CN103696239A - Preparation method of carbon nano-fiber film - Google Patents
Preparation method of carbon nano-fiber film Download PDFInfo
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- CN103696239A CN103696239A CN201310654004.7A CN201310654004A CN103696239A CN 103696239 A CN103696239 A CN 103696239A CN 201310654004 A CN201310654004 A CN 201310654004A CN 103696239 A CN103696239 A CN 103696239A
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Abstract
The invention discloses a preparation method of a carbon nano-fiber film, and particularly discloses a method for preparing a high-strength polyacrylonitrile-based carbon nano-fiber film by using electrostatic spinning-high temperature carbonization in combination with a catalytic chemical vapor deposition process. The method comprises the following steps: preparing a polyacrylonitrile-based carbon nano-fiber porous reinforcement with high flexibility but low strength by using electrostatic spinning and high temperature carbonization; and further filling vapor growth carbon nano-fibers into the polyacrylonitrile-based carbon nano-fiber porous reinforcement by using a chemical vapor deposition technology to obtain the carbon nano-fiber film with high flexibility and high strength. Compared with a polyacrylonitrile-based carbon nano-fiber film prepared by merely using an "electrostatic spinning-high temperature carbonization" technology, the carbon nano-fiber film prepared with the method disclosed by the invention has the advantage that the in-plane tensile strength is increased by 80-120 percent.
Description
Technical field
The present invention relates to Material Field, specifically a kind of preparation method of carbon nano-fiber film
Background technology
Carbon nano-fiber film refers to the bidimensional porous material of the similar paper that the disordered carbon nanofiber by certain length forms, be also sometimes referred to as carbon nano-fiber paper, as periodical literature " Zhang Na etc.; the impact of carbon nano-fiber paper-glass epoxy composite material on wind power generation blade; composite journal; 2013,90-95 "; Periodical literature " Shafi Ullah Khan etc.; Improved interlaminar shear properties of multiscale carbon fiber composites with bucky paper interleaves made from carbon nanofibers; CARBON; 2012,5265-5277 "; Shown in patent documentation " Xiao Hui, a kind of carbon nano-fiber paper and preparation method thereof, publication number: CN103015256A ".Present stage, carbon nano-fiber paper for the interlaminar shear strength that improves fiberglass/resin composite (as " Shafi Ullah Khan etc., Improved interlaminar shear properties of multiscale carbon fiber composites with bucky paper interleaves made from carbon nanofibers, CARBON, 2012, 5265-5277 "), improve the anti-solid particle erosion polishing machine of blade of wind-driven generator (as " Zhang Na etc., the impact of carbon nano-fiber paper-glass epoxy composite material on wind power generation blade, composite journal, 2013, 90-95 ") etc. field.
The preparation technology of carbon nanotube paper (being Buckie paper) has mainly been continued to use in the preparation of carbon nano-fiber film at present, be about to carbon nano-fiber, surfactant and water are mixed into slurry by a certain percentage, adopt suction filtration mode to obtain carbon nano-fiber film, wherein carbon nano-fiber is made by chemical vapor deposition method, is referred to as again the carbon nano-tube fibre of vapor phase growth.About this preparation method, in document " Shao G etc.; Ceramic nanocomposites reinforced with a high volume fraction of carbon nanofibers; Materials Letter; 2012; 108-111 " and document " Zhang Na etc., the impact of carbon nano-fiber film-glass epoxy composite material on wind power generation blade, composite journal; 2013,90-95 ", there is comparatively full and accurate narration.Yet, because the carbon nano-fiber length of vapor phase growth mostly is micron level, being generally no more than 1 millimeter, this makes the carbon nano-fiber film pliability of preparation poor, is easy to fracture, and is not easy to the through engineering approaches of product.
