CN113880071A - Multichannel and embedded hollow Co3O4Nano-particle carbon nanofiber aerogel and preparation method thereof - Google Patents

Multichannel and embedded hollow Co3O4Nano-particle carbon nanofiber aerogel and preparation method thereof Download PDF

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CN113880071A
CN113880071A CN202111071543.9A CN202111071543A CN113880071A CN 113880071 A CN113880071 A CN 113880071A CN 202111071543 A CN202111071543 A CN 202111071543A CN 113880071 A CN113880071 A CN 113880071A
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杨冬芝
张铭
于中振
王雪娇
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Beijing University of Chemical Technology
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Abstract

Multichannel and embedded hollow Co3O4A carbon nanofiber aerogel of nanoparticles and a preparation method thereof belong to the field of energy materials. The nanofiber membrane prepared by mixing polyacrylonitrile/polystyrene/ZIF-67 and an electrostatic spinning method is used as a raw material, and is sequentially subjected to shearing dispersion, freeze drying, carbonization and oxidation heat treatment to construct the three-dimensional nanofiber aerogel, the unique double-hollow structure can effectively relieve the common problem of volume expansion and contraction of an electrode material caused by the charge and discharge processes of an active substance, more electrochemical active sites are exposed, and meanwhile, the continuous three-dimensional welding network structure among fibers eliminates the interfaceContact resistance and good conductivity, facilitating rapid electron transport. The three-dimensional nanofiber aerogel as an electrode material of a supercapacitor shows excellent integration performance of high specific capacitance, high rate and ultra-long cycle stability.

Description

Multichannel and embedded hollow Co3O4Nano-particle carbon nanofiber aerogel and preparation method thereof
The technical field is as follows:
the invention belongs to the field of energy materials, and relates to a functional nanofiber aerogel material, in particular to a multichannel hollow Co-embedded aerogel material3O4A nano-particle carbon nanofiber aerogel and a preparation method thereof.
Background art:
with the development of modern society, Supercapacitors (SCs) with short charging time, high power density, long cycle life and good safety performance as high-efficiency energy storage devices are more and more concerned by the industry and academia. However, the main problem of SCs is that the energy density is low, which can be increased by constructing Asymmetric Supercapacitors (ASCs) and increasing the specific capacitance of the electrode material, wherein the selection and structural design of the high-performance electrode material are the key to solve the problem.
The transition metal oxide has attracted attention because of its characteristics such as high theoretical specific capacitance, abundant natural storage capacity, low cost and environmental friendliness (e.g., CoO)x，NiO，RuO2And MnO2Etc.). Wherein Co3O4(theoretical specific capacity 3560F g)-1) And is considered to be an ideal positive electrode material. The capacitor performance and rate performance are unsatisfactory due to slow reaction kinetics and poor conductivity, and in addition, the cycle stability is poor due to volume expansion/contraction of the active material during charge and discharge. In order to improve and overcome the defects of transition metal oxides, the transition metal oxides are often compounded with other electrochemically active substances or with carbon materials with good conductivity and stability to prepare novel multifunctional composite electrode materials.
By searching, it relates to Co3O4Typical patents for the use of base cathode materials in the context of SCs are: porous flower-like NiCo2O4/Co3O4A preparation method of the electrode material of the/NiO super capacitor (CN 108807013A); nano flower-shaped Co3O4Modified N, P doped porous carbon super capacitor and preparation method (CN 112927953A); co3O4A nano-box, a method for its preparation, use and a supercapacitor (CN 103130283A); carbon-coated Co with shell-core structure3O4Supercapacitor electrode materials and methods of making same (CN 111508719A); nitrogen-doped carbon nanosheet-Co3O4Preparation method and application of composite material (CN 109859956A); loaded Co3O4A preparation method of the carbon fiber composite material of the nano particles and an obtained product (CN105332097A) and the like. Zero-dimensional powder, one-dimensional fiber, two-dimensional film or microstructure single Co3O4The materials, often one of the other, have difficulty in bringing about the desired enhancement effect in terms of capacity, rate and cycling stability. The invention solves the challenge of preparing an electrode material integrating a plurality of excellent properties through structural design.
