CN109763210B - Method for preparing cellulose-based carbon fiber or carbon film by ionic liquid - Google Patents
Method for preparing cellulose-based carbon fiber or carbon film by ionic liquid Download PDFInfo
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Abstract
The invention relates to a method for preparing a cellulose-based carbon fiber or carbon film by using an ionic liquid. Taking the ionic liquid as a solvent to efficiently dissolve cellulose and disperse carbon nano materials at the same time to obtain an ionic liquid-cellulose-carbon nano composite solution; spinning or scraping the composite solution to prepare a conductive fiber or a conductive film; and further preparing the cellulose-based carbon fiber or the carbon film with high conductivity by pre-oxidation and carbonization treatment. The method has the advantages of simple process, rich cellulose source, low price, environment-friendly and recoverable ionic liquid, and the carbon nano tube, the graphene and the conductive carbon black are added into the cellulose matrix, so that the conductivity of the carbon fiber or the carbon film is greatly improved, and the method can be applied to the fields of antistatic textiles, electric heating clothes, electromagnetic shielding fabrics and the like and has wide application prospect.
Description
Technical Field
The invention relates to a method for preparing a cellulose-based conductive carbon material by using an ionic liquid, in particular to a method for preparing a cellulose-based carbon fiber or carbon film by using the ionic liquid as a solvent, cellulose as a matrix and a carbon nano material as a conductive agent.
Background
The carbon fiber and the carbon film not only have intrinsic characteristics of carbon materials, but also have flexibility of textile fibers, are excellent reinforced fiber materials, can be used as antistatic materials, radiation-proof materials, heat-insulating materials, aerospace materials and the like, and are applied to the fields of aviation, aerospace, building, chemical engineering, textile, information and the like.
Carbon fibers are typically based on polyacrylonitrile-based fibers, pitch-based fibers, and cellulose-based fibers as precursors. Among them, polyacrylonitrile-based carbon fibers and pitch-based carbon fibers have formed many patents and have been reported in a great deal of research; the polyacrylonitrile-based carbon fiber has mature production technology and excellent comprehensive performance, and occupies a main position in the carbon fiber market. However, the polyacrylonitrile-based carbon fiber is mainly derived from petroleum, coal and other non-renewable resources, and in recent years, with the increasing consumption and scarcity of petroleum and coal resources, the exploration and development of cellulose-based fiber precursors for preparing carbon materials such as carbon fiber and film are of great significance. The cellulose-based carbon fiber has the characteristics of reproducibility, good biocompatibility, high purity, ablation resistance and the like, so that the cellulose-based carbon fiber has irreplaceable effects in the fields of aerospace, military medical treatment and the like.
At present, a precursor of cellulose-based carbon fiber is mainly viscose fiber, but due to the defects of low crystallinity and orientation degree, loose structure, broad bean-shaped section, skin-core structure and the like of the viscose fiber, the prepared carbon fiber has conductivity and mechanical properties which are difficult to compare favorably with those of polyacrylonitrile-based and asphalt-based carbon fiber, and the viscose fiber has the disadvantages of long production process route, serious pollution and high energy consumption, so that the further production of materials such as carbon fiber and carbon film is limited. The ionic liquid has been proved to be an effective solvent for cellulose by its excellent properties of low melting point, high stability, low vapor pressure, adjustable structure, recoverability and the like, and is widely applied to the research of cellulose-based materials. Patent CN102102231A "a method for preparing conductive cellulose fiber", which adopts imidazole ionic liquids such as 1-butyl-3-methylimidazolium chloride salt to dissolve cellulose and disperse carbon nanotubes and carbon black, and adopts dry-jet wet spinning or wet spinning process to prepare conductive fiber, but does not relate to techniques of preparing conductive film from composite solution, and preparing carbon fiber or carbon film by pre-oxidation and carbonization treatment. Patent CN104927090A "a flexible transparent conductive graphene/cellulose composite film and a preparation method thereof", adopts 1-allyl-3-methylimidazolium chloride to ultrasonically disperse graphene and simultaneously dissolve cellulose to prepare a transparent conductive film, but does not relate to technologies of preparing fibers by wet spinning of a composite solution, and preparing carbon fibers or carbon films by pre-oxidation and carbonization. Patent CN106283273A "a method for preparing cellulose ion-based carbon material", adopts a compound solvent of 1-ethyl-3-methylimidazolium acetate and dimethyl sulfoxide to dissolve cellulose, and after fibers are obtained by dry-jet wet spinning, cellulose-based carbon fibers are obtained by catalytic impregnation, drying, pre-oxidation and carbonization, but other ionic liquids capable of dissolving cellulose and dispersing carbon nano materials are not involved, and meanwhile, carbon nano materials are not added into a spinning solution, and catalytic impregnation treatment is required before subsequent carbonization treatment.
