CN109128211A - The method of micro-nano silver particle is prepared in water solution system - Google Patents
The method of micro-nano silver particle is prepared in water solution system Download PDFInfo
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- CN109128211A CN109128211A CN201810933698.0A CN201810933698A CN109128211A CN 109128211 A CN109128211 A CN 109128211A CN 201810933698 A CN201810933698 A CN 201810933698A CN 109128211 A CN109128211 A CN 109128211A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
The present invention relates to the methods that micro-nano silver particle is prepared in water solution system, comprise the following steps that the complex compound precursor solution that silver salt solution and complexing agent aqueous solution are mixed to prepare to silver, then it is added dropwise and mixes simultaneously with reducing agent aqueous solution, carry out a step reduction reaction, obtain micro-nano silver particle.The present invention reacts in aqueous solution at normal temperatures and pressures, does not have to high molecular polymer as protective agent and dispersing agent, makees reducing agent with hydrazine hydrate, restores the complex compound presoma of silver.Preparation method is simple, avoids high molecular polymer in the residual on silver powder surface, the flower shape micro-nano silver granule-morphology of preparation is regular, particle diameter distribution is uniform, good dispersion, size is controllable, yield is high.
Description
Technical field
The invention discloses the methods that micro-nano silver particle is prepared in water solution system, belong to the preparation of micro Nano material silver
Field.
Background technique
Silver-colored micro Nano material has unique physicochemical properties, has in fields such as electricity, catalysis, magnetics and SERS spectras
Broad application prospect.The factors such as the property of the micro Nano material of silver and character, size and structure are closely related.In recent years,
Nanoparticle and nano material have become one of hot spot of research of materials science field.The research and development of China's micro-nano silver
Arise from the beginning of the sixties, eight, the nineties enter Rapid development stage, big in this section of period governmental input, there are many units to participate in
The research of silver powder technology of preparing, and produce the silver powder of many series, fill up domestic blank.In China, silver powder is produced
Though producer is many, the unit that kind is complete, high-quality is few.It is compared with World Developed Countries, the silver powder kind of China's production at present
It is not also that very entirely, also there is also certain gaps with foreign countries for performance with series.In order to meet diversified actual demand, many is ground
Study carefully mechanism and research group and successfully synthesizes the micro nano structure with different shape, size and structure also with various methods
Ag material.Pattern control be one regulation metallic nanostructure reason and chemical property effective way, therefore silver pattern
Controllable preparation is still the focus studied at this stage.
Theoretical calculation and experimental result all show that the surface plasma body resonant vibration of silver nano-grain and surface-enhanced Raman dissipate
It penetrates property and is all highly dependent on pattern in them.The flower-shaped class silver powder of micro nano structure is by other nanotopographies such as nanometer sheet or stick
It constitutes, surface has certain roughness, has corner angle etc. not sharp in the micron-scale, can provide heat on individual particle surface
, it is the substrate of excellent surface-enhanced raman scattering effect；Conductive filler, the piece of flower-shaped class ball silver are used as in printing slurry ink
Face contact is formed with piece, the silver content under unit area significantly improves, and overcomes flake silver powder in a humidity environment
The shortcomings that easily migrating；There is good diffuse reflection effect for the ultraviolet light of Light Curing, applies in light-cured type
When electrically conductive ink, UV-curing technology is combined with electrically conductive ink technology, forms good printing precision, high speed printing
Property, adhesiveness and good electric conductivity and stability.
Structure is complicated for the flower-shaped silver prepared at present, is generally assembled by nano-sheet etc., because structure is complicated to make
It is prepared with physical method, specified conditions can only be controlled and prepared by chemical reduction method.Reducing agent mostly uses Vitamin C
Acid, ferrous sulfate, amino acid, catechol, hydrogen peroxide, ethylene glycol, polyvinylpyrrolidone etc..For example use PVP as protection
Agent and reducing agent restored under 100 degree silver nitrate prepare flower shape silver nano-grain (referring to He Hui etc., gold, 2013,34
(1))；Use polyvinylpyrrolidone as reducing agent, 80 degree or more of temperature can restore prepare flower shape silver powder (referring to: appoint
Shining chapter etc., non-ferrous metal, the 4th phase in 2017,52-57).It is thus found that using polyvinylpyrrolidone as reducing agent and dispersion
The system of agent, which has to heating water bath, can just prepare flower shape silver powder to certain temperature, and polyvinylpyrrolidone is post-processing
It is cleaner than more intractable in the process.