The invention takes the electrostatic spinning three-dimensional nanofiber aerogel as a carrier of an electrode material, and has the advantages of adjustable wettability, adjustable mechanical strength, large specific surface area, controllable components, light weight and the like. Firstly, preparing a polyacrylonitrile/polystyrene/ZIF-67 (PAN/PS/ZIF-67 for short) based nanofiber membrane by electrostatic spinning, and then preparing a multichannel embedded hollow Co membrane with good compression resilience by shearing dispersion, freeze drying, carbonization and oxidation heat treatment3O4Nanoparticle Carbon Nanofiber (CNFs) hybrid aerogels and as positive electrode materials. The 'double-hollow' and three-dimensional structural design presents unique structural advantages, namely, the continuous three-dimensional 'welding' network structure among the multi-channel CNFs eliminates interface contact resistance and provides good conductivity, and electrons are promoted to be rapidly transmitted; the multi-channel and multi-level pore structure shortens the ion transmission path and is Co3O4The outward volume expansion of the nanoparticles provides a suitable space; hollow structure Co3O4The nanoparticles expose more electrochemically active sites and provide adequate space for self-inward volume contraction. The characteristics endow the electrode material with excellent integration performance of high specific capacitance, high multiplying power and ultra-long cycle stability, and the integration performance is 1A g-1Exhibits a current density of 1600.6F g-1The current density increased by a factor of 20 to retain 72% of its initial specific capacitance. At the same time at 20A g-1The specific capacitance still keeps 90.5 percent of the initial capacitance value after 30000 charge-discharge cycles under high current density, and the coulombic efficiency is close to 100 percent.
The invention content is as follows:
the invention aims to provide a multi-channel hollow Co embedded in3O4Carbon nanofibers of nanoparticlesA preparation method of aerogel used for supercapacitor electrode materials. The electrode material prepared by the method has excellent integrated electrochemical performance.
The technical scheme for realizing the purpose of the invention is as follows:
multi-channel CNF embedded hollow Co3O4The nano-particle fiber aerogel and the preparation method thereof are characterized in that: firstly preparing a PAN/PS/ZIF-67-based nanofiber membrane by electrostatic spinning, then sequentially carrying out shearing, homogenizing, freeze drying, carbonization and oxidation heat treatment, wherein a polymer blend is subjected to phase separation in the electrostatic spinning process, polystyrene PS is decomposed while ZIF-67 is converted into solid metal Co simple substance nano particles in the high-temperature carbonization treatment process, and finally, solid metal Co simple substance is converted into hollow Co simple substance by the Cokendall effect through oxidation treatment3O4Nanoparticles, finally preparing the multi-channel CNF embedded hollow Co with good compression resilience3O4Nanoparticle hybrid aerogels.
The multichannel CNF embedded hollow Co3O4The nano-particle fiber aerogel is used for an SCs electrode material, and the preparation process comprises the following steps:
(1) preparation of ZIF-67 nanoparticles
Mixing Co (NO)3)2·6H2O and Co (NO) in molar mass3)2·6H2And respectively dissolving 2-methylimidazole with the amount of 5-8 times of O in DMF (dimethyl formamide), quickly mixing the two solutions together, and then magnetically stirring at room temperature for 3-6 hours. After the reaction, the product was centrifuged and washed several times with DMF, and then dried in a vacuum oven at 60 ℃ to obtain ZIF-67 nanoparticles.
(2) Preparation of PAN/PS/ZIF-67 based nanofiber membrane
PS (preferably Mw 192000) is first added to DMF solvent and stirred at room temperature; adding ZIF-67 with the mass 1-3 times of PS and PAN (preferably M) with the mass 1-3 times of PSw150000), magnetically stirring to obtain uniform spinning solution, and performing electrostatic spinning under the conditions of receiving distance of 15-20 cm, voltage of 12-20 KV and electrospinning flow rate of 1-3 mL h-1The grounded aluminum foil is used as a fiber receiver for receivingThe resulting PAN/PS/ZIF-67 based nanofiber membrane is dried under vacuum, such as at 60 ℃.
