CN109103026A - A kind of preparation method of the derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose - Google Patents
A kind of preparation method of the derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose Download PDFInfo
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- CN109103026A CN109103026A CN201811011218.1A CN201811011218A CN109103026A CN 109103026 A CN109103026 A CN 109103026A CN 201811011218 A CN201811011218 A CN 201811011218A CN 109103026 A CN109103026 A CN 109103026A
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- bacteria cellulose
- fluorine
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- doped
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 83
- 239000001913 cellulose Substances 0.000 title claims abstract description 83
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 241000894006 Bacteria Species 0.000 title claims abstract description 78
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 45
- 239000011737 fluorine Substances 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 42
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000004146 energy storage Methods 0.000 claims abstract description 4
- 239000011232 storage material Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 230000001580 bacterial effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000005255 carburizing Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920002749 Bacterial cellulose Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000005016 bacterial cellulose Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008104 plant cellulose Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000002837 Acetobacter xylinum Nutrition 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241001136169 Komagataeibacter xylinus Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 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
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- -1 carbonization Chemical compound 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to the preparation methods of a kind of fluorine, the derivative carbon nanofiber membrane of nitrogen co-doped bacteria cellulose, comprising: by bacteria cellulose membrane cover on ammonium fluoride, be carbonized, washing, it is dry to get.The present invention retains original tunica fibrosa pattern well, to remain the partially flexible and self-supporting energy and reproducible of bacteria cellulose, fluorine, nitrogen element content can regulate and control with ammonium fluoride additive amount.The method of the present invention is simple, and doping in one step, carburizing temperature is moderate, and the derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose being prepared, specific discharge capacity is very high, and cyclical stability is fine, and electric conductivity is fine.Bacteria cellulose is as recyclable materials, and environmentally protective, applying in flexible super capacitor energy storage material above has good prospect.
Description
Technical field
The invention belongs to the preparation field of hetero atom codope carbon material, in particular to a kind of fluorine, nitrogen co-doped bacterium are fine
The preparation method of the derivative carbon nanofiber membrane of dimension element.
Background technique
With the rapid development of industry, population is sharply increased, and the consumption of global energy just constantly adds at an amazing speed
Fastly, energy shortage and environmental pollution become current mankind and develop two test faced.Therefore must greatly develop low cost, can
Continue and environmental-friendly novel energy conversion meets the growth requirement of modern society with storage device and alleviates increasingly prominent
Environmental problem out.Sustainable and environment friendly material is mentioned, people expect being exactly carbon material first.The source of carbon material
It is very rich, be it is inexhaustible, chemical contamination is small.
Bacteria cellulose (BC) is free from the native cellulose of any impurity, it has fine network structure, higher
Mechanical strength, higher water suction and many unique properties such as water retention property, good biocompatibility and biological degradability.Cause
This is also considered as that performance is best, the highest cellulose of use value, becomes one of the hot spot of current international bio investigation of materials.
(1) bacteria cellulose purity with higher and crystallinity.Compared with plant cellulose, bacteria cellulose is without half
The impurity such as cellulose, lignin exist with 100% Cellulosed molded article.
(2) fine network structure.Bacteria cellulose fibre is that be combined into 20~100nm by the fento of 3~4nm of diameter thick
Fibre bundle, and be intertwined to form flourishing hyperfine network structure.
(3) Modulatory character when synthesizing.The different resulting cellulosic structures of fermentation condition and characteristic are also different, in order to improve fibre
The characteristic of dimension makes it be more suitably applied to each field, and modified method can be used, and improves the property of cellulose.
(4) degradability and reusing of bacteria cellulose.Under field conditions (factors), microorganism can be by cellulose degradation
For the sugar of small molecule, the pollution of environment not will cause.Bacteria cellulose is renewable and degradable biological resource, for construction
Environmentally protective national economy is significant.
