CN113470990B - Preparation method of high-flexibility integral nano carbon fiber membrane - Google Patents
Preparation method of high-flexibility integral nano carbon fiber membrane Download PDFInfo
- Publication number
- CN113470990B CN113470990B CN202110756616.1A CN202110756616A CN113470990B CN 113470990 B CN113470990 B CN 113470990B CN 202110756616 A CN202110756616 A CN 202110756616A CN 113470990 B CN113470990 B CN 113470990B
- Authority
- CN
- China
- Prior art keywords
- temperature
- electrostatic spinning
- coke
- nanofiber membrane
- flexibility
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 110
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 47
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 35
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000009987 spinning Methods 0.000 claims abstract description 50
- 238000003763 carbonization Methods 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000571 coke Substances 0.000 claims abstract description 18
- 239000002006 petroleum coke Substances 0.000 claims description 95
- 239000002121 nanofiber Substances 0.000 claims description 62
- 102000020897 Formins Human genes 0.000 claims description 33
- 108091022623 Formins Proteins 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 239000012298 atmosphere Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000011335 coal coke Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 3
- 230000003111 delayed effect Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000002010 green coke Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 abstract description 29
- 229920002239 polyacrylonitrile Polymers 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 28
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 28
- 239000007772 electrode material Substances 0.000 description 21
- 239000002243 precursor Substances 0.000 description 14
- 239000003245 coal Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000005452 bending Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011311 coal-based needle coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention provides a preparation method of a high-flexibility integral nano carbon fiber membrane, which comprises the following steps: the coke powder is treated by the mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in a refluxing way, and is washed and dried to obtain coke oxide powder, and the high-flexibility integral type carbon nanofiber membrane is prepared by electrostatic spinning, preoxidation and carbonization by taking the coke oxide powder as a raw material and PVB and/or PVP as a spinning aid and a pore-forming agent. The carbon nanofiber membrane prepared by the method has the characteristics of high flexibility, integral type, adjustable specific surface area, high conductivity and the like. The invention uses cheap and easily obtained coke as a carbon source to produce the flexible carbon nanofiber membrane, thereby realizing high-value utilization of the coke. Compared with the method for preparing the carbon nanofiber membrane by polyacrylonitrile electrostatic spinning, the method has the advantages of cheap and easily-obtained raw materials, good product flexibility, high specific surface area and the like. The high-flexibility integral nano carbon fiber membrane prepared by the method can be widely applied to the fields of electrochemical energy storage, adsorption separation, catalysis and the like.
Description
The technical field is as follows:
the invention belongs to the technical field of nano carbon materials, and particularly relates to a preparation method of a high-flexibility integral nano carbon fiber membrane.
Background art:
with the development of science and technology and society, flexible electronic products, such as flexible displays, smart clothes, electronic skins, implantable medical devices, etc., have begun to be widely used in production and life. In order to provide energy to these devices, it is necessary to develop energy storage devices that are also flexible. In order to adapt to the use scenario of the flexible electronic device, the flexible energy storage device still can ensure the continuous and stable energy supply to the electronic product under the extreme conditions of mechanical deformation, even dynamic deformation and the like caused by the action of external force, and simultaneously has basic performances of high safety and reliability, high power density and energy density, long cycle life and the like. As one of flexible energy storage devices, the flexible super capacitor has the advantages of good mechanical flexibility, high power density, long cycle life, high safety, diversified electrode materials and device structures and the like, and has huge application prospect in small-sized flexible electronic products. However, the flexible supercapacitor itself has low energy density and high preparation cost, which limits its large-scale popularization and use. The electrochemical performance of the flexible supercapacitor is mainly determined by the flexible electrode, and therefore, it is important to design and develop a flexible electrode with high performance and low cost.
Since the carbon nanofiber material has the characteristics of excellent flexibility, large specific surface area, good conductivity and the like, the carbon nanofiber material is considered to be one of the materials most suitable for preparing flexible electrodes. At present, the flexible carbon nanofiber electrode material is prepared by mainly using polyacrylonitrile as a precursor and obtaining the flexible carbon nanofiber membrane through processes of electrostatic spinning, pre-oxidation, carbonization and the like. However, because the polyacrylonitrile raw material has high cost and poor flexibility, the application of the carbon nanofibers in the flexible electrode is limited to a certain extent.
