CN116314565A - Sectional type flexible zinc electrode, preparation method thereof and flexible zinc ion battery - Google Patents

Sectional type flexible zinc electrode, preparation method thereof and flexible zinc ion battery Download PDF

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CN116314565A
CN116314565A CN202310367173.6A CN202310367173A CN116314565A CN 116314565 A CN116314565 A CN 116314565A CN 202310367173 A CN202310367173 A CN 202310367173A CN 116314565 A CN116314565 A CN 116314565A
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zinc
flexible
electrode
conductive substrate
segmented
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姚亚刚
王文惠
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Nanjing University
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Nanjing University
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    • 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
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • 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
    • H01M4/64—Carriers or collectors
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    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H01M50/593—Spacers; Insulating plates
    • 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
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The application discloses sectional type flexible zinc electrode and preparation method and flexible zinc ion battery thereof, sectional type flexible zinc electrode includes: a first flexible conductive substrate; the insulation layers are arranged on the surface of the first flexible conductive substrate, the insulation layers are sequentially arranged, and adjacent insulation layers are mutually spaced so that a plurality of discontinuous conductive areas are formed on the surface of the first flexible conductive substrate; and metallic zinc deposited on the plurality of conductive areas. The sectional type flexible zinc electrode prepared by the method adopts a sectional type structure, a plurality of sections of areas where metal zinc is deposited are formed on the surface of the sectional type flexible zinc electrode, gaps are formed between adjacent areas, the gaps are formed in a bendable mode, bending stress cannot act on the metal zinc, stress generated when a zinc negative electrode is mechanically deformed is remarkably reduced, and the fracture condition of the metal zinc and the interface separation condition of the metal zinc and electrolyte are avoided.

Description

Sectional type flexible zinc electrode, preparation method thereof and flexible zinc ion battery
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a sectional type flexible zinc electrode, a preparation method thereof and a flexible zinc ion battery.
Background
Currently, flexible wearable electronic devices such as flexible displays, flexible sensors, and the like have great market prospects. The development of flexible batteries to power flexible wearable devices is an important impetus for the development of the flexible wearable electronics industry.
Flexible batteries need to meet both flexibility and electrochemical performance requirements. The traditional lithium ion battery adopts organic electrolyte, has larger potential safety hazard, and influences the application of the lithium ion battery in flexible batteries. The zinc ion battery of the water-based electrolyte has high specific capacity (820 mAh/g), low cost and high safety, and is an ideal energy supply device of flexible wearable equipment. At present, the negative electrode of the zinc ion battery mostly adopts metal zinc, the metal zinc not only has a memory effect, but also can cause fracture due to stress generated during bending, and the interface separation of the metal zinc and electrolyte is also a problem, so that the application of the traditional metal zinc negative electrode in the flexible zinc ion battery is limited.
Disclosure of Invention
The invention aims to provide a sectional type flexible zinc electrode, a preparation method thereof and a flexible zinc ion battery, so as to solve the technical problems that in the prior art, metal zinc is adopted as a negative electrode of the zinc ion battery, the metal zinc has a memory effect, and stress generated during bending can cause fracture, interface separation between the metal zinc and electrolyte and the like, and the application of the traditional metal zinc negative electrode in the flexible zinc ion battery is limited.
In order to achieve the above purpose, a technical scheme adopted in the application is as follows:
there is provided a segmented flexible zinc electrode comprising:
a first flexible conductive substrate;
the insulation layers are arranged on the surface of the first flexible conductive substrate, the insulation layers are sequentially arranged, and adjacent insulation layers are mutually spaced so that a plurality of discontinuous conductive areas are formed on the surface of the first flexible conductive substrate;
metallic zinc deposited on the plurality of discrete electrically conductive regions.
In one or more embodiments, the first flexible conductive substrate comprises one or more combinations of carbon cloth, carbon nanotube fibers, carbon nanotube films, silver plated yarns, reduced graphene oxide films.
In one or more embodiments, the mass ratio of the metallic zinc to the first flexible conductive substrate is (1 to 1000): 1.
in order to achieve the above purpose, another technical scheme adopted in the application is as follows:
the preparation method of the segmented flexible zinc electrode comprises the following steps:
coating insulating polymer solution on the surface of the first flexible conductive substrate in a segmented manner, and drying the insulating polymer solution to form a plurality of discontinuous conductive areas on the surface of the first flexible conductive substrate;
and depositing metallic zinc on the discontinuous conductive areas to obtain the segmented flexible zinc electrode.
