CN109671572A - Electrode, supercapacitor and preparation method thereof - Google Patents
Electrode, supercapacitor and preparation method thereof Download PDFInfo
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- CN109671572A CN109671572A CN201810851144.6A CN201810851144A CN109671572A CN 109671572 A CN109671572 A CN 109671572A CN 201810851144 A CN201810851144 A CN 201810851144A CN 109671572 A CN109671572 A CN 109671572A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 155
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 154
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
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- 229910052782 aluminium Inorganic materials 0.000 claims description 16
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- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
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- 229920001155 polypropylene Polymers 0.000 description 2
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- 229910000570 Cupronickel Inorganic materials 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of electrodes, including the first foam metal layer, Graphene electrodes layer and the second foam metal layer being cascading；Graphene electrodes layer is set on the surface of the first foam metal layer；Second foam metal layer covers the surface of the first foam metal layer and Graphene electrodes layer, and the second foam metal layer and the pressing of the first foam metal layer connect.The present invention also provides the preparation methods of the electrode, comprising: preparation Graphene electrodes layer；It cuts foam metal and obtains the first foam metal layer and the second foam metal layer；Graphene electrodes layer is set on the surface of the first foam metal layer；Second foam metal layer is covered on to the surface of the first foam metal layer and Graphene electrodes layer；Compression moulding obtains electrode.The present invention also provides the supercapacitors and preparation method thereof including the electrode.The internal resistance for the supercapacitor for applying it is effectively reduced using foam metal package Graphene electrodes by the present invention, and then improves its power-performance.
Description
Technical field
The present invention relates to capacitor technology fields, in particular it relates to a kind of electrode, the super electricity using the electrode
The preparation method of container and the electrode, supercapacitor.
Background technique
The energy is the basis of human survival, and since the petrochemical industry class energy is increasingly depleted, energy crisis becomes countries in the world today
The sustainable development of problems faced, global economy and society is faced with stern challenge.Energy crisis includes the storage of the energy
It deposits, convert, transmitting and the exploitation of energetic material.Wherein, energy storage has great significance in human development.
With the improvement of people's living standards, green energy resource is continually developed using as hot spot concerned by people.Wherein,
Supercapacitor is novel green energy resource memory device, and energy density is the decades of times of traditional capacitor, and power density is
The hundreds of times of battery, efficiency for charge-discharge is higher than battery by 15% or so, and supercapacitor (Supercapacitor's) succeeds in developing
New hope is brought for the development of energy storage device.
Miniature flexible supercapacitor suffers from as a kind of energy storage device in wearable device, internet of things field broader
Application prospect.The graphene micro super capacitor of induced with laser method preparation is simply caused due to its preparation process and equipment
The attention of more and more people.But the inside fluff structure of the Graphene electrodes material due to Laser-induced processes preparation, causes to make
The internal resistance of standby supercapacitor is bigger than normal, thus, so that it is greatly limited in the application of power device.Mesh
Before, there are no be able to solve because the Graphene electrodes material internal fluff structure of Laser-induced processes preparation causes using the super of its
Grade capacitor internal resistance effective ways bigger than normal.
Summary of the invention
The purpose of the present invention is in view of the drawbacks of the prior art, providing a kind of electrode, using the super capacitor of the electrode
The preparation method of device and the electrode, supercapacitor, to solve the graphene electricity of Laser-induced processes preparation in the prior art
Pole material internal fluff structure leads to the problem bigger than normal using its supercapacitor internal resistance.
On one side, the present invention provides a kind of electrodes, including the first foam metal layer, the graphene being cascading
Electrode layer and the second foam metal layer；Wherein, Graphene electrodes layer is set on the surface of the first foam metal layer；Second foam
Metal layer covers the surface of the first foam metal layer and Graphene electrodes layer, and the second foam metal layer and the first foam metal
Connection is closed in lamination.
On the other hand, the present invention provides a kind of preparation methods of electrode, comprising the following steps: preparation Graphene electrodes
Layer；According to preset length and width, cuts foam metal and obtain the first foam metal layer and the second foam metal layer；In the first bubble
Graphene electrodes layer is set on the surface of foam metal layer；Second foam metal layer is covered on the first foam metal layer and graphene
The surface of electrode layer；Compression moulding obtains electrode so that the first foam metal layer and the pressing connection of the second foam metal layer.
On the other hand, the present invention provides a kind of supercapacitors, including above-mentioned electrode.
On the other hand, the present invention provides a kind of preparation methods of supercapacitor, comprising the following steps: will be according to above-mentioned
The two plate electrode faces that the preparation method of electrode obtains；Diaphragm is set between two plate electrodes；Encapsulated layer encapsulate two plate electrodes and
Diaphragm；The filling electrolyte in the cavity that two plate electrodes, diaphragm and encapsulated layer are formed, to obtain supercapacitor.
Technical solution of the present invention has the following beneficial effects:
(1) present invention is on the basis of Laser-induced processes prepare Graphene electrodes, by Graphene electrodes two sides point
Not Bao Guo two panels foam metal to strengthen the contact between Graphene electrodes, realize the reinforcing to electrode structure.
(2) supercapacitor of application electrode of the invention can be effectively reduced using Laser-induced processes preparation
The internal resistance of the supercapacitor of Graphene electrodes improves its power-performance.
