CN110085430B - Composite coating, manufacturing method thereof and electrode material - Google Patents
Composite coating, manufacturing method thereof and electrode material Download PDFInfo
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- CN110085430B CN110085430B CN201910364472.8A CN201910364472A CN110085430B CN 110085430 B CN110085430 B CN 110085430B CN 201910364472 A CN201910364472 A CN 201910364472A CN 110085430 B CN110085430 B CN 110085430B
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract
The invention discloses a composite coating, a manufacturing method and an electrode material, wherein the composite coating comprises a first coating and a second coating, the first coating comprises a high-molecular carrier and graphene oxide dispersed in the high-molecular carrier, the second coating comprises a high-molecular carrier, reduced graphene oxide and metal oxide, and the reduced graphene oxide and the metal oxide are dispersed in the high-molecular carrier. According to the invention, the reduced graphene oxide in the second coating has partial metal oxide, so that the surface of the reduced graphene oxide has positive charges, the surface of the reduced graphene oxide in the first coating has negative charges due to the existence of oxygen-containing groups, and a certain potential difference is formed due to the difference of the distribution of the charges.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a composite coating, a manufacturing method thereof and an electrode material.
Background
The capacitor is one of electronic elements widely used in electronic equipment, and is widely applied to aspects of blocking AC, coupling, bypassing, filtering, tuning loop, energy conversion, control and the like in a circuit. With the change of electronic information technology, the update speed of digital electronic products is faster and faster, and the production and sales volume of consumer electronic products such as flat panel televisions, notebook computers, digital cameras and the like is continuously increased, which drives the growth of capacitor industry.
With the recent development of capacitor materials, some supercapacitors have potential as power supply applications in some fields. However, the rapid self-discharge effect greatly limits its application as a endurance-type energy storage device. The reason why the self-discharge of the super capacitor is fast is that the mechanism of the energy storage material is charge interface adsorption, self-discharge is generated due to voltage and ion concentration factors in the charging process, and the self-discharge speed is much faster than that of a battery.
Therefore, how to improve the self-discharge phenomenon of the capacitor is a problem to be solved.
Disclosure of Invention
In order to effectively overcome the above defects in the prior art, embodiments of the present invention creatively provide a composite coating, a manufacturing method thereof, and an electrode material, where the composite coating includes a first coating and a second coating, the first coating includes a polymer carrier and graphene oxide dispersed in the polymer carrier, the second coating includes a polymer carrier, reduced graphene oxide, and a metal oxide, and the reduced graphene oxide and the metal oxide are both dispersed in the polymer carrier.
In one embodiment, the content of the graphene oxide in the first coating layer decreases in a gradient from the first coating layer to the second coating layer, and the content of the reduced graphene oxide and the content of the metal oxide in the second coating layer both decrease in a gradient from the second coating layer to the first coating layer.
In one embodiment, the raw material of the polymer carrier includes a polymer material.
In one embodiment, the polymer material is one or more selected from polyvinyl alcohol, polyvinylidene fluoride-hexafluoropropylene copolymer, acrylamide, and polyetherimide.
In an embodiment, the polymer material is monomeric polyvinyl alcohol, and the raw material of the polymer carrier further includes a cross-linking agent, and the cross-linking agent is preferably one or more of glutaraldehyde, glyoxal, and boric acid.
In another aspect, the present invention provides an electrode material comprising any one of the materials described above.
In another aspect, the present invention provides a method for manufacturing a composite coating, the method comprising: adding graphene oxide into the high-molecular dispersion liquid to form a composite material dispersion liquid; forming a first coating on the surface of a substrate by using the composite material dispersion liquid; and arranging a metal material on the surface of the first coating for doping treatment to form a composite coating.
In an embodiment, the forming a first coating on the surface of the substrate by using the composite material dispersion comprises: forming a dispersion coating on the surface of the substrate by using the composite dispersion; coating the dispersion with a crosslinking agent to form the first coating layer.
