CN108611793B - Preparation method of high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt - Google Patents
Preparation method of high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Abstract
A preparation method of a high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt belongs to the technical field of carbon fiber preparation. In the process of pre-oxidizing the electrospun polyacrylonitrile fiber felt, severe cyclization reaction and oxidation reaction in the pre-oxidation stage are avoided through at least three-stage (multi-temperature zone) short-time pre-oxidation, so that the phenomenon that the fiber is partially broken and loosened due to excessive structural defects in the fiber in the carbonization process is reduced, and the tensile strength of the carbon fiber felt is greatly improved. Further, the carbon fiber structure is prevented from being damaged due to serious decarburization caused by too long oxidation reaction caused by long-time preoxidation in the carbonization process, and the tensile strength of the carbon nanofiber felt is improved. The method can effectively improve the mechanical property of the electrostatic spinning acrylonitrile carbon nanofiber felt and improve the production efficiency.
Description
Technical Field
The invention relates to a preparation method of a high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt. Particularly, the three-stage (multi-temperature zone) short time is adopted to control the pre-oxidation time of the electrostatic spinning polyacrylonitrile fiber felt, the internal structure defects of the fibers during carbonization are reduced, and the mechanical properties of the carbon nanofiber felt are greatly improved.
Background
The electrostatic spinning carbon nanofiber felt has the advantages of large surface area (derived from the diameter of nanofibers), relatively high conductivity, complete structure, good electrochemical performance, good adsorption performance and the like, and is often applied to electrode materials of capacitors, electrochemical capacitance desalination carbon fiber nets, filter media, adsorption layers in protective clothing and the like. However, the improvement of the mechanical properties of the carbon fiber felt is currently a bottleneck. The carbon fiber felt has disadvantages in that: 1) brittle, 2) brittle, 3) poor mechanical properties. The strength of the electrostatic spinning PAN-based carbon nanofiber felt obtained by the current general test is not more than 100MPa, and the poor mechanical property is the reason that the electrostatic spinning PAN-based carbon nanofiber felt cannot be applied in a large range.
The carbon fiber belongs to a brittle material, and the mechanical property of the material is determined by two factors, namely the mechanical property of the material, namely the tensile strength; the second is self structural defect, the strength is determined by the structure, and the structure comprises a high-order morphological structure, an aggregation structure, a chemical structure and the like. The preoxidation process plays a decisive role in the mechanical properties of the carbon fibers. Therefore, the method effectively improves the pre-oxidation process, reduces the pre-oxidation time, and is the key for further improving the mechanical property of the carbon fiber.
However, the problem of preoxidation of the electrospun acrylonitrile non-woven fabric is not paid enough attention by the existing research, most researchers consider the problem of preoxidation of the traditional micron-sized precursor, and carry out a long-time (2-8 h) heat treatment method on the non-woven fabric, because the exothermic reaction and the cyclization reaction are severe in the preoxidation process, only the long-time reaction can be used for heat preservation, and a slow temperature rise process is needed at the same time, so that the severe reaction degree in the preoxidation process is relieved. Two defects are caused, namely high energy consumption and important reasons for influencing the mechanical property of the carbon fiber. Because of the thermochemical reaction characteristics of the pre-oxidation stage we cannot directly shorten the pre-oxidation time, otherwise the following two consequences would result: 1. the reaction degree is not enough; 2. the reaction transition is severe.
To solve this problem, we have devised the concept of at least three-stage gradient temperature rise, which solves the above problem by a stepwise reaction. The method adopts 40min (240 ℃/260 ℃/274 ℃) short-time multi-temperature-zone pre-oxidation, reduces the energy consumption by 80 percent, and improves the efficiency of the carbon fiber felt preparation process. Because the carbon nano fiber has small size, large specific surface area, fast combination with oxygen atoms and high permeation rate, the long pre-oxidation time can cause serious decarburization, the fiber structure is damaged to cause fiber relaxation, and the mechanical property of the carbon fiber felt is influenced. Therefore, we should use short-time multi-temperature zone pre-oxidation.
