CN110148726B - Graphene-coated PAN-based ladder-shaped polymer ultra-short nanofiber, and preparation method and application thereof - Google Patents
Graphene-coated PAN-based ladder-shaped polymer ultra-short nanofiber, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of preparation of nano fibers, and provides a preparation method of graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers, which at least comprises the following steps: (1) impregnating a polyacrylonitrile fiber felt and/or a non-woven fabric with the graphene dispersion liquid, drying and cutting into strips; (2) hot air drawing is carried out on the strip at the temperature of 80-150 ℃, and a graphene coated PAN electrospun oriented fiber tow is prepared; (3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain the graphene-coated PAN-based ladder-shaped polymer ultrashort nanofiber.
Description
Technical Field
The invention relates to the field of preparation of nano fibers, in particular to a graphene-coated PAN-based ladder-shaped polymer ultrashort nano fiber, and a preparation method and application thereof.
Background
With the continuous development of social economy, the global demand for novel fibers with special functions is increasing, and particularly, fibers with high strength and high conductivity are gradually explored and applied to the fields of reinforcing materials, functional clothing, new energy electrodes, electromagnetic fields, military affairs and the like. Modified fiber materials have become one of the hot spots in the field of composite research.
Graphene (Graphene) is a novel inorganic material, is made of cheap graphite, has the ultimate modulus of 1.01TPa and the ultimate strength of 116GPa, and has high thermal conductivity, high specific surface area and excellent electron transmission property, so that the Graphene is an ideal material for coating and modifying the surface of nanofiber, the surface of trapezoidal polymer nano short fiber is coated and modified by the Graphene, the thermal conductivity and the electric conductivity when the Graphene is used as an electrode material are greatly improved, and the rapid development of the new energy battery industry is promoted.
The ladder-shaped polymer is a high-performance polymer, the ladder-shaped polymer fiber formed by preoxidation and cyclization of Polyacrylonitrile (PAN) fiber is a high-performance polymer fiber, has excellent electrochemical performance besides the characteristics of high strength, high modulus, high temperature resistance and the like, is used as a new energy electrode material, has the theoretical storage capacity up to 2300mAh/g and is more than 6 times of the theoretical capacity of a graphite electrode, and is hopefully developed into a new energy electrode material with ultrahigh specific capacity. However, the conductivity of the trapezoidal polymer is lower and is less than 10-6S/cm, which is not as good as that of a semiconductor. As an electrode material, good conductivity is a key to fully exert the electricity storage function, and therefore, it is very necessary to develop a trapezoidal polymer nano short fiber with good conductivity and high dispersibility in order to create a new energy battery electrode material with ultrahigh electricity storage capacity.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing graphene-coated PAN-based ladder polymer ultrashort nanofibers, comprising the steps of:
(1) impregnating a polyacrylonitrile fiber felt and/or a non-woven fabric with the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drawing is carried out on the strip at the temperature of 80-150 ℃, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain the graphene-coated PAN-based ladder-shaped polymer ultrashort nanofiber.
As a preferable technical scheme, the solid content of the graphene dispersion liquid is 0.1-2 wt%.
In a preferred embodiment, the width of the strip is 0.5-5 cm.
As a preferable technical solution, in the present invention, the hot air drawing in the step (2) is two-stage hot air drawing: the first stage drafting temperature is 85-100 ℃, and the drafting ratio is 1-3 times; the second stage drawing temperature is 125-150 ℃, and the drawing ratio is 2-8 times.
As a preferable technical proposal, the temperature of the air oxidation is 210-270 ℃ and the time is 1.5-3.5 hours.
As a preferable technical scheme, the temperature of the inert gas cyclization in the invention is 350-620 ℃, and the time is 30-90 minutes.
In a preferred embodiment of the present invention, the inert gas is at least one selected from the group consisting of argon, helium, nitrogen, and neon.
As a preferable technical scheme, the length of the graphene-coated PAN-based ladder-shaped polymer ultrashort nano-fiber is 0.1-0.8 mm.
The invention provides a graphene-coated PAN-based ladder-shaped polymer ultra-short nanofiber prepared by the preparation method.
The third aspect of the invention provides an application of the graphene-coated PAN-based ladder-shaped polymer ultrashort nanofiber prepared by the preparation method, which is applied to manufacturing polymer composite materials and used as electrode materials.
