CN113097496B - Zinc cathode with composite nanofiber protective layer and preparation and application thereof - Google Patents

Zinc cathode with composite nanofiber protective layer and preparation and application thereof Download PDF

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CN113097496B
CN113097496B CN202110207860.2A CN202110207860A CN113097496B CN 113097496 B CN113097496 B CN 113097496B CN 202110207860 A CN202110207860 A CN 202110207860A CN 113097496 B CN113097496 B CN 113097496B
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zinc
composite nanofiber
protective layer
hollow
electrostatic spinning
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CN113097496A (en
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张晶晶
李光
彭威
郑丽媛
金俊弘
杨胜林
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Donghua 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a zinc cathode with a composite nanofiber protective layer and preparation and application thereof, wherein the method comprises the steps of preparing composite nanofibers through coaxial electrostatic spinning; removing the sacrificial high molecular polymer in the composite nanofiber to obtain the porous multi-hollow composite nanofiber; then mixing the porous multi-hollow composite nano fiber with an adhesive and a solvent C to obtain suspension slurry; finally, uniformly coating the suspension slurry on the surface of the zinc cathode substrate layer to obtain the zinc cathode with the composite nanofiber protective layer; the prepared zinc cathode comprises a zinc cathode substrate layer and a protective layer coated on the substrate layer; the protective layer is mainly formed by stacking porous multi-hollow composite nano fibers; the zinc cathode with the composite nanofiber protective layer is applied to the zinc-air battery, so that the cycling stability, the coulombic efficiency and the safety of the battery are obviously improved. And the protective layer can effectively inhibit the penetration of zinc dendrites, thereby greatly prolonging the service life of the material and widening the application field.

Description

Zinc cathode with composite nanofiber protective layer and preparation and application thereof
Technical Field
The invention belongs to the technical field of energy materials, and relates to a zinc cathode with a composite nanofiber protective layer, and preparation and application thereof.
Background
Energy crisis and environmental pollution have become the serious challenges facing all mankind today, forcing people to improve existing energy structures, develop clean, efficiently-available renewable energy and related technologies. The utilization of renewable energy sources including solar energy, tidal energy, wind energy, hydroenergy, nuclear energy, biomass energy and the like requires a matched energy storage battery to realize stable output, so that the development of a novel, environment-friendly and efficient energy storage device is very important.
The zinc cathode has the excellent performances of rich resources, low price, high energy density, environmental friendliness and the like, and is widely applied to zinc-air batteries, zinc ion batteries, zinc-silver batteries, zinc-nickel batteries, zinc-bromine flow batteries and the like. However, the severe zinc dendrite growth caused by uneven zinc dissolution and deposition in the circulation process leads to short cycle life and low coulombic efficiency of the zinc-based battery, and the practical application of the zinc-based battery is severely restricted. In the method for improving the zinc cathode, the construction of a stable zinc protection interface is one of the most direct and effective methods, and has very important significance. Chinese patent CN111162260A discloses that the electrochemical performance of an aqueous zinc ion battery is improved by coating a conductive polymer on the surface of a zinc negative electrode by electrochemical polymerization or chemical polymerization, but the mechanical strength of a single polymer is not enough to inhibit the growth and puncture of zinc dendrites. Chinese patent CN111600025A discloses a zinc cathode using a high molecular polymer and inorganic nanoparticles as a protective layer to improve the mechanical strength of the protective layer, but directly dispersing the nano-scale inorganic nanoparticles in the high molecular polymer is often accompanied by the problem of agglomeration or uneven dispersion of the inorganic nanoparticles. The protective layer material with the three-dimensional structure can improve the specific surface area of the material, thereby reducing the local current density of the electrode and inducing the uniform nucleation and deposition of zinc ions. Chinese patent CN110364732A discloses a method for preparing a zinc cathode with an inorganic function modification layer, in which a conductive material such as carbon fiber or carbon nanotube, an inorganic ceramic powder, a binder and a solvent are mixed and coated on the surface of the zinc cathode as a protective layer, but the slurry method is still applied to mix the conductive material such as carbon fiber or carbon nanotube and the inorganic ceramic powder, and the problems of non-uniform dispersion of the conductive material and the inorganic particles and easy agglomeration of the particles still exist. Meanwhile, the improvement of the specific surface area is limited only by relying on the three-dimensional stacking structure of the materials.
Therefore, the research on the zinc cathode material containing the ideal protective layer is of great significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a zinc cathode with a composite nanofiber protective layer, and preparation and application thereof. The three-dimensional porous hollow structure of the composite nanofiber protective layer has larger specific surface area, and can reduce the current density near the electrode, thereby slowing the growth of dendritic crystals; the multi-stage nano-pore structure and the hydrophilic and zinc-philic inorganic nano-particles are beneficial to uniform diffusion of electrolyte and zinc ions and reduction of mass transfer impedance of an electrolyte-electrode interface; meanwhile, the higher mechanical strength of the protective layer is ensured by adding the inorganic nano particles, so that the growth and the penetration of zinc dendrites are effectively inhibited. The zinc cathode with the composite nanofiber protective layer is applied to the zinc-air battery, so that the cycling stability, the coulombic efficiency and the safety of the battery are obviously improved. The zinc cathode with the protective layer can also be used for zinc ion batteries, zinc silver batteries, zinc nickel batteries, zinc bromine flow batteries and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the zinc cathode with the composite nanofiber protective layer comprises a zinc cathode substrate layer and a protective layer coated on the substrate layer; the protective layer is mainly formed by stacking porous multi-hollow composite nano fibers; the porous multi-hollow composite nanofiber refers to a composite nanofiber which is provided with a plurality of hollow pipelines and a three-dimensional through hole micro-nano structure from the surface to the hollow.
As a preferred technical scheme:
in the zinc negative electrode with the composite nanofiber protective layer, the material of the substrate layer is a zinc simple substance or a zinc alloy.
The zinc cathode with the composite nanofiber protective layer comprises the porous multi-hollow composite nanofiber containing inorganic nanoparticles, wherein the inorganic nanoparticles are TiO2And more than one of ZnO and SnO, wherein the particle size of the inorganic nano-particles is 2-50 nm.
The zinc cathode with the composite nanofiber protective layer further comprises a binder, and the porous multi-hollow composite nanofiber accounts for 70-99% of the total mass of the protective layer.
The stacking of the zinc cathode with the composite nanofiber protective layer refers to that the porous hollow composite nanofiber layers inside the protective layer are stacked layer by layer to form a three-dimensional interpenetrating network and a stacked pore structure.
According to the zinc cathode with the composite nanofiber protective layer, the average diameter of the porous multi-hollow composite nanofiber is 100-1000 nm, the fiber wall has a porous structure, and the pore diameter is 5-200 nm.
According to the zinc cathode with the composite nanofiber protective layer, the hollow pipelines of the porous multi-hollow composite nanofiber mean 2-15 hollow pipelines, and the diameter of each hollow pipeline is 10-150 nm.
In the zinc cathode with the composite nanofiber protective layer, the three-dimensional through hole is a through hole structure which connects the hollow part inside the fiber and the three-dimensional stacked holes between the fibers through the holes on the fiber wall.
The zinc negative electrode with the composite nanofiber protective layer comprises the porous multi-hollow composite nanofiber made of a single material or the porous multi-hollow composite nanofiber made of more than two different materials; the porous multi-hollow composite nanofiber is made of carbon materials and/or polymer materials.
The zinc negative electrode with the composite nanofiber protective layer has the thickness of not more than 200 μm, and the young modulus of the protective layer is 1GPa to 20 GPa.
The invention also provides a preparation method of the zinc cathode with the composite nanofiber protective layer, which comprises the following steps:
firstly, preparing composite nano fibers by coaxial electrostatic spinning; the outer layer solution of the coaxial electrostatic spinning consists of a sacrificial high molecular polymer, a retention high molecular polymer and a solvent A; the inner layer solution of the coaxial electrostatic spinning consists of a sacrificial high molecular polymer, a material which can generate a substance with semiconductor characteristics and low surface energy in the spinning process and a solvent B;
removing the sacrificial high molecular polymer in the composite nanofiber to obtain the porous multi-hollow composite nanofiber;
mixing the porous multi-hollow composite nano fiber with an adhesive and a solvent C to obtain suspension slurry;
and uniformly coating the suspension slurry on the surface of the zinc cathode substrate layer to obtain the zinc cathode with the composite nanofiber protective layer.