Chen's et al. studies have shown that restore silver nitrate with hydrogen peroxide under ultrasonic wave added, having produced partial size is about 0.5 micro-
The rice very high micro-nano structure silver powder of surface roughness, by the confirmatory experiment of Raman scattering detection trace level chemical substance, discovery should
Silver powder can be used as substrate use (referring to CHEN H J, Journal of physical chemistry C, 2009,113
(44): 19258-19262.).Wang Xiaoyu has studied contour using polyacrylamide and polyvinylpyrrolidone in academic dissertation
Stabilizer molecule and Small molecular surfactant citric acid prepare the micro-nano silver powder of rough surface, and wherein reducing agent is anti-
Bad hematic acid and hydroquinone.And its SERS activity is had studied, as a result, it has been found that shaggy micro-nano silver powder can obtain enhancing effect
Fruit apparent Raman absorption peak, realize rhodamine B trace detection (referring to Wang Xiaoyu, shaggy micro-nano silver powder
Preparation and its SERS activity research, East China University of Science's academic dissertation, 2013).
The report for preparing flower shape silver powder at room temperature does the more of reducing agent with ascorbic acid.Such as with silver nitrate and
Ascorbic acid is raw material, under the auxiliary of citric acid and polyvinylpyrrolidone, room temperature reaction 2h synthesis honeysuckle flower shape ball (referring to:
Wu Huijie etc., material Leader, in May, 2014, the album 23 of volume 28).By adjusting silver nitrate concentration, in polyvinylpyrrolidone
Auxiliary under, ascorbic acid reduction silver nitrate synthesized 500nm-2 microns flower-shaped silver particles (referring to H, Y.Liang,
Adbanced Materials,2009,21(45):4614-4618.).Containing polyvinylpyrrolidone and lemon with ascorbic acid
Silver nitrate is restored under conditions of lemon acid trisodium prepares flower-shaped Nano silver grain (referring to X.S.Shen etc., Physical
Chemistry Chemical Physics,2009,11(34):7450-7454.).It is a kind of to use nitre acid for adjusting pH value and citric acid
In the system that trisodium coexists, with the side for the flower-shaped silver-colored micro nano structure that ascorbic acid reduction silver nitrate preparation is made of nanometer sheet
Method, good pattern can just be obtained only when the pH value of solution is 3.5 or so by adjusting pH value using concentrated nitric acid in preparation method
Honeysuckle flower shape silver micro nano structure, diameter is about 1.5 μm.The experimental results showed that flower-shaped silver micro nano structure is as surface enhanced
The substrate of Raman scattering has very strong activity (referring to wave etc., Chemical Journal of Chinese Universities, 2010,8,1491-1495).
Using the preparation method of other reducing agents, for example Chinese patent document CN103273082A is also using ferrous sulfate
Partial size is made in the flower-like spherical silver powder of 0.5~3 μ m in former agent.Chinese patent document CN106424752A is then gone back using different
Two kinds of reducing agents of originality sufficiently react to obtain flower shape silver powder under -10~80 degree of degree.Silver powder obtained is applied to electrically conductive ink
In, the electric conductivity of electrically conductive ink can be promoted, and the printing of electrically conductive ink, printing precision are also preferable.Chinese patent document
CN107127355A uses amino acid as reducing agent, and being first adjusted to pH value with pH adjusting agent is 4-6, needs heating
Under conditions of 30-80 degree, reaction 5-10h reduction silver ammino solution obtains flower-shaped silver micron ball.
