CN115036146A - Flexible self-supporting porous carbon nanofiber membrane material and preparation method and application thereof - Google Patents
Flexible self-supporting porous carbon nanofiber membrane material and preparation method and application thereof Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a flexible self-supporting porous carbon nanofiber membrane material and a preparation method and application thereof. The porous carbon nanofiber membrane material is prepared by a pore-foaming agent and a carbon forming matrix; the porogen comprises a block polymer molecular brush having a topological structure, the block polymer molecular brush comprising hydrophilic units and hydrophobic units. The porous carbon nanofiber membrane material prepared by the invention provides a sufficient place for storing and entering electrolyte based on a larger specific surface area of the material, an ordered pore channel structure inside and a large number of mesopores and micropores, and an electrode prepared by taking the porous carbon nanofiber membrane material as an active substance shows good electrochemical performance.
Description
Technical Field
The invention relates to a block polymer molecular brush, a flexible self-supporting porous carbon nanofiber membrane material, and a preparation method and application thereof, and belongs to the field of preparation of flexible electrode materials.
Background
In the face of increasingly severe energy crisis and environmental crisis, countries raise traditional energy efficiency, develop renewable energy sources (solar energy, tidal energy, hydrogen energy, tidal energy and the like), and meanwhile, put higher demands on storage equipment of new energy sources, and strive to develop more efficient, safe and stable energy storage and conversion devices to realize sustainable utilization of green clean energy sources. Among various energy storage devices, a super capacitor is an advanced green electric energy storage device developed in recent years, and has the advantages of safety, reliability, high charge-discharge rate (seconds), long cycle life (millions of times), wide working temperature and the like, so that the short plate of the traditional capacitor on the energy storage capacity is fully made up, and the quick development and application are realized. Meanwhile, the rise of flexible displays, flexible electronics, portable and wearable devices has driven the continuous development of flexible energy storage technologies. As a core component in flexible energy storage devices, the preparation and assembly of flexible electrodes directly determines the performance level of the flexible energy storage devices. Therefore, there is an urgent need to develop a high-capacity electrode material that is flexible, light, thin, and bendable.
The selection of the electrode material is a key factor influencing the specific capacitive performance of the supercapacitor, and the material with high specific surface area, good conductivity and stable structure is generally selected. The one-dimensional carbon nanofiber has good conductivity, excellent chemical stability and thermal stability and higher specific surface area, simultaneously meets the requirements of devices on flexibility and bendability, and is undoubtedly the most promising material in flexible supercapacitor electrode materials. However, most carbon fibers have low utilization rate of specific surface area, poor hydrophilicity, low specific capacitance and energy density, and are difficult to meet the requirements of energy storage equipment. In order to increase the specific surface area of the carbon nanofibers and further improve the performance of the electrode material, a polymer pore-forming template material (such as PEO, PMMA, PVP, P4VP, etc.) is used as a pore-forming agent to form a hierarchical pore structure, so that the effective contact area between the electrolyte and the electrode material is increased. However, the common linear polymer is entangled among segments with the increase of molecular weight, and the pore size of the pore-forming material is generally small, which results in poor thermal stability and poor photoelectric properties of the material. In addition, the process of pore-forming by the polymer often makes the material become brittle, the flexibility is lost, and the preparation of the flexible electrode material with high specific capacitance is difficult to realize. Therefore, a proper pore-forming method is explored to obtain the porous carbon nanofiber with adjustable and controllable pore channel structure while the flexibility of the material is kept, and the method is very critical for further improving the specific capacitance performance of the electrode.
Disclosure of Invention
Aiming at the defect of pore formation of linear polymers in carbon nanofibers, the invention aims to develop a novel polymer and provide a porous carbon nanofiber membrane material with an ordered pore channel structure and flexibility and self-support and a preparation method of an electrode thereof.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a porous carbon nanofiber membrane material is prepared by a pore-foaming agent and a carbon-forming matrix; the porogen comprises a block polymer molecular brush having a topological structure, the block polymer molecular brush comprising hydrophilic units and hydrophobic units.
According to an embodiment of the present invention, in the block polymer molecular brush, the hydrophilic unit includes at least one of the following structural units:
the hydrophobic unit comprises at least one of the following structural units:
According to the embodiment of the invention, in the block polymer molecular brush, the number of hydrophilic units is x, x is any integer within 1-1000, the number of hydrophobic units is y, and y is any integer within 1-1000.
Preferably, x is any integer within 30-500 and y is any integer within 30-500.
According to an embodiment of the present invention, the block polymer molecular brush has a structure as shown in formula a:
wherein x is any integer within 1-1000, and y is any integer within 1-1000. Preferably, x is any integer within 30-500, and y is any integer within 30-500;
r, R' are independently selected from at least one of the hydrophilic units and hydrophobic units described above.
According to an embodiment of the present invention, the size of the block polymer molecular brush satisfies a good positive linear relationship with the molecular weight.
According to an embodiment of the invention, the molecular weight of the block polymer molecular brush is from 15 to 500 ten thousand.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has a porous structure.
Preferably, the porous structure comprises micropores and/or mesopores. Preferably, the pore structure of the porous structure is ordered.
According to the embodiment of the invention, the diameter of the fiber in the porous carbon nanofiber membrane material is 150-500 nm.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has good film forming properties. Preferably, the thickness of the membrane of the porous carbon nanofiber membrane material is 20-200 μm.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has flexibility.
According to the embodiment of the invention, the pore size of the porous structure of the porous carbon nanofiber membrane material can be effectively regulated and controlled by regulating and controlling the molecular weight of the pore-foaming agent.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has a large specific surface area. Preferably, the specific surface area is 180- 2 g -1 。
According to the embodiment of the invention, the specific capacitance value of the porous carbon nanofiber membrane material is not less than 90.0F g -1 E.g. 90-300F g -1 。
The invention also provides a preparation method of the porous carbon nanofiber membrane material, which comprises the following steps: inducing a pore-foaming agent to self-assemble into a spherical structure through a small molecular hydrogen bond donor; uniformly dispersing the spherical structure in a carbon forming matrix, performing electrostatic spinning to obtain a polymer fiber membrane, performing pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and performing pyrolysis on the pore-foaming agent in the carbon forming matrix to form a multi-stage pore channel structure, thereby preparing the porous carbon nanofiber membrane material.
According to an embodiment of the present invention, the preparation method specifically comprises:
(1) self-assembly of the block polymer molecular brush: inducing the block polymer molecular brush to self-assemble into a spherical structure by a small molecular hydrogen bond donor;
(2) preparing a porous carbon nanofiber membrane material: dispersing a spherical structure and a carbon-forming matrix polymer in a solvent to obtain a spinning solution, and performing electrostatic spinning on the spinning solution to obtain a polymer fiber membrane; and carrying out pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and cooling to obtain the porous carbon nanofiber membrane material.
