CN102699341A - Wet-chemical preparation method for silver micro/nanowires - Google Patents
Wet-chemical preparation method for silver micro/nanowires Download PDFInfo
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- CN102699341A CN102699341A CN2012101275271A CN201210127527A CN102699341A CN 102699341 A CN102699341 A CN 102699341A CN 2012101275271 A CN2012101275271 A CN 2012101275271A CN 201210127527 A CN201210127527 A CN 201210127527A CN 102699341 A CN102699341 A CN 102699341A
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Abstract
The invention relates to a preparation method for silver micro/nanowires, which comprises the following steps: adding a templating agent into the aqueous solution of silver salt under the condition of low temperature, adding a reducing agent dropwise, washing and drying to obtain the silver micro/nanowires. The preparation method for the silver micro/nanowires needs low operation temperature, no polymer protecting agent is added, and the materials react in an aqueous medium completely. The preparation method for the silver micro/nanowires is easy to operate and control and has environmental friendly reaction process and low cost.
Description
Technical field
The present invention relates to a kind of wet chemical preparation method of silver-colored micro-/ nano line, belong to the inorganic nanowires field of materials.
Background technology
Metal nanoparticle has high surface ability with respect to block materials, the synthetic focus that has become Recent study of special optical property, macroscopic property, physics and chemical property, especially anisotropy noble metal.Metal nanoparticle all plays important effect in many different fields and becomes the research focus, as for the experimental detection quantum confinement effect to the influence of electrical, magnetic and other correlated performances system that supplies a model; Also be widely used in simultaneously fields such as photodevelopment, catalysis, biomarker, photonic propulsion, photoelectronics, information storage and surperficial enhancement effect.The size of metal nanoparticle, shape, composition, degree of crystallinity and structures shape its character.
One-dimensional micro-nanometer structural material; Micro-nano rice noodles, nanometer rods and nanotube like noble metal Au, Ag and some other oxide, nitride; Because its unique electricity, optics, magnetics and thermal property, make that it is learned at microelectronic component, opto-electronic device, boundless application prospect arranged on the sensor and receive much concern.Explore preparation low dimension micro Nano material structurally ordered, function admirable is the focus of research always, and Ag micro-nano rice noodles also more and more receive people's attention, and main cause is that in all metals, Ag shows extraordinary conduction and heat conductivility.
The preparation method of Ag nanometer rods and/or nano wire is also many, is divided into 3 kinds substantially, hard template method, soft template method and wet chemistry method.
Hard template method is to utilize anodic oxidation Woelm Alumina, dna molecular chain, CNT etc. to be template, the Nano silver grain that deposition has the certain pore size size.For example utilize DNA network, nano-pore Al
2O
3, physical template such as flat AgBr crystal, mesoporous MCM-41 prepares Ag nano wire etc.The number of nanowires of the each preparation of hard template method is limited, nano wire and template separation difficulty, and damage easily in the separation process.
Soft template method is the rod-shaped micelle that utilizes formation such as surfactant provides the space for the growth of one dimension Nano silver grain.For example under the condition that surfactant polyvinylpyrrolidone (PVP) exists, as seed, reduce AgNO with the vinyl hexylene glycol with the Pt nano particle
3Solution obtains diameter 30-40nm under 160 ℃, controlled length reaches the nano silver wire of 50 μ m; Perhaps through UV photoreduction AgNO
3Solution synthesizes silver-colored line nano particle, and the nano silver wire diameter that obtains is 20-30nm, long 2.5 μ m.
The generalized definition of wet chemistry method is that method that liquid phase is participated in, prepare material through chemical reaction is arranged; Narrow sense says that coprecipitation is wet chemistry method.The electrochemistry precipitation method and hydro-thermal reaction all can be can be regarded as the category of wet chemistry method.Electrochemical deposition method is through the arc discharge heat release silver electrode constantly to be distributed in the liquid phase, forms ag nano-cluster.For example through solid-liquid phase arc discharge method (SLPAD), at the NaNO that makes electrode with silver
3Generate the colloidal solution include Ag group bunch in the solution, along with the prolongation of ageing time, nano silver wire is grown gradually.Hydro-thermal reaction is that what in closed container, to accomplish is chemical method, and water is under the HTHP (greater than critical point), improves the solubility of solid, the reaction between the accelerating solid.
