CN111785978B - Porous electrode for flow battery and preparation method thereof - Google Patents

Porous electrode for flow battery and preparation method thereof Download PDF

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CN111785978B
CN111785978B CN202010661974.XA CN202010661974A CN111785978B CN 111785978 B CN111785978 B CN 111785978B CN 202010661974 A CN202010661974 A CN 202010661974A CN 111785978 B CN111785978 B CN 111785978B
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porous electrode
organic ligand
polyacrylonitrile
metal salt
preparation
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CN111785978A (en
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赵天寿
孙静
范新庄
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Guangzhou HKUST Fok Ying Tung Research Institute
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Guangzhou HKUST Fok Ying Tung Research Institute
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/43—Acrylonitrile series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • 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
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • H01M4/96—Carbon-based electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a porous electrode for a flow battery and a preparation method thereof, and relates to the field of flow batteries. The preparation method comprises the following steps: s1, adding polyacrylonitrile and metal salt into N, N-dimethylformamide or N, N-dimethylacetamide, heating and mixing, and dissolving the polyacrylonitrile and the metal salt to obtain an electrospinning stock solution; s2, carrying out electrostatic spinning by using the electrospinning stock solution to obtain an electrospun fiber membrane; s3, dissolving an organic ligand in a solvent to obtain an organic ligand solution, soaking the electrospun fiber membrane in the organic ligand solution for a period of time, and allowing MOF particles to be generated on the surface of the electrospun fiber in situ; s4, pre-oxidizing the fiber filaments with the MOF particles deposited on the surfaces, and then carbonizing in an inert gas atmosphere to obtain the porous electrode. The porous electrode prepared by the method has larger specific surface area, is beneficial to reducing the activation loss of the battery and improving the performance of the battery, and is suitable for various flow batteries.

Description

Porous electrode for flow battery and preparation method thereof
Technical Field
The invention relates to the field of flow batteries, in particular to a porous electrode for a flow battery and a preparation method thereof.
Background
With the increasing problems of environmental pollution, climate warming, energy shortage and the like, the proportion of clean renewable energy sources in the total amount of global power generation is gradually increasing, wherein the total amount of clean renewable energy sources mainly comprises wind energy and solar energy. However, wind energy and solar energy power generation are influenced by factors such as time and weather, so that the power generation has intermittency and fluctuation. In order to improve the stability of renewable energy power generation grid connection, it is necessary to coordinate wind energy, photovoltaic power generation and a power grid by using an energy storage system. At present, the main energy storage systems include pumped storage, compressed air storage and battery storage, wherein the battery storage is widely concerned due to the characteristic that the battery storage is not limited by regions. In various battery energy storage systems, the flow battery can adjust the stored electric quantity by changing the volume of the liquid storage tank and control the output power by adjusting the size of the active area of the battery, so that the scale of the battery can be flexibly selected according to the needs of a user. In addition, the flow battery has high safety and long service life, and has attracted much attention in recent years as an energy storage system.
The electrodes, which serve as sites for electrochemical reactions, are one of the major components of flow batteries. In order to reduce the activation polarization, ohmic polarization and concentration polarization of the battery, the electrode needs to have good electrocatalytic activity, large specific surface area, high conductivity and good transmission performance. Currently, the most widely used electrode materials in flow batteries are commercial carbon fiber materials, including graphite felt, carbon paper, and carbon cloth. However, commercial electrodes cause a large activation loss to the battery due to poor electrochemical activity and small specific surface area. In order to reduce the activation loss of the flow battery, it is necessary to modify the commercial graphite electrode, and the main methods include modifying the catalyst on the surface of the electrode, or doping the carbon fiber with elements, and etching the surface of the electrode. The method for etching and forming the pores on the carbon fibers can greatly improve the specific surface area of the electrode, and the electrode structure with the hierarchical pores can realize the efficient operation of the flow battery under higher current density.
