CN110085430A - A kind of composite coating and its manufacturing method, electrode material - Google Patents
A kind of composite coating and its manufacturing method, electrode material Download PDFInfo
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- CN110085430A CN110085430A CN201910364472.8A CN201910364472A CN110085430A CN 110085430 A CN110085430 A CN 110085430A CN 201910364472 A CN201910364472 A CN 201910364472A CN 110085430 A CN110085430 A CN 110085430A
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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
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
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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
- H01G11/26—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
- H01G11/30—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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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 invention discloses a kind of composite coating and manufacturing methods, electrode material, wherein, composite coating includes first coating and second coating, the first coating includes macromolecule carrier and the graphene oxide that is dispersed in macromolecule carrier, the second coating includes macromolecule carrier, redox graphene and metal oxide, and the redox graphene and metal oxide Monodispersed are in macromolecule carrier.The present invention is due to the part of the metal oxide of the redox graphene minor matters in second coating, so that surface has positive charge, and the surface of graphene oxide contained in first coating due to oxygen-containing group presence and make surface with negative electrical charge, the distributional difference of charge results in certain potential difference, when composite coating is applied on electrode, composite coating is between two electrodes, self discharge caused by former supercapacitor is counteracted due to potential difference effectively reduces the self discharge effect of capacitor.
Description
Technical field
The present invention relates to electrode material technical field more particularly to a kind of composite coating and its manufacturing methods, electrode material.
Background technique
Capacitor is one of the electronic component largely used in electronic equipment, be widely used in separated by direct communication in circuit,
Coupling, bypass, filtering, resonant tank, energy conversion, control etc..With making rapid progress for electronic information technology, digital electricity
The update speed of sub- product is getting faster, consumer based on the products such as flat panel TV, laptop, digital camera
Electronic product volume of production and marketing sustainable growth has driven capacitor industry to increase.
With the continuous development of capacitor material in recent years, some supercapacitors have had in certain fields as electricity
The potentiality of source application.However, quickly self discharge effect significantly limits its application as continuation of the journey type energy storage device.It is super
The fast reason of capacitor self discharge be energy storage material mechanism be charge Interfacial Adsorption, during the charging process can because voltage and from
Sub- concentration factor generates self discharge, and the self discharge speed is much faster compared with than battery.
Therefore, the self-discharge phenomenon for how improving capacitor becomes current urgent problem to be solved.
Summary of the invention
The embodiment of the present invention creatively provides a kind of compound to effectively overcome drawbacks described above present in the prior art
Coating and its manufacturing method, electrode material, the composite coating include first coating and second coating, and the first coating includes
Macromolecule carrier and the graphene oxide being dispersed in macromolecule carrier, the second coating includes macromolecule carrier, oxygen reduction
Graphite alkene and metal oxide, the redox graphene and metal oxide Monodispersed are in macromolecule carrier.
In an embodiment, content of the graphene oxide in the first coating is from first coating to second
Coating is reduced in gradient, and the content of the redox graphene and metal oxide in the second coating is applied from second
Layer is reduced in gradient to first coating.
In an embodiment, the raw material of the macromolecule carrier includes high molecular material.
In an embodiment, the high molecular material be polyvinyl alcohol, Kynoar-hexafluoropropylene copolymer,
Middle one or more in acrylamide, polyetherimide.
In an embodiment, the high molecular material is monomer polyvinyl alcohol, and the raw material of the macromolecule carrier is also
Including crosslinking agent, the crosslinking agent be preferably one of glutaraldehyde, glyoxal, boric acid or more than one.
Another aspect of the present invention provides a kind of electrode material, and the electrode material includes material described in any of the above embodiments
Material.
Another aspect of the present invention provides a kind of manufacturing method of composite coating, which comprises by graphene oxide plus
Enter into high molecular dispersion liquid, forms composite material dispersion liquid；The is formed in matrix surface using the composite material dispersion liquid
One coating；On the first coating surface, setting metal material is doped processing, forms composite coating.
It is described to form first coating, packet in matrix surface using the composite material dispersion liquid in an embodiment
It includes: forming dispersion liquid coating on described matrix surface using the composite material dispersion liquid；Make the dispersion liquid using crosslinking agent
Coating forms the first coating.