However, when the pre-oxidation time is further shortened to 20min (240 ℃/260 ℃/274 ℃), the core in the fiber is not completely oxidized in the pre-oxidation stage, and a skin-core structure can be generated. The carbon fibers formed from the core-sheath fibers have poorer mechanical properties due to the fiber core being burned off during the carbonization step.
Disclosure of Invention
The invention mainly aims to provide a scientific and visual preoxidation process for electrospinning acrylonitrile-based fiber felt, and the carbon fiber felt with excellent mechanical properties can be obtained by adopting at least three stages (temperature zones) of short-time preoxidation. Aiming at the characteristics of the electrostatic spinning acrylonitrile fiber felt, the pre-oxidation process is reasonably optimized: by means of short-time pre-oxidation in a multi-temperature area, severe cyclization reaction and oxidation reaction in the pre-oxidation stage are avoided, so that excessive result defects in fibers are formed in the carbonization process, and the tensile strength of the carbon fiber felt is greatly improved. And the short-time pre-oxidation process of the electrostatic spinning acrylonitrile nano fiber felt really improves the production efficiency of the carbon fiber preparation process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows.
A preparation method of a high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt is characterized in that three-stage multi-temperature zone short-time pre-oxidation is adopted, so that the pre-oxidation time is shortened, and then carbonization is carried out; the multi-temperature zone short-time pre-oxidation is adopted, and the severe transition of cyclization reaction and oxidation reaction in the pre-oxidation process is avoided; therefore, serious decarburization caused by excessive structural defects in the fibers in the carbonization process is reduced, the phenomena of fiber breakage and relaxation are reduced, and the tensile strength of the carbon fiber felt is increased finally;
further, the cyclization degree can be measured by 1590cm in an infrared spectrum-1And 2243cm-1Calculating the peak intensity;
preferably, the multi-temperature zone short-time pre-oxidation comprises three stages: in the first stage, the reaction time is 5-20 min at 240-260 ℃; in the second stage, the reaction time is 5-20 min at 260-274 ℃; in the third stage, the reaction time is 5-15 min at 274-280 ℃ to obtain the electrostatic spinning acrylonitrile-based oxidized fiber felt; each stage is provided with 1-3 temperature areas, and the total time of each stage comprises the heat preservation and temperature rise time of the temperature areas; the acrylonitrile-based fiber felt is not subjected to the temperature rise process of the first temperature zone, and after the temperature is raised to the temperature of the first temperature zone, the acrylonitrile-based fiber felt is placed in the environment of the temperature of the first temperature zone; then the acrylonitrile-based fibrofelt is subjected to subsequent heating and heat preservation environments; the temperature rising stage between 240 ℃ and 260 ℃ is the time of the first stage, and the heat preservation time at 260 ℃ is the time of the second stage; the temperature rising stage between 260 ℃ and 274 ℃ is the time of the second stage, and the heat preservation time at 274 ℃ is the time of the third stage.
Wherein the total time of pre-oxidation can be reduced to 15-55min from the conventional 2-6 h. Further preferably, the total time of the three stages is 40-50 min.
Further, the tensile strength of the electrospun acrylonitrile-carbon nanofiber mat can be measured using a universal material testing machine (total length of the sample is 4cm, 1cm fixed up and down, effective length of 2cm, width of 0.5 cm).
The present invention provides an efficient method for preparing electrospun acrylonitrile-based carbon nanofiber mats that controls the pre-oxidation reaction rate of the fiber mats. Conventional long-time pre-oxidation, oxidation reaction transition in the pre-oxidation process, more carbon atoms can be combined in the carbonization process, so that the decarburization is serious, the internal structure of the fiber is damaged, and the mechanical strength of the carbon fiber felt is influenced. Compared with long-time pre-oxidation, the multi-temperature-zone short-time pre-oxidation can effectively control the oxidation reaction rate of the electrospun acrylonitrile-based oxidized fiber felt to reach the standard oxidation reaction degree, and the carbon nano-fiber has small size, large specific surface area, more contact with oxygen atoms and accelerated permeation rate, so the oxidation reaction degree in the pre-oxidation stage is reduced.
The carbonization according to the present invention may be a conventional carbonization under nitrogen.
