CN109537263A - A kind of flexible material and preparation method thereof of ZnO/ carbon fiber - Google Patents
A kind of flexible material and preparation method thereof of ZnO/ carbon fiber Download PDFInfo
- Publication number
- CN109537263A CN109537263A CN201811356985.6A CN201811356985A CN109537263A CN 109537263 A CN109537263 A CN 109537263A CN 201811356985 A CN201811356985 A CN 201811356985A CN 109537263 A CN109537263 A CN 109537263A
- Authority
- CN
- China
- Prior art keywords
- zno
- carbon fiber
- flexible material
- solution
- hydro
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 89
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 89
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000004744 fabric Substances 0.000 claims abstract description 30
- 239000002070 nanowire Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 55
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 29
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- 238000003618 dip coating Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229940031098 ethanolamine Drugs 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000835 fiber Substances 0.000 description 8
- 230000005684 electric field Effects 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of flexible materials and preparation method thereof of ZnO/ carbon fiber, which is characterized in that including carbon cloth and the ZnO nano-wire composite material for being grown in carbon cloth surface, the ZnO nano-wire length is 5~10 μm, and diameter is 30~50nm.The collosol and gel and hydro-thermal preparation process that the present invention uses are simple, and yield is high, and low in cost, suitable for mass production；The direct growing ZnO nano-wire material on carbon fiber, prepared nanocomposite form is uniform, cladding is close, and the flexible ability with carbon fiber, is a kind of excellent field-transmitting cathode filed emission cathode material.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of flexible material and preparation method thereof of ZnO/ carbon fiber.
Background technique
Field emission display develops extremely rapid as a kind of emerging flat-panel monitor.It combines cathode-ray
The plurality of advantages for managing (CRT) and flat-panel monitor, has broad application prospects.As broad stopband oxide semiconductor material,
ZnO nano material has good electronic emission performance, it has low threshold electric field, high mechanical strength, anti-oxidant, resistance to height
The features such as warm, this make ZnO nano material field electron microscope, Miniature X-ray Source, cold cathode microwave amplifier,
There is important application prospect in the devices such as flat-panel monitor and cathode-luminescence light source.Therefore, ZnO nano material becomes practical field
One of most potential nano material of emission electron sources.ZnO is broad stopband II-VI group oxide semiconductor material, because it
With good chemical stability, small even negative electron affinity, high thermal conductivity, good inoxidizability and high temperature resistant
Property, big disruptive field intensity and high carrier mobility, numerous good characteristics such as big emission current, therefore it is suitable for Flied emission
Cathode material.The study found that carbon fiber itself also has field emission performance, since planar structure limits its launching electronics
Ability, it is therefore, the progress of both materials of ZnO and carbon fiber is compound, ZnO/ carbon fibre material is constituted, is made compared on other substrates
Standby ZnO material is compared, and has significant raising in terms of field emission performance, and can be bent, to prepare bent panel type display part.
Therefore nanocomposite high-quality and with particular hierarchy can get by the growth of regulation ZnO nano-wire, upper
It states to apply and above be of great significance.
There are a large amount of researchers to be engaged in the compound of ZnO and carbon fiber at present and has achieved certain achievement, 2010
Year, entitled " the Flexible cold cathode with ultralow of one delivered on Nanotechnology periodical
The paper of threshold field designed through wet chemical route " is deposited using magnetron sputtering
Method and hydro-thermal method have prepared the nano material of ZnO cladding carbon fiber.2014, in The Journal of Physical
Entitled " the Fabrication of High-Activity Hybrid Pt@ZnO of one delivered on Chemistry C periodical
Catalyst on Carbon Cloth by Atomic Layer Deposition for Photoassisted
The paper of Electro-Oxidation of Methanol " uses atomic layer deposition method and hydro-thermal method has prepared ZnO cladding
The nano material of carbon fiber.Observing and controlling sputtering and atomic layer deposition side is respectively adopted in the two processes for being reported in preparation seed layer
Method needs the requirement of higher environment although the uniformity and quality of seed layer prepared by the two are all preferable, and equipment is expensive
Weight, and it is not easy extensive deposition, industrialized production cannot be achieved, and very intensive ZnO nanorod is readily synthesized in the process,
It is plane hexagon for top, rather than the hexagonal pyramid shape at tip, limit Field emission property and the application of material.In the system of hydro-thermal
During standby, a large amount of researcher all employs hexamethylenetetramine as hydrogen-oxygen root, and the speed of growth is slower, is grown
ZnO nano material curtailment, the growth time needed is longer, and using hexamethylenetetramine be hydrogen-oxygen root it is made
The top of standby ZnO nanorod is substantially plane hexagon, rather than therefore how the hexagonal pyramid shape at tip obtains big major diameter
The field-transmitting cathode flexible material of the ZnO/ carbon fiber brush shape of ratio, is always the research hotspot of industry.
