CN103924381A - Flexible transparent conductive oxide nanofiber membrane and preparation method thereof - Google Patents
Flexible transparent conductive oxide nanofiber membrane and preparation method thereof Download PDFInfo
- Publication number
- CN103924381A CN103924381A CN201410157908.3A CN201410157908A CN103924381A CN 103924381 A CN103924381 A CN 103924381A CN 201410157908 A CN201410157908 A CN 201410157908A CN 103924381 A CN103924381 A CN 103924381A
- Authority
- CN
- China
- Prior art keywords
- preparation
- transparent conductive
- flexible
- conductive oxide
- adhesive
- 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
Landscapes
- Manufacturing Of Electric Cables (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of photoelectric functional nano-materials, and particularly relates to a flexible transparent conductive oxide nanofiber membrane and a preparation method thereof. A precursor is composed of salt of a metallic oxide, salt of a doped element, an adhesive and a solvent, the precursor is sprayed on a substrate through electrospining equipment, and then high-temperature calcination is carried out to obtain the flexible transparent conductive oxide nanofiber membrane. The flexible transparent conductive oxide nanofiber membrane prepared with the method has flexibility, high conductivity and high visible-light permeability; no flexible substrate material is needed, and use of the flexible transparent conductive oxide nanofiber membrane is facilitated; the flexible transparent conductive oxide nanofiber membrane prepared with the electrostatic spinning method is controllable in size, high in repeatability, simple in process, high in efficiency and low in cost, and industrial preparation can be achieved.
Description
Technical field
The invention belongs to photoelectric functional technical field of nano material, be specifically related to a kind of flexibility, transparent conductive oxide nano fibrous membrane and preparation method thereof.
Background technology
Flexible and transparent conductive oxidation film (Transparent Conductive Oxide, TCO) not only visible light transmissivity is high, resistivity is low, collapsible, lightweight, non-friable, be easy to the advantages such as transport is produced, is convenient to large area and equipment investment is few, can be widely used in the fields such as flat-panel monitor, solar cell, agricultural transparent heat-insulated heat-insulation plastic greenhouse.At present, modal TCO is SnO
2base, In
2o
3base and zno-based material, the In wherein adulterating with Sn
2o
3(Sn:In
2o
3, ITO) and the ZnO(Al of Al doping: ZnO, AZO) apply comparatively extensive.And the technology of preparation TCO film mainly comprises vacuum vapour deposition (Vacuum Evaporation), sputtering method (Sputtering), chemical gaseous phase deposition method (Chemical Vapor Deposition, CVD), sol-gel process (Sol-Gel), spray pyrolysis (Spray Pyrolysis), pulsed laser deposition (Pulsed Laser Deposition, and atomic layer epitaxy (Atomic Layer Epitaxy, ALE) etc. PLD).For flexible TCO film, normally adopt physics or chemical method in flexible substrate (as plastics, rubber etc.) to prepare one deck TCO film.Wherein, the selection of flexible substrate to consider following some: the transmitance of (1) backing material; (2) matching of thermal coefficient of expansion between substrate and film; 3) adhesiveness of flexible substrate and transparent conductive film.As can be seen here, the use of flexible substrates, the technology of preparing and the scale that have seriously restricted TCO film are used.For example, the Chinese invention patent that application number is 201010162968.6, the mode of employing magnetron sputtering, at the two-layer SiO of the each sputter in the two sides of flexible substrate material
2, then at SiO
2on rete, while splash-proofing sputtering metal In and Sn, prepared transparent flexible conductive film.It is high that film prepared by magnetron sputtering method has quality of forming film, the advantage that large area is produced, but first this method needs to prepare high accuracy and highly purified target, and need expensive vacuum preparation, so industrial cost is high, be unfavorable for suitability for industrialized production.Application number is 200910236527.3 Chinese invention patent, adopt ultrasonic spray pyrolysis, first at the bottom of high temperature-resistant liner, prepare FTO film, then by translucent adhesive, FTO film and low temperature flexibility substrate are bonded together, finally obtaining thickness by chemical treatment is 150nm, sheet resistance is 280 Ω/cm, the flexible and transparent conductive FTO film that contains binding agent.This employing spray pyrolysis is prepared nesa coating, does not need expensive vacuum equipment, but in actual production by producing a large amount of pollution gas, need to additionally widen an exhaust gas processing device, limited suitability for industrialized production.Application number is 201210506069.2 Chinese invention patent, first Zinc diacetate dihydrate, aluminium salt and low boiling stabilizing agent are dissolved in to low boiling point solvent configuration spin coating liquid, be spun on the flexible substrate of hydrophilic treatment, then through aging, heat treatment and inert atmosphere annealing, obtain the flexible and transparent Al-Doped ZnO film of visible light transmissivity more than 80%.Sol-gel process does not need expensive vacuum equipment, cost is lower, and simple to operate, but sol-gel process need to be used poisonous organic solvent, need 150～300 DEG C of preliminary treatment, be unfavorable at the upper plated film of flexible substrate (general tolerable temperature is below 200 DEG C), and the conductance of common conducting film is lower, is difficult to meet actual requirement.Therefore the technology of preparing tool of, developing a kind of flexible transparent conducting film of, excellent performance low without flexible substrates, cost is of great significance.
