CN113937268B - Fibrous flexible water system zinc ion battery with ultra-long cycle life and preparation method - Google Patents

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

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CN113937268B
CN113937268B CN202111181242.1A CN202111181242A CN113937268B CN 113937268 B CN113937268 B CN 113937268B CN 202111181242 A CN202111181242 A CN 202111181242A CN 113937268 B CN113937268 B CN 113937268B
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oriented carbon
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CN113937268A (en
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赵阳
朱纪欣
卢宇飞
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Northwestern Polytechnical University
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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    • 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
    • H01M4/38—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
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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
    • H01M4/48—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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • H01M2004/028—Positive electrodes
    • 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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    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
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Abstract

The invention relates to a fibrous flexible water-based zinc ion battery with ultra-long cycle life and a preparation method thereof, wherein an oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber is used as a battery anode, an oriented carbon nano tube/metallic zinc nano sheet composite fiber is used as a battery cathode, and a mixed aqueous solution of zinc sulfate and cobalt sulfate is used as electrolyte. The positive composite fiber is prepared by a solution method and an annealing process, and the negative composite fiber is prepared by an electrodeposition method. In the invention, the obtained fibrous water-based zinc ion battery has excellent long-acting cycle performance and ultra-long cycle life. After being continuously bent for 2000 times at a bending angle of 120 degrees, the discharge specific capacity of the composite material can still be kept at 90.72% before bending, and the composite material has excellent flexibility. The obtained fibrous water-based zinc ion battery has high safety and reliability, can be woven into energy storage fabrics to supply energy to wearable equipment, and has good application prospect in the field of wearable electronic devices.