The technical features, content and advantages described in the previous sections of the invention will be more readily understood by reference to the following details.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. The sources of components not mentioned in the present invention are all commercially available.
The invention provides a preparation method of a graphene-coated PAN-based ladder polymer ultrashort nano fiber, which at least comprises the following steps:
(1) impregnating a polyacrylonitrile fiber felt and/or a non-woven fabric with the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drawing is carried out on the strip at the temperature of 80-150 ℃, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain the graphene-coated PAN-based ladder-shaped polymer ultrashort nanofiber.
The polyacrylonitrile is not specially limited, and the polyacrylonitrile which is generally purchased can be used in the invention, wherein PAN is the abbreviation of polyacrylonitrile; the polyacrylonitrile in the invention is purchased from Zhengzhou alpha chemical company Limited, model 25014-41-9.
In some embodiments, the drying temperature in step (1) is 80 ℃ to 110 ℃; preferably, the drying temperature in the step (1) is 100 ℃.
The drying temperature in the step (1) of the invention is 100 ℃.
In some embodiments, the electrospun polyacrylonitrile nanofiber mats and/or nonwovens of the present invention have a fiber diameter of 100-1500 nm; preferably, the electrospun polyacrylonitrile nanofiber felt and/or the nonwoven fabric have the fiber diameter of 300-1200 nm; more preferably, the electrospun polyacrylonitrile nanofiber felt and/or the nonwoven fabric have the fiber diameter of 500-1000 nm; further preferably, the electrospun polyacrylonitrile nanofiber felt or the nonwoven fabric has the fiber diameter of 700-900 nm; most preferably, the electrospun polyacrylonitrile nanofiber mat or the nonwoven fabric has a fiber diameter of 800 nm.
In some embodiments, the polyacrylonitrile fiber felt and/or the non-woven fabric in the step (1) is prepared by the following steps: adding polyacrylonitrile and a proper amount of solvent into a polymerization reaction kettle, stirring and dissolving to obtain a polyacrylonitrile solution, performing high-voltage electric field electrostatic spinning, and collecting by using a stainless steel mesh belt as a collector to obtain the electro-spun polyacrylonitrile nanofiber felt and/or the non-woven fabric.
In some embodiments, the solvent of the present invention is a polar organic solvent.
In some embodiments, the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, N-dimethylacetamide; preferably, the polar organic solvent is selected from one or more of N-methyl pyrrolidone, dimethyl sulfoxide and N, N-dimethyl acetamide; more preferably, the polar organic solvent is selected from one or more of N-methyl pyrrolidone, N-dimethyl acetamide; most preferably, the polar organic solvent is N, N-dimethylacetamide.
In some embodiments, the temperature for stirring and dissolving in the polymerization reaction kettle is 25-50 ℃, and the stirring and dissolving time is 5-15 hours; preferably, the temperature for stirring and dissolving in the polymerization reaction kettle is 30-45 ℃, and the time for stirring and dissolving is 8-12 hours; more preferably, the temperature for stirring and dissolving in the polymerization reaction kettle is 40 ℃, and the stirring and dissolving time is 10 hours.
In some embodiments, the absolute viscosity of the polyacrylonitrile solution is in the range of 1.5 to 5.5Pa · s; preferably, the absolute viscosity of the polyacrylonitrile solution is 2-5 Pa.s; more preferably, the absolute viscosity of the polyacrylonitrile solution is 3Pa · s.
The absolute viscosity values described in the present invention were measured using a digital display viscometer SNB-1.
In some embodiments, the collector is spaced from the spinning nozzle by 30-60 cm; preferably, the distance between the collector and the spinneret is 35-55 cm; more preferably, the distance between the collector and the spinning nozzle is 40-50 cm; most preferably, the collector is spaced 45cm from the spinning nozzle.
In some embodiments, the stainless steel mesh belt has a belt speed of 1 to 5 m/min; preferably, the belt traveling speed of the stainless steel mesh belt is 2-4 m/min; more preferably, the belt traveling speed of the stainless steel mesh belt is 3 m/min.