The porous multi-hollow composite nanofiber prepared by utilizing the coaxial electrostatic spinning technology has the advantages of controllable appearance, structure, mechanical strength, oxide content and the like. During spinning, the metal source is dispersed homogeneously in the spinning solution of high molecular polymer and hydrolyzed slowly into metal oxide grains of relatively small size, such as titania, tin oxide and zinc oxide. Since these metal oxides have low surface energy, they are uniformly diffused in the inner spinning solution. Meanwhile, based on the semiconductor characteristics of the metal oxide nanoparticles, the metal oxide nanoparticles can directionally migrate along the axial direction of the fiber under the action of an electric field, so that the metal oxide nanoparticles are directionally assembled in the polymer fiber. The metal oxide loading with different loading amounts can be realized by regulating the content of the metal source in the spinning solution. Through subsequent carbonization or solvent soaking, in the inner layer solution of electrostatic spinning, the sacrificial high molecular polymer is completely removed, and a multi-hollow structure is left; in the solution of the electrostatic spinning outer layer, the sacrificial high molecular polymer is completely removed, so that a through hole structure which is hollow inside the connection structure is generated. The metal oxide is generated in situ in the fiber and forms a continuous framework along the axial direction of the fiber, so that the metal oxide has better viscosity with the fiber, and the flexibility and the mechanical strength of the fiber are improved.
As a preferred technical scheme:
in the above-mentioned preparation method, the sacrificial polymer and the retention polymer are the sacrificial polymers that can be removed by retaining the retention polymer under a certain treatment condition.
According to the preparation method, in the coaxial electrostatic spinning inner layer solution, the molar ratio of a material capable of generating a substance with semiconductor characteristics and low surface energy to the sacrificial high polymer in the spinning process is 1-5000: 1; the mass ratio of the sacrificial high molecular polymer to the solvent is 20-50: 100; in the coaxial electrostatic spinning outer layer solution, the mass ratio of the retention type high molecular polymer to the sacrificial type high molecular polymer to the solvent A is 8-13: 2-7: 100.
In the above preparation method, the sacrificial polymer is at least one of polymethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol and polystyrene.
In the preparation method, the retention type high molecular polymer is more than one of polyacrylonitrile, phenolic resin and cellulose.
In the preparation method, the solvent A or the solvent B is more than one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and ethanol.
According to the preparation method, a material which can generate a substance with both semiconductor characteristics and low surface energy in the spinning process is taken as a metal source; the metal source is more than one of a titanium source, a zinc source and a tin source; the titanium source is tetrabutyl titanate, isopropyl titanate, tetraethyl titanate or titanium tetrachloride; the zinc source is zinc acetate, zinc nitrate or zinc chloride; the tin source is tin acetate, tin tetrachloride, stannous chloride, tin hydroxide, stannous sulfate or stannous oxalate.
The preparation method comprises the following steps: dissolving the sacrificial high molecular polymer in the solvent B at 15-60 ℃, stirring for 2-12 h, then adding a metal source, stirring for 0.5-12 h, and uniformly mixing; the preparation method of the coaxial electrostatic spinning outer layer solution comprises the following steps: dissolving a sacrificial high-molecular polymer and a retention high-molecular polymer in a solvent A at 15-60 ℃, stirring for 2-12 h, and uniformly mixing; the flow rate ratio of the inner layer solution to the outer layer solution of the coaxial electrostatic spinning is 1 (1-5), and the total liquid supply flow rate is 0.3-6 mL/h; the distance between the needle head and the receiving plate is 10-30 cm; the voltage is 1-40 kV; the ambient temperature is 10-50 ℃; the environmental humidity is 20-80%; the receiving device is a metal roller, and the rotating speed of the roller is 20-100 r/min.
The preparation method as described above, wherein the certain treatment condition is carbonization or solvent soaking.
According to the preparation method, in the carbonization process, the pre-oxidation temperature is 200-300 ℃, and the time is 0.5-2.5 h; the temperature of the carbonization treatment is 450-1000 ℃, and the time is 1-5 h.
In the preparation method, in the solvent soaking process, the solvent D is more than one of high-purity water, methanol, ethanol, propanol, butanol, cyclohexanol, chloroform, dichloromethane, propylene glycol, butanediol, glycerol, triethanolamine, acetic acid and carbonate, the soaking time is 1-24 h, and the soaked nanofibers are washed 3-5 times by the solvent D.
In the preparation method, the binder is perfluorosulfonic acid resin (Nafion), polyvinylidene fluoride, polyvinyl chloride, polyetherimide, polyacrylic acid group or carboxymethyl cellulose group, and the solvent C is ethanol, cyclohexanone, N-methyl pyrrolidone or high-purity water.
According to the preparation method, the concentration of the composite nano fibers in the suspension slurry is 5-100 mg/mL.
The invention also provides the application of the zinc cathode with the composite nanofiber protective layer, and the zinc cathode with the composite nanofiber protective layer is used as an anode to prepare the zinc-air battery.
As a preferred technical scheme:
in the above-described application, the air electrode of the zinc-air battery is a gas diffusion layer carrying a catalyst; the electrolyte of the zinc-air battery is a mixture of potassium hydroxide, zinc acetate and ultrapure water; the current collector of the zinc-air battery is a stainless steel mesh or a copper foil.
The preparation process of the gas diffusion layer comprises the following steps: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode;
Pt/C + IrO in dispersion2The concentration of the powder (the mass ratio is 1: 1) is 0.5-3 mg/mL, and the concentration is more preferably 2 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 0.8-1.2 mg/cm2More preferably 1mg/cm2。
In the above application, the concentration of potassium hydroxide in the mixture is 4-8 mol/L, more preferably 6mol/L, and the concentration of zinc acetate is 0.1-0.5 mol/L, more preferably 0.2 mol/L.
In the application, the zinc-air battery is subjected to a charge and discharge performance test, and the test result is as follows: at 5-50 mA/cm2The current density of the charge-discharge circuit is 10min, 5min of charge-discharge and 5min of charge-discharge are carried out in each period, and 100-1500 circles can be circulated.
The principle of the invention is as follows:
according to the zinc cathode with the porous multi-hollow composite nanofiber protective layer, the three-dimensional porous hollow structure of the composite nanofiber protective layer enables the composite nanofiber protective layer to have a large specific surface area, and the current density near the electrode can be reduced, so that the growth of dendritic crystals is slowed down; the multi-stage nano-pore structure and the hydrophilic and zinc-philic inorganic nano-particles are beneficial to uniform diffusion of electrolyte and zinc ions and reduction of mass transfer impedance of an electrolyte-electrode interface; meanwhile, the higher mechanical strength of the protective layer is ensured by adding the inorganic nano particles, so that the growth and the penetration of zinc dendrites are effectively inhibited. The zinc cathode with the composite nanofiber protective layer is applied to the zinc-air battery, so that the cycling stability, the coulombic efficiency and the safety of the battery are obviously improved. At 5-50 mA/cm2The current density of the charge-discharge circuit is 10min, 5min of charge-discharge and 5min of charge-discharge are carried out in each period, and 100-1500 circles can be circulated.
