CN102543484A - High-power flexible package supercapacitor pole piece and production method thereof - Google Patents
High-power flexible package supercapacitor pole piece and production method thereof Download PDFInfo
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- CN102543484A CN102543484A CN2012100856003A CN201210085600A CN102543484A CN 102543484 A CN102543484 A CN 102543484A CN 2012100856003 A CN2012100856003 A CN 2012100856003A CN 201210085600 A CN201210085600 A CN 201210085600A CN 102543484 A CN102543484 A CN 102543484A
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Abstract
The invention discloses a high-power flexible package supercapacitor pole piece and a production method thereof, which belong to the technical and relevant fields of energy materials. The high-power flexible package supercapacitor pole piece is characterized in that a current collector used by the supercapacitor pole piece is a metal net. First, a spraying device is used for coating the net current collector with a layer of electroconductive paste, and after drying, a coating machine is used for secondary coating of the pole piece coated with the electroconductive paste on the surface. In addition, during the process of producing supercapacitor active material paste, carbon nanofibers, single-walled carbon nanotubes and multi-walled carbon nanotubes are added, and the ultrasonic technology is utilized to disperse the conducting materials. By optimizing the order of adding the materials and utilizing the ultrasonic technology for mixing the materials, conductive additives and binding agents are evenly dispersed among the active materials. The high-power flexible package supercapacitor pole piece and the production method effectively improve supercapacitor high-power charge-discharge abilities. Meanwhile, flexible package is used for packaging the supercapacitor so that production efficiency of the supercapacitor is greatly improved and production cost is lowered.
Description
Technical field
The present invention relates to the introducing of a kind of processing method of high-power super capacitor electrode material, particularly conducting resinl and the adding of CNT or carbon nano-fiber the high power discharge performance of ultracapacitor is obviously improved, belong to energy and material technology association area.
Background technology
Ultracapacitor also is called electrochemical capacitor in double electrode layer, and its electrode active material is made up of the raw material of wood-charcoal material of high-specific surface area.The energy density of ultracapacitor and has advantages such as instantaneous large-current discharges and recharges, operating temperature range is wide, have extended cycle life, security performance is good between traditional capacitor and battery.
The operation principle of ultracapacitor is that pair of electrodes all is immersed in the electrolyte solution, and when applying the decomposition voltage that is lower than electrolyte solution to electrode, at the interface of solid electrode and electrolyte solution, electric charge can be arranged evenly in extremely short distance.As compensation; Positively charged positive pole can attract the anion in the solution, and is opposite, and negative pole attracts cation; Thereby form electric double layer closely; The stored charge at the interface of electrode and electrolyte solution, but electric charge can not pass the interface of electrode and electrolyte solution, and the electric current that in this process, is produced is to be reset and the displacement current of generation by electric charge basically.Its energy is stored in the surface of electrode material with electric charge or concentrated electronics.
CNT is a kind of hollow tube, specific area is big, degree of crystallinity is high, good conductivity with and micropore all concentrate within the specific limits, be a kind of desirable conductive electrode material.Wherein the outermost electronics of carbon atom passes through SP
2Hydridization and three adjacent carbon atoms form stable plane covalent bond, are in the big π key that electronics on the vertical direction Z axle has then formed delocalization.Therefore have the electronics that can move freely in a large number at the CNT tube wall, and these electron distributions are at the tube wall surface of CNT, so CNT has the excellent conductivity of leading.And carbon nano-fiber is a kind of carbon fiber with nanoscale, has outside low-density, high ratio modulus, high specific strength, the high conduction performance, has also that defects count is few, specific area is big and advantage such as compact structure.
A key factor of known decision ultracapacitor internal resistance be exactly electrode active material with metal collector between contact, whether the distribution of conductive materials between the electrode active material even.If in the ultracapacitor pole piece, introduce CNT and/or carbon nano-fiber, under a spot of condition of adding, just can obviously improve the conductivity of pole piece, thereby further improve the high-power charge-discharge performance of ultracapacitor.
