CN108847492B - N-doped metal cobalt carbon nanofiber composite material and preparation method and application thereof - Google Patents
N-doped metal cobalt carbon nanofiber composite material and preparation method and application thereof Download PDFInfo
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- H01M4/8605—Porous electrodes
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of an N-doped metal cobalt carbon nanofiber composite material, and belongs to the technical field of air fuel cells. According to the invention, the soluble cobalt salt is directly used for electrostatic spinning preparation, the cobalt nanoparticles are directly formed and grown in the self-supporting multilayer porous carbon fiber substrate with high conductivity, the spinning amount of the metal active material is greatly increased, the overall appearance of the prepared composite material presents a nanofiber net structure, the metal cobalt is wrapped in the carbon nanofibers in the form of cobalt nanoparticles, the electron transfer rate can be accelerated, the composite material has the advantages of porosity, high conductivity and good mechanical property, and the electrochemical performance of the lithium-oxygen battery is improved.
Description
Technical Field
The invention relates to the technical field of air fuel cells, in particular to an N-doped metal cobalt carbon nanofiber composite material and a preparation method and application thereof.
Background
In recent years, shortage of petroleum resources and increasing environmental problems have forced the development of cleaner and more efficient energy storage devices. Among all energy storage devices, lithium air batteries are widely used due to their high energy density and other characteristics. Meanwhile, the requirements of people for energy storage equipment are gradually diversified, and the research and development of flexible electrode materials become an important scientific research subject. The electrostatic spinning has the advantages of simple preparation device, low cost, more spinnable materials, strong process controllability, easy industrial popularization and the like. In all studies relating to flexible electrode materials, the electrospinning method has received much attention as a means for preparing flexible electrode materials.
Currently, research on the electrospinning method mainly focuses on obtaining a metal-doped carbon nanofiber composite material by dispersing a metal active material inside a fiber. The method can solve the problem of large volume expansion of most electrode materials, can increase the conductivity of the materials, is beneficial to improving the electrochemical performance of the electrode materials, and has the problem of low discharge capacity of the prepared battery.
Disclosure of Invention
In view of this, the present invention aims to provide an N-doped metal cobalt carbon nanofiber composite material, and a preparation method and an application thereof. The preparation method of the N-doped metal cobalt carbon nanofiber composite material provided by the invention directly uses soluble cobalt salt in the electrostatic spinning process, so that the discharge capacity of the battery is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of an N-doped metal cobalt carbon nanofiber composite material comprises the following steps:
(1) mixing polymethyl methacrylate, polyacrylonitrile and N, N-dimethylformamide to obtain a polymer solution;
(2) mixing the polymer solution obtained in the step (1) with soluble cobalt salt to obtain an electrostatic spinning solution, and then performing electrostatic spinning to obtain a composite nanofiber membrane;
(3) sintering the composite nanofiber membrane obtained in the step (2) in air to obtain a sintered product;
(4) and (4) carrying out heat treatment on the sintered product obtained in the step (3) in nitrogen to obtain the N-doped metal cobalt carbon nanofiber composite material.
Preferably, the mass ratio of the polymethyl methacrylate to the polyacrylonitrile to the soluble cobalt salt is 5:5: 0.5-1.5.
Preferably, the conditions of the electrostatic spinning in the step (2) are as follows: the temperature is 25-30 ℃, the relative humidity is less than 30 ℃, the electrostatic voltage is 12-21 kV, and the receiving distance is 15-20 cm.
Preferably, the sintering temperature in the step (3) is 250-280 ℃, and the sintering time is 5-8 h.
Preferably, the temperature of the heat treatment in the step (4) is 700-900 ℃, and the time of the heat treatment is 1.5-2 h.
The invention also provides the N-doped metal cobalt carbon nanofiber composite material prepared by the preparation method in the technical scheme, the overall appearance of the N-doped metal cobalt carbon nanofiber composite material presents a nanofiber net structure, the metal cobalt is wrapped in the carbon nanofibers in the form of cobalt nanoparticles, and the nitrogen is loaded on the surfaces of the carbon nanofibers in the form of graphitized nitrogen, pyrrole nitrogen and pyridine nitrogen.
Preferably, the mass content of the cobalt nanoparticles in the N-doped metal cobalt carbon nanofiber composite material is 26-42%.
Preferably, the particle size of the cobalt nanoparticles in the N-doped metal cobalt carbon nanofiber composite material is 5-100 nm.