Advantageous effects
(1) The zinc cathode with the composite nanofiber protective layer, which is prepared by the invention, has better mechanical strength on the premise of ensuring larger specific surface area of the material, solves the problems of fragility, low mechanical strength and the like of a porous composite fiber material and a single hollow fiber material, can effectively inhibit penetration of zinc dendrites, and greatly expands the service life and application field of the material;
(2) according to the zinc cathode with the composite nanofiber protective layer, fibers in the protective layer are provided with a plurality of hollow pipelines and a three-dimensional through hole micro-nano structure from the surface to the hollow, and the abundant multi-stage nano hole structures can guide electrolyte to be uniformly diffused to the surface of the zinc cathode, so that zinc ions can be transferred in a limited domain and uniformly deposited. Meanwhile, the special pore structure of the protective layer material also has wide practical application value, and can be applied to the technical fields of lithium ion batteries, solid-state lithium ion batteries, lithium-sulfur batteries, metal air batteries, solar batteries, optical catalysis, filtration, membrane separation and the like;
(3) the electrostatic spinning technology used in the invention has the advantages of simple equipment, low cost and more spinnable raw materials, and the porous multi-hollow carbon composite nanofiber protective layer material prepared by the method has lower carbonization temperature and shorter carbonization time; the porous multi-hollow polymer composite nanofiber protective layer material is removed by utilizing the characteristic that the sacrificial high molecular polymer is dissolved in some solvents, so that the production cost is greatly reduced; according to the zinc cathode with the composite nanofiber protective layer, in the preparation of the protective layer, the carbonization temperature and the carbonization time for preparing the porous multi-hollow flexible carbon composite nanofiber membrane material are low; the porous multi-hollow flexible polymer composite nanofiber membrane material is prepared by soaking and removing the sacrificial high molecular polymer by utilizing the characteristic that the sacrificial high molecular polymer is dissolved in some solvents, and the process is simple;
(4) according to the zinc cathode with the composite nanofiber protective layer, the content of the metal oxide of the porous multi-hollow composite nanofiber material in the protective layer is controllable, the porous multi-hollow composite nanofiber material is easy to disperse, and the potential energy of large-scale production is high;
(5) according to the zinc cathode with the composite nanofiber protective layer, the three-dimensional porous structure and the multi-hollow pipeline of the composite nanofiber in the protective layer are beneficial to reducing the local current density of the electrode and the limited-domain transmission and uniform deposition of zinc ions. The uniformly dispersed metal oxide improves the wettability and zinc affinity of the electrolyte, improves the mechanical strength of the protective layer, and effectively inhibits the penetration of zinc dendrites and potential safety hazards caused by the penetration;
(6) the zinc cathode with the composite nanofiber protective layer prepared by the invention can also be used for zinc ion batteries, zinc silver batteries, zinc-nickel batteries, zinc-bromine flow batteries and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a porous multi-hollow composite nanofiber prepared in examples 1-7;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the porous multi-hollow composite nanofiber prepared in examples 1-6;
FIG. 3 is a thermogravimetric plot (TGA) of the porous multi-hollow composite nanofiber prepared in example 6;
fig. 4 is a nitrogen adsorption and desorption curve (left) and a pore size distribution curve (right) of the porous multi-hollow composite nanofiber prepared in example 6;
FIG. 5 is a Scanning Electron Microscope (SEM) image of a zinc negative electrode with a porous hollow titanium dioxide-carbon composite nanofiber protective layer prepared in example 21;
FIG. 6 is a zinc-air cell assembled by the zinc cathode with the porous hollow titanium dioxide-carbon composite nanofiber protective layer and the zinc cathode without the protective layer prepared in example 21 at 10mA/cm2Comparing the charge and discharge cycle performance under current density;
FIG. 7 is a zinc-air cell assembled from the zinc negative electrode with the porous hollow titanium dioxide-carbon composite nanofiber protective layer and the zinc negative electrode without the protective layer prepared in example 26 at 20mA/cm2Comparative graph of charge and discharge cycle performance at current density.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 42 ℃, stirring for 6 hours, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 8:2: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 36 ℃, stirring for 5 hours, then adding tetrabutyl titanate, stirring for 0.5 hour, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 48: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 20: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the inner layer solution to the outer layer solution in coaxial electrostatic spinning is 1:1, and the total liquid supply flow rate is 6 mL/h; the distance between the needle head and the receiving plate is 30 cm; the voltage is 40 kV; the ambient temperature is 50 ℃; the environmental humidity is 20%; the receiving device is a metal roller, and the rotating speed of the roller is 100 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
The scanning electron microscope image of the prepared porous multi-hollow composite nanofiber is shown in fig. 1(a), and the transmission electron microscope image is shown in fig. 2 (a); wherein the fiber is made of carbon material, the average diameter is 580nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 2
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 25 ℃, stirring for 12h, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 11:5: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 25 ℃, stirring for 12 hours, then adding tetrabutyl titanate, stirring for 2 hours, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 95: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 28: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 3:5, and the total liquid supply flow rate is 0.8 mL/h; the distance between the needle head and the receiving plate is 15 cm; the voltage is 21 kV; the ambient temperature is 20 ℃; the environmental humidity is 30%; the receiving device is a metal roller, and the rotating speed of the roller is 50 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
The scanning electron microscope image of the prepared porous multi-hollow composite nanofiber is shown in fig. 1(b), and the transmission electron microscope image is shown in fig. 2 (b); wherein the fiber is made of carbon material, the average diameter is 470nm, and the fiber wall has a porous structure with the aperture of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 3
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 15 ℃, stirring for 12h, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 9:3: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 52 ℃, stirring for 3 hours, then adding tetrabutyl titanate, stirring for 1 hour, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 191: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 22: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the inner layer solution to the outer layer solution in coaxial electrostatic spinning is 1:3, and the total liquid supply flow rate is 4 mL/h; the distance between the needle head and the receiving plate is 17 cm; the voltage is 15 kV; the ambient temperature is 44 ℃; the ambient humidity is 23%; the receiving device is a metal roller, and the rotating speed of the roller is 36 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
The scanning electron microscope image of the prepared porous multi-hollow composite nanofiber is shown in fig. 1(c), and the transmission electron microscope image is shown in fig. 2 (c); wherein the fiber is made of carbon material, the average diameter is 420nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 4
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 26 ℃, stirring for 10 hours, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 10:4: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 15 ℃, stirring for 12 hours, then adding tetrabutyl titanate, stirring for 4 hours, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 477: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 27: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:4, and the total liquid supply flow rate is 2.5 mL/h; the distance between the needle head and the receiving plate is 10 cm; the voltage is 1 kV; the ambient temperature is 31 ℃; the ambient humidity is 27%; the receiving device is a metal roller, and the rotating speed of the roller is 20 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
The scanning electron microscope image of the prepared porous multi-hollow composite nanofiber is shown in fig. 1(d), and the transmission electron microscope image is shown in fig. 2 (d); wherein the fiber is made of carbon material, the average diameter is 370nm, and the fiber wall has a porous structure with the aperture of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 5
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 31 ℃, stirring for 8 hours, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 11:5: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 22 ℃, stirring for 9 hours, then adding tetrabutyl titanate, stirring for 12 hours, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 955: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 28: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:5, and the total liquid supply flow rate is 0.8 mL/h; the distance between the needle head and the receiving plate is 22 cm; the voltage is 35 kV; the ambient temperature is 20 ℃; the environmental humidity is 30%; the receiving device is a metal roller, and the rotating speed of the roller is 80 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
The scanning electron microscope image of the prepared porous multi-hollow composite nanofiber is shown in fig. 1(e), and the transmission electron microscope image is shown in fig. 2 (e); wherein the fiber is made of carbon material, the average diameter is 340nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 6
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 55 ℃, stirring for 3h, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 12:6: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 28 ℃, stirring for 7 hours, then adding tetrabutyl titanate, stirring for 7 hours, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 1910: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 38: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:4, and the total liquid supply flow rate is 0.5 mL/h; the distance between the needle head and the receiving plate is 27 cm; the voltage is 28 kV; the ambient temperature is 16 ℃; ambient humidity 66%; the receiving device is a metal roller, and the rotating speed of the roller is 60 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
Scanning electron micrographs of the prepared porous multi-hollow composite nanofiber are shown in fig. 1(f) and (g), and transmission electron micrographs are shown in fig. 2 (f); wherein the fiber is made of carbon material, the average diameter is 280nm, and the fiber wall has a porous structure with the aperture of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm; the prepared porous multi-hollow composite materialThe nanofiber is subjected to thermogravimetric test, and as can be seen from fig. 3, the content of titanium dioxide in the porous multi-hollow flexible composite nanofiber is 38.3%. Carrying out nitrogen adsorption and desorption experiments on the prepared porous multi-hollow flexible composite nanofiber; the porous multi-hollow titanium dioxide-carbon composite nano-fiber in the figure 4 has larger specific surface area (75.2 m)2A/g) and a hierarchical pore structure with sizes of 2, 4 and 26 nm.
Example 7
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 60 ℃, stirring for 2h, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 13:7: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 60 ℃, stirring for 2 hours, then adding tetrabutyl titanate, stirring for 6 hours, and uniformly mixing; the molar ratio of tetrabutyl titanate to polymethyl methacrylate is 2592: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 50: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:3, and the total liquid supply flow rate is 0.3 mL/h; the distance between the needle head and the receiving plate is 25 cm; the voltage is 18 kV; the ambient temperature is 10 ℃; the environmental humidity is 80%; the receiving device is a metal roller, and the rotating speed of the roller is 45 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein the pre-oxidation temperature is 280 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 700 ℃ and the time is 2 h.