Petroleum coke is a byproduct generated in the crude oil refining process and mainly comprises polycyclic aromatic hydrocarbon, long-chain fat polycondensate, a small amount of low-molecular organic matters and a trace amount of inorganic matters. With the increase of crude oil production and the heavy crude oil production worldwide, the petroleum coke production is increased sharply, and how to make use of petroleum coke effectively becomes a problem which needs to be solved urgently.
Coal is a solid combustible mineral formed gradually by ancient plants buried underground and undergoing complex biochemical and physicochemical changes, is a natural carbon material and contains 60-90% of carbon. The main utilization form of coal resources at present is to directly burn the coal resources for power generation, and the economic benefit is low. The high-performance carbon material prepared by taking coal as a raw material has the advantages of wide raw material source, low price, high product added value and the like, and is a new way for efficiently utilizing coal resources.
The invention content is as follows:
the invention provides a method for preparing a flexible carbon nanofiber membrane electrode material by taking coke as a precursor, aiming at solving the problems of high raw material cost, poor flexibility, poor conductivity, value-added utilization of coke and the like of the conventional flexible carbon nanofiber membrane electrode material. The raw materials are cheap and easy to obtain, and the prepared flexible carbon nanofiber membrane has the advantages of excellent flexibility, large specific surface area, good conductivity and the like.
The technical scheme of the invention is as follows:
a preparation method of a high-flexibility integral nano carbon fiber film comprises the following steps:
(1) crushing coke, and screening to obtain coke powder;
(2) refluxing the coke powder with mixed acid solution (mixed acid) of concentrated sulfuric acid and concentrated nitric acid in water bath;
(3) washing the coke powder treated by the mixed acid to be neutral, and drying to obtain oxidized coke powder;
(4) dissolving the oxidized coke powder and the spinning aid in a solvent to obtain an electrostatic spinning solution; the spinning aid is at least one of polyvinyl butyral (PVB) and polyvinylpyrrolidone (PVP);
(5) preparing the prepared electrostatic spinning solution into a coke-based nanofiber membrane by an electrostatic spinning technology;
(6) and carrying out preoxidation and carbonization processes on the coke-based nanofiber membrane to obtain the flexible coke-based nanofiber membrane.
The coke in the step (1) is at least one of coal and petroleum coke green coke obtained after delayed coking.
The volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step (2) is 2-4, the water bath temperature during reflux treatment is 70-90 ℃, and the treatment time is 1-5 h; as a further preferable scheme, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 3, the water bath temperature in the reflux treatment is 80 ℃, and the treatment time is 4 hours.
And (4) the spinning aid in the step (4) is PVP.
The solvent in the step (4) is N, N-Dimethylformamide (DMF).
In the electrostatic spinning solution in the step (4), the mass fraction of the oxidized coke powder is 3.5-13%, and the mass fraction of the spinning aid is 4-12%. More preferably, the mass fraction of the oxidized coke powder is 9.1%, and the mass fraction of the spinning aid is 4.6%.
The electrostatic spinning parameters in the step (5) are as follows: the electrostatic spinning voltage is 12-25KV, the liquid inlet speed is 0.3-1.5ml/h, and the distance between the needle and the collector is 12-20 cm. As a further preferable scheme, the electrostatic spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle and a collector is 18 cm.
In the step (5), the spinning environment temperature is 15-40 ℃, and the spinning environment humidity is 1-40%.
The pre-oxidation heating rate in the step (6) is 1-5 ℃ for min -1 The pre-oxidation temperature is 250-350 ℃, and the protective atmosphere is air. As a further preferred scheme, the pre-oxidation heating rate is 2 ℃ min -1 The pre-oxidation temperature is 300 ℃.
The carbonization heating rate in the step (6) is 1-5 ℃ for min -1 The carbonization temperature is 800-1400 ℃, and the protective atmosphere is argon or nitrogen. As a further preferred scheme, the carbonization temperature rise rate is 3 ℃ for min -1 The carbonization temperature is 1200 ℃, and the protective atmosphere is argon.
The pre-oxidation time in the step (6) is 1-4 h; the carbonization time is 1-4 h.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, cheap and easily available coke is used as a carbon source, PVB and/or PVP is used as a spinning aid and a pore-forming agent, and the flexible carbon nanofiber membrane is produced under the synergistic effect, can withstand bending at 180 degrees, and realizes high value-added utilization of the coke.