(3) preparation method of electrode of the invention can synchronize introducing and fixed set during foam metal roll-in
Therefore ear, simplifies manufacture craft, saves process, reduce the production cost without additional welding.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the embodiment two of electrode provided by the invention；
Fig. 2 is the perspective view of the embodiment two of electrode provided by the invention；
Fig. 3 is the side view of the embodiment two of electrode provided by the invention；
Fig. 4 shows the inner walkway data of the supercapacitor of example 4；
Fig. 5 shows the inner walkway data using the graphene supercapacitor without the electrode after reinforcing；
Fig. 6 respectively illustrates the supercapacitor of example 4 and using the super electricity of graphene without the electrode after reinforcing
The charge and discharge data of container；
In figures 4 and 5, Z ' indicates impedance real part ,-Z " indicate imaginary impedance.
Specific embodiment
The present invention is done in detail by following specific embodiments for the purpose, feature and effect for fully understanding the present invention
Describe in detail bright, but the present invention is not restricted to this.
Electrode
Lead to the super capacitor using it for the Graphene electrodes material internal fluff structure of Laser-induced processes preparation
Device internal resistance problem bigger than normal, the present invention provides a kind of electrodes strengthened using foam metal.Below by embodiment one
It is described in detail with two pairs of electrodes of the invention of embodiment.
Embodiment one
Electrode in the embodiment of the present invention one includes the first foam metal layer being cascading, Graphene electrodes layer
With the second foam metal layer；Wherein, Graphene electrodes layer is set on the surface of the first foam metal layer；Second foam metal layer
The surface of the first foam metal layer and Graphene electrodes layer is covered, and the second foam metal layer and the first foam metal layer press
Connection.
Further, the Graphene electrodes layer in electrode includes basal layer and Graphene electrodes；Stone is provided on basal layer
Black alkene electrode；Graphene electrodes are prepared using the method for induced with laser.Wherein, polyimides or polyethers can be used in basal layer
Acid imide, certainly, those skilled in the art, which can also select, other can prepare Graphene electrodes as Laser-induced processes
Base layer material is not construed as limiting herein.
Further, the first foam metal layer in electrode can use nickel foam, foamed aluminium, foam copper, titanium foam, bubble
(such as: foam nichrome, foam pltine, foam monel, foam nickel chromium triangle tungsten close for foam silver, foamed iron and its alloy
Gold, foam dilval) in any one；The second foam metal layer in electrode can use nickel foam, foamed aluminium, foam
Copper, titanium foam, Foam silver, foamed iron and its alloy (such as: foam nichrome, foam pltine, foam monel,
Foam Nicrotung, foam dilval) in any one.The first foam metal layer and the second foam metal in electrode
Layer can also be using the other foam metals and its alloy in addition to previous materials, and those skilled in the art can be according to reality
It is selected, is not construed as limiting herein.
It should be noted that the material that material and the second foam metal layer that the first foam metal layer uses use can phase
Together, it can also be different, those skilled in the art can select according to actual needs, be not construed as limiting herein.
The first foam metal layer and for the ease of the production of the electrode in the embodiment of the present invention one, in preferred electrode
Two foam metal layers length and width having the same.
Optionally, the relationship between the length of the first foam metal layer and the length a of Graphene electrodes layer is: the first foam
The length of metal layer is (a+1) millimeter to (a+4) millimeter, preferably (a+4) millimeter, wherein a > 0；Second foam metal layer
Relationship between length and the length a of Graphene electrodes layer is: the length of the second foam metal layer is (a+1) millimeter to (a+4)
Millimeter, preferably (a+4) millimeter, wherein a > 0.Optionally, the width of the width of the first foam metal layer and Graphene electrodes layer
Relationship between b is: the width of the first foam metal layer is (b+1) millimeter to (b+4) millimeter, preferably (b+4) millimeter, wherein
B > 0；Relationship between the width of second foam metal layer and the width b of Graphene electrodes layer is: the width of the second foam metal layer
Degree is (b+1) millimeter to (b+4) millimeter, preferably (b+4) millimeter, wherein b > 0.
Embodiment two
Fig. 1 is the structural schematic diagram of the embodiment two of electrode provided by the invention, and Fig. 2 is the reality of electrode provided by the invention
The perspective view of example two is applied, Fig. 3 is the side view of the embodiment two of electrode provided by the invention.As shown in Figure 1 to Figure 3, implementing
In example two, which includes the first foam metal layer 1 being cascading, Graphene electrodes layer 2, collection ear 3 and the second foam
Metal layer 4.Wherein, 2 sum aggregate ear 3 of Graphene electrodes layer is located on the same floor, and the two is set to the first bubble without overlapping adjacent to each other
On the surface of foam metal layer 1；Second foam metal layer 4 covers the table of the first foam metal layer 1,2 sum aggregate ear 3 of Graphene electrodes layer
Face, and the second foam metal layer 4 and the pressing of the first foam metal layer 1 connect.
Further, Graphene electrodes layer 2 includes basal layer (not marking in figure) and Graphene electrodes (not marking in figure)；
Graphene electrodes are provided on basal layer；Graphene electrodes are prepared using the method for induced with laser.Wherein, basal layer can be adopted
With polyimides or polyetherimide, certainly, those skilled in the art, which can also select, other can be used as Laser-induced processes
The base layer material for preparing Graphene electrodes, is not construed as limiting herein.
