CN110957149A - Zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, preparation method thereof and capacitor - Google Patents
Zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, preparation method thereof and capacitor Download PDFInfo
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Abstract
The invention discloses a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, a preparation method thereof and a capacitor, wherein firstly, a graphene oxide dispersion solution is prepared; dissolving zinc salt, cobalt salt, CTAB and NH4F in water, and stirring to obtain a uniform mixed solution; mixing the graphene oxide dispersion liquid with the uniform mixed solution, stirring, and carrying out hydrothermal reaction to obtain a reaction product; performing extraction separation, washing and drying to obtain a zinc-cobalt-nickel oxide/rGO, and dissolving the zinc-cobalt-nickel oxide/rGO in DMSO to obtain a zinc-cobalt-nickel oxide/rGO solution; mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution, stirring, and performing vacuum filtration to perform layer-by-layer assembly to obtain the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode; the invention selects zinc-cobalt-nickel oxide as an energy storage material, rGO as a conductive material and a carrier, carbon black as a conductive agent to provide an electron transmission network structure, and ANF as an adhesive and a self-supporting three-dimensional framework network structure to prepare the self-supporting thin film electrode with high energy storage and high strength.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, a preparation method thereof and a capacitor.
Background
In recent years, with the gradual decrease of non-renewable energy sources such as petroleum and coal, people pay more attention to the development and utilization of green renewable energy sources, and the storage, transfer and release of the energy sources occupy an indispensable position; the super capacitor is used as a novel electrochemical energy storage device, has the characteristics of higher power density and longer cycle life than a lithium ion battery, and meanwhile, the energy density of the super capacitor is far higher than that of a common capacitor.
The performance of the super capacitor is mainly determined by electrode materials, and the super capacitor is distinguished according to the mechanism of electrode energy storage, and the types of the super capacitor can be divided into two types, namely a double-layer capacitor and a pseudo capacitor; the pseudo capacitor has more excellent electrochemical performance, and the composition material of the pseudo capacitor is mainly transition metal oxide; transition metal oxide, which is a semiconductor, has poor conductivity; carbon black is generally used as a conductive agent to provide a network structure for electron transport; vinylidene fluoride is used as a binder to bond active materials of the electrodes, but the formed electrode material has extremely poor mechanical properties, needs to be coated on a conductive current collector and cannot be directly used as an electrode of a pseudo capacitor, so that the application of the super capacitor in a flexible device is limited.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, a preparation method thereof and a capacitor, and aims to solve the technical problems that the electrode material in the prior art is poor in mechanical property and cannot be directly used as an electrode of a pseudo capacitor.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, which comprises the following steps:
step 1, preparing a graphene oxide dispersion liquid;
dissolving zinc salt, nickel salt, cobalt salt, CTAB and NH4F in water, and stirring to obtain a uniform mixed solution;
step 2, mixing the graphene oxide dispersion liquid with the uniform mixed solution, stirring to obtain a uniform mixed system I, and carrying out hydrothermal reaction to obtain a reaction product;
step 3, extracting, separating, washing and drying the reaction product to obtain a zinc-cobalt-nickel oxide/rGO;
step 4, dissolving zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist to obtain a zinc-cobalt-nickel oxide/rGO solution;
step 5, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution, and stirring to obtain a uniform mixed system II;
and 6, assembling the uniformly mixed system II layer by layer in a vacuum filtration mode to obtain the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Further, in step 1, when preparing the graphene oxide dispersion liquid, the method specifically comprises the following steps: adding graphene oxide into water, and performing ultrasonic dispersion until no solid particles exist and a uniform light black solution is obtained, wherein the uniform light black solution is the graphene oxide dispersion liquid; wherein the concentration of the graphene oxide dispersion liquid is 0.1-0.3 g/L.
Further, in step 1, zinc salt, nickel salt, cobalt salt, CTAB, NH4F and water according to the molar ratio of (0.2-0.8) to (2), (0.5-1) to (4-5): (50-60), wherein the sum of zinc salt and nickel salt is calculated according to molar ratio: cobalt salt 1: 2.
Further, in the step 2, the hydrothermal reaction is carried out for 1-12h at the temperature of 100-140 ℃.