According to an embodiment of the invention, the small molecule hydrogen bond donor is selected from at least one of p-hydroxybenzoic acid, gallic acid, terephthalic acid, oxalic acid, 2-hydroxybenzoic acid.
According to an embodiment of the invention, the mass ratio of the small molecule hydrogen bond donor to the block polymer molecular brush can be (0-0.8): 1.
According to an embodiment of the present invention, the block polymer molecular brush self-assembly is performed in an organic solvent.
Preferably, the self-assembly time can be 1-48 h.
According to an embodiment of the invention, the spherical structure comprises an inner hydrophobic phase and an outer hydrophilic phase.
According to the embodiment of the invention, the carbon-forming matrix is selected from at least one of phenolic resin, polyacrylonitrile, polyaniline, polyacrylamide, polythiophene, polyimide, polyethylene, polybenzothiazole, polythiophene and sodium polystyrene sulfonate.
According to the embodiment of the invention, the mass ratio of the carbon-forming matrix to the spherical structure can be 1 (0.05-5).
According to an embodiment of the present invention, in the step (2), the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, tetrahydrofuran, dichloromethane, dichloroethane, dimethylsulfoxide, ethanol, ethylene glycol, acetonitrile, acetone, glycerol, and methanol.
According to the embodiment of the invention, in the step (2), the spinning solution is uniformly stirred at 40-80 ℃.
According to the embodiment of the invention, the electrostatic spinning conditions specifically comprise: the spinning voltage is 15-30kV, the diameter of the needle is 0.5-1.5 mm, the propelling speed of the peristaltic pump is 0.5-5 mm/min, the distance from the needle to the receiving plate is 15-40 cm, the temperature is 25-45 ℃, and the humidity is 10-60%.
According to an embodiment of the present invention, the pre-oxidation treatment comprises the following specific steps: heating to 200-400 ℃ at the speed of 1-10 ℃/min in the air atmosphere, and staying for 60-150 min for pre-oxidation treatment.
According to an embodiment of the present invention, the carbonization treatment comprises the following specific steps: heating to 600-1000 ℃ at the speed of 2-20 ℃ in an inert atmosphere, and standing for 60-240 min for carbonization treatment.
The invention also provides application of the porous carbon nanofiber membrane material.
The invention also provides an electrode which comprises the porous carbon nanofiber membrane material.
Advantageous effects
1. The polymer fiber membrane prepared by the method has the fiber diameter of 150-500 nm and uniform thickness. Depending on good film forming property and flexibility of the polymer fiber film, the porous carbon nanofiber film material obtained after preoxidation treatment and carbonization treatment still keeps certain mechanical strength and can be bent at 90-180 degrees. In the process of preparing the electrode, different from common powdery carbon materials, the porous carbon nanofiber membrane material disclosed by the invention can be independently pressed on a current collector to prepare the electrode without using a conductive agent and a bonding agent, the preparation process is simple, convenient and quick, and the cost can be effectively saved.
2. The invention provides a new idea for a method for preparing the porous carbon material by pore-forming a polymer soft template. According to the porous carbon nanofiber membrane material and the preparation method thereof, the block polymer molecular brush is used as a pore-forming agent, the characteristics that the main chain conformation of the material is extended, no molecular chain entanglement exists and the aggregation state structure is controllable are fully utilized, on one hand, the design of the pore channel structure and the porous morphology in the porous carbon nanofiber membrane material can be realized by regulating and controlling the proportion of blocks in the block polymer molecular brush, on the other hand, the size and the molecular weight of the block polymer molecular brush meet a good positive linear relation, and the regulation of the pore size can be realized by regulating and controlling the molecular weight of the pore-forming agent.
3. In the invention, the pore channel distribution in the porous carbon nanofiber membrane material is regulated and controlled by a simple and feasible method. In the process of preparing the spinning solution, the hydrophilic component in the pore-foaming agent is induced to selectively enter the carbon-forming matrix component by using the small-molecular hydrogen bond donor as a central molecule through the bridging action of the small-molecular hydrogen bond donor, so that the physical movement and aggregation of the pore-foaming agent in the carbon-forming matrix phase are limited, the uniform dispersion of the pore-foaming agent in the carbon-forming matrix is realized, and channels in the carbonized porous carbon nanofiber membrane material are uniformly distributed.
4. The porous carbon nanofiber membrane material prepared by the invention provides a sufficient place for storing and entering electrolyte based on a larger specific surface area of the material, an ordered pore channel structure inside and a large number of mesopores and micropores, and an electrode prepared by taking the porous carbon nanofiber membrane material as an active substance shows good electrochemical performance.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of PDMS-NB, PEO-NB and PDMS-b-PEO BBCPs in examples 1-3.
FIG. 2 is a constant current charge and discharge curve diagram of the porous carbon nanofiber membrane materials prepared in examples 1-3 and the carbon nanofiber membrane material prepared in comparative example 1, and the tested current density is 1A g -1 。
FIG. 3 is a constant current charge and discharge curve diagram of the porous carbon nanofiber membrane materials prepared in examples 4 and 5, and the tested current density is 1A g -1 。
FIG. 4 is a plot of cyclic voltammetry for porous carbon nanofiber membrane materials prepared in examples 1-7 and carbon nanofiber membrane material prepared in comparative example 1, with scan rate of 5mV s -1 。
Fig. 5 is a cyclic voltammogram of the porous carbon nanofiber membrane material prepared in example 7 at different sweep rates.
Fig. 6 is a constant current charge and discharge curve diagram of the porous carbon nanofiber membrane material prepared in example 7 under different current densities.
FIG. 7 is a constant current charge and discharge curve of the porous carbon nanofiber membrane material prepared in comparative example 2, and the tested current density is 1A g -1 。
Fig. 8 is a microscopic morphology view of the carbon nanofiber membrane material prepared in comparative example 1.
FIG. 9 is a microscopic topography of the porous carbon nanofiber membrane material prepared in example 7.
Detailed Description
[ Block Polymer molecular Brush ]
A block polymer molecular brush, denoted BBCPs, having a topological structure, said block polymer molecular brush comprising hydrophilic units and hydrophobic units;
wherein the hydrophilic unit comprises at least one of the following structural units:
the hydrophobic unit comprises at least one of the following structural units:
According to the embodiment of the invention, in the block polymer molecular brush, the number of hydrophilic units is x, x is any integer within 1-1000, the number of hydrophobic units is y, and y is any integer within 1-1000.
Preferably, x is any integer within 30-500 and y is any integer within 30-500.
