CN106252099B - A kind of ultracapacitor - Google Patents
A kind of ultracapacitor Download PDFInfo
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- CN106252099B CN106252099B CN201610744986.2A CN201610744986A CN106252099B CN 106252099 B CN106252099 B CN 106252099B CN 201610744986 A CN201610744986 A CN 201610744986A CN 106252099 B CN106252099 B CN 106252099B
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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
The invention belongs to supercapacitor technologies field, a kind of more particularly to ultracapacitor, including electrode slice, barrier film, pole and shell, the top coat that electrode slice includes collector, is arranged at the primer coating of collection liquid surface and is arranged at primer coating surface, primer coating and top coat include active material, 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 material of primer coating and top coat includes carbon material and conducting polymer；Carbon material has core shell structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is manganese dioxide functional layer；Conducting polymer is at least one of polyaniline, polythiophene and polypyrrole.Relative to prior art, the present invention has good invertibity and electrochemical stability and bending resistance.
Description
Technical field
The invention belongs to supercapacitor technologies field, more particularly to a kind of there is good invertibity, electrochemically stable
The ultracapacitor of property and bending resistance.
Background technology
Ultracapacitor is a kind of efficient, environmentally friendly, new energy-storage travelling wave tube, and it has many of traditional capacitor and battery concurrently
Advantage, such as energy density are high, service life is long, stability is high, safety coefficient is high, environmentally friendly, fast charging and discharging, in consumption electricity
There are wide application space and development prospect in each field such as son, track traffic, Aero-Space, military affairs, national defence, is increasingly becoming
The emphasis of people's developmental research.
But the invertibity of ultracapacitor of the prior art is not good enough, electrochemical stability is also poor, counter-bending
Property is even more undesirable, it is impossible to meets people to the higher and higher requirement of ultracapacitor.
In view of this, a kind of there is the super of good invertibity, electrochemical stability and bending resistance it is necessory to provide
Level capacitor, to meet the needs of people.
The content of the invention
It is an object of the invention to：In view of the shortcomings of the prior art, providing a kind of has good invertibity, electrochemistry steady
The qualitative and ultracapacitor of bending resistance, to meet the needs 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, barrier film, pole and shell, the electrode slice include collector, set
In the collection liquid surface primer coating and be arranged at the top coat on the primer coating surface, the primer coating and institute
Stating top coat includes active material, conductive agent and bonding agent, and the bonding agent content of the primer coating is less than described
The content of the bonding agent of top coat；
The active material of the primer coating and the top coat includes carbon material and conducting polymer, the carbon materials
Expect and the mass ratio of the conducting polymer is（70~95）：（5~30）；
The carbon material has core shell structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is titanium dioxide
Manganese functional layer, the mass ratio of the graphene fiber and CNT are（50~80）：（20~50）；
The conducting polymer is at least one of polyaniline, polythiophene and polypyrrole.
One kind as ultracapacitor of the present invention is improved, a diameter of 500nm-3 μm of the graphene fiber, the stone
The length of black alkene fiber is 5 μm of -2mm, and the intensity of the graphene fiber is 100MPa-300MPa, the graphene fiber
Conductance is 2000S/m-5000S/m.
One kind as ultracapacitor of the present invention is improved, and the CNT is the CNT of single tube wall, and institute
The caliber for stating CNT is 2nm-8nm, and the wall thickness of the CNT is 0.6nm-2nm.
One kind as ultracapacitor of the present invention is improved, the weight average molecular weight of the conducting polymer for 5000 ~
100000。
One kind as ultracapacitor of the present invention is improved, and the thickness of the manganese dioxide functional layer is 80nm-1.5 μm.
One kind as ultracapacitor of the present invention is improved, and the conductive agent is acetylene black or carbon black.
One kind as ultracapacitor of the present invention is improved, and the bonding agent is Kynoar or polytetrafluoroethylene (PTFE).
One kind as ultracapacitor of the present invention is improved, and the mass content of the bonding agent of the primer coating is 5%-8%,
The content of the bonding agent of the top coat is 1%-4%.