Summary of the invention
The art of this patent overcomes the problem that existing flexible oxide conductive film exists, a kind of flexible transparent conducting film and preparation method of, excellent performance low without flexible substrates, cost are provided, the preparation method of this flexible transparent conducting film, that the salt of slaine, doped chemical, adhesive and solvent are made into presoma, be ejected in substrate by Electrospun equipment, then high-temperature calcination obtains flexible and transparent conductive oxide fibre film.
Flexible and transparent conductive oxide fibre film produced according to the present invention comprises the following steps:
1) salt of slaine, doped chemical, adhesive and solvent are made into presoma;
Described slaine is one or more the salt in Sn, In, Zn, is preferably metal chloride salt or hydrated metal chloride salt, and can by reaction and/calcining generates metal oxide; Doped chemical is selected from one or more in Sb, Ga, Bi, Co, La, Ce, W, Mo, Al, F, B;
Wherein doped chemical: the mol ratio of slaine is 1:3～1:100;
Described adhesive is one or more in polyethylene glycol, polyvinylpyrrolidone, polyethylene glycol oxide, polyvinyl alcohol, polyvinyl butyral;
Described solvent is one or more in ionized water, methyl alcohol, ethanol, isopropyl alcohol, DMF;
The gross mass of the salt of described slaine and doped chemical and the mass ratio of described adhesive are 0.5:1～3:1;
Wherein adhesive: the mass ratio of solvent is 1:3～1:10;
2) precursor solution of step 1) is directly injected in substrate by electrospinning device, obtains organic/inorganic composite nano fiber;
The operating voltage of described electrospinning device is 10～30KV, and described spray fiber tube is to the distance 10～30cm of substrate, the charging rate 0.1ml/h～1.0ml/h of described electrostatic spinning, the electrospinning time 1～120min of described electrostatic spinning;
Described substrate is aluminium-foil paper, wire netting, copper mesh;
3) by step 2) organic/inorganic composite nano fiber peel from substrate, be placed in temperature programmed control Muffle furnace, under air, nitrogen or argon atmosphere, heating rate is 0.5～10 DEG C/min, be warming up to 400～1000 DEG C, calcination time 2～8 hours, obtains flexible and transparent conductive oxide fibre film;
The flexible and transparent conductive oxide fibre film that the present invention obtains is of a size of 80～200 nanometers.
According to technical scheme of the present invention, the electric conductivity of the mol ratio capable of regulating nano fibrous membrane of the kind of nano material presoma and doped chemical and slaine; Electrospinning device parameter, calcining heat and time etc. are controlled size and the performance of nano fibrous membrane, thereby adjust permeability and the flexibility of the visible ray of nano fibrous membrane.
Compared with prior art, the invention has the advantages that:
1) nano fibrous membrane of preparing, has softness, high conductivity, high visible light permeability;
2) do not need flexible substrate material, be convenient to the use of flexible and transparent conductive oxidation film;
3) size of the flexible and transparent conductive oxide fibre film that prepared by method of electrostatic spinning is controlled, repeatability is high, technique is simple, efficiency is high, cost is low, can realize the preparation of industrialization.
