CN104927073A - Self-assembly preparation method of gas-liquid interface of silver nanowire/graphene polymer composite film - Google Patents
Self-assembly preparation method of gas-liquid interface of silver nanowire/graphene polymer composite film Download PDFInfo
- Publication number
- CN104927073A CN104927073A CN201510298820.8A CN201510298820A CN104927073A CN 104927073 A CN104927073 A CN 104927073A CN 201510298820 A CN201510298820 A CN 201510298820A CN 104927073 A CN104927073 A CN 104927073A
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- preparation
- graphene oxide
- nano silver
- 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.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 131
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 title claims abstract description 14
- 238000001338 self-assembly Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000002042 Silver nanowire Substances 0.000 title abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 239000000084 colloidal system Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 28
- 239000001509 sodium citrate Substances 0.000 claims description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 16
- 229940038773 trisodium citrate Drugs 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000011160 research Methods 0.000 description 9
- 238000007306 functionalization reaction Methods 0.000 description 7
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PHDUUMRDIHMMNC-UHFFFAOYSA-N 2-azidobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1N=[N+]=[N-] PHDUUMRDIHMMNC-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a silver nanowire/graphene polymer composite film and belongs to the field of chemistry. The preparation method comprises the following steps: (1) preparing graphene oxide aqueous solution colloid; (2) preparing silver nanowire/grapheme hybrid aqueous solution with certain concentration; (3) performing self-assembly on gas-liquid interface. With adoption of the preparation method, the ubiquitous defects in the preparation methods at present that a grapheme film is poor in characteristics and low in repeatability, and chemical reagents are polluted are overcome.
Description
Technical field
The present invention relates to a kind of preparation method of laminated film, particularly the preparation method of a kind of nano silver wire/graphene polymer laminated film, belongs to chemical field.
Background technology
Since finding from 2004, Graphene receives the general concern of scientific circles because of the performance of uniqueness and two-dimensional nanostructure, and is chosen as one of ten big sciences progress in 2009 by Science magazine.No matter in theory or experimental study, Graphene has shown great scientific meaning and using value all, based on the research of grapheme material also for the application of Graphene provides experiment and theoretical basis.However, the research of grapheme material is also just at the early-stage, the scope of research is also still limited, except the character research of Graphene inherence, manyly need further research based on graphene composite material problem, the interaction of the intermiscibility of the preparation problem of such as Graphene, the finishing of Graphene, Graphene and other superpolymer, Graphene and inorganic particulate, exploitation of composite properties etc.Graphene, owing to having high electron mobility and the high light transmittance in visible-range, is the ideal material preparing nesa coating.Thus substitute traditional conductive coating and conductive filler material, preparing various forms of conductive film, be applied in liquid crystal and solar cell, will be a good research direction in future undoubtedly.
The investigation and application that matrix material Graphene being combined processability uniqueness with both nanometer silvers has obtained widely owing to having the electric property of special construction and uniqueness, mechanical property and good chemical stability.Wherein monodimension nanometer material nano silver wire is due to radius-of-curvature little suitable " point discharge ", has excellent Flied emission and threshold field is less, emission and to launch bit density higher.One dimension nano silver wire is modified the fibrous texture advantage that both can give full play to nano wire of load on graphene sheet layer, in the carrier of graphene film, form conductive network better, tunnel conduction effect and the Flied emission conductive effect of nanoparticle can be played again.Nano silver wire functionalization graphene can form composite conducting polymer material as conduction persursor material together with polymeric substrate, it takes into account the workability of polymkeric substance and the electroconductibility of electro-conductive material, can be used as antistatic material, conducting film, electrically conducting coating, conductive plastics and phase-transfer catalyst etc.The method preparing graphene conductive film based on superpolymer substrate obtains a lot of concerns and research.
