CN102259190A - Method for quickly preparing nano silver wires with high length-diameter ratio in large batch - Google Patents
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Abstract
The invention provides a method for quickly preparing nano silver wires with a high length-diameter ratio in large batch. The method comprises the following steps of: (1) adding powder of silver nitrate or silver acetate to a liquid polyhydroxy organic substance to prepare a solution reaction system, adding a dispersing agent to the solution reaction system to prepare a solution system including silver ions; (2) adding a water-soluble halide to the liquid polyhydroxy organic substance, and stirring uniformly to obtain a clear solution system; (3) dropwise adding the clear solution system prepared in the step (2) and an acid solution to the solution system prepared in the step (1), and continuously stirring uniformly to obtain a reaction precursor; and (4) irradiating the reaction precursor obtained in the step (3) under microwaves to obtain a solution of nano silver wire material with the high length-diameter ratio, centrifuging and washing the solution obtained through microwave irradiation in water or absolute ethyl alcohol to obtain a uniform dispersion solution of the nano silver wire material with the high length-diameter ratio. Through the method for quickly preparing nano silver wires with the high length-diameter ratio in large batch, the control on the diameter size, in particular the high length-diameter ratio, of the nano silver wires is realized by the regulation of a pH value of a reaction solution, which is simple and has high efficiency.
Description
Technical field
The present invention relates to the nano-silver thread field of material preparation, refer in particular to a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities.
Background technology
In nano material, because the physical features sizes such as coherence length of nano-grade size and optical wavelength, de Broglie wavelength and superconducting state quite or littler, make that the periodic boundary condition of crystal is destroyed; Near the superficial layer of nanoparticle atomic density reduces; The mean free path of electronics is very short, and locality and coherence strengthen.Just because of this, the performance of nano material and its structure are closely related, and factors such as its size, geometry and degree of crystallinity all can have appreciable impact to its performance.Pattern control the becoming key means that material science man makes great efforts to seek the new material with special performance always to nano material.The material pattern can be square, rectangular pyramid, 1-dimention nano silver line, nanometer stub, nanometer plate or the like.One-dimensional nano line becomes the big focus of one in the investigation of materials in recent years owing to characteristics such as its unique light, electricity receive much concern.
Along with the appearance of the flexible and transparent electrode material that is used for alternative ito glass, the material supply section scholar has paid a large amount of effort and has had good electrical conductivity and light transmittance simultaneously to seek a kind of better conductive material.The nano silver wire material becomes the preferred material for preparing the flexible and transparent electrode with the electric conductivity of its superelevation and characteristic such as preparation and receiving much concern easily.Consider from the light transmittance and the electric conductivity angle of flexible and transparent electrode, people wish that more the nano-silver thread of being filled has suitable diameter, high draw ratio, be easy to preparation in enormous quantities, has high production efficiency simultaneously, higher draw ratio helps nano-silver thread and have still less node when being overlapped to form conductive network, and these nodes have very high node impedance just, causes adopting the flexible and transparent electrode of the less nano-silver thread preparation of draw ratio to have higher side's resistance and low light transmittance.The nano-silver thread that can prepare the draw ratio with suitable diameter and Geng Gao becomes the key technology of preparation transparency electrode, and industrial circle is also strong day by day for the demand with nano-silver thread of high length-diameter ratio more.
