CN103409852A - Preparation method for PVC-based carbon nanofiber - Google Patents
Preparation method for PVC-based carbon nanofiber Download PDFInfo
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- CN103409852A CN103409852A CN2013103107434A CN201310310743A CN103409852A CN 103409852 A CN103409852 A CN 103409852A CN 2013103107434 A CN2013103107434 A CN 2013103107434A CN 201310310743 A CN201310310743 A CN 201310310743A CN 103409852 A CN103409852 A CN 103409852A
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- base carbon
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011630 iodine Substances 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 11
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- 239000002585 base Substances 0.000 claims description 43
- 239000002121 nanofiber Substances 0.000 claims description 38
- 238000001523 electrospinning Methods 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical group [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- ITAMZXBSBDURQN-UHFFFAOYSA-N 3-bromopropyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)CCCBr ITAMZXBSBDURQN-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 60
- 239000004800 polyvinyl chloride Substances 0.000 description 60
- 239000000243 solution Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001417105 Clupea pallasii Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
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- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention related to a preparation method for carbon nanofiber. The preparation method is characterized in that: PVC and a catalyst precursor are mixed firstly by using an organic solvent, stirred at 40-50 DEG C to prepare a uniform electrostatic spinning solution; a PVC-based carbon nanofiber precursor is prepared from the spinning solution through an electrostatic spinning device; the PVC-based carbon nanofiber precursor is dried in a drying case, and the dried PVC-based carbon nanofiber precursor is subjected to iodine vapor treatment or alkaline liquor treatment to remove hydrogen chloride, and then the PVC-based carbon nanofiber precursor is put into a muffle furnace to perform preoxidation in an air environment and is forged into the PVC-based carbon nanofiber in a tube furnace under a condition of piping in inert gas continuously. By utilization of the method, resource reuse of the PVC can be achieved with simple equipment and easy operation, and large-scale preparation can be achieved. The PVC-based carbon nanofiber has a large specific surface area. The PVC-based carbon nanofiber is prone to recycle and can be reutilized. The PVC-based carbon nanofiber is suitable for applications in the fields of hydrogen storage, fuel cells, lithium ion batteries, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-fiber, be specifically related to prepare the preparation method of the PVC base carbon nano-fiber that can be used for comprising the aspects such as Chu Qing, lithium ion battery, fuel cell.
Background technology
Hydrogen is a kind of clean fuel, and Hydrogen Energy is one of following promising novel energy.The storage of hydrogen is the bottleneck of Hydrogen Energy present stage development and utilization.The storage method of hydrogen has 3 kinds of high-pressure gaseous storage, low temperature liquid storage and solid-state storages etc., and wherein high-pressure gaseous storage or low temperature liquid store and can not meet storage hydrogen target in the future.Solid-state storage hydrogen be by chemistry or physical absorption by hydrogen storage in solid-state material, its energy density is high and security good, is considered to the most promising a kind of hydrogen storage mode.
Carbon-based material is insensitive to a small amount of gaseous impurity, but and Reusability, reservoir vessel is lightweight, the shape choice is large and efficiency of storage is high, but its hydrogen-sucking amount is less, is difficult to make the material with suitable micro pore volume and shape, is difficult for determining suction hydrogen position etc.Gnf structure uniqueness, according to the angle of graphite linings and fiber axis and whether hollow, can be divided into four kinds of tabulars, Pacific herring herring-bone form, tubulose, cover cup-shaped.Wherein there is more marginal point in the tabular gnf with respect to other three kinds of surfaces, means more active performance (hydrogen catalyzed decomposition) and better absorption property.And graphite linings and interlamellar spacing are greater than 3.35A ° (kinetics of hydrogen diameter 2.89A °), like the hole, crack, be the ideal structure of Chu Qing.And the metals such as iron-cobalt-nickel can play the effect of catalyzed graphitization.
Polyvinyl chloride (following all mean with PVC) is one of five large general synthetic resins in synthetic material, and its output is only second to polyethylene, occupies second.Along with the growth of output and consumption figure, discarded PVC also increases thereupon, and how recycling ever-increasing PVC discarded object becomes problem in the urgent need to address.Traditional method is such as firing method can produce particularly bioxin of many pollutants.After carbonization, being prepared into carbon fiber is a kind of effective new technology that makes PVC resource recycling.