According to an embodiment of the present invention, the block polymer molecular brush has a structure as shown in formula a:
wherein x is any integer within 1-1000, and y is any integer within 1-1000. Preferably, x is any integer within 30-500, and y is any integer within 30-500;
r, R' are independently selected from at least one of the hydrophilic units and hydrophobic units described above.
According to an embodiment of the present invention, the size of the block polymer molecular brush satisfies a good positive linear relationship with the molecular weight.
According to an embodiment of the invention, the molecular weight of the block polymer molecular brush is 15 to 500 ten thousand, preferably 20 ten thousand, 40 ten thousand, 60 ten thousand, 80 ten thousand, 100 ten thousand, 120 ten thousand or 200 ten thousand.
According to an exemplary embodiment of the present invention, the block polymer molecular brush is selected from at least one of PS-b-PEO BBCPs, PDMS-b-PEO BBCPs, PLA-b-PEO BBCPs, PS-b-PVP BBCPs, PS-b-P4VP BBCPs, PDMS-b-PVP BBCPs, PDMS-b-P4VP BBCPs, PLA-b-P4VP BBCPs, PLA-b-PVP BBCPs, PCL-b-P4VP BBCPs, PCL-b-PEO BBCPs, PCL-b-PCP BBCPs, wherein PEO, PVP, P4VP, PS, PCL, PLA and PDMS respectively represent repeating units in polyethylene glycol (PEO), polyvinylpyrrolidone (PVP), poly-4-vinylpyridine (P4VP), Polystyrene (PS), Polycaprolactone (PCL), polylactic acid (PLA) and Polydimethylsiloxane (PDMS).
The invention also provides a synthesis method of the block polymer molecular brush, which comprises the following steps:
dissolving hydrophilic polymer macromolecules in an organic solvent to form a polymer solution 1, and dissolving hydrophobic polymer macromolecules in the organic solvent to form a polymer solution 2;
optionally adding a catalyst into the polymer solution 1 or 2 for reaction, and then mixing the polymer solution 1 and the polymer solution 2 for polymerization; finally, the reaction was terminated with vinyl ether to give block polymer molecular brushes, noted as BBCPs.
According to an embodiment of the present invention, the hydrophilic polymer macromolecule is selected from at least one of polyethylene glycol (PEO) having a norbornene reactive group at a single terminal, polyvinylpyrrolidone (PVP), and poly-4-vinylpyridine (P4 VP).
Wherein the structure of the norbornene active group comprises at least one of the following structures:
wherein, is the attachment site.
According to a preferred embodiment of the present invention, the hydrophilic polymer macromolecule is at least one selected from the group consisting of compounds having the structures represented by the following formulas I-1 to I-8:
wherein R is 1 、R 2 Identical or different, independently of one another, from at least one of the following structures:
According to an embodiment of the present invention, the molecular weight of the hydrophilic polymer macromolecule is between 0.4-20 kg/mol, preferably 5-10 kg/mol.
According to an embodiment of the present invention, the hydrophobic polymer macromolecule is selected from at least one of Polystyrene (PS), polylactic acid (PLA), Polydimethylsiloxane (PDMS), Polycaprolactone (PCL) having a norbornene active group at a single end.
Wherein the structure of the norbornene active group comprises at least one of the following structures:
wherein, is a ligation site.
According to a preferred embodiment of the present invention, the hydrophobic polymer macromolecule is at least one selected from the group consisting of compounds having the structures represented by the following formulae II-1 to II-8:
wherein R is 1 ’、R 2 ' same or different, independently from each other, at least one of the following structural units:
According to an embodiment of the invention, the molecular weight of the hydrophobic polymer macromolecules is between 0.6 and 20kg/mol, preferably between 4.8 and 8 kg/mol.
According to an embodiment of the present invention, the molar ratio of the hydrophilic polymer macromolecule to the hydrophobic polymer macromolecule may be (0.1 to 0.9): 0.9 to 0.1, and specifically may be (0.2 to 0.8): 0.8 to 0.2, such as 0.2:0.8, 0.3:0.7, 0.4:0.6, 0.5:0.5, 0.6:0.4, 0.7:0.3, 0.8: 0.2.
According to an embodiment of the invention, the polymerization reaction is carried out in an organic solvent.
Preferably, the organic solvent may be selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dichloromethane, dichloroethane, dimethylsulfoxide, acetone, ethanol, methanol, isopropanol, butanol, ethyl acetate, toluene, o-xylene, chloroform.
According to an embodiment of the present invention, the mass of the organic solvent may be 2 to 20 times, for example, 5 times, 10 times, 15 times, 20 times, the mass of the hydrophilic polymer macromolecule or the hydrophobic polymer macromolecule.
According to an embodiment of the invention, the catalyst may be a carbene complex of a metal.
Preferably, the metal in the carbene complex is a transition metal element, such as W, Ta, Ru, Ti, Mo, and the like, preferably Ru.
Illustratively, the catalyst is selected from Grubbs' catalysts having the formula:
according to an embodiment of the present invention, the mass of the catalyst may be 0.1 to 10%, specifically 0.5 to 5%, for example 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% of the total mass of the hydrophilic polymer macromolecule or the hydrophobic polymer macromolecule.
According to an embodiment of the present invention, the temperature of the polymerization reaction may be 0 to 50 ℃, specifically 0 to 30 ℃, and preferably 25 ℃.
According to an embodiment of the present invention, the time of the polymerization reaction may be 0.02 to 24 hours, specifically 0.05 to 12 hours, such as 0.05 hour, 1 hour, 3 hours, 6 hours, 9 hours or 12 hours.
According to an exemplary embodiment of the present invention, the block polymer molecular brush is synthesized according to formula II I:
wherein R is selected from the above R 1 And R 2 At least one of a structure; r' is selected from the above R 1 ' and R 2 ' at least one of the structures.
According to an embodiment of the present invention, the above block polymer molecular brush can be prepared by the above synthesis method.
[ application of Block Polymer molecular Brush ]
The invention also provides the use of the above-described block polymer molecular brush, for example, for a porogen.
The invention also provides a pore-foaming agent, which comprises the segmented polymer molecular brush.
[ porous carbon nanofiber Membrane Material ]
The invention also provides a porous carbon nanofiber membrane material which is prepared from the pore-foaming agent and the carbon-forming matrix.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has a porous structure.
Preferably, the porous structure comprises micropores and/or mesopores.
Preferably, the pore structure of the porous structure is ordered.
Preferably, the micropores refer to pores with a pore diameter of 0-2 nm.
Preferably, the mesopores refer to pores with a pore diameter of 2-50 nm.
According to an embodiment of the invention, the porous carbon nanofiber membrane material is flexible self-supporting.
According to the embodiment of the invention, the diameter of the fiber in the porous carbon nanofiber membrane material is 150-500 nm.
