CN116207410A - Neutral zinc air fiber battery and preparation method thereof - Google Patents

Neutral zinc air fiber battery and preparation method thereof Download PDF

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CN116207410A
CN116207410A CN202310347501.6A CN202310347501A CN116207410A CN 116207410 A CN116207410 A CN 116207410A CN 202310347501 A CN202310347501 A CN 202310347501A CN 116207410 A CN116207410 A CN 116207410A
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zinc
fiber
electrolyte
film
nano tube
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张晔
陈昊
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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

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Abstract

The invention discloses a neutral zinc-air fiber battery and a preparation method thereof, and belongs to the technical field of batteries. Aiming at the problem of poor charge-discharge effect caused by overlarge bending rigidity and bending in the prior art, the invention provides a neutral zinc-air fiber battery and a preparation method thereof. The method comprises the following steps: preparing a carbon nano tube/zinc powder composite fiber; preparing organic gel electrolyte; preparing a hydrogel electrolyte precursor, and enabling the hydrogel electrolyte precursor to gel on the composite fiber solidified by the organic gel electrolyte in situ to obtain a fiber negative electrode wrapped by double-layer gel; and winding the carbon nano tube film anode modified by the platinum/ruthenium oxide nano particles on the fiber cathode wrapped by the double-layer gel. The bending stiffness is small, and the bending strength has good charge-discharge curves for bending at different degrees.

Description

Neutral zinc air fiber battery and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a neutral zinc-air fiber battery and a preparation method thereof.
Background
With the demands of people for more convenience and convenience in life, the wearable electronic equipment obtains huge development opportunities and has wide development prospects. Meanwhile, in order to meet the daily energy supply demands of various wearable electronic devices, new wearable energy devices are receiving increasing attention. The existing battery types are beginning to be diversified.
The prior art has related technologies of zinc-air fiber batteries, such as China patent application, application number 202110991586.2, publication day 2021, 11 and 23, and discloses a novel cable type flexible zinc-air battery. Dissolving a strong alkaline electrolyte in deionized water to prepare an alkaline electrolyte with the concentration of 6 mol/L; the hollow composite fiber is fully soaked in electrolyte to be used as electrolyte material of a zinc-air battery, a flexible zinc rod is penetrated from the center of the fiber electrolyte, and an air electrode is wrapped on the outer layer, so that the cable type structure is assembled. The invention innovatively adopts the fiber electrolyte, thereby avoiding the complex process for preparing the traditional gel electrolyte and realizing the conversion from the water-based battery to the flexible battery. The assembled cable-type zinc-air battery shows all-round flexibility thanks to good water absorption and flexibility of the fibrous electrolyte, and the performance of the battery can be recovered after the alkaline solution is replenished when the performance of the battery is degraded or fails during operation. The novel cable type flexible zinc-air battery is simple to prepare, low in cost, high in operability and promising in wearable electronic products. However, the charge and discharge effect is poor, and the charge and discharge are deteriorated due to bending.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art that the bending stiffness is too large and cannot be bent, the charge and discharge effect is poor due to bending, and the charge and discharge effect is poor due to bending, the invention provides a neutral zinc-air fiber battery and a preparation method thereof.
2. Technical proposal
The aim of the invention is achieved by the following technical scheme.
The invention aims to provide a preparation method of a neutral zinc-air fiber battery, so as to meet the requirements of a wearable energy device on safety, flexibility and electrochemical performance.
The neutral zinc-air fiber battery provided by the invention is assembled by a carbon nano tube/zinc powder composite fiber cathode, a double-layer gel electrolyte and a platinum/ruthenium oxide modified carbon nano tube film anode in a coaxial structure.