The scanning electron microscope image of the prepared porous multi-hollow composite nanofiber is shown in fig. 1 (h); wherein the porous multi-hollow composite nanofiber is made of a carbon material, the average diameter of the porous multi-hollow composite nanofiber is 210nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 8
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and polyacrylonitrile in N, N-dimethylformamide at 15 ℃, stirring for 12h, and uniformly mixing; wherein the mass ratio of polyacrylonitrile to polymethyl methacrylate to N, N-dimethylformamide is 8:2: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylformamide at 15 ℃, stirring for 12h, then adding isopropyl titanate, stirring for 0.5h, and uniformly mixing; the molar ratio of isopropyl titanate to polymethyl methacrylate is 1: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylformamide is 20: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the inner layer solution to the outer layer solution in coaxial electrostatic spinning is 1:1, and the total liquid supply flow rate is 6 mL/h; the distance between the needle head and the receiving plate is 30 cm; the voltage is 40 kV; the ambient temperature is 50 ℃; the environmental humidity is 20%; the receiving device is a metal roller, and the rotating speed of the roller is 20 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; in the carbonization process, the pre-oxidation temperature is 200 ℃ and the time is 2.5 h; the temperature of the carbonization treatment is 450 ℃ and the time is 5 h.
The prepared porous multi-hollow composite nanofiber is made of a carbon material, the average diameter is 700nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 9
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polyvinylpyrrolidone and phenolic resin in ethanol at 23 ℃, stirring for 11h, and mixing uniformly; wherein the mass ratio of the phenolic resin to the polyvinylpyrrolidone to the ethanol is 9:3: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polyethylene glycol in ethanol at 23 ℃, stirring for 10h, then adding tetraethyl titanate, stirring for 1h, and mixing uniformly; the molar ratio of tetraethyl titanate to polyethylene glycol is 500: 1; the mass ratio of the polyethylene glycol to the ethanol is 22: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:5, and the total liquid supply flow rate is 4 mL/h; the distance between the needle head and the receiving plate is 17 cm; the voltage is 15 kV; the ambient temperature is 44 ℃; the ambient humidity is 23%; the receiving device is a metal roller, and the rotating speed of the roller is 37 r/min.
(3) Removing polyvinylpyrrolidone and polyethylene glycol in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber; wherein in the carbonization process, the pre-oxidation temperature is 300 ℃ and the time is 0.5 h; the temperature of the carbonization treatment is 1000 ℃ and the time is 1 h.
The prepared porous multi-hollow composite nanofiber is made of a carbon material, the average diameter is 380nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 10
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polystyrene and cellulose in tetrahydrofuran at 29 ℃, stirring for 9 hours, and uniformly mixing; wherein the mass ratio of the cellulose to the polystyrene to the tetrahydrofuran is 10:4: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polystyrene in tetrahydrofuran at 29 ℃, stirring for 8 hours, then adding titanium tetrachloride, stirring for 2 hours, and uniformly mixing; the molar ratio of titanium tetrachloride to polystyrene is 1000: 1; the mass ratio of the polystyrene to the tetrahydrofuran is 27: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:2, and the total liquid supply flow rate is 2.5 mL/h; the distance between the needle head and the receiving plate is 10 cm; the voltage is 1 kV; the ambient temperature is 31 ℃; the ambient humidity is 27%; the receiving device is a metal roller, and the rotating speed of the roller is 41 r/min.
(3) Removing polystyrene in the composite nanofiber through a carbonization process to obtain the porous multi-hollow composite nanofiber;
wherein in the carbonization process, the pre-oxidation temperature is 250 ℃ and the time is 1.5 h; the temperature of the carbonization treatment is 670 ℃ and the time is 3 h.
The prepared porous multi-hollow composite nanofiber is made of a carbon material, the average diameter is 340nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 11
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polyvinylpyrrolidone and polyacrylonitrile in N, N-dimethylformamide at 36 deg.C, stirring for 8 hr, and mixing; wherein the mass ratio of polyacrylonitrile, polyvinylpyrrolidone and N, N-dimethylformamide is 11:5: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polyvinylpyrrolidone in N, N-dimethylformamide at 36 deg.C, stirring for 7 hr, adding zinc acetate, stirring for 4 hr, and mixing; the molar ratio of zinc acetate to polyvinylpyrrolidone is 2200: 1; the mass ratio of the polyvinylpyrrolidone to the N, N-dimethylformamide is 28: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:3, and the total liquid supply flow rate is 0.8 mL/h; the distance between the needle head and the receiving plate is 22 cm; the voltage is 35 kV; the ambient temperature is 20 ℃; the environmental humidity is 30%; the receiving device is a metal roller, and the rotating speed of the roller is 55 r/min.
(3) Removing polyvinylpyrrolidone in the composite nanofiber through a solvent soaking process to obtain the porous multi-hollow composite nanofiber;
in the solvent soaking process, the solvent is high-purity water, the soaking time is 1h, and the soaked nano fibers are washed for 5 times by the solvent.
The prepared porous multi-hollow composite nanofiber is made of a polymer material, the average diameter is 260nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-150 nm.
Example 12
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polymethyl methacrylate and phenolic resin in N, N-dimethylacetamide at 44 ℃, stirring for 5h, and mixing uniformly; wherein the mass ratio of the phenolic resin to the polymethyl methacrylate to the N, N-dimethylacetamide is 12:6: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polymethyl methacrylate in N, N-dimethylacetamide at 44 ℃, stirring for 5 hours, then adding zinc nitrate, stirring for 6 hours, and uniformly mixing; the molar ratio of zinc nitrate to polymethyl methacrylate is 3000: 1; the mass ratio of the polymethyl methacrylate to the N, N-dimethylacetamide is 38: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:4, and the total liquid supply flow rate is 0.5 mL/h; the distance between the needle head and the receiving plate is 27 cm; the voltage is 28 kV; the ambient temperature is 16 ℃; ambient humidity 66%; the receiving device is a metal roller, and the rotating speed of the roller is 63 r/min.
(3) Removing polymethyl methacrylate in the composite nanofiber through a solvent soaking process to obtain the porous multi-hollow composite nanofiber;
in the solvent soaking process, the solvent is carbonic ester, the soaking time is 24 hours, and the soaked nano-fibers are washed for 3 times by the solvent.
The prepared porous multi-hollow composite nanofiber is made of a polymer material, the average diameter is 180nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-110 nm.
Example 13
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polyoxyethylene and cellulose in tetrahydrofuran at 50 ℃, stirring for 4h, and uniformly mixing; wherein the mass ratio of the cellulose to the polyoxyethylene to the tetrahydrofuran is 13:7: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polyoxyethylene in tetrahydrofuran at 50 ℃, stirring for 4 hours, then adding zinc chloride, stirring for 8 hours, and uniformly mixing; the molar ratio of zinc chloride to polyethylene oxide is 3500: 1; the mass ratio of polyoxyethylene to tetrahydrofuran is 50: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution at the inner layer and the solution at the outer layer of the coaxial electrostatic spinning is 1:2, and the total liquid supply flow rate is 0.3 mL/h; the distance between the needle head and the receiving plate is 25 cm; the voltage is 18 kV; the ambient temperature is 10 ℃; the environmental humidity is 80%; the receiving device is a metal roller, and the rotating speed of the roller is 75 r/min.
(3) Removing polyoxyethylene in the composite nanofiber through a solvent soaking process to obtain the porous multi-hollow composite nanofiber;
in the solvent soaking process, the solvent is high-purity water, the soaking time is 15 hours, and the soaked nano fibers are washed for 5 times by the solvent.
The prepared porous multi-hollow composite nanofiber is made of a polymer material, the average diameter is 150nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-80 nm.