(3) Preparation of hybrid nanofiber aerogels
The method comprises the steps of cutting a PAN/PS/ZIF-67-based nanofiber membrane into sheets, dispersing the sheets into a mixed solution of water and alcohol containing PVP, cutting the sheets for 20-50 min at the rotating speed of 9000-13000 r.p.m by a homogenizer, pouring the dispersion into a cylindrical mold, freezing the mold, and freeze-drying the mold in a freeze dryer to form the three-dimensional PAN/PS/ZIF-67-based nanofiber aerogel. Pre-oxidizing the freeze-dried PAN/PS/ZIF-67-based nanofiber aerogel in air at 220 ℃ for 1-3 h, and then pre-oxidizing in N2Calcining at 600-900 ℃ for 2-4 h in the atmosphere, naturally cooling to room temperature to obtain multichannel CNF embedded solid Co nano-metal particle fiber aerogel, finally oxidizing at 200-400 ℃ for 2-4 h in the air, and oxidizing the generated multichannel CNF embedded solid Co nano-metal particle aerogel into multichannel CNF embedded hollow Co nano-metal particle aerogel3O4Nanoparticle hybrid aerogels.
The invention relates to 3 basic principles:
(1) when preparing the electrospinning solution, due to the difference in interfacial tension, viscosity and elasticity between PAN and PS, the polymer blend undergoes phase separation, and PS forms a microemulsion which is drawn into a nanoscale thread in PAN-based fibers during electrospinning.
(2) In the high-temperature heat treatment process, PAN is carbonized into carbon, PS is decomposed to form a multi-channel structure, and ZIF-67 forms solid metal Co nanoparticles.
(3) During the oxidative heat treatment, solid metallic Co nanoparticles are converted into hollow Co due to the Cokendall effect3O4And (3) nanoparticles. The invention relates to a multi-channel CNF embedded hollow Co3O4The nanoparticle fiber aerogel is used as a supercapacitor electrode material and a key point of a preparation method thereof.
Drawings
FIG. 1 shows a multi-channel CNF embedded hollow Co3O4A flow chart for preparing the nano particle fiber aerogel.
FIG. 2a b is a ZIF-67 nanoparticle SEM and TEM image, respectively.
FIG. 3a b c d are the hollow Co embedded in the multi-channel CNF3O4SEM, SEM magnification, TEM and TEM magnification pictures of the nano particle fiber aerogel.
FIG. 4a b shows the multi-channel CNF embedded hollow Co of example 73O4The compressive stress-strain curves (e 20%, 40%, 60%, 80%) of the nanoparticulate fibrous aerogels and the stress-strain curves (e 50%) of the aerogels at different compression release cycles (1, 50, 100).
FIG. 5a b c d is a schematic diagram of the electrode material prepared in example 7 in the electrolyte, the constant current charging and discharging curve at different current densities, the specific capacitance curve at different current densities and the curve at 20A g-1Capacity retention versus cycle number curve.
Detailed Description
The present invention will be further described in the following examples, which are illustrative, not restrictive and are not intended to limit the scope of the invention.
Example 1.
ZIF-67 nanoparticles were first prepared by mixing 5mM Co (NO)3)2·6H2O and 25mM 2-methylimidazole were dissolved in 50mL DMF, respectively, and the two solutions were mixed together rapidly and then magnetically stirred at room temperature for 6 h. After the reaction, the product was centrifuged and washed several times with DMF, and then dried in a vacuum oven at 60 ℃ to obtain ZIF-67 nanoparticles.
In order to prepare a PAN/PS/ZIF-67-based nanofiber membrane, 0.5g of PS (Mw 192000) was first added to 9mL of DMF solvent, and the mixture was stirred at room temperature. 0.5g ZIF-67 and 0.5g PAN (M) were then addedw150000), magnetically stirring to obtain uniform spinning solution, and electrospinning under conditions of receiving distance of 15cm, voltage of 12KV, and electrospinning flow rate of 1mL h-1Grounded aluminum foil was used as a fiber receiver, and the received fiber film was vacuum dried at 60 ℃.
