CN111584895A - Oriented ordered electrode and preparation method and application thereof - Google Patents
Oriented ordered electrode and preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- Y02E60/30—Hydrogen technology
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Abstract
The invention provides a directional ordered electrode and a preparation method and application thereof, and relates to the technical field of flow batteries. The oriented ordered electrode comprises a carbon fiber group, wherein the carbon fiber group comprises a plurality of oriented carbon fiber filaments and a plurality of crossed carbon fiber filaments, and the number ratio of the oriented carbon fiber filaments to the crossed carbon fiber filaments is 70: 30-95: 5; the diameters of the oriented carbon fiber filaments and the crossed carbon fiber filaments are 200nm-20 μm. The directional ordered electrode can greatly reduce the transmission resistance of fluid, improve the active area of the electrode and further improve the distribution uniformity of electrolyte in the electrode, and is suitable for a redox flow battery.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to a directional ordered electrode and a preparation method and application thereof.
Background
In recent years, with the increasing energy crisis and environmental problems, new energy power generation is vigorously developed in all countries of the world, and solar energy and wind energy as renewable energy resources have continuously increased in the total amount of power generation in the world. However, the intermittent and fluctuating characteristics of solar energy and wind energy cause the unstable electric output. The energy storage system with a certain scale is matched, and the instability problem of power generation and power supply of renewable energy sources can be solved by supplementing and consuming the electric quantity of the renewable energy sources, so that the stability of grid connection of wind power and photovoltaic power generation is improved. The flow battery is considered to be one of the main directions of the energy storage system due to the advantages of mutual independence of capacity and power, good safety, long cycle life and the like.
The flow battery mainly comprises the following components: electrodes, separators, and active materials, wherein the electrodes are the sites of electrochemical reactions that affect various parts of the cell loss including activation polarization, ohmic polarization, and concentration polarization. At present, electrode materials used for the flow battery mainly comprise graphite felt, carbon paper and carbon cloth, and the materials have the characteristics of high electronic conductivity, corrosion resistance, high mechanical property and the like. In addition to these commercial carbon materials with fixed macrostructures, the use of electrospinning techniques to produce carbon fibers offers more possibilities for electrode structure design.
At the present stage, the carbon fiber prepared by electrostatic spinning has larger specific surface area of the electrode due to smaller fiber diameter, but the transmission performance of the electrode is also reduced due to the reduction of the fiber diameter. The direct use of electrospun electrodes as flow cell electrodes therefore results in greater flow resistance and concentration polarization. Although some researchers have attempted to improve the uniform distribution of the electrolyte in the electrode by specifically designing the macroscopic geometry of the carbon fiber electrode so as to reduce the flow resistance thereof, the problem has not been solved effectively until now. In addition, the battery structure having the flow channels may cause non-uniform distribution of the electrolyte in the electrodes, thereby causing excessive local current density to affect the overall performance of the battery.
Disclosure of Invention
Accordingly, there is a need to provide an oriented and ordered electrode, which can greatly reduce the transmission resistance of fluid, increase the active area of the electrode, and further improve the distribution uniformity of the electrolyte in the electrode. The electrode is suitable for redox flow batteries.
An oriented and ordered electrode, comprising a carbon fiber group, wherein the carbon fiber group comprises a plurality of oriented carbon fiber filaments and a plurality of crossed carbon fiber filaments, and the number ratio of the oriented carbon fiber filaments to the crossed carbon fiber filaments is 70: 30-95: 5; the diameters of the oriented carbon fiber filaments and the crossed carbon fiber filaments are 200nm-20 μm.
In the fiber filament group of the electrode, most of the carbon fiber filaments are arranged in an oriented manner to provide reaction sites for electrode reaction, and a small part of the carbon fiber filaments are distributed in a crossed manner to ensure the mechanical property of the electrode; because most of the carbon fiber yarns in the electrode are arranged in an oriented mode, the active area of the electrode can be increased, meanwhile, the flow resistance and concentration polarization of electrolyte can be reduced, and the distribution uniformity of the electrolyte in the electrode is improved.