Brief description of the drawings
Fig. 1 is the optical photograph of the flexible and transparent conductive oxide fibre film of the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the flexible and transparent conductive oxide fibre film of the embodiment of the present invention 1.
Fig. 3 is the UV-vis transmitted light spectrogram of the flexible and transparent conductive oxide fibre film of the embodiment of the present invention 1.
Detailed description of the invention
Embodiment 1: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of stannic chloride pentahydrate, doped chemical is that trichloride antimony, adhesive are that polyvinylpyrrolidone (PVP), solvent are DMF (DMF) and isopropyl alcohol mixed liquor.
1) under normal temperature, 1.865g stannic chloride pentahydrate and 0.135g trichloride antimony are mixed in 7g DMF and isopropyl alcohol mixed liquor, wherein the mass ratio of DMF and aqueous isopropanol is 2:1, constantly stirs.And then add 1g high molecular polymer PVP as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of trichloride antimony and stannic chloride pentahydrate is 1:9, and the mass ratio of the quality that trichloride antimony and stannic chloride pentahydrate are total and adhesive PVP is 2:1, adhesive PVP: solvent DMF and and the total mass ratio of isopropyl alcohol be 1:7.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 20KV, described spray fiber tube is to the distance 20cm of substrate, the charging rate 0.1ml/h of described electrostatic spinning, the electrospinning time 20min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 3 DEG C/min, is warming up to 600 DEG C, calcination time 3 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 120 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 80%.
Embodiment 2: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of stannic chloride pentahydrate, doped chemical is that cobalt chloride (hydration), adhesive are that polyethylene glycol, solvent are secondary deionized water.
1) under normal temperature, 1.865g stannic chloride pentahydrate and 0.061g cobalt chloride (hydration) are mixed in 6.8g secondary deionized water, constantly stir.And then add 1.2g polyethylene glycol as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, cobalt chloride (hydration) is 1:20 with the mol ratio of stannic chloride pentahydrate, the quality that cobalt chloride (hydration) and stannic chloride pentahydrate are total and the mass ratio of adhesive polyethylene glycol are 1.6:1, adhesive polyethylene glycol: the mass ratio of solvent secondary deionized water is 1:5.7.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 25KV, described spray fiber tube is to the distance 25cm of substrate, the charging rate 0.2ml/h of described electrostatic spinning, the electrospinning time 10min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 4 DEG C/min, is warming up to 700 DEG C, calcination time 4 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 150 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 82%.
Embodiment 3: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of zinc chloride, doped chemical is that alchlor, adhesive are that polyvinylpyrrolidone (PVP), solvent are ethanol and secondary deionized water.
1) under normal temperature, 1.363g zinc chloride and 0.222g alchlor are mixed in 6.83g ethanol and secondary deionized water, wherein the mass ratio of ethanol and secondary deionized water is 1:1, constantly stirs.And then add 1.585g high molecular polymer PVP as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of alchlor and zinc chloride is 1:16.7, and the mass ratio of the quality that alchlor and zinc chloride are total and adhesive PVP is 1:1, adhesive PVP: the total mass ratio of etoh solvent and secondary deionized water is 1:4.3.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 10KV, described spray fiber tube is to the distance 12cm of substrate, the charging rate 0.5ml/h of described electrostatic spinning, the electrospinning time 3min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 6 DEG C/min, is warming up to 800 DEG C, calcination time 3 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 140 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 85%.
Embodiment 4: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of inidum chloride, doped chemical is that gallium trichloride, adhesive are that acid polyethylene butyraldehyde, solvent are secondary deionized water.
1) under normal temperature, 2.211g inidum chloride and 0.018g gallium trichloride are mixed in 7g secondary deionized water, constantly stir.And then add 0.74g acid polyethylene butyraldehyde as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of alchlor and inidum chloride is 1:100, and the mass ratio of the quality that alchlor and inidum chloride are total and acid polyethylene butyraldehyde is 3:1, adhesive polyethylene acid butyraldehyde: the mass ratio of solvent secondary deionized water is 1:9.5.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 30KV, described spray fiber tube is to the distance 25cm of substrate, the charging rate 0.1ml/h of described electrostatic spinning, the electrospinning time 15min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 2 DEG C/min, is warming up to 500 DEG C, calcination time 5 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 90 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 83%.