Further, in the step 3, in the washing process, firstly, deionized water is adopted for washing for 2-4 times, and then, absolute ethyl alcohol is used for washing for 2-4 times;
the drying adopts freeze drying at 20-25 deg.C for 24-36 h.
Further, in the step 5, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution according to the mass ratio of (1-5) to 1; wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.1-0.3g/L, and the molar concentration of the ANF solution is 0.2-0.5 g/mol.
The invention also provides a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode prepared by the preparation method of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Furthermore, the first charge-discharge reversible capacity of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is 500-1000F/g, and the breaking strength is 10-50 MPa.
The invention also provides a capacitor, which is obtained by coating the solid electrolyte on the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Further, the capacitor is a flexible bendable or windable all-solid-state capacitor; the solid electrolyte comprises one or more of polyvinyl alcohol/sulfuric acid electrolyte, polyvinyl alcohol/potassium hydroxide electrolyte and polyvinyl alcohol/lithium chloride electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, wherein a zinc-cobalt-nickel oxide ternary transition metal material is selected as an energy storage material, graphene is used as a conductive material and a carrier, carbon black is used as a conductive agent of a super capacitor to provide an electron transmission network structure, and ANF is used as an adhesive and a self-supporting three-dimensional framework network structure; the ANF is used as a nano fibrous material, the amino group on the surface of the ANF enables the ANF to have certain adhesiveness, the ANF can have an adhesion effect on an electrode material, has a rigid macromolecular chain structure and excellent mechanical property, and also provides a support skeleton for the electrode material while being used as an adhesive, so that the self-supporting supercapacitor electrode material with high energy storage and high strength is prepared; the preparation method is simple, the prepared zinc-cobalt-nickel oxide/graphene/ANF composite film electrode has high mechanical property and energy storage property, the first charge-discharge reversible capacity is 500-1000F/g, the breaking strength is 10-50Mpa, and the electrode can be applied to the field of energy storage.
Drawings
Fig. 1 is an SEM image of a zinc cobalt nickel oxide/graphene/ANF composite thin film electrode prepared in example 1;
fig. 2 is an SEM image of the zinc cobalt nickel oxide/graphene described in example 1.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is exemplary in nature and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
The invention provides a preparation method of a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, which comprises the following steps:
step 1, preparing a graphene oxide dispersion liquid, which specifically comprises the following steps:
adding graphene oxide into water, and performing ultrasonic dispersion until no solid particles exist and a uniform light black solution is obtained, wherein the uniform light black solution is the graphene oxide dispersion liquid; wherein the concentration of the graphene oxide dispersion liquid is 0.1-0.3 g/L;
step 2, dissolving zinc salt, cobalt salt, CTAB and NH4F in water, and stirring to obtain a uniform mixed solution; zinc salt, nickel salt, cobalt salt, CTAB, NH4F and water according to the molar ratio of (0.2-0.8) to (2), (0.5-1) to (4-5): (50-60), wherein the nickel salt is one of nickel sulfate, nickel nitrate and nickel chloride; the cobalt salt is one of cobalt sulfate, cobalt nitrate and cobalt chloride;
step 3, mixing the graphene oxide dispersion liquid obtained in the step 1 with the uniformly mixed solution obtained in the step 2, and stirring until the solution is uniform and light black to obtain a uniformly mixed system I; carrying out hydrothermal reaction to obtain a reaction product; the hydrothermal reaction is carried out for 1-12h at the temperature of 100-140 ℃;
step 4, performing extraction separation, washing and freeze drying on the reaction product to obtain a zinc-cobalt-nickel oxide/rGO; washing for 2-4 times by using deionized water, and then washing for 2-4 times by using absolute ethyl alcohol; the freeze drying temperature is 20-25 deg.C, and the freeze drying time is 24-36 h.
Step 5, dissolving zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist and the solution is uniform black, so as to obtain a zinc-cobalt-nickel oxide/rGO solution;
step 6, mixing and stirring the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution to obtain a uniform mixed system II; mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution according to the mass ratio of (1-5) to 1; wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.1-0.3g/L, and the molar concentration of the ANF solution is 0.2-0.5 g/mol;
and 7, assembling the uniformly mixed system II layer by layer in a vacuum filtration mode to obtain the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
The invention also provides a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, which is prepared by the preparation method of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode; the first charge-discharge reversible capacity of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is 500-1000F/g, and the breaking strength is 10-50 Mpa.