The oriented and ordered electrode can be used as a framework of the electrode, and can be subjected to a plurality of chemical modifications on the basis, so that the electrochemical activity of the electrode is further improved.
In one embodiment, the diameter of the aligned carbon fiber filaments and the cross-aligned carbon fiber filaments is 200nm to 10 μm.
In one embodiment, the oriented ordered electrode further comprises a dense carbon fiber layer assembled with the carbon fiber group to form a double-layer electrode; the diameters of the oriented ordered carbon fiber filaments and the cross-arranged carbon fiber filaments in the carbon fiber group are 1-20 μm, and the diameters of the carbon fiber filaments in the compact carbon fiber layer are 200nm-1 μm. When the carbon fiber composite membrane is applied to a flow battery, the carbon fiber group is used as a transmission layer and is arranged on the side close to a flow channel, and the dense carbon fiber electrode is used as a catalyst layer and is arranged on the side close to a membrane.
In one embodiment, the surfaces of the directionally arranged carbon fiber filaments and the cross-arranged carbon fiber filaments are loaded with catalyst particles and/or carbon nanotubes. The activity of the electrode can be further improved by loading catalyst particles and/or carbon nanotubes.
The invention also provides a preparation method of the oriented and ordered electrode, which utilizes an electrostatic spinning technology to prepare the oriented and ordered carbon fiber yarns by adjusting the concentration of the spinning solution and the control parameters of electrostatic spinning. The preparation method comprises the following steps:
s1, dissolving polyacrylonitrile in a solvent to prepare a spinning solution, wherein the mass fraction of the polyacrylonitrile in the spinning solution is 12-20%;
s2, carrying out electrostatic spinning on the spinning solution, wherein the diameter of a needle head is 0.2-2mm, and the advancing speed of the spinning solution is 0.5-2 mL.h-1The rotation speed of the receiving end rotating wheel is 100-2000rpm, the distance between the needle head and the receiver is 10-50cm, and the voltage between the needle head and the receiving end is 0.8-1.2kV cm-1The temperature of electrostatic spinning is 20-35 ℃, the relative humidity is 40-70%, and the carbon fiber group is obtained after spinning;
and S3, pre-oxidizing the carbon fiber group in the air, and carbonizing the carbon fiber group in an inert gas atmosphere to obtain the oriented ordered electrode.
The motor prepared by the preparation method has the characteristic of ordered orientation, the transmission resistance of the electrolyte in the electrode is greatly reduced, and the distribution uniformity of the electrolyte in the electrode is improved.
Preferably, in the step S2, the rotation speed of the receiving end wheel is 100-500 rpm.
In one embodiment, the polyacrylonitrile has an average molecular weight of 25000-200000 g-mol-1The solvent is N, N-dimethylformamide and/or N, N-dimethylacetamide.
In one embodiment, in step S1, polyacrylonitrile is added into the solvent, and the mixture is heated and stirred at 40-80 ℃ for 10-20h to dissolve, so as to obtain the spinning solution.
In one embodiment, in the step S3, the pre-oxidation temperature is 220--1The pre-oxidation time is 1-3 h; the inert atmosphere is selected from: argon, nitrogen or a mixed gas of argon and hydrogen, wherein the mass fraction of the hydrogen in the mixed gas of argon and hydrogen is less than or equal to 10 percent; the carbonization temperature is 800-3000 ℃, the carbonization time is 0.5-5h, and the heating rate is 2-10 ℃ for min-1。
Preferably, for the electrode with the carbonization temperature higher than 2000 ℃, the oxidation activation is carried out in the air, the activation temperature is 300-400 ℃, and the activation time is 4-12 h.