Description

Fibrous flexible water system zinc ion battery with ultra-long cycle life and preparation method
Technical Field
The invention belongs to the technical and flexibility fields of zinc ion batteries, and relates to a fibrous flexible water system zinc ion battery with an ultra-long cycle life and a preparation method thereof.
Background
The portable and wearable electronic device has good application prospects in various fields such as electronic skin, health monitoring and the like, and development of a novel flexible battery with high specific capacity, long cycle life and high safety is needed in order to meet the power supply requirements of the portable and wearable electronic device. Among them, flexible aqueous zinc ion batteries have attracted extensive research attention due to their adequate reserves, low redox potential, high theoretical specific capacity and high safety. However, the existing flexible aqueous zinc ion batteries are limited by flexible electrode materials, generally have poor cycle life and low flexibility, which severely limit the development and practical application thereof in the field of flexible wearable electronic devices.
The positive electrode materials of flexible aqueous zinc-ion batteries can be generally classified into three types, i.e., inorganic materials, organic materials, and hybrid materials. Inorganic materials such as alum, manganese, and cobalt-based materials generally have high specific capacities and operating voltage plateau, with tricobalt tetraoxide (Co 3 O 4 ) Has high theoretical specific capacity and theoretical energy density in alkaline electrolyte. However, tricobalt tetroxide anodes typically have poor cycling performance in alkaline electrolytes due to the formation of irreversible discharge byproducts; more importantly, the use of toxic and corrosive alkaline electrolytes greatly increases their potential safety risks when applied to the field of wearable devices. Therefore, there is a need for development of 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 current water-based zinc ion battery is difficult to realize high specific capacity, long cycle performance and excellent flexibility at the same time, thereby better meeting the development requirement of flexible wearable equipment.
Technical proposal
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 an oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber; the negative electrode of the battery is an oriented carbon nano tube/metal zinc nano sheet 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, wherein the concentration range of the zinc sulfate is 0.5-3.0mol/L, and the concentration range of the cobalt sulfate is 0.0001-0.001mol/L.
The positive electrode and the negative electrode composite fiber electrode respectively penetrate into the heat shrinkage tube, the positive electrode and the negative electrode are separated by adopting a diaphragm, electrolyte is injected into the middle of the positive electrode and the negative electrode, and then the fibrous water system zinc ion battery is obtained through packaging.
The oriented carbon nano tube is prepared by adopting a floating chemical vapor deposition method, and the diameter 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, and the negative composite fiber is prepared by an electrodeposition method, and the specific steps are as follows:
step 1: preparing oriented carbon nanotube fibers by adopting a floating chemical vapor deposition method;
step 2, preparing an anode composite fiber: cobalt nitrate is dissolved in deionized water to obtain 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 solution with equal volumes, putting oriented carbon nanotube fibers into the 2-methylimidazole solution, adding 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, cleaning the fiber with ultrapure water, and vacuum drying the fiber at 40-100 ℃ for 8-24 hours;
annealing the dried fiber in air at 300-500 ℃ for 1-5 hours to obtain an oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber anode;
step 3, preparing a negative electrode composite fiber: preparing a zinc sulfate solution with the concentration of 0.5-2.0mol/L as an electroplating solution, using oriented carbon nano tube fibers as a working electrode, using polished metal zinc sheets as a counter electrode, immersing the working electrode and the counter electrode into the electroplating solution, and performing electrodeposition at the potential of-0.6V to-1.0V to obtain an oriented carbon nano tube/metal zinc nano sheet composite fiber negative electrode;
step 4: penetrating the positive and negative composite fiber electrodes into a heat shrinkage tube, separating the positive electrode from the negative electrode by using a diaphragm, injecting electrolyte, and packaging to obtain a fibrous water system 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 ultra-long cycle life and a preparation method thereof, wherein an oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber is used as a battery anode, an oriented carbon nano tube/metallic zinc nano sheet composite fiber is used as a battery cathode, and a mixed aqueous solution of zinc sulfate and cobalt sulfate is used as electrolyte. The positive composite fiber is prepared by a solution method and an annealing process, and the negative composite fiber is prepared by an electrodeposition method.
