CN104001930B - The preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder - Google Patents
The preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder Download PDFInfo
- Publication number
- CN104001930B CN104001930B CN201410181549.5A CN201410181549A CN104001930B CN 104001930 B CN104001930 B CN 104001930B CN 201410181549 A CN201410181549 A CN 201410181549A CN 104001930 B CN104001930 B CN 104001930B
- Authority
- CN
- China
- Prior art keywords
- lead
- silver powder
- preparation
- powder
- silver
- 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.)
- Active
Links
Abstract
The present invention relates to the preparation method of a kind of high-temperature electronic slurry lead/galactic nucleus shell composite powder, belong to new material technology field.High dispersiveness spherical micron/submicron silver powder is first prepared by chemical reduction method, the silver powder of preparation is dispersed in water, then prepare with certain order the electroless lead plating liquid had good stability by a certain percentage, again silver powder solution is joined in the electroless lead plating solution of stirring, be settled out the lead/silver-colored composite particles of high-tap density, high conductivity and controlled morphology.The present invention first uses chemical preparation micron/submicron silver powder, and behind dust technology activation silver powder surface, the growth of subsequent chemistry lead plating is carried out in silver-colored core surfaces with regard to preferential, and can completely parcel Argent grain, thickness of coating is controlled.
Description
Technical field
The present invention relates to the preparation method of a kind of high-temperature electronic slurry lead/galactic nucleus shell composite powder, belong to new material technology field.
Background technology
Silver powder can be used for electronics industry and manufactures conductor thick film slurry.Thick film ink serigraphy is formed on substrate the pattern of conducting wire.Then these circuits are dry and roasting is volatilized and is removed liquid organic carrier, then sinters Argent grain.
More intensive and the more accurate electronic circuit of printed wire technical requirement, for meeting these requirements, the width of wire has become narrower, and spacing between wire is also less.The silver powder that forming intensive closelypacked fine rule road needs must be as far as possible close to the spheroid of the dense packing of single size.Such as solar cell is a kind of semiconductor devices that solar energy can be converted to electric energy, and under the condition of illumination, solar cell can generation current, to be got up by electric collecting and transfer out by grid line and electrode.Front electrode of solar battery and grid line all have conductive silver paste to be made by the technique such as serigraphy, low temperature drying, high temperature sintering of high-speed, high precision.Solar cell front side silver paste mainly contain silver powder, glass dust, additive and organic carrier four part composition.Wherein, the performance of silver powder is particularly important.But silver powder is expensive, if plate the thin lead of one deck at silver powder, so not only can reduce the cost of electric slurry, also can improve the surface topography of silver powder simultaneously and improve the tap density of powder.
The many methods being used for manufacturing silver powder at present can be applicable to manufacture silver powder.Such as, can adopt thermal decomposition method, electrochemical process, physical method are as atomization or grinding, and chemical reduction method.Voluminous powder that thermal decomposition method probably produces sponge matter, that reunite, and electrochemical process is produced as the larger powder of crystalline form.General employing physical method prepares sheeting and very large spheric granules.Chemical deposition produces the silver powder of certain size scope and shape.Silver powder for electronic application generally adopts liquid-phase reduction method to prepare.Silver powder can adopt chemical reduction method to prepare, and makes the aqueous solution of the soluble-salt of silver and suitable reducing agent react under the condition that can precipitate silver powder in the method.Inorganic reducing agent comprises hydrazine hydrate, sulphite and formates, and inorganic reducing agent may produce very thick, the in irregular shape powder of granularity, and this powder has large size distribution because of reuniting.Organic reducing agent is alcohols, sugar or aldehydes such as, and organic reducing can be used from reduction silver nitrate with alkali metal hydroxide one.Reduction reaction rate is very fast; Therefore be difficult to control, the powder of generation is polluted by residual alkali ions.Although the granularity of these powder is very little, the out-of-shape of these powder, broad particle distribution, can not well pile up.The silver powder display of these types is difficult to control sintering, the lack of resolution of wire in thick film conductor circuits.
Therefore, the present invention wishes the preparation method developing a kind of lead/galactic nucleus shell structure composite powder, and described composite powder can high degree of dispersion, high conductivity and high-tap density.Method of the present invention is a kind of method of reducing, high dispersiveness spherical micron/submicron silver powder is first prepared by chemical reduction method in the method, the silver powder of preparation is dispersed in water, then prepare with certain order the electroless lead plating liquid had good stability by a certain percentage, again silver powder solution is joined in the electroless lead plating solution of stirring, be settled out the lead/silver-colored composite particles of high-tap density, high conductivity and controlled morphology.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides the preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder, the composite powder that the method is prepared has the performances such as high degree of dispersion, high conductivity and high-tap density.