Wherein, collection ear 3, can be using the metal or compound with conducting function as the contact point with electric action
Metal is made, such as aluminium, nickel, copper nickel plating etc., and those skilled in the art can select suitably to collect ear material according to actual needs,
Details are not described herein.
Preferably, collection ear 3 further includes the elongated portion stretched out in except electrode, it is highly preferred that being provided with collection ear in elongated portion
Glue 5, to be packaged fixation to electrode when using the electrode fabrication supercapacitor.In addition, collection ear glue 5 can be existing skill
Collection ear glue material in art, those skilled in the art can choice set ear glue according to actual needs material, be not construed as limiting herein.
Further, the first foam metal layer 1 can use nickel foam, foamed aluminium, foam copper, titanium foam, Foam silver, bubble
Foam iron and its alloy are (such as: foam nichrome, foam pltine, foam monel, foam Nicrotung, foam
Dilval) in any one；Second foam metal layer 4 can use nickel foam, foamed aluminium, foam copper, titanium foam, foam
Silver, foamed iron and its alloy (such as: foam nichrome, foam pltine, foam monel, foam Nicrotung,
Foam dilval) in any one.In addition, the first foam metal layer 1 and the second foam metal layer 4 can also be using before removing
Other foam metals and its alloy except material are stated, those skilled in the art can select according to actual needs, this
Place is not construed as limiting.
It should be noted that the material that uses of the material that uses of the first foam metal layer 1 and the second foam metal layer 4 can be with
It is identical, it can also be different, those skilled in the art can select according to actual needs, be not construed as limiting herein.
The first foam metal layer and for the ease of the production of the electrode in the embodiment of the present invention two, in preferred electrode
Two foam metal layers length and width having the same.
Optionally, the relationship between the length of the first foam metal layer 1 and the length a of Graphene electrodes layer 2 is: the first bubble
The length of foam metal layer 1 is (a+1) millimeter to (a+4) millimeter, preferably (a+4) millimeter, wherein a > 0；Second foam metal layer
Relationship between 4 length and the length a of Graphene electrodes layer 2 is: the length of the second foam metal layer 4 be (a+1) millimeter extremely
(a+4) millimeter, preferably (a+4) millimeter, wherein a > 0.Optionally, the width of the first foam metal layer 1 and Graphene electrodes layer
Relationship between the width c of 2 width b sum aggregate ear 3 is: the width of the first foam metal layer 1 is (b+c+1) millimeter to (b+c+
4) millimeter, preferably (b+c+4) millimeter, wherein b > 0 and c > 0；The width and Graphene electrodes layer 2 of second foam metal layer 4
Width b sum aggregate ear 3 width c between relationship be: the width of the second foam metal layer 4 is (b+c+1) millimeter to (b+c+4)
Millimeter, preferably (b+c+4) millimeter, wherein b > 0 and c > 0.
For the ease of making the electrode in the embodiment of the present invention two, preferably 2 sum aggregate ear 3 of Graphene electrodes layer is adjacent to each other
It is set to the center of the first foam metal layer 1 without overlapping.
In order to guarantee the first foam metal layer 1 and the second foam metal layer 4 during pressing connection not because of graphene
2 sum aggregate ear 3 of electrode layer overlaps and damages Graphene electrodes layer 2, it is necessary to assure 2 sum aggregate ear 3 of Graphene electrodes layer phase each other
Neighbour is set to without overlapping on the first foam metal layer 1, i.e. 2 sum aggregate ear 3 of Graphene electrodes layer is arranged without overlapping adjacent to each other
In on the first foam metal layer 1, and Graphene electrodes layer 2 is in contact with each other with collection ear 3；Alternatively, 2 sum aggregate ear of Graphene electrodes layer
3 are set on the first foam metal layer 1 without overlapping adjacent to each other, and Graphene electrodes layer 2 is not contacted each other with collection ear 3.
Above two set-up mode, those skilled in the art can flexible choice according to actual needs, be not construed as limiting herein.
The preparation method of electrode
The present invention also provides the preparation methods of the electrode in embodiment one and embodiment two, for the ease of art technology
The preparation method of the embodiment of the present invention one and the electrode in embodiment two is expressly understood in personnel, below by three He of embodiment
Example IV is respectively described in detail the preparation method of the electrode in the embodiment of the present invention one and embodiment two.
Embodiment three
The preparation method of electrode in the embodiment of the present invention one, comprising the following steps:
Step S101: preparation Graphene electrodes layer；
Step S102: it according to preset length and width, cuts foam metal and obtains the first foam metal layer and the second foam
Metal layer；
Step S103: Graphene electrodes layer is set on the surface of the first foam metal layer；
Step S104: the second foam metal layer is covered on to the surface of the first foam metal layer and Graphene electrodes layer；
Step S105: compression moulding obtains electrode so that the first foam metal layer and the pressing connection of the second foam metal layer.
Further, step S101 specifically comprises the following steps:
Step S1011: cleaning basal layer.Conventional method can be used to clean basal layer, such as: it is clear using ultrasonic wave
Washing machine clears up basal layer to remove the dust impurity on its surface etc..Wherein, basal layer can using polyimides or
The materials such as polyetherimide, those skilled in the art can select according to actual needs, and this will not be repeated here.
Step S1012: basal layer is fixed on the laser scanning region of laser and carries out induced with laser formation graphene
Electrode, obtain include basal layer and Graphene electrodes Graphene electrodes piece.Optionally, the laser power of laser be 2mW extremely
10mW, the scanning speed of laser are 1mm/s to 5mm/s.
