CN103722181A - Method for preparing nano silver powder by using dispersing agent through liquid-phase reduction method - Google Patents
Method for preparing nano silver powder by using dispersing agent through liquid-phase reduction method Download PDFInfo
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- CN103722181A CN103722181A CN201410027367.2A CN201410027367A CN103722181A CN 103722181 A CN103722181 A CN 103722181A CN 201410027367 A CN201410027367 A CN 201410027367A CN 103722181 A CN103722181 A CN 103722181A
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Abstract
The invention discloses a method for preparing nano silver powder by using a dispersing agent through a liquid-phase reduction method. The method comprises the following steps: adding dimethyl succinate as the dispersing agent to a silver-nitrate aqueous solution and a reducing agent, and carrying out liquid-phase reduction reaction to prepare the nano silver powder. The method disclosed by the invention has the main advantages that in the preparation process, the dimethyl succinate as the dispersing agent is added to obtain the nano silver powder with uniform distribution, small particle size and low aggregation degree, the aggregation degree of particles is reduced by the dispersing agent and the size of the secondary particles is reduced, so that the nano silver powder is obtained; when the adding amount of the dimethyl succinate is 2% of the mass of silver nitrate, the silver powder particles with the particle-diameter range being 30-70nm can be prepared; the used reactants are few, the steps are simple, the reaction speed is high and the reduction rate is 100%.
Description
Technical field
The invention belongs to solar cell size field, be specifically related to a kind of preparation method of raw material nano-silver powder of solar battery electrode slurry.
Background technology
Along with the high speed development of information industry, electric slurry is being played the part of important role as its critical material.Therefore high-performance, raw material will improve the competitiveness of electronic product greatly cheaply, also must become the necessary condition of electric slurry self industry development.The main component of the front of solar cell and back silver slurry is argent at present, and the performance of silver powder has conclusive impact to the performance of electrode slurry.
In prior art, there is the liquid phase reduction of employing to prepare silver powder.But the silver powder making is all generally micron-sized.But the high speed development along with information industry, requirement for electrode slurry is also more and more higher, therefore electrode slurry is also more and more pursued Nano grade for the requirement of main raw material(s) silver powder, and the performance of nano-silver powder can be far away higher than micron order silver powder, thereby affects the performance of electrode slurry.And affect the principal element of silver powder particle diameter except character, reaction temperature, addition manner, whipped form and the degree of reactant, the conditions such as use of interfacial agent, also due to comparatively serious gathering easily occurring between silver powder particles.Because the bigger serface of nano material especially nano-powder makes them have high activity energy, normally several or a plurality of grain colonies are got together, and become particle.When being of a size of 0-100nm, the aggregate of polycrystal powder is only the nano particle that performance is good.And the silver powder particles size that prior art liquid phase reduction makes is much larger than 100nm.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of liquid phase reduction uses dispersant to prepare the method for nano-silver powder, the method can make the nano-silver powder of particle diameter 30-70nm, and the method reactant used is few, step is simple, reaction speed is fast, percent reduction 100%.
The present invention for the technical scheme that solves its technical problem and adopt is:
Liquid phase reduction is used dispersant to prepare a method for nano-silver powder, and adopting silver nitrate aqueous solution and reducing agent and adding dimethyl succinate is that dispersant carries out Liquid reduction reaction process and makes nano-silver powder.
Say further, described silver nitrate aqueous solution is silver ammino solution.
Say further, described reducing agent is one or both in ascorbic acid and hydroquinones.
Furthermore, described silver nitrate aqueous solution is that silver nitrate content is the silver ammino solution of 20-100g/L, described reducing agent is that concentration is at least one in the ascorbic acid of 90%-100% and hydroquinones that concentration is 90%-100%, and reaction temperature is 30 ℃-45 ℃ (preferably 40 ℃).
Preferably, adopt the silver ammino solution that silver nitrate content is 50g/L, and pH value=10.5 of described silver ammino solution.