According to the embodiment of the invention, the porous carbon nanofiber membrane material has good membrane forming property, and preferably, the thickness of the membrane of the porous carbon nanofiber membrane material is 20-200 μm.
According to the embodiment of the invention, the porous carbon nanofiber membrane material has flexibility, and can be bent for 90-180 degrees.
According to the embodiment of the invention, the pore size of the porous structure of the porous carbon nanofiber membrane material can be effectively regulated and controlled by regulating and controlling the molecular weight of the pore-foaming agent.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has a large specific surface area. Preferably, the specific surface area is 180- 2 g -1 For example 185.6m 2 g -1 、245.8m 2 g -1 、338.9m 2 g -1 、440.6m 2 g -1 、481.2m 2 g -1 、501.5m 2 g -1 、563.2m 2 g -1 。
According to the embodiment of the invention, the specific capacitance value of the porous carbon nanofiber membrane material is not less than 90.0F g -1 . For example, 90-300F g -1 For example 95.4F g -1 、104.7F g -1 、125.7F g -1 、161.9F g -1 、183.2F g -1 、207.6F g -1 、254.1F g -1 。
[ preparation method of porous carbon nanofiber Membrane Material ]
The invention also provides a preparation method of the porous carbon nanofiber membrane material, which comprises the following steps: inducing a pore-foaming agent (a block polymer molecular brush) to self-assemble into a spherical structure through a small molecular hydrogen bond donor; uniformly dispersing the spherical structure in a carbon forming matrix, performing electrostatic spinning to obtain a polymer fiber membrane, performing preoxidation treatment and carbonization treatment on the polymer fiber membrane, performing pyrolysis on the pore-forming agent in the carbon forming matrix to form a multistage pore passage structure, and preparing to obtain the porous carbon nanofiber membrane material.
According to an embodiment of the present invention, the preparation method specifically comprises:
(1) self-assembly of the block polymer molecular brush: inducing the block polymer molecular brush to self-assemble into a spherical structure by a small molecular hydrogen bond donor;
(2) preparing a porous carbon nanofiber material: dispersing a spherical structure and a carbon-forming precursor polymer in a solvent to obtain a spinning stock solution, and performing electrostatic spinning on the stock solution to obtain a polymer fiber membrane; and carrying out pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and cooling to obtain the porous carbon nanofiber membrane material.
According to an embodiment of the invention, the small molecule hydrogen bond donor is selected from at least one of p-hydroxybenzoic acid (HBA), Gallic Acid (GA), terephthalic acid (PTA), Oxalic Acid (OA), 2-hydroxybenzoic acid (BHA). In the invention, the small molecular hydrogen bond donor provides a hydrogen bond bridging effect for the hydrophilic unit and the organic solvent of the block polymer molecular brush, so that the block polymer molecular brush is induced to self-assemble into a spherical structure. Meanwhile, the inventor also finds that the hydrophilic component in the block polymer molecular brush can selectively enter the carbon-forming matrix through the small-molecule hydrogen bond donor, so that the uniform dispersion of the pore-foaming agent in the carbon-forming matrix is regulated and controlled.
According to an embodiment of the present invention, the mass ratio of the small molecule hydrogen bond donor to the block polymer molecular brush may be (0-0.8): 1, specifically (0.02-0.6): 1, for example 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1 or 0.6: 1.
According to an embodiment of the invention, the block polymer molecular brush self-assembly is carried out in an organic solvent.
Preferably, the organic solvent has the meaning as described above, and may be selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dichloromethane, dichloroethane, dimethylsulfoxide, acetone, ethanol, methanol, isopropanol, butanol, ethyl acetate, toluene, o-xylene, chloroform, for example.
Preferably, the self-assembly time can be 1 to 48 hours, specifically 2 to 24 hours, for example 2 hours, 4 hours, 6 hours, 8 hours, 10 hours or 12 hours.
According to an embodiment of the present invention, in the step (1), the present invention does not specifically limit the mass of the organic solvent as long as the self-assembly of the block polymer molecular brush can be achieved, and for example, the mass may be 10 to 100 times, specifically 30 to 100 times, for example, 50 times, 60 times, 70 times, 80 times, 90 times or 100 times of the total mass of the small molecule hydrogen bond donor and the block polymer molecular brush.
According to an embodiment of the invention, the spherical structure comprises an inner hydrophobic phase and an outer hydrophilic phase.
According to an embodiment of the present invention, the carbon-forming matrix is selected from at least one of phenolic resin, polyacrylonitrile, polyaniline, polyacrylamide, polythiophene, polyimide, polyethylene, polybenzothiazole, polythiophene and sodium poly-p-styrenesulfonate.
According to an embodiment of the present invention, the mass ratio of the carbon-forming matrix to the spherical structure may be 1 (0.05-5), specifically 1 (0.2-5), such as 1:0.2, 1:0.5, 1:1.5, 1:2, 1:2.5 or 1: 3.
According to an embodiment of the present invention, the solvent in step (2) is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, tetrahydrofuran, dichloromethane, dichloroethane, dimethylsulfoxide, ethanol, ethylene glycol, acetonitrile, acetone, glycerol, and methanol.
According to the embodiment of the invention, in the step (2), the spinning solution is uniformly stirred at 40-80 ℃, and preferably stirred for more than 12 hours.
According to an embodiment of the present invention, in the step (2), the mass of the organic solvent is not particularly limited as long as the spinning solution for electrospinning can be prepared, and for example, the mass of the organic solvent may be 1.5 to 15 times, specifically 5 to 15 times, for example, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times of the total mass of the carbon-containing matrix and the spherical structure.
According to an embodiment of the present invention, the electrostatic spinning conditions specifically include: spinning voltage is 15-30kV, the diameter of the needle is 0.5-1.5 mm, the propelling speed of the peristaltic pump is 0.5-5 mm/min, the distance between the needle and the receiving plate is 15-40 cm, the temperature is 25-45 ℃, the humidity is 10-60%,
preferably, the receiving plate can be any one of aluminum foil, tin foil paper, release paper and steel sheet.
According to an embodiment of the present invention, the pre-oxidation treatment comprises the following specific steps: raising the temperature to 200-400 ℃ at a rate of 1-10 ℃/min in the air atmosphere, and staying for 60-150 min for pre-oxidation treatment, for example, raising the temperature to 250 ℃ at a rate of 2 ℃/min in the air atmosphere, and staying for 90 min.
According to an embodiment of the present invention, the carbonization treatment comprises the following specific steps: heating to 600-1000 ℃ at the speed of 2-20 ℃ in an inert atmosphere, and standing for 60-240 min for carbonization treatment.
Preferably, the inert atmosphere may be selected from Ar, N 2 Any one of the above.