At present the common method of preparation nano-silver thread material mainly contains template, the polyalcohol method, and other as the plasma physics method etc., specifically can list of references: Chem. Commun., 699 (1999), 700; Science, 294 (2001), 348; Chem. Material., 14 (2002), 4376; J.Phys.Chem.B, 108 (2004), 12877 etc.Above method all can prepare the nano silver wire material, but reaction condition is all very complicated, and the reaction time is very long, generally all needs 2～3 hours, and prepared nano silver wire draw ratio is all smaller, and output is also relatively low; Maybe need to introduce other particle,, cause product impure as in course of reaction, adding nano platinum particle as catalyst.Microwave method makes that preparation nano silver wire material becomes possibility fast, Chinese patent: (application number is the method for (1) preparing silver nano-wire in large batch: 200810019828.6), (2) (application number is: 200810163102.X) (application number is: 200910006131.X) (4) a kind of cation control microwave method prepares the method for controllable diameter nano silver wire to the method for (3) a kind of microwave auxiliary preparation of different-shape silver nanostructured material to a kind of method for preparing noble metal nano wire in enormous quantities, (application number is: 201010559335.9) respectively the auxiliary wet chemistry method of microwave is prepared the nano-silver thread material and report, though that is reported can both prepare the nano silver wire material, yet prepared nano-silver thread material diameter is all shorter, generally speaking all be no more than 30 microns, draw ratio is all smaller, like this when the preparation electrode material, under the same filling rate situation, the nano-silver thread that draw ratio is low is because the number of nodes nano-silver thread high than draw ratio increases greatly, and its electric conductivity will differ from an order of magnitude.So the preparation in enormous quantities fast that how to realize having the nano silver wire material of high length-diameter ratio becomes restriction flexible and transparent electrode material and realizes industrialized one big restraining factors.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities, prepared nano silver wire material is the draw ratio height not only, and the productive rate height, have very high production efficiency, overcome all lower weakness of nano-silver thread draw ratio of former microwave method preparation.
In order to reach above technique effect, the present invention adopts following technical scheme:
Said method comprising the steps of:
(1) silver nitrate or silver acetate powder are joined in the polyhydroxy liquid state organics, prepare argentiferous ion solution reaction system, again dispersant is joined in this solution reaction system, prepare argentiferous ion solution system;
(2) water-soluble halide is joined in the polyhydroxy liquid state organics, stir, obtain the settled solution system;
(3) in the prepared argentiferous ion solution of step (1) system, drip settled solution system and the acid solution that step (2) makes, continue to stir, obtain reacting precursor;
(4) method of employing microwave irradiation, reaction precursor irradiation under microwave that step (3) is obtained obtains the nano silver wire material solution of high length-diameter ratio, and again that the solution of gained behind this microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid.
The present invention can also adopt following further technical scheme:
Used silver nitrate of step (1) or silver acetate are that commercially available purity is at the technical grade powder more than 98%.
The used dispersant of step (1) is polyvinylpyrrolidone PVP, and the K value of PVP is more than 30 or 30.
The used polyhydroxy liquid state organics of step (1) is the mixture of ethylene glycol or glycerine or ethylene glycol and glycerine.
The used water-soluble halide of step (2) is a kind of or its mixture in the sodium chloride, manganese chloride, iron chloride, potassium chloride, magnesium chloride, zinc chloride, KBr, sodium bromide, cetab of technical grade.
The used acid solution of step (3) is the concentrated sulfuric acid (H
2SO
4), concentrated hydrochloric acid (HCl), red fuming nitric acid (RFNA) (HNO
3).
The molar concentration of silver nitrate or silver acetate is 0.02～0.3mol/L in the solution that makes in the step (1).
The mol ratio of silver nitrate or silver acetate powder and dispersant is in the solution that makes in the step (1): 1:1～1:6.
The net content of the cation controlling agent that is added in the step (3) and the molar ratio of silver nitrate or silver acetate are 1:1000～1:25.
The addition of used acid solution is 0.005 ~ 0.05mol/L in the step (3), and the pH value that adds the whole solution in back is 1.3 ~ 2.3.
By above technical scheme, the beneficial effect that the present invention has is:
1) preparation method is simple, the efficient height, and cost is low, all can repeat to prepare high-quality nano silver wire in very wide Reaction conditions range;
2) the present invention adopts microwave method, and the pH value by conditioned reaction solution has realized the particularly control of draw ratio of nano-silver thread diameter dimension, when obtaining high length-diameter ratio, has realized the high concentration preparation in enormous quantities fast of nano-silver thread.