Summary of the invention
For the defect and deficiency of existing technology of preparing, the present invention provides a kind of flexible material of ZnO/ carbon fiber and its
Preparation method solves the problems, such as that material can not combine bending and excellent field emission performance, and then obtains big L/D ratio
The field-transmitting cathode flexible material of ZnO/ carbon fiber brush shape.
To solve the above problems, the technical scheme adopted by the invention is as follows:
A kind of flexible material of ZnO/ carbon fiber, the flexible material of the ZnO/ carbon fiber includes carbon cloth and growth
ZnO nano-wire composite material on carbon cloth surface, the ZnO nano-wire length be 5~10 μm, diameter be 30~
50nm。
Further, the flexible material of the ZnO/ carbon fiber is successively made through sol-gal process and hydro-thermal method.
Specifically, the sol-gal process includes that zinc salt and stabilizer are dissolved in ethyl alcohol to obtain mixed solution, then
Above-mentioned mixed solution is aged to form colloidal sol, then the carbon that carbon cloth dip-coating is wrapped up in above-mentioned colloidal sol up to ZnO seed layer
Fibre structure；
The zinc salt includes zinc acetate, and the stabilizer includes ethanol amine, and the ethanol amine and zinc acetate rub
You are than being 1:1~2:1.
Specifically, the hydro-thermal method includes being added to zinc solution in strong base solution as precursor solution, then incite somebody to action
The carbon fiber structural of the ZnO seed layer package, which is added in the precursor solution, carries out hydro-thermal reaction；
The zinc solution concentration is 0.05~0.11mol/L, and the strong base solution concentration is 0.8~2.2mol/
L, the ratio between zinc ion and hydroxide ion concentration are 1:16~1:20 in the precursor solution.
Further, the temperature of the hydro-thermal reaction is 70~100 DEG C, and the time of hydro-thermal reaction is 3~4h.
A kind of preparation method of the flexible material of ZnO/ carbon fiber, specifically includes:
Step (1): carbon cloth pretreatment；
Step (2): sol-gal process prepares the carbon fiber structural of ZnO seed layer package
Stabilizer is added into zinc solution, stirs to get clear solution, then is aged the clear solution to be formed
Colloidal sol；Then it by carbon cloth dip-coating in the colloidal sol, is heat-treated and is annealed；
Step (3): hydro-thermal method prepares the flexible material of ZnO/ carbon fiber
Zinc solution is added in strong base solution as precursor solution, then the ZnO seed layer packet that step (2) is obtained
The carbon fiber structural wrapped up in is added in the precursor solution and carries out hydro-thermal reaction, and rear washing is drying to obtain.
Specifically, zinc salt described in step (2) includes zinc acetate, and the stabilizer includes ethanol amine, the second
The molar ratio of hydramine and zinc acetate is 1:1~2:1.
Further, the time in step (2) by carbon cloth dip-coating in colloidal sol is 10~15s, and the number immersed is 2
~4 times, annealing temperature is 550~650 DEG C.
Further, zinc solution concentration described in step (3) is 0.05~0.11mol/L, the strong base solution
Concentration is 0.8~2.2mol/L, and the ratio between zinc ion and hydroxide ion concentration are 1:16~1:20 in the precursor solution.
Further, the reaction temperature of hydro-thermal reaction described in step (3) is 70~100 DEG C, the reaction of hydro-thermal reaction
Time is 3~4h.
