CN108470636A - A kind of Graphene electrodes piece and preparation method thereof and the method for preparing ultracapacitor with it - Google Patents
A kind of Graphene electrodes piece and preparation method thereof and the method for preparing ultracapacitor with it Download PDFInfo
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- CN108470636A CN108470636A CN201810124956.0A CN201810124956A CN108470636A CN 108470636 A CN108470636 A CN 108470636A CN 201810124956 A CN201810124956 A CN 201810124956A CN 108470636 A CN108470636 A CN 108470636A
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/84—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
Abstract
The method that high specific energy, ultrahigh power graphite alkene ultracapacitor are prepared the present invention relates to a kind of Graphene electrodes piece and preparation method thereof and with it, belongs to new energy energy storage device technical field.The Graphene electrodes piece includes collector and Graphene electrodes slurry, and Graphene electrodes slurry includes 75 93% graphene of mass percent, 2 10% conductive agents, 5 15% binders, and collector is foamed aluminium collector.The specific surface area of graphene is 1000 1500m2/ g, tap density are 0.2 0.5g/cm3, aperture is 2 10nm, and particle size is 7 10 μm, and 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%, and total metal contents in soil is less than 100ppm.Graphene super capacitor energy density made from the electrode slice is 12Wh/kg, power density 30.14kW/kg.
Description
Technical field
High specific energy, ultrahigh power graphite alkene are prepared the present invention relates to a kind of Graphene electrodes piece and preparation method thereof and with it
The method of ultracapacitor 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.The U.S.《Discovery》It is classified as the big scientific and technological discovery in the world seven in 2006
One.It is national strategy new industry, is new-energy automobile core component and the core key energy storage device in energy-efficient field.But
Commercialization ultracapacitor monomer capacity is small at present, energy density is low, and conventional carbon base double layer capacitor energy density is
Near limit, power density are difficult to further be promoted, and there is an urgent need to develop new material, invention new processes to realize energy density and work(
Rate density is substantially improved.
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 is high specific energy, the ideal electrode material of ultra high power ultracapacitor.Texas,U.S Jane Austen branch school professor Ruoff couple
Reduced graphene carries out KOH activation, is prepared for a kind of three-dimensional porous graphene.It has the specific surface area of superelevation and high conduction
Property, laboratory test results show its super capacitor energy density close to lead-acid battery, are before one kind very having application
The electrode material for super capacitor of scape achieves success in laboratory stage.But grapheme material density is relatively low, liquid absorption amount is big,
Slurry solid content is low, and the machinability and portability to ultracapacitor propose challenge, and engineering application aspect faces huge
Technical barrier.
Invention content
The purpose of the present invention in view of the above problems, is providing a kind of Graphene electrodes piece and high ratio is made with it
The ultracapacitor of energy, ultra high power.
In order to reach foregoing invention purpose, the present invention uses following technical scheme：
A kind of Graphene electrodes piece, the Graphene electrodes piece include collector and Graphene electrodes slurry, wherein stone
Black alkene electrode slurry includes the bonding that mass percent is respectively the graphene of 75-93%, the conductive agent of 2-10%, 5-15%
Agent, collector are foamed aluminium collector.
In above-mentioned Graphene electrodes piece, the specific surface area of the graphene is 1000-1500m2/ g, tap density
For 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
Less than 0.35meq/g, water content is less than 0.40%, and total metal contents in soil is less than 100ppm.The physical parameter of graphene directly affects
The final performance of device, grapheme material aperture is moderate, and specific surface area is higher, is more conducive to the energy storage capacity for improving material.But
The specific surface area of graphene and density is to be mutually related, specific surface area is higher, and density is lower, cause pole piece to be difficult to
And energy density it is relatively low the problems such as.Based on this, the specific surface area of grapheme material should not be too big, and medium density is preferably.Aperture needs
To be matched with electrolyte intermediate ion size based on mesoporous.If aperture is too small, specific surface area utilization rate is low, the energy of storage
It is low, and seriously affect high rate performance.Secondly, the particle of grapheme material it is excessive or it is too small be all unfavorable for combination electrode at
Film, particle is excessive to influence the utilization rate and high rate performance of material, while being easy to form stress concentration, is unfavorable for coating film forming；
Grain is too small, needs to add more bonding agents, contact resistance increases, and reduces the performance of combination electrode.Again, grapheme material table
Functional group content, the metals content impurity in face are higher, under high potential, are easy to induce electrolyte decomposition aerogenesis, cause under capacity
Drop, internal resistance increase.Therefore, the present invention by the basic physical properties state modulator of grapheme material within the above range.
In above-mentioned Graphene electrodes piece, the thickness of foamed aluminium collector is 200-1500 μm, average pore size 50-
200 μm, porosity 85-95%.Quality proportion of the electrode material in ultracapacitor device is improved, in addition to electric from graphene
Except the design on material structure of pole, collector is another important factor in order.Existing aluminium foil is electrode slice prepared by collector
Thickness limits the promotion of graphene-supported amount in electrode, the new and effective collector of development and application is therein at 150-200 μm
One of approach.The porosity of novel foam aluminium may be up to 98%, and outstanding fillibility, retentivity sum aggregate can be provided for graphene
Electrically.Foamed aluminium afflux physical efficiency reduces the average distance between collector and active material graphene, and ohmic loss is smaller, electrode slice
Thickness may be up to 800 μm, improve the load capacity of pole piece active material.In addition, 3-dimensional metal aluminium conductive network energy in foamed aluminium
Internal resistance is significantly reduced, structural stability is good, and high voltage performance is good, can obtain the device of ultra high power density and high-energy density.