In recent years, the attention rate for electrostatic spinning technique is more and more higher.Electrostatic spinning is the way of the superfine fibre of a kind of manufacture from several nanometers to the hundreds of nanometer.Electrostatic spinning is to utilize high voltage to make the high polymeric solution on the pin mouth form injection stream, arrives the process that receiving plate cause is the volatilization formation solid fiber of solvent.With other method, compare, but electrostatic spinning has characteristics such as preparation technology is simple, Cheap highly effective continuous production are considered to a kind of the most useful method for preparing nanofiber.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of PVC base carbon nano-fiber, with PVC base carbon nano-fiber prepared by the method, can be used for the aspects such as Chu Qing, lithium ion battery, fuel cell, have the advantages such as cost is low, technological operation simple, reusable edible.
For realizing that purpose of the present invention adopts technical scheme as follows:
1, preparation electrostatic spinning liquid: PVC, catalyst precursor are blended under 40~50 ℃ and stir and be mixed with uniform electrostatic spinning liquid with organic solvent.
2, electrospinning prepares the composite nano fiber precursor: above spinning solution is prepared to PVC base carbon nano-fiber precursor by electrospinning device.
3, the preliminary treatment of precursor: step 2 is prepared to PVC base carbon nano-fiber precursor and be placed in drying baker and carry out drying, dried PVC base carbon nano-fiber precursor, by iodine vapor, process or alkali lye (containing phase transfer catalyst) is processed and to be removed hydrogen chloride, carry out pre-oxidation and be placed under Muffle furnace hollow atmosphere.
4,, by the PVC base carbon nano-fiber precursor after above pre-oxidation, make PVC base carbon nano-fiber continuing to pass under the condition of inert gas calcining in tube furnace.
Described organic solvent is nitrogen dimethylformamide, oxolane, cyclohexanone or dichloroethanes.
Described electrostatic spinning liquid, the weight part ratio of PVC wherein and catalyst precursor is 1:0~0.05.
Described catalyst precursor refers to nickel chloride, nickel acetate, nickelous sulfate, nickel acetylacetonate, iron chloride, ferric sulfate, ferric acetyl acetonade, cobalt chloride, cobaltous sulfate, copper chloride, copper sulphate, copper acetate, copper nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, aluminium chloride, aluminum sulfate or aluminum nitrate.
Described organic solvent is nitrogen dimethylformamide, oxolane, cyclohexanone or dichloroethanes.
Described electrostatic spinning, condition is: 28~35 ℃ of the feed flow velocity 0.6~1mL/h of voltage 25~30KV, electrostatic spinning liquid, electrospinning temperature.
Described oven dry, its temperature are 42~50 ℃, dry 8~10h.
Described iodine vapor is processed, and refers to that PVC base carbon nano-fiber precursor iodine vapor under vacuum state, 80 ℃ of conditions processes 48h.
Described alkali lye is processed, and refers to that PVC base carbon nano-fiber precursor processes 24h in 3.50~7.00mol/L alkali lye (containing 0.012~0.040mol/L phase transfer catalyst), under 70 ℃ of conditions.
Described alkali lye refers to NaOH, potassium hydroxide or barium hydroxide.
Described phase transfer catalyst refers to TBAB, bromo tetrapropyl ammonium or bromo triethyl group hexadecyldimethyl benzyl ammonium.
Described pre-oxidation, its Pre oxidation are 260~320 ℃, and calcination time is 1~3h.
Described calcining, calcining heat are 600~1200 ℃, and calcination time is 1~3h.
Describedly continue to pass into inert gas, the flow that passes into of inert gas is 300ml/min.
Advantage of the present invention is:
Adopt electrostatic spinning technique to prepare PVC base carbon nano-fiber, can realize the resource reutilization of PVC, equipment is simple, can prepare in a large number by processing ease; The PVC base carbon nano-fiber specific area of preparation is large, easily reclaims, and can be recycled, and is suitable for the application in the fields such as Chu Qing, fuel cell, lithium ion battery.
The accompanying drawing explanation
1, Fig. 1 is the X-ray diffractogram of the prepared nickeliferous PVC base carbon nano-fiber of the present invention.
2, Fig. 2 is the scanning electron microscope (SEM) photograph of the prepared nickeliferous PVC base carbon nano-fiber of the present invention.
3, Fig. 3 is the transmission electron microscope picture of the prepared nickeliferous PVC base carbon nano-fiber of the present invention.
The specific embodiment
Embodiment 1
1, preparation electrostatic spinning solution: with 1.4g PVC(K value 72-71), 0.0560g nickel chloride and 18.6mL nitrogen dimethylformamide mix, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by electrospinning device, under 35 ℃ of conditions of feed flow velocity 0.6mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC/NiCl
2The composite nano fiber precursor.
The PVC/NiCl that 3, will prepare
2The composite nano fiber precursor is dry 8h in baking oven (temperature 50 C).