Example 14
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving polyethylene glycol and cellulose in N, N-dimethylformamide at 53 ℃, stirring for 3h, and mixing uniformly; wherein the mass ratio of the cellulose to the polyethylene glycol to the N, N-dimethylformamide is 9:3: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving polyethylene glycol in N, N-dimethylformamide at 53 deg.C, stirring for 3 hr, adding tin acetate, stirring for 12 hr, and mixing; the molar ratio of the tin acetate to the polyethylene glycol is 4000: 1; the mass ratio of the polyethylene glycol to the N, N-dimethylformamide is 22: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the inner layer solution to the outer layer solution in coaxial electrostatic spinning is 1:4, and the total liquid supply flow rate is 4 mL/h; the distance between the needle head and the receiving plate is 17 cm; the voltage is 15 kV; the ambient temperature is 44 ℃; the ambient humidity is 23%; the receiving device is a metal roller, and the rotating speed of the roller is 89 r/min.
(3) Removing polyethylene glycol in the composite nanofiber through a solvent soaking process to obtain the porous multi-hollow composite nanofiber;
in the solvent soaking process, the solvent is ethanol, the soaking time is 10 hours, and the soaked nano-fibers are washed by the solvent for 4 times.
The prepared porous multi-hollow composite nanofiber is made of a polymer material, the average diameter is 130nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-60 nm.
Example 15
A preparation method of porous multi-hollow composite nano-fiber comprises the following specific steps:
(1) preparing an outer layer solution of coaxial electrostatic spinning and an inner layer solution of coaxial electrostatic spinning;
preparation of outer layer solution for coaxial electrospinning: dissolving a mixture of polymethyl methacrylate and polyvinylpyrrolidone in a mass ratio of 1:1 and a mixture of polyacrylonitrile and cellulose in a mass ratio of 1:1 in a mixture of tetrahydrofuran and N, N-dimethylformamide in a mass ratio of 1:1 at 60 ℃, stirring for 2 hours, and uniformly mixing; wherein the mass ratio of the mixture of polyacrylonitrile and cellulose, the mixture of polymethyl methacrylate and polyvinylpyrrolidone to the mixture of tetrahydrofuran and N, N-dimethylformamide is 10:4: 100;
preparing a coaxial electrostatic spinning inner layer solution: dissolving a mixture of polymethyl methacrylate and polyvinylpyrrolidone in a mass ratio of 1:1 in a mixture of tetrahydrofuran and N, N-dimethylformamide in a mass ratio of 1:1 at the temperature of 60 ℃, stirring for 2 hours, then adding stannic chloride, stirring for 11 hours, and uniformly mixing; the molar ratio of tin tetrachloride to the mixture of polymethyl methacrylate and polyvinylpyrrolidone is 5000: 1; the mass ratio of the mixture of polymethyl methacrylate and polyvinylpyrrolidone to the mixture of tetrahydrofuran and N, N-dimethylformamide is 27: 100;
(2) pouring the outer layer solution of the coaxial electrostatic spinning and the inner layer solution of the coaxial electrostatic spinning into a disposable syringe with the capacity of 10mL, placing the disposable syringe in a propulsion pump, and carrying out coaxial electrostatic spinning to obtain composite nanofibers;
wherein in the electrostatic spinning process, the flow rate ratio of the solution on the inner layer and the solution on the outer layer of the coaxial electrostatic spinning is 1:1, and the total liquid supply flow rate is 2.5 mL/h; the distance between the needle head and the receiving plate is 10 cm; the voltage is 1 kV; the ambient temperature is 31 ℃; the ambient humidity is 27%; the receiving device is a metal roller, and the rotating speed of the roller is 100 r/min.
(3) Removing polymethyl methacrylate and polyvinylpyrrolidone in the composite nanofiber through a solvent soaking process to obtain the porous multi-hollow composite nanofiber;
in the solvent soaking process, the solvent is a mixture of high-purity water and carbonic ester with the mass ratio of 1:1, the soaking time is 24 hours, and the soaked nano fibers are washed for 3 times by the solvent.
The prepared porous multi-hollow composite nanofiber is made of a polymer material, the average diameter is 100nm, and the fiber wall has a porous structure with the pore diameter of 5-200 nm; the porous multi-hollow composite nanofiber has 2-15 hollow pipeline structures with diameters of 10-30 nm.
Example 16
The specific steps of the preparation method of the porous multi-hollow composite nanofiber are basically the same as those of the embodiment 1, the difference is only that the adopted metal source is different, and stannous chloride is adopted, and the performance index of the prepared porous multi-hollow composite nanofiber is shown in the following table 1.
Example 17
The specific steps of the preparation method of the porous multi-hollow composite nanofiber are basically the same as those of the embodiment 2, the difference is only that the adopted metal source is different, and tin hydroxide is adopted, and the performance indexes of the prepared porous multi-hollow composite nanofiber are shown in the following table 1.
Example 18
The specific steps of the preparation method of the porous multi-hollow composite nanofiber are basically the same as those of the embodiment 3, the difference is only that the adopted metal source is different, and stannous sulfate is adopted, and the performance index of the prepared porous multi-hollow composite nanofiber is shown in the following table 1.
Example 19
The specific steps of the preparation method of the porous multi-hollow composite nanofiber are basically the same as those of the embodiment 4, the difference is only that the adopted metal source is different, and stannous oxalate is adopted, and the performance index of the prepared porous multi-hollow composite nanofiber is shown in the following table 1.
Example 20
The specific steps of the preparation method of the porous multi-hollow composite nanofiber are basically the same as those of the example 5, the difference is only that the adopted metal source is different, the mixture of stannous chloride and tetraethyl titanate with the mass ratio of 1:1 is adopted, and the performance index of the prepared porous multi-hollow composite nanofiber is shown in the following table 1.
TABLE 1
Example number Unit of Example 16 Example 17 Example 18 Example 19 Example 20
Average diameter nm 600 500 410 380 340
Pore diameter nm 5～200 5～200 5～200 5～200 5～200
Number of hollow pipes An 2～15 2～15 2～15 2～15 2～15
Diameter of hollow pipe nm 10～150 10～150 10～150 10～150 10～150
Example 21
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) mixing the porous multi-hollow composite nanofiber prepared in the embodiment 2 with Nafion and ethanol to obtain suspension slurry; wherein the concentration of the composite nano-fiber in the slurry is 10 mg/mL; the porous multi-hollow composite nanofiber accounts for 80% of the total mass of the porous multi-hollow composite nanofiber and the Nafion;
(2) and uniformly coating the suspension slurry on the surface of a zinc cathode substrate layer (pure zinc foil) to obtain the zinc cathode with the composite nanofiber protective layer.
The prepared zinc cathode with the composite nanofiber protective layer comprises a zinc cathode substrate layer and a protective layer coated on the zinc cathode substrate layer (a scanning electron microscope of the zinc cathode is shown in figure 5, the thickness of the zinc cathode is 25 mu m, and the Young modulus of the zinc cathode is 2 GPa); fig. 5 shows that the composite nanofibers are uniformly dispersed in the protective layer, the protective layer is composed of porous hollow composite nanofibers and Nafion, and the porous hollow composite nanofibers are stacked layer by layer inside the protective layer to form a three-dimensional interpenetrating network and a stacked pore structure; the porous multi-hollow composite nanofiber comprises 2-15 hollow pipelines with the diameter of 10-150 nm and a plurality of three-dimensional through hole micro-nano structures from the surface to the hollow part; the three-dimensional through hole is a through hole structure which is connected with the hollow part of the fiber and the three-dimensional stacking holes among the fibers through the holes on the fiber wall.
The zinc cathode with the composite nanofiber protective layer is used as an anode to prepare a zinc-air battery, and the process is as follows:
(1) preparing an air electrode: the preparation process of the gas diffusion layer comprises the following steps: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode; wherein, Pt/C + IrO in the dispersion liquid2The concentration of the powder is 2 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 1mg/cm2。
Preparing an electrolyte: preparing a mixture of potassium hydroxide, zinc acetate and ultrapure water; the concentration of potassium hydroxide in the mixture is 6mol/L, and the concentration of zinc acetate is 0.2 mol/L.
