CN118060552A - Preparation method of silver powder with high sintering activity - Google Patents
Preparation method of silver powder with high sintering activity Download PDFInfo
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- CN118060552A CN118060552A CN202410495350.3A CN202410495350A CN118060552A CN 118060552 A CN118060552 A CN 118060552A CN 202410495350 A CN202410495350 A CN 202410495350A CN 118060552 A CN118060552 A CN 118060552A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000005245 sintering Methods 0.000 title claims abstract description 36
- 230000000694 effects Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007853 buffer solution Substances 0.000 claims abstract description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 60
- 238000010907 mechanical stirring Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- QNPCWVPCAXGWPL-UHFFFAOYSA-L disodium hydrogen carbonate acetate Chemical compound [Na+].[Na+].CC([O-])=O.OC([O-])=O QNPCWVPCAXGWPL-UHFFFAOYSA-L 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010130 dispersion processing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000000034 method Methods 0.000 abstract description 23
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001958 silver carbonate Inorganic materials 0.000 abstract description 6
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000013049 sediment Substances 0.000 abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- -1 silver ions Chemical class 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000011535 reaction buffer Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a preparation method of high sintering activity silver powder, and relates to the field of chemical preparation of metal powder. According to the invention, sodium dodecyl benzene sulfonate is added in the process of preparing silver solution, sodium carbonate and acetic acid are utilized to prepare buffer solution, the pH value of the whole reaction process is regulated and controlled by adding the buffer solution into the silver solution in the reaction process, silver powder with small particles is prepared by reducing silver carbonate sediment by formaldehyde, then aging treatment is carried out, and meanwhile, the aging process of the silver powder is regulated and controlled by utilizing sodium dodecyl benzene sulfonate, so that the finally generated silver powder presents a size doped state. Through the mode, the reaction system and the aging conditions can be effectively controlled, and the silver powder doped with large particles and small particles can be obtained through one-time reaction and natural aging, wherein the particle size of the large particles is 2-8 mu m, the particle size of the small particles is 0.2-0.6 mu m, and the silver powder has high sintering activity.
Description
Technical Field
The invention relates to the technical field of chemical preparation methods of metal powder, in particular to a preparation method of silver powder with high sintering activity.
Background
Silver powder is widely used in various conductive materials due to its unique conductivity and oxidation resistance. According to different application scenes, the silver powder particles have different requirements on morphology and size. In the prior art, common preparation methods of silver powder are divided into a physical method and a chemical method, wherein the physical method comprises an atomization method, a vapor phase evaporation method, a grinding method and the like, the chemical method comprises a sol-gel method, a liquid phase reduction method, a physical vapor deposition method (PVD), a hydrothermal method, a chemical vapor deposition method (CVD) and the like, and the liquid phase reduction method is still most commonly used for preparing the high-temperature sintered silver powder required by the photovoltaic field at present.
At present, when silver powder is prepared by adopting a liquid phase reduction method, a common mode is to prepare silver powder by reducing silver ammine complex by formaldehyde. For example, patent publication No. CN102699345A provides a method for preparing micron-sized high-activity spherical silver powder, which comprises adding formaldehyde solution into silver-ammonia solution prepared from silver nitrate, sodium hydroxide, ammonia water and deionized water, reacting to obtain spherical silver powder slurry, solid-liquid separating, and drying to obtain silver powder. However, this approach yields silver powder of a single particle size. Aiming at the application scene of high-temperature sintering silver paste, the silver powder with single granularity can not well meet the requirements of the sintering process, and in order to obtain better sintering performance on the premise of keeping the basic performance of the original silver paste, small-particle silver powder and large-particle silver powder are often mixed for use in industry.
In order to directly prepare silver powder doped with large and small particles, the patent with the publication number CN117047121A provides a preparation method of silver powder, and the patent firstly adds reducing agent formaldehyde to reduce most of silver ions in a system by controlling the types and the sequence of adding the reducing agent, then adds ascorbic acid to quickly react with the rest of silver ions in the system to generate a large number of new crystal nuclei to grow into smaller silver powder particles, so that the silver ions in the system are completely reduced, and the mixed silver powder doped with the large and small particles is prepared at one time. However, this method requires multiple dosing reactions to achieve and needs to be further simplified.