Embodiment 5: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of stannic chloride pentahydrate, doped chemical is that ammonium fluoride, adhesive are that polyvinyl alcohol, solvent are the mixed liquor of secondary deionized water and methyl alcohol.
1) under normal temperature, 2.104g stannic chloride pentahydrate and 0.074g ammonium fluoride are mixed in 7.72g secondary deionized water and methyl alcohol, wherein the mass ratio of methyl alcohol and secondary deionized water is 1:1, constantly stirs.And then add 0.858g polyvinyl alcohol as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of ammonium fluoride and stannic chloride pentahydrate is 1:3, and the mass ratio of the quality that ammonium fluoride and stannic chloride pentahydrate are total and adhesive polyethylene alcohol is 2.5:1, adhesive polyethylene alcohol: the total mass ratio of solvent secondary deionized water and methyl alcohol is 1:9.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 18KV, described spray fiber tube is to the distance 25cm of substrate, the charging rate 0.3ml/h of described electrostatic spinning, the electrospinning time 15min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 0.5 DEG C/min, is warming up to 700 DEG C, calcination time 6 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 160 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 84%.
Embodiment 6: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of stannic chloride pentahydrate, doped chemical is that bismuth chloride and lanthanum nitrate hexahydrate, adhesive are that polyvinylpyrrolidone (PVP), solvent are ethanol.
1) under normal temperature, 1.000g stannic chloride pentahydrate, 0.011 bismuth chloride and 0.016g lanthanum nitrate hexahydrate are mixed in 6.162g ethanol, constantly stir.And then add 2.054g high molecular polymer PVP as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of cobalt chloride and lanthanum nitrate hexahydrate and stannic chloride pentahydrate is 1:40, and the mass ratio of the quality that cobalt chloride, lanthanum nitrate hexahydrate and stannic chloride pentahydrate are total and adhesive PVP is 0.5:1, adhesive PVP: the mass ratio of etoh solvent is 1:3.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 15KV, described spray fiber tube is to the distance 10cm of substrate, the charging rate 1.0ml/h of described electrostatic spinning, the electrospinning time 2min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 7 DEG C/min, is warming up to 900 DEG C, calcination time 5 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 200 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 80%.
Embodiment 7: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of stannic chloride pentahydrate, doped chemical is that tungsten chloride, adhesive are that polyvinylpyrrolidone (PVP), solvent are methyl alcohol.
1) under normal temperature, 1.753g stannic chloride pentahydrate, 0.039 tungsten chloride are mixed in 7.170 methyl alcohol, constantly stir.And then add 1.195g high molecular polymer PVP as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of tungsten chloride and stannic chloride pentahydrate is 1:50, and the mass ratio of the quality that tungsten chloride and stannic chloride pentahydrate are total and adhesive PVP is 1.5:1, adhesive PVP: the mass ratio of solvent methanol is 1:6.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 25KV, described spray fiber tube is to the distance 25cm of substrate, the charging rate 0.2ml/h of described electrostatic spinning, the electrospinning time 10min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 10 DEG C/min, is warming up to 1000 DEG C, calcination time 4 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 130 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 85%.
Embodiment 8: prepare flexible and transparent conductive sull.
The slaine that the present embodiment adopts is that the salt of inidum chloride, doped chemical is that molybdenum pentachloride, adhesive are that polyethylene glycol oxide, solvent are secondary deionized water.
1) under normal temperature, 2.211g inidum chloride and 0.034g molybdenum pentachloride are mixed in 7.48g secondary deionized water, constantly stir.And then add 0.748g polyethylene glycol oxide as adhesive, and continue to stir, form that to have the presoma of certain viscosity for subsequent use.Wherein, the mol ratio of molybdenum pentachloride and inidum chloride is 1:80, and the quality that molybdenum pentachloride and inidum chloride are total and the mass ratio of polyethylene glycol oxide are 3:1, adhesive polyethylene glycol oxide: the mass ratio of solvent secondary deionized water is 1:10.