In addition, Chinese patent document CN101875130A discloses preparation and the separation method of a kind of nano-Ag particles.First
Prepare AgNO3With the mixed aqueous solution of its complexing agent, a certain amount of surfactant, and the pH value of regulation system are added, is stirred
Mixing is completely dissolved surfactant be added, then reducing agent is added dropwise dropwise into above-mentioned solution under violent stirring, control
Reaction temperature processed is in room temperature, and after reducing agent is added dropwise, being further continued for stirring to reaction terminates to get nano silver colloidal sol；Use pH value
The pH value of nano silver colloidal sol is adjusted to subacidity or neutrality (pH=2-7) by regulator, and solid is precipitated, is isolated, hereafter with having
Solvent washs the solid, separates again, and the nano-Ag particles of " wet " can be obtained, vacuum dried up to nano-Ag particles.This
The sheet subelement not easily generated of major part complexing agent used in method, is not easy to grow up to the pattern of flower shape Argent grain, therefore in table
Be made nano silver colloidal sol under the adjusting of face activating agent and acid-base property, after nano-Ag particles.
Above in the prior art, it prepares micro-nano silver particle and mostly uses polyvinylpyrrolidone or polyacrylamide etc.
High molecular polymer etc. is used as surface protectant and dispersing agent, and reducing agent is ascorbic acid, ferrous sulfate, amino acid, neighbour
Benzenediol, hydrogen peroxide, ethylene glycol, polyvinylpyrrolidone etc., some need heating or high temperature hydro-thermal reaction in technique；Have
Reaction process need with acid-base accommodation pH value, or carry out the complicated processes such as reduction reaction using two kinds of reducing agents substeps.And
Without high molecular polymer as surface protectant and dispersing agent, and use hydrazine hydrate as reduction preparation under the room temperature of reducing agent
The flower shape micro-nano silver particle of clean surface, has not been reported.For this purpose, proposing the present invention.
Summary of the invention
In view of the deficiencies of the prior art, the method that micro-nano silver particle is prepared in water solution system of the present invention, at normal temperature
In aqueous systems, do not have to high molecular polymer, largely to prepare clean surface only with the complex compound presoma of hydrazine hydrate reduction silver
The spherical micro-nano silver powder of flower shape.
Technical scheme is as follows:
The method that micro-nano silver particle is prepared in water solution system, comprises the following steps that
Silver salt solution and complexing agent aqueous solution are mixed to prepare to the complex compound precursor solution of silver, then with reducing agent water
Mixing is added dropwise in solution simultaneously, carries out a step reduction reaction, obtains micro-nano silver particle.
, according to the invention it is preferred to, the silver salt is silver nitrate, silver acetate, silver sulfate；
Preferably, the concentration of silver salt solution is 0.01-8g/mL, further preferably 0.05-1g/mL.
, according to the invention it is preferred to, the complexing agent is citric acid, trisodium citrate, ethylenediamine tetra-acetic acid or second two
Amine tetraacethyl disodium；
Preferably, the concentration of complexing agent aqueous solution is 0.02-0.2g/mL.
, according to the invention it is preferred to, the molar ratio of complexing agent and silver salt is 0.1-10, further preferred 0.2-5.
, according to the invention it is preferred to, the reducing agent is hydrazine hydrate；Preferably, the concentration of reducing agent aqueous solution is
1%-30%, further preferred 2%-10%.
, according to the invention it is preferred to, it is added dropwise in mixed process, complex compound precursor solution drips simultaneously with reducing agent aqueous solution
It is added in water and carries out hybrid reaction.
, according to the invention it is preferred to, the mixed feed time of the dropwise addition is 5-60min, further preferably 10-
30min；
, according to the invention it is preferred to, the time of the reduction reaction is 10-300min, further preferably 30-
120min。
According to the present invention, obtain uniform dark brown solution after reduction reaction, after washing two or three time freeze-drying be
Obtain flower shape micro-nano silver particle.
The micro-nano silver particle that the present invention obtains, crystallite dimension is between 200nm~2000nm.
