CN110844880A - Preparation method of fluorine-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material - Google Patents

Preparation method of fluorine-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material Download PDF

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CN110844880A
CN110844880A CN201911069139.0A CN201911069139A CN110844880A CN 110844880 A CN110844880 A CN 110844880A CN 201911069139 A CN201911069139 A CN 201911069139A CN 110844880 A CN110844880 A CN 110844880A
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pfsa
alkali metal
hydrogen storage
pan
porous carbon
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CN110844880B (en
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陈晓红
薛志勇
曾宏
张永明
武英
任宇
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Beijing Huadian New Energy Electrical Materials Research Institute Co Ltd
North China Electric Power University
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Beijing Huadian New Energy Electrical Materials Research Institute Co Ltd
North China Electric Power University
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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    • B22—CASTING; POWDER METALLURGY
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
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    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • Y02E60/32—Hydrogen storage

Abstract

The invention discloses a preparation method of a fluorine-doped porous carbon nanofiber loaded alkali metal hydrogen storage material, belonging to the technical field of hydrogen storage; the method prepares the porous nano-fiber by an electrostatic spinning method and a hydrothermal method; and then replacing the porous PAN/PFSA nano-fiber with an alkali metal solution to form the lithium/calcium-porous PAN/PFSA nano-fiber, and calcining to prepare the hydrogen storage material which has a large specific surface area, is doped with fluorine and is compounded by uniformly dispersing alkali metal in the porous carbon nano-fiber. The alkali metal and the porous carbon nanofiber are favorable for improving the mass hydrogen storage density, and fluorine doping is favorable for not only the mass hydrogen storage density of the composite material, but also the dehydrogenation temperature of the composite material, so that reversible hydrogen absorption and desorption are realized. The porous carbon nanofiber loaded alkali metal hydrogen storage material is applied to fuel cells, lithium ion batteries and super capacitors; can also be used as carbon-supported alkali metal catalyst.

Description

Preparation method of fluorine-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material
Technical Field
The invention belongs to the technical field of hydrogen storage, and particularly relates to a preparation method of a fluorine-doped porous carbon nanofiber loaded alkali metal hydrogen storage material; in particular to a fluorine-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material, a preparation method thereof and application thereof in the field of hydrogen storage
Background
As society develops, the increasing air pollution and limited traditional energy sources have enhanced the opportunity to find sustainable and renewable energy sources. Hydrogen energy is one of the ideal energy sources, and it is clean, non-toxic and abundant. However, efficient and safe hydrogen storage is a major bottleneck for large-scale application of hydrogen energy. Therefore, the search for efficient, safe and stable hydrogen storage materials has become a hotspot and difficulty in hydrogen energy research in recent years. At present, there are many existing hydrogen storage methods, such as high-pressure hydrogen storage, low-temperature liquefied hydrogen storage, metal hydride hydrogen storage, metal organic framework material and solid adsorbent hydrogen storage. In recent years, carbon-based nano-adsorption materials have attracted great interest to researchers due to their unique electronic characteristics, light weight, large surface area, safe hydrogen storage, high hydrogen absorption and desorption performance and the like. Such hydrogen storage materials include carbon nanotubes, fullerenes, graphene, carbon nanofibers, and the like. The pure carbon-based nano material and the hydrogen are physically adsorbed mainly through Van der Waals force, electrostatic field force and the like, so that the hydrogen storage is realized. However, pure carbon nanomaterials have weak hydrogen adsorption and low hydrogen storage capacity, and are far from meeting the requirements of practical application.
At present, heterogeneous atoms and alkali metals are mainly adopted to load or dope carbon-based nano materials as hydrogen storage materials, including:
(1) heterogeneous atomic nitrogen (N) and fluorine (F) doped carbon-based nanomaterials. The N atoms are doped into the porous carbon material, so that the hydrogen adsorption energy of adjacent carbon can be improved, the hydrogen storage density of the porous carbon material is 18% higher than that of a pure carbon material, and the hydrogen storage performance of the porous carbon material is greatly improved. Similarly, when F atoms are doped into the carbon material, the F atoms are formed to have sp by the high electronegativity and the change of the electron arrangement of the adjacent carbon atoms2The hybridized carbon structure delocalized conjugated system strengthens the adsorption of the carbon structure with hydrogen so as to improve the hydrogen storage performance of the carbon structure. However, the doping amount of the F-doped carbon material is low due to the high doping difficulty, and the hydrogen storage performance of the F-doped carbon material is limited. Therefore, a reliable and stable fluorine source and a carbon-based material with a large specific surface area are key to such hydrogen storage materials.