Adopt flexible package that the electric core of ultracapacitor is encapsulated in addition in the present invention, thereby can reduce the quality of monomer ultracapacitor, under the constant prerequisite of ultracapacitor static capacity, can improve the energy density of ultracapacitor.
Summary of the invention
The purpose of this invention is to provide high-power, the flexible packed super-capacitor of a kind of making.At first at the certain thickness conducting resinl of wire netting collection liquid surface coating one deck; And then carry out secondary coating; Through after in electrode material, adding small amount of carbon nanotubes and/or carbon nano-fiber, can significantly improve the high-power charge-discharge performance of ultracapacitor then.After using flexible package that ultracapacitor is encapsulated, can significantly reduce the quality of monomer ultracapacitor, thereby can under the prerequisite that does not change the ultracapacitor static capacity, can improve the energy density of ultracapacitor.
The objective of the invention is to realize like this:
Use wire netting to be electrode current collecting body; Add a kind of strong alkalinity anion surfactant; Use ultrasonic technology that collection liquid surface is carried out abatement processes 1-5min; Clean the back with secondary deionized water it is carried out 80 vacuumize 10min, and then use a kind of fluorine-containing surfactant that collector is carried out finishing 3-5min, just can obtain the substrate material that a certain type of organo-functional group is rich on surface no-pollution and surface.Wherein the perforate mode of wire netting can be corrosion perforate, punching press perforate, laser beam drilling; Perhaps use braiding silk screen, oblique wire drawing net.The material of the used wire netting of electrode can be aluminium, copper, stainless steel or nickel plating stainless steel.The thickness of wire netting is between 0.02mm-0.1mm.The shape of metal mesh opening can be irregularly shaped for circle, rhombus, rectangle or other.The surfactant that scrubbing is used is alkaline anion surfactant.Coating material uses fluorine-containing surfactant; Comprising anion surfactant, cationic surfactant, non-ionic surface active agent and special surface activating agent.Ultrasonic wave dirty handle (1-5min) that dispel, ultrasonic surface is modified (1-5min).Used frequency of ultrasonic is 40KHZ, and decentralized medium is the quartzy Asia deionized water that boils, and jitter time is 18-30min, and temperature is 40-55 ℃.
After wire netting handled, begin once to be coated with, just earlier conducting resinl is coated the surface of wire netting, the single face wet-film thickness of conducting resinl is about 10 μ m.It is the EB-815 or the EB-012 of Main Ingredients and Appearance that conducting resinl can be selected with the electrically conductive graphite.
When the preparation electrode active material slurry, add surfactant, ultrasonic Treatment (1-3min) earlier; After adding adhesive again; Ultrasonic Treatment (3-5min) adds CNT and/or carbon nano-fiber again, and CNT and/or carbon nano-fiber account for the 1%-2% of solid content; Ultrasonic Treatment 3-5min adds active carbon ultrasonic Treatment 1-5min at last.
Active material slurry with method for preparing prepares ultracapacitor pole piece, 1MLiPF
6Electrolyte (EC/DEC=1:1), PP or PE are barrier film, use the aluminum plastic film flexible package to seal.Core is anodal ︱ barrier film ︱ negative pole laminated structure, on the charge-discharge test appearance, carries out 0-2.5V, 0-2.8V loop test, charging current 50A.The experiment proof prepares the high-power charge-discharge performance that electrode of super capacitor can significantly improve ultracapacitor through method of the present invention.
The present invention has compared with prior art significantly improved the high-power charge-discharge performance of ultracapacitor, under the prerequisite that does not change the ultracapacitor static capacity, uses flexible package to encapsulate the mass energy density that has increased ultracapacitor.Its principle is: use the strong alkalinity anion surfactant, not only can dispel the pollutant of collection liquid surface, can also play roughened is carried out on the surface of collector, to increase the contact area of itself and active material.Next conducting resinl is coated the surface of metal mesh opening collector, conducting resinl is riddled in the hole of metal mesh opening collector, therefore a very short time through indirect increase electrode active material and metal collector touches area, has increased the approach of electrical conductivity.CNT of introducing in the system in addition and/or carbon nano-fiber have improved the electronic conductivity of integral material to a great extent, thereby make the prepared ultracapacitor of the present invention have high-power charge-discharge performance.Because CNT and/or carbon nano-fiber are not easy to be scattered in uniformly in the slurry; Therefore used ultrasonic wave to disperse; The mixing of using ultrasonic wave to carry out material has not only significantly been shortened the time of mixing of materials with dispersion, but also can make the mixture homogeneity of material in the shortest time, reach best.