In view of the above, there is a need to devise an improved method for preparing silver powder with high sintering activity to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of silver powder with high sintering activity, which prepares a silver powder product doped with large and small particles through one-step reaction so as to have better sintering performance.
In order to achieve the above object, the present invention provides a method for preparing silver powder with high sintering activity, comprising the steps of:
S1, preparing silver solution
Fully mixing deionized water and silver nitrate, adding polyvinylpyrrolidone, fully dissolving, adding sodium dodecyl benzene sulfonate, and stirring until the sodium dodecyl benzene sulfonate is fully dissolved to obtain a silver solution;
wherein the proportion of deionized water, silver nitrate, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate is 100 mL:18.5-19.5 g, 0.19-0.76 g and 0.002-0.02 g;
S2, preparing sodium carbonate-acetic acid buffer solution
Mixing deionized water and sodium carbonate according to the proportion of 51 mL:9 g, stirring until the deionized water and the sodium carbonate are completely dissolved, and then dropwise adding acetic acid under the condition of mechanical stirring until the pH value of the solution reaches 10.8 to obtain a sodium carbonate-acetic acid buffer solution;
S3, oxidation-reduction reaction
Adding the sodium carbonate-acetic acid buffer solution into the silver solution under the conditions of 30 ℃ and mechanical stirring, keeping mechanical stirring, adding formaldehyde aqueous solution, continuously mechanically stirring until the reaction is sufficient, and then aging to obtain a silver powder initial product; the volume concentration of formaldehyde in the formaldehyde aqueous solution is 37%;
the volume ratio of the deionized water used in the step S1, the deionized water used in the step S2 and the formaldehyde aqueous solution used in the step S3 is 100:51:4-6;
s4, product surface treatment
Washing and filtering the silver powder initial product, performing dispersion treatment, and sequentially performing filtration, drying and crushing treatment on the product after the dispersion treatment to obtain high-sintering-activity silver powder;
The high-sintering-activity silver powder simultaneously contains large-particle silver powder with the particle size of 2-8 mu m and small-particle silver powder with the particle size of 0.2-0.6 mu m.
As a further improvement of the present invention, in step S3, the aging treatment is: heating at 55-65 ℃ for 40-50 min under the condition of mechanical stirring.
As a further improvement of the present invention, in step S3, the aging treatment is: and continuously mechanically stirring for 10-14 h at room temperature.
As a further improvement of the present invention, in step S3, the aqueous formaldehyde solution is added after maintaining mechanical stirring for 1min, and the duration of the mechanical stirring is 3h.
As a further improvement of the present invention, in step S3, the aqueous formaldehyde solution is added in a single addition.
As a further improvement of the present invention, in step S4, the manner of the dispersion processing includes: dispersing in a polyvinyl alcohol aqueous solution with the mass concentration of 1%, stirring for 10-15 min, and filtering; then dispersing the mixture in an ethanol solution of oleic acid with the mass concentration of 0.5 percent, and stirring the mixture for 10 to 15 minutes.
As a further development of the invention, in step S1, the polyvinylpyrrolidone has a type K30.
The beneficial effects of the invention are as follows:
According to the preparation method of the silver powder with high sintering activity, a one-time reaction and natural aging mode is adopted, a reaction buffer system is established through sodium carbonate and acetic acid, the pH value in the whole reaction process is regulated and controlled, silver powder with small particles is prepared by reducing silver carbonate sediment through formaldehyde, and the aging process of the silver powder is regulated and controlled through sodium dodecyl benzene sulfonate. In the aging process, the silver powder with smaller particles can be higher than the silver powder with large particles due to the surface free energy, so that the concentration of silver ions around the silver powder is higher than that of the silver powder with large particles, and finally, the silver powder with small particles gradually dissolves and disappears due to the diffusion of silver ions to low concentration. The sodium dodecyl benzene sulfonate has hydrophobic and hydrophilic groups, and can form micelles or liquid drops in the solution, so that a certain wrapping protection effect is achieved on the small-particle silver powder, and the finally generated silver powder is in a size doped state. Through the control of the reaction system and the aging conditions, the effect of doping large and small particles which can be realized by multiple reactions in the prior art can be achieved by only one reaction.
Drawings
FIG. 1 is a scanning electron micrograph of the silver powder produced in example 1.
