CN106252099A - A kind of ultracapacitor - Google Patents
A kind of ultracapacitor Download PDFInfo
- Publication number
- CN106252099A CN106252099A CN201610744986.2A CN201610744986A CN106252099A CN 106252099 A CN106252099 A CN 106252099A CN 201610744986 A CN201610744986 A CN 201610744986A CN 106252099 A CN106252099 A CN 106252099A
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- CN
- China
- Prior art keywords
- primer coating
- ultracapacitor
- bonding agent
- cnt
- top coat
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Classifications
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/40—Fibres
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/48—Conductive polymers
-
- 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 belongs to supercapacitor technologies field, particularly relate to a kind of ultracapacitor, including electrode slice, isolating membrane, pole and shell, electrode slice includes collector, the primer coating being arranged at collection liquid surface and is arranged at the top coat on primer coating surface, primer coating and top coat all include active substance, conductive agent and bonding agent, and the bonding agent content of primer coating is less than the content of the bonding agent of top coat；The active substance of primer coating and top coat all includes material with carbon element and conducting polymer；Material with carbon element has nucleocapsid structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide functional layer；Conducting polymer is at least one in polyaniline, polythiophene and polypyrrole.Relative to prior art, the present invention has good reversibility and electrochemical stability and bending resistance.
Description
Technical field
The invention belongs to supercapacitor technologies field, particularly relate to a kind of there is good reversibility, electrochemically stable
Property and the ultracapacitor of bending resistance.
Background technology
Ultracapacitor be a kind of efficiently, environmental protection, novel energy-storage travelling wave tube, it has the many of traditional capacitor and battery concurrently
Advantage, such as energy density height, length in service life, stability height, safety coefficient height, environmental protection, fast charging and discharging etc., is consuming electricity
All there are wide application space and development prospect in each fields such as son, track traffic, Aero-Space, military affairs, national defence, are increasingly becoming
The emphasis of people's developmental research.
But, the reversibility of ultracapacitor of the prior art is the best, and electrochemical stability is the most poor, counter-bending
Property is the most undesirable, it is impossible to meet the requirement that people are the highest to ultracapacitor.
In view of this, necessary offer is a kind of the super of good reversibility, electrochemical stability and bending resistance
Level capacitor, to meet the demand of people.
Summary of the invention
It is an object of the invention to: for the deficiencies in the prior art, and provide a kind of and have good reversibility, electrochemistry steady
The qualitative ultracapacitor with bending resistance, to meet the demand of people.
In order to achieve the above object, the present invention adopts the following technical scheme that
A kind of ultracapacitor, including electrode slice, isolating membrane, pole and shell, described electrode slice includes collector, is arranged at institute
State the primer coating of collection liquid surface and be arranged at the top coat on described primer coating surface, described primer coating and described top
Layer coating all includes active substance, conductive agent and bonding agent, and the bonding agent content of described primer coating is less than described top layer
The content of the bonding agent of coating；
The active substance of described primer coating and described top coat all includes material with carbon element and conducting polymer, described material with carbon element and
The mass ratio of described conducting polymer is (70 ~ 95): (5 ~ 30)；
Described material with carbon element has nucleocapsid structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide merit
Ergosphere, the mass ratio of described graphene fiber and CNT is (50 ~ 80): (20 ~ 50)；
Described conducting polymer is at least one in polyaniline, polythiophene and polypyrrole.
As a kind of improvement of ultracapacitor of the present invention, a diameter of 500nm-3 μm of described graphene fiber, described stone
The a length of 5 μm-2mm of ink alkene fiber, the intensity of described graphene fiber is 100MPa-300MPa, described graphene fiber
Conductivity is 2000S/m-5000S/m.
As a kind of improvement of ultracapacitor of the present invention, described CNT is the CNT of single tube wall, and institute
The caliber stating CNT is 2nm-8nm, and the wall thickness of described CNT is 0.6nm-2nm.
As a kind of improvement of ultracapacitor of the present invention, the weight average molecular weight of described conducting polymer is 5000 ~
100000。
As a kind of improvement of ultracapacitor of the present invention, the thickness of described manganese dioxide functional layer is 80nm-1.5 μm.
As a kind of improvement of ultracapacitor of the present invention, described conductive agent is acetylene black or white carbon black.
As a kind of improvement of ultracapacitor of the present invention, described bonding agent is Kynoar or politef.
As a kind of improvement of ultracapacitor of the present invention, the mass content of the bonding agent of described primer coating is 5%-8%,
The content of the bonding agent of described top coat is 1%-4%.
