CN104959622B - Synthesis method for copper nanowire with different length-diameter ratios - Google Patents
Synthesis method for copper nanowire with different length-diameter ratios Download PDFInfo
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Abstract
The invention relates to a synthesis method for a copper nanowire with different length-diameter ratios. The method includes the following steps that 1, a mixed water solution A of bivalent copper salt and glucose is prepared; 2, an absolute ethyl alcohol solution B of oleylamine and oleic acid is prepared; 3, an ethanol solution C of polyvinylpyrrolidone is prepared; 4, the solution A, the solution B and the solution C are mixed, diluted with water and then stirred for 2 h-12 h at the temperature of 30 DEG C-80 DEG C; and 5, a solution obtained in the step 4 is reacted for 4 h-24 h at the temperature of 100 DEG C-130 DEG C. The method overcomes the defects of high process complexity, high reaction temperature, low product yield, low product purity and the like of a present conventional synthesis method. The copper nanowire which is good in controllability and dispersity, large in length-diameter ratio and free of tail end particles can be obtained.
Description
Technical field
The present invention relates to one-dimensional metal nano material, more particularly to a kind of synthesis side of the copper nano-wire of different draw ratios
Method.
Background technology
Copper nano-wire because its high conductivity, high permeability and excellent flex capability in touch screen, solaode, can wear
Wearing the fields such as equipment, Organic Light Emitting Diode has wider utilization prospect, it is considered to be expected to replace tin indium oxide(ITO)New one
For transparent conductive material.And synthesize the premise that high-quality copper nano-wire is the excellent transparent conductive material of processability.
At present, synthesizing the method for copper nano-wire mainly has:
1st, including template, method of electrostatic spinning, vapour deposition process, solid phase reduction method etc. " it is hard ' method.Wherein, template is
With corresponding template as mould, with either physically or chemically filling after respective material, material is gone to control or drawn as main structure body
Admittance rice Material growth, and as reaction is carried out, template autophage falls, and then obtain specific morphology product.Its main feature
For the reaction controllability that either occurs in gas phase or liquid phase preferably, however by must previously prepared corresponding template limited
System, its Product yields is extremely limited, and its polycrystalline product is also the main weak point of template.Although method of electrostatic spinning can connect
Continuously preparing nano line, but easily receive environmental factorss such as temperature, humidity, process control parameters such as voltage, flow velocity, and solution parameter
Such as surface tension, viscosity factor affect.Vapour deposition process needs to complete in a vacuum, and condition is more harsh.Solid phase reduction method
Need to complete under the high temperature conditions, energy consumption is big and efficiency is low.These " hard " methods, or severe reaction conditions, complex steps,
Relatively costly, poor controllability, thus be difficult to realize large-scale production.
2nd, at present, it is the main stream approach of synthesis copper nano-wire based on " soft " method of liquid solution, mainly includes hydro-thermal also
Former method and solvent-thermal method etc..Although these methods have, and cost is relatively low, controllability is good, the advantages of easily realize large-scale production,
It is also to be respectively present many technical problems:Copper nano-wire is synthesized using hydrothermal reduction method, or its synthesis step is relatively complicated,
The copper nano-wire terminal being synthesized has granule, have impact on the photoelectric properties of thin film.And solvent-thermal method is although simple to operate, but
Generally higher temperature (>150 DEG C) under, and need just to be completed under inert gas shielding.
Chinese patent 201080062895.1 reports liquid phase reduction and prepares copper nano-wire, its copper nano-wire diameter 100
± 10nm, and terminal is with granule, can affect film conductivity and transmitance.
Chinese patent 201110144380.2 is prepared for monocrystal copper nanowires by liquid phase reduction, due to reactant concentration
Low, it yields poorly.
Chinese patent 201210323822.4 reports overlong nanowire(1500μm)Synthetic method, which use expensive
Metal is used as catalyst, and reaction temperature is higher(190℃).