2) precursor solution of step 1) is directly injected on wire netting by electrospinning device, wherein the operating voltage of electrospinning device is 30KV, described spray fiber tube is to the distance 30cm of substrate, the charging rate 1ml/h of described electrostatic spinning, the electrospinning time 5min of described electrostatic spinning, forms nanofiber;
3) by step 2) nanofiber peel from wire netting, be placed in temperature programmed control Muffle furnace, under air atmosphere, heating rate is 6 DEG C/min, is warming up to 800 DEG C, calcination time 6 hours obtains flexible and transparent conductive oxide fibre film;
The diameter of the flexible and transparent conductive oxide fibre film that the present embodiment obtains is 80 nanometers, and within the scope of visible ray 300nm～800nm, transmitance reaches 84%.
Claims (16)
1. a preparation method for flexible and transparent conductive oxide fibre film, is characterized in that, comprises the following steps:
(1) salt of slaine, doped chemical, adhesive and solvent are made into presoma;
(2) precursor solution of step (1) is directly injected in substrate by electrospinning device, obtains organic or inorganic composite nano fiber;
(3) the organic or inorganic composite nano fiber of step (2) is peeled from substrate, be placed in stove and calcine, obtain flexible and transparent conductive oxide fibre film.
2. a preparation method according to claim 1, is characterized in that, described slaine is one or more the salt in Sn, In, Zn.
3. a preparation method according to claim 2, is characterized in that, described slaine can by reaction and/calcining generate metal oxide.
4. a preparation method according to claim 1 and 2, is characterized in that, described doped chemical is selected from one or more in Sb, Ga, Bi, Co, Ta, La, Ce, W, Mo, Al, F, B.
5. a preparation method according to claim 1, is characterized in that, the salt of doped chemical: the mol ratio of slaine is 1:3～1:100.
6. a preparation method according to claim 1, is characterized in that, described adhesive is one or more in polyethylene glycol, polyvinylpyrrolidone, polyethylene glycol oxide, polyvinyl alcohol, polyvinyl butyral.
7. a preparation method according to claim 1, is characterized in that, described solvent is one or more in secondary deionized water, methyl alcohol, ethanol, DMF.
8. a preparation method according to claim 1, is characterized in that, the gross mass of the salt of described slaine and doped chemical and the mass ratio of described adhesive are 0.5:1～3:1.
9. a preparation method according to claim 1, is characterized in that, adhesive: the mass ratio of solvent is 1:3～1:10.
10. a preparation method according to claim 1, it is characterized in that, the operating voltage of described electrospinning device is 10～30KV, and spray fiber tube is to the distance 10～30cm of substrate, charging rate 0.1ml/h～the 1.0ml/h of electrostatic spinning, the electrospinning time 1～120min of electrostatic spinning.
11. 1 kinds of preparation methods according to claim 1, is characterized in that, described substrate is aluminium-foil paper or wire netting or copper mesh.
12. 1 kinds of preparation methods according to claim 1, is characterized in that, described stove is temperature programmed control Muffle furnace.
13. 1 kinds of preparation methods according to claim 1, is characterized in that, in described step (3), under air, nitrogen or argon atmosphere, calcine.
14. 1 kinds according to the preparation method described in claim 1 or 13, it is characterized in that, in described step (3), calcine technology is: heating rate is 0.5～10 DEG C/min, is warming up to 400～1000 DEG C, calcination time 2～10 hours.
15. 1 kinds according to the prepared flexible and transparent conductive oxide fibre film of the preparation method described in claim 1-14 any one, it is characterized in that, described flexible and transparent conductive oxide fibre film is of a size of 80～200 nanometers.