In above-mentioned Graphene electrodes piece, the conductive agent is combined conductive agent, including carbon black, carbon nano-fiber, carbon
One or more of nanotube, graphene conductive agent.
Preferably, the conductive agent is carbon black, the combined conductive agent of carbon nanotube and graphene.Further preferably,
Carbon black, carbon nanotube and graphene mass ratio are 1:1:1.The carbon black of zero dimension is contacted by " point-point ", and one-dimensional electric agent passes through
" line-line " contacts, and two-dimensional graphene conductive agent contacts structure three-dimensional conductive access by " surface-to-surface ".Different dimensions composite conducting
Agent will produce synergistic effect, is more easy to structure conductive path by " point-line-face " contact method, reduces the additive amount of conductive agent.
It is another object of the present invention to provide a kind of preparation method of above-mentioned Graphene electrodes piece, the preparation sides
Method includes the following steps：
By mass percentage (75-93) by graphene, conductive agent：(2-10) carries out superpower shearing and obtains premix；It will
Premix puts into kneader, and the aqueous emulsion of appropriate binder is added, stirs to get in doughy electrode slurry preform；
Electrode slurry preform is put into the agitator tank of blender, matter is pressed according to graphene, conductive agent and bonding agent
Measure percentage (75-93)：(2-10)：The aqueous emulsion of remaining binder is added in (5-15), and deionized water is added in agitator tank, stirs
Mix to obtain electrode slurry；
Electrode slurry is coated in collector, through rolling, cutting or being punched into Graphene electrodes piece.
In the preparation method of above-mentioned Graphene electrodes piece, the solid content of electrode slurry is 10-30%, and the viscosity of slurry is
800-1200Pa·s。
In the preparation method of above-mentioned Graphene electrodes piece, described rolls as hot pressing, pressure 100-300MPa, hot pressing
Temperature is 100-200 DEG C.The size of pressure influences thickness, density and the density of final graphene pole piece in the present invention.If
Pressure is too small, and Graphene electrodes void is larger, and density is relatively low, and pole piece is thicker；Reverse pressure is too big, and pole piece fold is even opened
It splits.The foamed aluminium collector that the present invention uses has porosity, and technology for preparing electrode difficulty is far above conventional non-porous collector.
The problems such as material leakage, broken belt occurs using conventional flat coating processes handling ease.To solve the above problems, using vertical in the present invention
Straight coating machine ensures the preparation of high-density graphite alkene electrode slice.
Preferably, the pressure rolled is 120-250MPa.Still further preferably, the pressure rolled is
150MPa。
Preferably, the thickness of Graphene electrodes piece is 300-500 μm after hot pressing, the density of electrode slice is in 0.6-0.8g/
mL。
It is another object of the present invention to provide a kind of method preparing ultracapacitor with above-mentioned Graphene electrodes piece,
The method includes the following steps：
It is prepared by battery core：By positive plate, diaphragm and negative plate Graphene electrodes piece lamination or it is wound into battery core semi-finished product；
Battery core is dry, assembles：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber,
Keep the pressure in tank in 100pa hereinafter, drying chamber is heated to 120-200 DEG C, then vacuum drying is assembled into super capacitor
Device preform；
Fluid injection, sealing：Organic electrolyte is injected into ultracapacitor preform, and carries out sealing treatment, is made super
Capacitor.
In battery core preparation, lamination type electric core is by positive plate, negative plate and diaphragm according to " Z " type mode lamination, and folded
Heteropleural of the lug in battery core when piece.To reduce internal resistance, raising current-carrying capability, pole piece retains full lug and draws water conservancy diversion foil when being punched,
Heteropleural of the lug in battery core when lamination.The setting of progress battery core thickness is required according to the size of final products.
Takeup type battery core is to place positive plate, negative plate and diaphragm on the winder, according to monomer capacity and size
Design requirement inputs winding parameters, and up- coiler is automatically performed electric core winding.