In an embodiment, the disposing a metal material on the surface of the first coating layer to perform a doping treatment to form a composite coating layer includes: arranging a metal plate or a metal foil on the surface of the first coating, sealing, and then placing in an oven for baking; and after finishing drying, taking down the metal plate or the metal foil, and carrying out freeze drying treatment on the first coating to form the composite coating.
In one embodiment, the metal material comprises one or more of zinc, tin, iron, tantalum, niobium, titanium, and aluminum.
The invention provides a composite coating, a manufacturing method and an electrode material, wherein the composite coating is prepared by dispersing graphene oxide in a high-molecular dispersion liquid to form a first coating capable of being adhered to a substrate, and then doping the first coating with metal, so that the graphene oxide composite material on the surface of the coating can be reduced to a certain extent to form a reduced graphene oxide composite material with gradient, and a second coating containing reduced graphene oxide, metal oxide and a high-molecular carrier is formed. The reduced graphene oxide in the second coating is branched to form partial metal oxide, so that the surface of the reduced graphene oxide is positively charged, the surface of the reduced graphene oxide in the first coating is negatively charged due to the existence of oxygen-containing groups, and a certain potential difference is formed due to the difference of charge distribution.
Drawings
The above and other objects, features and advantages of exemplary embodiments of the present invention will become readily apparent from the following detailed description read in conjunction with the accompanying drawings. Several embodiments of the invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which:
in the drawings, the same or corresponding reference numerals indicate the same or corresponding parts.
FIG. 1 is a schematic structural diagram of a composite coating and an electrode material according to an embodiment of the present invention;
FIG. 2 is a comparison of self-discharge performance of electrodes according to an embodiment of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Fig. 1 is a schematic structural diagram of a composite coating and an electrode material according to an embodiment of the present invention.
Referring to fig. 1, an embodiment of the present invention provides a composite coating 1, including a first coating 11 and a second coating 12, where the first coating 11 includes a polymer carrier and graphene oxide dispersed in the polymer carrier, and the second coating 12 includes a polymer carrier, reduced graphene oxide, and a metal oxide, both of which are dispersed in the polymer carrier.
According to the composite coating 1 provided by the embodiment of the invention, the graphene oxide is dispersed in the polymer carrier by utilizing the characteristic of good dispersibility of the graphene oxide, the surface of the graphene oxide in the first coating 11 is negatively charged due to the existence of oxygen-containing groups, and the reduced graphene oxide in the second coating 12 is branched to form partial metal oxide, so that the surface is positively charged, and the distribution difference of the charges causes a certain potential difference.
Referring to fig. 1, when the composite coating is applied to the negative electrode 2 of the capacitor, the first coating 11 is connected with the negative electrode 2, the second coating 12 is connected with the positive electrode 3, and the self-discharge of the original super capacitor caused by the potential difference can be counteracted through the potential difference formed on the composite coating 1, so that the self-discharge effect of the capacitor is effectively reduced.
The composite coating 1 in the embodiment of the invention can be suitable for various electrolytes and different electrode systems by selecting different types of polymer carriers. The electrode modified by the composite coating can generate lower self-discharge current than an unmodified electrode under the same condition. Wherein the polymer carrier is further used for adhering to the substrate, and comprises a polymer monomer or a polymer, and the invention is not limited herein. Similarly, the size, structure, and the like of the graphene oxide, the reduced graphene oxide, and the metal oxide are not particularly limited in the embodiments of the present invention.
In one embodiment, the content of the graphene oxide in the first coating layer 11 decreases in a gradient from the first coating layer 11 to the second coating layer 12, and the content of the reduced graphene oxide and the content of the metal oxide in the second coating layer 12 both decrease in a gradient from the second coating layer 12 to the first coating layer 11. In the embodiment of the invention, the content of the metal oxide is the largest on the side of the second coating 12 away from the first coating 11, and the content of the graphene oxide is the largest on the side of the first coating 11 away from the second coating 12, so that the composite coating finally forms a distribution condition with gradient change of polarity and surface charge.