The electrostatic spinning collecting device involved in the method is a speed regulating roller, a speed regulating turntable, a parallel plate electrode, a speed regulating parallel plate rotating rod, a static water collecting bath or a flowing water collecting bath.
The acrylonitrile involved in the method is an acrylonitrile homopolymer or an acrylonitrile copolymer containing one or more comonomers with the mass fraction of below 15%, and the comonomers contain one or more of carboxyl, amido or ester groups.
The acrylonitrile-based fiber felt involved in the method is produced by solution spraying in the electrospinning process, and the drying of the formed acrylonitrile-based fiber felt is directly carried out by volatilization of an organic solvent in the electrospinning process.
The reaction degree in the pre-oxidation stage is characterized by cyclization degree and oxygen content; the oxygen content can be obtained by analyzing test elements, the oxidation reaction degree in the pre-oxidation stage is represented, the standard oxygen content of the electrostatic spinning pre-oxidized fiber felt is 8-12%, and the cyclization degree is 1590cm in an infrared spectrogram-1And 2243cm-1The peak intensity at (a) is calculated.
The invention has the advantages that:
(1) by adopting three-stage (at least three temperature zones) short-time pre-oxidation, severe cyclization reaction and oxidation reaction in the pre-oxidation stage are avoided, so that excessive result defects in the fibers are formed in the carbonization process, the tensile strength of the carbon fiber felt is greatly improved, the tensile strength of the corresponding carbon nano fiber felt can reach more than 200MPa when being detected, meanwhile, the cost of the electrostatic spinning pre-oxidation process is effectively reduced, and the working efficiency is improved.
(2) By adopting three-stage (at least three temperature zones) short-time pre-oxidation, the oxygen content of the electrostatic spinning acrylonitrile pre-oxidized fiber mat can be effectively controlled.
(3) And collecting the electrospun acrylonitrile-based non-woven fabric by using a speed regulating roller.
Drawings
FIG. 1 is a sample graph of a process for pre-oxidation of an acrylonitrile fiber mat.
Fig. 2 is a bar graph of carbon fiber mat test tensile strength.
FIG. 3 shows the DSC analysis curves of the PAN nonwoven fabric and the PAN nonwoven fabric under the following pre-oxidation times (0min, 20min, 40min, 300 min).
Wherein 1 corresponds to comparative examples 1, 2 to examples 3 and 3 to comparative examples 2, 4 to PAN nonwoven without pre-oxidation.
Detailed Description
In the following embodiment, the same homopolyacrylonitrile is adopted to carry out electrostatic spinning and pretreatment under the same conditions to prepare the electrostatic spinning acrylonitrile fiber felt, and a series of suitable pre-oxidation processes are comprehensively analyzed and prepared by a series of testing means such as DSC, infrared spectroscopy, elemental analysis and the like.
Comparative example 1
The electrostatic spinning acrylonitrile fiber felt is pre-oxidized in a muffle furnace under the same tension without drawing and under normal pressure in an air medium, and the total time is 300 min. The temperature was raised from room temperature (10 ℃) to 280 ℃ at a heating rate of 1.5 ℃/min and the temperature was maintained at 280 ℃ for 120 min. And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared by the method is 80 MPa.
Example 1
The electrostatic spinning acrylonitrile fiber felt is subjected to 4 pre-oxidation temperature zones in an air blowing drying box under the same tension without drawing and under normal pressure in an air medium, and the total time is 50 min. The reaction temperature of the first temperature zone is 240 ℃, the reaction time is 5min, the temperature is increased to 240-260 ℃ for 15min, the reaction temperature of the second temperature zone is 260 ℃, the reaction time is 5min, the temperature is increased to 260-274 ℃ for 11min, the reaction temperature of the third temperature zone is 274 ℃, the reaction time is 5min, the temperature is increased to 274-280 ℃ for 4min, the reaction temperature of the fourth temperature zone is 280 ℃, and the reaction time is 5min (firstly, the electrostatic spinning acrylonitrile fiber felt is directly placed in a 240 ℃ furnace, the temperature is increased in the first process, the electrospinning acrylonitrile fiber felt is not in the furnace, and the electrostatic spinning acrylonitrile fiber felt is placed in the furnace until the reaction is finished). And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared by the method is 181.2 MPa.
