CN109853087B - Lignin/cellulose acetate based epoxy modified carbon fiber and preparation method and application thereof - Google Patents
Lignin/cellulose acetate based epoxy modified carbon fiber and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 45
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Abstract
The invention discloses lignin/cellulose acetate based epoxy modified carbon fiber and a preparation method and application thereof. The lignin/cellulose acetate based spinning solution is prepared by chemical modification reaction of lignin and cellulose acetate in the presence of epichlorohydrin, a carbon fiber precursor is prepared by an electrostatic spinning method, and carbon fiber is prepared by pre-oxidation treatment and carbonization treatment. Proper amount of epichlorohydrin is added to react with hydroxyl on lignin and cellulose acetate, but epoxy does not open ring, so that the lignin and cellulose acetate are easier to form filaments in the spinning process. In the pre-oxidation process, the epoxy ring-opening enables chemical bonds to be formed between lignin and cellulose acetate, the thermal stability of the lignin is improved, and the occurrence of a phase separation phenomenon is reduced. The carbon fiber prepared by the method has good fiber form, high mechanical property and adsorption property, has good application prospect in the aspects of being used as an electrode, a reinforcing material and an adsorbent, and provides guarantee for producing the full biomass-based carbon fiber with high quality, environmental protection and low cost.
Description
Technical Field
The invention belongs to the technical field of biomass material processing, and particularly relates to lignin/cellulose acetate based epoxy modified carbon fiber and a preparation method and application thereof.
Background
In recent years, global warming, energy crisis, and environmental pollution have attracted much attention. The use of alternative energy sources is an effective way to address these problems, such as various electrochemical energy storage and conversion devices. Low energy density and high cost are bottlenecks that limit the development of electrochemical capacitors. To solve this problem, the development of new electrode materials for electrochemical capacitors is an important and effective approach. Carbon fiber has attracted more and more attention as an electrode material for electrochemical capacitors because of its high specific mass capacity, good conductivity, surface open pores, ability to provide a good reaction path, and excellent strength and formability.
At present, the main raw material for preparing carbon fiber is petroleum high polymer such as polyacrylonitrile, however, further application and development of carbon fiber prepared by using the carbon fiber as the raw material in the civil field are restricted due to non-renewable property and high price of fossil energy. Because of the advantages of high carbon content, low cost, reproducibility and the like, the lignin is developed into an excellent raw material for producing low-cost civil carbon fibers by replacing petroleum-based raw materials.
However, due to the existence of a large number of hydroxyl groups in the chemical structure of cellulose, phase separation occurs in the physical mixing spinning process of the cellulose and lignin containing aromatic hydrocarbon structures, and the service performance of the cellulose is greatly reduced.
Disclosure of Invention
In view of the problems of the prior art, the invention aims to provide a method for preparing lignin/cellulose acetate based epoxy modified carbon fiber, and the carbon fiber prepared by the method takes all biomass raw materials as a base material.
The technical scheme of the invention is as follows:
a preparation method of lignin/cellulose acetate based epoxy modified carbon fiber comprises the steps of preparing lignin/cellulose acetate based spinning solution into a carbon fiber precursor by an electrostatic spinning method, preparing carbon fiber by pre-oxidation treatment and carbonization treatment, and carrying out chemical modification reaction on lignin and cellulose acetate in the presence of epichlorohydrin to obtain the lignin/cellulose acetate based spinning solution.
In the technical scheme, the reaction temperature of the chemical modification reaction is 0-10 ℃, and the reaction time is 6-12 h.
In the technical scheme, in the chemical modification reaction, the addition amount of the lignin and the cellulose acetate is 30: 70-70: 30 by mass, and the addition amount of the lignin and the cellulose acetate is 10-30% of the mass of the reaction system.
In the technical scheme, in the chemical modification reaction, the addition amount of the epichlorohydrin is 2-20% of the mass of the reaction system, preferably 5-16%, and more preferably 8-12%.