The method for etching and forming the pores on the carbon fibers can greatly improve the specific surface area of the electrode, and the electrode structure with the hierarchical pores can realize the efficient operation of the flow battery under higher current density. However, pore formation on commercial electrode surfaces often results in additional energy loss and loss of mechanical strength. At present, in addition to commercial graphite materials, carbon fiber electrodes are prepared by utilizing electrostatic spinning, and the electrode structure can be designed, so that the requirements of large specific area, high conductivity and high transmission performance are met. The traditional electrostatic spinning carbon fiber can provide a larger specific area due to the smaller diameter of the fiber filament, but simultaneously sacrifices the transmission performance of an electrode, and causes great concentration polarization.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing a porous electrode for a flow battery, in which MOF (metal organic framework) particles are grown in situ on the surface of an electrospun fiber by using an electrospinning technique, and the MOF particles etch the surface of the carbon fiber during high-temperature carbonization to form a porous carbon fiber electrode, wherein the porous carbon fiber has a hierarchical pore structure and a large specific surface area, and is helpful for reducing activation loss of the battery, improving battery performance, and being applicable to the flow battery.
A preparation method of a porous electrode for a flow battery comprises the following steps:
s1, adding polyacrylonitrile and metal salt into N, N-dimethylformamide or N, N-dimethylacetamide, heating and mixing, and dissolving the polyacrylonitrile and the metal salt to obtain an electrospinning stock solution;
s2, carrying out electrostatic spinning by using the electrospinning stock solution to obtain an electrospun fiber membrane;
s3, dissolving an organic ligand in a solvent to obtain an organic ligand solution, soaking the electrospun fiber membrane in the organic ligand solution for a period of time, and allowing MOF particles to be generated on the surface of the electrospun fiber in situ;
s4, pre-oxidizing the fiber filaments with the MOF particles deposited on the surfaces, and then carbonizing in an inert gas atmosphere to obtain the porous electrode.
According to the preparation method, the electrospinning filament is obtained by utilizing the electrospinning technology, the MOF particles grow on the surface of the electrospinning filament in situ, the surface of the carbon fiber is etched by the MOF particles in the high-temperature carbonization process, and a porous carbon fiber electrode is formed. Moreover, the method for etching the surface of the carbon fiber does not cause redundant energy consumption in the carbonization process. The porous electrode can be suitable for various flow batteries and has a wide application range.
In one embodiment, in the step S1, the polyacrylonitrile has an average molecular weight of 25000-200000g mol-1。
In one embodiment, in step S1, the metal salt is an inorganic salt selected from: zinc salts and/or cobalt salts.
In one embodiment, in step S1, the metal salt is selected from: one or more of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, cobalt acetate, cobalt nitrate and cobalt chloride.
In one embodiment, in step S1, in the electrospinning solution, the mass fraction of polyacrylonitrile is 5 to 20 wt%, and the mass fraction of the metal salt is 1 to 10 wt%.
In one embodiment, in the step S1, the heating temperature is 40 to 80 ℃, and the stirring and mixing are performed for 10 to 20 hours.
In one embodiment, in step S2, the process parameters of electrostatic spinning are: the diameter of the needle is 0.2-2mm, and the advancing speed of the electrospinning stock solution is 0.2-2mL h-1The rotating speed of the rotating wheel at the receiving end is 100-1000rpm, the distance between the needle head and the receiver is 10-50cm, the voltage between the needle head and the receiving end is 10-50kV, the temperature of electrostatic spinning is 20-35 ℃, and the relative humidity is 40-70%; the thickness of the electrospun fiber membrane is 100 mu m-5 mm.
In one embodiment, in step S3, the organic ligand is 2-methylimidazole, and the solvent is selected from: one or more of methanol, ethanol, and water. Preferably, the solvent is a mixed solution of methanol and ethanol, and the volume ratio of the methanol to the ethanol is 1: 1.
in one embodiment, in step S3, the soaking time is 2-24h, and stirring is performed during the soaking.
