CN103882559B - High-ratio surface porous carbon fiber and preparation method thereof and application - Google Patents
High-ratio surface porous carbon fiber and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of high-ratio surface carbon fiber and preparation method thereof.The method, comprises the steps: the spinning solution be made up of pore creating material, macromolecule and organic solvent to carry out carbonization pickling after spinning, obtains described high-ratio surface carbon fiber.The method tool has the following advantages: a) preparation is simple, and output is high, and cost is low; B) porous carbon fiber with high-ratio surface can be prepared by the method; C) this carbon fiber has micropore and meso-hole structure simultaneously.
Description
Technical field
The present invention relates to a kind of carbon fiber and preparation method thereof and application, relate to a kind of high-ratio surface porous carbon fiber and preparation method thereof and application particularly.
Background technology
Carbon fiber is used as the filtration of large molecule absorption material, ultracapacitor, battery, catalyst carrier, gas or liquid and FED material etc. widely due to the structure of its uniqueness and characteristic.Method of electrostatic spinning is the very easy and efficient method of one preparing carbon fiber, and due to the extensive concern receiving everybody with low cost.But carbon fiber prepared by common method of electrostatic spinning is the carbon fiber of non-porous structure, and specific area is all lower, which greatly limits the application of carbon fiber.For this shortcoming, high-ratio surface porous carbon fiber and preparation thereof in recent years causes people and studies interest widely, becomes the focus of research and development.
Still following problem is there is: the poration process very complicated in described method, cost are high, and difficulty realizes suitability for industrialized production in high-ratio surface porous carbon fiber reported in current document and preparation method thereof; The porous carbon fiber that the problems referred to above strongly limit preparation is as the application in catalyst carrier, ultracapacitor and lithium ion battery etc.Therefore, develop a kind of performance more superior be applicable to have very important significance as the porous carbon fiber of the aspects such as catalyst carrier, ultracapacitor and lithium ion battery and preparation method simple, with low cost thereof.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, a kind of high-ratio surface porous carbon fiber be applicable to as aspects such as catalyst carrier, ultracapacitor, lithium ion battery and filter membranes of superior performance is provided.
Another object of the present invention is the preparation method simply efficient, with low cost providing a kind of above-mentioned high-ratio surface porous carbon fiber.
Another object of the present invention is to provide a kind of above-mentioned high-ratio surface porous carbon fiber as the application in catalyst carrier, ultracapacitor, lithium ion battery and filter membrane etc.
The present invention adopts following technical scheme:
A kind of high-ratio surface porous carbon fiber, its specific area is greater than 100m
2/ g, has micropore and meso-hole structure simultaneously, and the diameter of described carbon fiber is between 100nm-10 μm.
According to the present invention, preferably, its specific area is greater than 300m
2/ g; More preferably, its specific area is greater than 600m
2/ g, also more preferably, its specific area is greater than 800m
2/ g.
According to the present invention, the diameter of described carbon fiber is preferably between 100nm-1 μm.
According to the present invention, described high-ratio surface porous carbon fiber is prepared by the method comprised the steps: the spinning solution comprising pore creating material, macromolecule and organic solvent is carried out carbonization after spinning, obtain described high-ratio surface porous carbon fiber after overpickling drying; Wherein, described pore creating material is selected from potassium sulfide.
According to the present invention, described macromolecule is selected from least one in polyacrylonitrile, polyimides, pitch, polyvinyl alcohol, polyvinylpyrrolidone and phenolic resins.
According to the present invention, the number-average molecular weight of described polyacrylonitrile is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described polyimides is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described pitch and polyvinyl alcohol is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described polyvinylpyrrolidone is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described phenolic resins is 50w-300w, is preferably 150w.
The present invention also discloses following technical scheme:
Prepare a method for high-ratio surface porous carbon fiber, comprise the steps: the spinning solution comprising pore creating material, macromolecule and organic solvent to carry out carbonization after spinning, after overpickling drying, obtain described high-ratio surface porous carbon fiber; Wherein, described pore creating material is selected from potassium sulfide.