It is described to be doped processing in first coating surface setting metal material in an embodiment, it is formed
Composite coating, comprising: metal plate or metal foil are set on the first coating surface, sealing is placed on baking oven baking；Terminate to dry
The metal plate or metal foil are removed after system, and freeze-drying process is carried out to the first coating, forms composite coating.
In an embodiment, the metal material include one of zinc, tin, iron, tantalum, niobium, titanium, aluminium or it is a kind of with
On.
The present invention provides a kind of composite coating and manufacturing methods, electrode material, and wherein composite coating will be by that will aoxidize stone
Black alkene is dispersed in high molecular dispersion liquid, and forms the first coating that can be attached on matrix, then pass through gold to first coating
Category is doped processing, and the graphene oxide composite material of coating surface is reduced into a certain degree as with gradient
Redox graphene composite material, formed containing redox graphene, metal oxide and macromolecule carrier second
Coating.Due to the part of the metal oxide of the redox graphene minor matters in second coating, so that surface has positive charge, and
The surface of graphene oxide contained in first coating due to oxygen-containing group presence and make surface with negative electrical charge, the distribution of charge
Difference results in certain potential difference, and when composite coating is applied on electrode, composite coating supports between two electrodes
Self discharge caused by former supercapacitor disappeared due to potential difference effectively reduces the self discharge effect of capacitor.
Detailed description of the invention
The following detailed description is read with reference to the accompanying drawings, above-mentioned and other mesh of exemplary embodiment of the invention
, feature and advantage will become prone to understand.In the accompanying drawings, if showing by way of example rather than limitation of the invention
Dry embodiment, in which:
In the accompanying drawings, identical or corresponding label indicates identical or corresponding part.
Fig. 1 is the structural schematic diagram of composite coating of the embodiment of the present invention and electrode material；
Fig. 2 is the electrode self-discharge performance comparison schematic diagram of one embodiment of the invention.
Specific embodiment
To keep the purpose of the present invention, feature, advantage more obvious and understandable, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
It is only a part of the embodiment of the present invention, and not all embodiments.Based on the embodiments of the present invention, those skilled in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.Moreover, particular features, structures, materials, or characteristics described
It may be combined in any suitable manner in any one or more of the embodiments or examples.In addition, without conflicting with each other, this
The technical staff in field can be by the spy of different embodiments or examples described in this specification and different embodiments or examples
Sign is combined.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic." first " is defined as a result, the feature of " second " can be expressed or hidden
It include at least one this feature containing ground.In the description of the present invention, the meaning of " plurality " is two or more, unless otherwise
Clear specific restriction.
Fig. 1 is the structural schematic diagram of composite coating of the embodiment of the present invention and electrode material.
Referring to Fig. 1, the embodiment of the present invention provides a kind of composite coating 1, including first coating 11 and second coating 12, and first
Coating 11 includes macromolecule carrier and the graphene oxide being dispersed in macromolecule carrier, and second coating 12 includes that macromolecule carries
Body, redox graphene and metal oxide, redox graphene and metal oxide Monodispersed are in macromolecule carrier.
Composite coating 1 provided in an embodiment of the present invention, the characteristics of using graphene oxide favorable dispersibility, by graphite oxide
Alkene is dispersed in macromolecule carrier, and the surface of graphene oxide in first coating 11 is since there are oxygen-containing groups therefore to have negative electricity
Lotus, and the part of the metal oxide of the redox graphene minor matters in second coating 12, so that surface has positive charge, charge
Distributional difference result in certain potential difference, when composite coating be applied to electrode on when, composite coating 1 is located at two electrodes
Between, self discharge caused by counteracting former supercapacitor due to potential difference effectively reduces putting certainly for capacitor
Electrical effect.
Referring to Fig. 1, when this composite coating is applied on the negative electrode 2 of capacitor, first coating 11 and negative electrode 2 connect
Connect, second coating 12 is connect with positive electrode 3, by the potential difference formed on composite coating 1, can offset former supercapacitor by
The self discharge caused by potential difference reason, therefore effectively reduce the self discharge effect of capacitor.
Composite coating 1 in the embodiment of the present invention can be suitable for all kinds of by choosing different types of macromolecule carrier
Electrolyte and Different electrodes system.The more unmodified electrode of electrode that composite coating is modified through the invention under the same conditions can
Enough generate lower self-discharge current.Wherein macromolecule carrier is also used to be adhered on matrix, including high polymer monomer or polymerization
Object, the present invention are not particularly limited herein.Likewise, the embodiment of the present invention to graphene oxide, redox graphene and
Size and structure of metal oxide etc. are not particularly limited.