(5) extraction process is simple.The extraction process of bacteria cellulose is mainly that the aqueous slkali heating of low concentration is impregnated, can be complete
It is complete to remove the impurity such as remaining thallus and culture medium on fiber, and plant fiber needs the higher lye hot digestion ability of concentration
Remove the impurity such as hemicellulose, the lignin in conjunction with cellulose.
(6) good hydrophily and gas permeability.There are a large amount of hydrophilic radical inside bacteria cellulose, it is intermolecular and point
Sub- inside is connected with each other by hydrogen bond, therefore determines that bacteria cellulose is a kind of hydrogel, wherein combining water to account for major part, freely
Water only accounts for 10%.The cellulose network of purified processing has many ducts, can be permeable and ventilative well, because its is this solely
Special performance, bacteria cellulose is for studying artificial skin.
(7) high-tensile and Young's modulus.For bacteria cellulose after being dried, Young's modulus is to close up to 10MPa
At 4 times of cellulose.
(8) ultra-fine property.The diameter of the bacteria cellulose produced by acetobacter xylinum is natural between 0.01~0.1 μm
Nanometer materials.And about 10 μm of the diameter of plant cellulose, it is hundred times of bacteria cellulose.
Doping is a kind of common method of modifying, is adulterated from initial one-component, and nitrogen, boron, phosphorus, sulphur etc. carry out carbon material
It is modified, to multicomponent codope in recent years.Wherein N doping can inhibit oxygen content, reduce self discharge behavior and electronic contact
Resistance improves carbon surface wettability.Meanwhile the carbon of N doping is by wide coverage because the electronegativity (3.04) of nitrogen can induce
The Charge scaling of adjacent atom on nitrogen-doped carbon surface, this will greatly improve carbon electro-catalysis or generate faraday's reaction, contribution
Part fake capacitance.Although N doping can effectively improve the chemical property of carbon material, excessive nitrogen will lead to material itself
Resistance becomes larger, and nitrogen-containing functional group blocks duct, to reduce the electric conductivity of material.It is fluorine member that electronegativity is maximum in nature
Element, since big electronegativity is conducive to chemical property, researcher is natural it is also envisaged that being adulterated with fluorine element.So in recent years,
People have also carried out many fluorine, nitrogen co-doped research.Fluorine and the nitrogen high electronegativity of its own and the synergistic effect of the two, greatly
The big chemical property for improving carbon material.Either there is biggish mention to electrocatalysis characteristic or capacitance and stability
It rises.Fluorine is adulterated in carbon material and always needs a large amount of Fluorine source, is extremely difficult into porous carbon matrix by Fluorin doped.Mesh
Before, ammonium fluoride is most common one kind, and ammonium fluoride pyrolytic allows material carbon under the atmosphere at ammonia and hydrogen fluoride gas
Change, carries out fluorine, nitrogen co-doped.
Compared with traditional fluorine, nitrogen co-doped, we carry out dual element doping with this substance one-step method of ammonium fluoride.Sodium fluoride
It is heated to decompose and slowly release ammonia and hydrogen fluoride gas, under this double atmosphere, bacteria cellulose membrane material is carried out
Modification.It overcomes twin flue to be passed through ammonia and be fluorinated the tedious steps of nitrogen atmosphere, and provides a slow release fluorination hydrogen
The benign environment of atmosphere.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of fluorine, the derivative carbon nano-fiber of nitrogen co-doped bacteria cellulose
The preparation method of film overcomes twin flue to be passed through ammonia and is fluorinated the tedious steps of nitrogen atmosphere, and provides a slow release fluorine
Change the benign environment of nitrogen atmosphere, this method is simple, and doping in one step, carburizing temperature is moderate, and the fluorine of preparation, nitrogen co-doped bacterium are fine
The derivative carbon nanofiber membrane of dimension element retains original tunica fibrosa pattern well, thus remain bacteria cellulose partially flexible and
Self-supporting energy.