Example 2
The electrostatic spinning acrylonitrile fiber felt is subjected to 4 pre-oxidation temperature zones in an air blowing drying box under the same tension without drawing and under normal pressure in an air medium, and the total time is 45 min. The reaction temperature of the first temperature zone is 240 ℃, the reaction time is 5min, the temperature is increased to 240-260 ℃ for 14min, the reaction temperature of the second temperature zone is 260 ℃, the reaction time is 5min, the temperature is increased to 260-274 ℃ for 10min, the reaction temperature of the third temperature zone is 274 ℃, the reaction time is 5min, the temperature is increased to 274-280 ℃ for 4min, the reaction temperature of the fourth temperature zone is 280 ℃, and the reaction time is 2min (firstly, the electrostatic spinning acrylonitrile fiber felt is directly placed in a 240 ℃ furnace, the temperature is increased in the first process, the electrospinning acrylonitrile fiber felt is not in the furnace, and the electrostatic spinning acrylonitrile fiber felt is placed in the furnace until the reaction is finished). And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared by the method is 196.6 MPa.
Example 3
The electrostatic spinning acrylonitrile fiber felt is subjected to 3 pre-oxidation temperature zones in an air blowing drying box under the same tension without drawing and under normal pressure in an air medium, and the total time is 40 min. The reaction temperature of the first temperature zone is 240 ℃, the reaction time is 5min, the temperature is increased to 240-260 ℃ for 15min, the reaction temperature of the second temperature zone is 260 ℃, the reaction time is 5min, the temperature is increased to 260-274 ℃ for 10min, the reaction temperature of the third temperature zone is 274 ℃, and the reaction time is 5min (firstly, the electrostatic spinning acrylonitrile fiber felt is directly placed in a 240 ℃ furnace, the temperature is increased in the process, the electro-spinning acrylonitrile fiber felt is not in the furnace, and the electro-spinning acrylonitrile fiber felt is placed in the furnace until the reaction is finished). And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared by the method is 230 MPa.
Comparative example 2
The electrostatic spinning acrylonitrile fiber felt is subjected to 4 pre-oxidation temperature zones in an air blowing drying box under the same tension without drawing and under normal pressure in an air medium, and the total time is 20 min. The reaction temperature of the first temperature zone is 240 ℃, the reaction time is set to be 5min, the reaction temperature of the second temperature zone is 260 ℃, the reaction time is set to be 5min, the reaction temperature of the third temperature zone is 274 ℃, the reaction time is set to be 5min, the reaction temperature of the fourth temperature zone is 280 ℃, and the reaction time is set to be 5min (only after the corresponding temperature zone temperature is reached, the electrostatic spinning acrylonitrile fiber felt is put into a furnace for reaction, and the electrostatic spinning acrylonitrile fiber felt does not react in the furnace in the temperature rising process). And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared according to the method is 67 MPa.
Comparative example 3
The electrostatic spinning acrylonitrile fiber felt is subjected to 4 pre-oxidation temperature zones in an air blowing drying box under the same tension without drawing and under normal pressure in an air medium, and the total time is 17 min. The reaction temperature of the first temperature zone is 240 ℃, the reaction time is set to be 5min, the reaction temperature of the second temperature zone is 260 ℃, the reaction time is set to be 5min, the reaction temperature of the third temperature zone is 274 ℃, the reaction time is set to be 5min, the reaction temperature of the fourth temperature zone is 280 ℃, and the reaction time is set to be 2min (only after the corresponding temperature zone temperature is reached, the electrostatic spinning acrylonitrile fiber felt is put into a furnace for reaction, and the electrostatic spinning acrylonitrile fiber felt does not react in the furnace in the temperature rising process). And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared by the method is 74 MPa.