The preparation method of the neutral zinc-air fiber battery provided by the invention comprises the following specific steps:
(1) Preparing a carbon nano tube/zinc powder composite fiber electrode;
(2) Preparing an organic gel electrolyte, soaking the fiber electrode manufactured in the step (1) in the organic gel electrolyte for 1-5 min, taking out and airing in the air for 5-15 min, and curing the organic gel electrolyte;
(3) Preparing a hydrogel electrolyte precursor;
(4) In-situ gel is carried out on the hydrogel electrolyte precursor on the fiber cathode treated in the step (2);
(5) Winding a carbon nano tube film anode decorated by platinum/ruthenium oxide nano particles on the fiber cathode treated in the step (3).
In the invention, the preparation steps of the carbon nano tube/zinc powder composite fiber electrode are as follows: (1) Adding 75mg-125mg of zinc powder into 4mL-8mL of absolute ethyl alcohol, and performing ultrasonic treatment on the zinc powder to form a relatively uniform dispersion liquid A; (2) Drawing a layer of carbon nanotube film with the length of 3cm-5cm and the width of 0.5cm-1.5cm from the super-parallel carbon nanotube array, sucking 20 mu L-60 mu L of dispersion liquid A, uniformly dripping the dispersion liquid A on the carbon nanotube film, and standing for 1min-5min for airing; (3) Repeating the step (2) for a plurality of times, such as 2-4 times, on the film manufactured in the step (2) to obtain a carbon nano tube/zinc powder composite film; the two steps from pulling to dripping are repeated to form a layer of sandwich-like structure to form a composite film; (4) And (3) rolling the film manufactured in the step (3) along the length direction, and twisting the film into fibers to obtain the carbon nano tube/zinc powder composite fiber negative electrode. The super-cis-carbon nanotube array of the scheme is the existing content and can be prepared by adopting the method in the following prior art: continuously spinnable carbon nanotube filaments, fan Shoushan, etc., nature 2002, volume 419, page 801. And will not be described in detail herein.
In the invention, the preparation steps of the organic gel electrolyte are as follows: (1) Mixing dichloromethane and acetone according to the mass ratio of (20-30): 1 to obtain a solution A; (2) 0.8g-1.4g of polyethylene oxide and 1g-2g of zinc bistrifluoromethane sulfonyl imide are mixed with 5-10mL of solution A, and the mixture is fully stirred, so as to obtain the organogel electrolyte.
In the invention, the preparation steps of the hydrogel electrolyte precursor are as follows: (1) 8mL-12mL of ultrapure water is measured; (2) Adding 1g-1.5g of acrylamide, 2.5g-3.5g of zinc acetate and 1g-2g of potassium chloride into the ultrapure water in the step (1), stirring and dissolving at normal temperature to form a uniform solution A; (3) 0.06g-0.12g ammonium persulfate, 0.006g-0.012g N, N' -methylene bisacrylamide and 0.01g-0.04g ethylene diamine tetraacetic acid dipotassium are added into the solution A, stirred and dissolved at normal temperature to form a uniform solution and stirred continuously.
In the invention, the hydrogel electrolyte is in-situ gelled on the fiber electrode as follows: (1) Filling a mixed solution of a water gel electrolyte precursor and tetramethyl ethylenediamine in a volume ratio of (20-40) in a tubular mold with an inner diameter of 300-500 μm; (2) Placing the fiber electrode into a mold, and waiting for 5-15 min to enable the precursor electrolyte to gel on the fiber electrode in situ.
In the invention, the preparation steps of the platinum/ruthenium oxide nanoparticle modified carbon nanotube film anode are as follows: (1) Drawing a layer of carbon nanotube film with the length of 3cm-5cm and the width of 0.5cm-1cm from the super-parallel carbon nanotube array, continuously and repeatedly drawing for a plurality of times, such as 4-8 times, overlapping the drawn films, then dripping absolute ethyl alcohol on the overlapped films, and airing; firstly, absolute ethyl alcohol is dripped on a carbon nano tube film and can permeate into the whole film, then the absolute ethyl alcohol volatilizes, the space between carbon tubes is reduced due to the action of surface tension, and Van der Waals force is enhanced, so that the carbon nano tube film pulled for multiple times forms a whole; (2) Electrodepositing 0.3mg-0.6mg of platinum particles on the film manufactured in the step (1) by adopting an arbitrary potentiostatic method; (3) Mixing 25mg-50mg of ruthenium oxide powder with 10mL-15mL of absolute ethyl alcohol, and performing ultrasonic treatment to form uniform dispersion A; (4) And (3) dropwise adding 40-80 mu L of dispersion liquid A on the film treated in the step (2), and airing the dispersion liquid A to obtain the platinum/ruthenium oxide nanoparticle modified carbon nanotube film anode.
