CN103042230A - Preparation method for micron spherical silver powder for electronic paste - Google Patents
Preparation method for micron spherical silver powder for electronic paste Download PDFInfo
- Publication number
- CN103042230A CN103042230A CN2013100014103A CN201310001410A CN103042230A CN 103042230 A CN103042230 A CN 103042230A CN 2013100014103 A CN2013100014103 A CN 2013100014103A CN 201310001410 A CN201310001410 A CN 201310001410A CN 103042230 A CN103042230 A CN 103042230A
- Authority
- CN
- China
- Prior art keywords
- silver powder
- preparation
- ascorbic acid
- solution
- ball shape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a preparation method for micron spherical silver powder for electronic paste. The preparation method includes the steps of taking bovine serum albumin as a biological template (as a dispersant), adding alkaline silver salt solution and ascorbic acid to mix with the template, stirring the template to realize uniform reaction, and drying the precipitation to obtain the micron silver powder which is of high sphericity, smooth surface and narrow particle size distribution range. The spherical silver powder prepared by the method is of granularity controllable within the range of 0.2-1 micrometer. Furthermore, the spherical silver powder is safe, environment-friendly, low in production cost, simple in process, short in preparation cycle and easy to be subjected to mass production.
Description
Technical field
The invention belongs to electric slurry manufacturing technology field, be specifically related to the preparation method that a kind of micron order electric slurry is used ball shape silver powder.
Background technology
Developing rapidly of electronics and information industry driven the development of electric slurry and super fine silver powder industry.Electric slurry is a kind of high-tech electronics functional material that integrates metallurgy, chemical industry, electronic technology, be to make one of requisite material of electronic devices and components, be widely used in and make in thick film integrated circuit, multilayer ceramic capacitor, electrically conductive ink, electrode of solar battery and other electronic components.Yin Yin has optimum normal temperature electric conductivity and thermal conductivity and is widely used in the electronics industry, and electric slurry has received increasing concern with silver powder.
The key technical index such as the conductance after the quality of silver paste, the conductive silver paste film forming and compactness all are the performance decisions by super fine silver powder.The factors such as the shape of silver powder, granularity will affect the performance of silver slurry, so that the preparation of silver powder seems is particularly important.
Silver powder in the existing conductive silver paste generally adopts the liquid phase chemical reduction legal system for obtaining, but existing preparation technology is the process relative complex not only, manufacturing cycle is longer, environmental pollution is heavier, and the product that makes often is difficult to satisfy the requirement of subsequent applications on the performance characteristics such as purity, particle diameter, pattern.
Summary of the invention
The object of the present invention is to provide that a kind of particle size distribution range is narrow, dispersiveness is good, sphericity is high, any surface finish is good, and technical process is simple, manufacturing cycle short, the favorable reproducibility of preparation process, preparation Environmental security close friend's micron order electric slurry is with the preparation method of ball shape silver powder.
For achieving the above object, the technical solution used in the present invention is:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.02～0.8mol/L and the ascorbic acid solution C of 0.02～0.8mol/L, the bovine serum albumin of getting silver nitrate quality 5～15% is dissolved in and is mixed with mass fraction in the distilled water is 0.5%～2% solution B;
2) A solution is poured in the B solution, adding ammoniacal liquor adjusting starting ph is 8～10 again, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1～1.5 ︰ 1 adds ascorbic acid solution or ascorbic acid pressed powder fast, react after ten minutes, stop to stir, leave standstill, separate, wash rear drying finally by crossing after ultrasonic wave disperses, namely obtain micron spherical silver powder.
The mass concentration of described ammoniacal liquor is 25～28%.
Described ultrasonic dispersion is to adopt ultrasonic wave to process 6～10min.
Described washing is to adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time.
Described drying is at 50～60 ℃ of lower dry 4～8h.
Press the particle diameter of the prepared ball shape silver powder of preparation method of the present invention at 0.2～1 μ m, sphericity is high, and particle size distribution range is narrow, is particularly suitable for preparing the silver-colored ball shape silver powder of starching of electrode of solar battery and electrically conductive ink.
