CN108660547B - Lignin-based carbon nanofiber, preparation method thereof and carbon fiber electrode - Google Patents
Lignin-based carbon nanofiber, preparation method thereof and carbon fiber electrode Download PDFInfo
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- CN108660547B CN108660547B CN201710206267.XA CN201710206267A CN108660547B CN 108660547 B CN108660547 B CN 108660547B CN 201710206267 A CN201710206267 A CN 201710206267A CN 108660547 B CN108660547 B CN 108660547B
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- 229920005610 lignin Polymers 0.000 title claims abstract description 114
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 25
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 90
- 239000000243 solution Substances 0.000 claims abstract description 89
- 238000009987 spinning Methods 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 45
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 45
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
-
- 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
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/121—Halogen, halogenic acids or their salts
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a lignin-based carbon nanofiber and a preparation method thereof, and a carbon fiber electrode, and belongs to the technical field of carbon nanofiber preparation. The embodiment of the invention is realized by the following steps: (1) mixing a mixed solution of a graphene material and polyvinyl alcohol with a lignin alkali solution to obtain a spinning solution, and spinning the spinning solution to obtain a lignin fiber membrane; (2) curing the obtained lignin fiber membrane; (3) carbonizing the cured lignin fiber membrane; the graphene material comprises one or more of graphene, biomass graphene, graphene oxide and a lamellar structure thereof. The method solves the problem of poor dispersion of the graphene in the prior art, and greatly improves the mechanical property and the conductivity of the lignin-based carbon fiber.
Description
Technical Field
The invention relates to the technical field of preparation of carbon nanofibers, and particularly relates to a lignin-based carbon nanofiber and a preparation method thereof.
Background
The nano carbon fiber is a novel one-dimensional nano carbon material, and is widely applied to the fields of energy storage, catalysis, adsorption and the like due to the advantages of small diameter, good conductivity, large specific surface area, good chemical stability and the like. The method for preparing the nano carbon fiber mainly comprises an electrostatic spinning method, a hydrothermal method, a chemical vapor deposition method and the like. Compared with other methods, the electrostatic spinning method is widely applied due to simple and easy process. At present, the raw materials for preparing the nano carbon fiber mainly take high polymers such as polyacrylonitrile, phenolic resin and the like, but with the increasing shortage of fossil energy, the problem of the shortage of chemicals based on the fossil energy comes along with the shortage, and the research of supplementing petroleum-based high polymer materials by using biomass-based chemicals is widely concerned.
Lignin is a second class of aromatic polymeric materials, second only to cellulose in quantity, is mainly a byproduct of the wood hydrolysis industry and the paper industry, and seriously pollutes the environment because of insufficient utilization. Therefore, the commercial application of the lignin is realized, and the purpose of changing waste into valuable is long-standing. This goal becomes more prominent as people have increased awareness of the energy crisis. The lignin has high carbon content (55-66 percent), is renewable and low in cost, and lignin molecules contain a large amount of aromatic groups, so that the lignin can be used as a carbon fiber raw material. The lignin structure contains a plurality of functional groups and chemical bonds such as methoxy, phenolic hydroxyl, carboxyl, carboxymethyl and the like, so that the lignin has strong reaction activity and provides possibility for chemical modification and comprehensive utilization of the lignin.
But the lignin has poor spinnability, and the existing lignin-based carbon nanofiber has low strength and cannot meet the increasing market demand.
Disclosure of Invention
The first purpose of the present invention is to provide a method for preparing a lignin-based filamentous nanocarbon, which can solve the problems of poor spinnability of lignin and low strength of the conventional filamentous nanocarbon.
The second purpose of the invention is to provide the lignin-based carbon nanofiber which has high strength and good electrical conductivity.
The third purpose of the invention is to provide a carbon fiber electrode which has good electrical conductivity.
