CN115036146B - 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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- CN115036146B CN115036146B CN202210622066.9A CN202210622066A CN115036146B CN 115036146 B CN115036146 B CN 115036146B CN 202210622066 A CN202210622066 A CN 202210622066A CN 115036146 B CN115036146 B CN 115036146B
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- 239000000463 material Substances 0.000 title claims abstract description 132
- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 26
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- 238000009987 spinning Methods 0.000 claims description 55
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
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- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 claims description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004642 Polyimide Substances 0.000 claims description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003792 electrolyte Substances 0.000 abstract description 4
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- 238000006243 chemical reaction Methods 0.000 description 16
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- 239000004088 foaming agent Substances 0.000 description 14
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- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 7
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- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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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-forming 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 large specific surface area of the material, an internally ordered pore channel structure 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 flexible electrode material preparation.
Background
In the face of increasingly severe energy crisis and environmental crisis, various countries put higher demands on new energy storage devices while improving traditional energy efficiency and developing renewable energy (solar energy, tidal energy, hydrogen energy, tidal energy and the like), and are devoted to developing more efficient, safe and stable energy storage and conversion devices to realize sustainable utilization of green clean energy. Among various energy storage devices, the super capacitor is an advanced green electric energy storage device developed in recent years, has the advantages of safety, reliability, high charge and discharge rate (several seconds), long cycle life (millions), wide working temperature and the like, fully makes up for the short plate of the traditional capacitor in energy storage capacity, and is rapidly developed and applied. At the same time, the rise of flexible displays, flexible electronics, portable and wearable devices has driven the continued development of flexible energy storage technology. As a core component in the flexible energy storage device, the preparation and assembly of the flexible electrode directly determines the performance level of the flexible energy storage device. Therefore, there is an urgent need to develop a soft, lightweight, and flexible electrode material with high capacitance.
The choice of electrode materials is a key factor affecting the specific capacitance performance of the supercapacitor, and materials with high specific surface area, good conductivity and stable structure are generally selected. The one-dimensional carbon nanofiber has good conductivity, excellent chemical stability and thermal stability and higher specific surface area, meets the requirements of the device on flexibility and bendability, and is certainly the most promising material in the electrode materials of the flexible super capacitor. However, most carbon fibers have low specific surface area utilization ratio, poor hydrophilicity, low specific capacitance and low energy density, and are difficult to meet the demands of energy storage devices. In order to increase the specific surface area of the carbon nanofiber and thus the performance of the electrode material, a polymer pore-forming template material (such as PEO, PMMA, PVP, P VP) is required to be used as a pore-forming agent to form a multi-stage pore structure, so that the effective contact area between the electrolyte and the electrode material is increased. However, as the molecular weight of the conventional linear polymer increases, entanglement occurs between chain segments, and the pore diameter of the pore is generally smaller, so that the thermal stability and the photoelectric performance of the material are poor. In addition, the polymer pore-forming process often causes the material to become brittle, the flexibility is lost, and the preparation of the flexible electrode material with high specific capacitance is difficult to realize. Therefore, exploring a suitable pore-forming method to obtain porous carbon nanofibers with adjustable pore structures while maintaining the flexibility of the material is critical for further improving the specific capacitance performance of the electrode.
Disclosure of Invention
Aiming at the defect that the linear polymer is used for pore-forming in the carbon nanofiber, the invention aims to develop a novel polymer and provide a preparation method of a porous carbon nanofiber membrane material with ordered pore channel structure and flexible self-support and an electrode thereof.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
the porous carbon nanofiber membrane material is prepared from a pore-forming 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:
wherein n, m, p are independently selected from any integer within 10-200;
the hydrophobic unit comprises at least one of the following structural units:
wherein a, b, c, d is a linking site independently selected from any integer within 10-200.
According to an embodiment of the present invention, in the block polymer molecular brush, the number of hydrophilic units is x, x is any integer within 1 to 1000, and the number of hydrophobic units is y, y is any integer within 1 to 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 from 1 to 1000, and y is any integer from 1 to 1000. Preferably, x is any integer from 30 to 500 and y is any integer from 30 to 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 block polymer molecular brush has a size and molecular weight that satisfy a good positive linear relationship.
According to an embodiment of the present invention, the molecular weight of the block polymer molecular brush is 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 canal structure of the porous structure is ordered.
According to an embodiment of the present invention, the diameter of the fibers in the porous carbon nanofiber membrane material is 150 to 500nm.
According to the embodiment of the invention, the porous carbon nanofiber membrane material has good film forming property. 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 by regulating the molecular weight of the pore-foaming agent.
According to an embodiment of the present invention, the porous carbon nano-meterThe fibrous membrane material has a relatively large specific surface area. Preferably, the specific surface area is 180-800m 2 g -1 。
According to an embodiment of the present invention, the specific capacitance value of the porous carbon nanofiber membrane material is not less than 90.0. 90.0F g -1 For example 90-300F g -1 。
The invention also provides a preparation method of the porous carbon nanofiber membrane material, which comprises the following steps: inducing the pore 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, carrying out electrostatic spinning to obtain a polymer fiber membrane, carrying out pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and carrying out pyrolysis on the pore-forming agent in the carbon forming matrix to form a multi-stage pore canal structure, thereby preparing the porous carbon nanofiber membrane material.