2. The high-flexibility integral carbon nanofiber membrane prepared by the method solves the problems of poor flexibility, low specific surface area, poor conductivity and the like of the polyacrylonitrile-based carbon nanofiber membrane.
3. The high-flexibility integrated carbon nanofiber membrane prepared by the method can be directly used as a flexible supercapacitor electrode material, and a current collector, a conductive agent and a binder are not needed.
4. The high-flexibility integral nano carbon fiber membrane prepared by the invention contains a large number of micropores, has the characteristic of high specific capacitance when being used as a flexible super capacitor electrode material, and has the current density of 0.5Ag -1 Then, its specific capacitance value is 189.8F g -1 (ii) a Has wide application prospect in the fields of electrochemical energy storage, adsorption separation, catalysis and the like.
Description of the drawings:
fig. 1 is an optical photograph of the highly flexible integrated filamentous nanocarbon membrane obtained in example 5 in a bent state.
FIG. 2 is a scanning electron microscope picture of the highly flexible monolithic carbon nanofiber membrane obtained in example 5.
Fig. 3 is a nitrogen adsorption and desorption isotherm of the highly flexible integrated filamentous nanocarbon membrane obtained in example 5.
FIG. 4 shows that the high-flexibility integrated carbon nanofiber membrane obtained in example 5 is directly used as an electrode material of a supercapacitor in an electrolyte solution of 6mol L -1 Cyclic voltammograms at different scan rates in a three electrode system of KOH.
FIG. 5 shows that the high-flexibility integrated carbon nanofiber membrane obtained in example 5 is directly used as an electrode material of a supercapacitor in an electrolyte solution of 6mol L -1 Constant current charge and discharge curve in three electrode system of KOH.
FIG. 6 shows that the high-flexibility integrated nano carbon fiber film obtained in example 5 is directly used as an electrode material of a supercapacitor in an electrolyte solution of 6mol L -1 Specific capacitance-current density change in the three-electrode system of KOH.
Fig. 7 is an optical photograph of the petroleum coke/PAN composite filamentous nanocarbon film obtained in comparative example 1 after being bent.
Fig. 8 is an optical photograph of the PAN-based filamentous nanocarbon film obtained in comparative example 2 after being bent.
The specific implementation mode is as follows:
the technical solution of the present invention will be further described with reference to specific examples, but the present invention is not limited to these examples.
Example 1
According to the preparation method of the high-flexibility integral nano carbon fiber membrane, delayed coking petroleum coke is used as a raw material, and the preparation method sequentially comprises the following steps:
(1) and crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 0.5g of the oxidized petroleum coke powder obtained in the step (3) and 1.0g of the spinning assistant polyvinylpyrrolidone in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 4.6%, the mass fraction of the spinning assistant polyvinylpyrrolidone is 9.1%, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 15KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to room temperature, so that the high-flexibility integral nano carbon fiber membrane can withstand bending at 180 degrees.
And (4) using the high-flexibility integrated nano carbon fiber film obtained in the step (7) as a flexible supercapacitor electrode material without a current collector, a conductive agent and a binder. At 6 mol/l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Its specific capacitance value is 166.5F g -1 。
Example 2
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 0.8g of the oxidized petroleum coke powder obtained in the step (3) and 0.7g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 7.3 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 6.4 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 15KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to room temperature, so that the high-flexibility integral nano carbon fiber membrane can withstand bending at 180 degrees.
And (4) using the high-flexibility integrated nano carbon fiber film obtained in the step (7) as a flexible supercapacitor electrode material without a current collector, a conductive agent and a binder. At 6 mol/l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Then, its specific capacitance value is 189.8F g -1 。
Example 3
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (4) dissolving 1.0g of the oxidized petroleum coke powder obtained in the step (3) and 0.5g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 9.1 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 4.6 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane can withstand bending at 180 degrees.
(7) Placing the pre-oxidized nanofiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the argon atmosphere -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the high-flexibility integral nano carbon fiber membrane is obtained.