Water-soluble high-molecular compound is one of the most valued current polymkeric substance, on no matter still applying in production, is all in the stage developed rapidly.Worldwide be subject to more and more higher attention, because it is to Energy production, environment protection, recycling economy etc. all play an important role.And current, the performance that the novel nano-material such as nano silver wire, Graphene shows is outstanding equally, and numerous scientific worker is just being devoted to the properties research of material.Be expected to participate in various Modified Polymer, particularly prepare in water-soluble high-molecular compound, by being cast into embrane method, the process application such as solution blended process are in industries such as coating, papermaking and water treatments.But because Graphene has higher specific surface area, higher Young's modulus, so can prepare matrix material as Nano filling.But because perfect graphenic surface is without any functional group, so it easily reunites in polymeric matrix, be even again piled into graphite, the specific surface area of the RGO powder after gathering only has 1/10 of theoretical value.Therefore much research is devoted to how to make graphene dispersion evenly in polymeric matrix.Stankovich etc. (Carbon 2007,45 (7): 1558-1565.) utilize the sulfurization of diazoamino Phenylsulfonic acid to process graphene oxide, make sulfonate radical (-SO
3h) be grafted on redox graphene lamella, finally fall remaining oxygen-containing functional group with hydrazine reduction again, prepared the Graphene that surface is connected to sulfonate radical.Rely on Graphene top layer with sulfonate radical between the electrostatic repulsion that produces, sulfonated graphene just can be dispersed in water or polar solvent preferably, and conductivity have also been obtained recovery to a certain degree.This method can improve graphene dispersion, but other character such as the high conductivity of Graphene do not have real recovery.The further exploitation of personnel so the dispersing method of Graphene in superpolymer requires study.
Summary of the invention
For above this present situation of prior art present situation, the invention provides the preparation method of a kind of nano silver wire/graphene polymer laminated film.
The liquid-gas interface self-assembly preparation method thereof of nano silver wire provided by the present invention/graphene polymer laminated film, comprises the following steps:
(1) graphene oxide water solution colloid is prepared;
(2) water-DMF solution of equal-volume and isocyatic sodium citrate aqueous solution and Silver Nitrate is being mixed, as solution A, add a certain amount of B solution, described B solution is the graphene oxide water solution after diallyl dimethyl ammoniumchloride modified, supersound process 30min under normal temperature, then lucifuge condition lower magnetic force stirs 10 ~ 12 hours, be warming up to 130 DEG C and continue reaction 3h, and then add Trisodium Citrate and the xitix reductive agent as graphene oxide, graphene oxide is by xitix, Trisodium Citrate and diallyl dimethyl ammoniumchloride are in a mild condition, through being reduced into conductive graphene sheet, last fully washing, nano silver wire/Graphene hybrid solid is obtained after centrifugal treating, be mixed with certain density nano silver wire/Graphene hybrid aqueous solution,
(3) liquid-vapo(u)r interface self-assembly is improved: measure that nano silver wire/the Graphene hybrid aqueous solution joins in aqueous solutions of polymers in certain mass ratio, magnetic agitation evenly uses ultrasonic disperse again, after making it dissolve completely, form uniform mixture cool to room temperature, de-bubbled is left standstill in vacuum chamber, obtain film-casting liquid, again in 40 ~ 80 DEG C of water-baths, leave standstill the nano silver wire-Graphene/polymeric film obtaining thickness after some hours and do not wait on liquid level, further, Hummers method is adopted to prepare graphene oxide water solution colloid in step (1), concentration is 4 ~ 6mg/ml, further, solution A described in step (2) is water-DMF (V/V=1:1 ~ 1.5) solution of equal-volume and isoconcentration sodium citrate aqueous solution and Silver Nitrate, wherein sodium citrate aqueous solution concentration is 0.1-0.5M, in the water-DMF solution of Silver Nitrate, the volume ratio of water and DMF is 1:1.5, further, in B solution described in step (2), the corresponding diallyl dimethyl ammoniumchloride solution of every 100mg graphene oxide is 6 ~ 9ml, diallyl dimethyl ammoniumchloride volume fraction in solution is 35%, according to silver: graphene oxide mass ratio is that 1:4 ~ 1:5 regulates the amount adding graphene oxide solution, further, the Trisodium Citrate added in step (2) and xitix quality are 10 ~ 20 times and 80 ~ 100 times of graphene oxide quality respectively, further, step (2) graphene oxide is reduced agent at 60 ~ 90 DEG C, conductive graphene is reduced into through 7 ~ 10 hours, step (2) whole process needs lucifuge process, further, in step (3), the mass ratio of nano silver wire/Graphene hybrid aqueous solution and aqueous solutions of polymers is 1:5-80, the mass concentration of described aqueous solutions of polymers is 20 ~ 30%, 2h is stirred at 90 DEG C of lower magnetic forces, use 100 ~ 300W ultrasonic disperse lh again, it is made to dissolve completely, further, wherein step (3) is formed in uniform mixture vacuum chamber and leaves standstill de-bubbled 1 ~ 2h, low vacuum is in 0.1MPa, further, the polymkeric substance adopted in step (3) Liquid preparation methods comprises polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyoxyethylene glycol, polymine, further, in step (2), the nano silver wire/Graphene hybrid concentration of aqueous solution of preparation is 12 ~ 15mg/ml.