In battery core assembling, lamination type electric core water conservancy diversion foil is welded to by high-power ultrasonic on aluminium pole ears, for the company of reduction
Internal resistance is connect, tab welding improves solder joint density by the way of full weld in the process in the present invention, reduces connection internal resistance.Pole will be welded
The battery core of ear is put into plastic-aluminum shell, is carried out the sealing of top margin and side, is completed stacked ultracapacitor preform.Convoluted electricity
Positive terminal and negative terminal first by the water conservancy diversion foil dense extrusion at both ends, are welded on battery core both ends by core with Laser Welding.It welded
Again by solder joint density is improved by the way of full weld in journey, to reduce internal resistance.The battery core for being welded with positive and negative electrode terminal is put
Enter in shell, through-hole of the positive and negative electrode leading-out terminal boss directly through cover board and shell.It is this that directly lead out structure design very big
Ground reduces internal resistance, improves the power-performance of ultracapacitor.It is put into an insulated ring in the shell of positive terminal, will be close to
The concave ring being recessed inwardly is pressed into the peripheral surface of the shell of shell positive terminal with book joint setting machine；Shell is placed on shell trimmer
On, insulated ring is placed on the medial surface of concave ring, lid is buckled on insulated ring, rubber seal is placed in lid upper periphery position
Circle, then use sealing machine, shell is inwardly carried out flange compressing rubber sealing ring seal；Again by between shell and cathode weld seam,
Welding between lid and positive terminal is welded with Laser Welding, forms ultracapacitor preform.
In battery core fluid injection, stacked ultracapacitor preform injects organic electrolyte from unsealed side, takes out true
Sky stands half an hour so that electrolyte fully infiltrates inside pole piece to 280-320Pa.Behavior of spiral wound supercapacitor preform is first taken out
Vacuum injects organic electrolyte to 280-320Pa, and from the liquid injection port of ultracapacitor preform, by liquid injection port rubber plug plug
Tightly.
Preferably, the organic electrolyte is spiro quaternary ammonium tetrafluoroborate (SBP-BF4), solvent is acetonitrile.Electricity
Solving liquid influences one of the performance factor of capacitor, tetraethyl ammonium tetrafluoroborate/acetonitrile electrolyte (TEA-BF4/ AN) and tetrem
Base ammonium tetrafluoroborate/propene carbonate (TEA-BF4/ PC) it is that electrolyte is commonly used in industry, operating voltage is only 2.5~
2.7V, energy density is relatively low, and power density has to be hoisted.It is preferable to use the smaller spiro quaternary ammonium tetrafluoros of ionic radius in the present invention
Borate (SBP-BF4), except deionization radius is small, proof voltage ability is stronger, the high acetonitrile solvent of the preferred conductivity of solvent,
SBP-BF4/ AN electrolyte operating voltages are up to 3.0V.
Preferably, a concentration of 1-2moL/L of the organic electrolyte.The concentration of electrolyte also influences the appearance of capacitor
Amount and power-performance.
Further preferably, a concentration of 1.2-1.8moL/L of the organic electrolyte.Still further preferably, electrolyte is dense
Degree is 1.5-1.6moL/L.
In addition, additive is also another factor for influencing capacitor performance, additive of the present invention is sulfolane (SL), fluorine
For one or more of ethylene carbonate (FEC), vinylethylene carbonate (VEC), ionic liquid (ILs) etc..Preferably,
Ion liquid addictive is -3 methyl imidazolium tetrafluoroborate (EMIBF of 1- ethyls4)。
In sealing treatment, stacked ultracapacitor preform is put into vacuum Prepackaging machine, is sealed after vacuumizing；
Behavior of spiral wound supercapacitor preform Laser Welding is by liquid injection port sealing welding.
In conclusion the present invention selects main energy storage material of the suitable grapheme material as ultracapacitor, graphite
Alkene has the specific surface area of superelevation and excellent electric conductivity, it is considered to be a kind of high specific energy, the storage of ultra high power ultracapacitor
It can material.But grapheme material there are density the problems such as low, pole piece is difficult in the prior art, the present invention uses foamed aluminium
Collector.This collector porosity is up to 98%, and outstanding fillibility, retentivity and electrical collector can be provided for graphene.
Foamed aluminium afflux physical efficiency reduces the average distance between collector and active material graphene, and ohmic loss is smaller, the thickness of electrode slice
Up to 800 μm of degree, improves the load capacity of pole piece active material.In addition, 3-dimensional metal aluminium conductive network can be significantly in foamed aluminium
Internal resistance is reduced, structural stability is good, and high voltage performance is good.Graphene electrodes piece pole piece density after hot pressing reaches 0.7-0.8g/mL,
The energy density of device is ensured.
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.The use of combined conductive agent
Amount is lower, improves the content of active material in electrode, under the premise of ensureing power density, improves the energy density of device.
Again, the present invention uses the quaternary ammonium tetrafluoroborate acetonitrile solution of the more stable spirane structure of structure, because its
The particularity of cationic structural, such salt can obtain higher concentration and more stable electrochemistry in organic solvent
Energy.In addition, its cation radius is less than conventional electrolysis liquid cation radius, the utilization rate of electrode material specific surface area increases.This
The Graphene electrodes material used in project, it is a kind of crystalline carbon material, has higher proof voltage energy compared to activated carbon
Power.SBP-BF in the present invention4/ AN electrolyte operating voltages are up to 3.0V, can further provide for the energy density and power of device
Density.
Finally, in terms of super capacitor device structure design of the present invention, using full lug lead-out mode, battery core water conservancy diversion foil with draw
Go out between terminal to weld by the way of laser full weld and improves solder joint density.It is directly led out using terminal in addition, winding round monomer
Water conservancy diversion foil is directly welded on leading-out terminal by technology, the boss of leading-out terminal directly through shell through-hole and stretch out shell
Except body, this structure design that directly leads out greatly reduces internal resistance, improves the power-performance of ultracapacitor.