And (4) using the high-flexibility integrated carbon nanofiber membrane obtained in the step (7) as an electrode material of a super capacitor without a current collector, a conductive agent and a binder. At 6 mol/l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and current densityIs 0.5Ag -1 Then, its specific capacitance value is 186.6F g -1 。
Example 4
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) And (2) adding 4g of the petroleum coke powder obtained in the step (1) into mixed acid with the volume ratio of concentrated sulfuric acid to concentrated nitric acid being 3:1, and treating for 2h under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 1.0g of the oxidized petroleum coke powder obtained in the step (3) and 0.5g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 9.1 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 4.6 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 1000 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the high-flexibility integral nano carbon fiber membrane can be obtained and can withstand bending of 180 degrees.
Directly using the high-flexibility integrated nano carbon fiber film obtained in the step (7) as a super capacitor electrode material without a current collector, a conductive agent and a binder, wherein the total volume of the high-flexibility integrated nano carbon fiber film is 6mol l -1 With KOH as the electrolyteElectrochemical performance test is carried out in a three-electrode system, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 When it is used, its specific capacitance value is 183.1F g -1 。
Example 5
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) And (2) adding 4g of the petroleum coke powder obtained in the step (1) into mixed acid with the volume ratio of concentrated sulfuric acid to concentrated nitric acid being 3:1, and treating for 2h under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 1.0g of the oxidized petroleum coke powder obtained in the step (3) and 0.5g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely that the mass fraction of the oxidized petroleum coke is 9.1 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 4.6 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 1200 ℃ at the temperature raising rate, and the temperature is kept for 2 hours at the temperature for 2 min -1 The temperature is reduced to 1000 ℃ at the cooling rate, and then the temperature is naturally reduced to room temperature, so that the high-flexibility integral nano carbon fiber membrane is obtained.
The synthesized integrated carbon nanofiber membrane has excellent flexibility and can withstand 180-degree bending, as shown in figure 1.
Fig. 2 is a scanning electron microscope picture of the high-flexibility monolithic carbon nanofiber membrane synthesized in the present embodiment.
FIG. 3 is the nitrogen adsorption and desorption isotherm of the highly flexible integrated nano-carbon fiber membrane synthesized in this example, which has a BET specific surface area of 677m 2 g -1 。
Directly using the high-flexibility integrated nano carbon fiber film obtained in the step (7) as a flexible supercapacitor electrode material without a current collector, a conductive agent and a binder, wherein the total volume of the high-flexibility integrated nano carbon fiber film is 6mol l -1 The KOH of the test piece is used as electrolyte, and electrochemical performance test is carried out in a three-electrode system. Fig. 4 is a cyclic voltammetry curve of the high-flexibility integrated carbon nanofiber membrane synthesized in the embodiment directly used as a supercapacitor electrode material at different scanning speeds. Fig. 5 is a constant current charge and discharge curve of the high-flexibility monolithic carbon nanofiber membrane synthesized in the present embodiment as an electrode material. Fig. 6 shows the specific capacitance-current density variation of the highly flexible integrated carbon nanofiber membrane synthesized by the present embodiment as an electrode material.
The test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Then, its specific capacitance value is 184.1F g -1 。
Example 6
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) And (2) adding 4g of petroleum coke powder obtained in the step (1) into mixed acid with the volume ratio of concentrated sulfuric acid to concentrated nitric acid being 3:1, and treating for 2h under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 1.0g of the oxidized petroleum coke powder obtained in the step (3) and 0.5g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 9.1 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 4.6 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is increased to 1400 ℃ at the temperature increasing rate, and the temperature is kept for 2 hours at the temperature for 2 min -1 The temperature is reduced to 1000 ℃ at the cooling rate, and then the temperature is naturally reduced to room temperature, so that the high-flexibility integral nano carbon fiber which can withstand 180-degree bent films is obtained.
(8) Directly using the high-flexibility integral nano carbon fiber film obtained in the step (7) as a super capacitor electrode material without a current collector, a conductive agent and a binder, wherein the total volume of the high-flexibility integral nano carbon fiber film is 6mol l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Then, its specific capacitance value is 130.1F g -1 。
Example 7
(1) And crushing the petroleum coke by using a crusher, and screening by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 0.8g of the oxidized petroleum coke powder obtained in the step (3) and 0.7g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 7.3 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 6.4 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (5) performing electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle and a collector is 18cm to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 1200 ℃ at the temperature raising rate, and the temperature is kept for 2 hours at the temperature for 2 min -1 The temperature is reduced to 1000 ℃ at the cooling rate, and then the temperature is naturally reduced to room temperature, so that the high-flexibility integral nano carbon fiber membrane can withstand bending of 180 degrees.
