two measure-alike electrodes, by after two electrode riveted joint lead-in wires, sandwich 20 μ m thick every utmost point film, every utmost point film, adopt porous polyimide, porosity every utmost point film is 90%, and aperture is 0.1 μ m, and being wound into diameter is Φ 30mm, be highly the fuse of 100mm, by the vacuumize 72 hours at 100 ℃ of this fuse;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, fuse by dipping after organic electrolyte is at 50 ℃ of additional 2.7V direct voltages energising 10h, finally be loaded in circular aluminum hull, both positive and negative polarity seals after adopting laser machine to be welded on respectively the upper and lower two ends of aluminum hull, obtains the ultracapacitor product of rated operational voltage 2.7V1200F.
Described collector electrode adopts purity more than 99.9wt%, the metallic aluminium of copper content below 0.005wt%.
Described active material is the mixture of active carbon, carbon black, carbon nano-tube, Graphene and the expanded graphite of stable electrochemical property, mass ratio 1:1:1:1:1, and wherein active carbon specific area is 2000 m
2/ g, carbon black specific surface is 500 m
2/ g, carbon nano-tube 200 m
2/ g, Graphene specific area 1500 m
2/ g, expanded graphite specific area 100 m
2/ g.
The electric conducting material of selecting is graphite, and granularity is 2 μ m.
The organic electrolyte of selecting is (the C of 1.0mol/L
2h
5) NBF
4carbonic acid diethyl ester solution.
In ambient temperature, it is 50 ℃, direct voltage is from 2.7V to 1.35V, electric current is, under the condition of 100A, the ultracapacitor of the present embodiment is discharged and recharged to cycle experiment, after 20000 times, capability retention is 92%, temperature is under the condition of 65 ℃, to carry out the same cycle that discharges and recharges experiment around, and capability retention is 88% after 10,000 times; When separating metallic aluminium collector electrode and pole piece with cutter, at the active material of the residual volume of collector electrode one side.
Claims (7)
1. the manufacture method of ultracapacitor, according to following steps, carry out:
(1) prepare collector electrode: choose feed metal aluminum or aluminum alloy, after surperficial AC corrosion roughening is processed, as collector electrode;
(2) prepare pole piece: active material and electric conducting material are mixed, compoiste adhering agent solution is joined in the above-mentioned material mixing and is uniformly dispersed, form mixture, wherein by mass percentage, compoiste adhering agent content is 0.5-3%, active material is 80-94.5%, and electric conducting material is 5-10%, then said mixture is pressed into the pole piece that thickness is 30-100 μ m;
(3) prepare electrode: by collector electrode surface-coated one deck conducting resinl, pole piece is sticked to the one or both sides of collector electrode, form electrode;
(4) prepare fuse: by after two measure-alike electrode connecting lead wires, sandwich therebetween 10-50 μ m thick every utmost point film, being wound into diameter is that Φ 3-Φ 65mm is highly the fuse of 5-165mm, then vacuumize 8-72 hour at 100-150 ℃;
(5) encapsulation: fuse is flooded to organic electrolyte under vacuum condition, and the 10h that then switches under 50 ℃ of additional 2.7V direct voltages, is finally packaged in circular aluminum hull, obtains ultracapacitor product;
It is characterized in that described compoiste adhering agent solution is that material and the polytetrafluoroethylene with general formula (1) structure is mixed to form compound binding agent, be dissolved in water, ethanol, isopropyl alcohol or acetone solvent and be uniformly dispersed, the solution forming, material 35-55% by weight general formula (1), polytetrafluoroethylene is 45-65%, and the structure of matter of general formula (1) is:
[NH-R-CO-R-CO]
x （1）
x=1-1000，R:C
nH
2n，n=1-10。
2. the manufacture method of ultracapacitor according to claim 1, is characterized in that the described raw material as collector electrode is that purity is at least 99.9wt%, the metal aluminum or aluminum alloy of copper content below 0.005wt%.
3. the manufacture method of ultracapacitor according to claim 1, active material described in it is characterized in that is selected active carbon, carbon black, carbon nano-tube, Graphene or expanded graphite one or more compositions that mix in any proportion wherein, and wherein the specific area of activated carbon is 800-3000m
2/ g, carbon black specific surface is 100-600m
2/ g, the specific area of carbon nano-tube is 200-600m
2/ g, the specific area of Graphene is 500-1500m
2/ g, expanded graphite specific area is 100-300m
2/ g.
4. the manufacture method of ultracapacitor according to claim 1, is characterized in that described electric conducting material is graphite, carbon black or acetylene black, and granularity is 0.1-2 μ m.
5. the manufacture method of ultracapacitor according to claim 1, is characterized in that described conducting resinl is graphite conductive adhesive, cupric powder conductive adhesive or sliver-powder conducting glue.
6. the manufacture method of ultracapacitor according to claim 1, described in it is characterized in that is cellulose paper, porous polypropylene, porous Teflon, porous Kynoar, porous polyethylene, the laminating film of porous polypropylene polyethylene or porous polyimide every utmost point film, requirement is 60-95% every the porosity of utmost point film, thickness 10-100 μ m, aperture 0.05-0.2 μ m.
7. the manufacture method of ultracapacitor according to claim 1, is characterized in that described organic electrolyte is the salt R that contains dissociative
1r
2r
3r
4nY or R
1r
2r
3r
4nPY is dissolved in and forms in organic solvent, R
1r
2r
3r
4for alkyl, identical or not identical, Y is BF
4 -, PF
6 -clO
4 -or CF
3sO
3 -anion, described organic solvent is propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, sulfolane, acetonitrile or oxolane, or more than one mixed solvents that are mixed to form according to arbitrary proportion wherein.
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| CN103413693B (en) * | 2013-05-24 | 2016-01-13 | 宁波南车新能源科技有限公司 | A kind of manufacture method of ultracapacitor |
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| CN101299398A (en) * | 2008-05-29 | 2008-11-05 | 锦州凯美能源有限公司 | Method for preparing super capacitor |
| CN101710538A (en) * | 2009-11-27 | 2010-05-19 | 锦州凯美能源有限公司 | Method for manufacturing long-life electrode of super capacitor |
| CN101709204A (en) * | 2009-12-08 | 2010-05-19 | 南京双登科技发展研究院有限公司 | Binding agent for electrode of super capacitor |
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| CN101299398A (en) * | 2008-05-29 | 2008-11-05 | 锦州凯美能源有限公司 | Method for preparing super capacitor |
| CN101710538A (en) * | 2009-11-27 | 2010-05-19 | 锦州凯美能源有限公司 | Method for manufacturing long-life electrode of super capacitor |
| CN101709204A (en) * | 2009-12-08 | 2010-05-19 | 南京双登科技发展研究院有限公司 | Binding agent for electrode of super capacitor |
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