In one or more embodiments, the method of applying in the step of applying the insulating polymer solution to the surface segment of the first flexible conductive substrate includes one or more combinations of drop coating, blade coating, spin coating.
In one or more embodiments, the method of depositing in the step of depositing metallic zinc on the number of discrete electrically conductive regions includes one or more combinations of electrodeposition, electroplating, and evaporation.
In one or more embodiments, the insulating polymer solution includes a dispersion solvent and a polymer dispersed in the dispersion solvent; the polymer comprises one or more combinations of polyvinyl formal, polyvinyl butyral, polyurethane, and polyvinylidene fluoride, and the dispersion comprises one or more combinations of N-methylpyrrolidone, N-dimethylformamide, and an ethanol solution.
In order to achieve the above object, another technical solution adopted in the present application is:
there is provided a flexible zinc-ion battery comprising:
a negative electrode using the segmented flexible zinc electrode according to any one of the embodiments described above;
the positive electrode comprises a second flexible conductive substrate and a positive electrode active material coated on the surface of the second flexible conductive substrate;
a diaphragm;
an electrolyte;
and (5) packaging.
In one or more embodiments, the second flexible conductive substrate comprises one or more combinations of carbon cloth, carbon nanotube fiber, carbon nanotube film; the positive electrode active material includes one or more combinations of manganese dioxide, vanadium dioxide, prussian blue analogues, and polyanionic compounds.
In one or more embodiments, the electrolyte comprises a zinc salt comprising one or more combinations of polyvinyl alcohol, polyacrylamide, gelatin, sodium carboxymethyl cellulose, and a hydrogel comprising one or more combinations of zinc acetate, zinc sulfate, zinc chloride, zinc trifluoromethane sulfonate, zinc lactate, zinc gluconate, and zinc perchlorate;
the material of the diaphragm is one or a combination of more of aluminum oxide, polyethylene, polypropylene and glass fiber;
the packaging material is one or a combination of more of polypropylene, polyethylene, polydimethylsiloxane and polyethylene terephthalate.
The beneficial effect of this application is, in contrast to prior art:
the sectional type flexible zinc electrode prepared by the method adopts a sectional type structure, a plurality of sections of areas deposited with metal zinc are formed on the surface of the sectional type flexible zinc electrode, gaps are formed between adjacent areas, the gaps can be formed in a bending mode, bending stress can not act on the metal zinc, stress generated when a zinc cathode is mechanically deformed is remarkably reduced, and the situation of metal zinc fracture and the situation of interface separation between the metal zinc and electrolyte are avoided;
the preparation method of the sectional type flexible zinc electrode is simple to operate, low in cost, suitable for large-scale production and wide in application prospect in the field of flexible batteries;
according to the zinc ion battery, the sectional type zinc cathode structure is adopted, so that the circulation stability of the flexible zinc ion battery in a bending state can be remarkably improved, the battery capacity is still kept close to 100% after the flexible zinc ion battery circulates for 200 times in the bending state, and excellent circulation stability is shown.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method of preparing a segmented flexible zinc electrode of the present application;
FIG. 2 is an optical photograph of a segmented flexible zinc electrode prepared in example 1;
FIG. 3 is a scanning electron microscope image of the segmented flexible zinc electrode prepared in example 1;
FIG. 4 is a cyclic voltammogram of effect example 2 of the present application;
fig. 5 is a cycle stability test chart of effect example 3 of the present application.
Detailed Description
The present application will be described in detail with reference to the embodiments shown in the drawings. The embodiments are not intended to be limiting and structural, methodological, or functional changes made by those of ordinary skill in the art in light of the embodiments are intended to be included within the scope of the present application.
As background technology increases in market prospect, development of flexible batteries to power flexible wearable devices is an important motive force to drive the development of flexible wearable electronics.
Flexible batteries need to meet both flexibility and electrochemical performance requirements. Because the traditional lithium ion battery adopts organic electrolyte to generate larger potential safety hazard, the development of the flexible battery with high performance and high safety is particularly important.