The present invention has following advantage relative to other graphene films: 1) this film has the feature of better electricity, optics, biology and water absorption resistance compared to simple Graphene or graphene oxide film.Product performance index all can change by regulating test parameter, is suitable for large-scale promotion, has wide application prospect.2) silver ions is assembled into the surface of graphene oxide of diallyl dimethyl ammoniumchloride functionalization because electrostatic adsorption is in bond, improve the charge capacity of nanometer silver on Graphene, also change the static charge of graphenic surface, improve the stability of Graphene.3) nano silver wire improves the solvability of graphene composite material in polar solvent by electrostatic together with diallyl dimethyl ammoniumchloride.4) pinning effect of diallyl dimethyl ammoniumchloride slow down the migration of silver.5) xitix (L-AA) is also as molecule-type control agent, form colloids of silver salts or change the reduction rate of silver ions, the initial stage nucleation process of crystal seed is affected with this, and realize the morphology controllable of product further, thus prepare nano silver wire/graphene nano hybrid material by the method for original position induction silver nanowire growth on Graphene.It is poor that the present invention compensate for ubiquitous graphene film characteristic in present stage preparation method, and repeatability is not high, and chemical reagent has the shortcoming of pollution.
Accompanying drawing explanation
Fig. 1 is the multiple one field emission scanning electron microscope figure on the nano silver wire-Graphene/PVA (PVOH) FILM surface of preparation.
Fig. 2 is the multiple two field emission scanning electron microscope figure on the nano silver wire-Graphene/PVA (PVOH) FILM surface of preparation.
Embodiment
The material parameters adopted in the present invention: polyvinyl alcohol molecular-weight average: 110000 ~ 130000g/mol, polyacrylic acid molecular-weight average: 2000 ~ 4000 g/mol, polyacrylamide molecular-weight average: 2000000 ~ 15000000g/mol, polyoxyethylene glycol molecular-weight average: 1800 ~ 2200 g/mol, polymine molecular-weight average: 4300 ~ 6500g/mol.
Embodiment 1:
(1) Hummers method is adopted to prepare graphene oxide colloid (GO, 4mg/ml);
(2) equal volume and the sodium citrate aqueous solution of concentration (5ml, 0.1M) and the water-DMF solution (V/V=1:1) of Silver Nitrate are mixed, as solution A in there-necked flask.Add the graphene oxide water solution 54ml after 12.96ml diallyl dimethyl ammoniumchloride (PDDA) modified (silver: graphene oxide mass ratio is 1:4) as B solution.Ultrasonic 30min under normal temperature, then lucifuge condition lower magnetic force stirs 12 hours.Magnetic agitation 3h in 130 DEG C of oil bath pans.And then add the reductive agent of Trisodium Citrate 2.16g and xitix 17.28g as graphene oxide.Graphene oxide is by xitix, and Trisodium Citrate and diallyl dimethyl ammoniumchloride, at 90 DEG C, were reduced into conductive graphene sheet through 10 hours, the centrifugal nano silver wire/Graphene hybrid concentration of aqueous solution being mixed with 12mg/ml of last fully washing;
(3) improving liquid-vapo(u)r interface self-assembly method is: measuring functionalization graphene aqueous solution 416ml that nano silver wire modifies, to join mass concentration by 1:5 mass ratio be in the polyvinyl alcohol water solution of 20%, 2h is stirred at 90 DEG C of lower magnetic forces, use 100W ultrasonic disperse lh again, make it dissolve completely.Form uniform mixture cool to room temperature, leave standstill de-bubbled 1h under vacuum tightness 0.09MPa, obtain film-casting liquid.In 40 DEG C of water-baths, after leaving standstill 1h, on liquid level, obtain nano silver wire-Graphene/PVA (PVOH) FILM that thickness is 2um.