To sum up, 12Wh/kg is reached based on graphene super capacitor energy density produced by the present invention, power density reaches
30.14kW/kg, and the super capacitor energy density of Maxwell companies is 6Wh/kg, power density 12kW/kg at present.
Therefore, graphene ultracapacitor produced by the present invention has the characteristic of high specific energy, ultra 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 foamed aluminium collector stereoscan photograph of the embodiment of the present invention.
Fig. 3 is 1 Graphene electrodes electronic photo of the embodiment of the present invention.
Fig. 4 is 1 Graphene electrodes stereoscan photograph of the embodiment of the present invention.
Fig. 5 is 6 stacked graphene capacitor arrangement figure of the embodiment of the present invention.
Fig. 6 is 8 takeup type graphene capacitor arrangement figure of the embodiment of the present invention.
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 and conductive agent by mass percentage 88：6, which carry out superpower shearing, obtains premix；Premix is thrown
Enter kneader, the aqueous emulsion of appropriate binder is added, stirring 30min obtains being in doughy electrode slurry preform.Wherein, stone
The specific surface area of black alkene is 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size 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 contents in soil
Less than 100ppm, microscopic appearance is as shown in Figure 1；Collector is the foamed aluminium collector of three-dimensional porous structure, microscopic appearance
As shown in Fig. 2, the thickness of foamed aluminium collector is 200-1500 μm, average pore size is 50-200 μm, porosity 85-95%；
Conductive agent is carbon black, carbon nanotube and graphene in mass ratio 1:1:The combined conductive agent of 1 composition.
Electrode slurry preform is put into the agitator tank of blender, matter is pressed according to graphene, conductive agent and bonding agent
Measure percentage 88：6：6 are added the aqueous emulsion of remaining binder, deionized water are added in agitator tank, agitator tank is evacuated to
250pa, stirring 120min obtain electrode slurry, and the solid content of electrode slurry is 25%, and the viscosity of slurry is 1000Pas.
Foamed aluminium collector is mounted on the unreeling shaft of vertical application machine, foamed aluminium free end passes through coating machine parallel rollers
Between gap, and across vertical oven and on Scroll.When coating, foamed aluminium collector is immersed in slurry tank
In slurry, there is one group of path flat roll on the both sides of collector, and by the dipping of short time, extra slurry can flow back on collector
In slurry tank.Select the mode of vertical application that can both meet the requirement of three-dimensional porous foams aluminium collector coating.
By coated graphene pole piece be mounted on roller unreeling shaft on, pole piece free end pass through roller two pairs of rollers it
Between gap, and on Scroll.The pressure for adjusting roller is 150MPa, and hot pressing temperature is 150 DEG C.Roll rear graphite
The thickness of alkene pole piece is at 400 μm, and the density of electrode slice is in 0.76g/mL.According to the requirement of the stacked size to electrode slice, grind
Graphene electrodes piece is made by cutting successively in graphene pole piece after pressure.The photo of Graphene electrodes piece is as shown in Figure 3.Graphite
Alkene electrode stereoscan photograph is as shown in figure 4, the detection of scanned Electronic Speculum finds that graphene active material is filled into foamed aluminium afflux
In the hole of body, foamed aluminium collector keeps three-dimensional conductive back bone network structure.
Embodiment 2
By graphene and conductive agent by mass percentage 90：4, which carry out superpower shearing, obtains premix；Premix is thrown
Enter kneader, the aqueous emulsion of appropriate binder is added, stirring 35min obtains being in doughy electrode slurry preform.Wherein, stone
The specific surface area of black alkene is 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size 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 contents in soil
Less than 100ppm；Collector is the foamed aluminium collector of three-dimensional porous structure, and the thickness of foamed aluminium collector is 200-1500 μm,
Average pore size is 50-200 μm, porosity 85-95%；Conductive agent is carbon black, carbon nanotube and graphene in mass ratio 1:
0.8:The combined conductive agent of 1.2 compositions.
Electrode slurry preform is put into the agitator tank of blender, matter is pressed according to graphene, conductive agent and bonding agent
Measure percentage 90：4：6 are added the aqueous emulsion of remaining binder, deionized water are added in agitator tank, agitator tank is evacuated to
220pa, stirring 130min obtain electrode slurry, and the solid content of electrode slurry is 20%, and the viscosity of slurry is 900Pas；
Foamed aluminium collector is mounted on the unreeling shaft of vertical application machine, foamed aluminium free end passes through coating machine parallel rollers
Between gap, and across vertical oven and on Scroll.When coating, foamed aluminium collector is immersed in slurry tank
In slurry, there is one group of path flat roll on the both sides of collector, and by the dipping of short time, extra slurry can flow back on collector
In slurry tank.Select the mode of vertical application that can both meet the requirement of three-dimensional porous foams aluminium collector coating.