The present invention has following advantageous effects compared to the prior art:
(1) length of the ZnO/ carbon fiber flexible material that the present invention is prepared, ZnO nano-wire is 5~10 μm, and diameter is
30~50nm；It can be observed from microstructure, ZnO/ carbon fiber flexible material has very big specific surface area and more hair
Tip is penetrated, is in " brush and sac like "；There are a large amount of hetero-junctions, the compound reduction of photo-generated carrier, electronics for ZnO/ carbon fiber flexible material
Hole is to efficiently separating, to increase service life and the carrier concentration of carrier；From physical property fusion, ZnO/ carbon fiber is soft
Property material had both had ZnO nano-wire to the good emissivities of field emission electron, it may have the flexible ability of carbon fiber is
A kind of excellent field-transmitting cathode filed emission cathode material.
(2) present invention is when preparing ZnO/ carbon fiber flexible material, using collosol and gel and hydro-thermal method in carbon fiber side table
Developing ZnO monocrystal nano wire on face is not necessarily to any template and catalyst in preparation process, and simple process, yield is high, and at low cost
It is honest and clean, it is suitable for mass production；
(3) growing ZnO nano-wire on carbon fiber side surface, prepared nanocomposite form is uniform, cladding is tight
It is close.
Detailed description of the invention
Fig. 1 is the flexible material XRD spectrum of the ZnO/ carbon fiber of embodiment 1 in the present invention；
Fig. 2 is the flexible material SEM photograph of the ZnO/ carbon fiber of embodiment 1 in the present invention；
Fig. 3 is the flexible material Flied emission J-E figure of the ZnO/ carbon fiber of embodiment 1 in the present invention；
Fig. 4 is the flexible material Flied emission F-N figure of the ZnO/ carbon fiber of embodiment 1 in the present invention；
Fig. 5 is the flexible material SEM photograph of the ZnO/ carbon fiber of embodiment 2 in the present invention；
Fig. 6 is the flexible material SEM photograph of the ZnO/ carbon fiber of embodiment 2 in the present invention；
Fig. 7 is the flexible material SEM photograph of the ZnO/ carbon fiber of embodiment 3 in the present invention；
Fig. 8 is the flexible material SEM photograph of the ZnO/ carbon fiber of embodiment 4 in the present invention；
Fig. 9 is the flexible material SEM photograph of the ZnO/ carbon fiber of comparative example 1 in the present invention；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific embodiment
The flexible material of ZnO/ carbon fiber prepared by the present invention, using simple sol-gal process and hydro-thermal method in carbon fiber
Growing ZnO nano-wire on surface, using carbon fiber as primary structure, ZnO nano-wire is the complicated grading structure material of secondary structure.
ZnO seed layer is mainly prepared on carbon fiber side surface using sol-gal process, to zinc salt concentration, zinc salt and stabilization
Ratio, the time of immersion of agent, the reaction factors such as the dip-coating number of plies, annealing temperature and soaking time are controlled；Using hydro-thermal method, pass through
The concentration of zinc salt in control reaction system, alkali salt obtain a kind of ZnO/ carbon fiber than factors such as, reaction temperature, reaction time
Flexible material is not necessarily to any template and catalyst in preparation process, and simple process, yield is high, and low in cost, is suitble to batch raw
It produces；Carbon cloth is as the direct growing ZnO nano-wire of trunk structure, and prepared single crystal ZnO nanometer line morphology is uniform, in carbon fiber
On be evenly coated, (conductive flexible is hydrophilic from Shanghai Li Shuo composite material Science and Technology Ltd. for the carbon cloth that the present invention uses
Carbon cloth).
In order to which objects and advantages of the present invention are more clearly understood, the present invention is carried out below in conjunction with drawings and examples
It is further described.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit this
Invention.