Description of drawings
The stereoscan photograph of the nano silver wire material of Fig. 1 embodiment 1 preparation;
The stereoscan photograph of the nano silver wire material of Fig. 2 embodiment 2 preparations;
The stereoscan photograph of the nano silver wire material of Fig. 3 embodiment 3 preparations;
The stereoscan photograph of the nano silver wire material of Fig. 4 embodiment 4 preparations;
The stereoscan photograph of the nano silver wire material that Fig. 5 comparative example 1 is prepared;
The stereoscan photograph of the nano silver wire material that Fig. 6 comparative example 2 is prepared;
The XRD of the nano silver wire of Fig. 7 embodiment 1 preparation characterizes.
Fig. 8 has listed the nano silver wire diameter, length and the major diameter that make among embodiment 1-4 and comparative example 1-2 nano-silver thread productive rate (output in the ethylene glycol solution of unit volume in the unit interval) table when.
The specific embodiment
The present invention is a kind of auxiliary wet chemistry method of microwave of the quick preparing silver nano-wire in large batch of regulating by the pH value, specifically may further comprise the steps:
(1) silver nitrate or silver acetate powder are joined in the polyhydroxy liquid state organics, prepare argentiferous ion solution reaction system, again dispersant is joined in this solution reaction system, prepare argentiferous ion solution system;
(2) water-soluble halide is joined in the polyhydroxy liquid state organics, stir, obtain the settled solution system;
(3) in the prepared argentiferous ion solution of step (1) system, drip settled solution system and the acid solution that step (2) makes, continue to stir, obtain reacting precursor;
(4) method of employing microwave irradiation, reaction precursor irradiation under microwave that step (3) is obtained obtains the nano silver wire material solution of high length-diameter ratio, and again that the solution of gained behind this microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid.
Used silver nitrate of step (1) or silver acetate are that commercially available purity is at the technical grade powder more than 98%.
The used dispersant of step (1) is polyvinylpyrrolidone PVP, and the K value of PVP is more than 30 or 30.
The used polyhydroxy liquid state organics of step (1) is the mixture of ethylene glycol or glycerine or ethylene glycol and glycerine.
The used water-soluble halide of step (2) is a kind of or its mixture in the sodium chloride, manganese chloride, iron chloride, potassium chloride, magnesium chloride, zinc chloride, KBr, sodium bromide, cetab of technical grade.
The used acid solution of step (3) is the concentrated sulfuric acid (H
2SO
4), concentrated hydrochloric acid (HCl), red fuming nitric acid (RFNA) (HNO
3).
The molar concentration of silver nitrate or silver acetate is 0.02～0.3mol/L in the solution that makes in the step (1).
The mol ratio of silver nitrate or silver acetate powder and dispersant is in the solution that makes in the step (1): 1:1～1:6.
The net content of the cation controlling agent that is added in the step (3) and the molar ratio of silver nitrate or silver acetate are 1:1000～1:25.
The addition of used acid solution is 0.005 ~ 0.05mol/L in the step (3), and the pH value that adds the whole solution in back is 1.3 ~ 2.3.
Used microwave irradiation power is 320W～560W, and exposure time is 6～30 minutes, and the frequency of microwave is 2.45GHz.
The diameter of gained nano silver wire material of the present invention is between 80nm～500nm, and its length is between 30 microns～150 microns, and the draw ratio of gained nano-silver thread is greater than 100 simultaneously.
Resulting high length-diameter ratio nano-silver thread cleans three to four times through deionized water, absolute ethyl alcohol or acetone, is scattered in then in deionized water, absolute ethyl alcohol or the acetone, obtains uniform dispersion liquid.
Below describe in detail by specific embodiment:
Embodiment 1:
Carry out according to preparation process: (1) joins the silver nitrate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.3mol again joins in this solution system, prepares argentiferous ion solution system; (2) the NaCl powder with 0.1mmol joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip ethylene glycol solution and the red fuming nitric acid (RFNA) 0.01mol of the 20mlNaCl that step (2) makes, the molar concentration of nitric acid is 0.02mol/L in the solution, the pH value of solution value is 1.7, continue to stir, obtain reacting precursor, (4) method of employing microwave irradiation, this precursor irradiation 14min under the 400W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the sem test sample is that sample is sticked on the aluminium base sample platform, and Fig. 1 has provided the nano silver wire SEM photo that obtains according to embodiment 1.As can be seen from Figure 1, the nano silver wire complete form for preparing, average diameter are 320nm, line length is above 50 microns, draw ratio is greater than 150, and single can be prepared and surpass 80% the nano-silver thread with above draw ratio, and the single production efficiency of nano-silver thread is up to 65g/ (L*h); Fig. 7 is that the XRD of the nano silver wire of embodiment 1 preparation characterizes, as can be seen from Figure 7 the nano silver wire perfect crystalline.