Different from the existing method preparing porous carbon fiber, the present invention adopts potassium sulfide as pore creating material in method, but not existing alkali activation method, steam activation method and pyrolytic copolymer port-creating method etc., preparation process is simply efficient and with low cost, and the porous carbon fiber of preparation has high-ratio surface and abundant micropore and meso-hole structure.
According to the present invention, the specific area of described high-ratio surface porous carbon fiber is greater than 100m
2/ g, has micropore and meso-hole structure simultaneously, and the diameter of described carbon fiber is between 100nm-10 μm.
According to the present invention, preferably, its specific area is greater than 300m
2/ g; More preferably, its specific area is greater than 600m
2/ g, also more preferably, its specific area is greater than 800m
2/ g.
According to the present invention, the diameter of described carbon fiber is preferably between 100nm-1 μm.
According to the present invention, the described macromolecule in said method is selected from least one in polyacrylonitrile, polyimides, pitch, polyvinyl alcohol, polyvinylpyrrolidone and phenolic resins.
According to the present invention, the number-average molecular weight of described polyacrylonitrile is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described polyimides is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described pitch and polyvinyl alcohol is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described polyvinylpyrrolidone is 50w-300w, is preferably 150w.
According to the present invention, the number-average molecular weight of described phenolic resins is 50w-300w, is preferably 150w.
According to the present invention, the described organic solvent in said method is selected from least one in DMF, 1-METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO).
According to the present invention, the mass percentage of described pore creating material in spinning solution is 1-10%, is specially 1% or 3% or 5% or 8%; The mass percentage of described macromolecule in spinning solution is 5-20%, is specially 8% or 10% or 15%.
According to the present invention, in described spinning process, spinning process is electrostatic spinning.Spinning process can make Polymer Solution stretch, solidify and fibration.
According to the present invention, in described electrostatic spinning, voltage is 10-35kV, is specially 25kV; The flow velocity of spinning solution is 0.5-5.0mL/h, is specially 1.5mL/h or 1mL/h; Temperature is 15-40 DEG C, is specially 15 DEG C or 30 DEG C or 15-30 DEG C; Collecting board is aluminium foil; Needle point is 5-50cm from the distance of aluminium foil, is specially 15cm.
According to the present invention, described carburising step comprises the high temperature cabonization in aerial pre-oxidation and inert atmosphere successively.
According to the present invention, in described pre-oxidation step, temperature is 180-280 DEG C, is specially 230 DEG C or 260 DEG C or 230-280 DEG C or 180-230 DEG C or 180-260 DEG C; Time is 1-4 hour, is specially 2 hours; Atmosphere is air atmosphere.
According to the present invention, in described high temperature cabonization step, described inert atmosphere is N
2or Ar atmosphere.
According to the present invention, in described high temperature cabonization step, described carburizing temperature is 600-1000 DEG C, is specially 600 DEG C or 900 DEG C or 1000 DEG C or 600-900 DEG C or 600-1000 DEG C or 900-1000 DEG C; Heating rate is 1-10 DEG C/min, is specially 4 DEG C/min; Carbonization time is 1-4 hour, is specially 2 hours.
In this process, when carburizing temperature is higher than 600 DEG C, potassium sulfide activated carbon fiber thus formed microcellular structure, at this moment formed high-ratio surface carbon fiber has micropore and meso-hole structure concurrently.
According to the present invention, in described acid pickling step, acid is selected from least one in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid and nitric acid; The concentration of described acid is 0.1-12M, is specially 2M; Time is 0.5-4 hour, is specially 2 hours.The object of pickling is the potassium sulfide in order to remove fibrous inside.
The high-ratio surface porous carbon fiber prepared according to the method described above, also belongs to protection scope of the present invention.
The present invention also discloses following technical scheme:
A kind of catalyst carrier, ultracapacitor, lithium ion battery or filter membrane, it comprises above-mentioned high-ratio surface porous carbon fiber.