(8) Directly using the high-flexibility integral nano carbon fiber film obtained in the step (7) as a flexible supercapacitor electrode material without a current collector, a conductive agent and a binder, wherein the total volume of the high-flexibility integral nano carbon fiber film is 6mol l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Its specific capacitance value is 179.5F g -1 。
Example 8
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 0.4g of the oxidized petroleum coke powder obtained in the step (3) and 1.35g of the spinning assistant polyvinylpyrrolidone in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 3.5%, the mass fraction of the spinning assistant polyvinylpyrrolidone is 12%, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 15KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane can withstand bending at 180 degrees.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the high-flexibility integral nano carbon fiber membrane is obtained.
And (4) using the high-flexibility integrated nano carbon fiber film obtained in the step (7) as a flexible supercapacitor electrode material without a current collector, a conductive agent and a binder. At 6 mol/l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Then, its specific capacitance value is 150.5F g -1 。
Example 9
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 1.5g of the oxidized petroleum coke powder obtained in the step (3) and 0.45g of the spinning assistant polyvinylpyrrolidone in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 13 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 4 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 15KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane can withstand bending at 180 degrees.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the high-flexibility integral nano carbon fiber membrane is obtained.
And (4) using the high-flexibility integral nano carbon fiber film obtained in the step (7) as a flexible supercapacitor electrode material without a current collector, a conductive agent and a binder. At 6 mol/l -1 The electrochemical performance test is carried out in a three-electrode system with KOH as electrolyte, and the test result shows that the material has good electrochemical performance and the current density is 0.5Ag -1 Then, its specific capacitance value is 162F g -1 。
Example 10
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) Adding 4g of petroleum coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1, treating for 2h under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 0.7g of the oxidized petroleum coke powder obtained in the step (3) and 0.8g of a spinning assistant polyvinyl butyral (PVB) in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 6.4%, the mass fraction of the spinning assistant polyvinyl butyral is 7.3%, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 15KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to room temperature, so that the high-flexibility integral nano carbon fiber membrane can withstand bending at 180 degrees.
Example 11
(1) And crushing the coal-based needle coke by using a crusher, and screening by using a 200-mesh sieve to obtain coal-based coke powder.
(2) Adding 4g of the coal-based coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, treating for 2h under the condition of water bath reflux at the temperature of 80 ℃.
(3) And (3) washing the coal-based coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain the coal-based coke powder.
(4) And (4) dissolving 0.8g of the coal-based coke powder obtained in the step (3) and 0.7g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 7.3 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 6.4 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the high-flexibility integral nano carbon fiber membrane is obtained.
Example 12
(1) And crushing the coal by using a crusher, and screening by using a 200-mesh sieve to obtain the coal coke powder.
(2) Adding 4g of the coal coke powder obtained in the step (1) into concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, treating for 2 hours under the condition of water bath reflux at the temperature of 80 ℃.
(3) And (3) washing the coal-based coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain the coal-based coke powder.
(4) And (3) dissolving 0.8g of the coal coke powder obtained in the step (3) and 0.7g of polyvinylpyrrolidone spinning aid in 10ml of N, N-dimethylformamide to obtain an electrostatic spinning solution. Namely, the mass fraction of the oxidized petroleum coke is 7.3 percent, the mass fraction of the spinning assistant polyvinylpyrrolidone is 6.4 percent, and an electrostatic spinning precursor solution is prepared.
(5) And (3) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(7) Placing the pre-oxidized nano fiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to room temperature, so that the high-flexibility integral nano carbon fiber membrane can withstand bending at 180 degrees.
Comparative example 1 (not according to the invention)
(1) And crushing the petroleum coke by using a crusher, and screening the crushed petroleum coke by using a 200-mesh sieve to obtain petroleum coke powder.
(2) And (2) adding 4g of the petroleum coke powder obtained in the step (1) into mixed acid with the volume ratio of concentrated sulfuric acid to concentrated nitric acid being 3:1, and treating for 2h under the condition of water bath reflux at the temperature of 80 ℃.
(3) Washing the petroleum coke powder treated by the mixed acid liquor obtained in the step (2) to be neutral, and drying to obtain oxidized petroleum coke powder.
