CN105014091A - Super-long copper-nickel alloy nanowire and manufacturing method thereof - Google Patents
Super-long copper-nickel alloy nanowire and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a super-long copper-nickel alloy nanowire and a manufacturing method thereof. The method comprises: a) dissolving a cationic-type surfactant in an organic reducing agent; b) adding copper salt used as a copper source in the organic reducing agent obtained in the step a), and adding precious metal nano-particles which is used as a catalyst, reacting at the temperature of first specified temperature; c) adding nickel salt used as a nickel source in the reducing agent after reaction in the step b), reacting at the temperature of second temperature, cleaning and drying obtained products, and the product is the copper-nickel alloy nanowire.
Description
Technical field
The present invention relates to a kind of corronil nano wire and preparation method thereof, be specifically related to a kind of super long copper nickel alloy nano wire and preparation method thereof.
Background technology
In recent years, one-dimensional material due to optical, electrical, the magnetic property of its uniqueness, particularly its huge applications prospect shown by Transparence Display, opto-electronic conversion and sensor field and receive extensive concern.Because the current ITO material flexibility used in electrically conducting transparent field is poor, cost is high, so metal nano material nesa coating will become the important alternative materials of ITO.Relative to nano silver wire, copper nano-wire has good electric conductivity equally, and unique mechanics, optical property, make cost significantly reduce simultaneously.Therefore, copper nano-wire receives the favor of people, can be applied to energy conversion technique, sensing technology, micro-processing technology, biotechnology field.But, after the size of copper is reduced to nanoscale, because surface energy increases, very easily oxidized, and alloying is a kind of raising copper nano-wire antioxygenic property important method.In addition, the formation of corronil structure, also can improve the light transmission of nano wire conductive film, and introduces new magnetic property.
At present, the method for synthesizing corronil nano wire mainly contains: template assists synthetic method (reference literature 6), solwution method (reference literature 1) etc.Template assists synthetic method to have the advantage that in building-up process, device is simple, processing ease, form are controlled.But assist the copper nickel nanowire length prepared by synthetic method shorter by masterplate, draw ratio is little, is unfavorable for the raising of conductive film light transmission rate and electric conductivity.And the aftertreatment technology of the copper nickel nano wire of assisting synthetic method to obtain by masterplate is loaded down with trivial details, often need to remove template with strong acid, highly basic or other organic solvent.Solwution method synthesis corronil nano wire mostly with alkali or acid for reducing agent, reaction condition is harsher, is difficult to promote.And solvent for use is water, the nano wire prepared is easy to reunite, and not easily disperses, and brings difficulty for subsequent applications.
Therefore, the corronil nano wire that how processability is excellent, length is larger also prepares conductive film based on this, is the study hotspot in this field.
Prior art document:
Non-patent literature 1
1.Rathmell,A.R.,et al.,Synthesis of oxidation-resistant cupronickel nanowires for transparentconducting nanowire networks.Nano Lett,2012.12(6):p.3193-9;
Non-patent literature 2
2.Hecht,D.S.,L.Hu,and G.Irvin,Emerging transparent electrodes based on thin films of carbonnanotubes,graphene,and metallic nanostructures.Adv Mater,2011.23(13):p.1482-513;
Non-patent literature 3
3.Zhao,Y.,et al.,Large-scale synthesis of Cu nanowires with gradient scales by using“hard”strategies and size effects on electrical properties.CrystEngComm,2013.15(2):p.332;
Non-patent literature 4
4.Han,B.,et al.,Uniform Self-Forming Metallic Network as a High-Performance TransparentConductive Electrode.Advanced Materials,2013:p.n/a-n/a;
Non-patent literature 5
5.Guo,H.,et al.,Facile synthesis of Cu and Cu@Cu-Ni nanocubes and nanowires inhydrophobic solution in the presence of nickel and chloride ions.Nanoscale,2013.5(6):p.2394-402;
Non-patent literature 6
Guo,et al.,Ordered Ni-Cu Nanowire Array with Enhanced Coercivity.Chemistry of Materials,2003.15(3):p.664-667。
Summary of the invention
The present invention is intended to overcome the existing deficiency preparing corronil nanowire approach, the invention provides a kind of super long copper nickel alloy nano wire and preparation method thereof.