Technical scheme of the present invention is: first prepare high dispersiveness spherical micron/submicron silver powder by chemical reduction method, the silver powder of preparation is dispersed in water, then prepare with certain order the electroless lead plating liquid had good stability by a certain percentage, again silver powder solution is joined in the electroless lead plating solution of stirring, be settled out the lead/silver-colored composite particles of high-tap density, high conductivity and controlled morphology.Concrete preparation process comprises:
(1) take ascorbic acid as reducing agent, silver nitrate is silver salt, and PVP and PEG-4000 are dispersant, prepares polymolecularity micron/submicron ball shape silver powder, dry under vacuum after then being cleaned respectively with alcohol and distilled water successively by silver powder;
(2) first prepare sodium hypophosphite solution, then add pyrovinic acid, pyrovinic acid lead, EDTA, complexing agent A, ascorbic acid and thiocarbamide successively, obtained electroless lead plating liquid after fully dissolving;
(3) be 0.03 ~ 0.3mol/L dust technology washing activation step (1) dispersed micron/submicron ball shape silver powder of preparing by concentration, and then this silver powder to be dispersed in concentration be 4 × 10
-6~ 8 × 10
-4in the dispersant PVP of mol/L and PEG-4000 solution, then joined by this mixed solution in the chemical plating fluid in stirring and react 20 ~ 45 minutes, reaction temperature is 40 ~ 95 DEG C, and centrifugation is stand-by; Then use deionized water and alcohol centrifugal deposition and ultrasonic dispersion cycle to clean, remove reaction residue, finally obtain single dispersing lead/galactic nucleus shell composite powder.
In described step (1), the preparation of polymolecularity micron/submicron ball shape silver powder is that first compound concentration is the liquor argenti nitratis ophthalmicus of 0.25 ~ 1.5mol/L, concentration is the ascorbic acid solution of 0.3 ~ 4.5mol/L, then be that 0.01 ~ 0.1:1 gets the raw materials ready according to the mass ratio of dispersant and silver nitrate, dispersant is divided into two parts, add in liquor argenti nitratis ophthalmicus and ascorbic acid solution respectively, be 3 ~ 6 by ammoniacal liquor adjust ph, again liquor argenti nitratis ophthalmicus is poured in ascorbic acid solution, first stir 5 minutes with the speed being less than 50r/min, 15 ~ 25min is stirred again with the speed of 150 ~ 500r/min, centrifugation obtains dispersed micron/submicron ball shape silver powder.
Silver powder cleans 4 times respectively with alcohol and distilled water successively in described step (1), then drying 4 hours under vacuum condition at 50 DEG C.
The concrete composition of described electroless lead plating liquid is 4 ~ 25g/L sodium hypophosphite, 10 ~ 50g/L pyrovinic acid, 4 ~ 20g/L pyrovinic acid lead, 10 ~ 30g/LEDTA, 5 ~ 20g/L complexing agent A, 2 ~ 10g/L ascorbic acid and 10 ~ 80g/L thiocarbamide, often plants after the material added dissolves completely and add lower one again during preparative chemistry plating solution.
The invention has the beneficial effects as follows: the present invention first uses chemical preparation micron/submicron silver powder, behind dust technology activation silver powder surface, the growth of subsequent chemistry lead plating is carried out in silver-colored core surfaces with regard to preferential, and can completely parcel Argent grain, thickness of coating is controlled.Due to the stabilization of dispersant, the nucleocapsid composite powder good dispersion obtained.Silver powder sphere size is homogeneous, determines the dimensional homogeneity of nucleocapsid composite powder.Gained lead of the present invention/galactic nucleus shell composite powder can be used for the conductive phase of high-temperature electronic slurry.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
The preparation method of the high-temperature electronic slurry lead/galactic nucleus shell composite powder of embodiment 1 ~ 10 is:
(1) take ascorbic acid as reducing agent, silver nitrate is silver salt, PVP and PEG-4000 are dispersant, first compound concentration is the liquor argenti nitratis ophthalmicus of 0.25 ~ 1.5mol/L, concentration is the ascorbic acid solution of 0.3 ~ 4.5mol/L, then be that 0.01 ~ 0.1:1 gets the raw materials ready according to the mass ratio of dispersant and silver nitrate, dispersant is divided into two parts, add in liquor argenti nitratis ophthalmicus and ascorbic acid solution respectively, be 3 ~ 6 by ammoniacal liquor adjust ph, again liquor argenti nitratis ophthalmicus is poured in ascorbic acid solution, first stir 5 minutes with the speed being less than 50r/min, 15 ~ 25min is stirred again with the speed of 150 ~ 500r/min, centrifugation obtains dispersed micron/submicron ball shape silver powder, then silver powder is cleaned 4 times respectively with alcohol and distilled water successively, then at 50 DEG C under vacuum condition dry 4 hours,
(2) first prepare sodium hypophosphite solution, then add pyrovinic acid, pyrovinic acid lead, EDTA, complexing agent A, ascorbic acid and thiocarbamide successively, obtained electroless lead plating liquid after fully dissolving; The concrete composition of electroless lead plating liquid is 4 ~ 25g/L sodium hypophosphite, 10 ~ 50g/L pyrovinic acid, 4 ~ 20g/L pyrovinic acid lead, 10 ~ 30g/LEDTA, 5 ~ 20g/L complexing agent A, 2 ~ 10g/L ascorbic acid and 10 ~ 80g/L thiocarbamide, the concrete composition of electroless lead plating liquid is 4 ~ 25g/L sodium hypophosphite, 10 ~ 50g/L pyrovinic acid, 4 ~ 20g/L pyrovinic acid lead, 10 ~ 30g/LEDTA, 5 ~ 20g/L complexing agent A, 2 ~ 10g/L ascorbic acid and 10 ~ 80g/L thiocarbamide, often plants after the material added dissolves completely and add lower one again during preparative chemistry plating solution.