(2) The alkali metal is loaded on the carbon-based nano material. The alkali metal has small cohesive energy and atomic mass, so that the action between the carbon-based nano material loaded by the alkali metal and hydrogen molecules is enhanced, higher hydrogen storage capacity and lower dehydrogenation temperature are achieved, and great interest of researchers is aroused. The advantages of alkali metals are mainly represented by: (i) the hydrogen storage performance is increased. The alkali metals Li, Na and Ca are loaded on the carbon-based nano material, and the hydrogen storage performance of the carbon-based nano material is obviously improved. After Ca is loaded on three-dimensional (3D) porous graphene, the hydrogen storage density can reach 5-6 wt% under certain temperature and pressure. (ii) The dehydrogenation temperature is reduced. de Jong et al treated NaAlH4After the carbon nanofiber is loaded, compared with pure carbon nanofibers, the hydrogen absorption dehydrogenation performance of the carbon nanofiber is obviously improved, and the dehydrogenation temperature is reduced to 160 ℃. [9]Of particular note is the doping of F atoms to NaMgH3The formation enthalpy and the reaction enthalpy can be reduced, so that the thermodynamic property is changed, the hydrogen release is facilitated, and the dehydrogenation temperature is reduced. Therefore, F atoms can be doped into the carbon-based material to improve the hydrogen storage capacity of the carbon-based material, and can also be doped into alkali metal to reduce the dehydrogenation temperature of the carbon-based material.
However, the bonding energy of the alkali metal loaded on the carbon-based nanomaterial is less than that of the alkali metal crystal, so that the alkali metal is easy to agglomerate on the surface of the nanomaterial in practical application, and the hydrogen storage capacity is greatly reduced. Therefore, research and design are made on a method for preparing the carbon-based material, which can improve the doping amount of F atoms, and enable alkali metal atoms to be loaded on the carbon-based material, not to be easily agglomerated and uniformly dispersed in the carbon-based material, so as to improve the mass hydrogen storage density and reduce the dehydrogenation temperature. Therefore, the F-doped carbon-based nano material loaded by the alkali metal is a hydrogen storage material with great potential.
Disclosure of Invention
The invention aims to provide a preparation method of a fluorine-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material, which is characterized by comprising the following steps of:
(1) immersing Polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP) and perfluorosulfonic acid (PFSA) powder into N, N-Dimethylformamide (DMF), and stirring the mixed system at normal temperature for 20-48 hours;
(2) preparing the uniformly dispersed mixed solution in the step (1) into porous nano fibers by an electrostatic spinning method and a hydrothermal method;
(3) replacing the porous PAN/PFSA nanofibers obtained in the step (2) with an alkali metal solution to form lithium/calcium-porous PAN/PFSA nanofibers;
(4) putting the lithium/calcium-porous PAN/PFSA nano-fiber in the step (3) into a graphite cup, putting the graphite cup into a tubular quartz furnace, heating to 600-1000 ℃ at a heating rate of 1-10 ℃/min under the protection of inert gas flow with gas flow of 60-100 mL/min, and preserving heat for 2-5 hours to finish the carbonization process; cooling to obtain F-doped porous carbon nanofiber loaded alkali metal;
the molecular weight of polyacrylonitrile in the step (1) is 150000; the PVP molecular weight is 300000; the mass ratio of polypropylene polyacrylonitrile to polyvinylpyrrolidone is 1: 1 or 2: 1;
the PFSA powder in the step (1) accounts for 1-5 wt% of the total weight of the PAN and the PVP.
And (2) the PAN, PVP and PFSA powder in the mixed solution in the step (1) accounts for 8-12 wt% of the total weight of the solution.
The electrostatic spinning process in the step (2) comprises the following steps: putting the mixed solution in the step (1) into a 5mL syringe, and extruding by a push pump at the speed of 0.05 mL/h-0.25 mL/h; the spinning voltage is 10-20 kV, and the distance from a spinning nozzle to a receiver is 15-20 cm; and drying the obtained fiber in an oven at 80 ℃ for 6-8 hours, and removing the solvent N, N-dimethylformamide to obtain the PAN/PVP/PFSA nano fiber.
The hydrothermal process in the step (2): and soaking the PAN/PVP/PFSA nano-fiber in water, then placing the nano-fiber in a muffle furnace, keeping the temperature at 110 ℃ for 24-48 hours, and removing the PVP to form the porous PAN/PFSA nano-fiber.
