CN108470635A - A kind of low internal resistance, high power graphene super capacitor electrode slice and preparation method thereof - Google Patents
A kind of low internal resistance, high power graphene super capacitor electrode slice and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 35
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
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- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
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- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims 1
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- 238000004146 energy storage Methods 0.000 abstract description 8
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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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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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to graphene super capacitor electrode slice more particularly to a kind of low internal resistances, high power graphene super capacitor electrode slice and preparation method thereof, belong to new energy energy storage device technical field.The Graphene electrodes piece includes collector and Graphene electrodes slurry, wherein Graphene electrodes slurry include mass percent be respectively 75 93% graphene, 2 10% conductive agent, 5 15% binder, collector is coated aluminum foil.The thickness of Graphene electrodes piece is 100 200 μm, and surface density is 0.5 0.7g/cm3.Ultracapacitor Graphene electrodes piece has the characteristics such as low internal resistance, high power.The ultracapacitor Graphene electrodes piece of the present invention has the characteristics such as low internal resistance, high power.
Description
Technical field
The present invention relates to graphene super capacitor electrode slice more particularly to a kind of low internal resistance, high power graphene are super
Capacitor electrode slice and preparation method thereof belongs to new energy energy storage device technical field.
Background technology
Ultracapacitor has high safety, million cycle lives, super high power characteristic, low temperature performance well, environment
Close friend is the strong selection for substituting accumulator.It is national strategy new industry, is new-energy automobile core component and energy-efficient
The core key energy storage device in field.But commercialization ultracapacitor monomer capacity is small at present, energy density is low, conventional carbon
Near limit, power density are difficult to further be promoted base double layer capacitor energy density, and there is an urgent need to develop new material, exploitations
New process is to realize being substantially improved for energy density and power density.
The specific surface area of graphene Yin Qigao, excellent electric conductivity, high electron mobility and special two-dimension flexible knot
Structure, more than ten years of past have caused great concern in energy storage field.Ultracapacitor is considered as most possibly realizing in a short time
The industrial field of graphene scale application.Applied to ultracapacitor, graphene can play the dual of " conduction " and " energy storage "
Characteristic, a large amount of experimental result confirm that graphene is low internal resistance, the ideal electrode material of high-capacity super capacitor.But graphene
Density of material is relatively low, liquid absorption amount is big, slurry solid content is low, and traditional wet coating technique is difficult to realize the system of Graphene electrodes piece
It is standby.
Invention content
The purpose of the present invention is being directed to graphene super capacitor electrode slice, a kind of high ratio is provided
Energy, low internal resistance, high power graphene super capacitor electrode slice.
To achieve the above object of the invention, technical solution of the present invention includes the following steps：
A kind of low internal resistance, high power graphene super capacitor electrode slice, the Graphene electrodes piece include collector with
And Graphene electrodes slurry, it is respectively the graphene of 75-93%, 2-10% that wherein Graphene electrodes slurry, which includes mass percent,
Conductive agent, 5-15% binder, collector is coated aluminum foil.
The power density for improving Graphene electrodes, in addition to other than Graphene electrodes design on material structure, graphene carbon film
Interfacial structure design between collector is also to pay close attention to, and interface contact resistance directly affects the internal resistance of device.Graphite
Alkene density of material is relatively low, large specific surface area, and normal aluminium foil collector is difficult to ensure the adhesion of graphene carbon film and collector.Cause
It is very necessary that this carries out proper treatment to aluminium collector.The surface of industrial large capacity ultracapacitor aluminium foil carries out
Etching processing etches later aluminium foil and is known as etched foil, and corrosive aluminum foil substantially increases carbon film and afflux because of its rough surface
Cohesiveness between body, and capacitor performance is more stablized.But electric conductivity reduces after aluminium foil is etched, while mechanical property
It reduces.The thickness of corrosive aluminum foil is typically maintained in 20 μm or more in commercial Application, because the thickness of corrosive aluminum foil determines its power
Performance is learned, especially during mass automatic production double layer capacitor, thickness is opposite less than 20 μm of corrosive aluminum foil
It is easy broken belt.It develops relatively thin and keep high electrical conductivity, more excellent mechanical property and flexible novel aluminium foil, is reduced in device
Resistance, and be the effective way for reducing the occupied quality of collector and improving device than energy.