The application of above-mentioned high-ratio surface porous carbon fiber, it is for as catalyst carrier, ultracapacitor, lithium ion battery or filter membrane etc.
The high-ratio surface porous carbon fiber provided due to the invention described above has high-ratio surface, and has micropore and meso-hole structure simultaneously, makes this high-ratio surface porous carbon fiber have good advantage for the mass transfer of ion.Thus, porous carbon fiber of the present invention is adapted at preparing the application in ultracapacitor, lithium ion battery, catalyst carrier or filter membrane.
Beneficial effect of the present invention is:
Carbon fiber of the present invention has very high specific area, has micropore and meso-hole structure concurrently simultaneously, is specially adapted to preparing the application in ultracapacitor, lithium ion battery, catalyst carrier or filter membrane.
Compared with existing high-ratio surface carbon fiber production method, method tool provided by the invention has the following advantages:
A) carbon fiber utilizing the method to prepare has very high specific area, and for having the porous carbon fiber of micropore and meso-hole structure concurrently simultaneously, at this moment the method for prior art cannot realize.
B) different from the existing method preparing porous carbon fiber, the present invention introduces potassium sulfide as pore creating material in method, but not existing alkali activation method, steam activation method and pyrolytic copolymer port-creating method etc., preparation process is simply efficient and with low cost, and the porous carbon fiber of preparation has high-ratio surface and abundant micropore and meso-hole structure.
Accompanying drawing explanation
Fig. 1 is high-ratio surface porous carbon fiber nitrogen adsorption desorption curve obtained by embodiment 1.
Fig. 2 is high-ratio surface porous carbon fiber TEM Electronic Speculum detection figure obtained by embodiment 1.
Fig. 3 is high-ratio surface porous carbon fiber nitrogen adsorption desorption curve obtained by embodiment 2.
Fig. 4 is high-ratio surface porous carbon fiber TEM Electronic Speculum detection figure obtained by embodiment 2.
Fig. 5 is high-ratio surface porous carbon fiber nitrogen adsorption desorption curve obtained by embodiment 3.
Fig. 6 is high-ratio surface porous carbon fiber TEM Electronic Speculum detection figure obtained by embodiment 3.
Detailed description of the invention
The present invention is elaborated further below by embodiment; but those skilled in the art understand; embodiments of the invention are not limiting the scope of the invention, and any improvement of making on basis of the present invention and change, all within protection scope of the present invention.
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
In following embodiment, adopt the structure of JEOLJEM-1011 type transmission electron microscope (TEM) characterizing porous carbon fiber.Employing QuantachromeAutosorb-1 type specific area and pore size distribution analyzer characterize the pore structure in porous carbon fiber, and adsorbed gas is N
2, degassing temperature is 200 DEG C.Electrostatic spinning uses DC high-voltage power supply SPL50P60Spellman, micro-injection pump KDS-200, StoeltingCo, injector for medical purpose, medical tack stainless pin head.
Embodiment 1
1) the pore creating material potassium sulfide of 0.5g is joined in 10g organic solvent DMF dissolve, add the macromolecule polypropylene nitrile that 1.0g number-average molecular weight is 150w, stir the thick solution that 1h forms mulberry at 80 DEG C, be spinning solution.
2) electrostatic spinning process is carried out on single spraying pipe electric spinning equipment, is made up of DC high-voltage power supply, single capillary spinning head, collecting board and ground wire, and wherein collecting board is aluminium foil, and electrospinning temperature is 15 DEG C.
Concrete preparation process is: transfer in 10mL injector for medical purpose by the above-mentioned mulberry precursor solution prepared, be expelled in spinning head with the flow velocity of 1.5mL/h, between spinning head and collecting board, apply that high voltage electric field makes spinning solution be stretched, refinement, form fiber after solidification and drop on aluminium foil collecting board.Operating voltage is 25kV, and needle point is 15cm from the distance of aluminium foil.