The invention also provides a capacitor, which is obtained by coating the solid electrolyte on a composite film electrode, wherein the composite film electrode adopts the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode; the capacitor is a flexible bendable or windable all-solid-state capacitor; the solid electrolyte comprises one or more of polyvinyl alcohol/sulfuric acid electrolyte, polyvinyl alcohol/potassium hydroxide electrolyte and polyvinyl alcohol/lithium chloride electrolyte.
The invention provides a preparation method of a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, which comprises the steps of firstly, selecting a zinc-cobalt-nickel oxide ternary transition metal material as an energy storage material, taking rGO as a conductive material and a carrier, taking carbon black as a conductive agent of a super capacitor, providing an electronic transmission network structure, and taking ANF as an adhesive and a self-supporting three-dimensional framework network structure, thereby preparing a self-supporting super capacitor electrode material with high energy storage and high strength; the preparation method is simple, the prepared zinc-cobalt-nickel oxide/graphene/ANF composite film electrode has high mechanical property and energy storage property, the first charge-discharge reversible capacity is 500F/g, the breaking strength is 50Mpa, and the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode can be applied to the field of energy storage.
Example 1
Embodiment 1 provides a method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, including the following steps:
step 1, adding 0.05g of graphene oxide into 500mL of deionized water, and performing ultrasonic dispersion until no solid particles exist and the graphene oxide is uniform and light black, so as to obtain a graphene oxide dispersion liquid with the concentration of 0.1 g/L;
step 2, weighing 0.5mol of cobalt sulfate, 0.5mol of nickel sulfate, 2mol of cobalt sulfate, 0.5mol of CTAB and 4mol of NH respectively4F was dissolved in 900g of deionized waterStirring the mixture until the mixture is uniform and reddish to obtain a uniform mixed solution;
step 3, mixing 50ml of the graphene oxide dispersion liquid obtained in the step 1 with 50ml of the uniform mixed solution obtained in the step 2, and stirring until the solution is uniform and light black to obtain a uniform mixed system I; carrying out hydrothermal reaction at 140 ℃ for 1h to obtain a reaction product;
step 4, carrying out suction filtration separation on the reaction product, washing the separated substance for 2-4 times by using deionized water, then washing for 2-4 times by using absolute ethyl alcohol, and carrying out freeze drying for 24 hours at the temperature of 25 ℃ to obtain zinc-cobalt-nickel oxide/rGO;
step 5, dissolving the zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist and the solution is uniform and black, so as to obtain a zinc-cobalt-nickel oxide/rGO solution, wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.1 g/L;
step 6, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution according to the mass ratio of 1:1:1, stirring the mixture until the mixture is uniform and black to obtain a uniform mixed system II, wherein the molar content of ANF is 0.2 g/mol;
and 7, assembling the uniform mixing system II layer by layer in a vacuum filtration mode until the thickness of the film is 30 mu m, and obtaining the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Detecting the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode prepared in the example 1 by using a constant current charge-discharge mode of an electrochemical workstation, wherein the reversible charge-discharge capacity of the electrode for the first time is 500F/g; the fracture strength of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is 50 Mpa.
The zinc-cobalt-nickel oxide/rGO/ANF composite film electrode has high mechanical property and energy storage property, can be applied to the field of energy storage, and is a flexible bendable or windable all-solid-state capacitor obtained by coating a solid electrolyte on the composite film electrode; the solid electrolyte comprises one or more of polyvinyl alcohol/sulfuric acid electrolyte, polyvinyl alcohol/phosphoric acid electrolyte, polyvinyl alcohol/potassium hydroxide electrolyte and polyvinyl alcohol/lithium chloride electrolyte.
As shown in fig. 1, fig. 1 shows an SEM image of the zinc-cobalt-nickel oxide/graphene/ANF composite film prepared in example 1, and as can be seen from fig. 1, the zinc-cobalt-nickel oxide/graphene and ANF are uniformly layered in the film system, so that sufficient contact between the electrode active material and the electrolyte is ensured, the reaction area is increased, and the electron transmission path is reduced, thereby enhancing the energy storage performance of the electrode material.