In the technical scheme, in the chemical modification reaction, lignin and cellulose acetate are dissolved in a mixed solvent of a solvent A and a solvent B, wherein the mixing ratio of the solvent A to the solvent B is 1-2: 1 by volume, and the solvent A/the solvent B in the mixed solution is acetone/N, N-dimethylformamide, glacial acetic acid/N, N-dimethylformamide, acetone/N, N-dimethylacetamide or glacial acetic acid/N, N-dimethylacetamide.
In the technical scheme, in the electrostatic spinning method, the electrostatic voltage is 15-35 KV, the receiving distance is 10-35cm, the rotating speed of a receiving roller is 200-700 r/min, and the pushing speed of spinning solution is 0.1-1 ml/h.
In the technical scheme, the pre-oxidation treatment is to pre-oxidize the carbon fiber precursor in an air atmosphere, wherein the pre-oxidation is started from room temperature, the temperature is increased to 200-300 ℃ at the speed of 0.01-2.00 ℃/min, and the temperature is kept for 8-12h at the temperature, so that the pre-oxidized fiber is obtained.
In the technical scheme, the carbonization treatment is to heat and carbonize the pre-oxidized fiber obtained by the pre-oxidation treatment under the protection of inert gas, heat the pre-oxidized fiber to 600-1400 ℃ at the speed of 2-10 ℃/min, and preserve heat at the temperature for 2-6 hours to obtain the lignin/cellulose acetate based electrostatic spinning carbon fiber.
In the invention, the mass of the reaction system refers to the total mass of the reaction solution after each reactant is added in the chemical modification reaction, and the reaction solution is subjected to the chemical modification reaction for 6-12 hours under a proper condition, such as the reaction temperature of 0-10 ℃, so as to prepare the lignin/cellulose acetate base spinning solution.
The invention also provides application of the lignin/cellulose acetate based epoxy modified carbon fiber prepared by the method in preparation of electrode materials of capacitors.
In the invention, the lignin is derived from biomass, such as lignin separated from coniferous wood, hardwood and non-wood fiber raw materials, and lignin which can be obtained by different separation methods comprises formic acid lignin, acetic acid lignin, ethanol lignin and the like. The lignin separated by different means can be obtained from the market, and can also be prepared according to the published documents.
In the invention, the cellulose acetate is derived from acetic acid modification of biomass natural cellulose. The cellulose acetate of the present invention preferably has an acetyl group content of 37% to 40%.
In the process of preparing the lignin/cellulose acetate spinning solution, a proper amount of epichlorohydrin is added to react with hydroxyl groups on lignin and cellulose acetate to form an epoxy structure, so that the hydrogen bond effect between the hydroxyl groups of biomass can be reduced, and the lignin/cellulose acetate spinning solution is easier to filature in the spinning process. And the added epichlorohydrin does not undergo ring opening before spinning, and epoxy ring opening in the pre-oxidation process enables chemical bonds to be formed between lignin and cellulose acetate, so that the thermal stability of the cellulose acetate is increased along with the ring opening of epoxy, and the occurrence of a phase separation phenomenon is reduced to a great extent.
On the other hand, the lignin and the cellulose acetate are treated in the process of preparing the spinning solution, the spinning solution is directly used for spinning, and the lignin/cellulose acetate-based carbon fibers can be continuously prepared, so that the problems that the continuous production of the carbon fibers cannot be carried out due to the post-treatment after the precursor fibers are prepared in the conventional preparation method, and the preparation energy consumption is increased are well solved.
The raw materials for preparing the carbon fiber do not contain any fossil raw materials, and the biomass raw materials of lignin and cellulose acetate are used as carbon sources of the carbon fiber, so that the carbon fiber is wide in source, low in price, easy to regenerate and environment-friendly. The prepared carbon fiber has good fiber shape, high mechanical property and good adsorption property, can replace polyacrylonitrile-based carbon fiber, and has good application prospect in the aspect of being used as an electrode and a reinforcing material.