Chinese patent 201410346038.4 reports that draw ratio is big, the synthetic method of the copper nano-wire that purity is high, it
It is in higher temperature(150℃)Under complete synthesize.
Chinese patent 201410362522.6 reports continuous production and is combined to copper nano-wire, although its yield is higher, but
It is that synthesis step is loaded down with trivial details, and the copper nano-wire terminal for preparing is with granule.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of the copper nano-wire of different draw ratios, the synthetic method overcomes
Complex process, reaction temperature present in current conventional synthesis process are high, Product yields low-purity low shortcoming, and can be obtained can
Control property is good, draw ratio is big, good dispersion, and the agranular copper nano-wire of terminal.
The present invention is achieved through the following technical solutions above-mentioned technical purpose:
A kind of synthetic method of the copper nano-wire of different draw ratios, it is characterised in that it is followed the steps below:
(1) the mixed aqueous solution A of cupric salt and glucose is prepared;
(2) the ethanol solution B of oleyl amine and Oleic acid is prepared;
(3) polyvinylpyrrolidone is prepared(PVP)Ethanol solution C;
(4) A, B and C are mixed, after dilute with water, 2~12h is stirred at 30~80 DEG C;
(5) by step(4)Middle resulting solution reacts 4~24h at 100~130 DEG C, you can.
In order to be further purified obtained copper nano-wire, the synthetic method of the copper nano-wire of above-mentioned different draw ratios is gone back
Include step (6):By step(5)It is middle reacted after gained solution normal hexane and the mixed liquor of isopropanol, 8000~
12000rpm/min centrifuge washings for several times, in being dispersed in isopropanol, you can.
Above-mentioned cupric salt, specifically may be selected to be copper chloride, copper sulfate, Schweinfurt green or copper nitrate.
The consumption of cupric salt, glucose, oleyl amine, Oleic acid and PVP in above-mentioned synthetic method, matches somebody with somebody according to following mol ratio
Put:Cupric salt:Glucose:Oleyl amine:Oleic acid:PVP=1:0.5~2:4~8:0.05~0.12:0.5~2.2.As more entering one
Preferably, it is specifically configured according to following mol ratio on step ground:Cupric salt:Glucose:Oleyl amine:Oleic acid:PVP=1:1:6:0.06:
1.1。
Above-mentioned polyvinylpyrrolidone, preferable weight-average molecular weight is the one kind in 55000,360000 or 1300000.
Above-mentioned steps(3)In the ethanol solution C of the PVP of middle preparation, the mass fraction of PVP is 2%~7%.
As further optimizing, the synthetic method of the copper nano-wire of above-mentioned different draw ratios, specifically according to following step
Suddenly carry out:
(1) 1.7~6.8g copper chlorides and 1.98~7.92g glucoses are weighed, 500ml deionized waters are added, is stirred under room temperature
Mix and uniformly obtain blue solution A;
(2) 20~80ml oleyl amines, 20~80 μ l Oleic acid and 140ml dehydrated alcohol are measured, is uniformly mixing to obtain under room temperature mixed
Close liquid B;
(3) 5~20g of PVP that relative molecular mass is 55000 are weighed, adds 50ml absolute ethyl alcohol and stirrings uniform, obtained
Mixed liquor C;
(4) above-mentioned A, B and C are mixed, deionized water is diluted to 1000~4000ml, and at 30~80 DEG C, heating is stirred
2~12h is mixed, cinerouss solution is obtained;
(5) by step(4)Middle resulting solution is transferred in reactor, and 4~24h is reacted at 110~130 DEG C;Wherein, control
The system reaction different time, you can obtain the copper nano-wire of different draw ratios, the response time is longer, the copper nano-wire major diameter for obtaining
Than bigger;
(6) by step(5)The solution natural cooling of gained after middle reaction completely, is 0.5~2 with volume ratio:1 just oneself
The mixed liquor of alkane and isopropanol, centrifuge washing 4 times under the conditions of 8000~12000rpm/min, in being dispersed in isopropanol, you can.