Embodiment 2:
(1) Hummers method is adopted to prepare graphene oxide colloid (GO, 4.5mg/ml);
(2) equal volume and the sodium citrate aqueous solution of concentration (5ml, 0.2M) and the water-DMF solution (V/V=1:1.2) of Silver Nitrate are mixed, as solution A in there-necked flask.Add the graphene oxide water solution 96ml after 30.24ml diallyl dimethyl ammoniumchloride (PDDA) modified (silver: graphene oxide mass ratio is 1:4) as B solution.Ultrasonic 30min under normal temperature, then lucifuge condition lower magnetic force stirs 10 hours.Magnetic agitation 3h in 130 DEG C of oil bath pans again.And then add 8.64g Trisodium Citrate and the 34.56g xitix reductive agent as graphene oxide.Graphene oxide is by xitix, and Trisodium Citrate and diallyl dimethyl ammoniumchloride, under 60 DEG C of conditions, were reduced into conductive graphene sheet through 7 hours, the centrifugal nano silver wire/Graphene hybrid concentration of aqueous solution being mixed with 14mg/ml of last fully washing;
(3) improving liquid-vapo(u)r interface self-assembly method is: measuring the functionalization graphene aqueous solution that 142ml nano silver wire modifies, to join mass concentration by 1:10 mass ratio be in the polyacrylic acid aqueous solution of 20%, 2h is stirred at 90 DEG C of lower magnetic forces, use 200W ultrasonic disperse lh again, make it dissolve completely.Form uniform mixture cool to room temperature, under vacuum tightness 0.08MPa, leave standstill de-bubbled 1h, obtain film-casting liquid.In 80 DEG C of water-baths, after leaving standstill 2h, on liquid level, obtain nano silver wire-Graphene/polyacrylic film that thickness is 10um.
Embodiment 3:
(1) Hummers method is adopted to prepare graphene oxide colloid (GO, 5mg/ml);
(2) equal volume and the sodium citrate aqueous solution of concentration (5ml, 0.3M) and the water-DMF solution (V/V=1:1.2) of Silver Nitrate are mixed, as solution A in there-necked flask.Add the graphene oxide water solution 129.6ml after 51.84ml diallyl dimethyl ammoniumchloride (PDDA) modified (silver: graphene oxide mass ratio is 1:4) as B solution.Ultrasonic 30min under normal temperature, then lucifuge condition lower magnetic force stirs 10 hours.Magnetic agitation 3h in 130 DEG C of oil bath pans again.And then add 12.96g Trisodium Citrate and the 58.32g xitix reductive agent as graphene oxide.Graphene oxide is by xitix, and Trisodium Citrate and diallyl dimethyl ammoniumchloride, under 70 DEG C of conditions, were reduced into conductive graphene sheet through 8 hours, the centrifugal nano silver wire/Graphene hybrid concentration of aqueous solution being mixed with 15mg/ml of last fully washing;
(3) improving liquid-vapo(u)r interface self-assembly method is: measuring the functionalization graphene aqueous solution that 42ml nano silver wire modifies, to join mass concentration by 1:40 mass ratio be in the polyacrylamide solution of 25%, 2h is stirred at 90 DEG C of lower magnetic forces, use 100W ultrasonic disperse lh again, make it dissolve completely.Form uniform mixture cool to room temperature, vacuum tightness 0.09MPa leaves standstill de-bubbled 2h, obtains film-casting liquid.In 80 DEG C of water-baths, after leaving standstill 6h, on liquid level, obtain nano silver wire-Graphene/polyacrylamide film that thickness is 10um.
