CN113937268A - Fibrous flexible water-based zinc ion battery with ultra-long cycle life and preparation method thereof - Google Patents

Fibrous flexible water-based zinc ion battery with ultra-long cycle life and preparation method thereof Download PDF

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CN113937268A
CN113937268A CN202111181242.1A CN202111181242A CN113937268A CN 113937268 A CN113937268 A CN 113937268A CN 202111181242 A CN202111181242 A CN 202111181242A CN 113937268 A CN113937268 A CN 113937268A
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ion battery
zinc
composite fiber
solution
carbon nanotube
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CN113937268B (en
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赵阳
朱纪欣
卢宇飞
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Northwestern Polytechnical University
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • 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
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    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a fibrous flexible water-based zinc ion battery with an ultra-long cycle life and a preparation method thereof. The anode composite fiber is prepared by a solution method and an annealing process, and the cathode composite fiber is prepared by an electrodeposition method. According to the invention, the obtained fibrous water-based zinc ion battery has excellent long-acting cycle performance and ultra-long cycle life. After the bending is continuously performed for 2000 times at the bending angle of 120 degrees, the specific discharge capacity can still be kept at 90.72% before bending, and the flexibility is excellent. The obtained fibrous water-based zinc ion battery has high safety and reliability, can be woven into energy storage fabric to supply energy to wearable equipment, and has good application prospect in the field of wearable electronic devices.

Description

Fibrous flexible water-based zinc ion battery with ultra-long cycle life and preparation method thereof
Technical Field
The invention belongs to the technical field of zinc ion batteries and flexibility, and relates to a fibrous flexible water system zinc ion battery with an ultra-long cycle life and a preparation method thereof.
Background
Portable, wearable electron device all show good application prospect in a plurality of fields such as electron skin, health monitoring, in order to satisfy its power supply demand, need to develop the novel flexible battery that has high specific capacity, long cycle life, high security urgently. Among them, the flexible aqueous zinc ion battery attracts extensive research attention because the metallic zinc negative electrode has sufficient reserve, low oxidation-reduction potential, high theoretical specific capacity and high safety. However, limited by the flexible electrode materials, existing flexible water-based zinc-ion batteries generally have poor cycle life and low flexibility, which severely limits their development and their practical application in the field of flexible wearable electronics.
The positive electrode material of the flexible water-based zinc-ion battery can be generally classified into three types, i.e., inorganic materials, organic materials, and hybrid materials. Inorganic materials such as vanadium-, manganese-and cobalt-based materials typically have high specific capacities and operating voltage plateaus, among which, tricobalt tetraoxide (Co)3O4) Has high theoretical specific capacity and theoretical energy density in alkaline electrolyte. However, the cobaltosic oxide positive electrode generally has poor cycle performance in alkaline electrolytes due to the generation of irreversible discharge byproducts; more importantly, the use of toxic and corrosive alkaline electrolytes greatly increases their potential safety risks when applied in the field of wearable devices. Therefore, there is a need to develop an aqueous zinc ion battery having excellent cycle performance, high safety, high specific capacity, and excellent flexibility.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a fibrous flexible water-based zinc ion battery with an ultra-long cycle life and a preparation method thereof, and solves the problem that the conventional water-based zinc ion battery is difficult to realize high specific capacity, long cycle performance and excellent flexibility at the same time, so that the development requirement of flexible wearable equipment is better met.
Technical scheme
A fibrous flexible aqueous zinc ion battery with ultra-long cycle life comprises a battery anode, a battery cathode and electrolyte; the method is characterized in that the positive electrode of the battery is oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber; the negative electrode of the battery is oriented carbon nanotube/metal zinc nanosheet composite fiber; the electrolyte is a mixed aqueous solution of zinc sulfate and cobalt sulfate.
The electrolyte is a mixed aqueous solution of zinc sulfate and cobalt sulfate, the concentration range of the zinc sulfate is 0.5-3.0mol/L, and the concentration range of the cobalt sulfate is 0.0001-0.001 mol/L.
And the positive and negative composite fiber electrodes respectively penetrate into the heat-shrinkable tube, the positive and negative electrodes are separated by adopting a diaphragm, and the electrolyte is injected into the middle of the positive and negative composite fiber electrodes for packaging to obtain the fibrous water-based zinc ion battery.
