CN103882559A - High-specific surface porous carbon fiber, preparation method and application of carbon fiber - Google Patents
High-specific surface porous carbon fiber, preparation method and application of carbon fiber Download PDFInfo
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Abstract
The invention discloses a high-specific surface porous carbon fiber and a preparation method of the carbon fiber. The method comprises the following steps: spinning through a spinning solution consisting of a pore forming substance, a high polymer and an organic solvent, carbonizing, and carrying out pickling to obtain the high-specific surface carbon fiber. The method has the following advantages that (a) the porous carbon fiber is simple to prepare, high in yield and low in cost; (b) the porous carbon fiber with high specific surface can be prepared through the method; (c) the carbon fiber simultaneously has micro-porous and mesoporous structures.
Description
Technical field
The present invention relates to a kind of carbon fiber and preparation method thereof and application, relate to particularly a kind of high-ratio surface porous carbon fiber and preparation method thereof and application.
Background technology
Carbon fiber is because its unique structure and characteristic are used as filtration and the FED material etc. of large molecule absorption material, ultracapacitor, battery, catalyst carrier, gas or liquid widely.Method of electrostatic spinning is the very easy and efficient method of one of preparing carbon fiber, and due to the extensive concern that has been subject to 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, and this has limited the application of carbon fiber greatly.For this shortcoming, high-ratio surface porous carbon fiber and preparation thereof in recent years caused that people study interest widely, become the focus of research and development.
In high-ratio surface porous carbon fiber of reporting in document at present and preparation method thereof, still there is following problem: the pore-creating process very complicated in described method, cost are high, and difficulty realizes suitability for industrialized production; The problems referred to above have greatly limited the porous carbon fiber of preparation in the application as aspects such as catalyst carrier, ultracapacitor and lithium ion batteries.Therefore, developing more superior being applicable to of a kind of performance has 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 overcome the defect of above-mentioned prior art, a kind of high-ratio surface porous carbon fiber as aspects such as catalyst carrier, ultracapacitor, lithium ion battery and filter membranes that is applicable to of superior performance is provided.
Another object of the present invention is to provide a kind of preparation method simply efficient, with low cost of above-mentioned high-ratio surface porous carbon fiber.
A further object of the present invention is to provide a kind of above-mentioned high-ratio surface porous carbon fiber in the application as aspects such as catalyst carrier, ultracapacitor, lithium ion battery and filter membranes.
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 μ m.
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 μ m.
According to the present invention, described high-ratio surface porous carbon fiber is prepared by the method comprising the steps: the spinning solution that comprises pore creating material, macromolecule and organic solvent is carried out to carbonization after spinning, after overpickling is dry, obtain described high-ratio surface porous carbon fiber; 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 that comprises pore creating material, macromolecule and organic solvent to carry out carbonization after spinning, after overpickling is dry, obtain described high-ratio surface porous carbon fiber; Wherein, described pore creating material is selected from potassium sulfide.
Different from the existing method of 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 simple 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 μ m.
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 μ m.
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 quality percentage composition of described pore creating material in spinning solution is 1-10%, is specially 1% or 3% or 5% or 8%; The quality percentage composition of described macromolecule in spinning solution is 5-20%, is specially 8% or 10% or 15%.
According to the present invention, in described spinning step, 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 is included in the high temperature cabonization in airborne 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 during higher than 600 DEG C, thereby potassium sulfide activated carbon fiber forms microcellular structure, and the high-ratio surface carbon fiber that at this moment formed 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 preparing 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 providing 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.Thereby 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 in the application of preparing in ultracapacitor, lithium ion battery, catalyst carrier or filter membrane.
Compared with existing high-ratio surface carbon fiber preparation method, method tool provided by the invention has the following advantages:
A) utilize carbon fiber prepared by the method to have very high specific area, for have 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 of preparing porous carbon fiber, the present invention has introduced 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 simple efficient and with low cost, and the porous carbon fiber of preparation has high-ratio surface and abundant micropore and meso-hole structure.
Brief description of the drawings
Fig. 1 is the obtained high-ratio surface porous carbon fiber of embodiment 1 nitrogen adsorption desorption curve.
Fig. 2 is the obtained high-ratio surface porous carbon fiber of embodiment 1 TEM Electronic Speculum detection figure.
Fig. 3 is the obtained high-ratio surface porous carbon fiber of embodiment 2 nitrogen adsorption desorption curve.
Fig. 4 is the obtained high-ratio surface porous carbon fiber of embodiment 2 TEM Electronic Speculum detection figure.
Fig. 5 is the obtained high-ratio surface porous carbon fiber of embodiment 3 nitrogen adsorption desorption curve.