One kind as ultracapacitor of the present invention is improved, and the preparation method of the carbon material comprises the following steps：
The first step, the structure of three-electrode system：
Electrolyte：0.5mol/L-2mol/L MnSO4The aqueous solution；
Working electrode：The mixture of graphene fiber and CNT；
To electrode：A diameter of 0.5mm-2mm platinum filament；
Reference electrode：Ag/AgCl, 2mol/L-4mol/L KCl；
Second step, negative electrode galvanostatic deposition：It is 200 μ A/cm to set cathode electrode electric current2-600μA/cm2, sedimentation time is
10min-1h, sedimentation products are rinsed well repeatedly, freeze, produce.
Relative to prior art, active material of the invention has core shell structure, and its stratum nucleare includes graphene fiber and carbon
Nanotube, its shell are manganese dioxide functional layer, and graphene fiber, CNT and manganese dioxide have given full play to transition metal
The cooperative effect of oxide and carbon material, so as to maximumlly play the potentiality of every kind of component, it is set to obtain as far as possible fully
Utilize, chemical property is improved.Specifically, by the graphene fiber with higher electron conduction and CNT with
Manganese dioxide with higher fake capacitance is combined, and manganese dioxide can shorten the path of electronics Mobile Transmission again, so as to big
Amplitude improves the specific capacity and cycle performance of composite.And because fiber has preferable pliability so that table of the present invention
Reveal higher counter-bending and deformability, therefore the present invention can use in terms of wearable device.
In addition, manganese dioxide nano particle deposition, on graphene, good interracial contact adds electrode between the two
Electric conductivity and its contact area between electrolyte, make MnO2Effective rate of utilization greatly improve, show good reversible
Property and electrochemical stability, specifically, manganese dioxide nano particle passes through tunnel-effect（Quantum effect）, realize efficiently reversible
Redox reaction, fake capacitance is produced, and synergy, thus electrochemical performance are produced with graphene, had well
Charge-discharge characteristic and cyclical stability.
The specific capacity of conducting polymer is 5-6 times of carbon material, and energy density and power density are up to 30-50Wh respectively
kg-1With 2-20kW kg-1.The advantages of this two class material of the mixed binding of carbon material and conducting polymer, and show collaboration
Effect, conducting polymer provides fake capacitance, and carbon material serves as skeleton in the composite, and support is played to conducting polymer and is made
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 be contacted with collector, and bonding agent content therein is in normal range (NR), to ensure primer coating and collection
The strong bond of fluid, and top coat is directly to be contacted with primer coating, it needs less bonding agent content can
To realize the strong bond with primer coating, the content of bonding agent in whole coating can be thus reduced, is improved living in coating
Property material content, and then improve ultracapacitor specific capacity and electrical property.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the specific embodiment party of the present invention
Formula is not limited to this.
Embodiment 1
Present embodiments provide a kind of ultracapacitor, including electrode slice, barrier film, pole and shell, the electrode slice
Including collector, it is arranged at the primer coating of the collection liquid surface and is arranged at the top coat on the primer coating surface,
The primer coating and the top coat include active material, conductive agent and bonding agent, and the primer coating is viscous
Connect content of the agent content less than the bonding agent of the top coat；
The active material of the primer coating and the top coat includes carbon material and conducting polymer, the carbon materials
The mass ratio of material and the conducting polymer is 90：10；
The carbon material has core shell structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is titanium dioxide
Manganese functional layer, the mass ratio of the graphene fiber and CNT is 70：30；
The conducting polymer is polyaniline.
A diameter of 500nm-3 μm of graphene fiber, the length of the graphene fiber are 5 μm of -2mm, the graphene
The intensity of fiber is 100MPa-300MPa, and the conductance of the graphene fiber is 2000S/m-5000S/m.
CNT is the CNT of single tube wall, and the caliber of the CNT is 2nm-8nm, the 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 carbon material comprises the following steps：
The first step, the structure of three-electrode system：
Electrolyte：1mol/L MnSO4The aqueous solution；
Working electrode：The mixture of graphene fiber and CNT；
To electrode：A diameter of 102mm platinum filament；
Reference electrode：Ag/AgCl, 3mol/L KCl；
Second step, negative electrode galvanostatic deposition：It is 400 μ A/cm to set cathode electrode electric current2, sedimentation time 40min will
Sedimentation products are rinsed well repeatedly, are freezed, are produced.