The preparation method of a kind of fluorine, the derivative carbon nanofiber membrane of nitrogen co-doped bacteria cellulose of the invention, comprising:
By bacteria cellulose membrane cover on ammonium fluoride, carbonization, ammonia and ammonium fluoride are film modified to bacteria cellulose, washing,
It is dry, obtain the derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose.
The preferred embodiment of above-mentioned preparation method is as follows:
The bacteria cellulose film, ammonium fluoride mass ratio be 1:5-40, further preferred bacteria cellulose film, ammonium fluoride
Mass ratio be 1:20.
Bacteria cellulose BC dispersion liquid is filtered by vacuum, is extracted to form bacteria cellulose film with vacuum pressure pump.
The solid content of the bacteria cellulose dispersion liquid is 0.60~0.70%.
The solid content 0.65% of further preferred bacteria cellulose BC dispersion liquid.
The bacteria cellulose film quality is 6~7mg, and thickness is about 2.5~3.5 μm.
The further preferred extraction bacteria cellulose film is 6.5mg, and thickness is about 3 μm.
The carbonization are as follows: it is carried out in argon atmosphere, the temperature of carbonization is 500-600 DEG C, heating rate is 3-5 DEG C/
Min, soaking time 0.5-2h.
The further preferably described carbonization carries out in argon atmosphere；The temperature of carbonization be 600 DEG C, heating rate be 5 DEG C/
Min, soaking time 2h.
The ammonium fluoride NH4F is crystalline particles.
The washing are as follows: first acid foam washing uses mass concentration to wash 1-3h for 5% dilute hydrochloric acid, removes a small amount of inorganic salts
Impurity；
Then washing, which is adopted, is washed with deionized 0.5-1h.
The drying is 60 DEG C of dry 6-12h in vacuum drying oven.
The further preferred drying is 60 DEG C of dry 12h in vacuum drying oven.
The present invention also provides a kind of derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose of the method preparation.
The present invention further provides a kind of fluorine of above method preparation, the derivative carbon nano-fiber of nitrogen co-doped bacteria cellulose
Application of the film in the energy storage material of flexible super capacitor.
Beneficial effect
(1) fluorine of the invention being prepared with pyrolysis one step of ammonium fluoride carbonization, nitrogen co-doped bacteria cellulose derived carbon
Nano fibrous membrane retains original tunica fibrosa pattern well, to remain the partially flexible and self-supporting of bacteria cellulose
Can and it is reproducible, fluorine, nitrogen element content can regulate and control with ammonium fluoride additive amount；
(2) the method for the present invention is simple, and doping in one step, carburizing temperature is moderate, and twin flue is overcome to be passed through ammonia and fluorination hydrogen
The tedious steps of atmosphere, while the benign environment of a slow release fluorination nitrogen atmosphere is provided, the fluorine being prepared, nitrogen are total
The derivative carbon nanofiber membrane of the bacteria cellulose of doping, the very high (1A/g in the sulfuric acid electrolyte of 1mol/L of specific discharge capacity
With the specific capacity of 350F/g under current density), cyclical stability is fine, and bacteria cellulose is as recyclable materials, green ring
It protects, above has good prospect in the application of flexible super capacitor energy storage material.
