CN108597903B - Novel preparation method for compounding magnetic oxide and vertical graphene array and application of novel preparation method in supercapacitor - Google Patents
Novel preparation method for compounding magnetic oxide and vertical graphene array and application of novel preparation method in supercapacitor Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 75
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 title claims abstract description 25
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- 239000002131 composite material Substances 0.000 claims abstract description 23
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
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- 229910000473 manganese(VI) oxide Inorganic materials 0.000 abstract description 4
- 239000002356 single layer Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- 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
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
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- 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
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Abstract
The invention provides a novel preparation method for compounding a magnetic oxide and a vertical graphene array. The preparation method of the nano material is characterized in that graphene and perovskite type magnetic oxide (such as ferromagnetic La) are firstly used0.67Sr0.33MnO3Nano-powder and the like), using graphene as a framework, uniformly dispersing the nano-powder on the surface of single-layer graphite, then, acting an external magnetic field on the graphene/magnetic oxide composite material, and directionally arranging the magnetic oxide and the graphene under the action of the magnetic field force to form an array of the vertical graphene/magnetic oxide composite material on the surface of a conductive substrate. The electrode of the super capacitor prepared by the method can simultaneously realize the preparation of the vertical graphite array and the highly uniformly dispersed perovskite type oxide electrode material, and the composite super capacitor with the double electric layer capacitance and the pseudo capacitance is manufactured, so that the energy density of the super capacitor is improved.
Description
The technical field is as follows:
the invention relates to a novel preparation method for compounding a magnetic oxide and a vertical graphene array and application of the magnetic oxide and the vertical graphene array in a super capacitor, and belongs to the field of super capacitors.
Background art:
a supercapacitor is a new type of power supply device, also called an electrochemical capacitor, which is a capacitor that stores energy through an electrochemical process at an electrode/solution interface, and can be considered as a new type of power supply device between a physical capacitor and a secondary battery. Compared with the traditional energy storage device, the super capacitor has the advantages of high charging and discharging speed, long service life, high energy conversion efficiency, cyclic utilization, safety, environmental protection and the like. Particularly, the super capacitor has great advantages in the application fields of electric automobiles, aerospace and the like due to the high specific power density. However, compared with conventional energy storage devices such as secondary batteries, the energy density of the super capacitor is relatively low, the improvement of the energy density of the super capacitor requires that an electrode material has a large specific capacity, and how to improve the specific capacity of the electrode is one of the main problems in large-scale industrial application of the super capacitor.
Generally, electrode materials of the super capacitor are divided into two types, one type is that an electric double layer is formed at a solid/liquid interface through electrostatic action to store charges, the materials are mainly carbon materials, and the manufactured super capacitor is called as an electric double layer capacitor; another class of materials, based on transition metal oxides, such as: in MnO2NiO and the like are used as electrode materials.
Graphene is an important electrode material of a double-battery super capacitor, the theoretical specific capacitance of the graphene-based capacitor can reach 550F/g, but the maximum specific capacitance which can be reached by current research reports is only about 200F/g, mainly because the surface of the graphene cannot be in full contact with electrolyte and cannot be completely and effectively utilized due to the irregular arrangement of the graphene in an electrode, the specific capacitance of the capacitor is reduced. According to the manufacturing requirements of the graphene-based supercapacitor with high specific capacitance, the electrode material with graphene regularly arranged along the vertical direction is prepared.
On the other hand, the perovskite type oxide has good conductivity and very stable chemical property as a novel electrode material of the super capacitor, pseudo-capacitance storage charges can be generated through oxygen-inserted reversible redox reaction in an ionic solution, and theoretically, the perovskite type oxide is adopted as the electrode material of the super capacitor, and the specific capacitance of the electrode can be up to thousands of farads per gram. However, studies have reported that the maximum specific capacitance achievable with perovskite-type oxide electrode materials is often only a few hundred faradays per gram, as: perovskite type LaMnO doped with Sr3-δThe specific capacitance of the electrode of the super capacitor made of the nano powder is only 230F/g (X.W.Wang et al. journal of Alloys and Compounds2016,675, 195-200). The reason is mainly because the nano powder particles are agglomerated, the specific surface area of the material is small, andthe perovskite material actually plays an energy storage role in the electrochemical process is only a few.