According to an embodiment of the present invention, the preparation method specifically includes:
(1) Self-assembly of the block polymer molecular brush: the small molecular hydrogen bond donor induces the self-assembly of the block polymer molecular brush into a spherical structure;
(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 stock solution, and carrying out electrostatic spinning on the stock solution to obtain a polymer fiber membrane; and (3) performing 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 embodiments of the invention, the mass ratio of the small molecule hydrogen bond donor to the block polymer molecular brush may be (0 to 0.8): 1.
According to an embodiment of the invention, the self-assembly of the block polymer molecular brush is performed in an organic solvent.
Preferably, the self-assembly time may be 1 to 48 hours.
According to an embodiment of the invention, the spherical structure comprises an inner layer being a hydrophobic phase and an outer layer being a hydrophilic phase.
According to an embodiment of the present invention, the carbon-forming matrix is at least one selected from the group consisting of phenolic resin, polyacrylonitrile, polyaniline, polyacrylamide, polythiophene, polyimide, polyethylene, polybenzothiazole, polythiophene, and sodium poly-p-styrenesulfonate.
According to embodiments of the present invention, the mass ratio of the carbon-forming matrix to the spherical structure may be 1 (0.05 to 5).
According to an embodiment of the present invention, in step (2), the solvent 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, methanol.
According to an embodiment of the present invention, in the step (2), the spinning dope is uniformly stirred at 40 to 80 ℃.
According to an embodiment of the present invention, the conditions of electrospinning specifically include: the spinning voltage is 15-30kV, the diameter of the needle is 0.5-1.5 mm, the advancing 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 ℃, and the humidity is 10-60%.
According to an embodiment of the invention, the specific steps of the pre-oxidation treatment are: heating to 200-400 ℃ at a speed of 1-10 ℃/min in an air atmosphere, and staying for 60-150 min for pre-oxidation treatment.
According to an embodiment of the invention, the carbonization treatment comprises the following specific steps: heating to 600-1000 ℃ at a rate of 2-20 ℃ in inert atmosphere, and staying 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 fiber diameter of the polymer fiber membrane prepared by the invention is 150-500 nm, and the thickness of the fiber membrane is uniform. The porous carbon nanofiber membrane material obtained by pre-oxidation treatment and carbonization treatment still maintains a certain mechanical strength depending on good film forming property and flexibility of the polymer fiber membrane, and can be bent at 90-180 degrees. In the electrode preparation process, unlike the common powdery carbon material, the porous carbon nanofiber membrane material can be independently pressed on a current collector to prepare the electrode without using a conductive agent and an adhesive, the preparation process is simple and quick, and the cost can be effectively saved.
2. The invention provides a new idea for the method for preparing the porous carbon material by pore-forming of the polymer soft template. According to the invention, the block polymer molecular brush is used as a pore-forming agent, the characteristics of main chain conformational extension, no intermolecular entanglement and controllable aggregation state structure of the material are fully utilized, on one hand, the design of pore channel structure and porous morphology in the porous carbon nanofiber membrane material can be realized through regulating and controlling the block proportion in the block polymer molecular brush, and on the other hand, the size and molecular weight of the block polymer molecular brush meet good positive linear relation, and the regulation of pore size can be realized through regulating and controlling the molecular weight of the pore-forming agent.
3. The pore channel distribution in the porous carbon nanofiber membrane material is regulated and controlled by a simple and easy method. In the preparation process of the spinning solution, the hydrophilic component in the pore-forming agent is induced to selectively enter the carbon-forming matrix component by taking 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-forming agent in a carbon-forming matrix phase are limited, the uniform dispersion of the pore-forming agent in the carbon-forming matrix is realized, and the pore channel distribution in the carbonized porous carbon nanofiber membrane material is uniform.
4. The porous carbon nanofiber membrane material prepared by the invention provides a sufficient place for storing and entering electrolyte based on a large specific surface area of the material, an internally ordered pore channel structure 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 of examples 1-3.
FIG. 2 is a constant current charge-discharge graph of the porous carbon nanofiber membrane material prepared in examples 1-3 and the carbon nanofiber membrane material prepared in comparative example 1, and the tested current density was 1A g -1 。
FIG. 3 is a constant current charge-discharge curve of the porous carbon nanofiber membrane materials prepared in examples 4 and 5, and the tested current density was 1A g -1 。
FIG. 4 is a cyclic voltammogram of the porous carbon nanofiber membrane materials prepared in examples 1-7 and the carbon nanofiber membrane material prepared in comparative example 1, tested at a 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 graph of the porous carbon nanofiber membrane material prepared in example 7 at 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, tested with a current density of 1A g -1 。
Fig. 8 is a microscopic morphology diagram of the carbon nanofiber membrane material prepared in comparative example 1.
Fig. 9 is a microscopic morphology graph 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, comprising hydrophilic and hydrophobic units;
wherein the hydrophilic unit comprises at least one of the following structural units:
wherein n, m, p are independently selected from any integer within 10-200;
The hydrophobic unit comprises at least one of the following structural units:
wherein a, b, c, d is a linking site independently selected from any integer within 10-200.