Based on the current research situation, the invention adopts a series of ionic liquids as a dispersing agent and a solvent to realize good dispersion of the carbon nano material and efficient dissolution of cellulose, uses deionized water or ethanol as a coagulating bath, prepares a conductive fiber or film by spinning or film scraping, and further prepares the high-conductivity cellulose-based carbon fiber or carbon film by pre-oxidation and carbonization treatment. The invention has simple production process, low cost of raw materials and environment-friendly solvent. The cellulose-based carbon fiber or carbon film with high conductivity can be applied to the fields of antistatic textiles, electric heating clothes, electromagnetic shielding fabrics and the like.
Disclosure of Invention
The invention provides a method for preparing cellulose-based carbon fibers or carbon films by using ionic liquid, aiming at the problems of high energy consumption and heavy pollution of cellulose-based carbon materials in a viscose method.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a cellulose-based carbon fiber or carbon film by using ionic liquid mainly comprises the following steps:
step one, preparing an ionic liquid-cellulose-carbon nano composite solution: dispersing the carbon nano material by using ionic liquid as a solvent at 15-30 ℃ by adopting a grinding method; simultaneously dissolving cellulose at 80-130 ℃ by taking ionic liquid as a solvent; mechanically stirring the two solutions at 80-130 ℃ for 1-3 h, and defoaming in vacuum to obtain an ionic liquid-cellulose-carbon nano composite solution;
step two, spinning or film scraping of the ionic liquid-cellulose-carbon nano composite solution: placing the ionic liquid-cellulose-carbon nano composite solution in spinning equipment for spinning or in film scraping equipment for scraping a film, and drying to obtain a conductive fiber or film to be subjected to pre-oxidation and carbonization treatment;
step three, conducting fiber or film pre-oxidation and carbonization treatment: pre-oxidizing the dried conductive fiber or film in an air atmosphere, and then carbonizing the conductive fiber or film in an inert atmosphere to obtain the cellulose-based carbon fiber or carbon film;
wherein, the ionic liquid in the first step is selected from: 1-R2-3-R1Imidazolium chloride salt, 1-R2-3-R1Imidazole acetate, 1-R2-3-R1Imidazole phosphoric acid dimethyl (ethyl, butyl) ester, 1-R2Pyridinium chloride salt, 1-R23-methylpyridinium chloride salt, 1-R2-1, 5-diazabicyclo [4.3.0]Dimethyl (ethyl, butyl) 5-nonene phosphate, 1-allyl-3-methylimidazolium chloride, R1＝CnH2n+1，R2＝CmH2m+1N and m are positive integers between 1 and 20;
the carbon nanomaterial is selected from carbon nanotubes, graphene and conductive carbon black or a combination of two or three of the carbon nanotubes, wherein the carbon nanotubes are multi-wall or single-wall carbon nanotubes modified by carboxylation, the graphene is multi-layer or single-layer graphene modified by carboxylation, and the conductive carbon black is carbon black modified by carboxylation;
step three, pre-oxidation and carbonization treatment, namely heating the dried conductive fiber or conductive film to 150-300 ℃ from normal temperature in the air, wherein the heating rate is 1-20 ℃/min, and keeping the temperature at 150-300 ℃ for 0.5-4 h; and then heating to 500-1500 ℃ in inert gas, wherein the inert gas is any one of nitrogen and argon, the heating rate is 1-20 ℃/min, and naturally cooling to normal temperature after heat preservation is carried out for 1-5 h at 500-1500 ℃, so as to finally obtain the cellulose-based carbon fiber or carbon film.
The cellulose is selected from natural cellulose and microcrystalline cellulose in cotton pulp, wood pulp, corncobs, straws, fibrilia and bamboo fiber, and the polymerization degree is 200-2000.
Dispersing a carbon nano material by using an ionic liquid as a solvent at 15-30 ℃ by adopting a grinding method, wherein the mass fraction of the carbon nano material is 1-10 wt%; the ionic liquid is used as a solvent to dissolve cellulose at the temperature of 80-130 ℃, and the mass fraction of the cellulose is 0.1-5 wt%.
