CN108660547A - A kind of lignin-base nano carbon fibre and preparation method thereof, carbon fiber electrode - Google Patents
A kind of lignin-base nano carbon fibre and preparation method thereof, carbon fiber electrode Download PDFInfo
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- CN108660547A CN108660547A CN201710206267.XA CN201710206267A CN108660547A CN 108660547 A CN108660547 A CN 108660547A CN 201710206267 A CN201710206267 A CN 201710206267A CN 108660547 A CN108660547 A CN 108660547A
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- 239000000835 fiber Substances 0.000 title claims abstract description 54
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 18
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 82
- 239000000243 solution Substances 0.000 claims abstract description 74
- 229920005610 lignin Polymers 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 41
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 239000002028 Biomass Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000007711 solidification Methods 0.000 claims abstract description 6
- 230000008023 solidification Effects 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims 1
- 238000001523 electrospinning Methods 0.000 claims 1
- 239000002134 carbon nanofiber Substances 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 5
- 229940068984 polyvinyl alcohol Drugs 0.000 description 36
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 36
- 238000000034 method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001336 alkenes Chemical class 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
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material 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 present invention provides a kind of lignin-base nano carbon fibre and preparation method thereof, carbon fiber electrodes, belong to carbon nano-fiber preparing technical field.What the embodiment of the present invention was realized in：(1) mixed solution of grapheme material and polyvinyl alcohol and lignin aqueous slkali are mixed to get spinning solution, lignin fibre film will be obtained after spinning solution spinning；(2) obtained lignin fibre film is cured；(3) the lignin fibre film after solidification is carbonized；Grapheme material includes the one or more of graphene, biomass graphene, graphene oxide and its their lamellar structure.The present invention not only solves the bad problem of previous graphene dispersion, while also greatly improving the mechanical property and electric conductivity of lignin-base carbon fiber.
Description
Technical field
The present invention relates to carbon nano-fiber preparing technical fields, in particular to a kind of lignin-base nano carbon fibre
And preparation method thereof.
Background technology
Carbon nano-fiber is a kind of novel nano carbon material in one dimension, due to its, good conductivity small with diameter, specific surface
It accumulates big and good chemical stability and is widely used in the fields such as energy storage, catalysis and absorption.Prepare carbon nano-fiber
Method include mainly method of electrostatic spinning, hydro-thermal method, chemical vapour deposition technique etc..Compared to other methods, method of electrostatic spinning by
In simple for process and widely applied.The raw material of carbon nano-fiber is prepared mainly with polyacrylonitrile, phenolic aldehyde tree at present
Based on the high polymers such as fat, but with the worsening shortages of fossil energy, the shortage problem of the chemicals based on fossil energy
Thereupon, it is got the attention using Biomass-based chemicals to supplement the research of petroleum base high molecular material.
Lignin is the second class aromatic polymer material that cellulose is only second in quantity, predominantly wood hydrolysis industry
With the by-product of paper industry environment is seriously polluted due to being not fully utilized.Therefore the commercialization of lignin is realized
Using it is the target of people for a long time to turn waste into wealth.With the continuous improvement that people recognize energy crisis, this target becomes
It obtains more prominent.It is lignin phosphorus content higher (55%-66%), renewable, of low cost, and contain in lignin molecule
A large amount of aromatic group, therefore can be used as carbon fiber material and utilized.Contain methoxyl group, phenolic hydroxyl group, carboxylic in lignin structure
Many functional groups such as base and carboxymethyl and chemical bond carry out chemical modification for it, realize synthesis so there is very strong reactivity
Using providing possibility.
But lignin spinnability is poor, while existing lignin-base nano carbon fibre intensity is low, cannot meet and increasingly increase
The long market demand.
Invention content
The first object of the present invention is to provide a kind of preparation method of lignin-base nano carbon fibre, can solve wood
The low problem of the problem and existing carbon nano-fiber intensity of quality spinnability difference.
The second object of the present invention is to provide a kind of lignin-base nano carbon fibre, and intensity is high, conducts electricity very well.
The third object of the present invention is to provide a kind of carbon fiber electrode, conduct electricity very well.