Illustratively, the carbonization treatment comprises the following specific steps: heating to 900 deg.C at a rate of 5 deg.C/min in nitrogen atmosphere, and standing for 90min
[ application of porous carbon nanofiber Membrane Material ]
The invention also provides application of the porous carbon nanofiber membrane material, such as an electrode.
The invention also provides an electrode which comprises the porous carbon nanofiber membrane material.
According to an embodiment of the present invention, the method of preparing the electrode comprises: and (3) clamping the porous carbon nanofiber membrane material between current collectors, and tabletting to obtain the electrode.
According to an embodiment of the present invention, the current collector may be selected from current collectors known in the art, for example from nickel foam.
According to an embodiment of the present invention, the compression pressure may be 5 to 20MPa, preferably 10MPa, when tabletting.
According to an embodiment of the invention, the porous carbon nanofiber membrane material may be tailored to any shape, e.g. rectangular, circular, and e.g. 1 × 1cm 2 Is square.
The electrode prepared by the invention does not need to use a conductive agent and a bonding agent.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples and comparative examples are all commercially available products, or can be prepared by known methods.
In the following examples and comparative examples, the porous carbon nanofiber membrane material prepared was cut into about 1X 1cm 2 The square sample piece is clamped between two pieces of foam nickel, and the pressed piece is used as a porous carbon nanofiber electrode without using a conductive agent or an adhesive. The electrochemical performance test of the electrode is carried out in 6M KOH alkaline electrolyte by taking the porous carbon nanofiber electrode as a working electrode, Ag/AgCl (saturated KCl) as a reference electrode and a platinum sheet electrode as a counter electrode.
The electrochemical properties of the materials in the following examples and comparative examples were measured at room temperature using an electrochemical workstation model CHI1600E, manufactured by Chensinensis instruments, Inc. of Shanghai.
The microscopic morphologies of the materials in the following examples and comparative examples were obtained by scanning with an S-8020 scanning electron microscope.
Example 1
Polyacrylonitrile is used as a carbon forming matrix, PDMS-b-PEO BBCPs is used as a pore-foaming agent, and the preparation method of the porous carbon nanofiber membrane material comprises the following steps:
(1) preparation of a block polymer molecular brush: 1.0g of polyethylene glycol having a norbornene group at the single terminal (PEO-NB, Mw ═ 5kg/mol) and 1.0g of polydimethylsiloxane having a norbornene group at the single terminal (PDMS-NB, Mw ═ 4.8kg/mol) were dissolved in 10g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into a PEO-NB solution, stirring for reaction for 0.2h, pouring into a PDMS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a segmented polymer molecular brush with the molecular weight of 20 ten thousand, and taking the segmented polymer molecular brush as PDMS-b-PEO BBCPs as a pore-foaming agent.
(2) And (2) blending PDMS-b-PEO BBCPs obtained in the step (1) and 20 wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4h, and fully drying to obtain the pore-foaming agent which is self-assembled into a spherical structure.
(3) And (3) adding 1.0g of polyacrylonitrile powder and 0.4g of pore-foaming agent with the spherical structure in the step (2) into 9g of N, N-dimethylformamide, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 32 ℃ and 28% of humidity, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver was 15cm, the applied voltage was 18kV, the spinning solution in a 5ml syringe was pushed to the needle by a pushing device at a pushing speed of 2mm/min, and the white polymer fiber film was received on a tin foil collector under the action of an electric field.
(4) And (4) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 90 min. After the pre-oxidation process is finished, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material which is named as PCNFs-1.
The specific capacitance values of the porous carbon nanofiber electrode prepared in this example are shown in table 1.
Example 2
Polyacrylonitrile is used as a carbon forming matrix, PDMS-b-PEO BBCPs is used as a pore-foaming agent, and the preparation method of the porous carbon nanofiber membrane material comprises the following steps:
(1) preparing a block polymer molecular brush: 1.0g of polyethylene glycol having a norbornene group at the single terminal (PEO-NB, Mw ═ 5kg/mol) and 1.0g of polydimethylsiloxane having a norbornene group at the single terminal (PDMS-NB, Mw ═ 4.8kg/mol) were dissolved in 10g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into a PEO-NB solution, stirring for reaction for 0.2h, pouring into a PDMS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a block polymer molecular brush with the molecular weight of 20 ten thousand, marking as PDMS-b-PEO BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (2) blending the PDMS-b-PEO BBCPs obtained in the step (1) and 20 wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4h, and fully drying to obtain the pore-foaming agent which is self-assembled into a spherical structure.
(3) And (3) adding 1.0g of polyacrylonitrile powder and 0.8g of pore-foaming agent with a spherical structure in the step (2) into 12g of N, N-dimethylformamide, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 32 ℃ and 28% of humidity, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver was 15cm, the applied voltage was 18kV, the spinning solution in a 5ml syringe was pushed to the needle by a pushing device at a pushing speed of 2mm/min, and the white polymer fiber film was received on a tin foil collector under the action of an electric field.
(4) And (4) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 90 min. After the pre-oxidation process is finished, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material named as PCNFs-2.
The specific capacitance values of the porous carbon nanofiber electrode prepared in this example are shown in table 1.
Example 3
Polyacrylonitrile is used as a carbon forming matrix, PDMS-b-PEO BBCPs is used as a pore-foaming agent, and the preparation method of the porous carbon nanofiber membrane material comprises the following steps:
(1) 1.0g of polyethylene glycol having a norbornene group at the single terminal (PEO-NB, Mw ═ 5kg/mol) and 1.0g of polydimethylsiloxane having a norbornene group at the single terminal (PDMS-NB, Mw ═ 4.8kg/mol) were dissolved in 10g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into a PEO-NB solution, stirring for reaction for 0.2h, pouring into a PDMS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a block polymer molecular brush with the molecular weight of 40 ten thousand, marking as PDMS-b-PEO BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (2) blending PDMS-b-PEO BBCPs obtained in the step (1) and 20 wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4h, and fully drying to obtain the pore-foaming agent which is self-assembled into a spherical structure.
(3) And (3) adding 1.0g of polyacrylonitrile powder and 0.8g of pore-foaming agent with the spherical structure in the step (2) into 12g of N, N-dimethylformamide, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 32 ℃ and 28% of humidity, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver was 15cm, the applied voltage was 18kV, the spinning solution in a 5ml syringe was pushed to the needle by a pushing device at a pushing speed of 2mm/min, and the white polymer fiber film was received on a tin foil collector under the action of an electric field.
(4) And (4) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 90 min. After the pre-oxidation process is finished, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material which is named as PCNFs-3.
The specific capacitance values of the porous carbon nanofiber electrode prepared in this example are shown in table 1.
