CN109637841A - A kind of preparation method of carbon-fiber beam electrode material - Google Patents
A kind of preparation method of carbon-fiber beam electrode material Download PDFInfo
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- CN109637841A CN109637841A CN201811394817.6A CN201811394817A CN109637841A CN 109637841 A CN109637841 A CN 109637841A CN 201811394817 A CN201811394817 A CN 201811394817A CN 109637841 A CN109637841 A CN 109637841A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 103
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 103
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000007772 electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008014 freezing Effects 0.000 claims abstract description 9
- 238000007710 freezing Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229920000128 polypyrrole Polymers 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical class 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical class C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 206010011224 Cough Diseases 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010257 thawing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a kind of preparation methods of carbon-fiber beam electrode material, belong to novel energy resource material technology field.Described method includes following steps: carrying out surface cleaning processing to carbon fiber bundle with organic solvent first, secondly the carbon fiber bundle surface corona after cleaning treatment is activated, then atomic layer deposition is carried out to the carbon fiber bundle after cleaning activation, freezing interfacial polymerization finally is carried out to the carbon fiber bundle after atomic layer deposition and obtains carbon-fiber beam electrode material.The preparation method process flow is simple, pollution-free, and cost is relatively low, and condition is easily-controllable, consuming little energy, when obtained carbon-fiber beam electrode is used for supercapacitor, has the characteristics that specific capacity is high, stability is good, conductivity is high, be conducive to the industrialized production of high-performance super capacitor.
Description
Technical field
The present invention relates to a kind of preparation methods of carbon-fiber beam electrode material, belong to novel energy resource material technology field.
Background technique
Supercapacitor combines the advantage of battery Yu conventional dielectric capacitor, high-energy density and high power density
The blank between battery and conventional dielectric capacitor is filled up.A kind of material of the conducting polymer as electrode of super capacitor
Material has very high specific capacity, while being easy to close since such material is also the redox reaction occurred in charge and discharge
It is lower at, preparation cost, so developing in recent years in supercapacitor field extremely rapid.After carbon fiber is the 1950s
A kind of reinforcing material of development, it has high specific strength, high ratio modulus, high temperature resistant, conduction and thermal expansion coefficient small etc. a series of
Excellent performance.Atomic layer deposition is a kind of special chemical vapour deposition technique, is by replacing vaporous precursors pulse
It is passed through reaction chamber and a kind of method that Chemisorption forms film occurs on depositing base surface, have excellent three-dimensional total
The features such as shape, the uniformity of large area and accurate subband structures film thickness monitoring.
China Patent Publication No. CN108335919A, publication date on July 27th, 2018, inventing a kind of entitled metal has machine frame
Frame/conducting polymer composite material, its preparation and application.This method is using carbon fiber bundle as electrode basement, with electrodeposit metals
Organic frame/conducting polymer composite material be electrode active material, using polyvinyl alcohol-electrolyte gel be solid electrolyte with
Diaphragm prepares resulting fibrous supercapacitor and shows excellent capacitive property.The ratio of supercapacitor made from the method
Capacity is smaller, and stability is poor.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of preparation methods of carbon-fiber beam electrode material.
To achieve the goals above, technical solution of the invention is.
A kind of preparation method of carbon-fiber beam electrode material, the method carry out according to the following steps.
A. carbon fiber bundle is immersed in the container for filling organic solvent, then container is placed in super by bath raio 1:50-100
It is cleaned by ultrasonic 1-4h in sound wave cleaning device, removes the glue-line and its attachment on carbon fiber bundle surface, then by the carbon fiber after cleaning
Beam is dried up with compressed nitrogen.
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active,
Wherein, corona irradiation temperature is 10-45 DEG C, voltage 16-25Kv, and distance is 1-3cm, and the processing time is 5-15min.
C. use halide or organometallic complex as the first presoma, ammonium hydroxide is high as the second presoma
The nitrogen or helium of purity are as carrier gas, 90-150 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.05-0.2s,
Exposure duration 8-15s, carrier gas purge time 15-30s, so that one layer of carbon fiber bundle outside deposition fine and close metal oxidation
Object film.
D. this cyclic deposition number is repeated 10-1000 times by step c the method, deposit thickness is 1- after completing deposition
100nm。
E., carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L
In, 30 DEG C of temperature is kept, 100ml 0.2-1mol/L FeCl is added dropwise into container3Solution, time for adding 30min are generated
Container, is put into refrigerator after being added dropwise to complete solution being frozen into ice by orange flocculent deposit, and cryogenic temperature is -4--15 DEG C.
