CN105304350A - Abuse capacitor with wide temperature range and manufacturing method of abuse capacitor - Google Patents
Abuse capacitor with wide temperature range and manufacturing method of abuse capacitor Download PDFInfo
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- CN105304350A CN105304350A CN201510787920.7A CN201510787920A CN105304350A CN 105304350 A CN105304350 A CN 105304350A CN 201510787920 A CN201510787920 A CN 201510787920A CN 105304350 A CN105304350 A CN 105304350A
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- capacitor
- abuse
- temperature range
- electrolyte
- wide temperature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Abstract
The invention discloses an abuse capacitor with a wide temperature range and a manufacturing method of the abuse capacitor. A pole piece of an abuse super capacitor is prepared from a current collector containing carbon or a high conducting polymer and a mesoporous carbon material, wherein a membrane of the abuse super capacitor is a hydrophilic membrane; an electrolyte of the abuse super capacitor is an ionic liquid electrolyte or a mixed electrolyte of an ionic liquid and an organic solvent; the stable working voltage range of the super capacitor is 0-10V; the stable working temperature range is minus 90 DEG C to minus 300 DEG C; the ionic liquid electrolyte is nontoxic, free of pollution and free of combustion; available membranes are wide in variety and source; and the abuse capacitor is a safe and environment-friendly abuse super capacitor with high energy density in a real sense.
Description
Technical field
The present invention relates to one and can abuse ultracapacitor and manufacture method thereof, belong to electrochemical field.
Background technology
Ultracapacitor developed novel green energy storage device rapidly in the last few years, and it has fast charging and discharging characteristic, and power density is tens times of common batteries even hundred times.In addition, it has extended cycle life, and charge and discharge cycles number of times can reach 100000 times, is the hundred times even several thousand times of common batteries.Based on this special performance of ultracapacitor, some countries comprising China start and use ultracapacitor as the power supply of motor vehicle and the development project to the tuning energy storage of the intermittent renewable such as wind energy, the solar energy energy.But also there is operating voltage low (energy density is lower) in ultracapacitor, poor stability and the large weakness of capacity attenuation under high temperature.The electrolyte boiling point of commercial organic system capacitor is low, decomposition voltage is low, toxic, there is larger safety and environmental protection hidden danger, cannot 55 degrees Celsius of lower stable operations be greater than, cause use inconvenient.Such as, during summer, often can there is " high temperature failure alarms " in the super appearance bus run in Shanghai, add operation cost.How upgrading further material system, improve operating voltage (specific energy) and the safety and environmental protection performance of ultracapacitor, is key issue urgently to be resolved hurrily in ultracapacitor research and development and industry development.
Summary of the invention
The object of the invention is to overcome above deficiency, providing a kind of safety, environmental protection, high-energy-density, the wide temperature range that can abuse can abuse capacitor and manufacture method thereof.
Object of the present invention is achieved through the following technical solutions: a kind of wide temperature range can abuse capacitor, and this pole piece can abusing ultracapacitor forms by carbon containing or containing high-conductivity polymer collector and rich meso-porous carbon material; This barrier film can abusing ultracapacitor is hydrophily barrier film; This electrolyte can abusing ultracapacitor is the mixed electrolytic solution of il electrolyte or ionic liquid and organic solvent; This stable operating voltage scope can abusing ultracapacitor is at 0-10V, and the temperature range of its steady operation is-90-300 DEG C.
Further improvement of the present invention is: carbon containing or containing in high-conductivity polymer collector, and carbon containing collector is inner or there is the collector of High-conductivity carbon on surface, is the collector that there is high-conductivity polymer on surface containing high-conductivity polymer collector.
Further improvement of the present invention is: rich meso-porous carbon material is a kind of material with carbon element of classifying porous three-dimensional structure, and wherein containing micropore, mesoporous and large micropore composition, its large micropore and mesoporous aperture are 1-50nm.
Further improvement of the present invention is: meso-hole structure is the three-dimensional structure of being piled up by very thin class Graphene carbon-coating.
Further improvement of the present invention is: rich meso-porous carbon material BET specific surface area is at 3000-4000m
2/ g, its large micropore and mesoporous pore volume account for more than 80% of total pore volume, and pore-size distribution is narrow, concentrates on 1-5nm, and its average pore size is at 2-4nm.
Further improvement of the present invention is: rich meso-porous carbon material is fixed on carbon containing by self assembly or bonding agent or containing on high-conductivity polymer collector, this bonding agent is the large micelle aqueous adhesive of emulsion-type.
Further improvement of the present invention is: hydrophily barrier film is mine tailings and pulverized coal-ash-based porous film, Woelm Alumina, porous silica or the membrane for polymer through surface hydrophilic modification, and polymer is polypropylene, polyethylene.