In above-mentioned low internal resistance, high power graphene super capacitor electrode slice, the thickness of the Graphene electrodes piece is
100-200 μm, surface density 0.5-0.7g/cm3.If the blocked up high rate performance that can influence material of electrode slice, if electrode slice is excessively thin,
The energy density of final integral device can then be reduced.And the density of Graphene electrodes piece is too small, influences the volume of ultracapacitor
Energy density is unfavorable for vehicle-mounted accumulation power supply in rail traffic and uses.The present invention Graphene electrodes piece thickness it is moderate, density compared with
Height can guarantee that device has higher volume energy density.
Preferably, the thickness of the Graphene electrodes piece is 140-180 μm, surface density 0.55-0.65g/cm3。
In above-mentioned low internal resistance, high power graphene super capacitor electrode slice, the specific surface area of the graphene is
1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is more than
99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm.Graphite
The physical parameter of alkene directly affects the final performance of device, and grapheme material aperture is moderate, and specific surface area is higher, is more conducive to carry
The energy storage capacity of high material.But the specific surface area of graphene is to be mutually related with density, specific surface area is higher, and density is got over
It is low, cause pole piece to be difficult to and the problems such as energy density is relatively low.Based on this, the specific surface area of grapheme material should not be too
Greatly, medium density is preferably.Aperture needs based on mesoporous, matches with electrolyte intermediate ion size.If aperture is too small, specific surface
Product utilization rate is low, and the energy of storage is low, and influences high rate performance.Secondly, the particle of grapheme material it is excessive or it is too small not
Conducive to the film forming of Graphene electrodes, particle is excessive to influence the utilization rate and high rate performance of material, while being easy to form stress concentration,
It is unfavorable for forming a film；Particle is too small, needs to add more bonding agents, contact resistance increases, and reduces the performance of combination electrode.Again
Secondary, functional group content, the metals content impurity on grapheme material surface are higher, under high potential, are easy to induce electrolyte decomposition
Aerogenesis causes capacity to decline, and internal resistance increases.Therefore, the present invention by the basic physical properties state modulator of grapheme material in above-mentioned model
In enclosing.
In above-mentioned low internal resistance, high power graphene super capacitor electrode slice, coated aluminum foil thickness is 10-20 μm, is applied
Layer thickness is 100nm-2 μm.
Preferably, the thickness of the coated aluminum foil is 12-16 μm, coating layer thickness is 500nm-1 μm.
In above-mentioned low internal resistance, high power graphene super capacitor electrode slice, the conductive agent is conductive carbon black, receives
One or more of rice carbon fiber, carbon nanotube, graphene conductive agent.
Preferably, the conductive agent is combined conductive agent, it is that carbon black, carbon nanotube and graphene three-phase composite are conductive
Agent.The carbon black of zero dimension is contacted by " point-point ", and one-dimensional electric agent is contacted by " line-line ", and two-dimensional graphene conductive agent passes through
" surface-to-surface " contact structure three-dimensional conductive access.Different dimensions combined conductive agent will produce synergistic effect, be connect by " point-line-face "
Tactile method is more easy to structure conductive path, reduces the additive amount of conductive agent in electrode.
Further preferably, the mass ratio of carbon black, carbon nanotube and graphene is 1：(0.8-1.2)：(0.8-1.2).
In above-mentioned low internal resistance, high power graphene super capacitor electrode slice, the bonding agent is Kynoar
(PVDF), polytetrafluoroethylene (PTFE) (PTFE), butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), polyvinylpyrrolidone
(PVP), the one or more of Kynoar-hexafluoropropene (PVDF-HFP), native cellulose.
