CN109763210A - The method that ionic liquid prepares cellulose base carbon fiber or carbon film - Google Patents
The method that ionic liquid prepares cellulose base carbon fiber or carbon film Download PDFInfo
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Abstract
The present invention relates to the methods that ionic liquid prepares cellulose base carbon fiber or carbon film.Cellulose is dissolved using ionic liquid as solvent high-efficiency, disperses carbon nanomaterial simultaneously, obtains ionic liquid-cellulose-carbon nanocomposite solution；Spinning is carried out to composite solution or scrapes film preparation conductive fiber or conductive film；The cellulose base carbon fiber or carbon film of high conductivity are further prepared with carbonization treatment by pre-oxidizing.This method simple process, cellulose origin is abundant, cheap, ionic liquid is environmental-friendly, recyclable, carbon nanotube, graphene, conductive black are added in cellulosic matrix, the electric conductivity of carbon fiber or carbon film greatly improved, it can be applied to the fields such as antistatic textile, electric heating clothes, Electromagnetically shielding fabrics, have broad application prospects.
Description
Technical field
The present invention relates to a kind of methods that ionic liquid prepares cellulose base conductive carbon material, and in particular to one kind is with ion
Liquid is solvent, cellulose is matrix, carbon nanomaterial is conductive agent, the method for preparing cellulose base carbon fiber or carbon film.
Background technique
The intrinsic property that carbon fiber and carbon film not only have carbon material intrinsic, while there is the flexibility of textile fabric, it is one
The excellent reinforcing fiber materials of kind, are also used as anti-static material, radiation proof material, heat-insulating heat-preserving material and aerospace material
Material etc. is applied to the fields such as Aeronautics and Astronautics, building, chemical industry, weaving, information.
Carbon fiber is usually using pan based fibers, pitch-based fiber and cellulose-based fiber as presoma.Wherein, poly- third
Alkene itrile group carbon fiber and asphalt base carbon fiber form many patents, have there is numerous studies report；Polyacrylonitrile-based carbon fibre
Because production technology is mature, excellent combination property, main status is occupied in carbon fiber market.But polyacrylonitrile-based carbon fibre,
The non-renewable resources such as oil and coal are mainly derived from, in recent years, with the increasingly consumption and rare, spy of petroleum coal resources
Rope and development cellulose-based fiber presoma are significant to prepare the carbon materials such as carbon fiber and film.Cellulose base carbon fiber has
The characteristics such as reproducibility, good biocompatibility, high-purity and resistance to ablation, therefore in the fields such as aerospace and Military Medical
With irreplaceable role.
Currently, the presoma of cellulose base carbon fiber is mainly viscose fiber, but viscose fiber is due to its lower knot
The disadvantages of brilliant degree and the degree of orientation, loose structure, the section of fabiform, skin-core structure, the carbon fiber guiding electrical property prepared and
Mechanical performance is difficult to match in excellence or beauty with polyacrylonitrile-radical and asphalt base carbon fiber, and viscose fiber production process route is tediously long, pollution
Seriously, energy consumption is high, limits it and further produces the materials such as carbon fiber and carbon film.Ionic liquid with its low melting point, high stability,
Low-steam pressure, structure are adjustable, the excellent property such as recyclable, have been found the active solvent for cellulose, are widely used in fibre
Tie up the research of plain sill.Patent CN102102231A " a kind of preparation method of conductive cellulose fiber ", using 1- butyl -3-
The glyoxaline ion liquids such as methylimidazole villaumite dissolve cellulose and dispersing Nano carbon tubes and carbon black, using dry-jet wet-spinning or wet
Spinning process prepares conductive fiber, but is not directed to composite solution and prepares conductive film, pre-oxidation and carbonization treatment to prepare carbon fiber or carbon
The technologies such as film.Patent CN104927090A " a kind of flexible and transparent conductive graphene/cellulose composite membrane and preparation method thereof ", is adopted
It dissolves cellulose preparation transparent conductive film simultaneously with 1- allyl -3- methylimidazole villaumite ultrasonic disperse graphene, but is not directed to
Fiber, pre-oxidation and carbonization, which are prepared, to composite solution wet spinning prepares the technologies such as carbon fiber or carbon film.Patent CN106283273A " one
The preparation method of kind cellulose ion base carbon material ", it is molten using 1- ethyl-3-methylimidazole acetate and dimethyl sulfoxide compounding
Cellulose is dissolved in agent, after dry-jet wet-spinning obtains fiber, by obtaining cellulose base carbon fiber after catalysis dipping, dry, pre-oxidation, carbonization
Dimension, but be not directed to that other, cellulose can be dissolved, disperse the ionic liquid of carbon nanomaterial, while carbon is not added in spinning solution
Nano material, subsequent carbonization treatment need to be catalyzed impregnation before.