The present invention is dispersant with bovine serum albumin as biological template, and take ascorbic acid as reducing agent, reaction temperature is controlled at 15 ℃～30 ℃.Reaction temperature is all influential to the silver powder particles size that makes, surface smoothness, dispersiveness etc.Improving reaction temperature will make the speed of nucleation and growth all will increase, when reducing agent adds fashionable with fast speed, course of reaction acutely is unfavorable for obtaining the silver powder of surface smoothness and good uniformity, and temperature raises also has material impact to protein structure, when excess Temperature was found in experiment, silver powder sphericity and any surface finish can descend equally.Therefore, reaction temperature is unsuitable too high or too low, preferably maintains near 20 ℃.
Find that through experiment if liquor argenti nitratis ophthalmicus concentration is excessively low, an output of silver powder is very few, can not satisfy needs of production; Silver nitrate concentration excessive if (for example surpass 1mol/L), the reduction reaction process may be too violent, react inhomogeneous, causes easily that the silver powder surface topography for preparing is bright and clean not to broaden with particle size distribution range.Based on this, in above-mentioned preparation method's the step (1), the concentration of described liquor argenti nitratis ophthalmicus preferably is controlled at 0.02～0.8mol/L.
If the consumption of bovine serum albumin is very few, the silver powder sphericity that then prepares is bad, and agglomeration is to a certain degree arranged, and ball shape silver powder disperses inhomogeneous easily; If the consumption of bovine serum albumin is excessive, the silver powder particle diameter then constantly reduces, and it is irregular that pattern becomes easily, and simultaneously, bovine serum albumin is too much in the solution, makes the washing of silver powder become relatively difficult, has also improved preparation cost.Based on this, the amount of bovine serum albumin is controlled at 5%～15% of silver nitrate quality.
Same through the raising of experiment discovery along with silver nitrate concentration, pH value also must improve just can make the sphericity height, the high-quality silver powder of good dispersion is also found the addition manner of reducing agent to the impact of morphologies and granularity simultaneously, and preferential the employing fast of this experiment adds.
Compare with prior art, the inventive method has the following advantages or good effect:
1) do biological template (dispersant) with bovine serum albumin, dispersive property is good, and good water solubility is cheap, and nontoxic pollution-free is gentle to reaction environment, is convenient to cleaning and filtering.
2) traditional synthetic method generally adopts high temperature, surfactant and organic solvent etc., this and not meet the micro/nano material synthetic method simple, process environmental protection, extensive synthetic development trend.The present invention adopts bovine serum albumin as biological template (dispersant), utilizes the functional groups such as the structural hydroxyl of bovine serum albumin and sulfydryl and chemical bond that some inorganic zwitterions are had the silver-colored particle that stronger affinity is induced the synthesizing spherical structure.
3) size of silver powder particles and the uniformity are obvious on the electrical property impact of silver slurry, ball shape silver powder smooth surface, good uniformity, good dispersion, the glossiness of this invention preparation are good, impurity content is little, and particle diameter is distributed in 0.2～1 μ m, can finely be useful in the silver paste of solar cells material.
Description of drawings
Fig. 1 is the SEM photo of the ball shape silver powder of the embodiment of the invention 1 preparation.
Fig. 2 is the SEM photo of the ball shape silver powder of the embodiment of the invention 3 preparations.
Fig. 3 is the XRD figure of the silver powder that makes of the embodiment of the invention 4.
The specific embodiment
Following embodiment implements under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.02mol/L and the ascorbic acid solution C of 0.02mol/L, the bovine serum albumin of getting silver nitrate quality 5% is dissolved in and is mixed with solution B in the distilled water;
2) under 15 ℃, A solution is poured in the B solution, adding mass concentration again and be 25～28% ammoniacal liquor, to regulate starting ph be 8, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1:1 adds ascorbic acid solution C fast, react after ten minutes, stop to stir, after leaving standstill, separate, adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time behind the mistake ultrasonic wave dispersion 6min, descend dry 8h at 50 ℃, namely obtain the ball shape silver powder that average grain diameter is 0.96 μ m, as shown in Figure 1.