When applied to the negative electrode 2 of a capacitor, in contact with the surface of the negative electrode 2 is a first coating layer 11, which is negatively charged due to the presence of oxygen-containing groups on the graphene oxide; the second coating 12 is in contact with the surface of the positive electrode 3 material, and the surface of the second coating is positively charged due to the fact that the reduced graphene oxide branches contain partial metal oxides, so that a certain potential difference is formed, self-discharge of the original super capacitor caused by the potential difference is counteracted, and the self-discharge phenomenon of the capacitor is effectively improved.
In one embodiment, the material of the polymeric carrier comprises a polymeric material. The polymer material includes a polymer monomer or a polymer, and the specific type of the polymer material is not limited herein, as long as a polymer carrier adhered to the surface of the electrode can be formed, and the composite coating 1 is finally formed.
In one embodiment, the polymer material is one or more selected from polyvinyl alcohol, polyvinylidene fluoride-hexafluoropropylene copolymer, acrylamide, and polyetherimide.
The polymer material in the embodiment of the invention is a polymer monomer and/or a polymer. Preferably, the polymer material is a mixture of one or more of polyvinyl alcohol, polyvinylidene fluoride-hexafluoropropylene copolymer, acrylamide and polyetherimide, for example, the polymer material may be a polyvinyl alcohol material, or a mixture of polyvinyl alcohol and acrylamide, as long as graphene oxide can be dispersed in the polymer material to facilitate crosslinking to form the composite coating 1. The composite material produced can be applied to aqueous, organic, and ionic liquids and other different electrolyte systems depending on the use and the ratio of the polymer material. For example, polyvinyl alcohol is generally soluble in water, so that a polyvinyl alcohol solution can be applied to an aqueous electrolyte solution, and polyvinylidene fluoride-hexafluoropropylene can be applied to an organic electrolyte solution and an ionic liquid electrolyte solution.
In one embodiment, the polymer material is polyvinyl alcohol monomer, and the raw material of the polymer carrier further includes a cross-linking agent, and the cross-linking agent is preferably one or more of glutaraldehyde, glyoxal, and boric acid. Of course, the present invention is not limited to glutaraldehyde, glyoxal, and boric acid, but may select different cross-linking agents for different polymer materials, as long as the cross-linking agent can cause the corresponding polymer material to have a better cross-linking effect. Specifically, for example, the crosslinked structure of the polyvinyl alcohol film can be generally formed by reacting the hydroxyl group of the polyvinyl alcohol film with the functional group of the crosslinking agent. Examples of the functional group that reacts with a hydroxyl group of polyvinyl alcohol include an aldehyde group, a hydroxyl group, and a carboxyl group. Thus, compounds having at least 2 aldehyde groups, hydroxyl groups or carboxyl groups can be cited as crosslinking agents. As the crosslinking agent having at least 2 aldehyde groups, glutaraldehyde, malondialdehyde, succindialdehyde, adipaldehyde, o-phthalaldehyde and the like can be cited, for example. Boric acid, borate, ethylene glycol, propylene glycol, glycerin, and the like can also be cited as the crosslinking agent having at least 2 hydroxyl groups. As the crosslinking agent having at least 2 carboxyl groups, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid and the like can be cited. Among these crosslinking agents, glutaraldehyde is particularly preferably used because it can perform a crosslinking reaction at a relatively low temperature without damaging the dielectric layer.
When a polymer such as polyvinylidene fluoride-hexafluoropropylene is used as a polymer material, crosslinking is not required when the polymer is applied to an organic system or an ionic liquid, and therefore, a corresponding crosslinking agent is not required to be selected.
In one embodiment, the graphene oxide has a sheet diameter of 0.1 to 30 μm. The graphene oxide in the preferred sheet diameter range has a good dispersion effect in the high polymer material.