In an embodiment, content of the graphene oxide in first coating 11 is from first coating 11 to second coating
12 are reduced in gradient, and the content of redox graphene and metal oxide in second coating 12 is from second coating 12 to
One coating 11 is reduced in gradient.In the embodiment of the present invention due to metal oxide content in second coating 12 far from first coating 11
One side on it is maximum, and graphene oxide content on one side of the first coating 11 far from second coating 12 is maximum, finally
So that composite coating forms the distribution situation that a polarity and surface charge change in gradient.
When on the negative electrode 2 for being applied to capacitor, contacting with 2 surface of negative electrode is first coating 11, because containing
Oxygen-containing group present on graphene oxide and have negative electrical charge；It is second coating 12 with 3 material surface contact of positive electrode,
Make surface with positive charge because of the redox graphene minor matters that contain part of the metal oxide, therefore forms certain
Potential difference, self discharge caused by counteracting former supercapacitor due to potential difference, to be effectively improved putting certainly for capacitor
Electrical phenomena.
In an embodiment, the raw material of macromolecule carrier includes high molecular material.High molecular material includes macromolecule
Monomer or polymer, do not limit the concrete type of high molecular material herein, are adhered to electrode surface as long as being capable of forming
Macromolecule carrier, ultimately form composite coating 1.
In an embodiment, high molecular material is polyvinyl alcohol, Kynoar-hexafluoropropylene copolymer, propylene
Middle one or more in amide, polyetherimide.
High molecular material in the embodiment of the present invention is high polymer monomer and/or high molecular polymer.Preferably, macromolecule
Material is one of polyvinyl alcohol, Kynoar-hexafluoropropylene copolymer, acrylamide, polyetherimide or a variety of materials
The mixing of material can be such as the mixing of polyvinyl alcohol material or polyvinyl alcohol and acrylamide, allow graphite oxide as long as being able to achieve
Alkene is dispersed in high molecular material, is convenient for being cross-linked to form composite coating 1.Moreover, according to the use of high molecular material
And proportion, the composite material produced can be suitable for the electrolyte of the different systems such as water system, organic system and ionic liquid.
Such as, since polyvinyl alcohol usually can be dissolved in water, poly-vinyl alcohol solution can be suitably used for aqueous electrolyte, and polyvinylidene fluoride
Alkene-hexafluoropropene is then applicable to organic electrolyte and il electrolyte.
In an embodiment, high molecular material is monomer polyvinyl alcohol, and the raw material of macromolecule carrier further includes crosslinking
Agent, crosslinking agent be preferably one of glutaraldehyde, glyoxal, boric acid or more than one.Certainly, the present invention is not only limited in penta 2
Aldehyde, glyoxal, boric acid these types crosslinking agent can be selected for different high molecular materials, and Lai Xiangying selects different crosslinkings
Agent, as long as used crosslinking agent can make corresponding high molecular material that preferable cross-linking effect occur.Specifically, for example
The cross-linked structure of polyvinyl alcohol film is generally possible to the functional group reactions of hydroxyl and crosslinking agent by making polyvinyl alcohol film and is formed.
The functional group reacted as the hydroxyl with polyvinyl alcohol can enumerate aldehyde radical, hydroxyl, carboxyl etc..It therefore, can as crosslinking agent
Enumerate the compound at least two aldehyde radical, hydroxy or carboxy.Can such as enumerate glutaraldehyde, malonaldehyde, butanedial, hexandial,
O-phthalaldehyde etc. is as the crosslinking agent at least two aldehyde radical.Can also enumerate boric acid, borate, ethylene glycol, propylene glycol,
Glycerine etc. is as the crosslinking agent at least two hydroxyl.Can enumerate oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Phthalic acid etc. is as the crosslinking agent at least two carboxyl.In these crosslinking agents, since glutaraldehyde can be to dielectric
Layer brings the lower temperature of damage to carry out cross-linking reaction, therefore particularly preferably uses.
It should be noted that, as high molecular material, being answered when using high molecular polymers such as Kynoar-hexafluoropropenes
For not needing to be crosslinked when organic system and ionic liquid, there is no need to choose corresponding crosslinking agent.