FIG. 2 is a scanning electron micrograph of the silver powder produced in example 2.
FIG. 3 is a scanning electron micrograph of the silver powder produced in example 3.
FIG. 4 is a scanning electron micrograph of the silver powder produced in example 4.
FIG. 5 is a scanning electron micrograph of the silver powder produced in example 5.
FIG. 6 is a scanning electron micrograph of the silver powder produced in comparative example 1.
FIG. 7 is a scanning electron micrograph of the silver powder produced in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of high sintering activity silver powder, which comprises the following steps:
S1, preparing silver solution
Fully mixing deionized water and silver nitrate, adding polyvinylpyrrolidone, fully dissolving, adding sodium dodecyl benzene sulfonate, and stirring until the sodium dodecyl benzene sulfonate is fully dissolved to obtain a silver solution;
wherein the proportion of deionized water, silver nitrate, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate is 100 mL:18.5-19.5 g, 0.19-0.76 g and 0.002-0.02 g;
S2, preparing sodium carbonate-acetic acid buffer solution
Mixing deionized water and sodium carbonate according to the proportion of 51 mL:9 g, stirring until the deionized water and the sodium carbonate are completely dissolved, and then dropwise adding acetic acid under the condition of mechanical stirring until the pH value of the solution reaches 10.8 to obtain a sodium carbonate-acetic acid buffer solution;
S3, oxidation-reduction reaction
Adding the sodium carbonate-acetic acid buffer solution into the silver solution under the conditions of 30 ℃ and mechanical stirring, keeping mechanical stirring, adding formaldehyde aqueous solution, continuously mechanically stirring until the reaction is sufficient, and then aging to obtain a silver powder initial product; the volume concentration of formaldehyde in the formaldehyde aqueous solution is 37%;
the volume ratio of the deionized water used in the step S1, the deionized water used in the step S2 and the formaldehyde aqueous solution used in the step S3 is 100:51:4-6;
s4, product surface treatment
And washing and filtering the silver powder initial product, performing dispersion treatment, and sequentially performing filtration, drying and crushing treatment on the product subjected to dispersion treatment to obtain the silver powder with high sintering activity.
Based on the mode, the invention can establish a reaction buffer system through sodium carbonate and acetic acid, regulate and control the pH of the whole reaction process, form silver carbonate sediment, under the condition, the further added formaldehyde can reduce the silver carbonate sediment to prepare small-particle silver powder, and on the basis, the silver powder is aged, and the aging process is regulated and controlled by utilizing sodium dodecyl benzene sulfonate in silver solution. In the aging process, the silver powder with smaller particles can have higher concentration of silver ions than the silver powder with large particles due to higher surface free energy, and the silver ions diffuse to low concentration to gradually disappear the silver powder with small particles. Based on the primary reaction and natural aging mode designed in the preparation method and the synergistic effect among the medicaments used in each step, the finally prepared silver powder with high sintering activity can be in a size doped state, and the silver powder simultaneously contains large-particle silver powder with the particle size of 2-8 mu m and small-particle silver powder with the particle size of 0.2-0.6 mu m, so that the silver powder has better sintering performance.
In some embodiments of the present invention, the corresponding steps and parameters involved in the above steps may be further preferred.
For example, in step S1, the polyvinylpyrrolidone is preferably K30.
In the step S3, after the sodium carbonate-acetic acid buffer solution is added into the silver solution, maintaining mechanical stirring for 1min, adding the formaldehyde aqueous solution at one time, and aging after continuous mechanical stirring for 3 h; the aging treatment mode is as follows: heating at 55-65 ℃ for 40-50 min under the condition of mechanical stirring, or continuously mechanically stirring at room temperature for 10-14 h.
In step S4, the manner of the dispersion processing includes: dispersing in a polyvinyl alcohol aqueous solution with the mass concentration of 1%, stirring for 10-15 min, and filtering; then dispersing the mixture in an ethanol solution of oleic acid with the mass concentration of 0.5 percent, and stirring the mixture for 10 to 15 minutes.
The method for preparing the silver powder with high sintering activity provided by the invention is described in detail below with reference to specific examples.