What the embodiment of the present invention was realized in：
A kind of preparation method of lignin-base nano carbon fibre, includes the following steps：
(1) mixed solution of grapheme material and polyvinyl alcohol and lignin aqueous slkali are mixed to get spinning solution, will spun
Lignin fibre film is obtained after silk liquid spinning；
(2) obtained lignin fibre film is cured；
(3) the lignin fibre film after solidification is carbonized；
Grapheme material includes one kind of graphene, biomass graphene, graphene oxide and its their lamellar structure
Or it is several.
A kind of lignin-base nano carbon fibre is prepared according to the preparation method of above-mentioned lignin-base nano carbon fibre
Made of.
A kind of carbon fiber electrode, the raw material for preparing the carbon fiber electrode include above-mentioned lignin-base nano carbon fibre.
Compared with prior art, the advantageous effect of the embodiment of the present invention is：
The present invention improves the mechanical property of carbon nano-fiber by grapheme material, and lignin is improved using polyvinyl alcohol
Spinnability, and polyvinyl alcohol overcomes the problems, such as graphene dispersion unevenness also as the dispersant of grapheme material.The present invention is not
The bad problem of previous graphene dispersion is addressed only, while also greatly improving the mechanical property of lignin-base carbon fiber and leading
Electrical property, and The present invention reduces the additions more than organic solvent, have saved cost of material, have simplified preparation process.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The principle of the preparation method of the lignin-base nano carbon fibre of the embodiment of the present invention is using grapheme material as raw material
The intensity of carbon nano-fiber is improved, the spinnability of lignin is realized by polyvinyl alcohol, while polyvinyl alcohol can be used as stone
The dispersant of black alkene, the dispersibility of graphene in the solution can be improved by being mixed with graphene, reduce graphene in the solution
Reunite.
The preparation method of the lignin-base nano carbon fibre of the embodiment of the present invention includes the following steps：
Step 1：Prepare spinning solution
Grapheme material and polyvinyl alcohol are configured to solution respectively and mixed.It will be matched by grapheme material and polyvinyl alcohol
Mixed solution made of system is added in the lignin aqueous slkali being formulated by alkaline solution, is mixed to get spinning solution.This hair
The grapheme material of bright embodiment include graphene, biomass graphene, graphene oxide and its their lamellar structure one
Kind is several.The grapheme material can be by mechanically pulling off the conventional fabrication process such as method, oxidation-reduction method and be prepared；
Further include being prepared by techniques such as high temperature carbonizations using biomass resource (such as cellulose, lignin etc.).
Step 1.1：Prepare grapheme material/polyvinyl alcohol solution
Prepare grapheme material solution.Preferably, a concentration of 0.2-0.8wt% of grapheme material solution, more preferably
Ground, a concentration of 0.2wt%, 0.4wt%, 0.5wt, 0.6wt% or 0.8wt% of grapheme material solution.Preferably graphene
The aqueous solution of material.Grapheme material solution can also directly bought on the market other than preparation.Utilize supersonic cell
Crusher is fully dispersed in the solution by grapheme material, obtains finely dispersed grapheme material solution.
Prepare or buy poly-vinyl alcohol solution.Preferably, compound concentration is the poly-vinyl alcohol solution of 0.2-0.8wt%.It is poly-
Glycohol solution is the aqueous solution of polyvinyl alcohol.
Above-mentioned grapheme material solution is mixed with poly-vinyl alcohol solution, it is molten to obtain grapheme material/polyvinyl alcohol
The weight ratio 1 of liquid, wherein grapheme material and polyvinyl alcohol：(150-180).Preferably, grapheme material and polyvinyl alcohol
Weight ratio is 1：150.Preferably, the weight ratio 1 of grapheme material and polyvinyl alcohol：160.It is highly preferred that grapheme material with
The weight ratio of polyvinyl alcohol is 1：180.
Preferably, above-mentioned grapheme material is graphene oxide.