Preferably, the mass content of nitrogen in the N-doped metal cobalt carbon nanofiber composite material is 0.84-2.97%
The invention also provides application of the N-doped metal cobalt carbon nanofiber composite material in the technical scheme as a cathode of a lithium air fuel cell.
The invention provides a preparation method of an N-doped metal cobalt carbon nanofiber composite material, which comprises the following steps: mixing polymethyl methacrylate, polyacrylonitrile and N, N-dimethylformamide to obtain a polymer solution; mixing the polymer solution with soluble cobalt salt to obtain an electrostatic spinning solution, and then performing electrostatic spinning to obtain a composite nanofiber membrane; sintering the composite nanofiber membrane in air to obtain a sintered product; and carrying out heat treatment on the sintered product in nitrogen to obtain the N-doped metal cobalt carbon nanofiber composite material. According to the invention, the soluble cobalt salt is directly used for electrostatic spinning preparation, the cobalt nanoparticles are directly formed and grown in the self-supporting multilayer porous carbon fiber substrate with high conductivity, the spinning amount of the metal active material is greatly increased, the overall appearance of the prepared composite material presents a nanofiber net structure, the metal cobalt is wrapped in the carbon nanofibers in the form of the cobalt nanoparticles, the electron transfer rate can be accelerated, the lithium-oxygen battery has the advantages of porosity, high conductivity and good mechanical property, and the electrochemical performance of the lithium-oxygen battery is improved. The data of the embodiment shows that the N-doped metal cobalt carbon nanofiber composite material prepared by the invention is assembled into a lithium air battery for testing, the first discharge capacity of the battery is 4508.9mAh/g under the discharge current of 100mA/g, and the battery can be circulated for 50 times when the discharge capacity is cut off by 500 mAh/g.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an SEM spectrum of an N-doped metal cobalt carbon nanofiber composite material prepared in example 1;
FIG. 2 is a first charge-discharge curve of the N-doped cobalt carbon nanofiber composite material prepared in examples 1-5;
FIG. 3 is a graph showing the cycle performance of the N-doped cobalt carbon nanofiber composites prepared in examples 1 to 5.
Detailed Description
The invention provides a preparation method of an N-doped metal cobalt carbon nanofiber composite material, which comprises the following steps:
(1) mixing polymethyl methacrylate, polyacrylonitrile and N, N-dimethylformamide to obtain a polymer solution;
(2) mixing the polymer solution obtained in the step (1) with soluble cobalt salt to obtain an electrostatic spinning solution, and then performing electrostatic spinning to obtain a composite nanofiber membrane;
(3) sintering the composite nanofiber membrane obtained in the step (2) in air to obtain a sintered product;
(4) and (4) carrying out heat treatment on the sintered product obtained in the step (3) in nitrogen to obtain the N-doped metal cobalt carbon nanofiber composite material.
According to the invention, polymethyl methacrylate, polyacrylonitrile and N, N-dimethylformamide are mixed to obtain a polymer solution. In the invention, the ratio of the mass of the polymethyl methacrylate to the mass of the polyacrylonitrile to the volume of the N, N-dimethylformamide is preferably 5g:5g:12 mL. In the invention, the polymethyl methacrylate and the polyacrylonitrile are polymer matrixes, and provide a carbon fiber framework for the composite material. The mixing method is not particularly limited in the present invention, and the mixing method known to those skilled in the art may be adopted, specifically, stirring.
After the polymer solution is obtained, the polymer solution and soluble cobalt salt are mixed to obtain an electrostatic spinning solution, and then electrostatic spinning is carried out to obtain the composite nanofiber membrane. In the invention, the mass ratio of the polymethyl methacrylate to the polyacrylonitrile to the soluble cobalt salt is preferably 5:5: 0.5-1.5. In the invention, too little soluble cobalt salt causes too little cobalt nanoparticles in the N-doped metal cobalt carbon nanofiber composite material to achieve the effect of catalyzing oxygen and cannot completely decompose Li2O2So that the cycle performance of the lithium-air fuel cell is weakened, and excessive soluble cobalt salt can cause the agglomeration of cobalt nanoparticles, so that the cobalt nanoparticles are easily coated by a discharge product, but the catalytic effect is weakened, and the ideal cycle performance cannot be achieved.
The soluble cobalt salt is not particularly limited in the present invention, and those known to those skilled in the art, such as cobalt acetate, can be used. In the present invention, the conditions of the electrospinning are preferably: the temperature is 25-30 ℃, the relative humidity is less than 30 ℃, the electrostatic voltage is 12-21 kV, the receiving distance is 15-20 cm, and the electrostatic voltage is more preferably 20 kV. The electrospinning device of the present invention is not particularly limited, and any electrospinning device known to those skilled in the art may be used.