As a kind of improvement of ultracapacitor of the present invention, the preparation method of described material with carbon element comprises the steps:
The first step, the structure of three-electrode system:
The MnSO of electrolyte: 0.5mol/L-2mol/L4Aqueous solution；
Working electrode: graphene fiber and the mixture of CNT；
To electrode: the platinum filament of a diameter of 0.5mm-2mm；
Reference electrode: the KCl of Ag/AgCl, 2mol/L-4mol/L；
Second step, negative electrode galvanostatic deposition: arranging cathode electrode electric current is 200 μ A/cm2-600μA/cm2, sedimentation time is
10min-1h, rinses well repeatedly by sedimentation products, and lyophilizing to obtain final product.
Relative to prior art, the active substance of the present invention has nucleocapsid structure, and its stratum nucleare includes graphene fiber and carbon
Nanotube, its shell is manganese dioxide functional layer, and graphene fiber, CNT and manganese dioxide have given full play to transition metal
Oxide and the cooperative effect of material with carbon element, thus the potentiality of maximized every kind of component of performance so that it is obtain as far as possible fully
Utilizing, chemical property is improved.Specifically, by have the graphene fiber of higher electron conduction and CNT with
The manganese dioxide with higher fake capacitance combines, and manganese dioxide can shorten again the path of electronics Mobile Transmission, such that it is able to greatly
Amplitude improves specific capacity and the cycle performance of composite.And owing to fiber has preferable pliability so that table of the present invention
Revealing higher counter-bending and deformability, therefore the present invention can use in terms of wearable device.
Additionally, manganese dioxide nano particle is deposited on Graphene, interracial contact good between the two adds electrode
Electric conductivity and and electrolyte between contact area, make MnO2Effective rate of utilization be greatly improved, show good reversible
Property and electrochemical stability, specifically, manganese dioxide nano particle pass through tunnel-effect (quantum effect), it is achieved the most reversible
Redox reaction, produces fake capacitance, and produces synergism, thus electrochemical performance with Graphene, have good
Charge-discharge characteristic and cyclical stability.
The specific capacity of conducting polymer is that 5-6 times of material with carbon element, energy density and power density are up to 30-50Wh respectively
kg-1With 2-20kW kg-1.The mixed binding of material with carbon element and the conducting polymer advantage of this two classes material, and show collaborative
Effect, conducting polymer provides fake capacitance, and material with carbon element serves as skeleton in the composite, conducting polymer plays support and makees
With, to keep its stability during charge and discharge cycles.
On the other hand, in the present invention, the bonding agent content of primer coating is less than the content of the bonding agent of top coat, due to
Primer coating is directly to contact with collector, and bonding agent content therein is within normal range, to guarantee primer coating and collection
The strong bond of fluid, and top coat is directly to contact with primer coating, it has only to less bonding agent content and just may be used
To realize the strong bond with primer coating, thus can reduce the content of bonding agent in whole coating, improve in coating and live
Property material content, and then improve the specific capacity of ultracapacitor and electrical property.
Detailed description of the invention
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in detail, but the specific embodiment party of the present invention
Formula is not limited to this.
Embodiment 1
Present embodiments providing a kind of ultracapacitor, including electrode slice, isolating membrane, pole and shell, described electrode slice includes
Collector, it is arranged at the primer coating of described collection liquid surface and is arranged at the top coat on described primer coating surface, described
Primer coating and described top coat all include active substance, conductive agent and bonding agent, and the bonding agent of described primer coating
Content is less than the content of the bonding agent of described top coat；
The active substance of described primer coating and described top coat all includes material with carbon element and conducting polymer, described material with carbon element and
The mass ratio of described conducting polymer is 90:10；
Described material with carbon element has nucleocapsid structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide merit
Ergosphere, the mass ratio of described graphene fiber and CNT is 70:30；
Described conducting polymer is polyaniline.
A diameter of 500nm-3 μm of graphene fiber, a length of 5 μm-2mm of described graphene fiber, described Graphene
The intensity of fiber is 100MPa-300MPa, and the conductivity of described graphene fiber is 2000S/m-5000S/m.
CNT is the CNT of single tube wall, and the caliber of described CNT is 2nm-8nm, described carbon nanometer
The wall thickness of pipe is 0.6nm-2nm.
The weight average molecular weight of conducting polymer is 70000.
The thickness of manganese dioxide functional layer is 80nm-1.5 μm.
Conductive agent is acetylene black, and bonding agent is Kynoar.
The mass content of the bonding agent of primer coating is 7%, and the content of the bonding agent of top coat is 3%.
