CN107723847A - A kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer - Google Patents
A kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer Download PDFInfo
- Publication number
- CN107723847A CN107723847A CN201711011540.XA CN201711011540A CN107723847A CN 107723847 A CN107723847 A CN 107723847A CN 201711011540 A CN201711011540 A CN 201711011540A CN 107723847 A CN107723847 A CN 107723847A
- Authority
- CN
- China
- Prior art keywords
- lignin
- heat transfer
- prepared based
- filamentous nanocarbon
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229920005610 lignin Polymers 0.000 claims abstract description 27
- 238000009987 spinning Methods 0.000 claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 13
- 239000000661 sodium alginate Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 7
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- 238000005554 pickling Methods 0.000 claims abstract description 3
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 13
- 239000002121 nanofiber Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 241001124569 Lycaenidae Species 0.000 description 4
- 235000014987 copper Nutrition 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000002360 preparation method Methods 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
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, purifying lignin is dissolved in alkaline solution, successively addition sodium alginate and Nanometer Copper, and hybrid material is obtained through depressurizing rotary evaporation after ultrasonic agitation;Hybrid material is added in centrifugal box-spinning machine at 200~250 DEG C and carries out melting centrifugal spinning, obtains hybridized fiber;Hybridized fiber is placed in high temperature furnace, rises to 280~300 DEG C with 0.01~3 DEG C/min heating rate, 1~6h of constant temperature;1000~2000 DEG C are then heated to, is carbonized, the time is 0.5~12h, and carbon nano-fiber is obtained after pickling.The mesoporous content height of carbon nano-fiber, the pore space structure prepared the beneficial effects of the invention are as follows lignin is controllable.
Description
Technical field
The invention belongs to the preparing technical field of porous carbon fiber, being related to one kind, based on heat transfer to prepare lignin-base porous
The method of carbon nano-fiber.
Background technology
From black liquid lignin due to have the advantages that phosphorus content is high, resource is renewable, it is cheap and quite
It is concerned.It is mostly burned to use but the diversity of the complexity of its component and performance strongly limit its further application
It is extremely low in generating, effective rate of utilization.Lignin is prepared into activated carbon fibre through processes such as spinning technique, pre-oxidation, carbonization and activation
Dimension turns into the effective way for improving its added value.Further to expand lignin-base active carbon material answering in intelligent clothing field
With the inexpensive porous carbon fiber that structure specific surface area is big, mesoporous content is high, pore space structure is controllable turns into key.Patent CN
105862173A discloses a kind of alkali lignin base electrostatic spinning carbon fiber and preparation method and application, by by alkali lignin
It is dissolved in polyacrylonitrile after DMF and lignin-base nano fiber is prepared for using electrospinning process, and through pre-
Carbon nano-fiber is obtained after oxidation and carbonization.But spinning process yields poorly along with the use of a large amount of organic solvents, it is difficult to advises
Modelling produces.The mesoporous content of gained carbon nano-fiber is low simultaneously, pore structure not easy-regulating.Compared to electrostatic spinning, melt from
Heart spinning has then prevented the use of organic solvent, has the advantages that spinning speed is fast, and gained fiber fineness is high.But the knot of lignin
Structure and component are complicated, it is difficult to carry out melting centrifugal spinning.
The content of the invention
It is an object of the invention to provide a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, solution
The mesoporous content that current lignin of having determined prepares carbon nano-fiber is low, pore structure not easy-regulating the problem of.
The technical solution adopted in the present invention is to follow the steps below:
Step 1:Purifying lignin is dissolved in alkaline solution, successively addition sodium alginate and Nanometer Copper, after ultrasonic agitation
Hybrid material is obtained through depressurizing rotary evaporation;Hybrid material is added in centrifugal box-spinning machine and melted at 200~250 DEG C
Centrifugal spinning, obtain hybridized fiber;
Step 2:Step 1 gained hybridized fiber is placed in high temperature furnace, risen to 0.01~3 DEG C/min heating rate
280~300 DEG C, 1~6h of constant temperature;1000~2000 DEG C are then heated to, is carbonized, the time is 0.5~12h, after pickling
To carbon nano-fiber.
Further, the lignin hydroxy radical content after purification in step 1 is more than 6mmol/g, the connection side between construction unit
Formula is mainly β-β and β -1.
Further, the weight average molecular weight of the sodium alginate in step 1 be less than 100,000, addition for gross mass 0.05~
10%.
Further, the addition of the Nanometer Copper in step 1 is the 0.1~5% of gross mass.
Further, the turntable rotation speed of centrifugal box-spinning machine is 1000~20000 revs/min in step 1.
Further, a diameter of 50~900nm of porous filamentous nanocarbon in step 2, it is continuous multi-stage pore structure, aperture is
1~80nm.