The invention provides a kind of method preparing super long copper nickel alloy nano wire, described method comprises:
A) cationic surface active agent is dissolved in organic reducing agent;
B) add mantoquita in the organic reducing agent obtained in step a) as copper source, and add noble metal nano particles as catalyst, react under the first set point of temperature;
C) in step b), add nickel salt in reacted reducing agent as nickel source, react under the second set point of temperature, products obtained therefrom cleaning, drying, obtain described corronil nano wire.
In the present invention, in the process of synthesis super long copper nickel alloy nano wire, typical employing adds organic or inorganic nickel salt after copper nano-wire begins to take shape in solution, by the existence of organic reducing agent in solution nickel salt is reduced into nickle atom and is attached to the surface of copper nano-wire.Especially, prioritizing selection nickel acetate joins in solution as nickel source.Like this, in the organic reaction system described in invention, the rate of reduction of nickel acetate makes the nickle atom restored form uniform clad on copper nano-wire surface just, within the reaction time described in invention, be no matter that copper nano-wire or nickle atom layer all can well-crystallized, effectively improve the electric conductivity of nano wire.The present invention can obtain inner rich copper, the corronil nano wire of outer rich nickel, its diameter can control at 60-150nm, and length can control at tens to 500 microns, prepares that light transmission rate is high, the conductive film of good conductivity, good stability by vacuum filtration process or method such as line rod coating etc.
Preferably, described organic reducing agent can be chain alkyl amine.
Preferably, described organic reducing agent can be cetylamine or octadecylamine.
Preferably, described cationic surface active agent can be softex kw.
Preferably, described cationic surface active agent at 100-250 DEG C, can be dissolved in organic reducing agent.
Preferably, described mantoquita can be acetylacetone copper.
Preferably, described nickel salt can be nickel acetate.
Preferably, the mol ratio of described organic reducing agent, mantoquita, nickel salt can be 330:(5 ~ 10): (2 ~ 15).
Preferably, in described step b), the first set point of temperature can be 120-200 DEG C, and the reaction time can be 2-15 hour.
Preferably, in described step b), noble metal nano particles can be the Pt nano particle or Au nano particle that synthesize in glycol system.
Preferably, in described step c), the second set point of temperature can be 200-250 DEG C, and the reaction time can be 30 minutes-10 hours.
The present invention also provides a kind of corronil nano wire prepared according to said method, and the diameter of described corronil nano wire can be 60 ~ 150nm, and length is 10 ~ 500 microns.
Beneficial effect of the present invention:
1) super long copper nickel alloy nano wire is with an organic solvent synthesized;
2) use nickel acetate as nickel source, the addition of nickel acetate is all applicable in a big way, and can in a certain degree for nano wire in the content of nickel element regulated and controled;
3) reaction time and reaction temperature are all applicable in a big way;
4) organic surface active agent is used to improve the adhesion of nano wire and substrate of glass;
5) this corronil nano wire has the advantages that draw ratio is high, appearance and size is controlled, be easy to disperse formation nano wire ink.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of an exemplary sample prepared by the inventive method;
Fig. 2 is the scanning electron microscope (SEM) photograph of an exemplary sample prepared by the inventive method;
Fig. 3 is an exemplary sample ESEM composition surface analysis collection of illustrative plates prepared by the inventive method;
Fig. 4 is an exemplary sample transmission electron microscope picture prepared by the inventive method;
Fig. 5 is the application of super long copper nickel alloy nano wire in conductive film.
Detailed description of the invention
Also with reference to accompanying drawing, the present invention is described in further detail by following detailed description of the invention; be interpreted as; following embodiment is only explanation of the present invention; not the restriction to content of the present invention, any still protection scope of the present invention is fallen into the technical scheme that content of the present invention does not do material alteration.
