CN114210996A - High-sintering-activity nano silver powder and preparation method thereof - Google Patents
High-sintering-activity nano silver powder and preparation method thereof Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 238000005245 sintering Methods 0.000 title claims abstract description 35
- 230000000694 effects Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 36
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- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 20
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- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
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- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
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- 230000035484 reaction time Effects 0.000 claims abstract description 3
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- 239000006228 supernatant Substances 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 8
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- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000007791 liquid phase Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 239000006254 rheological additive Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 150000007524 organic acids Chemical class 0.000 description 2
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- 238000004438 BET method Methods 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 229940116411 terpineol Drugs 0.000 description 1
Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to high sintering activity nano silver powder and a preparation method thereof. Mixing silver nitrate and water to obtain silver source liquid, mixing sodium hydroxide, a dispersing agent, a reducing agent and water to obtain a reducing liquid, and adjusting the pH value of the reducing liquid to be 9-12. Then theAnd under the condition of stirring, quickly pouring the silver source liquid into the reducing liquid to carry out reduction reaction to obtain the nano-silver dispersion liquid. And (3) centrifugally separating the nano silver dispersion liquid, washing and purifying by using deionized water, and drying to obtain the nano silver powder. The preparation method has the advantages of simple process and equipment, low process cost, short reaction time and high efficiency, and can realize low-cost batch production. The obtained silver nanoparticles have good dispersibility, particle diameter of 10-50nm, and specific surface area of 30-50m2Between/g, a distinct sintering neck was observed at 180 ℃.
Description
Technical Field
The invention relates to the technical field of precious metal nano material preparation, in particular to high-sintering-activity nano silver powder and a preparation method thereof.
Background
Silver powder is a noble metal powder which is most widely applied in the electronic device industry. With the development of electronic devices towards small size, multiple functions, high reliability and the like, high-frequency high-power packaging technology plays an increasingly important role in the field of electronic packaging. The nano silver powder with low-temperature sinterability can bear the working temperature of more than 500 ℃ after being sintered, can effectively avoid the problem of joint remelting of electronic devices in the subsequent processing and using processes, and further obviously improves the reliability. The low-temperature sintering nano silver powder is considered to be an indispensable novel interface connection material in the electronic device industry, and has important value and significance for the development of electronic devices.
The preparation method of the nano silver powder comprises a gas phase method, a solid phase method and a liquid phase method. Wherein the liquid phase method comprises a hydrothermal reduction method, a micro-emulsion method, a liquid phase chemical reduction method and the like. The liquid phase chemical reduction method is that silver ions are reduced into nano silver particles coated by a dispersant by a reducing agent in a liquid phase system with the dispersant or a protective agent. The method has the advantages of simple process, low cost, controllable particle size and the like, and is a common method for preparing the nano silver powder on a large scale.
However, in the process of preparing the silver nanoparticles by the liquid-phase chemical reduction method, in order to control the particle size of the silver nanoparticles, organic macromolecules or organic high-molecular polymers are often added as dispersants, typically polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), gum arabic, gelatin, and the like. The decomposition temperature of the high molecular dispersing agents is very high, so that the sintering activity of the prepared nano silver powder is reduced, the initial sintering temperature exceeds 250 ℃, carbon residue in the sintering process is increased, and the electric conductivity, the heat conductivity and the application reliability of the nano silver joint are greatly reduced.
In addition, many silver nanopowders have specific surface areas of less than 20m2/g, and some even less than 10m 2/g. When the nano silver powder is applied to low-temperature sintering silver paste, particularly silver paste with low silver content, the rheological properties of the silver paste, such as viscosity, thixotropy and the like, can not meet the requirements of construction processes. In order to adjust rheological properties, rheological additives such as ethyl cellulose, cellulose acetate butyrate, polyamide wax and the like are often required to be added, and the high-molecular rheological additives can also reduce the sintering activity of the nano silver powder, increase the sintering temperature and sinter carbon residue, and reduce the joint performance.