CN02159098.2 discloses a kind of employing N, and dinethylformamide prepares the method for nano silver wire as medium at butyl titanate and acetylacetone,2,4-pentanedione as reducing agent.At first with butyl titanate and acetylacetone,2,4-pentanedione by volume 1: (0.2-5) mixed changes in the cucurbit after evenly again; Then with AgNO
3The aqueous solution and the pure N of analysis, dinethylformamide (DMF) is mixed, wherein AgNO
3Concentration range is 10 in DMF
-4-0.1g/ml adds its mixed evenly back in the cucurbit, constantly stirs simultaneously; Mixed liquid reacted under 50-70 ℃ 2-24 hour, and centrifugation obtains nano silver wire.
CN200810019828.6 discloses a kind of employing ethylene glycol as reducing agent, and PVP is as protective agent, reduces silver nitrate under the condition of heating using microwave, the method for preparing silver nano-wire in large batch.It is 99.9% anhydrous nitric acid silver AgNO that said method is selected concentration for use
3, concentration is 99.8% no water glycol C
2H
6O
2, concentration is that 98% polyvinylpyrrolidone PVP molecular weight 55000 is raw material, in the auxiliary environment of microwave, adopts the method for reduction of ethylene glycol silver nitrate to prepare nano silver wire in large quantity.
It is template that CN201110200278.X discloses the anodised multiaperture pellumina of a kind of employing, in its hole, utilizes the way deposition of chemical deposition to fill silver bromide, utilizes the decomposition under ultraviolet light of silver bromide again, removes the method that template obtains nano silver wire.
The preparation method of nano silver wires such as soft template method, hard template method, electrochemical deposition method, control procedure is complicated, and reaction temperature is high, and the reaction time is long.
A kind of directed agents that does not need surfactant or polymer as nanowire growth of having reported for work such as Caswell does not need the simple wet chemical synthesis of other shape derivants yet.This method is under 100 ℃ of conditions, in NaOH solution, with citric acid reduction AgNO
3Make metal A g, obtaining average diameter is 35nm, the nano-silver thread of length 12 μ m.(Surfactantless Wet Chemical Synthesis of Silver Nanowires [J]., Caswell, K.K., Bender; C.M., Murphy, C.J.Seedless, NANOLETTERS; 2003,3 (5): the 667-669.) method of reporting for work such as Caswell, reaction temperature high (wanting 100 ℃ at least), simultaneously; The addition of NaOH solution has very big-difference to the form of product, and reaction is responsive, inconvenient operation.
The preparation method of existing nano silver wire exists course of reaction complicated, inconvenient operation, and reaction temperature is high, wants 100 ℃ just can carry out at least.Therefore, it is lower how to develop a kind of reaction temperature, and preparation technology is simple, and operation is the preparation method of silver-colored easily micro-/ nano line again, is a problem demanding prompt solution.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of preparation method of silver-colored micro-/ nano line.The preparation method of silver-colored micro-/ nano line of the present invention is a wet chemical preparation method, and particularly, said method is under cryogenic conditions; Template is added in the silver salt solution; After wherein splashing into reducing agent, dropwising, obtain silver-colored micro-/ nano line then through washing, drying.
The present invention carries out in aqueous media, does not add any macromolecule dispersant, does at the compound that contains citrate ion under the condition of template, adopts at a lower temperature, and the reduction silver nitrate is prepared the method for silver-colored micro-/ nano line.Low temperature according to the invention is below 60 ℃.
Nano wire is a kind of nanoscale (1 nanometer=10
-9Rice) line changes a kind of saying, and nano wire can be defined as a kind of one-dimentional structure that is limited in 100 nanometers following (vertically not having restriction) in the horizontal that has.Micro-/ nano line of the present invention is meant to have and is limited in the horizontal below 50 microns, and diameter is less than 1 micron one-dimentional structure.
The preparation method of silver-colored micro-/ nano line of the present invention is under the condition that template exists, and through reducing agent the silver salt solution reduction is obtained silver-colored micro-/ nano line, and said reducing agent is a ferrous salt, and said template is the compound that contains citrate ion.
Reaction principle of the present invention is following: the complexing of utilizing citrate; At first generate the complex compound of silver salt and citrate with the silver salt complexing, this complex compound takes place to reduce under the effect of reducing agent to react and obtains silver-colored micro-/ nano particle then, with the silver-colored micro-/ nano particle that the obtains seed that is grow nanowire; Under the lasting reduction of reducing agent; The complex compound of silver salt and citric acid continues to be reduced, and theoretical through the Ostwald slaking, finally generates silver-colored micro-/ nano line.