Embodiment 2:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.04mol/L and the ascorbic acid solution C of 0.08mol/L, the bovine serum albumin of getting silver nitrate quality 8% is dissolved in and is mixed with solution B in the distilled water;
2) under 20 ℃, A solution is poured in the B solution, adding mass concentration again and be 25～28% ammoniacal liquor, to regulate starting ph be 9, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1.2 ︰ 1 adds ascorbic acid solution C fast, react after ten minutes, stop to stir, after leaving standstill, separate, adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time behind the mistake ultrasonic wave dispersion 8min, descend dry 6h at 55 ℃, namely obtain the ball shape silver powder that average grain diameter is 0.53 μ m.
Embodiment 3:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.8mol/L and the ascorbic acid solution C of 0.8mol/L, the bovine serum albumin of getting silver nitrate quality 10% is dissolved in and is mixed with solution B in the distilled water;
2) under 25 ℃, A solution is poured in the B solution, adding mass concentration again and be 25～28% ammoniacal liquor, to regulate starting ph be 8.5, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1.4 ︰ 1 adds ascorbic acid solution C fast, react after ten minutes, stop to stir, after leaving standstill, separate, adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time behind the mistake ultrasonic wave dispersion 10min, descend dry 7h at 52 ℃, namely obtain the ball shape silver powder that average grain diameter is 0.34 μ m, as shown in Figure 2.
Embodiment 4:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.5mol/L, the ascorbic acid solution C of 0.8mol/L, the bovine serum albumin of getting silver nitrate quality 12% is dissolved in and is mixed with solution B in the distilled water;
2) under 20 ℃, A solution is poured in the B solution, adding mass concentration again and be 25～28% ammoniacal liquor, to regulate starting ph be 9.5, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1.5 ︰ 1 adds ascorbic acid solid solution C fast, react after ten minutes, stop to stir, after leaving standstill, separate, adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time behind the mistake ultrasonic wave dispersion 7min, descend dry 5h at 58 ℃, namely obtain the ball shape silver powder that average grain diameter is 0.88 μ m, its XRD as shown in Figure 3.
Embodiment 5:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.5mol/L, the bovine serum albumin of getting silver nitrate quality 15% is dissolved in and is mixed with solution B in the distilled water;
2) under 30 ℃, A solution is poured in the B solution, adding mass concentration again and be 25～28% ammoniacal liquor, to regulate starting ph be 10, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1.3 ︰ 1 adds the ascorbic acid pressed powder fast, react after ten minutes, stop to stir, after leaving standstill, separate, adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time behind the mistake ultrasonic wave dispersion 9min, descend dry 4h at 60 ℃, namely obtain the ball shape silver powder that average grain diameter is 0.21 μ m.
Claims (5)
1. a micron order electric slurry is characterized in that may further comprise the steps with the preparation method of ball shape silver powder:
1) respectively with the liquor argenti nitratis ophthalmicus A of distilled water preparation 0.02～0.8mol/L and the ascorbic acid solution C of 0.02～0.8mol/L, the bovine serum albumin of getting silver nitrate quality 5～15% is dissolved in and is mixed with mass fraction in the distilled water is 0.5%～2% solution B;
2) under 15 ℃～30 ℃, A solution is poured in the B solution, adding ammoniacal liquor adjusting starting ph is 8～10 again, after stirring again by ascorbic acid: the mol ratio of silver nitrate=1～1.5 ︰ 1 adds ascorbic acid solution or ascorbic acid pressed powder fast, react after ten minutes, stop to stir, leave standstill, separate, wash rear drying finally by crossing after ultrasonic wave disperses, namely obtain micron spherical silver powder.
2. micron order electric slurry according to claim 1 is with the preparation method of ball shape silver powder, and it is characterized in that: the mass concentration of described ammoniacal liquor is 25～28%.
3. micron order electric slurry according to claim 1 is with the preparation method of ball shape silver powder, and it is characterized in that: described ultrasonic dispersion is to adopt ultrasonic wave to process 6～10min.
4. micron order electric slurry according to claim 1 is with the preparation method of ball shape silver powder, and it is characterized in that: described washing is to adopt successively distilled water and absolute ethyl alcohol respectively to wash 1～3 time.