Finally, preparing the hybrid nanofiber aerogel, and cutting 1g of PAN/PS/ZIF-67-based nanofiber membrane into pieces (about 1 multiplied by 1 cm)-2) Dispersed in a solvent containing 1mg mL-1PVP in water/tert-butanol solution (wherein the mass ratio of water to tert-butanol is 3:1) was homogenized with IKA T18 disperser at 9000rpm for 20min to form a homogeneous nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. Pre-oxidizing PAN/PS/ZIF-67 based aerogel in air at 220 ℃ for 1h, and then carrying out N oxidation at 900 ℃2Carbonizing for 2h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 2h at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Example 2.
ZIF-67 nanoparticles were first prepared by mixing 5mM Co (NO)3)2·6H2O and 40mM 2-methylimidazole were dissolved in 50mL DMF, respectively, and the two solutions were mixed together rapidly and then stirred magnetically at room temperature for 3 h. After the reaction, the product was centrifuged and washed several times with DMF, and then dried in a vacuum oven at 60 ℃ to obtain ZIF-67 nanoparticles.
In order to prepare a PAN/PS/ZIF-67-based nanofiber membrane, 0.5g of PS (Mw 192000) was first added to 9mL of DMF solvent, and the mixture was stirred at room temperature. Then 1g ZIF-67 and 1g PAN (M) were addedw150000), magnetically stirring to obtain uniform spinning solution, and electrospinning under conditions of receiving distance of 15cm, voltage of 12KV, and electrospinning flow rate of 1mL h-1Grounded aluminum foil was used as a fiber receiver, and the received fiber film was vacuum dried at 60 ℃.
Finally, preparing the hybrid nanofiber aerogel, and cutting 1g of PAN/PS/ZIF-67-based nanofiber membrane into pieces (about 1 multiplied by 1 cm)-2) Dispersed in a solvent containing 1mg mL-1PVP is homogenized in a water/tert-butanol solution of PVP (wherein the mass ratio of water to tert-butanol is 1:1) with an IKA T18 disperser at 10000rpm for 30min to form a uniform nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. PAN/PS/ZIF-67 based aerogel is put in air at 220 DEG CPreoxidized for 1h, and then oxidized at 900 ℃ under N2Carbonizing for 2h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 3 hours at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Example 3.
Preparation of ZIF-67 nanoparticles as in example 2, and further preparation of PAN/PS/ZIF-67 based nanofiber membranes, 0.5g of PS (Mw 192000) was first added to 9mL of DMF solvent and stirred at room temperature. Then 1.5g ZIF-67 and 1g PAN (M) were addedw150000), magnetically stirring to obtain uniform spinning solution, and electrospinning under conditions of receiving distance of 15cm, voltage of 12KV, and electrospinning flow rate of 1mL h-1Grounded aluminum foil was used as a fiber receiver, and the received fiber film was vacuum dried at 60 ℃.
Finally, preparing the hybrid nanofiber aerogel, and cutting 1g of PAN/PS/ZIF-67-based nanofiber membrane into pieces (about 1 multiplied by 1 cm)-2) Dispersed in a solvent containing 1mg mL-1PVP in water/tert-butanol solution (with a volume ratio of water to tert-butanol of 3:1) was homogenized with an IKA T18 disperser at 9000rpm for 50min to form a homogeneous nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. Pre-oxidizing PAN/PS/ZIF-67 based aerogel in air at 220 ℃ for 3h, and then carrying out N oxidation at 900 ℃2Carbonizing for 4h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 4 hours at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Example 4.
Preparation of ZIF-67 nanoparticles as in example 2, and further preparation of PAN/PS/ZIF-67 based nanofiber membranes, 0.5g of PS (Mw 192000) was first added to 9mL of DMF solvent and stirred at room temperature. 0.5g ZIF-67 and 1g PAN (M) were then addedw150000), magnetically stirring to obtain uniform spinning solution, and electrostatic spinning under the condition of graftingThe collecting distance is 20cm, the voltage is 20KV, and the electrospinning flow rate is 3mL h-1Grounded aluminum foil was used as a fiber receiver, and the received fiber film was vacuum dried at 60 ℃.