Therefore, in order to further improve the specific capacity of the electrode material of the supercapacitor, it is necessary to prepare an electrode material of a vertical graphene array and a perovskite-type oxide electrode material in which nano-powder is highly uniformly dispersed.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and provides a novel preparation method for compounding a perovskite type magnetic oxide and a vertical graphene array and application of the perovskite type magnetic oxide and the vertical graphene array in a super capacitor.
The technical scheme of the invention is as follows: graphene and perovskite-type magnetic oxides (e.g., ferromagnetic La)0.67Sr0.33MnO3-δNano powder) compounding comprises the following steps:
(1) firstly, taking graphene oxide with the sheet diameter within the range of 200-2000nm as a raw material, weighing the graphene oxide, adding deionized water to prepare a solution with the graphene concentration of 1-2mg/l, carrying out ultrasonic dispersion for 2-20h, wherein the ultrasonic power is more than 300W, and stirring the solution while carrying out ultrasonic treatment;
(2) diluting the prepared supernatant of the graphene oxide solution into 0.5mg/L solution, adding magnetic perovskite type oxide nano powder into the solution, ultrasonically dispersing for 1-2h, and then stirring for 3 days to obtain uniform dispersed solution, wherein the mass ratio of graphene oxide to nano powder in the solution is 0.1-1;
(3) then, transferring the solution to a round-bottom flask, adding hydrazine hydrate for reduction, wherein the mass ratio of the hydrazine hydrate to the graphene oxide is 0.7-1, and then refluxing the solution in an oil bath at the temperature of 90-95 ℃ for 1-8 h. Then filtering, cleaning and vacuum drying at 70 ℃ for 24 hours to obtain the graphene and perovskite type magnetic oxidized composite nano material;
(4) the composite nano material of graphene and perovskite type magnetic oxidation, the conductive carbon black and the adhesive are respectively as follows according to the mass percentage: 10-55%, 70-80% and 10-15% of the total weight of the electrode slice are dispersed in absolute ethyl alcohol, a uniform dispersion system is formed after ultrasonic treatment is carried out for 0.5-2h, the mixture is placed in a 0.02-2T magnetic field for 0.5-2h, the mixture is coated on a conductive substrate, the conductive substrate is dried at the temperature of 60-100 ℃ under the action of a 0.02-2T external magnetic field, and the electrode slice is pressed into an electrode slice, and the electrode slice is assembled into a super capacitor.
The mechanism of the invention is as follows: it is proposed to use graphene and perovskite-type magnetic oxides (e.g., ferromagnetic La)0.67Sr0.33MnO3Nano powder) is compounded, graphene is used as a framework, the nano powder is uniformly dispersed on the surface of single-layer graphite, then an external magnetic field acts on graphene/magnetic oxide, the magnetic oxide and the graphene are directionally and uniformly arranged under the action of the magnetic field force, and a magnetic oxide composite vertical graphene array is formed on the surface of a conductive substrate.
Has the advantages that: the electrode of the super capacitor prepared by the method can simultaneously realize the preparation of the vertical graphite array and the highly uniformly dispersed perovskite type oxide electrode material, greatly improve the specific capacitance of the electrode material and prepare the composite super capacitor simultaneously having double electric layer capacitance and pseudo capacitance.
Description of the drawings:
fig. 1 is a schematic diagram of preparation of a graphene and perovskite type magnetic oxide composite electrode material.
Fig. 2 is a schematic diagram of a single-layer graphene and perovskite-type magnetic oxide composite material.