Therefore, how to develop simple forming method, the good carbon nano-fiber film of preparation pliability becomes one, this field problem demanding prompt solution.Electrostatic spinning technique is the process of current unique a kind of can preparation of " the rice order of magnitude " length carbon nano-fiber.This technology is processed in conjunction with high temperature cabonization, can prepare the carbon nano-fiber that length is larger.In conjunction with high temperature cabonization treatment technology, prepare aspect carbon nano-fiber film or thin-film material utilizing electrostatic spinning, all there is more report both at home and abroad, as document " Chan Kim etc., utilize carbon nano-fiber net prepared by electrostatic spinning technique to make the positive electrode of lithium rechargeable battery, external chemical fibre technology, 46 " and document " F.Agend etc., Fabrication and electrical characterization of electrospun polyacrylonitrile-derived carbon nanofibers, Journal of Applied Polymer Science, 2007, 255-259 " stated related content.Carbon nano-fiber thin-film material pliability prepared by the method is better, and thickness is controlled.But the face interior mechanics intensity of this material is poor, be unfavorable for that it strengthens the performance of effect.Through retrieval, there is no at present the in-plane strength how bibliographical information improves polyacrylonitrile-radical carbon nano-fiber porous film material.
Summary of the invention
Poor for overcoming the face interior mechanics intensity existing in prior art, be unfavorable for that it strengthens the deficiency of the performance of effect, the present invention proposes a kind of preparation method of carbon nano-fiber film.
Detailed process of the present invention is:
Step 1, configuration polyacrylonitrile-DMF solution:
Step 3, heat treatment.To obtaining polyacrylonitrile based nano-fiber porous preform, heat-treat.
Adopt conventional method to heat-treat the polyacrylonitrile based nano-fiber porous preform obtaining.In heat treatment, the temperature of Muffle furnace is warming up to 250～350 ℃ with the speed of 5～10 ℃/min from room temperature, and is incubated 1～3h.After insulation finishes, obtain through heat treated polyacrylonitrile based nano-fiber porous preform.
Step 4, carbonization treatment: to carrying out carbonization treatment through heat treated polyacrylonitrile based nano-fiber porous preform, prepare polyacrylonitrile-radical carbon nano-fiber porous reinforcement in carbide furnace.
To be laid between two graphite flat boards through heat treated polyacrylonitrile based nano-fiber porous preform.The graphite flat board that accompanies polyacrylonitrile based nano-fiber porous preform is positioned in the carbide furnace of nitrogen atmosphere, described polyacrylonitrile based nano-fiber porous preform is carried out to carbonization treatment.In described carbonization treatment, make carbide furnace from room temperature, be warming up to 800～1000 ℃ and be incubated 1～5h with the heating rate of 1～3 ℃/min, obtain polyacrylonitrile-radical carbon nano-fiber reinforcement, stand-by.
Step 5, preparation seven water nickel nitrate-acetone solns: adopt conventional method, according to formula w%=[w
1÷ (w
1+ w
2)] * 100% preparation seven water nickel nitrate-acetone solns, wherein, W% is the mass fraction of seven water nickel nitrates, w
1be the quality of seven water nickel nitrates, w
2quality for acetone.In described seven water nickel nitrate-acetone solns, the mass fraction of seven water nickel nitrates is 0.3～2.0%.The seven water nickel nitrate-acetone solns that obtain configuring, and be statically placed in atmospheric environment stand-by.
Step 6, soaks: the polyacrylonitrile-radical carbon nano-fiber reinforcement obtaining is soaked in described seven water nickel nitrate-acetone solns, and soak time is to take out after 1～12h, at room temperature dries in the shade.Obtain the carbon nano-fiber film that contains seven water nickel nitrates.
Step 7, chemical vapour deposition (CVD): the carbon nano-fiber film that contains seven water nickel nitrates obtaining is carried out to chemical vapour deposition (CVD), with growth in situ carbon nano-fiber in carbon nano-fiber film.Specifically:
The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates is placed in to chemical vapor deposition stove, and passes into nitrogen in stove, nitrogen flow is 100L/h.In chemical deposition stove, temperature rises to 300～500 ℃ with the speed of 10 ℃/min, and keeps 10～40min.In insulating process, in chemical vapor deposition stove, pass into hydrogen, the flow of described hydrogen is 40～200L/h.After insulation finishes, close hydrogen, and make the interior temperature of chemical deposition stove continue to rise to 650～850 ℃ with the speed of 10 ℃/min, and keep 10～60min.Between soak, in chemical vapor deposition stove, pass into propylene and hydrogen; The flow of described propylene and hydrogen is respectively 10～40L/h and 100～300L/h.When temperature retention time finishes, stop in stove, passing into propylene and hydrogen, and close heating power supply, make chemical vapor deposition stove naturally be cooled to room temperature, obtain polyacrylonitrile-radical polyacrylonitrile-based carbon nano-fiber film.In said process, keep nitrogen with the flow of 100L/h, to pass in stove all the time.