As shown in fig. 2, fig. 2 shows an SEM image of the zinc-cobalt-nickel oxide/graphene prepared in example 1, and it can be seen from fig. 1 that the zinc-cobalt-nickel oxide is uniformly loaded on the surface of the graphene, and the graphene is used as a conductive framework to improve the conductivity of the electrode, reduce the internal resistance of the electrode, and improve the electrochemical energy storage performance of the material.
Example 2
Embodiment 2 provides a method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, including the following steps:
step 1, adding 0.1g of graphene oxide into 500mL of deionized water, and performing ultrasonic dispersion until no solid particles exist and the graphene oxide is uniform and light black, so as to obtain a graphene oxide dispersion liquid with the concentration of 0.2 g/L;
step 2, weighing 0.8mol of zinc nitrate, 0.2mol of nickel nitrate, 2mol of cobalt nitrate, 0.1mol of CTAB and 5mol of NH respectively4Dissolving F in 1080g of deionized water, and stirring until the mixture is uniform and reddish to obtain a uniform mixed solution;
step 3, mixing 50ml of the graphene oxide dispersion liquid obtained in the step 1 with 100ml of the uniform mixed solution obtained in the step 2, and stirring until the solution is uniform and is light black to obtain a uniform mixed system I; carrying out hydrothermal reaction at 140 ℃ for 1h to obtain a reaction product;
step 4, carrying out suction filtration separation on the reaction product, washing the separated substance for 2-4 times by using deionized water, then washing for 2-4 times by using absolute ethyl alcohol, and carrying out freeze drying for 36 hours at the temperature of 20 ℃ to obtain zinc-cobalt-nickel oxide/rGO;
step 5, dissolving the zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist and the solution is uniform and black, so as to obtain a zinc-cobalt-nickel oxide/rGO solution, wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.3 g/L;
step 6, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution according to the mass ratio of 5:5:1, stirring the mixture until the mixture is uniform and black to obtain a uniform mixed system II, wherein the molar content of ANF is 0.5 g/mol;
and 7, assembling the uniform mixing system II layer by layer in a vacuum filtration mode until the thickness of the film is 35 mu m, and obtaining the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Detecting the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode prepared in the example 2 by using a constant current charge-discharge mode of an electrochemical workstation, wherein the reversible charge-discharge capacity for the first time is 1000F/g; the breaking strength of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is 10 Mpa.
Example 3
Embodiment 3 provides a method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, including the following steps:
step 1, adding 0.15g of graphene oxide into 500mL of deionized water, and performing ultrasonic dispersion until no solid particles exist and the graphene oxide is uniform and light black, so as to obtain a graphene oxide dispersion liquid with the concentration of 0.3 g/L;
step 2, weighing 0.2mol of zinc chloride, 0.8mol of nickel chloride, 2mol of cobalt chloride, 0.75mol of CTAB and 4.5mol of NH respectively4Dissolving F in 990g of deionized water, and stirring until the mixture is uniform and reddish to obtain a uniform mixed solution;
step 3, mixing 50ml of the graphene oxide dispersion liquid obtained in the step 1 with 75ml of the uniformly mixed solution obtained in the step 2, and stirring until the solution is uniform and is light black to obtain a uniformly mixed system I; carrying out hydrothermal reaction at 120 ℃ for 6 hours to obtain a reaction product;
step 4, carrying out suction filtration separation on the reaction product, washing the separated substance for 2-4 times by using deionized water, then washing for 2-4 times by using absolute ethyl alcohol, and carrying out freeze drying for 30h at the temperature of 23 ℃ to obtain zinc-cobalt-nickel oxide/rGO;
step 5, dissolving the zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist and the solution is uniform and black, so as to obtain a zinc-cobalt-nickel oxide/rGO solution, wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.2 g/L;
step 6, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution according to the mass ratio of 3:3:1, stirring the mixture until the mixture is uniform and black to obtain a uniform mixed system II, wherein the molar content of ANF is 0.3 g/mol;
and 7, assembling the uniform mixing system II layer by layer in a vacuum filtration mode until the thickness of the film is 32 mu m, and obtaining the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Detecting the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode prepared in the example 3 by using a constant current charge-discharge mode of an electrochemical workstation, wherein the reversible charge-discharge capacity of the electrode for the first time is 700F/g; the breaking strength of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is 30 Mpa.