The specific implementation mode is as follows:
in FIG. 1, the network structure represents graphene, and the small spheres dispersed on the surface of the network structure represent perovskite type oxide nanoparticles
Firstly, graphene oxide with the sheet diameter within the range of 200-2000nm is taken as a raw material, the graphene oxide is weighed and added into deionized water to prepare a solution with the graphene concentration of 1-2mg/l, the solution is ultrasonically dispersed for 2-20h, the ultrasonic power is greater than 300W, and the solution is ultrasonically stirred. Diluting the supernatant of the prepared graphene oxide solution to 0.5mg/L, and adding magnetic perovskite oxide (such as ferromagnetic La) into the solution0.67Sr0.33MnO3-δNano powder) nano powder, the grain diameter of the powder is controlled to be 3-50 nanometers, ultrasonic dispersion is carried out for 1-2 hours, then stirring is carried out for 3 days, uniform dispersion solution is obtained, and the mass ratio of graphene oxide to nano powder in the solution is0.1-1. Then, transferring the solution to a round-bottom flask, adding hydrazine hydrate to reduce graphene oxide, wherein the mass ratio of hydrazine hydrate to graphene oxide is 0.7-1, and refluxing in an oil bath at the temperature of 90-95 ℃ for 1-8 h. And then filtering, cleaning and drying in vacuum at 70 ℃ for 24 hours to obtain the graphene and perovskite type magnetic oxidation composite nano material.
The preparation method of the magnetic oxide composite vertical graphene array under the action of the external magnetic field comprises the following steps: the preparation method comprises the steps of dispersing graphene, perovskite type magnetic oxidized composite nano material, conductive carbon black and adhesive (such as polyvinylidene fluoride (PVDF)) in a proper amount of absolute ethyl alcohol according to a certain proportion (such as 1.5:7:1.5), performing ultrasonic treatment for 0.5-2h to form a uniform dispersion system, putting the uniform dispersion system into a 0.02-2T magnetic field for 0.5-2h, coating the uniform dispersion system on a conductive substrate (such as foamed nickel or carbon paper) and drying the conductive substrate at 60-100 ℃ under the action of an external magnetic field to prepare a magnetic oxide composite vertical graphene array, and applying the magnetic oxide composite vertical graphene array to a super capacitor after pressing into an electrode plate.
Example 1 (manganese-based oxide having ferromagnetism is La)0.67Sr0.33MnO3)
Firstly, graphene oxide with the sheet diameter within the range of 200-2000nm is taken as a raw material, the graphene oxide is weighed and added into deionized water to prepare a solution with the graphene concentration of 1mg/l, ultrasonic dispersion is carried out for 2-20h, the ultrasonic power is 500W, and the solution is stirred while ultrasonic treatment is carried out. Taking the supernatant of the prepared graphene oxide solution, diluting the supernatant into 0.5mg/L solution, and adding ferromagnetic La into the solution0.67Sr0.33MnO3And (3) carrying out ultrasonic dispersion on the nano powder for 2 hours, and then stirring for 3 days to obtain a uniform dispersion solution, wherein the mass ratio of the graphene oxide to the nano powder in the solution is within 0.2. Then, the solution was transferred to a round bottom flask, to which hydrazine hydrate was added in a mass ratio of 0.7 to 1, followed by oil bath refluxing at a temperature of 95 ℃ for 8 hours. And then filtering, cleaning and drying in vacuum at 70 ℃ for 24 hours to obtain the graphene and perovskite type magnetic oxidation composite nano material.
Weighing graphene and perovskite type magnetic oxidized composite nano material, conductive carbon black and adhesive (such as polyvinylidene fluoride)PVDF) is dispersed in a proper amount of absolute ethyl alcohol according to the proportion of 1.5:7:1.5, ultrasonic treatment is carried out for 0.5h to form a uniform dispersion system, the uniform dispersion system is placed in a 1T magnetic field for 1h, the coating is applied to a foamed nickel conductive substrate, drying is carried out at 70 ℃, and then pressing is carried out to form a layer of 1cm2The electrode sheet of (2) is used for a super capacitor.