The maximum charge-discharge current of the neutral zinc-air fiber battery with high multiplying power and high energy efficiency is 160mA/g, and the maximum energy efficiency is 68%, so that the high-efficiency neutral zinc-air fiber battery reaches an advanced level in the field of neutral zinc-air batteries; the fiber battery has extremely low bending rigidity on the whole, can still work normally under the condition of complex deformation, and has application potential in the field of wearable new energy.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
the invention takes the carbon nano tube/zinc powder composite fiber as the negative electrode to replace the traditional zinc wire or zinc foil negative electrode, so the whole battery has better flexibility. In addition, the ultrahigh specific surface area of the zinc powder brings a larger reaction contact area with the electrolyte, so that the problem of poor reactivity of zinc metal in the neutral electrolyte is solved, and the rate performance and the energy efficiency of the battery are improved.
Drawings
FIG. 1 is a schematic diagram of a neutral zinc-air fiber battery of the present invention;
FIG. 2 is a graph comparing bending stiffness curves of a zinc-air cell of an embodiment with a conventional zinc wire negative electrode;
FIG. 3 shows charge and discharge curves in three bending states according to an embodiment;
fig. 4 is a graph comparing the performance of an example with a neutral zinc-air cell previously reported.
Detailed Description
The invention will now be described in detail with reference to the drawings and the accompanying specific examples.
Example 1
The following description is exemplary and helps to further understand the present invention, but the specific details of the embodiments are only for illustrating the present invention, and not for representing all technical solutions under the concept of the present invention, and therefore should not be construed as limiting the general technical solutions of the present invention, and some insubstantial additions and modifications, such as simple changes or substitutions with technical features having the same or similar technical effects, which do not deviate from the concept of the present invention, are considered by the skilled person, and all fall within the scope of the present invention.
As shown in fig. 1, the steps of this embodiment are as follows:
preparing the carbon nano tube/zinc powder composite fiber electrode. Adding 75mg of zinc powder into 4mL of absolute ethyl alcohol, and performing ultrasonic treatment on the zinc powder to form a relatively uniform dispersion liquid A; drawing a layer of carbon nanotube film with the length of 3cm and the width of 0.5cm from the super-parallel carbon nanotube array, sucking 20 mu L of dispersion liquid A, uniformly dripping the dispersion liquid A on the carbon nanotube film, standing for 1min to air, and repeating the steps for 2 times to obtain a carbon nanotube/zinc powder composite film; and rolling the film along the length direction, and twisting the film into fibers to obtain the carbon nano tube/zinc powder composite fiber negative electrode.
And preparing the organic gel electrolyte. Mixing dichloromethane and acetone according to the mass ratio of 20:1 to obtain a solution A; 0.8g of polyethylene oxide and 1.0g of zinc bistrifluoromethane sulfonyl imide were mixed with 5mL of solution A, and the mixture was sufficiently stirred to obtain an organogel electrolyte.
Preparing a hydrogel electrolyte precursor. 8mL of ultrapure water is measured; adding 1g of acrylamide, 2.5g of zinc acetate and 1g of potassium chloride into ultrapure water, stirring at normal temperature for dissolution to form a uniform solution A; 0.05g of ammonium persulfate, 0.005g of N, N' -methylenebisacrylamide and 0.01g of dipotassium ethylenediamine tetraacetate were added to the solution A, and the solution was dissolved by stirring at normal temperature to form a uniform solution and stirring was continued.