After the composite nanofiber membrane is obtained, the composite nanofiber membrane is sintered in the air to obtain a sintered product. In the invention, the sintering temperature is preferably 250-280 ℃, and the sintering time is preferably 5-8 h. In the present invention, the rate of temperature rise to the sintering temperature is preferably 1 ℃/min. In the present invention, the sintering functions to decompose PMMA (polymethyl methacrylate) and convert cobalt acetate into simple cobalt.
After a sintered product is obtained, the sintered product is subjected to heat treatment in nitrogen to obtain the N-doped metal cobalt carbon nanofiber composite material. In the invention, the temperature of the heat treatment is preferably 700-900 ℃, and more preferably 800 ℃; the time of the heat treatment is preferably 1.5-2 h. In the present invention, the rate of temperature rise to the heat treatment temperature is preferably 2 ℃/min. In the present invention, the heat treatment is performed to completely carbonize PAN (polyacrylonitrile) to form a graphitized carbon fiber structure.
The invention also provides the N-doped metal cobalt carbon nanofiber composite material prepared by the preparation method in the technical scheme, the overall appearance of the N-doped metal cobalt carbon nanofiber composite material presents a nanofiber net structure, the metal cobalt is wrapped in the carbon nanofibers in the form of cobalt nanoparticles, and the nitrogen is loaded on the surfaces of the carbon nanofibers in the form of graphitized nitrogen, pyrrole nitrogen and pyridine nitrogen.
In the invention, the mass content of the cobalt nanoparticles in the N-doped metal cobalt carbon nanofiber composite material is preferably 26-42%, and more preferably 30-35%.
In the invention, the particle size of the cobalt nanoparticles is preferably 5-100 nm, and more preferably 5-60 nm.
In the invention, the mass content of nitrogen element in the N-doped metal cobalt carbon nanofiber composite material is preferably 0.84-2.97%, and more preferably 1.02-2.0%.
The invention also provides application of the N-doped metal cobalt carbon nanofiber composite material in the technical scheme as a cathode of a lithium air fuel cell.
The present invention provides an N-doped cobalt carbon nanofiber composite material, a preparation method and applications thereof, which are described in detail below with reference to examples, but the scope of the present invention should not be construed as being limited thereto.
Example 1:
5g of Polyacrylonitrile (PAN) polymer and 5g of polymethyl methacrylate (PMMA) were added to 12mL of an N, N-Dimethylformamide (DMF) organic solution at room temperature, stirred for six hours, then added with 0.5g of cobalt acetate, and then stirred for one hour to prepare an electrospinning solution.
Preparing a composite nanofiber membrane by adopting an electrostatic spinning method: the electrostatic spinning process parameters used were: the temperature was 25 ℃, the relative humidity was <30 °, the electrostatic voltage was 20kV, and the receiving distance was 20 cm.
The composite nanofiber membrane is heated at 250 ℃ in air atmosphere at the heating speed of 1 ℃/min for 5 hours; and then carrying out heat treatment at 800 ℃ in a nitrogen atmosphere at the heating rate of 2 ℃/min for 2 hours to obtain the final product N-doped metal cobalt carbon nanofiber composite material, wherein the label is 0.5 Co/CNT-800. The mass content of the cobalt nanoparticles in the composite material is 26%, the particle size of the cobalt nanoparticles is 5-35 nm, and the mass content of nitrogen element is 0.84%.
SEM characterization of the 0.5Co/CNT-800 prepared in this example shows that as shown in FIG. 1, the 0.5Co/CNT-800 prepared in FIG. 1 has a cross-sectional diameter of about 300nm and a rough surface, which is caused by decomposition of cobalt acetate and polymer during air sintering, and the rough surface is an active site for adsorbing oxygen.
The composite material is assembled into a lithium air battery for testing, and the first discharge capacity of the battery is 1624mAh/g (relative to the whole cathode quality) under the discharge current of 100 mA/g; when the discharge capacitance of 500mAh/g is cut off, the cycle can be performed for 15 times.
Example 2:
5g of Polyacrylonitrile (PAN) polymer and 5g of polymethyl methacrylate (PMMA) were added to 12mL of an N, N-Dimethylformamide (DMF) organic solution at room temperature, stirred for six hours, then added with 1.0g of cobalt acetate, and then stirred for one hour to prepare an electrospinning solution.