4, dry rear PVC/NiCl
2Composite nano fiber precursor iodine vapor under vacuum, 80 ℃ of conditions is processed 48h.
5, nanofiber 320 ℃ of calcining 1h in Muffle furnace after above iodine preliminary treatment
6, after above pre-oxidation, nanofiber is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 1000 ℃ of calcining 1h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
As shown in Figure 1, as shown in Figure 2, transmission electron microscope picture as shown in Figure 3 for scanning electron microscope (SEM) photograph for X ray, Electronic Speculum and transmission scan that the PVC base carbon nano-fiber that the present embodiment is prepared is correlated with, Electronic Speculum figure such as X-ray diffractogram.
Embodiment 2
1, preparation electrostatic spinning solution: with 1.4g PVC(K value 72-71), 0.0560g nickel chloride and 18.6mL nitrogen dimethylformamide mix, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by electrospinning device, under 35 ℃ of conditions of feed flow velocity 0.6mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC/NiCl
2The composite nano fiber precursor.
The PVC/NiCl that 3, will prepare
2The composite nano fiber precursor is dry 8h in baking oven (temperature 50 C).
4, dry rear PVC/NiCl
2The composite nano fiber precursor is 70 ℃ of processing 24h in alkali lye (6.25mol/L NaOH, 0.037mol/L TBAB).
5, nanofiber 260 ℃ of calcining 3h in Muffle furnace after above Alkaline pretreatment.
6, the nanofiber after above pre-oxidation is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 1000 ℃ of calcining 1h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
Embodiment 3
1, preparation electrostatic spinning solution: with 1.4g PVC(K value 72-71), 0.0560g nickel acetate and 18.6mL nitrogen dimethylformamide mix, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by electrospinning device, under 35 ℃ of conditions of feed flow velocity 0.6mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC/ (CH
3COO)
2Ni composite nano fiber precursor.
PVC/ (the CH that 3, will prepare
3COO)
2Ni composite nano fiber precursor is dry 8h in baking oven (temperature 50 C).
4, dry rear PVC/ (CH
3COO)
2Ni composite nano fiber precursor iodine vapor under vacuum, 80 ℃ of conditions is processed 48h.
5, nanofiber 320 ℃ of calcining 1h in Muffle furnace after above iodine preliminary treatment.
6, the nanofiber after above pre-oxidation is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 1000 ℃ of calcining 1h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
Embodiment 4
1, preparation electrostatic spinning solution: with 1.4g PVC(K value 72-71), 0.0560g magnesium chloride and 18.6mL nitrogen dimethylformamide mix, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by electrospinning device, under 35 ℃ of conditions of feed flow velocity 0.8mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC/ MgCl
2The composite nano fiber precursor.
The PVC/ MgCl that 3, will prepare
2The composite nano fiber precursor is dry 8h in baking oven (temperature 50 C).
4, dry rear PVC/MgCl
2The composite nano fiber precursor is 70 ℃ of processing 24h in alkali lye (6.25mol/L NaOH, 0.037mol/L TBAB).
5, nanofiber 260 ℃ of calcining 3h in Muffle furnace after above Alkaline pretreatment.
6, the nanofiber after above pre-oxidation is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 750 ℃ of calcining 2h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
Embodiment 5
1, preparation electrostatic spinning solution: with 1.4g PVC(K value 72-71) with the 18.6mL nitrogen dimethylformamide, mix, after under 50 ° of C, stirring a period of time, form the spinning solution of homogeneous.
2, by electrospinning device, under 35 ℃ of conditions of feed flow velocity 1mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC nanofiber precursor.
The PVC nanofiber precursor that 3, will prepare dry 8h in baking oven (temperature 50 C).
4, dry rear PVC nanofiber precursor 70 ℃ of processing 8h in alkali lye (3.75mol/L potassium hydroxide, 0.013mol/L TBAB).
5, nanofiber 260 ℃ of calcining 3h in Muffle furnace after above Alkaline pretreatment.
6, the nanofiber after above pre-oxidation is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 1000 ℃ of calcining 1h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
Embodiment 6
1, preparation electrostatic spinning solution: with 1.4g PVC(K value 72-71) with the 18.6mL nitrogen dimethylformamide, mix, after under 50 ℃, stirring a period of time, form the spinning solution of homogeneous.
2, by electrospinning device, under 35 ℃ of conditions of feed flow velocity 1mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC nanofiber precursor.
The PVC nanofiber precursor that 3, will prepare dry 8h in baking oven (temperature 50 C).