Description of drawings
Fig. 1 ultracapacitor external form sketch map
Fig. 2 wire netting collector of the present invention sketch map
Fig. 3 pole piece structural representation of the present invention
Fig. 4 lamination type electric core structural representation of the present invention
Among Fig. 11 is positive pole ear, and 2 is negative lug.Among Fig. 31 is the metal forming lug, and Fig. 2 is an active material layer.
Case study on implementation 1:
Getting the breadth width is that 300mm, thickness are the collector of the metallic aluminium net of 0.1mm as electrode active material, and wherein the mesh areas width is 260mm, and the 20mm imperforate section is respectively reserved on both sides.Then the metallic aluminium net is done following processing; Add a kind of strong alkalinity anion surfactant; Use ultrasonic technology that collection liquid surface is carried out abatement processes 1.5min; Clean the back with secondary deionized water it is carried out 80 ° of C vacuumize 10min, and then use fluorine-containing surfactant that collector is carried out finishing 4min.Be coated with conducting resinl, the wire netting of handling well is coated with conducting resinl, conducting resinl single face wet-film thickness is 15 μ m.When the preparation electrode active material slurry, at first in the 150ml absolute ethyl alcohol, add CNT 8g, utilize ultrasonic wave to disperse; And then take by weighing 20g polyvinylidene fluoride PVDF and be dissolved in the 200g N-methyl pyrrolidone (NMP); Stirring is fully dissolved it, carries out ultrasonic Treatment 3min then, and then takes by weighing the 20gSuper-P conductive carbon black; Take by weighing the 200g active carbon and in stirring ball mill, fully carry out the ball milling stirring as electrode active material; Mixture with conductive black behind the above-mentioned stirring ball-milling and active carbon joins in the CNT of ultrasonic dispersing again, said mixture is joined among the NMP of PVDF again, then this slurry is transferred in the homogenizer; Stirred 1.5 hours with 3200 rev/mins rotating speeds, add the 500gNMP dilution again and obtain the liquid slurry that viscosity is 6000pas.And then slurry carried out ultrasonic Treatment 15min.It is online to use the transfer type coating machine that this slurry is coated on the above-mentioned aluminium that is coated with conducting resinl uniformly, and coating single face thickness is 200 μ m.120 ° of C vacuumize 8 hours uses twin rollers that pole piece is depressed into 150 μ m then, obtains the ultracapacitor positive pole, the die-cut pole piece of processing length * wide=120mm * 55mm.
With the above-mentioned positive/negative plate that is complementary, be barrier film with U.S. celgard 2400, fold by the top-down order of anodal ︱ barrier film ︱ negative pole ︱ septum electrode, obtain stacked core body.Use flexible package that core body is encapsulated.In the glove box that is full of Ar gas of drying, to the housing that electric core is housed, inject an amount of 1MLiPF from liquid injection port
6Electrolyte (EC/DEC=1:1).Sealing the back is taken out by glove box.10A discharges and recharges, and the internal resistance of ultracapacitor is 0.43m Ω, and static capacity is 2200F.
Case study on implementation 2:
Change the CNT in the case study on implementation 1 into carbon nano-fiber.Slurry mixes, pole piece is made and the assembling of battery and test condition and case study on implementation 1 in consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 0.55m Ω, and static capacity is 2100F.
Case study on implementation 3
Change the CNT in the case study on implementation 1 mixture of Nano carbon fibers peacekeeping CNT into, and the quality summation of the two is constant.Slurry mixes, pole piece is made and the assembling of battery and test condition and case study on implementation 1 in consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 0.49m Ω, and static capacity is 2100F.