F. the cyclohexane solution for the 100ml 0.01-1.5mol/L pyrroles for being cooled to 5-10 DEG C in advance in advance is poured into step e
It is frozen into the container of ice, then container is placed in freezing reaction at -4--15 DEG C and for 24 hours, is deposited on the outer surface of carbon fiber bundle poly-
Pyrroles is thawed after the reaction was completed, and then the carbon fiber bundle that polypyrrole is deposited on outer surface is placed in equipped with 0.05-1.5mol/L
Acid solution in infiltrate 0.5-2h, ion doping is carried out to it, inhibits the effect that detaches of counter ion, then by the carbon fiber after infiltration
Beam is cleaned repeatedly with second alcohol and water, is then taken out drying 3h, is obtained carbon-fiber beam electrode material.
The organic solvent has ethyl alcohol or one of propyl alcohol or acetone.
First presoma refers to TiCl4Or titanium tetraisopropylate or MnCl2Or NiCl2One of.
The acid solution is one of p-methyl benzenesulfonic acid or 2- naphthalene sulfonic acids.
Compared with prior art, advantage significant (1) is easily controllable using ALD deposition process, post-depositional by the present invention
Active material film has splendid uniformity, and can completely coat carbon fiber bundle comprehensively, and ALD sinks by active material
There is very big advantage in terms of product to 3-D nano, structure.(2) it using ammonium hydroxide as the second presoma, is mentioned by the way that N is atom doped
High particle conduction efficiency.(3) methyl orange and FeCl3Reaction generates soft mode version, is grown on polypyrrole cladding in soft mode version and is formed
Tubular morphology.(4) freezing interfacial polymerization slowly makes the film of poly pyrrole on carbon fiber felt surface because of reaction speed at low temperature
Finer and close stability and conductivity to improve polypyrrole structure.(5) the preparation method process flow is simple, pollution-free, cost
Lower, condition is easily-controllable, consuming little energy, when obtained carbon-fiber beam electrode is used for supercapacitor, has specific capacity high, stable
The features such as property is good, conductivity is high, is conducive to the industrialized production of high-performance super capacitor.
Specific embodiment
Combined with specific embodiments below, present invention is further described in detail.
A kind of preparation method of carbon-fiber beam electrode material, the preparation method carry out according to the following steps.
A. carbon fiber bundle is immersed in the container for filling organic solvent, then container is placed in super by bath raio 1:50-100
It is cleaned by ultrasonic 1-4h in sound wave cleaning device, removes the glue-line and its attachment on carbon fiber bundle surface, then by the carbon fiber after cleaning
Beam is dried up with compressed nitrogen.
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active,
Wherein, corona irradiation temperature is 10-45 DEG C, voltage 16-25Kv, and distance is 1-3cm, and the processing time is 5-15min.
C. use halide or organometallic complex as the first presoma, ammonium hydroxide is high as the second presoma
The nitrogen or helium of purity are as carrier gas, 90-150 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.05-0.2s,
Exposure duration 8-15s, carrier gas purge time 15-30s, so that one layer of carbon fiber bundle outside deposition fine and close metal oxidation
Object film.
D. this cyclic deposition number is repeated 10-1000 times by step c the method, deposit thickness is 1- after completing deposition
100nm。
E., carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L
In, 30 DEG C of temperature is kept, 100ml 0.2-1mol/L FeCl is added dropwise into container3Solution, time for adding 30min are generated
Container, is put into refrigerator after being added dropwise to complete and is frozen into ice by orange flocculent deposit, and cryogenic temperature is -4--15 DEG C.
F. the cyclohexane solution for the 100ml 0.01-1.5mol/L pyrroles for being cooled to 5-10 DEG C in advance in advance is poured into step e
It is frozen into the container of ice, then container is placed in freezing reaction at -4--15 DEG C and for 24 hours, is deposited on the outer surface of carbon fiber bundle poly-
Pyrroles is thawed after the reaction was completed, and then the carbon fiber bundle that polypyrrole is deposited on outer surface is placed in equipped with 0.05-1.5mol/L
Acid solution in infiltrate 0.5-2h, ion doping is carried out to it, inhibits the effect that detaches of counter ion, then by the carbon fiber after infiltration
Beam is cleaned repeatedly with second alcohol and water, is then taken out drying 3h, is obtained carbon-fiber beam electrode material.
The organic solvent has ethyl alcohol or one of propyl alcohol or acetone.
First presoma refers to TiCl4Or titanium tetraisopropylate or MnCl2Or NiCl2One of.