The zinc ion battery using the aqueous electrolyte has high specific capacity (820 mAh/g), low cost and high safety, and is an ideal energy supply device of flexible wearable equipment. The zinc ion battery mainly comprises a positive electrode material, a zinc negative electrode, a diaphragm, electrolyte and a packaging material. The majority of currently used cathodes are metallic zinc or are deposited on flexible conductive substrates. However, when metallic zinc or metallic zinc deposited on a flexible conductive substrate has not only a memory effect but also a problem that stress generated upon bending may cause breakage thereof and may cause a problem of interfacial separation of metallic zinc and electrolyte.
In order to solve the problems, the applicant develops a sectional type flexible zinc electrode which can be used as a negative electrode in a flexible zinc ion battery, effectively avoids the problem of metal zinc fracture caused by stress during bending by a sectional method, and avoids the problem of interface separation between the metal zinc and electrolyte caused by bending, thereby providing a new scheme for the development of a new generation of flexible zinc ion batteries.
Specifically, referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a segmented flexible zinc electrode according to the present application.
The preparation method comprises the following steps:
s100, coating an insulating polymer solution on the surface of the first flexible conductive substrate in a segmented mode, and drying to enable the surface of the first flexible conductive substrate to form a plurality of discontinuous conductive areas.
The conductive areas are sequentially arranged and spaced from one another to form a plurality of conductive segments, and the conductive segments are electrically connected into a whole through the inside of the first flexible conductive substrate.
Specifically, in one application scenario, the first flexible conductive substrate may include one or more combinations of carbon cloth, carbon nanotube fibers, carbon nanotube films, silver plated yarns, reduced graphene oxide films.
In other application scenarios, other conductive flexible materials may be used, which can achieve the effects of the present embodiment.
In one application scenario, the insulating polymer solution may include a dispersion solvent and a polymer dispersed in the dispersion solvent.
Specifically, the polymer may include one or more combinations of polyvinyl formal, polyvinyl butyral, polyurethane, and polyvinylidene fluoride, and the dispersion solvent may include one or more combinations of N-methylpyrrolidone, N-dimethylformamide, and an ethanol solution.
In other application scenarios, other insulating materials may be used for the polymer, which may enable insulating the surface after application to the first flexible conductive substrate surface.
In one application scenario, the method of sectionally applying the insulating polymer solution to the surface of the first flexible conductive substrate may be one or more combinations of drop coating, blade coating, spin coating.
And S200, depositing metal zinc on the discontinuous conductive areas to obtain the segmented flexible zinc electrode.
After forming a plurality of conductive areas on the surface of the first flexible conductive substrate, metal zinc can be deposited on each conductive area, thereby forming a segmented flexible zinc electrode.
In one application scenario, the method of deposition may include one or more combinations of electrodeposition, electroplating, evaporation.
In one application scenario, the metallic zinc may include sheet zinc, spherical zinc, powder zinc, and the like, all of which can achieve the effects of the present embodiment.
It can be understood that the sectional type flexible zinc electrode prepared by the preparation method is characterized in that a plurality of conductive areas are sequentially arranged and spaced, so that the metal zinc deposited on each conductive area forms a sectional type electrode structure.
When the segmented flexible zinc electrode is applied to the negative electrode of the flexible battery, the segmented flexible zinc electrode can be bent at the gap between adjacent conductive areas, so that the influence of stress on metal zinc during bending is effectively avoided, and the problems of zinc electrode fracture phenomenon and interface separation of the metal zinc and electrolyte are avoided.
The applicant has also developed a zinc-ion battery employing the above segmented flexible zinc electrode, in particular, in one embodiment, the zinc-ion battery of the present application may include a negative electrode, a positive electrode, a separator, an electrolyte, and a package.
Wherein, the negative electrode adopts the sectional type flexible zinc electrode of any one of the embodiments.
The anode can comprise a second flexible conductive substrate and an anode active material coated on the surface of the second flexible conductive substrate, and in one application scene, the second flexible conductive substrate comprises one or more of carbon cloth, carbon nano tube fiber, carbon fiber and carbon nano tube film; the positive electrode active material may include one or more combinations of manganese dioxide, vanadium dioxide, prussian blue analogues, and polyanion compounds.
In one application scenario, the material of the separator may be one or a combination of more of aluminum oxide, polyethylene, polypropylene, and glass fiber.
In one application scenario, the electrolyte may include a zinc salt and a hydrogel, the hydrogel may include one or more combinations of polyvinyl alcohol, polyacrylamide, gelatin, sodium carboxymethyl cellulose, and the zinc salt may include one or more combinations of zinc acetate, zinc sulfate, zinc chloride, zinc trifluoromethane sulfonate, zinc lactate, zinc gluconate, and zinc perchlorate.