Fig. 6 is the obtained high-ratio surface porous carbon fiber of embodiment 3 TEM Electronic Speculum detection figure.
Detailed description of the invention
Further elaborate the present invention 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 variation, all within protection scope of the present invention.
The experimental technique using in following embodiment if no special instructions, is conventional method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
In following embodiment, adopt JEOL JEM-1011 type transmission electron microscope (TEM) to characterize the structure of porous carbon fiber.Adopt Quantachrome Autosorb-1 type specific area and pore size distribution analyzer to characterize the pore structure in porous carbon fiber, adsorbed gas is N
2, degassed temperature is 200 DEG C.Electrostatic spinning uses DC high-voltage power supply SPL50P60Spellman, micro-injection pump KDS-200, Stoelting Co, 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 and dissolved, adding 1.0g number-average molecular weight is the macromolecule polypropylene nitrile of 150w, stirs 1h at 80 DEG C and form the thick solution of mulberry, is 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: the above-mentioned mulberry precursor solution preparing is transferred in 10mL injector for medical purpose, be expelled in spinning head with the flow velocity of 1.5mL/h, applying between spinning head and collecting board that high voltage electric field makes that spinning solution is stretched, refinement, form fiber after solidifying 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, rise to 900 DEG C of carbonization 2h with the programming rate of 4 DEG C/min, after being down to room temperature, the carbon fiber of black is put in the hydrochloric acid solution of 2M and washed and within 0.5 hour, wash away potassium sulfide, the dry porous carbon fiber that obtains of finally washing.
Fig. 1 is the nitrogen adsorption desorption curve of high-ratio surface carbon fiber, in relative pressure is the micropore absorption region below 0.05, has higher adsorbance, illustrates that this carbon fiber exists a large amount of microcellular structures.Meanwhile, in the scope that is 0.42-0.9, have hysteretic loop at relative pressure, this explanation 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 it is fibrous that carbon fiber diameter is between 100-130nm.
Embodiment 2
1) the pore creating material potassium sulfide of 0.5g is joined in 10g organic solvent DMF and dissolved, adding 1.0g number-average molecular weight is the macromolecule polypropylene nitrile of 150w, stirs 1h at 80 DEG C and form the thick solution of mulberry, is spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning;
3) carry out pre-oxidation, carbonization according to embodiment 1 step 3), only the temperature of carburising step is replaced with to 1000 DEG C, after being down to room temperature, the carbon-fiber film of black is put in the sulfuric acid solution of 2M and washed and within 1 hour, wash away potassium sulfide, the dry high-ratio surface carbon fiber that obtains of finally washing.
Fig. 3 is the nitrogen adsorption desorption curve of this carbon fiber, in relative pressure is the micropore absorption region below 0.05, has higher adsorbance, illustrates that this carbon fiber exists a large amount of microcellular structures.Meanwhile, in the scope that is 0.42-0.9, have hysteretic loop at relative pressure, this explanation 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 it is fibrous that carbon fiber diameter is between 100-130nm.
Embodiment 3
1) the pore creating material potassium sulfide of 0.3g is joined in 10g organic solvent DMF and dissolved, adding 1.0g number-average molecular weight is the macromolecule polypropylene nitrile of 150w, stirs 1h at 80 DEG C and form the thick solution of mulberry, is spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning, only electrospinning temperature is replaced with to 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 to 230 DEG C, carburizing temperature replaces with 1000 DEG C.
Fig. 5 is the nitrogen adsorption desorption curve of this carbon fiber, in relative pressure is the micropore absorption region below 0.05, has higher adsorbance, illustrates that this carbon fiber exists a large amount of microcellular structures.Meanwhile, in the scope that is 0.42-0.9, have hysteretic loop at relative pressure, this explanation 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 it is fibrous that carbon fiber diameter is between 100-130nm.
Embodiment 4
1) the pore creating material potassium sulfide of 0.1g is joined in 10g organic solvent DMF and dissolved, adding 1.0g number-average molecular weight is the macromolecule polypropylene nitrile of 150w, stirs 1h at 80 DEG C and form the thick solution of mulberry, is spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning, only electrospinning temperature is replaced with to 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 to 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 and dissolved, adding 1.0g number-average molecular weight is the macromolecule polypropylene nitrile of 150w, stirs 1h at 80 DEG C and form the thick solution of mulberry, is spinning solution.
2) according to embodiment 1 step 2) carry out electrostatic spinning, only electrospinning temperature is replaced with to 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 to 260 DEG C.
With embodiment 1 acquired results without substantive difference.
Claims (10)
1. a high-ratio surface porous carbon fiber, is characterized in that, the specific area of described 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 μ m.