(3) be 0.03 ~ 0.3mol/L dust technology washing activation step (1) dispersed micron/submicron ball shape silver powder of preparing by concentration, and then this silver powder to be dispersed in concentration be 4 × 10
-6~ 8 × 10
-4in the dispersant PVP of mol/L and PEG-4000 solution, then joined by this mixed solution in the chemical plating fluid in stirring and react 20 ~ 45 minutes, reaction temperature is 40 ~ 95 DEG C, and centrifugation is stand-by; Then use deionized water and alcohol centrifugal deposition and ultrasonic dispersion cycle to clean, remove reaction residue, obtain single dispersing lead/galactic nucleus shell composite powder.Silver powder sphere size is homogeneous, determines the dimensional homogeneity of nucleocapsid composite powder.
The parameter distribution of table 1 detailed description of the invention 1 ~ 10
Above the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (4)
1. a preparation method for high-temperature electronic slurry lead/galactic nucleus shell composite powder, is characterized in that concrete steps comprise:
(1) take ascorbic acid as reducing agent, silver nitrate is silver salt, and PVP and PEG-4000 are dispersant, prepares polymolecularity micron/submicron ball shape silver powder, dry under vacuum after then being cleaned respectively with alcohol and distilled water successively by silver powder;
(2) first prepare sodium hypophosphite solution, then add pyrovinic acid, pyrovinic acid lead, EDTA, complexing agent, ascorbic acid and thiocarbamide successively, obtained electroless lead plating liquid after fully dissolving;
(3) be 0.03 ~ 0.3mol/L dust technology washing activation step (1) dispersed micron/submicron ball shape silver powder of preparing by concentration, and then this silver powder to be dispersed in concentration be 4 × 10
-6~ 8 × 10
-4in the dispersant PVP of mol/L and PEG-4000 solution, then joined by this mixed solution in the chemical plating fluid in stirring and react 20 ~ 45 minutes, reaction temperature is 40 ~ 95 DEG C, and centrifugation is stand-by; Then use deionized water and alcohol centrifugal deposition and ultrasonic dispersion cycle to clean, remove reaction residue, finally obtain single dispersing lead/galactic nucleus shell composite powder.
2. the preparation method of high-temperature electronic slurry lead according to claim 1/galactic nucleus shell composite powder, be characterised in that: in described step (1), the preparation of polymolecularity micron/submicron ball shape silver powder is that first compound concentration is the liquor argenti nitratis ophthalmicus of 0.25 ~ 1.5mol/L, concentration is the ascorbic acid solution of 0.3 ~ 4.5mol/L, then be that 0.01 ~ 0.1:1 gets the raw materials ready according to the mass ratio of dispersant and silver nitrate, dispersant is divided into two parts, add in liquor argenti nitratis ophthalmicus and ascorbic acid solution respectively, be 3 ~ 6 by ammoniacal liquor adjust ph, again liquor argenti nitratis ophthalmicus is poured in ascorbic acid solution, first stir 5 minutes with the speed being less than 50r/min, 15 ~ 25min is stirred again with the speed of 150 ~ 500r/min, centrifugation obtains dispersed micron/submicron ball shape silver powder.
3. the preparation method of high-temperature electronic slurry lead according to claim 1/galactic nucleus shell composite powder, is characterized in that: silver powder cleans 4 times respectively with alcohol and distilled water successively in described step (1), then drying 4 hours under vacuum condition at 50 DEG C.