(2) Assembling an air electrode, an electrolyte, an anode (the prepared zinc negative electrode with the composite nanofiber protective layer) and a current collector (a stainless steel net or a copper foil) into a zinc-air battery;
the obtained zinc cathode is assembled into a zinc-air battery to carry out a cycle performance test result chart, which is shown in fig. 6; as can be seen in fig. 6: at 10mA/cm2And (3) charging and discharging under current density, wherein each period is 10min, 5min discharging and 5min charging, and the zinc cathode with the composite nanofiber protective layer is assembled into a zinc-air battery, so that the stability can be kept for a long time in the charging and discharging process, and 485 circles can be circulated. In contrast, the zinc-air battery formed by assembling the zinc cathode without the protective layer begins to polarize after only 150 circles, the polarization becomes more and more obvious with the lapse of time, and the serious attenuation begins to appear after 180 circles of operation, which shows that the porous hollow battery provided by the invention has multiple holesThe zinc-air battery assembled by the zinc cathode of the titanium dioxide-carbon composite nanofiber protective layer has better charge and discharge stability.
Example 22
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) mixing the porous multi-hollow composite nanofiber prepared in example 1 with polyvinylidene fluoride and N-methyl pyrrolidone to obtain suspension slurry; wherein the concentration of the composite nano-fiber in the slurry is 100 mg/mL; the porous multi-hollow composite nanofiber accounts for 70% of the total mass of the porous multi-hollow composite nanofiber and the polyvinylidene fluoride base;
(2) and uniformly coating the suspension slurry on the surface of a zinc cathode substrate layer (a pure zinc plate) to obtain the zinc cathode with the composite nanofiber protective layer.
The prepared zinc negative electrode with the composite nanofiber protective layer comprises a zinc negative electrode substrate layer and a protective layer (the thickness is 200 mu m, and the Young modulus is 3GPa) coated on the zinc negative electrode substrate layer; the protective layer is composed of porous multi-hollow composite nano fibers and polyvinylidene fluoride base, and the porous multi-hollow composite nano fibers in the protective layer are stacked layer by layer to form a three-dimensional interpenetrating network and a stacked pore structure; the porous multi-hollow composite nanofiber comprises 2-15 hollow pipelines with the diameter of 10-150 nm and a plurality of three-dimensional through hole micro-nano structures from the surface to the hollow part; the three-dimensional through hole is a through hole structure which is connected with the hollow part of the fiber and the three-dimensional stacking holes among the fibers through the holes on the fiber wall.
The zinc cathode with the composite nanofiber protective layer is used as an anode to prepare a zinc-air battery, and the process is as follows:
(1) preparing an air electrode: the preparation process of the gas diffusion layer comprises the following steps: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode; wherein, Pt/C + IrO in the dispersion liquid2The concentration of the powder is 0.5 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 0.8mg/cm2。
Preparing an electrolyte: preparing a mixture of potassium hydroxide, zinc acetate and ultrapure water; the concentration of potassium hydroxide in the mixture is 6mol/L, and the concentration of zinc acetate is 0.2 mol/L.
(2) Assembling an air electrode, an electrolyte, an anode (the prepared zinc negative electrode with the composite nanofiber protective layer) and a current collector (a stainless steel net or a copper foil) into a zinc-air battery; the zinc-air battery is subjected to charge and discharge performance test, and the test result is as follows: at 40mA/cm2The charging and discharging are carried out under the current density of (1), each period is 10min, 5min discharging and 5min charging are carried out, and 150 cycles can be carried out.
Example 23
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) mixing the porous multi-hollow composite nanofiber prepared in the embodiment 6 with polyvinyl chloride and cyclohexanone to obtain suspension slurry; wherein the concentration of the composite nanofiber in the slurry is 50 mg/mL; the porous multi-hollow composite nanofiber accounts for 99% of the total mass of the porous multi-hollow composite nanofiber and the polyvinyl chloride;
(2) and uniformly coating the suspension slurry on the surface of a zinc cathode substrate layer (a zinc alloy sheet) to obtain the zinc cathode with the composite nanofiber protective layer.
The prepared zinc negative electrode with the composite nanofiber protective layer comprises a zinc negative electrode substrate layer and a protective layer (the thickness is 150 mu m, and the Young modulus is 5GPa) coated on the zinc negative electrode substrate layer; the protective layer is composed of porous multi-hollow composite nanofibers and polyvinyl chloride, and the porous multi-hollow composite nanofibers in the protective layer are stacked layer by layer to form a three-dimensional interpenetrating network and a stacked pore structure; the porous multi-hollow composite nanofiber comprises 2-15 hollow pipelines with the diameter of 10-150 nm and a plurality of three-dimensional through hole micro-nano structures from the surface to the hollow part; the three-dimensional through hole is a through hole structure which is connected with the hollow part of the fiber and the three-dimensional stacking holes among the fibers through the holes on the fiber wall.
The zinc cathode with the composite nanofiber protective layer is used as an anode to prepare a zinc-air battery, and the process is as follows:
(1) preparing an air electrode: preparation of gas diffusion layerThe process is as follows: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode; wherein, Pt/C + IrO in the dispersion liquid2The concentration of the powder is 1.5 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 0.9mg/cm2。
Preparing an electrolyte: preparing a mixture of potassium hydroxide, zinc acetate and ultrapure water; the concentration of potassium hydroxide in the mixture was 4mol/L and the concentration of zinc acetate was 0.1 mol/L.
(2) Assembling an air electrode, an electrolyte, an anode (the prepared zinc negative electrode with the composite nanofiber protective layer) and a current collector (a stainless steel net or a copper foil) into a zinc-air battery; the zinc-air battery is subjected to charge and discharge performance test, and the test result is as follows: at 30mA/cm2The charging and discharging are carried out under the current density, each period is 10min, 5min discharging and 5min charging are carried out, and 200 circles can be circulated.
Example 24
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) mixing the porous multi-hollow composite nanofiber prepared in the embodiment 4 with polyetherimide and N-methyl pyrrolidone to obtain suspension slurry; wherein the concentration of the composite nanofiber in the slurry is 30 mg/mL; the porous multi-hollow composite nanofiber accounts for 80% of the total mass of the porous multi-hollow composite nanofiber and the polyetherimide;
(2) and uniformly coating the suspension slurry on the surface of a zinc cathode substrate layer (pure zinc foil) to obtain the zinc cathode with the composite nanofiber protective layer.
The prepared zinc negative electrode with the composite nanofiber protective layer comprises a zinc negative electrode substrate layer and a protective layer (the thickness is 75 mu m, and the Young modulus is 6.5GPa) coated on the zinc negative electrode substrate layer; the protective layer is composed of porous multi-hollow composite nano fibers and polyetherimide, and the porous multi-hollow composite nano fibers in the protective layer are stacked layer by layer to form a three-dimensional interpenetrating network and a stacking pore structure; the porous multi-hollow composite nanofiber comprises 2-15 hollow pipelines with the diameter of 10-150 nm and a plurality of three-dimensional through hole micro-nano structures from the surface to the hollow part; the three-dimensional through hole is a through hole structure which is connected with the hollow part of the fiber and the three-dimensional stacking holes among the fibers through the holes on the fiber wall.
The zinc cathode with the composite nanofiber protective layer is used as an anode to prepare a zinc-air battery, and the process is as follows:
(1) preparing an air electrode: the preparation process of the gas diffusion layer comprises the following steps: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode; wherein, Pt/C + IrO in the dispersion liquid2The concentration of the powder is 3 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 1.2mg/cm2。
Preparing an electrolyte: preparing a mixture of potassium hydroxide, zinc acetate and ultrapure water; the concentration of potassium hydroxide in the mixture is 5mol/L, and the concentration of zinc acetate is 0.5 mol/L.
(2) Assembling an air electrode, an electrolyte, an anode (the prepared zinc negative electrode with the composite nanofiber protective layer) and a current collector (a stainless steel net or a copper foil) into a zinc-air battery; the zinc-air battery is subjected to charge and discharge performance test, and the test result is as follows: at 5mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 1500 cycles can be carried out.
Example 25
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) mixing the porous multi-hollow composite nanofiber prepared in the example 5 with polyacrylic acid group and high-purity water to obtain suspension slurry; wherein the concentration of the composite nanofiber in the slurry is 70 mg/mL; the porous multi-hollow composite nanofiber accounts for 90% of the total mass of the porous multi-hollow composite nanofiber and the polyacrylic acid group;
(2) and uniformly coating the suspension slurry on the surface of a zinc cathode substrate layer (a pure zinc plate) to obtain the zinc cathode with the composite nanofiber protective layer.