Embodiment 2
Present embodiments provide a kind of ultracapacitor, including electrode slice, barrier film, pole and shell, the electrode slice
Including collector, it is arranged at the primer coating of the collection liquid surface and is arranged at the top coat on the primer coating surface,
The primer coating and the top coat include active material, conductive agent and bonding agent, and the primer coating is viscous
Connect content of the agent content less than the bonding agent of the top coat；
The active material of the primer coating and the top coat includes carbon material and conducting polymer, the carbon materials
The mass ratio of material and the conducting polymer is 80：20；
The carbon material has core shell structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is titanium dioxide
Manganese functional layer, the mass ratio of the graphene fiber and CNT is 60：40；
The conducting polymer is polythiophene.
A diameter of 500nm-3 μm of the graphene fiber, the length of the graphene fiber are 5 μm of -2mm, the stone
The intensity of black alkene fiber is 100MPa-300MPa, and the conductance of the graphene fiber is 2000S/m-5000S/m.
The CNT is the CNT of single tube wall, and the caliber of the CNT is 2nm-8nm, the carbon
The wall thickness of nanotube is 0.6nm-2nm.
The weight average molecular weight of the conducting polymer is 30000.
The thickness of the manganese dioxide functional layer is 80nm-1.5 μm.
Conductive agent is carbon black, and bonding agent is polytetrafluoroethylene (PTFE).
The mass content of the bonding agent of primer coating is 6%, and the content of the bonding agent of the top coat is 2%.
The preparation method of carbon material comprises the following steps：
The first step, the structure of three-electrode system：
Electrolyte：0.7mol/L MnSO4The aqueous solution；
Working electrode：The mixture of graphene fiber and CNT；
To electrode：A diameter of 1.5mm platinum filament；
Reference electrode：Ag/AgCl, 2.5mol/L KCl；
Second step, negative electrode galvanostatic deposition：It is 300 μ A/cm to set cathode electrode electric current2, sedimentation time 30min will
Sedimentation products are rinsed well repeatedly, are freezed, are produced.
Embodiment 3
Present embodiments provide a kind of ultracapacitor, including electrode slice, barrier film, pole and shell, the electrode slice
Including collector, it is arranged at the primer coating of the collection liquid surface and is arranged at the top coat on the primer coating surface,
The primer coating and the top coat include active material, conductive agent and bonding agent, and the primer coating is viscous
Connect content of the agent content less than the bonding agent of the top coat；
The active material of the primer coating and the top coat includes carbon material and conducting polymer, the carbon materials
The mass ratio of material and the conducting polymer is 75：25；
The carbon material has core shell structure, and its stratum nucleare includes graphene fiber and CNT, and its shell is titanium dioxide
Manganese functional layer, the mass ratio of the graphene fiber and CNT is 75：25；
The conducting polymer is polypyrrole.
A diameter of 500nm-3 μm of the graphene fiber, the length of the graphene fiber are 5 μm of -2mm, the stone
The intensity of black alkene fiber is 100MPa-300MPa, and the conductance of the graphene fiber is 2000S/m-5000S/m.
The CNT is the CNT of single tube wall, and the caliber of the CNT is 2nm-8nm, the carbon
The wall thickness of nanotube is 0.6nm-2nm.
The weight average molecular weight of the 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 polytetrafluoroethylene (PTFE).
The mass content of the bonding agent of primer coating is 5.5%, and the content of the bonding agent of the top coat is 2.5%.
The preparation method of the carbon material comprises the following steps：
The first step, the structure of three-electrode system：
Electrolyte：1.5mol/L MnSO4The aqueous solution；
Working electrode：The mixture of graphene fiber and CNT；
To electrode：A diameter of 0.7mm platinum filament；
Reference electrode：Ag/AgCl, 3.5mol/L KCl；
Second step, negative electrode galvanostatic deposition：It is 500 μ A/cm to set cathode electrode electric current2, sedimentation time 20min will
Sedimentation products are rinsed well repeatedly, are freezed, are produced.