Step S1013: size as required cuts the Graphene electrodes piece including basal layer and Graphene electrodes, thus
Obtain Graphene electrodes layer.
In step s 102, for the ease of the production of electrode of the invention, preferably the first foam metal layer and the second foam
Metal layer length and width having the same.
Further, in step s 102, preset length and width can according to the length a (a > 0) of Graphene electrodes layer and
Width b (b > 0) is determined.Preferably, preset length can be (a+1) millimeter to (a+4) millimeter, and more preferably (a+4) milli
Rice；Predetermined width can be (b+1) millimeter to (b+4) millimeter, and more preferably (b+4) millimeter.That is, the first foam is golden
The length and width for belonging to layer and/or the second foam metal layer can be according to the length a (a > 0) and width b (b of Graphene electrodes layer
> 0) it determines, i.e. the length of the first foam metal layer is (a+1) millimeter to (a+4) millimeter, preferably (a+4) millimeter, wherein a
> 0；The length of second foam metal layer is (a+1) millimeter to (a+4) millimeter, preferably (a+4) millimeter, wherein a > 0；First
The width of foam metal layer is (b+1) millimeter to (b+4) millimeter, preferably (b+4) millimeter, wherein b > 0；Second foam metal
The width of layer is (b+1) millimeter to (b+4) millimeter, preferably (b+4) millimeter, wherein b > 0.
Optionally, the first foam metal layer in electrode using nickel foam, foamed aluminium, foam copper, titanium foam, Foam silver,
Foamed iron and its alloy are (such as: foam nichrome, foam pltine, foam monel, foam Nicrotung, bubble
Foam dilval) in any one；The second foam metal layer in electrode uses nickel foam, foamed aluminium, foam copper, foam
Titanium, Foam silver, foamed iron and its alloy are (such as: foam nichrome, foam pltine, foam monel, foam nickel chromium triangle
Tungsten alloy, foam dilval) in any one.The first foam metal layer and the second foam metal layer in electrode can be with
Using the other foam metals and its alloy in addition to previous materials, those skilled in the art can carry out according to actual needs
Selection, is not construed as limiting herein.
It should be noted that the material that material and the second foam metal layer that the first foam metal layer uses use can phase
Together, it can also be different, those skilled in the art can select according to actual needs, be not construed as limiting herein.
In step s105, the first foam metal layer and the second foam metal layer can be made to press by the way of roll-in to connect
It connects, to obtain integrally formed electrode (electrode i.e. in the embodiment of the present invention one).
Example IV
The electrode (electrode i.e. in embodiment one) and use being prepared using the preparation method in embodiment three are implemented
Electrode (electrode i.e. in embodiment two) that preparation method in example four is prepared the difference is that, using example IV
In the electrode that is prepared of preparation method further include collection ear, wherein collection ear may include the elongated portion stretched out in except electrode, stretch
It may be provided with collection ear glue in long portion.
As shown in Figures 1 to 3, the preparation method of the electrode in the embodiment of the present invention two, comprising the following steps:
Step S201: preparation Graphene electrodes layer 2；
Step S202: it according to preset length and width, cuts foam metal and obtains the first foam metal layer 1 and the second foam
Metal layer 4；
Step S203: 2 sum aggregate ear 3 of Graphene electrodes layer is set on the surface of the first foam metal layer 1；
Step S204: the second foam metal layer 4 is covered on the first foam metal layer 1,2 sum aggregate ear 3 of Graphene electrodes layer
Surface on；
Step S205: compression moulding obtains electricity so that the first foam metal layer 1 and the pressing connection of the second foam metal layer 4
Pole.
Further, step S201 specifically comprises the following steps:
Step S2011: cleaning basal layer.Conventional method can be used to clean basal layer, such as: it is clear using ultrasonic wave
Washing machine clears up basal layer to remove the dust impurity on its surface etc..Wherein, basal layer can using polyimides or
The materials such as polyetherimide, those skilled in the art can select according to actual needs, and this will not be repeated here.
Step S2012: basal layer is fixed on the laser scanning region of laser and carries out induced with laser formation graphene
Electrode, obtain include basal layer and Graphene electrodes Graphene electrodes piece.Optionally, the laser power of laser be 2mW extremely
10mW, the scanning speed of laser are 1mm/s to 5mm/s.
Step S2013: size as required cuts the Graphene electrodes piece including basal layer and Graphene electrodes, thus
Obtain Graphene electrodes layer 2.
In step S202, for the ease of the production of electrode of the invention, preferably the first foam metal layer 1 and the second foam
The length and width having the same of metal layer 4.
Further, in step S202, preset length and width can be according to the length a (a > 0) and width of Graphene electrodes layer
It spends b (b > 0) and collects the width c (c > 0) of ear 3 to determine.Preferably, preset length can be (a+1) millimeter to (a+4) milli
Rice, and more preferably (a+4) millimeter；Predetermined width can be (b+c+1) millimeter to (b+c+4) millimeter, and more preferably (b+c+
4) millimeter.That is, the length and width of the first foam metal layer 1 and/or the second foam metal layer 4 can be according to graphene
The length a (a > 0) and width b (b > 0) of electrode layer and collect the width c (c > 0) of ear 3 to determine, i.e. the first foam metal layer
1 length is (a+1) millimeter to (a+4) millimeter, preferably (a+4) millimeter, wherein a > 0；The length of second foam metal layer 4
It is (a+1) millimeter to (a+4) millimeter, preferably (a+4) millimeter, wherein a > 0；The width of first foam metal layer 1 is (b+c+
1) millimeter is to (b+c+4) millimeter, preferably (b+c+4) millimeter, wherein b > 0 and c > 0；The width of second foam metal layer 4 is
(b+c+1) millimeter is to (b+c+4) millimeter, preferably (b+c+4) millimeter, wherein b > 0 and c > 0.