Drawings
FIG. 1 is an SEM image of lignin/cellulose acetate based epoxy modified carbon fiber obtained in example 1 of the present invention. a is an electron microscope picture of carbon fiber prepared when the addition amount of epoxy chloropropane is 0 wt%, b is an electron microscope picture of carbon fiber prepared when the addition amount of epoxy chloropropane is 2 wt%, c is an electron microscope picture of carbon fiber prepared when the addition amount of epoxy chloropropane is 4 wt%, d is an electron microscope picture of carbon fiber prepared when the addition amount of epoxy chloropropane is 6 wt%, e is an electron microscope picture of carbon fiber prepared when the addition amount of epoxy chloropropane is 8 wt%, and f is an electron microscope picture of carbon fiber prepared when the addition amount of epoxy chloropropane is 10 wt%.
Fig. 2 is a molecular weight distribution diagram of a lignin/cellulose acetate based epoxy modified carbon fiber precursor obtained in example 1 of the present invention.
Fig. 3 is a cyclic voltammetry spectrum of lignin/cellulose acetate based epoxy modified carbon fiber obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the following detailed description, but the present invention is not limited to these embodiments. In the following examples, unless otherwise specified, the experimental methods used were all conventional methods, and materials, reagents and the like used were all available from biological or chemical companies.
Materials used in the following examples:
poplar prehydrolysis liquid lignin: obtained from Shanghai Dongshi technologies, Inc. and had a lignin purity of 93%.
Cellulose acetate: shanghai Aladdin Biochemical technology Co., Ltd, model No. 9004-35-7, acetyl content 39.8 wt%.
An electrostatic spinning machine: shenzhen Tong force micro nano technology Limited, model number is TL-Pro.
The GPC measurement used was waters (water Co.).
Example 1
Preparing lignin/cellulose acetate based epoxy modified carbon fiber according to the following method:
(1) dissolving poplar prehydrolysis liquid lignin/cellulose acetate in a mixed solvent of acetone/N, N-dimethylformamide (v/v:2:1) according to a mass ratio of 50/:50(w/w), adding a certain amount of Epichlorohydrin (ECH) after completely dissolving, wherein the final concentration of the epichlorohydrin in a reaction system is respectively 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt% and 10 wt%, the final concentration of the poplar prehydrolysis liquid lignin and the cellulose acetate is 20%, reacting for 6h at 0 ℃, filtering to remove unreacted ECH after the reaction is finished, and standing for 1h to obtain lignin-cellulose acetate copolymer spinning solution;
(2) preparing a lignin/cellulose acetate based carbon fiber precursor from the spinning solution prepared in the step (1) by an electrostatic spinning method, wherein electrostatic spinning conditions are as follows: the electrostatic voltage is 25KV, the receiving distance is 20cm, the rotating speed of a receiving roller is 500r/min, and the advancing speed of the spinning solution is 0.2 mL/h;
(3) placing the prepared carbon fiber precursor in a tube furnace, heating to 200 ℃ at a heating rate of 0.01 ℃/min in the air atmosphere, and preserving heat for 200min for pre-oxidation treatment; and then heating to 600 ℃ at the speed of 4 ℃/min under the protection of nitrogen, and preserving heat for 480min to carry out heating carbonization treatment to obtain the lignin/cellulose acetate based electrostatic spinning carbon fiber.
The electron micrographs of the carbon fibers obtained in the examples are shown in FIG. 1a to FIG. 1f, which are prepared when the amount of epichlorohydrin added is 0 wt% (ECH-0), 2 wt% (ECH-2), 4 wt% (ECH-4), 6 wt% (ECH-6), 8 wt% (ECH-8) and 10 wt% (ECH-10), respectively. As can be seen in FIG. 1, with the increase of the addition amount of ECH, the fiber adhesion phenomenon gradually disappears, and the filamentous morphology tends to be uniform, which shows that the thermal stability of the carbon fiber can be effectively improved by adding epoxy.