And step one, obtaining the ionic liquid-cellulose-carbon nano composite solution after vacuum defoaming, wherein the vacuum defoaming time is 1-8 hours, and the vacuum degree is 10-100 kPa.
And spinning the ionic liquid-cellulose-carbon nano composite solution, namely regenerating the spinning solution into filaments by using deionized water or ethanol as a coagulating bath, wherein the flow rate of the spinning solution is 0.1-20 mL/min, the inner diameter of a spinning needle is 0.06-1.54 mm, and the length-diameter ratio of a spray head is 1: 1-4: 1.
And step two, scraping the membrane by using the ionic liquid-cellulose-carbon nano composite solution, regenerating the membrane by using deionized water or ethanol as a coagulating bath, and scraping the membrane by using a scraper, wherein the membrane thickness is set to be 100-1000 um.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the matrix raw material for preparing the carbon fiber or the carbon film is derived from natural cellulose abundant in the nature, the solvent is selected from ionic liquid which is easy to recover and environment-friendly, the efficient dissolution of the cellulose is realized, the good dispersion of the carbon nano material is realized, and the uniform and stable ionic liquid-cellulose-carbon nano composite solution can be obtained.
2. The invention prepares the conductive fiber or the conductive film by spinning or scraping the film and regenerating by taking water or ethanol as a coagulating bath, and further obtains the cellulose-based carbon fiber or the carbon film by pre-oxidation and carbonization treatment.
3. According to the invention, the carbon nano tube, the graphene and the conductive carbon black are added into the cellulose matrix, so that the mechanical property of the carbon fiber or the carbon film can be improved, and the conductivity of the carbon fiber or the carbon film can be greatly improved.
4. The cellulose-based carbon fiber or carbon film prepared by the method disclosed by the invention is high in strength, good in flexibility, easy to process and high in conductivity, the conductivity of the prepared cellulose-based carbon fiber is about 1-3000S/m, and the conductivity of the cellulose-based carbon film is about 500-3000S/m, so that the cellulose-based carbon fiber or carbon film can be applied to the fields of antistatic textiles, electric heating clothes, electromagnetic shielding fabrics and the like.
Detailed Description
Example 1
Weighing 1g of cotton pulp cellulose (the polymerization degree is 720), adding the cotton pulp cellulose into a round bottom flask containing 50g of 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid, and mechanically stirring the mixture in an oil bath at 90 ℃ for 1 h; weighing 50g of 1-ethyl-3-methylimidazol diethyl phosphate ionic liquid in an agate mortar, adding 2g of carboxylated modified multi-walled carbon nanotubes, grinding at normal temperature for 1h, adding the mixture into an ionic liquid cellulose solution at 90 ℃, mechanically stirring and mixing for 2h, and defoaming for 1h under the vacuum degree of 100kPa to obtain the ionic liquid-cellulose-carbon nanotube composite solution. Placing the composite solution in spinning equipment, setting the spinning flow rate to be 0.1mL/min, the inner diameter of a spinning needle to be 0.34mm, the length-diameter ratio of a spray head to be 2:1, and regenerating into filaments by using deionized water as a coagulating bath; heating the dried conductive fiber from normal temperature to 200 ℃ in air, wherein the heating rate is 5 ℃/min, and keeping the temperature at 200 ℃ for 1 h; then heating to 800 ℃ in nitrogen atmosphere, wherein the heating rate is 10 ℃/min, and keeping the temperature at 800 ℃ for 1 h; and naturally cooling to normal temperature to obtain the cellulose-based carbon fiber with the conductivity of 1S/m.
Example 2
Weighing 1g of wood pulp cellulose (polymerization degree is 900), adding the wood pulp cellulose into a round bottom flask containing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid, and mechanically stirring the mixture in an oil bath at the temperature of 80 ℃ for 1 hour; weighing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid in an agate mortar, adding 3g of carboxylated modified multi-layer graphene, grinding at normal temperature for 1h, adding the obtained product into an ionic liquid cellulose mixed solution at 80 ℃, mechanically stirring and mixing for 2h, and defoaming for 2h under the vacuum degree of 80kPa to obtain the ionic liquid-cellulose-graphene composite solution. Placing the composite solution in film scraping equipment, setting the film thickness to be 200um, and regenerating a film by using deionized water as a coagulating bath; and (2) heating the dried conductive film to 180 ℃ from the normal temperature in the air, wherein the heating rate is 10 ℃/min, preserving heat for 1.5h at 180 ℃, then heating to 1200 ℃ in an argon atmosphere, the heating rate is 15 ℃/min, preserving heat for 2h at 1200 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon film with the conductivity of about 1200S/m.