In one embodiment, the oxygen content of the graphene oxide is 20-80%, and the graphene oxide prepared in this preferred oxygen content range has better performance, and the composite coating 1 prepared has better performance and structural stability.
In another aspect, the present invention provides an electrode material comprising any one of the materials described above.
The composite coating 1 is arranged on the surface of the electrode material provided by the embodiment of the invention, graphene oxide is dispersed in a polymer carrier, the surface of the graphene oxide in the first coating 11 is negatively charged due to the existence of oxygen-containing groups, and the reduced graphene oxide in the second coating 12 is branched to part of metal oxide, so that the surface is positively charged, and a certain potential difference is formed due to the distribution difference of the charges. The composite coating 1 in the embodiment of the invention can be suitable for various electrolytes and different electrode systems by selecting different types of polymer carriers. Compared with an unmodified electrode, the electrode modified by the composite material can generate lower self-discharge current under the same condition, and the self-discharge effect of the electrode is effectively reduced.
In another aspect, the present invention provides a method for manufacturing a graphene oxide composite coating 1, including: adding graphene oxide into the high-molecular dispersion liquid to form a composite material dispersion liquid; forming a first coating 11 on the surface of the substrate by using the composite dispersion; and arranging a metal material on the surface of the first coating 11 for doping treatment to form the composite coating 1.
According to the embodiment of the invention, the graphene oxide dispersion liquid can be prepared firstly, wherein the preferable content of the graphene oxide dispersion liquid is 0.1-10mg/ml, and the mass fraction is calculated by the net content of graphene oxide. And then adding the graphene oxide dispersion liquid into the high-molecular dispersion liquid, and uniformly mixing to obtain the composite material dispersion liquid. The mixing and stirring may be performed by magnetic stirring, ultrasonic treatment, or the like, without limitation. The polymer material used in the polymer dispersion may be a polymer monomer or a polymer, and specifically may be one of polyvinyl alcohol, polyvinylidene fluoride-hexafluoropropylene copolymer, acrylamide, and polyetherimide, or a mixture thereof. Preferably, the content of the polymer material is 5-40%, and the content can be adjusted according to different contents of graphene oxide. And then forming a first coating layer 11 on the surface of the substrate by using the composite material dispersion liquid, thereby realizing better connection dispersion effect with the substrate. Finally, a metal material is arranged on the surface of the first coating 11 for doping treatment to form the composite coating 1, wherein the metal material includes but is not limited to one or more of zinc, tin, iron and the like, and the metal material can be a metal foil or a metal plate, when the surface of the base material is regular in shape, the metal plate or the metal foil can be used for doping, and when the surface of the base material is irregular, the metal foil with good ductility can be used for covering to achieve the doping effect. The composite coating 1 prepared by the method and composed of the graphene oxide and the graft modification component can be suitable for various electrolytes and different electrode systems when the composite coating 1 is attached to the surface of the electrode of the supercapacitor. Compared with an unmodified electrode, the electrode modified by the composite coating 1 can generate lower self-discharge current under the same condition, so that the self-discharge effect of the super capacitor can be effectively reduced, and the material is convenient to obtain and low in cost.
In one embodiment, the metal material comprises one or more of zinc, tin, iron, tantalum, niobium, titanium, and aluminum.
In the embodiment of the invention, the parameters of the metal material can be correspondingly set according to the thickness of the composite coating 1, for example, when the thickness of the coating is larger, a metal plate with larger thickness can be adopted to realize better doping effect, and when the thickness of the coating is smaller, a metal foil is adopted, so that the ductility is good, the quality is small, and the damage of the metal material to the coating structure is avoided.