Embodiment 2:
Carry out according to preparation process: (1) joins the silver acetate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.3mol again joins in this solution system, prepares argentiferous ion solution system; (2) with the MnCl of 0.5mmol
2Powder joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the 20mlMnCl that step (2) makes
2Ethylene glycol solution and red fuming nitric acid (RFNA) 0.0125mol, the molar concentration of nitric acid is 0.025mol/L in the solution, the pH value of solution value is 1.6, continue to stir, obtain reacting precursor, (4) method of employing microwave irradiation, with this precursor irradiation under the 480W microwave that obtains, 15min obtains the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the sem test sample is that sample is sticked on the aluminium base sample platform, and Fig. 2 has provided the nano silver wire SEM photo that obtains according to embodiment 2.As can be seen from Figure 2, the nano silver wire complete form for preparing, average diameter are 160nm, and line length surpasses 40 microns, and draw ratio is greater than 200; Single can be prepared and surpass 90% the nano-silver thread with above draw ratio, and the single production efficiency of nano-silver thread is up to 73g/ (L*h).
Embodiment 3:
Carry out according to preparation process: (1) joins the silver nitrate of 0.05mol in the 240ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.2mol again joins in this solution system, prepares argentiferous ion solution system; (2) with the MnCl of 0.2mmol
2Powder joins in the 10ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the 10mlMnCl that step (2) makes
2Ethylene glycol solution and red fuming nitric acid (RFNA) 0.0125mol, the molar concentration of nitric acid is 0.05mol/L in the solution, the pH value of solution value is 1.3, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 17min under the 320W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the sem test sample is that sample is sticked on the aluminium base sample platform, and Fig. 3 has provided the nano silver wire SEM photo that arrives according to embodiment 3.As can be seen from Figure 3, the nano silver wire complete form for preparing, average diameter are 110nm, line length is above 25 microns, draw ratio is greater than 200, and single can be prepared and surpass 70% the nano-silver thread with above draw ratio, and the single production efficiency of nano-silver thread is up to 57g/ (L*h).
Embodiment 4:
Carry out according to preparation process: (1) joins the silver acetate of 0.01mol in the 90ml glycerine, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 90 0.01mol again joins in this solution system, prepares argentiferous ion solution system; (2) with the FeCl of 0.3mmol
3Powder joins in the 10ml glycerine, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the FeCl of the 0.3mmol that step (2) makes
3Glycerine solution and red fuming nitric acid (RFNA) 0.001mol, the molar concentration of nitric acid is 0.01mol/L in the solution, the pH value of solution value is 2, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 7min under the 320W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the sem test sample is that sample is sticked on the aluminium base sample platform, and Fig. 4 has gone out the nano silver wire SEM photo that arrives according to embodiment 4.As can be seen from Figure 3, the nano silver wire complete form for preparing, average diameter are 90nm, line length is above 25 microns, draw ratio is greater than 250, and single can be prepared and surpass 68% the nano-silver thread with above draw ratio, and the single production efficiency of nano-silver thread is up to 49g/ (L*h).
Embodiment 5
Carry out according to preparation process: (1) is that the polyvinylpyrrolidone of 30 0.015mol joins in the 45ml ethylene glycol with the silver acetate of 0.005mol and K value, prepares argentiferous ion solution reaction system, and (2) are with the MnCl of 0.1mmol
2Powder joins in the 5ml glycerine, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the 5mlMnCl that step (2) makes
2Glycerine solution and red fuming nitric acid (RFNA) 0.00025mol, the molar concentration of nitric acid is 0.005mol/L in the solution, the pH value of solution value is 2.3, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 6min under the 320W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, and the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid.The nano silver wire complete form for preparing, average diameter are 110nm, and line length surpasses 40 microns, and draw ratio is greater than 300.