Preferably, the bonding agent is PTFE.Because PTFE has good linear deformation mode, of the invention
Preferably PTFE makees good bonding agent during dry process Graphene electrodes piece.
It is another object of the present invention to provide a kind of above-mentioned low internal resistance, high power graphene super capacitor electrode slices
Preparation method, the preparation method includes the following steps：
By mass percentage (75-93) by graphene, conductive agent and bonding agent：(2-10)：(5-15) is pre-mixed, and
It is sheared, then gained dry mixture is carried out vertically rolling successively and is rolled with level, obtain graphene carbon film；
Graphene carbon film is pasted together with collector by conducting resinl, be heating and curing to obtain graphene super capacitor electrode
Pole piece.
Above-mentioned low internal resistance, high power graphene super capacitor electrode slice preparation method in, vertically roll and horizontal
The pressure rolled is 100-300MPa.In the present invention the size of pressure influence the thickness of final graphene carbon film, density and
Density.If pressure is too small, carbon film void is larger, and density is relatively low, and pole piece is thicker；Reverse pressure is too big, and carbon film fold is even
Cracking.
Preferably, the pressure rolled is 120-250MPa.Still further preferably, the pressure rolled is
150MPa。
Above-mentioned low internal resistance, high power graphene super capacitor electrode slice preparation method in, the temperature that is heating and curing
It it is 100-200 DEG C, the time being heating and curing is 10-30min.
Compared with prior art, the present invention selects main energy storage material of the suitable grapheme material as ultracapacitor
Material, graphene have the specific surface area of superelevation and excellent electric conductivity, it is considered to be a kind of low internal resistance, high-capacity super capacitance
Device energy storage material.For the problems such as grapheme material density is low, pole piece is difficult to, the present invention uses dry method electrode machining work
Skill, and apply novel microthin coating aluminium foil.Coated aluminum foil has coarse surface, can guarantee graphene carbon film and collector it
Between good cohesiveness.Compared to corrosive aluminum foil, coated aluminum foil has better electric conductivity, and stone can be reduced using coated aluminum foil
The internal resistance of black alkene electrode slice.In addition, coated aluminum foil has better mechanical property and flexibility, in the premise for ensureing machinability
Under, coated aluminum foil can be thinner, can reduce the occupied quality of collector and improve device and compare energy.
Secondly, the present invention uses carbon black/carbon nano tube/graphene three-phase composite conductive agent, makes full use of different geometry knots
Synergistic effect between the conductive agent of structure builds three-dimensional conductive network by " point-line-face " way of contact, reduces pole piece internal resistance, carry
The power density of high device.
Therefore, ultracapacitor Graphene electrodes piece of the invention has the characteristics such as low internal resistance, high power.
Description of the drawings
Fig. 1 is 1 grapheme material stereoscan photograph of the embodiment of the present invention.
Fig. 2 is 1 coating aluminium collector schematic diagram of the embodiment of the present invention.
Fig. 3 is 1 coated aluminum foil of the embodiment of the present invention, corrosive aluminum foil collector capacity accelerated aging curve.
Fig. 4 is 1 coated aluminum foil of the embodiment of the present invention, corrosive aluminum foil collector internal resistance accelerated aging curve.
Specific implementation mode
The following is specific embodiments of the present invention is described with reference to the drawings, and is further retouched to technical scheme of the present invention work
It states, however, the present invention is not limited to these examples.
Embodiment 1
By graphene, conductive agent and bonding agent by mass percentage 88:6:6 uniformly mixing in advance, above-mentioned gained is mixed
Object is closed to exceed the speed limit shear-mixed under conditions of shear velocity is 10000rpm, then under 150MPa pressure, dry mixture according to
Secondary progress " vertical " and two step of "horizontal" roll, and obtain graphene carbon film in homogeneous thickness.The specific surface area of the graphene
For 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is big
In 99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm,
Microscopic appearance is as shown in Figure 1.The conductive agent be conductive carbon black, carbon nanotube and graphene three-phase composite conductive agent, three
The mass ratio of person is 1:1:1.Combined conductive agent powder is as obtained by freeze-drying after the mixing of liquid phase grinding distribution.The bonding
Agent is PTFE.