The inventive method has advantages below:
(1) the method is simple, controllability is good, easy to operate, with low cost, and yield is high, it is easy to produce in batches;
(2) the method is by only changing the response time, and can obtain the copper nano-wire of different draw ratios, its product
Diameter is controllable in 30~100nm, 20~120 μm of length;
(3) using product copper nano-wire obtained in the method, its pattern is uniform, terminal is without granule, good dispersion, Jing centrifugations
After washing, there is extensive utilization prospect in transparent conductive material field.
Description of the drawings
Fig. 1 is the XRD figure of the copper nano-wire synthesized in the embodiment of the present invention 1.
Fig. 2 is scanning electron microscope (SEM) figure of the copper nano-wire synthesized in the embodiment of the present invention 1.
Fig. 3 is the absorption spectrogram of the copper nano-wire dispersion liquid synthesized in the embodiment of the present invention 1.
Fig. 4 is transmission electron microscope of the copper nano-wire synthesized in the embodiment of the present invention 1 under different amplification
(TEM) figure.
Fig. 5-7 is SEM figure of the copper nano-wire synthesized in the embodiment of the present invention 1 under different amplification.
Fig. 8 is the SEM figures of the copper nano-wire synthesized in the embodiment of the present invention 2.
Fig. 9 is the TEM figures of the copper nano-wire synthesized in the embodiment of the present invention 2.
Figure 10-12 is SEM figure of the copper nano-wire synthesized in the embodiment of the present invention 2 under different amplification.
Figure 13 is the SEM figures of the copper nano-wire synthesized in the embodiment of the present invention 3.
Figure 14 is the TEM figures of the copper nano-wire synthesized in the embodiment of the present invention 3.
Specific embodiment
The present invention is specifically described below by embodiment, but following examples are served only for entering the present invention traveling one
The explanation of step, it is impossible to be interpreted as the restriction to its protection domain, the person skilled in the art in the field can be according to the above pair
The present invention makes some nonessential modifications and adaptations.
Embodiment 1
A kind of synthetic method of the copper nano-wire of different draw ratios, it is followed the steps below:
(1) copper chloride of 0.02mol and the glucose of 0.02mol are weighed, is added and dissolved under 1000ml deionized water room temperatures
Stir, obtain blue solution A;
(2) 40ml oleyl amines, 40 μ l Oleic acid, and 70ml dehydrated alcohol are measured, is stirred for uniformly being configured to mix under room temperature
Close liquid B;
(3) PVP that 20ml mass fractions are 3% is configured(Mw=360000)- ethanol solution C;
(4) A, B and C are mixed, after deionized water dilution, magnetic agitation 5h is heated under the conditions of 80 DEG C;
(5) by step(4)Middle resulting solution is proceeded in reactor, and at 120 DEG C 6h is reacted;
(6) by step(5)The middle solution natural cooling for having reacted rear gained, uses again afterwards volume ratio to be 2:1 hexane and
The mixed liquor of isopropanol, 8000rpm/min centrifuge washings 4 times with isopropanol, that is, obtain well dispersed copper nano-wire point
Dispersion liquid.
1~7 understand with reference to the accompanying drawings, be pure face-centred cubic copper nano-wire obtained in this method;The copper nano-wire
, at 40~60 μm, diameter is in 60~80nm, and the copper nano-wire does not have terminal granule for length.
Embodiment 2
A kind of synthetic method of the copper nano-wire of different draw ratios, it is followed the steps below:
(1) copper chloride of 0.04mol and the glucose of 0.04mol are weighed, is added and dissolved under 2000ml deionized water room temperatures
Stir, obtain blue solution A;
(2) 80ml oleyl amines, 80 μ l Oleic acid, and 140ml dehydrated alcohol are measured, is stirred for uniformly being configured to mix under room temperature
Close liquid B;
(3) PVP that 40ml mass fractions are 3% is configured(Mw=55000)- ethanol solution C;
(4) A, B and C are mixed, after deionized water dilution, magnetic agitation 8h is heated under the conditions of 50 DEG C;
(5) by step(4)Middle resulting solution is proceeded in reactor, and at 120 DEG C 12h is reacted;
(6) by step(5)The middle solution natural cooling for having reacted rear gained, uses again afterwards volume ratio to be 1:1 hexane and
The mixed liquor of isopropanol, 12000rpm/min centrifuge washings 4 times with isopropanol, that is, obtain well dispersed copper nano-wire
Dispersion liquid.