And preparing the carbon nano tube film anode modified by the platinum/ruthenium oxide nano particles. Drawing a layer of carbon nanotube film with the length of 3cm and the width of 0.5cm from the super-parallel carbon nanotube array, continuously and repeatedly drawing for 4 times to ensure that the layers of film are overlapped into a whole film, then dripping absolute ethyl alcohol on the film, and airing the film; electrodepositing 0.3mg of platinum particles on the carbon nano tube film by adopting an arbitrary potentiostatic method; mixing 25mg of ruthenium oxide powder with 10mL of absolute ethyl alcohol, and performing ultrasonic treatment to form uniform dispersion A; and (3) dropwise adding 40 mu L of dispersion liquid A on the carbon nano tube film deposited with the platinum nano particles, and airing the dispersion liquid A to obtain the anode of the carbon nano tube film modified by the platinum/ruthenium oxide nano particles.
And assembling the neutral zinc-air battery. Soaking the carbon nano tube/zinc powder composite fiber cathode in the organic gel electrolyte for 1min, taking out, and airing in the air for 5min to solidify the organic gel electrolyte. Filling a mixed solution of a water gel electrolyte precursor and tetramethyl ethylenediamine in a tubular mold with an inner diameter of 300 mu m according to a volume ratio of 20:1; placing the fiber electrode coated by the organic gel electrolyte into a mold, and waiting for 5min to enable the precursor electrolyte to gel on the fiber electrode in situ; and (5) demolding, and taking out the fiber negative electrode wrapped by the hydrogel. Winding the anode of the carbon nano tube film decorated by the platinum/ruthenium oxide nano particles on the cathode of the carbon nano tube/zinc powder composite fiber wrapped by the double-layer gel.
The invention takes the carbon nano tube/zinc powder composite fiber as the negative electrode to replace the traditional zinc wire or zinc foil negative electrode, so the whole battery has better flexibility. In addition, the ultrahigh specific surface area of the zinc powder brings a larger reaction contact area with the electrolyte, so that the problem of poor reactivity of zinc metal in the neutral electrolyte is solved, and the rate performance and the energy efficiency of the battery are improved. The fiber battery can perform charge and discharge reaction with the energy efficiency of 68% at the highest in the air, and the maximum charge and discharge current is 160mA/g, so that the fiber battery reaches an advanced level in the field of neutral zinc-air batteries; the fiber battery has extremely low bending rigidity on the whole, can still work normally under the condition of complex deformation, and has application potential in the field of wearable new energy. As can be seen from fig. 2, 3 and 4, the carbon nanotube/zinc powder composite fiber manufactured by the scheme generates much smaller stress than zinc wires when being bent, and shows excellent flexibility. The neutral zinc-air battery maintains good charge and discharge performance under different deformation states. Has advantages in terms of current density and energy efficiency.
Example 2
Preparing the carbon nano tube/zinc powder composite fiber electrode. Adding 100mg of zinc powder into 6mL of absolute ethyl alcohol, and performing ultrasonic treatment on the zinc powder to form a relatively uniform dispersion liquid A; drawing a layer of carbon nano tube film with the length of 4cm and the width of 0.8cm from the super-parallel carbon nano tube array, sucking 40 mu L of dispersion liquid A, uniformly dripping the dispersion liquid A on the carbon nano tube film, standing for 2min to air, and repeating the steps for 3 times to obtain a carbon nano tube/zinc powder composite film; and rolling the film along the length direction, and twisting the film into fibers to obtain the carbon nano tube/zinc powder composite fibers.
And preparing the organic gel electrolyte. Mixing dichloromethane and acetone according to the mass ratio of 25:1 to obtain a solution A; 1.2g of polyethylene oxide and 1.5g of zinc bistrifluoromethane sulfonyl imide were mixed with 7.5mL of solution A, and the mixture was sufficiently stirred to obtain an organogel electrolyte.