The preparation method of material with carbon element comprises the steps:
The first step, the structure of three-electrode system:
The MnSO of electrolyte: 1mol/L4Aqueous solution；
Working electrode: graphene fiber and the mixture of CNT；
To electrode: the platinum filament of a diameter of 102mm；
Reference electrode: the KCl of Ag/AgCl, 3mol/L；
Second step, negative electrode galvanostatic deposition: arranging cathode electrode electric current is 400 μ A/cm2, sedimentation time is 40min, will deposition
Product is rinsed well repeatedly, lyophilizing, to obtain final product.
Embodiment 2
Present embodiments providing a kind of ultracapacitor, including electrode slice, isolating membrane, pole and shell, described electrode slice includes
Collector, it is arranged at the primer coating of described collection liquid surface and is arranged at the top coat on described primer coating surface, described
Primer coating and described top coat all include active substance, conductive agent and bonding agent, and the bonding agent of described primer coating
Content is less than the content of the bonding agent of described top coat；
The active substance of described primer coating and described top coat all includes material with carbon element and conducting polymer, described material with carbon element and
The mass ratio of described conducting polymer is 80:20；
Described material with carbon element has nucleocapsid structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide merit
Ergosphere, the mass ratio of described graphene fiber and CNT is 60:40；
Described conducting polymer is polythiophene.
A diameter of 500nm-3 μm of described graphene fiber, a length of 5 μm-2mm of described graphene fiber, described stone
The intensity of ink alkene fiber is 100MPa-300MPa, and the conductivity of described graphene fiber is 2000S/m-5000S/m.
Described CNT is the CNT of single tube wall, and the caliber of described CNT is 2nm-8nm, described carbon
The wall thickness of nanotube is 0.6nm-2nm.
The weight average molecular weight of described conducting polymer is 30000.
The thickness of described manganese dioxide functional layer is 80nm-1.5 μm.
Conductive agent is white carbon black, and bonding agent is politef.
The mass content of the bonding agent of primer coating is 6%, and the content of the bonding agent of described top coat is 2%.
The preparation method of material with carbon element comprises the steps:
The first step, the structure of three-electrode system:
The MnSO of electrolyte: 0.7mol/L4Aqueous solution；
Working electrode: graphene fiber and the mixture of CNT；
To electrode: the platinum filament of a diameter of 1.5mm；
Reference electrode: the KCl of Ag/AgCl, 2.5mol/L；
Second step, negative electrode galvanostatic deposition: arranging cathode electrode electric current is 300 μ A/cm2, sedimentation time is 30min, will deposition
Product is rinsed well repeatedly, lyophilizing, to obtain final product.
Embodiment 3
Present embodiments providing a kind of ultracapacitor, including electrode slice, isolating membrane, pole and shell, described electrode slice includes
Collector, it is arranged at the primer coating of described collection liquid surface and is arranged at the top coat on described primer coating surface, described
Primer coating and described top coat all include active substance, conductive agent and bonding agent, and the bonding agent of described primer coating
Content is less than the content of the bonding agent of described top coat；
The active substance of described primer coating and described top coat all includes material with carbon element and conducting polymer, described material with carbon element and
The mass ratio of described conducting polymer is 75:25；
Described material with carbon element has nucleocapsid structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide merit
Ergosphere, the mass ratio of described graphene fiber and CNT is 75:25；
Described conducting polymer is polypyrrole.
A diameter of 500nm-3 μm of described graphene fiber, a length of 5 μm-2mm of described graphene fiber, described stone
The intensity of ink alkene fiber is 100MPa-300MPa, and the conductivity of described graphene fiber is 2000S/m-5000S/m.
Described CNT is the CNT of single tube wall, and the caliber of described CNT is 2nm-8nm, described carbon
The wall thickness of nanotube is 0.6nm-2nm.
The weight average molecular weight of described conducting polymer is 50000.
The thickness of manganese dioxide functional layer is 80nm-1.5 μm.
Conductive agent is acetylene black, and bonding agent is politef.
The mass content of the bonding agent of primer coating is 5.5%, and the content of the bonding agent of described top coat is 2.5%.
The preparation method of described material with carbon element comprises the steps:
The first step, the structure of three-electrode system:
The MnSO of electrolyte: 1.5mol/L4Aqueous solution；
Working electrode: graphene fiber and the mixture of CNT；
To electrode: the platinum filament of a diameter of 0.7mm；
Reference electrode: the KCl of Ag/AgCl, 3.5mol/L；
Second step, negative electrode galvanostatic deposition: arranging cathode electrode electric current is 500 μ A/cm2, sedimentation time is 20min, will deposition
Product is rinsed well repeatedly, lyophilizing, to obtain final product.