Therefore, the nano silver powder with high sintering activity and high specific surface area is prepared by selecting a proper reaction system and a proper dispersant or protective agent, and the low-temperature sintering performance of the nano silver powder is favorably improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the nano silver powder with high sintering activity and the preparation method thereof. The nano silver powder has good dispersibility, the particle size is between 10 and 50nm, and the specific surface area is between 30 and 50m2Between/g, a distinct sintering neck was observed at 180 ℃.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high sintering activity nano silver powder comprises the following steps:
mixing silver nitrate and water to obtain silver source liquid, mixing sodium hydroxide, a dispersing agent, a reducing agent and water to obtain reducing liquid, and adjusting the pH value of the reducing liquid to be 9-12. Then, under the condition of stirring, quickly pouring the silver source liquid into the reducing liquid to carry out reduction reaction, thereby obtaining the nano-silver dispersion liquid. And centrifuging and filtering the nano silver dispersion liquid, washing with deionized water, and drying to obtain the nano silver powder.
Preferably, the dispersant is one or more of n-decanoic acid, undecanoic acid and lauric acid, and the reducing agent is one or more of formic acid, formaldehyde, glucose, hydrazine hydrate, carbohydrazide, sodium borohydride and ascorbic acid.
Preferably, the molar ratio of the dispersant to the silver nitrate is (1.0-4.0):1, and the molar ratio of the reducing agent to the silver nitrate is (1.0-4.0): 1.
Preferably, the stirring speed of the stirring is greater than 2000 rpm.
Preferably, the reaction time of the silver source solution and the reducing solution is 30-90min, and the reaction temperature is 20-40 ℃.
Preferably, the steps of centrifugal separation and washing purification are that the nano silver powder dispersion liquid is centrifuged for 3-5min at the rotation speed of 5000-8000rpm, the supernatant is poured off, deionized water is added, ultrasonic dispersion is carried out for 5-10min at the temperature of below 40 ℃, then centrifugation is carried out for 3-5min at the rotation speed of 5000-8000rpm, and the supernatant is poured off.
Preferably, the silver powder is dried for 12 to 24 hours in a forced air drying oven set at a temperature of 40 to 70 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) organic acid with poor water solubility is used as a dispersing agent, the pH value of a reaction system is adjusted, the dissolving condition of the dispersing agent in a reaction solution is changed, and the coating thickness of dispersing agent molecules on the surfaces of nano silver particles is controlled, so that the nano silver powder with small particle size and high specific surface area is obtained. In addition, in the process of cleaning the nano silver powder by using deionized water, the dispersing agent is not easy to fall off from the surface of the nano silver particles, and the agglomeration of the nano silver particles can be effectively prevented.
(2) The carbon chain length of the used organic acid dispersant is 10-12, so that a good coating effect can be provided in the processes of preparation, cleaning and storage of the nano silver powder, the sintering activity of the nano silver powder can be improved and the quantity of carbon residue after sintering can be reduced due to the short carbon chain, the small molecular weight and the low decomposition temperature, and particularly, the obvious sintering neck of the nano silver powder can be observed at 180 ℃.
(3) The nano silver powder prepared by the invention has high specific surface area and high oil absorption, and can reduce or even not use a high-molecular rheological additive which is difficult to decompose to adjust the rheological property of the silver paste when preparing the silver paste, particularly the silver paste with low silver content, thereby improving the sintering property of the silver paste and improving the electric conduction and heat conduction properties of a joint.
(4) The whole process of the invention adopts water as a reaction and cleaning solvent, the reaction is carried out at the temperature of 20-40 ℃, and the invention has the advantages of environmental protection, energy saving and consumption reduction.