In the invention, the obtained fibrous water-based zinc ion battery has excellent long-acting cycle performance, the specific capacity of the fibrous water-based zinc ion battery is kept at 97.27% of the first cycle after being circularly charged and discharged 10000 times under the current density of 5A/g, and the fibrous water-based zinc ion battery has ultra-long cycle life.
In the invention, after the obtained fibrous water-based zinc ion battery is continuously bent for 2000 times under the bending angle of 120 degrees, the specific discharge capacity of the fibrous water-based zinc ion battery can still be kept at 90.72 percent before bending, and the fibrous water-based zinc ion battery has excellent flexibility.
The fibrous water-based zinc ion battery has high safety and reliability, is easy to weave and integrate, can be woven into energy storage fabrics to supply energy to wearable equipment, and has good application prospect in the field of wearable electronic devices.
Compared with the prior art:
limited by the poor stability of the electrode materials, the cycle life of existing flexible aqueous zinc-ion batteries is typically less than 5000 times. Through new electrode materials and device designs, tricobalt tetraoxide nano-sheets are obtained by in-situ compounding on oriented carbon nano-tube fibers, and a novel composite fiber electrode material with high stability is obtained; the invention further designs the zinc sulfate and cobalt sulfate mixed water-based electrolyte, and the circulation stability of the fibrous water-based zinc ion battery is greatly improved through the unique design and interaction of the electrode material and the electrolyte; the specific capacity of the fibrous water-based zinc ion battery obtained by the invention is kept at 97.27% of the first circle after 10000 times of cyclic charge and discharge under the current density of 5A/g, and the fibrous water-based zinc ion battery has an ultra-long cycle life.
Limited by the poor flexibility and stability of the electrode materials and devices, the number of times the existing flexible aqueous zinc-ion cells can be bent is typically less than 1000 times. Based on oriented carbon nanotube fiber with excellent flexibility and conductivity, an in-situ composite nano-sheet electrode material is arranged on the fiber through a solution method, an in-situ electrodeposition method and the like, and an anode and cathode composite fiber electrode material with high flexibility and stability is designed and prepared, so that the flexibility of the obtained fibrous battery is greatly improved; after the fibrous water-based zinc ion battery obtained by the invention is continuously bent for 2000 times under the 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.
Currently, aqueous zinc ion batteries using tricobalt tetraoxide as a positive electrode material mostly use alkaline electrolytes, however, the use of toxic and corrosive alkaline electrolytes greatly increases their potential safety risks, especially when applied in the field of wearable devices. The neutral aqueous solution of the fibrous aqueous zinc ion battery is used as electrolyte, so that the safety and reliability of the fibrous aqueous zinc ion battery are greatly improved, and the fibrous aqueous zinc ion battery has better development and application prospects in the field of wearable electronic devices.
Drawings
Fig. 1 is a schematic structural view of a fibrous flexible aqueous zinc ion battery, from which the structure and composition of the fibrous battery can be seen.
FIG. 2 is a structural representation of a positive and negative composite fiber electrode. Wherein a-b are respectively low-power and high-power scanning electron microscope pictures of the positive electrode of the oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber. c-d, respectively scanning electron microscope pictures of low power and high power of the negative electrode of the oriented carbon nano tube/metal zinc nano sheet composite fiber. From the figure, it can be seen that both cobaltosic oxide and metallic zinc are nano-sheet structures.
FIG. 3 is a graph showing the long-term cycle performance (current density: 5A/g) of a fibrous aqueous zinc-ion battery. From the graph, after 10000 times of cyclic charge and discharge under the current density of 5A/g, the specific capacity of the fibrous water-based zinc ion battery is still kept at 97.27% of the first circle, and the fibrous water-based zinc ion battery has extremely long cycle life.
Fig. 4 shows the charge and discharge curves (current density 5A/g) of a fibrous aqueous zinc-ion battery after being bent at an angle of 120 ° for different times. As can be seen from the figure, after continuous bending for 2000 times at a bending angle of 120 degrees, the discharge specific capacity of the fibrous aqueous zinc-ion battery can still be kept at 90.72% before bending, and the fibrous aqueous zinc-ion battery has excellent flexibility.
Fig. 5 is a photograph of a fibrous water-based zinc ion battery woven into a sweater to charge an electronic watch, which proves that the fibrous water-based zinc ion battery is easy to weave and integrate, can be woven into a fabric to supply energy to wearable equipment, and has good application prospect in the field of wearable electronic devices.
Detailed Description
The invention will now be further described with reference to examples, figures:
example 1
(1) The oriented carbon nanotube fiber (diameter 80 μm) was prepared by a floating chemical vapor deposition method.