The alkali metal solution in the step (3) is lithium hydroxide and calcium hydroxide.
The invention has the following beneficial effects:
(1) PFSA is used as a carbon source, a fluorine source and a precursor, and F atoms and alkali metal can be introduced simultaneously, wherein the doping amount of F in the carbon nanofiber is greatly improved. And alkali metal atoms are also uniformly dispersed in the porous carbon-based nanofiber. Therefore, the method for simultaneously introducing F atoms and alkali metals into carbon nanofibers by adopting PFSA is universal and reliable.
(2) The lithium-, sodium-and calcium-F-doped porous nanofiber is used as a hydrogen storage material, wherein F atoms not only change the surface of the carbon material to improve the hydrogen storage performance of the carbon material, but also reduce the dehydrogenation temperature of alkali metal, thereby comprehensively improving the hydrogen storage performance of the Li-, Na-and Ca-F-doped porous nanofiber material.
(3) The prepared F-doped porous carbon nanofiber loaded alkali metal hydrogen storage material is applied to fuel cells, lithium ion batteries and super capacitors; can also be used as carbon-supported alkali metal catalyst.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of PAN/PVP/PFSA composite nanofibers
FIG. 2 is an SEM image of Li-F-doped porous carbon nanofibers
FIG. 3 is a graph of hydrogen storage performance of Li-F-doped porous carbon nanofibers
Detailed Description
The invention provides a preparation method of a fluorine-doped porous carbon nanofiber loaded alkali metal hydrogen storage material, which comprises the following steps:
(1) immersing Polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP) and perfluorosulfonic acid (PFSA) powder into N, N-Dimethylformamide (DMF), and stirring the mixed system at normal temperature for 20-48 hours; wherein the mass ratio of polypropylene polyacrylonitrile to polyvinylpyrrolidone is 1: 1 or 2: 1; the PFSA powder accounts for 1-5 wt% of the total weight of the PAN and the PVP. The PAN, PVP and PFSA powder in the mixed solution accounts for 8-12 wt% of the total weight of the solution.
(2) Preparing the uniformly dispersed mixed solution in the step (1) into porous nano fibers by an electrostatic spinning method and a hydrothermal method;
(3) replacing the porous PAN/PFSA nanofibers obtained in the step (2) with an alkali metal solution to form lithium/calcium-porous PAN/PFSA nanofibers;
(4) putting the lithium/calcium-porous PAN/PFSA nano-fiber in the step (3) into a graphite cup, putting the graphite cup into a tubular quartz furnace, heating to 600-1000 ℃ at a heating rate of 1-10 ℃/min under the protection of inert gas flow with gas flow of 60-100 mL/min, and preserving heat for 2-5 hours to finish the carbonization process; and cooling to obtain the F-doped porous carbon nanofiber loaded alkali metal hydrogen storage material. The invention is further described below with reference to the figures and examples. The raw materials used in the examples of the present invention are all commercially available products unless otherwise specified.
Example 1
1. Preparing a spinning solution, putting 0.5g of PAN, 0.5g of PVP (1: 1) and 0.01g of PFSA into 9g of DMF, mixing and dissolving, wherein the PAN, PVP and PFSA powder in the mixed solution accounts for 10 wt% of the total weight of the solution; stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions of voltage of 18kV, receiving distance of 15cm, spinning solution pushing speed of 0.2mL/h and electrospinning temperature of 30 ℃, the PAN/PVP/PFSA composite nanofiber (shown in figure 1) is obtained through electrostatic spinning, and the PAN/PVP/PFSA composite nanofiber is placed in a vacuum drying oven at 80 ℃ and dried for 8 h.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
Li-porous PAN/PFSA nanofibers: and (2) soaking the porous PAN/PFSA nano-fiber in a (0.01g/mL) lithium hydroxide solution, refluxing for 48h at 80 ℃, taking out, washing with deionized water, and drying for 8h at 80 ℃ in an oven.
5. Pre-oxidation: and pre-oxidizing the dried Li porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Li-F-doped porous carbon nanofiber alkali metal-loaded hydrogen storage material.
7. Testing hydrogen storage performance: the Li-F-doped porous carbon nanofiber loads alkali metal, the hydrogen absorption amount within 10800s under the conditions of 273K and 10MPa reaches 0.6 wt%, and the Li-F-doped porous carbon nanofiber shows good hydrogen storage performance.