Drawings
FIG. 1 is an SEM picture of high sintering activity nano silver powder prepared by the invention before sintering;
FIG. 2 is an SEM picture of the high sintering activity nano silver powder prepared by the invention after sintering for 90min at 180 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to better explain the present invention and to facilitate an understanding of the objects, advantages, and aspects of the present invention. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1:
(1) adding 17.0g of silver nitrate into 100g of deionized water, stirring and dissolving to obtain a silver source liquid, and maintaining the temperature of the silver source liquid at 30 +/-2 ℃;
(2) adding 34.4g of n-decanoic acid and 9.2g of formic acid into 800g of deionized water, adjusting the pH of the solution to 10 by using a NaOH aqueous solution under the condition of stirring to obtain a reducing solution, and maintaining the temperature of the reducing solution at 30 +/-2 ℃;
(3) continuously stirring the reducing solution at the rotating speed of 2500rpm, pouring the silver source solution into the reducing solution at one time, and reacting for 90min under the condition of continuous stirring;
(4) stopping stirring after reacting for 90min, and centrifuging the obtained nano silver dispersion liquid for 5min at the rotating speed of 6000 rpm;
(5) pouring out the supernatant, adding deionized water, and ultrasonically dispersing at 40 deg.C below for 10 min;
(6) after the ultrasonic dispersion is finished, centrifuging for 5min at 8000rpm, and pouring out the supernatant to obtain wet nano silver particles;
(7) transferring the wet nano silver particles into an air drying oven, adjusting the temperature to 40 ℃, and drying for 24h to obtain nano silver powder;
example 2:
(1) taking 34.0g of silver nitrate, adding 100g of deionized water, stirring and dissolving to obtain a silver source liquid, and maintaining the temperature of the silver source liquid at 30 +/-2 ℃;
(2) adding 80.1g of lauric acid and 27.6g of formic acid into 1500g of deionized water, adjusting the pH of the solution to 10 by using a NaOH aqueous solution under the condition of stirring to obtain a reducing solution, and maintaining the temperature of the reducing solution at 30 +/-2 ℃;
(3) continuously stirring the reducing solution at the rotating speed of 2500rpm, pouring the silver source solution into the reducing solution at one time, and reacting for 60min under the condition of continuous stirring;
(4) after reacting for 60min, stopping stirring, and centrifuging the obtained nano-silver dispersion liquid for 5min at the rotating speed of 6000 rpm;
(5) pouring out the supernatant, adding deionized water, and ultrasonically dispersing at 40 deg.C below for 10 min;
(6) after the ultrasonic dispersion is finished, centrifuging for 5min at 8000rpm, and pouring out the supernatant to obtain wet nano silver particles;
(7) transferring the wet nano silver particles into an air drying oven, adjusting the temperature to 60 ℃, and drying for 12h to obtain nano silver powder;
example 3
(1) Adding 51.0g of silver nitrate into 200g of deionized water, stirring and dissolving to obtain a silver source liquid, and maintaining the temperature of the silver source liquid at 30 +/-2 ℃;
(2) adding 103.2g of n-decanoic acid and 105.6g of ascorbic acid into 3000g of deionized water, adjusting the pH of the solution to 10 by using a NaOH aqueous solution under the condition of stirring to obtain a reducing solution, and maintaining the temperature of the reducing solution at 30 +/-2 ℃;
(3) continuously stirring the reducing solution at the rotating speed of 3000rpm, pouring the silver source solution into the reducing solution at one time, and reacting for 60min under the condition of continuous stirring;
(4) after reacting for 60min, stopping stirring, and centrifuging the obtained nano-silver dispersion liquid for 5min at the rotating speed of 6000 rpm;
(5) pouring out the supernatant, adding deionized water, and ultrasonically dispersing at 40 deg.C below for 10 min;
(6) after the ultrasonic dispersion is finished, centrifuging for 5min at 8000rpm, and pouring out the supernatant to obtain wet nano silver particles;
(7) transferring the wet nano silver particles into an air drying oven, adjusting the temperature to 40 ℃, drying for 24h,
comparative example 1:
(1) adding 17.0g of silver nitrate into 100g of deionized water, stirring and dissolving to obtain a silver source liquid, and maintaining the temperature of the silver source liquid at 30 +/-2 ℃;
(2) slowly adding 30g of PVA1788 into 3000g of deionized water under the condition of stirring, continuously stirring to completely dissolve the PVA to be transparent, then adding 35.2g of ascorbic acid to obtain reducing solution, and maintaining the temperature of the reducing solution at 30 +/-2 ℃;
(3) continuously stirring the reducing solution at the rotating speed of 3000rpm, pouring the silver source solution into the reducing solution at one time, and reacting for 60min under the condition of continuous stirring;
