CN103409852A - Preparation method for PVC-based carbon nanofiber - Google Patents
Preparation method for PVC-based carbon nanofiber Download PDFInfo
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108862187A (en) * | 2018-07-25 | 2018-11-23 | 宁波革创新材料科技有限公司 | A kind of preparation method of the environmentally friendly hydrogen storage material with hierarchical structure |
| CN109056122A (en) * | 2018-07-04 | 2018-12-21 | 吉林农业大学 | A method of tool three-dimensional structure nanofiber aerogel material is prepared by electrostatic spinning |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109056122A (en) * | 2018-07-04 | 2018-12-21 | 吉林农业大学 | A method of tool three-dimensional structure nanofiber aerogel material is prepared by electrostatic spinning |
| CN108862187A (en) * | 2018-07-25 | 2018-11-23 | 宁波革创新材料科技有限公司 | A kind of preparation method of the environmentally friendly hydrogen storage material with hierarchical structure |
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