Embodiment 4:
(1) Hummers method is adopted to prepare graphene oxide colloid (GO, 5.5mg/ml);
(2) equal volume and the sodium citrate aqueous solution of concentration (5ml, 0.4M) and the water-DMF solution (V/V=1:1.3) of Silver Nitrate are mixed, as solution A in there-necked flask.Add the graphene oxide water solution 157ml after 77.76ml diallyl dimethyl ammoniumchloride (PDDA) modified (silver: graphene oxide mass ratio is 1:4) as B solution.Ultrasonic 30min under normal temperature, then lucifuge condition lower magnetic force stirs 10 hours.Magnetic agitation 3h in 130 DEG C of oil bath pans again.And then add 17.28g Trisodium Citrate and the 82g xitix reductive agent as graphene oxide.Graphene oxide is by xitix, and Trisodium Citrate and diallyl dimethyl ammoniumchloride, under 80 DEG C of conditions, were reduced into conductive graphene sheet through 9 hours, the nano silver wire/Graphene hybrid concentration of aqueous solution of last fully washing centrifugal preparation 15mg/ml;
(3) improving liquid-vapo(u)r interface self-assembly method is: measuring the functionalization graphene aqueous solution that 33ml nano silver wire modifies, to join mass concentration by 1:60 mass ratio be in the Aqueous Solutions of Polyethylene Glycol of 30%, 2h is stirred at 90 DEG C of lower magnetic forces, use 200W ultrasonic disperse lh again, make it dissolve completely.Form uniform mixture cool to room temperature, vacuum tightness 0.07MPa leaves standstill de-bubbled 1h, obtains film-casting liquid.In 80 DEG C of water-baths, after leaving standstill 3h, on liquid level, obtain nano silver wire-Graphene/polyoxyethylene glycol film that thickness is 30um.
Embodiment 5:
(1) Hummers method is adopted to prepare graphene oxide colloid (GO, 6mg/ml);
(2) equal volume and the sodium citrate aqueous solution of concentration (5ml, 0.5M) and the water-DMF solution (V/V=1:5) of Silver Nitrate are mixed, as solution A in there-necked flask.Add the graphene oxide water solution 225ml after 121.5ml diallyl dimethyl ammoniumchloride (PDDA) modified (silver: graphene oxide mass ratio is 1:5) as B solution.Ultrasonic 30min under normal temperature, then lucifuge condition lower magnetic force stirs 10 hours.Magnetic agitation 3h in 130 DEG C of oil bath pans again.And then add 27g Trisodium Citrate and the 135g xitix reductive agent as graphene oxide.Graphene oxide is by xitix, and Trisodium Citrate and diallyl dimethyl ammoniumchloride, under 80 DEG C of conditions, were reduced into conductive graphene sheet through 9 hours, the centrifugal nano silver wire/Graphene hybrid concentration of aqueous solution being mixed with 15mg/ml of last fully washing;
(3) improving liquid-vapo(u)r interface self-assembly method is: measuring the functionalization graphene aqueous solution that 25ml nano silver wire modifies, to join mass concentration by 1:80 mass ratio be in the aq. polyethyleneimine of 30%, 2h is stirred at 90 DEG C of lower magnetic forces, use 300W ultrasonic disperse lh again, make it dissolve completely.Form uniform mixture cool to room temperature, under vacuum tightness 0.09MPa, leave standstill de-bubbled 1h, obtain film-casting liquid.In 80 DEG C of water-baths, after leaving standstill 4h, on liquid level, obtain nano silver wire-Graphene/polymine film that thickness is 20um.
In order to observe nano silver wire-Graphene/PVA (PVOH) FILM surface fine structure, by sample on masking foil after abundant drying film forming, in sample table after ion sputtering instrument is gold-plated, observe its surface by the scanning electron microscope (SUPRA55-SEM) of Germany-Zeiss company.Photo in accompanying drawing is the product observations of embodiment 1.Can snap on nano silver wire-Graphene/PVA (PVOH) FILM surface, except the roughness of some nano-scales, all films are all even compacts, more smooth, do not have large fold, and silver-colored line is uniformly dispersed, and have good continuity.The Graphene of stratiform is also by partial contour that matrix embeds.Nano silver wire diameter Distribution is 60 ~ 65nm, and length is 3 ~ 5um, is distributed on graphene film, and some silver-colored line is clipped between multi-layer graphene film, in half naked state, this just self-assembly process prepare the embodiment of multi-layer nano level film feature.