Graphene carbon film obtained above is pasted together with coated aluminum foil collector by conducting resinl, is added at 160 DEG C
Heat cure can obtain Graphene electrodes piece after twenty minutes.The thickness of the coated aluminum foil is 14 μm, and the thickness of floating coat is 1
μm.The Graphene electrodes piece thickness is 150 μm, surface density 0.66g/cm3, electronic photo is as shown in Figure 3.
Graphene electrodes piece is prepared into convoluted stone by cutting, winding, assembling, dry, fluid injection and packaging technology successively
Black alkene ultracapacitor.Monomer capacity 3600F after testing, internal resistance 0.12m Ω.Coated aluminum foil collector ultracapacitor and corrosion
The accelerated aging curve of specific capacity and DC internal resistance of the aluminum foil current collector ultracapacitor under the conditions of 65 DEG C of -2.85V is shown in figure
3, shown in 4.As seen from the figure, during accelerating lifetime testing, coated aluminum foil capacity of super capacitor conservation rate is higher than corrosive aluminum foil
Ultracapacitor, and internal resistance increase tendency is less than corrosive aluminum foil ultracapacitor.
Embodiment 2
By graphene, conductive agent and bonding agent by mass percentage 90：4：6 uniformly mixing in advance, above-mentioned gained is mixed
Object is closed to exceed the speed limit shear-mixed under conditions of shear velocity is 11000rpm, then under 200MPa pressure, dry mixture according to
Secondary progress " vertical " and two step of "horizontal" roll, and obtain graphene carbon film in homogeneous thickness.The specific surface area of the graphene
For 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is big
In 99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm.Institute
The conductive agent stated is the three-phase composite conductive agent of conductive carbon black, carbon nanotube and graphene, and the mass ratio of three is 1:1.1:
0.9.Combined conductive agent powder is as obtained by freeze-drying after the mixing of liquid phase grinding distribution.The binder is Kynoar
(PVDF)。
Graphene carbon film obtained above is pasted together with coated aluminum foil collector by conducting resinl, is added at 180 DEG C
Heat cure can obtain Graphene electrodes piece after 12 minutes.The coated aluminum foil thickness is 12 μm, coating layer thickness 600nm.It is described
Graphene electrodes piece thickness is 140 μm, surface density 0.63g/cm3。
Graphene electrodes piece is prepared into convoluted stone by cutting, winding, assembling, dry, fluid injection and packaging technology successively
Black alkene ultracapacitor.Monomer capacity 3500F after testing, internal resistance 0.13m Ω.
Embodiment 3
By graphene, conductive agent and bonding agent by mass percentage 85：8：7 uniformly mixing in advance, above-mentioned gained is mixed
It is the shear-mixed that exceeds the speed limit under conditions of 9000rpm that object, which is closed, in shear velocity, and then under 250MPa pressure, dry mixture is successively
It carries out " vertical " and two step of "horizontal" rolls, obtain graphene carbon film in homogeneous thickness.The specific surface area of the graphene is
1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is more than
99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm.It is described
Conductive agent be conductive carbon black, carbon nanotube and graphene three-phase composite conductive agent, the mass ratio of three is 1:0.9:1.1.
Combined conductive agent powder is as obtained by freeze-drying after the mixing of liquid phase grinding distribution.The binder is butadiene-styrene rubber (SBR).
Graphene carbon film obtained above is pasted together with coated aluminum foil collector by conducting resinl, is added at 140 DEG C
Heat cure can obtain Graphene electrodes piece after 28 minutes.The coated aluminum foil thickness is 16 μm, and coating layer thickness is 1 μm.It is described
Graphene electrodes piece thickness is 160 μm, surface density 0.62g/cm3。
Graphene electrodes piece is prepared into convoluted stone by cutting, winding, assembling, dry, fluid injection and packaging technology successively
Black alkene ultracapacitor.Monomer capacity 3410F after testing, internal resistance 0.14m Ω.