Contrast case 1:
Getting the breadth width is that 300mm, thickness are the collector of the metallic aluminium net of 0.1mm as electrode active material, and wherein the mesh areas width is 260mm, and the 20mm imperforate section is respectively reserved on both sides.Slurry mixes, pole piece is made and the assembling of battery and test condition and case study on implementation 1 in consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.48m Ω, and static capacity is 2200 F.
Contrast case 2:
Change the CNT in the contrast case 1 into carbon nano-fiber.The assembling of slurry mixing, pole piece making and battery is with test condition and contrast in the case 1 consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.36m Ω, and static capacity is 2100F.
Contrast case 3:
Change the CNT of contrast in the case 1 mixture of carbon nano-fiber and CNT into, and the quality summation of the two is constant.The assembling of slurry mixing, pole piece making and battery is with test condition and contrast in the case 1 consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.41m Ω, and static capacity is 2200F.
Contrast case 4:
Getting the breadth width is that 300mm, thickness are the collector of the atresia metallic aluminium of 0.1mm as electrode active material, and wherein the mesh areas width is 260mm, and the 20mm imperforate section is respectively reserved on both sides.The processing of metal forming, slurry mix, pole piece is made and the assembling of battery and test condition and case study on implementation 1 in consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.52m Ω, and static capacity is 1800F.
Contrast case 5:
Change the CNT in the contrast case 4 into carbon nano-fiber.The assembling of slurry mixing, pole piece making and battery is with test condition and contrast in the case 1 consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.41m Ω, and static capacity is 1800F.
Contrast case 6:
Change the CNT in the contrast case 4 into carbon nano-fiber.The assembling of slurry mixing, pole piece making and battery is with test condition and contrast in the case 1 consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.53m Ω, and static capacity is 1800F.
Contrast case 7:
Getting the breadth width is that 300mm, thickness are the collector of the atresia metallic aluminium of 0.1mm as electrode active material, and wherein the mesh areas width is 260mm, and the 20mm imperforate section is respectively reserved on both sides.In this Comparative Examples, metal forming is not handled.Slurry mixes, pole piece is made and the assembling of battery and test condition and case study on implementation 1 in consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.87m Ω, and static capacity is 1800F.
Contrast case 8:
Change the CNT in the contrast case 7 into carbon nano-fiber.The assembling of slurry mixing, pole piece making and battery is with test condition and contrast in the case 1 consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.72m Ω, and static capacity is 1800F.
Contrast case 9:
Change the CNT in the contrast case 7 into carbon nano-fiber.The assembling of slurry mixing, pole piece making and battery is with test condition and contrast in the case 1 consistent.10A discharges and recharges, and the internal resistance of ultracapacitor is 1.81m Ω, and static capacity is 1800F.
Claims (16)
1. high-power flexible packed super-capacitor pole piece and manufacturing approach thereof; It is characterized in that: the used collector of ultracapacitor pole piece is a wire netting; At first use coating machine on the net collector, to apply one deck conducting resinl, with coating machine the pole piece of surface coverage conducting resinl is carried out the secondary coating again after the drying.
2. high-power flexible packed super-capacitor pole piece and manufacturing approach thereof is characterized in that: added carbon nano-fiber, SWCN and multi-walled carbon nano-tubes in the process of preparation ultracapacitor active material slurry.
3. high-power flexible packed super-capacitor pole piece and manufacturing approach thereof is characterized in that: use ultrasonic wave that CNT and/or carbon nano-fiber are disperseed, optimize material interpolation order.
4. high-power flexible packed super-capacitor pole piece and manufacturing approach thereof, it is characterized in that: flexible package is adopted in the shell encapsulation of ultracapacitor.
5. a kind of high-power flexible packed super-capacitor pole piece according to claim 1 and manufacturing approach thereof is characterized in that: the perforate mode of wire netting can be corrosion perforate, punching press perforate, laser beam drilling; Perhaps use braiding silk screen, oblique wire drawing net.
6. a kind of high-power flexible packed super-capacitor pole piece according to claim 1 and manufacturing approach thereof is characterized in that: the material of the used wire netting of electrode can be aluminium, copper, stainless steel or nickel plating stainless steel.