The technical scheme of the present application is further elaborated below in conjunction with specific embodiments.
Example 1: a zinc ion battery is prepared by the following steps:
(1) Preparing a segmented flexible zinc electrode:
the ethanol solution of polyvinyl formal acetal is dripped on the surface of the carbon nano tube fiber in a sectionalized way by using the dripping technology, and the surface of the carbon nano tube fiber is dried to form a plurality of conductive areas in a sectionalized way.
Immersing 10ml of the carbon nanotube fiber serving as a working electrode, a metal zinc sheet serving as a counter electrode and an Ag/AgCl electrode serving as a reference electrode in a solution containing 5.76g of ZnSO 4 ·7H 2 Zinc O sulfate, 0.71g Na 2 SO 4 、0.1g H 3 BO 3 Is used as an electrolyte. Depositing zinc metal on the surface of carbon nanotube fiber by constant current deposition technique with deposition current density of-20mA.cm -2 The deposition time is 30min, and a segmented flexible zinc electrode is obtained;
(2) Preparing a flexible positive electrode:
mixing zinc iron cyanide, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1 by taking N-methyl pyrrolidone as a dispersing agent, coating the mixture on the cleaned carbon nano tube fiber, and drying the carbon nano tube fiber in a vacuum oven to obtain a flexible anode;
(3) The flexible positive electrode was used as a positive electrode, and the segmented flexible zinc electrode was used as a negative electrode, and contained 1M Zn (CF 3 SO 3 ) 2 The flexible zinc ion battery is prepared by taking polyvinyl alcohol as electrolyte, a glass fiber membrane as a diaphragm and polyethylene as a packaging material.
Example 2: a zinc ion battery is prepared by the following steps:
(1) Preparing a segmented flexible zinc electrode:
the N-methyl pyrrolidone solution of polyvinylidene fluoride is dripped on the surface of the carbon nano tube film in a sectionalized way by using a dripping technology, and the surface of the carbon nano tube film is baked to form a plurality of conductive areas in a sectionalized way.
Immersing the carbon nanotube film as a working electrode, a metallic zinc sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode in 10ml of a solution containing 5.76g ZnSO 4 ·7H 2 Zinc O sulfate, 0.71g Na 2 SO 4 、0.1g H 3 BO 3 Is used as an electrolyte. Depositing zinc metal on the surface of the carbon nanotube film by adopting constant current deposition technology, wherein the deposition current density is-30 mA cm -2 The deposition time is 20min, and a segmented flexible zinc electrode is obtained;
(2) Preparing a flexible positive electrode:
mixing manganese dioxide, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1 by taking N-methyl pyrrolidone as a dispersing agent, coating the mixture on the surface of a cleaned carbon nano tube film, and drying in a vacuum oven to obtain a flexible anode;
(3) The flexible anode is used as an anode, the segmented flexible zinc electrode is used as a cathode, polyacrylamide containing 1M zinc acetate is used as electrolyte, a glass fiber membrane is used as a diaphragm, and polyethylene is used as a packaging material to prepare the flexible zinc ion battery.
Example 3: a zinc ion battery is prepared by the following steps:
(1) Preparing a segmented flexible zinc electrode:
and (3) dripping the N-methyl pyrrolidone solution of polyvinylidene fluoride on the surface of the silver-plated yarn in a sectional manner by using a dripping technology, and drying to enable the surface of the silver-plated yarn to be conductive in a sectional manner to form a plurality of conductive areas.
Immersing the silver-plated yarn as a working electrode, a metal zinc sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode in 10ml of a solution containing 5.76g ZnSO 4 ·7H 2 Zinc O sulfate, 0.71g Na 2 SO 4 、0.1g H 3 BO 3 Is used as an electrolyte. Depositing zinc metal on the surface of silver-plated yarn by adopting constant current deposition technology, wherein the deposition current density is-40 mA cm -2 The deposition time is 15min, and a segmented flexible zinc electrode is obtained;
(2) Preparing a flexible positive electrode:
mixing vanadium dioxide, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1 by taking N-methyl pyrrolidone as a dispersing agent, coating the mixture on the surface of the cleaned carbon nano tube film, and drying in a vacuum oven to obtain a flexible anode;
(3) The flexible anode is used as an anode, the segmented flexible zinc electrode is used as a cathode, sodium carboxymethylcellulose containing 1M zinc sulfate is used as electrolyte, a glass fiber membrane is used as a diaphragm, and polyethylene is used as an encapsulation material to prepare the flexible zinc ion battery.