The acid solution is one of p-methyl benzenesulfonic acid or 2- naphthalene sulfonic acids.
Specific embodiment
Embodiment one
A. carbon fiber bundle is immersed in ethyl alcohol, then the container for filling carbon fiber bundle and propyl alcohol is placed in by bath raio 1:50
It is cleaned by ultrasonic 1h in ultrasonic washing instrument, removes the glue-line and its attachment on carbon fiber bundle surface, then by the carbon fiber after cleaning
Beam is dried up with compressed nitrogen.
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active,
Wherein, corona irradiation temperature is 10 DEG C, voltage 16Kv, and distance is 1cm, and the processing time is 5min.
C. TiCl is used4As the first presoma, ammonium hydroxide is as the second presoma, and the nitrogen or helium of high-purity are as load
Gas, 90 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.05s, exposure duration 8s, carrier gas purge time 15s, thus
So that carbon fiber bundle surface deposits one layer of fine and close metal-oxide film.
D. this cyclic deposition number is repeated 100 times by step c the method, deposit thickness is 10nm after completing deposition.
E., carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L
In, 30 DEG C of temperature is kept, 100ml 0.2mol/L FeCl is added dropwise into container3Solution, time for adding 30min generate orange
Container, is put into refrigerator after being added dropwise to complete solution being frozen into ice by color flocculent deposit, and cryogenic temperature is -4 DEG C.
F. the cyclohexane solution for the 100ml 0.01mol/L pyrroles for being cooled to 5 DEG C in advance in advance is poured into step e and is frozen into ice
Container in, then container is placed at -4 DEG C freezing reaction for 24 hours, deposits polypyrrole on the outer surface of carbon fiber bundle, reacted
At rear defrosting, it is molten that the carbon fiber bundle that polypyrrole is deposited on outer surface is then placed in the p-methyl benzenesulfonic acid equipped with 0.05mol/L
0.5h is infiltrated in liquid, ion doping is carried out to it, inhibits the effect that detaches of counter ion, then by the carbon fiber bundle ethyl alcohol after infiltration
It is cleaned repeatedly with water, then takes out drying 3h, obtain carbon-fiber beam electrode material.
Embodiment two
A. carbon fiber bundle is immersed in propyl alcohol, then the container for filling carbon fiber bundle and propyl alcohol is placed in by bath raio 1:80
It is cleaned by ultrasonic 2h in ultrasonic washing instrument, removes the glue-line and its attachment on carbon fiber bundle surface, then by the carbon fiber after cleaning
Beam is dried up with compressed nitrogen.
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active,
Wherein, corona irradiation temperature is 25 DEG C, voltage 20Kv, and distance is 2cm, and the processing time is 10min.
C. MnCl is used2As the first presoma, ammonium hydroxide is as the second presoma, and the nitrogen or helium of high-purity are as load
Gas, 100 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.1s, exposure duration 10s, carrier gas purge time 20s, by
This makes carbon fiber bundle surface deposit one layer of fine and close metal-oxide film.
D. this cyclic deposition number is repeated 200 times by step c the method, deposit thickness is 20nm after completing deposition.
E., carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L
In, 30 DEG C of temperature is kept, 100ml 0.3mol/L FeCl is added dropwise into container3Solution, time for adding 30min generate orange
Container, is put into refrigerator after being added dropwise to complete solution being frozen into ice by color flocculent deposit, and cryogenic temperature is -8 DEG C.
F. the cyclohexane solution for the 100ml 0.1mol/L pyrroles for being cooled to 8 DEG C in advance in advance is poured into step e and is frozen into ice
Container in, then container is placed at -10 DEG C freezing reaction for 24 hours, deposits polypyrrole on the outer surface of carbon fiber bundle, reacted
At rear defrosting, then the carbon fiber bundle that polypyrrole is deposited on outer surface is placed in the 2- naphthalene sulfonic acids solution equipped with 0.1mol/L
1h is infiltrated, ion doping is carried out to it, inhibits the effect that detaches of counter ion, then the carbon fiber bundle after infiltration is anti-with second alcohol and water
Multiple cleaning then takes out drying 3h, obtains carbon-fiber beam electrode material.
Embodiment three
A. carbon fiber bundle is immersed in acetone, then the container for filling carbon fiber bundle and acetone is placed in by bath raio 1:100
It is cleaned by ultrasonic 4h in ultrasonic washing instrument, removes the glue-line and its attachment on carbon fiber bundle surface, then by the carbon fiber after cleaning
Beam is dried up with compressed nitrogen.