5. micron order electric slurry according to claim 1 is with the preparation method of ball shape silver powder, and it is characterized in that: described drying is at 50～60 ℃ of lower dry 4～8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100014103A CN103042230A (en) | 2013-01-05 | 2013-01-05 | Preparation method for micron spherical silver powder for electronic paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100014103A CN103042230A (en) | 2013-01-05 | 2013-01-05 | Preparation method for micron spherical silver powder for electronic paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103042230A true CN103042230A (en) | 2013-04-17 |
Family
ID=48055222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100014103A Pending CN103042230A (en) | 2013-01-05 | 2013-01-05 | Preparation method for micron spherical silver powder for electronic paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103042230A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722776A (en) * | 2015-04-09 | 2015-06-24 | 中南大学 | Synthesis process of silver nano clusters |
| CN104985190A (en) * | 2013-10-30 | 2015-10-21 | 江苏理工学院 | Synthetic method for flower type silver micron particles |
| CN106493389A (en) * | 2016-11-28 | 2017-03-15 | 上海无线电设备研究所 | A kind of preparation method of composite-grain diameter nano silver paste |
| CN107971502A (en) * | 2017-11-01 | 2018-05-01 | 昆明理工大学 | A kind of preparation method of high dispersiveness spherical silver powder |
| CN109887673A (en) * | 2018-12-27 | 2019-06-14 | 深圳市欧科力科技有限公司 | A kind of preparation method of composite conductive ceramic slurry |
| CN111659901A (en) * | 2020-06-17 | 2020-09-15 | 中船重工黄冈贵金属有限公司 | Preparation method of submicron silver powder |
| CN112098388A (en) * | 2020-08-18 | 2020-12-18 | 上海交通大学 | Preparation method and application for constructing micro-fluidic chip based on silver microsphere monolithic column |
| CN113118453A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Silver nano particle, preparation method thereof and photoinduction device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567628A (en) * | 1989-10-27 | 1996-10-22 | Abbott Laboratories | Surface-enhanced raman spectroscopy immunoassay method, composition and kit |
| US20060115495A1 (en) * | 2004-11-12 | 2006-06-01 | Board Of Regents, The University Of Texas System | Protein-noble metal nanoparticles |
| US20080081340A1 (en) * | 2006-09-29 | 2008-04-03 | Anil Patwardhan | Enzymatic and chemical method for increased peptide detection sensitivity using surface enhanced raman scattering (SERS) |
| CN102515276A (en) * | 2011-12-30 | 2012-06-27 | 四川大学 | Method for preparing manganese dioxide nanoparticles with bovine serum albumin as template |
| CN102689021A (en) * | 2012-07-02 | 2012-09-26 | 昆明理工大学 | Method for preparing micron spherical silver powder |
| CN102818826A (en) * | 2012-07-21 | 2012-12-12 | 上海师范大学 | Electrochemical cell-based biosensor based on nanometer Ag@BSA biomimetic interface and preparation method thereof |
-
2013
- 2013-01-05 CN CN2013100014103A patent/CN103042230A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567628A (en) * | 1989-10-27 | 1996-10-22 | Abbott Laboratories | Surface-enhanced raman spectroscopy immunoassay method, composition and kit |
| US20060115495A1 (en) * | 2004-11-12 | 2006-06-01 | Board Of Regents, The University Of Texas System | Protein-noble metal nanoparticles |
| US20080081340A1 (en) * | 2006-09-29 | 2008-04-03 | Anil Patwardhan | Enzymatic and chemical method for increased peptide detection sensitivity using surface enhanced raman scattering (SERS) |
| CN102515276A (en) * | 2011-12-30 | 2012-06-27 | 四川大学 | Method for preparing manganese dioxide nanoparticles with bovine serum albumin as template |
| CN102689021A (en) * | 2012-07-02 | 2012-09-26 | 昆明理工大学 | Method for preparing micron spherical silver powder |
| CN102818826A (en) * | 2012-07-21 | 2012-12-12 | 上海师范大学 | Electrochemical cell-based biosensor based on nanometer Ag@BSA biomimetic interface and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| AJAY V.SINGH等: ""Synthesis of gold, silver and their alloy nanoparticles using bovine serum albumin as foaming and stabilizing agent"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| 王晓坡等: ""利用牛血清蛋白合成CdS纳米棒和网状纳米线"", 《物理化学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104985190A (en) * | 2013-10-30 | 2015-10-21 | 江苏理工学院 | Synthetic method for flower type silver micron particles |