Example 2
1. Preparing a spinning solution, putting 1g of PAN, 0.5g of PVP (2: 1) and 0.05g of PFSA into 13.5g of DMF, mixing and dissolving, wherein the PAN, PVP and PFSA powder in the mixed solution accounts for 10 wt% of the total weight of the solution; stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
Li-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.01g/mL) in lithium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the dried Li porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Li-F-doped porous carbon nanofiber alkali metal-loaded hydrogen storage material.
7. Testing hydrogen storage performance: the Li-F-doped porous carbon nanofiber has the hydrogen absorption amount of 0.7 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance.
Example 3
1. Preparing a spinning solution, putting 0.5g of PAN, 0.5g of PVP (1: 1) and 0.1g of PFSA into 9g of DMF, mixing and dissolving, wherein the mass fraction of PAN, PVP and PFSA powder in the mixed solution accounts for 10 wt% of the total weight of the solution. Stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nanofiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
Li-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.01g/mL) in lithium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the dried Li porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the temperature for 2h, and then cooling to room temperature to obtain the Li-F-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material (shown in figure 2).
7. Testing hydrogen storage performance: the Li-F-doped porous carbon nanofiber has the hydrogen absorption amount of 1.0 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance (as shown in figure 3).
Example 4
1. Preparing a spinning solution, putting 1g of PAN, 0.5g of PVP (2: 1) and 0.2g of PFSA into 13.5g of DMF, mixing and dissolving, wherein the mass fraction of PAN, PVP and PFSA powder in the mixed solution accounts for 10 wt% of the total weight of the solution. Stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
4. Li-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.01g/mL) in lithium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the dried Li porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Li-F-doped porous carbon nanofiber alkali metal-loaded hydrogen storage material.
7. Testing hydrogen storage performance: the Li-F-doped porous carbon nanofiber has the hydrogen absorption amount of 0.90 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance.
Example 5
1. Preparing a spinning solution, putting 0.5g of PAN, 0.5g of PVP (1: 1) and 0.2g of PFSA into 12.5g of DMF, mixing and dissolving, wherein the mass fraction of PAN, PVP and PFSA powder in the mixed solution accounts for 8 wt% of the total weight of the solution. Stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
4. Li-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.01g/mL) in lithium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the dried Li porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Li-F-doped porous carbon nanofiber alkali metal-loaded hydrogen storage material.
7. Testing hydrogen storage performance: the Li-F-doped porous carbon nanofiber has the hydrogen absorption amount of 1.2 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance.
Example 6
1. Preparing a spinning solution, putting 1g of PAN, 0.5g of PVP (2: 1) and 0.2g of PFSA into 11g of DMF, mixing and dissolving, wherein the mass fraction of PAN, PVP and PFSA powder in the mixed solution accounts for 12wt% of the total weight of the solution. Stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
4. Li-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.01g/mL) in lithium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the dried Li porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Li-F-doped porous carbon nanofiber alkali metal-loaded hydrogen storage material.
7. Testing hydrogen storage performance: the Li-F-doped porous carbon nanofiber has the hydrogen absorption amount of 1.5 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance.
Example 7
1. Preparing a spinning solution, and putting 0.5g of PAN, 0.5g of PVP and 0.1g of PFSA into 9g of DMF for mixing and dissolving, wherein the mass fraction of PAN, PVP and PFSA powder in the mixed solution accounts for 10 wt% of the total weight of the solution. Stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
4. Ca-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.02g/mL) in calcium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the Ca porous PAN/PFSA nano-fiber obtained by drying in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Ca-F-doped porous carbon nanofiber-loaded alkali metal hydrogen storage material.
7. Testing hydrogen storage performance: the Ca-F-doped porous carbon nanofiber has the hydrogen absorption amount of 1.4 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance.
Example 8
1. Preparing a spinning solution, and putting 0.5g of PAN, 0.5g of PVP and 0.1g of PFSA into 9g of DMF for mixing and dissolving, wherein the mass fraction of PAN, PVP and PFSA powder in the mixed solution accounts for 10 wt% of the total weight of the solution. Stirring for more than 24h at 25 ℃ to completely dissolve and form uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the conditions that the voltage is 18kV, the receiving distance is 15cm, the spinning solution pushing speed is 0.2mL/h and the electrospinning temperature is 30 ℃, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven to be dried for 8h at the temperature of 80 ℃.