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active,
Wherein, corona irradiation temperature is 45 DEG C, voltage 25Kv, and distance is 3cm, and the processing time is 15min.
C. NiCl is used2As the first presoma, ammonium hydroxide is as the second presoma, and the nitrogen or helium of high-purity are as load
Gas, 150 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.2s, exposure duration 15s, carrier gas purge time 30s, by
This makes carbon fiber bundle surface deposit one layer of fine and close metal-oxide film.
D. this cyclic deposition number is repeated 1000 times by step c the method, deposit thickness is after completing deposition
100nm。
E., carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L
In, 30 DEG C of temperature is kept, 100ml 1mol/L FeCl is added dropwise into container3Solution, time for adding 30min are generated orange
Container, is put into refrigerator after being added dropwise to complete solution being frozen into ice by flocculent deposit, and cryogenic temperature is -10 DEG C.
F. the cyclohexane solution for the 100ml 1.5mol/L pyrroles for being cooled to 10 DEG C in advance in advance is poured into step e and is frozen into ice
Container in, then container is placed at -15 DEG C freezing reaction for 24 hours, deposits polypyrrole on the outer surface of carbon fiber bundle, reacted
At rear defrosting, then the carbon fiber bundle that polypyrrole is deposited on outer surface is placed in the p-methyl benzenesulfonic acid solution equipped with 1.5mol/L
Middle infiltration 2h carries out ion doping to it, inhibits the effect that detaches of counter ion, then by the second alcohol and water of the carbon fiber bundle after infiltration
It cleans repeatedly, then takes out drying 3h, obtain carbon-fiber beam electrode material.
Example IV
A. carbon fiber bundle is immersed in ethyl alcohol, then the container for filling carbon fiber bundle and ethyl alcohol is placed in by bath raio 1:90
It is cleaned by ultrasonic 3h in ultrasonic washing instrument, removes the glue-line and its attachment on carbon fiber bundle surface, then by the carbon fiber after cleaning
Beam is dried up with compressed nitrogen.
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active,
Wherein, corona irradiation temperature is 30 DEG C, voltage 22Kv, and distance is 2cm, and the processing time is 12min.
C. use titanium tetraisopropylate as the first presoma, ammonium hydroxide is as the second presoma, the nitrogen or helium of high-purity
As carrier gas, 120 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.15s, exposure duration 12s, the carrier gas purge time
25s, so that carbon fiber bundle surface deposits one layer of fine and close metal-oxide film.
D. this cyclic deposition number is repeated 500 times by step c the method, deposit thickness is 50nm after completing deposition.
E., carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L
In, 30 DEG C of temperature is kept, 100ml 0.5mol/LFeCl is added dropwise into container3Solution, time for adding 30min generate orange
Container, is put into refrigerator after being added dropwise to complete solution being frozen into ice by color flocculent deposit, and cryogenic temperature is -8 DEG C.
F. the cyclohexane solution for the 100ml 1.2mol/L pyrroles for being cooled to 8 DEG C in advance in advance is poured into step e and is frozen into ice
Container in, then container is placed at -8 DEG C freezing reaction for 24 hours, deposits polypyrrole on the outer surface of carbon fiber bundle, reacted
At rear defrosting, then the carbon fiber bundle that polypyrrole is deposited on outer surface is placed in the 2- naphthalene sulfonic acids solution equipped with 1.2mol/L
1.5h is infiltrated, ion doping is carried out to it, inhibits the effect that detaches of counter ion, then by the second alcohol and water of the carbon fiber bundle after infiltration
It cleans repeatedly, then takes out drying 3h, obtain carbon-fiber beam electrode material.