The embodiment of the invention is realized by the following steps:
a preparation method of lignin-based carbon nanofibers comprises the following steps:
(1) mixing a mixed solution of a graphene material and polyvinyl alcohol with a lignin alkali solution to obtain a spinning solution, and spinning the spinning solution to obtain a lignin fiber membrane;
(2) curing the obtained lignin fiber membrane;
(3) carbonizing the cured lignin fiber membrane;
the graphene material comprises one or more of graphene, biomass graphene, graphene oxide and a lamellar structure thereof.
The lignin-based carbon nanofiber is prepared by the preparation method of the lignin-based carbon nanofiber.
The raw materials for preparing the carbon fiber electrode comprise the lignin-based carbon nanofiber.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the invention, the mechanical property of the carbon nanofiber is improved through the graphene material, the spinnability of lignin is improved by using polyvinyl alcohol, and the polyvinyl alcohol is also used as a dispersing agent of the graphene material, so that the problem of uneven dispersion of graphene is solved. The invention not only solves the problem of poor dispersion of the graphene in the past, but also greatly improves the mechanical property and the conductivity of the lignin-based carbon fiber, reduces the addition of more organic solvent, saves the cost of raw materials and simplifies the preparation process.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The principle of the preparation method of the lignin-based carbon nanofiber provided by the embodiment of the invention is that the graphene material is used as a raw material to improve the strength of the carbon nanofiber, the spinnability of lignin is realized through polyvinyl alcohol, and meanwhile, the polyvinyl alcohol can be used as a dispersing agent of graphene, and the dispersion of the graphene in a solution can be improved by mixing the polyvinyl alcohol with the graphene, so that the agglomeration of the graphene in the solution is reduced.
The preparation method of the lignin-based carbon nanofiber provided by the embodiment of the invention comprises the following steps:
step 1: preparation of the spinning dope
And respectively preparing the graphene material and the polyvinyl alcohol into solutions and mixing. Adding a mixed solution prepared from a graphene material and polyvinyl alcohol into a lignin alkali solution prepared from an alkaline solution, and mixing to obtain a spinning solution. The graphene material provided by the embodiment of the invention comprises one or more of graphene, biomass graphene, graphene oxide and a lamellar structure thereof. The graphene material can be prepared by conventional preparation processes such as a mechanical stripping method, an oxidation-reduction method and the like; the biomass material is prepared by using biomass resources (such as cellulose, lignin and the like) through processes such as high-temperature carbonization and the like.
Step 1.1: preparation of graphene material/polyvinyl alcohol mixed solution
And preparing a graphene material solution. Preferably, the concentration of the graphene material solution is 0.2-0.8 wt%, more preferably, the concentration of the graphene material solution is 0.2 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, or 0.8 wt%. Preferably an aqueous solution of the graphene material. Besides preparation, the graphene material solution can be directly purchased from the market. Fully dispersing the graphene material in the solution by using an ultrasonic cell crushing instrument to obtain a uniformly dispersed graphene material solution.
Preparing or purchasing polyvinyl alcohol solution. Preferably, a polyvinyl alcohol solution is prepared at a concentration of 0.2 to 0.8 wt%. The polyvinyl alcohol solution is an aqueous solution of polyvinyl alcohol.
Mixing the graphene material solution with a polyvinyl alcohol solution to obtain a graphene material/polyvinyl alcohol mixed solution, wherein the weight ratio of the graphene material to the polyvinyl alcohol is 1: (150-180). Preferably, the weight ratio of the graphene material to the polyvinyl alcohol is 1: 150. preferably, the weight ratio of the graphene material to the polyvinyl alcohol is 1: 160. more preferably, the weight ratio of graphene material to polyvinyl alcohol is 1: 180.
preferably, the graphene material is graphene oxide.
The graphene oxide is used as a precursor or a derivative of graphene, the surface of the graphene oxide contains rich oxygen-containing functional groups, and active sites are improved for the further chemical reaction of the graphene oxide. Therefore, in the embodiment of the invention, graphene oxide is used to replace graphene, so that the excellent mechanical property of the graphene oxide is exerted, and the reaction activity can be further improved, thereby being beneficial to further improving the mechanical property of the carbon nanofiber.