The invention also provides a preparation method of the oriented ordered electrode with the catalyst particles loaded on the surface of the carbon fiber yarn. The preparation method comprises the following steps:
s1, dissolving polyacrylonitrile and metal salts in a solvent to prepare a mixed spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 12-25%, and the mass fraction of the metal salts is 1-10 wt%;
s2, carrying out electrostatic spinning on the mixed spinning solution, wherein the diameter of a needle is 0.2-2mm, and the advancing speed of the spinning solution is 0.2-2 mL.h-1The rotation speed of the receiving end rotating wheel is 100-2000rpm, the distance between the needle head and the receiver is 10-50cm, and the voltage between the needle head and the receiving end is 0.8-1.2kV cm-1The temperature of electrostatic spinning is 20-35 ℃, the relative humidity is 40-70%, and the carbon fiber group is obtained after spinning;
and S3, pre-oxidizing the carbon fiber group in the air, and carbonizing the carbon fiber group in an inert gas atmosphere to obtain the oriented ordered electrode.
In one embodiment, in step S1, polyacrylonitrile and metal salts are added to a solvent, and the mixture is heated and stirred at 40-80 ℃ for 10-20 hours to dissolve, so as to obtain a mixed spinning solution.
In one embodiment, the metal salt is selected from: one or more of manganese acetate, manganese nitrate, nickel acetate, nickel nitrate, zinc acetate and zinc nitrate.
Preferably, in the step S2, the rotation speed of the receiving end wheel is 100-500 rpm.
In one embodiment, in the step S3, the pre-oxidation temperature is 220--1The pre-oxidation time is 1-3 h; the inert atmosphere is selected from: argon, nitrogen, or a mixed gas of argon and hydrogen; the carbonization temperature is 800-3000 ℃, the carbonization time is 0.5-5h, and the heating rate is 2-10 ℃ for min-1。
Preferably, for the electrode with the carbonization temperature higher than 2000 ℃, the oxidation activation is carried out in the air, the activation temperature is 300-400 ℃, and the activation time is 4-12 h.
The motor prepared by the preparation method has the characteristic of ordered orientation, the transmission resistance of electrolyte in the electrode is greatly reduced, and the carbon fiber wires of the electrode are loaded with catalyst particles, so that the activity of the electrode is further promoted.
The invention also provides an application of the oriented ordered electrode in the preparation of a flow battery. The flow battery manufactured by the oriented ordered electrode has small flow resistance and high battery efficiency.
Compared with the prior art, the invention has the following beneficial effects:
in the fiber filament group of the oriented and ordered electrode, most of the carbon fiber filaments are oriented and arranged to provide reaction sites for electrode reaction, and a small number of the carbon fiber filaments are in cross distribution to ensure the mechanical property of the electrode; because most of the carbon fiber yarns in the electrode are arranged in an oriented mode, the active area of the electrode can be increased, meanwhile, the flow resistance and concentration polarization of electrolyte can be reduced, and the distribution uniformity of the electrolyte in the electrode is improved.
The directional ordered electrode prepared by the preparation method can greatly reduce the transmission resistance of fluid, improve the active area of the electrode and further improve the distribution of electrolyte in the electrode.
Drawings
FIG. 1 is an SEM picture of an oriented ordered electrode of an example;
FIG. 2 shows that the total vanadium redox flow battery in the embodiment is 60-250mA cm-2Constant current charging and discharging curves under different operating current densities;
FIG. 3 shows that the total vanadium redox flow battery in the embodiment is 60-250mA cm-2Constant current charge-discharge efficiency under different operating current densities;
FIG. 4 is an SEM picture of an oriented ordered electrode with catalyst particles generated on the surface of carbon fiber filaments in the example;
FIG. 5 is an SEM picture of an oriented ordered electrode in which carbon nanotubes are grown on the surface of carbon fiber filaments in the examples.
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.
Example 1
An oriented ordered electrode prepared by the following method:
(1) weighing 3g of Polyacrylonitrile (PAN) and 17g N, N-dimethylformamide, mixing, heating and dissolving in a water bath at 70 ℃ to prepare a 15 wt% spinning precursor solution.
(2) 15mL of 15 wt% PAN solution was taken, a 15G needle (inner diameter 1.40mm) was attached, and the solution advancing speed was set to 1.0 mL. multidot.h-1. The voltage of electrospinning is set to be 17kV, the distance from the needle head to the receiving end is 17cm, and the rotating speed of the receiving rotating wheel is 500 rpm. The ambient temperature of electrospinning was 25 ℃ and the relative humidity was 55%. Taking down after spinning for 10 h.