Abundant oxygen-containing function is contained on presoma or derivative of the graphene oxide as a kind of graphene, surface
Group can further occur chemical reaction for graphene oxide and improve active site.Therefore, the embodiment of the present invention is to aoxidize stone
Black alkene replaces graphene playing its excellent mechanical performance while can also further increase reactivity, is conducive to further change
The mechanical property of kind carbon nano-fiber.
On the one hand polyvinyl alcohol is mixed with grapheme material is conducive to the dispersibility of grapheme material in the solution, another party
Face is used as spinning-aid agent, is conducive to the spinnability for improving lignin, plays a dual role of disperseing and helping spinning.
Step 1.2：Prepare lignin aqueous slkali
Lignin is dissolved in aqueous slkali, lignin aqueous slkali is made.Preferably, the aqueous slkali of the embodiment of the present invention is strong
Aqueous slkali.Similarly, lignin aqueous slkali can also directly be bought from market.The weight of lignin and alkali in lignin aqueous slkali
Than being 1：(0.5-4).Strong base solution can be the mixed liquor of NaOH solution or KOH solution or both.Preferably, strong base solution
For KOH solution, a concentration of 10-40wt%.Preferably, the weight ratio of lignin and highly basic is 1：0.8.Preferably, wooden
The weight ratio of element and highly basic is 1：1.Preferably, the weight ratio of lignin and highly basic is 1：4.
The embodiment of the present invention introduces lye, is on the one hand conducive to lignin dissolution, on the other hand in follow-up carbonization process
It can play the role of activating pore-creating, this prepares carbon fiber compared with existing preparation method, such as using DMF, also eliminates
The activation step in later stage, simplification of flowsheet.
Step 1.3：Mixing
Grapheme material/polyvinyl alcohol solution is added into lignin aqueous slkali, and spinning solution is made.In mixing, lead to
Cross the dosage of control grapheme material/polyvinyl alcohol solution so that the content of spinning solution grapheme material accounts for lignin weight
The 0.1-1% of amount.
It should be noted that including but not limited to above range for the concentration of grapheme material solution of the embodiment of the present invention
0.2-0.8wt% can be any concentration, in preparation process, it is only necessary to meet graphene material in the spinning solution finally obtained
The content of material accounts for the 0.1-1wt% of lignin weight, and the concentration of grapheme material solution is bigger, a certain amount of for obtaining
Grapheme material spinning solution, addition grapheme material solution dosage it is fewer, conversely, grapheme material solution is dense
Spend smaller, dosage is more, and those skilled in the art can adjust accordingly according to the grapheme material solution actually prepared.Together
Sample, the present invention is not also particularly limited the concentration of poly-vinyl alcohol solution, can also be except above-mentioned concentration range its
He only need to meet grapheme material and poly- second by concentration when buying or preparing grapheme material/polyvinyl alcohol solution
The weight ratio 1 of enol：(150-180), can be to it according to poly-vinyl alcohol solution those skilled in the art of various concentration
Dosage is adaptively adjusted.
In preferred embodiments of the present invention, the viscosity of above-mentioned spinning solution is adjusted to 900- with distilled water and polyvinyl alcohol
1200mPa·s。
Step 2：Spinning
Above-mentioned spinning solution is subjected to spinning, lignin fibre film is made.Spinning process can be：Electrostatic spinning or air spinning
Silk.
Preferably, spinning process of the embodiment of the present invention is electrostatic spinning.
After above-mentioned spinning solution is stood, preferably stand for 24 hours.It is preferred that spinning condition is：It is 15-25kV, spins in spinning voltage
Flight lead from be 20-40 DEG C for 15-25cm, spinning temperature, spinning under conditions of spinning humidity is 30-50%.Meanwhile spinning
The propulsion rate of liquid is 1-3ml/h.
Spinning is carried out under these conditions, obtains lignin fibre film.
Step 3：Solidification
The lignin fibre film obtained after electrostatic spinning is cured into 0.5- under conditions of temperature is 90-120 DEG C
1.5h。
Step 4：Charing
Lignin fibre film after will be cured is placed in high temperature furnace, is warming up to the heating rate of 2-5 DEG C/min
750-850 DEG C, keep the temperature 1.5-2.5h.