The polyvinyl alcohol and the graphene material are mixed, so that the dispersibility of the graphene material in a solution is facilitated, and the polyvinyl alcohol and the graphene material are used as a spinning aid, so that the spinnability of lignin is improved, and double functions of dispersion and spinning aid are achieved.
Step 1.2: preparation of lignin alkali solution
Dissolving lignin in alkali solution to obtain lignin alkali solution. Preferably, the alkaline solution of the present embodiment is a strong alkaline solution. Likewise, the lignin base solution can also be purchased directly from the market. The weight ratio of lignin to alkali in the lignin alkali solution is 1: (0.5-4). The strong alkaline solution can be NaOH solution or KOH solution or the mixture of the NaOH solution and the KOH solution. Preferably, the strong alkaline solution is a KOH solution having a concentration of 10 to 40 weight percent. Preferably, the weight ratio of lignin to strong base is 1: 0.8. preferably, the weight ratio of lignin to strong base is 1: 1. preferably, the weight ratio of lignin to strong base is 1: 4.
the embodiment of the invention introduces the alkali liquor, which is beneficial to dissolving lignin on one hand and can play a role in activating and pore-forming in the subsequent carbonization process on the other hand, compared with the existing preparation method, such as preparing carbon fiber by using DMF, the later activation step is also omitted, and the process flow is simplified.
Step 1.3: mixing
And adding the graphene material/polyvinyl alcohol mixed solution into the lignin alkali solution to prepare the spinning solution. During mixing, the addition of the graphene material/polyvinyl alcohol mixed solution is controlled, so that the content of the spinning solution graphene material accounts for 0.1-1% of the weight of lignin.
It should be noted that, for the embodiment of the present invention, the concentration of the graphene material solution includes, but is not limited to, the above range of 0.2 to 0.8 wt%, which may be any concentration, in the preparation process, it is only required to satisfy that the content of the graphene material in the finally obtained spinning solution accounts for 0.1 to 1 wt% of the weight of the lignin, the larger the concentration of the graphene material solution is, the less the graphene material solution is added to obtain a certain amount of the spinning solution of the graphene material, and conversely, the smaller the concentration of the graphene material solution is, the more the graphene material solution is added, and those skilled in the art can correspondingly adjust the concentration according to the actually prepared graphene material solution. Likewise, the concentration of the polyvinyl alcohol solution is not particularly limited in the present invention, and may be other concentration levels than the above concentration range, and when purchasing or preparing the graphene material/polyvinyl alcohol mixed solution, the weight ratio of the graphene material to the polyvinyl alcohol is only required to be 1: (150-180), the addition amount can be adjusted by one skilled in the art according to different concentrations of polyvinyl alcohol solution.
In a preferred embodiment of the invention, the viscosity of the spinning solution is adjusted to 900-1200 mPas with distilled water and polyvinyl alcohol.
Step 2: spinning
And spinning the spinning solution to obtain the lignin fiber membrane. The spinning method can be as follows: electrostatic spinning or air-flow spinning.
Preferably, the spinning method of the embodiment of the invention is electrostatic spinning.
The spinning solution is preferably left to stand for 24 hours. The preferred spinning conditions are: spinning under the conditions of spinning voltage of 15-25 kV, spinning distance of 15-25 cm, spinning temperature of 20-40 ℃ and spinning humidity of 30-50%. Meanwhile, the advancing speed of the spinning solution is 1-3 ml/h.
Spinning is carried out under the conditions to obtain the lignin fiber membrane.
And step 3: curing
Curing the lignin fiber membrane obtained by electrostatic spinning for 0.5-1.5 h at the temperature of 90-120 ℃.
And 4, step 4: charring
The cured lignin fiber membrane is placed in a high temperature furnace, the temperature is raised to 750 ℃ and 850 ℃ at the temperature raising rate of 2-5 ℃/min, and the temperature is kept for 1.5-2.5 h.
After the steps, the lignin-based carbon nanofiber is prepared.