The mesoporous content height of carbon nano-fiber, the pore space structure prepared the beneficial effects of the invention are as follows lignin is controllable.
Embodiment
With reference to embodiment, the present invention is described in detail.
Lignin used is the sulphur purchased from (Suzano Papel e Celulose S.A.) company in following examples
Hydrochlorate lignin, purified using ceramic membrane filter equipment, purifying precision is 5kDa.
Embodiment 1:98g is purified into lignin (weight average molecular weight is 4,000) in single-necked flask and is dissolved in pH=12 alkalescence
In solution, 1g sodium alginates (weight average molecular weight is 70,000) and 1g Nanometer Coppers, ultrasonic disperse 30min (ultrasonic powers are successively added
120W, supersonic frequency 40KHz), lignin/sodium alginate/copper is then obtained using Rotary Evaporators rotary evaporation at 80 DEG C
Hybrid material;Gained hybrid material is added in melting centrifugal box-spinning machine and carries out spinning, spinning temperature is 240 DEG C, centrifugation speed
Spend for 6000 revs/min, obtain lignin/sodium alginate/Nanometer Copper Hybrid nanofibers.By gained Hybrid nanofibers in pipe
Pre-oxidized, be carbonized and activated in formula stove, be first warming up to 280 DEG C with 0.01 DEG C/min heating rate, constant temperature 1h.Then with
1 DEG C/min heating rate is warming up to 1000 DEG C and is carbonized, carbonization time 1h.By gained activated carbon fiber in hydrofluoric acid
Lignin-base porous filamentous nanocarbon is obtained after immersion 12h.Gained carbon nano-fiber has hierarchical porous structure, a diameter of
850nm, specific surface area 520m2/ g, mesoporous pore volume are 0.11cm3/g。
Embodiment 2:96g is purified into lignin (weight average molecular weight is 4,000) in single-necked flask and is dissolved in pH=12 alkalescence
In solution, 2g sodium alginates (weight average molecular weight is 70,000) and 2g Nanometer Coppers, ultrasonic disperse 30min (ultrasonic powers are successively added
120W, supersonic frequency 40KHz), lignin/sodium alginate/copper is then obtained using Rotary Evaporators rotary evaporation at 80 DEG C
Hybrid material;Gained hybrid material is added in melting centrifugal box-spinning machine and carries out spinning, spinning temperature is 250 DEG C, centrifugation speed
Spend for 8000 revs/min, obtain lignin/sodium alginate/Nanometer Copper Hybrid nanofibers.By gained Hybrid nanofibers in pipe
Pre-oxidized, be carbonized and activated in formula stove, be first warming up to 280 DEG C with 0.03 DEG C/min heating rate, constant temperature 3h.Then with
3 DEG C/min heating rate is warming up to 1200 DEG C and is carbonized, carbonization time 2h.By gained activated carbon fiber in hydrofluoric acid
Lignin-base porous filamentous nanocarbon is obtained after immersion 12h.Gained carbon nano-fiber has hierarchical porous structure, a diameter of
760nm, specific surface area 610m2/ g, mesoporous pore volume are 0.26cm3/g。
Embodiment 3:96g is purified into lignin (weight average molecular weight is 4,000) in single-necked flask and is dissolved in pH=12 alkalescence
In solution, 1g sodium alginates (weight average molecular weight is 70,000) and 3g Nanometer Coppers, ultrasonic disperse 30min (ultrasonic powers are successively added
120W, supersonic frequency 40KHz), lignin/sodium alginate/copper is then obtained using Rotary Evaporators rotary evaporation at 80 DEG C
Hybrid material;Gained hybrid material is added in melting centrifugal box-spinning machine and carries out spinning, spinning temperature is 240 DEG C, centrifugation speed
Spend for 10000 revs/min, obtain lignin/sodium alginate/Nanometer Copper Hybrid nanofibers.Gained Hybrid nanofibers are existed
Pre-oxidized, be carbonized and activated in tube furnace, be first warming up to 280 DEG C with 0.05 DEG C/min heating rate, constant temperature 3h.Then
1200 DEG C are warming up to 3 DEG C/min heating rate to be carbonized, carbonization time 3h.By gained activated carbon fiber in hydrofluoric acid
Lignin-base porous filamentous nanocarbon is obtained after middle immersion 12h.Gained carbon nano-fiber has hierarchical porous structure, a diameter of
620nm, specific surface area 660m2/ g, mesoporous pore volume are 0.32cm3/g。
Embodiment 4:90g is purified into lignin (weight average molecular weight is 4,000) in single-necked flask and is dissolved in pH=12 alkalescence
In solution, 5g sodium alginates (weight average molecular weight is 70,000) and 5g Nanometer Coppers, ultrasonic disperse 30min (ultrasonic powers are successively added
120W, supersonic frequency 40KHz), lignin/sodium alginate/copper is then obtained using Rotary Evaporators rotary evaporation at 80 DEG C
Hybrid material;Gained hybrid material is added in melting centrifugal box-spinning machine and carries out spinning, spinning temperature is 250 DEG C, centrifugation speed
Spend for 15000 revs/min, obtain lignin/sodium alginate/Nanometer Copper Hybrid nanofibers.Gained Hybrid nanofibers are existed
Pre-oxidized, be carbonized and activated in tube furnace, be first warming up to 290 DEG C with 0.1 DEG C/min heating rate, constant temperature 3h.Then
1100 DEG C are warming up to 5 DEG C/min heating rate to be carbonized, carbonization time 2h.By gained activated carbon fiber in hydrofluoric acid
Lignin-base porous filamentous nanocarbon is obtained after middle immersion 12h.Gained carbon nano-fiber has hierarchical porous structure, a diameter of
460nm, specific surface area 720m2/ g, mesoporous pore volume are 0.41cm3/g。
It is also an advantage of the present invention that:
(1) the lignin-base porous filamentous nanocarbon provided in the present invention possesses that production cost is low, specific surface area is big, hole
Hole structure-controllable, it is easy to the advantages that industrialized production.