In some embodiments, the electric field strength of the high-voltage electric field is 300-500 kV/m; preferably, the electric field intensity of the high-voltage electric field is 350-450 kV/m; more preferably, the electric field intensity of the high-voltage electric field is 400 kV/m.
In some embodiments, the solid content in the graphene dispersion is 0.1-2 wt%; preferably, the solid content in the graphene dispersion liquid is 0.5-1.5 wt%; more preferably, the solid content in the graphene dispersion liquid is 0.6-1 wt%; further preferably, the solid content in the graphene dispersion liquid is 0.7 wt%.
In some embodiments, a dispersant is further included in the graphene dispersion.
In some embodiments, the weight ratio of dispersant to graphene in the graphene dispersion is 1 (0.1-1); preferably, the weight ratio of the dispersing agent to the graphene in the graphene dispersion liquid is 1 (0.5-1); more preferably, the weight ratio of the dispersing agent to the graphene in the graphene dispersion liquid is 1 (0.6-0.9); most preferably, the weight ratio of the dispersing agent to the graphene in the graphene dispersion liquid is 1: 0.8.
In some embodiments, the solvent of the graphene dispersion is water.
In some embodiments, the dispersant is not particularly limited, and is preferably polyethyleneimine; the CAS number of the polyethyleneimine is 9002-98-6, and a purchasing manufacturer does not make special limitation and can be applied to the polyethyleneimine; the polyethyleneimine described in the present invention is purchased from the company Gobekie, GBK-PEI 9 series.
In some embodiments, the width of the strip is 0.5-5 cm; preferably, the width of the strip is 1-4 cm; more preferably, the width of the strip is 2-3 cm; further preferably, the width of the strip is 2.5 cm.
In some embodiments, the hot air draw in step (2) is a two-stage hot air draw: the first stage drafting temperature is 85-100 ℃, and the drafting ratio is 1-3 times; the second stage drawing temperature is 125-150 ℃, and the drawing ratio is 2-8 times.
In some embodiments, the hot air draw in step (2) is a two-stage hot air draw: the first-stage drafting temperature is 85-100 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber non-woven fabric strip coil is 2-8 m/min, and the drafting ratio is 1-3 times; the second stage drawing temperature is 125-150 ℃, the unwinding speed is 3-8 m/min, and the drawing ratio is 2-8 times.
In some preferred embodiments, the hot air drawing in step (2) is a two-stage hot air drawing: the first stage drafting temperature is 90-95 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber non-woven fabric strip coil is 3-7 m/min, and the drafting ratio is 1.5-2.5 times; the second stage drafting temperature is 135-145 ℃, the unwinding speed is 4-8 m/min, and the drafting ratio is 4-7 times.
In some more preferred embodiments, the hot air drawing in step (2) is a two-stage hot air drawing: the first-stage drafting temperature is 92 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber non-woven fabric strip coil is 5m/min, and the drafting ratio is 2 times; the second stage drafting temperature is 140 ℃, the unreeling speed is 6 m/min, and the drafting ratio is 5.5 times.
The applicant finds that the polyacrylonitrile fiber felt and/or the non-woven fabric are/is firstly soaked in the graphene dispersion liquid and then subjected to air hot drawing in two temperature stages to form continuous fiber bundles with fiber filaments in parallel orientation, and particularly, the applicant finds that the graphene dispersion liquid with the solid content of 0.1-2 wt% is adopted in the invention, and the preparation of the nano fiber bundles which are coated with graphene on the surface of the fiber and can form macromolecules in the fiber bundles in high orientation can be finally realized under the conditions of specific drawing ratio and drawing temperature; the reason is that the electrospun polyacrylonitrile nano-fiber filament bundle can slide well in the drawing and drawing process by adopting the graphene with the mass concentration of 1-5 wt%, so that knotting or adhesion between the fiber filaments is avoided, the graphene can be facilitated to permeate into polyacrylonitrile molecules and fiber surface layers under the condition of high hot air drafting, the adhesion amount of the graphene molecules can be effectively improved, and in addition, the influence of the permeated graphene molecules on the molecular orientation of the fiber bundle can be avoided through the two-stage hot air drafting.
In some embodiments, the temperature of the air oxidation is 210-; preferably, the temperature of the air oxidation is 230-260 ℃, and the time is 2-3 hours; more preferably, the temperature of the air oxidation is 250 ℃ and the time is 2.5 hours.