Preferably, the addition of dimethyl succinate is the 1%-5% of silver nitrate quality and does not contain 1% and 5%.
Best, the addition of dimethyl succinate is 2% of silver nitrate quality.
Say further, prepared nano-silver powder particle size is 30-70nm.
Preferably, silver nitrate aqueous solution, reducing agent and dimethyl succinate are added in filter simultaneously and start immediately suction filtration, the filter opening of the filter membrane of filter is of a size of 100nm.
The invention has the beneficial effects as follows: it is raw material that the present invention adopts silver nitrate aqueous solution, adopt at least one in ascorbic acid and hydroquinones is reducing agent, and to adopt dimethyl succinate be that dispersant is prepared nano-silver powder, can make the silver powder particles that particle diameter is distributed as 30-70nm, the method reactant used is few, step is simple, reaction speed is fast, percent reduction 100%.
Accompanying drawing explanation
Fig. 1 is the ESEM contrast photo that adds nano-Ag particles prepared by different proportion dimethyl succinate;
Wherein, a figure does not add dispersant to make silver powder particles size 200-800nm; B figure adds 1% dispersant to make silver powder particles size 150-400nm; C figure adds 2% dispersant to make silver powder particles size 30-70nm; D figure adds 5% dispersant to make silver powder particles size 200-500nm.
The specific embodiment
Embodiment:
Comparative analysis reaction when the inventive method does not add dispersant: the silver ammino solution that is 50g/L with pH=10.5 and silver nitrate content, concentration is the VC(ascorbic acid of 90%-100%) be reducing agent, in the situation of 40 ℃, silver ammino solution and reductant solution are directly poured in filter simultaneously, 0.1 μ m filter membrane for filter, start immediately suction filtration, time is no more than 2 seconds, in filtrate, without Ag, exist, illustrate that percent reduction has reached 100%, this result shows, this reduction reaction speed is exceedingly fast, and in complete mixed moment reaction, completes.
The formation mechanism of silver powder is to infer like this, Ag
+size exist
(dust) is 0.1nm, so AgNO3 solution is transparent, reducing agent adds fashionable, Ag
+obtaining an electron production nucleus, is crystal grain (this crystal grain becomes primary particle) by nuclei growth, then by crystal grain, is condensed into the spheric granules (this spheric granules is offspring) of 1 μ m left and right.
In order to prove above-mentioned inferring, silver powder has been carried out to X-diffraction, with the brief summary crystal face diffraction maximum of Ag (2 θ: near the diffraction maximum being 38.1 ℃) half amplitude, according to Scherrer(Scherrer) equation, calculate the crystallite dimension of silver powder, equation is as follows:
D=Kλ/βcosθ
Wherein D is crystallite dimension, λ is incident ray wavelength, β is diffraction maximum half amplitude, θ is the angle of diffraction, K is Scherrer constant (0.9), to above-mentioned standard VC, at pH=10.5 and temperature, be the spheric granules (offspring) about the 1 μ m obtaining after reduction under 40 ℃ of conditions, the size of the crystal grain calculating after X-diffraction (primary particle) is 20nm left and right.
Therefore, obtain the silver ammino solution that conclusion adopts pH=10.5, VC(ascorbic acid) be reducing agent, in the situation of 40 ℃, it is 20nm left and right crystal grain (primary particle) that reduction before this forms size, by crystal grain (primary particle), be agglomerated into again the spheric granules (offspring) of 1 μ m left and right, percent reduction 100%, and reaction speed is exceedingly fast.
And crucial part of the present invention is just: in above-mentioned preparation process, add dimethyl succinate dispersant and obtain be evenly distributed, particle size is little, degree of aggregation is low nano-silver powder, with dispersant, reduce particle agglomeration degree, make offspring size reduction, thereby obtain nano-silver powder.; the silver ammino solution that is 50g/L with pH=10.5 and silver nitrate content; concentration is 90%-100%VC(ascorbic acid) be reducing agent; in the situation of 40 ℃; silver ammino solution, reductant solution and dispersant dimethyl succinate are directly poured in filter simultaneously; 0.1 μ m filter membrane for filter, starts suction filtration immediately.