Example 4
The preparation method of the porous carbon nanofiber membrane material by taking phenolic resin as a carbon forming matrix and PS-b-PVP BBCPs as a pore-forming agent comprises the following steps:
(1) 1.6g of polyvinylpyrrolidone having a norbornene group at the single terminal (PVP-NB, Mw 15kg/mol) and 0.4g of polystyrene having a norbornene group at the single terminal (PS-NB, Mw 6kg/mol) were dissolved in 16g of dichloromethane and 0.6g of dichloromethane, respectively. Adding a proper amount of Grubbs catalyst into the PVP-NB solution, stirring for reaction for 0.4h, pouring the solution into the PS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a block polymer molecular brush with the molecular weight of 80 ten thousand, marking as PS-b-PVP BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (2) blending the PS-b-PVP BBCPs obtained in the step (1) and 10 wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours, and fully drying to obtain the pore-foaming agent which is self-assembled into a spherical structure.
(3) And (3) adding 1.0g of phenolic resin and 1.0g of the pore-foaming agent with the spherical structure in the step (2) into 14g of tetrahydrofuran, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 30 ℃ of temperature and 25% of humidity, wherein the specific parameters of the spinning are as follows: the distance from the syringe needle to the receiver is 15cm, the applied voltage is 20kV, the spinning solution in the 5ml syringe is pushed to the needle by the pushing device at the pushing speed of 0.5mm/min, and the white polymer fiber film is received on the tin foil collector under the action of the electric field.
(4) And (4) flatly placing the polymer fiber membrane obtained in the step (3) in a tube furnace, heating to 900 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, standing for 60min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material named as PCNFs-4.
The specific capacitance values of the porous carbon nanofiber electrode prepared in this example are shown in table 1.
Example 5
Polyacrylonitrile is used as a carbon forming matrix, PS-b-PVP BBCPs is used as a pore-foaming agent, and the preparation method of the porous carbon nanofiber membrane material comprises the following steps:
(1) 1.6g of polyvinylpyrrolidone having a norbornene group attached thereto (PVP-NB, Mw 15kg/mol) and 0.4g of polystyrene having a norbornene group attached thereto (PS-NB, Mw 6kg/mol) were dissolved in 16g of methylene chloride and 0.6g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into the PVP-NB solution, stirring for reaction for 0.4h, pouring the solution into the PS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a block polymer molecular brush with the molecular weight of 80 ten thousand, marking as PS-b-PVP BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (2) blending the PS-b-PVP BBCPs obtained in the step (1) and 10 wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours, and fully drying to obtain the pore-foaming agent which is self-assembled into a spherical structure.
(3) And (3) adding 1.0g of polyacrylonitrile powder and 1.0g of pore-foaming agent with a spherical structure in the step (2) into 14g of N, N-dimethylformamide, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 25 ℃ of temperature and 35% of humidity, wherein the specific parameters of the spinning are as follows: the distance between the syringe needle and the receiver is 15cm, the applied voltage is 20kV, the spinning solution placed in a 5ml syringe is pushed to the needle by a pushing device at the pushing speed of 5mm/min, and the white nanofiber membrane is received on a tin foil collector under the action of an electric field.
(4) And (4) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 280 ℃ at the speed of 4 ℃/min in the air atmosphere, and staying for 90 min. After the pre-oxidation process is finished, heating to 900 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, staying for 60min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material which is named as PCNFs-5.
The specific capacitance values of the porous carbon nanofiber electrode prepared in this example are shown in table 1.
Example 6
Polyacrylonitrile is taken as a carbon forming matrix, PS-b-P4VP BBCPs are taken as pore-forming agents, and the preparation method of the porous carbon nanofiber membrane material is as follows:
(1) 1.2g of poly-4-vinylpyridine having a norbornene group as a terminal end (P4VP-NB, Mw: 20kg/mol) and 0.8g of polystyrene having a norbornene group as a terminal end (PS-NB, Mw: 15kg/mol) were each dissolved in 10g of methylene chloride. Adding a proper amount of Grubbs catalyst into the P4VP-NB solution, stirring for reaction for 0.5h, pouring the solution into the PS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a block polymer molecular brush with the molecular weight of 100 ten thousand, and taking the block polymer molecular brush as PS-b-P4VP BBCPs as a pore-foaming agent.
(2) And (2) blending the PS-b-P4VP BBCPs obtained in the step (1) and 20 wt% of P-hydroxybenzoic acid in tetrahydrofuran, stirring for 4h, and fully drying to obtain the pore-foaming agent self-assembled into a spherical structure.
(3) And (3) adding 1.0g of polyacrylonitrile powder and 1.5g of pore-foaming agent with a spherical structure in the step (2) into 15g of N, N-dimethylformamide, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 26 ℃ and 28% of humidity, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver was 15cm, the applied voltage was 20kV, the spinning solution in the 5ml syringe was pushed to the needle by the pusher at a pushing speed of 2mm/min, and the white polymer fiber film was received on the tinfoil collector under the action of the electric field.
(4) And (4) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 120 min. After the pre-oxidation process is finished, heating to 800 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material which is named as PCNFs-6.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 7
Polyacrylonitrile is used as a carbon forming matrix, PS-b-PEO BBCPs are used as pore-forming agents, and the preparation method of the porous carbon nanofiber membrane material comprises the following steps:
(1) 1.2g of polyethylene glycol having a norbornene group at one end (PEO-NB, Mw ═ 5kg/mol) and 0.8g of polystyrene having a norbornene group at one end (PS-NB, Mw ═ 3kg/mol) were dissolved in 10g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into a PEO-NB solution, stirring for reaction for 0.05h, pouring a PS-NB solution, reacting overnight, quenching the reaction by vinyl ethyl ether, preparing a block polymer molecular brush with the molecular weight of 120 ten thousand, marking as PS-b-PEO BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (2) blending the PS-b-PEO BBCPs obtained in the step (1) and 20 wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4h, and fully drying to obtain the pore-foaming agent which is self-assembled into a spherical structure.
(3) And (3) adding 1.0g of polyacrylonitrile powder and 1.8g of pore-foaming agent with a spherical structure in the step (2) into 20g of N, N-dimethylformamide, and stirring at 60 ℃ to obtain uniform and transparent spinning solution. Spinning by using an electrostatic spinning device under the conditions of 28 ℃ of temperature and 28% of humidity, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver was 15cm, the applied voltage was 20kV, the spinning solution in a 5ml syringe was pushed to the needle by a pushing device at a pushing speed of 2mm/min, and the white polymer fiber film was received on a tin foil collector under the action of an electric field.