3) by step 2) the complete potassium sulfide-polyacrylonitrile fibre membrane collected of spinning 280 DEG C of pre-oxidation 2h under air atmosphere in tube furnace, subsequently air atmosphere is converted into argon gas atmosphere, 900 DEG C of carbonization 2h are risen to the programming rate of 4 DEG C/min, the carbon fiber of black is put in the hydrochloric acid solution of 2M to wash after being down to room temperature and wash away potassium sulfide in 0.5 hour, finally wash drying and obtain porous carbon fiber.
Fig. 1 is the nitrogen adsorption desorption curve of high-ratio surface carbon fiber, at relative pressure be less than 0.05 micro pores attract within the scope of have higher adsorbance, illustrate that this carbon fiber exists a large amount of microcellular structures.Meanwhile, in the scope that relative pressure is 0.42-0.9, there is hysteretic loop, this illustrates that high-ratio surface carbon fiber has micropore and meso-hole structure simultaneously.Nitrogen adsorption desorption shows that its specific area is 835.0m
2/ g.
Fig. 2 is the transmission electron microscope photo of this high-ratio surface carbon fiber, and carbon fiber diameter is threadiness between 100-130nm.
Embodiment 2
1) the pore creating material potassium sulfide of 0.5g is joined in 10g organic solvent DMF dissolve, add the macromolecule polypropylene nitrile that 1.0g number-average molecular weight is 150w, stir the thick solution that 1h forms mulberry at 80 DEG C, be spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning;
3) pre-oxidation, carbonization is carried out according to embodiment 1 step 3), only the temperature of carburising step is replaced with 1000 DEG C, the carbon-fiber film of black is put in the sulfuric acid solution of 2M to wash after being down to room temperature and wash away potassium sulfide in 1 hour, finally wash drying and obtain high-ratio surface carbon fiber.
Fig. 3 is the nitrogen adsorption desorption curve of this carbon fiber, at relative pressure be less than 0.05 micro pores attract within the scope of have higher adsorbance, illustrate that this carbon fiber exists a large amount of microcellular structures.Meanwhile, in the scope that relative pressure is 0.42-0.9, there is hysteretic loop, this illustrates that high-ratio surface carbon fiber has micropore and meso-hole structure simultaneously.Nitrogen adsorption desorption shows that its specific area is 614.8m
2/
g.
Fig. 4 is the transmission electron microscope photo of this carbon fiber, and carbon fiber diameter is threadiness between 100-130nm.
Embodiment 3
1) the pore creating material potassium sulfide of 0.3g is joined in 10g organic solvent DMF dissolve, add the macromolecule polypropylene nitrile that 1.0g number-average molecular weight is 150w, stir the thick solution that 1h forms mulberry at 80 DEG C, be spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning, only electrospinning temperature is replaced with 30 DEG C, flow velocity replaces with 1.0mL/h, and operating voltage replaces with 30kV;
3) carry out pre-oxidation, carbonization and pickling according to embodiment 1 step 3), only Pre oxidation is replaced with 230 DEG C, carburizing temperature replaces with 1000 DEG C.
Fig. 5 is the nitrogen adsorption desorption curve of this carbon fiber, at relative pressure be less than 0.05 micro pores attract within the scope of have higher adsorbance, illustrate that this carbon fiber exists a large amount of microcellular structures.Meanwhile, in the scope that relative pressure is 0.42-0.9, there is hysteretic loop, this illustrates that high-ratio surface carbon fiber has micropore and meso-hole structure simultaneously.Nitrogen adsorption desorption shows that its specific area is 325.6m
2/ g.
Fig. 6 is the transmission electron microscope photo of this carbon fiber, and carbon fiber diameter is threadiness between 100-130nm.
Embodiment 4
1) the pore creating material potassium sulfide of 0.1g is joined in 10g organic solvent DMF dissolve, add the macromolecule polypropylene nitrile that 1.0g number-average molecular weight is 150w, stir the thick solution that 1h forms mulberry at 80 DEG C, be spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning, only electrospinning temperature is replaced with 30 DEG C, operating voltage replaces with 30kV;
3) carry out pre-oxidation, carbonization and pickling according to embodiment 1 step 3), only Pre oxidation is replaced with 260 DEG C, carburizing temperature replaces with 800 DEG C.