8~12 understand with reference to the accompanying drawings, copper nano-wire internal structure obtained in this method is continuous, size is more uniform;The copper
, at 80~100 μm, diameter is in 30~45nm, and the copper nano-wire does not have terminal granule for the length of nano wire.
Embodiment 3
A kind of synthetic method of the copper nano-wire of different draw ratios, it is followed the steps below:
(1) copper chloride of 0.02mol and the glucose of 0.02mol are weighed, is added and dissolved under 1000ml deionized water room temperatures
Stir, obtain blue solution A;
(2) 40ml oleyl amines, 40 μ l Oleic acid, and 70ml dehydrated alcohol are measured, is stirred for uniformly being configured to mix under room temperature
Close liquid B;
(3) PVP that 20ml mass fractions are 3% is configured(Mw=1300000)- ethanol solution C;
(4) A, B and C are mixed, after deionized water dilution, magnetic agitation 7h is heated under the conditions of 60 DEG C;
(5) by step(4)Middle resulting solution is proceeded in reactor, and at 110 DEG C 4h is reacted;
(6) by step(5)The middle solution natural cooling for having reacted rear gained, uses again afterwards volume ratio to be 0.5:1 hexane
With the mixed liquor of isopropanol, 12000rpm/min centrifuge washings 4 times, with isopropanol, that is, well dispersed copper nanometer is obtained
Line dispersion liquid.
13 and 14 understand that the length of the copper nano-wire at 10~25 μm, in 90~110nm, receive diameter by the copper with reference to the accompanying drawings
Rice noodle does not have terminal granule.
Embodiment 4
A kind of synthetic method of the copper nano-wire of different draw ratios, it is followed the steps below:
(1) copper nitrate of 0.02mol and the glucose of 0.02mol are weighed, is added and dissolved under 1200ml deionized water room temperatures
Stir, obtain blue solution A;
(2) 40ml oleyl amines, 40 μ l Oleic acid, and 80ml dehydrated alcohol are measured, is stirred for uniformly being configured to mix under room temperature
Close liquid B;
(3) PVP that 20ml mass fractions are 7% is configured(Mw=1300000)- ethanol solution C;
(4) A, B and C are mixed, after deionized water dilution, magnetic agitation 10h is heated under the conditions of 40 DEG C;
(5) by step(4)Middle resulting solution is proceeded in reactor, and at 130 DEG C 5h is reacted;
(6) by step(5)The middle solution natural cooling for having reacted rear gained, uses again afterwards volume ratio to be 1.5:1 just oneself
The mixed liquor of alkane and isopropanol, 10000rpm/min centrifuge washings 3 times with isopropanol, that is, obtain well dispersed copper and receive
Rice noodle dispersion liquid.
Claims (6)
1. a kind of synthetic method of the copper nano-wire of different draw ratios, it is characterised in that it is followed the steps below:
(1) the mixed aqueous solution A of cupric salt and glucose is prepared;
(2) the ethanol solution B of oleyl amine and Oleic acid is prepared;
(3) the ethanol solution C of polyvinylpyrrolidone is prepared;
(4) A, B and C are mixed, after dilute with water, 2~12h is stirred at 30~80 DEG C;
(5) by step(4)Middle resulting solution reacts 4~24h at 100~130 DEG C;
The consumption of cupric salt therein, glucose, oleyl amine, Oleic acid and polyvinylpyrrolidone, configures according to following mol ratio:
Cupric salt:Glucose:Oleyl amine:Oleic acid:Polyvinylpyrrolidone=1:0.5~2:4~8:0.05~0.12:0.5~2.2.