The present invention under normal temperature and pressure conditions, does not have to high molecular polymer as protective agent and dispersing agent, only uses hydrazine hydrate
Make reducing agent, restores the complex compound presoma of silver, prepare the spherical micro-nano granules of flower shape of clean surface.First by nitric acid
Silver aqueous solution and complexing agent aqueous solution be mixed to prepare silver complex compound presoma, then under reducing agent hydrazine hydrate room temperature simultaneously
It is added dropwise, carries out hybrid reaction, that is, generate the flower-shaped micro-nano silver particle of finely dispersed size uniformity clean surface.Using network
The complex compound presoma of silver is first made in mixture with silver nitrate, not only improves the sheet subelement that reaction generates flower-shaped micro-nano silver,
Redox reaction rate can be slowed down again, prevent particle agglomeration.Advantage using hydrazine hydrate is that hydrazine hydrate itself is alkaline solution,
The precursor solution that silver is restored in alkaline environment is also easy in the case where no high molecular polymer is as surface protection
The self assembly of flower shape structure is formed, and is not in cold-welding effect, therefore appearance and size uniformly flower-shaped micro-nano silver can be made
Particle.Hybrid reaction is added dropwise using the complex compound presoma and reducing agent of silver simultaneously, the mode that is added dropwise is different from silver-colored source and is added dropwise
Mode into reducing agent solution is added drop-wise to the mode in silver-colored source solution also different from reducing agent, and it is excessive to avoid the silver-colored source in part
Or local reduction agent excessively leads to the side effect of the excessively high generation of local concentration, to preferably control the growth side of silver nanoparticle crystalline substance
Formula.
Beneficial effects of the present invention:
The present invention reacts in aqueous solution at normal temperatures and pressures, does not have to high molecular polymer as protective agent and dispersing agent,
Make reducing agent with hydrazine hydrate, restores the complex compound presoma of silver.Preparation method is simple, avoids high molecular polymer on silver powder surface
Residual, the flower shape micro-nano silver granule-morphology of preparation is regular, particle diameter distribution uniformly, good dispersion, size be controllable, yield
It is high.The dosage of raw material is adjusted by using different complexing agents using method of the invention, controls reaction temperature, raw material adds
Enter the reaction conditions such as speed, the diameters of the controllable flower-shaped spherical nano-Ag particles being synthetically prepared 200nm~2000nm it
Between.
Detailed description of the invention
Fig. 1 is the low enlargement ratio scanning electron microscope (SEM) photograph of flower shape ball shaped nano Argent grain made from embodiment 1.
Fig. 2 is the high magnification scanning electron microscope (SEM) photograph of flower shape ball shaped nano Argent grain made from embodiment 2.
Fig. 3 is the low enlargement ratio scanning electron microscope (SEM) photograph of flower shape ball shaped nano Argent grain made from embodiment 3.
Fig. 4 is the high magnification scanning electron microscope (SEM) photograph of flower shape ball shaped nano Argent grain made from embodiment 4.
Fig. 5 is the high magnification scanning electron microscope (SEM) photograph of sample made from comparative example 1.
Fig. 6 is the high magnification scanning electron microscope (SEM) photograph of sample made from comparative example 2.
Fig. 7 is the low enlargement ratio scanning electron microscope (SEM) photograph of sample made from comparative example 3.
Fig. 8 is the high magnification scanning electron microscope (SEM) photograph of sample made from comparative example 4.
Specific embodiment:
Below by specific embodiment and in conjunction with attached drawing, the invention will be further described, but not limited to this.
Uniform dark brown solution is obtained in embodiment after reduction reaction, flower-like nanometer Argent grain is obtained after processing.
Processing step is as follows: with washing 3 times three times, removing upper liquid after sedimentation, is freeze-dried up to flower shape micro-nano silver particle.
Embodiment 1
It weighs trisodium citrate to be dissolved in deionized water, compound concentration is the trisodium citrate aqueous solution of 0.11g/mL.It will
Silver nitrate is dissolved in deionized water, and compound concentration is the silver nitrate aqueous solution of 0.5g/mL.Take 40mL trisodium citrate aqueous solution with
10mL silver nitrate aqueous solution first mixes, and stirs 30min, obtains the complex solution of uniform silver, for the precursor solution of silver.It will
Hydrazine hydrate is added in deionized water, the hydrazine hydrate reduction agent solution that compound concentration is 6%.Then 50mL reducing agent solution and 50mL
The precursor solution of silver is added drop-wise in the water of 200mL with metering pump carries out hybrid reaction, feed time 15min, then in temperature
At 10 DEG C of degree temperature, under 600 revs/min of stirrings, continues to be stirred to react 60min, obtain uniform dark brown solution, after post-processing
To Argent grain, such as Fig. 1, shape is flower shape micro-nano granules, and good dispersion, particle diameter distribution is uniform, average particle size 550nm.