3. Porous composite fiber: and (2) soaking the PAN/PVP/PFSA composite nanofiber in water, putting the obtained product into a high-pressure kettle, then putting the obtained product into a muffle furnace, filtering and drying the obtained product at 110 ℃ for 24 hours to obtain the porous PAN/PFSA nanofiber.
4. Na-porous PAN/PFSA nanofibers: the porous PAN/PFSA nanofibers were soaked (0.02g/mL) in sodium hydroxide solution and refluxed at 80 ℃ for 48 h. Taking out, washing with deionized water, and drying in an oven at 80 deg.C for 8 h.
5. Pre-oxidation: and pre-oxidizing the dried Na porous PAN/PFSA nano fiber in a tubular quartz furnace for 2h at 240 ℃ in an air atmosphere.
6. And (3) calcining: and heating the pre-oxidized fiber to 900 ℃ at the heating rate of 2 ℃/min under the argon atmosphere of 80mL/min, preserving the heat for 2h, and then cooling to room temperature to obtain the Na-F-doped porous carbon nanofiber alkali metal-loaded hydrogen storage material.
7. Testing hydrogen storage performance: the Na-F-doped porous carbon nanofiber has the hydrogen absorption amount of 1.3 wt% within 10800s under the conditions of 273K and 10MPa, and shows good hydrogen storage performance.

Claims (7)

1. A preparation method of a fluorine-doped porous carbon nanofiber loaded alkali metal hydrogen storage material is characterized by comprising the following steps:
(1) immersing Polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP) and perfluorosulfonic acid (PFSA) powder into N, N-Dimethylformamide (DMF), and stirring the mixed system at normal temperature for 20-48 hours;
(2) preparing the uniformly dispersed mixed solution in the step (1) into porous nano fibers by an electrostatic spinning method and a hydrothermal method;
(3) replacing the porous PAN/PFSA nanofibers obtained in the step (2) with an alkali metal solution to form lithium/calcium-porous PAN/PFSA nanofibers;
(4) putting the lithium/calcium-porous PAN/PFSA nano-fibers in the step (3) into a graphite cup, putting the graphite cup into a tubular quartz furnace, and under the protection of inert gas flow with gas flow of 60-100 mL/min, heating at a rate of 1-10oC/min, heating to 600-1000oC, preserving heat for 2-5 hours to finish the carbonization process; and cooling to obtain the F-doped porous carbon nanofiber loaded alkali metal.
2. The preparation method of the fluorine-doped porous carbon nanofiber-supported alkali metal hydrogen storage material according to claim 1, wherein the molecular weight of polyacrylonitrile in the step (1) is 150000; PV P has a molecular weight of 300000; the mass ratio of polypropylene polyacrylonitrile to polyvinylpyrrolidone is 1: 1 or 2: 1.
3. the preparation method of the fluorine-doped porous carbon nanofiber-supported alkali metal hydrogen storage material according to claim 1, wherein the PFSA powder in the step (1) accounts for 1-5 wt% of the total weight of the PAN and the PVP.
4. The preparation method of the fluorine-doped porous carbon nanofiber-supported alkali metal hydrogen storage material according to claim 1, wherein PAN, PVP and PFSA powder in the mixed solution in the step (1) account for 8-12 wt% of the total weight of the solution.
5. The preparation method of the fluorine-doped porous carbon nanofiber-supported alkali metal hydrogen storage material according to claim 1, wherein the electrostatic spinning process in the step (2): putting the mixed solution in the step (1) into a 5mL injector, and extruding the mixed solution by a push pump at the speed of 0.05 mL/h-0.25 mL/h; the spinning voltage is 10-20 kV, and the distance from a spinning nozzle to a receiver is 15-20 cm; the resulting fiber is placed in an oven 80oC. And drying for 6-8 hours, and removing the solvent N, N-dimethylformamide to obtain the PAN/PVP/PFSA nano-fiber.
6. The preparation method of the fluorine-doped porous carbon nanofiber-supported alkali metal hydrogen storage material according to claim 1, wherein the hydrothermal process in the step (2): soaking the PAN/PVP/PFSA nano-fiber in water, and then placing the nano-fiber in a muffle furnace at 110 DEGoAnd C, keeping for 24-48 hours, and removing PVP to form the porous PAN/PFSA nano-fiber.
7. The preparation method of the fluorine-doped porous carbon nanofiber-supported alkali metal hydrogen storage material as claimed in claim 1, wherein the alkali metal solution in the step (3) is lithium hydroxide and calcium hydroxide.
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