Optionally, the first foam metal layer 1 in electrode using nickel foam, foamed aluminium, foam copper, titanium foam, Foam silver,
Foamed iron and its alloy are (such as: foam nichrome, foam pltine, foam monel, foam Nicrotung, bubble
Foam dilval) in any one；The second foam metal layer 4 in electrode uses nickel foam, foamed aluminium, foam copper, foam
Titanium, Foam silver, foamed iron and its alloy are (such as: foam nichrome, foam pltine, foam monel, foam nickel chromium triangle
Tungsten alloy, foam dilval) in any one.The first foam metal layer 1 and the second foam metal layer 4 in electrode may be used also
With using other foam metals and its alloy in addition to previous materials, those skilled in the art can according to actual needs into
Row selection, is not construed as limiting herein.
It should be noted that the material that uses of the material that uses of the first foam metal layer 1 and the second foam metal layer 4 can be with
It is identical, it can also be different, those skilled in the art can select according to actual needs, be not construed as limiting herein.
Further, in step S203, for the ease of making electrode of the invention, preferably 2 sum aggregate ear 3 of Graphene electrodes layer
It is set to the center of the first foam metal layer 1 without overlapping adjacent to each other.
In addition, in step S203, in order to guarantee that the first foam metal layer 1 and the second foam metal layer 4 are connected in pressing
During do not damage Graphene electrodes layer 2 due to 2 sum aggregate ear 3 of Graphene electrodes layer overlaps, it is necessary to assure graphene electricity
Pole layer 2 sum aggregate ear 3 be set on the first foam metal layer 1 without overlapping adjacent to each other, i.e., 2 sum aggregate ear 3 of Graphene electrodes layer that
This is adjacent to be set to without overlapping on the first foam metal layer 1, and Graphene electrodes layer 2 is in contact with each other with collection ear 3；Alternatively,
2 sum aggregate ear 3 of Graphene electrodes layer is set on the first foam metal layer 1 without overlapping adjacent to each other, and Graphene electrodes layer 2
It is not contacted each other with collection ear 3.Above two set-up mode, those skilled in the art can flexible choice according to actual needs, this
Place is not construed as limiting.
Further, in step S205, the first foam metal layer 1 and the second foam metal can be made by the way of roll-in
4 pressing connection of layer, to obtain integrally formed electrode, as shown in Figure 3.
Supercapacitor
The present invention also provides a kind of supercapacitor, which includes that electrode of the invention is (i.e. of the invention
The electrode in electrode and/or embodiment two in embodiment one).
Specifically, supercapacitor of the invention includes: anode, cathode, diaphragm, encapsulated layer and electrolyte；Wherein, positive
Electrode of the invention (i.e. electrode in the embodiment of the present invention one and/or the electrode in embodiment two) is respectively adopted with cathode；
Diaphragm is arranged between positive electrode and negative electrode；Encapsulated layer, for sealing clad anode, cathode and diaphragm；Electrolyte is filled in just
In the cavity that pole, cathode, diaphragm and encapsulated layer are formed.
Wherein, above-described embodiment one can refer into example IV to electricity of the invention for the description of anode and cathode
The description of pole, details are not described herein again.
Wherein, the material of diaphragm can be non-woven fabrics diaphragm, cellulosic separator etc., and certainly, those skilled in the art may be used also
To select other diaphragm materials according to actual needs, it is not construed as limiting herein.
Wherein, the material of encapsulated layer is aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyphenyl second
Alkene (PS), polymethyl methacrylate (PMMA), polyformaldehyde (POM), gathers acrylonitrile-butadiene-styrene copolymer (ABS)
Any one in carbonic ester (PC) and polyamide (PA).
Wherein, the system of electrolyte can be tetraethylammonium tetrafluoroborate-propene carbonate system, tetrafluoro boric acid tetraethyl
Ammonium-second cyanogen system, tetrafluoro boric acid methyl triethyl ammonium-second cyanogen system, tetrafluoro boric acid methyl triethyl ammonium-propene carbonate body
System, any one in tetrafluoro boric acid methyl triethyl ammonium-second cyanogen+other dicyandiamide solutions, those skilled in the art can basis
Actual needs is selected, and is not construed as limiting herein.
The preparation method of supercapacitor
The present invention also provides a kind of preparation methods of supercapacitor, specifically comprise the following steps:
Step S301: electrode of the invention is respectively adopted as anode and cathode, makes in anode and cathode with graphene
The surface of electrode is oppositely arranged；
Step S302: diaphragm is set between a positive electrode and a negative electrode；
Step S303: the positive electrode, the negative electrode and the separator is encapsulated using encapsulated layer；
Step S304: the filling electrolyte in the cavity that anode, cathode, diaphragm and encapsulated layer are formed, to obtain the present invention
Above-mentioned supercapacitor.