The present invention does not have concrete qualification to the compound of citrate ion, can select any material that citrate can be provided.In the compound of citrate ion, the counter ion counterionsl gegenions of citrate can be selected from the combination of any a kind or at least 2 kinds in alkali metal ion, alkaline-earth metal ions and the transition metal ions, for example Na
+, K
+, Mg
2+, Fe
3+, Al
3+In the combination of any a kind or at least 2 kinds, the ion of said combination such as Na
+/ K
+, i.e. potassium citrate sodium.Citric acid itself has three hydrogen atoms, and in the compound of citrate ion, counter ion counterionsl gegenions can replace 1 hydrogen, 2 hydrogen or 3 hydrogen.The example that replaces 1 hydrogen has natrium citricum, potassium citrate etc.; The example that replaces 2 hydrogen has disodium citrate, citric acid dipotassium, potassium citrate sodium etc.; The example that replaces 3 hydrogen has trisodium citrate, citric acid tri potassium etc.Those skilled in the art can or consult pertinent literature the compound of citrate ion is selected according to the professional knowledge of oneself grasping.
Preferably; The compound of citrate ion of the present invention is selected from 1 in citric acid, trisodium citrate, disodium citrate, natrium citricum, potassium citrate, potassium citrate sodium, citric acid dipotassium and the citric acid tri potassium or at least 2 kinds combination; Said combination is natrium citricum/potassium citrate, natrium citricum/citric acid/disodium citrate, citric acid/potassium citrate/citric acid dipotassium/citric acid tri potassium etc. for example; 1 kind or at least 2 kinds combination in optimization citric acid, natrium citricum and the potassium citrate, further optimization citric acid.
Reducing agent of the present invention is a ferrous salt.Fe
2+Be ferrous ion, his salt just is ferrous salt.Ferrous salt can be oxidized to Fe
3+, can be reduced to Fe again.The present invention utilizes the reproducibility of ferrous salt, and silver salt is reduced into simple substance silver.
The present invention does not have special qualification to the selection of ferrous salt yet, and can select anyly can provide ferrous compound.In the ferrous salt, the counter ion counterionsl gegenions of ferrous ion are selected from sulfate radical, nitrate anion etc., the principle of selection be ferrous salt must be water-soluble and contend with particle can not with silver ion generation chemical reaction.Those skilled in the art can or consult pertinent literature ferrous salt is selected according to the professional knowledge of oneself grasping.
Preferably, ferrous salt according to the invention is selected from a kind or at least 2 kinds combination in ferrous sulfate, the ferrous nitrate, and said combination is ferrous sulfate/ferrous nitrate, ferrous sulfate etc. for example, preferred ferrous nitrate and/or ferrous sulfate, and further preferably sulfuric acid is ferrous.
Silver salt of the present invention is that cation is the salt of silver ion, anyly can all can be used for the present invention, for example silver nitrate, silver acetate etc. by silver salt soluble in water.Preferred silver nitrate of silver salt according to the invention and/or silver acetate, further preferred silver nitrate.
As optimal technical scheme, the preparation method of silver-colored micro-/ nano line according to the invention comprises the steps:
(1) gets silver salt, reducing agent and template and be dissolved in the water respectively, preparation silver salt solution, the reducing agent aqueous solution and the template aqueous solution;
(2) template is joined in the silver salt solution heat tracing;
(3) in the solution that step (2) obtains, drip reducing agent;
(4) dropwise, centrifugalize deposition, through washing, dry silver-colored micro-/ nano line.
Preparation process of the present invention is with silver salt and citrate complexing, and the product reduction that then complexing is obtained under the effect of citrate as template, prepares silver-colored micro-/ nano line.Reaction temperature required for the present invention is not high, in the process that the dropping reducing agent reduces, needs heat tracing, and the temperature of insulation is 40-60 ℃, and for example 40 ℃, 42 ℃, 47 ℃, 53 ℃, 58 ℃, 60 ℃ etc., preferred 45-55 ℃, further preferred 50 ℃.