Based on the above present Research, the present invention uses a series of ionic liquid for dispersing agent and solvent, and Lai Shixian carbon is received
The rice fine dispersion of the material and high-efficiency dissolution of cellulose spinning or is scraped film preparation and is led using deionized water or ethyl alcohol as coagulating bath
Electric fiber or film further prepare the cellulose base carbon fiber or carbon film of high conductivity by pre-oxidizing with carbonization treatment.It should
Invention simple production process, low raw-material cost, solvent environment are friendly.The cellulose base carbon fiber or carbon film of high conductivity can answer
For fields such as antistatic textile, electric heating clothes, Electromagnetically shielding fabrics.
Summary of the invention
The present invention provides a kind of ionic liquid aiming at the problem that viscose process cellulose base carbon material high energy consumption, heavily contaminated
The method for preparing cellulose base carbon fiber or carbon film.
In order to achieve the above object, technical scheme is as follows:
The method that ionic liquid prepares cellulose base carbon fiber or carbon film mainly comprises the steps that ionic liquid-fiber
Element-carbon nanocomposite solution preparation, composite solution spinning or knifing, the pre-oxidation of conductive fiber or film, carbonization treatment.
Step 1: ionic liquid-cellulose-carbon nanocomposite solution preparation: using the method for grinding at 15~30 DEG C
Disperse carbon nanomaterial by solvent of ionic liquid；Cellulose is dissolved at 80~130 DEG C using ionic liquid as solvent simultaneously；It will
It is multiple to obtain ionic liquid-cellulose-carbon nanometer by above two solution 1~3h of mechanical stirring at 80~130 DEG C after vacuum defoamation
Close solution；
Step 2: ionic liquid-cellulose-carbon nanocomposite solution spinning or knifing: by ionic liquid-cellulose-carbon
Nanocomposite solution, which is placed in spinning equipment spinning or is placed in, scrapes knifing in film device, obtains wait pre-oxidize, carbonization treatment
Conductive fiber or film；
Step 3: conductive fiber or film pre-oxidation, carbonization treatment: conductive fiber or film after dry are first in air atmosphere
Pre-oxidation, is then carbonized in an inert atmosphere, obtains the cellulose base carbon fiber or carbon film.
The ionic liquid includes: 1-R2-3-R1Imidazoles villaumite, 1-R2-3-R1Imidazoles acetate, 1-R2-3-R1Imidazoles
Phosphoric acid diformazan (second, fourth) ester, 1-R2Pyridine villaumite, 1-R2- 3- picoline villaumite, 1-R2- 1,5- diazabicyclo
[4.3.0] -5 nonene phosphoric acid diformazan (second, fourth) ester, 1- allyl -3- methylimidazole chlorine；Wherein R1=CnH2N+1, n value 1~
20；R2=CmH2M+1, m value 1~20 (n, m take positive integer).
The carbon nanomaterial, the combination including carbon nanotube, graphene, conductive black or in which two kinds and three kinds,
Middle carbon nanotube is the modified multi wall of carboxylated or single-walled carbon nanotube, and graphene is the modified multilayer of carboxylated or mono-layer graphite
Alkene, conductive black are the modified carbon black of carboxylated.