While configuring polyacrylonitrile-DMF solution in step 1, using polyacrylonitrile as solute, DMF, as solvent, mixes both, and polyacrylonitrile is dissolved in DMF.Wherein, in every 100ml DMF solvent, the quality of polyacrylonitrile is 5g～30g.The polyacrylonitrile of weighing is mixed with DMF and stir, standing 12h in atmospheric environment.Obtain polyacrylonitrile-DMF solution.
The present invention is a kind of electrostatic spinning-high temperature cabonization that utilizes, then in conjunction with catalytic chemical gaseous phase deposition technique, prepares the method for high-strength polypropylene itrile group carbon nano-fiber film.
First the present invention utilizes electrostatic spinning and high temperature cabonization to prepare the good but polyacrylonitrile-radical carbon nano-fiber porous reinforcement that intensity is lower of pliability, recycling chemical vapour deposition technique has further been filled the carbon nano-fiber of vapor phase growth in polyacrylonitrile-radical carbon nano-fiber porous reinforcement, and then has made the carbon nano-fiber film that pliability is good, intensity is high.The polyacrylonitrile-based carbon nano-fiber film that carbon nano-fiber film prepared by the method is prepared than simple utilization " electrostatic spinning-high temperature cabonization " technology, face in-draw intensity has improved 80～120%.
Accompanying drawing explanation
Fig. 1 is flow chart of the present invention;
Fig. 2 is the scanning electron micrograph of the carbon nano-fiber porous membrane prepared of prior art;
The scanning electron micrograph of carbon nano-fiber film prepared by Fig. 3 the present invention;
The contrast of face in-draw intensity between the carbon nano-fiber film that high strength carbon nano-fiber film prepared by Fig. 4 the present invention and prior art obtain, wherein, the 1st, the TENSILE STRENGTH of prior art, the 2nd, TENSILE STRENGTH of the present invention.
The specific embodiment
Embodiment 1:
The present embodiment is executed a kind of preparation method of carbon nano-fiber film, and detailed process is:
Step 1, configuration polyacrylonitrile-DMF solution.Using polyacrylonitrile as solute, and DMF, as solvent, mixes both, and polyacrylonitrile is dissolved in DMF.Wherein, in every 100ml DMF solvent, the quality of polyacrylonitrile is 5g.The polyacrylonitrile of weighing is mixed with DMF and stir, standing 12h in atmospheric environment.Obtain polyacrylonitrile-DMF solution.
Utilize SS-2535DC type Electrospun spinning apparatus polyacrylonitrile based nano-fiber porous preform.Specifically:
By in 5ml polyacrylonitrile-DMF solution suction syringe.Vertical range between aluminium sheet and the spray fiber tube of SS-2535DC type Electrospun equipment is adjusted to 100mm.Start spinning.The detailed process of described spinning is: by SS-2535DC type Electrospun equipment, between spray fiber tube and aluminium sheet, applied the voltage of 10kV and keep this voltage.Polyacrylonitrile-DMF solution in syringe is sprayed to surface of aluminum plate.Effect due to voltage between spray fiber tube and aluminium sheet, after polyacrylonitrile-DMF solution is ejected, form polyacrylonitrile based nano-fiber, and evenly tile, be interweaved on the surface of aluminium sheet, obtain polyacrylonitrile based nano-fiber porous preform porous preform.During injection, by regulating medical injection pump, making the ejection speed of polyacrylonitrile-DMF solution in needle tubing is 0.1ml/h, till having sprayed.
Step 3, heat treatment.To obtaining polyacrylonitrile based nano-fiber porous preform, heat-treat.
