CN108766779B - Cobalt-nickel-based supercapacitor, powder thereof and preparation method of powder - Google Patents
Cobalt-nickel-based supercapacitor, powder thereof and preparation method of powder Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of cobalt-nickel-based super capacitor powder, which is characterized by comprising the following steps of: the method comprises the following steps: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; and calcining the second composite powder to obtain the cobalt-nickel-based super capacitor powder. The modified carbon nano tube and the modified graphene are doped, so that the conductivity of the oxide is greatly improved.
Description
Technical Field
The invention belongs to the technical field of capacitors, and relates to a cobalt-nickel-based supercapacitor, powder thereof and a preparation method of the powder.
Background
The super capacitor is a novel green energy storage device, and has higher power density than a battery and higher energy density than a traditional capacitor. Meanwhile, the super capacitor has the advantages of long cycle life, high specific capacitance, wide use temperature range, large charging and discharging current, environmental protection and the like, and has good application prospects in the fields of aerospace, mobile communication, electric automobiles, smart power grids and the like, so that the super capacitor is widely concerned by global researchers, and the electrode material has important influence on the performance of the super capacitor. The metal oxide NiCoO-based oxide is considered to be one of the most promising electrode materials to replace noble metal electrodes at present because of its high specific capacity. Although NiCoO has twice the conductivity of NiO and Co3O4, it is only 10-2S/cm, poor conductivity, and influence on the rate capability of the metal oxide, so that the metal oxide can not be applied under a large current. In order to solve the problem of poor conductivity of NiCoO-based oxides, the most common method is to compound NiCoO-based oxides with a carbon material having high conductivity.
In order to solve the technical problem of compounding NiCoO-based oxides with high-conductivity carbon materials, the prior art provides a technology for preparing modified carbon nanotube-doped NiCoO-based oxides by a chemical synthesis method. However, the prior art has at least the following disadvantages: 1. doping only the modified carbon nanotubes does not greatly increase the conductivity of the oxide, generally speaking, the conductivity is increased by less than one order of magnitude. 2. Due to the powder method for preparing the super capacitor, if only the modified carbon nano tube is added, the capacitor material is easy to be pulverized and broken. 3. The capacitor performance is affected due to the complicated chemical method and the unreasonable manufacturing process.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a cobalt-nickel-based supercapacitor, powder thereof and a preparation method of the powder, thereby overcoming the problems in the prior art.
In order to achieve the purpose, the invention provides a preparation method of cobalt-nickel-based supercapacitor powder, which is characterized by comprising the following steps of: the method comprises the following steps: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; and calcining the second composite powder to obtain the cobalt-nickel-based super capacitor powder.
Preferably, in the above technical scheme, the modifying treatment of graphene specifically comprises: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the graphene accounts for 5-10 parts by weight, the hydrogen peroxide accounts for 40-50 parts by weight, and the dilute hydrochloric acid accounts for 10000 parts by weight; heating the first modified solution at 90-95 ℃ for 2-3h to obtain a second modified solution; and filtering the second modification solution to obtain the modified graphene.
Preferably, in the above technical solution, the modification treatment of the carbon nanotube specifically comprises: putting the carbon nano tube into dilute nitric acid; adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein the carbon nano tube accounts for 5-10 parts by weight, the potassium permanganate accounts for 10-20 parts by weight, and the dilute nitric acid accounts for 10000 parts by weight of 5000-; heating the third modified solution at 90-95 ℃ for 4-5h to obtain a fourth modified solution; and filtering the fourth modification solution to obtain the modified carbon nano tube.
Preferably, in the above technical solution, in the first mixed solution, by weight, 50 to 100 parts of cobalt hydroxide powder, 50 to 100 parts of nickel hydroxide powder, 5 to 10 parts of modified graphene, and 5 to 10 parts of modified carbon nanotube are included.
Preferably, in the above technical scheme, the first drying specific process is: the drying is carried out under vacuum condition, the drying temperature is 90-95 ℃, and the drying time is 4-5 h.
Preferably, in the above technical scheme, the second drying specific process is as follows: the drying is carried out under the vacuum condition, the drying temperature is 120-130 ℃, and the drying time is 4-5 h.
Preferably, in the above technical scheme, the specific process of calcining is as follows: the calcination is carried out under the vacuum condition, the calcination temperature is 400-450 ℃, and the calcination time is 2-3 h.