The prepared zinc negative electrode with the composite nanofiber protective layer comprises a zinc negative electrode substrate layer and a protective layer (the thickness is 180 mu m, and the Young modulus is 8GPa) coated on the zinc negative electrode substrate layer; the protective layer is composed of porous multi-hollow composite nanofibers and polyacrylic acid groups, and the porous multi-hollow composite nanofibers in the protective layer are stacked layer by layer to form a three-dimensional interpenetrating network and a stacking pore structure; the porous multi-hollow composite nanofiber comprises 2-15 hollow pipelines with the diameter of 10-150 nm and a plurality of three-dimensional through hole micro-nano structures from the surface to the hollow part; the three-dimensional through hole is a through hole structure which is connected with the hollow part of the fiber and the three-dimensional stacking holes among the fibers through the holes on the fiber wall.
The zinc cathode with the composite nanofiber protective layer is used as an anode to prepare a zinc-air battery, and the process is as follows:
(1) preparing an air electrode: the preparation process of the gas diffusion layer comprises the following steps: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode; wherein, Pt/C + IrO in the dispersion liquid2The concentration of the powder is 3 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 1.2mg/cm2。
Preparing an electrolyte: preparing a mixture of potassium hydroxide, zinc acetate and ultrapure water; the concentration of potassium hydroxide in the mixture is 8mol/L, and the concentration of zinc acetate is 0.4 mol/L.
(2) Assembling an air electrode, an electrolyte, an anode (the prepared zinc negative electrode with the composite nanofiber protective layer) and a current collector (a stainless steel net or a copper foil) into a zinc-air battery; the zinc-air battery is subjected to charge and discharge performance test, and the test result is as follows: at 50mA/cm2The charging and discharging are carried out under the current density, each period is 10min, 5min discharging and 5min charging are carried out, and 100 circles can be circulated.
Example 26
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) mixing the porous multi-hollow composite nano-fiber prepared in the embodiment 3 with carboxymethyl cellulose base and high-purity water to obtain suspension slurry; wherein the concentration of the composite nanofiber in the slurry is 5 mg/mL; the porous multi-hollow composite nanofiber accounts for 75% of the total mass of the porous multi-hollow composite nanofiber and the carboxymethyl cellulose base;
(2) and uniformly coating the suspension slurry on the surface of a zinc cathode substrate layer (pure zinc foil) to obtain the zinc cathode with the composite nanofiber protective layer.
The prepared zinc negative electrode with the composite nanofiber protective layer comprises a zinc negative electrode substrate layer and a protective layer (the thickness is 10 mu m, and the Young modulus is 11GPa) coated on the zinc negative electrode substrate layer; the protective layer is composed of porous multi-hollow composite nanofibers and carboxymethyl cellulose base, and the porous multi-hollow composite nanofibers inside the protective layer are stacked layer by layer to form a three-dimensional interpenetrating network and a stacked pore structure; the porous multi-hollow composite nanofiber comprises 2-15 hollow pipelines with the diameter of 10-150 nm and a plurality of three-dimensional through hole micro-nano structures from the surface to the hollow part; the three-dimensional through hole is a through hole structure which is connected with the hollow part of the fiber and the three-dimensional stacking holes among the fibers through the holes on the fiber wall.
The zinc cathode with the composite nanofiber protective layer is used as an anode to prepare a zinc-air battery, and the process is as follows:
(1) preparing an air electrode: the preparation process of the gas diffusion layer comprises the following steps: mixing Pt/C + IrO2Dispersing the powder (catalyst) in ethanol containing Nafion to form dispersion liquid, and then spraying the dispersion liquid on hydrophobic carbon paper to obtain an air electrode; wherein, Pt/C + IrO in the dispersion liquid2The concentration of the powder is 2 mg/mL; the content of the catalyst on the hydrophobic carbon paper is 1mg/cm2。
Preparing an electrolyte: preparing a mixture of potassium hydroxide, zinc acetate and ultrapure water; the concentration of potassium hydroxide in the mixture is 6mol/L, and the concentration of zinc acetate is 0.2 mol/L.
(2) Assembling an air electrode, an electrolyte, an anode (the prepared zinc negative electrode with the composite nanofiber protective layer) and a current collector (a stainless steel net or a copper foil) into a zinc-air battery;
assembling the prepared zinc cathode into a result graph of a zinc-air battery for cycle performance test; as shown in fig. 7, it can be seen from fig. 7 that: at 20mA/cm2Charging and discharging at current density, each period is 10min, 5min discharging and 5min charging, the zinc cathode with the composite nanofiber protective layer is assembled into a zinc-air battery, and the charge and discharge process of the zinc-air battery can be kept stable for a long time and can be circulated for 250 circles. In contrast, the zinc-air battery formed by assembling the zinc cathode without the protective layer begins to show serious attenuation after only 130 circles, which shows that the zinc-air battery assembled by the zinc cathode with the porous multi-hollow titanium dioxide-carbon composite nanofiber protective layer provided by the invention has better charge and discharge stability.
Example 27
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 21, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 7, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 5mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 1500 cycles can be carried out.
Example 28
The preparation method of the zinc negative electrode with the composite nanofiber protective layer is basically the same as that in the example 22, except that the porous multi-hollow composite nanofiber in the zinc negative electrode with the composite nanofiber protective layer is prepared in the example 8, the prepared zinc negative electrode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 5mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 1500 cycles can be carried out.
Example 29
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 23, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 9, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 10mA/cm2Is charged and discharged at a current density of (1), each cycleDischarging for 10min, discharging for 5min, and charging for 5min, and circulating for 490 circles.
Example 30
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 24, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 10, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 5mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 1400 cycles can be carried out.
Example 31
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 25, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 11, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 10mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 450 circles can be circulated.
Example 32
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 26, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 12, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 20mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 230 cycles can be carried out.
Example 33
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that of the zinc cathode in example 21, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared from the zinc cathode prepared in example 13, and the prepared zinc cathode is prepared according to the embodimentThe zinc-air battery is manufactured by the method of the embodiment, and the test result of the charge and discharge performance is as follows: at 5mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 1500 cycles can be carried out.
Example 34
The preparation method of the zinc negative electrode with the composite nanofiber protective layer is basically the same as that in the example 22, except that the porous multi-hollow composite nanofiber in the zinc negative electrode with the composite nanofiber protective layer is prepared in the example 14, the prepared zinc negative electrode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 10mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 490 circles can be circulated.
Example 35
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 23, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 15, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 20mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 260 cycles can be carried out.
Example 36
The preparation method of the zinc negative electrode with the composite nanofiber protective layer is basically the same as that in the example 24, except that the porous multi-hollow composite nanofiber in the zinc negative electrode with the composite nanofiber protective layer is prepared in the example 16, the prepared zinc negative electrode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 30mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 210 cycles can be carried out.
Example 37
The preparation method of the zinc cathode with the composite nanofiber protective layer comprises the steps which are basically the same as the steps in the example 25Except that the porous multi-hollow composite nanofibers in the zinc negative electrode with the composite nanofiber protective layer were prepared in example 17, the prepared zinc negative electrode was prepared into a zinc-air battery according to the method of this example, and subjected to the charge and discharge performance test, with the test results: at 40mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 160 cycles can be carried out.
Example 38
The preparation method of the zinc negative electrode with the composite nanofiber protective layer is basically the same as that in the example 26, except that the porous multi-hollow composite nanofiber in the zinc negative electrode with the composite nanofiber protective layer is prepared in the example 18, the prepared zinc negative electrode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 50mA/cm2The current density of the battery is 10min, 5min discharging and 5min charging are carried out in each period, and 110 cycles can be carried out.
Example 39
The preparation method of the zinc cathode with the composite nanofiber protective layer is basically the same as that in the example 21, except that the porous multi-hollow composite nanofiber in the zinc cathode with the composite nanofiber protective layer is prepared in the example 19, the prepared zinc cathode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 10mA/cm2The charging and discharging are carried out under the current density of (1), each period is 10min, 5min discharging and 5min charging are carried out, and 500 cycles can be carried out.
Example 40
The preparation method of the zinc negative electrode with the composite nanofiber protective layer is basically the same as that in the example 22, except that the porous multi-hollow composite nanofiber in the zinc negative electrode with the composite nanofiber protective layer is prepared in the example 7, the prepared zinc negative electrode is prepared into a zinc-air battery according to the method in the example, and the test result of the charge and discharge performance is as follows: at 40mA/cm2The charging and discharging are carried out under the current density of (1), each period is 10min, 5min discharging and 5min charging are carried out, and 150 cycles can be carried out.