According to an embodiment of the present invention, in the block polymer molecular brush, the number of hydrophilic units is x, x is any integer within 1 to 1000, and the number of hydrophobic units is y, y is any integer within 1 to 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 from 1 to 1000, and y is any integer from 1 to 1000. Preferably, x is any integer from 30 to 500 and y is any integer from 30 to 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 block polymer molecular brush has a size and molecular weight that satisfy a good positive linear relationship.
According to an embodiment of the present 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 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-PVP BBCPs, PCL-b-P4VP BBCPs, PCL-b-PEO BBCPs, PCL-b-PCP cps, wherein PEO, PVP, P-VP, PS, PCL, PLA, PDMS represent a repeating unit of polyethylene glycol (PEO), polyvinylpyrrolidone (PVP), poly-4-vinylpyridine (P4 VP), polystyrene (PS), polycaprolactone (PCL), polylactic acid (PLA), polydimethylsiloxane (PDMS), respectively.
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 reaction; finally, the reaction was terminated with vinyl diethyl ether to give a block polymer molecular brush, designated BBCPs.
According to an embodiment of the present invention, the hydrophilic polymer macromolecule is selected from at least one of polyethylene glycol (PEO), polyvinylpyrrolidone (PVP), poly-4-vinylpyridine (P4 VP) containing 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 the site of attachment.
According to a preferred embodiment of the present invention, the hydrophilic polymer macromolecule is selected from at least one of the 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, at least one of the structures described belowOne or two of:
wherein n, m, p are independently selected from any integer within 10-200.
According to an embodiment of the invention, the molecular weight of the hydrophilic polymer macromolecules is between 0.4 and 20kg/mol, preferably between 5 and 10kg/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) containing norbornene active groups at a single end.
Wherein the structure of the norbornene active group comprises at least one of the following structures:
Wherein is the site of attachment.
According to a preferred embodiment of the present invention, the hydrophobic polymer macromolecule is selected from at least one of the compounds having the structures represented by the following formulas II-1 to II-8:
wherein R is 1 ’、R 2 'same or different', independently of each other, from at least one of the following structural units:
wherein a, b, c, d is an integer independently selected from 10-200.
According to an embodiment of the invention, the molecular weight of the hydrophobic polymer macromolecules is between 0.6 and 20kg/mol, preferably 4.8 and 8kg/mol.
According to embodiments of the invention, the molar ratio of the hydrophilic polymer macromolecule to the hydrophobic polymer macromolecule may be (0.1-0.9): (0.9-0.1), in particular (0.2-0.8): (0.8-0.2), for example 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 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 macromolecules or the hydrophobic polymer macromolecules.
According to embodiments 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, 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% by weight of the total mass of the hydrophilic polymer macromolecule or the hydrophobic polymer macromolecule, and may be specifically 0.5 to 5% by weight, for example, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, or 5% by weight.
According to an embodiment of the present invention, the polymerization reaction temperature may be 0 to 50 ℃, specifically 0 to 30 ℃, preferably 25 ℃.
According to embodiments of the invention, the polymerization time may be 0.02 to 24 hours, in particular 0.05 to 12 hours, for example 0.05 hours, 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 the following formula II:
Wherein R is selected from the above R 1 And R is 2 At least one of the structures; 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 block polymer molecular brush described above, for example for porogens.
The invention also provides a pore-foaming agent, which comprises the block polymer molecular brush.
[ porous carbon nanofiber Membrane Material ]
The invention also provides a porous carbon nanofiber membrane material, which is prepared from the pore-forming 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 canal structure of the porous structure is ordered.
Preferably, the micropores refer to pores with a pore diameter of 0-2 nm.
Preferably, the mesoporous refers to pores with the pore diameter of 2-50 nm.
According to an embodiment of the invention, the porous carbon nanofiber membrane material is flexible and self-supporting.
According to an embodiment of the present invention, the diameter of the fibers in the porous carbon nanofiber membrane material is 150 to 500nm.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material has good film forming properties, and 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, for example, can be bent by 90 to 180 °.
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 by regulating 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 180-800m 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 an embodiment of the present invention, the specific capacitance value of the porous carbon nanofiber membrane material is not less than 90.0. 90.0F g -1 . For example 90-300F g -1 For example 95.4. 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 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, carrying out electrostatic spinning to obtain a polymer fiber membrane, carrying out pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and carrying out pyrolysis on the pore-forming agent in the carbon forming matrix to form a multi-stage pore canal structure, thereby preparing the porous carbon nanofiber membrane material.
According to an embodiment of the present invention, the preparation method specifically includes:
(1) Self-assembly of the block polymer molecular brush: the small molecular hydrogen bond donor induces the self-assembly of the block polymer molecular brush into a spherical structure;
(2) Preparation of porous carbon nanofiber material: dispersing a spherical structure and a carbon-forming precursor polymer in a solvent to obtain a spinning solution, and carrying out electrostatic spinning on the spinning solution to obtain a polymer fiber membrane; and (3) performing 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 present 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 discovers that the hydrophilic component in the block polymer molecular brush can be selectively introduced into the carbon-forming matrix through the small molecular hydrogen bond donor, so that the uniform dispersion of the pore-foaming agent in the carbon-forming matrix is regulated.