Detailed description of the invention
Fig. 1 be carry out fluorine, it is nitrogen co-doped after BC membrane material SEM figure, wherein (a) be carry out fluorine, it is nitrogen co-doped after
The section SEM of BC membrane material schemes；(b) the surface SEM figure of the BC membrane material after being progress fluorine, is nitrogen co-doped；
Fig. 2 is the SEM figure of BC membrane material of not being carbonized, wherein (a) is the sectional view of BC membrane material of not being carbonized；It (b) is non-carbon
Change the exterior view of BC membrane material；
Fig. 3 be carry out fluorine, it is nitrogen co-doped after BC membrane material surface TEM figure；
Fig. 4 is the XRD diagram of the derivative carbon nanofiber membrane of bacteria cellulose in embodiment 1-5 and comparative example；
Fig. 5 is that the Raman of the derivative carbon nanofiber membrane of bacteria cellulose in embodiment 1-5 and comparative example schemes；
Fig. 6 is specific surface area (BET) figure of the derivative carbon nanofiber membrane of bacteria cellulose in embodiment 1 and comparative example 1；
Fig. 7 is the graph of pore diameter distribution of the derivative carbon nanofiber membrane of bacteria cellulose in embodiment 1 and comparative example 1；
Fig. 8 is bacteria cellulose derived carbon micro/nano fibrous membrane material in embodiment 1-5 and comparative example under 10mV/s rate
CV circulation figure；
Fig. 9 is bacteria cellulose derived carbon micro/nano fibrous membrane material in embodiment 1-5 and comparative example in 1A/g current density
Under charging and discharging curve；
Figure 10 is fluorine, nitrogen co-doped bacteria cellulose derived carbon micro/nano fibrous membrane material in embodiment 1 in different scanning
CV under rate recycles figure；
Figure 11 is fluorine, nitrogen co-doped bacteria cellulose derived carbon micro/nano fibrous membrane material in embodiment 1 in different electric currents
Charging and discharging curve under density.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) the bacteria cellulose dispersion liquid of commercial solid content 0.65% is diluted 10 times, 10ml dispersion liquid is taken to be transferred to very
Empty suction funnel is pumped into a bacterial cellulose film by vacuum pressure pump.The film is lyophilized with freeze dryer, is weighed
6.5mg, 3 μm of thickness (bacterial cellulose film used in following embodiment and comparative example is all this specification).It is lyophilized thin after removing
Fungin film and 130mg ammonium fluoride (BC:NH4F mass ratio is 1:20) it is placed in graphite crucible, under an argon, with 5
DEG C/heating rate of min, it rises to 600 DEG C and keeps the temperature 2h, with 5% concentration salt acid elution 1-3h after taking-up, deionized water washing is each
The derivative carbon nanofiber membrane FN-BC-20 of bacteria cellulose is made in 0.5-1h, last 60 DEG C of vacuum drying 12h.
(2) by 70mg step (1) bacteria cellulose derive carbon nanofiber membrane BC, 20mg acetylene black, 10mg 10%
The mixing of concentration PVDF binder, then uses mortar grinder 30min, is subsequently added into the dilution of 500 μ L N-methyl pyrrolidones (NMP),
The active material is applied on the carbon paper of known quality again, application area 1cm2, last 60 DEG C of vacuum drying 6h, weighing calculating
1~1.5mg of active material quality.
(3) the close carbon paper assembling electric double layer symmetric capacitor of two panels active mass is taken, electrolyte selects 1mol/L sulfuric acid molten
Liquid tests its chemical property with Shanghai Chen Hua electrochemical workstation.
Fig. 1 (a) shows: from section, SEM figure finds out the fluorine of embodiment 1, nitrogen co-doped bacteria cellulose film carbonized fiber
Part fusing bonding.
Fig. 1 (b) shows: fluorine, the nitrogen co-doped bacteria cellulose film carbonized fiber pattern of embodiment 1 are found out from SEM figure
It is effectively maintained, there is a little bonding.
Fig. 3 shows: being apparent from 50 nanometers of the fibre diameter of embodiment 1 from TEM figure hereinafter, and stacking close.
Fig. 8, Fig. 9 show: the specific capacity that FN-BC-20 in embodiment 1 is calculated by charge and discharge electrograph is highest, reaches 350F/
G, same current sweep maximum CV circulation area under speed and also further illustrate specific capacity maximum, and the nearly rectangular area of the material illustrates have
There are good cyclical stability and outstanding high rate performance.
With the specific capacity of 350F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L.
Embodiment 2
It is prepared according to the preparation method of embodiment 1, unlike, the ammonium fluoride is 32.5mg (BC:NH4F=1:
5) the derivative carbon nanofiber membrane FN-BC-5 of fluorine, nitrogen co-doped bacteria cellulose, is made.