It should be noted that when using the electrode in the embodiment of the present invention two as anode and/or cathode, due to collection
Ear can not be with encapsulated layer hot sealing, and therefore, the collection ear in anode and cathode is by being arranged in the elongated portion of collection ear
Collect ear glue and encapsulated layer carries out hot sealing, so that the supercapacitor can be fully sealed in encapsulated layer.
In the present invention, foam metal is respectively adopted in the two sides of the Graphene electrodes layer of induced with laser method preparation to be wrapped
Wrap up in, enhance the contact between Graphene electrodes, therefore, when by the application of electrode after foam metal is strengthened in super capacitor
When device, the internal resistance of the supercapacitor can be effectively reduced, and improve its power-performance.
Example
The implementation of method of the invention is illustrated below by specific example, it should be understood by those skilled in the art that
It is that this is understood not to the limitation to scope of the invention as claimed.
Example 1: the preparation of Graphene electrodes layer
(1) polyimide-based bottom is cleared up using supersonic wave cleaning machine to remove the dust impurity on its surface
Deng.
(2) polyimide-based bottom is adhered on the laser scanning region of laser；Then by the laser power of laser
It is set as 8mW, the scanning speed of laser is set as 3mm/s, carries out induced with laser and generates Graphene electrodes, to be included
The Graphene electrodes piece of basal layer and Graphene electrodes.
(3) the Graphene electrodes piece including basal layer and Graphene electrodes is cut according to the size of 20mm × 30mm, thus
Obtain needing the Graphene electrodes layer of size.
Example 2: electrode
Electrode in this example includes the first foam metal layer, Graphene electrodes layer and the second foam being cascading
Metal layer；Graphene electrodes layer is set on the surface of the first foam metal layer；Second foam metal layer covers the first foam gold
Belong to the surface of layer and Graphene electrodes layer, and the second foam metal layer and the pressing of the first foam metal layer connect.Wherein, first
The foam nichrome that size is 21mm × 32mm is respectively adopted in foam metal layer and the second foam metal layer；Graphene electrodes
Layer is using the Graphene electrodes layer being prepared in example 1.
Electrode in this example the preparation method is as follows:
(a) it according to the preset length of 21mm × 32mm and width, cuts foam nichrome and obtains the first foam metal
Layer and the second foam metal layer.
(b) the first foam metal layer surface is arranged in close to center in the Graphene electrodes layer being prepared in example 1
On position.
(c) the second foam metal layer is covered on to the surface of the first foam metal layer and Graphene electrodes layer, and makes first
The alignment of the edge of foam metal layer and the second foam metal layer.
(d) the first foam metal layer, Graphene electrodes layer and the second foam metal of order will be stacked using twin rollers
Layer roll-forming, obtains the electrode in the embodiment of the present invention one.
Example 3: electrode
Electrode in this example includes the first foam metal layer being cascading, Graphene electrodes layer, collection ear and the
Two foam metal layers；Graphene electrodes layer sum aggregate ear is located on the same floor, the two it is adjacent to each other non-overlapping and between seamlessly set
It is placed on the surface of the first foam metal layer；Second foam metal layer covers the first foam metal layer, Graphene electrodes layer sum aggregate
The surface of ear, and the second foam metal layer and the pressing of the first foam metal layer connect.Wherein, the first foam metal layer and second
The nickel foam that size is 29mm × 34mm is respectively adopted in foam metal layer；Graphene electrodes layer is using being prepared in example 1
Graphene electrodes layer；Collect ear and use aluminum strip, size is 5mm × 55mm, is set at one end (i.e. one end of elongated portion) 10mm
It is equipped with collection ear glue.
Electrode in this example the preparation method is as follows:
(a) it according to the preset length of 29mm × 34mm and width, cuts nickel foam and obtains the first foam metal layer and second
Foam metal layer.
(b) by the Graphene electrodes layer sum aggregate ear being prepared in example 1 it is adjacent to each other non-overlapping and between seamlessly
First foam metal layer surface is set on the position at center, guarantee collection ear be equipped with collection ear glue one end stretch out electrode it
Outside, and guarantee that collect the ear other end is aligned with the corresponding edge of Graphene electrodes layer.
(c) the second foam metal layer is covered on to the surface of the first foam metal layer, Graphene electrodes layer sum aggregate ear, and is made
The alignment of the edge of first foam metal layer and the second foam metal layer.
(d) the first foam metal layer, Graphene electrodes layer, collection ear and the second foam of order will be stacked using twin rollers
Metal layer roll-forming obtains the electrode in the embodiment of the present invention two.
Example 4: supercapacitor
Supercapacitor in this example includes: anode and cathode, and the electrode being prepared in example 3 is respectively adopted；It is fine
Plain diaphragm is tieed up, is arranged between positive electrode and negative electrode；Aluminum plastic film encapsulated layer, sealing clad anode, cathode and diaphragm；And electrolysis
Liquid is filled in the cavity that anode, cathode, diaphragm and encapsulated layer are formed, using tetraethylammonium tetrafluoroborate-propene carbonate body
System.
Supercapacitor in this example the preparation method is as follows:
(1) surface in anode and cathode with Graphene electrodes is oppositely arranged.
(2) cellulosic separator is set between a positive electrode and a negative electrode.
(3) using aluminum plastic film encapsulated layer encapsulation anode, cathode and cellulosic separator.