Embodiment 1:
Step (1): carbon cloth pretreatment
By (1.5*1.5cm2) carbon cloth concentrated nitric acid is in 100 DEG C of immersion 1h, with deionized water, ethyl alcohol, deionized water
Ultrasonic cleaning 3 times, each 30min, drying later is in case use；
Step (2): sol-gal process prepares the carbon fiber structural of ZnO seed layer package
The acetic acid dihydrate zinc for weighing 2.2172g (0.20mol/L) is dissolved in 50mL ethyl alcohol, 30min is stirred at room temperature, then delay
The molar ratio of slow instillation 1.2mL ethanol amine, ethanol amine and zinc acetate is 1:1, continues stir about 30min or more, obtains uniform shallow
Acquired solution is finally put into baking oven by clear solution, is aged one day at 60 DEG C, is obtained colloidal sol.Later again by carbon cloth
Dip-coating is taken out after 10s in above-mentioned colloidal sol, the carbon cloth after dip-coating is placed on 90 DEG C of warm table and is heat-treated 10min, weight
Carbon cloth twice, is put into Muffle furnace after dip-coating and anneals by multiple above-mentioned dip-coating heating process, is warming up to 650 DEG C of (heatings
Speed is 5 DEG C/min), 120min is kept the temperature, the carbon fiber structural of ZnO seed layer package is prepared.
Step (3): hydro-thermal method prepares the flexible material of ZnO/ carbon fiber
By the Zn (CH of 0.08mol/L (1.240g)3COOH)2Powder is added in the deionized water of 40ml, and shape is sufficiently stirred
At Zn (CH3COOH)2The NaOH powder of 1.6mol/L (4.6667g) is added in the deionized water of 30mL, sufficiently stirs by solution
It mixes to form NaOH solution, then by Zn (CH3COOH)2Solution is slowly added in NaOH solution, forms uniform precursor solution,
The ratio between zinc ion and hydroxide ion concentration are 1:20 in precursor solution.
The carbon fiber structural that the ZnO seed layer being prepared in step (2) wraps up is put into again molten equipped with above-mentioned presoma
The reaction kettle (volume of liner is 50mL) of the polytetrafluoroethyllining lining of liquid carries out hydro-thermal reaction, is sealed against being placed in 100 DEG C of bakings
4h is kept the temperature in case, to after reaction constantly clean carbon cloth, and is washed with deionized repeatedly, until the pH=of filtrate
7, then carbon cloth is placed in 60 DEG C of baking ovens and is dried, the ZnO/ carbon fibre composite i.e. flexible material of ZnO/ carbon fiber is obtained
Material.X-ray diffractogram spectrum analysis, scanning electron microscope analysis and field emission performance analysis are carried out to obtained flexible material；
Specific X ray diffracting spectrum as shown in Figure 1, XRD the result shows that: the product is ZnO/ carbon fibre composite；Scanning electron
Microscope photo is as shown in Figure 2；It can be seen that ZnO/ carbon fibre composite is the core-shell structure that surface is in brush and sac like, prepared list
Brilliant ZnO nano-wire form is uniform, is evenly coated on carbon fiber, and the length of obtained ZnO nano-wire is tested to be 7~8 μm, directly
Diameter is 30~40nm.Fig. 3 and Fig. 4 illustrates the threshold electric field point of the flexible material of the ZnO/ carbon fiber of carbon cloth and " hairbrush shape "
It Wei not 1.109V/ μm and 0.615V/ μm of (threshold electric field: when current density reaches 10 μ A/cm2When electric field), ZnO/ carbon fiber
Flexible material threshold field be 1.128V/ μm of (threshold field: when current density reaches 1mA/cm2When electric field), carbon fiber
The field enhancement factor of the flexible material of the ZnO/ carbon fiber of Wei Bu and " hairbrush shape " is respectively 10635 and 23987.ZnO/ carbon fiber
The threshold electric field of flexible material, threshold field compared to prepared on Zn substrate ZnO nanowire array (threshold electric field:
3.16V/ μm, field enhancement factor: 2889) low, field enhancement factor is relatively high, therefore, the flexibility of the ZnO/ carbon fiber of " hairbrush shape "
Material has good field emission performance.
Embodiment 2:
Step (1) and step (2) are same as Example 1；
Step (3) hydro-thermal method prepares the flexible material of ZnO/ carbon fiber
By the Zn (CH of 0.05mol/L3COOH)2Solution is added dropwise to dropwise in the NaOH solution of 0.9mol/L, after the completion of titration
Uniform precursor solution is persistently stirred to get, making the ratio between zinc ion and hydroxide ion concentration in precursor solution is 1:16.