Example 1
The embodiment provides a preparation method of high sintering activity silver powder, which comprises the following steps:
S1, preparing silver solution
Under the condition of mechanical stirring, 18.9 g silver nitrate is added into 100mL deionized water, the mixture is fully mixed, then 0.76 g polyvinylpyrrolidone (PVP-K30) is added, after complete dissolution, 0.02g sodium dodecyl benzene sulfonate is added, and the mixture is stirred until complete dissolution is achieved, thus obtaining silver solution.
S2, preparing sodium carbonate-acetic acid buffer solution
Adding 9 g sodium carbonate into 51 mL deionized water under the condition of mechanical stirring, stirring until the sodium carbonate and the acetic acid are completely dissolved, and dropwise adding acetic acid into the solution under the condition of mechanical stirring until the pH value of the solution reaches 10.8, so as to obtain a sodium carbonate-acetic acid buffer solution.
S3, oxidation-reduction reaction
And (2) adding all the sodium carbonate-acetic acid buffer solution prepared in the step (S2) into the silver solution prepared in the step (S1) under the conditions of constant temperature of 30 ℃ and mechanical stirring, keeping mechanical stirring, adding 5mL volume percent of 37% formaldehyde aqueous solution after 1 min, continuously mechanically stirring for 3 h, and then aging in a manner of mechanically stirring for 45 min at 60 ℃ to obtain a silver powder initial product after aging, wherein a scanning electron microscope photo of the silver powder is shown in figure 1. As can be seen from FIG. 1, the silver powder contains both large particle silver powder with a particle size range of 2-8 μm and small particle silver powder with a particle size range of 0.2-0.6 μm.
S4, product surface treatment
Washing and filtering the silver powder initial product, dispersing the silver powder initial product into an aqueous solution of polyvinyl alcohol with the mass concentration of 1%, stirring the aqueous solution for 15 min%, filtering the aqueous solution, dispersing the aqueous solution into an ethanol solution of oleic acid with the mass concentration of 0.5%, stirring the aqueous solution for 15 min, and sequentially filtering, drying and crushing the aqueous solution to separate the pseudo-agglomerated silver powder, thereby obtaining the silver powder with high sintering activity.
Examples 2 to 3
Examples 2 to 3 respectively provide a method for preparing silver powder with high sintering activity, which is different from example 1 only in that the amount of polyvinylpyrrolidone used in step S1 is changed, the amount of polyvinylpyrrolidone used in example 2 is 0.39 g, the amount of polyvinylpyrrolidone used in example 3 is 0.19 g, and the remaining steps and parameters are the same as those in example 1, and are not repeated here.
The scanning electron micrographs of the silver powder with high sintering activity prepared in examples 2-3 are shown in fig. 2-3, and are in a state of doping with large and small particles, and have high sintering activity.
Examples 4 to 5 and comparative example 1
Examples 4 to 5 and comparative example 1 respectively provide a method for preparing silver powder, which is different from example 1 only in that the amount of sodium dodecyl benzene sulfonate used in step S1 is changed, the amount of sodium dodecyl benzene sulfonate used in example 4 is 0.004 g, the amount of sodium dodecyl benzene sulfonate used in example 5 is 0.002 g, the amount of sodium dodecyl benzene sulfonate used in comparative example 1 is 0.2 g, and the remaining steps and parameters are the same as those of example 1, and are not repeated here.
Scanning electron micrographs of the silver powders prepared in examples 4 to 5 and comparative example 1 are shown in FIGS. 4 to 6, respectively. As can be seen from comparison of fig. 4 to 6, the amount of sodium dodecyl benzene sulfonate needs to be controlled within a certain range, and excessive sodium dodecyl benzene sulfonate excessively affects the growth of crystal nuclei during reaction, so that the number of large-particle silver powder in the silver powder product and the particle size of the silver powder are greatly reduced.
Comparative example 2
Comparative example 2 provides a method for preparing silver powder, which is different from example 1 only in that the pH of the sodium carbonate-acetic acid buffer solution in step S2 is changed, the pH in comparative example 2 is 11.8, and the remaining steps and parameters are identical to those of example 1, and will not be described again.
A scanning electron micrograph of the silver powder obtained in comparative example 2 is shown in FIG. 7. As can be seen from comparing fig. 1 and fig. 7, compared with example 1, increasing the pH of the buffer solution in comparative example 2 affects the initial speed of the reduction reaction of silver carbonate by formaldehyde, so that the concentration of silver atoms in the initial stage of reduction is changed, and thus the particle size of the silver powder is affected, and the silver powder doped with large and small particles cannot be produced through the subsequent aging process.