The speed that drips reducing agent is also influential to the outward appearance of the silver-colored micro-/ nano line for preparing; In order to prepare the bigger silver-colored micro-/ nano line of draw ratio; The speed that the present invention controls the said dropping reducing agent of step (3) is 0.1-0.5mL/min; For example 0.10mL/min, 0.11mL/min, 0.13mL/min, 0.25mL/min, 0.29mL/min, 0.35mL/min, 0.38mL/min, 0.44mL/min, 0.50mL/min etc., preferred 0.2-0.35mL/min, further preferred 0.33mL/min.
If the concentration of silver salt, reducing agent is too high then cause the effects of ion excessive concentration among the present invention, the complexing of citrate ion is caused the waste of citrate ion by other ions consumption except that silver ion; Cause the growth insufficient raw material of silver-colored micro-/ nano line if the concentration of silver salt, reducing agent is too low, cause that the length of silver-colored micro-/ nano line is shorter.
Preferably; In the step according to the invention (1); The concentration of silver salt solution is 0.5-5.0g/L, for example 0.5g/L, 0.8g/L, 1.2g/L, 1.8g/L, 2.0g/L, 2.7g/L, 3.2g/L, 3.8g/L, 4.5g/L, 5.0g/L etc., preferably 1.0g/L-3.5g/L.
Preferably; The concentration of the said reducing agent aqueous solution of step of the present invention (1) is 2g/L-10g/L, for example preferred 2-8g/L such as 2.0g/L, 2.2g/L, 2.9g/L, 3.5g/L, 3.9g/L, 4.3g/L, 4.8g/L, 5.9g/L, 6.4g/L, 7.0g/L, 8.7g/L, 9.8g/L, 10g/L.
Among the present invention, the excessive or too small waste that all can cause raw material of the ratio of reducing agent and silver salt.Therefore, the mass ratio of preferred said reducing agent of the present invention and silver salt is (5-1): 1, and for example 5: 1,4.8: 1,4.0: 1,3.7: 1,3.2: 1,2.5: 1,2.1: 1,1.7: 1,1.3: 1,1: 1 etc., preferred (3.5-1): 1.
The concentration of the said template of step of the present invention (1) in silver salt solution is 0.5-5g/L, for example 0.5g/L, 0.6g/L, 0.9g/L, 1.1g/L, 1.6g/L, 2.6g/L, 3.3g/L, 4.1g/L, 4.8g/L, 5.0g/L, preferably 1.0-3.5g/L;
Preferably, said wet concentration a kind in deionized water, distilled water and redistilled water.
As optimal technical scheme, the wet chemical preparation method of silver-colored micro-/ nano line according to the invention comprises the steps:
(1) silver nitrate ferrous sulfate and citric acid are dissolved in respectively in the deionized water, obtain silver nitrate aqueous solution, ferrous sulfate aqueous solution and aqueous citric acid solution;
(2) join aqueous citric acid solution in the silver nitrate aqueous solution, heating gained mixed solution, insulation, the control temperature is at 40-60 ℃;
(3) the mixed solution and dripping ferrous sulfate that obtains to step (2), rate of addition are 0.1-0.3mL/min;
(4) dropwise, centrifugalize deposition, through washing, dry silver-colored micro-/ nano line.
As optional technical scheme, the wet chemical preparation method of silver-colored micro-/ nano line according to the invention comprises the steps: to be dissolved into wiring solution-forming in the deionized water to an amount of silver nitrate, ferrous sulfate and citric acid respectively.Drip the citric acid solution of appropriate amount then in the liquor argenti nitratis ophthalmicus, form the liquor argenti nitratis ophthalmicus that contains citric acid.Be heated to 50 ℃ to this solution then, keep constant, and in this solution, drip an amount of copperas solution with suitable rate of addition.After dropwising, from solution, isolate sediment, water and absolute alcohol wash 3-4 time successively, obtain silver-colored micro wire through vacuum drying at last.
Two of the object of the invention provides a kind of silver-colored micro-/ nano line, and said silver-colored micro-/ nano line is prepared by the method for the invention.Diameter≤0.6 of the silver-colored micro-/ nano line that the present invention prepares micron, preferred diameter is the 0.2-0.6 micron; Controlled length is the 3-30 micron.
Compared with prior art, the present invention has following beneficial effect:
(1) operating temperature of the method for the invention is low, and whole process all can carried out below 60 ℃, compared with prior art; Reaction temperature reduces greatly, has not only practiced thrift the energy, provides cost savings; And greatly reduce the difficulty of operation, improved the security for preparing silver-colored micro-/ nano line.100 ℃ reacting phase ratio in the wet-chemical synthetic method of for example reporting for work with Caswell etc., reaction temperature reduces greatly.