The cellulose includes cotton paddle, wood pulp, corncob, stalk, flaxen fiber, the native cellulose in bamboo fibre and micro-
Crystalline cellulose, the degree of polymerization are 200~2000.
The method for using grinding disperses carbon nanomaterial, carbon nanometer material by solvent of ionic liquid at 15~30 DEG C
Material mass fraction is 1~10wt%；It is described that cellulose, cellulose quality are dissolved at 80~130 DEG C by solvent of ionic liquid
Score is 0.1~5wt%.
Ionic liquid-cellulose-carbon nanocomposite solution is obtained after the vacuum defoamation, the vacuum defoamation time is 1~8h,
Vacuum degree is 10kPa~100kPa.
Ionic liquid-the cellulose-carbon nanocomposite solution spinning is regenerated using deionized water or ethyl alcohol as coagulating bath
At silk, spinning solution flow is 0.1~20mL/min, and the internal diameter of spinning syringe needle is 0.06~1.54mm, spray head draw ratio be 1:1~
4:1。
Ionic liquid-the cellulose-carbon nanocomposite solution knifing is regenerated using deionized water or ethyl alcohol as coagulating bath
Film, using scraper knifing, film thickness is set as 100~1000um.
The pre-oxidation, carbonization treatment are to be warming up to the conductive fiber after drying or conductive film by room temperature in air
150~300 DEG C, 1~20 DEG C/min of heating rate, and 0.5~4h is kept the temperature at 150~300 DEG C；Then in inert gas (nitrogen
Gas or argon gas) in be warming up to 500~1500 DEG C, heating rate is 1~20 DEG C/min, and at 500~1500 DEG C heat preservation 1~
After 5h, it is naturally cooling to room temperature, finally obtains cellulose base carbon fiber or carbon film.
The present invention compared with the existing technology, has the following advantages and benefits:
1. the present invention prepares the matrix material of carbon fiber or carbon film from nature native cellulose abundant, solvent choosing
Yi Huishou, environmental-friendly ionic liquid are selected, not only realizes the high-efficiency dissolution of cellulose, while realizing the good of carbon nanomaterial
Good dispersion, can get uniform, stable ionic liquid-cellulose-carbon nanocomposite solution.
2. the present invention prepares conductive fiber or conduction by the method for spinning or knifing, using water or ethyl alcohol as coagulating bath regeneration
Film further obtains cellulose base carbon fiber or carbon film by pre-oxidation and carbonization treatment, and preparation method and process flow are simple,
Without catalyst dipping process, it is easy batch production.
3. the present invention adds carbon nanotube, graphene, conductive black in cellulosic matrix, carbon fiber not only can be improved
Or the mechanical performance of carbon film, while the electric conductivity of carbon fiber or carbon film can be greatly improved.
4. cellulose base carbon fiber prepared by the present invention or carbon film, intensity is high, flexible, easy processing, with higher to lead
Electrically, prepared cellulose base electric conduction of carbon fiber rate is about 1~3000S/m, and cellulose base carbon film conductivity is about 500~
3000S/m can be applied to the fields such as antistatic textile, electric heating clothes, Electromagnetically shielding fabrics.
Specific embodiment
Embodiment 1
1g cotton pulp cellulose (degree of polymerization=720) is weighed, is added to equipped with 50g1- ethyl-3-methylimidazole p diethylaminobenzoic acid
In the round-bottomed flask of ester ionic liquid, the mechanical stirring 1h in 90 DEG C of oil baths；Weigh 50g1- ethyl-3-methylimidazole phosphoric acid
For diethylester ionic liquid in agate mortar, the modified multi-walled carbon nanotube of addition 2g carboxylated, room temperature grinds 1h, then will
In its ionic liquid cellulose solution for adding to 90 DEG C, mechanical stirring mixes 2h, and deaeration 1h, obtains ion under 100kPa vacuum degree
Liquid-cellulose-carbon nano-tube composite solution.Composite solution is placed in spinning equipment, setting spinning flow 0.1mL/min,
The internal diameter of spinning syringe needle is 0.34mm, spray head draw ratio is 2:1, the use of deionized water is that coagulating bath regenerates silk；After drying
Conductive fiber is started to warm up by room temperature to 200 DEG C in air, and heating rate is 5 DEG C/min, and keeps the temperature 1h at 200 DEG C；So
800 DEG C are warming up in nitrogen atmosphere afterwards, heating rate is 10 DEG C/min, and in 800 DEG C of heat preservation 1h；Room temperature is naturally cooling to,
Obtaining conductivity is 1S/m cellulose base carbon fiber.