Finally, preparing the hybrid nanofiber aerogel, and cutting 1g of PAN/PS/ZIF-67-based nanofiber membrane into pieces (about 1 multiplied by 1 cm)-2) Dispersed in a solvent containing 3mg mL-1PVP in water/tert-butanol solution (with a volume ratio of water to tert-butanol of 1:1) was homogenized with an IKA T18 disperser at 13000rpm for 20min to form a uniform nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. Pre-oxidizing PAN/PS/ZIF-67 based aerogel in air at 220 ℃ for 1h, and then carrying out N reaction at 600 DEG2Carbonizing for 2h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 3 hours at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Example 5.
Preparation of ZIF-67 nanoparticles and preparation of PAN/PS/ZIF-67-based nanofiber membranes in the same example 2, and finally preparation of hybrid nanofiber aerogel, cutting 1g of PAN/PS/ZIF-67-based nanofiber membranes into pieces (about 1 × 1 cm)-2) Dispersed in a solvent containing 3mg mL-1PVP in water/tert-butanol solution (wherein the volume ratio of water to tert-butanol is 1:1) was homogenized with IKA T18 disperser at 10000rpm for 20min to form uniform nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. Pre-oxidizing PAN/PS/ZIF-67 based aerogel in air at 220 ℃ for 1h, and then carrying out N oxidation at 900 ℃2Carbonizing for 4h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 2h at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Example 6
Preparation of ZIF-67 nanoparticles andpreparation of PAN/PS/ZIF-67 based nanofiber Membrane As in example 2, and finally preparation of hybrid nanofiber aerogel, 1g of PAN/PS/ZIF-67 based nanofiber membrane was cut into pieces (1X 1 cm)-2) Dispersed in a solvent containing 1mg mL-1PVP in water/tert-butanol solution (4: 1 volume ratio of water to tert-butanol) was homogenized with IKA T18 disperser at 10000rpm for 20min to form uniform nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. Pre-oxidizing PAN/PS/ZIF-67 based aerogel in air at 220 ℃ for 1h, and then carrying out N reaction at 600 DEG2Carbonizing for 2h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 2h at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Example 7
Preparation of ZIF-67 nanoparticles and preparation of PAN/PS/ZIF-67-based nanofiber membranes in the same example 2, and finally preparation of hybrid nanofiber aerogel, cutting 1g of PAN/PS/ZIF-67-based nanofiber membranes into pieces (about 1 × 1 cm)-2) Dispersed in a solvent containing 1mg mL-1PVP in water/tert-butanol solution (with a volume ratio of water to tert-butanol of 3:1) was homogenized with an IKA T18 disperser at 10000rpm for 20min to form a homogeneous nanofiber dispersion. The dispersion was poured into a custom-made mold, frozen at-80 ℃ and freeze-dried for 48h to prepare PAN/PS/ZIF-67 based aerogel. Pre-oxidizing PAN/PS/ZIF-67 based aerogel in air at 220 ℃ for 1h, and then carrying out N oxidation at 900 ℃2Carbonizing for 2h in the atmosphere to generate the multi-channel CNF embedded solid Co nanoparticle (MCNF @ Co) aerogel. Finally oxidizing the mixture for 3 hours at 300 ℃ in the air, and oxidizing the generated MCNF @ Co aerogel into a multichannel CNF embedded hollow Co3O4Nanoparticle hybrid aerogels (MCNF @ HCo)3O4)。
Results of the implementation
For examples 1, 2, 3, 4, 5, 6, the current density was 1A g-1Specific capacity was 1142.7F g respectively-1、1400.8F g-1、1506.0F g-1、1352F g-1、1489.4F g-1And 1477.9F g-1. For example 7, at a current density of 1A g-1When the specific capacity reaches 1600.6F g-1And the circulation is 20000 times, the capacity retention rate is 90.5%; the current density increase by a factor of 20 retains 72% of its initial specific capacitance. At the same time at 20A g-1The specific capacitance still keeps 90.5 percent of the initial capacitance value after 30000 charge-discharge cycles under high current density, and the coulombic efficiency is close to 100 percent.