(2) the present invention does not add any macromolecule dispersant, in aqueous media, carries out fully, does not produce harmful substance, very environmental protection.
(3) preparation technology's method of silver-colored micro-/ nano line provided by the invention, simple to operate, easy control has very wide industrial prospect.
Description of drawings
Fig. 1 is that embodiment one prepared silver-colored micro-/ nano line amplifies 2000 times SEM figure;
Fig. 2 is that embodiment one prepared silver-colored micro-/ nano line amplifies 3000 times SEM figure;
Fig. 3 is the XRD figure of the prepared silver-colored micro-/ nano line of embodiment one;
Fig. 4 is that embodiment two gained silver micro-/ nano line amplifies 2000 times SEM figure;
Fig. 5 is that embodiment three gained silver micro-/ nano line amplifies 2000 times SEM figure.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment one
21mg silver nitrate and 50mg ferrous sulfate are dissolved into respectively in the 10mL deionized water, are dissolved into the 19.2mg citric acid in the 3mL deionized water and are made into citric acid solution.Behind citric acid solution adding liquor argenti nitratis ophthalmicus,, make it to remain on 50 ℃ to this mixed solution heating; Then toward this mixed solution and dripping 8mL copperas solution; In 30min, dropwise back (rate of addition 0.33mL/min), centrifugation deposition, spend the deionised water several times after; With absolute ethanol washing 2-3 time, last vacuum drying obtains silver-colored micro-/ nano line.Fig. 1 is that embodiment one gained silver micro-/ nano line amplifies 2000 times SEM figure; Fig. 2 is that embodiment one gained silver micro-/ nano line amplifies 3000 times SEM figure; Fig. 3 is the XRD figure of embodiment one gained silver micro-/ nano line.
Embodiment two
10.5mg silver nitrate and 50mg ferrous sulfate are dissolved into respectively in the 10mL deionized water, are dissolved into the 19.2mg citric acid in the 3mL deionized water and are made into citric acid solution.Behind citric acid solution adding liquor argenti nitratis ophthalmicus,, make it to remain on 50 ℃ to this mixed solution heating; Then toward this mixed solution and dripping 5mL copperas solution; After in 30min, dropwising, centrifugation deposition, spend the deionised water several times after; With absolute ethanol washing 2-3 time, last vacuum drying obtains silver-colored micro wire.Fig. 4 is that embodiment two gained silver micro-/ nano line amplifies 2000 times SEM figure.
Embodiment three
30mg silver nitrate and 100mg ferrous sulfate are dissolved into respectively in the 10mL deionized water, are dissolved into 32mg citric acid and disodium citrate 10mg in the 3mL deionized water and are made into citric acid solution.Behind citric acid solution adding liquor argenti nitratis ophthalmicus,, make it to remain on 60 ℃ to this mixed solution heating; Then toward this mixed solution and dripping 5mL copperas solution; After in 30min, dropwising, centrifugation deposition, spend the deionised water several times after; With absolute ethanol washing 2-3 time, last vacuum drying obtains silver-colored micro wire.Fig. 5 is that embodiment three gained silver micro-/ nano line amplifies 2000 times SEM figure.
Embodiment four
5mg silver nitrate and 10mg ferrous sulfate are dissolved into respectively in the 10mL deionized water, are dissolved into the 5mg potassium citrate in the 3mL deionized water and are made into citric acid solution.Behind citric acid solution adding liquor argenti nitratis ophthalmicus,, make it to remain on 40 ℃ to this mixed solution heating; Then toward this mixed solution and dripping 5mL copperas solution; After in 50min, dropwising, centrifugation deposition, spend the deionised water several times after; With absolute ethanol washing 2-3 time, last vacuum drying obtains silver-colored micro-/ nano line.The diameter of resulting nano silver wire is 0.6 micron, and controlled length is 150 microns.
Embodiment five
The 4mg silver nitrate is dissolved into the 8mL deionized water and the 30mg ferrous sulfate is dissolved in the 3mL deionized water, is dissolved into the 4mg potassium citrate in the 3mL ionized water and is made into citric acid solution.Behind citric acid solution adding liquor argenti nitratis ophthalmicus,, make it to remain on 60 ℃ to this mixed solution heating; Then toward this mixed solution and dripping 2mL copperas solution; After in 20min, dropwising, centrifugation deposition, spend the deionised water several times after; With absolute ethanol washing 2-3 time, last vacuum drying obtains silver-colored micro-/ nano line.The diameter of resulting nano silver wire is 0.3 nanometer, and controlled length is 30 microns.