Embodiment 2
Weigh 1g wood pulp cellulose (degree of polymerization=900), be added to equipped with 50g1- ethyl-3-methylimidazole acetate from
In the round-bottomed flask of sub- liquid, the mechanical stirring 1h in 80 DEG C of oil baths；Weigh 50g1- ethyl-3-methylimidazole acetate ion
For liquid in agate mortar, the modified multi-layer graphene of addition 3g carboxylated, room temperature grinds 1h, then added to 80 DEG C from
In sub- liquid fiber element mixed solution, mechanical stirring mixes 2h, and the deaeration 2h under 80kPa vacuum degree obtains ionic liquid-fiber
Element-graphene composite solution.Composite solution is placed in and is scraped in film device, film thickness is set as 200um, the use of deionized water is solidification
Bath regeneration film forming；Conductive film after drying is started to warm up by room temperature to 180 DEG C in air, and heating rate is 10 DEG C/min, and
1.5h is kept the temperature at 180 DEG C, 1200 DEG C is then warming up in argon atmosphere, heating rate is 15 DEG C/min, and at 1200 DEG C
Lower heat preservation 2h, taking-up obtains the cellulose base carbon film that conductivity is about 1200S/m after being naturally cooling to room temperature.
Embodiment 3
It is plain (degree of polymerization=350) to weigh 1g corn cob fiber, be added to equipped with 50g1- butyl -3- methylimidazole villaumite from
In the round-bottomed flask of sub- liquid, the mechanical stirring 1h in 100 DEG C of oil baths；Weigh 50g1- butyl -3- methylimidazole villaumite ionic liquid
In agate mortar, the modified conductive black of addition 2g carboxylated, room temperature grinds 2h, is then added to 100 DEG C of ion body
In liquid fiber element mixed solution, mechanical stirring mixes 2h, and the deaeration 4h under 60kPa vacuum degree obtains ionic liquid-cellulose-
Conductive black composite solution.Composite solution is placed in spinning equipment, sets spinning flow as 0.5mL/min, spinning syringe needle
Internal diameter is 0.84mm, spray head draw ratio is 1:1, the use of ethyl alcohol is that coagulating bath regenerates silk；Conductive fiber after drying, in air
In started to warm up by room temperature to 180 DEG C, heating rate is 6 DEG C/min, and keeps the temperature 1h at 180 DEG C, then in argon atmosphere
650 DEG C are warming up to, heating rate is 8 DEG C/min, and keeps the temperature 1h at 650 DEG C, and taking-up obtains conductance after being naturally cooling to room temperature
Rate is about 0.6S/m cellulose base carbon fiber.
Embodiment 4
The cellulose (degree of polymerization=500) extracted in 1g stalk is weighed, is added to equipped with 50g1- allyl -3- methyl miaow
In the round-bottomed flask of azoles chloride salt ions liquid, in 110 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- allyl -3- methylimidazole chlorine
In agate mortar, the multi-walled carbon nanotube of addition 1g carboxylated modified multi-layer graphene and 4g, room temperature is ground ionic liquid
2h is ground, is then added in 110 DEG C of ionic liquid cellulose mixed solution, mechanical stirring mixes 2h, in 30kPa vacuum degree
Lower deaeration 5h obtains ionic liquid-cellulose-graphene/carbon nano-tube composite solution.Composite solution is placed in and is scraped in film device,
Film thickness is set as 600um, the use of ethyl alcohol is coagulating bath regeneration film forming；Conductive film after drying, rises by room temperature in air
For temperature to 300 DEG C, heating rate is 15 DEG C/min, and 1h is kept the temperature at 300 DEG C, and 1500 DEG C are then warming up in nitrogen atmosphere,
Heating rate is 15 DEG C/min, and keeps the temperature 2h at 1500 DEG C, is naturally cooling to take out after room temperature and obtains conductivity and be about
The cellulose base carbon film of 1300S/m.