(4) after reacting for 60min, stopping stirring, and centrifuging the obtained nano-silver dispersion liquid for 5min at the rotating speed of 6000 rpm;
(5) pouring out the supernatant, adding deionized water, and ultrasonically dispersing at 40 deg.C below for 10 min;
(6) after the ultrasonic dispersion is finished, centrifuging for 5min at 8000rpm, and pouring out the supernatant to obtain wet nano silver particles;
(7) transferring the wet nano silver particles into an air drying oven, adjusting the temperature to 70 ℃, and drying for 12h to obtain nano silver powder;
for the silver powders prepared in the above examples and comparative examples, performance tests were performed:
(1) specific surface area: measuring the specific surface area of the silver powder by adopting a BET method;
(2) and (3) testing the particle size of the silver powder: testing the particle size of the silver powder by using a scanning electron microscope;
(3) volume resistivity: taking 5g of silver powder, adding 1-5g of terpineol (the specific addition amount can be different according to the specific surface area of the silver powder), stirring for 2min at 2000rpm by using a rotation revolution stirrer, then dispersing for 10 times by using a three-roll grinder to obtain silver paste, coating the silver paste on a glass slide with lines with the length of 50mm, the width of 5mm and the thickness of 30 mu m, putting the glass slide into a 180 ℃ oven for sintering for 90min, taking out the glass slide, cooling to the room temperature, measuring the resistance of the lines and calculating the volume resistivity;
(4) and (4) observing a sintering neck: coating the silver paste on a copper foil, putting the copper foil into a 180 ℃ oven for sintering for 90min, taking out the copper foil, cooling, and observing whether a sintering neck appears by using a scanning electron microscope; see in particular figures 1-2 of the drawings.
The results of the property tests of the silver powders of the examples and comparative examples are shown in Table 1.
TABLE 1
In comparison with examples 1 to 3, comparative example 1, in which silver powder was prepared using an organic high molecular polymer PVA as a dispersant, the prepared silver powder could not be sintered at 180 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of nano silver powder with high sintering activity is characterized by comprising the following steps:
s1, mixing silver nitrate and water to obtain silver source liquid;
s2, mixing sodium hydroxide, a dispersing agent, a reducing agent and water to obtain a reducing solution, and adjusting the pH value of the reducing solution to 9-12;
s3, rapidly pouring the silver source liquid into the reducing liquid under the condition of stirring, and carrying out reduction reaction to obtain a nano-silver dispersion liquid;
and S4, centrifugally separating the nano silver dispersion liquid, washing and purifying with deionized water, and drying to obtain the nano silver powder.
2. The method for preparing nano silver powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the dispersing agent is one or more of n-decanoic acid, undecanoic acid and lauric acid, and the reducing agent is one or more of formic acid, formaldehyde, glucose, hydrazine hydrate, carbohydrazide, sodium borohydride and ascorbic acid.
3. The method for preparing the nano silver powder with high sintering activity according to claim 2, wherein the method comprises the following steps: the molar ratio of the dispersing agent to the silver nitrate is (1.0-4.0):1, and the molar ratio of the reducing agent to the silver nitrate is (1.0-4.0): 1.
4. The method for preparing the nano silver powder with high sintering activity according to claim 3, wherein the method comprises the following steps: in the step S3, the stirring speed is higher than 2000 rpm.
5. The method for preparing nano silver powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the reaction time of the silver source liquid and the reducing liquid is 30-90min, and the reaction temperature is 20-40 ℃.
6. The method for preparing nano silver powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the steps of centrifugal separation, washing and purification are that the nano silver powder dispersion liquid is centrifuged for 3-5min at the rotation speed of 5000-plus-8000 rpm, the supernatant is poured off, deionized water is added, ultrasonic dispersion is carried out for 5-10min at the temperature of below 40 ℃, and then centrifugation is carried out for 3-5min at the rotation speed of 5000-plus-8000 rpm, and the supernatant is poured off.
7. The method for preparing nano silver powder with high sintering activity according to claim 1, wherein the method comprises the following steps: the drying condition of the nano silver powder is that the nano silver powder is dried for 12 to 24 hours in a forced air drying oven with the temperature set to be 40 to 70 ℃.
8. The high sintering activity nano silver powder prepared by any one of claims 1 to 7, wherein the nano silver powder has a particle size of 10 to 50nm and a specific surface area of 30 to 50m2In terms of a/g, a pronounced sintering neck was observed at 180 ℃.
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