(2) the lignin-base porous filamentous nanocarbon provided in the present invention, can using melting centrifugal spinning method
The property spun is good, and fiber quality is excellent, and production cost is greatly reduced, and can carry out continuous production.
(3) the lignin-base porous filamentous nanocarbon provided in the present invention possesses hierarchical porous structure, and mesoporous content is high, hole
Road diameter is big, is expected to be widely used in the fields such as intelligent clothing as fibrous electrode of super capacitor, wide market.
Described above is only the better embodiment to the present invention, not makees any formal limit to the present invention
System, any simple modification that every technical spirit according to the present invention is made to embodiment of above, equivalent variations and modification,
Belong in the range of technical solution of the present invention.
Claims (6)
- A kind of 1. method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, it is characterised in that enter according to following steps OK:Step 1:Purifying lignin is dissolved in alkaline solution, successively addition sodium alginate and Nanometer Copper, through subtracting after ultrasonic agitation Pressure rotary evaporation obtains hybrid material;Hybrid material is added in centrifugal box-spinning machine at 200~250 DEG C and carries out melting centrifugation Spinning, obtain hybridized fiber;Step 2:Step 1 gained hybridized fiber is placed in high temperature furnace, 280 are risen to 0.01~3 DEG C/min heating rate~ 300 DEG C, 1~6h of constant temperature;1000~2000 DEG C are then heated to, is carbonized, the time is 0.5~12h, and nanometer is obtained after pickling Carbon fiber.
- 2. according to a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, its feature described in claim 1 It is:Lignin hydroxy radical content after purification in the step 1 is more than 6mmol/g, and the connected mode between construction unit is main For β-β and β -1.
- 3. according to a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, its feature described in claim 1 It is:The weight average molecular weight of sodium alginate in the step 1 is less than 100,000, and addition is the 0.05~10% of gross mass.
- 4. according to a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, its feature described in claim 1 It is:The addition of Nanometer Copper in the step 1 is the 0.1~5% of gross mass.
- 5. according to a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, its feature described in claim 1 It is:The turntable rotation speed of centrifugal box-spinning machine is 1000~20000 revs/min in the step 1.
- 6. according to a kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer, its feature described in claim 1 It is:A diameter of 50~the 900nm of porous filamentous nanocarbon in the step 2, is continuous multi-stage pore structure, aperture is 1~ 80nm。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711011540.XA CN107723847B (en) | 2017-10-26 | 2017-10-26 | Method for preparing lignin-based porous carbon nanofibers based on heat conduction |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711011540.XA CN107723847B (en) | 2017-10-26 | 2017-10-26 | Method for preparing lignin-based porous carbon nanofibers based on heat conduction |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107723847A true CN107723847A (en) | 2018-02-23 |
CN107723847B CN107723847B (en) | 2020-10-13 |
Family
ID=61212711
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711011540.XA Active CN107723847B (en) | 2017-10-26 | 2017-10-26 | Method for preparing lignin-based porous carbon nanofibers based on heat conduction |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107723847B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101078137A (en) * | 2007-06-29 | 2007-11-28 | 东华大学 | Lignin-base nano carbon fibre and preparation method thereof |
CN104114756A (en) * | 2012-01-23 | 2014-10-22 | 茵芬提亚公司 | Method for stabilizing lignin fiber for further conversion to carbon fiber |
CN104499096A (en) * | 2014-12-21 | 2015-04-08 | 东南大学 | Preparation method of nano carbon fiber-metal composite capable of removing medium/low-concentration volatile organic compounds |
CN104797751A (en) * | 2012-09-20 | 2015-07-22 | 格拉弗技术国际控股有限公司 | Carbon fibers derived from lignin |
US20160258082A1 (en) * | 2015-03-06 | 2016-09-08 | Ut-Battelle, Llc | Low temperature stabilization process for production of carbon fiber having structural order |
-
2017