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; The diameter of described carbon fiber is preferably between 100nm-1 μ m.
2. high-ratio surface porous carbon fiber according to claim 1, it is characterized in that, described high-ratio surface porous carbon fiber is prepared by the method comprising the steps: the spinning solution that comprises pore creating material, macromolecule and organic solvent is carried out to carbonization after spinning, after overpickling is dry, obtain described high-ratio surface porous carbon fiber; Wherein, described pore creating material is selected from potassium sulfide.
3. high-ratio surface porous carbon fiber according to claim 2, is characterized in that, described macromolecule is selected from least one in polyacrylonitrile, polyimides, pitch, polyvinyl alcohol, polyvinylpyrrolidone and phenolic resins.
Preferably, the number-average molecular weight of described polyacrylonitrile is 50w-300w, is preferably 150w.
Preferably, the number-average molecular weight of described polyimides is 50w-300w, is preferably 150w.
Preferably, the number-average molecular weight of described pitch and polyvinyl alcohol is 50w-300w, is preferably 150w.
Preferably, the number-average molecular weight of described polyvinylpyrrolidone is 50w-300w, is preferably 150w.
4. 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 that comprises pore creating material, macromolecule and organic solvent to carry out carbonization after spinning, after overpickling is dry, obtains described high-ratio surface porous carbon fiber; Wherein, described pore creating material is selected from potassium sulfide.
5. method according to claim 4, 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 μ m.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; The diameter of described carbon fiber is preferably between 100nm-1 μ m.
6. according to the method described in claim 4 or 5, it is characterized in that, described macromolecule is selected from least one in polyacrylonitrile, polyimides, pitch, polyvinyl alcohol, polyvinylpyrrolidone and phenolic resins.
Preferably, the quality percentage composition of described pore creating material in spinning solution is 1-10%, is specially 1% or 3% or 5% or 8%.
The quality percentage composition of described macromolecule in spinning solution is 5-20%, is specially 8% or 10% or 15%.
Preferably, the number-average molecular weight of described polyacrylonitrile is 50w-300w, is preferably 150w.
Preferably, the number-average molecular weight of described polyimides is 50w-300w, is preferably 150w.
Preferably, the number-average molecular weight of described pitch and polyvinyl alcohol is 50w-300w, is preferably 150w.
Preferably, the number-average molecular weight of described polyvinylpyrrolidone is 50w-300w, is preferably 150w.
7. according to the method described in any one in claim 4 to 6, in described spinning step, spinning process is electrostatic spinning; Preferably, 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.
8. according to the method described in any one in claim 4 to 7, described carburising step is included in the high temperature cabonization in airborne pre-oxidation and inert atmosphere successively;
Preferably, 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.
Preferably, in described high temperature cabonization step, described inert atmosphere is N
2or Ar atmosphere;
Preferably, 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.
Preferably, 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.
9. catalyst carrier, ultracapacitor, lithium ion battery or a filter membrane, it comprises the high-ratio surface porous carbon fiber that in the high-ratio surface porous carbon fiber described in any one in claims 1 to 3 or claim 4 to 8, described in any one, method prepares.
10. the application of the high-ratio surface porous carbon fiber that in claims 1 to 3, in the high-ratio surface porous carbon fiber described in any one or claim 4 to 8, described in any one, method prepares, it is for as catalyst carrier, ultracapacitor, lithium ion battery or filter membrane etc.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225695A (en) * | 1996-05-15 | 1999-08-11 | 海珀里昂催化国际有限公司 | High surface area nanofibers |
| CN1567493A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院电工研究所 | A composite carbon-based electrode material for super capacitor and method for making same |
| CN101455975A (en) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof |
| CN101702379A (en) * | 2009-11-20 | 2010-05-05 | 青岛生物能源与过程研究所 | Method for preparing non-symmetrical electrochemical supercapacitor and electrode materials |
| CN102345189A (en) * | 2010-08-05 | 2012-02-08 | 同济大学 | Method for preparing porous magnetic and catalytic double-functional one-dimensional composite material |