In some embodiments, the temperature of the inert gas cyclization is 350-620 ℃ for 30-90 minutes; preferably, the temperature for the inert gas cyclization is 380-600 ℃, and the time is 40-80 minutes; more preferably, the temperature of the inert gas cyclization is 400-550 ℃, and the time is 50-70 minutes; further preferably, the temperature of the inert gas cyclization is 520 ℃ and the time is 60 minutes.
In some embodiments, the inert gas is selected from at least one of argon, helium, nitrogen, neon; preferably, the inert gas is selected from at least one of argon, helium and nitrogen; more preferably, the inert gas is selected from at least one of argon and helium; further preferably, the inert gas is argon.
According to the invention, the PAN electrospun oriented fiber tows are coated on the graphene, air oxidation is carried out at the temperature of 270 ℃ for 1.5-3.5 hours in a temperature range of 210 ℃ and inert gas cyclization is carried out at the temperature of 620 ℃ for 30-90 minutes in a temperature range of 350 ℃ so as to prepare the PAN-based ladder-shaped polymer nanofiber oriented tows coated on the graphene, which have good conductivity and can be used as electrode materials. Probably because PAN electrospun fiber tows are subjected to air oxidation at the temperature of 210 ℃ and 270 ℃ for 1.5-3.5 hours and inert gas cyclization at the temperature of 350 ℃ and 620 ℃ for 30-90 minutes to form PAN-based ladder-shaped polymer which is an intermediate product in the PAN carbonization process, the applicant unexpectedly finds that the formed PAN-based ladder-shaped polymer can be used as an electrode material to store electric energy, and the highly oriented PAN fiber tows coated by graphene can not only improve the fiber conductivity but also promote the conversion of the PAN-based ladder-shaped polymer due to the action of the graphene under the special oxidation and cyclization conditions, so that the conductivity of the PAN-based ladder-shaped polymer nanofiber is further improved, and the application field of the material is widened.
In some embodiments, the graphene-coated PAN-based ladder polymer ultrashort nanofibers have a length of 0.1-0.8 mm; preferably, the length of the graphene-coated PAN-based ladder polymer ultra-short nanofiber is 0.2-0.7 mm; more preferably, the graphene-coated PAN-based ladder polymer ultra-short nanofibers have a length of 0.3-0.5 mm; further preferably, the length of the graphene-coated PAN-based ladder polymer ultra-short nanofiber is 0.4 mm.
In some embodiments, the graphene-coated PAN-based ladder polymer ultrashort-nanofibers are cut using a mechanical cutting knife or a laser slitter.
The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.
Example 1
The preparation method of the ultra-short nanofiber with the graphene coated PAN-based ladder-shaped polymer comprises the following steps:
(1) soaking a polyacrylonitrile non-woven fabric in the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drafting is carried out on the strip, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers;
the preparation of the polyacrylonitrile non-woven fabric in the step (1) is as follows: adding polyacrylonitrile and a proper amount of solvent into a polymerization reaction kettle, stirring and dissolving to obtain a polyacrylonitrile solution, performing high-voltage electric field electrostatic spinning, and collecting by using a stainless steel mesh belt as a collector to obtain the electro-spun polyacrylonitrile nano non-woven fabric; the electro-spun polyacrylonitrile nano non-woven fabric has the fiber diameter of 820 nm; the solvent is N, N-dimethylacetamide, and the CAS number is 127-19-5; the stirring and dissolving temperature in the polymerization reaction kettle is 40 ℃, and the stirring and dissolving time is 10 hours; the absolute viscosity of the polyacrylonitrile solution is 3.1 Pa.s; the distance between the collector and the spinning nozzle is 45 cm; the belt travelling speed of the stainless steel mesh belt is 3 m/min; the electric field intensity of the high-voltage electric field is 400 kV/m;
the solid content of the graphene dispersion liquid is 0.7 wt%, the graphene dispersion liquid also comprises a dispersing agent, and the weight ratio of the dispersing agent to graphene in the graphene dispersion liquid is 1: 0.8; the width of the strip is 2.5 cm; the hot air drafting in the step (2) is two-section hot air drafting: the first-stage drafting temperature is 92 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber non-woven fabric strip coil is 5m/min, and the drafting ratio is 2 times; the second section drafting temperature is 140 ℃, the unreeling speed is 6 m/min, and the drafting ratio is 5.5 times; the temperature of the air oxidation is 250 ℃, and the time is 2.5 hours; the temperature of the inert gas cyclization is 520 ℃, and the time is 60 minutes; the inert gas is argon; the length of the graphene-coated PAN-based ladder-shaped polymer ultra-short nanofiber is 0.4 mm; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2500 meters.