Preparing a composite nanofiber membrane by adopting an electrostatic spinning method: the electrostatic spinning process parameters used were: the temperature was 25 ℃, the relative humidity was <30 °, the electrostatic voltage was 20kV, and the receiving distance was 20 cm.
The composite nanofiber membrane is heated at 250 ℃ in air atmosphere at the heating speed of 1 ℃/min for 5 hours; and then carrying out heat treatment at 800 ℃ in a nitrogen atmosphere at the heating rate of 2 ℃/min for 2 hours to obtain the final product N-doped metal cobalt carbon nanofiber composite material marked as 1.0 Co/CNT-800. The mass content of the cobalt nanoparticles in the composite material is 30%, the particle size of the cobalt nanoparticles is 5-60 nm, and the mass content of nitrogen element is 2.97%.
The composite material is assembled into a lithium air battery for testing, and the first discharge capacity of the battery is 4508.9mAh/g (relative to the quality of the whole cathode) under the discharge current of 100 mA/g; when the discharge capacitance of 500mAh/g is cut off, the cycle can be carried out for 43 times.
Example 3:
5g of Polyacrylonitrile (PAN) polymer and 5g of polymethyl methacrylate (PMMA) were added to 12mL of an N, N-Dimethylformamide (DMF) organic solution at room temperature, stirred for six hours, then added with 1.5g of cobalt acetate, and then stirred for one hour to prepare an electrospinning solution.
Preparing a composite nanofiber membrane by adopting an electrostatic spinning method: the electrostatic spinning process parameters used were: the temperature was 25 ℃, the relative humidity was <30 °, the electrostatic voltage was 20kV, and the receiving distance was 20 cm.
The composite nanofiber membrane is heated at 250 ℃ in air atmosphere at the heating speed of 1 ℃/min for 5 hours; and then carrying out heat treatment at 800 ℃ in a nitrogen atmosphere at the heating rate of 2 ℃/min for 2 hours to obtain the final product N-doped metal cobalt carbon nanofiber composite material marked as 1.5 Co/CNT-800. The mass content of the cobalt nanoparticles in the composite material is 42%, the particle size of the cobalt nanoparticles is 5-100 nm, and the mass content of nitrogen is 1.24%.
The composite material is assembled into a lithium air battery for testing, and the first discharge capacity of the battery is 2155.1mAh/g (relative to the quality of the whole cathode) under the discharge current of 100 mA/g; when the discharge capacitance of 500mAh/g is cut off, the cycle can be performed for 23 times.
Example 4:
5g of Polyacrylonitrile (PAN) polymer and 5g of polymethyl methacrylate (PMMA) were added to 12mL of an N, N-Dimethylformamide (DMF) organic solution at room temperature, stirred for six hours, then added with 1.0g of cobalt acetate, and then stirred for one hour to prepare an electrospinning solution.
Preparing a composite nanofiber membrane by adopting an electrostatic spinning method: the electrostatic spinning process parameters used were: the temperature was 25 ℃, the relative humidity was <30 °, the electrostatic voltage was 20kV, and the receiving distance was 20 cm.
The composite nanofiber membrane is heated at 250 ℃ in air atmosphere at the heating speed of 1 ℃/min for 5 hours; and then carrying out heat treatment at 700 ℃ in a nitrogen atmosphere at the heating rate of 2 ℃/min for 2 hours to obtain the final product N-doped metal cobalt carbon nanofiber composite material marked as 1.0 Co/CNT-700. The mass content of the cobalt nanoparticles in the composite material is 35%, the particle size of the cobalt nanoparticles is 5-60 nm, and the mass content of nitrogen element is 2.58%.
The composite material is assembled into a lithium air battery for testing, and the first discharge capacity of the battery is 433.61mAh/g (relative to the quality of the whole cathode) under the discharge current of 100 mA/g; when the discharge capacitance of 500mAh/g is cut off, the cycle can be performed for 42 times.
Example 5:
5g of Polyacrylonitrile (PAN) polymer and 5g of polymethyl methacrylate (PMMA) were added to 12mL of an N, N-Dimethylformamide (DMF) organic solution at room temperature, stirred for six hours, then added with 1.0g of cobalt acetate, and then stirred for one hour to prepare an electrospinning solution.
Preparing a composite nanofiber membrane by adopting an electrostatic spinning method: the electrostatic spinning process parameters used were: the temperature was 25 ℃, the relative humidity was <30 °, the electrostatic voltage was 20kV, and the receiving distance was 20 cm.