(4) the filling electrolyte tetrafluoro boric acid in the cavity that anode, cathode, cellulosic separator and aluminum plastic film encapsulated layer are formed
Tetraethyl ammonium-propene carbonate system, thus the supercapacitor for the electrode being applied in the embodiment of the present invention two.
It should be noted that when using the electrode in example 3 as anode and/or cathode, since collection ear can not be with
Encapsulated layer hot sealing, therefore, the collection ear in anode and cathode are the collection ear glue and envelope by being arranged in the elongated portion of collection ear
It fills layer and carries out hot sealing, so that the supercapacitor can be fully sealed in encapsulated layer.
Example 5: supercapacitor
Supercapacitor in example 5 is identical as the structure of the supercapacitor in example 4 and preparation method, and difference only exists
Be respectively adopted the electrode being prepared in example 2 in: the anode and cathode of supercapacitor in example 5, it is other with example 4
In it is identical to the description of the preparation method of supercapacitor, details are not described herein again.
Performance test:
To example 4 (i.e. the supercapacitor of electrode of the application after strengthening) and the super electricity of graphene in the prior art
The performance of container (i.e. using the supercapacitor without the electrode after reinforcing) is tested.
It is tested for the property using electrochemical workstation, test condition is: test frequency 1KHz, cathodal current
(Cathodic i) 0.001A, positive electrode current (Anodic i) 0.001A, data memory gap (Data Interval) 0.01s,
Maximum potential (High E Limit) 2.3V, potential minimum (Low ELimit) 0V, charge and discharge supercapacitor 4mF, charging electricity
Flow 1mA, discharge current 1mA.
It is found by test, the internal resistance of the supercapacitor in example 4 is 2.8 ohm, and graphene in the prior art is super
The internal resistance of grade capacitor is 21 ohm, as shown in Figure 4 and Figure 5, and by comparing as can be seen that electrode is strong by foam metal
After change, the internal resistance of supercapacitor is significantly reduced.In addition, being found with will be appreciated also that by Fig. 6, using above-mentioned item
Part is super without the 4mF graphene of the electrode after reinforcing using the 4mF supercapacitor and application of the electrode after strengthening
Grade capacitor charging/discharging, using the supercapacitor of the electrode after strengthening and using the graphite without the electrode after reinforcing
Alkene supercapacitor has (the i.e. charge and discharge of the supercapacitor of electrode of the application after strengthening of approximately uniform charge-discharge performance
Electric curve and application are overlapped without the charging and discharging curve approximation of the graphene supercapacitor of the electrode after reinforcing).Namely
It says, using the supercapacitor of the electrode after strengthening and using the graphene supercapacitor without the electrode after reinforcing
It compares, is significantly reduced using the supercapacitor internal resistance of the electrode after strengthening, and electrode of the application after strengthening is super
Grade capacitor can also reach identical charge-discharge performance without the graphene supercapacitor of the electrode after reinforcing with application.
Finally it should be noted that: the above enumerated are only specific embodiments of the present invention son, the technology of certain this field
Personnel can be modified to the present invention and modification, if these modifications and variations belong to the claims in the present invention and its equivalent skill
Within the scope of art, it is considered as protection scope of the present invention.
Claims (20)
1. a kind of electrode, which is characterized in that including the first foam metal layer, the Graphene electrodes layer and second being cascading
Foam metal layer；Wherein,
The Graphene electrodes layer is set on the surface of first foam metal layer；
Second foam metal layer covers the surface of first foam metal layer and the Graphene electrodes layer, and described
Second foam metal layer and first foam metal layer pressing connect.
2. electrode according to claim 1, which is characterized in that the Graphene electrodes layer includes basal layer and graphene electricity
Pole；
The Graphene electrodes are provided on the basal layer；
The Graphene electrodes are prepared using the method for induced with laser.
3. electrode according to claim 1 or 2, which is characterized in that the electrode further includes collection ear；
The collection ear and the Graphene electrodes layer are set to the surface of first foam metal layer without overlapping adjacent to each other
On；Second foam metal layer covers the surface of first foam metal layer, the Graphene electrodes layer and the collection ear.
4. electrode according to claim 3, which is characterized in that the collection ear includes: to stretch out in stretching except the electrode
Long portion is provided with collection ear glue in the elongated portion.
5. electrode according to any one of claims 1 to 4, which is characterized in that first foam metal layer and described the
Two foam metal layers length and width having the same.
6. electrode according to any one of claims 1 to 5, which is characterized in that the length of first foam metal layer with
Relationship between the length a of the Graphene electrodes layer is: the length of first foam metal layer is (a+1) millimeter to (a+
4) millimeter, preferably (a+4) millimeter, wherein a > 0；The length of second foam metal layer and the Graphene electrodes layer
Relationship between length a is: the length of second foam metal layer is (a+1) millimeter to (a+4) millimeter, preferably (a+4)
Millimeter, wherein a > 0；And/or
Relationship between the width of first foam metal layer and the width b of the Graphene electrodes layer is: first bubble
The width of foam metal layer is (b+1) millimeter to (b+4) millimeter, preferably (b+4) millimeter, wherein b > 0；The second foam gold
The relationship belonged between the width of layer and the width b of the Graphene electrodes layer is: the width of second foam metal layer is (b+
1) millimeter is to (b+4) millimeter, preferably (b+4) millimeter, wherein b > 0.