And 5: post-treatment
And (3) soaking the lignin-based nano carbon fiber in a 5% dilute hydrochloric acid solution for 24 hours, and then washing the lignin-based nano carbon fiber to be neutral by using distilled water to obtain the lignin-based activated nano carbon fiber. This step is an optional step. The embodiment of the invention soaks the obtained lignin-based carbon nanofiber in dilute hydrochloric acid, which is beneficial to removing alkaline substances, ash and other impurities of the lignin-based carbon nanofiber so as to improve the product purity.
According to the embodiment of the invention, the graphene material is uniformly dispersed in the polyvinyl alcohol aqueous solution and is mixed with lignin with a very rich source to obtain the graphene material/lignin mixed solution (i.e. spinning solution), and the lignin-based carbon nanofiber membrane is obtained by taking the graphene material/lignin mixed solution as a precursor through steps of spinning, curing, carbonizing and the like. The preparation method provided by the embodiment of the invention not only solves the problem of poor dispersion of the graphene in the past, but also greatly improves the mechanical property and conductivity of the lignin-based carbon fiber. In addition, other additional organic solvents (such as DMF) are not required to be introduced in the embodiment of the invention, the raw material cost is reduced, the preparation process is simplified, the alkali liquor is introduced, the lignin is favorably dissolved, and the function of activating and pore-forming can be achieved in the subsequent carbonization process, so that compared with the existing preparation method for preparing the carbon fiber by using DMF, the later activation step is omitted, and the process flow is further simplified.
The lignin-based carbon nanofiber is prepared by the preparation method of the lignin-based carbon nanofiber.
The carbon fiber electrode comprises the lignin-based carbon nanofiber as a raw material.
It should be noted that the preparation process of the carbon fiber electrode according to the embodiment of the present invention and other raw material components not mentioned in the specification are prior art, and will not be described in detail herein.
The present invention will be further described with reference to the following examples.
Example 1
And ultrasonically dispersing graphene oxide in distilled water to prepare a graphene oxide aqueous solution with the concentration of 0.5 wt%. Meanwhile, preparing a polyvinyl alcohol (PVA) aqueous solution with the concentration of 10 wt%, mixing 10g of 0.5 wt% graphene oxide solution with 90g of 10 wt% PVA solution, and stirring at a high speed to obtain a uniformly mixed graphene oxide/polyvinyl alcohol (GO/PVA) mixed solution.
10g of alkali lignin is dissolved in 100g of KOH solution with the concentration of 10 wt%, and the mixture is uniformly mixed and stirred to obtain uniform lignin alkali solution. Adding a certain amount of GO/PVA mixed solution into a lignin alkali solution, stirring and mixing uniformly to obtain a spinning solution, wherein the content of graphene oxide in the spinning solution is 0.1% of the weight of lignin.
And (3) taking a certain amount of spinning solution, adding a certain amount of distilled water and PVA to adjust the viscosity of the spinning solution to 1000 mPa.s. And (3) placing the spinning solution into an injector, loading voltage of 20kV, spinning distance of 20cm, spinning temperature of 20 ℃, spinning humidity of 30 percent, spinning at an extrusion rate of 1ml/h for 1h, and finally obtaining the lignin fiber membrane.
And curing the fiber membrane at 100 ℃ for 1 h. And (3) putting the lignin fiber membrane in a tubular resistance furnace, heating to 800 ℃ at a heating rate of 3 ℃/min, carbonizing, and keeping the temperature for 2 hours to obtain the lignin-based carbon nanofiber membrane. And (3) soaking the carbon nanofiber membrane in a 5% dilute hydrochloric acid solution for 24 hours, then washing the carbon nanofiber membrane to be neutral by using distilled water, and drying the carbon nanofiber membrane to obtain the lignin-based activated carbon nanofiber.
Examples 2 to 5
Examples 2-5 compared to example 1, only the content of graphene oxide in the spinning dope was changed. In the spinning solutions of examples 2 to 5, the contents of graphene oxide were 0.2%, 0.4%, 0.6%, and 1% by weight of lignin, respectively, and the other conditions were completely the same.