Example 3
Weighing 1g of corncob cellulose (polymerization degree is 350), adding the corncob cellulose into a round-bottom flask containing 50g of 1-butyl-3-methylimidazolium chloride ionic liquid, and mechanically stirring the corncob cellulose in an oil bath at 100 ℃ for 1 hour; weighing 1g of butyl-3-methylimidazolium chloride ionic liquid in an agate mortar, adding 2g of carboxylation modified conductive carbon black, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 100 ℃, mechanically stirring and mixing for 2h, and defoaming under the vacuum degree of 60kPa for 4h to obtain the ionic liquid-cellulose-conductive carbon black composite solution. Placing the composite solution in spinning equipment, setting the spinning flow rate to be 0.5mL/min, the inner diameter of a spinning needle to be 0.84mm, the length-diameter ratio of a spray head to be 1:1, and regenerating into filaments by using ethanol as a coagulating bath; and (2) heating the dried conductive fiber from the normal temperature to 180 ℃ in the air, wherein the heating rate is 6 ℃/min, preserving heat for 1h at 180 ℃, then heating to 650 ℃ in the argon atmosphere, the heating rate is 8 ℃/min, preserving heat for 1h at 650 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon fiber with the conductivity of about 0.6S/m.
Example 4
Weighing 1g of cellulose (polymerization degree is 500) extracted from straws, adding the cellulose into a round-bottom flask containing 50g of 1-allyl-3-methylimidazolium chloride ionic liquid, and mechanically stirring the mixture in an oil bath at 110 ℃ for 1 hour; weighing 50g of 1-allyl-3-methylimidazolium chloride ionic liquid into an agate mortar, adding 1g of carboxylated modified multi-layer graphene and 4g of multi-walled carbon nanotubes, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 110 ℃, mechanically stirring and mixing for 2h, and defoaming for 5h under the vacuum degree of 30kPa to obtain the ionic liquid-cellulose-graphene/carbon nanotube composite solution. Placing the composite solution in film scraping equipment, setting the film thickness to be 600um, and regenerating a film by using ethanol as a coagulating bath; and (2) heating the dried conductive film to 300 ℃ from the normal temperature in the air, wherein the heating rate is 15 ℃/min, preserving heat for 1h at 300 ℃, then heating to 1500 ℃ in a nitrogen atmosphere, the heating rate is 15 ℃/min, preserving heat for 2h at 1500 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon film with the conductivity of about 1300S/m.
Example 5
Weighing 1g of cellulose (polymerization degree is 1200) extracted from fibrilia, adding the cellulose into a round-bottom flask containing 50g of 1, 5-diazabicyclo [4.3.0] -5 nonene acetate ionic liquid, and mechanically stirring for 1h in an oil bath at 100 ℃; weighing 50g of 1, 5-diazabicyclo [4.3.0] -5 nonene acetate ionic liquid into an agate mortar, adding 1g of carboxylated modified multilayer graphene, 1g of single-walled carbon nanotube and 1g of conductive carbon black, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 100 ℃, mechanically stirring and mixing for 2h, and defoaming in vacuum at 10kPa for 8h to obtain the ionic liquid-cellulose-carbon nanotube/graphene/conductive carbon black composite solution. Placing the composite solution in spinning equipment, setting the spinning flow rate to be 1mL/min, the inner diameter of a spinning needle to be 0.51mm and the length-diameter ratio of a spray head to be 4:1, and regenerating into filaments by using deionized water as a coagulation bath; and (2) heating the dried conductive fiber from the normal temperature to 160 ℃ in the air, wherein the heating rate is 6 ℃/min, preserving heat for 2h at 160 ℃, then heating to 1600 ℃ in the argon atmosphere, the heating rate is 18 ℃/min, preserving heat for 1h at 1600 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon fiber with the conductivity of about 5S/m.