Embodiment 2
It weighs trisodium citrate to be dissolved in deionized water, compound concentration is the trisodium citrate aqueous solution of 0.16g/mL.It will
Silver nitrate is dissolved in deionized water, and compound concentration is the silver nitrate aqueous solution of 0.1g/mL.Take 50mL trisodium citrate aqueous solution with
50mL silver nitrate aqueous solution first mixes, and stirs 30min, obtains the complex solution of uniform silver, for the precursor solution of silver.It will
Hydrazine hydrate is added in deionized water, the hydrazine hydrate reduction agent solution that compound concentration is 4%.Then 100mL reducing agent solution with
The precursor solution of 100mL silver is added drop-wise in the water of 100mL with metering pump carries out hybrid reaction, feed time 25min, then
At 20 DEG C of temperature, under 600 revs/min of stirrings, continues to be stirred to react 60min, uniform dark brown solution is obtained, after post-processing
Argent grain, such as Fig. 2 are obtained, shape is flower shape micro-nano granules, and good dispersion, particle diameter distribution is uniform, and average particle size is
750nm。
Embodiment 3
It weighs disodium ethylene diamine tetraacetate to be dissolved in deionized water, compound concentration is the ethylenediamine tetra-acetic acid two of 0.06g/mL
Sodium water solution.Silver nitrate is dissolved in deionized water, compound concentration is the silver nitrate aqueous solution of 0.1g/mL.Take 60mL ethylenediamine
Tetraacethyl disodium aqueous solution is first mixed with 50mL silver nitrate aqueous solution, stirs 30min, obtains the complex solution of uniform silver,
For the precursor solution of silver.Hydrazine hydrate is added in deionized water, the hydrazine hydrate reduction agent solution that compound concentration is 5%.Then
The precursor solution of 110mL reducing agent solution and 110mL silver is added drop-wise in the water of 80mL with metering pump carries out hybrid reaction, feeds
Time is 30min, then at 15 DEG C of temperature, under 600 revs/min of stirrings, continues to be stirred to react 60min, reaction terminates.Then
It washes 2 times three times, Argent grain, such as Fig. 3 is obtained after post-processing, shape is flower shape micro-nano granules, good dispersion, particle diameter distribution
Uniformly, average particle size 900nm.
Embodiment 4
It weighs citric acid to be dissolved in deionized water, obtains the aqueous citric acid solution that concentration is 0.18g/mL.Silver nitrate is molten
In deionized water, the silver nitrate aqueous solution that concentration is 0.14g/mL is obtained.Take 35mL aqueous citric acid solution and 35mL silver nitrate
Aqueous solution first mixes, and stirs 30min, obtains the complex solution of uniform silver, for the precursor solution of silver.Hydrazine hydrate is added
In deionized water, the hydrazine hydrate reduction agent solution that concentration is 5% is obtained.Then the presoma of 70mL reducing agent solution and 70mL silver
Solution is added drop-wise in the water of 160mL with metering pump and carries out hybrid reaction, feed time 20min, then at 20 DEG C of temperature temperature,
Under 600 revs/min of stirrings, continues to be stirred to react 60min, obtain uniform dark brown solution, Argent grain is obtained after post-processing, such as
Fig. 4, shape are flower shape micro-nano granules, and good dispersion, particle diameter distribution is uniform, and average particle size is 1.3 μm.
Comparative example 1
Remaining is same as Example 2 for the synthetic method of this comparative example, the difference is that feed time:
100mL reducing agent solution is added drop-wise in the water of 100mL with metering pump with the precursor solution of 100mL silver and is mixed
Reaction, feed time 30s under 600 revs/min of stirrings, continue to be stirred to react 60min, obtain palm fibre then at 20 DEG C of temperature
Dark solution, SEM result such as Fig. 5 of product, what is obtained is rough particle.
Comparative example 2
Remaining is same as Example 2 for the synthetic method of this comparative example, the difference is that feed time:
100mL reducing agent solution is added drop-wise in the water of 100mL with metering pump with the precursor solution of 100mL silver and is mixed
Reaction, feed time 120min under 600 revs/min of stirrings, continue to be stirred to react 60min, obtain then at 20 DEG C of temperature
To dark brown solution, SEM result such as Fig. 6 of product, what is obtained be into large stretch of petal-shaped pattern, rather than flower shape, micro-nano
The sphericity of meter Yin is bad.