The polyacrylonitrile based nano-fiber porous preform obtaining is placed in Muffle furnace and is heat-treated.In heat treatment, the temperature of Muffle furnace is warming up to 250 ℃ with the speed of 5 ℃/min from room temperature, and keeps 1h, itrile group in stove is received to polyacrylonitrile based nano-fiber porous preform, heat-treats.After heat treatment, close Muffle furnace power supply.In Muffle furnace, temperature is down to after room temperature, obtains through heat treated polyacrylonitrile based nano-fiber porous preform.
Step 4, carbonization treatment.In carbide furnace, to carrying out carbonization treatment through heat treated polyacrylonitrile based nano-fiber porous preform, prepare polyacrylonitrile-radical carbon nano-fiber porous reinforcement.
To be laid between two graphite flat boards through heat treated polyacrylonitrile based nano-fiber porous preform.The graphite flat board that accompanies polyacrylonitrile based nano-fiber porous preform is positioned in the carbide furnace of nitrogen atmosphere, described polyacrylonitrile based nano-fiber porous preform is carried out to carbonization treatment.In described carbonization treatment, make carbide furnace from room temperature, be warming up to 800 ℃ and be incubated 1h with the heating rate of 1 ℃/min, obtain polyacrylonitrile-radical carbon nano-fiber reinforcement, stand-by.
Step 5, preparation seven water nickel nitrate-acetone solns.Utilize Sai Duolisi LA310S high accuracy analysis balance, take respectively seven water nickel nitrate and acetone of certain mass.Seven water nickel nitrates are as solute, and acetone is solvent, and both are mixed, and seven water nickel nitrates are dissolved in acetone, and according to formula w%=[w
1÷ (w
1+ w
2)] the acetone soln of * seven water nickel nitrates that 100% configuration quality mark is 0.3%.Wherein, w% is the mass fraction of join seven water nickel nitrates in solution, w
1the quality of the seven water nickel nitrates that take for high accuracy analysis balance, w
2the quality of the acetone taking for high accuracy analysis balance.During preparation, take respectively the seven water nickel nitrates of 0.3g and the acetone of 99.7g.Seven water nickel nitrates are joined in acetone and mixed, seven water nickel nitrates are dissolved in acetone completely.Subsequently, the above-mentioned solution left standstill configuring is stand-by in atmospheric environment.
Step 6, soaks.The polyacrylonitrile-radical carbon nano-fiber reinforcement obtaining is soaked in described seven water nickel nitrate-acetone solns, and soak time is 1h.Sample is taken out, at room temperature dry in the shade.Obtain the carbon nano-fiber film that contains seven water nickel nitrates.
Step 7, chemical vapour deposition (CVD).The carbon nano-fiber film that contains seven water nickel nitrates obtaining is carried out to chemical vapour deposition (CVD), and object is growth in situ carbon nano-fiber in carbon nano-fiber film.Specifically:
The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates is placed in to chemical vapor deposition stove, and passes into nitrogen in stove, nitrogen flow is 100L/h.In chemical deposition stove, temperature rises to 300 ℃ with the speed of 10 ℃/min, and keeps 10min.In insulating process, in chemical vapor deposition stove, pass into hydrogen, the flow of described hydrogen is 40L/h.After insulation finishes, close hydrogen, and make the interior temperature of chemical deposition stove continue to rise to 650 ℃ with the speed of 10 ℃/min, and keep 10min.Between soak, in chemical vapor deposition stove, pass into propylene and hydrogen; The flow of described propylene and hydrogen is respectively 10L/h and 100L/h.When temperature retention time finishes, stop in stove, passing into propylene and hydrogen, and close heating power supply, make chemical vapor deposition stove naturally be cooled to room temperature, obtain polyacrylonitrile-radical polyacrylonitrile-based carbon nano-fiber film.In said process, keep nitrogen with the flow of 100L/h, to pass in stove all the time.
The polyacrylonitrile-based carbon nano-fiber film obtaining in the present embodiment has good pliability, and the polyacrylonitrile-radical carbon nano-fiber porous membrane that intensity is prepared than simple utilization " electrostatic spinning-high temperature cabonization " technology has improved 80%.