According to embodiments of the invention, the mass ratio of the small molecule hydrogen bond donor to the block polymer molecular brush may be (0-0.8): 1, in particular (0.02-0.6): 1, e.g. 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 self-assembly of the block polymer molecular brush is performed 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 may be 1 to 48 hours, and in particular may be 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 mass of the organic solvent is not particularly limited as long as self-assembly of the block polymer molecular brush can be achieved, and may be, for example, 10 to 100 times, particularly 30 to 100 times, for example, 50 times, 60 times, 70 times, 80 times, 90 times or 100 times, 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 layer being a hydrophobic phase and an outer layer being a hydrophilic phase.
According to an embodiment of the present invention, the carbon-forming matrix is at least one selected from the group consisting of phenolic resin, polyacrylonitrile, polyaniline, polyacrylamide, polythiophene, polyimide, polyethylene, polybenzothiazole, polythiophene, and sodium poly-p-styrenesulfonate.
According to embodiments of the present invention, the mass ratio of the carbon-forming matrix to the spherical structure may be 1 (0.05-5), and specifically may be 1 (0.2-5), for example, 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, dimethyl sulfoxide, ethanol, ethylene glycol, acetonitrile, acetone, glycerol, methanol.
According to an embodiment of the present invention, in the step (2), the spinning dope is uniformly stirred at 40 to 80 ℃, preferably for 12 hours or more.
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 dope for electrospinning can be prepared, for example, the mass of the organic solvent may be 1.5 to 15 times, particularly 5 to 15 times, for example, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times the total mass of the carbon-forming matrix and the spherical structure.
According to an embodiment of the present invention, the conditions of electrospinning specifically include: the spinning voltage is 15-30kV, the diameter of the needle is 0.5-1.5 mm, the advancing 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 ℃ and the humidity is 10-60%,
preferably, the receiving plate may be any one of aluminum foil, tinfoil paper, release paper and steel sheet.
According to an embodiment of the invention, the specific steps of the pre-oxidation treatment are: the temperature is increased to 200-400 ℃ at a speed of 1-10 ℃/min in an air atmosphere, and the pre-oxidation treatment is carried out for 60-150 min, for example, the temperature is increased to 250 ℃ at a speed of 2 ℃/min in the air atmosphere, and the pre-oxidation treatment is carried out for 90min.
According to an embodiment of the invention, the carbonization treatment comprises the following specific steps: heating to 600-1000 ℃ at a rate of 2-20 ℃ in inert atmosphere, and staying for 60-240 min for carbonization treatment.
Preferably, the inert atmosphere may be selected from Ar, N 2 Any one of them.
Illustratively, the carbonization treatment specifically comprises the following steps: heating to 900 ℃ at a rate of 5 ℃/min in nitrogen atmosphere, and staying for 90min
[ application of porous carbon nanofiber Membrane Material ]
The invention also provides application of the porous carbon nanofiber membrane material, for example, application to 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 for preparing an electrode includes: and (3) sandwiching the porous carbon nanofiber membrane material between current collectors, and tabletting to obtain the electrode.
According to an embodiment of the 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.
According to an embodiment of the present invention, the porous carbon nanofiber membrane material may be cut into any shape, such as rectangular, circular, and 1×1cm, for example 2 Is a square of (c).
The electrode prepared by the invention does not need to use conductive agent and adhesive.
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples and comparative examples are commercially available or may be prepared by known methods.
The porous carbon nanofiber membrane material prepared in each of the following examples and comparative examples was cut to about 1X 1cm 2 The square sample is clamped between two pieces of foam nickel, and the pressed sample is used as a porous carbon nanofiber electrode without using a conductive agent and an adhesive. The electrochemical performance test of the electrode was performed in 6M KOH alkaline electrolyte with the porous carbon nanofiber electrode as the working electrode, ag/AgCl (saturated KCl) as the reference electrode, and a platinum sheet electrode as the counter electrode.
The electrochemical properties of the materials in the following examples and comparative examples were obtained by testing at room temperature using a CHI1600E type electrochemical workstation manufactured by Shanghai Chen Hua instruments Co., ltd.
The microscopic morphologies of the materials in the following examples and comparative examples were obtained by scanning electron microscopy using S-8020.
Example 1
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and PDMS-b-PEO BBCPs as a pore-forming agent comprises the following steps:
(1) Preparing a block polymer molecular brush: 1.0g of polyethylene glycol (PEO-NB, mw=5 kg/mol) having norbornene groups as a terminal and 1.0g of polydimethylsiloxane (PDMS-NB, mw=4.8 kg/mol) having norbornene groups as a terminal were each dissolved in 10g of methylene chloride. An appropriate amount of Grubbs catalyst was added to the PEO-NB solution, and after stirring for 0.2h, the reaction was poured into the PDMS-NB solution and allowed to react overnight, after which the reaction was quenched with vinyl diethyl ether to prepare a 20-thousand molecular weight block polymer molecular brush, designated PDMS-b-PEO BBCPs, which was used as a porogen.