After above-mentioned steps, lignin-base nano carbon fibre is made.
Step 5：Post-processing
Lignin-base nano Carbon fibe is placed in 5% dilute hydrochloric acid solution and is impregnated for 24 hours, in being then washed to using distillation
Property, obtain lignin-base active nano Carbon fibe.This step is optional step.The embodiment of the present invention receives the lignin-base of acquisition
Rice carbon fiber impregnates in dilute hydrochloric acid, is conducive to the alkaline matter for removing lignin-base nano carbon fibre and ash grades impurity, with
Improve product purity.
Grapheme material is dispersed in polyvinyl alcohol water solution by the embodiment of the present invention first, and very rich with source
Rich lignin mixing obtains grapheme material/lignin mixed liquor (i.e. spinning solution), with grapheme material/lignin mixed liquor
For presoma, by spinning, solidification and charing and etc. obtain lignin-base nano carbon fibre film.The system of the embodiment of the present invention
Preparation Method not only solves the bad problem of previous graphene dispersion, while greatly improving the mechanical property of lignin-base carbon fiber
Energy and electric conductivity.In addition, the embodiment of the present invention need not introduce other additional organic solvents (such as DMF), original is reduced
Expect cost, simplifies preparation process, and by introducing lye, not only contribute to lignin dissolution, and carbonized subsequently
It can play the role of activating pore-creating in journey, after this is also eliminated compared with the existing preparation method for being prepared carbon fiber using DMF
The activation step of phase, is further simplified technological process.
A kind of lignin-base nano carbon fibre is prepared according to the preparation method of above-mentioned lignin-base nano carbon fibre
Made of.
A kind of carbon fiber electrode, raw material include above-mentioned lignin-base nano carbon fibre.
It should be noted that the preparation process of the carbon fiber electrode of the embodiment of the present invention and other do not carry in the description
And material composition be the prior art, be no longer described in detail herein.
With reference to embodiment, the present invention is further described.
Embodiment 1
By graphene oxide ultrasonic disperse in distilled water, compound concentration is the graphene oxide water solution of 0.5wt%.Together
When compound concentration be 10wt% polyvinyl alcohol (PVA) aqueous solution, and take 10g 0.5wt% graphene oxide solutions and 90g
The PVA solution of 10wt% mixes, and uniformly mixed graphene oxide/polyvinyl alcohol (GO/PVA) mixing is obtained after high-speed stirred
Solution.
It takes 10g alkali lignins to be dissolved in the KOH solution of a concentration of 10wt% of 100g, is mixed evenly, obtain uniform
Lignin aqueous slkali.A certain amount of GO/PVA mixed solutions are added in lignin aqueous slkali and are uniformly mixed, are spun
Silk liquid so that the content of graphene oxide is the 0.1% of lignin weight in spinning solution.
A certain amount of spinning solution is taken, a certain amount of distilled water is added and PVA adjusts its viscosity to 1000mPa.s.By spinning
Liquid is placed in syringe, on-load voltage 20kV, and spinning distance is 20cm, and spinning temperature is 20 DEG C, and spinning humidity is 30%, and
Spinning is carried out with the rate of extrusion of 1ml/h, the spinning time is 1h, finally obtains a lignin fibre film.
Tunica fibrosa is placed at 100 DEG C and is cured, hardening time 1h.Lignin fibre film is placed in tube type resistance furnace
In be warming up to 800 DEG C with the heating rate of 3 DEG C/min and carbonized, constant temperature 2h obtains lignin-base nano carbon fibre film.It will receive
Rice Carbon fibe film, which is placed in 5% dilute hydrochloric acid solution, to be impregnated for 24 hours, is then washed to neutrality with distillation and is dried, obtains lignin
Base active nano carbon fiber.
Embodiment 2-5
Embodiment 2-5 only changes the content of graphene oxide in spinning solution compared with Example 1.The spinning of embodiment 2-5
In silk liquid, the content of graphene oxide is respectively 0.2%, 0.4%, the 0.6% and 1% of the weight of lignin, and other conditions are complete
It is complete consistent.