Example 2: the present embodiment is executed a kind of preparation method of carbon nano-fiber film, and detailed process is:
Step 1, configuration polyacrylonitrile-DMF solution.Using polyacrylonitrile as solute, and DMF, as solvent, mixes both, and polyacrylonitrile is dissolved in DMF.Wherein, in every 100ml DMF solvent, the quality of polyacrylonitrile is 15g.The polyacrylonitrile of weighing is mixed with DMF and stir, by the solution configuring standing 12h in atmospheric environment.Obtain polyacrylonitrile-DMF solution.
Utilize SS-2535DC type Electrospun spinning apparatus polyacrylonitrile based nano-fiber porous preform.Specifically:
By in 10ml polyacrylonitrile-DMF solution suction syringe.Vertical range between aluminium sheet and the spray fiber tube of SS-2535DC type Electrospun equipment is adjusted to 200mm.Start spinning.The detailed process of described spinning is: by SS-2535DC type Electrospun equipment, between spray fiber tube and aluminium sheet, applied the voltage of 13kV and keep this voltage.Polyacrylonitrile-DMF solution in syringe is sprayed to surface of aluminum plate.Due to the effect of voltage between spray fiber tube and aluminium sheet, after polyacrylonitrile-DMF solution is ejected, forms polyacrylonitrile based nano-fiber, and evenly tile, be interweaved on the surface of aluminium sheet, obtain polyacrylonitrile based nano-fiber porous preform.During injection, by regulating medical injection pump, making the ejection speed of polyacrylonitrile-DMF solution in needle tubing is 0.25ml/h, till having sprayed.
Step 3, heat treatment.To obtaining polyacrylonitrile based nano-fiber porous preform, heat-treat.
The polyacrylonitrile based nano-fiber porous preform obtaining is placed in Muffle furnace and is heat-treated.In heat treatment, the temperature of Muffle furnace is warming up to 300 ℃ with the speed of 8 ℃/min from room temperature, and keeps 2h, so that polyacrylonitrile based nano-fiber porous preform in stove is heat-treated.After heat treatment, close Muffle furnace power supply.In Muffle furnace, temperature is down to after room temperature, obtains through heat treated polyacrylonitrile based nano-fiber porous preform.
Step 4, carbonization treatment.In carbide furnace, to carrying out carbonization treatment through heat treated polyacrylonitrile based nano-fiber porous preform, prepare polypropylene-base carbon nano-fiber porous reinforcement.
To be laid between two graphite flat boards through heat treated polyacrylonitrile based nano-fiber porous preform.The graphite flat board that accompanies polyacrylonitrile based nano-fiber porous preform is positioned in the carbide furnace of nitrogen atmosphere, described polyacrylonitrile based nano-fiber porous preform is carried out to carbonization treatment.In described carbonization treatment, make carbide furnace from room temperature, be warming up to 900 ℃ and be incubated 3h with the heating rate of 2 ℃/min, obtain polyacrylonitrile-radical carbon nano-fiber porous reinforcement, stand-by.
Step 5, preparation seven water nickel nitrate-acetone solns.Utilize Sai Duolisi LA310S high accuracy analysis balance, take respectively seven water nickel nitrate and acetone of certain mass.Seven water nickel nitrates are as solute, and acetone is solvent, and both are mixed, and seven water nickel nitrates are dissolved in acetone, and according to formula w%=[w
1÷ (w
1+ w
2)] the acetone soln of * seven water nickel nitrates that 100% configuration quality mark is 0.8%.Wherein, w% is the mass fraction of join seven water nickel nitrates in solution, w
1the quality of the seven water nickel nitrates that take for high accuracy analysis balance, w
2the quality of the acetone taking for high accuracy analysis balance.During preparation, take respectively the seven water nickel nitrates of 0.8g and the acetone of 99.2g.Seven water nickel nitrates are joined in acetone and mixed, seven water nickel nitrates are dissolved in acetone completely.Subsequently, the above-mentioned solution left standstill configuring is stand-by in atmospheric environment.