With the specific capacity of 279F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L.
Embodiment 3
It is prepared according to the preparation method of embodiment 1, unlike, the ammonium fluoride is 65mg (BC:NH4F=1:
10) the derivative carbon nanofiber membrane FN-BC-10 of fluorine, nitrogen co-doped bacteria cellulose, is made.
With the specific capacity of 314F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L
Embodiment 4
It is prepared according to the preparation method of embodiment 1, unlike, the ammonium fluoride is 195mg (BC:NH4F=1:
30) the derivative carbon nanofiber membrane FN-BC-30 of fluorine, nitrogen co-doped bacteria cellulose, is made.
With the specific capacity of 304F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L
Embodiment 5
It is prepared according to the preparation method of embodiment 1, unlike, the ammonium fluoride is 260mg (BC:NH4F=1:
40) the derivative carbon nanofiber membrane FN-BC-40 of fluorine, nitrogen co-doped bacteria cellulose, is made.
With the specific capacity of 261F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L.
From fig. 4, it can be seen that finding out from XRD, as ammonium fluoride dosage increases, 25 ° of broad peak slightly deviates to the left, and broad peak represents
002 crystal face of agraphitic carbon, illustrate that the carbon of degree of graphitization occurs in carbonization.
As seen from Figure 5, can find out from Raman map, two peaks respectively represent the unordered degree I of graphitizationDHave with graphitization
Sequence degree IG, from ID/IGValue be gradually increased, it will be seen that graphitized ordered degree reduces, and is because fluorine, nitrogen heteroatom doping destroy
The order of graphitic carbon.
As seen from Figure 6, can find out from BET map, fluorine in embodiment 1, it is nitrogen co-doped after bacteria cellulose than comparative example 1
In the bacterial fibers specific surface area that is not doped increased.
As seen from Figure 7, find out from pore-size distribution, fluorine in embodiment 1, it is nitrogen co-doped after bacteria cellulose than comparative example 1
In undoped bacterial fibers pore-size distribution more there is hierarchy, a hierarchical porous structure that is microporous mesoporous and depositing is presented, and
Aperture portion is more wide in range.
By Fig. 8, Fig. 9 as it can be seen that the CV of embodiment and comparative example at 10mV/s recycles figure, illustrate to implement by ring specific area
Example 1 has highest electrochemical specific capacity, this is attributed to appropriate fluorine, nitrogen co-doped amount allows it to have more relative activities higher
Half ionic bond of C-F, while Heteroatom doping appropriate is conducive to the infiltration of electrolyte and does not sacrifice its electric conductivity.
By Figure 10, Figure 11 as it can be seen that CV circulation figure of the embodiment 1 under different surface sweeping rates closes nearly rectangle, illustrate to have good
Good cyclical stability, with the specific capacity of 350F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L.
Comparative example 1
Bacterial cellulose film is prepared according to the preparation method of embodiment 1, unlike, the bacterial fibers after removing are lyophilized
Plain film is directly carbonized in argon atmosphere；The temperature of carbonization is 600 DEG C, and heating rate is 5 DEG C/min, and soaking time is
2h.With 5% concentration salt acid elution 1-3h after taking-up, deionized water washs each 0.5-1h, and last 60 DEG C of vacuum drying 12h are obtained not
The derivative carbon nanofiber membrane BC of the bacteria cellulose of doping.
With the specific capacity of 178F/g under the current density of 1A/g in the sulfuric acid electrolyte of 1mol/L.
Fig. 2 (a) shows: be not carbonized about 3 μm of bacteria cellulose film thickness degree, and the fiber of comparative example 1 are found out from SEM figure
It is fine and close.
Fig. 2 (b) shows: finding out that the bacteria cellulose film fibre compact that is not carbonized of comparative example 1 stacks from SEM figure.