Embodiment 6
Carry out according to preparation process: (1) joins in the 900ml ethylene glycol after the silver acetate of the silver nitrate of 0.15mol and 0.15mol is mixed, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.9mol again joins in this solution system, prepares argentiferous ion solution system; (2) with the MnCl of 0.3mmol
2Powder joins in the 100ml glycerine, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the 100mlMnCl that step (2) makes
2Glycerine solution and red fuming nitric acid (RFNA) 0.01mol, the molar concentration of nitric acid is 0.01mol/L in the solution, the pH value of solution value is 2, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 30min under the 320W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, and the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid.The nano silver wire complete form for preparing, average diameter are 160nm, and line length surpasses 35 microns, and draw ratio is greater than 200.
Embodiment 7
Carry out according to preparation process: (1) is that the polyvinylpyrrolidone of 90 0.06mol joins in the 900ml glycerine with the silver acetate of 0.02mol and K value, prepares argentiferous ion solution reaction system; (2) with the FeCl of 0.2mmol
3Powder and 0.2mmolNaCl join in the 100ml ethylene glycol, stir, and obtain the settled solution system; (3) in the prepared solution of step (1), drip the FeCl of the 100ml that step (2) makes
3Ethylene glycol mixed solution and red fuming nitric acid (RFNA) 0.015mol with NaCl, the molar concentration of nitric acid is 0.015mol/L in the solution, the pH value of solution value is 1.82, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 17min under the 560W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 110nm, line length surpasses 34 microns, and draw ratio is greater than 300.
Embodiment 8
Carry out according to preparation process: (1) joins the silver acetate of 0.05mol in the 240ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.05mol again joins in this solution system, prepares argentiferous ion solution system; (2) the KBr powder with 0.2mmol joins in the 10ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip ethylene glycol solution and the concentrated hydrochloric acid 0.0025mol of the 10mlKBr that step (2) makes, the molar concentration of hydrochloric acid is 0.01mol/L in the solution, the pH value of solution value is 2, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 8min under the 400W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 80nm, line length surpasses 30 microns, and draw ratio is greater than 350.
Embodiment 9
Carry out according to preparation process: (1) joins in the 480ml ethylene glycol after the silver acetate of the silver nitrate of 0.1mol and 0.05mol is mixed, prepare argentiferous ion solution reaction system, be that the polyvinylpyrrolidone of 30 0.3mol and K value are to join in this solution system after the polyvinylpyrrolidone of 90 0.1mol mixes again with the K value, prepare argentiferous ion solution system; (2) with the MnCl of 0.2mmol
2Join in the 20ml ethylene glycol with the NaBr powder of 0.2mmol, stir, obtain the settled solution system; (3) in the prepared solution of step (1), drip the MnCl of the 0.2mmol that step (2) makes
2Ethylene glycol solution and concentrated sulfuric acid 0.0025mol with the NaBr powder of 0.2mmol, the molar concentration of sulfuric acid is 0.005mol/L in the solution, the pH value of solution value is 2, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 15min under the 480W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 100nm, line length surpasses 30 microns, and draw ratio is greater than 300.
Embodiment 10
Carry out according to preparation process: (1) joins in the 480ml ethylene glycol after the silver acetate of the silver nitrate of 0.1mol and 0.05mol is mixed, prepare argentiferous ion solution reaction system, be that the polyvinylpyrrolidone of 30 0.3mol and K value are to join in this solution system after the polyvinylpyrrolidone of 90 0.1mol mixes again with the K value, prepare argentiferous ion solution system; (2) the cetab powder with 0.2mmol joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution and the red fuming nitric acid (RFNA) 0.005mol of the cetab of the 0.2mmol that step (2) makes, the molar concentration of nitric acid is 0.01mol/L in the solution, the pH value of solution value is 2, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 15min under the 480W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 500nm, line length surpasses 150 microns, and draw ratio is greater than 300.