16. 1 kinds of flexible and transparent conductive oxide fibre films according to claim 15, is characterized in that, described flexible and transparent conductive oxide fibre film is that visible light transmissivity within the scope of 300nm～800nm is not less than 80% to wavelength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410157908.3A CN103924381B (en) | 2014-04-18 | Flexible and transparent conductive oxide nanofiber film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410157908.3A CN103924381B (en) | 2014-04-18 | Flexible and transparent conductive oxide nanofiber film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103924381A true CN103924381A (en) | 2014-07-16 |
| CN103924381B CN103924381B (en) | 2016-11-30 |
Family
ID=
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150881A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible manganese oxide nano fibrous membrane and preparation method thereof |
| CN104153124A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible rare-earth oxide nanofiber membrane and preparation method thereof |
| CN104153123A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible titanium oxide nanofiber membrane and preparation method thereof |
| CN104153125A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible ferric oxide nanofiber membrane and preparation method |
| CN104178822A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible inorganic fiber material and preparation method thereof |
| CN104178928A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible tin oxide nanofiber membrane and preparation method thereof |
| CN104372525A (en) * | 2014-12-03 | 2015-02-25 | 北京航空航天大学 | High-transparent flexible hollow metal nanofiber membrane and manufacturing method thereof |
| CN104451612A (en) * | 2014-12-31 | 2015-03-25 | 长春迪高实业有限公司 | Transparent conductive oxide film and preparation method thereof |
| CN106012305A (en) * | 2016-07-06 | 2016-10-12 | 海安县中山合成纤维有限公司 | Flexible high-strength silicon dioxide nano inorganic fiber membrane |
| CN106024099A (en) * | 2016-05-30 | 2016-10-12 | 兰州大学 | Preparation method of flexible transparent conductive thin film of electrospun silver nanofiber network |
| CN106345314A (en) * | 2016-09-23 | 2017-01-25 | 江苏大学 | Porous ferric oxide-titanium oxide-activated carbon complex fiber membrane and preparation method |
| CN106373669A (en) * | 2016-10-10 | 2017-02-01 | 福建农林大学 | Preparation method for cellulose-based aluminum-doped zinc oxide transparent conductive material |
| CN106592108A (en) * | 2016-12-15 | 2017-04-26 | 清华大学 | Preparation method of flexible transparent conductive film, and obtained product |
| CN106995948A (en) * | 2017-04-10 | 2017-08-01 | 吉林大学 | A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications |
| CN108615585A (en) * | 2018-05-15 | 2018-10-02 | 盐城工学院 | A kind of preparation method of doped stannum oxide composite conductive thin film |
| CN109306550A (en) * | 2017-07-27 | 2019-02-05 | Tcl集团股份有限公司 | A kind of inorganic, metal oxide and preparation method thereof |
| CN109457391A (en) * | 2018-12-11 | 2019-03-12 | 东华大学 | A kind of PcH/ZIF nano fibrous membrane and preparation method thereof |
| CN110042506A (en) * | 2019-04-30 | 2019-07-23 | 湘潭大学 | A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber |
| CN112844060A (en) * | 2020-12-31 | 2021-05-28 | 上海工程技术大学 | Manufacturing method of 3D composite air filtering material |
| CN114016206A (en) * | 2021-06-28 | 2022-02-08 | 南通大学 | Flexible V for catalytic degradation of erosive agents2O5Preparation method of nanofiber membrane |
| CN114561720A (en) * | 2022-01-19 | 2022-05-31 | 东华大学 | High-infrared-emissivity flexible calcium chromate lanthanum/silicon oxide composite fiber material and preparation method and application thereof |
| CN115467091A (en) * | 2022-08-26 | 2022-12-13 | 东华大学 | Composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and preparation method thereof |
| US11936052B2 (en) * | 2019-04-19 | 2024-03-19 | Korea Institute Of Science And Technology | Fluorine-doped tin oxide support and Pt catalyst for fuel cell comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845676A (en) * | 2010-05-18 | 2010-09-29 | 北京航空航天大学 | Multifunctional composite fiber and preparation method thereof |