Example 2
The preparation method of the ultra-short nanofiber with the graphene coated PAN-based ladder-shaped polymer comprises the following steps:
(1) impregnating a polyacrylonitrile fiber felt into the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drafting is carried out on the strip, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers;
the preparation of the polyacrylonitrile fiber felt in the step (1) is as follows: adding polyacrylonitrile and a proper amount of solvent into a polymerization reaction kettle, stirring and dissolving to obtain a polyacrylonitrile solution, performing high-voltage electric field electrostatic spinning, and collecting to obtain an electro-spun polyacrylonitrile nanofiber felt by using a stainless steel mesh belt as a collector; the electrospun polyacrylonitrile nanofiber felt is characterized in that the fiber diameter is 110 nm; the solvent is N, N-dimethylacetamide, and the CAS number is 127-19-5; the stirring and dissolving temperature in the polymerization reaction kettle is 25 ℃, and the stirring and dissolving time is 5 hours; the absolute viscosity of the polyacrylonitrile solution is 1.6 Pa.s; the distance between the collector and the spinning nozzle is 30 cm; the belt travelling speed of the stainless steel mesh belt is 1 m/min; the electric field intensity of the high-voltage electric field is 300 kV/m;
the solid content of the graphene dispersion liquid is 0.1 wt%, the graphene dispersion liquid also comprises a dispersing agent, and the weight ratio of the dispersing agent to graphene in the graphene dispersion liquid is 1: 0.1; the width of the strip is 0.5 cm; the hot air drafting in the step (2) is two-section hot air drafting: the first-stage drafting temperature is 85 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber felt strip coil is 2m/min, and the drafting ratio is 1 time; the second section drafting temperature is 125 ℃, the unwinding speed is 3m/min, and the drafting ratio is 2 times; the temperature of the air oxidation is 210 ℃, and the time is 1.5 hours; the temperature of the inert gas cyclization is 350 ℃, and the time is 30 minutes; the inert gas is argon; the length of the graphene-coated PAN-based ladder-shaped polymer ultrashort nano fiber is 0.1 mm; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 1500 meters.
Example 3
The preparation method of the ultra-short nanofiber with the graphene coated PAN-based ladder-shaped polymer comprises the following steps:
(1) impregnating a polyacrylonitrile fiber felt into the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drafting is carried out on the strip, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers;
the preparation of the polyacrylonitrile fiber felt in the step (1) is as follows: adding polyacrylonitrile and a proper amount of solvent into a polymerization reaction kettle, stirring and dissolving to obtain a polyacrylonitrile solution, performing high-voltage electric field electrostatic spinning, and collecting to obtain an electro-spun polyacrylonitrile nanofiber felt by using a stainless steel mesh belt as a collector; the diameter of the electrospun polyacrylonitrile nanofiber felt is 1530 nm; the solvent is N, N-dimethylacetamide, and the CAS number is 127-19-5; the stirring and dissolving temperature in the polymerization reaction kettle is 50 ℃, and the stirring and dissolving time is 15 hours; the absolute viscosity of the polyacrylonitrile solution is 5.3 Pa.s; the distance between the collector and the spinning nozzle is 60 cm; the belt travelling speed of the stainless steel mesh belt is 5 m/min; the electric field intensity of the high-voltage electric field is 500 kV/m;
the solid content of the graphene dispersion liquid is 2 wt%, the graphene dispersion liquid also comprises a dispersing agent, and the weight ratio of the dispersing agent to graphene in the graphene dispersion liquid is 1: 1; the width of the strip is 5 cm; the hot air drafting in the step (2) is two-section hot air drafting: the first-stage drafting temperature is 100 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber felt strip coil is 8 m/min, and the drafting ratio is 3 times; the second section drafting temperature is 150 ℃, the unreeling speed is 8 m/min, and the drafting ratio is 8 times; the temperature of the air oxidation is 270 ℃, and the time is 3.5 hours; the temperature of the inert gas cyclization is 620 ℃, and the time is 90 minutes; the inert gas is helium; the length of the graphene-coated PAN-based ladder-shaped polymer ultrashort nano fiber is 0.8 mm; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Example 4
The preparation method of the ultra-short nanofiber with the graphene coated PAN-based ladder-shaped polymer comprises the following steps:
(1) soaking a polyacrylonitrile non-woven fabric in the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drafting is carried out on the strip, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers;
the preparation of the polyacrylonitrile non-woven fabric in the step (1) is as follows: adding polyacrylonitrile and a proper amount of solvent into a polymerization reaction kettle, stirring and dissolving to obtain a polyacrylonitrile solution, performing high-voltage electric field electrostatic spinning, and collecting by using a stainless steel mesh belt as a collector to obtain the electro-spun polyacrylonitrile nano non-woven fabric; the diameter of the electro-spun polyacrylonitrile nano non-woven fabric is 520 nm; the solvent is N, N-dimethylacetamide, and the CAS number is 127-19-5; the stirring and dissolving temperature in the polymerization reaction kettle is 30 ℃, and the stirring and dissolving time is 8 hours; the absolute viscosity of the polyacrylonitrile solution is 2.2 Pa.s; the distance between the collector and the spinning nozzle is 35 cm; the belt travelling speed of the stainless steel mesh belt is 2 m/min; the electric field intensity of the high-voltage electric field is 350 kV/m;
the solid content of the graphene dispersion liquid is 0.5 wt%, the graphene dispersion liquid also comprises a dispersing agent, and the weight ratio of the dispersing agent to graphene in the graphene dispersion liquid is 1: 0.5; the width of the strip is 1 cm; the hot air drafting in the step (2) is two-section hot air drafting: the first-stage drafting temperature is 90 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber non-woven fabric strip coil is 3m/min, and the drafting ratio is 1.5 times; the second section drafting temperature is 135 ℃, the unreeling speed is 4m/min, and the drafting ratio is 4 times; the temperature of the air oxidation is 230 ℃, and the time is 2 hours; the temperature of the inert gas cyclization is 400 ℃, and the time is 50 minutes; the inert gas is helium; the length of the graphene-coated PAN-based ladder-shaped polymer ultrashort nano fiber is 0.2 mm; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Example 5
The preparation method of the ultra-short nanofiber with the graphene coated PAN-based ladder-shaped polymer comprises the following steps:
(1) soaking a polyacrylonitrile non-woven fabric in the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drafting is carried out on the strip, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers;
the preparation of the polyacrylonitrile non-woven fabric in the step (1) is as follows: adding polyacrylonitrile and a proper amount of solvent into a polymerization reaction kettle, stirring and dissolving to obtain a polyacrylonitrile solution, performing high-voltage electric field electrostatic spinning, and collecting by using a stainless steel mesh belt as a collector to obtain the electro-spun polyacrylonitrile nano non-woven fabric; the diameter of the electro-spun polyacrylonitrile nano non-woven fabric is 1080 nm; the solvent is N, N-dimethylacetamide, and the CAS number is 127-19-5; the stirring and dissolving temperature in the polymerization reaction kettle is 45 ℃, and the stirring and dissolving time is 12 hours; the absolute viscosity of the polyacrylonitrile solution is 5.1 Pa.s; the distance between the collector and the spinning nozzle is 55 cm; the belt travelling speed of the stainless steel mesh belt is 4 m/min; the electric field intensity of the high-voltage electric field is 450 kV/m;
the solid content of the graphene dispersion liquid is 1 wt%, the graphene dispersion liquid also comprises a dispersing agent, and the weight ratio of the dispersing agent to graphene in the graphene dispersion liquid is 1: 0.9; the width of the strip is 4 cm; the hot air drafting in the step (2) is two-section hot air drafting: the first-stage drafting temperature is 95 ℃, the unreeling speed of the graphene coated electro-spinning PAN fiber non-woven fabric strip coil is 7 m/min, and the drafting ratio is 2.5 times; the second section drafting temperature is 145 ℃, the unreeling speed is 8 m/min, and the drafting ratio is 4 times; the temperature of the air oxidation is 260 ℃, and the time is 3 hours; the temperature of the inert gas cyclization is 550 ℃, and the time is 70 minutes; the inert gas is argon; the length of the graphene-coated PAN-based ladder-shaped polymer ultrashort nano fiber is 0.5 mm; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Comparative example 1
The difference from example 1 is that the concentration of the graphene dispersion is 3 wt%; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 1500 meters.