The invention also provides cobalt-nickel-based super capacitor powder, which is prepared by the preparation method.
The invention also provides a cobalt-nickel-based supercapacitor which comprises the cobalt-nickel-based supercapacitor powder.
Compared with the prior art, the invention has the following beneficial effects: 1. the modified carbon nano tube and the modified graphene are doped, so that the conductivity of the oxide is greatly improved, and generally speaking, the improvement of the conductivity can reach one order of magnitude. 2. Because the modified carbon nano tube and the modified graphene are simultaneously doped, the generated capacitor material cannot be pulverized and crushed. 3. The invention redesigns the equipment method, optimizes various process parameters, ensures the produced capacitor to have stable quality, and ensures that the performance of the capacitor is not influenced by the preparation process.
Detailed Description
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
The cobalt-nickel-based supercapacitor powder is prepared by the following method: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; and calcining the second composite powder to obtain the cobalt-nickel-based super capacitor powder. The modification treatment of the graphene specifically comprises the following steps: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the first modified solution comprises 5 parts by weight of graphene, 40 parts by weight of hydrogen peroxide and 5000 parts by weight of dilute hydrochloric acid; heating the first modified solution at 90 ℃ for 3h to obtain a second modified solution; and filtering the second modification solution to obtain the modified graphene. The specific modification treatment of the carbon nano tube is as follows: putting the carbon nano tube into dilute nitric acid; adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein 5 parts by weight of carbon nano tube, 10 parts by weight of potassium permanganate and 5000 parts by weight of dilute nitric acid are added; heating the third modified solution at 90 ℃ for 5h to obtain a fourth modified solution; and filtering the fourth modification solution to obtain the modified carbon nano tube. In the first mixed solution, 50 parts by weight of cobalt hydroxide powder, 50 parts by weight of nickel hydroxide powder, 10 parts by weight of modified graphene, and 10 parts by weight of modified carbon nanotubes are contained. The first drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 90 ℃, and the drying time is 5 h. The second drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 120 ℃, and the drying time is 5 h. The specific process of calcination is as follows: the calcination is carried out under the vacuum condition, the calcination temperature is 400 ℃, and the calcination time is 3 h.
Example 2
The cobalt-nickel-based supercapacitor powder is prepared by the following method: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; and calcining the second composite powder to obtain the cobalt-nickel-based super capacitor powder. The modification treatment of the graphene specifically comprises the following steps: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the graphene accounts for 10 parts by weight, the hydrogen peroxide accounts for 50 parts by weight, and the dilute hydrochloric acid accounts for 10000 parts by weight; heating the first modified solution at 95 ℃ for 2h to obtain a second modified solution; and filtering the second modification solution to obtain the modified graphene. The specific modification treatment of the carbon nano tube is as follows: putting the carbon nano tube into dilute nitric acid; adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein the carbon nano tube accounts for 10 parts by weight, the potassium permanganate accounts for 20 parts by weight, and the dilute nitric acid accounts for 10000 parts by weight; heating the third modified solution at 95 ℃ for 4h to obtain a fourth modified solution; and filtering the fourth modification solution to obtain the modified carbon nano tube. In the first mixed solution, 100 parts by weight of cobalt hydroxide powder, 100 parts by weight of nickel hydroxide powder, 5 parts by weight of modified graphene, and 5 parts by weight of modified carbon nanotubes are contained. The first drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 95 ℃, and the drying time is 4 h. The second drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 130 ℃, and the drying time is 4 h. The specific process of calcination is as follows: the calcination is carried out under the vacuum condition, the calcination temperature is 450 ℃, and the calcination time is 2 h.