Example 4:
a zinc ion battery is prepared by the following steps:
(1) Preparing a segmented flexible zinc electrode:
and (3) sectionally dripping the N-methyl pyrrolidone solution of the polyvinylidene fluoride on the surface of the reduced graphene oxide film by using a dripping technology, and drying to ensure that the surface of the reduced graphene oxide film is sectionally conductive to form a plurality of conductive areas.
Immersing 10ml of the reduced graphene oxide film serving as a working electrode, a metal zinc sheet serving as a counter electrode and an Ag/AgCl electrode serving as a reference electrode in a solution containing 5.76g of ZnSO 4 ·7H 2 Zinc O sulfate, 0.71g Na 2 SO 4 、0.1g H 3 BO 3 Electrolyte of (2)Is a kind of medium. Depositing metallic zinc on the surface of the reduced graphene oxide film by adopting a constant current deposition technology, wherein the deposition current density is-40 mA cm -2 The deposition time is 15min, and a segmented flexible zinc electrode is obtained;
(2) Preparing a flexible positive electrode:
mixing vanadium dioxide, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1 by taking N-methyl pyrrolidone as a dispersing agent, coating the mixture on the surface of the cleaned carbon nano tube film, and drying in a vacuum oven to obtain a flexible zinc electrode;
(3) The flexible anode is used as an anode, the segmented flexible zinc electrode is used as a cathode, gelatin containing 0.5M zinc lactate is used as electrolyte, a glass fiber membrane is used as a diaphragm, and polyethylene is used as a packaging material to prepare the flexible zinc ion battery.
Comparative example 1: a zinc ion battery is prepared by the following steps:
1) Preparation of Flexible Positive electrode
Mixing zinc iron cyanide (Zn-HCF), acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1 by taking N-methylpyrrolidone as a dispersing agent, coating the mixture on the cleaned carbon nano tube fiber, and drying the carbon nano tube fiber in a vacuum oven to obtain the flexible anode (CNTF-Zn-HCF).
2) Preparation of flexible zinc ion battery
CNTF-Zn-HCF is used as positive electrode, metallic zinc wire is used as negative electrode, and contains 1M Zn (CF 3 SO 3 ) 2 The flexible zinc ion battery is prepared by taking polyvinyl alcohol as electrolyte, a glass fiber membrane as a diaphragm and polyethylene as a packaging material.
Effect example 1:
characterization analysis was performed on the segmented flexible zinc electrode prepared in example 1, resulting in fig. 2 and 3.
Referring to fig. 2, fig. 2 is an optical photograph of the segmented flexible zinc electrode prepared in example 1, wherein the right view is a partially enlarged view of the left view. As shown in fig. 2, the surface of the segmented flexible zinc electrode prepared in example 1 is deposited with metallic zinc in a segmented manner, and gaps are arranged between adjacent metallic zinc segments.
Referring to fig. 3, fig. 3 is a scanning electron microscope image of the segmented flexible zinc electrode prepared in example 1, wherein the left image is a scanning electron microscope image of adjacent metal zinc gaps, and the right image is a scanning electron microscope image of metal zinc deposited on the surface. As shown in fig. 3, the surface of the segmented flexible zinc electrode prepared in example 1 is deposited with metallic zinc in a segmented manner, and gaps are arranged between adjacent metallic zinc segments.
From the above characterization analysis, it can be seen that the segmented flexible zinc electrode prepared in example 1 adopts a segmented structure, and a plurality of segments of regions deposited with metallic zinc are formed on the surface, and gaps are formed between adjacent regions. It can be understood that when the zinc electrode with the sectional structure is applied to the flexible battery, the gap can be flexibly arranged, bending stress can not act on metal zinc, stress generated when the zinc cathode is mechanically deformed is obviously reduced, and the mechanical stability of the flexible zinc ion battery is improved.
Effect example 2:
the zinc ion battery prepared in example 1 was subjected to cyclic voltammetry at room temperature with a test voltage range of 1.4 to 2.1V and a scan rate of 1 to 2mV/s to give fig. 4.
Referring to FIG. 4, FIG. 4 is a cyclic voltammogram of effect example 2 of the present application, and as shown in FIG. 4, the zinc ion cell prepared in example 1 is capable of performing electrochemical reduction and oxidation reactions stably at a scan rate of 1mV/s and 2mV/s, and has stable electrochemical performance.