7. according to the described in any item electrodes of claim 3 to 5, which is characterized in that the length of first foam metal layer with
Relationship between the length a of the Graphene electrodes layer is: the length of first foam metal layer is (a+1) millimeter to (a+
4) millimeter, preferably (a+4) millimeter, wherein a > 0；The length of second foam metal layer and the Graphene electrodes layer
Relationship between length a is: the length of second foam metal layer is (a+1) millimeter to (a+4) millimeter, preferably (a+4)
Millimeter, wherein a > 0；And/or
Between the width c of the width b and the collection ear of the width of first foam metal layer and the Graphene electrodes layer
Relationship is: the width of first foam metal layer is (b+c+1) millimeter to (b+c+4) millimeter, preferably (b+c+4) millimeter,
Wherein b > 0 and c > 0；The width b's and the collection ear of the width of second foam metal layer and the Graphene electrodes layer
Relationship between width c is: the width of second foam metal layer is (b+c+1) millimeter to (b+c+4) millimeter, preferably (b
+ c+4) millimeter, wherein b > 0 and c > 0.
8. electrode according to any one of claims 1 to 7, which is characterized in that first foam metal layer uses foam
Any one in nickel, foamed aluminium, foam copper, titanium foam, Foam silver, foamed iron and its alloy；
Second foam metal layer is using in nickel foam, foamed aluminium, foam copper, titanium foam, Foam silver, foamed iron and its alloy
Any one.
9. according to the described in any item electrodes of claim 2 to 8, which is characterized in that the basal layer is using polyimides or gathers
Etherimide.
10. according to the described in any item electrodes of claim 3 to 9, which is characterized in that the Graphene electrodes layer and the collection ear
It is set to the center of first foam metal layer without overlapping adjacent to each other.
11. according to the described in any item electrodes of claim 3 to 10, which is characterized in that the Graphene electrodes layer and the collection
Ear is set to without overlapping adjacent to each other on first foam metal layer, and the Graphene electrodes layer and the collection ear that
This contact；Alternatively, the Graphene electrodes layer and the collection ear are set to first foam metal without overlapping adjacent to each other
On layer, and the Graphene electrodes layer is not contacted each other with the collection ear.
12. a kind of preparation method of electrode as described in any one of claim 1 to 11, which comprises the following steps:
Prepare Graphene electrodes layer；
According to preset length and width, cuts foam metal and obtain the first foam metal layer and the second foam metal layer；
The Graphene electrodes layer is set on the surface of first foam metal layer；
Second foam metal layer is covered on to the surface of first foam metal layer and the Graphene electrodes layer；
Compression moulding obtains the electrode so that first foam metal layer and second foam metal layer pressing connection.
13. the preparation method of electrode according to claim 12, which is characterized in that the step of the preparation Graphene electrodes layer
Suddenly include:
Clean basal layer；
The basal layer is fixed on the laser scanning region of laser and carries out induced with laser formation Graphene electrodes, is wrapped
Include the Graphene electrodes piece of the basal layer and the Graphene electrodes；
The Graphene electrodes piece is cut, the Graphene electrodes layer of preset length and width is obtained.
14. the preparation method of electrode according to claim 13, which is characterized in that the laser power of the laser is
2mW to 10mW, the scanning speed of the laser are 1mm/s to 5mm/s.
15. the preparation method of 2 to 14 described in any item electrodes according to claim 1, which is characterized in that described described first
In the step of Graphene electrodes layer is set on the surface of foam metal layer, on the surface of first foam metal layer further
Setting collection ear；Wherein, the collection ear and the Graphene electrodes layer are non-overlapping adjacent to each other.
16. the preparation method of electrode according to claim 15, which is characterized in that described by second foam metal layer
In the step of being covered on the surface of first foam metal layer and the Graphene electrodes layer, by second foam metal layer
It is covered on the surface of first foam metal layer, the Graphene electrodes layer and the collection ear.
17. the preparation method of electrode according to claim 15 or 16, which is characterized in that the collection ear includes stretching out in institute
The elongated portion except electrode is stated, collection ear glue is provided in the elongated portion.
18. a kind of supercapacitor, which is characterized in that including the described in any item electrodes of claim 1 to 11.
19. supercapacitor according to claim 18 characterized by comprising
Anode；
Cathode；
Diaphragm, setting is between the anode and the cathode；
Encapsulated layer, for sealing the cladding anode, the cathode and the diaphragm；
Electrolyte is filled in the cavity that the anode, the cathode, the diaphragm and the encapsulated layer are formed；
Wherein, the described in any item electrodes of claim 1 to 11 are respectively adopted in the anode and the cathode.
20. a kind of preparation method of the supercapacitor as described in claim 18 or 19, which is characterized in that including following step
It is rapid:
The two plate electrode faces that according to claim 1, the preparation method of any one of 2 to 17 electrodes is obtained；
Diaphragm is set between two plate electrode；
Encapsulated layer encapsulates two plate electrode and the diaphragm；
The filling electrolyte in the cavity that two plate electrode, the diaphragm and the encapsulated layer are formed, it is described super to obtain
Capacitor.
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| CN112035015A (en) * | 2020-09-02 | 2020-12-04 | 安徽宇航派蒙健康科技股份有限公司 | Graphene touch device preparation method based on additive manufacturing technology |
| CN113571227A (en) * | 2021-07-28 | 2021-10-29 | 攀枝花学院 | Graphene metal composite wire and preparation method thereof |
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