Embodiment 4
By graphene, conductive agent and bonding agent by mass percentage 78：8：14 uniformly mixing in advance, above-mentioned gained is mixed
Object is closed to exceed the speed limit shear-mixed under conditions of shear velocity is 11000rpm, then under 220MPa pressure, dry mixture according to
Secondary progress " vertical " and two step of "horizontal" roll, and obtain graphene carbon film in homogeneous thickness.The specific surface area of the graphene
For 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is big
In 99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm.Institute
The conductive agent stated is conductive carbon black, carbon nanotube in mass ratio 1：The combined conductive agent of 1 composition.Combined conductive agent powder is to pass through
It is freeze-dried gained after the mixing of liquid phase grinding distribution.The binder is sodium carboxymethylcellulose (CMC).
Graphene carbon film obtained above is pasted together with coated aluminum foil collector by conducting resinl, is added at 120 DEG C
Heat cure can obtain Graphene electrodes piece after 25 minutes.The coated aluminum foil thickness is 18 μm, coating layer thickness 600nm.It is described
Graphene electrodes piece thickness is 120 μm, surface density 0.58g/cm3。
Graphene electrodes piece is prepared into convoluted stone by cutting, winding, assembling, dry, fluid injection and packaging technology successively
Black alkene ultracapacitor.Monomer capacity 3350F after testing, internal resistance 0.15m Ω.
Embodiment 5
By graphene, conductive agent and bonding agent by mass percentage 93：2：5 uniformly mixing in advance, above-mentioned gained is mixed
Object is closed to exceed the speed limit shear-mixed under conditions of shear velocity is 12000rpm, then under 100MPa pressure, dry mixture according to
Secondary progress " vertical " and two step of "horizontal" roll, and obtain graphene carbon film in homogeneous thickness.The specific surface area of the graphene
For 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is big
In 99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm.Institute
The conductive agent stated is the three-phase composite conductive agent of conductive carbon black, carbon nanotube and graphene, and the mass ratio of three is 1:1.1:
0.9.Combined conductive agent powder is as obtained by freeze-drying after the mixing of liquid phase grinding distribution.The binder is polyvinyl pyrrole
Alkanone (PVP).
Graphene carbon film obtained above is pasted together with coated aluminum foil collector by conducting resinl, is added at 100 DEG C
Heat cure can obtain Graphene electrodes piece after 30 minutes.The coated aluminum foil thickness is 10 μm, coating layer thickness 100nm.It is described
Graphene electrodes piece thickness is 100, surface density 0.56g/cm3。
Graphene electrodes piece is prepared into convoluted stone by cutting, winding, assembling, dry, fluid injection and packaging technology successively
Black alkene ultracapacitor.Monomer capacity 3280F after testing, internal resistance 0.11m Ω.
Embodiment 6
By graphene, conductive agent and bonding agent by mass percentage 75：10：15 uniformly mixing in advance, by above-mentioned gained
Mixture exceeds the speed limit shear-mixed under conditions of shear velocity is 8000rpm, then under 300MPa pressure, dry mixture according to
Secondary progress " vertical " and two step of "horizontal" roll, and obtain graphene carbon film in homogeneous thickness.The specific surface area of the graphene
For 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size is 7-10 μm, and carbon content is big
In 99.8%, oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, and total metal contents in soil is less than 100ppm.Institute
The conductive agent stated is carbon nano-fiber.Combined conductive agent powder is as obtained by freeze-drying after the mixing of liquid phase grinding distribution.Institute
It is Kynoar-hexafluoropropene (PVDF-HFP) to state binder.
Graphene carbon film obtained above is pasted together with coated aluminum foil collector by conducting resinl, is added at 200 DEG C
Heat cure can obtain Graphene electrodes piece after ten minutes.The coated aluminum foil thickness is 20 μm, and coating layer thickness is 2 μm.The stone
Black alkene electrode slice thickness is 200 μm, surface density 0.54g/cm3。
Graphene electrodes piece is prepared into convoluted stone by cutting, winding, assembling, dry, fluid injection and packaging technology successively
Black alkene ultracapacitor.Monomer capacity 3300F after testing, internal resistance 0.16m Ω.