Step 6, soaks.The polyacrylonitrile-radical carbon nano-fiber porous reinforcement obtaining is soaked in described seven water nickel nitrate-acetone solns, and soak time is 6h.Sample is taken out, at room temperature dry in the shade.Obtain the polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates.
Step 7, chemical vapour deposition (CVD).The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates obtaining is carried out to chemical vapour deposition (CVD), and object is growth in situ carbon nano-fiber in polyacrylonitrile-radical carbon nano-fiber porous reinforcement.Specifically:
The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates is placed in to chemical vapor deposition stove, and passes into nitrogen in stove, nitrogen flow is 100L/h.In chemical deposition stove, temperature rises to 400 ℃ with the speed of 10 ℃/min, and keeps 25min.In insulating process, in chemical vapor deposition stove, pass into hydrogen, the flow of described hydrogen is 100L/h.After insulation finishes, close hydrogen, and make the interior temperature of chemical deposition stove continue to rise to 780 ℃ with the speed of 10 ℃/min, and keep 40min.Between soak, in chemical vapor deposition stove, pass into propylene and hydrogen; The flow of described propylene and hydrogen is respectively 25L/h and 200L/h.When temperature retention time finishes, stop in stove, passing into propylene and hydrogen, and close heating power supply, make chemical vapor deposition stove naturally be cooled to room temperature, obtain polyacrylonitrile-based carbon nano-fiber film.In said process, keep nitrogen with the flow of 100L/h, to pass in stove all the time.
The polyacrylonitrile-based carbon nano-fiber film obtaining in the present embodiment has good pliability, and the polyacrylonitrile-radical carbon nano-fiber porous membrane that intensity is prepared than simple utilization " electrostatic spinning-high temperature cabonization " technology has improved 100%.
Example 3: the present embodiment is executed a kind of preparation method of carbon nano-fiber film, and detailed process is:
Step 1, configuration polyacrylonitrile-DMF solution.Using polyacrylonitrile as solute, and DMF, as solvent, mixes both, and polyacrylonitrile is dissolved in DMF.Wherein, in every 100ml DMF solvent, the quality of polyacrylonitrile is 30g.The polyacrylonitrile of weighing is mixed with DMF and stir, by the solution configuring standing 12h in atmospheric environment.Obtain polyacrylonitrile-DMF solution.
Utilize SS-2535DC type Electrospun spinning apparatus polyacrylonitrile based nano-fiber porous preform.Specifically:
By in 20ml polyacrylonitrile-DMF solution suction syringe.Vertical range between aluminium sheet and the spray fiber tube of SS-2535DC type Electrospun equipment is adjusted to 300mm.Start spinning.The detailed process of described spinning is: by SS-2535DC type Electrospun equipment, between spray fiber tube and aluminium sheet, applied the voltage of 15kV and keep this voltage.Polyacrylonitrile-DMF solution in syringe is sprayed to surface of aluminum plate.Due to the effect of voltage between spray fiber tube and aluminium sheet, after polyacrylonitrile-DMF solution is ejected, forms polyacrylonitrile based nano-fiber, and evenly tile, be interweaved on the surface of aluminium sheet, obtain polyacrylonitrile based nano-fiber porous preform.During injection, by regulating medical injection pump, making the ejection speed of polyacrylonitrile-DMF solution in needle tubing is 0.4ml/h, till having sprayed.
Step 3, heat treatment.To obtaining polyacrylonitrile based nano-fiber porous preform, heat-treat.
The polyacrylonitrile based nano-fiber porous preform obtaining is placed in Muffle furnace and is heat-treated.In heat treatment, the temperature of Muffle furnace is warming up to 350 ℃ with the speed of 10 ℃/min from room temperature, and keeps 3h, so that polyacrylonitrile based nano-fiber porous preform in stove is heat-treated.After heat treatment, close Muffle furnace power supply.In Muffle furnace, temperature is down to after room temperature, obtains through heat treated polyacrylonitrile based nano-fiber porous preform.