Example 3
The cobalt-nickel-based supercapacitor powder is prepared by the following method: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; and calcining the second composite powder to obtain the cobalt-nickel-based super capacitor powder. The modification treatment of the graphene specifically comprises the following steps: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the graphene accounts for 5-10 parts by weight, the hydrogen peroxide accounts for 40-50 parts by weight, and the dilute hydrochloric acid accounts for 10000 parts by weight; heating the first modified solution at 90-95 ℃ for 2-3h to obtain a second modified solution; and filtering the second modification solution to obtain the modified graphene. The specific modification treatment of the carbon nano tube is as follows: putting the carbon nano tube into dilute nitric acid; adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein the carbon nano tube accounts for 5-10 parts by weight, the potassium permanganate accounts for 10-20 parts by weight, and the dilute nitric acid accounts for 10000 parts by weight of 5000-; heating the third modified solution at 90-95 ℃ for 4-5h to obtain a fourth modified solution; and filtering the fourth modification solution to obtain the modified carbon nano tube. In the first mixed liquid, 50-100 parts by weight of cobalt hydroxide powder, 50-100 parts by weight of nickel hydroxide powder, 5-10 parts by weight of modified graphene and 5-10 parts by weight of modified carbon nanotubes are used. The first drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 90-95 ℃, and the drying time is 4-5 h. The second drying specific process comprises the following steps: the drying is carried out under the vacuum condition, the drying temperature is 120-130 ℃, and the drying time is 4-5 h. The specific process of calcination is as follows: the calcination is carried out under the vacuum condition, the calcination temperature is 400-450 ℃, and the calcination time is 2-3 h.
Example 4
The difference from example 3 is: graphene is not provided.
Example 5
The difference from example 3 is: graphene is not modified.
Example 6
The difference from example 3 is: the carbon nanotubes are not modified.
Example 7
The difference from example 3 is: the modification treatment of the graphene specifically comprises the following steps: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the graphene accounts for 15 parts by weight, the hydrogen peroxide accounts for 45 parts by weight, and the dilute hydrochloric acid accounts for 8000 parts by weight; heating the first modified solution at 93 ℃ for 2.5 hours to obtain a second modified solution; and filtering the second modification solution to obtain the modified graphene.
Example 8
The difference from example 3 is: heating the first modified solution at 100 ℃ for 1h to obtain a second modified solution; and filtering the second modification solution to obtain the modified graphene.
Example 9
The difference from example 3 is: the specific modification treatment of the carbon nano tube is as follows: putting the carbon nano tube into dilute nitric acid; and adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein the carbon nano tube accounts for 20 parts by weight, the potassium permanganate accounts for 8 parts by weight, and the dilute nitric acid accounts for 8000 parts by weight.
Example 10
The difference from example 3 is: heating the third modified solution at 100 ℃ for 2h to obtain a fourth modified solution; and filtering the fourth modification solution to obtain the modified carbon nano tube.
Example 11
The difference from example 3 is: in the first mixed solution, by weight, 120 parts of cobalt hydroxide powder, 120 parts of nickel hydroxide powder, 8 parts of modified graphene and 8 parts of modified carbon nanotubes are used.
Example 12
The difference from example 3 is: in the first mixed solution, by weight, 80 parts of cobalt hydroxide powder, 80 parts of nickel hydroxide powder, 15 parts of modified graphene, and 15 parts of modified carbon nanotubes are used.
Example 13
The difference from example 3 is: the first drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 100 ℃, and the drying time is 2 h.
Example 14
The difference from example 3 is: the first drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 85 ℃, and the drying time is 6 h.
Example 15
The difference from example 3 is: the second drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 140 ℃, and the drying time is 3 h.
Example 16
The difference from example 3 is: the second drying specific process comprises the following steps: the drying is carried out under vacuum condition, the drying temperature is 110 ℃, and the drying time is 6 h.
Example 17
The difference from example 3 is: the specific process of calcination is as follows: the calcination was carried out under vacuum conditions at a calcination temperature of 470 ℃ for 1.5 h.
Example 18
The difference from example 3 is: the specific process of calcination is as follows: the calcination is carried out under vacuum condition, the calcination temperature is 350 ℃, and the calcination time is 4 h.
Specific capacitance and conductivity were measured on the powders prepared in examples 1 to 18, and the method for measuring conductivity was according to the four-probe method, which is the prior art (for example, "preparation of CNTs/cobalt nickel oxide composite supercapacitor powder and related performance research", zhao qing qiang, academic thesis of Shandong university). The specific capacitance of the invention refers to the specific capacitance tested under the condition of current density of 4A/g. For ease of comparison, all test results were normalized based on example 1.