Comparative example 3
Remaining is same as Example 2 for the synthetic method of this comparative example, the difference is that reducing agent:
It weighs trisodium citrate to be dissolved in deionized water, compound concentration is the trisodium citrate aqueous solution of 0.16g/mL.It will
Silver nitrate is dissolved in deionized water, and compound concentration is the silver nitrate aqueous solution of 0.1g/mL.Take 50mL trisodium citrate aqueous solution with
50mL silver nitrate aqueous solution first mixes, and stirs 30min, obtains the complex solution of uniform silver, for the precursor solution of silver.It will
Ascorbic acid is added in deionized water, and compound concentration is the ascorbic acid reducing agent solution of 0.14g/mL.Then 100mL reducing agent
The precursor solution of solution and 100mL silver is added drop-wise in the water of 100mL with metering pump carries out hybrid reaction, and feed time is
25min under 600 revs/min of stirrings, continues to be stirred to react 60min, obtains dark brown solution then at 20 DEG C of temperature, rear to locate
Reason obtains Argent grain, such as Fig. 7, and flower shape Argent grain is less, mainly some irregular particles of pattern.
The reaction system for using ascorbic acid as reducing agent is acidity, and pH value is 3 or so, makees reducing agent different from hydrazine hydrate
Alkaline reaction system, pH value 8-9.Different acid-base property system needs are just adjustable under suitable conditions prepares target
Pattern.
Comparative example 4
Remaining is same as Example 2 for the synthetic method of this comparative example, the difference is that PVP is added in system:
It weighs trisodium citrate to be dissolved in deionized water, compound concentration is the trisodium citrate aqueous solution of 0.16g/mL.It will
Silver nitrate is dissolved in deionized water, and compound concentration is the silver nitrate aqueous solution of 0.1g/mL.Take 50mL trisodium citrate aqueous solution with
50mL silver nitrate aqueous solution first mixes, and stirs 30min, obtains the complex solution of uniform silver, for the precursor solution of silver.It will
Hydrazine hydrate is added in deionized water, the hydrazine hydrate reduction agent solution that compound concentration is 4%.Then 100mL reducing agent solution with
The precursor solution of 100mL silver is added drop-wise in the water of the 100mL containing mass fraction 5.2%PVP with metering pump mix instead
It answers, feed time 25min, then at 20 DEG C of temperature, under 600 revs/min of stirrings, continues to be stirred to react 60min, obtain palm fibre
Dark solution obtains Argent grain, such as Fig. 8 after post-processing, obtained pattern is the accumulation body of sheet and particle.Although PVP is added
It can play the role of dispersion, but the presence of PVP can induce the same sex to grow, so that it is more to grow up to particle.
Claims (10)
1. the method for preparing micro-nano silver particle in water solution system, comprises the following steps that
Silver salt solution and complexing agent aqueous solution are mixed to prepare to the complex compound precursor solution of silver, then with reducing agent aqueous solution
Mixing is added dropwise simultaneously, carries out a step reduction reaction, obtains micro-nano silver particle.
2. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that described
Silver salt is silver nitrate, silver acetate, silver sulfate.
3. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that silver salt water
The concentration of solution is 0.01-8g/mL, preferably 0.05-1g/mL.
4. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that described
Complexing agent is citric acid, trisodium citrate, ethylenediamine tetra-acetic acid or disodium ethylene diamine tetraacetate.
5. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that complexing agent
The concentration of aqueous solution is 0.02-0.2g/mL.
6. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that complexing agent
It is 0.1-10 with the molar ratio of silver salt ,=preferred 0.2-5.
7. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that described
Reducing agent is hydrazine hydrate；The concentration of reducing agent aqueous solution is 1%-30%, preferably 2%-10%.
8. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that be added dropwise mixed
During conjunction, complex compound precursor solution and reducing agent aqueous solution are added drop-wise in water simultaneously and carry out hybrid reaction.
9. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that described
It is 5-60min, preferably 10-30min that mixed feed time, which is added dropwise,.
10. preparing the method for micro-nano silver particle in water solution system according to claim 1, which is characterized in that described
The time of reduction reaction is 10-300min, preferably 30-120min.
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