Examples 6 to 8
Examples 6-8 compared to example 1, only the concentration of the KOH solution was changed, which was 20 wt%, 30 wt%, 40 wt%, respectively, and the other conditions were completely the same.
Examples 9 to 11
Examples 9-11 only the viscosity of the dope was changed compared to example 1. The viscosities of the spinning solutions of examples 9 to 11 were adjusted to 900 mPas, 1100 mPas and 1200 mPas, respectively, with distilled water and polyvinyl alcohol, and the other conditions were completely the same.
Examples 12 to 14
Examples 12-14 only varied the spinning parameters compared to example 1.
The spinning parameters for example 12 were: the spinning voltage is 15kV, the spinning distance is 15cm, the spinning temperature is 25 ℃, the spinning humidity is 35%, the advancing speed of the spinning solution is 1.5ml/h, and other conditions are completely consistent.
The spinning parameters for example 13 were: the spinning voltage is 22kV, the spinning distance is 24cm, the spinning temperature is 30 ℃, the spinning humidity is 40%, the advancing speed of the spinning solution is 3ml/h, and other conditions are completely consistent.
The spinning parameters for example 14 were: the spinning voltage is 25kV, the spinning distance is 25cm, the spinning temperature is 40 ℃, the spinning humidity is 50%, the advancing speed of the spinning solution is 2.5ml/h, and other conditions are completely consistent.
Examples 15 to 17
Examples 15-17 changed only the fiber film curing and charring conditions compared to example 1, with the other conditions being completely identical.
Example 15
And curing the fiber membrane at 90 ℃ for 1.5 h. And (3) putting the lignin fiber membrane in a tubular resistance furnace, heating to 750 ℃ at the heating rate of 2 ℃/min, carbonizing, and keeping the temperature for 1.5 hours to obtain the lignin-based carbon nanofiber membrane.
Example 16
And curing the fiber membrane at 110 ℃ for 1 h. And (3) putting the lignin fiber membrane in a tubular resistance furnace, heating to 800 ℃ at a heating rate of 4 ℃/min, carbonizing, and keeping the temperature for 2 hours to obtain the lignin-based carbon nanofiber membrane.
Example 17
And curing the fiber membrane at 120 ℃ for 1 h. And (3) putting the lignin fiber membrane in a tubular resistance furnace, heating to 850 ℃ at the heating rate of 5 ℃/min, carbonizing, and keeping the temperature for 2.5 hours to obtain the lignin-based carbon nanofiber membrane.
Examples 18 to 19
Examples 18-19 are compared to example 1 with the difference that graphene oxide is replaced by graphene (example 18) and biomass graphene (example 19).
The invention also comprises other combinations not shown of the above embodiments.
Comparative example 1
The comparative example is different from the example 1 in that the mixed solution of graphene material/polyvinyl alcohol is not added, and the spinning is directly carried out, and the other conditions are the same as the example 1, specifically:
10g of alkali lignin is dissolved in 100g of 10% KOH solution, and the mixture is uniformly mixed and stirred to obtain a uniform lignin alkali solution. Adding a certain amount of distilled water and PVA to adjust the viscosity to 1000mPa.s to obtain a spinning solution, placing the spinning solution into an injector, loading the voltage to 20kV, spinning the spinning solution at the spinning distance of 20cm, spinning at the extrusion rate of 1ml/h for 1h, and finally obtaining a fiber membrane.
And curing the fiber membrane at 100 ℃ for 1 h. And (3) placing the nano-carbon fiber membrane in a tubular resistance furnace, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain the nano-carbon fiber membrane.
Comparative example 2
This comparative example is a conventional PAN/DMF spin dope, and the other conditions are the same as in example 1. Specifically, the method comprises the following steps:
dissolving 10g of alkali lignin in 100g of Dimethylformamide (DMF), and uniformly mixing and stirring to obtain a uniform lignin alkali solution. Adding a certain amount of Polyacrylonitrile (PAN) to adjust the viscosity of the polyacrylonitrile to 1000mPa.s to obtain spinning solution, placing the spinning solution in an injector, loading the voltage to 20kV, spinning the spinning solution at the spinning distance of 20cm, spinning at the extrusion rate of 1ml/h for 1h, and finally obtaining a fiber membrane.