| CN104985190B (en) * | 2013-10-30 | 2017-06-13 | 江苏理工学院 | A kind of synthetic method of flower-shaped silver-colored micron particles |
| CN104722776A (en) * | 2015-04-09 | 2015-06-24 | 中南大学 | Synthesis process of silver nano clusters |
| CN104722776B (en) * | 2015-04-09 | 2018-03-06 | 中南大学 | A kind of silver receives the synthesis technique of cluster |
| CN106493389A (en) * | 2016-11-28 | 2017-03-15 | 上海无线电设备研究所 | A kind of preparation method of composite-grain diameter nano silver paste |
| CN107971502A (en) * | 2017-11-01 | 2018-05-01 | 昆明理工大学 | A kind of preparation method of high dispersiveness spherical silver powder |
| CN107971502B (en) * | 2017-11-01 | 2020-07-31 | 昆明理工大学 | Preparation method of high-dispersity spherical silver powder |
| CN109887673A (en) * | 2018-12-27 | 2019-06-14 | 深圳市欧科力科技有限公司 | A kind of preparation method of composite conductive ceramic slurry |
| CN113118453A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Silver nano particle, preparation method thereof and photoinduction device |
| CN111659901A (en) * | 2020-06-17 | 2020-09-15 | 中船重工黄冈贵金属有限公司 | Preparation method of submicron silver powder |
| CN112098388A (en) * | 2020-08-18 | 2020-12-18 | 上海交通大学 | Preparation method and application for constructing micro-fluidic chip based on silver microsphere monolithic column |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103042230A (en) | Preparation method for micron spherical silver powder for electronic paste | |
| CN101716685B (en) | Method for preparing spherical superfine silver powder by using chemical reduction method | |
| CN102632248B (en) | Spherical silver powder and preparation method thereof | |
| CN101554664B (en) | Method for preparing nano-scale silver powder | |
| CN103100722B (en) | Preparation method of high tap density monodisperse silver powder | |
| CN103962570B (en) | A kind of preparation method of nano-nickel powder | |
| CN103231072A (en) | Preparation method of silicon dioxide/silver core-shell composite powder for high temperature electronic paste | |
| CN102407341A (en) | surface modified particle diameter mixed silver powder and preparation method thereof | |
| CN102000835A (en) | Method for preparing micron spherical silver powder | |
| CN107716944B (en) | The method that chemical method prepares nano-grade silver powder | |
| CN102220045A (en) | Low-temperature-sintered solvent-based nano-silver electroconductive ink and preparation process thereof | |
| CN105345023B (en) | The preparation method of the super fine silver powder of good dispersion | |
| CN103079726A (en) | Silver particles and a process for making them | |
| CN108672718A (en) | A kind of preparation method of the spherical silver powder of high specific area and its silver powder obtained | |
| CN104096850A (en) | Method for preparing superfine spherical silver powder by reducing silver-ammonia complex with aminophenol | |
| CN104084599A (en) | Method for producing ultrafine spherical silver powder for conductive silver paste | |
| CN108405869A (en) | A kind of preparation method of small particle flake silver powder | |
| CN102114546A (en) | Method for preparing spherical silver powder | |
| CN101745645B (en) | Preparation method of nano-copper-nickel alloy by liquid phase method | |
| CN116618675A (en) | Preparation method of low-temperature sintering silver powder for heterojunction solar cell | |
| CN103433502A (en) | High-dispersing silver powder and preparation method thereof | |
| CN107293410B (en) | A kind of CeO2The preparation method of the porous composite nano-microspheres of/Ni/NiO | |
| CN103624249A (en) | Preparation method of high-tap-density silver powder | |
| CN105081343B (en) | A kind of manufacture method of conductive silver powder for touch-screen UV type laser engraving silver pastes | |
| CN102746795A (en) | Polishing solution for printed circuit microsections and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130417 |