Further improvement of the present invention is: il electrolyte is one or more mixed ionic liquid electrolyte of imidazoles, pyridines, pyrrolidines, quaternary amines, morpholine class, piperidines.
Further improvement of the present invention is: in the mixed electrolytic solution of il electrolyte and organic solvent, described il electrolyte is one or more mixed ionic liquid electrolyte of imidazoles, pyridines, pyrrolidines, quaternary amines, morpholine class, piperidines, and described organic solvent is Merlon or butyrolactone.
Further improvement of the present invention is: rich meso-porous carbon material, aqueous adhesive and conductive agent are prepared slurry according to the quality of 75-90%:3-15%:3-15% than mixing and water adding; This slurry is coated in carbon containing or contains on high-conductivity polymer collector, pole piece is made in dry also compacting; Soft Roll capacitor made by employing il electrolyte, hydrophily barrier film.
Further improvement of the present invention is: aqueous adhesive is butadiene-styrene rubber, PTFE, CMC or polyacrylic acid.
Further improvement of the present invention is: conductive agent is conductive black, Super-P, carbon nano-fiber, CNT (carbon nano-tube), Graphene or conducting polymer.
The present invention compared with prior art has the following advantages: the present invention proposes one and can abuse ultracapacitor and manufacture method thereof, the stable operating voltage scope of this ultracapacitor is at 0-10V, the temperature range of its steady operation is-90-300 DEG C, and il electrolyte nontoxic, pollution-free, do not burn, the kind wide material sources of available membrane are safety truly, environmental protection, high-energy-density, the ultracapacitor that can abuse.
accompanying drawing illustrates:
The charging and discharging curve of capacitor in Fig. 1 example 1 at 25 DEG C.
Capacitor in Fig. 2 example 1 circulate at 25 DEG C 10000 circle performances.
The charging and discharging curve of capacitor in Fig. 3 example 2 at 150 DEG C.
Capacitor in Fig. 4 example 2 circulate at 150 DEG C 10000 circle performances.
The charging and discharging curve of capacitor in Fig. 5 example 3 at-40 DEG C.
Capacitor in Fig. 6 example 4 circulate at-40 DEG C 10000 circle performances.
embodiment:
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.The element described in one embodiment of the invention and feature can combine with the element shown in one or more other execution mode and feature.It should be noted that for purposes of clarity, in explanation, eliminate expression and the description of unrelated to the invention, parts known to persons of ordinary skill in the art and process.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not paying creative work, all belongs to the scope of protection of the invention.
This capacitor can at steady operation under 0-10V, and, the stabilized operating temperature interval of this capacitor is-90-300 DEG C, again, this capacitor can not combustion explosion under acupuncture, extruding, high temperature, a series of extreme condition such as to fall, and electrolyte is nontoxic, pollution-free, be safety truly, environmental protection, high-energy-density, the ultracapacitor that can abuse.
This pole piece can abusing ultracapacitor forms by carbon containing or containing high-conductivity polymer collector and rich meso-porous carbon material.This barrier film can abusing ultracapacitor is hydrophily barrier film.This electrolyte can abusing ultracapacitor is the mixed electrolytic solution of il electrolyte or ionic liquid and organic solvent.This stable operating voltage scope can abusing ultracapacitor is at 0-10V, and the temperature range of its steady operation is-90-300 DEG C.
This carbon containing collector is the collector that there is High-conductivity carbon on inside or surface.Collector protects by the method that High-conductivity carbon covers carbon through high-temperature carburizing or low temperature, prevents in the process of discharge and recharge, and il electrolyte produces corrosion to the surface of collector under electrochemical conditions.Be the collector that there is high-conductivity polymer on surface containing high-conductivity polymer collector, protected by collector, prevent in the process of discharge and recharge, il electrolyte produces corrosion to the surface of collector under electrochemical conditions.Carbon containing or all play containing high-conductivity polymer and reduce the effect of capacitor internal resistance.
This material with carbon element is a kind of material with carbon element of classifying porous three-dimensional structure, wherein containing a small amount of micropore, in a large number mesoporous and a small amount of macropore composition.Meso-hole structure is wherein the three-dimensional structure of being piled up by very thin class Graphene carbon-coating.This material with carbon element BET specific surface area is at 3000-4000m
2/ g, the pore volume of its large micropore and mesoporous (aperture is at 1-50nm) accounts for more than 80% of total pore volume, and pore-size distribution is narrow, concentrates on 1-5nm, and its average pore size is at 2-4nm.Larger mesoporously so that large il electrolyte ion turnover, can guarantee that material with carbon element still has good kinetic effect at low temperatures.
This material with carbon element by self assembly or bonding agent fixing on carbon containing collector, this bonding agent is the large micelle aqueous adhesive of emulsion-type.The micelle of this bonding agent should enough large (being greater than 50nm), to avoid the duct blocking rich meso-porous carbon material, and high pressure resistant and high temperature.