Practice have shown that：The cycle-index of the ultracapacitor of embodiment 1 to 3 is more than 200,000 times.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (8)
1. a kind of ultracapacitor, it is characterised in that including electrode slice, barrier film, pole and shell, it is characterised in that：It is described
Electrode slice includes collector, is arranged at the primer coating of the collection liquid surface and is arranged at the top layer on the primer coating surface
Coating, the primer coating and the top coat include active material, conductive agent and bonding agent, and the primer coating
Bonding agent content be less than the top coat bonding agent content；
The active material of the primer coating and the top coat includes carbon material and conducting polymer, the carbon material and
The mass ratio of the conducting polymer is (70~95)：(5~30)；The carbon material has core shell structure, and its stratum nucleare includes stone
Black alkene fiber and CNT, its shell are manganese dioxide functional layer, and the mass ratio of the graphene fiber and CNT is
(50~80)：(20~50)；
The conducting polymer is at least one of polyaniline, polythiophene and polypyrrole；
The preparation method of the carbon material comprises the following steps：
The first step, the structure of three-electrode system：
Electrolyte：0.5mol/L-2mol/L MnSO4The aqueous solution；
Working electrode：The mixture of graphene fiber and CNT；
To electrode：A diameter of 0.5mm-2mm platinum filament；
Reference electrode：Ag/AgCl, 2mol/L-4mol/L KCl；
Second step, negative electrode galvanostatic deposition：It is 200 μ A/cm to set cathode electrode electric current2-600μA/cm2, sedimentation time is
10min-1h, sedimentation products are rinsed well repeatedly, freeze, produce.
2. ultracapacitor according to claim 1, it is characterised in that a diameter of 500nm-3 μ of the graphene fiber
M, the length of the graphene fiber are 5 μm of -2mm, and the intensity of the graphene fiber is 100MPa-300MPa, the graphite
The conductance of alkene fiber is 2000S/m-5000S/m.
3. ultracapacitor according to claim 1, it is characterised in that the CNT is the carbon nanometer of single tube wall
Pipe, and the caliber of the CNT is 2nm-8nm, and the wall thickness of the CNT is 0.6nm-2nm.
4. ultracapacitor according to claim 1, it is characterised in that the weight average molecular weight of the conducting polymer is
5000~100000.
5. ultracapacitor according to claim 1, it is characterised in that the thickness of the manganese dioxide functional layer is
80nm-1.5μm。
6. ultracapacitor according to claim 1, it is characterised in that the conductive agent is acetylene black or carbon black.
7. ultracapacitor according to claim 1, it is characterised in that the bonding agent is Kynoar or polytetrafluoro
Ethene.
8. ultracapacitor according to claim 1, it is characterised in that the mass content of the bonding agent of the primer coating
For 5%-8%, the content of the bonding agent of the top coat is 1%-4%.
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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 |
| CN107868199B (en) * | 2017-11-02 | 2020-09-08 | 深圳市铭科科技有限公司 | Ferrocenyl-terminated polyurethane, supercapacitor 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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| CN101901694A (en) * | 2010-06-23 | 2010-12-01 | 万星光电子(东莞)有限公司 | Super capacitor electrode slice |
| CN102203891A (en) * | 2008-08-28 | 2011-09-28 | 日本瑞翁株式会社 | Electrode for lithium ion capacitor and lithium ion capacitor |
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| CN103779104A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Super capacitor electrode and preparation method thereof |
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| CN1264094C (en) * | 2002-09-06 | 2006-07-12 | 上海金诺网络安全技术发展股份有限公司 | Method for construction of computer application system using compact disc and mobile memory medium |
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| CN102203891A (en) * | 2008-08-28 | 2011-09-28 | 日本瑞翁株式会社 | Electrode for lithium ion capacitor and lithium ion capacitor |
| CN101562078A (en) * | 2009-05-15 | 2009-10-21 | 深圳清华大学研究院 | Super-capacitor and preparation method thereof |
| CN101901694A (en) * | 2010-06-23 | 2010-12-01 | 万星光电子(东莞)有限公司 | Super capacitor electrode slice |
| CN103779104A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Super capacitor electrode and preparation method thereof |
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