7. according to described a kind of high-power flexible packed super-capacitor pole piece of claim 1 and manufacturing approach thereof, it is characterized in that: the thickness of wire netting is between 0.02mm-0.1mm.
8. a kind of high-power flexible packed super-capacitor pole piece according to claim 1 and manufacturing approach thereof is characterized in that: the shape of metal mesh opening can be irregularly shaped for circle, rhombus, rectangle or other.
9. a kind of high-power flexible packed super-capacitor pole piece according to claim 1 and manufacturing approach thereof is characterized in that: conducting resinl is that electrically conductive graphite is the EB-815 or the EB-012 of Main Ingredients and Appearance.
10. a kind of high-power flexible packed super-capacitor pole piece according to claim 1 and manufacturing approach thereof is characterized in that: the single face wet-film thickness of conducting resinl is 15 μ m.
11. the diameter 50nm-200nm of carbon nano-fiber.
12. the caliber 2nm-20nm of SWCN and multi-walled carbon nano-tubes.
13. a kind of high-power flexible packed super-capacitor pole piece according to claim 2 and manufacturing approach thereof, it is characterized in that: CNT and/or carbon nano-fiber account for the 1%-2% of solid content.
14. a kind of high-power flexible packed super-capacitor pole piece according to claim 3 and manufacturing approach thereof; It is characterized in that: used frequency of ultrasonic is 40KHZ; Decentralized medium is the quartzy Asia deionized water that boils, and jitter time is 18-30min, and temperature is 40-55 ℃.
15. a kind of high-power flexible packed super-capacitor pole piece according to claim 3 and manufacturing approach thereof is characterized in that: the interpolation of each material is followed successively by in proper order, adhesive, conductive agent (CNT and/or carbon nano-fiber) and active carbon.
16. a kind of high-power flexible packed super-capacitor pole piece according to claim 4 and manufacturing approach thereof, it is characterized in that: the thickness of flexible package aluminum plastic film is 0.153mm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393311A (en) * | 2014-10-20 | 2015-03-04 | 哈尔滨工程大学 | Microbial fuel cell anode material with three-dimensional open structure and preparation method |
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| CN1483210A (en) * | 2000-05-12 | 2004-03-17 | ��ʤ�����ɷ�����˾ | Electrochemical double layer capacitor having carbon powder electrodes |
| CN101339848A (en) * | 2007-07-06 | 2009-01-07 | 中国科学院金属研究所 | Lithium ion super capacitor and assembling method thereof |
| CN101425381A (en) * | 2007-11-02 | 2009-05-06 | 清华大学 | Super capacitor and preparing method therefor |
| CN102306549A (en) * | 2011-06-30 | 2012-01-04 | 深圳市惠程电气股份有限公司 | Polyimide super capacitor and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483210A (en) * | 2000-05-12 | 2004-03-17 | ��ʤ�����ɷ�����˾ | Electrochemical double layer capacitor having carbon powder electrodes |
| CN101339848A (en) * | 2007-07-06 | 2009-01-07 | 中国科学院金属研究所 | Lithium ion super capacitor and assembling method thereof |
| CN101425381A (en) * | 2007-11-02 | 2009-05-06 | 清华大学 | Super capacitor and preparing method therefor |
| CN102306549A (en) * | 2011-06-30 | 2012-01-04 | 深圳市惠程电气股份有限公司 | Polyimide super capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104393311A (en) * | 2014-10-20 | 2015-03-04 | 哈尔滨工程大学 | Microbial fuel cell anode material with three-dimensional open structure and preparation method |
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Effective date of registration: 20151021 Address after: 410007, Hunan, Changsha Province, Shaoshan Road, North 243, Wang Jing ha B1023 Applicant after: Changsha subfamily Amperex Technology Limited Address before: 410007, Hong Jingming, B1024, 355 North Shaoshan Road, Yuhua District, Hunan, Changsha Applicant before: Changsha Haimite New Energy Technology Co.,Ltd. |
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Application publication date: 20120704 |