2. the as claimed in claim 1 synthetic method of the copper nano-wire of difference draw ratios, it is characterised in that it also includes step
(6):By step(5)The mixed liquor of the middle solution normal hexane and isopropanol for having reacted rear gained, in 8000~12000rpm/
Min centrifuge washings for several times, in being dispersed in isopropanol.
3. the as claimed in claim 1 or 2 synthetic method of the copper nano-wire of difference draw ratios, it is characterised in that:The cupric
Salt selects to be copper chloride, copper sulfate, Schweinfurt green or copper nitrate.
4. the as claimed in claim 3 synthetic method of the copper nano-wire of difference draw ratios, it is characterised in that cupric therein
The consumption of salt, glucose, oleyl amine, Oleic acid and polyvinylpyrrolidone, configures according to following mol ratio:Cupric salt:Glucose:
Oleyl amine:Oleic acid:Polyvinylpyrrolidone=1:1:6:0.06:1.1.
5. the as claimed in claim 4 synthetic method of the copper nano-wire of difference draw ratios, it is characterised in that:The polyvinyl pyrrole
It is one kind in 55000,360000 or 1300000 that alkanone is selected as weight average molecular weight;The step(3)The polyethylene of middle preparation
In the ethanol solution C of ketopyrrolidine, the mass fraction of polyvinylpyrrolidone is 2%~7%.
6. the as claimed in claim 1 synthetic method of the copper nano-wire of difference draw ratios, it is characterised in that it specifically according to
What lower step was carried out:
(1) 1.7~6.8g copper chlorides and 1.98~7.92g glucoses are weighed, 500ml deionized waters are added, stirs equal under room temperature
It is even to obtain blue solution A;
(2) 20~80ml oleyl amines, 20~80 μ l Oleic acid and 140ml dehydrated alcohol are measured, under room temperature mixed liquor is uniformly mixing to obtain
B;
(3) 5~20g of polyvinylpyrrolidone that relative molecular mass is 55000 is weighed, adds 50ml absolute ethyl alcohol and stirrings equal
It is even, obtain mixed liquor C;
(4) above-mentioned A, B and C are mixed, deionized water is diluted to 1000~4000ml, at 30~80 DEG C, heated and stirred 2~
12h, obtains cinerouss solution;
(5) by step(4)Middle resulting solution is transferred in reactor, and 4~24h is reacted at 110~130 DEG C;
(6) by step(5)The solution natural cooling of gained after middle reaction completely, is 0.5~2 with volume ratio:1 normal hexane and
The mixed liquor of isopropanol, centrifuge washing 4 times under the conditions of 8000~12000rpm/min, in being dispersed in isopropanol, you can.
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CN107052358B (en) * | 2016-12-14 | 2020-03-31 | 中国科学技术大学 | Preparation method of copper nanowire |
CN107103945A (en) * | 2017-06-23 | 2017-08-29 | 合肥工业大学 | A kind of copper nano-wire transparent conductive film and preparation method |
CN108376587A (en) * | 2018-03-07 | 2018-08-07 | 重庆文理学院 | A kind of high-performance stablizes the preparation method of copper nano-wire flexible transparent conductive film |
CN108436104B (en) * | 2018-06-05 | 2021-04-06 | 黔南民族师范学院 | Process for preparing copper nanowires by using acidic etching waste liquid |
CN110355379A (en) * | 2019-07-31 | 2019-10-22 | 江苏大学 | A kind of difference draw ratio NANO CRYSTAL COPPER WIRE and its synthetic method |
CN114603154A (en) * | 2022-03-22 | 2022-06-10 | 武汉纺织大学 | Preparation method of copper nanowire and copper nanowire prepared by same |
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US8764878B2 (en) * | 2012-03-05 | 2014-07-01 | David R. Whitcomb | Copper nanowire preparation methods and compositions |
JP5991510B2 (en) * | 2012-03-21 | 2016-09-14 | Dic株式会社 | Method for producing copper nanowires |
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