| CN102691175A (en) * | 2012-05-07 | 2012-09-26 | 北京航空航天大学 | Composite fibre membrane with unidirectional water permeable performance and preparation method thereof |
| CN102704190A (en) * | 2011-12-29 | 2012-10-03 | 浙江大学 | Method for preparing polyvinylidene fluoride and titanium dioxide (PVDF/TiO2) compounded nanofiber membrane |
| WO2013047264A1 (en) * | 2011-09-28 | 2013-04-04 | 株式会社クラレ | Extra-fine fiber sheet |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845676A (en) * | 2010-05-18 | 2010-09-29 | 北京航空航天大学 | Multifunctional composite fiber and preparation method thereof |
| WO2013047264A1 (en) * | 2011-09-28 | 2013-04-04 | 株式会社クラレ | Extra-fine fiber sheet |
| CN102704190A (en) * | 2011-12-29 | 2012-10-03 | 浙江大学 | Method for preparing polyvinylidene fluoride and titanium dioxide (PVDF/TiO2) compounded nanofiber membrane |
| CN102691175A (en) * | 2012-05-07 | 2012-09-26 | 北京航空航天大学 | Composite fibre membrane with unidirectional water permeable performance and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡沛然: "基于纤维模板的柔性导电材料制备及其性能研究", 《中国优秀硕士学位论文全文数据库》, 1 January 2012 (2012-01-01) * |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178822B (en) * | 2014-07-30 | 2016-08-24 | 东华大学 | Flexible inorganic fibrous material and preparation method thereof |
| CN104150881B (en) * | 2014-07-30 | 2016-02-10 | 东华大学 | A kind of flexible manganese oxide nano fibrous membrane and preparation method thereof |
| CN104153123A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible titanium oxide nanofiber membrane and preparation method thereof |
| CN104153125A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible ferric oxide nanofiber membrane and preparation method |
| CN104178822A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible inorganic fiber material and preparation method thereof |
| CN104178928A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible tin oxide nanofiber membrane and preparation method thereof |
| CN104153124A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible rare-earth oxide nanofiber membrane and preparation method thereof |
| CN104150881A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible manganese oxide nano fibrous membrane and preparation method thereof |
| CN104372525A (en) * | 2014-12-03 | 2015-02-25 | 北京航空航天大学 | High-transparent flexible hollow metal nanofiber membrane and manufacturing method thereof |
| CN104451612A (en) * | 2014-12-31 | 2015-03-25 | 长春迪高实业有限公司 | Transparent conductive oxide film and preparation method thereof |
| CN106024099B (en) * | 2016-05-30 | 2018-03-27 | 兰州大学 | A kind of preparation method of electrospinning silver nanoparticle network of fibers flexible transparent conductive film |
| CN106024099A (en) * | 2016-05-30 | 2016-10-12 | 兰州大学 | Preparation method of flexible transparent conductive thin film of electrospun silver nanofiber network |
| CN106012305A (en) * | 2016-07-06 | 2016-10-12 | 海安县中山合成纤维有限公司 | Flexible high-strength silicon dioxide nano inorganic fiber membrane |
| CN106345314A (en) * | 2016-09-23 | 2017-01-25 | 江苏大学 | Porous ferric oxide-titanium oxide-activated carbon complex fiber membrane and preparation method |
| CN106373669A (en) * | 2016-10-10 | 2017-02-01 | 福建农林大学 | Preparation method for cellulose-based aluminum-doped zinc oxide transparent conductive material |
| CN106592108A (en) * | 2016-12-15 | 2017-04-26 | 清华大学 | Preparation method of flexible transparent conductive film, and obtained product |
| CN106592108B (en) * | 2016-12-15 | 2019-02-05 | 清华大学 | A kind of preparation method and products therefrom of flexible transparent conductive film |
| CN106995948B (en) * | 2017-04-10 | 2019-07-12 | 吉林大学 | A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications |
| CN106995948A (en) * | 2017-04-10 | 2017-08-01 | 吉林大学 | A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications |
| CN109306550A (en) * | 2017-07-27 | 2019-02-05 | Tcl集团股份有限公司 | A kind of inorganic, metal oxide and preparation method thereof |