The oriented carbon nanotube is prepared by a floating chemical vapor deposition method, and the diameter of the oriented carbon nanotube is 20-200 mu m.
A method for preparing the fibrous flexible aqueous zinc ion battery with ultra-long cycle life, which is characterized in that: the positive composite fiber is prepared by a solution method and an annealing process, the negative composite fiber is prepared by an electrodeposition method, and the method comprises the following specific steps:
step 1: preparing the oriented carbon nanotube fiber by a floating chemical vapor deposition method;
step 2, preparing the positive composite fiber: dissolving cobalt nitrate in deionized water to obtain a cobalt nitrate solution with the concentration of 0.01-0.1 mol/L; dissolving 2-methylimidazole in deionized water to obtain a 2-methylimidazole solution with the concentration of 0.1-1.0 mol/L;
respectively taking cobalt nitrate and 2-methylimidazole solutions with equal volumes, putting the oriented carbon nanotube fiber into the 2-methylimidazole solution, adding the cobalt nitrate into the 2-methylimidazole solution to obtain a purple solution, and stirring at room temperature for 2-8 hours;
then taking out the fiber, washing with ultrapure water, and drying in vacuum for 8-24 hours at 40-100 ℃;
annealing the dried fiber in air at the temperature of 300-500 ℃ for 1-5 hours to obtain an oriented carbon nanotube/cobaltosic oxide nanosheet composite fiber anode;
step 3, preparing the negative composite fiber: preparing 0.5-2.0mol/L zinc sulfate solution as electroplating solution, using the oriented carbon nanotube fiber as a working electrode, using the polished metal zinc sheet as a counter electrode, immersing the working electrode and the counter electrode into the electroplating solution, and performing electrodeposition at a potential of-0.6V to-1.0V to obtain an oriented carbon nanotube/metal zinc nanosheet composite fiber cathode;
and 4, step 4: penetrating the positive and negative composite fiber electrodes into a heat shrink tube, separating the positive and negative electrodes by using a diaphragm, injecting electrolyte, and then packaging to obtain a fibrous water-based zinc ion battery; the electrolyte is a mixed aqueous solution of zinc sulfate and cobalt sulfate.
Advantageous effects
The invention provides a fibrous flexible water-based zinc ion battery with an ultra-long cycle life and a preparation method thereof. The anode composite fiber is prepared by a solution method and an annealing process, and the cathode composite fiber is prepared by an electrodeposition method.
According to the invention, the obtained fibrous water system zinc ion battery has excellent long-acting cycle performance, the specific capacity is kept at 97.27% of the first circle after the fibrous water system zinc ion battery is circularly charged and discharged for 10000 times under the current density of 5A/g, and the fibrous water system zinc ion battery has an ultra-long cycle life.
According to the invention, after the obtained fibrous water-based zinc ion battery is continuously bent for 2000 times at a bending angle of 120 degrees, the specific discharge capacity of the fibrous water-based zinc ion battery can still be kept at 90.72% before bending, and the fibrous water-based zinc ion battery has excellent flexibility.
According to the invention, the obtained fibrous water-based zinc ion battery has high safety and reliability, is easy to weave and integrate, can be woven into an energy storage fabric to supply energy to wearable equipment, and has a good application prospect in the field of wearable electronic devices.
Compared with the prior art:
the cycle life of the existing flexible water-based zinc ion battery is generally less than 5000 times due to poor stability of the electrode material. Through the design of a new electrode material and a new device, cobaltosic oxide nanosheets are obtained by in-situ compounding on the oriented carbon nanotube fibers, and a novel composite fiber electrode material with high stability is obtained; the invention further designs zinc sulfate and cobalt sulfate mixed aqueous electrolyte, and greatly improves the circulation stability of the fibrous aqueous zinc ion battery through the unique design and interaction of electrode materials and the electrolyte; the fibrous water system zinc ion battery obtained by the invention has the specific capacity kept at 97.27% of the first circle after being circularly charged and discharged for 10000 times under the current density of 5A/g, and has an ultra-long cycle life.