(4) And (4) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 120 min. After the pre-oxidation process is finished, heating to 800 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material which is named as PCNFs-7.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Comparative example 1
The preparation method of the carbon nanofiber membrane material by directly carbonizing polyacrylonitrile comprises the following steps:
(1) 1.0g of polyacrylonitrile powder was added to N, N-dimethylformamide, and stirred at 60 ℃ to obtain a uniform and transparent spinning dope having a concentration of 15 wt%. Under the conditions of temperature 32 ℃ and humidity 28%, the spinning solution placed in a 5ml syringe is pushed to the needle by a pushing device at a pushing speed of 2mm/min, enters an electric field of 18kV, and is received on a receiving plate 15cm away from the needle to obtain a white polymer fiber membrane.
(2) And (2) flatly placing the polymer fiber membrane in the step (1) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 120 min. After the pre-oxidation process is finished, heating to 800 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the carbon nanofiber membrane material named CNFs.
The specific capacitance values of the carbon nanofiber electrodes prepared in this comparative example are shown in table 1.
Comparative example 2
Polyacrylonitrile is used as a carbon forming matrix, linear PEO is used as a pore-foaming agent, and the preparation method of the porous carbon nanofiber membrane material comprises the following steps:
(1) 1.0g of polyacrylonitrile powder and 0.8g of PEO powder were added to 12g of N, N-dimethylformamide and stirred at 60 ℃ to obtain a uniform and transparent spinning dope in which the molecular weight of PEO was 40 ten thousand. Spinning by using an electrostatic spinning device under the conditions of 26 ℃ of temperature and 35% of humidity, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver is 15cm, the applied voltage is 20kV, the spinning solution in the 5ml syringe is pushed to the needle by the pushing device at the pushing speed of 0.5mm/min, and the white polymer fiber film is received on the tin foil collector under the action of the electric field.
(2) And (2) flatly placing the polymer fiber membrane in the step (1) in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min in the air atmosphere, and staying for 90 min. After the pre-oxidation process is finished, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, staying for 90min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material which is named as PCNFs contrast.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in the comparative example are shown in table 1.
Specific capacitance data of carbon nanofiber membranes prepared in Table 1, examples 1-7 and comparative examples 1-2
As can be seen from table 1: the specific capacitance value of the porous carbon nanofiber membrane material prepared by the method is obviously improved compared with that of the prior art, for example, compared with example 7 and comparative example 1, the specific capacitance value is 1A g -1 Specific capacitance value under current density is 88.0F g -1 Is lifted to 254.1F g -1 . The result shows that the porous carbon nanofiber membrane material prepared by the method has excellent specific capacitance performance.
TABLE 2 parameters of the Block Polymer molecular Brush, porous carbon nanofiber Membrane materials prepared in examples 1-7 and comparative examples 1-2
FIG. 1 is a nuclear magnetic resonance spectrum of PDMS-NB, PEO-NB and PDMS-b-PEO BBCPs in examples 1-3. As the polymerization reaction proceeded, the peak corresponding to the norbornene double bond H at 6.13ppm disappeared, indicating the success of the polymerization reaction.
FIG. 2 is a constant current charge and discharge curve diagram of the porous carbon nanofiber membrane materials prepared in examples 1-3 and the carbon nanofiber membrane material prepared in comparative example 1, and the tested current density is 1A g -1 . From comparative example 1 to examples 1-3, the discharge time gradually increased at the same current density, indicating an increase in the specific capacitance value of the material. The carbon-forming matrix used in the preparation of the porous carbon nanofibers in the three examples is the same as the porogen, but the porogen content is different in examples 1 and 2, and the molecular weight of the porogen is different in examples 2 and 3. In the embodiment, the higher the content of the pore-foaming agent is, the larger the specific capacitance value of the material is; the larger the molecular weight of the porogen, the higher the specific capacitance value of the material.
FIG. 3 is a constant current charge and discharge curve diagram of the porous carbon nanofiber materials prepared in examples 4 and 5, and the tested current density is 1A g -1 . The porogen types, molecular weights and doping levels in these two examples are identical, but the carbon-forming matrix used is different. In the examples, when polyacrylonitrile is used as the carbon forming matrix, the specific capacitance value of the material is higher.
FIG. 4 is a plot of cyclic voltammetry for porous carbon nanofiber membrane materials prepared in examples 1-7 and carbon nanofiber membrane material prepared in comparative example 1, with scan rate of 5mV s -1 . From examples 1-7, the cyclic voltammograms all exhibited a rectangular-like shape, indicating that the porous carbon nanofiber membrane materials all had ideal double layer capacitance performance and rapid charge and discharge capability. The cyclic voltammograms were subjected to a certain degree of bending deformation, which indicates that they all contained oneAnd (4) determining the pseudocapacitance. The size of the area enclosed by the cyclic voltammetry curve reflects the specific capacitance of the electrode material to a certain extent. It can be seen that the area surrounded by the cyclic voltammetry curves of the examples prepared after adding the porogen is significantly increased compared to comparative example 1, and thus the specific capacitance values of the electrode materials of the examples are increased.
FIG. 5 is a cyclic voltammogram of the porous carbon nanofiber membrane material prepared in example 7 at different sweep rates. With the gradual increase of the scanning speed, the shape of the cyclic voltammetry curve is not obviously deformed, which shows that the material has good reversibility in the charging and discharging processes.
Fig. 6 is a constant current charge and discharge curve diagram of the porous carbon nanofiber membrane material prepared in example 7 under different current densities. The shape of the curve remains substantially unchanged with the increase of the current density, further illustrating that the porous carbon nanofiber membrane material of example 7 has high specific capacitance value and excellent charge-discharge reversibility.
FIG. 7 is a constant current charge and discharge curve of the porous carbon nanofiber membrane material prepared in comparative example 2, and the tested current density is 1A g -1 . In comparative example 2, linear PEO was used as a porogen, and the molecular weight and the addition amount of the porogen were the same as those of example 3. The difference between them is that the linear polymer PEO is used as a porogen in comparative example 2, and PDMS-b-PEO BBCPs prepared in the present invention is used as a porogen in example 3. It can be seen that the specific capacitance value of comparative example 2 is only 96.6F g -1 While the specific capacitance value of example 3 is 125.7F g -1 . Compared with a linear polymer type pore-foaming agent, the segmented polymer molecular brush can bring a better pore-forming effect to the pore-foaming agent, so that a porous carbon nanofiber membrane material with higher specific capacitance performance is obtained.
Fig. 8 is a microscopic morphology view of the carbon nanofiber membrane material prepared in comparative example 1. It can be seen that the surface of the carbonized fiber is flat and smooth, a non-porous structure exists, the fiber diameter is 200-250nm, the overall diameter is uniform, and the excellent three-dimensional fiber morphology can be maintained after carbonization. Due to the maintenance of the internal fiber structure, the carbonized carbon nanofiber structure maintains certain mechanical strength, can be bent at multiple angles, and shows flexibility and self-supporting property.