The carbon fiber structural that the ZnO seed layer being prepared in step (2) wraps up is put into again molten equipped with above-mentioned presoma
The reaction kettle (volume of liner is 50mL) of the polytetrafluoroethyllining lining of liquid carries out hydro-thermal reaction, is sealed against being placed in 70 DEG C of baking ovens
Middle heat preservation 4h to after reaction constantly clean carbon cloth, and is washed with deionized repeatedly, until the pH=7 of filtrate,
Then carbon cloth is placed in 60 DEG C of baking ovens and is dried, obtain the ZnO/ carbon fibre composite i.e. flexible material of ZnO/ carbon fiber
Material.
Electron microscope analysis is scanned to obtained flexible material, photo such as Fig. 5 under different amplification, shown in 6；Fig. 5,
6 illustrate that the ZnO/ carbon fibre composite that embodiment two is prepared is the core-shell structure that surface is in brush and sac like, prepared monocrystalline
ZnO nano-wire form is uniform, is evenly coated on carbon fiber, and the top of ZnO nano-wire is hexagonal pyramid tip, obtained ZnO
Nano wire is 5~6 μm through measurement length, and diameter is 30~40nm.
Embodiment 3:
Step (1) and step (2) are same as Example 1；
Step (3) hydro-thermal method prepares the flexible material of ZnO/ carbon fiber
By the Zn (CH of 0.11mol/L3COOH)2Solution is added dropwise to dropwise in the NaOH solution of 2.2mol/L, after the completion of titration
Uniform precursor solution is persistently stirred to get, making the ratio between zinc ion and hydroxide ion concentration in precursor solution is 1:20.
The carbon fiber structural that the ZnO seed layer being prepared in step (2) wraps up is put into again molten equipped with above-mentioned presoma
The reaction kettle (volume of liner is 50mL) of the polytetrafluoroethyllining lining of liquid carries out hydro-thermal reaction, is sealed against being placed in 100 DEG C of bakings
3h is kept the temperature in case, to after reaction constantly clean carbon cloth, and is washed with deionized repeatedly, until the pH=of filtrate
7, then carbon cloth is placed in 60 DEG C of baking ovens and is dried, the ZnO/ carbon fibre composite i.e. flexible material of ZnO/ carbon fiber is obtained
Material.
The electron scanning micrograph of the product is as shown in Figure 7；Fig. 7 illustrates that product obtained by embodiment three is equally
Surface has the core-shell structure of brush and sac like, and obtained ZnO nano-wire is measured the length is 6~8 μm, and diameter is 40~50nm.
Embodiment 4:
Step (1) is the same as embodiment 1
Step (2) sol-gal process prepares the carbon fiber structural of ZnO seed layer package
The acetic acid dihydrate zinc for weighing 3.8801g (0.35mol/L) is dissolved in 50mL ethyl alcohol, 30min is stirred at room temperature, then delay
Slow to instill 2.1mL ethanol amine, the molar ratio 2:1 of ethanol amine and zinc acetate continues stir about 30min or more, it is saturating to obtain uniform shallow
Acquired solution, is finally put into baking oven by bright solution, is aged one day at 60 DEG C, obtains colloidal sol.Carbon cloth is soaked again later
It is coated in above-mentioned colloidal sol and is taken out after 15s, the carbon fiber after dip-coating is placed on 90 DEG C of warm table and is heat-treated 10min, in repetition
State dip-coating heating process twice, carbon fiber be put into Muffle furnace after dip-coating and is annealed, after Muffle furnace is warming up to 550 DEG C
(heating rate is 5 DEG C/min), keeps the temperature 120min, the carbon fiber structural of ZnO seed layer package is prepared.
Step (3) is the same as embodiment 2；
The electron scanning micrograph of the product is as shown in Figure 8；Fig. 8 illustrates the products therefrom surface of example IV in brush
The core-shell structure of sub- shape, the length for being measured obtained ZnO nano-wire is 5-7 μm, and diameter is 30~40nm.
Comparative example 1:
With embodiment 1, but unlike the first embodiment in step (3), by the Zn (CH of 0.11mol/L3COOH)2Solution by
It is added dropwise in the NaOH solution of 2.42mol/L, persistently stirs to get uniform precursor solution after the completion of titration, make presoma
The ratio between zinc ion and hydroxide ion concentration are 1:22 in solution.
