CN110844880B - 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 PDFInfo
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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
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 5-6wt% under certain temperature and pressure. (ii) The dehydrogenation temperature is reduced. de Jong et al treated NaAlH4After being loaded on the carbon nano fiber, compared with the pure carbon nano fiber, the hydrogen absorption and dehydrogenation performance of the carbon nano fiber are obviously improved, and the dehydrogenation temperature is reduced to 160 DEGoC。[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-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; cooling to obtain F-doped porous carbon nanofiber loaded alkali metal;
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;
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 method 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.
The hydrothermal method 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 DEGoC, holdingAnd removing PVP for 24-48 hours to form porous PAN/PFSA nano-fibers.
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-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 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 10wt% of the total weight of the solution; at 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oC, obtaining PAN/PVP/PFSA composite nano-fiber (shown in figure 1) through electrostatic spinning, and placing the composite nano-fiber in a vacuum drying oven 80oAnd C, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
Li-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.01 g/mL) lithium hydroxide solution, 80oC refluxing for 48h, taking out, washing with deionized water, and drying in an oven 80oC. Drying for 8 h.
5. Pre-oxidation: putting the dried Li porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, 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 10 MPa reaches 0.6wt%, 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 10wt% of the total weight of the solution; at 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
Li-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.01 g/mL) lithium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the dried Li porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: pre-oxidized fiber is put in 80mL/min argon gasUnder the atmosphere with 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, 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 0.7wt% within 10800s under the conditions of 273K and 10 MPa, 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 10wt% of the total weight of the solution. At 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
Li-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.01 g/mL) lithium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the dried Li porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, 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 (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 10 MPa, 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 10wt% of the total weight of the solution. At 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
4. Li-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.01 g/mL) lithium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the dried Li porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, 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 10 MPa, and shows good hydrogen storage performance.
Example 5
1. Preparing spinning solution, and adding 0.5g PAN, 0.5g PVP (1: 1) and 0.2g PFSAMixing and dissolving in 12.5 g of DMF, 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. At 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
4. Li-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.01 g/mL) lithium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the dried Li porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, 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 10 MPa, 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. At 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: in the electricityThe pressure is 18 kV, the receiving distance is 15cm, the pushing speed of the spinning solution is 0.2mL/h, and the electrospinning temperature is 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
4. Li-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.01 g/mL) lithium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the dried Li porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, 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 10 MPa, 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 10wt% of the total weight of the solution. At 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: the PANSoaking the/PVP/PFSA composite nano-fiber in water, putting the soaked/PVP/PFSA composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
4. Ca-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibers in (0.02 g/mL) calcium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the Ca porous PAN/PFSA nano-fiber obtained by drying in a tubular quartz furnace in an air atmosphere of 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, and then cooling to room temperature to obtain the Ca-F-doped porous carbon nanofiber alkali metal-loaded 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 10 MPa, 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 10wt% of the total weight of the solution. At 25oAnd C, stirring for more than 24 hours, and completely dissolving to form a uniform spinning solution.
2. Preparing composite fiber by electrospinning: under the voltage of 18 kV, the receiving distance of 15cm, the pushing speed of the spinning solution of 0.2mL/h and the electrospinning temperature of 30oUnder the condition of C, the PAN/PVP/PFSA composite nano-fiber is obtained through electrostatic spinning and is placed in a vacuum drying oven 80oC, drying for 8 h.
3. Porous composite fiber: soaking the PAN/PVP/PFSA composite nano-fiber in water, putting the soaked composite nano-fiber into an autoclave, and then putting the autoclave into a muffle furnace to obtain 110 partsoAnd C, filtering and drying after 24 hours to obtain the porous PAN/PFSA nano fiber.
4. Na-porous PAN/PFSA nanofibers: soaking the porous PAN/PFSA nanofibersIn (0.02 g/mL) sodium hydroxide solution, 80oC, refluxing for 48 h. Taking out, washing with deionized water, and oven 80oC, drying for 8 h.
5. Pre-oxidation: putting the dried Na porous PAN/PFSA nano-fiber in a tubular quartz furnace in an air atmosphere 240oC, pre-oxidizing for 2 h.
6. And (3) calcining: the pre-oxidized fiber was placed under an argon atmosphere of 80mL/min at a rate of 2oHeating to 900 deg.C/minoAnd C, preserving the heat for 2 hours, 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 10 MPa, and shows good hydrogen storage performance.
Claims (1)
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;
the electrostatic spinning method comprises the following steps: putting the mixed solution 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. Drying for 6-8 hours, and removing the solvent N, N-dimethylformamide to obtain PAN/PVP/PFSA nano-fibers;
the hydrothermal method comprises the following steps: soaking the PAN/PVP/PFSA nano-fiber in water, and then placing the nano-fiber in a muffle furnace at 110 DEGoKeeping for 24-48 hours under the condition of C, and removing PVP to form porous PAN/PFSA nano-fibers;
(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; the alkali metal solution is lithium hydroxide and calcium hydroxide;
(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 alkali metal-loaded hydrogen storage material.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048259A1 (en) * | 2002-11-21 | 2004-06-10 | California Institute Of Technology | Carbon-based compositions for reversible hydrogen storage |
CN104805535A (en) * | 2015-04-14 | 2015-07-29 | 华南理工大学 | Preparation method of porous carbon nanofiber |
CN105480975A (en) * | 2016-02-25 | 2016-04-13 | 黑龙江省科学院大庆分院 | Method for preparing high-specific-surface-area porous carbon with hemp stems as carbon source |
CN108774810A (en) * | 2018-06-25 | 2018-11-09 | 上海交通大学 | A kind of preparation method of nitrogen, fluorine codope micropore carbon nano-fiber |
CN109767928A (en) * | 2018-12-18 | 2019-05-17 | 武汉纽赛儿科技股份有限公司 | The synthetic method and its application of Fluorin doped carbon coating silica nano particle@carbon nano tube compound material |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048259A1 (en) * | 2002-11-21 | 2004-06-10 | California Institute Of Technology | Carbon-based compositions for reversible hydrogen storage |
CN104805535A (en) * | 2015-04-14 | 2015-07-29 | 华南理工大学 | Preparation method of porous carbon nanofiber |
CN105480975A (en) * | 2016-02-25 | 2016-04-13 | 黑龙江省科学院大庆分院 | Method for preparing high-specific-surface-area porous carbon with hemp stems as carbon source |
CN108774810A (en) * | 2018-06-25 | 2018-11-09 | 上海交通大学 | A kind of preparation method of nitrogen, fluorine codope micropore carbon nano-fiber |
CN109767928A (en) * | 2018-12-18 | 2019-05-17 | 武汉纽赛儿科技股份有限公司 | The synthetic method and its application of Fluorin doped carbon coating silica nano particle@carbon nano tube compound material |
Non-Patent Citations (1)
Title |
---|
"Activation of polymer blend carbon nanofibres by alkaline hydroxides and their hydrogen storage performances";F.Suarez-Garcia et al.;《international journal of hydrogen energy》;20091002;第34卷(第22期);第9141-9150页 * |
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