By coated graphene pole piece be mounted on roller unreeling shaft on, pole piece free end pass through roller two pairs of rollers it
Between gap, and on Scroll.The pressure for adjusting roller is 200MPa, and hot pressing temperature is 180 DEG C.Roll rear graphite
The thickness of alkene pole piece is at 350 μm, and the density of electrode slice is in 0.75g/mL.According to the requirement of the stacked size to electrode slice, grind
Graphene electrodes piece is made by cutting in graphene pole piece after pressure.
Embodiment 3
By graphene and conductive agent by mass percentage (80：8, which carry out superpower shearing, obtains premix；By premix
Kneader is put into, the aqueous emulsion of appropriate binder is added, stirring 25min obtains being in doughy electrode slurry preform.Wherein,
The specific surface area of graphene is 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size 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%, and total metal contains
Amount is less than 100ppm；Collector is the foamed aluminium collector of three-dimensional porous structure, and the thickness of foamed aluminium collector is 200-1500 μ
M, average pore size are 50-200 μm, porosity 85-95%；Conductive agent is carbon black, carbon nanotube and graphene in mass ratio 1:
1.2:The combined conductive agent of 0.8 composition.
Electrode slurry preform is put into the agitator tank of blender, matter is pressed according to graphene, conductive agent and bonding agent
Measure percentage 80：8：12 are added the aqueous emulsion of remaining binder, deionized water are added in agitator tank, agitator tank is evacuated to
280pa, stirring 110min obtain electrode slurry, and the solid content of electrode slurry is 28%, and the viscosity of slurry is 1100Pas；
Foamed aluminium collector is mounted on the unreeling shaft of vertical application machine, foamed aluminium free end passes through coating machine parallel rollers
Between gap, and across vertical oven and on Scroll.When coating, foamed aluminium collector is immersed in slurry tank
In slurry, there is one group of path flat roll on the both sides of collector, and by the dipping of short time, extra slurry can flow back on collector
In slurry tank.Select the mode of vertical application that can both meet the requirement of three-dimensional porous foams aluminium collector coating.
By coated graphene pole piece be mounted on roller unreeling shaft on, pole piece free end pass through roller two pairs of rollers it
Between gap, and on Scroll.The pressure for adjusting roller is 250MPa, and hot pressing temperature is 120 DEG C.Roll rear graphite
The thickness of alkene pole piece is at 450 μm, and the density of electrode slice is in 0.74g/mL.According to Wound capacitor wanting to the size of electrode slice
It asks, Graphene electrodes piece is made by punching in the graphene pole piece after rolling.
Embodiment 4
By graphene and conductive agent by mass percentage 75：10, which carry out superpower shearing, obtains premix；By premix
Kneader is put into, the aqueous emulsion of appropriate binder is added, stirring 30min obtains being in doughy electrode slurry preform.Wherein,
The specific surface area of graphene is 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size 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%, and total metal contains
Amount is less than 100ppm；Collector is the foamed aluminium collector of three-dimensional porous structure, and the thickness of foamed aluminium collector is 200-1500 μ
M, average pore size are 50-200 μm, porosity 85-95%；Conductive agent is carbon black, carbon nano-fiber in mass ratio 1:1 composition
Combined conductive agent.
Electrode slurry preform is put into the agitator tank of blender, matter is pressed according to graphene, conductive agent and bonding agent
Measure percentage 75：10：15 are added the aqueous emulsion of remaining binder, deionized water are added in agitator tank, agitator tank is evacuated to
300pa, stirring 110min obtain electrode slurry, and the solid content of electrode slurry is 30%, and the viscosity of slurry is 1200Pas；
Foamed aluminium collector is mounted on the unreeling shaft of vertical application machine, foamed aluminium free end passes through coating machine parallel rollers
Between gap, and across vertical oven and on Scroll.When coating, foamed aluminium collector is immersed in slurry tank
In slurry, there is one group of path flat roll on the both sides of collector, and by the dipping of short time, extra slurry can flow back on collector
In slurry tank.Select the mode of vertical application that can both meet the requirement of three-dimensional porous foams aluminium collector coating.
By coated graphene pole piece be mounted on roller unreeling shaft on, pole piece free end pass through roller two pairs of rollers it
Between gap, and on Scroll.The pressure for adjusting roller is 100MPa, and hot pressing temperature is 100 DEG C.Roll rear graphite
The thickness of alkene pole piece is at 300 μm, and the density of electrode slice is in 0.68g/mL.According to Wound capacitor wanting to the size of electrode slice
It asks, Graphene electrodes piece is made by punching in the graphene pole piece after rolling.
Embodiment 5
By graphene and conductive agent by mass percentage 93：2, which carry out superpower shearing, obtains premix；Premix is thrown
Enter kneader, the aqueous emulsion of appropriate binder is added, stirring 30min obtains being in doughy electrode slurry preform.Wherein, stone
The specific surface area of black alkene is 1000-1500m2/ g, tap density 0.2-0.5g/cm3, aperture 2-10nm, particle size 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 contents in soil
Less than 100ppm；Collector is the foamed aluminium collector of three-dimensional porous structure, and the thickness of foamed aluminium collector is 200-1500 μm,
Average pore size is 50-200 μm, porosity 85-95%；Conductive agent is carbon nano-fiber, graphene in mass ratio 1:0.8 composition
Combined conductive agent.