Embodiment 11
Carry out according to preparation process: (1) joins the silver nitrate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.3mol again joins in this solution system, prepares argentiferous ion solution system; (2) the magnesium chloride powder with 0.2mmol joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution and the red fuming nitric acid (RFNA) 0.01mol of the magnesium chloride of the 0.2mmol that step (2) makes, the molar concentration of nitric acid is 0.02mol/L in the solution, the pH value of solution value is 1.7, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 15min under the 480W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through acetone, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 89nm, line length surpasses 25 microns, and draw ratio is greater than 200.
Embodiment 12
Carry out according to preparation process: (1) joins the silver nitrate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.3mol again joins in this solution system, prepares argentiferous ion solution system; (2) the potassium chloride powder with 0.4mmol joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution and the red fuming nitric acid (RFNA) 0.01mol of the potassium chloride of the 0.4mmol that step (2) makes, the molar concentration of nitric acid is 0.02mol/L in the solution, the pH value of solution value is 1.7, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 15min under the 480W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 320nm, line length surpasses 42 microns, and draw ratio is greater than 100.
Embodiment 13
Carry out according to preparation process: (1) joins the silver nitrate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.3mol again joins in this solution system, prepares argentiferous ion solution system; (2) the potassium chloride powder with 0.4mmol joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution and the red fuming nitric acid (RFNA) 0.01mol of the potassium chloride of the 0.4mmol that step (2) makes, the molar concentration of nitric acid is 0.02mol/L in the solution, the pH value of solution value is 1.7, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 15min under the 480W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the nano silver wire complete form for preparing, average diameter is 320nm, line length surpasses 42 microns, and draw ratio is greater than 100.
Embodiment 14
Carry out according to preparation process: (1) joins the silver nitrate of 0.02mol in the 150ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.06mol again joins in this solution system, prepares argentiferous ion solution system; (2) the sodium bromide powder with 0.04mmol joins in the 50ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution and the red fuming nitric acid (RFNA) 0.004mol of the sodium bromide of the 0.04mmol that step (2) makes, the molar concentration of nitric acid is 0.02mol/L in the solution, the pH value of solution value is 1.7, continue to stir, obtain reacting the method that precursor (4) adopts microwave irradiation, this precursor irradiation 8min under the 400W microwave that obtains is obtained the nano silver wire material of high length-diameter ratio, the solution of gained behind the microwave irradiation is obtained its uniform dispersion liquid through the acetone centrifuge washing, the nano silver wire complete form for preparing, average diameter is 90nm, line length surpasses 32 microns, and draw ratio is greater than 300.
Comparative example 1:
Carry out according to preparation process: (1) joins the silver nitrate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.3mol again joins in this solution system, prepares argentiferous ion solution system; (2) the NaCl powder with 0.1mmol joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution of the 20mlNaCl that step (2) makes; (4) method of employing microwave irradiation, this precursor irradiation 25min under the 320W microwave that obtains is obtained the nano silver wire material, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the sem test sample is that sample is sticked on the aluminium base sample platform, and Fig. 5 has provided the nano silver wire SEM photo that obtains according to comparative example 1.As can be seen from Figure 5, the nano silver wire complete form for preparing, average diameter are 220nm, 14 microns of line lengths, draw ratio is 64, and single can be prepared and surpass 70% the nano-silver thread with above draw ratio, and the single production efficiency of nano-silver thread is up to 35g/ (L*h).
Comparative example 2:
Carry out according to preparation process: (1) joins the silver acetate of 0.1mol in the 480ml ethylene glycol, prepare argentiferous ion solution reaction system, the polyvinylpyrrolidone that with the K value is 30 0.5mol again joins in this solution system, prepares argentiferous ion solution system; (2) with the MnCl of 0.1mmol
2Powder joins in the 20ml ethylene glycol, stirs, and obtains the settled solution system; (3) in the prepared solution of step (1), drip the ethylene glycol solution of the 20mlMnCl2 that step (2) makes; (4) method of employing microwave irradiation, this precursor irradiation 25min under the 3200W microwave that obtains is obtained the nano silver wire material, the solution of gained behind the microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid, the sem test sample is that sample is sticked on the aluminium base sample platform, and Fig. 6 has provided the nano silver wire SEM photo that obtains according to comparative example 2.As can be seen from Figure 6, the nano silver wire complete form for preparing, average diameter are 120nm, 11 microns of line lengths, draw ratio is 92, and single can be prepared and surpass 90% the nano-silver thread with above draw ratio, and the single production efficiency of nano-silver thread is up to 44g/ (L*h).