The composite nanofiber membrane is heated at 250 ℃ in air atmosphere at the heating speed of 1 ℃/min for 5 hours; and then carrying out heat treatment at 900 ℃ in a nitrogen atmosphere at the heating rate of 2 ℃/min for 2 hours to obtain the final product N-doped metal cobalt carbon nanofiber composite material marked as 1.0 Co/CNT-900. The mass content of the cobalt nanoparticles in the composite material is 31%, the particle size of the cobalt nanoparticles is 5-60 nm, and the mass content of nitrogen element is 2.69%.
The composite material is assembled into a lithium air battery for testing, and the first discharge capacity of the battery is 4378.8mAh/g (relative to the quality of the whole cathode) under the discharge current of 100 mA/g; when the discharge capacitance of 500mAh/g is cut off, the cycle can be carried out for 43 times.
The first charge and discharge performance of the N-doped metal cobalt carbon nanofiber composite materials prepared in examples 1 to 5 was tested, and the results are shown in fig. 2, and it can be seen from fig. 2 that 1.0Co/CNF-800 shows the highest discharge capacity of 4508.9mAh/g (relative to the whole cathode mass) at a discharge current of 100 mA/g; the discharge capacities of 1.0Co/CNF-700 and 1.0Co/CNF-900 were 4378.8mAh/g and 4336.1mAh/g, respectively, and it can be seen that the heat treatment temperature had no significant effect on the first discharge performance of the battery. When the content of cobalt acetate was varied, the first discharge capacities of 0.5Co/CNF-800 and 1.5Co/CNF-800 were divided into 1624mAh/g and 2155.1 mAh/g.
FIG. 3 is a cycle performance test curve of the N-doped cobalt carbon nanofiber composite material prepared in examples 1-5, and it can be seen from FIG. 3 that 1.0Co/CNF-800 can be cycled for 43 times when the discharge capacitance is cut off at 500mAh/g (relative to the whole cathode mass) under a discharge current of 100 mA/g; the 1.0Co/CNF-700 and 1.0Co/CNF-900 cycles 36 and 40 times, while when the content of cobalt acetate precursor was changed, the 0.5Co/CNF-800 and 1.5Co/CNF-800 cycles 15 and 23 times, respectively.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of an N-doped metal cobalt carbon nanofiber composite material comprises the following steps:
(1) mixing polymethyl methacrylate, polyacrylonitrile and N, N-dimethylformamide to obtain a polymer solution;
(2) mixing the polymer solution obtained in the step (1) with soluble cobalt salt to obtain an electrostatic spinning solution, and then performing electrostatic spinning to obtain a composite nanofiber membrane; the mass ratio of the polymethyl methacrylate to the polyacrylonitrile to the soluble cobalt salt is 5:5: 1.0;
(3) sintering the composite nanofiber membrane obtained in the step (2) in air to obtain a sintered product; the sintering temperature in the step (3) is 250-280 ℃, the sintering time is 5-8 h, and the heating rate of heating to the sintering temperature is 1 ℃/min;
(4) and (4) carrying out heat treatment on the sintered product obtained in the step (3) in nitrogen to obtain the N-doped metal cobalt carbon nanofiber composite material.
2. The production method according to claim 1, wherein the conditions for the electrospinning in the step (2) are: the temperature is 25-30 ℃, the relative humidity is less than 30 ℃, the electrostatic voltage is 12-21 kV, and the receiving distance is 15-20 cm.
3. The method according to claim 1, wherein the temperature of the heat treatment in the step (4) is 700 to 900 ℃ and the time of the heat treatment is 1.5 to 2 hours.
4. The N-doped metal cobalt carbon nanofiber composite material prepared by the preparation method of any one of claims 1 to 3, wherein the overall appearance of the N-doped metal cobalt carbon nanofiber composite material is in a nanofiber net structure, the metal cobalt is wrapped in the carbon nanofibers in the form of cobalt nanoparticles, and the nitrogen is doped in the carbon nanofibers in the form of graphitized nitrogen, pyrrole nitrogen and pyridine nitrogen.
5. Use of the N-doped metallic cobalt carbon nanofiber composite of claim 4 as a cathode for a lithium air fuel cell.
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| CN111048795A (en) * | 2019-11-29 | 2020-04-21 | 上海应用技术大学 | Cobalt-nitrogen co-doped mesoporous carbon sphere electrocatalyst and preparation method and application thereof |
| CN113707888A (en) * | 2021-07-23 | 2021-11-26 | 浙大宁波理工学院 | Self-supporting flexible film and preparation method and application thereof |
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