The invention discloses a kind of synthetic method of super long copper nickel alloy nano wire and the preparation method of corronil nano wire conductive film: make it dissolve completely using adding acetylacetone copper after softex kw and cetylamine dissolve completely as copper source.Using noble metal nano particles as catalyst, be obtained by reacting copper nano-wire, then add nickel acetate as nickel source, fully shake up, reaction certain hour.Reaction system is cooled to room temperature.By the organic solvent such as toluene, ethanol, cyclic washing is carried out for product.And by SEM (SEM), transmission electron microscope (TEM), the means such as X-ray diffraction to the pattern of the copper nickel nano wire obtained, constituent, and crystal structure characterizes.SEM result shows that the average length of obtained copper nickel nano wire about has 200 μm; The alloy nano-wire prepared by said method is carried out ultrasonic disperse in the organic solvent such as toluene, ethanol, the homogeneous transparent solution obtained is filtered by cellulose mixture film, under 50 DEG C ~ 100 DEG C vacuum conditions, film is transferred to glass, in the plastic supporting base such as silicon chip or PET, obtain corronil nano wire conductive film.Film is carried out the combination of annealing in process or plasma treatment or two kinds of processing modes, obtain the corronil nano wire conductive film that electric conductivity is good.The method has easy, the advantage such as cost is low, reproducible, output is high, process control, and the corronil nano wire draw ratio of preparation is high, appearance and size is controlled, easily disperse, for Conducting Films with High Performance and electronic installation thereof provide a kind of elite clone.
The invention provides a kind of synthetic method of super long copper nickel alloy nano wire, the method is as follows:
A kind of cationic surface active agent and organic solvent are dissolved under 100-250 DEG C of condition, obtains solution A, acetylacetone copper is dissolved in solution A completely as copper source, fully shake up and obtain blackish green solution B.In solution B, add noble metal nano particles as catalyst, under 120-200 DEG C of condition, react 2-15 hour, take out this solution, add nickel acetate wherein as the also fully mixing of nickel source, be warming up to 210-250 DEG C of reaction 30min-10 hour.Reaction system is cooled to room temperature.The conventional organic solvent such as ethanol, toluene is used to carry out cleaning and disperseing.Through to stir and of short duration ultrasonic, nano wire can be in organic solvent dispersed.
The present invention adopts organic system to synthesize super long copper nickel alloy nano wire.
The organic reducing agent that the present invention uses is the chain alkyl such as cetylamine, octadecylamine amine.
The organic surface active agent used can be cationic surfactant softex kw, but does not get rid of the applicable possibility of other surfactant.
Use noble metal nano particles as the catalyst of catalytic copper ion reduction, but do not get rid of the feasibility of other catalyst.
Building-up process is divided into two stages, and first stage temperature is 120-200 DEG C, and be the growth phase of copper nano-wire, second stage is 200 DEG C-250 DEG C, is mainly the formation stages of corronil nano wire.
In described course of reaction, the time first using synthesis copper nano-wire is 2-15 hour, and the time of carrying out synthesizing corronil nano wire is 1-10 hour.But obtain the possibility of same structure nano material under being not precluded within other times length condition.
The cleaning of product is suitable for conventional organic solvent toluene, ethanol etc.
Described copper source is acetylacetone copper, but does not get rid of the applicability in other copper sources.
Described nickel source is nickel acetate, but does not get rid of the applicability in other nickel sources.
The invention provides the preparation method preparing a kind of corronil nano wire conductive film, the method is as follows:
Use the super long copper nickel alloy nano wire of preparation, obtain alloy nano-wire ink through dispersion treatment such as of short duration ultrasonic, stirrings, then filter through vacuum, the method such as line rod coating is prepared into conductive film.
In the preparation method of corronil nano wire conductive film, cationic surface active agent is used to improve the adhesion strength of nano wire and substrate of glass.