Example 2 (iron-based oxide with magnetic properties is La)0.67Sr0.33FeO3):
Firstly, graphene oxide with the sheet diameter within the range of 200-2000nm is taken as a raw material, the graphene oxide is weighed and added into deionized water to prepare a solution with the graphene concentration of 1mg/l, ultrasonic dispersion is carried out for 2-20h, the ultrasonic power is 500W, and the solution is stirred while ultrasonic treatment is carried out. Taking the supernatant of the prepared graphene oxide solution, diluting the supernatant into 0.5mg/L solution, and adding ferromagnetic La into the solution0.67Sr0.33FeO3And (3) ultrasonically dispersing the nano powder for 0.5h, and then stirring for 3 days to obtain a uniform dispersion solution, wherein the mass ratio of the graphene oxide to the nano powder in the solution is within 0.2. Then, the solution was transferred to a round bottom flask, to which hydrazine hydrate was added in a mass ratio of 0.7 to 1, followed by oil bath refluxing at a temperature of 95 ℃ for 8 hours. And then filtering, cleaning and drying in vacuum at 70 ℃ for 24 hours to obtain the graphene and perovskite type magnetic oxidation composite nano material. Weighing graphene, perovskite type magnetic oxidized composite nano material, conductive carbon black and adhesive (such as polyvinylidene fluoride PVDF) according to the proportion of 1:8:1, dispersing in a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 2h to form a uniform dispersion system, putting the uniform dispersion system into a 2T magnetic field for 0.5h, coating the uniform dispersion system on a foamed nickel conductive substrate, drying at 100 ℃, and pressing into a 1 cm-thick film2The electrode sheet of (2) is used for a super capacitor.
Claims (4)
1. A preparation method for compounding a magnetic oxide and a vertical graphene array is characterized in that the compounding of graphene and perovskite type magnetic oxide comprises the following steps:
(1) firstly, taking graphene oxide with the sheet diameter within the range of 200-2000nm as a raw material, weighing the graphene oxide, adding deionized water to prepare a solution with the graphene concentration of 1-2mg/l, carrying out ultrasonic dispersion for 2-20h, wherein the ultrasonic power is more than 300W, and stirring the solution while carrying out ultrasonic treatment;
(2) diluting the prepared supernatant of the graphene oxide solution into 0.5mg/L solution, adding magnetic perovskite type oxide nano powder into the solution, ultrasonically dispersing for 1-2h, and then stirring for 3 days to obtain uniform dispersed solution, wherein the mass ratio of graphene oxide to nano powder in the solution is 0.1-1;
(3) then, transferring the solution to a round-bottom flask, adding hydrazine hydrate for reduction, wherein the mass ratio of the hydrazine hydrate to the graphene oxide is 0.7-1, and then performing reduction at 90-95oRefluxing in oil bath at C for 1-8 hr, filtering, washing, and heating to 70 deg.CoC, vacuum drying for 24 hours to obtain a composite nano material of graphene and perovskite type magnetic oxide;
(4) the composite nano material of graphene and perovskite type magnetic oxide, the conductive carbon black and the adhesive are respectively 1-1.5: 7-8: dispersing the mixture in absolute ethyl alcohol according to the proportion of 1-1.5, performing ultrasonic treatment for 0.5-2h to form a uniform dispersion system, putting the uniform dispersion system into a 0.02-2T magnetic field for 0.5-2h, coating the uniform dispersion system on a conductive substrate, drying the conductive substrate at 60-100 ℃ under the action of a 0.02-2T external magnetic field, pressing the conductive substrate into an electrode plate, and assembling the electrode plate into a super capacitor.
2. The method for preparing an oxide and vertical graphene array composite according to claim 1, wherein the perovskite type magnetic oxide is a manganese-based oxide or iron-based oxide nanopowder having ferromagnetism.
3. The method for preparing the composite of the oxide and the vertical graphene array according to claim 2, wherein the perovskite manganese-based oxide is La1-xSrxMnO3-δThe perovskite type iron-based oxide is La1-xSrxFeO3-δ。
4. The application of the composite nano material of graphene and perovskite type magnetic oxide prepared by the preparation method of claim 1 as an electrode material in a super capacitor.
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