In an embodiment, graphene oxide sheet diameter is 0.1-30 μm.Oxidation stone under preferred piece diameter range herein
Black alkene has preferable dispersion effect in high molecular material.
In an embodiment, the oxygen content of graphene oxide is 20-80%, made under preferred oxygen content range herein
The graphene oxide obtained has better performance, and obtained composite coating 1 has preferable performance and structural stability.
Another aspect of the present invention provides a kind of electrode material, and electrode material includes the material of any of the above-described.
Electrode material surface provided in an embodiment of the present invention is provided with above-mentioned composite coating 1, by by graphene oxide
Be dispersed in macromolecule carrier, due to the surface of graphene oxide in first coating 11 due to there are oxygen-containing group therefore have it is negative
Charge, and the part of the metal oxide of the redox graphene minor matters in second coating 12, so that surface has positive charge, electricity
The distributional difference of lotus results in certain potential difference, and when composite coating is applied on electrode, composite coating 1 is located at two electricity
Between pole, self discharge caused by counteracting former supercapacitor due to potential difference effectively reduces oneself of capacitor
Discharge effect.Composite coating 1 in the embodiment of the present invention can be suitable for all kinds of by choosing different types of macromolecule carrier
Electrolyte and Different electrodes system.The more unmodified electrode of electrode that composite material is modified through the invention under the same conditions can
Lower self-discharge current is enough generated, the self discharge effect of electrode is effectively reduced.
Another aspect of the present invention provides a kind of manufacturing method of graphene oxide composite coating 1, and method includes: that will aoxidize stone
Black alkene is added in high molecular dispersion liquid, forms composite material dispersion liquid；It is formed using composite material dispersion liquid in matrix surface
First coating 11；On 11 surface of first coating, setting metal material is doped processing, forms composite coating 1.
Graphene oxide dispersion can be first made in the embodiment of the present invention, wherein the preferred content of graphene oxide dispersion
For 0.1-10mg/ml, mass fraction is with the calculating of graphene oxide net content.Then macromolecule is added in graphene oxide dispersion
It is uniformly mixed in dispersion liquid, obtains composite material dispersion liquid.Mixing can be by magnetic agitation or ultrasonic treatment etc., herein
With no restrictions.Wherein high molecular material used in high molecular dispersion liquid can be high polymer monomer or polymer, specifically,
Can be one of polyvinyl alcohol, Kynoar-hexafluoropropylene copolymer, acrylamide, polyetherimide, or it is more in
Mixing material.Preferably, the content of high molecular material be 5-40%, specifically can according to different graphene oxide contents come into
The corresponding adjustment of row.Then first coating 11 is formed in matrix surface using composite material dispersion liquid, to realize between matrix
Better connection dispersion effect.Finally on 11 surface of first coating, setting metal material is doped processing, forms compound painting
Layer 1, wherein metal material includes but is not limited to the alloy of one of metal material such as zinc, tin, iron or Multiple components, metal material
The shape of material can be that metal foil or metal plate can use metal plate or gold when substrate material surface shape is more regular
Belong to foil to be doped, when substrate material surface is irregular, can be covered using the preferable metal foil of ductility, it is real
Now adulterate effect.The composite coating 1 constituted with graphene oxide and scion grafting modification component produced by the method for the invention, when multiple
When conjunction coating 1 is attached to electrode of super capacitor surface, all kinds of electrolyte and Different electrodes system can be suitable for.By this hair
The more unmodified electrode of electrode that bright composite coating 1 is modified can generate lower self-discharge current under the same conditions, therefore
It can be effectively reduced the self discharge effect of supercapacitor, and material obtains convenience, it is low in cost.
In an embodiment, metal material include one of zinc, tin, iron, tantalum, niobium, titanium, aluminium or more than one.
In the embodiment of the present invention, it can be correspondingly arranged metal material parameter according to the thickness of composite coating 1, such as work as coating
Thickness can realize preferably doping effect using thickness metal plate bigger than normal when bigger than normal, and when coating layer thickness is smaller just uses
Metal foil, ductility is good, and quality is small, avoids metal material and damages to coating structure.