In one embodiment, in the step S4, the pre-oxidation is performed in air or oxygen atmosphere, the pre-oxidation temperature is 220--1The pre-oxidation time is 1-3 h; the inert atmosphere in the carbonization process is argon or nitrogen, the carbonization temperature is 800-3000 ℃, and the heating rate is 2-10 ℃ for min-1The carbonization time is 0.5-5 h.
Preferably, the carbonization temperature is 1000-.
In one embodiment, the step S4 is further followed by a step S5: and (4) carrying out acid washing, water washing and drying on the obtained porous electrode. The acid washing can remove the impurities remained on the surface.
In one embodiment, in step S5, the acid used for pickling is selected from: one or more than two of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid.
The invention also provides a porous electrode prepared by the method. The carbon fiber surface of the porous electrode has a uniform porous structure, the specific surface area of the material is improved, the activation loss of the battery is reduced, and the inside of the fiber yarn is of a solid structure, so that the mechanical property and the conductivity of the fiber yarn are ensured.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, the electrospinning filament is obtained by utilizing an electrostatic spinning technology, the MOF particles grow on the surface of the electrospinning filament in situ, the surface of the carbon fiber is etched by the MOF particles in the high-temperature carbonization process, and a porous carbon fiber electrode is formed. Moreover, the method for etching the surface of the carbon fiber does not cause redundant energy consumption in the carbonization process.
According to the porous electrode, the surface of the carbon fiber has a uniform porous structure, the specific surface area of the material is improved, the activation loss of a battery is reduced, and the internal part of the fiber yarn is of a solid structure, so that the mechanical property and the conductivity of the fiber yarn are ensured. The porous electrode can be suitable for various flow batteries and has a wide application range.
Drawings
FIG. 1 is an electrospun fiber of MOF particles grown in situ in example 1.
FIG. 2 is an SEM image of a porous carbon fiber electrode from example 1 using zinc nitrate as the source for forming the MOF.
FIG. 3 is an SEM image of a porous carbon fiber electrode from example 2 using zinc acetate as the source for the formation of the MOF.
FIG. 4 is a charging and discharging curve of a porous carbon fiber electrode applied to a vanadium flow battery.
Fig. 5 is an efficiency curve of a porous carbon fiber electrode applied to a vanadium flow battery.
Detailed Description
To facilitate an understanding of the invention, a more complete description of the invention will be given below in terms of preferred embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
A porous electrode prepared by the following method:
(1) weighing 2g of Polyacrylonitrile (PAN), 1g of zinc nitrate and 17g N, N-dimethylformamide, mixing, heating in a water bath at 70 ℃ for dissolving, and preparing into an electrospinning stock solution.
(2) Taking 15mL of electrospinning stock solution in the step 1, and connecting a 20G (inner diameter of 0.60mm) needleA head, setting the advancing speed of the electrospinning stoste to be 1.0mL h-1The voltage of electrospinning is 17kV, the distance from the needle to the receiving end is 20cm, and the rotating speed of the receiving rotating wheel is 200 rpm. The ambient temperature of electrospinning was 25 ℃ and the relative humidity was 55%. And taking down the electrospun fiber membrane after spinning for 10 hours.
(3) Weighing 1g of 2-methylimidazole, dissolving in 200mL of methanol and ethanol in a volume ratio of 1: 1, cutting the electrospun fiber membrane (4cm multiplied by 4cm) in the step 2, soaking the electrospun fiber membrane in a 2-methylimidazole solution, stirring for 12 hours, taking out the electrospun fiber membrane, washing the electrospun fiber membrane twice by using alcohol, and drying the electrospun fiber membrane at the temperature of 60 ℃ to obtain the fiber filament of the in-situ grown MOF particles, wherein the SEM of the fiber filament is shown in figure 1.
(4) Placing the electrospun fiber membrane in which the MOF particles grow in situ in the step 3 in a muffle furnace, pre-oxidizing for 2h at 250 ℃ in the air atmosphere, and raising the temperature at 1 ℃ for min-1(ii) a Placing the preoxidized fiber in nitrogen atmosphere, carbonizing at 1500 deg.C for 1h, and heating at 5 deg.C for 5 min-1。
(5) And (4) soaking the electrode obtained in the step (4) in dilute hydrochloric acid for 12 hours, then washing with water twice, and drying.