FIG. 2 shows the GPC results of the precursor fiber obtained in step (2) of example, and it was found that the molecular weight distribution was not changed by the addition of epichlorohydrin, indicating spinningThe epoxy does not open during the process. In fig. 2, Lignin and CA represent Lignin and cellulose acetate, respectively, as raw materials. The Mw, Mn and PDI of each product in fig. 2 are: mw 1280g mol-1，Mn＝213g mol-1，PDI＝6.01； CA:Mw＝33325g mol-1，Mn＝2857g mol-1，PDI＝11.66；ECH-0:Mw＝15220g mol-1，Mn＝750g mol-1，PDI＝20.29；ECH-2:Mw＝15275g mol-1，Mn＝749g mol-1， PDI＝20.40；ECH-4:Mw＝15880g mol-1，Mn＝804g mol-1，PDI＝19.65；ECH-6: Mw＝15488g mol-1，Mn＝718g mol-1，PDI＝21.57；ECH-8:Mw＝15668g mol-1， Mn＝748g mol-1，PDI＝20.95；ECH-10:Mw＝15820g mol-1，Mn＝757g mol-1， PDI＝20.89。
The electrochemical performance of the carbon fiber obtained in the embodiment is detected by cyclic voltammetry, and fig. 3 is a lateral cyclic voltammetry spectrogram, and it can be seen in the graph that as the addition amount of ECH increases, the rectangular area gradually increases, indicating that the specific capacitance is larger and larger. From the cyclic voltammetry spectrum, it can be seen that the specific capacitance of the capacitor gradually increases with the increase of the addition amount of the epoxy.
Example 2
Preparing lignin/cellulose acetate based epoxy modified carbon fiber according to the following method:
(1) dissolving poplar prehydrolysis liquid lignin/cellulose acetate in a mixed solvent of acetone/N, N-dimethylformamide (v/v:2:1) according to a mass ratio of 40/:60(w/w), adding epichlorohydrin after complete dissolution, wherein the final concentration of the epichlorohydrin in a reaction system is 10 wt%, the final concentration of the poplar prehydrolysis liquid lignin and the cellulose acetate is 15%, reacting at 0 ℃ for 6 hours, filtering to remove unreacted ECH after the reaction is finished, and standing for 2 hours to obtain lignin and cellulose acetate copolymer spinning solution;
(2) preparing a lignin/cellulose acetate based carbon fiber precursor from the spinning solution prepared in the step (1) by an electrostatic spinning method, wherein electrostatic spinning conditions are as follows: the electrostatic voltage is 25KV, the receiving distance is 25cm, the rotating speed of a receiving roller is 600r/min, and the advancing speed of the spinning solution is 0.5 mL/h;
(3) placing the prepared carbon fiber precursor in a tube furnace, heating to 250 ℃ at a heating rate of 0.2 ℃/min in the air atmosphere, and preserving heat for 480min to carry out pre-oxidation treatment; and then heating to 800 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and preserving heat for 120min for heating carbonization treatment to obtain the lignin/cellulose acetate based electrostatic spinning carbon fiber. The electrochemical performance test result shows excellent electrochemical performance.