(2) And (3) blending the PDMS-b-PEO BBCPs obtained in the step (1) with 20wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours and sufficiently drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of polyacrylonitrile powder and 0.4g of the pore-forming agent with spherical structure in the step (2) are added into 9g of N, N-dimethylformamide, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of 32 ℃ and 28% humidity by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver is 15cm, the applied voltage is 18kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at a propelling speed of 2mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, and heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 90min. After the pre-oxidation process is completed, the temperature is raised to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and the mixture is cooled to room temperature, so that the porous carbon nanofiber membrane material is obtained and is named as PCNFs-1.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 2
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and PDMS-b-PEO BBCPs as a pore-forming agent comprises the following steps:
(1) Preparing a block polymer molecular brush: 1.0g of polyethylene glycol (PEO-NB, mw=5 kg/mol) having norbornene groups as a terminal and 1.0g of polydimethylsiloxane (PDMS-NB, mw=4.8 kg/mol) having norbornene groups as a terminal were each dissolved in 10g of methylene chloride. An appropriate amount of Grubbs catalyst was added to the PEO-NB solution, and after stirring for 0.2h, the reaction was poured into the PDMS-NB solution and allowed to react overnight, after which the reaction was quenched with vinyl diethyl ether to prepare a 20-thousand molecular weight block polymer molecular brush, designated PDMS-b-PEO BBCPs, which was used as a porogen.
(2) And (3) blending the PDMS-b-PEO BBCPs obtained in the step (1) with 20wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours and sufficiently drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of polyacrylonitrile powder and 0.8g of the pore-forming agent with spherical structure in the step (2) are added into 12g of N, N-dimethylformamide, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of 32 ℃ and 28% humidity by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver is 15cm, the applied voltage is 18kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at a propelling speed of 2mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, and heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 90min. After the pre-oxidation process is completed, the temperature is raised to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and the mixture is cooled to room temperature, so that the porous carbon nanofiber membrane material is obtained and is named as PCNFs-2.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 3
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and PDMS-b-PEO BBCPs as a pore-forming agent comprises the following steps:
(1) 1.0g of polyethylene glycol (PEO-NB, mw=5 kg/mol) having norbornene groups as a terminal and 1.0g of polydimethylsiloxane (PDMS-NB, mw=4.8 kg/mol) having norbornene groups as a terminal were each dissolved in 10g of methylene chloride. An appropriate amount of Grubbs catalyst was added to the PEO-NB solution, and after stirring for 0.2h, the reaction was poured into the PDMS-NB solution and allowed to react overnight, after which the reaction was quenched with vinyl diethyl ether to prepare a 40-kilo molecular weight block polymer molecular brush, designated PDMS-b-PEO BBCPs, which was used as a porogen.
(2) And (3) blending the PDMS-b-PEO BBCPs obtained in the step (1) with 20wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours, and fully drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of polyacrylonitrile powder and 0.8g of the pore-forming agent with spherical structure in the step (2) are added into 12g of N, N-dimethylformamide, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of 32 ℃ and 28% humidity by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the syringe needle to the receiver is 15cm, the applied voltage is 18kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at a propelling speed of 2mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, and heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 90min. After the pre-oxidation process is completed, the temperature is raised to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and the mixture is cooled to room temperature, so that the porous carbon nanofiber membrane material is obtained and is named as PCNFs-3.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 4
The preparation method of the porous carbon nanofiber membrane material takes phenolic resin as a carbon forming matrix and PS-b-PVP BBCPs as a pore-forming agent is as follows:
(1) 1.6g of polyvinylpyrrolidone (PVP-NB, mw=15 kg/mol) having norbornene groups as a single terminal and 0.4g of polystyrene (PS-NB, mw=6 kg/mol) having norbornene groups as a single terminal were dissolved in 16g of methylene chloride and 0.6g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into PVP-NB solution, stirring for reaction for 0.4h, pouring into PS-NB solution, reacting overnight, and quenching the reaction with vinyl diethyl ether to obtain a block polymer molecular brush with a molecular weight of 80 ten thousand, namely PS-b-PVP BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (3) blending the PS-b-PVP BBCPs obtained in the step (1) with 10wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours, and fully drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of phenolic resin and 1.0g of the spherical structure pore-forming agent in the step (2) are added into 14g of tetrahydrofuran, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of 30 ℃ and 25% humidity by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the needle of the syringe to the receiver is 15cm, the applied voltage is 20kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at the propelling speed of 0.5mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, heating to 900 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, staying for 60min, and cooling to room temperature to obtain the porous carbon nanofiber membrane material named PCNFs-4.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 5
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and takes PS-b-PVP BBCPs as a pore-forming agent is as follows:
(1) 1.6g of polyvinylpyrrolidone (PVP-NB, mw=15 kg/mol) having norbornene groups as a single terminal and 0.4g of polystyrene (PS-NB, mw=6 kg/mol) having norbornene groups as a single terminal were dissolved in 16g of methylene chloride and 0.6g of methylene chloride, respectively. Adding a proper amount of Grubbs catalyst into PVP-NB solution, stirring for reaction for 0.4h, pouring into PS-NB solution, reacting overnight, and quenching the reaction with vinyl diethyl ether to obtain a block polymer molecular brush with a molecular weight of 80 ten thousand, namely PS-b-PVP BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (3) blending the PS-b-PVP BBCPs obtained in the step (1) with 10wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours, and fully drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of polyacrylonitrile powder and 1.0g of the pore-forming agent with spherical structure in the step (2) are added into 14g of N, N-dimethylformamide, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of 25 ℃ and 35% humidity by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the needle of the syringe to the receiver is 15cm, the applied voltage is 20kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at a propelling speed of 5mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white nanofiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, and heating to 280 ℃ at a speed of 4 ℃/min under the air atmosphere, and staying for 90min. After the pre-oxidation process is completed, the temperature is raised to 900 ℃ at the speed of 10 ℃/min in a nitrogen atmosphere, the mixture stays for 60min, and the mixture is cooled to room temperature, so that the porous carbon nanofiber membrane material is obtained and is named as PCNFs-5.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 6
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and takes PS-b-P4VP BBCPs as a pore-forming agent comprises the following steps:
(1) 1.2g of poly-4-vinylpyridine (P4 VP-NB, mw=20 kg/mol) having norbornene groups in the single terminal and 0.8g of polystyrene (PS-NB, mw=15 kg/mol) having norbornene groups in the single terminal 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 PS-NB solution, reacting overnight, and quenching the reaction with vinyl diethyl ether to prepare the block polymer molecular brush with the molecular weight of 100 ten thousand, namely PS-b-P4VP BBCPs, and taking the block polymer molecular brush as a pore-foaming agent.