Fig. 8, Fig. 9 show: the specific capacity of undoped bacteria cellulose membrane material is poor in the comparative example, with fluorine, nitrogen
Bacteria cellulose membrane material gap after codope is obvious, illustrates that ammonium fluoride is modified with great role to bacteria cellulose film.
Claims (10)
1. a kind of preparation method of the derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose, comprising:
It by bacteria cellulose membrane cover on ammonium fluoride, is carbonized, washs, it is dry, obtain fluorine, nitrogen co-doped bacteria cellulose derived carbon
Nano fibrous membrane.
2. preparation method according to claim 1, which is characterized in that the bacteria cellulose film, ammonium fluoride mass ratio be
1:5-40。
3. preparation method according to claim 1, which is characterized in that the bacteria cellulose film specifically: by bacterial fibers
Plain dispersion liquid is filtered by vacuum, and bacteria cellulose film is formed.
4. preparation method according to claim 3, which is characterized in that the solid content of the bacteria cellulose dispersion liquid is 0.60
~0.70%.
5. preparation method according to claim 1, which is characterized in that the bacteria cellulose film quality is 6~7mg, thickness
About 2.5~3.5 μm.
6. preparation method according to claim 1, which is characterized in that the carbonization are as follows: it is carried out in argon atmosphere, carbonization
Temperature is 500-600 DEG C, and heating rate is 3-5 DEG C/min, soaking time 0.5-2h.
7. preparation method according to claim 1, which is characterized in that the washing are as follows: first pickling uses mass concentration for 5%
Dilute hydrochloric acid wash 1-3h；Then washing, which is adopted, is washed with deionized 0.5-1h.
8. preparation method according to claim 1, which is characterized in that the drying is 60 DEG C of dry 6- in vacuum drying oven
12h。
9. a kind of derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose of claim 1 the method preparation.
10. a kind of derivative carbon nanofiber membrane of fluorine, nitrogen co-doped bacteria cellulose of claim 1 the method preparation is in flexibility
Application in the energy storage material of supercapacitor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048134A (en) * | 2019-05-27 | 2019-07-23 | 河南师范大学 | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst |
| CN112341546A (en) * | 2020-10-27 | 2021-02-09 | 北京化工大学 | Preparation method of fluorinated biomass membrane material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101629164B1 (en) * | 2015-01-08 | 2016-06-13 | 서울대학교산학협력단 | Carbonaceous material doped with non-metallic elements for the electrode of supercapacitor |
| CN106229157A (en) * | 2016-08-17 | 2016-12-14 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of polyatom co-doped nano carbon fiber and one one step preparation method and purposes |
| CN108281635A (en) * | 2018-01-26 | 2018-07-13 | 北京化工大学 | A kind of nitrogen P elements codope carbon material and its preparation method and application |
-
2018
- 2018-08-31 CN CN201811011218.1A patent/CN109103026B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101629164B1 (en) * | 2015-01-08 | 2016-06-13 | 서울대학교산학협력단 | Carbonaceous material doped with non-metallic elements for the electrode of supercapacitor |
| CN106229157A (en) * | 2016-08-17 | 2016-12-14 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of polyatom co-doped nano carbon fiber and one one step preparation method and purposes |
| CN108281635A (en) * | 2018-01-26 | 2018-07-13 | 北京化工大学 | A kind of nitrogen P elements codope carbon material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HUI-JUAN ZHANG, ET AL.: ""Simultaneous Doping of Nitrogen and Fluorine into Carbon (NFC) as Metal-Free Oxygen Reduction Electrocatalysts"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| ZHAOXIA HU, ET AL.: ""N,P-co-doped carbon nanowires prepared from bacterial cellulose for supercapacitor"", 《J MATER SCI》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048134A (en) * | 2019-05-27 | 2019-07-23 | 河南师范大学 | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst |
| CN112341546A (en) * | 2020-10-27 | 2021-02-09 | 北京化工大学 | Preparation method of fluorinated biomass membrane material |
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