With embodiment 1 acquired results without substantive difference.
Embodiment 5
1) the pore creating material potassium sulfide of 0.8g is joined in 10g organic solvent DMF dissolve, add the macromolecule polypropylene nitrile that 1.0g number-average molecular weight is 150w, stir the thick solution that 1h forms mulberry at 80 DEG C, be spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning, only electrospinning temperature is replaced with 30 DEG C, operating voltage replaces with 30kV;
3) carry out pre-oxidation, carbonization and pickling according to embodiment 1 step 3), only Pre oxidation is replaced with 260 DEG C.
With embodiment 1 acquired results without substantive difference.
Claims (31)
1. a high-ratio surface porous carbon fiber, is characterized in that, the specific area of described fiber is greater than 300m
2/ g, has micropore and meso-hole structure simultaneously, and the diameter of described carbon fiber is between 100nm-10 μm;
Described high-ratio surface porous carbon fiber is prepared by the method comprised the steps: the spinning solution comprising pore creating material, macromolecule and organic solvent is carried out carbonization after spinning, obtain described high-ratio surface porous carbon fiber after overpickling drying; Wherein, described pore creating material is selected from potassium sulfide.
2. high-ratio surface porous carbon fiber according to claim 1, is characterized in that, the specific area of described high-ratio surface porous carbon fiber is greater than 600m
2/ g.
3. high-ratio surface porous carbon fiber according to claim 1, is characterized in that, the specific area of described high-ratio surface porous carbon fiber is greater than 800m
2/ g.
4. the high-ratio surface porous carbon fiber according to any one of claim 1-3, is characterized in that, the diameter of described carbon fiber is between 100nm-1 μm.
5. high-ratio surface porous carbon fiber according to claim 1, is characterized in that, described macromolecule is selected from least one in polyacrylonitrile, polyimides, pitch, polyvinyl alcohol, polyvinylpyrrolidone and phenolic resins.
6. high-ratio surface porous carbon fiber according to claim 5, is characterized in that, the number-average molecular weight of described polyacrylonitrile is 50w-300w;
The number-average molecular weight of described polyimides is 50w-300w;
The number-average molecular weight of described pitch and polyvinyl alcohol is 50w-300w.
7. high-ratio surface porous carbon fiber according to claim 6, its feature exists, and the number-average molecular weight of described polyacrylonitrile is 150w;
The number-average molecular weight of described polyimides is 150w;
The number-average molecular weight of described pitch and polyvinyl alcohol is 150w;
The number-average molecular weight of described polyvinylpyrrolidone is 150w.
8. prepare the method for the high-ratio surface porous carbon fiber of claim 1 for one kind, it is characterized in that, it comprises the steps: the spinning solution comprising pore creating material, macromolecule and organic solvent to carry out carbonization after spinning, obtains described high-ratio surface porous carbon fiber after overpickling drying; Wherein, described pore creating material is selected from potassium sulfide;
The specific area of described high-ratio surface porous carbon fiber is greater than 300m
2/ g, has micropore and meso-hole structure simultaneously, and the diameter of described carbon fiber is between 100nm-10 μm.
9. method according to claim 8, is characterized in that, the specific area of described high-ratio surface porous carbon fiber is greater than 600m
2/ g.
10. method according to claim 9, is characterized in that, the specific area of described high-ratio surface porous carbon fiber is greater than 800m
2/ g.
11. methods according to Claim 8 described in-10 any one, it is characterized in that, the diameter of described carbon fiber is preferably between 100nm-1 μm.
12. methods according to claim 8, is characterized in that, described macromolecule is selected from least one in polyacrylonitrile, polyimides, pitch, polyvinyl alcohol, polyvinylpyrrolidone and phenolic resins.