Step 4, carbonization treatment.In carbide furnace, to carrying out carbonization treatment through heat treated polyacrylonitrile based nano-fiber porous preform, prepare polyacrylonitrile-radical carbon nano-fiber porous reinforcement.
To be laid between two graphite flat boards through heat treated polyacrylonitrile based nano-fiber porous preform.The graphite flat board that accompanies polyacrylonitrile based nano-fiber porous preform is positioned in the carbide furnace of nitrogen atmosphere, described polyacrylonitrile based nano-fiber porous preform is carried out to carbonization treatment.In described carbonization treatment, make carbide furnace from room temperature, be warming up to 1000 ℃ and be incubated 5h with the heating rate of 3 ℃/min, obtain polyacrylonitrile-radical carbon nano-fiber porous reinforcement, stand-by.
Step 5, preparation seven water nickel nitrate-acetone solns.Utilize Sai Duolisi LA310S high accuracy analysis balance, take respectively seven water nickel nitrate and acetone of certain mass.Seven water nickel nitrates are as solute, and acetone is solvent, and both are mixed, and seven water nickel nitrates are dissolved in acetone, and according to formula w%=[w
1÷ (w
1+ w
2)] the acetone soln of * seven water nickel nitrates that 100% configuration quality mark is 2.0%.Wherein, w% is the mass fraction of join seven water nickel nitrates in solution, w
1the quality of the seven water nickel nitrates that take for high accuracy analysis balance, w
2the quality of the acetone taking for high accuracy analysis balance.During preparation, take respectively the seven water nickel nitrates of 2g and the acetone of 98g.Seven water nickel nitrates are joined in acetone and mixed, seven water nickel nitrates are dissolved in acetone completely.Subsequently, the above-mentioned solution left standstill configuring is stand-by in atmospheric environment.
Step 6, soaks.The polyacrylonitrile-radical carbon nano-fiber porous reinforcement obtaining is soaked in described seven water nickel nitrate-acetone solns, and soak time is 12h.Sample is taken out, at room temperature dry in the shade.Obtain the polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates.
Step 7, chemical vapour deposition (CVD).The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates obtaining is carried out to chemical vapour deposition (CVD), and object is growth in situ carbon nano-fiber in polyacrylonitrile-radical carbon nano-fiber porous reinforcement.Specifically:
The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates is placed in chemical vapor deposition stove, and passes into nitrogen in stove, and nitrogen flow is 100L/h.In chemical deposition stove, temperature rises to 500 ℃ with the speed of 10 ℃/min, and keeps 40min.In insulating process, in chemical vapor deposition stove, pass into hydrogen, the flow of described hydrogen is 200L/h.After insulation finishes, close hydrogen, and make the interior temperature of chemical deposition stove continue to rise to 850 ℃ with the speed of 10 ℃/min, and keep 60min.Between soak, in chemical vapor deposition stove, pass into propylene and hydrogen; The flow of described propylene and hydrogen is respectively 40L/h and 300L/h.When temperature retention time finishes, stop in stove, passing into propylene and hydrogen, and close heating power supply, make chemical vapor deposition stove naturally be cooled to room temperature, obtain polyacrylonitrile-based carbon nano-fiber film.In said process, keep nitrogen with the flow of 100L/h, to pass in stove all the time.
The polyacrylonitrile-based carbon nano-fiber film obtaining in the present embodiment has good pliability, and the polyacrylonitrile-radical carbon nano-fiber porous membrane that intensity is prepared than simple utilization " electrostatic spinning-high temperature cabonization " technology has improved 120%.