Electrode slurry preform is put into the agitator tank of blender, matter is pressed according to graphene, conductive agent and bonding agent
Measure percentage 93：2：5 are added the aqueous emulsion of remaining binder, deionized water are added in agitator tank, agitator tank is evacuated to
200pa, stirring 125min obtain electrode slurry, and the solid content of electrode slurry is 12%, and the viscosity of slurry is 800Pas；
Foamed aluminium collector is mounted on the unreeling shaft of vertical application machine, foamed aluminium free end passes through coating machine parallel rollers
Between gap, and across vertical oven and on Scroll.When coating, foamed aluminium collector is immersed in slurry tank
In slurry, there is one group of path flat roll on the both sides of collector, and by the dipping of short time, extra slurry can flow back on collector
In slurry tank.Select the mode of vertical application that can both meet the requirement of three-dimensional porous foams aluminium collector coating.
By coated graphene pole piece be mounted on roller unreeling shaft on, pole piece free end pass through roller two pairs of rollers it
Between gap, and on Scroll.The pressure for adjusting roller is 300MPa, and hot pressing temperature is 200 DEG C.Roll rear graphite
The thickness of alkene pole piece is at 500 μm, and the density of electrode slice is in 0.66g/mL.According to Wound capacitor wanting to the size of electrode slice
It asks, Graphene electrodes piece is made by punching in the graphene pole piece after rolling.
Embodiment 6
It is prepared by battery core：By negative plate Graphene electrodes piece made from battery core positive plate, diaphragm and embodiment 1 according to " Z " type
Mode lamination, lug requires the setting for carrying out battery core thickness according to the size of final products, obtains electric in the heteropleural of battery core when lamination
Core semi-finished product.
Battery core is dried：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber, tank is kept
Interior pressure hereinafter, drying chamber is heated to 150 DEG C, is dried in vacuo 10 hours in 100pa.
Assembling：Drying chamber is transported in drying shed or dry glove box, battery core is taken out.Lamination type electric core water conservancy diversion foil passes through
High-power ultrasonic is welded on aluminium pole ears, is connected internal resistance to reduce, is used the side of full weld in the present invention during tab welding
Formula improves solder joint density, reduces connection internal resistance.The battery core of soldering polar ear is put into plastic-aluminum shell, the close of top margin and side is carried out
Envelope, completes stacked ultracapacitor preform.
Fluid injection：Stacked ultracapacitor injects 1.6moL/L SBP-BF from unsealed side4/ AN electrolyte, electrolysis
The additive of addition 1%, additive EMIBF in liquid4, it is evacuated to 300Pa, stands half an hour so that electrolyte fully infiltrates
Inside pole piece.
Sealing：Stacked ultracapacitor preform is put into vacuum Prepackaging machine, is sealed after vacuumizing, and is made super
Capacitor, structure chart are as shown in Figure 5.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment
Reach 12.8Wh/kg, power density reaches 30.44kW/kg, is above the performance of current similar products at home and abroad.
Embodiment 7
It is prepared by battery core：By negative plate Graphene electrodes piece made from battery core positive plate, diaphragm and embodiment 2 according to " Z " type
Mode lamination, lug requires the setting for carrying out battery core thickness according to the size of final products, obtains electric in the heteropleural of battery core when lamination
Core semi-finished product.
Battery core is dried：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber, tank is kept
Interior pressure hereinafter, drying chamber is heated to 160 DEG C, is dried in vacuo 12 hours in 100pa.
Assembling：Drying chamber is transported in drying shed or dry glove box, battery core is taken out.Lamination type electric core water conservancy diversion foil passes through
High-power ultrasonic is welded on aluminium pole ears, is connected internal resistance to reduce, is used the side of full weld in the present invention during tab welding
Formula improves solder joint density, reduces connection internal resistance.The battery core of soldering polar ear is put into plastic-aluminum shell, the close of top margin and side is carried out
Envelope, completes stacked ultracapacitor preform.
Fluid injection：Stacked ultracapacitor injects 1.2moL/L SBP-BF from unsealed side4/ AN electrolyte, electrolysis
The additive of addition 0.8%, additive EMIBF in liquid4, it is evacuated to 280Pa, stands half an hour so that electrolyte fully soaks
Moisten inside pole piece.
Sealing：Stacked ultracapacitor preform is put into vacuum Prepackaging machine, is sealed after vacuumizing, and is made super
Capacitor.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment reaches 12.6Wh/kg, power
Density reaches 30.22kW/kg, is above the performance of current similar products at home and abroad.
Embodiment 8
It is prepared by battery core：Takeup type battery core by negative plate Graphene electrodes piece made from the anode of one fixed width, embodiment 3 with
Diaphragm is placed on the winder, inputs winding parameters according to the design requirement of monomer capacity and size, up- coiler is automatically performed electricity
Core is wound.
Battery core is dried：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber, tank is kept
Interior pressure hereinafter, drying chamber is heated to 180 DEG C, is dried in vacuo 12 hours in 100pa.