(2) Preparing a composite fiber positive electrode: 0.582g of cobalt nitrate and 1.34g of 2-methylimidazole were each dissolved in 40mL of deionized water, and stirred for 15 minutes. The oriented carbon nanotube fiber was put into a 2-methylimidazole solution, and then a cobalt nitrate solution was rapidly added to the 2-methylimidazole solution to obtain a purple solution, which was stirred at room temperature for 4 hours. The fibers were then removed, rinsed with ultrapure water, and dried in vacuo at 60℃for 12 hours. And (3) annealing the dried fiber in the air at 350 ℃ for 3 hours, wherein the heating rate is 10 ℃/min, and the oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber anode can be obtained.
(3) Preparation of a composite fiber negative electrode: a1 mol/L zinc sulfate solution was prepared as a plating solution. The method comprises the steps of using oriented carbon nano tube fibers as a working electrode, using polished metal zinc sheets (10 multiplied by 15 mm) as a counter electrode, immersing the working electrode and the counter electrode into electroplating solution, and performing electrodeposition under the potential of-0.8V to obtain the oriented carbon nano tube/metal zinc nano sheet composite fibers as a battery cathode.
(4) Preparing an electrolyte: and 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 0.0005mol/L.
(5) Assembling a fibrous water-based zinc ion battery: penetrating the positive and negative composite fiber electrodes into the heat shrinkage tube, separating the positive electrode from the negative electrode by using a glass fiber diaphragm, injecting the aqueous electrolyte, and packaging the heat shrinkage tube to obtain the fibrous aqueous zinc ion battery.
Example 2
(1) The oriented carbon nanotube fiber (diameter 20 μm) was prepared by a floating chemical vapor deposition method.
(2) Preparing a composite fiber positive electrode: 1.164g of cobalt nitrate and 2.68g of 2-methylimidazole were each dissolved in 40mL of deionized water, and stirred for 15 minutes. The oriented carbon nanotube fiber was put into a 2-methylimidazole solution, and then a cobalt nitrate solution was rapidly added to the 2-methylimidazole solution to obtain a purple solution, which was stirred at room temperature for 6 hours. The fibers were then removed, rinsed with ultrapure water, and dried in vacuo at 80℃for 12 hours. And (3) annealing the dried fiber in the air at 400 ℃ for 4 hours, wherein the heating rate is 10 ℃/min, and the oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber anode can be obtained.
(3) Preparation of a composite fiber negative electrode: a zinc sulfate solution of 1.5mol/L was prepared as a plating solution. The method comprises the steps of using oriented carbon nano tube fibers as a working electrode, using polished metal zinc sheets (10 multiplied by 15 mm) as a counter electrode, immersing the working electrode and the counter electrode into electroplating solution, and performing electrodeposition under the potential of-0.9V to obtain the oriented carbon nano tube/metal zinc nano sheet composite fibers as a battery cathode.
(4) Preparing an electrolyte: and 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 0.0001mol/L.
(5) Assembling a fibrous water-based zinc ion battery: penetrating the positive and negative composite fiber electrodes into the heat shrinkage tube, separating the positive electrode from the negative electrode by using a glass fiber diaphragm, injecting the aqueous electrolyte, and packaging the heat shrinkage tube to obtain the fibrous aqueous zinc ion battery.
Example 3
(1) The oriented carbon nanotube fiber (diameter 200 μm) was prepared by a floating chemical vapor deposition method.
(2) Preparing a composite fiber positive electrode: 0.582g of cobalt nitrate and 1.34g of 2-methylimidazole were each dissolved in 40mL of deionized water, and stirred for 15 minutes. The oriented carbon nanotube fiber was put into a 2-methylimidazole solution, and then a cobalt nitrate solution was rapidly added to the 2-methylimidazole solution to obtain a purple solution, which was stirred at room temperature for 4 hours. The fibers were then removed, rinsed with ultrapure water, and dried in vacuo at 60℃for 12 hours. And (3) annealing the dried fiber in the air at 350 ℃ for 5 hours, wherein the heating rate is 10 ℃/min, and the oriented carbon nano tube/cobaltosic oxide nano sheet composite fiber anode can be obtained.
(3) Preparation of a composite fiber negative electrode: a zinc sulfate solution of 0.5mol/L was prepared as a plating solution. The method comprises the steps of using oriented carbon nano tube fibers as a working electrode, using polished metal zinc sheets (10 multiplied by 15 mm) as a counter electrode, immersing the working electrode and the counter electrode into electroplating solution, and performing electrodeposition under the potential of-0.8V to obtain the oriented carbon nano tube/metal zinc nano sheet composite fibers as a battery cathode.
(4) Preparing an electrolyte: and 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 0.001mol/L.
(5) Assembling a fibrous water-based zinc ion battery: penetrating the positive and negative composite fiber electrodes into the heat shrinkage tube, separating the positive electrode from the negative electrode by using a glass fiber diaphragm, injecting the aqueous electrolyte, and packaging the heat shrinkage tube to obtain the fibrous aqueous zinc ion battery.

Claims (4)

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