| CN102505403A (en) * | 2011-09-29 | 2012-06-20 | 大连理工大学 | Method for preparing hierarchically porous activated carbon fiber membrane |
| CN102517692A (en) * | 2011-12-02 | 2012-06-27 | 清华大学 | PAN (Polyacrylonitrile)-based porous carbon nanofiber for removing NOx from air, and preparation method and application thereof |
| CN103014921A (en) * | 2012-12-17 | 2013-04-03 | 中国科学院化学研究所 | Multi-hole carbon fiber and preparation method thereof |
| CN103215693A (en) * | 2013-02-01 | 2013-07-24 | 清华大学 | Graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and preparation method thereof |
| CN103225135A (en) * | 2013-05-09 | 2013-07-31 | 中国科学院化学研究所 | Porous carbon fiber, and preparation method and application thereof |
-
2014
- 2014-03-13 CN CN201410092927.2A patent/CN103882559B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225695A (en) * | 1996-05-15 | 1999-08-11 | 海珀里昂催化国际有限公司 | High surface area nanofibers |
| CN1567493A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院电工研究所 | A composite carbon-based electrode material for super capacitor and method for making same |
| CN101455975A (en) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof |
| CN101702379A (en) * | 2009-11-20 | 2010-05-05 | 青岛生物能源与过程研究所 | Method for preparing non-symmetrical electrochemical supercapacitor and electrode materials |
| CN102345189A (en) * | 2010-08-05 | 2012-02-08 | 同济大学 | Method for preparing porous magnetic and catalytic double-functional one-dimensional composite material |
| CN102505403A (en) * | 2011-09-29 | 2012-06-20 | 大连理工大学 | Method for preparing hierarchically porous activated carbon fiber membrane |
| CN102517692A (en) * | 2011-12-02 | 2012-06-27 | 清华大学 | PAN (Polyacrylonitrile)-based porous carbon nanofiber for removing NOx from air, and preparation method and application thereof |
| CN103014921A (en) * | 2012-12-17 | 2013-04-03 | 中国科学院化学研究所 | Multi-hole carbon fiber and preparation method thereof |
| CN103215693A (en) * | 2013-02-01 | 2013-07-24 | 清华大学 | Graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and preparation method thereof |
| CN103225135A (en) * | 2013-05-09 | 2013-07-31 | 中国科学院化学研究所 | Porous carbon fiber, and preparation method and application thereof |
Cited By (23)
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|---|---|---|---|---|
| CN106521717A (en) * | 2015-09-11 | 2017-03-22 | 五邑大学 | Preparation method of porous carbon fiber with high specific surface area |
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| CN108472567A (en) * | 2015-12-17 | 2018-08-31 | W.L.戈尔及同仁股份有限公司 | catalytic filter material |
| CN108472567B (en) * | 2015-12-17 | 2021-05-25 | W.L.戈尔及同仁股份有限公司 | Catalytic filter material |
| CN105603585A (en) * | 2016-02-05 | 2016-05-25 | 扬州大学 | Preparation method of hollow carbon fibers with controllable scale |
| CN105696115B (en) * | 2016-04-06 | 2018-02-02 | 天津工业大学 | A kind of method that electrode material for super capacitor is prepared based on rotor spinning method |
| CN105696115A (en) * | 2016-04-06 | 2016-06-22 | 天津工业大学 | Method for preparing electrode materials for supercapacitors on basis of airflow spinning processes |
| CN105780198B (en) * | 2016-05-12 | 2018-02-09 | 天津工业大学 | A kind of preparation method of order mesoporous carbon nano-fiber |
| CN105780198A (en) * | 2016-05-12 | 2016-07-20 | 天津工业大学 | Preparation method of ordered mesoporous carbon nanofibers |
| CN109154108A (en) * | 2016-05-19 | 2019-01-04 | 株式会社神户制钢所 | Manufacturing method, carbon fiber and the electric double layer capacitor pole of carbon fiber |
| CN107142557A (en) * | 2017-06-29 | 2017-09-08 | 苏州夸克新材料科技有限公司 | A kind of method that utilization method of electrostatic spinning prepares zeolite carbon composite fibre sound-absorbing material |
| CN110158200A (en) * | 2018-03-30 | 2019-08-23 | 北京纳米能源与***研究所 | Porous carbon nanofiber and preparation method thereof and lithium-sulfur cell |
| CN110158200B (en) * | 2018-03-30 | 2022-04-08 | 北京纳米能源与***研究所 | Porous carbon nanofiber, preparation method thereof and lithium-sulfur battery |
| CN108557799A (en) * | 2018-06-04 | 2018-09-21 | 河南工程学院 | A kind of high-purity high conductivity class graphene grading-hole porous charcoal and preparation method thereof |
| CN109137263A (en) * | 2018-06-21 | 2019-01-04 | 中国科学院山西煤炭化学研究所 | A kind of high-specific surface area polyacrylonitrile carbon fiber non-woven fabrics and preparation method |
| CN110359098A (en) * | 2019-06-19 | 2019-10-22 | 五邑大学 | A kind of mesoporous carbon fiber electrode material and preparation method thereof |
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| CN114775113A (en) * | 2022-05-26 | 2022-07-22 | 中国科学院宁波材料技术与工程研究所 | Self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, and preparation method and application thereof |
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