The specific doping method of the embodiment of the present invention can be with are as follows: directly metal foil or metal plate is placed on coating,
1-72 hour is stood, specific time of repose can be determined according to the thickness of coating, such as when coating layer thickness is larger, be arranged longer
Time of repose shorter time of repose is then set, is sufficiently mixed so that metal material is able to carry out and when coating layer thickness is smaller
It is miscellaneous, and the time is saved, it obtains with the preferable composite coating 1 for reducing electrode self-discharge reaction effect.When this method is applied to
When on the electrode of capacitor, the coating being uniformly connected on matrix is since the graphene oxide in outer surface is restored by metal material
At redox graphene, and metal material is then oxidized to metal oxide, and the reduction-oxidation graphite generated accordingly
Alkene meeting minor matters part of the metal oxide, therefore form the second coating 12 with positive charge.And inner surface by metal material also
Former degree is lower, and main component is graphene oxide, surface of graphene oxide due to having negative electricity there are oxygen-containing group, this
Sample is formed the composite coating 1 with certain reduction gradient and potential difference, and when composite coating 1 is applied to capacitor
Electrode on when, when being especially applied on negative electrode 2, by the potential difference formed on composite coating 1, can offset former super
Capacitor due to potential difference caused by self discharge, effectively reduce the self discharge effect of capacitor, and the present invention
Embodiment method is easy, low in cost, is suitable for industrial production.
In an embodiment, forming first coating 11 in matrix surface using composite material dispersion liquid includes: to utilize
Composite material dispersion liquid forms dispersion liquid coating in matrix surface；Dispersion liquid coating is set to form first coating 11 using crosslinking agent.
The embodiment of the present invention is specifically as follows, and composite material dispersion liquid is handled by blade coating, matrix surface is dispersed in, is formed and divided
Dispersion liquid coating, wherein dispersion liquid coating layer thickness is preferably 100-2000nm, because cannot sufficiently obtain when coating layer thickness is excessively thin
The reducing effect of leakage current, and the blocked up electrode that may result in of coating layer thickness is blocked.Then it is applied using crosslinking agent in dispersion liquid
Layer surface sprays crosslinking agent, is crosslinked dispersion liquid coating, forms first coating 11.It is preferred that the method scratched can make it is compound
Material dispersion liquid can be connected firmly with matrix, and thickness is easily controllable, then the method by spraying crosslinking agent to be crosslinked
Coating afterwards is more bonded substrate material surface, and method is simple, is suitble to industrial production.
Certainly the present invention can also be crosslinked using other methods, be such as impregnated into the solution containing crosslinking agent and handed over
Connection, specifically, when glutaraldehyde is as crosslinking agent, oxidation can first for example be made when using polyvinyl alcohol as high molecular material
Graphene dispersing solution, wherein the content of graphene oxide dispersion is 0.1-10mg/ml, and the polyvinyl alcohol of 10wt% is then added
Aqueous solution made the two be uniformly dispersed by magnetic agitation 1 hour.Then electrode is impregnated in this composite material dispersion liquid centainly
Time further takes out, dry, forms dispersion liquid coating in electrode surface.Then the glutaraldehyde as crosslinking agent is dissolved in pure water
In, 1% glutaraldehyde water solution is made, then in the aqueous solution by the electrode dipping for foring dispersion liquid coating, then lift
And place 30 minutes, it is crosslinked dispersion liquid coating, first coating 11 is formed, then dries.This electrode is finally immersed in pure water
In, with the surface of pure water cleaning electrode material first coating 11, unreacted substance is removed.
In an embodiment, on 11 surface of first coating, setting metal material is doped processing, forms compound painting
Layer 1, comprising: metal plate or metal foil are set on 11 surface of first coating, sealing is placed on baking oven baking；Terminate to remove after baking
Metal plate or metal foil carry out freeze-drying process to first coating 11, form composite coating 1.
The embodiment of the present invention, specifically can be according to first coating by the way that metal or metal foil is arranged on 11 surface of first coating
11 thickness carrys out corresponding selection metal material type, is then sealed and is placed in baking oven and is baked, baked temperature is preferably
50 degrees Celsius, corresponding baking time is preferably 3 hours, and certainly when baked temperature correspondinglys increase, corresponding baking time is also answered
It is reduced when corresponding.In addition, it can be increase accordingly baked temperature or time when coating layer thickness is larger, to keep degree of drying,
The present invention does not do concrete restriction to baked temperature and time herein.Certainly, the present invention can also be not interposing in baking oven and bake,
Progress room temperature baking processing can also be placed under room temperature, when be placed under room temperature carry out baking processing when, corresponding standing time is excellent
It is selected as 10 hours.