The specific doping method of the embodiment of the invention can be as follows: directly placing the metal foil or the metal plate on the coating, and standing for 1-72 hours, wherein the specific standing time can be determined according to the thickness of the coating, and if the thickness of the coating is larger, setting longer standing time, and if the thickness of the coating is smaller, setting shorter standing time, so that the metal material can be fully doped, saving time and obtaining the composite coating 1 with better effect of reducing the self-discharge reaction of the electrode. When the method is applied to an electrode of a capacitor, the coating uniformly connected to the substrate forms the second coating 12 having a positive charge because graphene oxide in the outer surface is reduced to reduced graphene oxide by a metal material, the metal material is correspondingly oxidized to a metal oxide, and the resulting reduced graphene oxide is branched to a metal oxide. The inner surface is reduced by a metal material to a lower degree, the main component is graphene oxide, the surface of the graphene oxide is negatively charged due to the presence of oxygen-containing groups, so that the composite coating 1 with a certain reduction gradient and potential difference is formed, and when the composite coating 1 is applied to an electrode of a capacitor, particularly a negative electrode 2, the self-discharge of the original super capacitor caused by the potential difference can be counteracted through the potential difference formed on the composite coating 1, so that the self-discharge effect of the capacitor is effectively reduced.
In one embodiment, forming the first coating 11 on the surface of the substrate using the composite dispersion comprises: forming a dispersion coating on the surface of the substrate by using the composite dispersion; the dispersion is coated with a crosslinking agent to form the first coating layer 11. Specifically, the embodiment of the present invention may be that the composite dispersion is uniformly dispersed on the surface of the substrate by blade coating treatment to form the dispersion coating, wherein the thickness of the dispersion coating is preferably 100-. Then, a crosslinking agent is sprayed on the surface of the dispersion coating by using the crosslinking agent to crosslink the dispersion coating, thereby forming a first coating 11. The preferable blade coating method can ensure that the composite material dispersion liquid can be firmly connected with the matrix, the thickness is easy to control, the cross-linked coating is more attached to the surface of the matrix material by spraying the cross-linking agent, and the method is simple and suitable for industrial production.
Of course, the present invention can also adopt other methods to carry out crosslinking, such as dipping into a solution containing a crosslinking agent to carry out crosslinking, specifically, for example, when polyvinyl alcohol is used as a high molecular material and glutaraldehyde is used as a crosslinking agent, a graphene oxide dispersion liquid can be prepared, wherein the content of the graphene oxide dispersion liquid is 0.1-10mg/ml, then 10 wt% of polyvinyl alcohol aqueous solution is added, and the two are uniformly dispersed by magnetic stirring for 1 hour. Then, the electrode is immersed in the composite dispersion for a certain period of time, and then taken out and dried to form a dispersion coating on the surface of the electrode. Glutaraldehyde as a crosslinking agent was then dissolved in pure water to prepare a 1% glutaraldehyde aqueous solution, and the electrode on which the dispersion coating was formed was immersed in the aqueous solution, then lifted and left for 30 minutes to crosslink the dispersion coating to form the first coating 11, and then dried. Finally, the electrode was immersed in pure water, and the surface of the first coating layer 11 of the electrode material was cleaned with pure water to remove unreacted substances.
In an embodiment, disposing a metal material on the surface of the first coating 11 to perform a doping treatment to form the composite coating 1 includes: arranging a metal plate or a metal foil on the surface of the first coating 11, sealing and then placing in an oven for baking; and after finishing drying, taking down the metal plate or the metal foil, and carrying out freeze drying treatment on the first coating 11 to form the composite coating 1.
In the embodiment of the invention, by arranging the metal or the metal foil on the surface of the first coating 11, the type of the metal material can be selected correspondingly according to the thickness of the first coating 11, then the metal material is sealed and placed in the oven for baking, the baking temperature is preferably 50 ℃, the corresponding baking time is preferably 3 hours, and certainly when the baking temperature is correspondingly increased, the corresponding baking time should be correspondingly reduced. In addition, when the coating thickness is larger, the drying temperature or time can be correspondingly increased to maintain the drying degree, and the drying temperature and time are not specifically limited in the invention. Of course, the present invention may be placed in a room temperature for baking without being placed in an oven, and when the room temperature for baking is placed, the corresponding time is preferably 10 hours.