Example 4
Embodiment 4 provides a method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode, including the following steps:
step 1, adding 0.1g of graphene oxide into 500mL of deionized water, and performing ultrasonic dispersion until no solid particles exist and the graphene oxide is uniform and light black, so as to obtain a graphene oxide dispersion liquid with the concentration of 0.2 g/L;
step 2, weighing 0.6mol of zinc chloride, 0.4mol of nickel nitrate, 2mol of cobalt sulfate, 0.7mol of CTAB and 4mol of NH respectively4Dissolving F in 1000g of deionized water, stirring until the solution is uniform and reddish to obtain a uniform mixed solution;
step 3, mixing 50ml of the graphene oxide dispersion liquid obtained in the step 1 with 70ml of the uniformly mixed solution obtained in the step 2, and stirring until the solution is uniform and is light black to obtain a uniformly mixed system I; carrying out hydrothermal reaction at 110 ℃ for 3h to obtain a reaction product;
step 4, carrying out suction filtration separation on the reaction product, washing the separated substance for 2-4 times by using deionized water, then washing for 2-4 times by using absolute ethyl alcohol, and carrying out freeze drying for 26 hours at the temperature of 21 ℃ to obtain zinc-cobalt-nickel oxide/rGO;
step 5, dissolving the zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist and the solution is uniform and black, so as to obtain a zinc-cobalt-nickel oxide/rGO solution, wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.2 g/L;
step 6, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution according to the mass ratio of 5:5:1, stirring the mixture until the mixture is uniform and black to obtain a uniform mixed system II, wherein the molar content of ANF is 0.3 g/mol;
and 7, assembling the uniform mixing system II layer by layer in a vacuum filtration mode until the thickness of the film is 34 mu m, and obtaining the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
Detecting the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode prepared in the embodiment 4 by using a constant current charge-discharge mode of an electrochemical workstation, wherein the reversible charge-discharge capacity of the electrode for the first time is 600F/g; the rupture strength of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is 40 Mpa.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (10)
1. A preparation method of a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is characterized by comprising the following steps:
step 1, preparing a graphene oxide dispersion liquid;
dissolving zinc salt, nickel salt, cobalt salt, CTAB and NH4F in water, and stirring to obtain a uniform mixed solution;
step 2, mixing the graphene oxide dispersion liquid with the uniform mixed solution, stirring to obtain a uniform mixed system I, and carrying out hydrothermal reaction to obtain a reaction product;
step 3, extracting, separating, washing and drying the reaction product to obtain a zinc-cobalt-nickel oxide/rGO;
step 4, dissolving zinc-cobalt-nickel oxide/rGO in DMSO, and performing ultrasonic dispersion until no solid particles exist to obtain a zinc-cobalt-nickel oxide/rGO solution;
step 5, mixing the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution, and stirring to obtain a uniform mixed system II;
and 6, assembling the uniformly mixed system II layer by layer in a vacuum filtration mode to obtain the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode.
2. The method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode according to claim 1, wherein in the step 1, the step of preparing the graphene oxide dispersion liquid specifically comprises the following steps: adding graphene oxide into water, and performing ultrasonic dispersion until no solid particles exist and a uniform light black solution is obtained, wherein the uniform light black solution is the graphene oxide dispersion liquid; wherein the concentration of the graphene oxide dispersion liquid is 0.1-0.3 g/L.
3. The method for preparing the Zn-Co-Ni oxide/graphene/ANF composite film electrode as claimed in claim 1, wherein in step 1, Zn salt, Ni salt, Co salt, CTAB, NH4F and water according to the molar ratio of (0.2-0.8) to (2), (0.5-1) to (4-5): (50-60), wherein the sum of zinc salt and nickel salt is calculated according to molar ratio: cobalt salt 1: 2.
4. The method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode as claimed in claim 1, wherein in the step 2, the hydrothermal reaction is performed for 1-12h at a temperature of 100 ℃ and 140 ℃.
5. The method for preparing the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode according to claim 1, wherein in the step 3, the washing process comprises washing with deionized water for 2-4 times, and then washing with absolute ethyl alcohol for 2-4 times;
the drying adopts freeze drying at 20-25 deg.C for 24-36 h.