Embodiment 6-8
Embodiment 6-8 only changes the concentration of KOH solution compared with Example 1, is respectively 20wt%, 30wt%,
40wt%, other conditions are completely the same.
Embodiment 9-11
Embodiment 9-11 only changes the viscosity of spinning solution compared with Example 1.It is adjusted and is implemented with distilled water and polyvinyl alcohol
The viscosity of the spinning solution of example 9-11 is respectively 900mPas, 1100mPas and 1200mPas, and other conditions are completely the same.
Embodiment 12-14
Embodiment 12-14 only changes spinning parameter compared with Example 1.
The spinning parameter of embodiment 12 is：Spinning voltage is 15kV, spinning distance is 15cm, spinning temperature is 25 DEG C, spins
Silk humidity is 35%, and the propulsion rate of spinning solution is 1.5ml/h, and other conditions are completely the same.
The spinning parameter of embodiment 13 is：Spinning voltage is 22kV, spinning distance is 24cm, spinning temperature is 30 DEG C, spins
Silk humidity is 40%, and the propulsion rate of spinning solution is 3ml/h, and other conditions are completely the same.
The spinning parameter of embodiment 14 is：Spinning voltage is 25kV, spinning distance is 25cm, spinning temperature is 40 DEG C, spins
Silk humidity is 50%, and the propulsion rate of spinning solution is 2.5ml/h, and other conditions are completely the same.
Embodiment 15-17
Embodiment 15-17 only changes tunica fibrosa solidification compared with Example 1 and carbonization condition, other conditions are completely the same.
Embodiment 15
Tunica fibrosa is placed at 90 DEG C and is cured, hardening time 1.5h.Lignin fibre film is placed in tubular electric resistance
750 DEG C are warming up in stove with the heating rate of 2 DEG C/min to be carbonized, constant temperature 1.5h obtains lignin-base nano carbon fibre film.
Embodiment 16
Tunica fibrosa is placed at 110 DEG C and is cured, hardening time 1h.Lignin fibre film is placed in tube type resistance furnace
In be warming up to 800 DEG C with the heating rate of 4 DEG C/min and carbonized, constant temperature 2h obtains lignin-base nano carbon fibre film.
Embodiment 17
Tunica fibrosa is placed at 120 DEG C and is cured, hardening time 1h.Lignin fibre film is placed in tube type resistance furnace
In be warming up to 850 DEG C with the heating rate of 5 DEG C/min and carbonized, constant temperature 2.5h obtains lignin-base nano carbon fibre film.
Embodiment 18-19
Compared with Example 1, distinctive points are graphene oxide replacing with graphene (embodiment embodiment 18-19
And biomass graphene (embodiment 19) 18).
The invention also includes other unshowned combinations by above-described embodiment.
Comparative example 1
Difference lies in the mixed solutions for being not added with grapheme material/polyvinyl alcohol with embodiment 1 for this comparative example, directly will
It carries out spinning, and other conditions are same as Example 1, specifically：
It takes 10g alkali lignins to be dissolved in the KOH solution of 100g 10%, is mixed evenly, obtain uniform lignin alkali
Solution.A certain amount of distilled water is added and PVA adjusts its viscosity to 1000mPa.s, obtains spinning solution, spinning solution is placed in
In syringe, on-load voltage 20kV, spinning distance is 20cm, and carries out spinning with the rate of extrusion of 1ml/h, and the spinning time is
1h finally obtains a tunica fibrosa.
Tunica fibrosa is placed at 100 DEG C and is cured, hardening time 1h.Nano fibrous membrane is placed in tube type resistance furnace
It is warming up to 800 DEG C, and constant temperature 2h with the heating rate of 3 DEG C/min, obtains carbon nano-fiber film.
Comparative example 2
This comparative example is existing PAN/DMF spinning solutions, and other conditions are same as Example 1.Specifically：
It takes 10g alkali lignins to be dissolved in 100g dimethylformamides (DMF), is mixed evenly, obtain uniform wooden
Plain aqueous slkali.A certain amount of polyacrylonitrile (PAN) is added and adjusts its viscosity to 1000mPa.s, obtains spinning solution, by spinning original
Liquid is placed in syringe, on-load voltage 20kV, and spinning distance is 20cm, and carries out spinning, spinning with the rate of extrusion of 1ml/h
Time is 1h, finally obtains a tunica fibrosa.