(2) And (3) blending the PS-b-P4VP BBCPs obtained in the step (1) with 20wt% of P-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours, and fully drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of polyacrylonitrile powder and 1.5g of the pore-forming agent with spherical structure in the step (2) are added into 15g of N, N-dimethylformamide, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of temperature 26 ℃ and humidity 28% by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the needle of the syringe to the receiver is 15cm, the applied voltage is 20kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at a propelling speed of 2mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, and heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 120min. After the pre-oxidation process is completed, the temperature is raised to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and the mixture is cooled to room temperature to obtain the porous carbon nanofiber membrane material which is named PCNFs-6.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this example are shown in table 1.
Example 7
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and PS-b-PEO BBCPs as a pore-forming agent is as follows:
(1) 1.2g of polyethylene glycol (PEO-NB, mw=5 kg/mol) having norbornene groups as a single terminal and 0.8g of polystyrene (PS-NB, mw=3 kg/mol) having norbornene groups as a single terminal were each dissolved in 10g of methylene chloride. An appropriate amount of Grubbs catalyst was added to the PEO-NB solution, after stirring for 0.05h, the PS-NB solution was poured, reacted overnight, after which the reaction was quenched with vinyl diethyl ether to prepare a 120-kilo molecular weight block polymer molecular brush, designated PS-b-PEO BBCPs, which was used as a porogen.
(2) And (3) blending the PS-b-PEO BBCPs obtained in the step (1) with 20wt% of p-hydroxybenzoic acid in tetrahydrofuran, stirring for 4 hours and sufficiently drying to obtain the self-assembled pore-foaming agent with a spherical structure.
(3) 1.0g of polyacrylonitrile powder and 1.8g of the pore-forming agent with spherical structure in the step (2) are added into 20g of N, N-dimethylformamide, and the mixture is stirred at 60 ℃ to obtain a uniform and transparent spinning solution. Spinning under the conditions of 28 ℃ and 28% humidity by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the needle of the syringe to the receiver is 15cm, the applied voltage is 20kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at a propelling speed of 2mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(4) And (3) flatly placing the polymer fiber membrane in the step (3) in a tube furnace, and heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 120min. After the pre-oxidation process is completed, the temperature is raised to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and the mixture is cooled to room temperature, so that the porous carbon nanofiber membrane material is obtained and 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 for preparing 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 give a uniform and transparent spinning dope having a concentration of 15% by weight. Under the conditions of the temperature of 32 ℃ and the humidity of 28%, the spinning solution in a 5ml syringe is pushed to a needle head by a pushing device at a pushing speed of 2mm/min to enter an electric field of 18kV, and the spinning solution is received on a receiving plate 15cm away from the needle head to obtain a white polymer fiber membrane.
(2) And (3) flatly placing the polymer fiber membrane in the step (1) in a tube furnace, heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 120min. After the pre-oxidation process is completed, the temperature is raised to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and after cooling to room temperature, the carbon nanofiber membrane material is obtained and is named as CNFs.
The specific capacitance values of the carbon nanofiber electrodes prepared in this comparative example are shown in table 1.
Comparative example 2
The preparation method of the porous carbon nanofiber membrane material takes polyacrylonitrile as a carbon forming matrix and linear PEO as a pore-forming agent 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 give a homogeneous transparent spinning dope in which the molecular weight of PEO was 40 ten thousand. Spinning under the conditions of temperature 26 ℃ and humidity 35% by using an electrostatic spinning device, wherein the specific spinning parameters are as follows: the distance from the needle of the syringe to the receiver is 15cm, the applied voltage is 20kV, the propelling device pushes the spinning solution in the 5ml syringe to the needle at the propelling speed of 0.5mm/min, and the spinning solution is received on the tin foil collector under the action of an electric field to obtain the white polymer fiber membrane.