The microstructure of the porous electrode prepared in this example is shown in fig. 2. The surface area of the porous electrode of the embodiment can reach 276.85m2 g-1。
Cell testing using the porous electrode of this example:
a porous electrode with the thickness of 700 mu m and the area of 2cm multiplied by 2cm is taken as an electrode of the all-vanadium redox flow battery, and the electrode, a polytetrafluoroethylene pad, a Nafion @ NR-212 diaphragm, a graphite plate with an interdigital flow field, a gold-plated copper collector plate, an aluminum end plate and an bakelite plate are fastened and assembled into a single cell through bolts. Wherein the positive electrolyte is 20mL of 1M VO2++3M H2SO4The solution was 20mL of 1M V as a negative electrode electrolyte3++3M H2SO4And (3) solution. The electrolyte passes through a double-channel peristaltic pump for 77mL min-1The pump speed is cycled.
The all-vanadium redox flow battery based on the porous electrode in the embodiment is 100-400mAcm-2Constant current charging and discharging at 200mA cm under different operating current densities-2At current density, the energy efficiency of the cell was 83.2%.
Example 2
A porous electrode prepared by the following method:
(1) weighing 2g of polyacrylonitrile, 1g of zinc acetate and 17g N, N-dimethylformamide, mixing, heating in a water bath at 70 ℃ for dissolving, and preparing into an electrospinning stock solution.
(2) Taking 15mL of the electrospinning raw liquid obtained in the step 1, connecting a 20G (inner diameter of 0.60mm) needle head, and setting the propelling speed of the electrospinning raw liquid to be 1.0mL h-1The voltage of electrospinning is 17kV, the distance from the needle to the receiving end is 20cm, and the rotating speed of the receiving rotating wheel is 200 rpm. The ambient temperature of electrospinning was 25 ℃ and the relative humidity was 55%. And taking down the electrospun fiber membrane after spinning for 10 hours.
(3) Weighing 1g of 2-methylimidazole, dissolving in 200mL of methanol and ethanol in a volume ratio of 1: 1, cutting the electrospun fiber membrane (4cm multiplied by 4cm) in the step 2, soaking the electrospun fiber membrane in a 2-methylimidazole solution, stirring for 12 hours, taking out the electrospun fiber membrane, washing the electrospun fiber membrane twice by using alcohol, and drying the electrospun fiber membrane at the temperature of 60 ℃. The resulting filaments of in situ grown MOF particles had SEM similar to fig. 1.
(4) Placing the electrospun fiber membrane in which the MOF particles grow in situ in the step 3 in a muffle furnace, pre-oxidizing for 2h at 250 ℃ in the air atmosphere, and raising the temperature at 1 ℃ for min-1Placing the preoxidized fiber yarn in a nitrogen protective atmosphere, carbonizing at 1500 deg.C for 1h, and heating at 5 deg.C for min-1。
(5) And (4) soaking the electrode obtained in the step (4) in dilute hydrochloric acid for 12 hours, then washing with water twice, and drying.
The microstructure of the porous electrode prepared in this example is shown in fig. 3.
The battery test using the porous electrode of this example was conducted in the same manner as in the example.
The surface area of the porous electrode of the embodiment can reach 97.84m2 g-1The porous electrode prepared in this example was assembled into an all-vanadium redox flow battery according to the battery assembly method of example 1, and a constant current charge and discharge test was performed. The charge-discharge curve and the efficiency curve of the battery are respectively as followsShown in FIGS. 4 and 5, in which the thickness is 400mA cm-2At current density, the cell energy efficiency was 79.3%.
Comparative example 1
A smooth filament electrode prepared by the following method:
(1) weighing 2g of polyacrylonitrile and 18g N, N-dimethylformamide, mixing, and heating in a water bath at 70 ℃ for 12h to prepare a 10 wt% spinning precursor solution.