Fig. 9 is a microscopic morphology view of the porous carbon nanofiber membrane material prepared in example 7. It can be seen that after pre-oxidation and carbonization, the inside of the porous carbon nanofiber membrane material still maintains a nano-scale fiber structure, the fiber diameter is 150-200nm, and as the pore-forming agent is pyrolyzed at high temperature and overflows in a gas form, the fiber section has obvious mesoporous and microporous shapes, the specific surface area of the carbon fiber material is increased, and thus the electrochemical performance of the material is improved.
In conclusion, the invention provides a novel method for preparing a porous carbon nanofiber membrane material, which is different from the conventional process of pore-forming a linear polymer in a fiber, the invention utilizes a block polymer molecular brush with a special topological structure as a pore-forming agent, and regulates and controls the uniform dispersion of the pore-forming agent in a carbon-forming matrix through the bridging action of a small-molecular hydrogen bond donor between the carbon-forming matrix and the pore-forming agent, so that the carbonized porous carbon nanofiber membrane material can still maintain a good three-dimensional fiber network structure in the interior, has good flexibility and bending capability, and is obviously improved in electrochemical performance, and can be used as a flexible electrode material.
The above description is directed to exemplary embodiments of the present invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A porous carbon nanofiber membrane material is characterized in that the porous carbon nanofiber membrane material is prepared by a pore-foaming agent and a carbon-forming matrix; the porogen comprises a block polymer molecular brush having a topological structure, the block polymer molecular brush comprising hydrophilic units and hydrophobic units.
2. The porous carbon nanofiber membrane material according to claim 1, wherein in the block polymer molecular brush, the hydrophilic unit comprises at least one of the following structural units:
the hydrophobic unit comprises at least one of the following structural units:
Preferably, in the block polymer molecular brush, the number of hydrophilic units is x, x is any integer within 1-1000, the number of hydrophobic units is y, and y is any integer within 1-1000.
Preferably, x is any integer within 30-500 and y is any integer within 30-500.
3. The porous carbon nanofiber membrane material according to claim 1 or 2, wherein the block polymer molecular brush has a structure as shown in formula a:
wherein x is any integer within 1-1000, and y is any integer within 1-1000. Preferably, x is any integer within 30-500, and y is any integer within 30-500;
r, R' are independently selected from at least one of the hydrophilic units and hydrophobic units described above.
Preferably, the molecular weight of the block polymer molecular brush is 15 to 500 ten thousand.
4. A porous carbon nanofiber membrane material according to any of claims 1 to 3, characterized in that it has a porous structure.
Preferably, the porous structure comprises micropores and/or mesopores. Preferably, the pore structure of the porous structure is ordered.
Preferably, the diameter of the fiber in the porous carbon nanofiber membrane material is 150-500 nm.
Preferably, the porous carbon nanofiber membrane material has good membrane forming property. Preferably, the thickness of the membrane of the porous carbon nanofiber membrane material is 20-200 μm.
Preferably, the porous carbon nanofiber membrane material has flexibility.
Preferably, the pore size of the porous structure of the porous carbon nanofiber membrane material can be effectively regulated and controlled by regulating and controlling the molecular weight of the pore-foaming agent.
Preferably, the porous carbon nanofiber membrane material has a large specific surface area. Preferably, the specific surface area is 180- 2 g -1 。
Preferably, the specific capacitance value of the porous carbon nanofiber membrane material is not less than 90.0F g -1 E.g. 90-300F g -1 。
5. A preparation method of a porous carbon nanofiber membrane material as claimed in any one of claims 1 to 4, characterized in that the preparation method comprises: inducing a pore-foaming agent to self-assemble into a spherical structure through a small molecular hydrogen bond donor; uniformly dispersing the spherical structure in a carbon forming matrix, performing electrostatic spinning to obtain a polymer fiber membrane, performing pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and performing pyrolysis on the pore-foaming agent in the carbon forming matrix to form a multi-stage pore channel structure, thereby preparing the porous carbon nanofiber membrane material.
6. The preparation method according to claim 5, wherein the preparation method specifically comprises:
(1) self-assembly of the block polymer molecular brush: inducing the block polymer molecular brush to self-assemble into a spherical structure by a small molecular hydrogen bond donor;
(2) preparing a porous carbon nanofiber membrane material: dispersing a spherical structure and a carbon-forming matrix polymer in a solvent to obtain a spinning solution, and performing electrostatic spinning on the spinning solution to obtain a polymer fiber membrane; and carrying out pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and cooling to obtain the porous carbon nanofiber membrane material.
7. The method of claim 5 or 6, wherein the small molecule hydrogen bond donor is at least one selected from the group consisting of p-hydroxybenzoic acid, gallic acid, terephthalic acid, oxalic acid, and 2-hydroxybenzoic acid.
Preferably, the mass ratio of the small molecule hydrogen bond donor to the block polymer molecular brush can be (0-0.8): 1.
Preferably, the block polymer molecular brush self-assembly is performed in an organic solvent.
Preferably, the self-assembly time can be 1-48 h.
Preferably, the spherical structure comprises an inner hydrophobic phase and an outer hydrophilic phase.
Preferably, the carbon-forming matrix is at least one selected from phenolic resin, polyacrylonitrile, polyaniline, polyacrylamide, polythiophene, polyimide, polyethylene, polybenzothiazole, polythiophene and sodium polyterephnylsulfonate.
Preferably, the mass ratio of the carbon-forming matrix to the spherical structure can be 1 (0.05-5).
8. The process according to any one of claims 5 to 7, wherein in the step (2), the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, toluene, tetrahydrofuran, dichloromethane, dichloroethane, dimethylsulfoxide, ethanol, ethylene glycol, acetonitrile, acetone, glycerol and methanol.
Preferably, in the step (2), the spinning solution is uniformly stirred at 40-80 ℃.
Preferably, the electrostatic spinning conditions specifically include: the spinning voltage is 15-30kV, the diameter of the needle is 0.5-1.5 mm, the propelling speed of the peristaltic pump is 0.5-5 mm/min, the distance from the needle to the receiving plate is 15-40 cm, the temperature is 25-45 ℃, and the humidity is 10-60%.
Preferably, the pre-oxidation treatment comprises the following specific steps: heating to 200-400 ℃ at the speed of 1-10 ℃/min in the air atmosphere, and staying for 60-150 min for pre-oxidation treatment.
Preferably, the carbonization treatment comprises the following specific steps: heating to 600-1000 ℃ at the speed of 2-20 ℃ in an inert atmosphere, and standing for 60-240 min for carbonization treatment.
9. Use of a porous carbon nanofiber membrane material as claimed in any of claims 1 to 4.
10. An electrode comprising the porous carbon nanofiber membrane material as claimed in any one of claims 1 to 4.
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