Embodiment 7
With differing only in for embodiment 1, the specific surface area of the graphene in the embodiment 7 is 700-1000m2/ g, shakes
Real density is 0.3-0.5g/cm3.Monomer capacity 3000F after testing, internal resistance 0.12m Ω.Embodiment 8
With differing only in for embodiment 1, the conductive agent in the embodiment 8 is carbon nanotube and graphene in mass ratio 1:
The conductive agent of 1 composition, is made ultracapacitor.Monomer capacity 3400F after testing, internal resistance 0.13m Ω.
Embodiment 9
With differing only in for embodiment 1, the coated aluminum foil thickness in the embodiment 9 is 25 μm, and coating layer thickness is 2.5 μ
Ultracapacitor is made in m.Monomer capacity 3180F after testing, internal resistance 0.16m Ω.Comparative example 11
With differing only in for embodiment 1, the collector in the comparative example 1 is corrosive aluminum foil, and thickness is 20 μm, other steps
Suddenly it compares, is not repeated herein.Monomer capacity 3220F after testing, internal resistance 0.19m Ω.Specific capacity under the conditions of 65 DEG C of -2.85V
It is as shown in Figure 3,4 with the accelerated aging curve of DC internal resistance.
The ultracapacitor initial internal resistance of coated aluminum foil is significantly lower than corrosive aluminum foil, and initial capacity is also higher by about 10%.By
Comparison is it is found that coated aluminum foil is long-life, low internal resistance, the preferable selection of high-power current collector of super capacitor.
In addition, right in place of the non-limit of claimed technical scope midrange and in embodiment technical solution
The same replacement of single or multiple technical characteristics is formed by new technical solution, equally all in claimed model
In enclosing；Simultaneously the present invention program it is all enumerate or unrequited embodiment in, parameters in the same embodiment are only
Indicate an example (i.e. a kind of feasible scheme) for its technical solution.
Specific embodiment described herein is only an example for the spirit of the invention.Technology belonging to the present invention is led
The technical staff in domain can do various modifications or supplement to described specific embodiment or substitute by a similar method, but simultaneously
The spirit or beyond the scope defined by the appended claims of the present invention is not deviated by.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious that can make various changes or correct without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of low internal resistance, high power graphene super capacitor electrode slice, which is characterized in that the Graphene electrodes piece includes
Collector and Graphene electrodes slurry, wherein Graphene electrodes slurry include the graphite that mass percent is respectively 75-93%
The binder of alkene, the conductive agent of 2-10%, 5-15%, collector are coated aluminum foil.
2. low internal resistance according to claim 1, high power graphene super capacitor electrode slice, which is characterized in that described
The thickness of Graphene electrodes piece is 100-200 μm, surface density 0.5-0.7g/cm3。
3. low internal resistance according to claim 1, high power graphene super capacitor electrode slice, which is characterized in that described
Graphene specific surface area be 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size
It it is 7-10 μm, carbon content is more than 99.8%, and oxygen-containing functional group content is less than 0.35meq/g, and water content is less than 0.40%, total metal
Content is less than 100ppm.
4. low internal resistance according to claim 1, high power graphene super capacitor electrode slice, which is characterized in that coating
Aluminum foil thickness is 10-20 μm, and coating layer thickness is 100nm-2 μm.
5. low internal resistance according to claim 1, high power graphene super capacitor electrode slice, which is characterized in that described
Conductive agent be conductive carbon black, carbon nano-fiber, carbon nanotube, one or more of graphene conductive agent.
6. low internal resistance, high power graphene super capacitor electrode slice according to claim 1 or 5, which is characterized in that institute
The conductive agent stated is combined conductive agent, is carbon black, carbon nanotube and graphene three-phase composite conductive agent.