- 2017-10-26 CN CN201711011540.XA patent/CN107723847B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101078137A (en) * | 2007-06-29 | 2007-11-28 | 东华大学 | Lignin-base nano carbon fibre and preparation method thereof |
CN104114756A (en) * | 2012-01-23 | 2014-10-22 | 茵芬提亚公司 | Method for stabilizing lignin fiber for further conversion to carbon fiber |
CN104797751A (en) * | 2012-09-20 | 2015-07-22 | 格拉弗技术国际控股有限公司 | Carbon fibers derived from lignin |
CN104499096A (en) * | 2014-12-21 | 2015-04-08 | 东南大学 | Preparation method of nano carbon fiber-metal composite capable of removing medium/low-concentration volatile organic compounds |
US20160258082A1 (en) * | 2015-03-06 | 2016-09-08 | Ut-Battelle, Llc | Low temperature stabilization process for production of carbon fiber having structural order |
Non-Patent Citations (2)
Title |
---|
XIANYING QIN等: "Fe3O4 nanoparticles encapsulated in electrospun porous carbon fibers with a compact shell as high-performance anode for lithium ion batteries", 《CARBON》 * |
麻彬彬等: "磁性多孔碳复合材料的简易合成及其吸附性能", 《华北理工大学学报》 * |
Also Published As
Publication number | Publication date |
---|---|
CN107723847B (en) | 2020-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103422194B (en) | A kind of strong-hydrophobicity porous carbon nanofiber and preparation method thereof | |
CN102522568B (en) | Method for preparing electrode material for all-vanadium flow battery | |
CN103882559B (en) | High-ratio surface porous carbon fiber and preparation method thereof and application | |
CN105734724B (en) | A kind of method that electrostatic spinning prepares carbon nano-fiber | |
CN109440228B (en) | Preparation method of cellulose-based carbon nanofiber | |
CN109763210B (en) | Method for preparing cellulose-based carbon fiber or carbon film by ionic liquid | |
CN108597901A (en) | A kind of method that the double spray of electrostatic spinning prepare cobalt acid nickel carbon fiber flexibility electrode material | |
CN103111274B (en) | Preparation method of graphene/TiO2 fiber | |
CN104332640A (en) | Preparation method of thermally-reduced graphene oxide/nano carbon fiber composite electrode for full-vanadium flow battery | |
CN105603585B (en) | A kind of preparation method of the controllable hollow carbon fiber of yardstick | |
CN106757538A (en) | A kind of electrical spinning method prepares porous carbon fiber preparation method | |
CN111321487B (en) | Preparation method of carbon nanofiber with graphene structure on surface | |
CN106435841A (en) | Polyacrylonitrile porous carbon fiber preparation method | |
KR20050040872A (en) | Preparation method of polyacrylonitrile(pan)/polyimide(pi) composite nano-fibers by electrospinning, and carbon fibers, activated carbon fibers therefrom | |
Hu et al. | Lignin-based/polypyrrole carbon nanofiber electrode with enhanced electrochemical properties by electrospun method | |
CN111100603A (en) | High-thermal-conductivity phase-change energy storage material based on electrostatic spinning and preparation method thereof | |
CN107021549A (en) | The preparation method of graphene/carbon nano-tube/carbon nanofiber membrane tri compound structure capacitance desalination electrode | |
CN107604479A (en) | A kind of preparation method of lignin-base multi-stage porous activated carbon fiber | |
CN109659152A (en) | A kind of three-dimensional micro charcoal-aero gel/ruthenium-oxide combination electrode material and preparation method for supercapacitor | |
CN107604480A (en) | A kind of lignin-base activated carbon fiber preparation method for electrode of super capacitor | |
CN107723847A (en) | A kind of method that lignin-base porous filamentous nanocarbon is prepared based on heat transfer | |
CN110592700B (en) | Method for preparing porous cellulose diacetate fibers by normal-temperature dry spinning, and product and application thereof | |
CN108642861A (en) | A kind of electrostatic spinning prepares the compound film method of conduction absorption of nano-metal-oxide doping | |
CN109629227B (en) | Preparation method of fiber-based carbon nanotube conductive material | |
CN107761195B (en) | Preparation method of lignin-based carbon nanofiber for supercapacitor electrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information |
Address after: 266100 No. 7 East Hongkong Road, Laoshan District, Shandong, Qingdao Applicant after: QINGDAO University Address before: 266071 Ningxia Road, Shandong, China, No. 308, No. Applicant before: QINGDAO University |
|
CB02 | Change of applicant information | ||
GR01 | Patent grant | ||
GR01 | Patent grant |