6. The method for preparing a zinc-cobalt-nickel oxide/graphene/ANF composite film electrode as claimed in claim 1, wherein in the step 5, the zinc-cobalt-nickel oxide/rGO solution, the carbon black and the ANF solution are mixed according to the mass ratio of (1-5): 1; wherein the concentration of the zinc-cobalt-nickel oxide/rGO solution is 0.1-0.3g/L, and the molar concentration of the ANF solution is 0.2-0.5 g/mol.
7. A zinc-cobalt-nickel oxide/graphene/ANF composite film electrode is characterized by being prepared by the preparation method of the zinc-cobalt-nickel oxide/graphene/ANF composite film electrode as claimed in any one of claims 1 to 6.
8. The Zn-Co-Ni oxide/graphene/ANF composite film electrode as claimed in claim 7, wherein the Zn-Co-Ni oxide/graphene/ANF composite film electrode has a first charge-discharge reversible capacity of 500-1000F/g and a breaking strength of 10-50 MPa.
9. A capacitor obtained by coating a solid electrolyte on a composite thin film electrode, wherein the composite thin film electrode is the zinc-cobalt-nickel oxide/graphene/ANF composite thin film electrode according to any one of claims 7 or 8.
10. A capacitor according to claim 9, wherein the capacitor is a flexible bendable or rollable all-solid-state capacitor; the solid electrolyte comprises one or more of polyvinyl alcohol/sulfuric acid electrolyte, polyvinyl alcohol/potassium hydroxide electrolyte and polyvinyl alcohol/lithium chloride electrolyte.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115083789A (en) * | 2022-06-23 | 2022-09-20 | 横店集团东磁股份有限公司 | CNF/zinc-cobalt-nickel oxide/graphene aerogel electrode and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950992A (en) * | 2014-04-21 | 2014-07-30 | 西安交通大学 | Method for growing vertical transition metal oxide nanosheets on surface of graphene |
| CN104952636A (en) * | 2015-05-14 | 2015-09-30 | 北京化工大学 | Preparation method of nanocarbon/hydrotalcite array composite |
| US20170054137A1 (en) * | 2012-12-21 | 2017-02-23 | Lawrence Livermore National Security, Llc | Methods for making graphene-supported metal oxide monolith |
| CN107359054A (en) * | 2016-05-09 | 2017-11-17 | 国家纳米科学中心 | Composite electrode material, preparation method and application thereof |
| CN109524243A (en) * | 2018-12-07 | 2019-03-26 | 江西克莱威纳米碳材料有限公司 | A kind of Whole fiber type lithium-ion capacitor and preparation method thereof |
-
2019
- 2019-12-24 CN CN201911348812.4A patent/CN110957149B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170054137A1 (en) * | 2012-12-21 | 2017-02-23 | Lawrence Livermore National Security, Llc | Methods for making graphene-supported metal oxide monolith |
| CN103950992A (en) * | 2014-04-21 | 2014-07-30 | 西安交通大学 | Method for growing vertical transition metal oxide nanosheets on surface of graphene |
| CN104952636A (en) * | 2015-05-14 | 2015-09-30 | 北京化工大学 | Preparation method of nanocarbon/hydrotalcite array composite |
| CN107359054A (en) * | 2016-05-09 | 2017-11-17 | 国家纳米科学中心 | Composite electrode material, preparation method and application thereof |
| CN109524243A (en) * | 2018-12-07 | 2019-03-26 | 江西克莱威纳米碳材料有限公司 | A kind of Whole fiber type lithium-ion capacitor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| KWON,S.R.A, ET AL.: "Mechanically Strong Graphene/Aramid Nanofiber Composite Electrodes for Structural Energy and Power", 《ACS NANO》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115083789A (en) * | 2022-06-23 | 2022-09-20 | 横店集团东磁股份有限公司 | CNF/zinc-cobalt-nickel oxide/graphene aerogel electrode and preparation method and application thereof |
| CN115083789B (en) * | 2022-06-23 | 2023-12-19 | 横店集团东磁股份有限公司 | CNF/zinc cobalt nickel oxide/graphene aerogel electrode and preparation method and application thereof |
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