Example 3
Preparing lignin/cellulose acetate based epoxy modified carbon fiber according to the following method:
(1) dissolving poplar prehydrolysis liquid lignin/cellulose acetate in a mixed solvent of acetone/N, N-dimethylformamide (v/v:2:1) according to a mass ratio of 60/:40(w/w), adding epichlorohydrin after completely dissolving, reacting for 6 hours at 0 ℃ with the final concentration of the epichlorohydrin in the reaction system being 12 wt% and the final concentration of the poplar prehydrolysis liquid lignin and the cellulose acetate being 25%, filtering to remove unreacted ECH after the reaction is finished, and standing for 2 hours to obtain lignin and cellulose acetate copolymer spinning solution;
(2) preparing a lignin/cellulose acetate based carbon fiber precursor from the spinning solution prepared in the step (1) by an electrostatic spinning method, wherein electrostatic spinning conditions are as follows: the electrostatic voltage is 20KV, the receiving distance is 30cm, the rotating speed of a receiving roller is 700r/min, and the advancing speed of the spinning solution is 0.8 mL/h;
(3) placing the prepared carbon fiber precursor in a tube furnace, heating to 220 ℃ at a heating rate of 0.5 ℃/min in the air atmosphere, and preserving heat for 720min for pre-oxidation treatment; and then heating to 1000 ℃ at the speed of 8 ℃/min under the protection of nitrogen, and preserving heat for 480min to carry out heating carbonization treatment to obtain the lignin/cellulose acetate based electrostatic spinning carbon fiber.
The obtained carbon fiber electron microscope still maintains excellent form, and the specific capacitance of the capacitor is gradually increased along with the increase of the addition amount of the epoxy as can be seen from a cyclic voltammetry spectrogram.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (8)
1. A preparation method of lignin/cellulose acetate based epoxy modified carbon fibers is characterized in that lignin/cellulose acetate based spinning solution is prepared into a carbon fiber precursor through an electrostatic spinning method, and carbon fibers are prepared through pre-oxidation treatment and carbonization treatment, and the lignin/cellulose acetate based spinning solution is prepared through chemical modification reaction of lignin and cellulose acetate in the presence of epoxy chloropropane, wherein the reaction temperature of the chemical modification reaction is 0-10 ℃, and the reaction time is 6-12 hours.
2. The preparation method according to claim 1, wherein in the chemical modification reaction, the addition amount of the lignin and the cellulose acetate is 30: 70-70: 30 by mass, and the addition amount of the lignin and the cellulose acetate is 10-30% by mass of the reaction system.
3. The preparation method according to claim 1, wherein in the chemical modification reaction, the addition amount of the epichlorohydrin is 2-20% of the mass of the reaction system.
4. The preparation method according to claim 1, wherein in the chemical modification reaction, the lignin and the cellulose acetate are dissolved in a mixed solvent of a solvent A and a solvent B, wherein the mixing ratio of the solvent A to the solvent B is 1-2: 1 by volume, and the solvent A/the solvent B in the mixed solvent is acetone/N, N-dimethylformamide, glacial acetic acid/N, N-dimethylformamide, acetone/N, N-dimethylacetamide or glacial acetic acid/N, N-dimethylacetamide.
5. The preparation method according to claim 1, wherein in the electrostatic spinning method, the electrostatic voltage is 15-35 KV, the receiving distance is 10-35cm, the rotating speed of a receiving roller is 200-700 r/min, and the pushing speed of the spinning solution is 0.1-1 ml/h.
6. The preparation method according to claim 1, wherein the pre-oxidation treatment is to pre-oxidize the carbon fiber precursor in an air atmosphere, the pre-oxidation is started from room temperature, the temperature is raised to 200 ℃ to 300 ℃ at a rate of 0.01 ℃ to 2.00 ℃/min, and the temperature is kept for 8 to 12 hours at the temperature, so as to obtain the pre-oxidized fiber.
7. The preparation method according to claim 1, wherein the carbonization treatment is to heat and carbonize the pre-oxidized fiber obtained by the pre-oxidation treatment under the protection of inert gas, heat the pre-oxidized fiber to 600 ℃ to 1400 ℃ at a speed of 2 ℃ to 10 ℃/min, and keep the temperature at the temperature for 2 to 6 hours to obtain the lignin/cellulose acetate based electrospun carbon fiber.
8. Use of the lignin/cellulose acetate based epoxy modified carbon fiber prepared by the method of any one of claims 1 to 7 in the preparation of an electrode material of a capacitor.
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