Embodiment six
The 20mg silver nitrate is dissolved into the 4ml deionized water and the 30mg ferrous sulfate is dissolved in the 30mL deionized water, is dissolved into the 20mg potassium citrate in the 3mL deionized water and is made into citric acid solution.Behind citric acid solution adding liquor argenti nitratis ophthalmicus,, make it to remain on 60 ℃ to this mixed solution heating; Then toward this mixed solution and dripping 20mL copperas solution; After in 40min, dropwising, centrifugation deposition, spend the deionised water several times after; With absolute ethanol washing 2-3 time, last vacuum drying obtains silver-colored micro-/ nano line.The diameter of resulting nano silver wire is 0.2 micron, and controlled length is 12 microns.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (9)
1. the preparation method of a silver-colored micro-/ nano line is characterized in that, said method is under cryogenic conditions, and template is added in the silver salt solution, after wherein splashing into reducing agent, dropwising, obtains silver-colored micro-/ nano line through washing, drying then;
Said low temperature is below 60 ℃; Said reducing agent is a ferrous salt; Said template is the compound that contains citrate ion.
2. preparation method as claimed in claim 1; It is characterized in that; The compound of said citrate ion is selected from 1 in citric acid, trisodium citrate, disodium citrate, natrium citricum, potassium citrate, potassium citrate sodium, citric acid dipotassium and the citric acid tri potassium or at least 2 kinds combination; 1 kind or at least 2 kinds combination in optimization citric acid, natrium citricum and the potassium citrate, further optimization citric acid.
3. according to claim 1 or claim 2 preparation method is characterized in that said ferrous salt is selected from a kind or at least 2 kinds combination in ferrous sulfate, the ferrous nitrate, preferred ferrous nitrate and/or ferrous sulfate, and further preferably sulfuric acid is ferrous.
4. like the described preparation method of one of claim 1-3, it is characterized in that said silver salt is selected from water-soluble silver salt, preferred silver nitrate and/or silver acetate, further preferred silver nitrate.
5. like the described preparation method of one of claim 1-4, it is characterized in that said method comprises the steps: that (1) get silver salt, reducing agent and template and be dissolved in the water respectively, preparation silver salt solution, the reducing agent aqueous solution and the template aqueous solution;
(2) template is joined in the silver salt solution heat tracing;
(3) in the solution that step (2) obtains, drip reducing agent;
(4) dropwise, centrifugalize deposition, through washing, dry silver-colored micro-/ nano line.
6. like the described preparation method of one of claim 1-5, it is characterized in that the concentration of the said silver salt solution of step (1) is 0.5-5.0g/L, preferred 1.0g/L-3.5g/L;
Preferably, the concentration of the said reducing agent aqueous solution of step (1) is 2g/L-10g/L, preferred 2-8g/L;
Preferably, the mass ratio of reducing agent and silver salt is 5-1, preferred 3.5-1;
Preferably, the concentration of the said template of step (1) in silver salt solution is 0.5-5g/L, preferred 1.0-3.5g/L;
Preferably, said wet concentration a kind in deionized water, distilled water and redistilled water.
7. like the described preparation method of one of claim 1-6, it is characterized in that the temperature of the described heat tracing of step (2) is 40-60 ℃, preferred 45-55 ℃, further preferred 50 ℃;
Preferably, the speed of the said dropping reducing agent of step (3) is 0.1-0.5mL/min, preferred 0.2-0.35mL/min, further preferred 0.33mL/min.
8. like the described preparation method of one of claim 1-7, it is characterized in that said method comprises the steps:
(1) silver nitrate, ferrous sulfate and citric acid are dissolved in respectively in the deionized water, obtain silver nitrate aqueous solution, ferrous sulfate aqueous solution and aqueous citric acid solution;
(2) join aqueous citric acid solution in the silver nitrate aqueous solution, heating gained mixed solution, insulation, the control temperature is at 40-60 ℃;
(3) the mixed solution and dripping ferrous sulfate that obtains to step (2), rate of addition are 0.1-0.3mL/min;
(4) dropwise, centrifugalize deposition, through washing, dry silver-colored micro-/ nano line.