Embodiment 5
The cellulose (degree of polymerization=1200) extracted in 1g flaxen fiber is weighed, is added to equipped with 50g1,5- diazabicyclo
In the round-bottomed flask of [4.3.0] -5 nonene acetate ionic liquid, in 100 DEG C of oil bath mechanical stirring 1h；Weigh 50g1,5- phenodiazine
Miscellaneous bicyclic [4.3.0] -5 nonene acetate ionic liquid is in agate mortar, the modified multi-layer graphene of addition 1g carboxylated, 1g
Single-walled carbon nanotube and 1g conductive black, room temperature grind 2h, then added to 100 DEG C ionic liquid cellulose mixing
In solution, mechanical stirring mix 2h, the vacuum defoamation 8h under 10kPa, obtain ionic liquid-cellulose-carbon nano-tube/graphene/
Conductive black composite solution.Composite solution is placed in spinning equipment, set spinning flow as 1mL/min, spinning syringe needle it is interior
Diameter is 0.51mm, spray head draw ratio is 4:1, the use of deionized water is that coagulating bath regenerates silk；Conductive fiber after drying, in sky
It is started to warm up by room temperature to 160 DEG C in gas, heating rate is 6 DEG C/min, and keeps the temperature 2h at 160 DEG C, then in argon atmosphere
In be warming up to 1600 DEG C, heating rate is 18 DEG C/min, and keeps the temperature 1h at 1600 DEG C, is naturally cooling to take out after room temperature to obtain
Conductivity is about 5S/m cellulose base carbon fiber.
Embodiment 6
1g microcrystalline cellulose (degree of polymerization=220) are weighed, are added to equipped with 50g 1, -5 nonyl of 5- diazabicyclo [4.3.0]
In the round-bottomed flask of alkenyl phosphoric acid diethylester ionic liquid, in 100 DEG C of oil bath mechanical stirring 1h；It is double to weigh 50g 1,5- diaza
- 5 nonene diethyl phosphate ionic liquid of ring [4.3.0] is in agate mortar, the modified single-layer graphene of addition 2g carboxylated
With the single-walled carbon nanotube of 2g, room temperature grinds 2h, is then added in 100 DEG C of ionic liquid cellulose mixed solution, machine
Tool is stirred 2h, and the deaeration 8h under 10kPa vacuum degree obtains ionic liquid-cellulose-graphene/carbon nano-tube composite solution.
Composite solution is placed in and is scraped in film device, film thickness is set as 600um, the use of ethyl alcohol is coagulating bath regeneration film forming；Leading after drying
Electrolemma is started to warm up by room temperature to 160 DEG C in air, and heating rate is 4 DEG C/min, and keeps the temperature 1h at 160 DEG C, is then existed
600 DEG C are warming up in argon atmosphere, heating rate is 8 DEG C/min, and keeps the temperature 1h at 600 DEG C, is taken after being naturally cooling to room temperature
The cellulose base carbon film that conductivity is about 2100S/m is obtained out.