Assembling：Convoluted battery core is first by the water conservancy diversion foil dense extrusion at both ends, by positive terminal and negative terminal Laser Welding
It is welded on battery core both ends.Again by solder joint density is improved by the way of full weld in welding process, to reduce internal resistance.It will weldering
There is the battery core of positive and negative electrode terminal to be put into shell, through-hole of the positive and negative electrode leading-out terminal boss directly through cover board and shell.This
Kind directly leads out structure design and greatly reduces internal resistance, improves the power-performance of ultracapacitor.In the shell of positive terminal
It is inside put into an insulated ring, will be close to be pressed into the concave ring being recessed inwardly in the peripheral surface of the shell of shell positive terminal with book joint setting machine；
Shell is placed on shell trimmer, insulated ring is placed on the medial surface of concave ring, lid is buckled on insulated ring, in lid
Upper periphery position place rubber seal, then use sealing machine, shell is inwardly carried out flange compressing rubber sealing ring seal；Again will
Weld seam, lid between shell and cathode and the welding between positive terminal are welded with Laser Welding, formed ultracapacitor in advance at
Product.
Fluid injection：Behavior of spiral wound supercapacitor preform is first evacuated to 310Pa, and from the fluid injection of ultracapacitor preform
Mouth injection organic electrolyte, liquid injection port is stoppered with rubber plug, and organic electrolyte is the spiro quaternary ammonium tetrafluoroborate of 1.8moL/L
(SBP-BF4), solvent is acetonitrile, and 1% additive, additive EMIBF are added in electrolyte4。
Sealing：Liquid injection port sealing welding is completed ultracapacitor by behavior of spiral wound supercapacitor preform Laser Welding
It makes, structure chart is as shown in Figure 6.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment reaches
To 12.5Wh/kg, power density reaches 30.23kW/kg, is above the performance of current similar products at home and abroad.
Embodiment 9
It is prepared by battery core：Takeup type battery core by negative plate Graphene electrodes piece made from the anode of one fixed width, embodiment 4 with
Diaphragm is placed on the winder, inputs winding parameters according to the design requirement of monomer capacity and size, up- coiler is automatically performed electricity
Core is wound.
Battery core is dried：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber, tank is kept
Interior pressure hereinafter, drying chamber is heated to 200 DEG C, is dried in vacuo 6 hours in 100pa.
Assembling：Convoluted battery core is first by the water conservancy diversion foil dense extrusion at both ends, by positive terminal and negative terminal Laser Welding
It is welded on battery core both ends.Again by solder joint density is improved by the way of full weld in welding process, to reduce internal resistance.It will weldering
There is the battery core of positive and negative electrode terminal to be put into shell, through-hole of the positive and negative electrode leading-out terminal boss directly through cover board and shell.This
Kind directly leads out structure design and greatly reduces internal resistance, improves the power-performance of ultracapacitor.In the shell of positive terminal
It is inside put into an insulated ring, will be close to be pressed into the concave ring being recessed inwardly in the peripheral surface of the shell of shell positive terminal with book joint setting machine；
Shell is placed on shell trimmer, insulated ring is placed on the medial surface of concave ring, lid is buckled on insulated ring, in lid
Upper periphery position place rubber seal, then use sealing machine, shell is inwardly carried out flange compressing rubber sealing ring seal；Again will
Weld seam, lid between shell and cathode and the welding between positive terminal are welded with Laser Welding, formed ultracapacitor in advance at
Product.
Fluid injection：Behavior of spiral wound supercapacitor preform is first evacuated to 320Pa, and from the fluid injection of ultracapacitor preform
Mouth injection organic electrolyte, liquid injection port is stoppered with rubber plug, and organic electrolyte is the spiro quaternary ammonium tetrafluoroborate of 2moL/L
(SBP-BF4), solvent is acetonitrile, and 1.2% additive, additive EMIBF are added in electrolyte4。
Sealing：Liquid injection port sealing welding is completed ultracapacitor by behavior of spiral wound supercapacitor preform Laser Welding
It makes, structure chart is as shown in Figure 6.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment reaches
To 12.1Wh/kg, power density reaches 30.18kW/kg, is above the performance of current similar products at home and abroad.
Embodiment 10
It is prepared by battery core：Takeup type battery core by negative plate Graphene electrodes piece made from the anode of one fixed width, embodiment 5 with
Diaphragm is placed on the winder, inputs winding parameters according to the design requirement of monomer capacity and size, up- coiler is automatically performed electricity
Core is wound.
Battery core is dried：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber, tank is kept
Interior pressure hereinafter, drying chamber is heated to 120 DEG C, is dried in vacuo 20 hours in 100pa.