Comparative example 4
The electrostatic spinning acrylonitrile fiber felt is subjected to 3 pre-oxidation temperature zones in an air blowing drying box under the same tension without drawing and under normal pressure in an air medium, and the total time is 15 min. The reaction temperature of the first temperature zone is 240 ℃, the reaction time is set to be 5min, the reaction temperature of the second temperature zone is 260 ℃, the reaction time is set to be 5min, the reaction temperature of the third temperature zone is 274 ℃, and the reaction time is set to be 5min (only after the corresponding temperature zone temperature is reached, the electrostatic spinning acrylonitrile fiber felt is put into a furnace for reaction, and the electrostatic spinning acrylonitrile fiber felt does not react in the furnace in the temperature rising process). And then carbonizing in nitrogen, heating from 0 to 300 ℃ at a speed of 5 ℃/min, heating from 300 ℃ to 700 ℃ at a speed of 4 ℃/min, heating from 700 ℃ to 1000 ℃ at a speed of 3 ℃/min, heating from 1000 ℃ to 1200 ℃ at a speed of 1.5 ℃, reacting for 2min at 1200 ℃, cooling to room temperature at the same speed, and taking out a sample to obtain the electrostatic spinning acrylonitrile-based carbon nanofiber felt. The tensile strength of the electrospun acrylonitrile-based carbon nanofiber felt prepared by the method is 87 MPa.
Claims (5)
1. A preparation method of high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt is characterized by comprising the following steps: by adopting multi-temperature-zone short-time pre-oxidation, the pre-oxidation time is shortened, and then carbonization is carried out; the multi-temperature zone short-time pre-oxidation is adopted, and the severe transition of cyclization reaction and oxidation reaction in the pre-oxidation process is avoided; the serious decarburization caused by excessive structural defects in the fibers in the carbonization process is reduced, so that the structural defects of the carbon nanofibers are reduced, and the tensile strength of the carbon nanofiber felt is increased finally;
wherein, the multi-temperature zone short-time pre-oxidation comprises three stages: in the first stage, the reaction time is 5-20 min at 240-260 ℃; in the second stage, the reaction time is 5-20 min at 260-274 ℃; in the third stage, the reaction time is 5-15 min at 274-280 ℃ to obtain the electrostatic spinning acrylonitrile-based oxidized fiber felt; each stage is provided with 1-3 temperature areas, and the total time of each stage comprises the heat preservation and temperature rise time of the temperature areas; the temperature rise stage between 240 ℃ and 260 ℃ is the time of the first stage, and the heat preservation time at 260 ℃ is the time of the second stage; the temperature rise stage between 260 ℃ and 274 ℃ is the time of the second stage, and the heat preservation time at 274 ℃ is the time of the third stage;
firstly, directly placing the electrostatic spinning acrylonitrile fiber felt into a furnace at 240 ℃, wherein the electrostatic spinning acrylonitrile fiber felt is not in the furnace in the previous heating process; after the addition, the reaction was continued until the end of the reaction.
2. The preparation method of the high-strength electrospun polyacrylonitrile-based carbon nanofiber mat as claimed in claim 1, wherein the total time of pre-oxidation is reduced to 15-55min from the conventional 2-6 h.
3. The method for preparing a high-strength electrospun polyacrylonitrile-based carbon nanofiber mat according to claim 1, wherein the total time of the three stages is 40-50 min.
4. The method for preparing a high-strength electrospun polyacrylonitrile-based carbon nanofiber felt according to claim 1, wherein the precursor is an acrylonitrile homopolymer or an acrylonitrile copolymer containing 15% or less of one or more comonomers, and the comonomer contains one or more of carboxyl, amino, amide or ester groups.
5. The method for preparing high-strength electrospun polyacrylonitrile-based carbon nanofiber felt according to claim 1, characterized in that the acrylonitrile-based fiber felt is produced by solution spraying in the electrospinning process, and the drying of the formed acrylonitrile-based fiber felt is directly carried out by volatilization of an organic solvent in the electrospinning process.
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| CN110205748B (en) * | 2019-04-30 | 2022-04-01 | 西南石油大学 | Composite nanofiber membrane of beta-FeOOH/polyacrylonitrile as well as preparation method and application thereof |
| CN113005567A (en) * | 2021-02-25 | 2021-06-22 | 同济大学 | Preparation and application of novel MXene modified porous carbon fiber composite electrode |
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