Embodiment 7
The cellulose (degree of polymerization=800) extracted in 1g bamboo fibre is weighed, is added to equipped with 50g1- ethyl -3- methyl miaow
In the round-bottomed flask of azoles acetate ionic liquid, in 90 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- ethyl-3-methylimidazole vinegar
Hydrochlorate ionic liquid is in agate mortar, the conductive black of addition 3g carboxylated modified single-layer graphene and 1g, room temperature grinding
Then 2h is added in 90 DEG C of ionic liquid cellulose mixed solution, mechanical stirring mixes 2h, under 100kPa vacuum degree
Deaeration 1h obtains ionic liquid-cellulose-graphene/conductive black composite solution.Composite solution is placed in spinning equipment, if
Determine that spinning flow is 1.6mL/min, the internal diameter of spinning syringe needle is 0.60mm, spray head draw ratio is 2:1, the use of ethyl alcohol is coagulating bath
Regenerate silk；Conductive fiber after drying is started to warm up by room temperature to 280 DEG C in air, and heating rate is 14 DEG C/min, and
1h is kept the temperature at 280 DEG C, 1400 DEG C is then warming up in nitrogen atmosphere, heating rate is 14 DEG C/min, and at 1400 DEG C
1h is kept the temperature, is naturally cooling to take out after room temperature that obtain conductivity be about 800S/m cellulose base carbon fiber.
Embodiment 8
1 cotton paddle cellulose (degree of polymerization=400) is weighed, is added to equipped with 50g1- ethyl-3-methylimidazole diethyl phosphate
In the round-bottomed flask of ionic liquid, in 90 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- ethyl-3-methylimidazole p diethylaminobenzoic acid
In agate mortar, the conductive black of addition 2g carboxylated modified single-layer carbon nano-tube and 1g, room temperature is ground ester ionic liquid
2h is ground, is then added in 90 DEG C of ionic liquid cellulose mixed solution, mechanical stirring mixes 2h, in 50kPa vacuum degree
Lower deaeration 4h obtains ionic liquid-cellulose-carbon nano-tube/conductive black composite solution.Composite solution is placed in and scrapes film device
In, film thickness is set as 1000um, the use of ethyl alcohol is coagulating bath regeneration film forming；Conductive film after drying, is opened by room temperature in air
Beginning is warming up to 240 DEG C, and heating rate is 8 DEG C/min, and keeps the temperature 1h at 240 DEG C, and 1600 are then warming up in argon atmosphere
DEG C, heating rate is 16 DEG C/min, and keeps the temperature 2h at 1600 DEG C, is naturally cooling to take out after room temperature and obtains conductivity and be about
The cellulose base carbon film of 500S/m.
Embodiment 9
1g wood pulp cellulose (degree of polymerization=1500) are weighed, are added to equipped with 50g1- ethyl-3-methylimidazole p diethylaminobenzoic acid
In the round-bottomed flask of ester ionic liquid, in 90 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- ethyl-3-methylimidazole di(2-ethylhexyl)phosphate
Ethyl ester ionic liquid is in agate mortar, the multi-walled carbon nanotube of addition 4g carboxylated modified multi-layer graphene and 1g, often
Temperature grinding 2h, is then added in 90 DEG C of ionic liquid cellulose mixed solution, and mechanical stirring mixes 2h, true in 30kPa
Deaeration 6h obtains ionic liquid-cellulose-graphene/carbon nano-tube composite solution under reciprocal of duty cycle.Composite solution is placed in spinning equipment
In, set spinning flow as the internal diameter of 2mL/min, spinning syringe needle be 1.19mm, spray head draw ratio is 3:1, use deionized water
Silk is regenerated for coagulating bath；Conductive fiber after drying is started to warm up by room temperature to 240 DEG C, heating rate 6 in air
DEG C/min, and 2h is kept the temperature at 240 DEG C, 1800 DEG C are then warming up in nitrogen atmosphere, heating rate is 18 DEG C/min, and
1h is kept the temperature at 1800 DEG C, is naturally cooling to take out after room temperature that obtain conductivity be about 900S/m cellulose base carbon fiber.