The electron scanning micrograph of the product is as shown in Figure 9；Only a small amount of ZnO nano particle covering can be observed
On carbon fiber.Obviously, in present case, ZnO/ carbon fiber structural cannot in precursor solution zinc ion and hydroxide ion
The ratio between concentration is 1/22 lower formation.
In conclusion sol-gal process of the present invention and hydro-thermal preparation process simple process, controllability is strong, yield
Height, it is low in cost, it is suitable for mass production.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of flexible material of ZnO/ carbon fiber, which is characterized in that the flexible material of the ZnO/ carbon fiber includes carbon fiber
Wei Bu and the ZnO nano-wire composite material for being grown in carbon cloth surface, the ZnO nano-wire length are 5~10 μm, diameter
For 30~50nm.
2. the flexible material of ZnO/ carbon fiber as described in claim 1, which is characterized in that the flexibility of the ZnO/ carbon fiber
Material is successively made through sol-gal process and hydro-thermal method.
3. the flexible material of ZnO/ carbon fiber as described in claim 1, which is characterized in that the sol-gal process includes will
Zinc salt and stabilizer, which are dissolved in ethyl alcohol, obtains mixed solution, then is aged above-mentioned mixed solution to form colloidal sol, then by carbon fiber
Cloth dip-coating is in above-mentioned colloidal sol up to the carbon fiber structural of ZnO seed layer package；
The zinc salt includes zinc acetate, and the stabilizer includes ethanol amine, the molar ratio of the ethanol amine and zinc acetate
For 1:1~2:1.
4. the flexible material of ZnO/ carbon fiber as claimed in claim 2, which is characterized in that the hydro-thermal method includes by zinc salt
Solution is added in strong base solution as precursor solution, then institute is added in the carbon fiber structural that the ZnO seed layer is wrapped up
Hydro-thermal reaction is carried out in the precursor solution stated；
The zinc solution concentration is 0.05~0.11mol/L, and the strong base solution concentration is 0.8~2.2mol/L, institute
The ratio between zinc ion and hydroxide ion concentration are 1:16~1:20 in the precursor solution stated.
5. the flexible material of ZnO/ carbon fiber as claimed in claim 4, which is characterized in that the temperature of the hydro-thermal reaction is
70~100 DEG C, the time of hydro-thermal reaction is 3~4h.
6. a kind of preparation method of the flexible material of ZnO/ carbon fiber, which is characterized in that specifically include:
Step (1): carbon cloth pretreatment；
Step (2): sol-gal process prepares the carbon fiber structural of ZnO seed layer package
Stabilizer is added into zinc solution, stirs to get clear solution, then is aged the clear solution to form colloidal sol；
Then it by carbon cloth dip-coating in the colloidal sol, is heat-treated and is annealed；
Step (3): hydro-thermal method prepares the flexible material of ZnO/ carbon fiber
Zinc solution is added in strong base solution as precursor solution, then the ZnO seed layer package that step (2) is obtained
Carbon fiber structural is added in the precursor solution and carries out hydro-thermal reaction, and rear washing is drying to obtain.
7. the preparation method of the flexible material of ZnO/ carbon fiber as claimed in claim 6, which is characterized in that institute in step (2)
The zinc salt stated includes zinc acetate, and the stabilizer includes ethanol amine, the molar ratio of the ethanol amine and zinc acetate be 1:1~
2:1。
8. the preparation method of the flexible material of ZnO/ carbon fiber as claimed in claim 6, which is characterized in that will in step (2)
Time of the carbon cloth dip-coating in colloidal sol is 10~15s, and the number immersed is 2~4 times, and annealing temperature is 550~650 DEG C.
9. the preparation method of the flexible material of ZnO/ carbon fiber as claimed in claim 6, which is characterized in that institute in step (3)
The zinc solution concentration stated is 0.05~0.11mol/L, and the strong base solution concentration is 0.8~2.2mol/L, before described
Driving the ratio between zinc ion and hydroxide ion concentration in liquid solution is 1:16~1:20.