4. the preparation method of high-temperature electronic slurry lead according to claim 1/galactic nucleus shell composite powder, it is characterized in that: the concrete composition of described electroless lead plating liquid is 4 ~ 25g/L sodium hypophosphite, 10 ~ 50g/L pyrovinic acid, 4 ~ 20g/L pyrovinic acid lead, 15 ~ 35g/LEDTA, 5 ~ 20g/L complexing agent, 2 ~ 10g/L ascorbic acid and 10 ~ 80g/L thiocarbamide, often plants after the material added dissolves completely and add lower one again during preparative chemistry plating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181549.5A CN104001930B (en) | 2014-05-04 | 2014-05-04 | The preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181549.5A CN104001930B (en) | 2014-05-04 | 2014-05-04 | The preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104001930A CN104001930A (en) | 2014-08-27 |
| CN104001930B true CN104001930B (en) | 2016-03-30 |
Family
ID=51362996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410181549.5A Active CN104001930B (en) | 2014-05-04 | 2014-05-04 | The preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104001930B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107742696B (en) * | 2017-10-10 | 2020-11-13 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of carbon-based additive for lead carbon negative electrode |
| CN112916851B (en) * | 2021-01-25 | 2023-11-28 | 江苏博迁新材料股份有限公司 | Preparation method of silver-nickel composite powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716685A (en) * | 2009-12-14 | 2010-06-02 | 昆明理工大学 | Method for preparing spherical superfine silver powder by using chemical reduction method |
| CN103506630A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院理化技术研究所 | Method for preparing flaky silver powder with ultralow apparent density |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI409979B (en) * | 2010-03-10 | 2013-09-21 | Ind Tech Res Inst | Method for manufacturing thermoelectric material |
-
2014
- 2014-05-04 CN CN201410181549.5A patent/CN104001930B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716685A (en) * | 2009-12-14 | 2010-06-02 | 昆明理工大学 | Method for preparing spherical superfine silver powder by using chemical reduction method |
| CN103506630A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院理化技术研究所 | Method for preparing flaky silver powder with ultralow apparent density |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104001930A (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103231072B (en) | Preparation method of silicon dioxide/silver core-shell composite powder for high temperature electronic paste | |
| CN103551586B (en) | A kind of preparation method of micron spherical silver powder for electroconductive silver paste | |
| CN102343441A (en) | Method for preparing monodispersed silver powder with high tap density and low agglomeration | |
| US8231704B2 (en) | Silver particles and processes for making them | |
| CN110026569B (en) | Preparation method of nano-silver | |
| US8372178B2 (en) | Silver particles and processes for making them | |
| CN110355380B (en) | Preparation method of hexagonal flaky micron-crystal silver powder | |
| CN103100722B (en) | Preparation method of high tap density monodisperse silver powder | |
| US8366799B2 (en) | Silver particles and a process for making them | |
| CN104341860A (en) | Nanometer conductive ink and preparing method thereof | |
| CN102554265A (en) | Preparation method of mono-dispersed highly crystalline silver powder with adjustable particle size | |
| CN103624267A (en) | Method for preparing silver powder in continuous mode | |
| CN102000835A (en) | Method for preparing micron spherical silver powder | |
| CN102220045A (en) | Low-temperature-sintered solvent-based nano-silver electroconductive ink and preparation process thereof | |
| CN107545941A (en) | A kind of method for preparing solar cell front side silver paste slurry | |
| CN101708555B (en) | Method for preparing flake silver powder | |
| CN108672718A (en) | A kind of preparation method of the spherical silver powder of high specific area and its silver powder obtained | |
| CN103042230A (en) | Preparation method for micron spherical silver powder for electronic paste | |
| CN102689016B (en) | Preparation method of superfine nickel powder | |
| CN102441675B (en) | Preparation method for high-crystallinity silver powder | |
| CN112828300A (en) | Nano silver, preparation method and application | |
| CN104001930B (en) | The preparation method of high-temperature electronic slurry lead/galactic nucleus shell composite powder | |
| CN102328094B (en) | Method for preparing ultrafine silver powder with uniform particle size | |
| CN103624249B (en) | A kind of preparation method of high tap density silver powder | |
| CN110449572A (en) | The preparation method of the functional silver powder of electric slurry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221111 Address after: 650106 No. 1369 Kegao Road, high tech Development Zone, Kunming, Yunnan Patentee after: KUNMING GAOJU TECHNOLOGY CO.,LTD. Address before: 650093 No. 253, Xuefu Road, Wuhua District, Yunnan, Kunming Patentee before: Kunming University of Science and Technology |
|
| TR01 | Transfer of patent right |