This hydrophily barrier film is mine tailings and pulverized coal-ash-based porous film, Woelm Alumina, porous silica or polymer (polypropylene, the polyethylene) barrier film through surface hydrophilic modification.
This il electrolyte is one or more mixed ionic liquid electrolyte of imidazoles, pyridines, pyrrolidines, quaternary amines, morpholine class, piperidines.Its decomposition voltage can reach 10V, and chemically stable temperature can reach 400 DEG C, and setting temperature is minimum reaches-90 DEG C.For improving the ionic conductivity of ionic liquid and reducing electrolyte viscosity, can by Merlon or the homo-ion liquid mixing of butyrolactone.
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
Embodiment 1
Rich meso-porous carbon material, butadiene-styrene rubber, CMC and conductive black prepare slurry according to the quality of 80:10:3:7 than mixing and water adding, are coated in by this slurry on utter misery aluminium foil, and pole piece is made in dry also compacting.Adopt EMIMBF
4as electrolyte, employing porous alumina membrane is barrier film, makes Soft Roll capacitor.This capacitor is at 25 DEG C and under 0-3.8V, and as shown in Figure 1, the specific capacity of this capacitor is 205F/g to the charging and discharging curve that test obtains, circulation 10000 circle capacity attenuations 5%, as shown in Figure 2.
Embodiment 2
Rich meso-porous carbon material, PTFE and conductive black prepare slurry according to the quality of 85:10:5 than mixing and water adding, are coated in graphene paper by this slurry, and pole piece is made in dry also compacting.Adopt BMIMBF
4as electrolyte, employing porous alumina membrane is barrier film, makes Soft Roll capacitor.This capacitor tests the charging and discharging curve that obtains as shown in Figure 3 at 150 DEG C, and the specific capacity of this capacitor is 350F/g, circulation 10000 circle capacity attenuations 10%, as shown in Figure 4.
Embodiment 3
Rich meso-porous carbon material, water system PVDF, CMC and conductive black prepare slurry according to the quality of 80:10:3:7 than mixing and water adding, are coated on nickel screen by this slurry, and pole piece is made in dry also compacting.Adopt EMIMBF
4with the mixed electrolytic solution of butyrolactone as electrolyte, employing porous silicon oxide membrane is barrier film, makes Soft Roll capacitor.This capacitor tests the charging and discharging curve that obtains as shown in Figure 5 at-40 DEG C, and the specific capacity of this capacitor is 140F/g, and circulation 10000 circle capacity are unattenuated, as shown in Figure 6.
Embodiment 4
Rich meso-porous carbon material, butadiene-styrene rubber, CMC and conductive black prepare slurry according to the quality of 80:10:5:5 than mixing and water adding, are coated in by this slurry on utter misery stainless steel, and pole piece is made in dry also compacting.Adopt the electrolyte of EMIMTFSI as electrolyte, adopt PP modified film to be barrier film, make Soft Roll capacitor.It is 160F/g that this capacitor records specific capacity at 60 DEG C, circulation 10000 circle capacity attenuation 4%.
Although last it is noted that described the present invention and advantage thereof in detail above, be to be understood that and can carry out various change when not exceeding the spirit and scope of the present invention limited by appended claim, substituting and converting.And scope of the present invention is not limited only to the specific embodiment of process, equipment, means, method and step described by specification.One of ordinary skilled in the art will readily appreciate that from disclosure of the present invention, can use perform the function substantially identical with corresponding embodiment described herein or obtain and its substantially identical result, existing and that will be developed in the future process, equipment, means, method or step according to the present invention.Therefore, appended claim is intended to comprise such process, equipment, means, method or step in their scope.
Claims (10)
1. wide temperature range can abuse a capacitor, it is characterized in that: this pole piece can abusing capacitor forms by carbon containing or containing high-conductivity polymer collector and rich meso-porous carbon material; This barrier film can abusing capacitor is hydrophily barrier film; This electrolyte can abusing capacitor is the mixed electrolytic solution of il electrolyte or ionic liquid and organic solvent; This stable operating voltage scope can abusing capacitor is at 0-10V, and the temperature range of its steady operation is-90-300 DEG C.
2. the wide temperature range of one according to claim 1 can abuse capacitor, it is characterized in that: described carbon containing or containing in high-conductivity polymer collector, described carbon containing collector is the collector that there is High-conductivity carbon on inside or surface, and described is the collector that there is high-conductivity polymer on surface containing high-conductivity polymer collector.
3. the wide temperature range of one according to claim 1 can abuse capacitor, it is characterized in that: described rich meso-porous carbon material is a kind of material with carbon element of classifying porous three-dimensional structure, wherein containing micropore, mesoporous and large micropore composition, its large micropore and mesoporous aperture are 1-50nm.