4, dry rear PVC nanofiber precursor 70 ℃ of processing 8h in alkali lye (6.25mol/L NaOH, 0.037mol/L bromo triethyl group hexadecyldimethyl benzyl ammonium).
5, nanofiber 260 ℃ of calcining 3h in Muffle furnace after above Alkaline pretreatment.
6, the nanofiber after above pre-oxidation is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 750 ℃ of 2h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
Embodiment 7
1, preparation electrostatic spinning solution: by 1.4g PVC(K value 72-71) be dissolved in 18.6mL nitrogen dimethylformamide and oxolane (volume ratio 1:1) mixed solvent, after under 50 ℃, stirring a period of time, form the spinning solution of homogeneous.
2, by electrospinning device, under 30 ℃ of conditions of feed flow velocity 1mL/h, electrospinning temperature of voltage 25KV, spinning solution, the spinning solution electrospinning prepares PVC nanofiber precursor.
The PVC nanofiber precursor that 3, will prepare is dry 8h in baking oven (50 ° of C of temperature).
4, dry rear PVC nanofiber precursor 70 ℃ of processing 24h in alkali lye (6.25mol/L NaOH, 0.037mol/L TBAB).
5, nanofiber 260 ℃ of calcining 3h in Muffle furnace after above Alkaline pretreatment.
6, the nanofiber after above pre-oxidation is at tube furnace, and nitrogen flow is with 2 ℃/min, to rise to 750 ℃ of calcining 2h under the condition of 300ml/min, obtains nickeliferous PVC base carbon nano-fiber.
Claims (12)
1. the preparation method of a PVC base carbon nano-fiber is characterized in that:
(1) preparation electrostatic spinning liquid: PVC, catalyst precursor are blended under 40~50 ℃ and stir and be mixed with uniform electrostatic spinning liquid with organic solvent;
(2) electrospinning prepares the composite nano fiber precursor: above spinning solution is prepared to PVC base carbon nano-fiber precursor by electrospinning device;
(3) preliminary treatment of precursor: step 2 is prepared to PVC base carbon nano-fiber precursor and be placed in drying baker and carry out drying, dried PVC base carbon nano-fiber precursor, by iodine vapor, process or the alkali lye that contains phase transfer catalyst is processed and to be removed hydrogen chloride, carry out pre-oxidation and be placed under Muffle furnace hollow atmosphere;
(4), by the PVC base carbon nano-fiber precursor after above pre-oxidation, make PVC base carbon nano-fiber continuing to pass under the condition of inert gas calcining in tube furnace; The flow that passes into of inert gas is 300ml/min.
2. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described organic solvent is nitrogen dimethylformamide, oxolane, cyclohexanone or dichloroethanes.
3. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described catalyst precursor is nickel chloride, nickel acetate, nickelous sulfate, nickel acetylacetonate, iron chloride, ferric sulfate, ferric acetyl acetonade, cobalt chloride, cobaltous sulfate, copper chloride, copper sulphate, copper acetate, copper nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, aluminium chloride, aluminum sulfate or aluminum nitrate.
4. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described alkali lye refers to NaOH, potassium hydroxide or barium hydroxide.
5. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described phase transfer catalyst comprises TBAB, bromo tetrapropyl ammonium or bromo triethyl group hexadecyldimethyl benzyl ammonium.
6. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described electrostatic spinning liquid, and the weight part ratio of PVC wherein and catalyst precursor is 1:0~0.05.
7. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described organic solvent is nitrogen dimethylformamide, oxolane, cyclohexanone or dichloroethanes.
8. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described electrostatic spinning, and condition is: 28~35 ℃ of the feed flow velocity 0.6~1mL/h of voltage 25~30KV, electrostatic spinning liquid, electrospinning temperature.
9. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described oven dry, and its temperature is 42~50 ℃, dries 8~10h; Described pre-oxidation, its Pre oxidation are 260~320 ℃; Described calcining, calcining heat are 600~1200 ℃, and calcination time is 1~3h.
10. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described iodine vapor processes, and refers to that PVC base carbon nano-fiber precursor iodine vapor under vacuum state, 80 ℃ of conditions processes 48h.
11. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, it is characterized in that described alkali lye processing, refer to that PVC base carbon nano-fiber precursor processes 24h in 3.50~7.00mol/L alkali lye, under 70 ℃ of conditions, in alkali lye, contain 0.012~0.040mol/L phase transfer catalyst.
12. the preparation method of a kind of PVC base carbon nano-fiber according to claim 1, is characterized in that described phase transfer catalyst refers to TBAB, bromo tetrapropyl ammonium or bromo triethyl group hexadecyldimethyl benzyl ammonium.
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