Claims (2)
1. a preparation method for carbon nano-fiber film, is characterized in that, detailed process is:
Step 1, configuration polyacrylonitrile-DMF solution:
Step 2, spinning:
By in 5ml polyacrylonitrile-DMF solution suction syringe; Vertical range between aluminium sheet and the spray fiber tube of Electrospun equipment is adjusted to 100～300mm; Adopt conventional method spinning; In described spinning process, between spray fiber tube and aluminium sheet, apply the voltage of 10～15kV and keep this voltage; It is 0.1～0.4ml/h that polyacrylonitrile-DMF solution sprays to the ejection speed of surface of aluminum plate;
Step 3, heat treatment:
To obtaining polyacrylonitrile based nano-fiber porous preform, heat-treat;
Adopt conventional method to heat-treat the polyacrylonitrile based nano-fiber porous preform obtaining; In heat treatment, the temperature of Muffle furnace is warming up to 250～350 ℃ with the speed of 5～10 ℃/min from room temperature, and is incubated 1～3h; After insulation finishes, obtain through heat treated polyacrylonitrile based nano-fiber porous preform;
Step 4, carbonization treatment:
In carbide furnace, to carrying out carbonization treatment through heat treated polyacrylonitrile based nano-fiber porous preform, prepare polyacrylonitrile-radical carbon nano-fiber porous reinforcement;
To be laid between two graphite flat boards through heat treated polyacrylonitrile based nano-fiber porous preform; The graphite flat board that accompanies polyacrylonitrile based nano-fiber porous preform is positioned in the carbide furnace of nitrogen atmosphere, described polyacrylonitrile based nano-fiber porous preform is carried out to carbonization treatment; In described carbonization treatment, make carbide furnace from room temperature, be warming up to 800～1000 ℃ and be incubated 1～5h with the heating rate of 1～3 ℃/min, obtain polyacrylonitrile-radical carbon nano-fiber reinforcement, stand-by;
Step 5, preparation seven water nickel nitrate-acetone solns:
Adopt conventional method, according to formula w%=[w
1÷ (w
1+ w
2)] * 100% preparation seven water nickel nitrate-acetone solns, wherein, W% is the mass fraction of seven water nickel nitrates, w
1be the quality of seven water nickel nitrates, w
2quality for acetone; In described seven water nickel nitrate-acetone solns, the mass fraction of seven water nickel nitrates is 0.3～2.0%; The seven water nickel nitrate-acetone solns that obtain configuring, and be statically placed in atmospheric environment stand-by;
Step 6, soak:
The polyacrylonitrile-radical carbon nano-fiber reinforcement obtaining is soaked in described seven water nickel nitrate-acetone solns, and soak time is to take out after 1～12h, at room temperature dries in the shade; Obtain the carbon nano-fiber film that contains seven water nickel nitrates;
Step 7, chemical vapour deposition (CVD):
The carbon nano-fiber film that contains seven water nickel nitrates obtaining is carried out to chemical vapour deposition (CVD), with growth in situ carbon nano-fiber in carbon nano-fiber film; Specifically:
The polyacrylonitrile-radical carbon nano-fiber porous reinforcement that contains seven water nickel nitrates is placed in to chemical vapor deposition stove, and passes into nitrogen in stove, nitrogen flow is 100L/h; In chemical deposition stove, temperature rises to 300～500 ℃ with the speed of 10 ℃/min, and keeps 10～40min; In insulating process, in chemical vapor deposition stove, pass into hydrogen, the flow of described hydrogen is 40～200L/h; After insulation finishes, close hydrogen, and make the interior temperature of chemical deposition stove continue to rise to 650～850 ℃ with the speed of 10 ℃/min, and keep 10～60min; Between soak, in chemical vapor deposition stove, pass into propylene and hydrogen; The flow of described propylene and hydrogen is respectively 10～40L/h and 100～300L/h; When temperature retention time finishes, stop in stove, passing into propylene and hydrogen, and close heating power supply, make chemical vapor deposition stove naturally be cooled to room temperature, obtain polyacrylonitrile-radical polyacrylonitrile-based carbon nano-fiber film; In said process, keep nitrogen with the flow of 100L/h, to pass in stove all the time.
2. the preparation method of carbon nano-fiber film as claimed in claim 1, is characterized in that, during configuration polyacrylonitrile-DMF solution, using polyacrylonitrile as solute, and DMF is as solvent, both are mixed, polyacrylonitrile is dissolved in DMF; Wherein, in every 100ml DMF solvent, the quality of polyacrylonitrile is 5g～30g; The polyacrylonitrile of weighing is mixed with DMF and stir, standing 12h in atmospheric environment; Obtain polyacrylonitrile-DMF solution.
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