(3) Pre-oxidizing the taken PAN fiber filaments in a muffle furnace at 250 ℃ for 2h at a heating speedThe rate is 1 ℃ min-1. Carbonizing the preoxidized fiber filaments at 1100 ℃ for 1h under the nitrogen protection atmosphere at the temperature rise rate of 5 ℃ per minute-1。
The microstructure of the oriented ordered electrode obtained in this example is shown in FIG. 1, and the diameter distribution range is 7-12 μm.
Cell testing on the oriented ordered electrode of this example:
taking a directional ordered electrode with the thickness of 700 mu M and the area of 2cm × 2cm as an all-vanadium redox flow battery electrode, and assembling the electrode, a polytetrafluoroethylene pad, a Nafion @ NR-212 diaphragm, a graphite plate with a serpentine flow field, a gold-plated copper current collecting plate, an aluminum end plate and an bakelite plate into a single cell through bolt fastening, wherein the positive electrolyte is 20mL of 1M VO (vacuum VO) VO (vacuum ion valve)2++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 76mL min-1The pump speed is cycled.
The all-vanadium redox flow battery based on the directional ordered electrode of the embodiment is 60-250 mA-cm-2The constant current charge and discharge curves at different operating current densities within the range are shown in fig. 2. The all-vanadium redox flow battery based on the directional ordered electrode of the embodiment is 60-250 mA-cm-2The constant current charge and discharge efficiency at different current densities within the range is shown in fig. 3. Wherein, at 150mA cm-2At current density, the voltage efficiency of the cell was 81.2% and the energy efficiency was 80.7%.
Example 2
A directional ordered carbon fiber and dense carbon fiber double-layer composite electrode is prepared by the following method:
(1) weighing 2g of polyacrylonitrile and 18g N, N-dimethylformamide, mixing, heating and dissolving in a water bath at 70 ℃ to prepare a 10 wt% spinning precursor solution.
(2) 10mL of 10 wt% PAN solution was taken and connected to 20G (inner diameter: 0.60mm), and the solution advancing speed was set to 1.0 mL. multidot.h-1. The voltage of electrospinning is set to be 17kV, the distance from the needle head to the receiving end is 20cm, and the rotating speed of the receiving rotating wheel is 100 rpm. The ambient temperature of electrospinning was 25 ℃ and the relative humidity was 40%. Spinning for 10hAnd (6) taking down.
(3) Pre-oxidizing the taken PAN fiber filaments in a muffle furnace at 250 ℃ for 2h at the heating rate of 1 ℃ min-1. Carbonizing the preoxidized fiber filaments at 1100 ℃ for 1h under the nitrogen protection atmosphere at the temperature rise rate of 5 ℃ per minute-1。
(4) The dense carbon fiber electrode with the thickness of 100 microns prepared in the steps and the directional ordered electrode with the thickness of 600 microns in the embodiment 1 are spliced to form a double-layer electrode.
The double-layer composite electrode of the present example was subjected to a battery test in the same manner as in example 1. Tested and tested at 150mA cm-2At current density, the voltage efficiency of the cell was 83.6% and the energy efficiency was 81.2%.
Example 3
An oriented ordered electrode with catalyst particles loaded on the surface of a fiber filament is prepared by the following method:
(1) weighing 2g of polyacrylonitrile, 1g of manganese nitrate granules and 17g N, N-dimethylformamide, mixing, heating in a water bath at 70 ℃ for dissolving, and preparing PAN (10 wt%)/Mn (NO)3)2(5 wt%) spinning precursor solution.
(2) 10mL of the mixed solution obtained in step 1 was taken and 20G (inner diameter: 0.60mm) was connected to the mixed solution, and the solution advancing speed was set to 0.6 mL. multidot.h-1. The voltage of electrospinning is set to be 17kV, the distance from the needle head to the receiving end is 17cm, and the rotating speed of the receiving rotating wheel is 500 rpm. The ambient temperature of electrospinning was 25 ℃ and the relative humidity was 55%. Taking down after spinning for 10 h.