Claims (22)

1. The zinc cathode with the composite nanofiber protective layer is characterized in that: the zinc-based negative electrode comprises a zinc negative electrode substrate layer and a protective layer coated on the substrate layer; the protective layer is mainly formed by stacking porous multi-hollow composite nano fibers; the porous multi-hollow composite nanofiber is a three-dimensional through hole micro-nano structure with a plurality of hollow pipelines and a hollow surface on the cross section of the composite nanofiber; the multiple hollow pipelines of the porous multiple hollow composite nanofiber refer to 2-15 hollow pipelines; the plurality of hollow conduits of the porous multi-hollow composite nanofiber are formed from inorganic nanoparticles;
the stacking refers to stacking porous multi-hollow composite nanofiber layers in the protective layer by layer to form a three-dimensional interpenetrating network and a stacking pore structure; the fiber wall of the porous multi-hollow composite nanofiber has a porous structure; the three-dimensional through hole is a through hole structure which is connected with the hollow part in the fiber and the three-dimensional stacking hole between the fibers through the holes on the fiber wall;
the porous multi-hollow composite nanofiber is made of a carbon material and/or a polymer material;
the preparation method of the zinc cathode with the composite nanofiber protective layer comprises the following steps:
(1) firstly, preparing composite nano fibers by coaxial electrostatic spinning; the outer layer solution of the coaxial electrostatic spinning consists of a sacrificial high molecular polymer, a retention high molecular polymer and a solvent A; the inner layer solution of the coaxial electrostatic spinning consists of a sacrificial high molecular polymer, a material which can generate a substance with semiconductor characteristics and low surface energy in the spinning process and a solvent B;
(2) removing the sacrificial high molecular polymer in the composite nanofiber to obtain the porous multi-hollow composite nanofiber;
(3) mixing the porous multi-hollow composite nano fiber with an adhesive and a solvent C to obtain suspension slurry;
(4) and uniformly coating the suspension slurry on the surface of the zinc cathode substrate layer to obtain the zinc cathode with the composite nanofiber protective layer.
2. The zinc negative electrode with the composite nanofiber protective layer as claimed in claim 1, wherein the material of the substrate layer is simple zinc or zinc alloy.
3. The zinc anode with the composite nanofiber protective layer as claimed in claim 1, wherein the inorganic nanoparticles are TiO2And more than one of ZnO and SnO, wherein the particle size of the inorganic nano-particles is 2-50 nm.
4. The zinc negative electrode with the composite nanofiber protective layer according to claim 1, wherein the protective layer further contains a binder, and the porous multi-hollow composite nanofibers account for 70-99% of the total mass of the protective layer.
5. The zinc anode with the composite nanofiber protective layer according to claim 1, wherein the porous multi-hollow composite nanofibers have an average diameter of 100 to 1000nm, and the pore diameter on the fiber wall is 5 to 200 nm.
6. The zinc anode with the composite nanofiber protective layer as claimed in claim 1, wherein the diameter of the hollow pipe is 10-150 nm.
7. The zinc anode according to claim 1, wherein said protective layer comprises a single material of said porous hollow composite nanofiber or two or more different materials of said porous hollow composite nanofiber.
8. The zinc negative electrode with the composite nanofiber protective layer according to claim 1, wherein the protective layer has a thickness of not more than 200 μm, and the young's modulus of the protective layer is 1GPa to 20 GPa.
9. The method for preparing the zinc cathode with the composite nanofiber protective layer as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) firstly, preparing composite nano fibers by coaxial electrostatic spinning; the outer layer solution of the coaxial electrostatic spinning consists of a sacrificial high molecular polymer, a retention high molecular polymer and a solvent A; the inner layer solution of the coaxial electrostatic spinning consists of a sacrificial high molecular polymer, a material which can generate a substance with semiconductor characteristics and low surface energy in the spinning process and a solvent B;
(2) removing the sacrificial high molecular polymer in the composite nanofiber to obtain the porous multi-hollow composite nanofiber;
(3) mixing the porous multi-hollow composite nano fiber with an adhesive and a solvent C to obtain suspension slurry;
(4) and uniformly coating the suspension slurry on the surface of the zinc cathode substrate layer to obtain the zinc cathode with the composite nanofiber protective layer.
10. The method according to claim 9, wherein the sacrificial polymer and the retentive polymer are the sacrificial polymer that can be removed while retaining the retentive polymer under a certain treatment condition.
11. The preparation method according to claim 9, wherein in the coaxial electrospinning inner layer solution, the molar ratio of a material capable of generating a substance having both semiconductor characteristics and low surface energy to the sacrificial high polymer in the spinning process is 1-5000: 1; the mass ratio of the sacrificial high-molecular polymer to the solvent B is 20-50: 100; in the coaxial electrostatic spinning outer layer solution, the mass ratio of the retention type high molecular polymer to the sacrificial type high molecular polymer to the solvent A is 8-13: 2-7: 100.
12. The method according to claim 9, wherein the sacrificial polymer is one or more of polymethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, and polystyrene.
13. The method according to claim 9, wherein the retention type high molecular polymer is one or more of polyacrylonitrile, a phenol resin, and cellulose.
14. The method according to claim 9, wherein the solvent A or the solvent B is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, and ethanol.
15. The method according to claim 9, wherein a material capable of producing a substance having both semiconductor characteristics and low surface energy in the spinning process is a metal source; the metal source is more than one of a titanium source, a zinc source and a tin source; the titanium source is tetrabutyl titanate, isopropyl titanate, tetraethyl titanate or titanium tetrachloride; the zinc source is zinc acetate, zinc nitrate or zinc chloride; the tin source is tin acetate, tin tetrachloride, stannous chloride, tin hydroxide, stannous sulfate or stannous oxalate.
16. The preparation method of claim 9, wherein the preparation method of the coaxial electrospinning inner layer solution comprises the following steps: dissolving the sacrificial high molecular polymer in the solvent B at 15-60 ℃, stirring for 2-12 h, then adding a metal source, stirring for 0.5-12 h, and uniformly mixing; the preparation method of the coaxial electrostatic spinning outer layer solution comprises the following steps: dissolving a sacrificial high-molecular polymer and a retention high-molecular polymer in a solvent A at 15-60 ℃, stirring for 2-12 h, and uniformly mixing; the flow rate ratio of the inner layer solution to the outer layer solution of the coaxial electrostatic spinning is 1 (1-5), and the total liquid supply flow rate is 0.3-6 mL/h; the distance between the needle head and the receiving plate is 10-30 cm; the voltage is 1-40 kV; the ambient temperature is 10-50 ℃; the environmental humidity is 20% -80%; the receiving device is a metal roller, and the rotating speed of the roller is 20-100 r/min.
17. The method of claim 10, wherein the certain treatment condition is carbonization or solvent soaking.
18. The preparation method according to claim 17, wherein in the carbonization process, the pre-oxidation temperature is 200-300 ℃ and the time is 0.5-2.5 h; the temperature of the carbonization treatment is 450-1000 ℃, and the time is 1-5 h.
19. The preparation method according to claim 17, wherein in the solvent soaking process, the solvent D is one or more of high-purity water, methanol, ethanol, propanol, butanol, cyclohexanol, chloroform, dichloromethane, propylene glycol, butylene glycol, glycerol, triethanolamine, acetic acid, and carbonate, the soaking time is 1-24 hours, and the soaked nanofibers are washed 3-5 times with the solvent D.
20. The method of claim 9, wherein the binder is Nafion, polyvinylidene fluoride, polyvinyl chloride, polyetherimide, polyacrylic acid or carboxymethyl cellulose, and the solvent C is ethanol, cyclohexanone, N-methyl pyrrolidone or high purity water.
21. The method according to claim 9, wherein the concentration of the composite nanofibers in the slurry is 5 to 100 mg/mL.
22. The use of a zinc anode with a composite nanofiber protective layer as claimed in any one of claims 1 to 8, wherein: preparing a zinc air battery by taking the zinc cathode with the composite nanofiber protective layer as an anode; the air electrode of the zinc-air battery is a gas diffusion layer loaded with a catalyst; the electrolyte of the zinc-air battery is a mixture of potassium hydroxide, zinc acetate and ultrapure water; the current collector of the zinc-air battery is a stainless steel mesh or a copper foil.
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