Example 6
Weighing 1g of microcrystalline cellulose (the polymerization degree is 220), adding the microcrystalline cellulose into a round-bottom flask containing 50g of 1, 5-diazabicyclo [4.3.0] -5 nonene diethyl phosphate ionic liquid, and mechanically stirring the mixture in an oil bath at 100 ℃ for 1 h; weighing 50g of 1, 5-diazabicyclo [4.3.0] -5 nonene diethyl phosphate ionic liquid in an agate mortar, adding 2g of carboxylation modified monolayer graphene and 2g of single-walled carbon nano tube, grinding for 2h at normal temperature, adding the mixture into an ionic liquid cellulose mixed solution at 100 ℃, mechanically stirring and mixing for 2h, and defoaming for 8h under the vacuum degree of 10kPa to obtain the ionic liquid-cellulose-graphene/carbon nano tube composite solution. Placing the composite solution in film scraping equipment, setting the film thickness to be 600um, and regenerating a film by using ethanol as a coagulating bath; and (2) heating the dried conductive film to 160 ℃ from the normal temperature in the air, wherein the heating rate is 4 ℃/min, preserving heat for 1h at 160 ℃, then heating to 600 ℃ in the argon atmosphere, the heating rate is 8 ℃/min, preserving heat for 1h at 600 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon film with the conductivity of about 2100S/m.
Example 7
Weighing 1g of cellulose (polymerization degree is 800) extracted from bamboo fiber, adding the cellulose into a round bottom flask containing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid, and mechanically stirring the mixture in an oil bath at 90 ℃ for 1 hour; weighing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid into an agate mortar, adding 3g of carboxylation modified single-layer graphene and 1g of conductive carbon black, grinding at normal temperature for 2h, then adding the mixture into an ionic liquid cellulose mixed solution at 90 ℃, mechanically stirring and mixing for 2h, and defoaming under the vacuum degree of 100kPa for 1h to obtain the ionic liquid-cellulose-graphene/conductive carbon black composite solution. Placing the composite solution in spinning equipment, setting the spinning flow rate to be 1.6mL/min, the inner diameter of a spinning needle to be 0.60mm, the length-diameter ratio of a spray head to be 2:1, and regenerating into filaments by using ethanol as a coagulating bath; and (2) heating the dried conductive fiber from the normal temperature to 280 ℃ in the air, wherein the heating rate is 14 ℃/min, preserving heat for 1h at 280 ℃, then heating to 1400 ℃ in the nitrogen atmosphere, wherein the heating rate is 14 ℃/min, preserving heat for 1h at 1400 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon fiber with the conductivity of about 800S/m.
Example 8
Weighing 1 cotton pulp cellulose (the polymerization degree is 400), adding the cellulose into a round bottom flask containing 50g of 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid, and mechanically stirring the mixture in an oil bath at 90 ℃ for 1 hour; weighing 50g of 1-ethyl-3-methylimidazol diethyl phosphate ionic liquid into an agate mortar, adding 2g of carboxylation modified single-layer carbon nanotubes and 1g of conductive carbon black, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 90 ℃, mechanically stirring and mixing for 2h, and defoaming under the vacuum degree of 50kPa for 4h to obtain the ionic liquid-cellulose-carbon nanotube/conductive carbon black composite solution. Placing the composite solution in film scraping equipment, setting the film thickness to be 1000um, and regenerating a film by using ethanol as a coagulating bath; and (2) heating the dried conductive film to 240 ℃ from the normal temperature in the air, wherein the heating rate is 8 ℃/min, preserving heat for 1h at 240 ℃, then heating to 1600 ℃ in the argon atmosphere, the heating rate is 16 ℃/min, preserving heat for 2h at 1600 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon film with the conductivity of about 500S/m.
Example 9
Weighing 1g of wood pulp cellulose (the polymerization degree is 1500), adding the wood pulp cellulose into a round bottom flask containing 50g of 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid, and mechanically stirring the mixture in an oil bath at 90 ℃ for 1 h; weighing 50g of 1-ethyl-3-methylimidazol diethyl phosphate ionic liquid into an agate mortar, adding 4g of carboxylated modified multi-layer graphene and 1g of multi-walled carbon nanotubes, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 90 ℃, mechanically stirring and mixing for 2h, and defoaming under the vacuum degree of 30kPa for 6h to obtain the ionic liquid-cellulose-graphene/carbon nanotube composite solution. Placing the composite solution in spinning equipment, setting the spinning flow rate to be 2mL/min, the inner diameter of a spinning needle to be 1.19mm and the length-diameter ratio of a spray head to be 3:1, and regenerating into filaments by using deionized water as a coagulation bath; and (2) heating the dried conductive fiber from the normal temperature to 240 ℃ in the air, wherein the heating rate is 6 ℃/min, preserving heat for 2h at 240 ℃, then heating to 1800 ℃ in the nitrogen atmosphere, the heating rate is 18 ℃/min, preserving heat for 1h at 1800 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon fiber with the conductivity of about 900S/m.