7. low internal resistance according to claim 6, high power graphene super capacitor electrode slice, which is characterized in that carbon black,
The mass ratio of carbon nanotube and graphene is 1：(0.8-1.2)：(0.8-1.2).
8. low internal resistance according to claim 1, high power graphene super capacitor electrode slice, which is characterized in that described
Bonding agent be Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE), butadiene-styrene rubber (SBR), sodium carboxymethylcellulose
(CMC), one kind or several of polyvinylpyrrolidone (PVP), Kynoar-hexafluoropropene (PVDF-HFP), native cellulose
Kind.
9. the preparation method of a kind of low internal resistance as described in claim 1, high power graphene super capacitor electrode slice, special
Sign is that the preparation method includes the following steps：
By mass percentage (75-93) by graphene, conductive agent and bonding agent：(2-10)：(5-15) is pre-mixed, and is carried out
Shearing, then gained dry mixture is carried out vertically rolling successively and is rolled with level, obtain graphene carbon film；
Graphene carbon film is pasted together with collector by conducting resinl, be heating and curing to obtain graphene electrode of super capacitor
Piece.
10. the preparation method of low internal resistance according to claim 9, high power graphene super capacitor electrode slice, special
Sign is, vertically rolls and the horizontal pressure rolled is 100-300MPa.
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|---|---|---|---|---|
| WO2019153907A1 (en) * | 2018-02-07 | 2019-08-15 | 宁波中车新能源科技有限公司 | Low internal resistance and high power graphene supercapacitor electrode sheet and preparation method therefor |
| CN114613605A (en) * | 2020-12-04 | 2022-06-10 | 山东圣泉新能源科技有限公司 | Capacitor pole piece, preparation method thereof and super capacitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104681306A (en) * | 2014-12-12 | 2015-06-03 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor cathode pulp |
| CN105489392A (en) * | 2015-11-26 | 2016-04-13 | 中国第一汽车股份有限公司 | Graphene pole piece and preparation method therefor |
| CN105551830A (en) * | 2015-12-22 | 2016-05-04 | 宁波南车新能源科技有限公司 | Preparation method of active graphene/active carbon composite electrode plate |
| CN107492665A (en) * | 2017-08-10 | 2017-12-19 | 重庆鲁岳新能源科技有限公司 | A kind of novel graphite alkene positive electrode piece of lithium-ion power battery and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| CN103839695A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene electrode plate, and preparation method and application thereof |
| CN103839694B (en) * | 2012-11-27 | 2016-09-07 | 海洋王照明科技股份有限公司 | A kind of preparation method of Graphene/metal collector |
| CN108470635A (en) * | 2018-02-07 | 2018-08-31 | 宁波中车新能源科技有限公司 | A kind of low internal resistance, high power graphene super capacitor electrode slice and preparation method thereof |
-
2018
- 2018-02-07 CN CN201810124398.8A patent/CN108470635A/en active Pending
- 2018-12-21 WO PCT/CN2018/122645 patent/WO2019153907A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104681306A (en) * | 2014-12-12 | 2015-06-03 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor cathode pulp |
| CN105489392A (en) * | 2015-11-26 | 2016-04-13 | 中国第一汽车股份有限公司 | Graphene pole piece and preparation method therefor |
| CN105551830A (en) * | 2015-12-22 | 2016-05-04 | 宁波南车新能源科技有限公司 | Preparation method of active graphene/active carbon composite electrode plate |
| CN107492665A (en) * | 2017-08-10 | 2017-12-19 | 重庆鲁岳新能源科技有限公司 | A kind of novel graphite alkene positive electrode piece of lithium-ion power battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019153907A1 (en) * | 2018-02-07 | 2019-08-15 | 宁波中车新能源科技有限公司 | Low internal resistance and high power graphene supercapacitor electrode sheet and preparation method therefor |
| CN114613605A (en) * | 2020-12-04 | 2022-06-10 | 山东圣泉新能源科技有限公司 | Capacitor pole piece, preparation method thereof and super capacitor |
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