(3) Pre-oxidizing the taken PAN fiber filaments in a muffle furnace at 250 ℃ for 2h at the heating rate of 1 ℃ min-1. Carbonizing the preoxidized fiber filaments at 1100 ℃ for 1h under the nitrogen protection atmosphere at the temperature rise rate of 5 ℃ per minute-1。
The oriented ordered electrode with the catalyst particles loaded on the surface of the carbon fiber filament is obtained by the method, and the microstructure of the electrode is shown in figure 4.
Example 4
A directional ordered electrode with carbon nanotubes loaded on the surface of a fiber filament is prepared by the following method:
(1) weighing 2g of polyacrylonitrile, 1g of nickel nitrate particles and 17g N, N-dimethylformamide, mixing, heating in a water bath at 70 ℃ for dissolving, and preparing PAN (10 wt%)/Ni (NO)3)2(5 wt%) spinning precursor solution.
(2) 10mL of the mixed solution obtained in step 1 was taken and 20G (inner diameter: 0.60mm) was connected to the mixed solution, and the solution advancing speed was set to 1.0 mL. multidot.h-1. The voltage of electrospinning is set to be 17kV, the distance from the needle head to the receiving end is 20cm, and the rotating speed of the receiving rotating wheel is 500 rpm. The ambient temperature of electrospinning was 25 ℃ and the relative humidity was 40%. Taking down after spinning for 10 h.
(3) Pre-oxidizing the taken PAN fiber filaments in a muffle furnace at 250 ℃ for 2h at the heating rate of 1 ℃ min-1. Adding a suitable carbon source into the preoxidized fiber filaments in a tubular furnace under the protection atmosphere of argon and hydrogen (the mass fraction of hydrogen is 10%), for example, placing some polyvinylpyrrolidone particles at the upstream position of the protection atmosphere in the tubular furnace, or introducing acetylene gas into the tubular furnace, carbonizing at 1100 ℃ for 1h at the heating rate of 5 ℃ per minute-1。
The oriented ordered electrode with the surface loaded with the carbon nanotubes is obtained by the method, and the microstructure of the electrode is shown in figure 5.
Comparative example 1
A nanometer-grade fiber wire electrode is prepared by the following steps:
(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% PAN solution was taken in a syringe and a 20G (inner diameter 0.6mm) needle was attached to set the solution advancing speed at 1 mL. h-1. The voltage of electrospinning is set to be 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 spinning is carried out for 10 hours and then the spinning is taken down.
(3) Pre-oxidizing the taken PAN fiber filaments in a muffle furnace at 250 ℃ for 2h at the heating rate of 1 ℃ min-1. Carbonizing the preoxidized fiber filaments at 1100 deg.C for 1h under nitrogen protection atmosphere at a heating rate of 5 deg.C·min-1。
And (3) assembling the electrode prepared in the comparative example into an all-vanadium redox flow battery according to the battery assembling method in the example 1, and carrying out constant-current charge and discharge tests. The electrode of this comparative example was set at 100mA cm-2At current density, the cell energy efficiency was 71.2%.
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 (10)
1. The oriented and ordered electrode is characterized by comprising a carbon fiber group, wherein the carbon fiber group comprises a plurality of oriented carbon fiber filaments and a plurality of crossed carbon fiber filaments, and the number ratio of the oriented carbon fiber filaments to the crossed carbon fiber filaments is 70: 30-95: 5; the diameters of the oriented carbon fiber filaments and the crossed carbon fiber filaments are 200nm-20 μm.
2. The oriented, ordered electrode of claim 1, wherein the oriented carbon fiber filaments and the cross-aligned carbon fiber filaments have a diameter of 200nm to 10 μm.
3. The oriented ordered electrode of claim 1, further comprising a layer of densified carbon fibers assembled with the set of carbon fibers to form a two-layer electrode; the diameters of the oriented ordered carbon fiber filaments and the cross-arranged carbon fiber filaments in the carbon fiber group are 1-20 μm, and the diameters of the carbon fiber filaments in the compact carbon fiber layer are 200nm-1 μm.