Effect example 3:
the zinc ion batteries prepared in example 1 and comparative example 1 were subjected to a cycle stability test in a bent state, resulting in fig. 5.
Referring to fig. 5, fig. 5 is a graph for testing the cycle stability of effect example 3 of the present application, and as shown in fig. 5, the zinc ion battery prepared in example 1 still maintains the battery capacity close to 100% after 200 cycles in a bent state, and shows excellent cycle stability.
The zinc ion battery prepared in comparative example 1 was gradually reduced in battery capacity with increasing cycle number in a bent state, and the battery capacity was only 80% of the initial battery capacity after 200 cycles.
From the above, it can be seen that the segmented flexible zinc electrode prepared in example 1 can significantly improve the cycling stability of the flexible zinc ion battery in a bending state after being applied to the negative electrode of the flexible zinc ion battery.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A segmented flexible zinc electrode, comprising:
a first flexible conductive substrate;
the insulation layers are arranged on the surface of the first flexible conductive substrate, the insulation layers are sequentially arranged, and adjacent insulation layers are mutually spaced so that a plurality of discontinuous conductive areas are formed on the surface of the first flexible conductive substrate;
metallic zinc deposited on the plurality of discrete electrically conductive regions.
2. The segmented flexible zinc electrode of claim 1, wherein the first flexible conductive substrate comprises one or more combinations of carbon cloth, carbon nanotube fibers, carbon nanotube films, silver plated yarns, reduced graphene oxide films.
3. The segmented flexible zinc electrode of claim 1, wherein the mass ratio of the metallic zinc to the first flexible conductive substrate is (1-1000): 1.
4. a method of preparing a segmented flexible zinc electrode according to any one of claims 1 to 3, comprising:
coating insulating polymer solution on the surface of the first flexible conductive substrate in a segmented manner, and drying the insulating polymer solution to form a plurality of discontinuous conductive areas on the surface of the first flexible conductive substrate;
and depositing metallic zinc on the discontinuous conductive areas to obtain the segmented flexible zinc electrode.
5. The method of claim 4, wherein the step of applying the insulating polymer solution to the surface of the first flexible conductive substrate comprises one or more of a combination of drop coating, knife coating, and spin coating.
6. The method of claim 4, wherein the method of depositing in the step of depositing metallic zinc on the plurality of discrete electrically conductive regions comprises one or more of electrodeposition, electroplating, and evaporation.
7. The method according to claim 4, wherein the insulating polymer solution comprises a dispersion solvent and a polymer dispersed in the dispersion solvent; the polymer comprises one or more combinations of polyvinyl formal, polyvinyl butyral, polyurethane, and polyvinylidene fluoride, and the dispersion comprises one or more combinations of N-methylpyrrolidone, N-dimethylformamide, and an ethanol solution.
8. A flexible zinc ion battery comprising:
a negative electrode employing the segmented flexible zinc electrode of any one of claims 1 to 3;
the positive electrode comprises a second flexible conductive substrate and a positive electrode active material coated on the surface of the second flexible conductive substrate;
a diaphragm;
an electrolyte;
and (5) packaging.
9. The flexible zinc-ion battery of claim 8, wherein the second flexible conductive substrate comprises one or more combinations of carbon cloth, carbon nanotube fiber, carbon nanotube film; the positive electrode active material includes one or more combinations of manganese dioxide, vanadium dioxide, prussian blue analogues, and polyanionic compounds.
10. The flexible zinc-ion battery of claim 8, wherein the electrolyte comprises a zinc salt and a hydrogel, the hydrogel comprising one or more combinations of polyvinyl alcohol, polyacrylamide, gelatin, sodium carboxymethyl cellulose, the zinc salt comprising one or more combinations of zinc acetate, zinc sulfate, zinc chloride, zinc trifluoromethane sulfonate, zinc lactate, zinc gluconate, and zinc perchlorate;
the material of the diaphragm is one or a combination of more of aluminum oxide, polyethylene, polypropylene and glass fiber;
the packaging material is one or a combination of more of polypropylene, polyethylene, polydimethylsiloxane and polyethylene terephthalate.
CN202310367173.6A 2023-04-07 2023-04-07 Sectional type flexible zinc electrode, preparation method thereof and flexible zinc ion battery Pending CN116314565A (en)

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