10. the preparation method of the flexible material of ZnO/ carbon fiber as claimed in claim 6, which is characterized in that institute in step (3)
The reaction temperature for the hydro-thermal reaction stated is 70~100 DEG C, and the reaction time of hydro-thermal reaction is 3~4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811356985.6A CN109537263B (en) | 2018-11-15 | 2018-11-15 | ZnO/carbon fiber flexible material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811356985.6A CN109537263B (en) | 2018-11-15 | 2018-11-15 | ZnO/carbon fiber flexible material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109537263A true CN109537263A (en) | 2019-03-29 |
| CN109537263B CN109537263B (en) | 2021-09-21 |
Family
ID=65847455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811356985.6A Expired - Fee Related CN109537263B (en) | 2018-11-15 | 2018-11-15 | ZnO/carbon fiber flexible material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109537263B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935822A (en) * | 2019-04-07 | 2019-06-25 | 朱焕光 | A kind of three-dimensional V2O5Nano-wire array/carbon cloth flexibility positive electrode and preparation method thereof |
| CN110318251A (en) * | 2019-07-29 | 2019-10-11 | 北京化工大学 | A method of in carbon fiber surface growth of one-dimensional zinc oxide nanowire |
| CN110318252A (en) * | 2019-08-16 | 2019-10-11 | 四川轻化工大学 | Composite material with spiral carbon nanofiber surface loaded with zinc oxide particles and preparation method and application thereof |
| CN111229287A (en) * | 2020-03-25 | 2020-06-05 | 吉林师范大学 | Carbon fiber cloth load tubular g-C3N4Photocatalytic material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951673A (en) * | 2012-11-29 | 2013-03-06 | 中国日用化学工业研究院 | Preparation method of nano zinc oxide rod |
| CN103397382A (en) * | 2013-04-01 | 2013-11-20 | 济南大学 | Preparation method of zinc-oxide nanorod array film |
| CN103663544A (en) * | 2012-09-25 | 2014-03-26 | 海洋王照明科技股份有限公司 | Preparation method of zinc oxide nanorod |
| CN104264131A (en) * | 2014-08-12 | 2015-01-07 | 西北大学 | Fibrous ZnO nanowire growing on ZnO nanowire array and preparation method thereof |
| CN108439457A (en) * | 2018-04-27 | 2018-08-24 | 陕西科技大学 | A kind of method that hydro-thermal electrophoresis prepares zinc oxide nano rod/carbon cloth friction material |
| CN108780723A (en) * | 2016-03-16 | 2018-11-09 | 光学实验室公司（瑞典） | The method of controllable growth ZnO nano-wire |
-
2018
- 2018-11-15 CN CN201811356985.6A patent/CN109537263B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663544A (en) * | 2012-09-25 | 2014-03-26 | 海洋王照明科技股份有限公司 | Preparation method of zinc oxide nanorod |
| CN102951673A (en) * | 2012-11-29 | 2013-03-06 | 中国日用化学工业研究院 | Preparation method of nano zinc oxide rod |
| CN103397382A (en) * | 2013-04-01 | 2013-11-20 | 济南大学 | Preparation method of zinc-oxide nanorod array film |
| CN104264131A (en) * | 2014-08-12 | 2015-01-07 | 西北大学 | Fibrous ZnO nanowire growing on ZnO nanowire array and preparation method thereof |
| CN108780723A (en) * | 2016-03-16 | 2018-11-09 | 光学实验室公司（瑞典） | The method of controllable growth ZnO nano-wire |
| CN108439457A (en) * | 2018-04-27 | 2018-08-24 | 陕西科技大学 | A kind of method that hydro-thermal electrophoresis prepares zinc oxide nano rod/carbon cloth friction material |
Non-Patent Citations (5)
| Title |
|---|
| BEN WANG 等: ""A controllable interface performance through varying ZnO nanowires dimensions on the carbon fibers"", 《APPLIED SURFACE SCIENCE》 * |
| HAOYING TANG 等: ""ZnO Nanowires Grown on Carbon Cloth for Flexible Cold Cathode"", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
| LEI ZHANG 等: ""Preparation and performance of ZnO nanowires modified carbon fibers reinforced NiFe2O4 ceramic matrix composite"", 《JOURNAL OF ALLOYS AND COMPOUNDS 》 * |
| MING-CHIENHUNG 等: ""Effectiveness of ZnO/carbon-based material as a catalyst for photodegradation of acrolein"", 《CARBON》 * |
| 陈善亮 等: ""柔性场发射阴极材料"", 《化学进展》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935822A (en) * | 2019-04-07 | 2019-06-25 | 朱焕光 | A kind of three-dimensional V2O5Nano-wire array/carbon cloth flexibility positive electrode and preparation method thereof |