Claims (10)
1. the liquid-gas interface self-assembly preparation method thereof of nano silver wire/graphene polymer laminated film, is characterized in that comprising the following steps:
(1) graphene oxide water solution colloid is prepared;
(2) water-DMF solution of equal-volume and isocyatic sodium citrate aqueous solution and Silver Nitrate is being mixed, as solution A, add a certain amount of B solution, described B solution is the graphene oxide water solution after diallyl dimethyl ammoniumchloride modified, supersound process 30min under normal temperature, then lucifuge condition lower magnetic force stirs 10 ~ 12 hours, be warming up to 130 DEG C and continue reaction 3h, and then add Trisodium Citrate and the xitix reductive agent as graphene oxide, graphene oxide is by xitix, Trisodium Citrate and diallyl dimethyl ammoniumchloride are in a mild condition, through being reduced into conductive graphene sheet, last fully washing, nano silver wire/Graphene hybrid solid is obtained after centrifugal treating, be mixed with certain density nano silver wire/Graphene hybrid aqueous solution,
(3) liquid-vapo(u)r interface self-assembly is improved: measure that nano silver wire/the Graphene hybrid aqueous solution joins in aqueous solutions of polymers in certain mass ratio, magnetic agitation evenly uses ultrasonic disperse again, after making it dissolve completely, form uniform mixture cool to room temperature, de-bubbled is left standstill in vacuum chamber, obtain film-casting liquid, then in 40 ~ 80 DEG C of water-baths, leave standstill the nano silver wire-Graphene/polymeric film obtaining thickness after some hours and do not wait on liquid level.
2. preparation method according to claim 1, is characterized in that: adopt Hummers method to prepare graphene oxide water solution colloid in step (1), concentration is 4 ~ 6mg/ml.
3. preparation method according to claim 1, it is characterized in that: the solution A described in step (2) is water-DMF (V/V=1:1 ~ 1.5) solution of equal-volume and isoconcentration sodium citrate aqueous solution and Silver Nitrate, wherein sodium citrate aqueous solution concentration is 0.1-0.5M, and in the water-DMF solution of Silver Nitrate, the volume ratio of water and DMF is 1:1.5.
4. preparation method according to claim 1, it is characterized in that: in the B solution described in step (2), the corresponding diallyl dimethyl ammoniumchloride solution of every 100mg graphene oxide is 6 ~ 9ml, diallyl dimethyl ammoniumchloride volume fraction in solution is 35%, according to silver: graphene oxide mass ratio is that 1:4 ~ 1:5 regulates the amount adding graphene oxide solution.
5. preparation method according to claim 1, is characterized in that: the Trisodium Citrate added in step (2) and xitix quality are 10 ~ 20 times and 80 ~ 100 times of graphene oxide quality respectively.
6. preparation method according to claim 1, is characterized in that: step (2) graphene oxide is reduced agent at 60 ~ 90 DEG C, is reduced into conductive graphene through 7 ~ 10 hours, and step (2) whole process needs lucifuge process.
7. preparation method according to claim 1, it is characterized in that: in step (3), the mass ratio of nano silver wire/Graphene hybrid aqueous solution and aqueous solutions of polymers is 1:5-80, the mass concentration of described aqueous solutions of polymers is 20 ~ 30%, 2h is stirred at 90 DEG C of lower magnetic forces, use 100 ~ 300W ultrasonic disperse lh again, make it dissolve completely.
8. preparation method according to claim 1, is characterized in that: wherein step (3) is formed in uniform mixture vacuum chamber and leaves standstill de-bubbled 1 ~ 2h, and low vacuum is in 0.1MPa.
9. preparation method according to claim 1, is characterized in that: the polymkeric substance adopted in step (3) Liquid preparation methods comprises polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyoxyethylene glycol, polymine.