The relevant process parameters in the electrochemical test method are as follows: weighing 1.0-3.0 mg of multichannel CNF embedded hollow Co3O4And (3) placing the nano-particle fiber aerogel between two pieces of cleaned nickel foam, and maintaining the pressure at 10MPa for 30s to prepare the electrode slice required by the test.

Claims (7)

1. Multi-channel and embedded hollow Co3O4The preparation method of the carbon nanofiber aerogel of the nanoparticles is characterized by comprising the following steps of:
(1) preparing ZIF-67 nanoparticles;
(2) preparation of PAN/PS/ZIF-67 based nanofiber membrane
Firstly, adding PS into a DMF solvent, and stirring at room temperature; adding 1-3 times of ZIF-67 and 1-3 times of PAN, magnetically stirring to obtain uniform spinning solution, wherein the electrostatic spinning conditions are respectively receiving distance of 15-20 cm, voltage of 12-20 KV and electrospinning flow rate of 1-3 mL h-1Taking a grounded aluminum foil as a fiber receiver, and drying the received PAN/PS/ZIF-67-based nanofiber membrane in vacuum;
(3) preparation of hybrid nanofiber aerogels
Cutting the PAN/PS/ZIF-67-based nanofiber membrane into sheets, dispersing the sheets into a mixed solution of water and alcohol containing PVP, cutting the sheets for 20-50 min at the rotating speed of 9000-13000 r.p.m by using a homogenizer, pouring the dispersion into a cylindrical mold, freezing the mold, and freeze-drying the mold in a freeze dryer to form the three-dimensional PAN/PS/ZIF-67-based nanofiber aerogel; pre-oxidizing the freeze-dried PAN/PS/ZIF-67-based nanofiber aerogel in air at 220 ℃ for 1-3 h, and then pre-oxidizing in N2Calcining at 600-900 ℃ for 2-4 h in the atmosphere, naturally cooling to room temperature to obtain multichannel CNF embedded solid Co nano-metal particle fiber aerogel, finally oxidizing at 200-400 ℃ for 2-4 h in the air, and oxidizing the generated multichannel CNF embedded solid Co nano-metal particle aerogel into multichannel CNF embedded hollow Co nano-metal particle aerogel3O4Nanoparticle hybrid aerogels.
2. A multi-channel and hollow Co-embedded system as claimed in claim 13O4The preparation method of the carbon nanofiber aerogel of the nanoparticles is characterized by comprising the following steps of: mixing Co (NO)3)2·6H2O and Co (NO) in molar mass3)2·6H2And respectively dissolving 2-methylimidazole with the amount of 5-8 times of O in DMF (dimethyl formamide), quickly mixing the two solutions together, and then magnetically stirring at room temperature for 3-6 hours. After the reaction, the product was centrifuged and washed several times with DMF, and then dried in a vacuum oven at 60 ℃ to obtain ZIF-67 nanoparticles.
3. A multi-channel and hollow Co-embedded system as claimed in claim 13O4The preparation method of the carbon nanofiber aerogel of the nano particles is characterized in that a medium for dispersing the electrostatic spinning nanofiber is alcohol, and the alcohol is ethanol or tert-butyl alcohol.
4. A multi-channel and hollow Co-embedded system as claimed in claim 13O4The preparation method of the carbon nanofiber aerogel of the nanoparticles is characterized in that in the step (3), the carbon nanofiber aerogel is dispersed in a water-alcohol mixed solution containing PVP in a dispersing process, wherein the PVP content is 1-3 mg mL-1。
5. A multi-channel and hollow Co-embedded system as claimed in claim 13O4The preparation method of the carbon nanofiber aerogel containing the nanoparticles is characterized in that in the step (3), the mass ratio of water to alcohol used in the dispersing process is 1: 1-4: 1.
6. A multichannel and hollow Co-embedded prepared by the method according to any one of claims 1 to 53O4A nanoparticulate carbon nanofiber aerogel.
7. A multichannel and hollow Co-embedded prepared by the method according to any one of claims 1 to 53O4Application of the carbon nanofiber aerogel of the nanoparticles as an electrode material of a super capacitor.
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