| CN109935822B (en) * | 2019-04-07 | 2021-10-12 | 河南城建学院 | Three-dimensional V2O5Nanowire array/carbon fiber cloth flexible positive electrode material and preparation method thereof |
| CN110318251A (en) * | 2019-07-29 | 2019-10-11 | 北京化工大学 | A method of in carbon fiber surface growth of one-dimensional zinc oxide nanowire |
| CN110318251B (en) * | 2019-07-29 | 2020-10-02 | 北京化工大学 | Method for growing one-dimensional zinc oxide nanowire on surface of carbon fiber |
| CN110318252A (en) * | 2019-08-16 | 2019-10-11 | 四川轻化工大学 | Composite material with spiral carbon nanofiber surface loaded with zinc oxide particles and preparation method and application thereof |
| CN111229287A (en) * | 2020-03-25 | 2020-06-05 | 吉林师范大学 | Carbon fiber cloth load tubular g-C3N4Photocatalytic material and preparation method thereof |
| CN111229287B (en) * | 2020-03-25 | 2022-10-21 | 吉林师范大学 | Carbon fiber cloth load tubular g-C 3 N 4 Photocatalytic material and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109537263B (en) | 2021-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109537263A (en) | A kind of flexible material and preparation method thereof of ZnO/ carbon fiber | |
| CN107681054B (en) | Preparation method of perovskite crystal nanowire | |
| CN107068872B (en) | It is a kind of to prepare perovskite Cs3Bi2I9The method of hull cell | |
| CN104264131B (en) | A kind of fibrous ZnO nano-wire of growth and preparation method thereof on ZnO nanowire array | |
| CN104911629B (en) | A kind of synthetic method of combination electrode | |
| CN108316008B (en) | A kind of vanadic sulfide/vanadium carbide composite nano plate assembly, its preparation and application | |
| CN107445199B (en) | Multilevel structure titanium dioxide nanowire array and preparation method thereof | |
| CN113336547B (en) | Oxide type solid electrolyte film and preparation method thereof | |
| CN102723208B (en) | Preparation method of composite nanowire array with one-dimensional ZnO(zinc oxide)-TiO2(titanium dioxide) core-shell structure | |
| CN110273170B (en) | Graphene-coated metal nanowire network and preparation method thereof | |
| CN205452361U (en) | Heterojunction solar cell based on plumbous iodine single crystal section of perovskite methylamine | |
| CN106986373A (en) | A kind of preparation method of ZnO nanorod | |
| CN105836789B (en) | A kind of method that original position prepares loose structure nanometic zinc oxide rod array | |
| CN111117602A (en) | Preparation method of large-size indium phosphide quantum dot with gradient core-shell structure | |
| CN113652753B (en) | Vanadium-doped single-crystal tungsten oxide electrochromism and energy storage material and preparation method thereof | |
| CN105870260A (en) | Reflection reducing structure and preparation method of graphene composite transparent conductive thin film | |
| CN108394928B (en) | Preparation method of zinc oxide/zinc stannate core-shell structure heterojunction | |
| CN111755256B (en) | Preparation method of three-dimensional ZnO/CuO nano heterogeneous hierarchical structure photoelectrode | |
| CN108545960A (en) | A kind of Y doping zinc oxide nanometers stick array preparation method | |
| CN104761154B (en) | A kind of method that utilization organic macromolecule material makees catalyst preparation ITO nano wires | |
| CN106830072B (en) | A kind of preparation method of titanium dioxide nanowire array | |
| CN106865617B (en) | A kind of bismuth tungstate film of porous network structure and its preparation method and application | |
| CN112625679B (en) | Heterojunction of all-inorganic halogen perovskite nanowire and preparation method thereof | |
| CN109019663A (en) | A kind of ZnO nanorod, QLED device and preparation method thereof | |
| CN108648883B (en) | Preparation method of transparent conductive film compounded by double-layer anti-reflection structure and graphene |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210921 |