The mechanism of action of dispersant can be summarized as sterically hindered effect and electrostatic stabilization effect.Sterically hindered effect is due in nucleation and growth course, and the long-chain molecule of organic dispersing agent makes silver powder form thin organic film around, and particle and particle are kept apart, and is difficult to assemble.And electrostatic stabilization effect is to form a charged protective barrier around because dispersant makes particle, the double-deck particle that surrounds, produces electrostatic repulsion between particle, make dispersion stable.For dispersant dimethyl succinate, its peptizaiton is due to sterically hindered effect.When silver powder particle has adsorbed after dispersant, particle size obviously reduces.
When dispersant adds in solution, the acidity of solution increases, and this is because the hydrogen ion in dimethyl succinate is adsorbed to around silver powder particle, makes silver powder particle positively charged.Due to the existence of Coulomb force, the silver powder particle of positively charged has attracted the electronegative long-chain molecule of dimethyl succinate, because sterically hindered effect makes silver powder separate particles, comes.Now, adsorbed the uniform growth that the silver powder particle of dispersant can be stable.The silver powder particle that does not add dispersant is unstable, there is no electrostatic repulsion or sterically hindered effect between silver powder particle, due to surface tension, reunites together mutually.
But the action effect of dimethyl succinate can't be always remarkable along with the increase of its addition, when dispersant adds when appropriate, silver powder particle surface is surrounded by the strand of dimethyl succinate completely, and silver powder particle is separated completely.Yet when dispersant is excessive, silver powder particle, after adsorbing excessive dispersant, bridging effect occurs, thereby causes the coagulation of micelle, particle size is increased.
Therefore, for the addition of dimethyl succinate dispersant, must can be determined by unlimited test.Because test number (TN) is more, in the present invention, can not exemplify one by one, therefore only take test end value and optimum value (addition of dimethyl succinate be silver nitrate quality 1%, 5%, 2%), confirm the impact of the addition of dimethyl succinate on dispersion effect as example.
As shown in a figure in Fig. 1, while adding dispersant, particle aggregation is not serious, and it is irregularly shaped that particle is, and distribution of sizes is extremely inhomogeneous, and particle size is 200-800nm; As shown in b figure in Fig. 1, when adding 1% dimethyl succinate, obtained the circular particle that is of a size of 150-400nm; As shown in c figure in Fig. 1, when the ratio of dispersant dimethyl succinate is 2%, particle size is reduced to 30-70nm; Yet as shown in d figure in Fig. 1, when dispersant addition continues to increase to 5% time, particle size but increases to 200-500nm, and occur to put up a bridge and reunite.As can be seen here, the addition of dispersant has a great impact particle size.
When adding 1% dimethyl succinate, owing to disperseing, dosage is less, and the negative electrical charge macromolecular chain of dimethyl succinate is adsorbed to around a part of silver powder particle, can not make silver powder separate particles completely.When adding 2% dispersant, silver powder particle surface is surrounded by the strand of dimethyl succinate completely, and silver powder particle is separated completely.Yet when disperseing dosage to be 5%, silver powder particle, after adsorbing excessive dispersant, bridging effect occurs, thereby causes the coagulation of micelle, particle size is increased.Visible dispersant addition makes particle size different, the 1%-5%(that effective addition of dispersant dimethyl succinate should be controlled at silver nitrate quality does not comprise endpoints thereof), optimized percentage is that the 2%(of silver nitrate quality now can obtain and be evenly distributed, particle size is little, the silver nano-grain of the 30-70nm that degree of aggregation is low).
Should be understood that above-described embodiment is only not used in and limits the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the claims in the present invention book limited range equally.