Terminate after baking, removes the metal plate or metal foil on 11 surface of first coating, then first coating 11 is carried out cold
Freeze and be dried, forms composite coating 1.Freeze-drying due to the structure of matter lose it is small, can better protective coating, therefore
Preferably, but the present invention be not limited only to a kind of this drying means, drying drying can also be carried out by other appropriate methods.
In the following, by specific embodiment, the present invention will be described, but the present invention is not limited to the following examples.
(embodiment 1)
Step 1: taking the graphene oxide aqueous dispersions of 0.5mg/mL concentration, (graphene oxide sheet diameter is having a size of 500-5000
μm), polyvinyl alcohol (PVA) aqueous solution of 10wt% is added, forms the composite material that graphene oxide mass ratio is 1:10 and disperses
Liquid, and keep the two fully dispersed uniformly through magnetic agitation 1h at normal temperature.
Step 2: the method for composite material dispersion liquid blade coating is scratched to the coating of 2000nm thickness in electrode surface.It takes
1% glutaraldehyde water solution is sprayed at coating surface, is crosslinked composite material dispersion liquid.
Step 3: taking zine plate to be placed in film surface, the baking oven that sealing is placed on 50 degrees Celsius bakes 3h.
Step 4: zine plate is removed, by coated electrode freeze-drying process.
Prepared coating treatment electrode (modification) is in phosphoric acid/PVA electrolyte compared with than non-coating treatment (unmodified)
Electrode self-discharge performance is as shown in Figure 2, it is known that under the same time, the more unmodified electrode of modified electrode can generate bigger electricity
Pressure, when the time is 2h, modified electrode voltage is 0.5V, and unmodified electrode voltage is 0.4 voltage, it is seen that real using the present invention
After the composite coating for applying example, the self discharge effect of electrode can be effectively reduced.
(embodiment 2)
Step 1: taking the graphene oxide aqueous dispersions of 1mg/mL concentration, (graphene oxide sheet diameter is having a size of 100-1000 μ
M), Kynoar-hexafluoropropene (PVDF-HFP) solution of 10wt% is added, solvent is acetone, forms graphene oxide matter
The composite material dispersion liquid than being 1:5 is measured, sonicated 2h keeps the two fully dispersed uniformly under room temperature.
Step 2: the method for composite material dispersion liquid spraying is scratched to the coating of 1000nm thickness in electrode surface.
Step 3: taking iron plate to be placed in film surface, sealing, which is placed under room temperature, handles 10h.
Step 4: iron plate is removed, 60 degrees Celsius of drying 6h of coated electrode are dry.Prepared coated electrode methylimidazole
Self discharge has obvious drop compared with than untreated samples self discharge speed in bis-trifluoromethylsulfoandimide salt (EMIMTFSI) ionic liquid
It is low.
(embodiment 3)
Step 1: taking the graphene oxide aqueous dispersions of 0.7mg/mL concentration, (graphene oxide sheet diameter is having a size of 500-5000
μm), polyvinyl alcohol (PVA) aqueous solution of 10wt% is added, forms the composite material that graphene oxide mass ratio is 1:7 and disperses
Liquid, and keep the two fully dispersed uniformly through magnetic agitation 1h at normal temperature.
Step 2: the method for composite material dispersion liquid blade coating is scratched to the coating of 1500nm thickness in electrode surface.It takes
1% glutaraldehyde water solution is sprayed at coating surface, is crosslinked composite material.
Step 3: taking sheet tin to be placed in film surface, sealing, which is placed under room temperature, bakes 10h.
Step 4: sheet tin is removed, by coated electrode freeze-drying process.Prepared coated electrode is in PVA/ potassium hydroxide
(KOH) self discharge is substantially reduced compared with than untreated samples self discharge speed in electrolyte.
(embodiment 4)
Step 1: taking the graphene oxide aqueous dispersions of 1mg/mL concentration, (graphene oxide sheet diameter is having a size of 100-1000 μ
M), polyvinyl alcohol (PVA) aqueous solution of 10wt% is added, forms the composite material dispersion liquid that graphene oxide mass ratio is 1:5,
And keep the two fully dispersed uniformly through magnetic agitation 1.5h at normal temperature.