The bending times of the existing flexible water system zinc-ion battery are generally less than 1000 times due to poor flexibility and stability of electrode materials and devices. Based on oriented carbon nanotube fibers with excellent flexibility and conductivity, a positive electrode composite fiber electrode material and a negative electrode composite fiber electrode material with high flexibility and stability are designed and prepared by compounding nano sheet electrode materials on the fibers in situ through a solution method, an in situ electrodeposition method and the like, so that the flexibility of the obtained fibrous battery is greatly improved; after the fibrous water-based zinc ion battery obtained in the invention is continuously bent for 2000 times at a bending angle of 120 degrees, the specific discharge capacity of the fibrous water-based zinc ion battery can still be kept at 90.72% before bending, and the fibrous water-based zinc ion battery has excellent flexibility.
At present, most of water-based zinc ion batteries adopting cobaltosic oxide as a positive electrode material adopt alkaline electrolyte, however, the use of toxic and corrosive alkaline electrolyte greatly increases the potential safety risk of the batteries, especially when the batteries are applied to the field of wearable devices. The neutral aqueous solution of the fibrous water-based zinc ion battery is used as the electrolyte, so that the safety and the reliability of the fibrous water-based zinc ion battery are greatly improved, and the fibrous water-based zinc ion battery has better development and application prospects in the field of wearable electronic devices.
Drawings
Fig. 1 is a schematic structural diagram of a fibrous flexible aqueous zinc ion battery, and the structure and composition of the fibrous battery can be seen from the diagram.
Fig. 2 is a structural representation of the positive and negative composite fiber electrodes. Wherein, a-b are respectively the low-power and high-power scanning electron microscope photos of the oriented carbon nanotube/cobaltosic oxide nanosheet composite fiber positive electrode. c-d are respectively low-power and high-power scanning electron microscope photos of the oriented carbon nanotube/metal zinc nanosheet composite fiber negative electrode. From the figure, it can be seen that cobaltosic oxide and metallic zinc both have a nanosheet structure.
FIG. 3 is a long-term cycle performance curve (current density: 5A/g) of the fibrous aqueous zinc-ion battery. It can be seen from the figure that the specific capacity of the fibrous water system zinc ion battery is still maintained at 97.27% of the first circle after 10000 times of charge and discharge cycles under the current density of 5A/g, and the fibrous water system zinc ion battery is proved to have an ultra-long cycle life.
Fig. 4 is a charge/discharge curve (current density 5A/g) of the fibrous aqueous zinc-ion battery after being bent at an angle of 120 ° for different times. As can be seen from the figure, after continuously bending for 2000 times at a bending angle of 120 degrees, the specific discharge capacity of the fibrous water-based zinc ion battery can still be maintained at 90.72% before bending, demonstrating excellent flexibility.
Fig. 5 is a photograph of an electronic watch charged by a fibrous aqueous zinc-ion battery woven into a sweater, which proves that the fibrous aqueous zinc-ion battery is easy to weave and integrate, can be woven into a fabric to supply energy to wearable equipment, and has a good application prospect in the field of wearable electronic devices.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
(1) The oriented carbon nanotube fiber (diameter 80 μm) is prepared by floating chemical vapor deposition.
(2) Preparing a composite fiber positive electrode: 0.582g of cobalt nitrate and 1.34g of 2-methylimidazole were dissolved in 40mL of deionized water, and the mixture was stirred for 15 minutes. The oriented carbon nanotube fiber is put into a 2-methylimidazole solution, then a cobalt nitrate solution is quickly added into the 2-methylimidazole solution to obtain a purple solution, and the purple solution is stirred for 4 hours at room temperature. The fibers were then removed, rinsed with ultra pure water and dried under vacuum at 60 ℃ for 12 hours. And annealing the dried fiber in air at 350 ℃ for 3 hours at the heating rate of 10 ℃/min to obtain the oriented carbon nanotube/cobaltosic oxide nanosheet composite fiber anode.
(3) Preparing a composite fiber negative electrode: 1mol/L zinc sulfate solution is prepared to be used as electroplating solution. Oriented carbon nanotube fibers are used as a working electrode, a polished metal zinc sheet (10 x 15mm) is used as a counter electrode, the working electrode and the counter electrode are immersed in electroplating solution, and electrodeposition is carried out at a potential of-0.8V, so that the oriented carbon nanotube/metal zinc nanosheet composite fibers can be obtained and used as a battery cathode.