Claims (9)
1. liquid phase reduction is used dispersant to prepare a method for nano-silver powder, it is characterized in that: adopting silver nitrate aqueous solution and reducing agent and adding dimethyl succinate is that dispersant carries out Liquid reduction reaction process and makes nano-silver powder.
2. liquid phase reduction as claimed in claim 1 is used dispersant to prepare nano-silver powder, it is characterized in that: described silver nitrate aqueous solution is silver ammino solution.
3. liquid phase reduction as claimed in claim 1 is used dispersant to prepare nano-silver powder, it is characterized in that: described reducing agent is one or both in ascorbic acid and hydroquinones.
4. liquid phase reduction as claimed in claim 1 is used dispersant to prepare nano-silver powder, it is characterized in that: described silver nitrate aqueous solution is that silver nitrate content is the silver ammino solution of 20-100g/L, described reducing agent is that concentration is at least one in the ascorbic acid of 90%-100% and hydroquinones that concentration is 90%-100%, and reaction temperature is 30 ℃-45 ℃.
5. liquid phase reduction as claimed in claim 4 is used dispersant to prepare nano-silver powder, it is characterized in that: adopt the silver ammino solution that silver nitrate content is 50g/L, and pH value=10.5 of described silver ammino solution.
6. liquid phase reduction as claimed in claim 4 is used dispersant to prepare nano-silver powder, it is characterized in that: the addition of dimethyl succinate is the 1%-5% of silver nitrate quality and does not contain 1% and 5%.
7. liquid phase reduction as claimed in claim 6 is used dispersant to prepare nano-silver powder, it is characterized in that: the addition of dimethyl succinate is 2% of silver nitrate quality.
8. liquid phase reduction as claimed in claim 7 is used dispersant to prepare nano-silver powder, it is characterized in that: prepared nano-silver powder particle size is 30-70nm.
9. liquid phase reduction as claimed in claim 4 is used dispersant to prepare nano-silver powder, it is characterized in that: silver nitrate aqueous solution, reducing agent and dimethyl succinate are added in filter simultaneously and start immediately suction filtration, and the filter opening of the filter membrane of filter is of a size of 100nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105880634A (en) * | 2016-07-01 | 2016-08-24 | 中国科学院化学研究所 | Preparation method of flake nanometer silver powder |
| CN108115150A (en) * | 2017-12-20 | 2018-06-05 | 南京医科大学第二附属医院 | A kind of preparation method of the nano silver of size adjustable |
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| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| KR20080035315A (en) * | 2006-10-19 | 2008-04-23 | 삼성전기주식회사 | Silver nano-particles and preparation method thereof |
| CN101618462A (en) * | 2008-07-03 | 2010-01-06 | 东进世美肯株式会社 | Method for manufacturing metal nanometer particle |
| CN101856726A (en) * | 2010-06-17 | 2010-10-13 | 哈尔滨得意药业有限责任公司 | Method for preparing multifunctional nano silver solution |
| CN102513544A (en) * | 2011-12-13 | 2012-06-27 | 江苏大学 | Method for preparing nanometer silver sol |
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Patent Citations (5)
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| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| KR20080035315A (en) * | 2006-10-19 | 2008-04-23 | 삼성전기주식회사 | Silver nano-particles and preparation method thereof |
| CN101618462A (en) * | 2008-07-03 | 2010-01-06 | 东进世美肯株式会社 | Method for manufacturing metal nanometer particle |
| CN101856726A (en) * | 2010-06-17 | 2010-10-13 | 哈尔滨得意药业有限责任公司 | Method for preparing multifunctional nano silver solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105880634A (en) * | 2016-07-01 | 2016-08-24 | 中国科学院化学研究所 | Preparation method of flake nanometer silver powder |
| CN108115150A (en) * | 2017-12-20 | 2018-06-05 | 南京医科大学第二附属医院 | A kind of preparation method of the nano silver of size adjustable |
| CN108115150B (en) * | 2017-12-20 | 2023-08-08 | 南京医科大学第二附属医院 | Preparation method of nano silver with adjustable size |
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