13. methods according to claim 8, is characterized in that, the mass percentage of described pore creating material in spinning solution is 1-10%;
The mass percentage of described macromolecule in spinning solution is 5-20%.
14. methods according to claim 13, is characterized in that, the mass percentage of described pore creating material in spinning solution is 1% or 3% or 5% or 8%;
The mass percentage of described macromolecule in spinning solution is 8% or 10% or 15%.
15. methods according to claim 12, is characterized in that, the number-average molecular weight of described polyacrylonitrile is 50w-300w;
The number-average molecular weight of described polyimides is 50w-300w;
The number-average molecular weight of described pitch and polyvinyl alcohol is 50w-300w;
The number-average molecular weight of described polyvinylpyrrolidone is 50w-300w.
16. methods according to claim 15, is characterized in that, the number-average molecular weight of described polyacrylonitrile is 150w;
The number-average molecular weight of described polyimides is 150w;
The number-average molecular weight of described pitch and polyvinyl alcohol is 150w;
The number-average molecular weight of described polyvinylpyrrolidone is 150w.
17. methods according to claim 8, in described spinning process, spinning process is electrostatic spinning.
18. methods according to claim 17, is characterized in that, in described electrostatic spinning, voltage is 10-35kV; The flow velocity of spinning solution is 0.5-5.0mL/h; Temperature is 15-40 DEG C; Collecting board is aluminium foil; Needle point is 5-50cm from the distance of aluminium foil.
19. methods according to claim 18, is characterized in that, in described electrostatic spinning, voltage is 25kV; The flow velocity of spinning solution is 1.5mL/h or 1mL/h; Temperature is 15-30 DEG C; Needle point is 15cm from the distance of aluminium foil.
20. methods according to claim 8, described carburising step comprises the high temperature cabonization in aerial pre-oxidation and inert atmosphere successively.
21. methods according to claim 20, is characterized in that, in described pre-oxidation step, temperature is 180-280 DEG C; Time is 1-4 hour; Atmosphere is air atmosphere.
22. methods according to claim 21, is characterized in that, in described pre-oxidation step, temperature is 230-280 DEG C; Time is 2 hours.
23. methods according to claim 21, is characterized in that, in described pre-oxidation step, temperature is 180-230 DEG C; Time is 2 hours.
24. methods according to claim 21, is characterized in that, in described pre-oxidation step, temperature is 180-260 DEG C; Time is 2 hours.
25. methods according to claim 20, is characterized in that, in described high temperature cabonization step, described inert atmosphere is N
2or Ar atmosphere; Described carburizing temperature is 600-1000 DEG C; Heating rate is 1-10 DEG C/min; Carbonization time is 1-4 hour.
26. methods according to claim 25, is characterized in that, in described high temperature cabonization step, described carburizing temperature is 600-900 DEG C; Heating rate is 4 DEG C/min; Carbonization time is 2 hours.
27. methods according to claim 25, is characterized in that, in described high temperature cabonization step, described carburizing temperature is 900-1000 DEG C; Heating rate is 4 DEG C/min; Carbonization time is 2 hours.
28. methods according to claim 8, is characterized in that, in described acid pickling step, acid is selected from least one in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid and nitric acid; The concentration of described acid is 0.1-12M; Time is 0.5-4 hour.
29. methods according to claim 28, is characterized in that, in described acid pickling step, the concentration of described acid is 2M; Time is 2 hours.
30. 1 kinds of catalyst carriers, ultracapacitor, lithium ion battery or filter membranes, it comprises the high-ratio surface porous carbon fiber that according to any one of high-ratio surface porous carbon fiber according to any one of claim 1 to 7 or claim 8 to 29, method prepares.
The application of the high-ratio surface porous carbon fiber that method prepares according to any one of high-ratio surface porous carbon fiber according to any one of 31. claims 1 to 7 or claim 8 to 29, it is for as catalyst carrier, ultracapacitor, lithium ion battery or filter membrane.
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