Preparing a hydrogel electrolyte precursor. Weighing 10mL of ultrapure water; adding 1.2g of acrylamide, 3g of zinc acetate and 1.2g of potassium chloride into ultrapure water, stirring and dissolving at normal temperature to form a uniform solution A; to the solution A, 0.08g of ammonium persulfate, 0.008g of N, N' -methylenebisacrylamide and 0.04g of dipotassium ethylenediamine tetraacetate were added, and the mixture was dissolved by stirring at normal temperature to form a uniform solution and stirring was continued.
And preparing the carbon nano tube film anode modified by the platinum/ruthenium oxide nano particles. Drawing a layer of carbon nanotube film with the length of 4cm and the width of 0.6cm from the super-parallel carbon nanotube array, continuously and repeatedly drawing for 5 times to ensure that the layers of film are overlapped into a whole film, then dripping absolute ethyl alcohol on the film, and airing the film; electrodepositing 0.4mg of platinum particles on the carbon nano tube film by adopting an arbitrary potentiostatic method; mixing 40mg of ruthenium oxide powder with 12mL of absolute ethyl alcohol, and performing ultrasonic treatment to form uniform dispersion A; and (3) dropwise adding 60 mu L of dispersion liquid A on the carbon nano tube film deposited with the platinum nano particles, and airing the dispersion liquid A to obtain the anode of the carbon nano tube film modified by the platinum/ruthenium oxide nano particles.
And assembling the neutral zinc-air battery. Soaking the carbon nano tube/zinc powder composite fiber cathode in the organic gel electrolyte for 2min, taking out, and airing in the air for 8min to solidify the organic gel electrolyte. Filling a mixed solution of a water gel electrolyte precursor and tetramethyl ethylenediamine in a tubular mold with an inner diameter of 350 mu m according to a volume ratio of 25:1; placing the fiber electrode coated by the organic gel electrolyte into a mold, and waiting for 8min to enable the precursor electrolyte to gel on the fiber electrode in situ; and demolding, and taking out the composite fiber wrapped by the hydrogel, wherein the composite fiber is used as a negative electrode. Winding the anode of the carbon nano tube film decorated by the platinum/ruthenium oxide nano particles on the cathode of the carbon nano tube/zinc powder composite fiber wrapped by the double-layer gel.
Example 3
Preparing the carbon nano tube/zinc powder composite fiber electrode. 125mg of zinc powder is added into 8mL of absolute ethyl alcohol, and ultrasonic treatment is carried out on the zinc powder to form a relatively uniform dispersion liquid A; drawing a layer of carbon nanotube film with the length of 5cm and the width of 1.5cm from the super-parallel carbon nanotube array, sucking 60 mu L of dispersion liquid A, uniformly dripping the dispersion liquid A on the carbon nanotube film, standing for 5min to air, and repeating the steps for 4 times to obtain a carbon nanotube/zinc powder composite film; and rolling the film along the length direction, and twisting the film into fibers to obtain the carbon nano tube/zinc powder composite fiber negative electrode.
And preparing the organic gel electrolyte. Mixing dichloromethane and acetone according to the mass ratio of 30:1 to obtain a solution A; 1.4g of polyethylene oxide and 2g of zinc bistrifluoromethane sulfonyl imide were mixed with 10mL of solution A and stirred well to obtain an organogel electrolyte.
Preparing a hydrogel electrolyte precursor. Measuring 12mL of ultrapure water; adding 1.5g of acrylamide, 3.5g of zinc acetate and 2g of potassium chloride into ultrapure water, stirring and dissolving at normal temperature to form a uniform solution A; 0.12g of ammonium persulfate, 0.012g of N, N' -methylenebisacrylamide and 0.03g of dipotassium ethylenediamine tetraacetate were added to the solution A, and stirred at normal temperature to dissolve, thereby forming a uniform solution and stirring continuously.