Embodiment 10
Weigh 1g microcrystalline cellulose (degree of polymerization=220), be added to equipped with 50g1- ethyl-3-methylimidazole acetate from
In the round-bottomed flask of sub- liquid, in 80 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- ethyl-3-methylimidazole acetate ion liquid
Body is in agate mortar, and the conductive black of addition 1g carboxylated modified single-layer graphene and 1g, room temperature grinds 2h, then by it
Add in 90 DEG C of ionic liquid cellulose mixed solution, mechanical stirring mix 1h, the deaeration 1h under 100kPa vacuum degree, obtain from
Sub- liquid-cellulose-graphene/conductive black composite solution.Composite solution is placed in and is scraped in film device, film thickness is set as
500um is coagulating bath regeneration film forming using deionized water；Conductive film after drying is started to warm up by room temperature to 220 in air
DEG C, heating rate is 10 DEG C/min, and 1h is kept the temperature at 220 DEG C, 1100 DEG C is then warming up in nitrogen atmosphere, heating rate
For 20 DEG C/min, and 1h is kept the temperature at 1100 DEG C, is naturally cooling to take out after room temperature to obtain the fiber that conductivity is about 500S/m
Plain base carbon film.
Embodiment 11
It is plain (degree of polymerization=400) to weigh 1g corn cob fiber, is added to equipped with 50g1- ethyl-3-methylimidazole di(2-ethylhexyl)phosphate
In the round-bottomed flask of ethyl ester ionic liquid, in 100 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- ethyl-3-methylimidazole phosphoric acid
Diethylester ionic liquid is in agate mortar, the single-walled carbon nanotube of addition 2g carboxylated modified single-layer graphene and 3g,
Room temperature grinds 2h, is then added in 100 DEG C of ionic liquid cellulose mixed solution, and mechanical stirring mixes 2h, in 40kPa
Deaeration 6h under vacuum degree obtains ionic liquid-cellulose-graphene/carbon nano-tube composite solution.Composite solution is placed in spinning to set
In standby, set spinning flow as the internal diameter of 6mL/min, spinning syringe needle be 1.54mm, spray head draw ratio is 2:1, be using ethyl alcohol
Coagulating bath regenerates silk；Conductive fiber after drying is started to warm up by room temperature to 300 DEG C in air, and heating rate is 15 DEG C/
Min, and 2h is kept the temperature at 300 DEG C, 1800 DEG C are then warming up in argon atmosphere, heating rate is 20 DEG C/min, and
1h is kept the temperature at 1800 DEG C, is naturally cooling to take out after room temperature that obtain conductivity be about 1000S/m cellulose base carbon fiber.
Embodiment 12
It is plain (degree of polymerization=800) to weigh 1g flaxen fiber, is added to equipped with 50g1- ethyl-3-methylimidazole acetate ion
In the round-bottomed flask of liquid, in 90 DEG C of oil bath mechanical stirring 1h；Weigh 50g1- ethyl-3-methylimidazole acetate ionic liquid
In agate mortar, the modified single-layer graphene of addition 5g carboxylated, middle room temperature grinds 2h, is then added to 90 DEG C of ion
In liquid fiber element mixed solution, mechanical stirring mixes 2h, and the deaeration 3h under 80kPa vacuum degree obtains ionic liquid-cellulose-
Graphene composite solution.Composite solution is placed in and is scraped in film device, film thickness is set as 800um, the use of deionized water is coagulating bath
Regeneration film forming；Conductive film after drying is started to warm up by room temperature to 280 DEG C in air, and heating rate is 10 DEG C/min, and
2h is kept the temperature at 280 DEG C, 1400 DEG C is then warming up in nitrogen atmosphere, heating rate is 10 DEG C/min, and is protected at 1400 DEG C
Warm 1h, taking-up obtains the cellulose base carbon film that conductivity is about 1900S/m after being naturally cooling to room temperature.