In summary, the invention provides a preparation method of high sintering activity silver powder, and relates to the field of chemical preparation of metal powder. According to the invention, sodium dodecyl benzene sulfonate is added in the process of preparing silver solution, sodium carbonate and acetic acid are utilized to prepare buffer solution, the pH value of the whole reaction process is regulated and controlled by adding the buffer solution into the silver solution in the reaction process, silver powder with small particles is prepared by reducing silver carbonate sediment by formaldehyde, then aging treatment is carried out, and meanwhile, the aging process of the silver powder is regulated and controlled by utilizing sodium dodecyl benzene sulfonate, so that the finally generated silver powder presents a size doped state. Through the mode, the reaction system and the aging conditions can be effectively controlled, and the silver powder doped with large particles and small particles can be obtained through one-time reaction and natural aging, wherein the particle size of the large particles is 2-8 mu m, the particle size of the small particles is 0.2-0.6 mu m, and the silver powder has high sintering activity.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the silver powder with high sintering activity is characterized by comprising the following steps of:
S1, preparing silver solution
Fully mixing deionized water and silver nitrate, adding polyvinylpyrrolidone, fully dissolving, adding sodium dodecyl benzene sulfonate, and stirring until the sodium dodecyl benzene sulfonate is fully dissolved to obtain a silver solution;
wherein the proportion of deionized water, silver nitrate, polyvinylpyrrolidone and sodium dodecyl benzene sulfonate is 100 mL:18.5-19.5 g, 0.19-0.76 g and 0.002-0.02 g;
S2, preparing sodium carbonate-acetic acid buffer solution
Mixing deionized water and sodium carbonate according to the proportion of 51 mL:9 g, stirring until the deionized water and the sodium carbonate are completely dissolved, and then dropwise adding acetic acid under the condition of mechanical stirring until the pH value of the solution reaches 10.8 to obtain a sodium carbonate-acetic acid buffer solution;
S3, oxidation-reduction reaction
Adding the sodium carbonate-acetic acid buffer solution into the silver solution under the conditions of 30 ℃ and mechanical stirring, keeping mechanical stirring, adding formaldehyde aqueous solution, continuously mechanically stirring until the reaction is sufficient, and then aging to obtain a silver powder initial product; the volume concentration of formaldehyde in the formaldehyde aqueous solution is 37%;
the volume ratio of the deionized water used in the step S1, the deionized water used in the step S2 and the formaldehyde aqueous solution used in the step S3 is 100:51:4-6;
s4, product surface treatment
Washing and filtering the silver powder initial product, performing dispersion treatment, and sequentially performing filtration, drying and crushing treatment on the product after the dispersion treatment to obtain high-sintering-activity silver powder;
The high-sintering-activity silver powder simultaneously contains large-particle silver powder with the particle size of 2-8 mu m and small-particle silver powder with the particle size of 0.2-0.6 mu m.
2. The method for producing a high sintering activity silver powder according to claim 1, characterized in that: in step S3, the aging process is: heating at 55-65 ℃ for 40-50 min under the condition of mechanical stirring.
3. The method for producing a high sintering activity silver powder according to claim 1, characterized in that: in step S3, the aging process is: and continuously mechanically stirring for 10-14 h at room temperature.
4. The method for producing a high sintering activity silver powder according to claim 1, characterized in that: in step S3, after maintaining mechanical stirring for 1min, adding the formaldehyde aqueous solution, wherein the duration of the mechanical stirring is 3h.
5. The method for producing a high sintering activity silver powder according to claim 1, characterized in that: in step S3, the formaldehyde aqueous solution is added in a single addition.
6. The method for producing a high sintering activity silver powder according to claim 1, characterized in that: in step S4, the manner of the dispersion processing includes: dispersing in a polyvinyl alcohol aqueous solution with the mass concentration of 1%, stirring for 10-15 min, and filtering; then dispersing the mixture in an ethanol solution of oleic acid with the mass concentration of 0.5 percent, and stirring the mixture for 10 to 15 minutes.
7. The method for producing a high sintering activity silver powder according to claim 1, characterized in that: in step S1, the polyvinylpyrrolidone has a model number K30.
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