And preparing the carbon nano tube film anode modified by the platinum/ruthenium oxide nano particles. Drawing a layer of carbon nanotube film with the length of 5cm and the width of 1cm from the super-parallel carbon nanotube array, continuously and repeatedly drawing for 8 times to ensure that the layers of film are overlapped into a whole film, then dripping absolute ethyl alcohol on the whole film, and airing the whole film; electrodepositing 0.6mg platinum particles on the carbon nano tube film by adopting an arbitrary potentiostatic method; mixing 50mg of ruthenium oxide powder with 15mL of absolute ethyl alcohol, and performing ultrasonic treatment to form uniform dispersion A; and (3) dropwise adding 80 mu L of dispersion liquid A on the carbon nano tube film deposited with the platinum nano particles, and airing the dispersion liquid A to obtain the anode of the carbon nano tube film modified by the platinum/ruthenium oxide nano particles.
And assembling the neutral zinc-air battery. Soaking the carbon nano tube/zinc powder composite fiber cathode in the organic gel electrolyte for 5min, taking out, and airing in the air for 15min to solidify the organic gel electrolyte. Filling a mixed solution of a gel electrolyte precursor and tetramethyl ethylenediamine into a tubular mold with an inner diameter of 500 μm according to a volume ratio of 30:1; placing the fiber electrode coated by the organic gel electrolyte into a mold, and waiting for 15min to enable the precursor electrolyte to gel on the fiber electrode in situ; and (5) demolding, and taking out the fiber negative electrode wrapped by the hydrogel. Winding the anode of the carbon nano tube film decorated by the platinum/ruthenium oxide nano particles on the cathode of the carbon nano tube/zinc powder composite fiber wrapped by the double-layer gel.
Example 4
The battery is made by the method, and the battery structure is composed of a carbon nano tube/zinc powder composite fiber cathode, a double-layer gel electrolyte and a platinum/ruthenium oxide nano particle modified carbon nano tube film anode in a coaxial structure.
The foregoing has been described schematically the invention and embodiments thereof, which are not limiting, but are capable of other specific forms of implementing the invention without departing from its spirit or essential characteristics. The drawings are also intended to depict only one embodiment of the invention, and therefore the actual construction is not intended to limit the claims, any reference number in the claims not being intended to limit the claims. Therefore, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical scheme are not creatively designed without departing from the gist of the present invention, and all the structural manners and the embodiment are considered to be within the protection scope of the present patent. In addition, the word "comprising" does not exclude other elements or steps, and the word "a" or "an" preceding an element does not exclude the inclusion of a plurality of such elements. The various elements recited in the product claims may also be embodied in software or hardware. The terms first, second, etc. are used to denote a name, but not any particular order.

Claims (9)

1. A preparation method of a neutral zinc-air fiber battery comprises the following steps:
preparing a carbon nano tube/zinc powder composite fiber;
preparing an organic gel electrolyte, soaking the prepared composite fiber electrode in the organic gel electrolyte, taking out and airing in air to solidify the organic gel electrolyte;
preparing a hydrogel electrolyte precursor, and enabling the hydrogel electrolyte precursor to gel on the composite fiber solidified by the organic gel electrolyte in situ to obtain a fiber negative electrode wrapped by double-layer gel;
and winding the carbon nano tube film anode modified by the platinum/ruthenium oxide nano particles on the fiber cathode wrapped by the double-layer gel.
2. The method for preparing the neutral zinc-air fiber battery according to claim 1, wherein the preparation steps of the carbon nano tube/zinc powder composite fiber are as follows:
adding 75mg-125mg of zinc powder into 4mL-8mL of absolute ethyl alcohol, and performing ultrasonic treatment to the zinc powder to form a dispersion liquid A;
drawing a layer of carbon nanotube film with the length of 3cm-5cm and the width of 0.5cm-1.5cm from the super-parallel carbon nanotube array, sucking 20 mu L-60 mu L of dispersion liquid A, uniformly dripping the dispersion liquid A on the carbon nanotube film, standing for 1min-5min, and airing;
repeating the steps of pulling out the carbon nanotube film and dripping the dispersion liquid A on the dried film for a plurality of times to obtain a carbon nanotube/zinc powder composite film;
and rolling the carbon nano tube/zinc powder composite film manufactured in the previous step along the length direction, and twisting the carbon nano tube/zinc powder composite film into fibers to be used as the carbon nano tube/zinc powder composite fibers.