Claims (9)
1. a kind of method that ionic liquid prepares cellulose base carbon fiber or carbon film, mainly comprises the steps that
Step 1: ionic liquid-cellulose-preparation of carbon nanocomposite solution: use the method ground at 15~30 DEG C with from
Sub- liquid is that solvent disperses carbon nanomaterial；Cellulose is dissolved at 80~130 DEG C using ionic liquid as solvent simultaneously；It will be above-mentioned
Two kinds of solution, 1~3h of mechanical stirring at 80~130 DEG C, it is nano combined molten to obtain ionic liquid-cellulose-carbon after vacuum defoamation
Liquid；
Step 2: ionic liquid-cellulose-carbon nanocomposite solution spinning or knifing: by ionic liquid-cellulose-carbon nanometer
Composite solution, which is placed in spinning equipment spinning or is placed in, scrapes knifing in film device, obtains after dry wait pre-oxidize, carbonization treatment
Conductive fiber or film；
Step 3: conductive fiber or film pre-oxidation, carbonization treatment: the first oxygen pre- in air atmosphere of conductive fiber or film after dry
Change, is then carbonized in an inert atmosphere, obtains the cellulose base carbon fiber or carbon film.
2. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, which is characterized in that step
Ionic liquid described in rapid one includes: 1-R2-3-R1Imidazoles villaumite, 1-R2-3-R1Imidazoles acetate, 1-R2-3-R1Imidazoles phosphorus
Sour diformazan (second, fourth) ester, 1-R2Pyridine villaumite, 1-R2- 3- picoline villaumite, 1-R2- 1,5- diazabicyclo [4.3.0] -5
Nonene phosphoric acid diformazan (second, fourth) ester, 1- allyl -3- methylimidazole chlorine；Wherein R1=CnH2n+1, n value 1~20；R2=
CmH2m+1, m value 1~20 (n, m take positive integer).
3. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
A rapid carbon nanomaterial, the combination including carbon nanotube, graphene, conductive black or in which two kinds and three kinds, wherein carbon
Nanotube is the modified multi wall of carboxylated or single-walled carbon nanotube, and graphene is the multilayer or single-layer graphene that carboxylated is modified,
Conductive black is the modified carbon black of carboxylated.
4. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
A rapid cellulose includes that cotton paddle, wood pulp, corncob, stalk, flaxen fiber, the native cellulose in bamboo fibre and crystallite are fine
Dimension element, the degree of polymerization are 200~2000.
5. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
Rapid one method for using grinding disperses carbon nanomaterial, carbon nanomaterial matter by solvent of ionic liquid at 15~30 DEG C
Amount score is 1~10wt%；It is described that cellulose, cellulose mass fraction are dissolved at 80~130 DEG C by solvent of ionic liquid
For 0.1~5wt%.
6. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
Ionic liquid-cellulose-carbon nanocomposite solution is obtained after a rapid vacuum defoamation, the vacuum defoamation time is 1~8h, vacuum
Degree is 10kPa~100kPa.
7. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
Ionic liquid-cellulose described in rapid two-carbon nanocomposite solution spinning is regenerated using deionized water or ethyl alcohol as coagulating bath
Silk, spinning solution flow are 0.1~20mL/min, and the internal diameter of spinning syringe needle is 0.06~1.54mm, and spray head draw ratio is 1:1~4:
1。
8. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
The rapid two ionic liquid-celluloses-carbon nanocomposite solution knifing is regenerated as coagulating bath using deionized water or ethyl alcohol and is formed a film,
Using scraper knifing, film thickness is set as 100~1000um.
9. the method that ionic liquid according to claim 1 prepares cellulose base carbon fiber or carbon film, it is characterised in that step
Rapid three pre-oxidation, carbonization treatment, be the conductive fiber after drying or conductive film are warming up to 150 by room temperature in air~
300 DEG C, 1~20 DEG C/min of heating rate, and 0.5~4h is kept the temperature at 150~300 DEG C；Then inert gas (nitrogen or
Argon gas) in be warming up to 500~1500 DEG C, heating rate is 1~20 DEG C/min, and after keeping the temperature 1~5h at 500~1500 DEG C,
It is naturally cooling to room temperature, finally obtains cellulose base carbon fiber or carbon film.
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