4. The oriented ordered electrode of claim 1, wherein the surface of the oriented carbon fiber filaments and the cross-aligned carbon fiber filaments are loaded with catalyst particles and/or carbon nanotubes.
5. A method of making an oriented ordered electrode according to any of claims 1 to 3, comprising the steps of:
s1, dissolving polyacrylonitrile in a solvent to prepare a spinning solution, wherein the mass fraction of the polyacrylonitrile in the spinning solution is 12-20%;
s2, carrying out electrostatic spinning on the spinning solution, wherein the diameter of a needle head is 0.2-2mm, and the advancing speed of the spinning solution is 0.5-2 mL.h-1The rotation speed of the receiving end rotating wheel is 100-2000rpm, the distance between the needle head and the receiver is 10-50cm, and the voltage between the needle head and the receiving end is 0.8-1.2kV cm-1The temperature of electrostatic spinning is 20-35 ℃, the relative humidity is 40-70%, and the carbon fiber group is obtained after spinning;
and S3, pre-oxidizing the carbon fiber group in the air, and carbonizing the carbon fiber group in an inert gas atmosphere to obtain the oriented ordered electrode.
6. The method as claimed in claim 5, wherein the polyacrylonitrile has an average molecular weight of 25000-200000 g-mol-1The solvent is N, N-dimethylformamide and/or N, N-dimethylacetamide.
7. The preparation method according to claim 5 or 6, wherein in the step S1, polyacrylonitrile is added into the solvent, heated and stirred at 40-80 ℃ for 10-20h to be dissolved, and then the spinning solution is obtained;
in the step S3, the pre-oxidation temperature is 220-300 ℃, and the temperature rise rate is 1-10 ℃ min-1The pre-oxidation time is 1-3 h; the inert atmosphere is selected from:argon, nitrogen, or a mixed gas of argon and hydrogen; the carbonization temperature is 800-3000 ℃, the carbonization time is 0.5-5h, and the heating rate is 2-10 ℃ for min-1。
8. A method of making an oriented ordered electrode according to claim 4, comprising the steps of:
s1, dissolving polyacrylonitrile and metal salts in a solvent to prepare a mixed spinning solution, wherein the mass fraction of polyacrylonitrile in the spinning solution is 12-25%, and the mass fraction of the metal salts is 1-10 wt%;
s2, carrying out electrostatic spinning on the mixed spinning solution, wherein the diameter of a needle is 0.2-2mm, and the advancing speed of the spinning solution is 0.2-2 mL.h-1The rotation speed of the receiving end rotating wheel is 100-2000rpm, the distance between the needle head and the receiver is 10-50cm, and the voltage between the needle head and the receiving end is 0.8-1.2kV cm-1The temperature of electrostatic spinning is 20-35 ℃, the relative humidity is 40-70%, and the carbon fiber group is obtained after spinning;
and S3, pre-oxidizing the carbon fiber group in the air, and carbonizing the carbon fiber group in an inert gas atmosphere to obtain the oriented ordered electrode.
9. The preparation method according to claim 8, wherein in step S1, polyacrylonitrile and metal salt are added into a solvent, heated and stirred at 40-80 ℃ for 10-20h to dissolve, and thus a mixed spinning solution is obtained; the metal salt is selected from: one or more of manganese acetate, manganese nitrate, nickel acetate, nickel nitrate, zinc acetate and zinc nitrate;
in the step S3, the pre-oxidation temperature is 220-300 ℃, and the temperature rise rate is 1-10 ℃ min-1The pre-oxidation time is 1-3 h; the inert atmosphere is selected from: argon, nitrogen, or a mixed gas of argon and hydrogen; the carbonization temperature is 800-3000 ℃, the carbonization time is 0.5-5h, and the heating rate is 2-10 ℃ for min-1。
10. Use of an oriented ordered electrode according to any one of claims 1 to 4 in the manufacture of a flow battery.
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