And curing the fiber membrane at 100 ℃ for 1 h. And (3) placing the nano-carbon fiber membrane in a tubular resistance furnace, heating to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain the nano-carbon fiber membrane.
Test examples
The carbon nanofiber membranes prepared in the examples and comparative examples were cut into a certain shape and used as electrode materials, electrochemical tests were performed in a three-electrode system, and the conductivity was simultaneously measured using a four-probe tester, as shown in table 1.
TABLE 1
In summary, according to the lignin-based carbon nanofibers and the preparation method thereof provided by the invention, aiming at the defects of poor spinnability of lignin, low strength of carbon nanofibers and the like, the lignin alkali solution and the PVA dispersion liquid of the graphene material are uniformly mixed to prepare a mixed spinning solution, the nanofibers are obtained in an electrostatic spinning mode, and the high-performance graphene modified lignin-based carbon nanofibers are obtained after carbonization and activation, and have high strength and good conductivity. Meanwhile, other additional organic solvents are not required to be introduced, so that the raw material cost is reduced, the preparation process is simplified, the activation step in the existing preparation method is omitted, and the process flow is further simplified.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The preparation method of the lignin-based carbon nanofiber is characterized by comprising the following steps of:
(1) mixing a mixed solution of a graphene material and polyvinyl alcohol with a lignin alkali solution to obtain a spinning solution, and spinning the spinning solution to obtain a lignin fiber membrane;
(2) curing the obtained lignin fiber membrane;
(3) carbonizing the cured lignin fiber membrane;
the graphene material comprises one or more of graphene, biomass graphene, graphene oxide and a lamellar structure thereof.
2. The method for preparing lignin-based filamentous nanocarbon according to claim 1, wherein the content of the graphene material in the spinning solution is 0.1 to 1% by weight of lignin.
3. The method for preparing lignin-based filamentous nanocarbon according to claim 1, wherein the viscosity of the spinning solution is 900-1200 mPa-s.
4. The method for preparing lignin-based filamentous nanocarbon according to claim 3, wherein the viscosity of the spinning solution is adjusted to 900-1200 mPa s with distilled water and polyvinyl alcohol.
5. The method for preparing lignin-based filamentous nanocarbon according to claim 1, wherein the spinning solution is spun using electrostatic spinning.
6. The method for preparing lignin-based filamentous nanocarbon according to claim 5, wherein the electrospinning conditions are: the voltage is 15-25 kV, the spinning distance is 15-25 cm, the spinning temperature is 20-40 ℃, the spinning humidity is 30-50%, and the advancing speed of the spinning solution is 1-3 ml/h.
7. The method for preparing lignin-based filamentous nanocarbon according to any one of claims 1 to 6, wherein in the step (1), the weight ratio of the graphene material to the polyvinyl alcohol in the mixed solution of the graphene material and the polyvinyl alcohol is 1: (150-180).
8. The method for preparing lignin-based filamentous nanocarbon according to claim 7, wherein the weight ratio of lignin to alkali in the lignin alkali solution is 1: (0.5-4).
9. The method for preparing lignin-based filamentous nanocarbon according to claim 8, wherein the curing temperature is 90-120 ℃ and the curing time is 0.5-1.5 h in the step (2).
10. The method for preparing lignin-based filamentous nanocarbon according to claim 9, wherein in the step (3), the carbonization temperature is 750-.
11. The method for preparing lignin-based filamentous nanocarbon according to claim 10, wherein a temperature increase rate of raising the temperature to the carbonization temperature is 2-5 ℃/min.
12. A lignin-based filamentous nanocarbon produced by the method for producing a lignin-based filamentous nanocarbon according to any one of claims 1 to 11.
13. A carbon fiber electrode, characterized in that a raw material for producing the carbon fiber electrode comprises the lignin-based filamentous nanocarbon of claim 12.
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