Example 10
Weighing 1g of microcrystalline cellulose (the polymerization degree is 220), adding the microcrystalline cellulose into a round-bottom flask containing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid, and mechanically stirring the mixture in an oil bath at the temperature of 80 ℃ for 1 hour; weighing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid into an agate mortar, adding 1g of carboxylation modified single-layer graphene and 1g of conductive carbon black, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 90 ℃, mechanically stirring and mixing for 1h, and defoaming for 1h under the vacuum degree of 100kPa to obtain the ionic liquid-cellulose-graphene/conductive carbon black composite solution. Placing the composite solution in film scraping equipment, setting the film thickness to be 500 mu m, and regenerating a film by using deionized water as a coagulating bath; and (2) heating the dried conductive film to 220 ℃ from the normal temperature in the air, wherein the heating rate is 10 ℃/min, preserving heat for 1h at 220 ℃, then heating to 1100 ℃ in a nitrogen atmosphere, the heating rate is 20 ℃/min, preserving heat for 1h at 1100 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon film with the conductivity of about 500S/m.
Example 11
Weighing 1g of corncob cellulose (the polymerization degree is 400), adding the corncob cellulose into a round-bottom flask containing 50g of 1-ethyl-3-methylimidazol diethyl phosphate ionic liquid, and mechanically stirring the corncob cellulose in an oil bath at 100 ℃ for 1 hour; weighing 50g of 1-ethyl-3-methylimidazol diethyl phosphate ionic liquid in an agate mortar, adding 2g of carboxylation modified monolayer graphene and 3g of single-walled carbon nanotubes, grinding at normal temperature for 2h, adding the mixture into an ionic liquid cellulose mixed solution at 100 ℃, mechanically stirring and mixing for 2h, and defoaming under the vacuum degree of 40kPa for 6h to obtain the ionic liquid-cellulose-graphene/carbon nanotube composite solution. Placing the composite solution in spinning equipment, setting the spinning flow rate to be 6mL/min, the inner diameter of a spinning needle to be 1.54mm and the length-diameter ratio of a spray head to be 2:1, and regenerating into filaments by using ethanol as a coagulating bath; and (2) heating the dried conductive fiber from the normal temperature to 300 ℃ in the air, wherein the heating rate is 15 ℃/min, preserving heat for 2h at 300 ℃, then heating to 1800 ℃ in the argon atmosphere, the heating rate is 20 ℃/min, preserving heat for 1h at 1800 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon fiber with the conductivity of about 1000S/m.
Example 12
Weighing 1g of hemp cellulose (polymerization degree is 800), adding the hemp cellulose into a round bottom flask containing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid, and mechanically stirring the hemp cellulose in an oil bath at 90 ℃ for 1 hour; weighing 50g of 1-ethyl-3-methylimidazolium acetate ionic liquid into an agate mortar, adding 5g of carboxylation modified single-layer graphene into the agate mortar, grinding the mixture at the medium and normal temperature for 2 hours, adding the mixture into an ionic liquid cellulose mixed solution at the temperature of 90 ℃, mechanically stirring and mixing the mixture for 2 hours, and defoaming the mixture for 3 hours under the vacuum degree of 80kPa to obtain the ionic liquid-cellulose-graphene composite solution. Placing the composite solution in film scraping equipment, setting the film thickness to be 800 microns, and regenerating a film by using deionized water as a coagulating bath; and heating the dried conductive film to 280 ℃ from the normal temperature in the air, wherein the heating rate is 10 ℃/min, preserving heat for 2h at 280 ℃, then heating to 1400 ℃ in a nitrogen atmosphere, the heating rate is 10 ℃/min, preserving heat for 1h at 1400 ℃, naturally cooling to the normal temperature, and taking out to obtain the cellulose-based carbon film with the conductivity of about 1900S/m.