Comparative example 2
The difference from example 1 is that the temperature of air oxidation is 150 ℃ and the temperature of inert gas cyclization is 300 ℃; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Comparative example 3
The difference from example 1 is that the temperature of the inert gas cyclization is 300 ℃; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Comparative example 4
The difference from example 1 is that the temperature of the inert gas cyclization is 800 ℃; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Comparative example 5
The difference from example 1 is that the time for the inert gas cyclization is 20 minutes; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2500 meters.
Comparative example 6
The difference from example 1 is that the time for the inert gas cyclization is 120 minutes; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 2000 meters.
Comparative example 7
The difference from the example 1 is that the hot air drawing in the step (2) is a one-stage hot air drawing; the continuous length of the graphene-coated PAN-based ladder polymer nanofiber oriented tows is more than 1500 meters.
Performance testing
The graphene-coated PAN-based ladder-shaped polymer nano-fibers prepared in examples 1-5 and comparative examples 1-7 are subjected to mechanical strength, conductivity and orientation degree tests, wherein the conductivity is tested by GB T32993-2016, the breaking strength and the breaking elongation are tested by GB/T14337-1993, and the orientation degree is tested by a wide-angle X-ray diffraction method; the test results are shown in table 1.
Table 1 results of performance testing
The foregoing examples are illustrative only, and serve to explain some of the features of the present disclosure. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. And that advances in science and technology will result in possible equivalents or sub-substitutes not currently contemplated for reasons of inaccuracy in language representation, and such changes should also be construed where possible to be covered by the appended claims.
Claims (6)
1. The preparation method of the ultra-short nanofiber with the PAN-based ladder-shaped polymer coated with the graphene is characterized by at least comprising the following steps:
(1) impregnating a polyacrylonitrile fiber felt and/or a non-woven fabric with the graphene dispersion liquid, drying and cutting into strips;
(2) hot air drawing is carried out on the strip at the temperature of 80-150 ℃, and a graphene coated PAN electrospun oriented fiber tow is prepared;
(3) carrying out air oxidation on the electrospun oriented fiber tows, cyclizing the electrospun oriented fiber tows by inert gas to form graphene-coated PAN-based ladder-shaped polymer nanofiber oriented tows, and further cutting the oriented tows to obtain graphene-coated PAN-based ladder-shaped polymer ultrashort nano fibers;
the width of the strip is 0.5-5 cm;
the hot air drafting in the step (2) is two-section hot air drafting: the first stage drafting temperature is 85-100 ℃, and the drafting ratio is 1-3 times; the second section drafting temperature is 125-150 ℃, and the drafting ratio is 2-8 times;
the temperature of the air oxidation is any one of 230-260 ℃, and the time is 2-3 hours;
the temperature of the inert gas cyclization is any one of 350-620 ℃, and the time is 30-90 minutes;
the graphene dispersion liquid also comprises a dispersing agent; the dispersant is polyethyleneimine; the weight ratio of the dispersing agent to the graphene in the graphene dispersion liquid is 1 (0.1-1).
2. The method of claim 1, wherein the graphene dispersion has a solid content of 0.1 to 2 wt%.
3. The method according to claim 1, wherein the inert gas is at least one selected from the group consisting of argon, helium, nitrogen, and neon.
4. The method of claim 1, wherein the graphene-coated PAN-based ladder polymer ultrashort nanofibers have a length of 0.1-0.8 mm.
5. A graphene-coated PAN-based ladder polymer ultra-short nanofiber prepared by the preparation method of any one of claims 1-4.
6. Use of the ultra-short nanofiber prepared from the graphene-coated PAN-based ladder polymer according to any one of claims 1-4 in the preparation of polymer composite materials and as electrode materials.
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