In the preparation method of corronil nano wire conductive film, use cationic surface active agent to be softex kw, but do not get rid of other organic surface active agents and can serve the same role.
In the preparation method of corronil nano wire conductive film, use the annealing in process of plasma treatment, hydrogen atmosphere or mixed atmosphere, or the combination of two kinds of processing modes, the organic surface active agent of removing nanowire surface, makes film have good electric conductivity.
The invention provides a kind of corronil nano wire conductive film, this film is that the corronil nano wire that synthesized by said method is random or align the network formed, network thickness be often tens nanometers to hundreds of micron, also can be thicker.
Film-substrate can be the rigid substrate such as glass, silicon chip, also can be the flexible substrate such as PET, polyacrylate, also can the linerless end.
A kind of electronic installation, employs corronil nano wire prepared by described method, or employs described corronil nano wire conductive film in device.
The present invention relates to a kind of synthetic method of controlledly synthesis super long copper nickel alloy nano wire, the dispersion of corronil nano wire, film preparation and post-processing approach thereof, be applicable to the preparation of corronil nano wire, dispersion, prepared by conductive film, and the various electronic device be made up of corronil nano wire conductive film and device.
Another problem of the present invention is to prepare corronil nano wire conductive film, and this film has that light transmission rate is high, the feature of good conductivity, good stability.
In order to solve the problem, the present invention is a kind of preparation method of super long copper nickel alloy nano wire.Inner rich copper is obtained, the corronil nano wire of outer rich nickel by the chemical reduction method in organic solvent.Its diameter can control at 60-150nm, and length can control at tens to 500 microns.
In the present invention, in the process of synthesis super long copper nickel alloy nano wire, typical employing adds organic or inorganic nickel salt after copper nano-wire begins to take shape in solution, by the existence of organic reducing agent in solution nickel salt is reduced into nickle atom and is attached to the surface of copper nano-wire.Especially, prioritizing selection nickel acetate joins in solution as nickel source.Like this, in the organic reaction system described in invention, the rate of reduction of nickel acetate makes the nickle atom restored form uniform clad on copper nano-wire surface just, within the reaction time described in invention, be no matter that copper nano-wire or nickle atom layer all can well-crystallized, effectively improve the electric conductivity of nano wire.
When being prepared by vacuum filtration method in the process of corronil nano wire conductive film, typically using the organic solvent dispersion such as toluene, ethanol nano wire, obtaining uniform corronil nano wire ink.Especially, add the chain alkyl amine such as cetylamine in a solvent as surfactant, effectively can improve the adhesion of nano wire and substrate of glass.Post plasma process or annealing in process, or the combination of two kinds of processing modes can remove this surfactant easily, makes conductive film have good electric conductivity.
Inventive features is:
1) super long copper nickel alloy nano wire is with an organic solvent synthesized;
2) use nickel acetate as nickel source;
3) addition of nickel acetate is all applicable in a big way, and can in a certain degree for nano wire in the content of nickel element regulated and controled;
4) reaction time and reaction temperature are all applicable in a big way;
5) organic surface active agent is used to improve the adhesion of nano wire and substrate of glass.
Fig. 1 is the XRD collection of illustrative plates of an exemplary sample prepared by the inventive method, therefrom comprises copper and nickel element in visible product simultaneously, and the two equal well-crystallized;
Fig. 2 is the scanning electron microscope (SEM) photograph of an exemplary sample prepared by the inventive method, therefrom visible gained nanowire length average out to more than 200 ~ 300 μm, and smooth surface, crystal property is good;
Fig. 3 is an exemplary sample ESEM composition surface analysis collection of illustrative plates prepared by the inventive method, and therefrom visible nickel element can be coated on copper nano-wire equably, forms inner rich copper, the alloy structure of outer rich nickel;
Fig. 4 is an exemplary sample transmission electron microscope picture prepared by the inventive method, and therefrom visible obtained nano wire has five heavy twin structures, and crystal property is good, smooth surface;
Fig. 5 is the application of super long copper nickel alloy nano wire in conductive film, therefrom visible Thin film conductive performance and light transmission better performances.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following technological parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.1g nickel acetate as nickel source, react 2 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is 100 ~ 200 μm.