Claims (6)
1. A method for preparing a cellulose-based carbon fiber or carbon film by using ionic liquid mainly comprises the following steps:
step one, preparing an ionic liquid-cellulose-carbon nano composite solution: dispersing the carbon nano material by using ionic liquid as a solvent at 15-30 ℃ by adopting a grinding method; simultaneously dissolving cellulose at 80-130 ℃ by taking ionic liquid as a solvent; mechanically stirring the two solutions at 80-130 ℃ for 1-3 h, and defoaming in vacuum to obtain an ionic liquid-cellulose-carbon nano composite solution;
step two, spinning or film scraping of the ionic liquid-cellulose-carbon nano composite solution: placing the ionic liquid-cellulose-carbon nano composite solution in spinning equipment for spinning or in film scraping equipment for scraping a film, and drying to obtain a conductive fiber or film to be subjected to pre-oxidation and carbonization treatment;
step three, conducting fiber or film pre-oxidation and carbonization treatment: pre-oxidizing the dried conductive fiber or film in an air atmosphere, and then carbonizing the conductive fiber or film in an inert atmosphere to obtain the cellulose-based carbon fiber or carbon film;
wherein, the ionic liquid in the first step is selected from: 1-R2-3-R1Imidazolium chloride salt, 1-R2-3-R1Imidazole acetate, 1-R2-3-R1Imidazole phosphoric acid dimethyl (ethyl, butyl) ester, 1-R2Pyridinium chloride salt, 1-R23-methylpyridinium chloride salt, 1-R2-1, 5-diazabicyclo [4.3.0]Dimethyl (ethyl, butyl) 5-nonene phosphate, 1-allyl-3-methylimidazolium chloride, R1＝CnH2n+1，R2＝CmH2m+1N and m are positive integers between 1 and 20;
the carbon nanomaterial is selected from carbon nanotubes, graphene and conductive carbon black or a combination of two or three of the carbon nanotubes, wherein the carbon nanotubes are multi-wall or single-wall carbon nanotubes modified by carboxylation, the graphene is multi-layer or single-layer graphene modified by carboxylation, and the conductive carbon black is carbon black modified by carboxylation;
step three, pre-oxidation and carbonization treatment, namely heating the dried conductive fiber or conductive film to 150-300 ℃ from normal temperature in the air, wherein the heating rate is 1-20 ℃/min, and keeping the temperature at 150-300 ℃ for 0.5-4 h; and then heating to 500-1500 ℃ in inert gas, wherein the inert gas is any one of nitrogen and argon, the heating rate is 1-20 ℃/min, and naturally cooling to normal temperature after heat preservation is carried out for 1-5 h at 500-1500 ℃, so as to finally obtain the cellulose-based carbon fiber or carbon film.
2. The method for preparing a cellulose-based carbon fiber or carbon film by using an ionic liquid as claimed in claim 1, wherein the cellulose in the step one is selected from natural cellulose and microcrystalline cellulose in cotton pulp, wood pulp, corncobs, straws, hemp fiber and bamboo fiber, and the polymerization degree is 200-2000.
3. The method for preparing a cellulose-based carbon fiber or carbon film by using an ionic liquid as claimed in claim 1, wherein the step one comprises dispersing carbon nano-materials by using the ionic liquid as a solvent at 15-30 ℃ by using a grinding method, wherein the mass fraction of the carbon nano-materials is 1-10 wt%; the ionic liquid is used as a solvent to dissolve cellulose at the temperature of 80-130 ℃, and the mass fraction of the cellulose is 0.1-5 wt%.
4. The method for preparing the cellulose-based carbon fiber or the carbon film by using the ionic liquid as claimed in claim 1, wherein the ionic liquid-cellulose-carbon nano composite solution is obtained after the vacuum defoamation in the step one, the vacuum defoamation time is 1-8 h, and the vacuum degree is 10 kPa-100 kPa.
5. The method for preparing a cellulose-based carbon fiber or carbon film by using an ionic liquid as claimed in claim 1, wherein the ionic liquid-cellulose-carbon nano composite solution is spun in step two, deionized water or ethanol is used as a coagulation bath to regenerate filaments, the flow rate of the spinning solution is 0.1-20 mL/min, the inner diameter of a spinning needle is 0.06-1.54 mm, and the length-diameter ratio of a nozzle is 1: 1-4: 1.
6. The method for preparing a cellulose-based carbon fiber or carbon film by using an ionic liquid as claimed in claim 1, wherein the ionic liquid-cellulose-carbon nanocomposite solution in the second step is scraped to form a film, deionized water or ethanol is used as a coagulating bath to regenerate the film, and the film is scraped by using a scraper, wherein the film thickness is set to be 100-1000 um.
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