(2) And (3) flatly placing the polymer fiber membrane in the step (1) in a tube furnace, heating to 250 ℃ at a speed of 2 ℃/min under the air atmosphere, and staying for 90min. After the pre-oxidation process is completed, the temperature is raised to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the mixture stays for 90min, and the mixture is cooled to room temperature, so that the porous carbon nanofiber membrane material is obtained and is named as PCNFs control.
The specific capacitance values of the porous carbon nanofiber electrodes prepared in this comparative example are shown in table 1.
Specific capacitance value 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 application is obviously improved compared with the prior art, as compared with the example 7 and the comparative example 1, the specific capacitance value is obviously improved in 1A g -1 The specific capacitance value at current density is 88.0F g -1 Lifting to 254.1 and 254.1F g -1 . The result shows that the porous carbon nanofiber membrane material prepared in the invention has excellent specific capacitance performance.
TABLE 2 parameters of block polymer molecular brushes and 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 of examples 1-3. As the polymerization proceeds, the peak corresponding to the norbornene double bond H at 6.13ppm disappears, indicating successful progress of the polymerization.
FIG. 2 is a constant current charge-discharge graph of the porous carbon nanofiber membrane material prepared in examples 1-3 and the carbon nanofiber membrane material prepared in comparative example 1, and the tested current density was 1A g -1 . From comparative example 1 to examples 1-3, the discharge time gradually increased at the same current density, indicating that the specific capacitance value of the material increased. The porous carbon nanofibers were prepared using the same carbon-forming matrix and porogen as in the preparation of the porous carbon nanofibers in the three examples, but with different porogen contents in examples 1 and 2 and different porogen molecular weights in examples 2 and 3. The higher the porogen content in the examples, the greater the specific capacitance value of the material; the larger the porogen molecular weight, the higher the specific capacitance of the material.
FIG. 3 is a constant current charge-discharge curve of the porous carbon nanofiber materials prepared in examples 4 and 5, and tested current density of 1A g -1 . The porogens used in these two examples were of the same type, molecular weight and doping level, but different carbon-forming matrices were used. 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 cyclic voltammogram of the porous carbon nanofiber membrane materials prepared in examples 1-7 and the carbon nanofiber membrane material prepared in comparative example 1, tested at a scan rate of 5mV s -1 . From examples 1-7, the cyclic voltammograms all exhibited rectangular-like shapes, demonstrating that the porous carbon nanofiber membrane materials all had desirable double layer capacitance properties and rapid charge and discharge capabilities. Cyclic voltammograms have some degree of bending deformation, which suggests that they all contain some pseudocapacitive composition. The size of the surrounding area of the cyclic voltammogram reflects the specific capacitance value of the electrode material to a certain extent. It can be seen that the cyclic voltammogram surrounding area of the example prepared after the addition of the porogen is significantly increased compared to comparative example 1, and thus the specific capacitance value of the electrode material of the example is increased.
Fig. 5 is a cyclic voltammogram of the porous carbon nanofiber membrane material prepared in example 7 at different sweep rates. Along with the gradual increase of the scanning speed, the shape of the cyclic voltammogram is not obviously deformed, which indicates that the material has good reversibility in the charge and discharge process.
Fig. 6 is a constant current charge and discharge graph of the porous carbon nanofiber membrane material prepared in example 7 at different current densities. The shape of the curve remains substantially unchanged as the current density increases, further illustrating the high specific capacitance and excellent charge-discharge reversibility of the porous carbon nanofiber membrane material of example 7.
FIG. 7 is a constant current charge and discharge curve of the porous carbon nanofiber membrane material prepared in comparative example 2, tested with a current density of 1A g -1 . In comparative example 2, linear PEO was used as a porogen, and the molecular weight and the amount of the porogen added were the same as in example 3. The difference between the two is that in comparative example 2, the linear polymer PEO was used as the porogen, while in example 3, the PDMS-b-PEO BBCPs prepared in the present invention was used as the porogen. As can be seen, the specific capacitance value of comparative example 2 was only 96.6F g -1 Whereas the specific capacitance value of example 3 was 125.7F g -1 . This shows that the block polymer molecular brush as a pore-forming agent can bring better pore-forming effect and obtain a porous carbon nanofiber membrane material with higher specific capacitance performance compared with the linear polymer type pore-forming agent.
Fig. 8 is a microscopic morphology diagram of the carbon nanofiber membrane material prepared in comparative example 1. It can be seen that the carbonized fiber has a flat and smooth surface and no hole structure, the fiber diameter is 200-250nm, the whole 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 a certain mechanical strength, can be bent at multiple angles, and shows flexibility and self-supporting property.
Fig. 9 is a microscopic morphology 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 nanoscale fiber structure, the fiber diameter is 150-200nm, and the pore-forming agent is pyrolyzed at high temperature and overflows in a gas form, and the fiber section has obvious mesoporous and microporous morphology, so that the specific surface area of the carbon nanofiber material is increased, and the electrochemical performance of the material is improved.
In summary, the invention provides a new method for preparing a porous carbon nanofiber membrane material, which is different from the conventional process of pore-forming of a linear polymer in a fiber, and the invention uses a block polymer molecular brush with a special topological structure as a pore-forming agent, and regulates and controls uniform dispersion of the pore-forming agent in a carbon-forming matrix through 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 better flexibility and bending capability, and also has obvious improvement in electrochemical performance, and can be used as a flexible electrode material.