Embodiment 2
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 2 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.From Figure of description Fig. 2, the diameter of gained corronil nano wire is about 80 ~ 100nm.Its length is average more than 300 μm.From Figure of description Fig. 3, nickel element is evenly coated on around copper nano-wire, forms inner rich copper, the corronil structure of outer rich nickel.From Figure of description Fig. 4, nano wire crystallization degree is good, smooth surface.
Embodiment 3
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.3g nickel acetate as nickel source, react 2 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.From Figure of description Fig. 1, in the product obtained, comprise copper and nickel element simultaneously, and the two crystallization all.From Figure of description Fig. 2, gained corronil nanowire diameter is about 80 ~ 100nm, and length is average more than 300 μm.
Embodiment 4
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.4g nickel acetate as nickel source, react 2 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.Along with the increase of nickel source addition, in corronil nano wire, the content of nickel element can regulate and control in a certain degree.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is more than 300 μm.
Embodiment 5
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 1.5 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is more than 300 μm.
Embodiment 6
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 3 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 100nm, and length is more than 300 μm.
Embodiment 7
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 5 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 100nm, and length is more than 300 μm.
Embodiment 8
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 8 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 100nm, and length is more than 300 μm.
Embodiment 9
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 10 hours at 210 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is more than 300 μm.Along with the increase in reaction time, the crystal property of the rich nickel dam of alloy nano-wire improves gradually.
Embodiment 10
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 2 hours at 200 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is more than 300 μm.
Embodiment 11
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 2 hours at 220 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is more than 300 μm.
Embodiment 12
0.5g softex kw and 8.0g cetylamine are dissolved completely under 180 DEG C of conditions, then add 0.2g acetylacetone copper as copper source, Pt nano particle, as catalyst, reacts 10 hours at 180 DEG C, add 0.2g nickel acetate as nickel source, react 2 hours at 230 DEG C.Clean for several times with gained sample toluene after being cooled to room temperature.Gained gray solid 80 DEG C of vacuum drying 2 hours.The diameter of gained corronil nano wire is 80 ~ 120nm, and length is more than 300 μm.
Embodiment 13
Obtained corronil nano wire is dispersed in toluene solution, use cellulose mixture film as filter membrane, through the method for vacuum filtration by nano wire suction filtration on filter membrane, 80 DEG C, carry out drying under vacuum environment after, use acetone removing filter membrane, corronil nano wire transparent conductive film can be transferred in glass substrate.As can be seen from Figure of description Fig. 5, corronil nano wire film has good electric conductivity and light percolating property.
Embodiment 14
Obtained corronil nano wire is dispersed in toluene solution, use cellulose mixture film as filter membrane, through the method for vacuum filtration by nano wire suction filtration on filter membrane, 90 DEG C, carry out drying under vacuum environment after, use acetone removing filter membrane, corronil nano wire transparent conductive film can be transferred in glass substrate.
Embodiment 15
Obtained corronil nano wire is dispersed in toluene solution, use cellulose mixture film as filter membrane, through the method for vacuum filtration by nano wire suction filtration on filter membrane, 60 DEG C, carry out drying under vacuum environment after, use acetone removing filter membrane, corronil nano wire transparent conductive film can be transferred in glass substrate.
Embodiment 16
Obtained corronil nano wire is dispersed in toluene solution, use cellulose mixture film as filter membrane, through the method for vacuum filtration by nano wire suction filtration on filter membrane, 100 DEG C, carry out drying under vacuum environment after, use acetone removing filter membrane, corronil nano wire transparent conductive film can be transferred in glass substrate.