(4) Preparing electrolyte: respectively adding zinc sulfate and cobalt sulfate into deionized water, and stirring until the zinc sulfate and the cobalt sulfate are dissolved to obtain a mixed solution of the zinc sulfate and the cobalt sulfate. Wherein the concentration of zinc sulfate is 2.0mol/L, and the concentration of cobalt sulfate is 0.0005 mol/L.
(5) Assembly of fibrous aqueous zinc ion battery: and (3) penetrating the positive and negative composite fiber electrodes into a heat-shrinkable tube, separating the positive and negative electrodes by using a glass fiber diaphragm, injecting aqueous electrolyte, and then packaging the heat-shrinkable tube to obtain the fibrous aqueous zinc ion battery.
Example 2
(1) The oriented carbon nanotube fiber (diameter 20 μm) is prepared by floating chemical vapor deposition.
(2) Preparing a composite fiber positive electrode: 1.164g of cobalt nitrate and 2.68g of 2-methylimidazole were dissolved in 40mL of deionized water, and the mixture was stirred for 15 minutes. The oriented carbon nanotube fiber is put into a 2-methylimidazole solution, then a cobalt nitrate solution is quickly added into the 2-methylimidazole solution to obtain a purple solution, and the purple solution is stirred for 6 hours at room temperature. The fibers were then removed, rinsed with ultra pure water and dried under vacuum at 80 ℃ for 12 hours. And annealing the dried fiber in air at 400 ℃ for 4 hours at the heating rate of 10 ℃/min to obtain the oriented carbon nanotube/cobaltosic oxide nanosheet composite fiber anode.
(3) Preparing a composite fiber negative electrode: 1.5mol/L zinc sulfate solution is prepared to be used as electroplating solution. Oriented carbon nanotube fibers are used as a working electrode, a polished metal zinc sheet (10 x 15mm) is used as a counter electrode, the working electrode and the counter electrode are immersed in electroplating solution, and electrodeposition is carried out at a potential of-0.9V, so that the oriented carbon nanotube/metal zinc nanosheet composite fibers can be obtained and used as a battery cathode.
(4) Preparing electrolyte: respectively adding zinc sulfate and cobalt sulfate into deionized water, and stirring until the zinc sulfate and the cobalt sulfate are dissolved to obtain a mixed solution of the zinc sulfate and the cobalt sulfate. Wherein the concentration of zinc sulfate is 0.5mol/L, and the concentration of cobalt sulfate is 0.0001 mol/L.
(5) Assembly of fibrous aqueous zinc ion battery: and (3) penetrating the positive and negative composite fiber electrodes into a heat-shrinkable tube, separating the positive and negative electrodes by using a glass fiber diaphragm, injecting aqueous electrolyte, and then packaging the heat-shrinkable tube to obtain the fibrous aqueous zinc ion battery.
Example 3
(1) The oriented carbon nanotube fiber (diameter 200 μm) is prepared by floating chemical vapor deposition.
(2) Preparing a composite fiber positive electrode: 0.582g of cobalt nitrate and 1.34g of 2-methylimidazole were dissolved in 40mL of deionized water, and the mixture was stirred for 15 minutes. The oriented carbon nanotube fiber is put into a 2-methylimidazole solution, then a cobalt nitrate solution is quickly added into the 2-methylimidazole solution to obtain a purple solution, and the purple solution is stirred for 4 hours at room temperature. The fibers were then removed, rinsed with ultra pure water and dried under vacuum at 60 ℃ for 12 hours. And annealing the dried fiber in air at 350 ℃ for 5 hours at the heating rate of 10 ℃/min to obtain the oriented carbon nanotube/cobaltosic oxide nanosheet composite fiber anode.
(3) Preparing a composite fiber negative electrode: 0.5mol/L zinc sulfate solution is prepared to be used as electroplating solution. Oriented carbon nanotube fibers are used as a working electrode, a polished metal zinc sheet (10 x 15mm) is used as a counter electrode, the working electrode and the counter electrode are immersed in electroplating solution, and electrodeposition is carried out at a potential of-0.8V, so that the oriented carbon nanotube/metal zinc nanosheet composite fibers can be obtained and used as a battery cathode.