Assembling：Convoluted battery core is first by the water conservancy diversion foil dense extrusion at both ends, by positive terminal and negative terminal Laser Welding
It is welded on battery core both ends.Again by solder joint density is improved by the way of full weld in welding process, to reduce internal resistance.It will weldering
There is the battery core of positive and negative electrode terminal to be put into shell, through-hole of the positive and negative electrode leading-out terminal boss directly through cover board and shell.This
Kind directly leads out structure design and greatly reduces internal resistance, improves the power-performance of ultracapacitor.In the shell of positive terminal
It is inside put into an insulated ring, will be close to be pressed into the concave ring being recessed inwardly in the peripheral surface of the shell of shell positive terminal with book joint setting machine；
Shell is placed on shell trimmer, insulated ring is placed on the medial surface of concave ring, lid is buckled on insulated ring, in lid
Upper periphery position place rubber seal, then use sealing machine, shell is inwardly carried out flange compressing rubber sealing ring seal；Again will
Weld seam, lid between shell and cathode and the welding between positive terminal are welded with Laser Welding, formed ultracapacitor in advance at
Product.
Fluid injection：Behavior of spiral wound supercapacitor preform is first evacuated to 280Pa, and from the fluid injection of ultracapacitor preform
Mouth injection organic electrolyte, liquid injection port is stoppered with rubber plug, and organic electrolyte is the spiro quaternary ammonium tetrafluoroborate of 1moL/L
(SBP-BF4), solvent is acetonitrile, and 1% additive, additive EMIBF are added in electrolyte4。
Sealing：Liquid injection port sealing welding is completed ultracapacitor by behavior of spiral wound supercapacitor preform Laser Welding
It makes, structure chart is as shown in Figure 6.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment reaches
To 12Wh/kg, power density reaches 30.14kW/kg, is above the performance of current similar products at home and abroad.
Embodiment 11
With differing only in for embodiment 10, the solvent propene carbonate of electrolyte in the embodiment.Through electro-chemical test,
Graphene super capacitor energy density made from the present embodiment reaches 8Wh/kg, and power density reaches 25.14kW/kg.
Embodiment 12
With differing only in for embodiment 10, the specific surface area of the graphene in the embodiment is 700-900m2/ g, jolt ramming
Density is 0.36-0.5g/cm3.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment reaches
9Wh/kg, power density reach 26.80kW/kg
Embodiment 13
With differing only in for embodiment 10, the collector in the embodiment 13 is industrial common 20 μm of corrosion aluminium
Foil.Through electro-chemical test, graphene super capacitor energy density made from the present embodiment reaches 7Wh/kg, and power density reaches
18.5kW/kg。
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 Graphene electrodes piece, which is characterized in that the Graphene electrodes piece includes collector and Graphene electrodes slurry
Material, it is respectively the graphene of 75-93%, the conductive agent of 2-10%, 5- that wherein Graphene electrodes slurry, which includes mass percent,
15% binder, collector are foamed aluminium collector.
2. Graphene electrodes piece according to claim 1, which is characterized in that 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.
3. Graphene electrodes piece according to claim 1, which is characterized in that the thickness of foamed aluminium collector is 200-1500
μm, average pore size is 50-200 μm, porosity 85-95%.
4. Graphene electrodes piece according to claim 1, which is characterized in that the conductive agent is combined conductive agent, including
One or more of carbon black, carbon nano-fiber, carbon nanotube, graphene conductive agent.
5. Graphene electrodes piece according to claim 4, which is characterized in that the conductive agent is carbon black, carbon nanotube
With the combined conductive agent of graphene.
6. a kind of preparation method of Graphene electrodes piece as described in claim 1, which is characterized in that the preparation method packet
Include following steps：
By mass percentage (75-93) by graphene, conductive agent：(2-10) carries out superpower shearing and obtains premix；It will premix
It closes object and puts into kneader, the aqueous emulsion of appropriate binder is added, stirs to get in doughy electrode slurry preform；
Electrode slurry preform is put into the agitator tank of blender, quality hundred is pressed according to graphene, conductive agent and bonding agent
Divide than (75-93)：(2-10)：The aqueous emulsion of remaining binder is added in (5-15), and deionized water is added in agitator tank, stirs
Electrode slurry；
Electrode slurry is coated in collector, through rolling, cutting or being punched into Graphene electrodes piece.
7. the preparation method of Graphene electrodes piece according to claim 6, which is characterized in that it is described to roll as hot pressing,
Pressure is 100-300MPa, and hot pressing temperature is 100-200 DEG C.
8. a kind of method preparing ultracapacitor with Graphene electrodes piece as described in claim 1, which is characterized in that described
Method include the following steps：
It is prepared by battery core：By battery core positive plate, diaphragm and negative plate Graphene electrodes piece lamination or it is wound into battery core semi-finished product；
Battery core is dry, assembles：Battery core semi-finished product are put in drying chamber and seal drying chamber, are vacuumized to drying chamber, are kept
For pressure in tank in 100pa hereinafter, drying chamber is heated to 120-200 DEG C, then it is pre- to be assembled into ultracapacitor for vacuum drying
Finished product；
Fluid injection, sealing：Organic electrolyte is injected into ultracapacitor preform, and is sealed, and ultracapacitor is made.
9. the method that Graphene electrodes piece according to claim 8 prepares ultracapacitor, which is characterized in that described has
Machine electrolyte is spiro quaternary ammonium tetrafluoroborate (SBP-BF4), solvent is acetonitrile.
10. the method that Graphene electrodes piece according to claim 8 or claim 9 prepares ultracapacitor, which is characterized in that described
Organic electrolyte be 1-2moL/L.
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