After finishing baking, the metal plate or the metal foil on the surface of the first coating 11 is removed, and then the first coating 11 is subjected to freeze drying treatment to form the composite coating 1. Freeze drying is preferred because it results in less loss of structure to the material and better protection of the coating, but the present invention is not limited to this drying method and may be dried by other suitable methods.
The present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples.
(example 1)
Step 1: taking graphene oxide aqueous dispersion with the concentration of 0.5mg/mL (the size of the sheet diameter of the graphene oxide is 500-: 10 and stirring the two solutions by magnetic force for 1 hour at normal temperature to fully and uniformly disperse the two solutions.
Step 2: and (3) coating the composite material dispersion liquid on the surface of the electrode by a doctor blade coating method to form a coating with the thickness of 2000 nm. Spraying 1% glutaraldehyde solution on the surface of the coating to make the composite material dispersion liquid cross-linked.
And step 3: and (3) placing the zinc plate on the surface of the film, sealing, and then placing in a 50 ℃ oven for baking for 3 h.
And 4, step 4: and (4) taking down the zinc plate, and carrying out freeze drying treatment on the coated electrode.
The self-discharge performance of the prepared coating treatment electrode (modified) in phosphoric acid/PVA electrolyte is shown in figure 2 compared with that of an electrode which is not treated with a coating (unmodified), and the self-discharge performance of the electrode can be effectively reduced after the composite coating of the embodiment of the invention is adopted, so that the modified electrode can generate larger voltage than the unmodified electrode at the same time, the modified electrode voltage is 0.5V and the unmodified electrode voltage is 0.4V when the time is 2 h.
(example 2)
Step 1: taking graphene oxide aqueous dispersion with the concentration of 1mg/mL (the size of the graphene oxide sheet diameter is 100-: 5, carrying out ultrasonic treatment for 2 hours at normal temperature to fully and uniformly disperse the two.
Step 2: the composite material dispersion liquid is coated with a coating with the thickness of 1000nm on the surface of an electrode by a blade coating method.
And step 3: placing the iron plate on the surface of the film, sealing, and treating at normal temperature for 10 h.
And 4, step 4: taking down the iron plate, and drying the coated electrode for 6h at the temperature of 60 ℃. Compared with an untreated sample, the self-discharge speed of the prepared coating electrode methylimidazole bistrifluoromethanesulfonimide salt (EMIMTFSI) ionic liquid is obviously reduced.
(example 3)
Step 1: taking graphene oxide aqueous dispersion with the concentration of 0.7mg/mL (the size of the sheet diameter of the graphene oxide is 500-: 7 and stirring the two solutions by magnetic force for 1 hour at normal temperature to fully and uniformly disperse the two solutions.
Step 2: and (3) carrying out blade coating on the surface of the electrode by using a blade coating method to coat the composite material dispersion liquid with a thickness of 1500 nm. Spraying 1% glutaraldehyde solution on the surface of the coating to make the composite material cross-linked.
And step 3: and (3) placing the tin plate on the surface of the film, sealing, and drying at normal temperature for 10 hours.
And 4, step 4: and (5) taking off the tin plate, and carrying out freeze drying treatment on the coated electrode. The self-discharge speed of the prepared coating electrode in PVA/potassium hydroxide (KOH) electrolyte is obviously reduced compared with that of an untreated sample.
(example 4)
Step 1: taking graphene oxide aqueous dispersion with the concentration of 1mg/mL (the size of the graphene oxide sheet diameter is 100-1000 mu m), and adding 10 wt% of polyvinyl alcohol (PVA) aqueous solution to form a graphene oxide aqueous dispersion with the mass ratio of 1: 5, and stirring the two solutions by magnetic force for 1.5h at normal temperature to fully and uniformly disperse the two solutions.