10. preparation method according to claim 1, is characterized in that: in step (2), the nano silver wire/Graphene hybrid concentration of aqueous solution of preparation is 12 ~ 15mg/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510298820.8A CN104927073A (en) | 2015-06-03 | 2015-06-03 | Self-assembly preparation method of gas-liquid interface of silver nanowire/graphene polymer composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510298820.8A CN104927073A (en) | 2015-06-03 | 2015-06-03 | Self-assembly preparation method of gas-liquid interface of silver nanowire/graphene polymer composite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104927073A true CN104927073A (en) | 2015-09-23 |
Family
ID=54114512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510298820.8A Pending CN104927073A (en) | 2015-06-03 | 2015-06-03 | Self-assembly preparation method of gas-liquid interface of silver nanowire/graphene polymer composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104927073A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499600A (en) * | 2015-12-15 | 2016-04-20 | 中国科学院上海高等研究院 | Method for preparing silver nanowire-graphene composite aerogel |
| CN106835082A (en) * | 2017-01-11 | 2017-06-13 | 东南大学 | The preparation method of the flexible self-supporting graphene film of metal nanoparticle doping |
| CN107910128A (en) * | 2017-10-13 | 2018-04-13 | 哈尔滨工业大学深圳研究生院 | A kind of method that graphene oxide self assembly compound silver nanometer line improves flexible device mechanical performance |
| CN108192483A (en) * | 2017-12-28 | 2018-06-22 | 安徽明珠颜料科技有限公司 | A kind of preparation method of graphene oxide Antimicrobial preservative coating |
| CN109135144A (en) * | 2018-07-11 | 2019-01-04 | 四川羽玺新材料股份有限公司 | A kind of graphene/acrylic resin laminated film and preparation method thereof |
| CN109575456A (en) * | 2018-10-26 | 2019-04-05 | 福建师范大学 | A kind of preparation method of multi-component hybridization anisotropy thermal diffusion film |
| CN109979642A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | Conductive film and its preparation method and application |
| CN113184838A (en) * | 2021-05-19 | 2021-07-30 | 重庆交通大学 | Preparation method of functionalized graphene material |
| CN113930037A (en) * | 2021-10-27 | 2022-01-14 | 苏州大学 | Filling type flexible strain sensing material and preparation method thereof |
| CN115194175A (en) * | 2022-07-01 | 2022-10-18 | 西安交通大学 | A kind of high-purity ultrafine silver nanowire and large-scale preparation method thereof |
| CN118553462A (en) * | 2024-07-26 | 2024-08-27 | 常州碳禾新材料科技有限公司 | Graphene-doped conductive silver paste and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613773A (en) * | 2013-11-07 | 2014-03-05 | 常州大学 | Preparation method of flexible transparent conducting polymer thin film with antibacterial properties |
-
2015
- 2015-06-03 CN CN201510298820.8A patent/CN104927073A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613773A (en) * | 2013-11-07 | 2014-03-05 | 常州大学 | Preparation method of flexible transparent conducting polymer thin film with antibacterial properties |
Non-Patent Citations (3)
| Title |
|---|
| BO-TAU LIU, ET AL.: ""Graphene/silver nanowire sandwich structures"", 《CARBON》 * |
| 邵桂雪 等: "" S2-控制剂对Ag纳米产物的形貌及光学性能的影响"", 《无机化学学报》 * |
| 陈昌: ""银纳米材料的形貌可控制备及其应用研究"", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499600A (en) * | 2015-12-15 | 2016-04-20 | 中国科学院上海高等研究院 | Method for preparing silver nanowire-graphene composite aerogel |
| CN106835082A (en) * | 2017-01-11 | 2017-06-13 | 东南大学 | The preparation method of the flexible self-supporting graphene film of metal nanoparticle doping |
| CN107910128A (en) * | 2017-10-13 | 2018-04-13 | 哈尔滨工业大学深圳研究生院 | A kind of method that graphene oxide self assembly compound silver nanometer line improves flexible device mechanical performance |
| CN107910128B (en) * | 2017-10-13 | 2020-01-21 | 哈尔滨工业大学深圳研究生院 | Method for improving mechanical property of flexible device by graphene oxide self-assembled composite silver nanowire |
| CN109979642A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | Conductive film and its preparation method and application |
| CN109979642B (en) * | 2017-12-27 | 2020-11-06 | Tcl科技集团股份有限公司 | Conductive film and its preparation method and application |