| CN108615585A (en) * | 2018-05-15 | 2018-10-02 | 盐城工学院 | A kind of preparation method of doped stannum oxide composite conductive thin film |
| CN109457391A (en) * | 2018-12-11 | 2019-03-12 | 东华大学 | A kind of PcH/ZIF nano fibrous membrane and preparation method thereof |
| US11936052B2 (en) * | 2019-04-19 | 2024-03-19 | Korea Institute Of Science And Technology | Fluorine-doped tin oxide support and Pt catalyst for fuel cell comprising the same |
| CN110042506A (en) * | 2019-04-30 | 2019-07-23 | 湘潭大学 | A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber |
| CN112844060A (en) * | 2020-12-31 | 2021-05-28 | 上海工程技术大学 | Manufacturing method of 3D composite air filtering material |
| CN114016206A (en) * | 2021-06-28 | 2022-02-08 | 南通大学 | Flexible V for catalytic degradation of erosive agents2O5Preparation method of nanofiber membrane |
| CN114016206B (en) * | 2021-06-28 | 2022-10-18 | 南通大学 | Flexible V for catalytic degradation of erosive agents 2 O 5 Preparation method of nanofiber membrane |
| CN114561720A (en) * | 2022-01-19 | 2022-05-31 | 东华大学 | High-infrared-emissivity flexible calcium chromate lanthanum/silicon oxide composite fiber material and preparation method and application thereof |
| CN114561720B (en) * | 2022-01-19 | 2024-04-26 | 东华大学 | High-infrared-emissivity flexible calcium lanthanum chromate/silicon oxide composite fiber material and preparation method and application thereof |
| CN115467091A (en) * | 2022-08-26 | 2022-12-13 | 东华大学 | Composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102646759B (en) | Preparing method for transparent conductive oxide film | |
| CN106191775A (en) | A kind of transparent conductive film and its preparation method and application | |
| CN104505149A (en) | Laminated transparent electrode and preparation method thereof | |
| JP2013509352A (en) | Conductive metal oxide film and photovoltaic device | |
| CN104575864A (en) | Method for directly preparing metal oxide/silver nanowire composite conductive network | |
| WO2011027115A2 (en) | Transparent conducting oxides | |
| CN102674335A (en) | Method for preparing graphene based on free radical reaction at low temperature | |
| CN104372525A (en) | High-transparent flexible hollow metal nanofiber membrane and manufacturing method thereof | |
| CN108091414B (en) | Silver nanowire composite transparent conductive film and preparation thereof | |
| CN102994975A (en) | Preparation method of aluminum-doped zinc oxide transparent conductive oxide film | |
| KR20110089354A (en) | Conductive film formation on glass | |
| CN103508484B (en) | Infrared low-emissivity nanocrystalline thin-film material SnO2 and preparation method thereof | |
| KR101066016B1 (en) | Fto transparent conductive coating comprising nanorod layer | |
| CN103938210B (en) | A kind of preparation method of AZO transparent conductive film | |
| JP2015124117A (en) | Method of producing metal oxide thin film | |
| CN103924381A (en) | Flexible transparent conductive oxide nanofiber membrane and preparation method thereof | |
| CN103924381B (en) | Flexible and transparent conductive oxide nanofiber film and preparation method thereof | |
| Olopade et al. | CHARACTERIZATION OF SnO_ {2}: F FILMS DEPOSITED BY ATMOSPHERIC PRESSURE CHEMICAL VAPOUR DEPOSITION FOR OPTIMUM PERFORMANCE SOLAR CELLS | |
| CN101704635B (en) | Method for preparing aluminum-doped zinc oxide film on optical solar reflector | |
| CN103757748A (en) | Preparation of tubular zinc stannate (ZnSnO3) material by using electrostatic spinning process | |
| CN103112880B (en) | Method for preparing alkali earth metal MF2 (M=Ba, Ca) film with trifluoroacetate solution | |
| US8337943B2 (en) | Nano-whisker growth and films | |
| KR101135792B1 (en) | Producing Method of Double-Layered FTO Film | |
| CN103113897B (en) | Method for preparing rare-earth metal fluoride REF3 film with trifluoroacetate solution | |
| KR101337967B1 (en) | Manufacturing Mothod of F-dopped Tin oxide film with bending processability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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: 20161130 Termination date: 20180418 |