Step 2: the method for composite material dispersion liquid blade coating is scratched to the coating of 2000nm thickness in electrode surface.It takes
1% glutaraldehyde water solution is sprayed at coating surface, is crosslinked composite material.
Step 3: taking sheet tin to be placed in film surface, it is dry that sealing is placed on 60 degrees Celsius of drying 6h.
Step 4: sheet tin is removed, by coated electrode freeze-drying process.Prepared coated electrode is in phosphoric acid/PVA electrolysis
Self discharge is substantially reduced compared with than untreated samples self discharge speed in liquid.
(embodiment 5)
Step 1: taking the graphene oxide aqueous dispersions of 0.5mg/mL concentration, (graphene oxide sheet diameter is having a size of 100-
1000 μm), Kynoar-hexafluoropropene (PVDF-HFP) solution of 10wt% is added, solvent is acetone, forms graphite oxide
Alkene mass ratio is the composite material dispersion liquid of 1:10, and sonicated 2h keeps the two fully dispersed uniformly under room temperature.
Step 2: the method for composite material dispersion liquid spraying is scratched to the coating of 1500nm thickness in electrode surface.
Step 3: taking iron plate to be placed in film surface, sealing, which is placed under room temperature, handles 15h.
Step 4: iron plate is removed, 60 degrees Celsius of drying 6h of coated electrode are dry.Prepared coated electrode is applicable to
Organic electrolyte and il electrolyte.In methylimidazole bis-trifluoromethylsulfoandimide salt (EMIMTFSI) ionic liquid certainly
Electric discharge is substantially reduced compared with than untreated samples self discharge speed.
More than, only a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, and it is any to be familiar with
Those skilled in the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all cover
Within protection scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (10)
1. a kind of composite coating, which is characterized in that including first coating and second coating, the first coating includes that macromolecule carries
Body and the graphene oxide being dispersed in macromolecule carrier, the second coating includes macromolecule carrier, redox graphene
And metal oxide, the redox graphene and metal oxide Monodispersed are in macromolecule carrier.
2. composite coating according to claim 1, which is characterized in that the graphene oxide is in the first coating
Content is reduced in gradient from first coating to second coating, and the redox graphene and metal oxide are applied described second
Content in layer is reduced from second coating to first coating in gradient.
3. composite coating according to claim 1, which is characterized in that the raw material of the macromolecule carrier includes macromolecule material
Material.
4. composite coating according to claim 3, which is characterized in that the high molecular material is polyvinyl alcohol, gathers inclined fluorine
Ethylene-hexafluoropropylene copolymer, acrylamide, the middle one or more in polyetherimide.
5. composite coating according to claim 4, which is characterized in that the high molecular material is monomer polyvinyl alcohol, institute
The raw material for stating macromolecule carrier further includes crosslinking agent, and the crosslinking agent is preferably one of glutaraldehyde, glyoxal, boric acid or one
Kind or more.
6. a kind of electrode material, which is characterized in that the electrode material includes of any of claims 1-5 compound
Coating.
7. a kind of manufacturing method of composite coating, which is characterized in that the described method includes:
It adds graphene oxide into high molecular dispersion liquid, forms composite material dispersion liquid；
First coating is formed in matrix surface using the composite material dispersion liquid；
On the first coating surface, setting metal material is doped processing, forms composite coating.
8. the method according to the description of claim 7 is characterized in that described utilize the composite material dispersion liquid in matrix surface
Form first coating, comprising:
Dispersion liquid coating is formed on described matrix surface using the composite material dispersion liquid；
The dispersion liquid coating is set to form the first coating using crosslinking agent.
9. the method according to the description of claim 7 is characterized in that it is described the first coating surface be arranged metal material into
Row doping treatment forms composite coating, comprising:
Metal plate or metal foil are set on the first coating surface, sealing is placed on baking oven baking；
Terminate to remove the metal plate or metal foil after baking, freeze-drying process is carried out to the first coating, is formed compound
Coating.
10. the method according to the description of claim 7 is characterized in that the metal material include zinc, tin, iron, tantalum, niobium, titanium,
One of aluminium or more than one.
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Cited By (1)
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| CN111392717A (en) * | 2020-03-25 | 2020-07-10 | 宁波石墨烯创新中心有限公司 | Preparation method of concentrated graphene oxide solution and heat conducting film |
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