3. The method for preparing a neutral zinc-air fiber battery according to claim 1, wherein the organogel electrolyte is prepared by the steps of:
mixing dichloromethane and acetone according to the mass ratio of (20-30): 1 to obtain a solution A;
0.8g-1.4g of polyethylene oxide and 1g-2g of zinc bistrifluoromethane sulfonyl imide are mixed with 5-10mL of solution A, and the mixture is fully stirred, so as to obtain the organogel electrolyte.
4. The method for preparing a neutral zinc-air fiber battery according to claim 1, wherein,
the preparation method of the hydrogel electrolyte precursor comprises the following steps:
8mL-12mL of ultrapure water is taken;
adding 1g-1.5g of acrylamide, 2.5g-3.5g of zinc acetate and 1g-2g of potassium chloride into ultrapure water, stirring and dissolving at normal temperature to form uniform precursor solution A;
0.05g-0.12g of ammonium persulfate, 0.005g-0.012g of N, N' -methylene bisacrylamide and 0.02g-0.04g of ethylene diamine tetraacetic acid dipotassium are added into the solution A, and stirred and dissolved at normal temperature to form a uniform hydrogel electrolyte precursor solution.
5. The method for preparing the neutral zinc-air fiber battery according to claim 1, wherein the specific step of curing the organogel electrolyte is that the fiber electrode is soaked in the organogel electrolyte for 1min to 5min, and then taken out and dried in the air for 5min to 15min.
6. The method for preparing a neutral zinc-air fiber battery according to claim 1 or 5, wherein the specific step of in-situ gelation of the hydrogel electrolyte precursor is,
filling a mixed solution of a water gel electrolyte precursor and tetramethyl ethylenediamine in a volume ratio of (20-40) in a tubular mold with an inner diameter of 300-500 μm;
and placing the composite fiber electrode coated by the organic gel electrolyte into a mold, and waiting for 5-15 min to enable the precursor electrolyte to gel on the fiber electrode in situ.
7. The method for preparing a neutral zinc-air fiber battery according to claim 1 or 2, wherein the preparation steps of the platinum/ruthenium oxide nanoparticle modified carbon nanotube film positive electrode are as follows:
drawing a layer of carbon nanotube film with the length of 3cm-5cm and the width of 0.5cm-1cm from the super-parallel carbon nanotube array, continuously and repeatedly drawing for a plurality of times, overlapping the drawn films, then dripping absolute ethyl alcohol on the overlapped films, and airing;
electrodepositing 0.3mg-0.6mg of platinum particles on the dried film;
mixing 25mg-50mg of ruthenium oxide powder with 10mL-15mL of absolute ethyl alcohol, and performing ultrasonic treatment to form uniform dispersion A;
and (3) dropwise adding 40-80 mu L of dispersion liquid A on the film deposited with the platinum particles through the steps, and airing the dispersion liquid A to obtain the carbon nano tube film anode modified by the platinum/ruthenium oxide nano particles.
8. The method of making a neutral zinc-air fiber battery according to claim 7, wherein the platinum particles are deposited using any potentiostatic method.
9. A neutral zinc-air fiber battery manufactured based on the method of any one of claims 1-8, which is characterized in that the battery structure is that a carbon nano tube/zinc powder composite fiber cathode arranged from inside to outside, a double-layer gel electrolyte and a platinum/ruthenium oxide nano particle modified carbon nano tube film anode are formed in a coaxial structure.
CN202310347501.6A 2023-04-03 2023-04-03 Neutral zinc air fiber battery and preparation method thereof Pending CN116207410A (en)

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