(2) 10mL of 10 wt% spinning precursor solution was taken in a syringe, and a 20G (inner diameter 0.6mm) needle was attached, and the solution advancing speed was set to 1mL h-1The voltage of electrospinning is 20kV, the distance from the needle head to the receiving end is 20cm, and the rotating speed of the receiving rotating wheel is 200 rpm. The environment temperature of electrospinning is 25 ℃, the relative humidity is 45%, and the PAN fiber filaments are taken down after 10h of spinning.
(3) Placing the taken PAN fiber in a muffle furnace, pre-oxidizing for 2h at 250 ℃ in the air atmosphere, and raising the temperature for 1 ℃ min-1。
(4) Placing the preoxidized fiber in nitrogen atmosphere, carbonizing at 1500 deg.C for 1h, and heating at 5 deg.C for 5 min-1。
The carbon fiber electrode of this comparative example had a specific surface area of 43.8m2 g-1。
The carbon fiber electrode prepared in the comparative example is assembled into an all-vanadium redox flow battery according to the battery assembly method in the example 1, and a constant current charge and discharge test is carried out. At 200mA cm-2At current density, the cell energy efficiency was 73.9%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A preparation method of a porous electrode for a flow battery is characterized by comprising the following steps:
s1, adding polyacrylonitrile and metal salt into N, N-dimethylformamide or N, N-dimethylacetamide, heating and mixing, and dissolving the polyacrylonitrile and the metal salt to obtain an electrospinning stock solution, wherein the mass fraction of the polyacrylonitrile is 5-20 wt%, and the mass fraction of the metal salt is 1-10 wt%; the metal salt is selected from: one or two of zinc acetate and zinc nitrate;
s2, carrying out electrostatic spinning by using the electrospinning stock solution to obtain an electrospun fiber membrane;
s3, dissolving an organic ligand in a solvent to obtain an organic ligand solution, soaking the electrospun fiber membrane in the organic ligand solution for a period of time, and allowing MOF particles to be generated on the surface of the fiber filaments in situ;
s4, pre-oxidizing the fiber filaments with the MOF particles deposited on the surfaces, and then carbonizing the fiber filaments in an inert gas atmosphere at the temperature of 1000-3000 ℃ to obtain the porous electrode.
2. The method as claimed in claim 1, wherein in step S1, the polyacrylonitrile has an average molecular weight of 25000-200000g mol-1。
3. The preparation method according to claim 1, wherein in the step S2, the electrostatic spinning process parameters are as follows: the diameter of the needle is 0.2-2mm, and the advancing speed of the electrospinning stock solution is 0.2-2mL h-1The rotating speed of the rotating wheel at the receiving end is 100-1000rpm, the distance between the needle head and the receiver is 10-50cm, the voltage between the needle head and the receiving end is 10-50kV, the temperature of electrostatic spinning is 20-35 ℃, and the relative humidity is 40-70%; the thickness of the electrospun fiber membrane is 100 mu m-5 mm.
4. The method according to claim 1, wherein in step S3, the organic ligand is 2-methylimidazole, and the solvent is selected from: one or more of methanol, ethanol and water.
5. The method as claimed in claim 1, wherein the soaking time is 2-24h in step S3, and stirring is performed during the soaking.
6. The method as claimed in any one of claims 1 to 5, wherein the pre-oxidation is performed in an air or oxygen atmosphere at a pre-oxidation temperature of 220-300 ℃ and a temperature increase rate of 1-10 ℃ for min in step S4-1The pre-oxidation time is 1-3 h; the inert atmosphere is argon or nitrogen during carbonization, and the heating rate is 2-10 deg.C for min-1The carbonization time is 0.5-5 h.
7. The method as claimed in claim 1, wherein the step S4 is further followed by a step S5: and (4) carrying out acid washing, water washing and drying on the obtained porous electrode.
8. A porous electrode prepared by the preparation method of any one of claims 1 to 7.
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