Claims (10)
1. method for preparing fast in enormous quantities the high length-diameter ratio nano-silver thread said method comprising the steps of:
(1) silver nitrate or silver acetate powder are joined in the polyhydroxy liquid state organics, prepare argentiferous ion solution reaction system, again dispersant is joined in this solution reaction system, prepare argentiferous ion solution system;
(2) water-soluble halide is joined in the polyhydroxy liquid state organics, stir, obtain the settled solution system;
(3) in the prepared argentiferous ion solution of step (1) system, drip settled solution system and the acid solution that step (2) makes, continue to stir, obtain reacting precursor;
(4) method of employing microwave irradiation, reaction precursor irradiation under microwave that step (3) is obtained obtains the nano silver wire material solution of high length-diameter ratio, and again that the solution of gained behind this microwave irradiation is centrifugal through water or absolute ethyl alcohol, washing obtains its uniform dispersion liquid.
2. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that used silver nitrate of step in the claim 1 (1) or silver acetate are that commercially available purity is at the technical grade powder more than 98%.
3. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the used dispersant of step in the claim 1 (1) is polyvinylpyrrolidone PVP, the K value of PVP is more than 30 or 30.
4. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the used polyhydroxy liquid state organics of step in the claim 1 (1) is the mixture of ethylene glycol or glycerine or ethylene glycol and glycerine.
5. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the used water-soluble halide of step in the claim 1 (2) is a kind of or its mixture in the sodium chloride, manganese chloride, iron chloride, potassium chloride, magnesium chloride, zinc chloride, KBr, sodium bromide, cetab of technical grade.
6. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the used acid solution of step in the claim 1 (3) is the concentrated sulfuric acid (H
2SO
4), concentrated hydrochloric acid (HCl), red fuming nitric acid (RFNA) (HNO
3).
7. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the molar concentration of silver nitrate or silver acetate is 0.02～0.3mol/L in the solution that makes in the step (1).
8. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the mol ratio of silver nitrate or silver acetate powder and dispersant is in the solution that makes in the step (1): 1:1～1:6.
9. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the net content of the cation controlling agent that is added in the step (3) and the molar ratio of silver nitrate or silver acetate are 1:1000～1:25.
10. according to the described a kind of method for preparing the high length-diameter ratio nano-silver thread fast in enormous quantities of claim 1, it is characterized in that the addition of used acid solution is 0.005 ~ 0.05mol/L in the step (3), the pH value that adds the whole solution in back is 1.3 ~ 2.3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101624761A CN102259190A (en) | 2011-06-16 | 2011-06-16 | Method for quickly preparing nano silver wires with high length-diameter ratio in large batch |
| US14/123,851 US20140102254A1 (en) | 2011-06-16 | 2012-06-15 | Methods of rapid preparation of silver nanowires with high aspect ratio |
| PCT/CN2012/077015 WO2012171486A1 (en) | 2011-06-16 | 2012-06-15 | Methods of rapid preparation of silver nanowires with high aspect ratio |
| CN201210201644.8A CN102744417B (en) | 2011-06-16 | 2012-06-15 | A kind of preparation method of nano silver wires with high length-diameter ratio |
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| CN2011101624761A CN102259190A (en) | 2011-06-16 | 2011-06-16 | Method for quickly preparing nano silver wires with high length-diameter ratio in large batch |
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| US (1) | US20140102254A1 (en) |
| CN (1) | CN102259190A (en) |
| WO (1) | WO2012171486A1 (en) |
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| WO2012171486A1 (en) | 2012-12-20 |
| US20140102254A1 (en) | 2014-04-17 |
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