9. a silver-colored micro-/ nano line for preparing like the preparation method of the described silver-colored micro-/ nano line of one of claim 1-8 is characterized in that, the diameter of said silver-colored micro-/ nano line≤0.6 micron, and preferred diameter is the 0.2-0.6 micron, controlled length is the 3-30 micron.
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| CN102974837A (en) * | 2012-11-29 | 2013-03-20 | 江苏技术师范学院 | Preparation method for flaky nanometer silver powder |
| CN103273082A (en) * | 2013-06-13 | 2013-09-04 | 昆山西微美晶电子新材料科技有限公司 | Flower-like spherical silver powder preparing method |
| CN104607655A (en) * | 2015-03-06 | 2015-05-13 | 苏州大学 | Silver nanowire preparation method |
| CN104625084A (en) * | 2014-12-31 | 2015-05-20 | 烟台佳隆纳米产业有限公司 | Colorless nano-silver sol preparation and preservation method utilizing cryogenic technology |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003268423A (en) * | 2002-03-12 | 2003-09-25 | Sumitomo Metal Mining Co Ltd | Method for manufacturing colloidal dispersions of silver particle |
| CN101626856A (en) * | 2007-03-30 | 2010-01-13 | 三菱麻铁里亚尔株式会社 | The manufacture method of fine silver particle, fine silver particle and the manufacturing installation of fine silver particle |
| JP2010225575A (en) * | 2008-10-22 | 2010-10-07 | Mitsubishi Materials Corp | Silver paste |
-
2012
- 2012-04-26 CN CN201210127527.1A patent/CN102699341B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003268423A (en) * | 2002-03-12 | 2003-09-25 | Sumitomo Metal Mining Co Ltd | Method for manufacturing colloidal dispersions of silver particle |
| CN101626856A (en) * | 2007-03-30 | 2010-01-13 | 三菱麻铁里亚尔株式会社 | The manufacture method of fine silver particle, fine silver particle and the manufacturing installation of fine silver particle |
| JP2010225575A (en) * | 2008-10-22 | 2010-10-07 | Mitsubishi Materials Corp | Silver paste |
Non-Patent Citations (1)
| Title |
|---|
| ZHAI AIXIA等: "A novel and facile wet-chemical method for synthesis of silver microwires", 《TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA》 * |
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| CN105268993B (en) * | 2012-11-29 | 2019-01-25 | 江苏理工学院 | A method of preparing flaky nanometer silver powder |
| CN102974837B (en) * | 2012-11-29 | 2016-01-06 | 江苏理工学院 | The preparation method of flaky nanometer silver powder |
| CN105268993A (en) * | 2012-11-29 | 2016-01-27 | 江苏理工学院 | Method for preparing silver nanoflakes |
| CN102974837A (en) * | 2012-11-29 | 2013-03-20 | 江苏技术师范学院 | Preparation method for flaky nanometer silver powder |
| CN103273082A (en) * | 2013-06-13 | 2013-09-04 | 昆山西微美晶电子新材料科技有限公司 | Flower-like spherical silver powder preparing method |
| CN104625084B (en) * | 2014-12-31 | 2016-08-24 | 烟台佳隆纳米产业有限公司 | A kind of method utilizing cryogenic technique to prepare and preserve colourless nano silver colloidal sol |
| CN104625084A (en) * | 2014-12-31 | 2015-05-20 | 烟台佳隆纳米产业有限公司 | Colorless nano-silver sol preparation and preservation method utilizing cryogenic technology |
| CN104607655B (en) * | 2015-03-06 | 2016-08-24 | 苏州大学 | A kind of preparation method of nano silver wire |
| CN104607655A (en) * | 2015-03-06 | 2015-05-13 | 苏州大学 | Silver nanowire preparation method |
| CN106694899A (en) * | 2016-11-15 | 2017-05-24 | 西南科技大学 | Preparing method for silver nano wire pipe with controllable size |
| CN106694899B (en) * | 2016-11-15 | 2018-07-03 | 西南科技大学 | A kind of preparation method of the controllable silver nanoparticle spool of size |
| CN108655414A (en) * | 2018-06-11 | 2018-10-16 | 合肥学院 | A kind of quick magnanimity prepares the simple and easy method of two dimension Ag micro Nano materials |
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