4. the wide temperature range of one according to claim 3 can abuse capacitor, it is characterized in that: meso-hole structure is the three-dimensional structure of being piled up by very thin class Graphene carbon-coating.
5. the wide temperature range of the one according to claim 3 or 4 can abuse capacitor, it is characterized in that: described rich meso-porous carbon material BET specific surface area is at 3000-4000m
2/ g, its large micropore and mesoporous pore volume account for more than 80% of total pore volume, and pore-size distribution is narrow, concentrates on 1-5nm, and its average pore size is at 2-4nm.
6. the wide temperature range of one according to claim 1 can abuse capacitor, it is characterized in that: described rich meso-porous carbon material is fixed on carbon containing by self assembly or bonding agent or containing on high-conductivity polymer collector, this bonding agent is the large micelle aqueous adhesive of emulsion-type.
7. the wide temperature range of one according to claim 1 can abuse capacitor, it is characterized in that: described hydrophily barrier film is mine tailings and pulverized coal-ash-based porous film, Woelm Alumina, porous silica or the membrane for polymer through surface hydrophilic modification, and polymer is polypropylene, polyethylene.
8. the wide temperature range of one according to claim 1 can abuse capacitor, it is characterized in that: described il electrolyte is one or more mixed ionic liquid electrolyte of imidazoles, pyridines, pyrrolidines, quaternary amines, morpholine class, piperidines; In the mixed electrolytic solution of described il electrolyte and organic solvent, described il electrolyte is one or more mixed ionic liquid electrolyte of imidazoles, pyridines, pyrrolidines, quaternary amines, morpholine class, piperidines, and described organic solvent is Merlon or butyrolactone.
9. wide temperature range can abuse a manufacture method for capacitor, it is characterized in that: rich meso-porous carbon material, aqueous adhesive and conductive agent are prepared slurry according to the quality of 75-90%:3-15%:3-15% than mixing and water adding; This slurry is coated in carbon containing or contains on high-conductivity polymer collector, pole piece is made in dry also compacting; Soft Roll capacitor made by employing il electrolyte, hydrophily barrier film.
10. the manufacture method of capacitor can be abused according to claim 9 wide temperature range, it is characterized in that: aqueous adhesive is butadiene-styrene rubber, PTFE, CMC or polyacrylic acid, conductive agent is conductive black, Super-P, carbon nano-fiber, CNT (carbon nano-tube), Graphene or conducting polymer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510787920.7A CN105304350A (en) | 2015-11-17 | 2015-11-17 | Abuse capacitor with wide temperature range and manufacturing method of abuse capacitor |
| PCT/CN2016/081801 WO2017084252A1 (en) | 2015-11-17 | 2016-05-12 | Abuse capacitor having wide temperature range, and manufacturing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510787920.7A CN105304350A (en) | 2015-11-17 | 2015-11-17 | Abuse capacitor with wide temperature range and manufacturing method of abuse capacitor |
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| CN105304350A true CN105304350A (en) | 2016-02-03 |
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| CN201510787920.7A Pending CN105304350A (en) | 2015-11-17 | 2015-11-17 | Abuse capacitor with wide temperature range and manufacturing method of abuse capacitor |
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| CN (1) | CN105304350A (en) |
| WO (1) | WO2017084252A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017084252A1 (en) * | 2015-11-17 | 2017-05-26 | 南通绿业中试技术研究院有限公司 | Abuse capacitor having wide temperature range, and manufacturing method therefor |
| CN106898495A (en) * | 2017-03-28 | 2017-06-27 | 江苏大学 | A kind of assay method of high temperature energy-storage device and its high temperature rated voltage |
| GB2561253A (en) * | 2017-04-07 | 2018-10-10 | Zapgo Ltd | Self-supporting carbon electrode |
| CN110462452A (en) * | 2017-03-29 | 2019-11-15 | 夏普株式会社 | Optical devices shell and Optical devices |
| CN111223686A (en) * | 2020-01-14 | 2020-06-02 | 清华大学 | Electrolyte of super capacitor, preparation method and performance |
| CN112614699A (en) * | 2020-11-03 | 2021-04-06 | 宁波工程学院 | Zigzag nitrogen-doped SiC nanowire-based high-temperature supercapacitor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105869913B (en) * | 2016-04-06 | 2018-07-20 | 江苏中天科技股份有限公司 | A kind of ultracapacitor and preparation method thereof |
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| CN111223686A (en) * | 2020-01-14 | 2020-06-02 | 清华大学 | Electrolyte of super capacitor, preparation method and performance |
| CN112614699A (en) * | 2020-11-03 | 2021-04-06 | 宁波工程学院 | Zigzag nitrogen-doped SiC nanowire-based high-temperature supercapacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017084252A1 (en) | 2017-05-26 |
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Application publication date: 20160203 |