(4) And (3) dissolving 1.0g of the oxidized petroleum coke powder obtained in the step (3) and 0.5g of Polyacrylonitrile (PAN) in 10ml of DMF to prepare an electrostatic spinning solution.
(5) And (5) performing electrostatic spinning on the electrostatic spinning solution obtained in the step (4) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle and a collector is 18cm to obtain the nanofiber membrane.
(6) Putting the electrostatic spinning nanofiber membrane obtained in the step (5) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is increased to 300 ℃ at the temperature increasing rate,and keeping the temperature for 2 hours, and then naturally cooling to room temperature to obtain the pre-oxidized nanofiber membrane.
(7) Placing the pre-oxidized nanofiber membrane obtained in the step (6) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the integral carbon nanofiber membrane is obtained.
The synthesized integrated carbon nanofiber membrane has poor flexibility, and brittle fracture occurs after the membrane is bent by 60 degrees, as shown in figure 7.
Comparative example 2 (not according to the invention)
(1) 1.0g of Polyacrylonitrile (PAN) and 0.5g of polyvinylpyrrolidone (PVP) were dissolved in 10ml of DMF to prepare an electrospinning solution.
(2) And (2) carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step (1) under the conditions that the temperature is 25 ℃, the humidity is 20%, the spinning voltage is 18KV, the liquid inlet speed is 1ml/h, and the distance between a needle head and a collector is 18cm, so as to obtain the nanofiber membrane.
(3) Putting the electrostatic spinning nanofiber membrane obtained in the step (2) into a muffle furnace, and performing air atmosphere at the temperature of 2 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the pre-oxidized nanofiber membrane is obtained.
(4) Placing the pre-oxidized nanofiber membrane obtained in the step (3) into a tubular carbonization furnace, and performing carbonization at 3 ℃ for min in the atmosphere of argon -1 The temperature is raised to 800 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally lowered to the room temperature, so that the integral carbon nanofiber membrane is obtained.
The synthesized integrated carbon nanofiber membrane has poor flexibility, and brittle fracture occurs after the membrane is bent by 60 degrees, as shown in figure 8.
The invention has been described in detail in order to enable those skilled in the art to make and use the invention, and it is not intended to limit the scope of the invention.
Claims (8)
1. A preparation method of a high-flexibility integral nano carbon fiber film is characterized by comprising the following steps: the method comprises the following steps:
(1) crushing coke, and screening to obtain coke powder;
(2) refluxing the coke powder with mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in water bath;
(3) washing the coke powder treated by the mixed acid solution to be neutral, and drying to obtain oxidized coke powder;
(4) dissolving the oxidized coke powder and the spinning aid in a solvent to obtain an electrostatic spinning solution; the spinning aid is at least one of PVB and polyPVP;
(5) preparing the prepared electrostatic spinning solution into a coke-based nanofiber membrane by an electrostatic spinning technology;
(6) and carrying out preoxidation and carbonization processes on the coke-based nanofiber membrane to obtain the flexible coke-based nanofiber membrane.
2. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: the coke in the step (1) is at least one of coal and petroleum coke green coke obtained after delayed coking.
3. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed acid in the step (2) is 2-4, the water bath temperature during reflux treatment is 70-90 ℃, and the treatment time is 1-5 h.
4. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: the solvent in the step (4) is DMF.
5. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: in the electrostatic spinning solution in the step (4), the mass fraction of the oxidized coke powder is 3.5-13%, and the mass fraction of the spinning aid is 4-12%.
6. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: the electrostatic spinning parameters in the step (5) are as follows: the electrostatic spinning voltage is 12-25KV, the liquid inlet speed is 0.3-1.5ml/h, and the distance between the needle and the collector is 12-20 cm.
7. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: the pre-oxidation heating rate in the step (6) is 1-5 ℃ for min -1 The pre-oxidation temperature is 250-350 ℃, and the protective atmosphere is air.