| CN108192483A (en) * | 2017-12-28 | 2018-06-22 | 安徽明珠颜料科技有限公司 | A kind of preparation method of graphene oxide Antimicrobial preservative coating |
| CN109135144A (en) * | 2018-07-11 | 2019-01-04 | 四川羽玺新材料股份有限公司 | A kind of graphene/acrylic resin laminated film and preparation method thereof |
| CN109135144B (en) * | 2018-07-11 | 2021-07-20 | 四川羽玺新材料股份有限公司 | Graphene/acrylic resin composite film and preparation method thereof |
| CN109575456A (en) * | 2018-10-26 | 2019-04-05 | 福建师范大学 | A kind of preparation method of multi-component hybridization anisotropy thermal diffusion film |
| CN113184838A (en) * | 2021-05-19 | 2021-07-30 | 重庆交通大学 | Preparation method of functionalized graphene material |
| CN113930037A (en) * | 2021-10-27 | 2022-01-14 | 苏州大学 | Filling type flexible strain sensing material and preparation method thereof |
| CN115194175A (en) * | 2022-07-01 | 2022-10-18 | 西安交通大学 | A kind of high-purity ultrafine silver nanowire and large-scale preparation method thereof |
| CN115194175B (en) * | 2022-07-01 | 2023-10-20 | 西安交通大学 | High-purity superfine silver nanowire and large-scale preparation method thereof |
| CN118553462A (en) * | 2024-07-26 | 2024-08-27 | 常州碳禾新材料科技有限公司 | Graphene-doped conductive silver paste and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104927073A (en) | Self-assembly preparation method of gas-liquid interface of silver nanowire/graphene polymer composite film | |
| Fan et al. | 3D conductive network-based free-standing PANI–RGO–MWNTs hybrid film for high-performance flexible supercapacitor | |
| CN110528314B (en) | A kind of composite sheet containing melt-blown polyphenylene sulfide ultrafine fiber and its preparation method and application | |
| CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| Zhang et al. | MnO2 nanoshells/Ti3C2Tx MXene hybrid film as supercapacitor electrode | |
| US10258932B2 (en) | Porous carbon films | |
| CN110982114A (en) | Aramid/carbon nanotube hybrid aerogel film, its preparation method and application | |
| CN107293377A (en) | A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film | |
| CN103253740A (en) | Preparation method of three-dimensional hierarchical graphene/porous carbon composite capacitive type desalination electrode | |
| CN107089707B (en) | Core-shell structure three-dimensional graphene composite material for capacitive desalination electrode and preparation method thereof | |
| CN104986758A (en) | Three-dimensional network graphene for lithium battery and preparing method thereof | |
| CN102875805A (en) | Three-dimensional graphene-poly dopamine-gold nanoparticle composite material and preparation method thereof | |
| CN106977771A (en) | Boron nitride silver/cellulose composite material and preparation method thereof | |
| CN106450234B (en) | A kind of preparation method of spherical titanium dioxide/graphene flexible composite material | |
| CN112646212B (en) | Preparation method of polyaniline-coated metal organic framework nano-array film, product and application thereof | |
| CN108047806B (en) | graphene/Ag-carbon microsphere aerogel coating and preparation method and application thereof | |
| Liu et al. | Lightweight sandwich fiber-welded foam-like nonwoven fabrics/graphene composites for electromagnetic shielding | |
| Cai et al. | Highly flexible reduced graphene oxide@ polypyrrole–polyethylene glycol foam for supercapacitors | |
| CN110581267B (en) | Nano-cellulose-silicon-graphite micron sheet flexible electrode material and preparation method and application thereof | |
| CN108232262A (en) | High-barrier, high tolerance compound proton exchange membrane and preparation method thereof | |
| Yang et al. | Intrinsic proton conductive deoxyribonucleic acid (DNA) intercalated graphene oxide membrane for high-efficiency proton conduction | |
| CN111686810A (en) | Preparation method of layer-by-layer self-assembled GQDs/3D-G/PANI composite film | |
| CN109727704B (en) | A kind of silver nanowire film and welding method thereof | |
| CN119008081A (en) | Graphene conductive paste with good dispersibility and preparation method thereof | |
| Tian et al. | Interface electrode and enhanced actuation performance of SiO2-GO/PFSA-based IPMC soft actuators |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150923 |