Step 2: and (3) coating the composite material dispersion liquid on the surface of the electrode by a doctor blade coating method to form a coating with the thickness of 2000 nm. Spraying 1% glutaraldehyde solution on the surface of the coating to make the composite material cross-linked.
And step 3: and (3) placing the tin plate on the surface of the film, sealing, and drying at 60 ℃ for 6 h.
And 4, step 4: and (5) taking off the tin plate, and carrying out freeze drying treatment on the coated electrode. The self-discharge speed of the prepared coating electrode in the phosphoric acid/PVA electrolyte is obviously reduced compared with that of an untreated sample.
(example 5)
Step 1: taking graphene oxide aqueous dispersion with the concentration of 0.5mg/mL (the size of the graphene oxide sheet diameter is 100-: 10, and performing ultrasonic treatment for 2 hours at normal temperature to fully and uniformly disperse the two.
Step 2: the composite material dispersion liquid is coated with a coating with the thickness of 1500nm on the surface of an electrode by a spraying method.
And step 3: placing the iron plate on the surface of the film, sealing, and treating at normal temperature for 15 h.
And 4, step 4: taking down the iron plate, and drying the coated electrode for 6h at the temperature of 60 ℃. The prepared coating electrode can be suitable for organic electrolyte and ionic liquid electrolyte. Compared with an untreated sample, the self-discharge rate of the ionic liquid is obviously reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A composite coating comprising a first coating layer and a second coating layer, wherein when the composite coating is applied to a negative electrode of a capacitor, the first coating layer is connected to the negative electrode and the second coating layer is connected to a positive electrode;
the first coating comprises a polymer carrier and graphene oxide dispersed in the polymer carrier, the second coating comprises a polymer carrier, reduced graphene oxide and metal oxide, and the reduced graphene oxide and the metal oxide are dispersed in the polymer carrier.
2. The composite coating according to claim 1, wherein the content of the graphene oxide in the first coating decreases in a gradient from the first coating to the second coating, and the content of the reduced graphene oxide and the content of the metal oxide in the second coating both decrease in a gradient from the second coating to the first coating.
3. The composite coating of claim 1, wherein the polymeric carrier material comprises a polymeric material.
4. The composite coating of claim 3, wherein the polymeric material is at least one of polyvinyl alcohol, polyvinylidene fluoride-hexafluoropropylene copolymer, acrylamide, polyetherimide.
5. The composite coating of claim 4, wherein the polymer material is a monomer polyvinyl alcohol, and the raw material of the polymer carrier further comprises a cross-linking agent.
6. The composite coating of claim 5, wherein the cross-linking agent is at least one of glutaraldehyde, glyoxal, boric acid.
7. An electrode material, characterized in that it comprises a composite coating according to any one of claims 1 to 6.
8. A method of manufacturing a composite coating according to any of claims 1 to 6, wherein the method comprises:
adding graphene oxide into the high-molecular dispersion liquid to form a composite material dispersion liquid;
forming a first coating on the surface of a substrate by using the composite material dispersion liquid;
arranging a metal plate or a metal foil on the surface of the first coating, sealing, and then placing in an oven for baking;
and after finishing drying, taking down the metal plate or the metal foil, and carrying out freeze drying treatment on the first coating to form the composite coating.
9. The method of claim 8, wherein the forming a first coating on the surface of the substrate using the composite dispersion comprises:
forming a dispersion coating on the surface of the substrate by using the composite dispersion;
coating the dispersion with a crosslinking agent to form the first coating layer.
10. The method of claim 8, wherein the metal plate or foil material comprises at least one of zinc, tin, iron, tantalum, niobium, titanium, aluminum.
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| CN106835326A (en) * | 2016-07-11 | 2017-06-13 | 济南圣泉集团股份有限公司 | High performance Graphene composite polyvinyl alcohol fiber and preparation method thereof, application |
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