Embodiment 17
Obtained corronil nano wire is dispersed in toluene solution, use cellulose mixture film as filter membrane, through the method for vacuum filtration by nano wire suction filtration on filter membrane, 60 DEG C, carry out drying under vacuum environment after, use acetone removing filter membrane, corronil nano wire transparent conductive film can be transferred on PET substrate.
Industrial applicability
Therefore, for the deficiency existed in prior art, problem of the present invention be to provide a kind of can the synthetic method of controlledly synthesis super long copper nickel alloy nano wire and the preparation method of conductive film thereof.This synthetic method has simple to operate, and cost is low, the feature of process control.This corronil nano wire has the advantages that draw ratio is high, appearance and size is controlled, be easy to disperse formation nano wire ink.
Claims (12)
1. prepare a method for super long copper nickel alloy nano wire, it is characterized in that, described method comprises:
A) cationic surface active agent is dissolved in organic reducing agent;
B) add mantoquita in the organic reducing agent obtained in step a) as copper source, and add noble metal nano particles as catalyst, react under the first set point of temperature;
C) in step b), add nickel salt in reacted reducing agent as nickel source, react under the second set point of temperature, products obtained therefrom cleaning, drying, obtain described corronil nano wire.
2. method according to claim 1, is characterized in that, described organic reducing agent is chain alkyl amine.
3. method according to claim 1 and 2, is characterized in that, described organic reducing agent is cetylamine or octadecylamine.
4., according to described method arbitrary in claim 1-3, it is characterized in that, described cationic surface active agent is softex kw.
5., according to described method arbitrary in claim 1-4, it is characterized in that, described cationic surface active agent, at 100-250 DEG C, is dissolved in organic reducing agent.
6., according to described method arbitrary in claim 1-5, it is characterized in that, described mantoquita is acetylacetone copper.
7., according to described method arbitrary in claim 1-6, it is characterized in that, described nickel salt is nickel acetate.
8., according to described method arbitrary in claim 1-7, it is characterized in that, the mol ratio of described organic reducing agent, mantoquita, nickel salt is 330:(5 ~ 10): (2 ~ 15).
9., according to described method arbitrary in claim 1-8, it is characterized in that, in described step b), the first set point of temperature is 120-200 DEG C, and the reaction time is 2-15 hour.
10., according to described method arbitrary in claim 1-9, it is characterized in that, in described step b), noble metal nano particles is the Pt nanoparticle or gold nano grain that synthesize in glycol system.
11. according to described method arbitrary in claim 1-10, and it is characterized in that, in described step c), the second set point of temperature is 200-250 DEG C, and the reaction time is 30 minutes-10 hours.
The corronil nano wire that in 12. 1 kinds of claim 1-11 prepared by arbitrary described method, is characterized in that, the diameter of described corronil nano wire is 60 ~ 150 nanometers, and length is 10 ~ 500 microns.
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| CN110576191A (en) * | 2019-10-18 | 2019-12-17 | 济宁学院 | Method for preparing copper-nickel alloy nano material with bevel bipyramid morphology characteristics in hydrophobic phase |
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| CN107639235B (en) * | 2017-09-07 | 2019-06-28 | 浙江工业大学 | A kind of preparation method and applications of gold copper nano-wire material |
| CN108355661A (en) * | 2018-01-03 | 2018-08-03 | 东南大学 | A kind of threadiness Cu-Ni alloy nanometer crystals and its synthetic method |
| CN110576191A (en) * | 2019-10-18 | 2019-12-17 | 济宁学院 | Method for preparing copper-nickel alloy nano material with bevel bipyramid morphology characteristics in hydrophobic phase |
| CN113441729A (en) * | 2021-06-25 | 2021-09-28 | 东北大学 | Method for directly synthesizing high-coercivity non-noble metal nanowire by wet chemical method |
| CN114481183A (en) * | 2022-03-02 | 2022-05-13 | 广东电网有限责任公司 | Copper-gold nanowire and preparation method and application thereof |
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