Tunica fibrosa is placed at 100 DEG C and is cured, hardening time 1h.Nano fibrous membrane is placed in tube type resistance furnace
It is warming up to 800 DEG C, and constant temperature 2h with the heating rate of 3 DEG C/min, obtains carbon nano-fiber film.
Test example
It is used as electrode material after carbon nano-fiber film made from embodiment and comparative example is cut to definite shape, in three electricity
Electro-chemical test is carried out under polar body system, while its conductivity is tested using four-point probe, is shown in Table 1.
Table 1
In conclusion a kind of lignin-base nano carbon fibre provided by the invention and preparation method thereof, it can for lignin
The disadvantages such as the property spun is poor, and carbon nano-fiber intensity is low, lignin aqueous slkali is uniformly mixed with the PVA dispersion liquids of grapheme material,
A kind of blend spinning liquid is prepared, nanofiber is obtained by way of electrostatic spinning, a kind of high-performance is obtained after carbonization-activation
Graphene modified lignin resin base nano carbon fibre, intensity is high, conducts electricity very well.Meanwhile the embodiment of the present invention need not introduce
Other additional organic solvents reduce cost of material, simplify preparation process, and also eliminate in existing preparation method
Activation step is further simplified technological process.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lignin-base nano carbon fibre, which is characterized in that include the following steps：
(1) mixed solution of grapheme material and polyvinyl alcohol and lignin aqueous slkali are mixed to get spinning solution, by the spinning
Lignin fibre film is obtained after silk liquid spinning；
(2) obtained lignin fibre film is cured；
(3) the lignin fibre film after solidification is carbonized；
The grapheme material includes one kind of graphene, biomass graphene, graphene oxide and its their lamellar structure
Or it is several.
2. the preparation method of lignin-base nano carbon fibre according to claim 1, which is characterized in that in the spinning solution
The content of grapheme material accounts for the 0.1-1% of lignin weight.
3. the preparation method of lignin-base nano carbon fibre according to claim 1, which is characterized in that the spinning solution
Viscosity is 900-1200mPas；
Preferably, the viscosity of the spinning solution is adjusted to 900-1200mPas with distilled water and polyvinyl alcohol.
4. the preparation method of lignin-base nano carbon fibre according to claim 1, which is characterized in that use electrostatic spinning
Spinning is carried out to the spinning solution；
Preferably, the electrospinning conditions are：Voltage 15-25kV, spinning distance 15-25cm, 20-40 DEG C of spinning temperature,
Spinning humidity 30-50%, the propulsion rate 1-3ml/h of spinning solution.
5. the preparation method of the lignin-base nano carbon fibre according to any one of claim 1-4, which is characterized in that
In step (1), grapheme material described in the mixed solution of the grapheme material and polyvinyl alcohol and the polyvinyl alcohol
Weight ratio 1：(150-180).
6. the preparation method of lignin-base nano carbon fibre according to claim 5, which is characterized in that the lignin alkali
The weight ratio of lignin and alkali is 1 in solution：(0.5-4).
7. the preparation method of lignin-base nano carbon fibre according to claim 6, which is characterized in that in step (2), Gu
It is 90-120 DEG C to change temperature, hardening time 0.5-1.5h.
8. the preparation method of lignin-base nano carbon fibre according to claim 7, which is characterized in that in step (3), charcoal
It is 750-850 DEG C to change temperature, keeps the temperature 1.5-2.5h；
Preferably, the heating rate for being warming up to the carbonization temperature is 2-5 DEG C/min.
9. a kind of lignin-base nano carbon fibre, which is characterized in that it is wooden according to claim 1-8 any one of them
What the preparation method of plain base nano carbon fibre was prepared.
10. a kind of carbon fiber electrode, which is characterized in that the raw material for preparing the carbon fiber electrode includes described in claim 9
Lignin-base nano carbon fibre.
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