Practice have shown that: the cycle-index of the ultracapacitor of embodiment 1 to 3 is all more than 200,000 times.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out suitable change and amendment.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to this
Some modifications and changes of invention should also be as falling in the scope of the claims of the present invention.Although additionally, this specification
In employ some specific terms, but these terms are merely for convenience of description, and the present invention does not constitute any restriction.
Claims (9)
1. a ultracapacitor, it is characterised in that include electrode slice, isolating membrane, pole and shell, it is characterised in that: described
Electrode slice includes collector, the primer coating being arranged at described collection liquid surface and is arranged at the top layer on described primer coating surface
Coating, described primer coating and described top coat all include active substance, conductive agent and bonding agent, and described primer coating
Bonding agent content less than the content of bonding agent of described top coat；
The active substance of described primer coating and described top coat all includes material with carbon element and conducting polymer, described material with carbon element and
The mass ratio of described conducting polymer is (70 ~ 95): (5 ~ 30)；
Described material with carbon element has nucleocapsid structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide merit
Ergosphere, the mass ratio of described graphene fiber and CNT is (50 ~ 80): (20 ~ 50)；
Described conducting polymer is at least one in polyaniline, polythiophene and polypyrrole.
Ultracapacitor the most according to claim 1, it is characterised in that a diameter of 500nm-3 μ of described graphene fiber
M, a length of 5 μm-2mm of described graphene fiber, the intensity of described graphene fiber is 100MPa-300MPa, described graphite
The conductivity of alkene fiber is 2000S/m-5000S/m.
Ultracapacitor the most according to claim 1, it is characterised in that described CNT is the carbon nanometer of single tube wall
Managing, and the caliber of described CNT is 2nm-8nm, the wall thickness of described CNT is 0.6nm-2nm.
Ultracapacitor the most according to claim 1, it is characterised in that the weight average molecular weight of described conducting polymer is
5000~100000。
Ultracapacitor the most according to claim 1, it is characterised in that the thickness of described manganese dioxide functional layer is
80nm-1.5μm。
Ultracapacitor the most according to claim 1, it is characterised in that described conductive agent is acetylene black or white carbon black.
Ultracapacitor the most according to claim 1, it is characterised in that described bonding agent is Kynoar or polytetrafluoro
Ethylene.
Ultracapacitor the most according to claim 1, it is characterised in that the mass content of the bonding agent of described primer coating
For 5%-8%, the content of the bonding agent of described top coat is 1%-4%.
Ultracapacitor the most according to claim 1, it is characterised in that the preparation method of described material with carbon element includes walking as follows
Rapid:
The first step, the structure of three-electrode system:
The MnSO of electrolyte: 0.5mol/L-2mol/L4Aqueous solution；
Working electrode: graphene fiber and the mixture of CNT；
To electrode: the platinum filament of a diameter of 0.5mm-2mm；
Reference electrode: the KCl of Ag/AgCl, 2mol/L-4mol/L；
Second step, negative electrode galvanostatic deposition: arranging cathode electrode electric current is 200 μ A/cm2-600μA/cm2, sedimentation time is
10min-1h, rinses well repeatedly by sedimentation products, and lyophilizing to obtain final product.
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| CN201610744986.2A CN106252099B (en) | 2016-08-29 | 2016-08-29 | A kind of ultracapacitor |
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| CN201610744986.2A CN106252099B (en) | 2016-08-29 | 2016-08-29 | A kind of ultracapacitor |
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| CN106252099B CN106252099B (en) | 2018-04-10 |
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| CN107768149A (en) * | 2017-10-18 | 2018-03-06 | 东莞市共和电子有限公司 | A kind of barium titanate super capacitance cell |
| CN107868199A (en) * | 2017-11-02 | 2018-04-03 | 深圳市铭科科技有限公司 | Ferrocenyl end-blocking type polyurethane, ultracapacitor and preparation method |
| CN108417408A (en) * | 2018-01-17 | 2018-08-17 | 莆田市超维二维科技发展有限公司 | A kind of ultracapacitor and preparation method thereof |
| CN115305706A (en) * | 2022-07-25 | 2022-11-08 | 南通大学 | MnO 2 Modified graphene nanocomposite material and preparation method and application thereof |
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| CN115305706A (en) * | 2022-07-25 | 2022-11-08 | 南通大学 | MnO 2 Modified graphene nanocomposite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106252099B (en) | 2018-04-10 |
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