The above description of exemplary embodiments of the invention has been provided. However, the scope of protection of the present application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (15)
1. The preparation method of the porous carbon nanofiber membrane material is characterized by comprising the following steps: inducing the pore agent to self-assemble into a spherical structure through a small molecular hydrogen bond donor; uniformly dispersing a spherical structure in a carbon forming matrix, carrying out electrostatic spinning to obtain a polymer fiber membrane, and carrying out pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, wherein the pore-forming agent is pyrolyzed in the carbon forming matrix to form a multi-stage pore structure, so as to prepare the porous carbon nanofiber membrane material;
the pore-forming agent comprises a block polymer molecular brush, wherein the block polymer molecular brush has a topological structure and comprises a hydrophilic unit and a hydrophobic unit;
the small molecule hydrogen bond donor is selected from at least one of p-hydroxybenzoic acid, gallic acid, terephthalic acid, oxalic acid and 2-hydroxybenzoic acid;
The carbon-forming matrix is selected from at least one of phenolic resin, polyacrylonitrile, polyaniline, polyacrylamide, polythiophene, polyimide, polyethylene, polybenzothiazole and sodium poly-p-styrene sulfonate;
the mass ratio of the small molecular hydrogen bond donor to the block polymer molecular brush is (0.02-0.8) 1; the mass ratio of the carbon-forming matrix to the spherical structure is 1 (0.05-5).
2. The method of claim 1, wherein in the block polymer molecular brush, the hydrophilic unit comprises at least one of the following structural units:
、/>、/>wherein, is a linking site, n, m, p are independently selected from any integer within 10-200;
the hydrophobic unit comprises at least one of the following structural units:
、/>、/>、，
wherein a, b, c, d is a linking site independently selected from any integer within 10-200.
3. The method according to claim 2, wherein in the block polymer molecular brush, the number of hydrophilic units is x, x is any integer within 1 to 1000, and the number of hydrophobic units is y, y is any integer within 1 to 1000.
4. A method of preparation according to claim 3 wherein x is any integer within 30-500 and y is any integer within 30-500.
5. The method of preparing according to claim 2, wherein the block polymer molecular brush has a structure as shown in formula a:
，
a is a kind of
Wherein x is any integer within 1-1000, and y is any integer within 1-1000; r, R' are independently selected from at least one of the hydrophilic units and hydrophobic units;
and/or the molecular weight of the block polymer molecular brush is 15-500 ten thousand.
6. The method of claim 5, wherein x is any integer from 30 to 500 and y is any integer from 30 to 500.
7. The preparation method of claim 1, wherein the self-assembly of the block polymer molecular brush is performed in an organic solvent, and the self-assembly time is 1-48 h;
and/or the spherical structure comprises an inner layer which is a hydrophobic phase and an outer layer which is a hydrophilic phase.
8. The method according to claim 1, wherein the conditions of electrospinning 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 between the needle and the receiving plate is 15-40 cm, the temperature is 25-45 ℃, and the humidity is 10-60%;
and/or, the specific steps of the pre-oxidation treatment are as follows: heating to 200-400 ℃ at a speed of 1-10 ℃/min in an air atmosphere, and staying for 60-150 min for pre-oxidation treatment;
And/or, the carbonization treatment specifically comprises the following steps: heating to 600-1000 ℃ at a rate of 2-20 ℃ in an inert atmosphere, and staying for 60-240 min for carbonization treatment.
9. The preparation method according to claim 1, characterized in that it comprises in particular:
(1) Self-assembly of the block polymer molecular brush: the small molecular hydrogen bond donor induces the self-assembly of the block polymer molecular brush into a spherical structure;
(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 stock solution, and carrying out electrostatic spinning on the stock solution to obtain a polymer fiber membrane; and (3) performing pre-oxidation treatment and carbonization treatment on the polymer fiber membrane, and cooling to obtain the porous carbon nanofiber membrane material.
10. The process according to claim 9, 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;
and/or in the step (2), the spinning solution is uniformly stirred at the temperature of 40-80 ℃.
11. A porous carbon nanofiber membrane material, characterized in that the porous carbon nanofiber membrane material is prepared by the method of any one of claims 1-10.
12. The porous carbon nanofiber membrane material of claim 11 wherein the porous carbon nanofiber membrane material has a porous structure; the diameter of the fiber in the porous carbon nanofiber membrane material is 150-500 nm; the thickness of the porous carbon nanofiber membrane material is 20-200 mu m.
13. The porous carbon nanofiber membrane material according to claim 12, wherein the porous structure comprises micropores and/or mesopores, and the pore canal structure of the porous structure is ordered;
the specific surface area of the porous carbon nanofiber membrane material is 180-800 m 2 g -1 ；
The specific capacitance value of the porous carbon nanofiber membrane material is 90-300 Fg -1 。
14. Use of the porous carbon nanofiber membrane material of any one of claims 11-13 in an electrode.
15. An electrode comprising the porous carbon nanofiber membrane material of any one of claims 11-13.
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| CN110170304A (en) * | 2019-06-11 | 2019-08-27 | 东华大学 | A kind of preparation method of spongy porous carbon fiber film |
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