(4) Preparing electrolyte: respectively adding zinc sulfate and cobalt sulfate into deionized water, and stirring until the zinc sulfate and the cobalt sulfate are dissolved to obtain a mixed solution of the zinc sulfate and the cobalt sulfate. Wherein the concentration of zinc sulfate is 3.0mol/L, and the concentration of cobalt sulfate is 0.001 mol/L.
(5) Assembly of fibrous aqueous zinc ion battery: and (3) penetrating the positive and negative composite fiber electrodes into a heat-shrinkable tube, separating the positive and negative electrodes by using a glass fiber diaphragm, injecting aqueous electrolyte, and then packaging the heat-shrinkable tube to obtain the fibrous aqueous zinc ion battery.

Claims (5)

1. A fibrous flexible aqueous zinc ion battery with ultra-long cycle life comprises a battery anode, a battery cathode and electrolyte; the method is characterized in that the positive electrode of the battery is oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber; the negative electrode of the battery is oriented carbon nanotube/metal zinc nanosheet composite fiber; the electrolyte is a mixed aqueous solution of zinc sulfate and cobalt sulfate.
2. The fibrous flexible aqueous zinc-ion battery with ultra-long cycle life according to claim 1, characterized in that: the electrolyte is a mixed aqueous solution of zinc sulfate and cobalt sulfate, the concentration range of the zinc sulfate is 0.5-3.0mol/L, and the concentration range of the cobalt sulfate is 0.0001-0.001 mol/L.
3. The fibrous flexible aqueous zinc-ion battery with ultra-long cycle life according to claim 1, characterized in that: and the positive and negative composite fiber electrodes respectively penetrate into the heat-shrinkable tube, the positive and negative electrodes are separated by adopting a diaphragm, and the electrolyte is injected into the middle of the positive and negative composite fiber electrodes for packaging to obtain the fibrous water-based zinc ion battery.
4. The fibrous flexible aqueous zinc-ion battery with ultra-long cycle life according to claim 1, characterized in that: the oriented carbon nanotube is prepared by a floating chemical vapor deposition method, and the diameter of the oriented carbon nanotube is 20-200 mu m.
5. A method of preparing the fibrous flexible aqueous zinc-ion battery having an ultra-long cycle life according to any one of claims 1 to 4, characterized in that: the positive composite fiber is prepared by a solution method and an annealing process, the negative composite fiber is prepared by an electrodeposition method, and the method comprises the following specific steps:
step 1: preparing the oriented carbon nanotube fiber by a floating chemical vapor deposition method;
step 2, preparing the positive composite fiber: dissolving cobalt nitrate in deionized water to obtain a cobalt nitrate solution with the concentration of 0.01-0.1 mol/L; dissolving 2-methylimidazole in deionized water to obtain a 2-methylimidazole solution with the concentration of 0.1-1.0 mol/L;
respectively taking cobalt nitrate and 2-methylimidazole solutions with equal volumes, putting the oriented carbon nanotube fiber into the 2-methylimidazole solution, adding the cobalt nitrate into the 2-methylimidazole solution to obtain a purple solution, and stirring at room temperature for 2-8 hours;
then taking out the fiber, washing with ultrapure water, and drying in vacuum for 8-24 hours at 40-100 ℃;
annealing the dried fiber in air at the temperature of 300-500 ℃ for 1-5 hours to obtain an oriented carbon nanotube/cobaltosic oxide nanosheet composite fiber anode;
step 3, preparing the negative composite fiber: preparing 0.5-2.0mol/L zinc sulfate solution as electroplating solution, using the oriented carbon nanotube fiber as a working electrode, using the polished metal zinc sheet as a counter electrode, immersing the working electrode and the counter electrode into the electroplating solution, and performing electrodeposition at a potential of-0.6V to-1.0V to obtain an oriented carbon nanotube/metal zinc nanosheet composite fiber cathode;
and 4, step 4: penetrating the positive and negative composite fiber electrodes into a heat shrink tube, separating the positive and negative electrodes by using a diaphragm, injecting electrolyte, and then packaging to obtain a fibrous water-based zinc ion battery; the electrolyte is a mixed aqueous solution of zinc sulfate and cobalt sulfate.
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