Claims (4)
1. a kind of preparation method of carbon-fiber beam electrode material, which is characterized in that the preparation method sequentially includes the following steps:
A. carbon fiber bundle is immersed in the container for filling organic solvent, then container is placed in ultrasonic wave by bath raio 1:50-100
It is cleaned by ultrasonic 1-4h in cleaning device, removes the glue-line and its attachment on carbon fiber bundle surface, then the carbon fiber bundle after cleaning is used
Compressed nitrogen drying；
B. the carbon fiber bundle surface after cleaning treatment is subjected to corona radiation treatment, obtains the carbon fiber bundle of surface active, wherein
Corona irradiation temperature is 10-45 DEG C, voltage 16-25Kv, and distance is 1-3cm, and the processing time is 5-15min；
C. use halide or organometallic complex as the first presoma, ammonium hydroxide is as the second presoma, high-purity
Nitrogen or helium as carrier gas, 90-150 DEG C of atomic layer deposition reaction temperature, presoma burst length 0.05-0.2s, exposure
Time 8-15s, carrier gas purge time 15-30s, so that one layer of fine and close metal oxide of carbon fiber bundle outside deposition is thin
Film；
D. this cyclic deposition number is repeated 10-1000 times by step c the method, deposit thickness is 1- after completing deposition
100nm；
E. the carbon fiber bundle after atomic layer deposition is put into the container for filling the methyl orange solution of 100ml 0.01mol/L, is protected
100ml 0.2-1mol/L FeCl is added dropwise into container for the temperature for holding 30 DEG C3Solution, time for adding 30min are generated orange
Container, is put into refrigerator after being added dropwise to complete solution being frozen into ice by flocculent deposit, and cryogenic temperature is -4--15 DEG C；
F. the cyclohexane solution for the 100ml 0.01-1.5mol/L pyrroles for being cooled to 5-10 DEG C in advance in advance is poured into step e and is freezed
In the container of Cheng Bing, then container is placed in freezing reaction at -4--15 DEG C and for 24 hours, poly- pyrrole is deposited on the outer surface of carbon fiber bundle
It coughs up, thaws after the reaction was completed, then the carbon fiber bundle for being deposited with polypyrrole on outer surface is placed in equipped with 0.05-1.5mol/L's
0.5-2h is infiltrated in acid solution, ion doping is carried out to it, inhibits the effect that detaches of counter ion, then by the carbon fiber bundle after infiltration
It is cleaned repeatedly with second alcohol and water, then takes out drying 3h, obtain carbon-fiber beam electrode material.
2. a kind of preparation method of carbon-fiber beam electrode material as described in claim 1, which is characterized in that organic in described
Solvent has ethyl alcohol or one of propyl alcohol or acetone.
3. a kind of preparation method of carbon-fiber beam electrode material as described in claim 1, which is characterized in that first forerunner
Body refers to TiCl4Or titanium tetraisopropylate or MnCl2Or NiCl2One of.
4. a kind of preparation method of carbon-fiber beam electrode material as described in claim 1, which is characterized in that the acid solution
For one of p-methyl benzenesulfonic acid or 2- naphthalene sulfonic acids.
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| CN112012007A (en) * | 2020-09-03 | 2020-12-01 | 河北多谱电子科技有限公司 | Preparation method of flexible electromagnetic protection material with meridian-shaped bionic skin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862948A (en) * | 2015-04-28 | 2015-08-26 | 武汉纺织大学 | Production method of color carbon fibers |
| CN106367947A (en) * | 2016-10-12 | 2017-02-01 | 武汉纺织大学 | Method for improving tensile mechanical property of fibers |
| CN107634233A (en) * | 2017-09-13 | 2018-01-26 | 深圳大学 | A kind of transition metal oxide elctro-catalyst and its preparation method and application |
| CN108063060A (en) * | 2017-12-05 | 2018-05-22 | 武汉纺织大学 | A kind of preparation method of paper substrate electrode material for super capacitor |
-
2018
- 2018-11-22 CN CN201811394817.6A patent/CN109637841A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862948A (en) * | 2015-04-28 | 2015-08-26 | 武汉纺织大学 | Production method of color carbon fibers |
| CN106367947A (en) * | 2016-10-12 | 2017-02-01 | 武汉纺织大学 | Method for improving tensile mechanical property of fibers |
| CN107634233A (en) * | 2017-09-13 | 2018-01-26 | 深圳大学 | A kind of transition metal oxide elctro-catalyst and its preparation method and application |
| CN108063060A (en) * | 2017-12-05 | 2018-05-22 | 武汉纺织大学 | A kind of preparation method of paper substrate electrode material for super capacitor |
Non-Patent Citations (4)
| Title |
|---|
| JIE XU等: "Fabric electrodes coated with polypyrrole nanorods for flexible supercapacitor application prepared via a reactive self-degraded template", 《ORGANIC ELECTRONICS》 * |
| XU JIE等: "Bacterial cellulose membranes coated by polypyrrole/copper oxide as flexible supercapacitor electrodes", 《J MATER SCI》 * |
| ZEQI CHEN等: "An all-solid-state yarn supercapacitor using cotton yarn electrodes coated with polypyrrole nanotubes"", 《CARBOHYDRATE POLYMERS》 * |
| 何小龙: "《2016世界军事电子发展年度报告》", 31 March 2017 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112012007A (en) * | 2020-09-03 | 2020-12-01 | 河北多谱电子科技有限公司 | Preparation method of flexible electromagnetic protection material with meridian-shaped bionic skin |
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