TABLE 1
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (4)
1. A preparation method of cobalt-nickel-based super capacitor powder is characterized by comprising the following steps: the preparation method comprises the following steps: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; calcining the second composite powder to obtain cobalt-nickel-based supercapacitor powder, wherein the step of modifying the graphene specifically comprises the following steps: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the first modified solution comprises 5 parts by weight of graphene, 40 parts by weight of hydrogen peroxide and 5000 parts by weight of dilute hydrochloric acid; heating the first modified solution at 90 ℃ for 3h to obtain a second modified solution; filtering the second modified solution to obtain modified graphene, wherein the modification treatment of the carbon nanotube specifically comprises: putting the carbon nano tube into dilute nitric acid; adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein 5 parts by weight of carbon nano tube, 10 parts by weight of potassium permanganate and 5000 parts by weight of dilute nitric acid are added; heating the third modified solution at 90 ℃ for 5h to obtain a fourth modified solution; filtering the fourth modified solution to obtain modified carbon nanotubes, wherein in the first mixed solution, by weight, 50 parts of cobalt hydroxide powder, 50 parts of nickel hydroxide powder, 10 parts of modified graphene and 10 parts of modified carbon nanotubes are added, and the first drying specific process comprises the following steps: the drying is carried out under the vacuum condition, the drying temperature is 90 ℃, the drying time is 5h, and the second drying specific process comprises the following steps: the drying is carried out under the vacuum condition, the drying temperature is 120 ℃, the drying time is 5h, and the specific calcining process comprises the following steps: the calcination is carried out under the vacuum condition, the calcination temperature is 400 ℃, and the calcination time is 3 h.
2. A preparation method of cobalt-nickel-based super capacitor powder is characterized by comprising the following steps: the preparation method comprises the following steps: providing graphene, and carrying out modification treatment on the graphene; providing carbon nanotubes and carrying out modification treatment on the carbon nanotubes; providing cobalt hydroxide powder and nickel hydroxide powder; putting cobalt hydroxide powder, nickel hydroxide powder, modified graphene and modified carbon nano tubes into deionized water to obtain a first mixed solution; putting the first mixed solution into a constant-temperature vacuum drying oven, and performing first drying on the first mixed solution to obtain a second mixed solution; filtering the second mixed solution to obtain first composite powder; carrying out second drying on the first composite powder to obtain second composite powder; calcining the second composite powder to obtain cobalt-nickel-based supercapacitor powder, wherein the step of modifying the graphene specifically comprises the following steps: putting graphene powder into dilute hydrochloric acid; adding hydrogen peroxide into a dilute hydrochloric acid solution to obtain a first modified solution, wherein the graphene accounts for 10 parts by weight, the hydrogen peroxide accounts for 50 parts by weight, and the dilute hydrochloric acid accounts for 10000 parts by weight; heating the first modified solution at 95 ℃ for 2h to obtain a second modified solution; filtering the second modified solution to obtain modified graphene, wherein the modification treatment of the carbon nanotube specifically comprises: putting the carbon nano tube into dilute nitric acid; adding potassium permanganate into the dilute nitric acid solution to obtain a third modified solution, wherein the carbon nano tube accounts for 10 parts by weight, the potassium permanganate accounts for 20 parts by weight, and the dilute nitric acid accounts for 10000 parts by weight; heating the third modified solution at 95 ℃ for 4h to obtain a fourth modified solution; filtering the fourth modified solution to obtain modified carbon nanotubes, wherein in the first mixed solution, by weight, 100 parts of cobalt hydroxide powder, 100 parts of nickel hydroxide powder, 5 parts of modified graphene and 5 parts of modified carbon nanotubes are added, and the first drying specific process comprises the following steps: the drying is carried out under the vacuum condition, the drying temperature is 95 ℃, the drying time is 4h, and the second drying specific process comprises the following steps: the drying is carried out under the vacuum condition, the drying temperature is 130 ℃, the drying time is 4h, and the specific process of calcining is as follows: the calcination is carried out under the vacuum condition, the calcination temperature is 450 ℃, and the calcination time is 2 h.
3. The utility model provides a cobalt nickel base ultracapacitor system powder which characterized in that: the cobalt-nickel-based supercapacitor powder is prepared by the preparation method according to any one of claims 1 to 2.
4. A cobalt-nickel-based super capacitor is characterized in that: the capacitor comprises the cobalt-nickel based supercapacitor powder of claim 3.
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