8. The method for preparing a highly flexible integrated filamentous nanocarbon film according to claim 1, wherein: the carbonization heating rate in the step (6) is 1-5 ℃ for min -1 The carbonization temperature is 800-1400 ℃, and the protective atmosphere is argon or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110756616.1A CN113470990B (en) | 2021-07-05 | 2021-07-05 | Preparation method of high-flexibility integral nano carbon fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110756616.1A CN113470990B (en) | 2021-07-05 | 2021-07-05 | Preparation method of high-flexibility integral nano carbon fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113470990A CN113470990A (en) | 2021-10-01 |
| CN113470990B true CN113470990B (en) | 2022-08-16 |
Family
ID=77878096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110756616.1A Active CN113470990B (en) | 2021-07-05 | 2021-07-05 | Preparation method of high-flexibility integral nano carbon fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113470990B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951218A (en) * | 2016-04-21 | 2016-09-21 | 天津工业大学 | Preparation of nano-carbon fiber with high specific surface area |
| CN106958053A (en) * | 2017-04-24 | 2017-07-18 | 中国石油大学(华东) | A kind of preparation method of porous petroleum coke base carbon fibre |
| CN111549449A (en) * | 2020-04-30 | 2020-08-18 | 西安工程大学 | Preparation method of lignin-based flexible carbon nanofiber self-supporting electrode material |
-
2021
- 2021-07-05 CN CN202110756616.1A patent/CN113470990B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951218A (en) * | 2016-04-21 | 2016-09-21 | 天津工业大学 | Preparation of nano-carbon fiber with high specific surface area |
| CN106958053A (en) * | 2017-04-24 | 2017-07-18 | 中国石油大学(华东) | A kind of preparation method of porous petroleum coke base carbon fibre |
| CN111549449A (en) * | 2020-04-30 | 2020-08-18 | 西安工程大学 | Preparation method of lignin-based flexible carbon nanofiber self-supporting electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 煤基碳纳米纤维复合材料的制备及其在超级电容器中的应用;宋贤丽;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20170215(第2017/02期);第21-25页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113470990A (en) | 2021-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108103616B (en) | Preparation method of nitrogen-doped lignin-based carbon fiber composite material | |
| CN102087921B (en) | Self-supporting super capacitor electrode material and preparation method thereof | |
| CN108841174B (en) | Preparation method and application of nitrogen-doped porous activated carbon/MnS composite nanofiber | |
| CN111118883B (en) | Cellulose-based carbon nanofiber composite material and preparation and application thereof | |
| CN111197187A (en) | Preparation method of biomass-based carbon nanofiber | |
| CN105761950B (en) | A kind of preparation method of porous rich nitrogen carbon fiber electrode | |
| CN108091497A (en) | A kind of preparation method of multidimensional structure carbon fiber flexible electrode | |
| CN106784856A (en) | A kind of carbon nano-fiber/metal foil double-layer composite material and preparation method thereof | |
| CN112593313B (en) | Preparation method and application of nitrogen and phosphorus doped porous hollow carbon nanofiber | |
| CN105734724A (en) | Novel method for preparing carbon nanofibers through electrospinning | |
| CN109755033A (en) | A kind of carbon fiber loaded cobalt/cobalt oxide composite material and preparation method and application | |
| CN108039285A (en) | A kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible | |
| CN109467082B (en) | Preparation method of graphitized porous corncob derived carbon electrode material | |
| CN109935472B (en) | Multi-morphology Fe-Mn composite carbon nanofiber and preparation and application thereof | |
| CN113200544B (en) | Preparation method of biomass charcoal-based supercapacitor electrode material | |
| CN113470990B (en) | Preparation method of high-flexibility integral nano carbon fiber membrane | |
| CN109741970B (en) | Preparation method of lignin modified active carbon high-performance energy storage material | |
| CN116487196A (en) | Self-supporting porous flexible fiber membrane for supercapacitor electrode material, and preparation method and application thereof | |
| CN115595691A (en) | Lignocellulose-based carbon fiber with excellent electrochemical performance and preparation method and application thereof | |
| CN110648853A (en) | Self-supporting electrode material with sandwich structure and preparation method thereof | |
| CN112233911B (en) | Vanadium dioxide nano carbon fiber composite material and preparation method and application thereof | |
| CN112142051B (en) | Method for removing active functional groups on surface of capacitance carbon by chemical covering method | |
| CN110060874B (en) | Preparation method of flexible supercapacitor electrode | |
| CN113363083B (en) | Carbon nanofiber composite material with three-dimensional hierarchical structure and preparation method thereof | |
| CN112820548B (en) | High-performance cellulose solution gel nano carbon material and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |